presenteD to
£be Xibran?
of tbe
Tllntvereitp of Toronto
Digitized by the Internet Archive
in 2010 with funding from
University of Toronto
http://www.archive.org/details/p1iecindustriale13amer
Chem%^i^f^
Cfte Journal or fntmsitrtal
ano engineering CJemtsrrp
PUBLISHED BY
%f)t &mertean Cfjemteal g>octetp
VOLUME XIII, 1921
2£>oart> of CDitors
Editor: CHAS. H. HERTY
Assistant Editor: Lois W. Woodford
Advisory Board
H. E. Barnard J. W. Beckman A. D. Little A. V. H. Mory
Chas. L. Reese Geo. D. Rosengarten T. B. Wagner
EASTON. PA.
ESCHENBACH PRINTING COMPANY
1921
/
:°
L /3
v. I3>
nt .1
11
TTPiq c/oztrnal <yP
INDU
RIAL
%> ENGINEERING
CHEMISTRY
Published Monthly by The American Chemical Society
Advisory Board: H. E. Barnard
Chas. L. Reese
Bditobial Offices :
One Madison Avenue, Room 343
New York City
Telephone: Gramercy 0613-0614
Editor: CHAS. H. HERTY
Assistant Editor: Lois W. Woodford
J. W. Beckman A. D. Little A. V. H. Mory
Geo. D. Rosengarten T. B. Wagner
Advbrtisinc Department:
1 70 Metropolitan Tower
New York City
Telephone: Gramercy 3880
Vok
13
JANUARY 1, 1921
No.
CONTENTS
Editorials:
Officers for 192 1 2
Will the Senate Act? 2
When a Law Defeats Itself — Repeal It! 3
Amenities de Luxe 3
Are Your Folks on the List? 3
No Time for Dullness 4
Expansion of the News Service 4
Equitable Distribution 5
Notes 5
Chemical Industry and Trade of France. O.P.Hopkins. 6
Fuel Symposium:
Low-Temperature Carbonization and Its Application
to High Oxygen Coals. S. W. Parr and T. E.
Layng 14
Carbonization of Canadian Lignite. Edgar Stansfield 17
The Commercial Realization of the Low-Temperature
Carbonization of Coal. Harry A. Curtis 23
By-Product Coking. F. W. Sperr, Jr., and E. H. Bird 26
By-Product Coke, Anthracite, and Pittsburgh Coal as
Fuel for Heating Houses. Henry Kreisinger 31
Some Factors Affecting the Sulfur Content of Coke and
Gas in the Carbonization of Coal. Alfred R.
Powell 33
The Distribution of the Forms of Sulfur in the Coal
Bed. H. F. Yancey and Thomas Fraser 35
.Colloidal Fuels, Their Preparation and Properties.
S. E. Sheppard 37
Fuel Conservation, Present and Future. Horace C.
Porter 47
Gasoline Losses Due to Incomplete Combustion in
Motor Vehicles. A. C. Fieldner, A. A. Straub and
G. W. Jones 51
Enrichment of Artificial Gas with Natural Gas. James
B. Garner 58
The Charcoal Method of Gasoline Recovery. G. A.
Burrell, G. G. Oberfell and C. L. Voress 58
Original Papers:
Studies on the Nitrotoluenes. V — Binary Systems
of o-Nitrotoluene and Another Nitrotoluene. James
M. Bell, Edward B. Cordon, Fletcher H. Spry and
Woodford White 59
The Preparation and Analysis of a Cattle Food Con-
sisting of Hydrolyzed Sawdust. E. C. Sherrard and
G. W. Blanco 61
The Effect of Concentration of Chrome Liquor upon
the Adsorption of Its Constituents by Hide Sub
stance. Arthur W. Thomas and Margaret W.
Kelly 65
— The Action of Certain Organic Accelerators in the
Vulcanization of Rubber. II— G. D. Kratz, A. H.
Flower and B. J. Shapiro 67
Electric Oven for Rapid Moisture Tests. Guilford L.
Spencer 70
Addresses and Contributed Articles:
—The Chemistry of Vitamines. Atherton Seidell 72
— The Mechanism of Catalytic Processes. Hugh S.
Taylor 7 1
Industrial and Agricultltral Chemistry in the British
West Indies, with Some Account of the Work of
Sir Francis Watts, Imperial Commissioner of
Agriculture. C. A. Browne 78
Research Problems in Colloid Chemistry. Wilder D.
Bancroft 83
Scientific Societies:
Crop Protection Institute Discusses War on Boll-
Weevil; American Institute of Chemical Engineers;
Association of Official Agricultural Chemists; Cal-
endar of Meetings; Perkin Medal Award; Corpora-
tion Members of the American Chemical Society.. . . Sq
Notes and Correspondence:
Pure Phthalic Anhydride; Standardization of Indus-
trial Laboratory Apparatus; American Institute of
Baking, Research Fellowships 91
Washington Letter '<-'
Paris Letter 94
London Letter 94
Personal Notes 95
Government Publications 'n
Book Reviews 99
New Publications 102
Market Report 103
Subscription to non-members. $7.50; single copy, 75 cents, to members. 60 cents. Foreign postage, 75 cents, Canada, Cuba and Mexico excepted.
Entered as Second class Matter December 19, 1908. at the Post Office at Easton. Pa., under the Act of March 3, 1879.
Acceptance for mailing at special rate of postage provided for in Section 1103, Act of October 3, 1917, authorized July 13, 1918.
Subscriptions and claims for lost copies should be referred to Charles L Parsons. Secretary. 1709 G Street. N W . Washington. D C
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol.
i 3, No. i
LDITORIALS
OFFICERS FOR 192 1
The result of the ballot, of the Council for officers of
the American Chemical Society for the current year
is as follows:
President
Edgar Pahs Smith
Directors
George D. Rosengarten
Henry P. Talbot
Councilors
H. E. Howe
C. L. Alsberc
Allen Rogers
Lauder W. Jones
WILL THE SENATE ACT?
The Sixty-sixth Congress ends on March 4, 192 1.
( tne^of the three months available for legislation at
this final session has passed into history, and the dye
bill still remains on the calendar of unfinished business.
The question is being asked by all "Will the Senate
act?" We repeat again our conviction that it will.
Every argument hitherto presented in behalf of the
legislation stands to-day as forceful as ever. To
these must be added now the easily evident fact
that the failure to pass this legislation has
brought about a degree of demoralization which is
lamentable. Contemplated expansion of plants has
been postponed because of the uncertainty of the
future, research staffs are being contracted, a short-
sighted policy on the part of manufacturers, but true
nevertheless in many cases, and the chilling effect of
this demoralization is making itself felt in the ranks of
our chemists and students of chemistry.
Now comes a new factor into the situation. In ad-
dition to the large amounts of new capital being called
for by the German dye cartel, the life of that cartel
has been extended from the year 1966 to 2000, and
its dissolution at that time made more difficult by
requiring a four-fifths instead of a two-thirds ma-
jority to effect its dissolution. Not content with this
unification the segregation of the nitrogen-fixation
industry under the Haber process has been accom-
plished by the formation of an organization capitalized
at 500,000,000 marks, which organization is placed
undei the eontrol of the dye cartel. Regaining
mastery in the field of dyes is now not sufficient, am-
bition is leading on to a world control of nitrogenous
products. That is a threat which no nation can
ignore. There is no secret about the matter. The
facts have all been published.
With this situation existing, can the Senate
afford not to act? On what grounds could delay
be justified? Senator Thomas' nightmare of an
American dye trust was refuted sufficiently by the
declaration of the great mass of small producers of
dyes, read on the floor of the Senate, that they would
be the first to go under in the price war which would
follow the failure to enact adequate legislation; but
the Senator's dream looks like thirty cents when com-
pared with the steps already taken in Germany to
secure domination of the world's dye and nitrogen
supplies. The press report that this fixed-nitrogen
organization is contemplating the erection of plants
in the United States and Japan may be erroneous,
but already the market situation is being felt out.
The following circular letter is being distributed in
the trade. One of our dye concerns, the Peerless
Color Company, Inc., of Bound Brook. N. J., has
furnished us a copy.
C. B. Peters Co., Inc.
15 Maiden Lane
New York
Peerless Color Co., Inc.,
Bound Brook, X. J.
Gentlemen:
nitrite of soda
As previously advised you, we have for distribution ia this
country through American fiscal agents, that portion of Nitrite
of Soda, as produced by the Badische Anilin- & Soda-Fabrik
of Germany through their atmospheric nitrogen development,
which has been allotted for consumption in the United
States.
Naturally because of the existing business depression, there-
is very little activity, with the result that prices have bee« re-
duced considerably; in fact for spot material we can offer, sub-
ject to change, ton lots as low as 6c per lb. ex warehouse at
New York, and for larger quantities it might be possible to
shade this figure with a firm bid in hand, although the feeling
here is very strong that the bottom of the market has been
reached. We have on hand at the present time in New York
approximately 50 tons, and no further shipments will come into
this country until orders are placed for shipment from
abroad.
We have instructions from Germany to find out the prospects
of Nitrite of Soda consumption in the United States over the
year 192 1, and for this reason we are taking the liberty of ad-
dressing you to ask if you will kindly let us have your opinion
in this regard. If the market has actually reached its lowest
level, this might be a good time to consider requirement con-
tracts for the coming year and any suggestions that buyers have,
we shall be happy to cable abroad. The quality of our material
is as good as that produced in any part of the world, and we
shall be pleased to forward samples upon request.
Awaiting with interest your reply, we remain
Yours very truly,
C. B. Peters Co., Inc.,
cbp-th (Signed) C. B. Peters, President
To this request the Company responded:
Please be advised that we shall not, under any conditions,
cooperate with you in supplying the information wanted by
the Germans nor will we knowingly buy one pound of the sur-
plus German air-fixation products at 6c per pound or any other
price.
Reports from Washington indicate that the Moses-
Thomas combination intends to filibuster as strenu-
ously as ever. Under ordinary procedure they can
defeat the bill. The favorable majority in the Sen-
ate, however, can thwart these tactics by adopting
a closure rule limiting debate on the bill. This is an
action rarely resorted to by the Senate, but the un-
yielding and inexplicably bitter opposition of this
very small minority, on the one hand, and the future
welfare of this country as involved in this new com-
bination threat from abroad, on the other hand,
justify and demand the adoption of the closure.
Jan., iQ2i
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
WHEN A LAW DEFEATS ITSELF— REPEAL IT!
A state law which is directly contrary to the spirit
and intent of a federal statute should be repealed.
Such is the case with portions of Paragraphs 8 and 9
of Chapter 911 of the Laws of New York, which
became effective May 24, 1920, placing an excise tax
on the production and sale of "tax-free" alcohol.
The National Prohibition Act was avowedly framed
for the two-fold purpose of prohibiting the manu-
facture and sale of intoxicating liquors and en-
couraging the production of alcohol for industrial and
scientific purposes. Due and ample provision is made
for the production and distribution, under govern-
mental supervision, of tax-free non-beverage alcohol.
The plain purpose of the law is to remove any dis-
crimination against alcohol as a chemical reagent in
industry and in scientific research. In the face of
this plain declaration by Congress the New Y<Jrk
law levies a tax of $0.30 on each gallon of such alcohol,
and $250 on each place where it is sold. The tax-
free use contemplated by the federal statute is nullified
by the excise tax of the state law.
A law which defeats itself should be repealed. What
has happened since the enactment of this law? The
large distributors of industrial alcohol have moved
their warehouses across the river, from New York
into New Jersey. The ferry fare is cheaper than the
excise tax. Large manufacturers who could readily
add to existing stocks of alcohol have found, in view
of the tax, that it is not worth while to put in de-
alcoholizers, and this potential source of an important
chemical reagent is lost.
The manufacture of alcohol in New York State is
dead, the expected revenue from the excise tax is nil.
Common sense demands that it be repealed. Why
burden the courts with litigation testing its con-
stitutionality?
Minister expressed his hearty support of Mr. Hoshi's intention.
Mr. Hoshi, thus assured of the correctness of his proposal,
brought the matter to the notice of the German representative.
AMENITIES DE LUXE
The following interesting item appeared in the
English monthly supplement of The Yakitgo Shuho,
issue of November 7, 1920, published at Tokyo.
2,000,000 MARK CONTRIBUTION TO GERMANY
Mr. Hajime Hoshi, President of the Hoshi Pharmaceutical
Co., is to be congratulated on the admiration he has elicited
among the Germans as well as his countrymen for his contri-
bution of 2,000,000 mark to Germany for the cause of science.
Under date of September 26, Mr. Hoshi addressed a letter to
Dr. Solf, German Ambassador in Tokyo, in which he expressed
his wish to contribute 2,000,000 mark to the German Govern-
ment to be used for the cause of chemical and pharmaceutical
science in Germany. Mr. Hoshi further stated in his letter
that he has been an admirer of Germany especially in respect
of chemical and pharmaceutical science made in Japan and
that his contribution is intended to repay in some way the great
debt Japan owes to Germany.
On October 5, Dr. Solf, German Ambassador, sent a reply to
Mr. Hoshi in which he said that Mr. Hoshi's offer for the 2,000,000
mark contribution had been forwarded to the German Govern-
ment which gladly accepted the donation and promised that
the money would be used for the purpose as intended by the
donor. Dr. Solf expressed his belief that Mr. Hoshi's generous
gift will have the effect of encouraging scientific researches and
•of bringing Japan and Germany into closer relations.
It is understood that Mr. Hoshi before broaching his offer to
the German Ambassador consulted the views of Baron Goto
about his intended offer to Germany and the former Foreign
It is easy to imagine the smile of genuine delight
as Mr. Hoshi takes down his Christmas stocking and
finds it filled with the oranges, raisins and nuts of
"admiration he has elicited among the Germans as
well as his countrymen." We fear, however, that he
will find the nuts not up to market standard, per-
haps rancid, the nuts of the Japanese dye manu-
facturers, who we learn in another column of the
same publication are in dire straits because of the
present lamentable condition of their industry.
What is meant by "an admirer of Germany especi-
ally in respect of chemical and pharmaceutical science
made in Japan" we frankly cannot guess, but we are
confident that it is a bouquet of some kind of Japanese
wild flowers.
The well-remembered former Minister of Foreign
Affairs, Dr. Solf, "promised that the money would
be used for the purpose as intended by the donor"- —
a comforting assurance, doubtless, if one is disposed
to forget little things like scraps of paper. Dr. Solf
is confident that the gift "will have the effect of en-
couraging scientific researches." That's fine. Never
mind about the drop being lost in the ocean, it's good
to know that "scientific researches" are going to be
encouraged in Germany. And then, too, every little
bit of outside help for research makes that much more
of the present large dividends from the prosperous
German chemical organizations available for invest-
ment in the enormous capitalization increase now in
progress.
Mr. Hoshi, possibly for fear of wounding the sen-
sibilities of those he would encourage, was not going
to take any chances as to "the correctness of his pro-
posal," so he sought the advice of the former Japanese
Foreign Minister, Baron Goto. The Baron said, "Go
to it!" At least that is a brief way of expressing his
concurrence. Thereupon Mr. Hoshi proceeded to
encourage. All in all it was an auspicious and il-
luminative occasion, and serves the purpose, as Dr.
Solf says, of "bringing Japan and Germany into
closer relations."
Maybe the example set by Mr. Hoshi will be fol-
lowed by the Oxford professors, now that they have
received the condescending forgiveness of their brother-
savants (not brother-servants as erroneously printed
in our December issue).
ARE YOUR FOLKS ON THE LIST ?
Is the firm or corporation with which you are con-
nected a corporation member of the American Chemi-
cal Society? If not, it should be.
If you can't answer the question look in the list of
corporation members on page 91 of this issue. If
you agree with the affirmation, and if the name is
not in that list, get busy!
The power of suggestion is strong. Try it on your
president or general manager. He should know how
many organizations are supporting the Society
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
through corporation membership. Let him know
that the Society is not an organization for the mere
selfish interest of its individual-chemist-members, but
that it seeks to serve the nation by creating a sound
public appreciation of the value of chemistry in every
line of industrial endeavor; that its activities are di-
rected to utilizing every legitimate agency to increase
the efficiency of the American chemist; that the in-
terest shown by this corporation membership is retro-
flexive through the quickened spirit of fellow-mem-
bership; and that there are certain direct perquisites
accruing to corporation members. These are given
in Section 7 of the Constitution of the Society.
Section 7. Any firm, corporation or association interested
in the promotion of chemistry may by vote of the Council be
elected to membership in the Society and shall after election
be known as a corporation member. A corporation member
shall have all the privileges of membership except that of holding
office, shall be sent the titles of all papers to be presented before
any General Section or Division of the Society; may on appli-
cation, made in advance of publication to the Editor of the
Journal of Industrial and Engineering Chemistry, be furnished
with not more than five reprints of any paper announced for
publication, and shall have the privilege of being represented
in any meeting of the Society by a delegate appointed by the
firm, corporation or association. Such firm, corporation or
association shall pay annual membership dues of twenty-five
dollars.
If you fail on the first attempt, go at it again. See
to it that when the supplemental lists are published
the name of your firm or corporation is included.
Secretary Parsons will furnish the application blank,
or write him that the preliminary work has received
a favorable response and that it is up to him to finish
the job. He'll do it.
Here is another phase of the question. Without
solicitation the Arthur H. Thomas Company has
become a corporation member, and Mr. Thomas and
six members of his firm are individual members of
the Society. Can you beat it? If so, send us the
facts, we will gladly publish them.
NO TIME FOR DULLNESS
From time to time we have heard it complained
that members are not interested in the local sections,
that times are dull, and programs for meetings difficult
to arrange.
In view of the tremendous amount of work waiting
to be done, of the many possibilities for useful service,
such lamentations raise the question, "Is the real
function of the local section understood?" Frankly,
we think that if such dull times prevail the funda-
mental atmosphere must be one of desire to get some-
thing out of the local section rather than to put some-
thing into it. If once the spirit of service prevailed,
innumerable activities would suggest themselves where-
by good might be done in our neighborhoods, and
interest in local section activities be keenly aroused. .
When a man gives to something, he begins to take
interest in that something.
A fine illustration of the point we are trying to
bring out is afforded by the Milwaukee Section.
They have not been content to meet at regular intervals
and listen to distinguished lecturers either from within
or without their membership, but their progressive
officers have looked about for a way to serve the City
of Milwaukee. One of the first fruits was a request
from the Mayor of Milwaukee that the Local Section
appoint a committee to study critically reports on
Milwaukee's water supply, and to make any other
suggestions which would overcome present difficulties
with the. water supply. Chairman John Arthur
Wilson appointed a live committee, and the Mayor
is so pleased with the spirit in which the Section
responded to his request that he has "expressed the
wish that the Section will take an interest in all mu-
nicipal affairs where its opinion may help the city
officials to do the right thing."
The public library in Milwaukee was found to be
inadequately equipped with chemical journals. It
was felt that this was a much broader question than
the selfish interest of the chemists themselves, and
that by improving this situation the City of Milwaukee
would be benefited. In this connection, Chairman
Wilson writes:
An investigation of Milwaukee's industries revealed a need
for a very complete file of the world's chemical publications.
It seemed meet and right that any expense incurred in gathering
together such a file should be borne by the industries that
would profit by it. The Committee therefore started a drive
for a fund of ten thousand dollars, the interest on which is to
be spent perpetually for the purchase of chemical journals to
be placed at the disposal of the public at the Milwaukee Li-
brary. Each firm is asked to contribute no more than it feels
it will profit by the undertaking, so there is no begging or asking
for charity involved. For the best results, it was deemed ad-
visable that the fund and all journals purchased from it should
remain the property of the Milwaukee Section, which has
pledged itself to place the journals at the Public Library or any
other place it may choose such that access to them shall be
had by the public. The Milwaukee Public Library in turn
has agreed to take care of the journals and place them at the
disposal of the public so long as is desired and has further agreed
to be guided in the matter of purchasing chemical books and
in other matters pertaining to the chemist by the advice of the
local section.
*****
The response of all firms thus far approached has been so hearty
and sympathetic that there seems to be no doubt about the
ultimate raising of the full ten thousand dollars, which should
give the Committee a steady income in excess of five hundred
dollars a year to be spent only for chemical and closely allied
journals. Any portion of the income not needed for current
numbers will be spent in getting all back numbers of the more
important journals and in binding.
A fine illustration of how the chemist can serve his
neighbors! It is a safe prediction that the lines of
public work thus opened are only forerunners of many
others which will prove beneficial to the City of Mil-
waukee, and that dullness will never enter that pub-
lic-spirited and enterprising local section.
The problems in each locality doubtless differ, but
the principle of service is the same in all, and its re-
ward will be equally stimulative.
EXPANSION OF THE NEWS SERVICE
The sympathetic interest of the Directors in the
work of the A. C. S. News Service makes possible
its expansion during the coming year. The line of
expansion is definitely marked out and is a logical
outcome of developments during the past year. The
weekly bulletins and monthly clip sheet, "The Chemi-
cal Round Table," have been sent to about nine
Jan., 192 1
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
hundred of the leading daily newspapers. Through
the efforts of the Technical Director, Mr. John Walker
Harrington, an organization furnishing "boiler-plate"
matter to a large number of weekly newspapers be-
came interested, and made use of our bulletins in the
material which it distributed to several thousand
weekly papers. It is proposed now to enlist the
interest of all the associations which furnish plate
matter and to give to each a special service, thereby
hoping to reach all the weekly newspapers. By this
means the matter sent out by the News Service will
receive a largely increased circulation.
To carry on this work effectively, it is necessary
that we have the strong cooperation of the Program
Committees of the various sections. Remember this
is a news service and the matter to be sent out will be
determined largely by papers read and announce-
ments made before the various local sections. A
certain amount of time is required for the preparation
and distribution of bulletins, which should reach their
destination several days in advance of the release date
if we are to obtain the best results.
In the offices of the News Service a diary is being
kept of the meetings to be held by each local section,
and it is urged that those in charge of the programs
notify Mr. Harrington regarding the lecturer and his
subject as quickly as possible after the program for
each meeting is determined. Then if speakers will
furnish the News Service well in advance a copy of
the address, or at least a full abstract, the work of
preparing accurate bulletins will be greatly facili-
tated.
There is a wonderful opportunity this year to get
results far exceeding the fine results of the last two
years. To make the most of this opportunity we
must pull together, leaving to Mr. Harrington's judg-
ment the question of whether or not the material
adapts itself to newspaper use. If chemistry is to
take its proper place in a democracy such as our
nation is, it can only be accomplished through the
agency of sympathetic, well-informed public under-
standing throughout our citizenry.
EQUITABLE DISTRIBUTION
Year by year The Chemical Engineering Catalog
has grown in size and contents, apace with the growth
of the American chemical industry. It is a veritable
chemical exposition on paper. With each succeeding
year the errors and omissions of previous years have
been corrected. To the chemist or purchasing agent
in need of supplies it is a mine of information.
In the shaping of these volumes the compilers have
had the benefit of the advice of special representatives
of each of the national organizations of chemists.
The volumes thus become in part the property of all
chemists and accordingly have in the past been fur-
nished on request, without charge. But this policy
led to an unfortunate result. The presence of one
volume in a library or laboratory created the desire
for more; consequently there was frequent congestion
in the distribution, and the edition was soon exhausted.
For the late-comers the banquet was over because
of gluttony.
In the light of this experience a new policy has been
adopted this year. The volume is now mailed on
receipt of a leasing fee of $2.00. The charging of
this small amount should deter no one who really
needs it from receiving a copy of the Catalog; at the
same time it is hoped thereby to distribute the edition
fairly throughout the industry.
Congratulations to the publishers of the 1920 vol-
ume! May their power of useful service increase as
the years go by!
The French are contemplating the holding of an-
nual expositions of their chemical industries.
A British court has ruled favorably on the legality
of the appropriation of £100,000 by Brunner, Mond
& Co., Ltd., for the furtherance of research and scien-
tific education.
The organization of the Rochester meeting is taking
shape rapidly as a result of the energetic action of
the following chairmen of sub-committees:
Entertainment Committee: Chari.es F. Hutchinson
Transportation Committee: Charles W. Markus
Excursion Committee: William Earle
Finance Committee: Herbert Eisenhardt
Publicity Committee: Benjamin V. Bush
Hotels Committee: Harry LeB. Gray
Registration and Information Committee: Harry A. Carpenter
Program Committee: ErlS M. Billinos
When in New York City you happen to see each
morning on Fulton Street an erect man, with pure
white hair and clear eye, walking eastward carrying
a lunch box — look close, it is Dr. Charles F. Chandler
on his daily walk to work at the offices of the Chemical
Foundation. He didn't worry when December the
sixth reminded him incidentally that he was 84 years
of age.
Harking back to the days of the controversy over
the use of platinum for jewelry as against its conserva-
tion for munitions, it was interesting to read in the
November 6, 1920, issue of the Saturday Evening
Post the following quotation written in 1875 by the
late W. Stanley Jevons: "The appearance of platinum
being inferior to that of silver or gold, it is seldom or
never employed for purposes of ornaments."
If the idea in the opening paragraph of a letter just
received becomes a habit among our fellow chemists
we may be able to make this section of This Journal
both interesting and serviceable:
"Whenever matters affecting the status of the
American chemical industries or of the Chemical
Warfare Service come to my attention the signal
flashes through my mind 'Tell it to Herty.' "
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
CHLMICAL INDUSTRY AND TRADE OF FRANCL1
By O. P. Hopkins
1824 Belmont Road, Washington, D. C.
One result of the war has been the growth of a keen
desire on the part of French manufacturers to achieve
independence of the German chemical industry.
Along certain limited lines the French had made good
progress before hostilities began, but probably in no
country was German dominance in the markets for
chemicals so pronounced as it was in France, and it is
common knowledge that in no other country to-day
is the desire to be free of German dominance in any
line so freely expressed as it is there.
The war struck directly at the French chemical
industry, as many of the factories were in the Nord
and Nord-Est districts. The effect of the loss of these
factories on the chemical industry can be judged from
the following figures for the whole country:
Before the war
End of August 1914.
End of August 1917
Number of
Chemical
Establishments
... 1,583
894
... 1.410
Number of
Workmen
78,892
35,470
93.667
In brief, the number of factories and workmen
engaged in manufacturing chemicals was reduced by
half as a result of the German invasion, but within
three years the number of workmen so engaged was
about 19 per cent greater than normal.
The chief effort, of course, was directed to organizing
chemical plants for the production of munitions and
medicinal supplies for the army, and to direct this
effort there was organized the "Office des produits
chimiques et pharmaceutiques," under Professor
Bethal, the success of which has been demonstrated
by actual results. The obstacles faced by the French
at the outset can be appreciated if we consider what
our own plight would have been if half our chemical
industries had been taken from us within a week or so
of our entrance into the war.
As in other countries, there is now a desire to utilize
to the full in peace times the productive capacity
created during the war, but, as in other countries,
there is a growing realization that similar development
along exactly similar lines occurred in other countries,
and that much of the capacity so recently developed
will have to be adapted to other products or allowed to
stand idle. It is understood that this condition points
to spirited competition from the greatest industrial
nations, including England, the United States, and
Germany, and that the way to chemical independence
will be a difficult and trying one.
The chief development during the war occurred in
the production of heavy chemicals, statistics of which
are shown in the following table:
1 Facts and figures in this article are based upon publications of the
French government, upon the semi-official "French Year Book," upon the
German "Gluckauf," and upon published material issued by the United
States Bureau of Foreign and Domestic Commerce.
1919
1913
Productive
Production
Capacity
Metric Tons
Metric Tons
Sulfuric acid, ^8°
1.160,000
2,500,000
Sulfuric acid, 66°
58,000
1,200,000
6,000
300,000
Nitric acid
20.000
360,000
Sodium salts
625,000
800,000
Liquid chlorine
300
90.000
Bromine
500
Calcium carbide
32,000
200,000
Cyanamide
7,500
300,000
Ammonium salts.
75,000
200,000
Nitrate of lime
250.000
Natural phosphate
. 2,700,000
3,000.000
Superphosphates
1,965,000
2,500.000
Phosphorus
300
3.600
The foregoing figures do not cover the newly acquired
capacity for producing potash, which is discussed in the
section devoted to Alsace-Lorraine. The increased
capacity for producing nitrogen products, so noticeable
in these statistics, is referred to under the heading
"Fertilizers," and further comment will be found
under the heading "Heavy Chemicals."
Before the war France exported something like
$30,000,000 worth of chemicals, but the export trade
has been slow in recovering. On the other hand, the
import trade was brisk for a considerable period after
the war, as stocks of certain essentials needed re-
plenishing. During the last year French exports in
general have increased, and it is presumed that chemi-
cals have benefited along with other lines.
ALSACE-LORRAINE
By the return of Alsace-Lorraine, France has come
into possession of a district rich in agriculture, mineral
resources, and manufacturing industries. Of these
the most important in the building up of a greater
chemical industry are the minerals, the production of
which under German control in 1013 was as follows
(according to the ''Gluckauf'):
Number
Minerals
Establish-
Production
Metric Tons
21 ,135.554
3,795,932
8
76,672
6
49.584
1
6,354
The acquisition of the iron-ore resources of Lorraine
will make it possible for France to produce 40,000,000
tons of ore annually, and place her a good second after
the United States in this respect. Before the war she
was third, between Germany and England. The loss
of these deposits is a very serious matter for Germany,
as she formerly depended upon them for three-fourths
of the ore she needed. The manufacture of iron and
steel in the Lorraine district is very highly developed.
In 1913 France consumed 63,000,000 tons of coal, of
which 23,000,000 tons were imported. The bulk of
the domestic supply came from mines in the Nord and
Pas-de-Calais regions which were destroyed or damaged
during the war. The production of the Lorraine mines
was approximately 4,000,000 tons under German
control, and the production of the mines in that portion
Jan., k).m
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
of the Saare basin to be held by France until the
plebiscite 15 years hence was 12,000,000 tons. The
acquisition of this total of 16,000,000 tons will not
make France independent of other coal-producing
countries, especially not until the Nord and Pas-de-
Calais mines have been repaired, but French engineers
believe that the annexed fields can be developed to a
point that will insure eventual independence. The
future will depend upon French initiative and organiza-
tion.
The potash resources of the annexed territory are
estimated at from one and a half to two billion tons
of raw salt (say, 300,000 tons of K20), and it is con-
sidered possible that within a few years the annual
production will amount to 4,000,000 tons. The
present output is far from that, although it is nearly
four times what it was under German control. For
the last eight years the amount of crude salts mined
has been as follows:
Year
1913
1914
1915.
1916
1917
1918
1919
1920
Metric Ton
155,341
325,886
114,358
204.474
!20, 131
333.499
592,000
1,200,000'
1 Average daily production for August multiplied by 300.
Alsatian potash production before the war was
admittedly low, and the explanation generally offered
is that the mines were all new and that the output
was limited by the Kali-Syndicat to prevent over-
production. During the war, production fell off for a
number of reasons. One mine was bombed, and others
suffered from neglect and flooding. It is said that
some of the mines farthest from the front were badly
operated in an effort to speed up production.
Not all the damage done during the war has been
repaired, but it is evident that the mines in operation
are producing more effectively than they did under
German control. For the present they can be divided
into two groups, those under control of the Sequestra-
tion Office and those independent of that official
organization. There is considerable agitation for re-
moving all the mines from such control. Daily pro-
duction of all mines in August was 4000 tons of crude
salts, while the capacity was put at 8500 tons (7000
tons for the mines under sequestration and 1500 tons
for the others). It is calculated that with all the mines
in operation the production four years hence should
reach 14,000 tons a day. Perhaps a third of the
present production is going to the United States.
HEAVY CHEMICALS
France has been able to supply its own needs for
many of the heavy chemicals, as the table of imports
will prove. Before the war sulfuric acid was produced
to the extent of more than 1,000,000 tons, nitric acid
to the extent of about 20,000 tons, and hydrochloric
acid to the extent of some 130,000 tons. Com-
paratively small quantities were imported and ex-
ported. The war about doubled the capacity for
producing sulfuric acid, and the output of nitric and
hydrochloric acids was also greatly stimulated, so
that after the armistice there was an excess for export
with but few buyers, as a number of other countries
were in the same predicament. Soda products were
also manufactured to a sufficient extent to meet
domestic demands before the war, with a surplus for
export, and doubtless the same will be true as to potash
products as soon as the chemical industry has grown
up to the possibilities of the newly acquired Alsatian
resources.
■ FERTILIZERS
The war has opened the way to complete inde-
pendence for French agriculture so far as foreign
fertilizers are concerned. The need of nitric acid
in the manufacture of munitions led to a great develop-
ment of the nitrogen industry, just as it did in many
other countries, and efforts are now being concentrated
on keeping these new plants in operation on such
products as cyanamide and calcium nitrate. Cyan-
amide is now manufactured to the extent of more
than 100,000 tons annually, as contrasted with 7500
tons before the war, and French authorities have high
hopes of getting along without the 300,000 tons of
sodium nitrate formerly brought from Chile, although
they appreciate the fact that other countries have
ambitions along the same line, especially Germany
with its Haber process.
The acquisition of Alsace-Lorraine assures inde-
pendence of the Kali-Syndicat, and some export busi-'
ness in addition.
The production of superphosphates now amounts to
nearly 2,000,000 tons a year, which is sufficient to
meet the domestic demand. This industry operates
on phosphates from Morocco and Algeria.
COAL-TAR DYES
France is one of the half-dozen countries (i. e.,
France, England, Switzerland, Italy, Japan, and the
United States) avowedly seeking to establish dyestuff
industries that will make them independent of the
German manufacturers who formerly dominated the
world markets. In some respects the obstacles she
has to overcome are more serious than those con-
fronting the United States and England. The home
market is not extensive (imports of German dyes did
not exceed $3,000,000 before the war), and it requires
less in the way of staples and much more in the way of
specialties, since the product of the silk, wool, and
cotton industries consists largely of the most highly
finished fabrics. And the fact that so many other
countries are in the dye-making business will make it
difficult to find markets abroad for French dyes. On
the other hand, the value of a dye industry to the
national defense is more generally recognized and con-
ceded than in some other countries, notably the United
States, and the government has already armed itself
with the power to regulate the importation of German
dyes. (See the section headed "Government Assis-
tance.")
Authoritative figures on the present production of
artificial dyes are apparently not to be had and no
attempt will be made in this article to estimate the
output, but it is certain that no success comparable
to that of the American industry has been attained
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol.
No.
up to this time; in fact, American dyes and dyestuffs
have been marketed in Prance in fairly large quantities.
PERFUMERY AND COSMETICS
Among the highly finished luxury goods for which
France is famous are included perfumery and cosmetics,
by which are meant perfumes, essential oils, scented
soaps, grease paints, beauty creams, etc. The pro-
duction of these articles totaled in value some
$30,000,000 before the war, and they were exported to
all corners of the earth. This was an industry
naturally hit very hard by the war, but just as naturally
it made a very quick recovery as soon as the armistice
was signed and the period of luxury-buying set in.
It is the only important French chemical industry
that fared better in the export trade in 191 9 than in
IOIJ-
For some time before the war the French manu-
facturers of natural perfumes were somewhat worried
by the competition from German artificial scents, but
the French themselves are now manufacturing these
synthetic perfumes on an increasing scale, coincident
with the production of artificial dyes, and it seems
logical to assume that the long-established supremacy
in the natural products will assure the success of the
new industry. Not only have the new artificial scents
been favorably received, but considerable success has
been attained in blending the natural and artificial
products.
OILS AND SOAP
Marseille was a commanding figure in the vegetable-
oil and soap business before the war, the product of
its crushers amounting to some 1000 tons a day,
while the output of soap reached a very high figure.
Oil-bearing materials were brought to this port from
points in the Mediterranean and especially from the
Indian Ocean and the Far East by way of the Suez
Canal, and considerable quantities of more or less
crude oils were brought in for refining. The total
value of the products of the oil industries was
$86,000,000, of which Marseille was credited with
$70,000,000, Nice with $10,000,000, and Bordeaux with
less than $3,000,000.
The war interfered greatly with the importation of
oil-bearing materials, and a fat famine lasted until
long after the armistice. Even in 19 19 the imports
of oil-bearing materials were less than half what they
were in 1913. Peanuts, the principal raw material
crushed at Marseille, were imported to the extent of
nearly 500,000 tons in 1913, but in 1919 the total
quantity was only 225,000 tons. The falling off in
receipts of linseed and copra, the next most important
materials, is equally striking. Imports of oils in
1919 were much greater than in 1913, whereas the
exports dropped from about 58,000 tons to less than
8,000. Eventually Marseille will recover much of its
former business, but the development of the oil in-
dustries in England and the United States, to say
nothing of the tendency to crush near the source of
supply of the raw materials, are factors that are re-
ceiving serious consideration in France.
The production of common soap was affected by the
scarcity of fats during the war and is slow to return
to normal. Exports, which totaled nearly 78,000.000
lbs. in 1913, were 43 per cent below that figure in
1 91 9. In striking contrast to the decline in sales of
common soap is the increase in exports of scented soap
from a little over 3,000,000 lbs. in 1913 to nearly
7.000,000 lbs. in 1919.
GOVERNMENT ASSISTANCE
Protection by the government is a most important
factor in the development of a self-contained and
independent chemical industry in any country, or
of any branch of the chemical industry, and the chances
of ultimate success in the numerous countries that have
announced their intention of going their own way since
the war started can be appraised with some measure
of accuracy by a study of the steps taken to restrain
outside competition, especially German, until the home
industry can establish itself on a sound basis.
In France, as in the United States, England, Italy,
and Japan, there have been more or less whole-
hearted and intelligent efforts to foster a number of
chemical industries (coal-tar dyestuffs and medicinals
in particular) in the hope of ending the former German
monopoly, and the French government has to date
placed its reliance on high tariffs plus control of German
imports. There was a tariff on intermediates and
finished dyestuffs before the war, but it was un-
scientific in that the duty on the finished dyes was
much higher than that on the intermediates and was
the same for an intermediate that required little
finishing as for one that required a great deal of manu-
facturing to finish. The result was that the Germans
established finishing plants in France and defeated
both the revenue and protective objects of the tariff.
The new tariff is frankly protective and the rates
are not only higher but so adjusted that intermediates
requiring little labor to finish are only slightly lower
than the finished dyes, thus making it unlikely that
foreign manufacturers will be tempted to establish
mere "assembling" plants in France.
As against Swiss, British, and American competition
the tariff is at present the only protection afforded the
French dye-maker, and there is a disposition to complain
of the extent to which non-German foreign dyes have en-
tered the market. Against dyes of German origin there
is a licensing provision in addition to the tariff, al-
though the reparation allotments come in free of duty.
The decree upon which the French licensing program
is based may be continued indefinitely, differing in
that respect from our own war-time power to license
imports. In brief, the French dye-maker is ap-
parently assured of adequate protection against the
German dye industry, and thus better prepared for
eventualities than our own manufacturers.
THE MARKET FOR IMPORTED CHEMICALS
A study of the following compilation from official
French statistics shows how the wTar has affected the
French market for foreign chemicals, and incidentally
reveals the fact that the United States did not figure
prominently in the pre-war trade. Statistics are not
available to show the origin of 19 19 imports.
Tan., iQ2i
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
hcals and Allied
1913
Pounds
Products
1916
HKM1CALS:
Acetate of copper, <
Acetate of lead ....
Germany
United States
Acetone
Germany
United Kingdom
United States
Acids :
Acetic
Arsenious
Carbonic, liquid
Citric, crystallize*
Citric, liquid
440
452,160
354.940
Fori
Gallic, crystallized
Hydrochloric
Hydrofluoric
HvdroftuosilK-ic
Lactic
Nitric
Oleic, of animal origin.
Belgium
Spain
United States
Oxalic
Germany
United Kingdom ...
United States
Phosphoric
Stearic
Belgium
Netherlands
United Kingdom... .
" lited States.
4.441 .210
2.709.040
845,910
107.810
5.510
653,670
147,490
268.740
63,270
250,440
141 ,320
14,550
6,399.800
34.390
4,850
561.520
1 .822,560
5.851.730
4.786,450
6.170
429,900
57,760
34,170
210,320
272,930
42,990
12,790
2,544,130
195,550
403.220
336,430
1.878,340
1,303,590
447,760
118.170
87,080
500,670
125,660
2,661,420
1 ,276,920
1,214,750
13,890
,750
178,790
18,960
95,680
4,594,210
302,470
,114,010
1.619,960
Sulfuric 21,827,300 139,634,170
Belgii
Germany
Italy
United States
Tannic
Germany
United States
Tartaric
Germany
Italy
Alcohol, amyl
Alum, ammonia or potash.
Aluminium:
Chloride
Hydrate
Oxide, anhydrous
Sulfate
Ammonia
63,757,680
6,697,200
$100,736
Sulfate, refined
United Kingdom. .
Salts, other, crude . .
Salts, other, refined. .
Germany
Norway
United Kingdom .
Antimony oxides
Germany
United Kingdom
United States
Arsenic sulfide
Ashes, vegetable, and ly
Ashes, beet-root
Barium dioxide
Bromides
Bromine, liquid
Germany
United States
Calcium:
Borate
Carbide
Chloride
Sulfide and bisulfide..
Chemicals, n. e. s. :
With alcoholic base:
Taxed by weight. . .
Taxed by value. . . .
Other:
Taxed by weight.
1 , 105,180
624,350
373,460
32,630
246.920
3,530
728.410
5,730
337,970
614.650
479.500
457,020
118,830
1,896,190
229,060
934.540
513,680
203,050
67,240
130,950
2,200
536,820
616,850
7,929,950
412,700
20,720
169.750
169.750
6,291.710
8,157.680
24,910
50,050
653,890
3,530
1,855,190
7,500
220
183,420
303.350
8,928,060
8,878,450
37,071,170
53,247,580
30,368,230
1,661,180
246,250
236;770
9,480
660
333,560
436,290
218,700
156,530
1 ,980
' 1^980
30,860
Taxed by value $2,438,390
Chlorine, liquefied
Chloroform
United Kingdom
United States
Citrate of calcium
Italy
Cobalt :
Oxide, pure
Zaffer, siliceous oxide, vitrified
oxides, smalt, and azure. . .
Salts, n. e. s
Cocaine, crude
Germany
Copper:
Oxide
Sulfate 41 .856,550
Belgium 1,287,270
United Kingdom 40 , 373 , 730
United States
IUher, acetic and sulfuric 47.840
Fluorides 168.880
See also Fertilizers.
72,320
440
4111
5,730
245,150
2 . 650
2,430
2,430
191 ,140
35,594,500
6,250,320
12,790
198,420
$3,200,490
7,425,830
77,600
72,750
4.850
2,113.130
2.080,500
440
S9,r>(.6, l-.il
908,300
44,970
358,690
1 ,570,570
280,650
881 .630
137,570
60,410
65,700
25,350
3,054,950
5,730
160,060
87,520
3,776,520
$245,496
330 ',030
6.830
12,130
2,430
6,090,270
2.047,430
2,973,590
262,350
809,540
17,640
222,890
2,308.240
35,208,480
11 ,083,520
91 ,930
558,870
$5,887,27 2
164,910
46,740
660
3,090
3,970
Of Chemicals
Chemicals {Continued) :
Formaldehyde
Germany
United States
Formates
Glycerol
Netherlands
United Kingdom
United States
Iodides and iodoform
Iodine, crude or refined
United Kingdom
United States
Iron:
Lactate
Oxide
Sulfate
Sulfate of iron and copper.
Lactates, n. e. s
Lactarine (casein)
Carbonate
Belgium
Germany. .
United States
Chromate
Oxide
Allied Products (Continued)
1913 1916 1919
Pounds Pounds Pound?
3.090
I .045,870
367,950
252,210
50,050
50!650
1,320
3,232,600
6.685,670
13,230
28,880
55,340
8,463,240
5,712,340
1,296,080
Germany
Salts, n. e. s .
Magnesia, calcined
Magnesium:
Carbonate
Italy
L'nited State-,
Chloride
Germany
United States
Sulfate
Germany
British India
Mercuric sulfide:
In lumps, natural or artificial .
Pulverized (vermilion)
Germany
United States
Methanol
Canada
Germany
United States
Milk sugar (lactose)
Nicotine salts
Germany
United States
Phosphorus:
Red
White
Potassium:'
Acetate
Arsenate
Chlorate
Carbonate and crude potash. .
Belgium
Germany
Russia
Chromate of potassium and
sodium
Germany
United Kingdom
Nitrate
Oxalate
Permanganate
Germany
Switzerland
Prussiate
Sulfite, bisulfite
Pyrolignites of:
Calcium
Iron
Lead
Quinine, sulfate, and other salts.
Silver salts
Sodium:
Acetate
Arsenate
Bicarbonate
Carbonate:
Crude
Refined
Chlorates of sodium, barium,
Hydroxide (caustic soda)
United Kingdom
United States
Hyposulfite
Silicate of sodium and potas-
Sulfate...'.'
Sulfite, bisulfite
Tetraborate (borax) :
Crude
Chile
United States
Refined or semi-refined
Salts, n. e. s
Tartrates:
Cream of tartar
Crude tartar
Crystals of tartar
1 See also Fertilizers
98.990
1 ,765,230
505,740
1 ,113,540
324.080
76.500
1 ,330,480
753,750
294,320
6.149,960
6,092,640
5,002,500
1 ,715,630
2.026,710
306,000
33,290
46,960
22.490
12,130
440
19,840
7.720
16,256,220
1,328,720
11.105,900
2,750,240
6.438,980
3,581,370
2,421,310
157.410
108,470
506,840
459,220
11,900
45,420
288.140
395,510
15.650
22,710
486,780
18,740
338,190
1 ,089,960
880
108,250
31,970
74.740
2,650
139,330
46,740
880
1 .363,120
561 ,520
2,200
1,100
29,320
6,827,350 10.325,130
1,330,050
108,250 38,360
1,204,830 6,568.230
3.208,830
324,960
1,895,750
1,676.170
4,035,340
1 ,283!.'>io
2, 458^370
1 ,760
570, 810
355,380
3,300
8,197,000 8,056,790
6,797,070
6.605,050
11 ,900
143,080
,149,570
32,630
63.050
81 ,570
37,480
30,640
18,300
345,020
2,144,660
505.740
212,520
1,032,640
30.860
3, 1 22. S50
251,100
47.377,780
30.084,050
1 .060.640
28,961.240
131,400
168,210
2,870
328,270
14,297,860
1 .102,970
8,465,530
46,960
670,420
37,040
603,630
14,990
THE JOURNAL OF IXDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 15. No. r
op Chemicals and Allied Products (.Continues)
1,751,790
17,860
4. 190
Chemicals {Concluded):
Tartrates (.Concluded):
Wine lees 21 . -
Other 71 .21(1
Thorium and cerium salts 3, J30
Tin
Chlorides 2.030,450
Germany 1 .853,850
United States 171,740
Oxide 103,620
Uranium oxide 102 . 290
Belgium 9,040
Germany 91,490
United kingdom 1,100
Zinc:
Oxide 12,888.760
Germany 4,146,190
Netherlands 4,515,460
United States 3,864,670 1
Sulfate 421,080 141.080
Sulfide 219,800
Coal-Tar Products
Products obtained directly by
distillation of coal tar 190,097,800
Belgium 36.267,880
Germany 84 . 665 , 000
Spain 1,080,480 2.7'>4.14"
United Kingdom 65,167,540 114.600.460
United States 1,653,890 1" 02
Products derived from products
obtained by distillation of
coal tar
Germany
Switzerland
United Kingdom
United States
Dyes derived from coal tar:
Alizarin, artificial
Germany
United Kingdom
Picric acid
Germany
United States
Other dyes
Germany
Switzerland
United Kingdom
United States
Dyeing and Tanning Materials:
Extracts of woods, barks, nuts,
and berries used for dyeing :
Black or violet extracts
British America
United States
» Garancine
United States
Indigo, natural
British India
Orchil, prepared:
Dried
Moist, in paste
Red or yellow extracts
Extracts of woods, barks, nuts,
and berries used for tanning
Chestnut and other
British India
United States
Nutgalls and
Switzerland
Quebracho . . .
Argentina
Germany . . .
ExPLOsrvHs:
Dynamite
Spain
Fireworks
Gunpowder
United States
Fertilizers
9,000.370
145.730
440
6. 420. '160 14.955.940
37,628.840 (.5.206.100
S, 422. 240
7,790,620
237 . 220
150,350
8.600
660
660
1,263 250
410,280
87.080
271 ,390
15,430
220
48,060
.190.
774.040
601 .200
11.101.810
7,952,950
783,960
6.598,650 11.383.130
862.670
1 .388,030
4,335,390
8,215 (00 21. '89. 250
802.920
170.200
44,530
533,960
349,210
169.320
2,200
2,200
336.200
9.920
660
440
74,080
381,620
197,980
105.820
241.180
189,380
6.508.480
6,507,380
65.100.070
71.870
Ammonium sulfate, crude
Belgium
Germany
United Kingdom
Calcium nitrate and cyanamide.
Norway
Sweden
Switzerland
Fertilizers, chemical, n e. s
Belgium
Germany
United Kingdom
United States
Potash :
Muriate (chloride)
Germany
Italy
Sulfate
Germany
Metric Tons
20,696
4,110
8,237
8,123
10.010
9,378
232
400
223,217
28,860
157,107
31,709
430,120
190,220
6.610
13,654,550
12.668.860
Metric Tons Metric Tons
19.121
20,709
1 '- l
Slag, basic ....
Sodium nitrate
Chile
Superphosphate
Belgium
Tunis
United Kingdom
Medicinal Preparations
Distilled waters:
Alcoholic
1 Included
(')
322,115
322.014
100,822
83,983
828
540.700
540.694
4.122
1.498
156.169
118.255
12.956
6,130
Imports op Chemicals
Medicinal Prepns. (Concluded):
Distilled waters (.Concluded):
Nonalcoholic
Other, taxed by weight
United Kingdom
United States
Other, taxed by value
Oils, Fixed Vegetable:
■I and pulghere
Belgium
United Kingdom
United States
Coconut, touloucouna. illipe
palm nut
Belgium
Germany
United Kingdom
Colza
United Kingdom
Allied PRODUCTS (Continued)
1913 1916 1919
Pounds Pounds Pounds
52.030
152,780
76,940
21,380
$8,472
27,120
341 .060
61,950
80,690
$18,690
459,660 2.557,140 13.687,620
27,780
430,120 2.266.130
123.460
7,821.120
968,710
4.922,260
1 .726,220
59,520
For manufacture of soap . . .
Other
Cottonseed:
For manufacture of soap
edible fats
United Kingdom
United States
other
1 nited Kingdom
United States
I. HI
"Fertilizers, chemical,
n]1913.
China
United Kingdom
Mustard
Olive
Algeria
Greece
Italy
Spain
Tunis
Palm
China
West Africa, British
West Africa. French
Peanut:
For manufacture of soap or
edible fats
China
Japan
Other
Japan
United Kingdom
Rape
Sesame :
For manufacture of soap or
edible fats
Other
Soy-bean:
For manufacture of soap
Other
Other oils
Oils, Volatile:
Rose
Bulgaria
Germany
Switzerland
Rose geranium and vlang-ylang.
Algeria
Reunion
Other
British India
Germany
Indo-China
Italy
United Kingdom
Paints. Pigments. Varnishes:
Blacks:
For engraving
Ivory
Lampblack, Spanish black . . .
United States
Mineral, in lumps
Mineral, ground
Blue, Prussian
Carmines:
Common
Fine
Colors:
Ground in oil
In paste
I Xher
Green, mountain, Brunswick,
and other greens resulting
from a mixture of chromate of
lead and Prussian blue
Green. Schweinfurth, mitis green,
mountain blue and green ashes
Lithopone
Belgium
Germany
Netherlands
United States
Ultramarine
Varnishes:
Spirit
Turpentine, oil, or mixed
Germany
United Kingdom
United States
Zinc yellow, or chromate of zinc.
31,927,120
2,173.760
2,320.800
2,738,800
2,403,260
21 .604.420
34,729.820
2.761.950
1 .327,840
29,553,840
28.440
i5|430
401,460
14,550
145.280
337
179.770
61 .488
92,987
1,308,880
119.930
154,980
269,400
184.300
88.630
5,950
11.240
.411,630
.589.750
219,800
840.400
222.890
24 , 690
14.909.860
1,385,390
9.867,890
3,062,660
237,660
69.890
5,771 ,670
403,450
2,519,220
543.440
35.050
3.123.730 21. 484.05(1
28.880
10.446.600
2.983,260
7,347.790
9,087,890
3,622.860
5.449,380
4,671,820
1 ,269,420
1.732,170
2,581.170
6.166.990
1.757,300
2,933,030
9,359
1.745
6.710
4.938
25.040
638
24,311
50,870
15,444
115
1,052
18,601
15,302
70,437
2,718
720 5
840
210 3
790 4
780
560 3
540 5
020
260
iio 121
260
080
480
500 68
060 51
460 52
960
630
610
140.470
073,170
273.140
4,209.160
1 ,076.080
2,192.940
2,521 .427
1 .538,830
363.100
8,160
939.390
800,940
117.250
4.485,300
3 . 1 44 . 230
4.630
9.260
1 ,722.230
6.751,880
268.080
97
206,553
105,919
94.351
1 ,462,320
148.150
52,651
2.4J8!9io
185.630
258.600
223.770
53,1 10
115.080
.698.680
1.372.380
$87^056
35.490
276.680
243.170
5, 145.370
2.650
$280,622
10.140
3,581 ,410
304 . 240
99,870
910,950
622.800
21,600
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
Imports op Chemicals and Allied Products {Concluded)
Exports op Chemicals and Allied Products (.Continued)
Perfumhry and Cosmetics:
Alcoholic, gal
Nonalcoholic, lbs * . .
Oils, fixed, scented
Synthetic perfumes
Germany
Switzerland
Toilet soap:
Transparent
United Kingdom
United States
Other, scented
United Kingdom
United States
Miscellaneous Products:
Albumin
China
United Kingdom
Blacking
Candles:
Tallow
Wax and other. .
Italy
United Kingdom
United States
Dextrin
Gelatin, in powder, sheets, etc.
Italy
Switzerland
Germany
Glucose
United States
6.973
266,760
408
254,190
178,570
48,500
3,044,580
2,880,340
65,040
724,000
287,260
339,510
42,110
100,090
35,940
24,910
68,560
40,570
37,700
2,830
826,290
760,590
64.370
1,312,850
721,350
520,070
9,470
220
3,632,340
874,130
2,693,830
33,730
140,650
285,940
118,390
124,340
Glu
Germany
Switzerland
United Kingdom
Inks:
Drawing, in tablets.
Writing or printing.
Germany
United Kingdom.
United States
Isinglass
United Kingdom
United States
Paper and pulp:
Pulp, mechanical. . .
Germany
Canada
Norway
Russia
Sweden
Pulp, chemical
Austria-Hungary.
Germany
Norway
Sweden
Switzerland
United States
4.152,400
1,222,020
199,520
1 ,195,570
2,870
391,540
143,960
144,180
14,770
171,300
82,890
43,650
7,396,290
4,809,820
997,160
28,026,040
197
144,180
14,990
172,400 255,740
77,380
61,070
Metric Tons Metric Tons Metric Tons
259,449 213,209 161,168
6,396
4,504
115,923
15,380
116,342
205,500
26,536
42,716
31,830
88,803
4,606
2,711
Pounds
,480,400
942,030
177,690
36,252
107,293
4,636
844
Pounds
4,025,200
Paper, fancy
Germany
United Kingdom. . . .
United States 1,550.950
Paper, other 29,110,270 236,251,960
Germany 7,900,260
Norway 724,880 79,138,230
Sweden 3,149,300 95,147,530
United Kingdom 14,833,800
United States
Resin oil
Soap, common
United Kingdom
United States
Sugar (expressed in terms of
fined)
146,908,760
Russia
United Kingdom
United States
Turpentine, resins, rosin, pitch,
resin lumps, and other res-
inous products
Turpentine, spirits of
152.560
3,863,820
996,490
1,808,010
Metric Tons
108,062
Pounds
9,279.480
2,291,040
1,651 ,700
16.457,500
11,399,220
6,830 54,230
17,272.330 36,474,600
14,294,110
2.591,530
Metric Tons Metric Tons
543.126 568,867
Pounds Pounds
4,718,330 6,816,030
916.460
1,562.640
291.230
THE EXPORT TRADE
The details of the falling off in French exports of
chemicals in 1019 as compared with 1913 are shown
in the following table, which is based upon official
French statistics:
Exports of Chemicals
Allied Products
Chemicals:
Acetate of copper:
Crude 1,655,230
Russia 1,572,780
United States 15,210
Refined, powdered 721, 350
Crystallized 203 , 270
Acetate of lead 52,470
2,870
67,680
32,850
27,340
40,790
91 ,710
Chemicals (Continued):
Acetone
Acids:
Acetic
Arsenious
Boric
Belgium
Spain
United Kingdom
Carbonic, liquid
Citric, crystallized
Germany
United Kingdom
United States
Citric, liquid. ...'....
Formic
Gallic, crystallized
Hydrochloric
Hydrofluoric
Hydrofluosilicie
Lactic
Nitric
Belgium
Italy
Switzerland
Oleic, of animal origin . . . .
Belgium
Italy
Switzerland
Oxalic
Phosphoric
Stearic
Algeria
Italy
Switzerland
United States
Sulfuric
Tannic
Tartaric
Algeria
Germany
Spain
Switzerland
United Kingdom
United States
Alcohol, amyl
Belgium
United States
Alum of ammonia or potash .
Aluminium:
Chloride
Hydrate
Oxide, anhydrous
Norway
Switzerland
Sulfate
Argentina
Italy
Spain
12.350
395,730
2,472,700
4,749,190
1.072,100
190.260
2,284,870
655,210
896.840
248,240
98,550
488,540
16,498,710
Sulfate, refined
Algeria
Belgium
Free zones
Salts, other, crude
Salts, other, refined
Antimony oxides
Germany
United Kingdom
United States
Arsenic sulfide
United Kingdom
United States
Ashes, vegetable, and lye of . . . .
Ashes, beet root
Barium dioxide
Italy
United Kingdom
Bromides
Bromine, liquid
Calcium:
Borate
Carbide
Algeria
Morocco
Chloride
Belgium
Spain
United Kingdom
United States
Sulfite and bisulfite
Chemicals, n. e. s. :
With alcoholic base
United Kingdom
Other
Algeria
Belgium
Germany
United Kingdom
United States
Chlorine, liquefied
Chloroform
Citrate of calcium
Cobalt:
Oxide, pure
Zaffer, siliceous oxide, vitrified
oxides, smalt and azure. . . .
Salts, n. e. s
1 See also Fertilizers.
13,139,750
541,900
104,940
154,320
100.970
278,220
892,650
628,100
6,830
39,680
472,890
171,520
2,788,180
849,220
103,400
1,477,100
27,120
6,170
306,220
3.497,630
1 ,364,880
484.800
568,130
6,170
880
180,560
14,924,620
10,626,930
1,316.600
25,043,380
6,942.130
7,105,270
2,400,390
2,057,130
29.100
153,880
112,430
26,153,850
2,505,110
10,046,230
2,462,340
1.132.730
425,710
1,540
13,230
3,310
20,940
105,600
397,490
3,483.960
57,540
4.850
440
3,921,360
41 ,010
3,310
13,010
4,701 ,570
4,289,970
31 ,080
5,338,490
1 ,888.920
1,481 ,950
288,140
101 ,850
39,020
2,838,890
330,910
993,400
21,160
161,820
9,146,530
305,560
2,677,730
376,550
223,990
208,560
587,530
73,630
40,780
408 , 740
386,690
250,440
115,300
337,710
10,800
289,460
440
401,020
13,813,060
13,728,620
4,373,090
1,732,170
1,461,660
495,600
2,037,510
26,245,370
197,750
916,460
25.016,290
286,820
95,460
509,710
92,810
332,900
249,780
226,860
1 1 , 240
440
160,940
36,820
3,750
16,750
16,310
3,261 ,740
1,325,420
329,150
464,070
51,370
171,520
21,788,720
1,195,660
72,970
5,274,340
2,879.680
440
13,450
397,270
17,420
630,740
233,910
2,856,090
541 ,670
410,060
63,930
44,970
245,370
734,140
220
2,052,720
22,490
3,090
6,610
2,274,070
69 , 890
234,790
45,640
745,600
56,440
1,320
14,990
1 .078.720
1,749,590
464,510
1.155,220
191,800
945,120
3,530
71,430
501,770
344,360
16,530
128,970
7,280
3,272.100
24,690
1 ,813,300
246,920
7,270
17.420
379.200
8,668,570
65,920
1,345.040
2.200
1 ,496.060
13,309,750
186,510
314,380
74,520
255,080
516.760
6,830
1,050,280
440
17,420
274,250
18,li8i020
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
:ih:mic.\i i
i ocaine, ci ude
( oppi I
Oxide
Sulfate
Algeria
United Kingdom
Kther, acetic and sulfui i<
Fluorides
Formaldehyde
formates
Glycerol
Belgium
Italy ...
I tailed Kingdom
United States
Iodides and iodoform
Iodine, crude or refined
Iron:
Lactate
Oxide
Stdfate
Sulfate of iron and copper.
Lactates, n e. s
Lactarine (caseiiO
Germany
United Kingdom
United States
Lead:
Carbonate
L'hromate
Oxide
Salts, n. e. s
Magnesia, calcined
Magnesium:
Carbonate
Chloride
Sulfate
Mercuric sulfide:
In lumps, natural 01 artificial
Pulverized (vermilion)
Methanol
Milk sugar (lactose)
Nicotine salts
Phosphorus:
Red
Japan
Russia
Switzerland
White
Potassium:1
Acetate
Arsenate
Carbonate and crude potash.
United Kingdom
Chlorate
British India
Italy
Russia
Chromatc of pot a-
sodium
Nitrate
Oxalate
Permanganate
Prussiate
Sulfite and bisulfite
Pyrolignites of:
Calcium
Allied Products (Continued)
1913 1916 1919
Tounds Pounds Pounds
220
57,980
10,305,500
6.981 ,800
I .141,770
182,540
12,790
47,840
n.l
Ir
Quinine, sulfate and other
salts
Salts of thorium, cerium, etc. . . .
Silver salts
Sodium:
Acetate
Arsenate
Bicarbonate
Carbonate (soda, natural or
artificial
Crude
Algeria
Italy
Norway
ttcfined, not containing more
than 38 per cent of pure
l artionate
Refined, other
Algeria
Belgium
Netherlands
Sw itzerland
Chlorates of sodium, barium.
etc
Italy
Russia
Hydroxide (caustic soda)
Belgium
Netherlands
Switzerland
16.778.040
7 28.400
668,660
3.129.910
s. J13.180
5 2, 470
8 , 600
vS5
n
f>;
r-t
SMI 1
2
,430
14.582,250
6.721 ,670
2.263,040
3.917,170
683,870
10.140
1 . 152,350
12,130
97,440
20,060
110,890
406,750
24,030
215,390
198,200
1,100
8.380
35,050
7,984,100
4.196,720
3,021,650
2.037,510
622,140
128.310
24,690
24.470
I ,561.090
7.720
36,820
1 ,207,250
186,730
695.120
588.630
34.180
40,790
36,820
21,830
898,820
582,680
37,040
Sulfate
Belgium
Brazil
Italy
' See also Fertilizers.
7 , 125,550
174,398,200
3.656,140
96,006,010
30.238,380
18,645,370
1.787,950
284,840
506,180
29.622,850
14.977,100
6,277,660
5,887,660
144,840
213.850
653,230
53,302,700
23,658,460
16,760
9,347,600
5,437,040
2,673,550
47,400
27,. HO
64,150
97,660
8.273,070
1.399,270
6,743,500
9.480
20.7 20
9 !60
220
1 ,032,640
1,310,650
220
1,100
7,376,450
557,550
13,000
897,940
5,070
31 ,750
39,460
22,050
176.370
2,650
47.840
20.280
4,410
160,720
52,030
49,600
22,270
135,360
132.940
53,350
71 .210
24.470
21.660
4,410
421 ,080
51 ,150
592,820
113.980
61 .950
I !
5.7 14 7 '10
4.190
I .980
220.680
631 ,620
9.480
h 1711
.546,810
135.360
63,710
772.940
369,940
23,590
83,330
13,230
121,250
440
3,530
722,460
38,140
377,210
143.080
765,440
582,28(1
880
1 !
1 ,043.010
101.850
440
8,160
242,290
17,420
855,390
42,550
36.380
12,130
37,260
15,650
284,840
39,460
1.847,910
10,055.500 11,027,300
29,100
4,054,740
5,342,460
6,566,030 7,550,390
49.686,450 127. . 01 <"
5.734,880
132.720
41 .310,880
44.588,700 8.054 810
1 .801 .180
54 ,230
4,609,200 18.781.400
2,976'.o2o ;; '"
584,220
691.590 532.410
950 1.017.880
38,957,440 10
1 .964,760
9,378,460
3.802,310
3,287.530
Exports of Chemicals and Allied Products (Continued)
Chemicals (Concluded):
Sodium (Concluded) :
Sulfite and bisulfite
Tetraborate (borax):
Crude
Refined or semi-refined.
Belgium
Netherlands
Switzerland
United Kingdom
Salts, n. e. s
Tartrates:
Cream of tartar
Australia
United Kingdom
Crude tartar
United Kingdom
United States
Crystals of tartar
Wine lees
Other
Tin:
Chlorides
Oxide
Uranium oxide
Oxide
Ru
Spain
United Kingdom
United State*
Sulfate
Sulfide
Coal-Tar Products:
Products obtained directly by
distillation of coal tar
Products derived from products
obtained by distillation of
coal tar
Switzerland
Dyes derived from coal tar:
Alizarin, artificial
Picric acid
United Kingdom
Other dves
United Kingdom
United States
Indo-China
Dyeing and Tanning Materials
Extracts of woods, barks, nuts,
and berries used for dyeing
Black or violet
8,745.290
3,651,290
4,174,230
18,681.310
2.512,830
10.973,730
1,320
3.952,670
5,730
79,150
182,540
4,630
7,899.160
1 .180,790
380,520
1 .336.440
689,820
17,860
4.630
855,390
1 ,033,080
4.390,060
4,500,960
1,311,090
2,978,880
8,250,800
1 ,934,550
6,263,110
440
1,318,360
24,250
48.940
39,693.780
1,874,370
17,860
5,069,090
232.150
322.310
2,183,020
1 ..'07. 25(1
67,680
660
432,550
449.740
342.600
100.970
4,850
17,407,250 1.449,980 5.247.490
Chii
Germany
United Kingdon
United States. .
916.900
40.340
15.870
580,040
8 833.700
893.310
2,652.600
1 ,158,090
90,610
228,180
227,520
134.480
39,680
220
25,570
17,640
536] (80
1,100
71,210
164,020
Indigo, natural.
Indigo pastil, indigo bluing
Orchil, prepared:
Dried 28,000
Moist, in paste 25 ,350
Red or yellow 5.279,850
Italv
Spain 163,580
United Kingdom 1 ,589,310
United States 332,900
Extracts of woods, barks, tints,
and berries used for tanning:
Chestnut and other 207.113,030
Belgium 30,011.080
Germany 37,854.690
Indo-China 253,530
United Kingdom 97.079.440
Nutgalls and sumac 118.830
Quebracho 18.754,500
714,960
65,260
4,410
55,120
64,370
148,810
142,640
4,644,260
1,349,450
566,370
1,692,930
186,290
440
408.740
30.200
11 ,460
49.160
1 .769,210
29.200,440 15 ,.i ,, |0
Belgium.
United Kingdo
Algeria
Explosives:
Dvnamite
Algeria
2,184,780
5.958,430
30,420
793,440
26,012,780
3,090
471.7')" 26.273.150
Ru
Fireworks
Gunpowder
Algeria
Italy
Russia
Fertilizers:
Ammonium sulfate, crude
Calcium nitrate and cyanamide.
Fertilizers, chemical, n e s
Algeria
Belgium
Germany
Italy
United States
Potash:
Muriate (chloride)
Sulfate
Slag, basic
Sodium nitrate (Chile saltpeter)
Superphosphate
Algeria
Belgium
Italy
Portugal
Spain
Switzerland
430,780
.107.410
.525.380
220,020
Metric Tons
1,036
839
403 , 296
7,929
135,790
219,805
22,982
1 ,000
127
730
0)
5,268
145. 226
9.692
30,212
20.974
11.815
57,389
5.521
270.510
12,994.710
470,11(1
12,105.800
71 ,430
23,142,800
517.870
16,901.080
4,465,460
Metric Tons
1 ,328
5,511
3,078
2,571
! Included under "Fertilizers, chemical.
4,101
11,792
12,363
526
176
530
1,550
5.151
1.538
( 1913.
45.358
538
6,209
Jan., ig2r
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
Medicinal Prefab
Distilled waters:
, Alcoholic
United States'
Other compound-.
Argentina
Brazil
Cuba
Mexico
Spain
United Kingdom
United States
Oils, Fixed Vegetable:
Castor and pulghere
Allied Prod
1913
Gallons
97,798
14,028
52,783
Pounds
950
200
640
160
760
450
570
050
640
440
280
2,270
1,877
1,083
1 ,065
239
765
479
7,177
United Kingdom
Coconut, touloucouna, illipe,
palm nut
Italy
Switzerland
United Kingdom
United States
Colza
United Kingdom
United Stales
Cottonseed
Linseed
Algeria
Switzerland
Tunis
Mustard
Niger
Olh
Belgium
United Kingdom
United States
Palm
Italy
Switzerland
United Kingdom
United States .
Peanut
Algeria
Italy
Switzerland
United Kingdom.
United States
Poppyseed:
Black
White
Rape
Sesame
Algeria
Switzerland .....
United States
Soy-bean
Other oils
Switzerland
United Kingdom.
United States
Oils, Volatile:
1,035
21.643
2,676
3,819
3,046
6,794
4,041
582
897
2,035
5,783
1,514
13,027
2,672
1 ,270
2.292
2,429
763
420
414
53,427
18,511
6,799
4,769
4,356
5,269
495
3,695
255
4.347
906
247
Ro
Switzerland
United States
Rose geranium and ylang-ylang.
Germany
Spain
Switzerland
United States
Other
Germany
United Kingdom
United States
Paints, Pigments. Varnishes:
Blacks:
For engraving
Ivory
Lampblack
Belgium
Germany
Italy
Mineral, in lumps
Mineral, ground
Blue, Prussian
1,923
645
Tun
United States.
United Kingdo
Carmines:
13,230
1,855,850
433,650
806,230
206,570
279,330
301,150
220,240
23,370
37,260
British India
Colors:
Ground in oil
Algeria
Belgium
United Kingdom
United States
In paste
Other
Green, mountain, Brunswick,
and greens resulting from a
mixture of chromate of lead
and'jPrussian blue
13,890
660
5.950
4,850
924,180
1,174,180
402,790
;cts {Continued)
1916 1919
Gallons Gallons
33,154
4,993
Pounds
1
,110,690
181 ,000
311. 290
9
708,270
1
,471 .800
1
235,250
1
.653,250
432,770
327,160
359,570
1
,148,730
158,730
168,4 (0
11
,436,700
1
740,350
4
678,210
487.880
7.
.373,270
1
251,790
653.670
275.140
6
043,970
(,411,01111
3
461 .260
352,740
220
4
347,960
119,710
335,760
762,780
6
310,950
790,170
1
040,140
87.300
1
869 , 740
»s
Kofi. 8x0
7
603,960
150,800
9
265,370
1
531,990
1
977,110
27,340
321,870
4
518,380
1
826.530
1
801 ,190
49,600
18,080
709,890
| !9,630
135,140
103,840
12,965
3,693
133,294
3,580
18,667
61,600
1
124,800
229,500
255,520
440
9 , 260
558,650
192 680
65 , 260
195, 110
178.350
21 ,645.860
3,102,560
2.659.880
953 ,060
1 .162.060
3,090
61 .730
418.660
5 ,950
1 I 5 ,960
200,1.10
,870 3,160,550 3,146,220
110,230
84,220 24,030
794,760 419.1011 284,620
1,489,220 733.480 714,300
Paints. Etc {Concluded)
Green. Schweinfurth, 11
green, mountain blue
Lithopone
Ultramarine. . . .
Algeria
Egypt
LTnited Kingdom
United States
Varnishes:
Spirit
Turpentine, oil, or mixed.
Belgium
Italy
Spain
United Kingdom
Zinc yellow, or chromate of z
Perfumery and Cosmetics
Alcoholic
Argentina
Belgium
United Kingdom
United States
i.lied Products {Concluded)
1913 1916 1919
Pounds Pounds Pounds
74,960
225,750
3.784,670
496,040
767,210
176.370
Nonalcoholic
Argentina
Brazil
Belgium
United Kingdom.
United States
Oils, fixed, scented
Synthetic perfumes
LTnited Kingdom
United States
Toilet soap:
Transparent
United States
Other, scented
Algeria
British India
Indo-China
United Kingdom
United Slates
Miscellaneous Products:
Albumin
Germany
United States
Switzerland
Blacking
Belgium
Italy
United States
Candles:
Tallow
Wax and other
Algeria
Madagascar
Dextrin
Gelatin, in powder, she* ts eti
United Kingdom
United Stales
Glucose
238,980
3,402,610
686.300
629,420
249,560
326,940
1 ,100
Gallons
448,376
69,979
35,504
56,849
32,467
Pounds
5,333.860
286,160
112.440
615,970
1 .510,600
884,050
31,182
32,410
7,500
3,310
98 , 5 50
20,940
3,072,800
251 ,770
23,370
816,150
393.080
309,310
364,200
162,700
42,990
18,960
1,691 ,600
238,980
235,010
26,010
Glu
Belgium
Germany
United Kingdom
United States
Inks:
Drawing, in tablets.
Writing or printing .
Belgium
Brazil
Italy
United Kingdom .
Isinglass
United Kingdom
United States
Paper and pulp:
Pulp, mechanical
Pulp, chemical
Paper, fancy
United Kingdom .
United States ....
Paper, other
Algeria
Egypt
United Kingdom.
" lited States
188
6,772
5,707
252
306
1,016
624
118
347
16,605
3,836
955
6,454
912
720
160
540
210
220
330
130
830
450
000
700
700
250
270
1 oil.
Re
Soap, common
Algeria
Italy
Switzerland. . .
Tunis
United Kingdo
United States.
Turpentine. resin> rosin, pitch,
resin lumps and other indig
enous resinous products. . .
Switzerland
United Kingdom
Turpentine, spirits of
Italy
Switzerland
2,420
4,376,610
538,810
308 , 200
321,430
756,190
260,370
3,300
19.840
Metric Tons
59
594
Pounds
3,924,230
' 1,345,040
76,940
90,756,590
29,489,690
7,637,910
9,288.510
6.675,150
58,420
77,568,530
28.784,210
8,830,390
3,340,220
3,913,420
4,042,610
1 ,546,760
Metric Tons
199.115
Pounds
1 ,153.900
59.300
36,160
.182,590
345,020
677,920
324,520
31,330
393,080
283,960
110,230
3.310
Gallons
345.703
47,710
34|423
48.952
5,394,930
369,270
235,890
1 ,132 ',070
1,630,320
4,528
170,420
41,890
84,440
52,470
5,070
2,065,070
568,570
172,620
160,060
140,880
55,120
400,580
352.740
2.251,140
58,860
1 ,005,090
22,270
168,650
5.651,770
4,947,830
93,920
253,750
542,340
231,050
43,210
230,600
5,560,060
8,1
64, [50
3,970
Gallons
421 ,627
55.780
6. 944! 341 1
109,350
5,358,330
4,035,340
173.720
7,107,920
1,569,690
577,830
Metric Tons
5.070
2,644,890
23, L50
261 .470
309.970
379,200
404,550
74,520
139,330
Metric Tons
6 15
117 25
Pounds Pounds
1,533,100 1,546,540
483,690
87,080
66,659,840 43.470,300
23,613,710
771,400
5,724,740
10,813,670
128,090 65,480
53,463,410 44,304,090
28. ITS. 200
4,567,100
2,626,810
2,718,300
1,227,750
771,180
Metric Tons Metric Tons
94,486
Pounds
454,590
78.851
Pounds
384,260
90,159.570 67,470.700 114,201,640
1,149,710 8,688,420
19,707,340 34,152,900
21,525,270 6,065,800 14,959,240
3,653,060 1,301,610
,1,244,760 2,091.970
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. i
FULL SYMPOSIUM
Papers presented before the Div
of Industrial and Engineering Chemistry at the 60th Meeting of the American Chemical Society. Chii
September 6 to 10, 1920.
LOW-TEMPERATURE CARBONIZATION AND ITS APPLI-
CATION TO HIGH OXYGEN COALS
By S. W. Parr and T. E. Layng
University ov Illinois, Urbana, Illinois
The low-temperature carbonization of coal is ordi-
narily understood to mean its destructive distilla-
tion at temperatures not in excess of 750° or 800°
C.
COMPARISONS WITH HIGH-TEMPERATURE CARBONIZATION
Certain features which accompany this particular
condition may be briefly enumerated as follows:
The demarkation of temperatures indicated by
750° to 8oo° C. is not arbitrarily chosen, but seems to
be a natural dividing line between the decomposition
processes which liberate heavy products which are
largely condensable and those reactions which deliver
light or noncondensable compounds. Another method
of stating the case would be to say that below 750°
the volatile products are tars or oils and some fixed
gases, while above 750° the volatile products are gases
only.
Again, under low-temperature conditions the vola-
tile constituents are largely the initial products of
decomposition, as set free by the various components
of the coal, and in the main they are not subject to
any great modification by secondary processes of
decomposition. By this it is not intended to affirm
that no secondary reactions occur. By their very
nature, these volatile products are susceptible to
change, but these changes are more in the nature of
interactions or reactions among themselves or with
the decomposing constituents; whereas, under high-
temperature conditions, there proceeds a very positive
breaking down of these easily decomposable compounds.
In other words, the high-temperature process accen-
tuates the matter of secondary decomposition so that
the ultimate products bear little relation to the char-
acter of the substances that first result from the
destructive distillation of the coal.
yields — This contrast in products leads to the
next statement as to yields. A bituminous coal,
which under the ordinary high-temperature process
yields 10 gal. per ton of condensable material, will,
where these secondary decompositions are lacking,
yield from 20 to 25 gal. per ton. Indeed, certain types
of coal have been found where the condensable prod-
ucts are in excess of 30 gal. per ton.
CHARACTER OF LOW-TEMPERATURE PRODUCTS — -Other
interesting features relate to the character of the
compounds that are discharged under the low-tempera-
ture range. No information along this line can be
gained from a study of high-temperature products,
because their character has been quite altered or
obscured by the secondary decomposition resulting
from the passage of the initial volatile constituents
over or through the highly heated passageways or
masses of coke. As a matter of fact; it is only by
a study of the products as they are discharged at
successive temperature stages that we can arrive at
any safe conclusions as to the character of the initial
products of decomposition. It will not be strange,
therefore, if we have to modify to a considerable
extent our present conception of the decomposition
procedure.
Briefly stated, we shall find the order to be: water,
carbon dioxide, and methane, with respective tempera-
ture ranges of approximately 2500 to 3000, 300* to
3500, and 350° to 4000 C. At the latter stage, there
begins also the discharge of ethane and heavier hydro-
carbons, with the beginning also of condensable products
in which the sulfur and oxygen compounds predomi-
nate. The latter show themselves in the form of tar
acids. The chief feature concerning the sulfur is
that the part which is in organic combination in the
coal is quickly discharged. A range of temperature,
however, seems to be attained where there is sub-
stantially no sulfur decomposition, as shown by an
almost total absence of this constituent in the gases.
However, at higher temperatures where decomposition
of the iron pyrites occurs, the volatile sulfur compounds
appear, largely in combination with the tar or oil
constituents.
This substantial absence of secondary decomposition
accounts for a number of characteristic variations
in the by-products. For example, the tars are thin
and light, having a consistency much more resembling
oils. They have a specific gravity so nearly approach-
ing unity that, the separation of water from the oil
is difficult. The tars contain practically no free car-
bon. The gas yield per pound is less, being from 60 to
80 per cent of the volume obtained by high-temperature
processes, and both gas and tar are free from naph-
thalene.
These differences are such as one would naturally
expect as a result of the presence or absence of secon-
dary decompositions. The argument in favor of the
tars is that, in addition to their much higher yield,
it would be better to carry out the possible decomposi-
tions upon them as a distinct process under exact
control and for the production of specific substances,
rather than to submit them to the more or less uncer-
tain and haphazard reactions which result from the
high-temperature decompositions.
Another method of stating the important feature
of oil or tar yield is from the viewpoint of our rapidly
vanishing petroleum supplies. If, for example, a
Scotch shale with a yield of 20 or 25 gal. of oil per ton
and no by-products of value is a workable proposition,
why may we not look with favor upon a bituminous
coal having a potential yield of liquid fuel of 20 or 30
gal. per ton and a by-product in the way of a smokeless
solid fuel of even greater value than the oil?
Jan., 1021
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
IS
COKING OF HIGH OXYGEN COALS
Since the most of our high volatile coals are, as a
matter of fact, also high oxygen coals, the question
at once arises as to the possibility of producing a mar-
ketable coke from high oxygen coals. Concerning
the coking of such coals, we shall doubtless be obliged
to recast to a certain extent our theories concerning
the chemistry of coal carbonization.
theoretical considerations^ — -In a general way,
it has been held that a coal with an oxygen content
above a certain amount, for example, an oxygen-
hydrogen ratio much in excess of 50-50, or, say, 6 per cent
of oxygen to 5 per cent of hydrogen, should be classed as
a noncoking coal. This would seem a harsh decree for
Illinois coals, which exceed this oxygen ratio by almost
50 per cent; especially since the reserve tonnage of such
coals within the boundary of Illinois exceeds the
reserve tonnage of any other state in the Union,
Pennsylvania and West Virginia not excepted. Now
the fact that a low oxygen content is characteristic
of the coals which make good coke by methods now
in use may be a coincidence and not a cause. At
least, there has never been any very good explanation
of why a high oxygen content should result in poor
coke. We are positive in this connection only of one
thing, namely, that we have found no explanation
which we can guarantee as satisfactory in all cases, or
in all respects. But, experiments have proceeded to
a point where a few fundamental propositions are
seemingly established. For example, that part of
the coal which is "phenol-soluble"1 has a definite
melting point, and this material in its final decomposi-
tion furnishes the binder for the production of coke.
It is largely composed, however, of highly unsaturated
compounds, and these, if allowed to come in contact
with certain decomposition products of the fully
oxygenated type, unite with the same to form com-
pounds having totally different characteristics, chief
among which is the absence of any melting point,
and consequently the absence of the coking property.
Let us go a step further in this illustration. A coal
which is finely divided and which has been exposed
to the air for sometime will have lost its coking property,
even though the coal be of the so-called coking type.
Now, if our reasoning is correct, such a coal might
be so handled in the coking process as to eliminate
those oxygen compounds in such a manner as to
avoid the disastrous reactions with the active coking
constituents. Experimental evidence is in hand show-
ing this can be done. The same reasoning, of course,
will and does hold true for the coals with a high normal
oxygen content. They may be dealt with in such a
manner as to produce a very weak and indifferent
coke, as seen in the ordinary gas-house product, or
under other conditions where deleterious interactions
are avoided, a coke of altogether different texture and
density may be the result.
Further, these considerations are not inconsistent
with the theories now being developed by Doctor
Thiessen as to the composition of coal. He seems to
1 Pan- and Olin, University of Illinois Engineering Experiment Station,
show that the phenol-soluble portion is the degrada-
tion product, through geological processes, of cellulosic
material; and not, as Lewes would have us believe,
of resinic bodies. From this standpoint, we should
say, then, that this material which constitutes the
true coking substance has a marked tendency towards
a reversion of type. This may show itself either in
the interaction which occurs during the destructive
distillation process or more readily in the effect of
weathering. A striking illustration of the effect of
weathering is occasionally found in the case of Illinois
coals, where the outcrop shows a marked reversion
of type to the extent that it has every characteristic
of a lignite, whereas the coal from the working face,
completely removed from weathering effects, shows
no such reversion.
temperature control — -Thus far this discussion
has dealt only with some of the theories underlying
the carbonization of high oxygen coals. The methods
which suggest themselves for securing the conditions
indicated involve a procedure whereby the changes
may be brought about in stages or what may fairly
well be designated as fractional decompositions. Such
a method implies an observance of temperature con-
trol, quite unknown and quite impossible under the
ordinary high-temperature conditions. This matter
of temperature control involves the entire question
of successfully carrying out any sort of a low-tempera-
ture program. Indeed, it is of such paramount im-
portance, and in all of its bearings upon the situation
involves so many factors, that its proper discussion
should' be reserved for a separate consideration. How-
ever, brief reference is made here for the purpose of
indicating that the preceding discussion is not purely
academic and theoretical, with no hope of possible
attainment in practice, but, as a matter of fact, may
be found the most logical procedure even under indus-
trial conditions.
The first question we meet is this: Can we carry
heat to the center of a nonconducting mass by con-
ductivity methods alone, without doing violence to
all ideas of temperature control? If we look to the
modern by-product oven for an answer, we shall be
obliged to say at once, "No." In this practice, for
the temperature at the center of a coal mass of 18-in.
cross-section to reach the beginning of the carboniza-
tion stage requires at least 14 out of the total of 18
hrs.; and even this is accomplished only by main-
taining a surrounding temperature of 10000 as an
impelling force against the nonconductivity conditions
prevailing. Obviously the low-temperature idea in
any of its bearings is incompatible with such procedure.
A number of methods have been proposed for meeting
this condition of nonconductivity without the use of
excessive temperature. The most frequent is the
application of temperatures within the prescribed
limit to a mass of coal so narrow in its cross-section
that the penetration of heat from the two sides would
be sufficiently uniform and rapid to meet the require-
ments so far as ultimate temperature throughout the
mass is concerned. The same idea is involved in any
briquetting process with subsequent application of
i6
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
heat to the briquets, the factor involved being the cross-
section of the individual briquet masses.
In the process as we have been developing it, utiliza-
tion has been made of the ability of the coal under
proper conditions to supply its own heat, which may
thus be made to proceed autogenously throughout
the mass without reference to its size or cross-section,
and without the application of any external heat in
excess of the prescribed maximum for the theoretical
conditions involved in the low-temperature idea.
Fortunately, these reactions which are responsible
for what is well recognized as the exothermic behavior
of coal in the process of carbonization occur well within
the prescribed limits. As a matter of fact, they are
most in evidence at temperatures of approximately
300° to 400°. Up to date our experiments have not
involved cross sections of coal greater than 16 in.
character of coke obtained — The appearance
of the material produced under these conditions
is strikingly characteristic. It is uniform in texture,
without any zoning evidence of progressive stages in
heat transmission, dense, and of good strength, and
without any of the fingering effect characteristic of
the high-temperature method. The volatile matter
retained under these conditions may vary from 5 to
15 per cent, depending on the coal and the ultimate
temperature attained. It contains no condensable
hydrocarbons, and if discharged by application of
further heat would appear almost entirely as hydrogen
and methane. As would naturally be expected where
an autogenous generation of heat is involved, the
time element for bringing about the carbonization is
greatly reduced, the average time being from 3 to 4
hrs. Experiments involving the exact measurement
of the amount of heat available from different coals,
the conditions for its greatest development, and the
limits as to mass wherein it may be made practically
operative are still matters of experimental research.
DISCUSSION
Mr. J. D. Davis: I should like to question Professor Parr in re-
gard to the temperature at which naphthalene products begin
to show carbonization. It seems to me that with a temperature
as high as 750° or 800° you would get an appreciable secondary
reaction.
Mr. Parr: I think that in general the point at which naph-
thalene products begin to show themselves is a pretty good line
of demarkation or an indication cf the beginning of secondary
decomposition.
Mr. A. R. Powell: Mr. Chairman, I was much interested
in the results on the sulfur in low-temperature carbonization.
From experiments on laboratory- and plant-scale gas retorts,
I found that the organic sulfur is only partially involved. A
large part is retained in the final coke and the pyrite is decom-
posed. It starts combustion about the same time that the
organic sulfur is evolved. The sulfur in the gas rapidly reaches
a maximum and then falls off, so that in the latter part of com-
bustion, in which we get a gas higher in hydrogen, the sulfur is
very low and there is not a building up of the sulfur later, as
Professor Parr says. I was wondering what the conditions in
low-temperature combustion were that made these results on
sulfur so different from the high-temperature combustion.
Mr. F. W. Sperr, Jr. : Mr. Chairman, I would like to ask Dr.
Parr if he can give some information regarding ammonia. What
amount of ammonia is evolved at the temperature at which he
worked?
Prop. E. P. Schoch: Mr. Chairman, I would like to ask
I 1 Parr to state whether the distillation was carried out by
filling the retort, heating it up and emptying it, as you might
call it, discontinuous; or whether he had a continuous furnace that
was being fed continuously at the top and emptied continuously
at the bottom, since naturally the materials would distil up
in the mass above in one case and not in the other.
Dr. H. L. Olin: Mr. Chairman, I would like to ask Professor
Parr if the low-temperature coke has been examined from the
standpoint .of use in glass furnaces, and his opinion of its value
as a furnace coke.
Mr. Parr: Mr. Chairman, with regard to Mr. Powell's
question as to the behavior of the sulfur, I think we shall have-
to defer our sulfur discussion until some future time. He is
finding out so much about sulfur, and we are also finding out so
many other things, that I am almost persuaded that we do not
know very much about sulfur. I have been taken to task by
somebody — Mr. Sperr, I think — in some of the statements I
have been making recently. I will say only this about sulfur,
and it will partly answer the question about nitrogen. Sulfur
and nitrogen, "and we believe oxygen, practically let go of their
original forms of combination; but just when and how, and
what the conditions are, is a little difficult as yet to understand.
They form in the finished coke new and unusual compound^
which are far removed from what they were in the coal. They
are not chemical compounds in the usual sense, and bear little
relation to anything we know in the way of chemical compounds.
They do not conform to any rule of definite proportion, but come
nearer perhaps to some of the attenuated stages of what for any
better term we may call an adsorbed condition. As an illus
tration, sulfur can be made to unite with a coke which has
absolutely no sulfur in it at all, like sugar carbon, in just about
the amount that we find it in coke. Now, there was no sulfur
in the sugar carbon, but you can make a compound of sulfur and
carbon, stable at 10000, or whatever temperature you choose
Nitrogen behaves in exactly the same way. We can make a
nitrogen carbon at 1000 °, starting with coke that has absolutely
no nitrogen in it. What is this new compound? It isn't an or-
ganic compound ; it isn't an inorganic compound ; and we say
we believe oxygen behaves the same way, and that it is often in
coke as a stable compound up to certain temperatures. I don't
think I care to go into that question, further than to say it is a
field which contains so much yet to be found out that I am
reluctant to venture very far into it. I think Dr. Powell might
perhaps go farther than I would be willing to.
As to Mr. Sperr's question about the ammonia yield, th
actual nitrogen in combination as ammonia is very nearly the
same in amount as is produced from the high-temperature pro-
cess, but it is not due to similar conditions. The high-tempera-
ture process has torn a lot of the ammonia to pieces, and they get
the residue, which is their yield. We do not decompose the
ammonia to the same extent; there is more of it but in other
forms as, for example, the amines in the tars, but the ultimate
nitrogen that we can recover as NH3 is about the same in amount
as from the high-temperature process.
As to furnace methods, this is a discontinuous process, very
much as any coking process is. I doubt very much if our method
would be applicable as a continuous process. We must observe
for the different stages rather exacting conditions, and when the
reactions are completed discharge the batch and begin on a new
lot. We are now attempting to measure the quantity of heat
involved in the exothermic reactions. All we know at this time
is that there is not enough heat generated to do all the work
involved in vaporization of the water, heating up the coal mass,
and supplying the loss due to escaping products and radiation :
hence the intermittent character of the method.
This in general will give you an idea of the procedure. AD
of our work is done with a comparatively small outfit in which
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
17
we can meet these conditions. We work on about 35-lb. samples
of coal.
Just one other word in regard to the inquiry about whether
the material is any good for metallurgical purposes. With Mr.
Sperr in the room, I would hardly attempt to pass judgment
on it in that particular. I asked a blast-furnace man not long
ago to describe what a good blast-furnace coke was. He said,
"After changing our minds so radically within the last few years,
we are not absolutely sure as we once were." Some will say
that it is entirely unsuited for blast furnace use. It does
violence, I think, to nearly everything that would ordinarily
be described by a blast-furnace man as being necessary. I
do not know, however, but that if we could make enough at the
rate of 35 lbs. per run to supply a blast furnace for a week, we
could find out for a certainty.
I want to say in that connection that the initial incentive for
all this work comes out of the great anthracite strike of 1902.
We thought it would be desirable to make smokeless fuel for
domestic purposes out of Illinois coal, and that has been the
main idea all along. We do not know much about metallurgical
coke, although I will say this, that so far as strength, and carrying
the burden, and a lot of those physical conditions are concerned,
it certainly looks very encouraging, but there are other condi-
tions, like high ash, etc., which would enter into the problem.
CARBONIZATION OF CANADIAN LIGNITE'
By Edgar Stansfield
Lignite Utilization Board, Ottawa, Canada
The researches on lignite outlined in this paper
were commenced early in 191 7 by the chemical staff
of the Fuel Testing Division of the Mines Branch,
Department of Mines, Ottawa, and the work is still
in progress. The primary object of the investigation
was to obtain accurate data essential for the scientific
design and control of a plant for the carbonization of
lignite on a commercial scale, rather than to design
such a plant.
In the summer of 1918 the Lignite Utilization Board
of Canada was created by an Order-in-Council of
the Dominion of Canada, supplemented by an agree-
ment as to finances with the provincial governments
of Manitoba and Saskatchewan. The Board was
created to establish an industry for the conversion
of the low-grade lignites of southern Saskatchewan,
and elsewhere, into a high-grade domestic fuel by
means of carbonization and briquetting. The labora-
tory investigations of the Lignite Board have been
carried out at the Fuel Testing Station of the Mines
Branch by members of the staff of the Board working
in cooperation with the members of the Mines Branch
Staff. This latter work has carried to a logical con-
clusion the earlier work of the Mines Branch. The
points essential for the successful carbonization of
lignite, under the economic conditions prevailing in
southern Saskatchewan, were first decided upon,
and then a carbonizer design was evolved which em-
bodied these features. A semicommercial-scale car-
bonizer was erected in Ottawa, and, after many trials
and modifications, successfully operated.
It is worthy of note that the experience and infor-
mation gained in the operation of the carbonizer at
Ottawa have been embodied by the engineer of the
1 Published by permission of Dr. Eugene Haanel, Director, Mines
Branch. Department of Mines. Ottawa. Canada.
board, Mr. R. De L. French, in the design of six
carbonizers for a plant now being erected by the
Board near Bienfait, Sask. This plant is expected
to treat about 200 tons of raw lignite per day.
This paper attempts to trace in outline the progress
of the investigation up to the operation of the car-
bonizer in Ottawa, and to show why this particular
design of carbonizer was adopted. No full report
of any stage of the work has yet been made, but the
methods employed and results obtained in the earlier
stages have been published in some detail.1
The work falls naturally into several stages, but
these are not chronologically distinct. The investi-
gation was commenced with lignite from the Shand
Mine in the Souris, or Estevan area, Sask. Later
other Souris lignites were studied. Now Alberta
lignites, and also peat, are being tested in a similar
manner.
Souris lignite when mined contains from 30 to 35
per cent of inherent moisture, and has a calorific
value of about 4000 cal. per gram. It loses moisture
rapidly when exposed, and the lumps then disinte-
grate. This lignite is employed in the raw state, but
it is a low-grade fuel, unsatisfactory for transporta-
tion or storage. By drying and carbonizing it, a
product is obtained which may have a calorific value
as much as 75 per cent higher than that of the original
coal.
SMALL-SCALE LABORATORY TESTS
In these experiments samples of from 3 to 10 g.
were employed. This allowed very exact control of
the conditions of the experiment, and also allowed a
large number of experiments to be carried out, under
widely varying conditions, within a reasonable time.
It was not possible, however, to study the by-products.
The results were used to cut down unnecessary work
in the larger tests, and were also valuable as checks
on the accuracy of control in all subsequent experi-
ments, and for the comparison of different lignites.
The factors determined included the yield, analysis,
and calorific value of the carbonized residue. The
conditions under which the lignite was carbonized
were varied in order to show the influence on the
results of the final temperature to which the charge
was heated, the rate of heating, the pressure in the
retort, and the atmosphere in the retort.
coal used — -The particular coal chosen for most
of these experiments was from the Shand mine of the
Saskatchewan Coal, Brick, and Power Co., Ltd.
The sample, which consisted of a single lump of coal
shipped by express from the mine in a wooden box,
was crushed and ground to a fine powder in a ball mill.
For convenience of manipulation, and as a preventative
of the rapid change which a powdered coal undergoes
owing to moisture loss and oxidation, this powder
was briquetted in a small hand press. The briquets
were cylindrical, 0.25 in. in diameter, about 0.25 in.
long, and ran about 5 or 6 to the gram. They were
stored in stoppered bottles until required, and from
1 Stansfield and Gilmore, "The Carbonization of Lignite," Trans.
Roy. Soc. Can., [31 11 (1917), 85; [31 12 (1918), 121. See also Mines Branch
Summary Reports for 1918 and 1919.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Temperature of Carbonization, degrees C
o o o 00000
.'K 1 1 1
^
,'''
*??'"'
\\
\ s
\ \
Carbonization of
western Dominion Lignite **I076
Full curves ~ determined
Dotted curves - calculated results
Analysis of Cool
Raw Dry
Moisture % 313
Ash % 8-0 HO
Volatile Matter % P8 O 4Q-B
fixed Carbon % 3Z7 4T6
Colorific Value c/jg 4190 6OSO
N
\ \
\ \
\ \
\
V
\
N
\
\
N
\
c!N
f'
\ V
\
5500
5000
\
V
y \
\
\
\- -
____.
_o-— "
J^=-
-^J^- — '
\ \
\ \
\ \
\ \
*■*• —
\
S
\
\
\
o\
\
V
.''
,.''
"
\
\
\
'N
\
\
\
\
4000
Yield on coal as charged, per cent
as ao
Yield on dry coal per cent
time to time moisture control determinations were
made upon them. It may be noted that during a
period of 2 mo. the moisture contents fell only 1 per
cent from an original of over 30 per cent.
The gross calorific value of this coal was 4260 cal.
per gram. Its average analysis was as follows:
Per cent
Moisture 31 .8
Ash 5.2
Volatile matter 28.9
Fixed carbon 34.1
apparatus — The apparatus used for most of the
experiments consisted of a cylindrical iron retort
1.5 in. high and 1.5 in. diameter, inside measurement,
having a lid which was held on by a small clamp, the
joint being rendered airtight by means of an asbestos
gasket. A small inlet tube was screwed into the
bottom of the crucible, and an outlet tube into the
lid, the inlet and outlet tubes being so arranged that
the retort could be completely immersed in an oil
or lead bath. For the experiments under pressure a
slightly larger and heavier retort was employed, with a
hexagonal screw cap rendered gastight with an asbestos-
copper gasket. The inlet tube was dispensed with,
and a pressure gage and relief valve connected with
the outlet tube.
method — The coal briquets were weighed out into
a quartz crucible which fitted inside the iron retort.
The heating was done by immersing the retort in a
bath, which for tests up to 3000 C. was of oil, and for
those above that temperature of lead. The lead
was contained in a 4-in. length of 4-in. iron pipe with
a capped end, and was heated in a gas-fired furnace
which gave a very uniform temperature throughout
the bath, and which permitted rapid heating and
easy control. The temperature was followed by two
pyrometers immersed in the lead.
For the regular tests, the retort was plunged into
the bath, previously heated to the desired temperature.
The temperature was kept constant until the evolu-
tion of gas ceased, and the retort was then removed,
cooled, and opened, and the contents weighed and
examined. In other tests, the retort was slowly heated
to about 2500 C. in an oil bath, then transferred to a
just molten lead bath, and the temperature slowly
raised to the desired point. In the vacuum tests,
the pressure in the retort was kept below 25 mm. of
mercury by means of a good water pump. In the
steam tests, a slow current of steam was passed through
the retort. In the pressure tests, the relief valve
was closed at the beginning of the test, but was opened
as required to maintain the pressure in the retort,
due to the escaping gases, at about 120 lbs. per sq.
in. Dry coal was employed for the pressure series.
A striking phenomenon, first observed in connec-
tion with the vacuum series, was later found to take
place with every sample of dried or carbonized lignite.
In every case the residue rapidly gained in weight
after removal from the retort, even when stored in a.
Jan., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
19
Temperature of Carbonization, degrees C
1
*'*
^s
^'
\ s
7500
MP''
\
gstfi?-
\ °- N
_„•» "
\S\
Carbonization of lignite *I507
from Tofield Coal Cos mine.
7000
\*r-Z.
Tofield, Alta.
\ \
full curves - determined
Dotted curves - calcu/ated resufts
Analysis of Coal
Raw Dry
6500
^s
s
/
\^ \
\
/
\
Moisture % 24 5 -
Nx
tf
?,'
. \
\ \
Ash % 5 6 7 4
Ns
Volatile Matter % 238 335
r,<V
6000
\ \
\ \
Calorific Value ?g 4830 6480
\ \
V
V'
\
5500
•' N
N*
*'
\*,
\ \
\ \
\l—
5000
\
.
k
\\
\
\\
\
\
\
\
\
1
M
4000
100 35
Yield on coal as charged, per cent
\45 40
I0O 95 90 85 80 75 70 65 60
Yield on dry coal, per cent
desiccator over sulfuric acid, its calorific value at
the same time decreasing. This was later shown
to be mainly due to an occlusion of air. All published
results are, with a few stated exceptions, for weights
and calorific values determined immediately after
the experiment.
Figs. 1 and 2 show in graphical form the principal
results obtained in the regular tests on one Saskatch-
ewan and one Alberta lignite.
In every lignite tested the calorific value of the
carbonized residue increases up to a maximum and
then decreases. The temperature for maximum calor-
ific value lies between 550° and 650° C, varying with
the lignite. But the yield of carbonized residue
for maximum calorific value has been found to be
remarkably constant when expressed on the basis
of the dry coal taken. Five out of six samples taken
from different areas in Saskatchewan and Alberta
gave a maximum value with about 67 per cent recovery,
the sixth with about 71 per cent.
LARGE-SCALE LABORATORY TEST
In these experiments the results determined include
the yield and calorific value of the carbonized residue;
the yield, composition, and calorific value of the gas
generated; the yield, calorific value, and economic
value of the tar produced; and the ammonium sulfate
yield available. The conditions under which the
[ignite was carbonized were, in the experiments here
described, varied only to show the influence op. the
results of the final temperature to which the charge
was heated, the rate of heating, and the moisture
conditions of the coal treated. Further experiments
have been commenced which show the effect of the
pressure in the retort and the atmosphere in the retort.
apparatus — The apparatus (Fig. 3) employed in
most of these tests embodies three important features:
(1) Accurate temperature control.
(2) Reduction, as far as possible, of the temperature lag
from the walls to the center of the charge.
(3) Complete removal and easy collection of the tar vapors.
The temperature control is effected by the use of
an electrically heated lead bath, B, with suitable
thermal insulation. The bath rests on a movable
platform which can be raised by the screw C. The
temperature is observed by means of a pyrometer
and regulated by switches and rheostat.
The reduction of lag is effected by the use of a tubu-
lar retort, A. This consists of seven 12-in. lengths of
2-in. boiler tubing, mounted in a cast-iron head. No
part of the charge is thus more than 1 in. from the
walls of the retort, which has a capacity, to the top
of the tubes, of 2300 g. of pea-size lignite with about
35 per cent moisture content. In later work, a cast-
iron retort of cruciform cross-section was employed.
This has a capacity of 3500 g.
collection of tar — A satisfactory method for
collecting the tar was evolved only after many weeks
THE JOURNAL OF INDl STRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 1
of work and many failures. Not only was it hard
to remove the last traces of tar fog, but the condensate
was usually in the form of a watery emulsion, very
difficult to handle.
The method employed was as follows: The hot
gases leaving the retort passed down through the center
tube of a small scrubber, D, made of iron pipe and
containing three interlacing coils of wire, and passed
up again through a surrounding annular space; the
whole scrubber being jacketed with superheated
steam. The heavy tar oils were here condensed in a
practically water-free condition, and dropped into a
weighed glass beaker. The lighter oils, steam, and
gases passed on and down' through the simple tubular
condenser E, where the two former condensed and
collected in a receiver, the oils floating on the water
and showing only a slight tendency to emulsify. The
cool gases leaving the condenser still contained some
tar fog; they were therefore passed down through a
tube scrubber, F, filled with glass beads and a thin
layer of glass wool (shown shaded), through which a
jet of steam from a weighed boiler was also passed.
The bottom half of this scrubber was water cooled.
This scrubber completely removed the tar fog from
the gas. The oil first condensed on the beads acted
as an oil scrubber collecting more of the tar, the steam
prevented the clogging of the scrubber by keeping the
tar hot and fluid, and also, when condensing at the
bottom, carried down with it any vapors still re-
maining. The gases were thus completely cleaned,
and all the liquid products, as well as the ammonia,
from the lignite were collected in the vessels and
could readily be weighed and examined. The tar
thus collected was reasonably free from water and
could be redistilled without excessive bumping or
frothing. The gases leaving the scrubber F passed
through a final cooling tube, G, through a gas meter,
If, ami into a gas holder which is not shown in the
figure.
For temperatures above 7000 C. a smaller apparatus
was employed, with no lead bath. The retort con-
sisted of a simple piece of 3-in. boiler tube, 16 in. long.
It was heated by placing it inside a tube of 3-in. bore
wound around the outside with a coil of nichrome
wire. A charge of 1000 g. was taken for all experi-
ments with this retort. The temperature of the
lignite was observed by means of two pyrometers,
one in the center and one near the wall of the retort.
method — In the regular series of tests, with rapid
heating, the retort was charged, usually with pea-
size lignite containing about 34 per cent moisture,
but in a few experiments with dried lignite, and con-
nected to the purifying train which was then swept
out with gas from a previous run. The lead bath,
heated to a temperature higher than that desired for
the test, in order to allow for the cooling effect of the
retort, was then raised to surround the retort. The
temperatures and pressures at the different parts of
the system and also the meter readings were recorded
at frequent intervals, and the experiments continued
until the evolution of gas had practically ceased.
The gas volumes were corrected for temperature,
pressure, and moisture content, being reduced to
moist gas at 6o° F. and 30 in. of mercury. All other
products were weighed, and all the products were
carefully analyzed. In a number of the experiments
the gas was collected in two separate holders, and the
two portions were analyzed separately. The gas
from the second half of the run is much richer than
that collected in the first holder.
In some tests slow heating was tried, and in others
the retort was evacuated, or was kept under pressure,
or a slow current of steam was passed through.
The results cannot be summarized. The following
are a few of the most important results obtained by
the rapid carbonization of Shand lignite at 555° C.
Weight Balance Sheet (Dry Coal Basis)
Per cent
Water of decomposition 11.7
Gas 17.0
Crude tar 4.1
Carbonized residue 66 . 7
Loss 0.5
Thermal Balance Sheet (Heat Content of
Products as Percentage of Heat in Original
Charge)
Gas 8.3
Tar 6.0
Carbonized residue 78.1
Loss 7.6
Commercial Products (Yields per 2000 Lbs.
of Moist Coal Charged)
Gas, cu. ft 3130
Ammonium sulfate, lbs 10.2
Tar. imp. gal 5.3
Carbonized residue, lbs 910
The coal charged contained 31.8 per cent moisture.
The gas had a gross calorific value of 385 B. t. u. per
cu. ft. and a density of 0.94. The crude tar had
a density of 1.00.
LOW-TEMPERATURE CARBONIZATION BY SHORT EX-
POSURE TO HIGH TEMPERATURES
Figs, i and 2 show that the maximum calorific value
of the residue is obtained by carbonization at a tem-
perature of about 600 ° C. It is clear from the shape
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
*o 2
30%
*s%
?ol
n
1
\v
o\/
4fjS
^alue__-G
V/J'S-
>
-0
if
,' <
uffleat aoO'C
-flayer 1' layer
7. 0 O
7. c A -
X ♦ «
*■ — m —
s of Coal as charged
/n
k"
'^7* x
\^z
AsiU^
""" ^
Ho.slure Z IO
/Isft % 13 5
le Matter % 35 5
Tie Value c/g 5 5 to
■"""*"=r=r7
/ /
/ /
J---/'
\*.
v'-C-t
"2
k
/ /
/ /
/
%■
""A
//
//
of these curves that if lignite is heated in a retort
under the conditions usually met in commercial opera-
tions, with the layers near the wall very distinctly
hotter than those in the center of the charge, no
regulation of the average temperature of the mass
will give a residue with the maximum obtainable
calorific value. The amount which the calorific value
of the residue falls below the optimum will increase
with the thickness of the charge and with the tempera-
ture gradient from the walls to the center.
method — Some preliminary experiments were car-
ried out to test the possibility of obtaining the equiva-
lent of carbonization at, say, 600° C, by short exposure
in a thin layer to a distinctly higher temperature.
Samples of dried Shand lignite, crushed to pass a 10-
mesh screen, were carbonized for a definite number of
minutes in a metal box in a muffle furnace electrically
heated to temperatures of 750° to 8oo° C. The boxes
were 6 in. X 3 in. X 1 in., inside dimensions, of No. 18
gage sheet iron, with loosely fitting lids of the same
metal. When making a test the muffle was brought
up to heat, and the lid of the box was also heated. A
charge either to half or quite fill the box was weighed
out and placed in the cold box. The heated cover
was put on, the box immediately placed on the floor
of the muffle, and the muffle door closed. At the ex-
piration of the desired time, the box with its contents
was removed from the muffle, cooled as rapidly as
possible, and the residue weighed and analyzed.
No great accuracy is claimed for the results, which
are shown graphically in Fig. 4. It is obvious that
the number of experiments should have been con-
siderably increased to render the curves reliable. They
do, however, show that the results of such rapid car-
bonization follow the lines which theory indicates,
and the advantage to be gained by further experiments
was not thought to be commensurate with the work
involved.
Comparison of the optimum results obtained with a
0.5-in. and i-in. layer with those obtained by com-
plete carbonization of the same sample at 5900 C.
and at 600° C, show, as might be expected, that the
yield and composition of the residue is approximately
the same in all cases, but that the calorific values
of 6760 and 6750 cal. per gram obtained with tempera-
ture control, fall to 6690 and 6590, respectively, with
the 0.5-in. and i-in. layers.
BEARING OF RESULTS ON DESIGN OF COMMERCIAL
CARBONIZER
The primary object of the Lignite Utilization Board
is to produce a domestic fuel from Souris lignite. It
is therefore desirable, unless other reasons are found
to outweigh this, to carbonize the lignite in such a
way as to give the residue with the maximum calorific
value. It has been shown that this is accomplished
by complete carbonization at a temperature of about
5750 C, and that the same result can be approxi-
mated by short exposure in a very thin layer to a dis-
tinctly higher temperature. As the object to be
attained is to bring all parts of the mass to the same
optimum temperature, a somewhat thicker layer
continually stirred should give the same result as a
thinner layer at rest. The economic advantage, in
the way of reduction of capital cost of equipment, to
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 1.3, No.'i
be gained by the acceleration of the process by the
use of high temperatures is too obvious to need ampli-
fication.
No increase in the yield of by-products can be at-
tained without a corresponding decrease in the yield
and calorific value of the residue. The gas obtained
at the above temperature is barely sufficient to provide
the heat necessary for the operations of drying and
carbonizing the lignite. The tar yield is also low.
The plant of the Board is situated in southern Saskatch-
ewan, remote from any large center of industry.
Under these conditions it does not appear probable
that, in the beginning of the industry, at least, the
possible profits to be made from the full recovery of
by-products will justify either the capital expenditure
necessary for a by-product recovery plant, or the
depreciation of the carbonized residue by any attempt
to increase the by-products. It is fully recognized,
however, that at a later date with a larger and well-
established industry this policy may require revision.
None of the results obtained give any indication that
the use of vacuum, pressure, steam, or other modified
method of carbonization would have any economic
advantage.
Finally, it has been found that Souris lignite does
not soften or become sticky at any stage of its car-
bonization. This is in marked distinction to the
behavior of bituminous coal, and permits a design of
carbonizer which is simpler and cheaper than can be
employed for the latter material.
DESIGN OF CARBONIZER
The design of carbonizer retort adapted to fulfil
the above conditions is briefly described below. The
actual details of construction are unimportant for the
purpose of this paper. It consists essentially of a
strongly heated surface, or retort floor, inclined at an
angle slightly steeper than the angle of repose of the
crushed lignite. The material to be treated flows
clown the heated surface from a hopper at the top,
passing under a succession of baffle plates, which con-
trol the thickness of the layer. The rate of flow of
the material is controlled entirely by the rate of with-
drawal from the bottom of the retort. This can be
accomplished by any suitable mechanism. The retort
is suitably enclosed at the sides and top, and gas
offtakes are provided in the cover. The thickness
of the layer is controlled by the difference between
the slope of the retort and the angle of repose of the
lignite, by the distance between successive baffles,
and by the clearance between the baffle and the retort
floor. The material is repeatedly stirred by its passage
under the baffles.
The heated surface may be heated from below with
gas. It should be hottest at the bottom of the retort
and progressively cooler towards the top. The
temperature of the lower part of the heated surface
may be as high as the materials of construction will
permit. The regulation of the degree of carboniza-
tion of the lignite is entirely controlled by the time
of its passage through the retort, that is, by the rate
of withdrawal from the bottom.
SEMICOMMERCIAL CARBONIZER
Some experiments have been carried out with a very
small model of the above design. In this model the
working surface varies from 2 in. to 4 in. in width,
is 4 ft. long, inclined at an angle of 45 °, and is electri-
cally heated. The bulk of the experiments, however,
were carried out in a retort approximately 10.5 in.
wide and 10 ft. long. The angle of inclination could
be varied at will, but 45° was found to be satisfactory.
Different materials were tried for the floor of the
retort, but ultimately carborundum slabs were adopted.
Twelve baffles were used in the final arrangement;
these were made of cast-iron and supported from the
floor by means of end plates. The clearance under
the baffles varied from 0.5 to 1 in. The lignite was
crushed to pass 0.25-in. mesh. It was found advisable
to dry it before treatment to a moisture content of
15 per cent or less.
The capacity of the retort varied widely with the
degree of carbonization produced, with the tempera-
ture attained in the gas flue below the retort floor,
and with the moisture in the lignite charge. It may
be rated roughly as equivalent to 200 lbs. of raw lignite
per hour.
The results obtained, with regard to output, ease of
control, and smoothness of operation, were regarded
as sufficient to warrant proceeding with the design
and construction of commercial carbonizers on the
same principle, for a plant capable of treating 200
tons of raw lignite per day.
DISCUSSION
Mr. R. De L. French: That I think is briefly what we have ac-
complished so far. While we do not believe that the work is
at an end, yet it was successful enough in our minds to warrant
us in going ahead with the construction of a plant on a commer-
cial scale. This plant is now under construction. We hope
to have it in operation sometime, and when we do, we hope to
be able to say just what this process will cost in dollars and
cents, and whether or not it is a commercially feasible thing
to carbonize Canadian lignite and to briquet the residue and
sell it as a passing fair substitute for anthracite coal, which a
week ago was selling for $22.60 a ton in the most easterly of the
western cities, and at a higher price further west; I think at about
$27 in Regina last week. Our raw coal will cost us about $1.80
at the mine. As we are in the middle of the field we should
have no difficulty in getting plenty of coal at a low price.
I might say that the lignite with which we are dealing is
probably about as low grade a lignite as we have on this conti-
nent. It has the following analysis:
Raw Lignite
Per cent
Moisture 31.8
Ash 5.2
Volatile matter 28 . 9
Fixed carbon 34. 1
Calories, per gram 4260
You can see it is a very wet lignite and hasn't a particularly
high calorific value. Practically all our work has been carried
out on this lignite because we started with it and because we
wished to compare our results we have endeavored to stick
to it all the way through.
Prof. E. P. Schoch (of the University of Texas, Austin,
Texas, who presented the following resume of "A Process for
the Economic Manufacture of Fuel from Texas Lignite") :
Lignites are characterized by a high water content, the prop-
erty of "slacking" on exposure to air, and a high content of
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
23
carbon dioxide (7 to 8 per cent in Texas lignites). It is this
32 to 40 per cent incombustible volatile matter which causes
briquets made from raw lignite to explode in the fire. Hence
lignite must be retorted to render it fit for briquetting. The
question arises: What is the most economic extent of retorting?
For our experimental study of this question, the lignite used was
obtained in the open market in Austin, but all of it was from the
same mine. The lignite thus obtained was of rather mediocre
quality. To our knowledge better lignite can be obtained even
at this mine and certainly in other localities, but what we used
is representative of much of the lignite now sold in Texas; hence,
the figures presented below may be considered to be safe for all
commercial lignites in Texas, but low for specially good lignites.
In our first set of experiments we retorted lots of 10 lbs. each
in powdered form with constant stirring and fractionated the
gas evolved as the temperature was raised. These experiments
revealed :
(1) The fact that the evolution of carbon dioxide ceases
abruptly at about 525 ° C.
(2) That the per cent by volume of carbon dioxide in the
gas collected up to this temperature is from 23 to 33 per cent.
(3) That the other constituents of the gas evolved up to 525 °
C. have high calorific powers, so that the mixture has a calorific
power of 410 B. t. u.
(4) That all the tar is evolved with this gas.
These results were obtained also with a different kind of a
lignite from a totally different field. The gas fractions obtained
at temperatures higher than 525 ° C. have heating powers of
410 B. t. u. per cu. ft. or less, and the total amount of gas ob-
tainable by retorting a ton of this lignite is not more than 6500
cu. ft. (the lignite from another region gave 6900 cu. ft.),
with an average heating power of the whole gas of 410 B. t. u.
This result is in marked contrast with the 10,000 cu. ft. of 400
B. t. u. reported heretofore.
The coke left after complete retorting has an ash content of
25 to 28 or even 30 per cent and a heating power of 10,000
B. t. u. or below. The relatively poor quality of this coke and
the fact that the gas obtained with it would have to be enriched
to make it fit for "city use" led us to consider the feasibility of
retorting the lignite with a maximum temperature of 525° C.
It was evident that by removing as much as possible of the
large per cent (about 30 per cent) of carbon dioxide from the
gas obtained up to 525° C, its heating power could be raised
substantially, and a simple trial showed that this could be done
readily to such an extent as to make the gas directly fit for
"city use."
To try out this whole procedure on a sufficiently large scale,
we constructed an apparatus which retorted 1100 lbs. of lignite
per 24 hrs. and purified all the gas. The retort was a 6-in. cast-
iron pipe placed vertically and surrounded by a brick furnace
7 ft. high, with gas burners at the bottom. The low temperature
required made it easy to operate in such a manner as not to injure
the iron retort; its life is likely to be great. The amount of
gas obtained was 2250 to 2500 cu. ft. per ton of raw lignite with
a heating power of 525 to 540 B. t. u.; the yield of coke was 900
lbs. of 11,000 B. t. u. (or more!), and the yield of dry tar was
2 per cent. The carbon dioxide was removed down to 2 per
cent by means of potassium and sodium carbonate solution.
Calculation shows that the amount of lignite needed as fuel
for retorting is about 7.5 per cent of the lignite retorted. The
coke comes out of the retort at a temperature just high enough
for briquetting, and not so high as to take fire on exposure to air.
The advantages of this procedure are :
(1) A coke of the highest heating power obtainable.
(2) A gas immediately usable in city mains.
(3) The maximum amount of tar obtainable.
(4) A cheap retort with large capacity, operating under mild
conditions, and yielding the coke at a temperature at which it
can be easily and immediately handled for briquetting.
Prof. Parr: I would like to ask Mr. French if he expects
sufficient binder for his briquet to come from the tars. One
of his numerical factors especially interests us. He says 7 per
cent of heat is lost in the final accounting for the heat. If he
finds it possible to locate, with sufficient accuracy, those per-
centages of heat in the various constituents, and then say pretty
accurately here is 7 per cent of heat unaccounted for, we would
like to know about it. It is one method of getting at the exo-
thermic quantity of heat. Seven per cent of 4000 cal. would
be somewhere within the range where we think the measurement
of quantity of exothermic heat resides. That factor, 7.6, is
exceedingly interesting to our work.
Mr. French : A remark of Prof. Schoch's reminds me I
should mention some things myself. We found exactly the same
things in the beginning of our work that he did. We never
got 10,000 cu. ft. of gas or anything like it. I suggest that some
of those high figures may be due to the method of carbonization,
because I know of one case where a man was actually operating
a carbonizer so designed that they fed moist coal to it. The
moisture that was driven off passed through the hot charge
and what you got was a gas producer on a small scale. This
person may have got 12,000 or 20,000 cu. ft. of gas, but he was
getting it at the expense of his residue. I judge from Prof.
Schoch's remarks that he was primarily after gas. We were
after residue, and it appears that with our own carbonizers we
had just about enough to operate the carbonizers, and not much
more.
Mr. Stansfield ran a series of experiments in the small retorts
under pressure, vacuum, and with a steam atmosphere, but
none of these seemed to show any advantage, and he went back
to practically atmospheric pressure.
In answer to Prof. Parr's question on tars, we took the tar and
distilled it at 325 ° C. On that basis, we got what we called
"available binder," a quantity of pitch representing 2.5 to 3
per cent of the carbonized residue, and that is not sufficient.
It is probably not a quarter of what is required. It takes a
large quantity of binder to make residue briquets, because physi-
cally the residue more nearly resembles charcoal than it does
coke. I imagine it will be similar to some coke which Prof.
Parr has here.
Answering Dr. Porter, the water is the water of constitution.
It is dry coal. It is dried at 105° C, and that is the water left
after drying.
Returning to Prof. Parr, so far as loss of heat is concerned,
I would prefer that Mr. Stansfield should answer that question
himself, because I do not know very much about his calculations,
except that I have a number of them, and I know the loss of
heat always runs around the figures given.
THE COMMERCIAL REALIZATION OF THE LOW-TEM-
PERATURE CARBONIZATION OF COAL
By Harry A. Curtis
International Coal Products Corporation, Irvington, New Jersey
The process herein described was developed for
converting bituminous coal into a uniform, smokeless
fuel resembling anthracite in properties. It was recog-
nized at the outset that the problem was one in which
small-scale tests alone would not yield the necessary
data for plant design, and while much valuable infor-
mation has been secured in small apparatus, the
development of the process has been very largely
through use of commercial-size units. For the past
four and a half years large-scale experimental work
has been carried on in parallel with laboratory tests.
The experimental plant, as finally developed, has a
capacity of about 100 tons of raw coal per day, but
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
a. View of Pla
since it was built only for experimental work, no
attempt has been made to operate all units at capacity.
In the course of experimental tests, the conversion of
coal has, however, frequently reached 40 tons per day,
and recently one of the commercial units was run
continuously for 5.5 mo. without a shutdown. The
experimental plant is fully equipped to handle all the
by-products, and includes a tar distilling unit of 100,000
gal. per month capacity to work up the tar into the
usual crude products.
During the World War construction of a com-
mercial plant was begun, as a government war project.
This plant was eventually completed and half of the
retorts put into operation in June 1920. The usual
minor difficulties of a new plant have been overcome
without trouble and the balance of the retorts are
now being put into operation.
DESCRIPTION OF PROCESS
The essential steps in the process are briefly as
follows:
The raw coal is crushed and subjected to low-tem-
perature distillation in horizontal retorts, the coal
being continually stirred and advanced through the
retort by paddles mounted on two heavy paddle-
shafts running lengthwise through the retort. The
retort is heated externally in a gas-fired furnace, and
the by-products are collected essentially as in coke-
oven practice.
During this low-temperature distillation. 8500 to
9500 F. in the gas phase, the volatile matter in the
coal is reduced from, say, 35 per cent to about 10 per
cent, the resulting semi-coke, being a soft, porous
material considerably different from ordinary coke
in structure. It can be used directly in a water-gas
producer or as a boiler fuel, either hand-fired or with
mechanical stokers. The material is not, however,
in good shape for transportation and marketing away
from the plant. The next step consists in grinding
the semi-coke, mixing it with hard pitch and briquet-
ting. The resulting briquets are somewhat like the
ordinary coal briquets on the market, except that they
burn with but little smoke. The final step consists
in charging these briquets into an inclined retort and
carbonizing them at about 18000 F. for 6 hrs. During
this carbonization the pitch is coked and the volatile
matter in the briquet reduced to about 3 per cent.
There is a shrinkage of approximately 30 per cent in
the size of the briquet and the final product is a hard,
uniform fuel, which burns with an entirely smokeless
flame. Its structure is still markedly different from
that of metallurgical coke, and the fuel burns more
freely than coke.
COALS SUITABLE FOR THE PROCESS
At the experimental plant more than a hundred
coals have been put through the process, and in no
case has it been found impossible to make a satisfac-
tory product. The procedure in briquetting has had
to be varied considerably with different coals, but the
hard, smokeless briquet has finally been produced in
every case.
Since the ash in the coal is accumulated in the prod-
uct, it is desirable, although not imperative, that the
ash in the coal be low. Also, if a high yield of by-
products is desired, a bituminous coal of high volatile
content should be used. The process, however, can
be applied to any coal.
It is, perhaps, of interest to mention that several
lignites have been successfully treated, including those
of Texas, Wyoming, Colorado, Saskatchewan, Japan,
and Brazil.
BY-PRODUCT YIELDS
The yield of by-products in any carbonizing process
will, of course, depend on the kind of coal used. In
Table I is given the average yield of various by-products
from twenty-nine different bituminous coals in which
the volatile matter ran from 32 to 41 percent, averaging
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
2$
37 per cent. These results are from small-scale
testing, charging about 33 lbs. of coal in the retort
and making three to six charges to each test.
In comparing these results with those obtained by
others working on the problem of low-temperature
carbonization, it must be remembered that in the
process under consideration both low- and high-
temperature carbonization are used, and the yields
obtained in the primary or low-temperature carboniza-
tion are augmented by those from the subsequent
high-temperature carbonization of the briquets. It
must also be borne in mind that the pitch, which is
one of the usual by-products, is returned to the process,
and yields, on carbonization, some by-products in
addition to the pitch coke which remains in the briquet.
Table T — Average Results from Twenty-nine
Coals Running over 32 Per cent Volatile
Matter
Average Analysis of Coal (Dry)
Per cent
Volatile 36.9
Fixed carbon 56.0
Ash 7.1
Total 100.0
Sulfur 1.1
B. t. u 13.783
Average Analysis of Finished Briquets
Per cent
Volatile 3.8
Fixed carbon 85.1
Ash 11.1
Total 100.0
Sulfur 0.68
B. t. u 12,874
Yield, per cent 66. 1
Yields of By-Products per Ton Dry Coal
Drv tar, gal 34
Gas, cu. ft 84S7
Ammonium sulfate, lbs 21
Light oil from gas. gal 1 .87
Other tar oils, gal 19.3
Pitch, per cent of tar 43
The by-product yields from the commercial retorts
are a little different from those obtained in the small
apparatus, due in part, at least, to the fact that the
primary distillation in the small apparatus is carried
out in an iron retort, whereas the commercial retort
is lined with carborundum, and in order to get capacity
it is necessary to carry a higher shell temperature in
the retort. This results in a little less primary tar
and a little more primary gas than found in the small-
scale tests.
COMPARISON WITH COKE-OVEN BY-PRODUCT YIELDS
Since coke-oven practice is established and well
known, it is of interest to compare the by-product
yields from this process with those from the ordinary
coke oven. If the two processes be compared for a
high volatile coal, say, 35 per cent, it must be assumed
that the coke oven could handle such a coal, and the
yields given in Table II will, therefore, appear a little
unusual for a coke oven.
A further point must be considered in that while
tar is a normal by-product of the coke oven, it is not,
strictly speaking, a by-product of the other process,
since the tar in the latter case is distilled and the
pitch returned to the process. In order to compare
the two processes, then, it must be assumed that
in each case the tar is distilled, and the pitch in the
Carbocoal process charged against the process. In
Table II this is done, the pitch being taken as 68 per
cent of the coke-oven tar and 50 per cent of the other
tar, these being representative figures in each case.
Table II — Products from One Ton of Dry Coal (35 per cent volatile,
7 per cent ash)
Coke Oven Carbocoal
Coke or Carbocoal 66% ( 1 % volatile) 68% (3% volatile)
Gas, cu. ft 10.000 9,000
Light oil from gas, gal 3
Ammonium sulfate, lbs 20 20
Tar oils, gal 3.8 15
Pitch, gal 8.2 None
While there are a few coals of 35 per cent volatile
which can be coked in an ordinary coke oven, such
as, for example, the Illinois coal recently used in a test
conducted by the Bureau of Standards at St. Paul,
coke-oven practice in general calls for a much lower
volatile coal. Instead of comparing the by-products
from a high volatile coal, as is done above, it is prob-
ably far more significant, economically speaking, to
compare the actual average by-product yields from
coke ovens the country over, with the yields which
the process secures, assuming logically that each pro-
cess will use coals to which it is particularly well
adapted. If we take the coke-oven data as the average
of 7800 by-product coke ovens operating in the United
States in 1917, the following figures obtain:
Coke Oven Carbocoal
Coke or Carbocoal, per cent .. . 71 68
Gas, cu. ft 11,000 (Estimated) 9.000
Light oil, gal 2.4 2
Ammonium sulfate, lbs 19 20
Tar oils, gal 2.3 15
Pitch, gal 4.8 None
In speaking of yields from the process, the particular
coal in question must always be considered. In coke-
Feed Mechak
Primary Retorts
oven practice, the range of coals is rather narrowly
limited and it is, therefore, permissible to refer to
average yields, but in the other process, where the
range of coals is not limited at all, no average or stand-
ard yields can be considered. It is, for example,
quite possible to use a coal yielding 20 gal. of tar oils
per ton, or one yielding 75 per cent of carbonized prod-
uct. In the tables above a coal of 35 per cent volatile
has been taken as one to which the process is particu-
larly well adapted.
INDUSTRIAL PLANT
The industrial plant was put into operation in June
1920. It has a capacity of 500 tons of raw coal per
26
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
day and, besides the main plant, includes equipment
for working up the by-products into the usual crude
products for the market. The coal is mined but a
few miles away, and is a good grade of high volatile
bituminous coal. As the coal comes from the cars
it is dumped into a track hopper and elevated to a
crusher, where it is crushed to pass a three-eighths-
inch screen. It is then delivered to six 80-ton bins
in the primary retort building. There are 24 primary
retorts, arranged in four batteries of six each. Each
retort is about 7 ft. in diameter and 20 ft. long, with
a capacity of a ton an hour. The crushed coal is fed
into the retorts by self-sealing screw conveyors and
is stirred and advanced slowly through the retorts by
a paddle mechanism. The by-products are led off
the discharge end of the retorts and handled as in
coke-oven practice.
.1 IKt
513 k
\J W.4t
ffi*3l
1 - VWTl 4'B-V ■
Top View of Secondary Retorts
The semi-coke which is discharged continuously
from the primary retorts is carried by covered con-
veyors to storage bins in the briquet building. Here
it is ground, fluxed with pitch, and briquetted. There
are two of these roll presses having a combined capacity
of about 24 tons of briquets per hour.
The raw briquets are carried slowly up a long cooling
conveyor to the storage bins at the secondary retorts.
From these bins they are drawn into larry cars and
charged into the secondary retorts. The secondary
retorts are built in two batteries of six and four, ten
retorts in all. Each retort consists of six rectangular
chambers, 21 ft. long and inclined at about 300. with
six charging and three discharging doors per retort,
the capacity of the retort being approximately 15 tons
of raw briquets.
The finished briquets are discharged into steel
quench cars and carried to a quenching and loading
station from which they are finally loaded into railroad
cars.
The by-products from the secondary carbonization
are combined with those from the primary, after a
preliminary cooling. The usual by-product equip-
ment is provided, including a light oil plant, and a
tar-distilling plant.
DISCUSSION
Prof. Parr: Mr. Chairman, I would like to ask Dr. On Us
how nearly the pitch residue from the oil or tar in the process
mi t the requirements of the binder for the briquets.
Dr. Curtis: It is about an even break on most high volatile
coals. The point is not one which bothers us at all. Having
a tar plant as a part of the equipment, we can if necessary bring
in outside tar and distil it at a profit, giving the required addi-
tional pitch. In the case of one plant there is a small shortage
and this is being done. The question of pitch yield depends,
of course, on the coal which is being used in the process.
Mr. Sperr: I should like to ask about the amount of gas
produced. As I understand it, the comparison of the yields
of this process with those obtained in by-product coke-oven
practice was made on the basis of the entire gas production.
That is evidently why the figure of 1 0,000 cu. ft. was given for
coke-oven production. Have you any figures that we could
use to compare the surplus gas produced by this process with
that obtained from the by-product coke oven?
Dr. Curtis: The plant at Clinchfield has not been running
long enough to give an accurate figure, but judging from results
obtained at the Irvington plant it takes about 7000 cu. ft. of
gas per ton of coal to run the process. At Clinchfield we do not
consider gas as one of the salable products of the plant, but in
case a plant were located near a city or industrial center, there
would be a few thousand cubic feet of gas which could be dis-
posed of. The gas yield depends, of course, on the coal used in
the process, and with most high volatile coals is somewhat more
than necessary for the retorts.
BY-PRODUCT COKING
By F. W. Sperr, Jr., and E. H. Bird
The Koppbrs Company Laboratory, Mellon Institl-te, Pittsburgh, Pa.
For nearly two years the production of by-product
coke in America has held the lead over that of bee-
hive coke. By-product coke manufacture is now
firmly established and continually growing, while
beehive coke is certain to decline to a position of minor
importance. Although the bulk of the coke and
gas manufactured in by-product ovens is now con-
sumed by iron and steel plants, there is an increasing
tendency for the by-product coke industry to assume
the position of an independent fuel industry, and its
relations are broadening to such an extent that they
must be considered in the study of almost every phase
of fuel economy.
INCREASING SHORTAGE OF NATURAL FUELS
Among the underlying causes of the many-sided
development of this comparatively new industry,
there is, first of all, the increasing shortage of the
important natural fuels — anthracite, natural gas, and
petroleum. The difficulty of obtaining adequate
supplies of anthracite and the inferior quality of the
material have combined to favor the substitution of
coke. Natural gas finds its most satisfactory supple-
ment in coke-oven gas and has a further accessory
in water gas made from by-product coke. Fuel oil
is being replaced to an increasing extent with tar and
tar oils, while benzene has been successfully intro-
duced as a motor fuel distinctly superior to gasoline,
although on account of the comparatively limited
amount of the former available, there is no question
of competition between the two. The high price and
poor quality of the gas oils now available are having
Jan., 19 2 1 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
27
the effect of discouraging the large-scale manufacture
of carbureted water gas, and, here again, coke-oven
gas appears as the most economical substitute. An im-
portant factor in this connection is the high cost of
labor, which has made the ordinary retort process of
manufacturing coal gas an expensive proposition,
and has forced the artificial gas industry to a recogni-
tion of the advantages of carbonizing coal in relatively
large charges, as is done in the by-product coke oven.
THE BY-PRODUCT OVEN AS A FUEL PRODUCER
With the exception of ammonia and its compounds,
each of the primary products of the modern coke
oven has a technically important fuel value. It is
with the primary products that we are the most con-
cerned. Popular fancy likes to speak of a by-product
coke plant as if it were a factory for dyes and drugs;
but this is, of course, a misconception. In America
it is very seldom that the organization of a by-product
coke plant proceeds farther than the production of
the primary products, and although some of these
products are indispensable to our rapidly growing
American chemical industries, it must be recognized
that, no matter how interesting and important this
sort of utilization may be, it is far outstripped, in
terms of dollars and cents, by the utilization of these
and the other products as fuel.
COMPARISON WITH THE BEEHIVE OVEN
It is of some interest from this standpoint to examine
these fuel values in detail. Such an examination will,
for instance, enable us to appreciate the great economy
of a by-product coke oven as compared with the bee-
hive oven which it is displacing. In coking one ton
of high-grade coal in a beehive oven, the following
fuel must be consumed:
Equivalent
B. t. u. Lbs. Coal
Gas, 11,000 cu. ft 6,160,000 440
Tar, 9 gal 1,401.000 100
Light oil, 4 gal 527.000 38
Coke, 100 lbs 1,300,000 93
Total 9,388,000 671
In coking one ton of the same coal in the by-product
oven, we consume simply: Gas 4300 cu. ft. = 2,408,000
B. t. u., equivalent to 172 lbs. coal. For every pound
of coal coked, the beehive oven consumes 9,388,000
B. t. u., or 33.5 per cent of the heating value of the
coal, while the by-product oven requires only 2,408,000
•B. t. u., or 8.6 per cent.
48,166,719 tons of coal were coked in beehive
ovens in 1918. If this had been coked in by-product
ovens there would have been saved the equivalent
of 11,993,513 tons of coal.
FUEL PROPERTIES OF COKE AND BY-PRODUCTS
Some data regarding the fuel properties of coke,
tar, pitch, and motor spirit (obtained by purifying the
benzenes recovered from coke-oven gas) are given
in Table I, while Table II gives information regarding
coke-oven gas obtained by different operating methods,
as compared with producer gas and water gas made
from by-product coke. The figures in these tables
are given as fairly typical, but there may naturally
be considerable variation, depending upon the kind of
coal used and upon operating conditions.
Table I — Fuel Properties of Coke, Tar, Pitch,
Motor Spirit
Air Flame
Require- *— Temp. ° C—
ment With With Air
Sp. Lbs. per -— B. t. u. per Lb.^ Cu. Ft. Cold Preheated
Gr. Cu. Ft. Gross Net per Lb. Air to 500° C.
Coke 12,900 12,860 132 1875 2085
Tar 1.165 72.7 16,120 15,575 162 1900 2115
Pitch 1.250 78.0 15,660 15,370 '155 1980 2230
Motor spirit. 0.877 54.7 18,060 17,360 176 1915 2165
BY-PRODUCT COKE IN THE IRON AND STEEL INDUSTRY
Although, as has been stated, the use of by-product
coke is rapidly being extended outside of the iron and
steel industry, the bulk of this fuel is still employed
in this industry, largely in the blast furnace and, to
a smaller extent, in the iron foundry. The achieve-
ments in the utilization of by-product coke in the
blast furnace are of the utmost importance from
the standpoint of fuel economy. With modern
methods of manufacture, and with a better under-
standing of the conditions affecting coke quality on
the part of the producer and of the conditions requisite
for efficient utilization on the part of the consumer,
the old prejudice in favor of beehive coke has been
almost entirely wiped out. It has been shown in
regular operation that the consumption of by-product,
coke per ton of pig iron is from ioo to 300 lbs. less
than the consumption of beehive coke, and blast-
furnace managers, as a rule, are now just as favorable
to the use of by-product coke as they were formerly
skeptical.
So remarkable a revolution in both opinion and prac-
tice would have been impossible without the develop-
ment of the modern by-product oven with its flexi-
bility of regulation and its means for exact heat con-
trol at every point. Having such an apparatus, a
proper study could be made of the various factors
affecting the quality of coke by-products, such as the
kind of coal and its preparation, oven dimensions,
and oven operating conditions. Simultaneously, the
effect of variation in coke quality upon blast-furnace
operation had to be determined. It was necessary
to go even farther than this — to break away from
old traditions of blast-furnace practice with beehive
coke and to determine what operating conditions of
the blast furnace would be necessary to give the best
results with by-product coke of a given quality.
It has not always been possible to make this sort of
investigation as a systematic procedure; but our
knowledge of the general subject has been gradually
built up to a point of considerable practical value.
There is still a wide field for further development of
this important subject.
DEVELOPMENT OF OTHER USES
A point which it is especially desired to emphasize
here is that the advances scored in the use of by-
product coke in the blast furnace may be repeated
in other lines of application if similar methods are
pursued. What is especially needed is cooperation
between the producer and consumer of coke, to arrive
at a correct understanding of the requirements for
each particular application. Since we have in the
by-product oven an apparatus of the utmost reliability,
capable of treating a very wide range of coals, the
possibilities of future development in the further
28
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Table 11 1
■ in, Producer and Water Gap,
Heating Value, Air Requirement,
Flame Temperature
Illumi-
CO3 nants O- CO
Straight coal gas before removing benzenes 2.2 3.5 0.3 6.8
Straight coal gas after removing Denzenes 2.2 2.6 0.3 6.9
Rich coal gas before removing benzenes 2.o 4.3 0.2 6.3
Rich coal gas after removing benzenes 2.6 3.2 0.2 6.4
Lean coal gas before removing benzenes 2.1 2.0 0.3 6.0
Lean coal gas after removing benzenes 2.1 1.0 0.3 6.1
Blue water gas 6.0 ... 1.0 39.0
Coke producer gas (cold) 5.0
Coke producer gas (preheated to 500° C.) 5.0 23 . 0
utilization of by-product coke are very great. One
of the most prominent phases of such development
is in relation to domestic fuel, and the systematic
investigations now being conducted by the U. S.
Bureau of Mines, proving the merit of coke for this
purpose, are typical of what ought to be done in con-
nection with other important applications. There
is no good reason for replacing a single pound of an-
thracite with any solid fuel other than by-product
coke, and there is every reason why the utilization
of by-product coke ought to go much further than the
replacement of anthracite.
Other leading uses of coke, outside of the manu-
facture of iron and steel, are in nonferrous metallurgy,
in the production of water gas, as railroad fuel, and as
fuel for general industrial heating, especially where
the avoidance of smoke is desirable. That quality,
physical or chemical, which is best suited for one
application is not necessarily the best for another.
The iron foundry needs coke of different characteristics
from that required by the blast furnace, and still other
characteristics become essential when we consider the
use of coke in a water-gas machine. These con-
siderations are important in making it possible for a
wide variety of coals, producing cokes of different
quality, to be economically and profitably treated
in the by-product oven.
UTILIZATION OF COKE BREEZE
One of the most interesting developments in fuel
economy resulting from by-product coke manufacture
has been in the utilization of coke breeze — a material
which, not more than a few years ago, was regarded
as nearly useless. This material, containing as much
as 85 per cent fixed carbon (dry basis) and having a
heating value of 11,500 to 12,500 B. t. u. per pound,
was formerly disposed of for filling purposes or else
completely wasted. Of late years, with the develop-
ment of improved stoking machinery, it has been
found possible to burn coke breeze for steam-raising
purposes with a high degree of efficiency, and it is
the general practice for by-product coke plants to
obtain their entire steam requirements from this
fuel. After satisfying plant requirements a surplus
of breeze may still be left for sale, and its utility as
fuel is becoming more and more recognized in the
general market.
TAR AS METALLURGICAL FUEL
The yield of tar obtained in by-product coking
varies with the kind of coal used. It may be as low
as 4, or as high as 12 gal. per ton of coal. With the
majority of coals now being coked in America, the
yield is from 9 to 10 gal. per ton. The use of tar for
fuel, especially in steel manufacture, has rapidly
i pure. Flame Temp. °C.
B t u ment Cu Ft. With With Air
per Cu Ft per Cu Ft. Cold Preheated
H: CHi Nl (Gross) Sp. Gr. I Air to 500° C.
47.3 33.9 6.0 591 0.44 5.08 1865 2095
47.8 34.2 6 0 562 0.42 4.99 1870 2100
46.3 35.0 5.3 630 0.45 S.25 1X70 210(1
46.8 35.4 5.4 605 0.42 5.15 1875 2105
57.0 27.0 5.6 528 (1.38 4.40 1875 2105
57.5 27.3 5.7 497 0.35 4.31 1880 2110
49.0 5.0 305 0.55 2.17 1920 2110
14.0 58.0 128 0.87 0.89 1495 1650
14.0 .... 58.0 128 0.87 0.89 1665 1815
increased during the past few years, and many of the
larger steel companies, operating their own by-product
coke plants, do not sell any of their tar for distillation
purposes, but use it exclusively for fuel. In open-
hearth practice, the consumption of tar per ton of
steel is io per cent less than the consumption of fuel
oil. It is advantageously employed in combination
with producer gas. The resulting flame has a much
better melting efficiency than that of straight producer
gas, and the increase in the capacity of the furnace
is much greater than would be accounted for on the
basis of the heating value of the fuel used. These
considerations are of great moment, in view of the
increasing price of fuel oil, and at a time when the
maximum output per unit of investment is essential.
TAR OILS AN'D PITCH
The various tar distillates have been extensively
used in Europe for fuel purposes; but the demands
for such products in American creosoting and chemical
industries will undoubtedly prevent this sort of utiliza-
tion here for some time to come. There has, however,
been a surplus production of one tar product, namely,
pitch, and its burning warrants some consideration.
It melts readily to a liquid similar to raw tar, and,
with a simple preheating arrangement, could probably
be used in the same way as tar. The employment of
pitch as fuel by direct combustion offers some present
promise, but, in view of the increased demand for it.
particularly in the electrochemical industries, it is a
question whether such application can be counted on
as permanent.
THE BENZENES AS MOTOR FUELS
Although the products from the crude light oils,
recoverable from coke-oven gas, are largely used in
chemical industries, the surplus production of these
materials since the close of the war has required their
sale as motor fuel, supplementing gasoline at an
opportune time. The lower boiling fractions of the
crude benzene (benzene, toluene, and xylene) are puri-
fied and used alone or in mixture with gasoline. This
sort of utilization is very important in Europe, where
there is much less petroleum available than in the
United Spates. Here, even if all our coke were manu-
factured in by-product ovens, the amount of benzene
recoverable would be only about io per cent of the
annual consumption of gasoline. However, the dem-
onstrated superiority of benzene motor fuels over
gasoline gives them considerable local importance in
districts where they are produced.1
1 In a certified dynamometer test by the Automobile Club of America,
90 per cent benzene showed 12.3 per cent less fuel consumption than gasoline.
At the same time the horse power was increased, depending on the speed.
At 2000 r. p. m. this was 19.4 per cent greater than that of gasoline. The
higher ignition point of benzene also eliminates knocking (pre-ignitionl.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
COKE-OVEN GAS
In recent years, an increasing number of by-product
coke plants have been built for the primary purpose
of supplying gas for industrial and domestic con-
sumption. The Koppers oven, using part of its gas
production for its own heating requirements, delivers
a surplus amounting to 60 per cent, or even more, of
the tot»l gas. This surplus is about 6600 cu. ft. per
net ton of coal charged, and, after the recovery of
benzenes, the gas has a heating value of 560 B. t. u.
per cu. ft. The heating value may be increased by
retention of the benzenes, by gas separation, or by
enrichment; but each of these courses of procedure
is, in the long run, uneconomical both to the consumer
and the producer of the gas, and is justifiable only where
arbitrary local standards of high heating values are
enforced. Straight coke-oven gas of 540 to 560 B. t. u.
per cu. ft. constitutes an ideal gaseous fuel for domestic
and industrial heating, and the demand for it is con-
tinually increasing. It is, when manufactured at the
rate of 1,000,000 cu. ft. or more per day, the cheapest
high-grade artificial gas. The carbonization of coal
in bulk, as in coke-oven practice, naturally effects
great economy in fixed charges, maintenance, and
operating labor as compared with the old retort process
for the manufacture of coal gas, while the quality of
the coke produced simultaneously with high-grade
gas is far superior.
Among the principal causes for the rising demand
for coke-oven gas are the increasing recognition of the
utility and convenience of gaseous fuel in general and
the growing shortage of natural gas. The relations
of the centers of production of by-product coke to
districts in which natural gas is largely used are
peculiarly fortunate. Coke-oven gas will be increas-
ingly employed to replenish the depleted supplies of
natural gas in these districts. For example, it has
been shown that the total amount of by-product
■coke-oven gas manufactured in the Cleveland-Pitts-
burgh district, which is the largest natural-gas con-
suming district in the United States, is considerably
more than the annual production of natural gas in the
state of Pennsylvania.
THE COMBINATION OVEN IN RELATION TO GAS SUPPLY
Considerations of this nature have given great
importance to the combination oven, which is the
only type of by-product coke oven that can be economi-
cally heated with either coke-oven gas or producer
gas. If producer gas is used, the entire output of
high-grade gas is rendered available for outside con-
sumption. The combination oven is being generally
adopted by those plants which are built primarily
for gas manufacture. Hitherto, the by-product coke
ovens installed in connection with iron and steel
plants have been designed to use their own gas exclu-
sively, and such ovens cannot be converted into the
combination type without rebuilding. In the future,
however, the price obtainable for coke-oven gas will
make it profitable for iron and steel companies to
build combination ovens whenever it becomes neces-
sary to replace or enlarge existing plants or to build
new plants. Combination ovens have been in con-
tinuous and successful operation in Europe for a
number of years, and one of the several installations
in America has been operating during the past 18
mo., partly on coke-oven gas and partly on pro-
ducer gas, in accordance with the demand for surplus
gas and coke. In considering the possible advantages
offered by the combination oven, it should be pointed
out that it can be heated with producer gas made
either from breeze and other small-sized coke, or from
low-grade coal containing either high ash, high sulfur,
or both. A high percentage of sulfur in the gas is not
detrimental to its use for oven heating. Furthermore,
the combination oven may be heated with blast-
furnace gas, which under certain conditions may be
a profitable procedure.
WATER GAS FROM BY-PRODUCT COKE
The growing importance of gaseous fuels for indus-
trial or domestic heating is such that we must look
beyond the direct production of coke-oven gas proper
and consider other gases that may be made in con-
nection with the operation of a by-product coke plant.
Carbureted water gas is being largely manufactured
from by-product coke to augment the supply of coke-
oven gas; but, as has been mentioned, the unsatis-
factory supply of gas oil has had a discouraging effect
upon the manufacture of this fuel. Blue water gas.
on the other hand, offers considerable promise. It
has a heating value of 300 B. t. u. per cu. ft. and thus
stands midway between coke-oven gas and the low-
grade gases, such as producer gas and blast-furnace
gas. It can be used for a wide variety of heating pur-
poses without the necessity of preheating gas or air,
which is not true of low-grade gases.
PRODUCER GAS AND COMPLETE GASIFICATION
Producer gas manufactured from coke also deserves
some consideration in this connection. Coke producer
gas may be manufactured in connection with the
operation of a by-product coke plant, not only for
heating the ovens, but also for furnishing an additional
supply of gas at relatively low cost to mix with and
augment the supply of coke-oven gas. This, together
with the possibilities offered in the manufacture of
blue water gas, brings up the question of complete
gasification of coal. With a process of complete
gasification which has been urged by many authorities
on fuel economy, the plant would ultimately produce
no solid fuel, but would convert all of the coke into
gas to be mixed with the regular coke-oven gas and
sold. Complete gasification offers more attraction
in rather densely populated industrial districts than
in localities where the gas would have to be distributed
over long distances. There can be no question but
that in the former case it will eventually be under-
taken on a large scale, and it is of interest to know the
amount and quality of the gas that would be produced.
Of course, in each case, allowance must be made for
the requirements of the by-product coke plant with
its necessary auxiliary equipment. If complete gasi-
fication were accomplished with the producer gas
system, the plant would produce 86,100 cu. ft. of mixed
gas per ton of coal having a heating value of 183
30
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
B. t. u. per cu. ft. With the blue water gas system,
there would be produced per ton of coal 33,100 cu. ft.
of mixed gas having a heating value of 380 to 385
B. t. u. per cu. ft. The latter gas would be satis-
factory for all domestic and industrial purposes, while
the former would be of more limited application.
TECHNICAL PROGRESS AND FUEL ECONOMY
It remains to mention very briefly the technical
developments in the by-product coke industry which
have contributed to fuel economy. There is, first
of all, the fundamental heating principle of the oven
with its provisions for economical heat regeneration,
accessibility, and convenient and exact temperature
regulation. This heating principle not only has
effected an improvement in coke quality and saving
of gas over any other oven system previously intro-
duced, but it has also made possible the combination
oven in which the regenerative system is adapted to
the necessary preheating of producer gas as well as air.
The same principle is retained in the new triangular-
flued oven system, and in a new type of gas oven that
is now being introduced.
The use of silica brick in the construction of by-
product coke ovens is now universal in American prac-
tice and has been an important factor in fuel economy.
By its superior heat conductivity, this material has
not only made possible a considerable saving in the
heat requirements of the oven, but has effected a re-
duction in the time required in coking a charge of coal,
and thus has increased the carbonizing capacity per
oven. Its highly refractory quality makes possible
the employment of higher flue temperatures, which
have also contributed to reduction of coking time.
From the standpoint of durability, it is superior to
any other available refractory material. Its use
has an important part in the acknowledged superiority
of American coking practice over European.
Of the number of new developments that are just
at their beginning, there should be especially men-
tioned those that are related to the by-product gas
producer, which is admirably adapted to economical
operation in combination with the by-product coke
plant. The by-product producer is used to a large
extent in Europe; but so far, conditions have not
been favorable to its introduction into America. The
future will, however, see much important progress in
this direction, and it is expected that the same degree
of superiority will be attained as has been achieved in
the introduction and development of the by-product
coke oven.
Work is actively in progress in connection with other
developments and improvements in by-product coking.
One general statement might be made in relation to
these. It has been our experience that improvements
made primarily for the betterment of coke quality
generally have a favorable effect upon the by-products.
In dealing with any given coal supply, it is not at all
necessary to sacrifice coke quality for good by-product
yields, as used to be supposed. This is important
because the profitable disposal of coke is an essential
factor in the success of any enterprise of by-product
coking.
DISCUSSION
Dr. E. W. Smith: Mr. Chairman, Mr. Sperr gave us a very-
low figure, a figure of 8 per cent for fuel oil by-product coking
plants. I should be very glad if he could tell us in connection
with that very low figure what percentage of by-product gas
he used for heating the ovens, and what was the temperature
of the combustion chambers, the volatile matter in his coke,
and the duration of charge. The figures that we are used to
on the other side are figures that are higher than those he has
been fortunate enough to get here. Mr. Sperr will probably
be well acquainted with the fact that the advance that he hopes
to make in this country in by-product producers was made in
Birmingham, England, in 1912, and has worked successfully
ever since. There they have a battery of 66 ovens heated
by means of by-product producer gas, and heated very success-
fully. Those ovens were put in as being the cheapest form of
gas making, because of low labor costs. Since that time, how-
ever, there have been other developments, and that particular
undertaking is installing on wholesale lines the vertical retort,
whtch with slight steaming yields up to about 6000 cu. ft. to the
ton of water gas; gas is made at a cost on a B. t. u. basis (and that is
about the only basis on which we can compare them) much
lower than those obtained from by-product coking, in spite
of the fact that in by-product coking there is a receipt of nearly
one pound per ton more for coke than is obtainable from the
coke from the vertical retorts, so that there are advances being
made in continuous working vertical retort practice of a very
large order, which I think the by-product retort people will
have to watch, if they are going to hold the position that they
have taken in this country.
Coke ovens are being installed here for the purpose of supply-
ing city gas, and the coke used for the production of water gas
and for domestic purposes. In so far as this is true, I am very
strongly of the opinion that gas engineers are not adopting either
the cheapest or the best means of producing city gas. It is an
accepted fact in England that hard coke such as is obtained from
coke ovens or from intermittent verticals does not give anything
like as good results as the special highly porous coke obtained
from continuous working vertical retorts, particularly in water-
gas manufacture.
Domestic coke here is usually hard coke, but when the con-
sumer has been educated into the use of more porous coke, I
am quite satisfied that here, as in England, a market can be
created where this is necessary. The other advantages of in-
stalling continuous working vertical retorts are too well known
to require elaboration and, of course, by-product recovery
is carried out in a similar way to methods employed in coke-
oven practice. I shall be glad if Mr. Sperr can give me those
figures.
Mr. George K. Brown: Mr. Chairman, I would like to ask
one other question: Is it possible to use a vertical continuous
retort similar to the Woodal type as installed by the Porter
Company on a by-product coke? Has it been used, or if it has
not, briefly, why not?
Mr. Sperr: Answering Dr. Smith's question I would say
that the figure for the amount of gas used in coking is based on
the actual operating records of several American plants, such as
the Minnesota By-Product Coke Company at St. Paul, the
Jones & Laughlin Steel Company at Pittsburgh, and the Raiuey-
Wood Coke Company near Philadelphia. I would say in a
well operated plant, not calling for perfection but what you
would reasonably expect in regular operation, you should use
from 38 to 42 per cent of the total gas for coking; the rest you
would recover as surplus. The kind of coal used is an important
factor in the amount of gas required.
The fact that much larger amounts of gas are used for coking
in English practice is due to differences in oven design, to smaller
oven capacities, and to the use of fire clay brick instead of silica
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
31
brick. As a rule, overcoking is somewhat prevalent in English
plants. Of course, in many cases allowance must be made
for the fact that most of the British plants have to use washed
coal, which is charged with a comparatively high percentage of
moisture; but those American plants which also use washed coal
show considerably less gas consumption than the British plants.
Answering the question as to the percentage of volatile matter
in the coal, I would state that this ranges from 31 to 33 per cent
at' the plants mentioned. With the ovens operating at 16 hrs.
coking time, the flue temperatures may be from 2500° to 26000 F.
Now as regards the use of gas producers in by-product coking
practice, we are very glad to give full credit and appreciation
to European technologists for the successful development and
application of the by-product producer. Conditions in Europe
have hitherto been more favorable to the application of by-prod-
uct producers than in this country, but it is certain that the next
few years will witness a great development in this direction here.
With reference to the installation of vertical retorts, adapted
to steaming, Dr. Smith will be interested to know that some of
our newest ovens are also adapted for steaming, and that this
method of increasing the gas production can be employed when
desired. Naturally this is of more interest where the by-product
coke oven is employed primarily as a source of gas than where
coke is the maiu product.
Answering the question of Mr. Brown, regarding the use of
vertical ovens, working on the principle of the continuous vertical
retort, I would say that I do not know of any such ovens that
have been in successful operation. The principle of the con-
tinuous vertical retort is such that it caimot be expected to
produce first-class coke. To attempt to explain the difference
l>etween the functioning of the vertical retort and the functioning
of the coke oven would be rather too long a story for this after-
noon.
Mr. Layng: Are there any ovens in the West using Illinois
coal entirely for coking purposes, and if not what percentage
of Illinois coal may be used in mixtures with Eastern class coals
in the West?
Mr. SpERR: That is a question that always arouses great
interest, particularly here in Chicago. The plant of the Indiana
Coke and Gas Company at Terre Haute, Ind., has used, for long
periods, straight Indiana coal, which is very similar to Illinois
coal. From time to time they have also used varying amounts
of Pocahontas coals in combination with the Indiana coal. These
amounts might range from 8 to 15 per cent. Illinois coal has
also been coked in other by-product plants, either straight or
mixed with different amounts of Eastern coals. I would say
that a large proportion of Illinois coals can be successfully coked
straight in the modern by-product coke oven. The coke has been
found by actual test to be suitable for blast-furnace purposes,
providing the percentage of sulfur is sufficiently low. It is
also adapted for domestic use, for the manufacture of water
gas, and for many other purposes. It is more difficult to make
good foundry coke from Illinois coals, and where the production
of foundry coke is important it is often advantageous to mix
some Eastern coal with the Illinois coal.
The statistics which Dr. Porter includes in his paper for the
year 1917 are, as he explains, not correct in respect to the
present relative proportions of by-product coking and beehive
coking. For nearly two years, beginning, I think, two years ago
this November, the production of by-product coke has been in
excess of the production of beehive coke.
BY-PRODUCT COKE, ANTHRACITE, AND PITTSBURGH
COAL AS FUEL FOR HEATING HOUSES
By Henry Kreisinger
Bureau of Mines, Pittsburgh, Pa.
This paper discusses the comparative value of by-
product coke, anthracite, and Pittsburgh coal, based
on tests made at the fuel laboratory of the Bureau of
Mines, Pittsburgh, Pa. The paper also describes the
methods of firing by-product coke and Pittsburgh coal
that were found to give the best results in actual heat-
ing service.
EXPERIMENTAL
description of fuels — In the tests made at
the Bureau's laboratory, the three fuels were of the
same size, passing over a 0.5-in. screen and through
a 2-in. screen. Their chemical composition is given
in Table I.
Table I — Analyses of Fuels Used in Tests
Proximate Analyses as Received
By-Product Pittsburgh
Constituent Anthracite Coke Coal
Moisture 4.11 0.79 2.23
Volatile matter 6.36 2.80 37.21
Fixed carbon 77.97 79.27 52.10
Ash 11.56 17.14 8.46
I "i\i 100.00 100.00 100.00
Ultimate Analyses of Dry Fuel
Hydrogen 2.58 0.60 5.00
Carbon 82.13 79.24 75.38
Nitrogen 0.87 1.27 1.36
Oxygen 1.32 0.72 7.66
Sulfur 1.04 0.89 1.95
Ash : 12.06 17.28 8.65
Total 100.00 100.00 100.00
Calorific value per lb., as received, B.
t. u 12636 11756 13239
Weights of fuels per cu. f t , lbs 52.5 34 . 5 47.0
The anthracite coal was taken from the Bureau's
stock purchased in 1916. It was a very clean, good-
looking coal, and in fact was considerably lower in
ash than the coal now obtainable on the market.
This fact must be kept in mind when comparing the
results of the tests.
The Pittsburgh coal was sized coal purchased from
a local dealer. It was of average quality as sold in
Pittsburgh.
The by-product coke was a mixture of 60 per cent
of 21-hr. and 40 per cent of 19-hr. by-product coke.
It was made from a mixture of coals coming from nine
different mines. The composition of a composite
sample of these coals is given in Table II.
Table II — Average Composition of Coals Used for By-Product Coke
Constituent Per cent
Moisture 2.77
Volatile matter 34. 17
Fixed carbon 56. 94
Ash 8.89
Sulfur 1.37
Total 100.00
description of tests — The tests were made in two
steam boilers of the size ordinarily used for heating
the average 7 -room house, and were conducted under
conditions conforming to those existing in actual
house heating practice. The tests were started Mon-
day morning and continued through the week until
Friday or Saturday morning. During each 24 hrs.
the fires were run at low rating for a period of 8 hrs.
in a manner similar to that existing over night under
actual heating conditions, and were run the other 16
hrs. to develop a determined percentage of the rating
of the boilers. Three tests were made with each fuel,
one at about 50 per cent, one at 80 to 100 per cent, and
one at 120 to 135 per cent of boiler rating.
On the low rating tests the firings were 8 hrs. apart,
on the medium rating tests about 6 hrs. apart, and on
the high rating tests about 4 hrs. apart. On the
32
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
tests at higher ratings the firings were made closer
together, because not enough fuel could be put in the
furnace to last over longer periods. Between firing
periods the fires were given no attention. Steam
was generated under a 3-lb. gage pressure and dis-
charged into the atmosphere. A large steam separator
was placed in the steam line to take the water out of
the steam. Water was weighed and fed into the
boiler every hour to keep the height of water in the
boiler nearly constant as it would be under actual
heating conditions.
economic results of tests — A summary of the
economic results of the tests is given in Table III.
The third column under each fuel gives the number
of B. t. u. absorbed by the boiler per pound of fuel.
The value per pound of anthracite is high because
the coal contained an unusually low percentage of
ash. Ordinarily the ash in the anthracite runs about
the same as the ash in by-product coke.
Table III — Economic Results of Tests (Averages of Dunning and
Arco Boilers)
, Coke > * Anthracite-
Effi- Ab-
Rating ciency sorbed
52.5 68.9 8105
99.6 70.6 8330
133.0 64.7 7490
Average Efficiency
All Ratings 68.1
Heat Value per Lb.
B. t. u. 11.75
B. t. u.
Effi- Ab-
Rating ciency sorbed
52.9 65.7 8300
89.6 68.40 8640
128.7 66.3 8380
66.8
. — Pittsburgh Coal — -
B. t. u.
Effi- Ab-
Rating ciency sorbed
48.0 55.8 7390
89.6 55.3 7350
108.5 54.4 7200
52.2
The table shows that the efficiency obtained with
the coke was a little better than that obtained with
anthracite coal, and io to 17 per cent better than
that obtained with Pittsburgh coal. The lower effi-
ciency with the anthracite coal is due to the fact
that the coal cracks in the fire and the small pieces of
coal that are cracked off fall through the grate and
increase the losses in the ashes. The low efficiency
obtained with the Pittsburgh coal is due to incomplete
combustion of coal gases and high-flue gas tempera-
tures for a period of i to 2 hrs. after each firing.
If the value of the three fuels is based on the amount
of heat actually absorbed by the boiler per pound
of fuel burned, then the coke is about 15 per cent
better than the Pittsburgh coal, and the anthracite
coal is about 9 per cent better than the coke. However,
as previously stated, the anthracite coal used on the
tests was cleaner than is the coal marketed at present.
With the present market qualities of the two fuels,
the results of the coke and the anthracite coal would
be closer together. Pittsburgh coal is usually low in
ash and high in heat value, so that the comparison
of the coke with the Pittsburgh coal, as shown in the
table, is about right.
No particular trouble was experienced with clinker
on any of the three fuels. Although the coke made
considerable more clinker than either of the coals,
it was light and porous. It formed a circular disk
covering the central part of the grate, and if the fire
was not too hot the whole disk was easily removed
in one piece through the firing door. With a hot
fire the clinker was soft and broke into small pieces
when attempt was made to remove it.
It should be borne in mind that the coke has some
advantages over Pittsburgh coal which cannot be
expressed in dollars and cents. Coke is a clean,
smokeless fuel, requires much less attention when
burned in an ordinary house heating apparatus, and
gives a uniform heat between long firing periods.
ACTUAL HOUSE HEATING TEST
In order to obtain data on the relative value of
coke and Pittsburgh coal under actual heating con-
ditions, the writer used coke at his house during the
months of November and December 191 9, and Pitts-
burgh coal during the months of January, February,
and March 1920. The heated part of the house con-
sisted of 8 large rooms and a bath room. The outside
walls of the house were built of solid concrete with
the wall paper pasted directly on the concrete walls.
On account of this construction the house was rather
difficult to keep warm. The heating plant consisted
of a hot-water boiler rated at 1100 sq. ft. of radiation
surface. The radiating surface of the radiators was
about 600 sq. ft. In two of the upstairs rooms the
heat was turned on about 8 p. m. and off about 7 a. m.
Heat in the other rooms was on all the time. A larger
boiler was installed in order to make it possible to run
the fire with two firings a day; one about 7 a. m. and
the other about 8 p. m. The most important data
for the period between November 1 and March 31 are
given in Table IV.
Table IV — Fuel Used and Weight of Refuse in Heating an 8-Room
House
Wt. of Fuel Wt. of Wt of
f — Burned Lbs. — - Ashes Clinker
Month Day Night Lbs. Lbs. Fuel Used
November 1200 1200 Coke
December 1940 2000 645 245 Coke
January 2890 2000 720 None Pittsburgh coat
February 1981 2162 413 None Pittsburgh coal
March 1570 1545 237 None Pittsburgh coal
During December, when coke was burned, the total
refuse was 890 lbs., of which 645 lbs. were ash pulled
out of the ash pit. The refuse was about 23 per cent
of the fuel fired, and 77 per cent of the refuse was ash.
In January the total refuse amounted to 720 lbs.,
all of which was ash from the ash pit. There was no
clinker. The refuse was 14.7 per cent of the coal fired.
These figures show that the coke had very high per-
centage of ash, which is the principal drawback from
the standpoint of the user. The clinker had to be
removed from the furnace every day or not less often
than every other day. The best time to remove the
clinker was in the morning or in the evening before
firing, and while the fire was not hot. The clinker
could then be removed in one piece, and the removal
was easy. After the clinker was removed the fire
was leveled, and a charge of 60 to 120 lbs. of coke
was put into the furnace. Owing to the greater bulk
of the coke the new charge covered the fire completely,
so that it took an hour or more before all of the new
charge was completely ignited. After the coke once
started to burn a very even rate of heating could be
maintained. The draft needed varied from 0.01 to
0.04 in. of water. The ability to maintain an even
rate of heating depends on the accuracy of draft
regulation. For this reason it is necessary to have
a sensitive draft gage which will easily measure
drafts of 0.01 in. of water. Regulation of draft by the
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
33
position of the damper is unreliable and very unsatis-
factory, and is probably responsible for the many
failures in burning coke. The coke is a clean fuel and
there is no soot deposit on the surfaces of the boiler.
After about 2 mo. of burning coke there was a thin
deposit of fine ash on the surfaces of the boiler varying
from one-thirty-second to one-eighth of an inch in
thickness.
. SECTION THROUGH AB
///J?////////////////////////////;/////////////
With the Pittsburgh coal there was no clinker.
However, to offset this, there was a heavy deposit of
soot on the surfaces of the boiler. If good results are
to be obtained the soot should be swept off of the
boiler surfaces every day or preferably before each
firing. With a proper design of the boiler, the soot
can be swept back into the fire pot, covered with fresh
coal, and burned. It was found that all the soot that
will stick to the surfaces of the boiler will accumulate
in one day. After one day further accumulation is
stopped by the soot burning off. The cubical volume
of one week's accumulation of soot is about the same
as one day's accumulation, but it is somewhat heavier
owing to the fact that a larger percentage of the soot
layer is ash.
The best method of firing Pittsburgh coal was found •
to be as follows: Immediately before firing, the hot
coals were pushed against the rear wall of the fire pot
and the space in the front part of the furnace was
completely filled with fresh coal. In cold weather the
fresh charge completely filled the front part of the
furnace up to the roof of the furnace, even blocking the
door with large lumps. Fig. 1 shows the furnace after
firing.
This method of firing virtually changes the furnace
into a coke oven. The coal in the front part of the
furnace is changed into coke, and the escaping coal
gases pass over the hot coke in the rear part of the
furnace and most of them burn. After 12 hrs., the
coal has been changed into coke; it is then moved
onto the rear part of the furnace and a fresh charge
of coal is put into the front part. The best tool for
moving the coke into the rear part of the furnace was
found to be a spading fork. The prongs of the fork
are inserted between the coke and the lower inside
edge of the firing door frame, and the coke is moved
by a prying motion.
Twelve-hour firing periods are made possible only
with a large furnace with sufficient capacity to hold
enough fuel for 12 hrs.
The writer is of the opinion that heating boilers-
should not be rated on the amount of heating surface
they contain, but on the capacity of the furnace to
hold large firings so that the furnace can be run long
periods without attention. The 12-hr. period is pref-
erable for most houses because the attention the
furnace needs can be supplied by the man, and the
housewife and other members of the family need not
disturb the fires at all.
SOME FACTORS AFFECTING THE SULFUR CONTENT OF
COKE AND GAS IN THE CARBONIZATION OF COAL1
By Alfred R. Powell
Pittsburgh Experiment Station, Bureau of Mines,
Pittsburgh, Pa.
SULFUR IN COAL
It is now known that sulfur exists in coal in three
general forms — pyrite or marcasite, organic sulfur
compounds, the exact nature of which has not yet
been determined, and small quantities of sulfates.
Methods of analysis have been devised for the deter-
mination of these different forms, which have furnished
the basis for investigations of a practical nature on
this most undesirable coal impurity.
Organic sulfur occurs in bituminous coal in quantities
ranging from 0.5 to 2.0 per cent. The quantity
present is very uniform for any given locality and
seam, and it is impossible to remove it from the coal
by any known method. Pyrite comprises practically
all the remainder of the coal sulfur, and the amount
of pyrite present is variable, even in the same mine.
Pyrite may be partially removed from the coal by
washing processes. Sulfates are almost absent in
freshly mined coal, but may increase as the coal stands
in storage.
PRIMARY REACTIONS OF COAL SULFUR DURING CAR-
BONIZATION
A rather detailed study has been made of the changes
these forms of sulfur undergo when subjected to the
coking process. This work has been done in the
laboratory on small quantities of coal in such a manner
that the temperatures could be closely controlled, and
• Published by permission of the Director, U. S. Bureau of Mines.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
quantitative study made of the sulfur compounds
in the resulting "products. This would give data on
the primary carbonization reactions, that is, the
reactions without the effects produced by the passage
through the coking mass of volatile matter from
another portion of the charge undergoing another
stage of carbonization.
'Pests on pure pyrite have shown that it is completely
.imposed at 1000° C. The resulting products
are ferrous sulfide and free sulfur, the latter being
I inverted into hydrogen sulfide if hydrogen is present.
A trace of the sulfur remains in the ferrous sulfide
in the form of a solid solution known as pyrrhotite
■ >r magnetic sulfide of iron. The quantity of sulfur
50 remaining, however, is so small that it may be
ed, and the pyritic sulfur may be regarded as
dividing equally between the residue and the volatile
1 1 er of the heated pyrite.
Carbonization tests on a variety of coals have
indicated the five following sulfur reactions:
1 — Complete decomposition of the pyrite to form pyrrhotite
II id hydrogen sulfide. This reaction begins at 300 ° C. is com-
plete at 600° C and reaches its maximum between 400 ° and 500 °
C.
j — -Reduction of sulfates to sulfides. This reaction is complete
» ■ : C.
3 — -Decomposition of one-quarter to one-third of the organic
Milfur to form hydrogen sulfide. This occurs for the most
part below 5000 C.
4 — -Decomposition of a small part of the organic sulfur to
form volatile organic sulfur compounds, most of which find
their way into the tar. - This decomposition occurs at the
lowei temperature of the coking process.
.s — Disappearance of a portion of the pyrrhotite, the- sulfur
apparently entering into combination with the carbon This
reaction seems to be most active at 5000 C. or higher.
The organic sulfur not accounted for by the above
reactions undergoes a decided change in character
between 4000 and 5000, and shows none of the proper-
ties of the original coal sulfur.
These investigations indicate that the total sulfur
of the coal is the most important factor affecting the
sulfur content of the coke, that the relative amounts
of sulfur forms present do not affect it materially, and
that certain other factors, particularly the nature of
the coal, will vary the amount of sulfur in the coke
to a limited extent.
SECONDARY REACTIONS OF SULFUR DURING CARBONI-
ZATION OF CO \I
As hydrogen sulfide travels through the red-hot
coking mass, it is partially converted into carbon
bisulfide. No carbon bisulfide has ever been detected
during the study of the primary reaction.
One of the most important secondary reactions is
that caused by the hydrogen of the gas as it travels
through the red-hot coke. Experiments have shown
that coke practically ceases giving off hydrogen sulfide
after the temperature has passed 600 ° C. However,
if hydrogen or gas containing hydrogen is passed
through coke above 6oo° C, a further and very de-
cided evolution of hydrogen sulfide is obtained.
Two important changes are caused by the passage
of hydrogen through the coking mass:
(1) FeS2 is caused to decompose at a lower tempera-
ture, the decomposition being practically complete
at 500°, whereas in the primary reactions it is only
partially decomposed at this temperature. The
net result of this is the speeding up of a reaction which
would be complete at the end of the coking process
without the hydrogen effect.
(2) The decomposition of the organic sulfur or
"carbon-sulfur" combination of the coke to form
hydrogen sulfide is enormously increased at tempera-
tures above 5000. This means that where the hydro-
gen from the distillation comes in contact with the
red-hot coke, this coke will contain less sulfur than
the primary reactions alone would indicate.
Experiments have been performed to determine
the equilibrium between the sulfur in the gas and the
sulfur in the coke. Hydrogen over a coke containing
r.2 per cent sulfur was found to reach saturation when
it contained about 0.25 lb. of sulfur per M. cu. ft.,
when the coke was at a temperature of 900° C. This
indicates that large quantities of hydrogen would be
required to remove an appreciable amount of sulfur
from coke. The reaction appears to go to equilibrium
very quickly, however. The essential conditions for
the transfer of the coke sulfur and the gas, therefore,
would consist in the passage of hydrogen through the
coke mass at a rapid rate.
These laboratory data on the effect of hydrogen on
the sulfur of the coke were well confirmed by large-
scale practice. Coke obtained in the laboratory, where
the by-products were swept away as fast as formed,
contained a larger percentage of sulfur than coke
made from the same coal at the same temperature
in by-product ovens, where the hydrogen-containing
gases had relatively long contact with the hot coke.
Experiments have shown that by-product coke-
oven gas. purified from sulfur, when passed back
through the oven, causes quite a marked decrease
in the sulfur content of the coke. The unpurified
gas, however, contained sulfur in excess of the satura-
tion point, and actually increased the sulfur in the
coke to some extent. This shows that the passage
of sulfur from coke into the gas may be reversible
under these conditions. These facts bear out the
laboratory data on the effect of hydrogen on the coke,
as well as confirming the fact that an equilibrium
point exists beyond which no sulfur is transferred
from the coke into the gas.
DESULFURIZATION OF COKE
The very interesting fact that hydrogen has such
a desulfurizing effect on coke brings up the question
as to a possible practical application. With this idea
in mind, work is being continued on a study of the
equilibrium relations between the sulfur in the coke
and the sulfur in the gas at different temperatures
and with different percentages of hydrogen. Large-
scale tests are also being conducted to determine how
much desulfurization is possible, as well as to get cost
data on any possible process.
With the supply of low-sulfur coals getting lower,
it has been stated that a reduction of the sulfur
Jan., 1021
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
35
content of the coke to the extent of 25 per cent will
increase the value of the coke $1.00 per ton. In the
laboratory, this figure has been greatly exceeded,
while in actual practice it has been approached. The
value of such a process, if developed to a commercial
scale, would be worth millions of dollars to the metal-
lurgical industries of the country.
DISCUSSION
Dr. Smith: It occurs to me that the Fourth Report of the
Gas Investigation of the Institution of Gas Engineers and the
Leeds University might prove of great interest to Dr. Powell.
They have carried out near Glasgow a long series of tests on
Scotch coals on the vertical retorts, both with steam and without,
and they have obtained figures of a complete balance sheet for
sulfur in all by-products of the coal, for nitrogen, carbon, and
heating value, and I think it will be of interest to Prof. Parr
to know that through all of the figures they have found that
there is an unaccounted-for heat loss of between 3 and 4 per cent,
practically constant, which may be accounted for, as suggested
by Prof. Parr, as having something to do with the exothermic
reaction of coal; but if Prof. Parr cares to see a copy of this report
I shall be very pleased to let him have it. I am sure the figures
there are, from an English point of view, classical.
Prof. Parr: Mr. Chairman, these figures are exceedingly
interesting. Now that I see them, it seems to me this work
is much more in accord with our conclusions than I had thought.
I would suggest as an explanation where there seems to be a
difference, that in Mr. Powell's apparatus there is almost lacking
that condition of purification in the delivered sulfur, for instance,
that we have in the coking chamber with a lot of coal. For
instance, as an illustration, if we take a coke in which there
is an absence of sulfur and pass hydrogen sulfide over it, it
purifies the gas and contaminates the coke; but in an apparatus
of this sort, if you get your products out of the way without
any of that reaction, you will get results which seem to be a
little different from ours. As a matter of fact, they are very
concordant, because, although you notice the decomposition
of the pyrite at a point where we say our gas is pretty nearly
free from sulfur, that is simply because of the powerful action of
that temperature, most active at about 500°, which contami-
nates the coke and purifies the gas, and it is quite in accord with
this chart.
The interesting thing in Mr. Powell's experience, and ours
too, is that this adsorption (for want of a better term) in the
coke reverses at higher temperatures so that its vapor pressure
is such that it can be given off slowly. Assuming that hydrogen
would do the same thing, it would take the place of sulfur, and
we can remove practically all the sulfur content in these arti-
ficially made sulfides of carbon, if that is a good name for them;
also your vapor will do the same thing, and I think that is an
exceedingly interesting phase of the work. I hope Mr. Powell
will follow it up, because I do believe that there is a possibility
of doing these things successively, first purifying the gas and
then purifying the coal. Now go on and collect the sulfur and
we shall have the circuit complete.
THE DISTRIBUTION OF THE FORMS OF SULFUR IN
THE COAL BED1
By H. F. Yancey and Thomas Fraser
Mining Experiment Station, U. S. Bureau ok Mines, Urbana, Illinois
The purpose of the work described in this paper was
to study the distribution of pyritic and organic sulfur
'in coal as it occurs in various sections, layers, or benches
1 Published with the permission of the Director, U. S. Bureau of Mines.
Abstract of a bulletin to be published by the University of Illinois, Engi-
neering Experiment Station; by permission of the Director.
of the coal seam. Sulfate sulfur was entirely disre-
garded because it was found to be very low in freshly
mined coal. It is well known that the variation of
total sulfur between sections or benches of the same
bed at a given place, in any except low sulfur coals, may
be quite marked. This is due principally to the heteroge-
neous or "spotted" distribution of iron pyrite. More
or less of the pyrite, depending on its physical form,
can be removed by coal-washing methods. This
brings up the question of the variations of organic
sulfur content.
Until recently no very satisfactory methods for
the determination of pyritic and organic sulfur in coal
have been available. Parr and Powell1 have given
very satisfactory methods for these determinations.
Wibaut and Stoffel,2 working in the Municipal Gas
Laboratory at Amsterdam, have also developed
methods recently, but those of Parr and Powell have
been used for this study.
While little or no information on this subject is
available in the literature, some previous work3 led
to the tentative conclusion that the organic sulfur
content of a given coal varies but little, and that at
least it is much more uniform than the pyritic and
total sulfur values. One of the objects of the present
work was to determine whether this is the actual
condition, or whether organic sulfur is segregated as
is pyritic sulfur. In case segregations or concentra-
tions of organic sulfur were found to exist, it would
be desirable to associate such occurrences with other
impurities or specifically recognizable conditions. If
organic sulfur segregated, it might then be possible
to remove some of it in the way that pyrite is removed.
METHOD OF SAMPLING AND ANALYSIS
It seemed that the only way to study the subject
was to take channel samples in the mine at the working
faces. Samples have been taken in three mines.
Seventy sectional bench samples were taken at twelve
working faces in the Middlefork mine of the U. S.
Fuel Co., near Benton, Illinois (No. 6 seam). Forty-
eight samples were taken in two mines in western
Kentucky operating in the Kentucky No. 9 and No. 12
seams.
At each place in the mine selected for sampling, the
coal face was marked off before cutting the samples
into from four to eight horizontal benches, and each
bench was sampled separately, according to the
Bureau of Mines method for sampling coal in the
mine.4
Total sulfur was determined by the method of
Eschka. Pyritic sulfur determinations were made
according to the method of Powell with Parr.6 The
values given for organic sulfur represent the difference
between total and pyritic sulfur. Only a few samples
were examined for sulfate sulfur. The highest value
obtained was 0.04 per cent, and this was on a sample
1 University of Illinois, Engineering Experiment Station, Bulletin 111
(1919), 44.
2 Rec. trav. chim., 38 (1919), 132.
8 Thomas Fraser and H. F. Yancey, Am. Inst. Mining Eng., Bulletin
153 (1919), 1817.
« J. A. Holmes, Bureau of Mines, Technical Paper 1.
* J.oc. cit.
36
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 1.3, No. 1
containing 6 per cent total sulfur which had been
mined 3 mo.
DISTRIBUTION OF FORMS OF SULFUR
The distribution of the forms of sulfur at a few
locations in one of the beds examined is shown graphi-
cally in Figs. 1 to 6. Distance from the top or roof
of the bed is represented on the ordinate axis and
the per cent of total, pyritic, and organic sulfur as
abscissas. The vertical lines showing per cent of
sulfur represent the average values for the forms of
sulfur occurring in a section of the length of the line.
The breaks are due to variations in the averages for
adjacent sections, and do not indicate that the sulfur
content changes abruptly at the point of the break.
The sulfur percentages plotted in the graphs represent
values for moisture-free coal.
per ctMT sulpur eta CENT SULFUR
II
1
TOP
!
]
S r
1
i-n
■;
—,
Bottom
Fi&l. I0°N.|SWN
PER CENT SULFUR
2 3-
I
1
TOP
-
1
i
:
SOTTOH ]
Fig. 2. 7HN,ICWN
PER CENT SULFUR
2
3 A
T
!
rw
i
1
hi
DM
Bor
nop
—
1
1
. 1
- -
~|
"i
- I
1
I -
1
"-
1
FlG.3. 4^N, Ist WN
PER C6NT SULFUR
j
1, r
J
j
1
tH l
! 1
-.,
t-f
I-
-'
BO
Fig. 4. /'Iain /North
Distribution 6f
Forms of Sulfur
in the Coal Bed'
Legend ,_'
I Pyritic Sulfur S
i Organic Sulfur
'; Total Sulfur
Fig. 5. 3"-»N, l5-TEN
p
a c
SULFUR
3
TOP
.
J/.
-;
;
i-1
1 1
BOTTOM
Fig. 6. I0T-=N, I'-'ES
In the Middlefork mine, No. 6 bed, represented by
these graphs, the total and pyritic sulfur at most of
the places sampled was higher in the top coal and
bottom coal than in the intervening part of the seam.
This was also true of the No. 12 seam examined in
Kentucky. In the No. 9 seam in Kentucky the bottom
coal was highest in total and pyritic sulfur, and the
top coal was lowest. The organic sulfur content,
on the other hand, shows no large variation between
different benches of the bed at any place sampled,
although, as shown in the graphs, it does not run
absolutely uniform. A closer approach to uniformity
for the values for organic sulfur, between the benches
at a given location, is not obtained by calculating
organic sulfur content on a moisture-, ash-, and pyritic-
sulfur-free basis. The general tendency at the places
shown in the figures which represent the north side
of the mine at Benton, Illinois, is for the organic sulfur
to decrease with increasing pyritic sulfur content. It will
be observed that on the individual graphs, where the
pyritic sulfur in any particular bench is higher than
in the bench adjacent above or below, the organic
sulfur is in most cases lower* This can hardly be
interpreted as supporting the idea that organic sulfur
contributes to the formation of pyritic sulfur, however,
for this tendency is not nearly so evident in the other
half of this mine or in the other two beds examined.
In order to secure additional data on the possible
relation of organic sulfur to pyritic sulfur, a number
of special samples were taken of coal immediately
surrounding or interbedded with bands or cat faces
of pyrite. These samples were found to be about
average or below the average in organic sulfur content.
There is no evidence of a concentration of organic
sulfur in the coal immediately adjacent to pyrite
deposits.
ORGANIC SULFUR IN VARIOUS COALS
The relatively high proportion of sulfur in the
organic form occurring in many coals has not been
generally recognized. It has often been considered
as constituting a negligible percentage of the total
amount of sulfur present. In estimating the wash-
ability of a coal the organic sulfur content is an im-
portant consideration. In thirteen out of the thirty-
four bench samples represented in the figures, the
organic sulfur exceeds the pyritic sulfur content.
This was true of twenty-three out of thirty samples
taken in the No. 12 bed of western Kentucky. Table I
shows the proportion of organic sulfur in samples of
a number of well-known coals.
Table I — Pyritic and Organic Sulfur in Various Coals
(Values in per cent on moisture-free basis)
Organic Sul-
fur as Per
cent of
Total Pyritic Organic Total
Location of Mine Coal Bed Sulfur Sulfur Sulfur Sulfur
Mahaffey. Pa.' C&D .148 .'.77 0.71 20.4
White Co.. Tenn... . Sewanee 4.87 3.59 1.17 24.0
Pike Co., Ky Freeburn 0.46 0.13 0.33 72.0
Herrin, 111..' No. 6 1.83 1.04 0.79 43.2
Greene Co., Ind No. 4 1.66 0.89 0.77 46.4
Benton. Ill No. 6 3.29 1.99 1.30 39.5
Western Kentucky . . No. 12 1.48 0.70 0.78 52.6
Western Kentucky. . No. 9 3.46 1.65 1.81 52.5
McDowel Co., W.Va« Pocahontas 0.55 0.08 0.46 83.7
No. 3
Letcher Co . Ky.'... Elkhorn 0.68 0.13 0.51 75.0
I H F. Yancey and Thomas Fraser, Coal Industry, 3 (1919), 36.
' A. R. Powell, This Journal, 12 (1920), 889.
FORMS OF SULFUR IN RAW AND WASHED COAL
It is evident that if organic sulfur segregated with
or was concentrated around pieces of pyrite, bone
coal, or shale of higher specific gravity, it would be
removed with these impurities as refuse in the washing
operation. On the contrary, removal of the non-coal
impurities, inorganic in nature, should result in a
slight increase in the organic sulfur content of the.
washed coal, depending upon the amount of inorganic
impurities removed. In order to obtain data on this
question, seven samples of run-of-mine coal were
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
obtained at the Middlefork mine, in addition to the
face samples collected in the mine. A large coal-
washing plant is maintained at the mine for washing
the entire tonnage. Each sample represents a day's
production for the mine, which varies between 2400
and 2800 tons. A sample of washed coal representing
one day's operation of the washery, on an average
day, was also obtained. The sulfur forms in these
samples are shown in Table II.
Table II — Forms of Sulfur in Raw and Washed Coals
(Values in per cent on moisture-free basis)
Total Pyritic Organic
Sample No. Sulfur Sulfur Sulfur
72 Raw coal 3.68 2.42 1.26
73 Raw coal 3.20 1.90 1.30
74 Raw coal 3.22 1.99 1.23
75 Raw coal 3.59 2.07 1.52
76 Raw coal 3.33 1.93 1.40
77 Raw coal 3.27 2.08 1.19
78 Raw coal 2.77 1.55 1.22
Average of raw coal 3.29 1.99 1.30
Average of face samples for
mine 3.30 1.92 1.38
Washed coal 2.25 0.92 1.33
Refuse 13.45
The values for organic sulfur in the average for the
run-of-mine raw coal, and in the washed coal are nearly
identical, namely, 1.30 per cent for the raw coal, and
1.33 per cent for the washed coal. Though the washed
coal sample does not necessarily represent the product
obtained by washing the identical coal of the run-of-
mine samples, it must be taken as further evidence
to show that organic sulfur is not segregated with or
concentrated around the high specific gravity pieces
of pyrite, nor is organic sulfur removable by gravita-
tional methods. The average values for the sulfur
forms in the run-of-mine raw coal are in close agreement
with the average for the sectional face samples col-
lected in the mine.
CONCLUSIONS
1 — Extreme irregularity of distribution is charac-
teristic of the pyritic sulfur of coal. This offers a
possibility of securing a low sulfur product by separate
mining of parts of the seam.
2 — In comparison with the large variations of pyritic
sulfur in the vertical span of the bed, the organic
sulfur is quite uniform.
3 — There is little evidence of a definite relationship
in the occurrence of organic and of pyritic sulfur.
High pyritic sulfur in a bench or section of the bed is
not indicative of high organic sulfur content.
4 — The proportion of the sulfur that is in organic
combination in various raw coals varies within wide
limits. High sulfur coals are ordinarily higher both
in organic and pyritic sulfur than low sulfur coals,
though organic sulfur makes up a greater percentage
of the total sulfur in the case of low sulfur coals
(Table I).
5 — The organic sulfur content of some coals is
sufficiently high to limit seriously the extent to which
these coals can be cleaned of sulfur by washing.
ACKNOWLEDGMENT
This investigation was carried out under the general
direction of Mr. E. A. Holbrook, Assistant Director,
and Mr. Geo. S. Rice, Chief Mining Engineer, U. S.
Bureau of Mines. To them and to Professors S. W.
Parr and H. H. Stoek, of the University of Illinois,
grateful acknowledgment is made. Mr. C. A. Meissner,
Chairman of the Coke Committee, U. S. Steel Corpo-
ration, and Mr. Thomas Moses, General Superin-
tendent, U. S. Fuel Co., have followed the progress of
the work with cordial cooperation.
COLLOIDAL FUELS, THEIR PREPARATION AND
PROPERTIES
By S. E. Sheppard
Research Laboratory, Eastman Kodak Co., Rochester, N. Y.
"Colloidal fuels" is the name given to a distinct
class of liquid to semiliquid blended fuels. They
were developed in this country during and subsequent
to the last two years of the Great War. In physical
consistency they range from liquids with a viscosity
at normal temperatures of some 30° Engler to very
plastic pastes, and weak jellies, these latter becoming,
however, relatively mobile and fluid when heated.
They are composites, in which either finely divided
carbonaceous solids or semisolids, or both, are so
suspended in and blended with liquid hydrocarbons
as to form relatively stable and atomizable fuels. They
have been developed primarily for burning with the
regular types of atomizing burners using ordinary
fuel oils, but have also possibilities for use in internal
combustion engines of the Diesel and semi-Diesel type.
WHY COLLOIDAL?
It may be said that there is nothing in this outline,
description to warrant the term "colloid." The term,
however, has a considerable elasticity. I do not
propose to add to the excess of definitions of colloids;
but will note two recent ones. According to Dr.
Wiley, colloid chemistry is the chemistry of "matter
without form and void," and is mentioned in the
first chapter of Genesis. This gives it a respectable
antiquity, and a latitude sufficient to embrace anything.
As against this universal scope, Professor Bancroft
tells us "it is the chemistry of finely divided masses,
in other words, of bubbles, drops, grains, filaments,
and films," and this more specific dictum is certainly
applicable to the systems under discussion. However,
without striving for a dictionary precision, it may be
said that the term is conveniently employed to describe
the product, both owing to certain of the fuels' impor-
tant colloidal characteristics, and because the process
of preparation may be justly termed "colloidalizing,"
in view of its essential dependence upon colloid chemical
processes and conceptions.
HISTORICAL
Before entering into details of the application of
colloid chemistry to the fuel problem, let me say a
few words on the history of the present class of ma-
terials. Theidea of burning a suspension of carbona-
ceous matter in mineral oils appears to be nearly
as old as the use of fuel oil, but no attempt appears
to have been made to investigate systematically its
possibilities.
The developments now described date from the
summer of 191 7. At that time a fellow-worker in
this laboratory, Mr. J. G. Capstaff, asked the author
38
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
as to the possibility of the use of powdered coal in
conjunction with oil to supplement the latter for oil-
burning ships. Actually, an adequate supply of fuel
oil was no less vital to the Allies than gasoline and
lubricants. The German submarine campaign was
threatening all of these. Having much faith in the
possibilities of colloid chemistry, the author prepared
some composites. They contained up to 30 per cent
of pulverized coal incorporated by a paint mill with
an ancient specimen of oil from a laboratory oil bath —
plus one or two things thrown in for luck. These
composites appeared promising as regards stability,
and we succeeded in burning them satisfactorily in an
air-pressure oil-fired furnace. Through Dr. Mees
these results were referred to Mr. Lindon W. Bates,
Engineering Chairman of the Submarine Defense
Association, who was already devoting his attention
to this very problem. At his instance and with
Mr. Eastman's sanction, the possibility of colloidally
combining pulverized coal and fuel oil was taken up
by the research laboratory, in close and constant
cooperation with the Submarine Defense Association,
under Mr. Bates' coordinating leadership; but for this,
and without his catholic knowledge and experience
of fuels and fuel problems, our initial experiment
would probably have remained a laboratory incident.
By "colloidally combining" is to be understood "stably
dispersing pulverized coal in fuel oil," that is, forming
a uniform composite,-the stability of which at ordinary
temperatures should be reckoned in months, while
amply sufficient at higher temperatures to permit
atomization by fuel oil burners. As stated, Mr. Bates
had already been actively considering the possibility
of supplementing oil for marine purposes by pulverized
coal, or oil and coal combined. The Association had
had assigned by Admiral Benson, Chief of Naval
Operation, the U. S. S. Gem, which was operated under
Mr. Bates' direction for research work during the war.
She was fitted with the highest class Normand destroyer
boilers. Whatever the ultimate rating of colloidal
fuels in commercial practice, the technical objective
was effected when, from April to July 1918, this
craft was successfully operated on a colloidal fuel,
containing 30 per cent pulverized coal, as efficiently
as with regular fuel oil. I shall return to these trials
in dealing with the properties of colloidal fuels. It
must be remembered that where a new paint or varnish
requires pounds and gallons for practical trial, a fuel
requires tons and tank loads. Much of the technology
of preparation and control had to be remodified as
the amount prepared increased to this scale, and in this
connection I take pleasure in referring to the constant
and invaluable help of my associate and assistant
chemist, Mr. L. W. Eberlin. First let us consider
briefly some chemical and technical aspects of their
preparation.
SOME PARADOXES OF COLLOID CHEMISTRY
In many ways the science of colloids is a science of
paradoxes. So much is evident in its development.
As is well known, the term colloid was first applied
by Graham to a group of substances, such as gelatin,
starch, silicic acid, or white of egg. He contrasted these
with crystalloids such as sugar, salt, etc., because of
their low or negligible diffusibility, difficulty in assum-
ing definite crystalline form, and relative chemical
inertness.
Graham grouped these properties under the con-
ception that colloids had inergia, that is, an inertia
of energy which made their state at any moment
dependent upon their previous history; whereas the
state of a crystalloid at any moment can be defined
without reference to its history, but is completely
defined by quantities independent of duration pre-
vious to that moment. He considered that they
formed a dynamic state of matter as compared with
the static state of crystalloids. And he believed that
this depended ultimately upon a difference in the mole-
cules of colloids, a greater content of idiochemical
affinity. Paradox shows itself now. The develop-
ment of colloid science in the last twenty years has
been toward quite opposite conclusions, on the whole.
It has been in the direction of regarding colloids as
physically rather than chemically specific. Briefly,
it is argued that any substance in the solid or liquid
state can be brought to the colloid condition if it be
mechanically subdivided so that its particles or drop-
lets are approximately between in and ifi/j. in diameter,
that is, less than 0.00001 cm., but greater than
0.0000001 cm., and kept so in suspension in an indiffer-
ent medium. In terms of this conception, colloids
form a particular intermediate region of dispersed
systems or dispersoids, expressed in the table:
Coarse Dispersoids
Diameters greater than
0.1 p, do not pass fil-
ter paper, can be re-
solved with micro-
scope (up to 2000)
Dispersoids
Colloids
Increasing Dispersity
1 fi ' o 1 fin, pass through
filter paper, not micro-
scopically resolved, do
not dialyze or diffuse
>
Molecular Dispersoids
Diameters smaller than
1mm, pass through
filter paper, not mi-
croscopically re-
solved, diffusible
and dialyzable
True solutions
It is admitted explicitly that the boundaries are
not sharply defined, but that we have a gradation.
It will be seen that this relatively clear-cut con-
ception marks a great change. Colloids and crystal-
loids are not antithetic, but connected by continuous
transitions. The crystalloid condition, involving di-
rected symmetry relations in space, is an internal
molecular condition; the colloid state is an external
one, depending upon the subdivision of multimolecular
masses, and possible to all chemical substances. The
properties of colloids, on this view, depend chiefly
upon the large accession of surface energy, parallel
with dispersity. Dispersity is defined most generally
„ total surface „,, , , ,
as ratio of , . Thus, a sphere has a lower
total volume
specific dispersity than a cube of the same volume,
because its surface is smaller in proportion to its volume.
A large number of properties of colloids can be
explained very reasonably on the view that spontaneous
changes in dispersoids will be in the direction of re-
ducing the dispersity, thus diminishing the free sur-
face energy, and by the conception of adsorption,
i. e., of surface concentration of (molecularly) dis-
solved substances on dispersed material. So far so
Jan., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
good. But paradox again asserts itself. Considera-
tions of this type are found to be most satisfactory
when applied to so-called suspensoids, i. e., colloid
or pseudo-colloid systems in which no intimate rela-
tion exists between the dispersion medium (solvent)
and the dispersed substance. Colloidal solution of
noble (nonoxidizable) metals, of many metallic
oxides, sulfides, and "insoluble salts" are largely cov-
ered. They show themselves optically heterogeneous
by Tyndall beam and ultramicroscope, and their be-
havior is largely representable by supporting the
idea of mechanical subdivision with that of specific
adsorption of electrically charged "ions" to their
surface, giving them an electric charge opposite to
that of the medium. But, it is precisely for the emul-
soid colloids primarily considered by Graham —
gelatin, albumin, globulin, rubber — the colloids par
excellence — that the conception just outlined appears
inadequate. Their properties and behavior appear
better explainable on a development of Graham's
original conception. Many of these emulsoids, when
carefully freed from electrolytes, show only the faintest
traces of optical discontinuity. The facts point to
their solutions being crystalloid in point of "dispersity,"
while their behavior to acids, alkalies, and salts is
best explained in terms of definite chemical reactions.
Their outstanding physical property, of forming very
viscous solutions readily passing to elastic gels, is ex-
plicable by the formation of tenuous networks, of
molecular and submolecular mesh, woven perhaps by
the idiochemical affinity of Graham.
The true colloids do, however, pass by easy transi-
tions into the pseudo-colloids, for which the behavior
is less dependent upon the chemical character of the
molecules than on dispersity of mass.
Although emulsoids might be supposed more kin
to emulsions than suspensoids, yet an emulsion is a
good model of a suspensoid. Hence, all in all, I
think we may say that the development of colloid
chemistry has been perfectly paradoxical. Like the
completely irregular Brownian movement, which has
formed a focus of certain aspects of colloid science,
it is impossible to fix even approximately a tangent
at any point of the trajectory of any particular develop-
ment of the science. And this atmosphere of unlimited
possibilities lends a fascination to what at first seems
a repellent medley of empiricism and speculation.
COLLOIDALIZING FUELS
In considering the problem of stabilizing a suspen-
sion of coal or other carbonaceous matter in oil we
can best start from a mathematical law for the fall of
bodies in a viscous medium, i. e., one offering resistance
to shearing. Stokes' law states that the steady
velocity of fall of a spherical body is given by the
formula:
y 3r»(S~S')g
go
where r = radius of particle
S = specific gravity of sphere
S' = specific gravity of fluid
g = acceleration per unit mass (gravity)
v = absolute viscosity of fluid
The pulverized coal first tried was a semi-anthracite
of sp. gr. 1.467; the specific gravity of the oil was
°-8oo7(2o-°). its absolute viscosity 6. The radius of
the coal particles could be taken as a first approxi-
mation as one-half the aperture of the screen they
passed through, or one-quarter of the reciprocal
of the mesh number. From these conditions we
should have had:
Mesh to Which .
Coal Was 2r Calci
Pulverized Cin. In. pi
50 0.0127 9
100 0.00635 1
200 0.00317
400 0.00158
-Rate of Fall
Actual
Inappreciable i
Appreciable in 4 weeks
The coal used was between ioo and 200 mesh fineness,
and there was about 30 per cent by weight present.
The wide deviation from Stokes' law was in the right
direction and so far promising. It could be tentatively
explained:
1 — -By nonspherical form of the particles. As platelets or
spicules they would not fall straight.
2 — By increased inner friction or mutual impedance in the
concentrated suspension. However, "clumping" would accel-
ii. id settling.
.; -By some kind of combination, e. g., capillary adsorption,
with the oil.
The oil first used was moreover a nondescript ma-
terial, very viscous — though not so viscous as Mexican
fuel oil. It so happened that the first supplies of oil
now brought for trial were either Texas Oil Company's
Naval Fuel oils, of relatively low viscosity (around
200 Engler) or Standard Oil Company's Naval Fuel
oils, of even lower viscosity. We soon found that
fuel oil is a very variable material. It is well known
that mineral oils vary greatly in chemical composition.
While Pennsylvania oils, of so-called paraffin base,
do contain considerable proportions of saturated open-
chain hydrocarbons, together with lower members of
the cyclic olefines, the midcontinental American oils
have more of the cyclic olefines, also asphaltie hydro-
carbons (malthenes, carbenes, etc.) and "free" carbon.
More important for present considerations is their
great variation in physical properties. Fuel oil
is a residual product, left by removal of the lighter
fractions suitable for gasoline, kerosene, etc., and now
still further diminished by various cracking processes.
The oil refiner grades his oils chiefly by gravity.
Expressed in terms of the Baum6 scale, they show
pretty wide variation, yet in terms of specific gravity
it is not so considerable. For the problem of stably
dispersing coal or carbon in oil, the variation of grav-
ity, from 0.85 to 0.96, is not so formidable as the range
of viscosity. This can and does vary from 1 to 30,000,
in terms of specific viscosity of water. Again, this
viscosity varies greatly with temperature.
In our first work, as stated, we encountered the thin
end of the wedge with oil of about 20 ° Engler. It
was not found possible to prepare stable composites
with this oil untreated, even with coal pulverized so
that 99 per cent passed 200 mesh. To discuss the
actual stages of treatment as the problem presented
itself would take too much time and space. It was
evidentthat it was necessary:
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. r
BHVJ t>90 ' 3UniYHidH2X
I — To find working standards for the minimum and maximum y — To find protective colloids adequately stabilizing the com-
viscosity permissible of the oil base. posite within permissible viscosity limits.
2— To approach the practicable viscosity minima of stable There are other factors, to be touched upon, but
composites to specification maxima for atomizable fuels. these three are dominant. Yet they are very closely
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
41
interwoven, and interdependent. First, they have
to be considered in regard to temperature. The
viscosity of fuel oils sinks rapidly with rising tempera-
ture, as shown in the diagrams (Fig. 1).
This has to be considered in relation to flash point.
It has been found1 that for effective atomization by
mechanical burners the viscosity should be reduced,
by preheating, to about 8° Engler. Greater reduction
gives no marked advantage. To secure this, the
temperature to which the oil may be heated must not
be higher than its flash point.
\
BINE
ER
- R
5. 01
,\
5%
>-
5i
•ox
«
^
A= STA
IDA
m
JIL
5%
p%
""""~
TO
1
0
131
Temperature Fahrenheit
Fig. 2 — Blended Oil Curves
We have then one terminal pair of values to be
worked to:
Viscosity, 8o° E.; Temperature, flash point
British naval specifications for the flash point were:
not lower than 1750 F. closed cup, or 2000 F. open
cup; U. S. A. specifications: 1500 F. closed cup, or 175°
F. open cup. Considering then, for the original pur-
pose, that a close approximation to naval standards
was desirable, it had to be aimed to make the terminal
pair of values of the viscosity-temperature curve of
the composite fuels 8° Engler at 150° F. There is,
however, evidently a certain latitude, in that with
higher flash points a higher preheating temperature for
the same viscosity is permissible. Again, the viscosity
depends upon the pressure of injection.
While blending at first was mainly a problem of
thickening thin oils to suitable minimum viscosity to
permit of practicable amounts of the "stabilizer"
or "fixateur" being used, it later became rather a
question of suitable maximum viscosity, so that too
thick a fuel did not result. It might be thought that
this latter condition simplifies the stabilizing problem,
in so far as stability depends upon viscosity. This
is partly true, but not entirely. In very viscous
fuel oils, such as Mexican Panuco, etc., there is a strong
tendency for "free carbon" and suspended carbon to
clot. So that there also the role of "protective
colloids" as also of peptizers and deflocculators is very
important. Before passing to these aspects, let me
point out in conclusion of this section that "blending"
meant adjusting the oil base to a standard viscosity-
temperature curve (Fig. 2).
So great are the varieties of these curves with differ-
ent materials, and so large the deviation from any law
1 E. H. Peabody, "Oil Fuel," Trans Internal. Eng. Cong., 1915.
of mixtures — whether for viscosities or fluidities —
that this has to be done by "trial and error" methods
in the main.1 But, technically, it has been adequately
solved, and a great amount of valuable data secured.
Commercially, it is subject to local and temporal
conditions of availability.
STABILIZATION AND PROTECTIVE COLLOIDS
As already stated, the problem of stabilizing sus-
pensions of carbon in oil is not solely one of getting
viscosity in the oil medium. While heavy paraffins
and cyclic defines give viscosity — and have also
much protective value as semicolloids themselves —
they are too valuable, as lubricants, to be very avail-
able in fuel oil. The more viscous residuals available
for increasing viscosity are asphaltic materials, con-
taining large amounts of "free carbon," in colloidal
suspension, but tending itself to clot and settle out.
There are two ways of stabilizing this, of which the
first we need consider is the use of protective colloids.
Protective colloids in aqueous systems are well known,
e. g., gum arabic, gelatin, glue, etc. They are classed
as emulsoids, or lyophile colloids — the first name
from the idea that they form a submicroscopic liquid
dispersed phase, the second from their affinity for the
solvent. It is the second conception which is the
/
,
/
/
/
/
,
/
1
11
/
1
/
[
/
1
.
//
1
'/
1
Q
/
!
S
7
g M
/
/
/
/
o
7
1
It
/
/
1
o
4
'
r
,"/
I
C
A
1
1
/
iJ
;
/
f
s
-
j
/
/
i
/
/
i
/
/
,,'
&
a?
i
'
/
i
'
i
_!
„
r
1 —
m
PERCENTAGE
Fio. 3 — Curves Showing Viscosity op Fixated Oil in Relation to
Concentration and State of Protective Colloid
more important. Substances forming emulsoid col-
loids in nonaqueous media are also known. Many
1 See the recent and valuable paper by W. H. Herschel, "Saybolt
Viscosity of Blends," Bureau of Standards, Technologic Paper 164 (1920).
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. i3> No.
soaps, particularly of the alkaline earth metals, such as
lime soaps, form emulsoid colloids with mineral oils.
It is a group of these which furnished the fixateur, or
protective colloid used to stabilize suspended carbon
in colloidal fuel.1 Like emulsoid colloids in water, the
preparations of these soaps in oil show a very rapid in-
crease in the viscosity with increasing concentration of
colloid (Fig. 3).
This viscosity-concentration curve is very irqportant
in judging the adequacy of dispersion of the colloid,
on the one hand, and the measure of its protective
action on the other. With the particular type of emul-
soids we have to deal with, the steepness of this curve
depends markedly on the mode of preparation. It
appears that every gradation exists between the mark-
edly emulsoid condition and suspensoid dispersion,
in which the system is much less stable.
QUANTITY OF FIXATEUR AND VISCOSITY
The amount of fixateur which could be used was
approximately fixed by conditions of cost, and varied
from 0.5 to 1. s per cent. Although the immediate
effect is to thicken the oil, i. c, increase its viscosity,
it is to be remarked that increase of viscosity alone is
not the sole condition conferring stability of suspension
of carbon or pulverized coal, coke, etc. Oils thickened
by other means, e. g., by vaseline, to the same viscosity,
gave much lower stabilities. It was repeatedly
found that viscosity, while an important factor, was
not the only one. This is already known to be the
case for the protective action of emulsoids on suspen-
soid colloids, and evidently extends to suspensions.
PLASTIC INNER FRICTION
On the whole, it is probable that the immediate
condition for protective action is strong adsorption of
the colloid to suspensoid or suspension. But this
does not entirely account for the mechanism of pro-
tection. ! believe we may account for this by the
tendency of these colloids to form heat reversible
gels. Such gels — not coagula — may be imagined as
very tenuous web-work or foams, the mesh or walls
1 The Submarine Defe e Association, a war organization, dissolved
and terminated its existence at the close of hostilities. During the w.ir
it sponsored the new fuel. All patents, trade-marks, copyright and other
rights in the fuel are in Mr. Lindon W. Bates' name and are vested in a
company. Release of patents since September 1920 has allowed explicit
statement of the fixateur to be made.
of which are very probably submolecular in dimensions;
or, if we like, the whole mass of colloid forms one
"molecule" uniformly dispersed through and partially
dissolving the solvent. By partially, I mean that part
only of the "molecule" of the emulsoid is consolute
with the solvent or dispergent, while the other part
of it is insoluble, and its atoms tend to unite, forming
a semirigid framework. Such a system would have
the following properties, which are observed in jellies:
1 — Offer little resistance, unless very concentrated, to diffu-
sion of solute.
2 — Offer little resistance to powerful shearing stress, or move-
ment of heavy bodies.
3 — Offer great resistance to very small shearing stress, or move-
ment of very small masses.
That is, such systems would behave as fluids for in-
ternal diffusion of solutes, and for shearing stress of
appreciable magnitudes, but approach the behavior
of elastic solids for internal movements of small magni-
tude. Internal friction of this type has been termed
"plastic," and is illustrated diagrammatically in Fig. 4.
Differential resistance of the kind noted is charac-
teristic of the plasmas or body fluids of organisms, and
it is such a plasma which is required for colloidal
fuel. Hence, it has really more than one coefficient
of inner friction, and the gross viscosity is not a com-
plete exponent of its inner state.
PEPTIZATION AND COLLOIDAL FUELS
I have said that there is a second method of im-
proving the stability of suspensoids and suspensions
of carbon in oils, other than the use of emulsoids or
protectives. This consists in peptization. The two
methods are probably connected. Protective action
probably means strong adsorption, and adsorption
leads to peptization. But it may not go so far. Pep-
tization for stabilizing graphite was employed by
Acheson, who used tannic acid as a defiocculator.
It was found in the present work that "free carbon"
in residual oils, such as pressure still oil and Mexican
oils, could be peptized and stabilized by addition of
certain by-products and distillates.1 This occurred
with a lowering of the total viscosity, due to the pre-
vention of clumping. Next, a still more remarkable
peptizing action of this type has been observed. This
was discovered as follows: We had found that the
peptizing of "free carbon" in petroleum residuals
could be extended to the problem of stabilizing dehy-
drated coal tars in mineral oil. Further, reasoning
by analogy with Pickering's emulsions, in which a
finely divided solid was found to stabilize an emulsion
of two immiscible liquids (oil and water), an attempt
was made to stabilize coal tar in oil by further addition
of pulverized coal. This attempt was largely suc-
cessful, a stability extending into weeks being secured.
We further added small amounts of peptizing substances
to these composites. On measuring the viscosity-
temperature curve of these, it was observed that when
maintained some time at relatively high temperatures
the viscosity, instead of diminishing, actually increased.
This thickening action was observed in detail. Dilu-
tion with xylene and microscopic examination, with
1 Notably creosote and naphthalene containing oils from tar.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
43
counting chamber, showed that the number of very
small to ultramicroscopic particles was greatly in-
creased, these showing lively Brownian movement.
Peptization or partial solution of coals by such means
is to be expected. The investigations of Bone, Wheeler
and others1 have shown that in general we may regard
coal as composed of three principal fractions, a, 0,
and y. Of these the a-portion is composed of com-
pounds insoluble in pyridine; the /3-portion is soluble
in pyridine but insoluble in chloroform; while the 7-,
--
P. S. O 1 u
— ■
'So '/too '/zoo /400 '/aoo '/1600 'Azoo '/6400 VlZBOO
Diameter of Particles inTrhctions of An Inch
Fig. 5 — Effect of Subdivision of Coal on Viscosity of Fuel
or resinic portion, is soluble both in pyridine and chloro-
form. It is well known that the oils distilled from
resinous bodies such as amber, copals, rosin, rubber,
etc., are solvents for these substances themselves,
the solutions, however, being generally incomplete
(peptization). The microscopic examination of coals1
tends to show that with certain exceptions coal is far
from being a physically or mechanically homogeneous
material, resultant of pyrogenic metamorphosis. To
quote Wheeler and Stopes:2
We conclude that coal is a conglomerate of morphological
organized plant tissues, natural plant substances devoid of
morphological organization (such, for instance, as resins) together
with the degradation products of a portion of the plant tissues
and cell contents comminuted, morphologically disorganized,
or present in the form of varying members of the ulmin group.
From this it will be seen that the efficiency of pep-
tization by tars and distillates is likely to vary con-
siderably from one coal to another, and again to some
extent with different particles of the same pulverized
coal. In practice, this is found to be the case. Ac-
tually, however, cannel, bituminous, and even an-
thracite coal have been found peptizable by these
methods. Such peptization does not, alone, neces-
sarily produce complete stabilization in the oil-tar
medium. Generally it is easy to secure 3 to 4
wks. of homogeneity. After this the composite
gradually separates into an oily supernatant top layer
over a more viscous mass. This lower layer, however,
is usually quite easily remixed, and only very slowly,
if at all, tends to pass to a dense, solid mass. Usually
the lower stratum forms a more or less mobile jelly,
1 M. C. Stopes and R. V. Wheeler, monograph on the "Constitution
of Coal," Department of Scientific and Industrial Research of Gt. Britain,
London, 1918.
J Loc. cit.
showing synaeresis, *. e., shrinkage, with exudation of
oil. We have provisionally termed these the B-type
colloidal fuels. They are, per se, more readily and
cheaply compounded than the A-type, in which
stabilization is effected by an external protective
colloid — the fixateur — and are perfectly satisfactory
as liquid fuels for land installations. Finally, processes
of this B-type may be combined with those of the A-
type.
limits of peptization — The peptization process,
as stated, increases the viscosity. This may be
partly due to an extraction of "resinoid" bodies, but
no doubt is also due to increased dispersity of the coal.
For, as the dispersity of a suspension is increased,
the viscosity, or rather the inner friction, is also. This
is illustrated in the diagram in Fig. 5, for the case of a
30 per cent coal suspension. It is evident that pep-
tization must not be pushed too far, to excessive vis-
cosity.
alternative methods of peptization — An alter-
native method of peptization involves an entirely
different method of attack, viz., attack on the cellulose
and "fixed carbon" portion by oxidative reagents,
either wet, or gaseous. Anthracite coals contain a
very condensed cellulose fraction which approaches
free carbon in behavior. Carbon and coal both yield
mellitic or graphitic acid (benzene hexacarboxylic
acid?) on oxidation. Partial oxidative attack need
be relatively slight, in percentage oxidation, while
giving considerable peptization, and this method is
also available for the production of colloidal fuels.
Hence, we have three methods or. stages of attack,
resulting in progressively more deep-seated attack:
Mechanical Solvent Chemical
Comminution Peptization Peptization
Fig. 6 — Rocking Storace Tank Sb
ig Two Positions
ACCESSORY TESTING METHODS
Just as the proof of a pudding is in the eating, so
the tests of a fuel are essentially keeping powers and
combustion efficiency. Of these I will speak directly.
But in the technologic development of these fuel?
various laboratory accessory tests were devised. It
has been stated that fuel oil on shipboard tends to
separate water which is not separated on land storage.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Fig. 7 — Capillarimeter
The fuels were therefore tested for such "seasickness"
in the apparatus shown in Fig. 6, which has a motion
approximating the pitching and heaving of a vessel,
and no difference .was observed. Rapid methods of
analysis for the free carbon in suspension were devised,
including a centrifuge for washing out the carbon
while running. Further, rapid centrifugal and capil-
lary methods of proximate stability testing were de-
vised. By these a partial prediction of the life of a
fuel is possible. The accelerated test by centrifuge
consists in determining the force required to effect a
given per cent separation, and this is calibrated on
5
$
t/
1 *
r
c
oj2-
??'-
—
\~
/
,
s
'
y
'
0
I
'
0
1
i
gravity stability trials. I say calibrated, because a
direct relationship does not exist here. The capillary
method is based on this. Oil plus fixateur plus carbon
are held by capillary chemical attraction, at the least.
If we put in a piece of standard porous paper, the oil
will climb this the faster, the less it is held back by the
combination (Figs. 7 and 8).
Further, it was necessary to determine the viscosity-
temperature curves of base oils, fixated oils, and com-
plete fuel. For proximate work, a pipet of special
type, running as many seconds as degrees Engler, was
used, as well as Engler and other viscosimeters. Other
essential determinations, on raw materials, inter-
mediate stages, and completed fuels, were specific
gravity, B. t. u., ash, sulfur, moisture, etc., also flash
points, and ignition temperatures.
METHOD OF COMPOUNDING
The machinery for compounding these fuels is
simple. It consists of a suitable mill for pulverizing
coal, coke, etc., storage and blending tanks for the
M/NUTES
-Showing Capillary Rise with On. and Fuel, Respectively
Fig. 9 — Cost Chart. Reproduced from a Pamphlet on "Colloidal.
Fuels, Properties, Tests and Costs," by Lindon W. Bates, 62 Lon-
don Wall. London, England
oil bases, and mixing kettles for compounding the
composite fuel. Little modification in existing types
of machinery is necessary, and the process is readily
made continuous. The cost of manufacture may be
reckoned at approximately $1.50 per ton, inclusive of
fixateur. The general relation to cost of oil is shown
in Fig. 9.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
PROPERTIES OF COLLOIDAL FUELS
It will be evident that the colloidalizing process is a
flexible one, allowing a great number of grades and
varieties to be produced. Standardization of grades
has already been commenced, but the flexibility possible
is valuable, in view of adjustment of the process to
local or temporary conditions of supply and demand.
1 U.J.Jnl Mil
|Cu.frJ | | | |
' " ." ' \\\\\\\\\\\^
1 1 1 1 1 1
k\\\\\\\\>
0.7MC.n OiL.0.4»«C»Fr fe«>ii»CoAi..ftKUCAr< R™cr«.ll»t
1 1 o'.L 1 1 1 1 fM^mU
1 1 1 1 1 1 1 1 1 1 | 1 M 1 1
07«Cuft0ii. OJ«J£«lt».-.»K..Co»L > - - 19.01
1 ln.1 1 1 1 1
1 1 1 1 1 1 1 1 1 M II
| V«.UMC or Oil »,IK 1«B6 WT. «S ICKrtCGU.MM.KW.
I I 1 1 I p;LVEaiieGCo«L 1 1 1 1 1
II II M 1 1
^^W^^^^^
^\^\N
1 1 jiygjjjjyiU 1
1 1 1
'II II
TTl"!TtTTiTi rr
| VoLO«toro.LB«v,NOSA«IHiAtu«,rjA5Uo.rT.coLLOio»i.F»Gu 1
Chart Comparing Volume of Coiloidal Fuel wit*
Aggregate Volumes of Coal andOil, and
•• * Oil = 16*69 " " Cool' i.i
K
0
Coo-
so
0.2 04 0.6 0.8 1.0 1.2
1.6 16 10
Fig. 10 — Volumetric Comparisons between Oil, Coal, and Colloidal
Fuel
This table shows graphically the volume occupied bv colloidal fuel after
manufacture; the volume before colloiding; and the volume of oil with the
same weight as a cubic foot of colloidal. 1.02 cu. ft. of oil have the same
heat units as 1.0 cu. ft. of colloidal fuel, which shows a gain in cruising
radius per unit of space for colloidal. The chart also shows that pulverized
coal is nearly twice as bulky as colloidal fuel for the same number of heat
units. To illustrate, if a high-grade navy oil is used with high-grade
Cardiff coal, we obtain the most compact fuel known per unit of space.
Meanwhile, the following brief summary of the proper-
ties of colloidal fuels is in order:
(1) They are liquid, and handle and atomize for combustion
like fuel oil.
(2) They can be made to contain more heat units per gallon
than fuel oils. This is a consequence of the law of mixtures.
The specific volume of the colloidal fuels is lower than that of
the oils they are made from. Fig. 10 shows graphically the rela-
tion of heat units to volume. In general, they will weigh from
8.75 lbs. to 1 1.5 lbs. per gal., according to kind and per cent
of carbon, e. g., coke, coal, pitch, or lignite, employed.
(3) They contain very little moisture and ash. The ash
obviously depends upon the kind and per cent of carbon incor-
porated, and can be kept very low by use of high-grade carbons
or de-ashed coals.
(4) Flash point is above 2000 F. They are immune from
spontaneous combustion. The so-called spontaneous combustion
of coal in piles, bunkers, and as powdered coal is due to initial
fixation of oxygen of the air. self-heat, and autocatalyzed autox-
idation.1 Immersion of the coal in oil prevents the first step,
the formation of addition complexes of oxygen and coal compo-
nents.
(5) Not only are they vaporless up to high temperatures, thus
avoiding explosive mixtures with air, but they may be fire-
proofed by a "water seal" of an inch or more of water, due to their
specific gravity being higher.
(6) Hence also they will sink if spilled blazing on the surface
of water, i. e., are self-quenching. They are quenchable by
water with ordinary fire apparatus where the surface may be
covered, as also by sand, Foamite, etc.
Summarizing their safety factors, their fire-risk is as low as
anthracite coal, and far safer than bituminous coal or ordinary
1 Porter and Ralston, "Study of the Oxidation of Coal," U. S. Bureau
of Mines, Technical Paper 65 (1914); R. B. Wheeler, "Oxidation and Igni-
tion of Coal," J. Chem. Sue., 113 (1918). 945.
fuel oil. These properties have been investigated by the National
Board of Fire Underwriters' Laboratory. They have substan-
tially confirmed them, and reported to the Fire Council that all
installation using colloidal fuel be given the benefit of standard
fire rates. The Council adopted the recommendations.
(7) Storage Test — They are the most compact fuels known.
A cubic foot contains 7.4805 U. S. gal. An average bituminous
colloidal grade contains 160,000 B. t. u. per gal., or 1,169,800
B. t. u. per cu. ft. With anthracites and cokes up to 1,346,490
B. t. u. per cu. ft. may be realized. The advantages of this are
obvious: increased radius for ships, and lessened storage space
in crowded cities.
COMBUSTION EFFICIENCY
The following table shows what was accomplished,
first with straight A-type fuel, stable for 6 mo. in marine
trials, and secondly, with A- and B-type fuels on land.
Table I — Typical Result of Steam Tests on U. S. S. Gem, S. P. 41, 1918
Fuel , : Colloidal . . Navy Oil .
System Standard Schutte & Koerting Mech. 1.7 Mm. Burners
Test number 2 4 6-B 12 3 6- A
Date April 18 April 30 May 3 June 22 April 19 May 3
Duration 2 hrs. 2.25hrs. 0.67 hr. 3.17 hr. 2 hrs. 1.5 hr.
Feed water temp
entering heater 72.1 83.3 81.0 95.3 77.5 71.3
Feed water temp.
entering boiler. 233 195.3 229 218 223 177
Flue gas temp,,
average 745.5 668.5 644.5 629.5 661.5
Air temperature,
outside 45.2 60.6 72 60.5'
Air temperature,
boiler room 66.7 75.6 65.8
Air temperature,
engine room. . . 81.0 80.0 68 82.2 .... 67
Fuel temperature 173.5 159.8 155 139 134.3 140
Fuel pressure, lbs. 131.8 149.5 156.5 101 96.1 125
Draft uptake in
WG 0.05 0.05 0.05 0.05 0.05 0.05
Draft pressure,
wind box, in
W. G 0.73 0.71 0.70 1.08 0.72 0.66
Vacuum 25.0 24.8 25.8 24.7 26.0 25.3
Barometer 29.88 29.91 25.90 29.71 30.35 29.90
Smoke average... 30% 0-10% 0-10% 0-10% 10% 0-10%
CO; 8.5 7.0 11.2 8.6
Boiler pressure,
lb. g 208.4 249 240 232 235 220
Engine pressure,
lb. g., average. 73.2 86.2 117.5 119 90.8 85.45
Intermediate pres-
sure, lb. g., av-
erage 17.35 22.9 35 35.4 25.0 22.8
R. P. M 214.5 231.6 260.5 268.2 243.5 230.5
I. H. P. main en-
gines 439 514 677.6 851.4 569 530.4
Knots by Log.... 11 13.64 14.64 12.25
Knots by Sanborn
gage 11 13.4 14.18 13.3
Fuel per hr, lbs.. 950 1030 1050 1493 938 1000
Assumed water
rate. lbs. per I.
H. P
Steam per hr.
from and at
212° F 10970
Factor of evapora-
tion 1.029
Evaporation per
hr 10660
Lbs. water per lb.
fuel 11.25 11.65 15.6
B. t. u. per lb. fuel 17100 17100 17100
Evaporative effi-
ciency, per cent 65.5 70.7 91.5
Lbs. water per sq.
ft. heating sur-
face 4.06 4.56 6.23 8.03 5.19 4.64
Lbs. fuel per I. H.
P. main en-
gines 2.16 2.0 1.55 1.75 1.65 1.9
gem tests — In this first trial under service condi-
tions, the fuel consisted of 31.2 per cent Pocahontas
coal of 13,974 B. t. u. and 67.8 per cent Texas fuel
oil of 18,669 B. t. u. The B. t. u. of the composite
was 17,100 per lb. 1 per cent fixateur. With fuel 3
to 4 mo. old, tests were made on Long Island Sound,
directed by H. O'Neill, then engineer of the West
Virginia Pulp and Paper Company. They were
witnessed by representatives of the American and
Allied navies, the U. S. Shipping Board, and other
fuel experts.
24.3
23.5
24.2
24.0
12850 16950 21300 14200 13250
1.071 1.035 1.048 1.039 1.088
12000 16370 21100 13660 12200
79.4 69.6
4«
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Table II— Da
and Results op Boiler Tests of Colloidal Fuel, 1919
Grate surface, sq. ft
Total heating surface, sq. ft
Date
Duration, hrs
Kind of liquid colloidal fuel, grade. .
Steam pressure by gage, lbs. per sq. in
Temperature of feed water entering boiler, deg
Percentage of moisture in steam or number of degrees of super-
heating, per cent or deg
Percentage of moisture in liquid colloidal fuel, per cent
Liquid colloidal fuel per hour, lb
Liquid fuel per sq. ft. grate surface per hour
Equivalent evap. per hour from and at 212°, lb
Equivalent evap. per hour from and at 212° per sq. ft. heating sur-
face, lb
Rated capacity per hour from and at 2 1 2°, lb
Percentage of rated capacity developed, per cent
Equivalent evap. from and at 212° per lb. of dry coal, lb
Equivalent evap. from and at 212° per lb. of combustible, lb
Calorific value of 1 lb. of fuel by calorimeter, B. t. u
Calorific value of 1 lb. of combustible by calorimeter, B t u
Efficiency of boiler, furnace, and grate, per cent
Efficiency based on combustible, per cent
3.61
403 b. h
126%
13.6
2.8
1076
i5942
3.29
403 b. h. p.
115%
14.72
16670'
85.3
1159.5
16200
403 '
110.6%
13.97
18482
-'3.3'
1146.5
17202
403
1221 ;
14.85
.94
1054.7
16567
403 '
118.8%
15.51
18482
79! 46
982.75
146i2
403"
105%
14.89
18482
7o!s'
Compositions — Colloidal Fuels
Grade
1 1
Per cent
Numbers
14
Per cent
Coal
Coal (Pocahontas).
Coal tar, etc
Fixateur
Mexican reduced.
Pressure still oil
The second series of trials took place on land at the
Standard Oil Refinery in Brooklyn. The boilers used
were old type tubular return, 5 to 7 per cent less efficient
than later B. & W. or Sterling types. Fuels of both
A- and B-types, and mixed grades were used; the
"peptization" process fuels were burned with complete
Fuel Oil
Floating on tyah
Colloia Colloidal Fuel
Sealed under Wafer Kepi 1 ueor under Water
Average efficiency, 76.37 per cent
Analysis Grade 13
Ash 3.20 per cent
Sulfur 1 . 27 per cent
Viscosity, 70° F 67.5° Engler
Sp. Gr , 70° F 1.0431
Flash 250° F.
Fire 285° F.
Moisture 0.2% per cent
Grade 14
Ash 2 per cent Sulfur 0.2 per cent
in the Bone-Court flameless superficial combustion
procedure. Now the atomized coal plus ash particles
provides an enormous internal surface. The fume
of partly burnt coal and ash particles in the combustion
space gives an added surface factor, which, under
proper conditions, makes the efficiency of these fuels
equal to or greater than that of higher grade straight
oils, having no solid particles present. Further, with
increased percentage of carbon there is less heat loss
by steam formation.1
1 As stated, the liquid types of colloidal fuel require no
special arrangements for burning, either air, steam
TIME IN MONTHS
I 9 ■* A. 5 £ 7 a
100 r
1 1
Typicm. "Life' Curves
*
s
1
1
1
1
1
i
/
/
/
1
*
1
1
>
-
/j
A
/
/
*"''
v"
1
Time in Months
-Life Curves of Colloidal Fuel — Show Prolongation
BY REAGITATING AFTER INITIAL SETTING
Excellent results were obtained with other fuels,
using 40 per cent anthracite rice (pulverized) contain-
ing 25 per cent ash. The remarkable fact that these
fuels, actually of lower grade than straight fuel oil. in
B. t. u. per lb., are capable of giving equal or higher
boiler efficiencies is, we believe, explained by the follow-
ing considerations. Combustion efficiency of oils and
gases is greatly increased by surface. This is shown
injection, or mechanical burners being suitable. It
is desirable to have a steam by-pass on the burners to
"blow-through" after turning down.
"life" curves
Finally, what is the period over which those fuels
can be made intrinsically stable? "Can" and "need"
1 The calorimetry and heat balance of these fuels will be discussed
more fully by Mr. H. O'Neill shortly.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
must be distinguished here. I believe that they can
be made just as stable as needed. Samples prepared
in the laboratory have lasted 12 to 18 mo. in quite
stable form (Fig. 12).
An important point here is that reagitation, before
sedimenting has progressed too far, will give a further
extension of life. The grade of fuel can be fitted to
the conditions of permanence and stability required,
and is technologically related to the dispersity gradient,
the varying properties of particles of different dimen-
sions in it. Colloidal fuel is a composite dispersoid,
the particles of which range from solution through the
colloid to suspensions. With every advance in the
technique of the subject, the right proportioning and
grading of those for a given purpose becomes better
understood, and the relation of the dispersity gradient
to stability and use becomes clearer.
FUEL CONSERVATION, PRESENT AND FUTURE
By Horace C. Porter
1833 Chestnut Street, Philadelphia, Pa.
Progress in the application of fuel to the needs of
mankind is being manifested in an improvement of
methods, a rise in the curve of efficiency, as well as
in that of total consumption. To-day, resulting from
increased use of scientific methods, we see greater
returns per ton of coal than 10 yrs. ago.
The per capita consumption of fuel in the United
States has increased by only 7.5 per cent in the last
10 yrs. — from 152.3 to 163.9 millions of B. t. u.
The increase has been in oil and gas, not coal. It
is cause for congratulation, therefore, that notwith-
standing greater industrialization, higher standards
of living, and the devoting of vastly increased indus-
trial yields to the benefit of other nations and of our-
selves, we have maintained so small an increase in
fuel consumption.
Fuel production is with difficulty, however, keeping
up to the demand. Under the trying conditions of
the last few years, transportation deficiency has
retarded fuel distribution and production, so that a
real shortage exists to-day. The loss of 50,000,000
tons from the normal coal production during the
nation-wide coal strike of 19 10 put industry in the
position of holding back needed improvements and
new construction which now are calling urgently for
more fuel. Stocks also need to be built up. Exports
from tidewater have leaped to 600 per cent in 2 yrs.,
and threaten to pass 25,000,000 tons for this year.
In the face of these facts, and of the impression
prevailing in many quarters of a dwindling coal pro-
duction, it is in a measure reassuring to note that for
the first 6 mo. of this year coal production is 19 per
cent greater than in the corresponding period of
last year, and oil is 15 per cent greater. As compared
similarly to 191 7 and 19 18, war years, coal has this
year fallen behind by 5 and 10 per cent, respectively.
Reconstruction now urges upon us the use of addi-
tional fuel. To emerge from the transition period
of 1919 and make this truly a reconstruction year,
our industries must be given the necessary coal and
oil. As to how far we fall short now of our proper
share in the world's reconstruction, the economists
can perhaps make better guesses than chemists and
engineers. But in point of coal consumption we may
make comparison with 1918 when expanded war in-
dustries brought this item to the highest point it has
ever reached in this country, before or since, and
find that our present rate is but 10 per cent in arrears,
of which probably half can be accounted for by increase
in exports.
Professionally, to the industrial chemist and engi-
neer, conservation appeals as an important aid in
removing or reducing fuel shortage. A reasonable
and practicable increase in fuel economy would help
materially in bringing supply and demand closer
together. There would be exerted in consequence of
it, also, an influence toward lowering of prices. No-
table advance has been made during recent years,
but the practical maximum of efficiency has by no
means been reached. There is not to be overlooked
or minimized the tendency of human nature to use
available natural resources to the limit, with little
regard for posterity. Yet in times of shortage in
supply, the consumer perhaps has his interest more
easily aroused in means of cutting down requirements
and reducing raw material costs.
Bituminous
Coal Used Per cent
(Net Tons) of Total
Possible Means of Conservation 1917 Consumption
(1) Industrial Power 130.150.000 23.4
(excl. steel mills and coking)
(a) Increased use of economizers,
superheaters, feed-water heaters, me-
chanical stoking
(6) Care in firing, with control of
flue-gas composition and temperature
(c) Use of gas engines in conjunc-
tion with steam, on power plants
where load is variable
(2) Steel and Iron Industry 90.000,000 16.2
(excl. coking)
(a) Increased use of gas for heating
and power, and of regeneration and
recuperation
(6) Increased use of waste heat
for steam generation
(c) Powdered coal and tar in heat-
ing furnaces
(3) Beehive Coking 52,250,000 9.4
(a) Gradual abandonment in favor
of by-product coking
(i>) Utilization of waste heat in
boiler firing
(4) By-product Coking 31 ,500,000 5.7
(a) Increased utilization of waste
heat through regeneration, recupera-
tion and steam generation; increase
in surplus gas and its utilization
(5) Railroads 156,150,000 28.0
(a) Use of feed-water heaters and
economizers on locomotives
(6) Economy of steam pressure by
idle locomotives
(6) Domestic 57,100,000 10.2
(a) Avoidance of unnecessary heat
in unused places and of excessive
temperature when not needed
(b) Economy of gas used as fuel by
adjustment of appliances
(7) Other Uses 39,700,000 7.1
(Gas manufacture, export, and bunk-
ering of vessels)
Total 556.850,000 100.0
Many of the expedients for raising the efficiency of
fuel utilization are of such a nature as to require large
changes of existing plant and equipment — the cen-
tralization of power development, for example, in
super-power stations, the electrification of railroads,
and the building of by-product recovery coke plants.
These changes go slowly, and depend greatly on general
financial conditions and the prevailing cost of capital
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. i3) No. i
•outlay. Other expedients afford in the meantime
quicker realization of efficiency gains, not as large,
but of distinct importance in practical conservation.
The preceding tabulation of the country's coal
consumption in 191 7, by classes of users, is taken from
the U. S. Geological Survey reports, and is coupled
with an outline of some of the means whereby con-
servation might be accomplished in the different
fields without great delay.
PRESENT CONDITIONS
It is to be noted that seven-tenths of all the coal
is burned under industrial and locomotive boilers and
in metallurgical heating furnaces. It is in this large
field that perhaps the most immediate opportunity
for improved efficiency exists.
boiler furnace EFFICIENCY — In boiler furnace
economy roughly half of the efficiency losses are due
to heat carried away in the chimney gases; under
commonly prevailing conditions an increase of 1 in
the percentage of C02 in the chimney gases means a
lowering of the excess air by about 10 per cent, a con-
sequent reduction in the B. t. u.'s carried away in
sensible heat, and a gain of 1.5 to 2 per cent in the
combined efficiency; a lowering of the flue-gas tempera-
ture by ioo° F. means an additional gain of over 3
per. cent in boiler and furnace efficiency. It is some-
what startling to those who have not stopped to con-
sider the matter carefully, to find that for every
pound of coal burned, 15 to 25 lbs. of chimney gases
result, carrying out their sensible heat to waste.
These efficiency gains are not in large figures, but
they mean a good deal when applied to the large ton-
nage of boiler fuel used.
Superheaters and feed-water heaters, if more gen-
erally applied, would add further to the saving. D. D.
Pendleton1 has recently estimated that only 15 per
cent of the steam raising capacity of the country
is equipped with superheat, and that the remainder
not so equipped would gain between 14 and 20 per
cent in efficiency by its use.
railway locomotive operation — In railway loco-
motive operation it is true that considerations other
than those of thermal efficiency are highly important
in obtaining the driving capacity required. On the
other hand, there are some opportunities for fuel
saving here, and it is a big field in point of total con-
sumption. In an article on "Locomotive Feed Water
Heating,"2 T. C. McBride has recently claimed that
devices for this purpose, utilizing the exhaust steam,
save on locomotives 10 to 13 per cent of the coal used,
as compared to injector operation. The maintaining
of high steam pressure unnecessarily in locomotives
standing idle in yards, the preventable part of the
so-called stand-by losses, is no doubt a factor in the
large railway consumption of coal.
industrial heating furnaces — A great deal of
coal is used in industrial heating furnaces for the
heat treatment and reworking of metals, the rolling
and forging of steel, and for tempering processes.
1 Blast Furnace and Steel Plant, 8 (1920). 350.
= Mech. Ens.. 42 (1920), 283.
Prof. H. M. Thornton1 has recently brought out the
great advantages and economy of gas as a fuel for
these furnaces. Records are presented showing com-
parative results in various sizes and types of furnaces
from the small rivet heaters to the large forging fur-
naces, the saving in fuel cost as compared to direct
coal, coke, and oil firing ranging from 40 to 60 per cent.
Indirect advantages also result in increased capacity
per unit and decreased labor cost. Prof. W. Trinks,2
of Pittsburgh, shows these economies in the use of
gas and of powdered coal in a series of articles on heat-
ing furnaces. The latter is pessimistic as to the
practicability of such savings, owing to the human
tendency of firemen to waste fuel when they can do
so easily by the turning of a valve. It would seem,
however, that under the inducements of a bonus
system this same ease of turning a valve might prove
a factor leading to conservation.
An actual record is given by A. A. Cole3 of a powdered
coal installation in a large heating furnace used in the
manufacture of rolled steel wheels, wherein an economy
of 30 to 40 per cent over direct hand firing was obtained,
and a labor saving equal to 1 5 per cent of the fuel cost.
At steel plants where by-product oven tar — an
excellent fuel for the open-hearth furnace — is available,
greater value frequently can be obtained from the
tar as fuel based on comparative coal cost at the
plant, than is obtainable in the open tar market.
Changes in open-hearth and heating furnace con-
struction designed to regulate combustion and length
of flame are proving in actual plant trials to effect
an increase in metal output, reduce waste heat losses,
and raise fuel economy by 10 per cent, without im-
pairing the life of the furnace.
waste heat boilers — More attention to waste
heat losses on industrial furnaces and in the older
by-product coke plants, with increased use, or more
efficient use of regeneration and recuperation would
pay well in fuel saved, giving added surplus gas at
the coke plants. Waste heat boilers are used on
many industrial gas-fired furnaces and by-product
coke plants. Their application could be widely ex-
tended with profit and an important degree of fuel
economy. Brick and pottery kilns, copper and zinc
and cement furnaces, and beehive coke ovens, show
waste gas temperatures from 12000 to 20000 F.
A large steel plant near Pittsburgh operates waste
heat boilers on the outlet flues of its rectangular non-
recovery coke ovens, obtaining thereby a steam output
which has reached 27 h. p. per oven. Reduced to the
basis of coal burned, this figure becomes in h. p.-hrs.
per pound of coal more than 25 per cent of the average
yield from complete combustion in steam plants.
miscellaneous — Large gas-engine-driven power
stations are being used by steel works on blast-
furnace gas with conspicuous success and large fuel
economy, as at Gary, Ind., by the U. S. Steel Corpo-
ration, and at Sparrows Point, Md., by the Bethlehem
Steel Corporation. Such means of power production
1 J. Roy. Soc. Arts, 68 (1920), 346.
* Blast Furnace and Steel Plant. 8 (192"
» Ibid. 8 (19J0), 417.
fan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
49
;an be extended, and a saving effected in coal more
than equivalent on a B. t. u. basis to the gas used,
swing to the comparatively high efficiency of the gas
;ngine.
Anthracite coal is being reclaimed from the river
bottoms in eastern Pennsylvania, and from the culm
banks by washing and briquetting. Culm also,
experimentally, has been mixed with pitch or bitu-
minous coal and carbonized.
In the domestic fuel field, comprising 10 per cent
Df the bituminous consumption (or 17 per cent based
Dn both anthracite and bituminous), the greatest
economies will eventually come from increased use of
jas and carbonized fuels. The domestic field will be
one of comparatively low efficiencies, however, as
long as small-sized fuel burning units remain. Econo-
mies can be made by using care as to overheating of
bouses, particularly of unused portions of houses.
Furthermore, in the burning of gas in domestic appli-
ances it has been shown by recent experiments at
Ohio State University1 that efficiency of utilization of
the heat may vary from 16 to 40 per cent, according
to the distances of the burner from the vessel heated.
FUTURE POSSIBILITIES
For the future, with the steady and permanent
growth of fuel economy through gradual adoption of
major improvements requiring time and large capital
outlay, there is reasonable prospect that the per capita
fuel consumption in this country may reach its peak
and begin to decrease, as in fact already the coal-
consumption curve, per capita, appears to have reached
almost its high level.
electrification of railroads — The most striking
possibility among these major improvements looking
to fuel conservation is the electrification of railroads.
It has been carefully figured by A. H. Armstrong, of
the General Electric Company, for the Committee
on Electrification of Steam Railroads, National Elec-
tric Light Association,2 that by universal electrification
of steam railroads in this country a direct saving of
122,500,000 tons of coal per annum, two-thirds of the
present railway fuel consumption, would result. This
leaves water power out of account and compares on
the basis of steam generated electric power in central
stations. Deduction is made from the present steam
engine ton-mile movement for company coal haulage
on cars and tenders.
The Chicago, Milwaukee and St. Paul Railway
has had in successful operation for over 4 yrs.
large electrified portions of its system in Montana and
Washington. The electrification now totals 645 route
miles. Power is purchased from the Montana Power
Company. In a detailed statement of actual operating
costs made to the^National Electric Light Association,
R. Beeuwkes, of the Milwaukee and St. Paul Company,
compares steam operated and electrically operated
divisions in respect to those items of expense affected
by the type of motive power used. For the totals of
these items electrical operation shows about 40 per
cent lower cost, and on the one item of train loco-
' Mich. Eng.. 42 (1920), 287.
» See Reports of this Committee, 1920.
motive power cost as against locomotive fuel used,
the saving amounts to 53 per cent, not taking into
account the cost of fuel haul.
These are direct savings, exclusive of the manifest
indirect advantages accruing from the release of freight
cars by gain in speed of haulage, the release to revenue-
bearing traffic of coal cars now hauling railway coal,
the avoidance of boiler feed-water expense, the im-
provement in reliability and safety of railway service,
and the increase of property valuation around railway
terminals. Most of these items will aid in decreasing
the menace of fuel shortage in the future.
High cost of installation, and the present difficulties
in the way of financing railway betterments, will act
to retard this great step in the progress of fuel con-
servation. The passage of the recent water power
legislation by Congress should, however, exert a large
influence in furthering such projects. Water power
development under favorable government regulation
not only affords low cost power, but releases coal car
equipment in greater measure than would central
steam stations. President A. H. Smith, of the New
York Central lines, has stated:
It is known that, generally speaking, the operating cost
(exclusive of fixed charges) of electric service is less than it would
be for a similar steam service; the further extension of
electric operation on steam railroads depends to a considerable
extent upon the cost of electric power; There is a point
where the cost of coal will cause the price at which electric power
is available to the railroad to result in sufficient saving to
warrant the expenditure for electrification.
centralization of power systems — The central
''super-power" station for general power service,
gradually displacing less efficient scattered units, will
effect large saving of power-plant fuel. The war
aroused all nations to a realization of the importance
of reliable and adequate industrial power, efficiently
produced, for maintaining industry and national
effectiveness at the maximum. The British Fuel
Research Board and the Nitrogen Products Committee
have made, and are continuing, comprehensive studies
of power development centralization. Our own Con-
gress has just provided $125,000 for investigation of a
possible super-power project for the Boston- Washing-
ton district.
There are installed now in the United States, or
nearing completion, central power stations aggregating
about 350,000-kw. capacity which use coal at or near
the mine mouth. These stations are laid out for an
ultimate capacity at least double that of the present
installation. They are consuming coal at an average
rate not far from 2.0 lbs. per kw.-hr. on the switchboard,
one-third less than the average consumption of public
utility power plants throughout the country, as shown
by statistical reports of the U. S. Geological Survey.
The advantages gained from the saving of freight
on coal and in reliability of service, add their weight
to those resulting from increased fuel economy, as
shown by the above figures. Reduction of overhead
and labor cost, and of the capital charges per unit
of power output unquestionably follows centralization
into large operating units, the gain being emphasized
5<=
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
by so choosing conditions as to permit of operation
under a high load factor. For this reason a super-
power station project may well take into account the
disposal of its output in part to chemical and electro-
chemical industries which can use power at night
or during the "off-peak" periods.
By-product recovery in connection with centralized
power development commends itself, on grounds of
conservation, to most careful investigation. Direct
coal-fired steam-turbo-electric stations afford a high
degree of fuel economy, but they waste entirely a
valuable national resource in the nitrogen of the coal,
vital to agriculture and to munitions of war. The
Nitrogen Products Committee of the British Ministry
of Munitions, after thorough investigation of various
systems of power production from coal, came to the
conclusion that the net cost of power in processes
involving carbonization or gasification of coal and
burning of the resulting coke and gas under boilers
was higher than in direct coal-fired steam turbine
stations, allowing a fair market value to the by-
products. Both high- and low-temperature carboniza-
tion were considered. The possibility of using gas
engines for power was dismissed by the Committee
as entirely impracticable for stations of the size neces-
sary for competitive operation under British conditions.
The reason advanced was the very high capital cost
of such installations and the cost for labor and repairs.
These conclusions do not necessarily apply to the
American problem of centralizing power development
for miscellaneous demand under a more widely varying
load. Gas engine power plants of 50,000-kw. capacity
on blast-furnace gas, in units of 2000 to 5000 kw.,
are operating successfully in this country at costs for
labor and repairs not materially higher than those for
equivalent steam turbine plants. It appears that
with due consideration of the returns from sale of by-
products and with due care so to restrict the scale of
operation as not to overload the by-product market,
a combination may be found practicable wherein gas
power would be used to meet the steady portion of
the plant load and coal-and-gas fired boilers to meet
the variable load. Surplus gas may be sold to the
gas companies for mixing with their own manufactured
outputs, or for reinforcing the waning supply of natural
gas.
The problem of choosing the best system for pro-
duction of gas and by-products in such central stations
is a many-sided one. To go into a detailed considera-
tion of it here would take us too far afield. A very
important phase requiring investigation is the mechani-
cal problem of proper design of engine to use gases of
high hydrogen content. This may or may not have
been sufficiently worked out at the present time. .
The gas-making process to be used in such an in-
stallation would be one permitting economical recov-
ery and high yield of ammonia, and at the same time
affording the highest thermal return from the coal.
Certain processes for the complete gasification of coal
by alternate production, in the same generator, of
distillation gases and of water gas by superheated
steam, have been developed to some extent and
show indications of being capable of higher thermal
efficiency than the two-stage gasification processes
now prevailing in coal-gas and water-gas manufacture.
Such a mixed gas would have a heating value of about
320 to 350 B. t. u. per cu. ft., a ton of coal yielding
about 50,000 cu. ft. if completely gasified. Ammonia
would be obtained in higher yield per ton than from
present carbonization processes. Other valuable by-
products would be recovered. The possible use of
oxygen produced electrolytically from off-peak power
on the plant to enrich the blast in such gas generators
is worthy of investigation for the sake of lowering the
content of nitrogen and hydrogen in the gas.
It may be found practicable in the future also, when
low-temperature carbonizing processes have been
further developed, to make use of them in such a cen-
tral station to a limited extent, possibly for raising
the heating value of the mixed gas and for producing
a clean, smokeless, solid fuel for disposal to the do-
mestic and small steam trade. Central power sta-
tions, distributing electric power only, are not likely
to displace steam plants for heating purposes, or for
chemical manufacture, dyeing, bleaching, etc. It
is desirable, however, in the interests of conservation
that carbonized fuels and gas be increasingly used for
this purpose.
gas manufacture — The trend in public gas supply
is toward the abolishing of lighting standards and the
substitution therefor of a thermal requirement lower
than has prevailed in the past. New Jersey has
recently adopted a 525 B. t. u. standard; the city of
Philadelphia has just agreed to a 530 standard; Massa-
chusetts has 528, and many other sections of the
country, including Chicago, are similarly progressive.
This means a lowering of the previous requirements
by 75 or 100 B. t. u., and will result in immense sav-
ings of oil in water-gas manufacture. It will permit
also the use of by-product coke-oven gas unenriched,
and in coal-gas manufacture the steaming of retorts
to give greater yields of both gas and by-products,
the increased gas yield permitting still more conser-
vation of oil in water gas. The cracking of oil in
water-gas manufacture is a wasteful process at best,
yielding soot and tar in place of available heat units,
and having lower thermal efficiency than the direct
burning of oil as fuel.
If gas companies were to be permitted still further
reduction of heating value, together with suitable
adjustment of rates to accord with the lower costs
of manufacture, there would undoubtedly result an
extension of the use of gas, particularly in the indus-
tries, with its attendant economies mentioned earlier
in this paper.
By-product coke ovens are steadily increasing in
number, but nearly half of the coke is still being made
by the old nonrecovery process, which burns, in
effecting the coking operation, 10 per cent of the coal
and all of the gas and by-products. If the 24,000,000
tons of coke now made annually in beehive ovens
were to be made in modern recovery ovens, it is safe
to say that a reduction of 8,000,000 to 10.000,000
tons in coal consumption would result, this being an
Jan., 19;
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
aggregate of the fuel equivalent of gas and tar saved,
increased coke yield, and improvement in blast-fur-
nace fuel efficiency. Ammonia and benzene recovery
would be an additional gain.
The conservation of coal by means of coking will
grow as the outlet for coke and by-products grows.
Extension in this field is not to be considered as limited
by the metallurgical demand for coke. Coke and
coke-oven gas as fuels, however, are likely to meet
strong competition eventually from cheap power
developed in central stations and from lower-cost
gas made by complete gasification processes.
colloidal fuel — Colloidal fuel deserves mention
in connection with fuel conservation. Colloidal sus-
pensions of pulverized coal in oil permit of the same
economies in application as either oil or powdered
coal alone, and have some advantages, notably per-
mitting the use of higher ash coals, higher sulfur oils,
and many carbonaceous waste products, concentra-
tion of heating value in relation to bulk, and decreasing
of fire hazard as compared to oil. It is of important
bearing, however, on the probable future development
of this new fuel to consider the oil reserves available
to the United States for fuel purposes.
SUMMARY
In general, why is fuel conservation to be needed
when our transportation systems shall become equipped
to deliver what is required? In the first place, effi-
ciency in the use of raw materials makes for increased
financial returns; secondly, waste promotes extrava-
gance and raises the cost of living; and lastly, our
high-grade fuel reserves are being exhausted at an
alarming rate. George H. Ashley, State Geologist
of Pennsylvania, estimates1 that practically all of the
easily workable coal beds of Pennsylvania, 6 ft. or more
in thickness, will disappear in 75 to 80 yrs. at the
present rate of increase in exhaustion. Low sulfur
coals for metallurgical purposes are becoming scarce,
so much so that steel men are investigating measures
for getting along without them. Yet the low sulfur
Pocahontas and New River coals are still sold in large
part for steaming purposes, where such low sulfur
content is not an essential quality.
There is a progressive tendency, however, in America
towards greater fuel economy, and future develop-
ments are likely to decrease materially our per capita
consumption.
DISCUSSION
Dr. Porter: It will perhaps bear repetition for the sake of
emphasis, that statistics show we are progressing remarkably
well in economic utilization of coal, and this paper accordingly
is not to be taken as a criticism of progress or lack of progress.
The consumption of coal per capita in the country has not in-
creased in the last few years, in spite of the fact that our iron and
steel production has gone up 50 per cent in 10 yrs., and
industrialization in general has very greatly expanded — the
production of automobiles, for instance, has multiplied itself
nearly ten times; also the standard of living to-day is much higher
in all classes than it was 10 yrs. ago, and yet the consumption
of coal per capita has remained practically on a level. Un-
doubtedly, therefore, we have made very material progress in
the efficiency of our application of coal.
1 By private communication supplementing published reports.
Dr. T. E. Layng: Mr. Chairman. I would like to ask Dr.
Porter about that 7. 1 per cent of coal used for gas making, export,
and bunkering. The exporting of coal has been severely criti-
cized; a great many people think it ought to be used in this
country. I should like to know about what percentage of that
7.1 per cent is exported.
Dr. Porter: My recollection of the figure for export this
year is that it is running now over 2,000,000 tons per month,
from tidewater, and a little less exported to Canada, which will
at that rate bring the total for this year close to 40,000,000 or
45,000,000 tons. The figures in the paper are for 19 17. The
export figures this year are very much higher than in 1917.
The export in 19 17, as I remember, was about 23,000,000 tons,
or 4.3 per cent of the total coal. Gas making required only
about 5,000,000 tons, or 1 per cent, and bunkering the balance.
GASOLINE LOSSES DUE TO INCOMPLETE COMBUSTION
IN MOTOR VEHICLES'
By A. C. Fieldner, A. A. Straub and G. W. Jones
Pittsburgh Experiment Station, U. S. Bureau op Min-e..
1 1 rrsBi
Pa.
The rapidly increasing use of motor vehicles in the
United States has introduced an entirely new problem
in the proper ventilation of tunnels, subways, and
other confined spaces through which such machines
must pass. This problem was brought to the atten-
tion of the Bureau of Mines last November by the
New York and New Jersey State Bridge and Tunnel
Commissions with reference to the ventilation of the
proposed vehicular tunnel under the Hudson River.
This tunnel, consisting of twin tubes 29 ft. in diameter
and 8500 ft. long between entrance and exit (Fig. 1),
presented an unprecedented problem in ventilation
both on account of its length and on account of the
traffic density, which is expected to reach a maximum
of 1900 vehicles per hour.
An exhaustive study by the tunnel engineers of all
available data on the amount and composition of
automobile exhaust gas disclosed very little informa-
tion on the percentage of carbon monoxide in motor
exhaust gas from the average run of automobiles and
trucks under actual operating conditions on the road.
It was well known that carburetor adjustment and
other operating factors changed the percentage of the
poisonous constituent, carbon monoxide, from prac-
tically o to 1 2 or 13 per cent; but no safe estimate could
be made of the most probable figure without further
investigation.
A series of tests was therefore undertaken in which
passenger cars and trucks were tested in exactly the
same condition as furnished by the owners from whom
they were borrowed. No change was made in car-
buretor adjustment or any other operating condition,
the prime object being to obtain information on existing
operating conditions and not the ideal conditions of
careful adjustment under which the usual test of the
automotive engineer is made. For this reason the
data are of especial value in showing the proportion
of gasoline wasted by the average automobile owner
and truck operator through imperfect combustion.
1 Published with the permission of the Director, U. S. Bureau of Mines
and of the Chief Engineer of the New York and New Jersey State Bridg
and Tunnel Commissions.
5-
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
+/£0S£r C/TY
HUDSON RIVER VEHICULAR TUNNEL
DIAGRAM SHOWING METHOD OF VENTILATION
PROFILE 4 SECTION
SECTION Or ONE TUNNEL
Fig. 1 — Plan, Profile,
PLATE N5
1 Sections op thk Hudson River Vehicular Tunnels
»&*s
METHOD OF CONDUCTING TESTS
All cars were tested in the same condition as re-
ceived, and with the same .brand of gasoline that the
car was using. Fig. 2 shows a 2.5-ton truck equipped
with gasoline measuring apparatus (in front of driver's
seat) and exhaust gas sampling tube (back of cab).
GASOLINE MEASURING APPARATUS The gasoline
measuring apparatus shown in Fig. 3 was connected
directly to the carburetor and to a reserve supply of
gasoline, v, through the copper pipes n and c, respec-
tively.
As the car crossed the boundary lines of the test
course at the predetermined speed for the test, the
gasoline feed was switched from the reserve supply
to the measuring tube /, by closing the cock e and
opening q. At the end of the test course, a reverse
operation of these cocks switched the supply hack to
the reserve supply tank.
The exhaust gas pressure was sufficient to maintain
a rapid stream of gas through the heavy-walled rubber
tube b connected to the glass tee a on the sampler
board. The main stream of exhaust gases passed on
through the rubber tube b and was discharged into
the atmosphere through the water seal c, thus pre-
venting any air from being sucked back into the
sample.
The exhaust gas sample was collected continuously
at a uniform rate over the whole period of the test,
in a 250-cc. glass sampling tube connected to the down-
ward branch of the tee a. One observer gave his
entire attention to regulating the flow of the water
from the sample tube, by adjusting the screw clamp
at the lower end of the tube. A 5 per cent solution
of sodium chloride previously saturated with exhaust
gas was used.
jkwrmmu. .
I TEST CAft 1 .
flfeS
saH*
Riiniii
MiUli
it
Bjfl 1
•J~tm
^}
t ~~ ■ - —
^^^B
Fig. 2 — 2.5 Ton Truck, Loaded and Equipped for Road Tests
SAMPLING AND ANALYSIS OF EXHAUST GASES The
exhaust gas sampling apparatus is shown in Fig. 4.
A 0.25-in. copper tube, g, bent at right angles, with
the opening turned toward the engine, was introduced
into the exhaust pipe between the engine and muffler.
Fig. 3 — Gasoline Measuring Appar
The samples were analyzed in duplicate for COj,
02, CO, H2, N2, and CH4 on a laboratory type Burrell-
Orsat apparatus1 as used in the Bureau of Mines for
Burrell and F. M. Seibert, "The Sampling
es and Natural Gas," Bulletin 42 (1913), 43.
ad Examination.
Jan., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
53
) Sp. Gr. Baui
0.713 66.
0.731 61.
0.730 61.
0.796 45.
Benzene mixture.
ate Analyse
Hydro-
n gen
15.7
15.7
14.8
117
First
Drop
Table I — Analyses of Gasoline Used
Distillation in 100 Cc. Engler Flask, T<
30%
176
214
214
214
40%
201
239
237
228
50%
225
266
259
248
60%
250
293
282
271
347
327
345
90%
381
394
363
381
239
282
259
264
5.0
3.0
3.0
2.0
complete gas analysis. The carbon dioxide was
absorbed in potassium hydroxide solution; the oxygen
in potassium pyrogallate; the carbon monoxide in two
bubbling pipets in series, containing acid cuprous
chloride solution; and the hydrogen, methane, and
any residual carbon monoxide were determined by
slow combustion in the presence of a hot platinum wire.
Fig. 4 — Exha
MPLING ApPA
In this method of analysis any gasoline vapor and
other hydrocarbons appear as methane. In other
words, the analysis gives the equivalent methane
value for all the hydrocarbons in the exhaust gas,
and the result is correct as regards carbon content for
computing the total volume of exhaust gases from the
gasoline consumption and the carbon content of the
gasoline. This relation was checked to within 6 per
cent by actual measurement of exhaust gas in a 50
cu. ft. container.
The determination of gasoline vapor as methane
causes the hydrogen value in the analysis to be some-
what less than its true value. This error in the hydro-
gen value has no effect on the calculation of the true
value of CO, CO2, and CH4 equivalent of total hydro-
carbons.
gasoline used — -Each car was tested with the same
brand of gasoline as the driver was using when the
car was submitted for test. Analyses of these various
brands are given in Table I.
test conditions — Tests were made under the
various conditions which might prevail in the tunnel,
at different times, as for example:
Car at rest with engine idling.
Car at rest with engine racing.
Car accelerating from rest to 15 mi. per hour on level and up a 3 per
cent grade.
Car running 3 mi. per hour on level grade, up 3 per cent grade down
3 per cent grade.
Car running 10 mi. per hour on level grade, up 3 per cent grade, down
3 per cent grade.
Car running 15 mi. per hour on level grade, up 3 per cent grade down
3 per cent grade.
The level and 3 per cent grade courses were each one
mile long; the surface was asphalt on the grade course,
and part asphalt and part macadam on the level
course.
Trucks and 7-passenger cars were tested with both
light load and full load, the light load consisting of
two observers, driver, and the necessary apparatus.
One hundred trucks and passenger cars were tested
in the entire investigation; twenty-three were tested
under winter conditions, and seventy-seven were tested
under spring and summer conditions.
RESULT OF TESTS UNDER WINTER CONDITIONS
A summary of the results of tests of twenty-three
passenger cars and trucks under winter conditions is
given in Tables II, III, and IV.
Table II — Average Results of Tests on Eleven 5-Passenger Cars
Condition
of Test
Engine racing
Engine idling
Up 3 per cent
grade :
15 mi. per hr.
10 mi. per hr.
3 mi. per hr.
Down 3 per cent
Com- Lbs.
plete- Air
Mi. ness of per Lb.
per Com- Gaso-
Gal. bustion line
15 :
Level i
15 r
. per hr.
. per hr.
. per hr.
-ade:
i. per hr.
. per hr.
. per hr.
24.5
22.8
9.9
16.9
16.9
7.5
12.6
13.0
12.2
12.3
12.3
12.9
13.4
12.7
12.6
Analysis of Exhaust Gas
. Per cent by Volume
CO2 Oi CO CHi H2
9 1 1.5 6.9 0.8 3.0 ;
10.2
9.9
9.8
9.5
8.6
9.5
9.3
9.3
9.1
1.4
1.4 .
1.5 6.0
2.2 5.6
1.9 6.3
1.6 6.7
0.6
0.5
0.6
6.5 0.9
7.0 0.7
" 0.7
2.6
2.6
3.0
0.8
0.6
0.6
2^7
,i'ii
78.8
79.2
79.6
79.3
78.8
79.0
Table III — Average Results of Tests on Seven 7-Passenger Ca
Condition
of Test
Engine racing
Engine idling
Up 3 per cent
15 mi. per hr.
10 mi. per hr
3 mi. per hr.
Down 3 per cent
15 mi. per hr
10 mi. per hr.
3 mi. per hr.
Level grade:
15 mi. per hr.
10 mi. per hr.
3 mi. per hr.
Com- Lbs
plete- Air
Mi. ness of per Lb
per Com- Gaso-
Gal. bustion line
Analysis of Exhaust Gas
* Per cent by Volume —
CO; O- CO CH4 Hi
7.3 3.5 7.8 1.4 2.9
8.0 4.3 6.3 1.2 2.0
16.9
19.4
9.4
14.0
14.9
15.3
6.4 6.0 6.8
6.9 5.0 6.:
6.9 5.0 6.3
2.4
2.2
2.4
6.5 0.9 2.8
6.4 1.1 2.8
7.0 1.0 3.0
54
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
^ ft
< °<
*'
" s. -,' % J- 3!v "~ ^4*
?
as%
- =. S S ^ *< 2* r'*^ =5P--dL
^ "^
ip-^ 5^ -t:
Vj 5
I — 1 — ! — > — ! — ! — J-—1 — ! — ! — ' ' '^ ' — ' — ' — ' — ' ' J — ' — ' — \_
erageso posse nper roaring cars
i s=~ — ^ ° ° Averages of II- 5 passenger touring cars
§
7 ^ X X Averages of 5lrucks; l-lton,h$ ton, _
T_ \ . Z speed trucks and 1- 10 passenger bus.
\
C5
~1 \ ~[_ S,
-h-"
\
/ .. v / *s
5
V
' ^'"v X _r V
*
\
A .-^__^ i, V 7- -.r- V.
\
7 T '^%, \ -f 2"v \ 4-
f
t * % s NZ v>^^ \,_
- Z N^ ^2' ^sO^
£ -
C-
^-/ ^ J' 'C'Ov,
s
v
tt ^S ;VSJ'
^
'
/
/
it.
Tr ir ^^ >r_
■3
\
S
iic5-'
>
y
10 ,nn
$
L S, 3.--<l ""^
?
L J>=.«^'"!* ^ ;>t, ^S.
V
, ^< "H^;'~. ^^^ >' *s j— 2E~i
^50'
!s»
S
7 ? J<s^^-,r-^r:.ir--s-^ ~1-ii
<^
u^
.<$*-- ^ — -^,
1
0
S.
0
5
>
D
%
a
m
j
PE
r
rcl
•^ S t^ t* 1^ 8 '^ t* "H
»1 ^ !Q ^ *>> ^ ^ <•>
VI GRADE. UP 3 PER CENT GRADE ON LEVEL GRADE
(DHR Winter
Fig. 5 is a graphical presentation of the important
figures as regards tunnel ventilation, namely, the aver-
age per cent of carbon monoxide in the exhaust gas,
the gallons of gasoline consumed per hour, and the
cubic feet of carbon monoxide per hour.
Table TV — Average Results of Tests on Five Light Trucks
Condition
per
of Com-
of Test
Gal.
bustion
Engine racing
64
Engine idling
57
I p 3 per cent
grade:
15 mi. per hr.
11.6
73
10 mi. per hr.
10.7
64
3 mi. per hr.
5.9
63
Down 3 per cent
grade:
15 mi. per hr.
21.6
63
in mi. per hr.
17.1
56
3 mi. per hr.
7.7
56
Level grade:
15 mi. per hr.
is.:
67
10 mi. per hr.
12.9
63
3 mi. per hr.
6.1
62
er Lb.
Gaso-
line
CO*
Analysis of Exhaust Gas
— Per cent bv Volume .
Ot CO CHi Hi N:
11.3
12.0
8.3
6.6
2.0
4.2
7.7
7.1
1.2
2.1
4.0
3.7
76.8
76.3
12.5
11. 0
11.2
9.6
9.0
8.1
1.5
1.3
1.6
6.2
7.0
8.5
0.6
1.3
1 .2
3.0
4. 1
4.4
79.1
76.2
12. 1
ii .:
12.3
7.5
6.5
6.5
3.1
4.1
3.6
7.1
7.7
7.5
1.4
3^6
3.4
77.4
7(. 1
76.8
11.8
12.0
12.0
9.0
7.7
7.4
1.5
2.1
2.9
7.0
8.0
7.7
1.1
1 .3
1.3
3.4
3.8
4.1
78.0
77.1
76.6
discussion of results of tests — It will be noted
from the plotted results that the average percentage
of carbon monoxide for each class of vehicles varies
between 5 per cent as a minimum and 9 per cent as a
maximum, the larger percentages tending to be pro-
duced when the engine is racing, idling, or running on
light load on the low gear at 3 mi. per hr. However,
the greatest amount of carbon monoxide per hour is
generated under conditions of greatest load, i. e.,
when accelerating or running up grade at the highest
speed.
The relative quantity of carbon monoxide produced
depends primarily on the gasoline consumption as
shown at a glance by the similar rise and fall of the
"gasoline" and "cubic feet of carbon monoxide"
curves.
The average percentage of carbon monoxide under
all conditions of test for each class of vehicles was
5-passenger cars 6.3; 7-passenger cars 6.8; and light
trucks 6.9.
These values are consistently higher than reported
by previous investigators. The most extensive road
tests heretofore made in this country are those re-
ported by Herbert Chase* in 1914- A comparison
of his results with the Bureau of Mines tests is given
in Table V.
Table V — Comparison
Hxhaust Gas Analyses of Tests by
y the Bureau op Mines
Average Exhaust Gas Analyses
-Per cent by Volume-
r — Carbon Monoxide—*
Chase B. of M. Din*.
Cars standing, engine idling 2.6 7.1 4.5
Cars accelerating to 10 mi.1
per hr. from rest 1.9 5.6 3.7
Car^ running 10 mi. per hr.
on level grade 2.3 6.7 4.4
Cars running 15 mi. per hr.
on level grade 2.5 6.3 3.8
Average 2.3 6.4 4.1
1 15 mi. per hour in Bureau of Mi
-Carbon Dioxide
Chase B. of M. Diff
8.4
10.1
9.7
9.5
9.4
9.5
8.8
9.0
0.3
0.6
0.9
0.5
0.6
'Exhaust Gas Analys
tests.
for Economy," The Automobile, 30 (Februa
Jan., iqj i
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
55
The average of all comparable tests shows 0.6 per cent
more carbon dioxide and 4.1 per cent less carbon
monoxide in the Chase tests than in the Bureau of
Mines tests.
The cause for the large difference in carbon monoxide
percentages is not clear, in view of the agreement in
the carbon dioxide results. If the carburation and
combustion of the less volatile present-day gasoline
is less efficient than in 1014 we should expect a corre-
sponding difference in the carbon dioxide percent-
ages.
Hood, Kudlich and Burrell,1 have shown that the
proportion of carbon monoxide in exhaust gases varies
from o to about 14 per cent, the amount depending
on a number of variables, chief of which are:
( 1 ) Ratio of air to gasoline
(2) Completeness of vaporization and mixing
(3) Speed of engines
(4) Temperature of air and jacket water
(5) Quality and time of spark
(6) Degree of compression
(7) Quality of gasoline or motor fuel
In view of this large number of variables it is not
surprising that extremely large variations in exhaust
gas composition were obtained in testing motor vehicles
taken from ordinary service without any adjustment
prior to test and driven in a variable manner with foot
accelerator or hand throttle by different drivers over
an approximately smooth course, but yet one with
some rough places requiring opening and closing the
throttle to maintain a constant speed.
It is, therefore, not possible to draw conclusions on
the effect on exhaust gas composition of the various
factors just enumerated, except with regard to the
first one, namely, "ratio of air to gasoline," or carburetor
adjustment.
EFFECT OF CARBURETOR ADJUSTMENT A Study of
all the tests shows that the variation in exhaust gas
composition due to carburetor adjustment is far greater
than any other factor; they do not throw much light
on the advantage of any particular make or type of
carburetor, nor should any conclusions be drawn
as to the merits or demerits of any particular make
of car.
Table VI — Best and Poorest Results Obta
SENTATIVE MAKES OF PASSENGER C
(All cars loaded)
&m -a § fl
1* ° :« si
3 a S. £« til
■gj g "~ So
to S P< fc
15 27.30 105.8 100
15 13.26 84
15 18.61 66.8 93
IS 11.16 61
15 15.39 44.5 90
15 10.66 59
10 6.55 36.2 87
10 4.81 65
15 10.26 49
O § fr<
1 C 5-passenger
9 C 5-passenger
11 G 7-passenger
10 G 7-passenger
84 X V.-t. truck
76 X »A-t. truck
38 Y 3.5-t. truck
57 Y 3.5-t. truck
44 D 5-passenger
Exhaust Gas Analysis
^J
, — Per cent by Volume — .
CO- O2 CO CH. H2
<
13.0 2.6 0 0 0
16.7
11.8 0.8 3.7 0.3 1.6
13.5
9.3 5.4 1.3 0 0.1
20.1
7.5 2.1 9.3 1.4 4.0
10.7
10.7 3.9 1.7 0.5 0.2
16.6
7.1 0.7 10.7 1.0 5.1
10.3
12.9 0.3 1 .9 0.8 0.4
13.9
7.5 0.8 10.6 1.0 4.9
10.2
5.3 1.0 13.2 1.9 7.1
9.0
Table VI gives a comparison of the best and poorest
tests obtained on several well-known makes of passenger
and greatest mileage of any car tested. Car No. 44,
cars and trucks. Car No. i had the best gas analysis,
also a 5-passenger car, had the poorest gas analysis
and the lowest mileage in its class. Both cars operated
without any apparent difficulty throughout the tests.
Car No. n did not operate smoothly and lacked flexi-
bility at low speed due to the mixture being too lean.
However, the mileage per gallon of gasoline was much
higher than the other cars in the same class. At
speeds above 15 mi. per hr. it operated smoothly and
gave a good illustration of the tremendous quantity
of fuel that may be saved by using lean mixtures.
It should be noted that in each case the car with the
leaner mixture shows the largest mileage per gallon of
gasoline. The percentage increase in mileage ranges
from 36 to 106 per cent.
The effect of various carburetor adjustments on an
individual car is shown in Table VII.
Table VII — Effect of Carburetor Adjustment on Gasoline Con-
sumption and Exhaust Gas Analysis
4-cylinder roadster, engine 41/b in. bore X 41/? in. stroke; Johnson
carburetor; intake air and manifold heated; using gasoline 66.4° Baume,
distillation 10%, 127° F.; 50%, 225° F., dry, 441° F.; average 239° F.
Tests at 15 mi. per hr. ascending a 3 per cent grade of asphalt in good con-
dition.
Gal.
per
Miles
per
Gal.
14.9
13.9
10.6
Mile
0.067
0.072
0.094
0.1142
-Exhaust clear, mixture too Ie
Qxhaust Gas
Analyses, Per cent
CO. O2
13.4 1.7
12.0 1.4
10.2 0.3
6.5 1.2
CO CH.
0.2 0.0 83.5
2.0 1.1 0.0 83.5
6.4 0.8 2.4 79.9
1.6 1.0 6.4 73.3
ithout
9.9 56
to operate
choke 1/4
■ .,1 .
"Gasoline Mine Locomotives
u of Mines, Bulletin 74 (1915)
Relation to Safety and Health,'
b — Exhaust clear, operation satisfactory,
part of test.
c — Exhaust slightly smoky; operation satisfactory. Car had good
"pick-up."
d — Smoky exhaust; mixture seemed too rich for satisfaT*tory operation.
Before putting this car. through the standard series
of "road tests the driver, an automobile mechanic, was
asked to place the carburetor in good adjustment.
He set it after the engine was warmed up to running
conditions, at i7/i6 turns of the needle valve. As
shown in the table this setting produced 6.4 per cent
carbon monoxide and 10.2 per cent carbon dioxide, a
little better than the average analysis of all the cars
tested. Tests were then repeated under identical
conditions with both richer and leaner settings. It
was found that i1/* turns of the carburetor needle
gave 12 per cent C02 and 2.0 per cent CO; and 31 per
cent greater mileage; also the car operated satisfac-
torily.
This test is typical of the great majority of the
passenger cars and trucks tested, they were invariably
adjusted safely on the rich side for greatest flexibility
of operation rather than for maximum economy of
gasoline.
REASONS FOR EXISTING USE OF RICH MIXTURES
One pound of ordinary motor gasoline of to-day,
such as was used in the tests just described, requires
approximately 15 lbs. of air for complete combustion.
56
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
•=t^
3§
■\
\ *'-
/
s "
;
/
\«!
/
<
/
/
-k
r
,5
N
i
>s
&
^"^
p
1
|
\ 1
/
\ \
/
\ '
,
/
/
/
1
\
/
,
1
J
!
zr.
18 n lb 15 14 13 12 II 10 9 B
RATIO OF AIR TO GASOl/Nf, POUNDS
ig. 6 — Curves Showing Relation between Braki
Thermal Efficiency at Various Air-Gasolin:
Berry
Horse Power and
Ratios. After
The maximum thermal efficiency is obtained at about
16 lbs.1 of air to 1 lb. of gasoline, and the maximum
power with 12 to 13 lbs. of air.2 Herein lies the reason
for the use of rich mixtures. The average driver
demands first of all power and flexibility of operation.
He sets his carburetor adjustment rich enough to
give good operation with a cold engine and for slow
driving in heavy traffic, with plenty of reserve power
for hill climbing and bad road. If he errs somewhat
on the rich side it does not become manifest in loss of
power, but only in the increased gasoline consumption,
which in many instances does not concern him at all.
An inspection of the average thermal efficiency and
power curves of Fig. 6 shows that the proportion of air
in the mixture can be reduced to 9.0 lbs. of air to 1 lb.
of gasoline with a loss of only 9 per cent in power,
although economy and efficiency are tremendously
reduced.
Fig. 7 shows the relation between the air-gasoline
rates and the percentage of carbon monoxide in the
exhaust gas for the first 23 passenger cars and trucks
tested at 15 mi. per hr. running up a 3 per cent grade.
The air ratios varied from 15.8 with about 1.0 per
cent carbon monoxide, to 9.7 lbs. air with 12.3 per
cent carbon monoxide. The average air-gasoline
ratio was 12.4, with an average carbon monoxide per
cent of 6.3, practically the exact figure for maximum
power. Obviously, carburetors are adjusted in prac-
tice for maximum power and not for maximum thermal
efficiency and economy of gasoline.
The average loss of gasoline due to the continuous
operation of a car at the point of maximum power is
shown in the accompanying computations from average
exhaust gas analyses, heat in the gasoline, and heat
in the unburned exhaust gas constituents.
1 With this mixture the engine develops about 85 per cent of its max-
imum power.
2 O. C. Berry, "Mixture Requirements of Automobile Engines," J,
Soc. Automotive Euc.. 5 (1919), 364.
1 nl ..hi dioxide
Level Grade
Per cent
8.9
2.3
Ascending 3 Per
cent Grade
Per cent
9.6
1 .3
0.9
0.6
Total
Cu. ft. exhaust gases at
29.92 in. Hg
65'
I-
100.0
ind
. . . 988
100. 0
Composition of Gasc
Sp. Gr 0.713
Carbon 84.3 per cent
Hydrogen 15.7 per cent
Calorific value . ... 21.300 B. t. u. per lb.
130,000 B. t. u per gallon
Exhaust Ga
prom I Gal. Gasoline oi
988 X 6,3 = 62.2 i
988 X 0.9 = 9.1 i
988 X 3.0 = 2.9 .
Level Grade Tests Contains
a. ft. CO
j. ft. CHi
J. ft. Hi
Total Heat in Unburned Gases pe
B. t. u.
62.2 X 320' = 19,900
38,500
1 Gross B. t. u. per cu. ft. at 65° F. and 29.92
38,500
130,000
29.6 per cent of the total heat of the gasolii
the form of combustible gases.
Gallon Gassune
= 29.6 per cent
goes out ia the exhaust
o
>- h
5 h
<:>
o
',.
i
0
0
<
ox\
8
*
1
1 _
\
c
o
5<
N^C
X
>
t
0
«.
X
pounds of air per pound of gasoline
Fig. 7 — Curve Showing Relation between Air-Gasoline Ratio and
Carbon Monoxide in Exhaust Gas of 23 Cars Tested at 15 Mms
per Hour Running up a 3 Per cent Grade
RESULTS OF TESTS UNDER SPRING AND SUMMER
CONDITIONS
While the data just given for winter conditions
show surprisingly large losses due to incomplete com
bustion, incomplete returns on the summer tests show
even larger losses. As shown in Table VIII, passenger
cars and the lighter trucks average from 6.0 per cent
to 7.6 per cent carbon monoxide.
Table VIII — Comparison of Percentage of Carbon Monoxide in
Exhaust Gas in Winter and .summer
Average Per cent Carbon
Type of Car . — Monoxide in Exhaust Gas1 — .
Winter Summer
5 -passenger car 6.3 7.6
7-passenger car 6.8 7.4
Trucks up to 1.5 tons 6.9 7.7
Trucks 1 .5 to 3 tons ■. 6.9
Trucks 3.5 to 4.5 tons 6,3
Trucks 5 tons and over 6.0
' Average of all conditions of test previously described.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
5 7
It appears that most cars are adjusted to start easily
in cold weather and then are permitted to remain the
same during the entire summer, thus increasing the
wastage of gasoline during the period of greatest con-
sumption.
Probably 50 to 75 per cent of the present daily loss
of gasoline due to the prevalent use of rich mixtures
could be prevented by proper adjustment of existing
forms of carburetors. Unfortunately, most drivers
do not care to change even a simple manually controlled
adjustment from the dash. They set it rich enough
for the heaviest load and then leave it the same for
all duties.
AUTOMATIC CARBURETOR NECESSARY
It is hoped that the results of these 23 tests and the
remaining 78 which will be published at an early date
will serve as a stimulus to automotive engineers to
design an automatic carburetor as suggested by
W. E. Lay,1 who states:
The ideal carburetor would be arranged so as to
supply primarily the mixture giving the best efficiency and
automatically supply the necessary additional fuel only when
operating conditions require it. The provisions made should
be so adequate that the economy under proper operating condi-
tions will never be sacrificed to obtain more power or better
operation under exceptional conditions.
SUMMARY
Road tests under winter conditions for the purpose
of determining the amount and composition of motor
exhaust gas from automobiles and trucks of various
sizes when operated on grades and at speeds similar
to those that will prevail in vehicular tunnels have
shown that:
(1) The exhaust gas composition of individual
machines varies greatly, and the controlling factor
is the air-gasoline ratio produced by the carburetor
adjustment.
(2) The percentage of carbon monoxide for the
majority of cars lies between 5 and 9 per cent.
(3) The average percentage of carbon monoxide
for 23 cars tested was 6.7 per cent, which is practically
the ratio for developing maximum power.
(4) The combustible gas in the average automobile
exhaust from one gallon of gasoline amounts to 30
per cent of the total heat in a gallon of gasoline.
(5) The great majority of motor cars and trucks
are operated on rich mixtures suitable for maximum
power but very wasteful from the standpoint of gaso-
line economy.
(6) On the average, carburetors are set in the winter
and not changed in the summer, as shown by the
higher percentages of carbon monoxide found in the
summer test.
(7) A simple and convenient dash adjustment for
instantly throwing a carburetor adjustment from the
condition of maximum thermal efficiency to maximum
power for steep hills and for starting the machine
would probably result in saving 20 to 30 per cent of
1 "Saving Fuel with the Carburetor," J. Soc. Automotive Eng., 7 (1920).
189.
the gasoline used, not a small item when we consider
the total gasoline used by the 7,500,000 automobiles
and trucks operating in 1919.
(8) An automatic self-changing carburetor which
gives rich mixtures for power only when needed would
be the solution of the problem of saving gasoline losses
from incomplete combustion.
DISCUSSION
George G. Brown: Mr. Chairman, I have been very much
interested in this proposition of combustion gas in the car-
buretor. Back in 1913, the time so many analyses were made,
the truck drivers were more careless with their carburetors than
they are now, although we found that some of them did fairly
well day after day under the same truck driver. One reason
for this change is that the carburetors have been improved.
But here are a few facts which may be interesting and which
have been checked by the Royal Automobile Club of England.
They have found the maximum power for a car runs about 12
parts by weight of air to 1 part of gasoline. That would give
an excess of gasoline, and therefore some carbon monoxide.
The maximum thermal efficiency runs about 17 parts of air by
weight to 1 part of gasoline. That is an excess of air; and for
complete combustion, depending on the kind of gasoline used,
it runs about 14.5 to 15 parts of air. As has been pointed
out, the key to the whole situation is really in the design of a
carburetor. A properly designed carburetor should give 12
parts of air to 1 part of gasoline when climbing a hill, and when
running on a level it should automatically give 17 parts of air
to 1 part of gasoline. In other words, what is wanted is the
uniform mixture for maximum economy; we want what most
carburetors do not give, a light mixture when the engine is
running light, when running at high speeds, and a heavy mix-
ture when the engine is running slow on heavy load. Most of
the carburetors on the market at the present time have just
the reverse action, because at a higher velocity all of the air
going through the carburetor causes a greater proportion of
gasoline to be drawn into the mixture than is the fact under
reverse conditions, so that in going at higher speeds we get a
richer mixture. At the point where you get the richest gas you
want the weakest.
We have been working on this, and we have got
thus far: We can get a light mixture when the engine is running
light and a heavy mixture when it is running heavy. If we can
get a carburetor on a car so that it will answer automatically
and scientifically all changes in road conditions and all changes
in temperature, and if we can then locate the carburetor so that
the driver cannot adjust it except with the aid of a service man,
I think we have gone a long way toward getting the maximum
efficiency out of the engine. We have got everything lined up
except the temperature, and we can work that out very
shortly.
I am not prepared to go into the theory of the whole proposi-
tion with you but, I thought I would bring this out at this time-
not only the adjustment of the carburetor, but what you want is
a scientific, fool-proof carburetor, and there is nothing of that
kind that I know of in the market at the present time.
Mr. R E. Wilson: I would like to ask if the amount of car-
bon monoxide is going to make the ventilation in that tunnel a
particularly difficult matter?
Mr. FiELDNER: No, it doesn't make it particularly difficult,
but it will take some power and machinery to do it. The engi-
neering difficulties are not so great as one might think. They
have to put through about 1,500,000 cu. ft. of air per minute.
In reference to Mr. Brown's remarks on carburetors, it is inter-
esting to point out that the average of the air-gasoline ratio on
the 10 cars tested by the Bureau of Mines was something like
5*
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. No. 1
12.5; in other words, carburetors are adjusted for maximum
power rather than maximum thermal efficiency.
.Mk. Brown: We figured out a few years ago that running
on a theoretically perfect combustion basis, that is, about 15
parts of air to 1 of gasoline, the mileage of a Ford would be a
little over 26 mi. per gal.; if you are getting 20 mi. per
gal. on a Ford you are getting what should be obtained without
any excess gasoline, without any carbon monoxide in your
exhaust. We have obtained as high as 38 mi. per gal.
with careful adjustment and careful driving, but over a long
period of driving through streets, etc., we have averaged over
28 mi. per gal. On the basis of getting a very light mixture,
we can get 26 mi. to a gallon on a Ford. Usually a man makes
22 or 23. A man in Long Island told me the best he knew was
19.5. There is a tremendous saving to be made there, aside
from the fact that we are relieving the engine from pumping
through 1,000,000 cu. ft. of air in a minute, because we have
found an average of less than 1 per cent carbon monoxide under
all conditions.
ENRICHMENT OF ARTIFICIAL GAS WITH NATURAL GAS
By James B. Garner
Director op Research and Development Department, Hope and
Peoples National Gas Companies. Pittsburgh, Pa.
ABSTRACT
The project of enriching artificial gas with natural
gas is of widespread interest because of the possibility
it offers of providing a supply of a clean domestic fuel
gas, uniform in quality, and of sufficient volume to
meet the requirements of the public. This is par-
ticularly the case in regions where natural gas has been
used.
There are in nature three potential sources of raw
materials adequate for the production of a future do-
mestic supply of manufactured gas: bituminous shale,
oil, and coal. Artificial gas, as produced on a com-
mercial scale, consists of the following varieties: shale
gas, oil gas, producer gas, water gas, carbureted water
gas, coal, and coke-oven gas.
Shale gas has been made and utilized with some de-
gree of efficiency in Scotland, and considerable experi-
mental work has been done in the United States look-
ing toward the development and utilization of our
vast beds of bituminous shale. With our present lack
of engineering and technical knowledge regarding the
use of bituminous shale as the future source of an
adequate supply of manufactured gas, its geographic
location and availability is such that bituminous shale
cannot now be considered as an immediately available
raw material.
Oil gas is the domestic gas of San Francisco, Oak-
land, Los Angeles, Portland, Tacoma, and San Diego.
Oil is used as the basis of gas manufacture in these
western cities because of the nonavailability of cheap
coal, while cheap oil is available. In all other sec-
tions of the United States, gas-oil or other products
from petroleum are so expensive that the manufacture
of oil gas is economically prohibited.
Producer gas, water gas, carbureted water gas,
coal, and coke-oven gas have all been made and used
with greater or less success for many years past.
Coal seems to be the only raw material which is at
present available as a basis for a future gas supply.
Producer gas is unsuited for use as a domestic gas for
two reasons:
1 Its high content of inert nitrogen, and (2) the excessive
cost of cleaning, cooling, and distributing.
Coke-oven and coal gas of a high quality are made,
but on account of the cost of installation and non-
flexibility of the plants wherein these gases are pro-
duced, these processes of manufacture are unfitted for
use in meeting the peak-load requirements of an ade-
quate domestic supply.
Blue water gas, although lower in heating value than
coke-oven or coal gas, can be made most economically;
and in a plant which is cheap in its cost of installation
and flexible in its operation, blue water gas is at present
the only rational basis for an adequate supply of
clean, uniform fuel gas to meet peak-load public re-
quirements. Blue water gas carbureted by means of
gas oil cannot, under present market conditions of
crude petroleum, be the kind of commercial gas for
an adequate public supply. In addition, this use of
the waning supply of crude petroleum is far from the
conservation of one of our greatest natural resources.
In order to carburet water gas of an initial heating
value of 325 B. t. u. per cu. ft. so that it will have
a heating value of 570 B. t. u. per cu. ft., it is
necessary to use 3 gal. of gas oil per 1000 cu. ft. of
gas. The present market on gas oil is 12 cents per
gallon. The enriching of 1000 cu. ft. of gas thus costs
the producer 36 cents without any overhead, produc-
tion, or depreciation charges. Natural gas, as pro-
duced in the Appalachian and Mid-Continent fields,
has an average heating value of 1100 B. t. u. per cu.
ft. It can readily be seen that less than 80 cu. ft.
of natural gas has an enriching value equal to one
gallon of gas oil. Natural gas can be mixed with blue
water gas easily, safely, and without any overhead,
production, and depreciation charges, and is, therefore,
the ideal enricher of water gas, in regions where nat-
ural gas is available.
The manufacture of a domestic supply of water gas.
enriched with natural gas, serves two purposes:
(1) It conserves in the highest possible manner our natural
resources of coal, oil, and gas.
It insures to the public an adequate supply at all times "I
a clean, uniform gas at the lowest possible cost.
Natural gas companies should no longer sell natural
gas as such at ridiculously low rates, but should utilize
it in the highest possible way, viz., as a means of en-
riching artificial gas. Such use of this natural resource
will insure to the public, for many years to come, a
supply of gas at a cost otherwise impossible.
THE CHARCOAL METHOD OF GASOLINE RECOVERY
By G. A. Burrell, G. G. Oberfell and C. L. Voress
Inasmuch as this paper has already been published
in another journal it is not included among the sym-
posium papers here.
Jan.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
ORIGINAL PAPERS
NOTICE TO AUTHORS: All drawings should be made with
India ink, preferably on tracing cloth. If coordinate paper 'is
used, blue must be chosen, as all other colors blur on re-
duction. The larger squares, curves, etc., which will show in
the finished cut, are to be inked in.
Blue prints and photostats are not suitable for reproduction.
Lettering should be even, and large enough to reproduce
well when the drawing is reduced to the width of a single column
of THIS JOURNAL, or less frequently to double column width.
Authors are requested to follow the Society's spellings on
drawings, e. «., sulfur, per cent, gage, etc.
STUDIES ON THE NITROTOLUENES. V— BINARY
SYSTEMS OF o-NITROTOLUENE AND
ANOTHER NITROTOLUENE'
By James M. Bell, Edward B. Cordon, Fletcher H. Spry and
Woodford White
University of North Carolina, Chapel Hill, N. C.
Received November 8, 1920
The third paper of this series, by Bell and Herty,2
records the results of studies of the binary systems
of the components: ^-nitrotoluene (MNT), 1,2,4-di-
nitrotoluene (DNT), and 1,2,4,6-trinitrotoluene (TNT).
The present paper contains the results of work upon
three binary systems in each of which o-nitrotoluene
(ONT) is one of the components, and one of the above
nitrotoluenes is the other component.
PURIFICATION OF THE NITROTOLUENES
Crude MNT was crystallized several times from
hot alcohol solution, filtered by suction, and allowed
to dry in a warm place. A constant melting point
(51.3 ° corr.) accorded well with the earlier work.3 In
a similar way DNT and TNT gave constant melting
points of 60.55° (corr.) and 80.35° (corr.), respectively.
Crude ONT was distilled under reduced pressure. The
distillate was then partially frozen and the mother
liquor decanted from the crystals. The crystals were
allowed to melt and this liquid was again partially
frozen and the mother liquor decanted from the crys-
tals. After several such treatments, in which the im-
purities in the original material are removed in the
liquid, a constant freezing point of — 10.5° was reached.
Frequently a supercooling of ONT to about — 16° was
observed before crystals appeared, after which the
thermometer rose to — 10.5°. On several occasions
another rise in temperature to — 4.45° was noticed,
accompanied by a crackling sound. The existence of
1 This paper is the fifth of a series dealing with the freezing points and
thermal properties of the nitrotoluenes, the investigation having been
undertaken at the request of the Division of Chemistry and Chemical
Technology of the National Research Council.
2 This Journal, 11 (1919), 1 124.
3 In the paper by Bell and Herty (page 1125) there is a discussion of
the various values for the melting point of MNT, many citations giving
54° while others are around 51.5°. We have recently found an explanation
of the discrepancy in an article by Holleman (Rec. trav. chim., 33 (1914),
5), who found a sample of the material originally used by van der Arend.
The melting point given by the latter, 54°, was the original of all the cita-
tions giving the higher value. From a redetermination of the melting point
with the same material as originally used, Holleman concludes that the pub-
lished value 54.4° is a misprint for 51.4°. This brings all the determinations
within a few tenths of a degree of agreement.
two freezing points indicates the existence of two dif-
ferent crystalline forms of ONT, an observation which
we found had already been made by several investiga-
tors.1
MELTING POINTS OF THE TWO FORMS OF ONT
The metastable form of ONT (a-ONT) always ap-
pears first, and frequently remains unchanged for sev-
eral hours even when the freezing liquid is stirred
vigorously. Where the stable form of ONT (/3-ONT)
was desired, von Ostromisslensky cooled the liquid to
— 50° or — 60 ° in solid carbon dioxide. At first the
metastable form appeared, but after a very short time
transition to the stable form took place with a crack-
ling sound. During our work a much simpler method
was found, based on an observation made in an at-
tempt to obtain the eutectic temperature for MNT
and a-ONT. All attempts to find this temperature
failed because of the change of metastable ONT to
the stable form. To get the stable form we seeded
liquid ONT at about — 10° with a few crystals from
the eutectic mixture above described. The tempera-
ture immediately rose to — 4-45° (corr.) and remained
constant to complete solidification. This material was
kept in a low-temperature bath for "seed" purposes.
is
10
MNT
ONT
These temperatures are very close to those found
by von Ostromisslensky: — ■10.56° and — 4.14°. The
earlier results, however, are more at variance with
these. Thus, von Schneider2 gives — 14.8°, and Lep-
sius, in a private communication to Knoevenagel, gives
1 von Ostromisslensky, Z. physik. Chem., 67 (1906), 341; Knoevenagel,
Ber., 40 (1907), 508; both of whom cite D. R. P. Kl. 120, No. 158,219.
1 Z. fhysik. Chem., 19 (1896), 157.
6o
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
- — 9. 40 and — 3-6°, the former figure being later revised
to — 8.95°.
The du Pont Company has kindly furnished us with
results on the binary system MNT-ONT, in which
the freezing point for MNT accords well with our de-
termination, but the freezing point for ONT is given
as — 3-3°- We are now unable to explain the rather
large difference between these results ranging from
— 3. 3° to — 4-45°. In our work we purified several
different lots of ONT by the method described above,
which is also the patented method cited above, and
obtained a constant freezing point unaltered by fur-
ther crystallizations.
BINARY SYSTEM: MNT nM1
The freezing points and compositions of the mix-
tures for this system are given in Table I and Fig. 1.
Table I — Binary System (j-Nitrotoi.usne-o-Nitrotoi.ubnk
Table II — Binary System: Dinitrotoluene-o-Nitrotoll
Per cent by
Weight
Freezing
MNT
ONT
Point
Solid Phase
0
KID
—4.45°;
10
90
8 !
0-ONT
20
80
—12.8 :
30
70
—6.13 |
40
60
6 !2
50
50
16.84 1
60
70
40
30
25 65
32 58
MNT
80
_'0
39 :: \
90
10
45.68
100
0
51,3 1
In the figure the points are observed to fall on two
curves, one representing mixtures from which MNT
is separating and the, other representing mixtures from
which /S-ONT is separating. The eutectic temper-
ature and composition are ■ — 15.73° and 26 per cent
MNT. We were able also to obtain one point on the
curve where a-ONT is the solid phase. This curve
begins at the freezing point for the metastable ONT
and is roughly parallel to the curve for the stable ONT.
In the diagram the unbroken lines represent conditions
which it was possible to attain, the unstable conditions
appearing as dotted lines.
A study of this system has already been made by
Holleman and Vermeulen,2 although their paper was
not found until the present work was completed. It
is interesting that they were able to follow to the
eutectic point the curve for a-ONT, and give for the
eutectic temperature — 20.6°. The unpublished re-
sults of the du Pont Company and the results of Holle-
man and Vermeulen are in general in close accord with
the present results. Our curve for MNT lies slightly
higher than the du Pont curve, which in turn is slightly
above the curve of Holleman and Vermeulen. The
three sets of results for the ONT curve also show dif-
ferences, as the curves cross at a slight angle. The
eutectic temperature is given as — 14. 6°, as — 15.73°,
and as — 16. 40, the first by Holleman and Vermeulen
and the last by the du Pont chart.
BINARY SYSTEM: DNT-ONT3
The data for this system are represented in Table
II and in Fig. 2. In this case, like the preceding
system, there are two curves crossing in a eutectic
point. The temperature and composition for the
! Experimental work by F. H. Spry.
' Rtc. Iras, chim., 33 (1914), 1.
1 Experimental work by E. B. Cordon.
Per cent by Weight
Freezing
DNT
ONT
Point
Solid Phase
0
100
— t.45°l
5.6
9.9
94.4
90.1
-6.2
—7.7
— 10.5 J
0-ONT
18.2
81.8
30
70
5.30 }
40
60
19.50
50
50
29.19
60
70
40
30
39.39
48.36
DNT
80
20
55.46
90
in
62.55
100
0
69.55
eutectic are — 11.45° and 21 per cent DNT. We were
able to follow the curve for the metastable ONT for
a short distance and have represented it by an un-
broken line in the figure, the continuation as a dotted
portion representing unstable conditions. The un-
broken portion of this line is plotted from two deter-
minations in which the metastable ONT was used as
seed and did not change over to the stable form before
the determination was complete.
DNT
ONT
BINARY SYSTEM: TNT-ONT1
The data for this system are given in Table III and
in Fig. 3. It was possible in this case to follow out
curves both for a-ONT and for 0-ONT to their respec-
tive eutectic points with TNT, the eutectic for TNT
1 Experimental work by W. White.
Jan.,
1921 THE JOURNAL OF
INDU
Ta
31.E III — Binary System:
Trinitrotoluene
-0-NlTROT<
Per cent by Weight
Freezing
TNT ONT
Point Solid Phase
0 100
— 4.45<\
4.77 95.23
-5.7
0-ONT
9.17 90.83
—6.85
15.28 84.72
—8.7
0 100
— 10.35
4.77 95.23
—12.00
■
a-ONT
9.17 90.83
—13.3
25 75
—0.2
30 70
10.2
40 60
25.7
50 50
37.1
60 40
47.4
TNT
70 30
56.5
80 20
65. 1
90 10
73.0
100 0
80.35 '
and 0-ONT falling at —9. 7° and 19.5 per cent TNT,
and the eutectic for TNT and a-ONT falling at— 15.6°
and 16 per cent TNT. In obtaining these freezing
points we used the seed of the stable ONT in every
mixture.
TNT
ONT
In this paper we have given the data for three binary
systems of the nitrotoluenes. one of these nitrotoluenes
having two crystal forms. In one case it was possible
to follow the freezing-point curve for the metastable
form right to the eutectic point.
61
THE PREPARATION AND ANALYSIS OF A CATTLE FOOD
CONSISTING OF HYDROLYZED SAWDUST1
By E. C. Sherrard and G. W. Blanco
Forest Products Laboratory, U. S. Department op Agriculture*
Madison, Wisconsin
Although the Forest Products Laboratory has con-
sidered for some time the advisability of invescigating
the nutritive value of hydrolyzed sawdust, it was not
until the severe drouth, which occurred last year in
the Northwest, called our attention to the pressing
need of such a material that the investigation was
undertaken. The product described in this paper
was prepared by this laboratory, and fed to three
dairy cows by the Wisconsin College of Agriculture
with highly gratifying results. While the experiment
is yet in the preliminary stages, it is deemed advisable
to describe the process of manufacture and present
the analysis of the original and digested sawdust.
PREPARATION OF MATERIAL
The sawdust was eastern white pine obtained from
a mill in Minnesota, and was representative of the
waste obtained from mills cutting this species. No ef-
fort was made to remove bark or other foreign sub-
stances that ordinarily are present in this material.
The sawdust was treated in the same way as for
the production of ethyl alcohol from wood; that is,
it was digested with 1.8 per cent sulfuric acid for 15
or 20 min. under a steam pressure of about 120 lbs.
per sq. in. Sufficient water was added along
with the sawdust to raise the ratio of water to dry
wood to about 1.251. After the steam pressure had
been blown off to atmospheric pressure, the treated
sawdust was removed from the digester, and a large
portion of the acid liquor removed by means of the
centrifuge. The centrifuged material was then placed
in towers, and the remainder of the sugar and sulfuric
acid extracted with hot water. The leach water was
mixed with the centrifuged liquor, and the whole
almost neutralized with calcium carbonate. After
the sludge had settled, the liquor was decanted or,
if necessary, filtered, and evaporated under reduced
pressure to the consistency of a thick sirup.
The leached material from the towers was screened
through a 6-mesh screen to remove the larger uncooked
pieces of wood, and the screenings dried by spreading
on the floor in a thin layer. The air-dried hydrolyzed
dust was then mixed with the sirup referred to above,
and the whole dried to about 1 2 per cent moisture.
Early in the experiment, when we were dependent
upon the air drying of the finished product, considerable
loss of sugar was experienced. For instance, in Cook
No. 139, 21.2 per cent of the dry weight of the original
wood was converted into sugar. The final wood meal,
however, contained only 16.39 per cent of sugar calcu-
lated upon the dry weight of the product. This
loss of almost 5 per cent sugar was partly due to the
mechanical treatment and partly to a slow fermentation
of the sugar in the moist product during the early
stages of drying. Table I shows the decrease of sugar
1 Presented before the Division of Industrial and Engineering Chem-
istry at the 60th Meeting of the American Chemical Society, Chicago,
111., September 6 to 10, 1920.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. i3, No. i
in samples containing over 12 per cent of moisture,
upon standing from 1 to 2 mo. at ordinary room tem-
perature.
Table I — Change in Sugar Content upon Drying
Date
7/3/19
7/3/19
7/3/19
7/21/19
7/31/19
8/15 '19
Moisture
Per cent
14.76
22.48
30.57
18.77
7.00
15.74
13.61
13.76
16.39
1 8 . 06
14.96
15.88
Date
9/22/19
, 1 1 lg
9/22/19
Moisture Sugar
Per cent Per cent
8.70 13.23
It will be noted that in the samples containing 15 per
cent or less of water, but little change in sugar con-
centration occurs upon standing. A gradual decrease
in sugar occurred in all samples that were air-dried.
0
''
'"
90
'
/
/
eo
/
/
' 1
1
1 J
1
1
j
1
P
1
/
1
0
)
fi
v
II
r
Ik
/
L
£
G
£
Nl
■>
1 J
5
\/f.
hi.
ri
■ >
1c
d
£
/
Tc
ra
/ A
ec
>«c
S
uq
Vr
/
/
//
/
/
'/
/
/
O
A/o of £xrracr/ons
Extraction ok Sugar and Sulfuric Acid
In order to overcome this difficulty, a drying oven
was installed and the moisture in both the leached
dust and final product reduced to less than 15 per
cent before storing. No loss in sugar has been noticed
in this material, even after storage of several months.
That the sugar content is but slightly lowered during
the drying is shown by Table III. The temperature
of the oven remained almost constant, but considerable
rise in temperature was noted in the dust. The
temperature of the latter was taken by a thermometer,
the bulb of which was covered with the drying ma-
terial.
During the course of the experiment it was found
desirable to determine the relative ease with which
the sugar and acid could be removed from the cen-
trifuged hydrolyzed wood. This was because of the
desirability of removing almost all of the sulfuric acid
and of leaching out as little sugar as possible. Under
ideal conditions a minimum quantity of water should
be used, thus lessening the volume to be evaporated
eventually.
Since it was also important that a complete analysis
be made of the original wood and the wood after
treatment, proportionate quantities of the centrifuged
dust and liquor were taken from Cook No. 164 and
the process completed on a laboratory scale, thus
avoiding some of the losses usually experienced in
working with large quantities.
LEACHING EXPERIMENT
In order to determine the quantity of water necessary
to remove the greater part of the sulfuric acid, 6.06
lbs. of the centrifuged digested sawdust, corresponding
to 2.81 lbs. of dry material, were placed in two per-
colators, and 2.81 lbs. of water added to the first.
The percolate was collected, weighed, and transferred
to the second percolator. The percolate from the
second percolator was again weighed and the acidity,
specific gravity, and sugar determined. It is re-
gretted that equal extraction periods were not used.
but because of the laboratory hours this was found to
be impracticable. The acidity is expressed in degrees,
and represents the number of cc. of 0.1 N sodium
hydroxide solution required to neutralize 10 cc. of
the extract.
The sugar was determined as dextrose by means
of the method recommended by the U. S. Bureau of
Chemistry1 with one or two minor modifications.
This method is briefly as follows:
The sugar solution is carefully neutralized with anhydrous
sodium carbonate and allowed to stand for about 3 hrs. The
precipitated material is filtered off, and the clear filtrate diluted
so that 25 cc. will contain not more than 0.250 g. of dextrose.
Thirty cc. of copper sulfate and 30 cc. of alkaline tartrate solution,
prepared according to AUihn's modification of Fehling's solu-
tion, are mixed in a 250 cc. beaker with 60 cc. of water, and heated
to boiling. Then 25 cc. (duplicate) of the solution to be examined
are added and the boiling is continued for 2 min., taking the
time when, one-half of the 25 cc. of solution has been added.
The precipitated cuprous oxide is readily filtered in a porcelain
Gooch crucible with asbestos pad, and washed thoroughly
with hot water without any effort to transfer the precipitate
to the filter. The cuprous oxide is dissolved in 1 to 1.5 cc. of
nitric acid (sp. gr. 1.42), the asbestos filtered off, and washed
thoroughly with hot water. The copper filtrate, which has been
diluted to approximately 225 cc, is warmed to 60 to 650 C,
and electrolyzed for 1.5 to 2 hrs., using a current density of
1.0 amp. per sq. dcm. of platinum gage cathode, and an e. m. f.
of 1 .6 volts. The cathode is removed while the generator is
still running, dipped into three changes of hot distilled water,
and finally washed with alcohol and ether. Afterward the
electrode is dried for 3 min. at 105° C, allowed to cool, and
weighed. From the amount of copper deposited the quantity
of reducing material can be calculated in terms of dextrose by
referring to Allihn's tables.
1 Bureau of Chemistry, Bulletin 107, 49.
J an . . 1021
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
T
4BI.E II— RE
UXTS
FROM
Leachino I
Experiment
Water Used ■ — Started .
Lbs. Pi P2
. -Fir
Pi
ished .
Pi
,-Ti
Pi
Hrs.
pT
Hrs.
Quantity-
Obtained
from Pi
Lbs.
Weight
Lbs.
-Obtained
f P
Per cent
Total
Sugar
Removed
Total
Sulfuric
Acid
Removed
Nc
Sp. Gr.
Reducing
Sii^ar
Per cent
I
2.81
3/26/20
11: 15 A.M.
3/26/20
3: 15 P.M.
3/26/20
3: 15 P.M
3/27/20
8: 15 A.M.
4
17
1.625
0.545
23.0°
1.032
5.37
9.40
10.34
II
2.81
3/26/20
3 : 20 P.M.
3/27/20
8: 25 A.M.
3/27/20
8: 15 AM
3/28/20
12 30 P.M
17
28
2.645
2 . 240
21 .2°
1 .029
5.01
36.02
37.64
III
2.81
3/27/20
8:40 A.M.
3/28/20
12:30 P.M.
3/28/20
[2:30 P.l
3/28/20
. 8: 30 A.M.
28
20
2.710
2.630
13.4°
1 018
3. 10
26. 15
27.86
IV
2.81
3/28/20
12:35 p.m.
3/29/20
8:30 a.m.
3/29/20
8:30 AM
3/30/20
8: 30 A.M.
20
24
2.755
2.715
6.9°
1 .010
1.69
15.02
15.23
V
Centrifuge
Liquor
2.81
3/29/20
9:00 A.M.
3/30/20
9:00 A.M.
3/30/20
8:30 A.M
3/31/20
8: 30 AM
24
24
2.760
2.725
2.850
3.1°
1 .004
0.71
0.33
6.25
i 0:
6.89
1 90
Original materia! 2.81 lbs. dry weight, contain
HiS04 : Vol. acid : : 4.2 : 3.
Pi — 1st Percolator : P2 — 2nd Percolator.
ng 1 1 .09 per
cent
total 1
educing sugar.
It will be noted from Table II and from the extraction
curves that all but 2.04 per cent of the total acid used is
removed by the fifth washing. Since only 1.8 per cent
sulfuric acid was used in the cook, there remains 0.026
per cent of acid in the finished stock food. The
liquor obtained by centrifuging the residue after the
final extraction contained 1.9 per cent of the total
sulfuric acid, so that in actual practice it would be
possible to remove practically all of the acid either
by centrifuging or by pressing. The sulfuric acid
concentrations used in the table and curves were
calculated from the total acidity using the ratio of
sulfuric acid to volatile acid as 4.2 : 3, as determined
by Kressman.1
The sugars were found to leach with a little more
difficulty, since 7.16 per cent of the total amount re-
mained in the residue after the fifth washing. This,
however, makes no difference in the final product,
since the sugar is not appreciably changed by
drying.
The liquor obtained from the extraction was com-
bined with the original digester or centrifuge liquor,
and the whole neutralized with dry calcium carbonate.
No change in the sugar concentration was noticeable
after neutralization. The mixed liquors were evap-
orated under reduced pressure to a thick sirup, and the
sirup mixed with the partially dried, extracted dust
which had previously been screened through a 6-mesh
sieve. The moist mixture was then placed in an oven
and dried. Although the per cent of total reducing
sugars decreased somewhat during the drying, the
fact that the total soluble solids remained almost
Table III — Analysis
Date
4/9
4/9
4/9
4/9
4/9
4/9
4/9
4/9
4/9
4/9
4/9
4/10
4/10
4/10
4/10
4/10
4/10
4/10
4/10
4/10
4/11
4/11
Hour
11:30 A.M
Noon
1 :30 p.m
2:00 P.M
2:30 P.M
3:00 P.M.
3:30
4:00 P.M
4:30 P.M
7:30 P.M
11:30 P.M
3:30 A.M
7:30 A.M
9:00 A.M
9:30 A.M
10:00 A M
1 1 :00 a m
Noon
6:00 P.M.
12:00 P.M
6:00 A.M
Noon
Temperature
Kiln Food Moisture
0 C. ° C. Per cent
75 Started 60.23
during Drying in Kiln
Total Ratio
Reducing Soluble Sugar
Sugars Solids Total to
Per cent Per cent Sol. Solids
18.63 26.15 71.3
50.38
45.59
40.93
35.50
17. 17
17.14
16.84
24 . 99
23 52
2,1 . 02
24.80
1 7 . 53
25.28
69.5
17.49
24.87
70.03
16.57
24.25
68.4
16.53
24.69
67.2
16.51
25.55
65.0
constant indicates that volatile reducing substances
were removed and that the sugar remained practically
unchanged. The progress of the drying experiment
may be observed from Table III.
After drying, the material contained considerable
finely powdered dust. The size of these particles was
roughly determined by screening.
Total weight of material
Material retained by 80-mesh
Material retained by 100-mesh
Material through a 100-mesh *
i = 499 g.
i = 13 g.
74.36 per cent
1 .93 per cent
22.50 per cent
Unpublished bulletin
Any loss of wood meal that occurs in handling con-
sists mostly of fine material, due to its sifting through
the bags or loosely made containers. It was therefore
analyzed separately, in order to determine its relative
value as compared with that of the coarser material.
The portion that passed through the ioo-mesh screen
was kept separate. The coarser material that was
retained by the ioo-mesh screen was ground to pass
through an 8o-mesh screen but to be retained by a
ioo-mesh. This was found to be impracticable,
owing to the fact that the coarse material ground itself
away on the screen and but little remained. Because
of this trouble, all of the coarse material was ground
to pass a ioo-mesh screen.
In this way two portions of the wood meal were
obtained: The portion that passed through the ioo-
mesh screen before grinding, labeled "unground food
through ioo mesh," and the ground portion labeled
"ground food through ioo mesh." For the purpose
of comparison a sample of the original white pine
sawdust was ground, and the portions passing through
8o-mesh and ioo-mesh screens were used for analysis.
It should be borne in mind that this analysis is not
comparable to the average wood analysis since no
effort was made to eliminate bark or other undesirable
portions of the wood. In fact the material used was
typical sawmill waste, and contained all the foreign
substances common to this product.
The two samples of stock food and the two samples
of unhydrolyzed sawdust were analyzed according to
A. W. Schorger's method.1
In both the untreated wood and the final product
the percentage of ash is higher in the fine material.
This is due possibly to the presence of sand and earth
that was contained in the original sawdust.
It will be noticed in examining the analytical data
in Table IV that the hot and cold water and alkali-
1 This Journal, 9 (1917), 556
64
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Table IV — Analysis of Wood Meal
Cold
Moisture Water
80-100 6.00 8.81
-Solubility of Sample i
Untreated White Pine Sawdust
Pento
Sample
Unhydrolyzed dust
mesh
6.46
Average 6.23
Unhydrolyzed dust through 6.38
100-mesh
6.39
Average 6.39
Unground wood meal through 4.15
100-mesh
4.09
Average 4.12
Ground wood meal through 3.64
100-mesh
4. 1 1
4.13 23.16
8.75
9.21
10.08
10.15
10.78
22.86
23.01
25.39
30.17 30.64
30.59
30.38
31.11
30.69
30.66
28.23
4.84
4.86
3.94
■V. 77
3.85
3.80
25.76
25.57
43.24
42.59
42.92
40.23
Average
iround wood meal thr.
80-100 mesh
2.83 3.83
1 This value is undoubtedly somewhat low since the condenser was accidentally removed before the flask had sufficiently cooled.
- Pento- Cellu- Cellu- Cellu- Crude
sail lose lose lose Lignin Fiber
... 56.31-56.00 31.45
2.37 56.63-57.50 8.00 1.65 (30.65) 63.87
Re-
ducing
Sugars
56.61
53.76
54.11
36.01
35.97
35.99
37.77
Ash
0.82
6!80
0.81
1.52
4.92
4.93
3.35
37.90
37.46
37.23
soluble materials have been greatly increased by the
hydrolysis, while the ether-soluble remains about the
same.
In comparing the yield of pentosans from the original
wood and from the completed stock food, it will be
seen that considerable difference exists. Since the
yield of finished stock food is about 90 to 94 per cent
of the original wood, the pentosan yield from the
stock food amounts to about 4.05 and 4.43 per cent,
respectively, when calculated upon the dry weight of
the original wood. In other words, about 45.4 per
cent of the original pentosan remains in the finished
product. This difference is best accounted for by
assuming a partial conversion of the pentoses liberated
by hydrolysis into volatile acids and furfural.1 Such
an assumption is necessary to account for the volatile
acid formed in the condensed blow-off and centrifuged
liquor. Although but little difference is apparent
in the quantity of acetic acid obtained by the acid
hydrolysis of the original wood and treated wood,
too much confidence should not be placed in the quan-
tity of acetic acid obtained from the stock food, since
there is a possibility that a portion of this was liberated
from the calcium salts formed during neutralization.
The methyl pentosans in the wood are almost un-
affected by the digestion with sulfuric acid.
The average yield of cellulose in both samples of the
original wood is 55.79 per cent, while the average
yield from the stock food is 37.08 per cent. When the
cellulose from the latter is recalculated upon the original
dry weight of the wood the average yield is 34.11
per cent. This indicates a loss of 21.68 per cent of
cellulose from which 15.5 per cent of total reducing
Sugars were produced. The latter value, which is also
calculated from the original dry weight of the wood,
shows a yield of sugar corresponding to 71.5 per cent
of the theoretical, assuming that all of the cellulose
that is removed goes to form reducing sugar. The
calculation is at best an approximation, since the com-
plexity of the cellulose molecule, and hence the number
of molecules of water entering into the reaction, is not
known.
LIGNIN DETERMINATION
The method used for the lignin determination was
■ Kressman's unpublished bulletin.
that described by Mahood and Cable,1 except that a
16-hr. digestion with 72 per cent sulfuric acid was
used, since in a more recent study these authors found
the longer period more desirable.
The lignin determination is of interest, since it
shows that the total quantity of lignin contained in
the wood is not appreciably altered. The values
contained in parenthesis are the ash-free values cal-
culated from the dry weight of the original wood and
indicate that no change has occurred in what is
ordinarily considered as the lignin complex. This
is of great interest since heretofore the assumption
has always been made that a large portion of the lignin
was removed.
DETERMINATION OF a-, j3-, AND 7-CELLULOSE
The determination of a-, /?-, and 7-cellulose2 was
carried out as follows: About 2 g. of cellulose obtained
by the chlorination method were thoroughly mixed
with 20 cc. of 17.5 per cent sodium hydroxide and
allowed to stand for exactly 30 min. at room tem-
perature. The mercerized fiber was then treated
with 20 cc. of water, thoroughly stirred, and filtered
on an alundum crucible with the use of strong suction.
The a-cellulose which remained in the crucible was
washed with 10 cc. portions of cold water until the
filtrate showed no alkaline reaction. It was then
treated with hot 10 per cent acetic acid, washed six
or eight times with hot water, dried at 1050 C, and
weighed. The alkaline filtrate was made distinctly
acid with concentrated acetic acid, which caused
the /3-cellulose to separate in a finely divided condition,
and the brownish color of the liquor to become lighter.
To coagulate the suspended material, the solution
was heated in a water bath until the particles settled
and the solution became clear. The /3-cellulose was
then filtered on an alundum crucible, washed six or
eight times with hot water, dried at 105 °, and weighed.
The portion of the cellulose permanently dissolved was
7-cellulose.
No difficulty was experienced in the determination
of a-, /?-, and 7-cellulose in the cellulose obtained from
' Paper, 26, No. 24.
2 Cross and Bevan, "Researches on Cellulose," 1908-10, Vol. Ill, p. 23;
Cross and Bevan, "Paper Making," 1916, p. 97; Schwalbe, "Chemie der
Cellulose," 1911, p. 637.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
"
the unhydrolyzed sawdust, except in one or two cases
where the filtration was slow, owing to the porosity of
the crucible. The results in Table V were obtained
using the original untreated sawdust.
Table V — Per cent a-, 0-,
1 Original
Cellulose Sample Obtained from a-Cellulose tf-Cellulose 7-CeIlulose
Unhydrolyzed dust through 80-100
mesh 57.3o 19.61 23.03
Mixing cellulose obtained from un-
hydrolyzed sawdust. 80-100 mesh,
and unhydrolyzed sawdust through
100-mesh, respectively 55.85 29.42 14.75
In the case of cellulose obtained from the hydrolyzed
wood, considerable difficulty was encountered, owing
to its character after treatment with the alkali. In
all cases it was impossible to filter in the 30 min. pre-
scribed by the method, so that the action of the alkali
continued in some cases for 8 or 10 hrs. This difficulty
could not be overcome, and no definite analysis could
be made. The cellulose, upon treatment with alkali
(17.5 per cent), became semitransparent and had
the appearance of collodion.
That portion that could be drawn through the
crucible reprecipitated upon mild dilution with water.
This precipitate coagulated upon warming, and it
behaved and looked very much like the usual /?-
cellulose. The coagulated precipitate was filtered
on an alundum crucible with suction, and the filtrate
acidified with strong acetic acid, with the result that
no further precipitate was obtained. Because of the
difficulties outlined above, no analytical data on the
a-, f$-, and 7 -cellulose from the cellulose from hydrolyzed
wood are contained in this paper. It is hoped that
further investigations will clarify this point.
In one case the alkali-treated cellulose from hy-
drolyzed wood was strongly diluted with water.
The fine white precipitate was warmed, and the
coagulated material filtered, washed, and dried. It
had the semitransparent appearance of dried collodion
and amounted to 06 per cent of the original sample.
Because of its peculiar properties it is apparently a
product intermediate between a- and /3-cellulose.
Since it is partially soluble in alkali it may be con-
cluded that it is more easily digested in the alkaline
intestinal tract than the true a-cellulose, especially
in the presence of enzymes present in the intestines.
METHOD FOR CRUDE FIBER DETERMINATION
The crude fiber was determined ' by the method
outlined in Bureau of Chemistry Bulletin 107, page
56, with minor modifications. It is briefly as follows:
Two grams of the sample are extracted with ether for 4 or
5 hrs. in a Soxhlet extractor. The excess of ether is removed
by suction and the material dried to constant weight. It is
then treated with 200 cc. of boiling 1.25 per cent sulfuric acid,
and boiled under a reflux condenser for 30 min. After filtering
with suction on an alundum crucible it is washed with hot water
and treated with 200 cc. of boiling 1.25 per cent sodium hy-
droxide solution. After boiling for another 30 min. under a
reflux condenser it is rapidly filtered with suction through an
alundum crucible and washed with hot water until free from
alkali. After drying to constant weight it is incinerated in an
electric muffle at 7000 to 8oo° C. The loss on incineration is
considered to be crude fiber-
It is interesting to note that the crude fiber has been
reduced from 14 to 15 per cent. Another interesting
feature is the fact that the sum of the cellulose and
lignin is greater than the quantity of crude fiber.
This indicates that at least a portion of either the
cellulose or lignin, or perhaps some of each, is removed
by successive treatments with dilute acid and alkali.
SUMMARY
1 — A method for the preparation of a stock food
from white pine sawdust is described.
2 — Leaching experiments carried out on the digested
dust indicate that five complete washings with a
quantity of water equivalent to the weight of the wood
are necessary to remove the sulfuric acid. The
sugars were found to leach with somewhat more
difficulty than the acid.
3 — It is pointed out that the sugars contained in
the moist product are not appreciably affected by
drying at temperatures ranging from 75° to 85 ° C.
While some decrease is noted in total reducing sugars,
the loss is apparently due to the removal of volatile
reducing substances.
4 — A complete analysis is given for eastern white
pine sawdust,' and for the product obtained from the
same after digesting with dilute acid under pressure.
Attention is directed to the changes resulting from
this treatment.
5 — The cellulose obtained from the digested wood
differs from that from the original wood in its be-
havior toward alkali. In the former practically all
of the cellulose is converted into a viscous semi-
transparent mass by 17.5 per cent sodium hydroxide,
while in the latter over 50 per cent is unaffected.
THE EFFECT OF CONCENTRATION OF CHROME LIQUOR
UPON THE ADSORPTION OF ITS CONSTITUENTS
BY HIDE SUBSTANCE^
By Arthur W. Thomas and Margaret W. Kelly
Chemical Laboratories, Columbia University, New Yore, N. Y
The concentration factor in the combination of hide
substance with chromic oxide and sulfuric acid in
chrome liquor has previously been reported by Miss
M. E. Baldwin.2 She studied the adsorption from
various liquors containing 0.038 to 6.640 g. of chromic
oxide per 100 cc. of liquor, and found that the adsorp-
tion reached a maximum at concentrations of 1.5
to 2.0 g. of chromic oxide per 100 cc, beyond which
concentration the adsorption by the hide substance
decreased.
Results obtained by J. A. Wilson and E. A. Gallun3
in their investigation of the retardation of chrome
tanning by neutral salts, led them to believe that, had
Miss Baldwin's liquors been carried to higher concen-
trations (to about 12 g. of chromic oxide per 100 cc),
a minimum point might have been obtained beyond
which increasing concentration would have caused
1 Presented before the Leather Chemistry Division at the 60th Meet-
ing of the American Chemical Society, Chicago, 111., September 6 to 10,
1920.
' J. Am. Leather Chem. Assoc, 14 (1919), 433.
'-Ibid., 15 (1920), 273.
66
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. No. 1
greater fixation of chrome. The experiments re-
ported in this paper were conducted to test this as-
sumption.
MATERIALS USED
The hide powder was American Standard (19 18)
of the same lot as used and analyzed by us.1
The chrome liquor contained 202 g. of chromic
oxide per liter. It was practically identical to that
used by Miss Baldwin. Eleven 200-cc. portions of
chrome liquor of various dilutions were made up from
this stock liquor.
METHOD
The various diluted liquors in 200-cc. portions were
poured into bottles containing 5.766 g. of hide powder,
equal to 5 g. of dry hide powder. Another portion of
each solution was set aside and at the expiration of 4S
hrs. the H+-ion concentration of the solutions was
determined. The bottles were shaken at intervals,
and at the end of 48 hrs. filtered off by suction. The
filtrates were set aside for analysis (the H+-ion con-
centrations determined immediately), and the chromed
hide powders, washed free of adhering liquor, were
air-dried. The methods of analysis were the same as
those reported by us in our earlier communications.
o
--rrr
=*-
^
^
1^,
t
"'--^-<
/
s'
^
■'-'
*
Original (a
fter 48 hours.)
The moisture was determined in each portion of the
chromed hide powders and all other figures calculated
to the water-free basis. The results are given in
Table I.
Table I — Composition of Chromed Hide Powder
G. CnOj per
100 Cc. of
Liquor before
Protein
Cr?Os
SO.
Ash
Adsorption
Per cent
Per cent
Per cent
Per cent
0.0363
98.19
1.30
1.09
1.59
0.2881
83.70
7.86
6.07
S.84
0.7738
76.63
10.58
8.18
11 .82
1.5526
75.90
10.85
8.67
12.12
3.0853
78.43
10.25
8.89
11.23
4.8073
80.17
9.36
8.25
10.09
7.3070
83.87
7.85
7.21
9.7267
84.83
5.92
6.12
6.50
12.175
89.77
3.86
5.19
4.89
14.754
90.67
2.35
4. 48
3.82
20.203
91.12
2.10
2.29
2.45
The analyses of the filtrates are given in Table II.
An aliquot part was taken in each case, the chromic
oxide in it determined and calculated to the basis of
100 cc. of liquor, assuming, erroneously, that no water
had been adsorbed by the hide — the common practice
in calculations of adsorption.
> J. Am. Leather Chem. Assoc., IS (1920), 487.
T\bi.r IT — Composition op Liquors apter Adsorption
N'timlier G. CnOi in 100 cc.
1 0.0096
2 0.0510
3 0.4464
4 1 . 2.SS6
5 2.8577
6 4.7587
7 7.4^0
8 10.0215
9 12.5820
10 15.4000
The H^-ion concentrations of the filtrates and of
the liquors (after 48 hrs.' standing) are to be found in
Table III and charted in Fig. 1. Those values which
are considered unreliable are in parentheses. In some of
the concentrated liquors we had difficulty in measuring
the H+-ion concentrations. The values obtained
show removal of hydrogen ion from the liquors up to
the solution of concentration of 7.4 g. chromic oxide
per 100 cc, beyond which the curves join and run
along together, indicating that if hydrogen ion was
removed the buffer action of the chromic sulfate
could take care of it. The solution which gave the
maximum adsorption of chrome in two days showed
a H+-ion concentration of 0.00056 mole per liter,
which checks Miss Baldwin's experience, where the
maximum adsorption of chrome in two days was
found to be from a solution of 0.0005 to 0.0006 mole
per liter concentration of hydrogen ion.
-Hydrogen-Ion Concentrations op Solutions
Filtrate from Liquor in
Contact with Hide Powder
for 48 Hrs.
Liquor after Standing
48 Hrs.
Mole per Liter of H +
0.00029
0.00039
(0.00060)
0.00056
0.00115
(0.00182)
0.00204
(0.00214)
0.00316
(0.00661)
Mole per Liter of H*
0.00004
0.00028
0.00042
0 . 00050
0.00083
(0.00110)
0.00186
0.00263
0.00316
(0.0045:
Table IV and Fig. 2 show the adsorption of chromic
oxide and sulfuric acid calculated to the basis of one
gram of dry hide substance.
Ms.
Cr-Oj ■
Ms SO,
From Analysis
From Analysis
From Analv
of Powder
of Liquor
of Powder
13.2
10.7
11.0
94.1
-
138.3
131.0
106.9
143.1
117.6
114 4
130.9
91.0
113.5
116.9
19.5
103. 1
93.7
—51.2
86.1
69.9
—118.0
72.3
43.1
—162.6
>, >)
26.0
— 25S.4
23.1
Solutions 3 and 4 showed the optimum concentra-
tion for a 2-day reaction with hide powder. The
chromed hide substance formed indicates a tetra-
chrome collagen, based on the equivalent weight of
collagen as 750, as suggested by Wilson.1 This again
checks Miss Baldwin's results quite closely.
The values based on analysis of the liquors, from
which the adsorption of water was ignored, show
lower values throughout, and from Solutions 7 to 1 1
J. Am. Leather Chem. As
12 (1917). 108.
Jan., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMIST R]
67
negative values are obtained, owing to the liquors
becoming more concentrated than they were originally,
on account of the collagen abstracting water from
them.
^ -210 —
-Crz03 from Analysis of Chromed Hide Ponder \
— ■— <T/> Oj from Analysis of Filtrate
Concentration of Liquor in Grams Cr20j per Liter
We would state our belief, based upon our experience
as presented in this and earlier papers, that the reaction
between chromic sulfate solutions and hide substance
is chemical and not physical, as contended by A. W.
Davison.1 If the adsorption were a simple physical
process, i. e., merely a partition of the chromic oxide
and sulfuric acid between the solid hide substance
phase and the solution phase, the curve should follow
Freundlich's adaptation of Henry's law: Ci = kC",
which is parabolic in shape; whereas Miss Baldwin's
and our experiments show that in a 2-day adsorption
the curve begins to slope steeply downward after the
concentration of the liquor exceeds approximately
16 g. of chromic oxide per liter in a solution of the com-
position of Cr(OH)S04, and reaches a minimum when
the concentration of chromic oxide is 147.5 S- Per liter,
this minimum being maintained at a concentration
of 202 g. per liter. This minimum confirms the pre-
diction of Wilson and Gallun in part. The most con-
centrated chrome liquor which we used was very
thick and about as concentrated as is possible to
handle; and therefore, we do not find it possible to test
further their prediction that increasing concentrations
beyond this minimum would cause greater fixation
of chrome.
ACKNOWLEDGMENTS
Acknowledgment is made of Mr. S. B. Foster's
assistance in the analytical work. We wish to express
our great appreciation of the generous support of
Messrs. A. F. Gallun and Sons Company in this
investigation.
J. Am. Leather Che
12 (1917). 258
THE ACTION OF CERTAIN ORGANIC ACCELERATORS IN
THE VULCANIZATION OF RUBBER— II'
By G. D. Kratz, A. H. Flower and B. J. Shapiro
The Falls Rubber Co., Cuyahoga Falls, Ohio
One of the early patents2 for the use of synthetic
nitrogenous organic substances in the vulcanization
of rubber refers to the dissociation constant of 1 X io~s
as the dividing line between accelerating and non-
accelerating bases. On the other hand, Peachey3
has pointed out that certain other substances which
are not basic, or but slightly so, are also exceedingly
active as accelerators. The number of examples in
this class, however, is relatively small.
In the course of the experimental work described in
this paper we have made a comparison of the sulfur
coefficients of a type mixture vulcanized with the as-
sistance of a number of accelerators closely related to
aniline and for which the dissociation constants are
known. We have also employed the hydrochlorides
of two of these substances, relatively weak and strong
bases, in order to observe the effect of the acid portion
during the vulcanization. The results obtained and
the conclusions drawn led us to employ the sulfides
of ammonia as accelerators and vulcanizing agents.
. Briefly summarizing these results, it was found
that with the substances tested there was apparently
no direct relationship between their dissociation con-
stants and their excess sulfur coefficients or physical
properties after vulcanization. In a closely related
series, such as aniline and its methyl derivatives, the
substance with the largest dissociation constant was
found to be the most active. However, the relative
activities of the members of this series were not pro-
portional to their dissociation constants. Generally
speaking, the activity of all of the substances could
be traced to the amino group, and depended to a large
extent upon whether or not substitution had taken
place in this group. In this respect, they should prob-
ably be regarded as substituted ammonias, rather
than as the more complex derivatives of other sub-
stances.
One effect of the basicity of two of the substances,
methylaniline and ^-toluidine, was determined with
the hydrochlorides of these two substances. Our
results showed that with substances of this type, the
first effect of the base is to neutralize the retarding
action of the acid formed in the decomposition of the
salt during vulcanization. We had previously sug-
gested this in a footnote in a former paper.4 We also
found that when the acid liberated in the decomposi-
tion of such a salt is neutralized by other substances
in the mixture, the activity of the hydrochloride is
very close to that of the free base. These results are
of particular interest, as Van Heurn5 has shown that,
whereas ammonium carbonate is moderately active
as an accelerator in a mixture of rubber and sulfur,
1 Presented before the Rubber Division at the 60th Meeting of the
American Chemical Society, Chicago, III., September 6 to 10, 1920.
2 D. R. P. 280,198 (1914).
3 J. Sac. Chem. Ind., 36 (1917), 950.
< Chem. & Met. Eng., 20 (1919), 420.
' Comm. of the Netherlands Government for Advising the Rubber
Trade and Industry, Part 6, 202.
68
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
ammonium chloride is inert. The former salt decom-
poses into ammonia and a weak acid, the latter into
ammonia and a strong acid, according to the following
reactions:
NHOsCOj — >
N'H.Cl
2NH3 + HjO + COa
— > NH3 + HC1
Our final experiments, wherein we found that in a
closed system rubber is vulcanized by heating with
ammonium polysulfide or ammonium hydrosulfide,
were carried on in order to obtain a reaction mix-
ture of undoubted basic character, which at the same
time would include H5S as one of the decomposition
products. The function of H2S in connection with
the vulcanization of rubber has long been made a sub-
ject of controversy. In the present instance it may
be regarded as a very weak acid.
Our results with ammonium polysulfide may be ex-
plained as due to the decomposition of this substance
into ammonia, hydrogen sulfide, and sulfur, the latter
substance being liberated in an active (nascent) form
which readily combines with the rubber. The analogy
between our results with ammonium polysulfide, and
those obtained years ago by Gerard1 with potassium
tri- and pentasulfides, is taken up in greater detail in
the experimental part of this paper. It is equally
evident, however, that if this explanation is advanced
in the case of ammonium polysulfide, vulcanization
with ammonium hydrosulfide requires that this sub-
stance decompose not into ammonia and hydrogen
sulfide only, but with the subsequent formation of a
polysulfide which liberates sulfur in the active form.-
It has been shown by Bedford and Scott3 that many
of the more complex substances which accelerate the
vulcanization of rubber react with sulfur, with the
liberation of H:S and the formation of thiourea deriva-
tives. In view of our results with the ammonium
sulfides, the action of such thiourea derivatives would
depend upon their ability to enter into a subsequent
reaction with the H;S formed, or the sulfur present in
the mixture, with the formation of a polysulfide.
Further, although the formation of a polysulfide in
this manner would, to a certain extent, be dependent
upon the basicity of the substance originally added
as the accelerator, it is obvious that the dissociation
constant of the reaction product would be a better in-
dication of its activity than the dissociation constant
of the original substance.
* R. Hoffer, "Treatise on Caoutchouc and Guttapercha" trans.
Brannt), H C. Baird & Co., London. 1883.
2 As an aqueous solution of XHtHS was employed, the action of this
substance may also be explained by its dissociation products. It would
dissociate with NHi* as the cation and HS~ the anion. As the HS~ion
itself is weakly acid, there would probably be many H+ and HS~ ions
and but few S ions in the aqueous solution. The H+ and S ions
in turn react to form H3S. On the other hand, (NHi)iS dissociates with
NH<+, the cation, and S , the anion. The latter, in the presence of
water, dissociates with the formation of OH" and HS" ions. Thus,
NH4HS dissociates with the formation of a greater number of H + ions than
in the case of (NHO:S, and consequently with a greater re-format:"-' of
H:S. This may account for the difference in the relative activities of the
two substances. The same may be true in the absence of water, as most
organic accelerators are apparently soluble in rubber, the high dielectric
constant of which indicates that this substance itself may be a good dis-
sociating medium.
' This Journal. 12 (1920). 31
In a previous paper1 we have suggested that the ac-
tivity of certain nitrogenous substances may be in-
terpreted on the basis of a change in valency of the
nitrogen, with the nitrogen functioning as a sulfur
carrier. This suggestion was made to assist in corre-
lating the nitrogen content with the activity of the
substances employed, although, as pointed out in the
above paper, results obtained by others already indi-
cated that the sulfur is not necessarily attached to
the nitrogen. While our present results show that
vulcanization may be effected by polysulfide forma-
tion, they do not exclude the possibility of the active
nitrogen group acting as a catalyst.
EXPERIMENTAL PART
The same general method of procedure was pursued
in the course of this work as was previously reported
in Part I.
The rubber was good quality, first latex, pale crepe,
and the same lot was employed for all mixtures. All
of the mixtures, the composition of which is shown at
the head of the various tables, were mixed and vul-
canized as before. Physical tests were made on a
Scott testing machine of the vertical type. Sulfur
estimations were made by our method, previously
described in detail.2
The accelerators were purified, and melted or boiled
at the temperature shown in the tables. All of the
accelerators were compared on a molecularly equiva-
lent basis, 0.01 g. molecule of the accelerator being
added for each ioo g. of rubber in the mixture.
expt. 1 — This experiment was carried on in
order to ascertain the relative accelerating effect of the
homologs of aniline and other closely related bases,
and also to compare the excess sulfur coefficients with
the dissociation constants of the substances originally
added as accelerators. The results obtained, together
with the physical constants of the substances em-
ployed as accelerators, are shown in Table I.
It is evident from this table that with aniline and
its methyl derivatives, or in the case of the two phenyl-
enediamines, the substance with the largest dissocia-
tion constant produces the greatest excess coefficient
of vulcanization. It is also apparent that this rela-
tionship is confined to more or less closely related
substances only, and that, as a general rule, the dis-
sociation constant is not a reliable guide to the ac-
tivity of a substance as an accelerator.3
Excess sulfur coefficients of equal magnitude (3.0)
were obtained from />-toluidine, ^-benzidine and m-
phenylenediamine. It is interesting to note that
the subtraction of the excess sulfur coefficient of any
one of these substances from that obtained for />-phenyl-
enediamine (5.2) leaves a figure very close to the
excess obtained for aniline (2.4"). Further, although
the mixtures vulcanized with the assistance of the three
substances in question were found to have the same
excess sulfur coefficient, all of them had widely differ-
1 This Jovrnal, 12 (1920). 317.
•■India Rubber World, 61 (1920), 356.
8 The dissociation constants given in Table I are taken from the Landolt-
Bornstein tables and are not strictly comparable, in that they were not all
determined by the same method.
Jan.. iQ2i THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
60
Substance Formula
Control
Aniline CtH.NH?
Methylaniline CH1NH.CH1
Dimethylaniline CsH.N(CHi).
/.-Toluidine CHj.C.H..NHi
ra-Phenylcnediaminc NHj.CsIft.NHj (1: 3
p-Phenylenediamine NHj.CeH«.NH2 (1 : '
^-Benzidine NH2.C«H1.CtH<.NH:
Phenylhydrazine C1H1NH.NH,
Hydrazobenzene* CtHsNH.NH.CsHs
All
■ belov
nd b. p. abo
Tabu! I
Sulfur
Vulcanized for 90 Min. at 148
0 C.
Determined
M. P. or B. P.
Dissociation
Excess
Strength
Constant K
Sulfur
Accelerator1
at 15° to 18° C
Coefficient
at Break
at Break
(2.581)
1229
1 83 . 1
3.50 X 10-"
2.400
2005
192. 0
2.55 X 10-'°
0.612
1665
192.5
2.42 X I0-i«
0.250
1938
1.60 X 10-»
2.987
2476
62.6
1.35 X 10-1=
2.986
1933
140.6
2.48 X 10-1= !
5.248
193
126.2
7.40 X 10-u >
3.056
1464
240.0
1.60 X 10-»
0.751
1052
126.0
0.777
2165
1140
ture of vulcaniz
ation. 3 Figure a
pplies to second "K "
3 Does not have basic properties.
ent physical properties. These substances may be
regarded as aniline in which hydrogen of the benzene
ring has been replaced by radicals.
On the other hand, (methylaniline), phenylhydra-
zine, and hydrazobenzene may be regarded as aniline
in which the hydrogen of the amino group has been re-
placed. The difference in the activity of these two
types of accelerators has already been mentioned in
Part I in connection with the phenylguanidines.
As in the previous instance, the same excess coeffi-
cient was obtained for (methylaniline), phenylhydra-
zine and hydrazobenzene, but the value was much
smaller (0.75) than before. The excess value found
for these three substances when subtracted from that ob-
tained for ^-phenylenediamine gives a figure equal to
about twice that obtained with aniline. Here, also,
the physical properties of the three mixtures were
greatly different.
I 1
*
1-
1 !-•
.-"Usis:
-.«
„.
'^M
■~t3?S*
irs^
**j"*
,•■■
t-i
r.
1
.
y
*
>--
^SiS-
13^-P1
r
/
3^S3
JgWafi^4-
/
7
A
/
k-
'
tensile strength in lbs per sq iv.
Fig 1
The discrepancy in the physical properties of mix-
tures vulcanized to the same sulfur coefficient by
means of different accelerators is of especial interest
and has been made the subject of a subsequent paper.
As our present results are based on one cure only, we
are not warranted in drawing many conclusions from
those recorded here. A comparison of the results
given in Table I, with the stress-strain curves shown
in Fig. 1, however, shows that these differences are
most evident at, or near, the point of break.1
The above results indicate that, irrespective of
whether or not an interaction between the accelera-
tor and other substances in the mixture takes place
during vulcanization, the activity of substances of
the type described is directly traceable to the amino
group, and particularly to the first amino group in
the benzene nucleus.
expt. 11 — In view of the results of Expt. I, they
should be analogous to those of ammonia or ammonium
salts. From a consideration of the work of Van
Heurn1 it seemed possible that certain other substances,
or their reaction products, active as accelerators, might
decompose with the formation of a (relatively) strong
base and a weak acid in an analogous manner; or that
some substances, which are not ordinarily classed as
accelerators, owing to their decomposition into a weak
base and strong acid, might be active if the acid so
formed was neutralized by another constituent of the
mixture. Aniline sulfate and />-toluidine hydro-
chloride, when employed in the presence of zinc oxide
are examples of the latter type.
Ta
BLE II
100
8. 1
Sulfur
8.1
r = 0.01 g. Mo
. of Substance
Vulcan
zed for 90 Min. at
148° C.
Physical
> — Properties—.
Sulfur
Sulfur
Tensile
Final
Coeffi-
Coeffi-
Strength Length
cient
cient
Lbs. per
Per
Sulfur
Over
Under
Sq. in.
Coeffi-
Control
Control
(At
(At
Mixture
cient
( + )
(— )
Break)
Break)
Rubber-Sulfur Control.
2.789
1265
1140
Zinc Oxide Control . .
~>.538
0.251
R-S Control + HCI
0.652
2.137
564
1250
ZnO Control + HCI
2.491
0.047
1783
820
5 . 568
2.779
2476
920
p-Toluidine + ZnO
5.371
2.833
1824
640
fi-Toluidine Hydrochloride
2.308
0.481
1070
1210
/>-Toluidine Hydrochloride
+ ZnO
3.990
1.460
2485
757
Methylaniline
3.193
0.404
1665
1050
Methylaniline + Zull
2.750
0.217
2237
800
Methylaniline Hydrochlo-
ride
1.012
1.777
530
1150
Methylaniline Hydrochlo
ride -f- ZnO
2.012
0.526
1731
840
i />-Phenylenedian:
suits could not be obta
so greatly
that concordant
for this substance.
In Table II are given the results obtained with
molecularly equivalent quantities of ^-toluidine and
/>-toluidine hydrochloride, in the presence and
absence of zinc oxide. Two control mixtures
were employed, one with and the other without zinc
oxide, no accelerator being added in either case. The
excess sulfur coefficients (+ or — ) shown in the third
and fourth columns of this table were obtained by the
subtraction of the coefficients of their respective con-
trols, depending upon whether or not they contained
zinc oxide.
From this tabic it is evident that zinc oxide itself ex-
erts a slight retarding action and that hydrochloric acid
THE JOURNAL 01 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
is a most effectual retardant, when employed in the ab-
sence of zinc oxide. When these two substances were
both present in the mixture, however, the sulfur
coefficient obtained was practically that of its control.
With />-toluidine, the same excess coefficient was
obtained in the presence and absence of zinc oxide,
a characteristic similar to that noted in the case of
aniline, and to be discussed in a subsequent paper.
In fact, />-toluidine hydrochloride did not greatly
retard the vulcanization even when employed in a
rubber-sulfur mixture, a fact which we attribute to
the strong basic nature of the />-toluidine. When
used in the presence of zinc oxide, ^-toluidine hydro-
chloride markedly accelerated the vulcanization. The
physical test results confirmed the sulfur coefficients.
Entirely different results were obtained, however,
with methylaniline hydrochloride.1 This substance,
although almost inactive in a mixture which con-
tained zinc oxide, acted as a retardant in a mixture
of rubber and sulfur only. In this instance, owing
to the weakly basic nature of the methylaniline. the
effect of the hydrochloric acid predominated. Here,
again, the physical properties of the mixtures were
roughly in accord with their sulfur coefficients.
The results show that the tendency of certain sub-
stances to decompose or dissociate into other sub-
stances with acid properties, or with acid properties
predominating, may cause the substance originally
added to be classed as inactive or as a retardant. In
such cases, the primary function of zinc oxide is to
neutralize the acidic constituents and permit the pre-
dominance of the accelerator, which is very probably
basic.
expt. in — Many years ago, Gerard2 noted that
vulcanization could be effected by boiling rubber in a
concentrated aqueous solution of "liver of sulfur," a
reaction which may possibly be represented in the
following manner:
4K2CO, + S10 • — > K:SO. + 3K2S-, + 4CO,
K0S3 + H,0 — *- 2KOH + H,S + S
The second reaction, which represents that found
by Gerard capable of effecting vulcanization, is analo-
gous to the decomposition of ammonium polysulfide:
(NH,):SX — > 2NH3 + H2S + Sx-i
In neither of the above instances is the possibility
of the formation of the hydrosulfide (KSH or NH«SH)
excluded, but it is regarded as an intermediate reac-
tion.
In the present case, where the ammonium sulfides3
were used, the resultant system can hardly be acid, no
matter how the decomposition or dissociation of the
sulfide is effected.
1 When heated to 350° C. methylaniline hydrochloride dissociates
into aniline and methyl halide, with the formation of the isomeric p-toluidine.
Methylaniline hydrochloride was chosen for comparison with p-toluidine
hydrochloride, in order to observe if such a rearrangement took place during
the vulcanization reaction. From the sulfur coefficients obtained, it is
obvious that this transformation did not occur.
! Loc. tit. The first use of alkaline sulfides, and particularly potassium
pentasulfide, for vulcanization, is often attributed to Gerard (compare
Charles Hancock, Brit. Patent 11,874 (1847), and Moulton, Brit. Patent
13,721 (1851))
s Compare the process of Moureley of Manchester, England, 1884.
A small sample of the rubber was sheeted thin on
the mill and cut into two 5-g. portions. Each portion
was placed in a glass bomb tube, and a concentrated
aqueous solution of ammonium polysulfide was added
to one, and ammonium hydrosulfide to the other.
Each solution contained approximately o. 5 g. of sulfide
sulfur. The tubes were sealed and heated for 6 hrs.
in an oil bath of 147 ° C.
Both samples appeared to be vulcanized to a slight
extent. The sample heated with ammonium poly-
sulfide was dark in color and quite sticky. The other
was lighter in color and not so sticky. Both samples
were extracted with acetone for 24 hrs., dried, and the
combined sulfur estimated.
The samples heated with ammonium polysulfide
and ammonium hydrosulfide were found to have sulfur
coefficients of 1.033 and 4-366, respectively.
CONCLUSIONS
1 — The activity of synthetic nitrogenous organic-
substances as accelerators is not proportional to the
dissociation constants of the original substances and.
with the exception of members of a closely related
series, no definite relationship exists between the activi-
ties and the dissociation constants of the original
substances.
2 — Substances which decompose or dissociate into
other substances of acid character, or react with other
components of the mixture to form substances of acid
character, do not accelerate unless a neutralizing
base or salt is present.
3 — Vulcanization is effected by heating rubber in
a closed system with concentrated aqueous solution of
ammonium sulfides.
ELECTRIC OVEN FOR RAPID MOISTURE TESTS
By Guilford L. Spencer
The Cuban-American* Sugar Co., New York and Cuba
The appreciation of the role of the moisture of raw
sugars in determining their storage qualities, and the
need of very prompt results of moisture tests in sugar-
cane bagasse, in controlling the mill work, led the
author to devise an oven for rapid tests. The ordinary
types of ovens are of great value in these tests, but
unfortunately the results in their use cannot be re-
ported with sufficient promptness to meet the needs
of thorough factory control. If raw sugar contains
more moisture than a certain safety factor indicates
is desirable, it may break down before it reaches the
market or refiner and serious loss of sucrose result. If
the residue of cane milling, the bagasse, contains ex-
cessive moisture, this necessitates a waste of fuel and
a loss of sugar.
The oven here described is the result of several
years' experimenting and the construction of several
models. As indicative of the rapidity that has been
achieved in the present model, raw sugar may be dried
in it in 10 min., and cane bagasse in about 30 min.
It was hoped to present comparative tests of several
materials and more systematic experiments with sugars.
' U. S. Patent 1.348,757.
1 Presented before the Section of Sugar Chemistry at the 60th Meeting,
of the American Chemical Society. Chicago, 111., September 6 to 10, 1920
Jan., 1 02 1
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
but the pressure of manufacturing duties prevented
the laboratories from doing more extended experiment-
ing.
DESCRIPTION OF OVEN
Briefly, the oven is a convenient device for convey-
ing a large volume of heated air through a capsule
containing the material to be dried. The current of
air is induced by a steam ejector or an air pump.
Connection is made with the vacuum system in sugar
factories. The heated air is carried against the cover
of the oven to promote mixing. The drying capsule
may be of metal or other construction, but, for sugar
work and a large proportion of general tests, metal
is most suitable. The bottom of the capsule is closed
with monel metal filter cloth, which freely passes air
but retains very fine powders. The capsule makes a
joint with its seat in the oven, over an annular channel
which connects several capsule openings, and leads to
the vacuum pump or ejector connection. The air
inlet to the oven may be regulated, if desired, for
operating under a partial vacuum. The air is drawn
over a heating element consisting of spiraled resis-
tance wire wound over a core. The travel of the air
is directed through a very narrow annular space, occu-
pied by the resistance wire, which forces it into inti-
mate contact with the resistor. The element is housed
inside the oven's drying chamber, thus reducing radia-
tion loss. The air pressure on the material in the
capsule forces the latter to a good seat and prevents
air leakage. The oven is made in two sizes, small
for general use and large for bulky materials.
The service wires are connected in series with a
sliding contact rheostat for temperature control, an
electric time switch or interval timer, and the heating
element. The time switch opens the circuit and rings
a bell at the termination of the drying period. The
heating element is housed conveniently for renewal.
OPERATION OF OVEN
The time switch is adjusted for the desired drying
period; the capsule, with the sample, is placed on its
seat in the oven and the unused openings are closed;
the vacuum or pump connection is opened; the time
switch is closed and the clock is started; the resistance
is rapidly cut out with the rheostat slide, and the tem-
perature is regulated. The drying now proceeds until
the time switch opens the circuit and rings a bell, sig-
naling the termination of the operation.
Any material that will freely pass a current of air
may be dried in this oven. Refinery press-cake, con-
sisting almost entirely of kieselguhr ("filter-eel") is
successfully dried. Liquids must be absorbed by a
suitable carrier and this be placed in a capsule. The
thermometer bulb must be located immediately over
the capsule. Owing to the short drying period, it has
not been found necessary to use a thermostat, though
provision is made for one. About one minute is re-
quired to heat the oven to the drying temperature.
The following experiment with absorbent cotton
indicates the rate of drying that may be attained: a
sample of cotton was dried to constant weight, then
saturated with distilled water, and in this condition
placed in a capsule in the cold oven and heated at
105 ° C.
Dry weight of cotton 0.8888
Weight after 5 min. drying 0.9858
Weight after an additional 5 min. drying 0.8889
COMPARATIVE TESTS WITH OLD TYPE OVEN
At intervals, this company distributes control sam-
ples among its laboratories, through its central control
laboratory. These samples are tested independently
by the chemists conducting the routine factory control,
and the results are reported to the author's office for
tabulation and comparison. The figures quoted below
are from such tests. A number of individual tests are
given to call attention to variations. In the tests of
raw sugar (Series I), the drying period was 20 min.
at 1050 C. with the new type of oven, starting with
the oven cold. In the usual types of electric oven, the
drying period was the customary 3.5 hrs. at 1050 C.
Series I
New Oven
Chemist A B C D' E1 F
Per cent moisture . .... . 0.72 0.73 0.72 0.78 0.78 0.70
Average per cent moisture = 0.74
Usual Type Electric Oven
Chemist G H I J K Control Laboratory
Per cent moisture . 0.68 0.74 0.69 0.72 0.75 0.76 0.79 0.77
Average of factory laboratories = 0.72
Average of control laboratory =0.77
Average of all tests =0.74
1 Kflluent air temperature, 95° C.
A second sample was sent to the various factory
laboratories, in which every precaution was observed
to assure thorough mixing of the sugar, and complete
filling and proper sealing of the bottles. A sugar of
very high moisture test was purposely selected. Four
heating periods were specified for the new oven, a
capsule of sugar for each, and the customary period
of 3.5 hrs. for the ordinary oven. The temperature
in each test was 1050 C. The results are tabulated
in Series II:
Chemist
Drying period, min. 3
Per cent moisture . . 1.36
Chemist .
Drying period, min. 3
Per cent moisture. . 1 . 28
Average = 1.45 (20 min )
H
SERIES II
New Oven
5 15 20
1.40 1.45 1.47
. A (retests)—
3 5 15
1.35 1.40 1.45
1.33 1.39 1.42
:ual Type Electric Over
1.38 1.42 1.44 1.44
Chemist
Per cent moisture. . 1.52 1.43 1.52
Average of 17 factory tests = 1 .48
' Effluent air temperature, 95" C.
1 . 43 1 . 50
ntrol Chemists
Lv., 1.50
The tests by Chemists D and E were made in an
early model of the oven in which the heating element
is immediately over the capsule. For this reason the
temperature of the air after passing through the cap-
sule is given. There is always danger of overheating
with this arrangement and it has been abandoned.
Most of these tests, except in the central control
laboratory, were made by young men with very little
laboratory experience. This applies to both ovens, so
these conditions were alike. Apparently the condi-
tions that lead to irregularities are no more in evidence
in the new than in the usual ovens. There is prob-
ably less danger of decomposition of the material dur-
ing desiccation in the new than in other ovens.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 1
by reason of the very short heating period and the
prompt removal of the vapors.
Cane bagasse apparently withstands high tempera-
tures and is usually dried in the ordinary ovens at
no" to 115° C. It may be dried in the new oven at
130° or even 1400 C. without decomposition that in-
troduces an appreciable error. A sample weighing 100
g. and containing 50 per cent moisture may be dried
in the large oven at 130° C. in 30 min., the drying
period depending somewhat upon the mechanical state
of the material. Samples have been dried at the high
temperature, during various periods ranging from 3c
min to 00 min., without increase in the indicated
moisture.
ADDRL55E5 AND CONTRIBUTED ARTICLES
THE CHEMISTRY OF VITAMINES1
By Atherton Seidell
Hygienic Laboratory, U S. Public Health Service, Washington, D. C
The first indication of the existence of the substances now
designated by the term vitamine was obtained some twelve
years ago during the investigation of the cause of beri beri,
a disease prevalent among people who consume rice as their
chief article of diet. This disease originated after the intro-
duction of modern milling methods in which the surface layers
of the rice are removed by a polishing process. It was found
that the disease could be prevented by adding to the diet rice
polishings or extracts of these.
In 191 1 Casimir Funk, who was engaged in attempts to isolate,
by chemical means, the constituent of rice polishings responsible
for the remarkable curative effects, proposed that this hitherto
unrecognized substance be called vitamine. He also developed
the conception of deficiency diseases and collected much evidence
to prove that the absence of these previously unrecognized sub-
stances from an otherwise adequate diet is the cause of serious
nutritional disturbances, resulting in characteristic abnormal
conditions. Among such diseases he included beri beri, poly-
neuritis in pigeons, scurvy, and pellagra. The term vitamine,
therefore, refers to one or more substances of unknown composi-
tion, extremely small amounts of which are necessary for normal
nutrition.
Although many attempts have been made to isolate vitamine,
none have so far been successful, and our knowledge of this
class of substances is, therefore, still limited almost entirely to
the physiological effects they produce.
Since it has not been possible to determine the vitamine con-
tent of foods by chemical methods, feeding experiments for
this purpose have been developed and extensively applied.
The principle on which these are based is the feeding of diets
which contain adequate amounts of the hitherto recognized
essential dietary constituents, namely, carbohydrates, protein,
fats, and inorganic salts, highly purified to insure that they con-
tain no vitamine, and simultaneously giving measured amounts
of the sample being tested for its vitamine content. On the
basis of such experiments tables have been constructed which
show the comparative amount of vitamine in a large number of
foodstuffs. Furthermore, this work has led to the differentia-
tion of at least three well-characterized vitamines. These are
the water-soluble antineuritic vitamine, the fat-soluble, growth-
promoting vitamine, and the antiscorbutic vitamine. Of these,
the first appears to be the most stable towards the chemical
manipulations required for its separation from the substances
with which it occurs naturally. It is this one, therefore, which
has received most attention at the hands of chemists. Although
the results which have been obtained so far have not greatly
clarified the problem as to the chemical nature of this unknown
essential dietary constituent, it is believed that a brief review
of the experiments along this line may prove of general
interest.
1 Address of the retiring president of the Chemical Society of Wash-
ington, November 11, 1920.
EXPERIMENTAL PROCEDURES
At the cime Funk began work on the problem the following
facts had been qualitatively established in regard to the anti-
neuritic vitamine. It is neither a salt nor a protein. It i>-
soluble in water and in alcohol. It is dialyzable. and is destroyed
by heating to 1300 C.
Funk and others have since shown that it is not destroyed by
hydrolysis for 24 hrs. with 20 per cent sulfuric acid. It has
also been found that phosphotungstic acid precipitates this
vitamine completely from aqueous solution. Funk's method
for its isolation is, accordingly, based upon the use of this re-
agent. In general, the procedure consists in extracting the raw
material with acidified alcohol, evaporating the extract to a small
volume, acidifying the aqueous solution with about 10 per cent
of sulfuric acid, and precipitating with phosphotungstic acid.
This precipitate is decomposed with excess of barium hydroxide,
and after removal of the excess of the latter, the solution is
acidified with hydrochloric acid and evaporated. The residue
is extracted with alcohol and the alcoholic solution further puri-
fied by precipitating with various reagents, such as lead acetate,
mercuric chloride, silver nitrate alone and followed by barium
hydroxide, phosphotungstic acid, silicotungstic acid, etc.
Funk at first reported that the crystalline material he suc-
ceeded in isolating from rice polishings, yeast, milk, bran, and
other materials, by means of phosphotungstic acid precipitation
and subsequent decomposition of this precipitate, was the anti-
neuritic vitamine. Later, in collaboration with Drummond he
was forced to abandon this position since the compound he
originally thought was vitamine proved to be nearly pure nicotinic
acid. Retraction was therefore made of the claim that isola-
tion of the curative substance had been effected.
A number of other investigators have followed this general pro-
cedure and have reported the isolation of crystalline compounds
with antineuritic properties. Thus, Suzuki, Shimamora, and
Odake have given the name oryzanin to an active product they
obtained from rice polishings by alcoholic extraction followed
by phosphotungstic acid precipitation. Their experiments
were repeated by Drummond and Funk but their results were
not confirmed. Edie and his co-workers isolated a crystalline!
product from yeast by methyl alcohol extraction and silverll
nitrate baryta precipitation to which they gave the name
loruliti. but for which further evidence is lacking that it is pure
vitamine
Numerous modifications of the general plan of extracting and
precipitating have been tried without success and many novel
procedures have been introduced. Thus Sugiura recently made
use of air dialysis to obtain crystalline vitamine from water
extracts of dried yeast. The yield was very minute and physio-
logical tests of the product did not indicate that it possessed an
exceptionally high degree of activity. McCollum reported that
although organic solvents, such as ether, benzene, and acetone,
do not extract the antineuritic vitamine directly, if the alcohol
extract of the vitamine-containing material is evaporated on dex-
trin, and this extracted with the organic solvent, benzene ap-
pears to dissolve the vitamine, but acetone does so to only a
very slight extent.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
73
Recently, Osborne and Wakeman have proposed a modifica-
tion by which it appears that the removal of a considerable
amount of nonvitamine material can be effected by a very simple
expedient. This consists in adding the fresh yeast to slightly
acidified boiling water and continuing to boil this mixture for
about 5 min. This coagulates the protein and permits its com-
plete removal by filtration. The protein-free filtrate appears
to contain all of the vitamine originally present in the yeast.
An attempt to precipitate the vitamine fractionally from the
evaporated filtrate by means of increasing concentrations of
added alcohol was, however, only partially successful.
A procedure which has been found to offer marked advantages
in separating vitamine from the major part of the substances
with which it occurs in natural products is based upon
the property of being selectively adsorbed by certain
varieties of fuller's earth The particular variety found to be
most useful in this respect is that obtained from Surry, England.
In the case of brewer's yeast, which is, perhaps, the raw ma-
terial so far used to greatest extent as a source of vitamine, the
fresh yeast is permitted to antolyze, and the thick liquid which
results is filtered. This clear red-brown filtrate contains about
23 per cent of solids and is very rich in vitamine. If fuller's
earth is added to it in the proportion of 50 g. per liter and kept
in intimate contact with the liquid for about one-half hour and
then removed by filtration, the yeast liquor is found to contain
practically the same 23 per cent of solids originally present, but
all of the vitamine is now firmly attached to the fuller's earth,
and repeated washing does not remove an appreciable amount of
vitamine from it.
This fuller's earth-vitamine combination has, for convenience,
been designated as "vitamine activated fuller's earth." Physio-
logical experiments have shown that no noticeable deterioration
occurred in samples of the "activated solid" kept for over 2
yrs. Large amounts of it can be readily accumulated and,
after being uniformly mixed, it can be standardized by physio-
logical tests for its vitamine content. Such material forms a
particularly satisfactory starting point for the comparative study
of various methods for the isolation of vitamine.
In order to remove the vitamine from its combination with
fuller's earth, the only plan so far devised is based upon the use
of dilute alkali. This is a serious disadvantage since vitamine is
particularly unstable in an alkaline medium. It is, therefore,
necessary to operate rapidly and return to neutral or acid con-
dition promptly. The aqueous solution thus obtained from
"activated fuller's earth" has been found by physiological tests
to contain only about one-half of the total vitamine originally
present in the solid. There is every reason to believe, however,
that aqueous solutions so obtained are as free from extraneous
material as it has been possible to obtain in any other way.
Tests of the stability of the vitamine contained in them, made
by passing in air or oxygen, showed that comparatively little
destruction resulted. It is, however, not known how long the
vitamine activity is retained by such solutions.
Using the aqueous vitamine solution prepared as just described,
various attempts have been made to recover from it the active
material in the pure solid state. These attempts have so far
been unsuccessful. By careful evaporation of the solution, the
products successively obtained show more or less activity by
physiological tests, but in no case does the resulting material
possess the appearance or character which a pure product would
be expected to show. The action of solvents such as benzene,
acetone, ethyl acetate, and chloroform on these residues fails
to effect a separation of active from inactive material.
The numerous experiments which have been made with these
comparatively pure vitamine solutions have shown that the
vitamine tends to divide itself between the several fractions ob-
tained, rather than to become concentrated in one or the other.
The experiments are, however, always attended with con-
siderable uncertainty on account of the difficulty of keeping
track quantitatively of the vitamine. The only tests avail-
able for this purpose are feeding experiments, and even the sim-
plest of these require several weeks and give very uncertain results.
PHYSIOLOGICAL TESTS
The physiological test used by Funk and others of the earlier
workers was the cure of polyneuritic pigeons. By this test the
birds were fed exclusively on rice until they developed typical
paralysis, which ordinarily occurred within 2 to 3 wks. They
were then given measured doses of the sample in question. If
this contained vitamine, a remarkable improvement in the con-
dition of the pigeon occurred within a few hours. The diffi-
culty, however, is that a great variety of compounds may cause
an improvement:, and in some cases a temporary alleviation of
the condition may occur spontaneously. It is, therefore, very
difficult to interpret the indications of the test, and erroneous
conclusions may easily be drawn from it. The use of this test,
no doubt, accounts for many of the unconfirmed claims and con-
clusions which have been published in regard to the isolation
of vitamine. This curative test has now been abandoned by
almost everyone engaged in efforts to isolate vitamine.
The physiological method which appears to yield the most
trustworthy indications, as to the amount of vitamine present
in a given sample, may be referred to as the protective method.
A pigeon is fed exclusively on polished rice and simultaneously
given measured doses of the sample containing the unknown
amount of vitamine. It is weighed at frequent intervals and
if no loss in weight occurs within 2 or 3 wks., it is apparent that
the sample in question is furnishing an adequate supply of vita-
mine to meet the needs of the pigeon. If the amount of vita-
mine supplied is insufficient, a characteristic curve of loss in
weight will be obtained. It is apparent, however, that this
test will fail to show whether the sample contains more vitamine
than is just required to maintain constant weight. Hence,
quantitative results often require repetition of the test, and,
therefore, call for expenditure of much time and patience.
There is, consequently, a very great need for a more rapid,
accurate, and trustworthy method for the estimation of vitamine
in unknown samples.
In this connection there has recently been proposed by Mr.
Roger J. Williams a very ingenious procedure, which, if the
anticipations of its utility are realized, may prove of the greatest
assistance in the solution of the problem as to the chemical
nature of vitamine. This method is based upon the observation
that yeast requires vitamine for its growth, and the amount of
growth depends upon the quantity of vitamine present in the
culture medium. The period of the test is relatively short, and
the manipulations and apparatus are simple. A synthetic
culture medium containing asparagine, ammonium sulfate, sugar,
and salts is treated with known amounts of the vitamine solu-
tion, sterilized, and seeded with a suspension of a known weight
of yeast taken from the center of a fresh Fleischmann's yeast
cake. The amount of growth which occurs within 18 hrs.
at 30° C. is determined by filtering the yeast on a prepared
Gooch crucible, drying at 103 °, and weighing. The weight
is reported to be directly proportional to the amount of vitamine
in the solution.
LOSS OF VITAMINE ACTIVITY ON FRACTIONATION
One point upon which there is general agreement by most
investigators is that the active material is rapidly dissipated
during the several manipulations involved in the isolation pro-
cess. Each successive fractionation yields products of diminish-
ing vitamine activity. Considering the relative stability of
vitamine in its natural state, the reason for its rapid loss of
activity, when separated from most of the substances with which
it is associated in foodstuffs, is difficult to explain. An ingenious
assumption in this connection was made some years ago by Mr.
74
THE JOURXAL OF IXDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
R. R. Williams, formerly of the Bureau of Chemistry. He-
suggested that the activity is associated with the tautomeric
change which the vitamine complex, in all probability, easily
undergoes. He even thought it possible, and sought to find
the conditions under which the change from active to inactive
form, and rice versa, takes place. With such knowledge it would
be expected that the activity could be restored to vitamine con-
centrates, which had become inactive through fractionation
processes. All experiments along this line, however, were un-
successful. Although this hypothesis of Williams is very in-
teresting and suggestive, it is obviously impossible to obtain ex-
perimental support for it at this stage of our knowledge of vita-
mines.
NATURE OF VITAMINE ACTIVITY
As already mentioned, there have been a number of investi-
gators who have reported the successful isolation of vitamine
in a more or less pure crystalline state. In practically all cases,
however, the crystalline products, although in each case showing
more or less activity by physiological tests, have turned out to
be well-known compounds, such as nicotinic acid, adenine, choline,
betaine, guanine, etc., in which the vitamine function could not
be expected to reside. The activity noted in such compounds
as these can, no doubt, be best explained on the assumption
that vitamine was present in or on the crystals as an impurity.
When it is remembered that relatively minute amounts of these
crystalline substances have been found to produce physiological
results, which must have been due to the vitamine present as
a contamination, the exceedingly small amount of vitamine
necessary to produce a noticeable effect is realized. This
raises the question as to whether vitamine takes part as such in
the nutritional processes, and is converted into less complex
compounds, in the same manner that the other ingredients of
the diet are transformed," or simply acts by its presence in in-
finitesimally small amounts, in the same way that enzymes and
co-enzymes accelerate certain chemical reactions.
The view that vitamine is metabolized exactly like the other
constituents of a normal diet was early adopted by Funk, and
it is this conception which has been tacitly accepted so far.
Judging from the nervous symptoms and fatty degeneration of
the nerve cells in vitamine deficiency, Funk considered it most
probable that vitamine is necessary for the metabolism of the
nervous tissue. Thus, he states:
The lack of vitamine in the food forces the animal to get
this substance from its own tissues. The result is an enormous
loss in weight. After this available stock begins to be scarce
there is a consequent breaking down of the nervous tissue,
with the result that nervous symptoms, such as are observed
in beri beri, manifest themselves.
The conception that vitamine plays the part of an enzyme has
recently been developed in considerable detail by F. M. R.
Walsche.1 This observer considers that the reported properties
of the antineuritic vitamine suggest the probability that it is
an enzyme and is concerned directly in the hydrolysis of carbo-
hydrates.
Walsche first calls attention to the experimental evidence
that vitamine influences carbohydrate metabolism in a marked
degree. He points out that Maurer, Funk, Braddon, and Cooper
have shown a direct relationship between the amount of carbo-
hydrate ingested and the rapidity of development of polyneuritis.
Funk concludes from his experiments that increasing amounts
of foodstuffs rich in carbohydrate hasten the onset of polyneuritis,
and, consequently, that vitamine plays a more important part
in carbohydrate than in other metabolism. The evidence in
regard to the influence of vitamine on carbohydrate metabolism,
therefore, appears to be well established.
It is next pointed out by Walsche that the clinical picture of
beri beri and polyneuritis accords more with an intoxication,
due to aberrant metabolism products of carbohydrates, resulting
1 Quart. J. Med., 11 (1917-18). 320
from absence of a specific accessory factor, than with a slowly
progressive diffuse degeneration of the nervous system, resulting
from a deficiency of a nutritive constituent required for this tissue.
These observations are believed to lend weight to the view
that the action of vitamine is of the type attributable to an
enzyme. It therefore appears of interest to compare the es-
tablished properties of vitamines with those of enzymes, and
ascertain if there are any characteristic differences which would
make it improbable that the two belong to the same general
class of substances.
COMPARISON OF VITAMINES WITH ENZYMES
Considering first the source of vitamines and of enzymes, it
is to be noted that both frequently occur together. Yeast,
which is perhaps the most prolific source of vitamine, also con-
tains several enzymes, namely, glyoxalase, invertase, and others.
The castor-oil bean and many fruit juices which furnish vitamine
also contain various enzymes.
In regard to the stability of vitamines and of enzymes towards
heat, it has been found that in aqueous solutions the antineuritic
vitamine is not destroyed at the boiling point, but is destroyed
when heated to no° for 2 hrs. In the dry state, in combination
with fuller's earth, it can be heated to at least 2000 without
appreciable destruction. The antiscorbutic vitamine, on the
other hand, is known to be much less stable toward heat and
drying than the antineuritic vitamine. In the case of enzymes,
the evidence appears to be that as a rule they are destroyed by
exposure to a temperature somewhat below 100°. It is not
known, however, whether the loss of activity caused by heating
is due to destruction of the enzyme, or due to some change in
the other components of the complex colloidal system of which
the enzyme forms a part. It cannot be said, therefore, that
enzymes may not be found, or the conditions realized, under
which a temperature equal to that withstood by the antineuritic
vitamine may not prove destructive.
Since, as mentioned above, vitamines and enzymes frequently
occur in the same raw material, similar methods for their re-
moval are employed. These may involve the use of the same
solvents or other purification agents. The solubility relation?
of the two classes of substances are, therefore, quite similar.
Both vitamines and enzymes readily form adsorption com-
pounds. This would indicate that vitamine possesses the same
colloidal type of structure as is believed to be common to enzymes.
On the other hand, it has been found that the antineuritic vita-
mine dialyzes readily through parchment paper. This raises a
doubt as to the colloidal character of the antineuritic vitamine.
As pointed out by Walsche, however, there are other substances
which show all the usual characters of colloids and pass slowly
through parchment paper. The colloidal aniline dyes exhibit
all degrees of diffusibility, while in invertase and diastase we
have examples of diffusible enzymes.
The next characteristic of vitamine which may be considered
is the ease with which the activity is destroyed in alkaline solu-
tion. Considering enzymes from this standpoint it is known that
some are active only in acid and others in an alkaline medium.
The instability of both vitamines and enzymes, under particular
conditions of the solution in which they exist, is, therefore, a
common characteristic.
In regard to the failure of the attempts which have been made
to isolate enzymes and vitamines, the striking feature in both
cases is the progressive loss of activity during the application of
the analytical processes designed for their isolation. It is known
that since enzymes are colloids they carry down with them, by
adsorption, various constituents of the solutions from which
they are precipitated Consequently, they may show tests for
carbohydrates, proteins, etc., which gradually diminish as the
purification processes are improved. Simultaneously, there is
a loss of activity of the enzyme, probably due to the removal o:
bodies necessary for the full activity of the enzyme. The ex-
Jan., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
perience with vitamines is of a similar character. It is, there-
fore, apparent that the two groups of substances conduct them-
selves, in respect to fractionation procedures, in an entirely
analogous manner.
The one outstanding characteristic of an enzyme, which should
serve to dilTcrentiate it from everything with which it might be
confused, is the property of accelerating chemical reactions,
without itself being destroyed. This has been demonstrated,
to a certain extent at least, in the case of some of the well-
characterized enzymes. That it can be shown in the case
of vitamines, however, is out of the question at present, since the
only test of the activity of a vitamine is by means of a living
organism, and in such cases the recovery of the vitamine at the
conclusion of its period of action is obviously impossible.
There is this in common, however, that the apparent amount
of vitamine required for a given result is of the same order of
magnitude as required for the transformations effected by
enzymes. Thus, for instance, it has been shown that invertase
can hydrolyze 200,000 times its weight of saccharose, and rennet
can clot 400,000 times its weight of caseinogen in milk. In
the case of vitamine, fractions have been prepared of which only
a few tenths of a milligram per day are sufficient to supply the
requirements of a pigeon maintained on a vitamine-free diet.
On the basis of the above comparison it is seen that, aside
from a possibly significant degree of dialyzability, there is no
outstanding evidence that vitamines should not be classed with
the enzymes.
This viewpoint is further strengthened by the negative evi-
dence that, even in spite of the repeated efforts of able investi-
gators, the original conception that vitamine is a well-charac-
terized chemical individual capable of being isolated has never
been realized. In conclusion, therefore, the question may well
be raised as to whether our knowledge of vitamines will not be
more rapidly advanced by tentatively including them in the
class of substances designated as enzymes.
THE MECHANISM OF CATALYTIC PROCESSES1
By Hugh S. Taylor
Princeton University, Princeton, New Jersey
HETEROGENEOUS CATALYSIS
!n reviewing the general field of contact catalysis, attention
cannot but be directed to the diversity of views obtaining in
reference to the mechanism of tha process, manj' of which are
capable of direct experimental check, which, unfortunately,
in so many cases, is not applied. Sabatier1 suggests that hy-
drogenation and dehydrogenation processes occurring in con
tact with finely divided metals are to be ascribed to the capacity
of these metals to form unstable hydrides which interact with
the other components of the system to yield the reaction prod-
ucts. Thus, for the catalytic hydrogeuation of ethylene in
contact with nickel, Sabatier suggests the following scheme:
H2 + Ni; = Ni2H2
Ni2H2 + C2H, = C2H6 + Ni2
Bancroft3 suggests that it seems natural to assume that the
selective adsorption of the reaction products is the determining
factor. This conclusion, however, Bancroft shows, is not en-
tirely satisfactory in view of the known experimental behavior
of certain reactions studied. Thus, ethylene can be produced
by catalytic dehydration of alcohol by means of alumina even
in the presence of a large amount of water vapor. The beauti-
ful^studies of catalytic actions at solid surfaces recently made
by_Armstrong and Hilditch4 lead to a conclusion which is the
1 Abstract of a lecture given before the New York Section of the Amer-
ican Chemical Society, December 10, 1920.
s "La Catalyse en Chimie Organique," 2nd Edition, 1920, p. 60.
3 Presidential Address, American Electrochemical Society, April 1920.
< Proc Roy. Soc, 96 (1919), 137, 322; 97 (1920), 259, 265; 98 (1920), 27.
antithesis of the views of Sabatier. Armstrong and Hilditch
are inclined to regard the affinity of the carbon compound rather
than that of the hydrogen to the metal as of prime importance,
indeed, as the determining factor. In the hydrogenation of
unsaturated oils their experimental data lead them to the con-
clusion that the process of catalytic hydrogenation in the solid-
liquid state involves the primary formation of an unstable
complex or. "intermediate compound" between nickel and the
unsaturated compound. Dehydration reactions subsequently
studied lead them to similar conclusions in reference to primary
formation of nickel-organic compound complexes. Lewis1 as-
sumes that the mechanism of hydrogenation involves essen-
tially the dissociation of hydrogen, either adsorbed on or ab-
sorbed by the nickel, followed by collisions between the charged
nickel particles and the unsaturated molecules. He concludes
that, in the case of hydrogenation of olein and of similar sub-
stances, adsorption of the unsaturated compound on the metal
does not take place, the adsorption being restricted to metal
hydrogen components.
Many observations made in the course of experimental work
at Princeton tend to show that in the case of a variety of different
substances there occurs a definitely measurable adsorption by
catalytic agents of one or other of the reactants in a catalytic
change. In the study of the reaction kinetics of various cata-
lytic processes, indirect evidence has led to the conclusion that,
inter alia, benzene vapor is strongly adsorbed by nickel, and carbon
monoxide by nickel at temperatures as high as 150° C. Car-
bon dioxide is apparently adsorbed by iron oxide at tempera-
tures up to 250° C. Water vapor is adsorbed by various metal
catalysts. Systematic study of the magnitude of the ad-
sorption effect with a series of gases and a variety of catalytic
agents has, therefore, been undertaken. The preliminary re-
sults obtained are remarkable and serve to show the advances
in our knowledge of mechanism of catalytic change which may
come from such experimental study.
nickel — With Mr. A. W. Gauger, the adsorptions by nickel
of hydrogen, carbon monoxide, carbon dioxide, and ethylene,
using nitrogen as the reference gas have been determined in the
temperature ranges in which these gases react with one another.
The material used was reduced nickel on a porous support of
Non-Pareil Diatomite Brick, 7.5 g. of the material being em-
ployed, containing 0.75 g. of metallic nickel. The porous sup-
port used was graded between 8- and 10-mesh sieves. Table I
shows the cubic centimeters of different gases measured at 0° C.
and 760 mm. pressure which were required to fill the vessel con-
taining the nickel catalyst at 760 mm. pressure and various
temperatures.
Table I
. Temperature of Absorption Vessel, ° C. .
Gas 21 175 200 225 250 275
Nitrogen 15.04 9.8 9.4 8.8 8.5 8.1
Hydrogen 13.6 13.2 ... 12.0
Carbon dioxide 11.1 10.6 9.9 9.4
Carbon monoxide 14.05
Ethylene 14.07
If it be assumed that the adsorption of nitrogen by nickel
is negligible, the following values for the adsorption of different
gases, per gram of nickel upon the given porous support, are
readily derived.
Adsorption in Cc. (at 0° C. and 760 Mm.) per Gram Ni
Temperature ° C. 175 200 225 250
Hi 5.2 5.1 ... 4.73
COi 1.7 1.6 1.5 1.33
CO 5.66
CjH. 6.5
With ethylene, only one set of experimental measurements
has, as yet, been made. It suffices, however, to show that this
gas is more adsorbed than any of the other gases studied. With
carbon monoxide, the measurements have been limited to the
one temperature because, at lower temperatures the question
1 J. Chem. Soc, 117 (1920). 623.
76
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. r
of the formation of nickel carbonyl, Ni(CO)i, would necessarily
intrude. Above the temperature of 175° C. the measurements
are complicated by the catalytic decomposition of carbon mon-
oxide to form carbon and carbon dioxide
2CO = CO, + C.
The adsorption of carbon dioxide is noteworthy, although smaller
in magnitude than that of the other gases studied. With hy-
drogen, the initial adsorption effect is followed by a secondary
slow solubility effect which causes a slow increase in the volume
of gas required to fill the reaction vessel. This secondary change
is, however, so slow that the initial adsorption effect can readily
be measured with an accuracy of 1 per cent.
The results thus obtained with nickel may be generalized.
The gases which take part in the following reactions:
CO -(- 3Ha = CH, + HsO
C02 + 4H« = CH4 + 2H,0
C2H4 -{- H, = C^He
are all markedly adsorbed by a nickel catalyst in the temperature
range in which they react to form the stated reaction products.
copper — Similar experiments with these gases have been
performed by Mr. R. M. Burns, employing copper obtained by
reduction, at low temperatures, of copper oxide. The oxide was
produced by calcination of the nitrate in a stream of air. The
interest attaching to this study arises from the observations of
Sabatier with respect to copper as a catalytic agent. Sabatier
states that, under no conditions, can copper induce the inter-
action of carbon monoxide or carbon dioxide with hydrogen to
form methane. On the contrary, above 160° C, ethylene and
hydrogen react in contact with copper to yield the saturated
hydrocarbon, ethane. Preliminary experiments showed that
the adsorption effects with this metal were of a much lower order
of magnitude than with nickel. Consequently a larger sample
of reduced metal, 22.9 g., was used for the determinations.
The measurements of adsorption were made at 25° C, 110° C,
and 2180 C, at a pressure of 760 mm. The gases studied were
again nitrogen, carbon monoxide, carbon dioxide, hydrogen, and
ethylene. As a check on the nitrogen determination, to show
that the figures obtained with this gas represented zero adsorp-
tion, one determination was made at 25 ° C, with a specially
purified sample of helium, obtained through the courtesy of
the U. S. Bureau of Mines. Table II shows the number of cubic
centimeters of the different gases (measured at 0° C. and 760
mm. pressure) which are required to fill the reaction vessel con-
taining the reduced copper, when this is maintained at the three
stated temperatures.
Table II
Cc. Gas Required to Fill Vessel at
Gas 25° C. 110° C. 218° C.
Helium '..... 22.35 ...
Nitrogen 22.4 17.46 13 9
Hydrogen 22.4 17.6 13.9
Carbon dioxide 22.55 17.5 13.9
Carbon monoxide 23.9 18.1 13.9
Ethylene 24.1 18.1 13.9
The experiments show that only with ethylene and carbon
monoxide is there a measurable adsorption and with these gases
only at the two lower temperatures. At the temperature of
2i8° C, the volume of gas adsorbed is immeasurably small
in every case.
The experiments with copper and with nickel both show,
therefore, a greater adsorption of the unsaturated compound
than of hydrogen. It is the view of Armstrong and Hilditch
rather than that of Sabatier and Lewis which the present experi-
mental observations, therefore, tend to support, though natu-
rally a wide extension of the experimental range will be necessary
before any definite conclusions can be reached. This extension
is in progress. We are engaged on measurements of ad-
sorption with a wide variety of metals and metallic oxides under
varied conditions.
In connection with the adsorption experiments with ethylene
on copper., it is interesting to note that at the temperature at
which hydrogenation commences (i6o°) the adsorption of ethyl-
ene is already quite low. In other words, at this temperature,
the ethylene evaporates rapidly from the copper surface after
condensation has occurred. The experimental results obtained
with the gas at lower temperatures show that the copper sur-
face must be relatively free from adsorbed ethylene at the
temperature of hydrogenation. This is probably true also in
the case of the nickel experiments previously described. This
factor appears to us to be of cardinal importance in a discussion
of the mechanism of contact action. Furthermore, the fact
that, as far as adsorption by copper is concerned, carbon monoxide
behaves like ethylene, whereas hydrogenation of carbon mon-
oxide in contact with copper cannot be achieved, shows that
further insight into the several factors prevailing is still needed .
We propose to obtain this by extending our studies on adsorp-
tion by various metallic catalysts .which either promote or are
inert in the hydrogenation process. Thus, in contact with co-
balt, carbon monoxide and hydrogen yield methane. With
iron, no methane is obtained.1
Since carbon monoxide and hydrogen do not interact in con-
tact with reduced copper it is possible to study the adsorption
of these gases from mixtures of the same. Similar studies can
be carried out with mixtures of ethylene and hydrogen at tem-
peratures below those at which these gases interact. In a
preliminary manner we have studied the adsorption of various
mixtures of hydrogen and carbon monoxide and hydrogen and
ethylene at 25 ° C. The results obtained are very remarkable
and promise further insight into the catalytic process. In
Table III are given the adsorptions in cubic centimeters of gas
absorbed by 22.9 g. of reduced copper with various mixtures
of the two pairs of gases. In the last column are given the cal-
culated values for adsorption, if the amounts adsorbed were
in direct proportion to the partial pressures of the gases present.
Table: III
Cc Gas Calculated Adsorption
(at 0°, 760 Mm.) if Proportional
Absorbed at 25° C. to Partial Pressures
Gas Mixture and 760 Mm. of Gases
0% Hi, 100% CO 1.5
50% H:, 50% CO 1.3 0.75
84.5% H2, 15.5% CO 0.9 0.23
100% Hs 0.0
0% Hi. 100% C3H4 1.7
53% Hs, 47% CjH. 1.2 0.8
100% Hi 0.0
It is thus apparent that carbon monoxide and ethylene are
much more markedly adsorbed at lower pressures than at higher
pressures, the adsorption tending to become independent of the
pressure as this increases.
THE KINETICS OF CATALYTIC ACTIONS
The abnormal variation of adsorption with pressure consti-
tutes a factor of considerable importance in regard to the mech-
anism of the catalytic process. If the catalytic reaction occur*
in the surface layer it is apparent that the pressure-adsorption
ratio determines the concentration of the reactants in the active
layer. For example, in the reaction
C2H4 "r H2 = C2H6
the rate of formation of ethane in the gas phase is
Ri = fc(/>C*H.)(fc&).
-where pc*Ri and pHi are the partial pressures of the inter-
acting gases. Similarly at the surface of the copper, the rate
of reaction is
R2 = fe(Cc2H.)(CH,1.
where Cc2H( and Ch* are the concentrations of the gases at the
surface. Now, if the experimental conditions were so chosen
that the concentration of ethylene in the surface layer was inde-
1 Sabatier, hoc. cil.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
77
pendent of the prevailing partial pressure of the gas, i. e ,
CCiH, = HpC2Kt)° = k,
the reaction in the surface layer would become
R2 = fc.fe.(CHs).
So, if the hydrogen concentration were governed by Henry's
law, the reaction would be bimolecular in the gas phase and ap-
parently monomolecular in the surface layer.
The same considerations might be extended to the question
of the equilibrium constant of the given reaction. In the case
cited, with the same assumptions as to the distribution ratio
between gas and surface layer, the equilibrium constant Kg
in the gas phase would be
K = ki(pc,H,)(pH,)
kziPdHe)
In the surface layer, however, if the hydrogen and ethane obeyed
Henry's law, but the ethylene concentration was independent
of the partial pressure of ethylene, the equilibrium constant,
Kj, would be
_ fe.fc.(CH.)
' WCCH.) '
It is apparent, therefore, that the position of equilibrium in
the surface layer could be markedly different from the true
equilibrium in the gas reaction. It cannot, however, be too
strongly emphasized that this does not mean that a catalyst
can shift the equilibrium of the gas reaction. The equilibrium
in the gas phase remains identically the same as it would be if
achieved thermally without a catalyst. An analogous case,
with two solutions, is that studied by Kuriloff,1 who investi-
gated the equilibrium between /3-naphthol and picric acid in
water and benzene solutions, in presence of solid picrate. The
product of the millimolar concentrations of free naphthol and
free undissociated picric acid varied widely in the two solvents,
being 2.89 in water and 7550 in benzene, in agreement with the
deductions from distribution experiments of the individual
substances. The presence of a benzene layer adjacent to the
aqueous layer, however, did not in any way disturb the equilib-
rium in the aqueous layer.
Table IV
1 (Hours)
*(SOi)
0.5
12
1.0
20
1.5
27
2.0
32
2.5
36
3.0
40
3.5
43.5
4.0
46.5
5.0
52
6.0
57
7.0
62
8.0
67
9.0
72
10. 0
76
11.0
80
■ 12.0
84
As a consequence of' these considerations it follows that the
study of the kinetics of catalytic reactions may give reaction
equations totally different from those to be expected from the
stoichiometric equation for the gas reaction. This is well
known from the experimental work of Fink on the mechanism
of the formation of sulfur trioxide from sulfur dioxide and oxygen,
of Bodenstein and his co-workers on carbon monoxide and oxygen,
and from the recent studies of Armstrong and Hilditch in liquid
media. Furthermore, since, as the experiments cited previously
show, the distribution of gas between the reaction space and
catalyst surface is different at different partial pressures, it fol-
lows that a given equation for the reaction kinetics, while valid
over one pressure range, may be invalid over another pressure
range. This is clearly shown in many of the kinetic studies
1 Z. physik. Chem., 26 (1898), 419.
quoted. Fink's results on sulfur trioxide formation show no
agreement with a termolecular reaction equation in the early
stages of an experiment. Towards the completion of the pro-
cess, however, an excellent termolecular constant, k3, is obtained
as Table IV shows.
On the interpretation given in the preceding paragraphs the
distribution of sulfur dioxide and oxygen between the gas phase
and the contact material must in the later stages of the reaction
follow Henry's law.
Bodenstein and Ohlmer found that the reaction between
oxygen and carbon monoxide in contact with quartz glass takes
place at a rate proportional to the pressure of oxygen and in-
versely proportional to the pressure of carbon monoxide. In
contact with crystalline quartz, however, the reaction followed
the ordinary stoichiometric equation, a result which should
have attracted a much greater attention in the discussion of
catalysis than it has yet done. On the interpretation here given,
this diversity of reaction mechanism, in the same reaction,
with the two catalysts, is to be ascribed to the different dis-
tribution ratios between the gas phase and the surface layer on
the contact mass. An experimental test of such a viewpoint
could be carried out.
HOMOGENEOUS CATALYSIS
For catalytic reactions in homogeneous systems the inter-
mediate compound theory appears to be generally applicable
For most such processes a probable cycle of successive reactions
can be postulated. In many cases the intermediate compounds
have been isolated. In other cases, the indirect evidence lead-
ing to such a conclusion is being steadily brought forward. For
example, Jones and Lewis' give evidence for the formation of an
intermediate sucrose-hydrogen-ion complex in the sugar inver-
sion process. In ester hydrolysis the systematic researches of
Kendall and his colleagues2 have established the existence of
binary and ternary compounds between ester, catalyzing acid,
an ' water. The tendency towards compound formation is the
more marked, the greater the chemical contrast between the
basic nature of the ester and the acidity of the catalytic agent
The concordance of this conclusion with the observation that
the catalytic activity in ester hydrolysis is greatest with the
strong acids and diminishes with decreasing strength of acid
forms a striking piece of evidence in favor of the intermediate
compound theory in such systems.
Development of the radiation theory of chemical action
(Trautz, Lewis, Perrin) has led to the supposition that the neces-
sary energy of reaction is supplied by suitable infra-red radia-
tion. In the beginning, the attempt was made simply to as-
sociate the critical energy increment with the heat of reaction
and to show that such relationships were plausible in view of the
infra-red absorption bands shown by the reacting substances.
Recently, Rideal and Hawkins3 have attempted to show that
infra-red radiations actually accelerate the velocity of hydrolysis
of methyl acetate. A pronounced positive result is claimed.
The conclusion, however, can be accepted only with reserve,
for the experimental conditions, as far as they may be de-
duced from the publication, were not ideal. Indeed they were
such that, if the positive effect attained is real, the magnitude
of the effect of the infra-red radiations must be enormous. The
experiments were carried out with 100 cc. of an aqueous solution
containing catalyzing acid and ester. The radiation was intro-
duced into the system from above. Owing to the opacity of
water to infra-red radiation it is therefore evident that only a
film of solution in the surface layer was being irradiated. Since
the stirring was only occasional, it is apparent that hy fir the
greater bulk of the solution was not acted upon by the infra-
' J. Chem. Soc . 117 (1920), 1120.
« J. Am. Chem Soc, 1914, el seq.
> J. Chem Sot., 117 (1920). 1288.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. n, No. i
red rays. These could be distributed through the solution only
by diffusion of the activated hydrogen ions or hydrogen-ion-
i/ster complexes from the surface into the interior.
The question, however, of the possible activity of infra-red
experiments should be undertaken. If such be done the choice
of a reaction system through which the radiation might readily
penetrate would facilitate the attainment of decisive experimental
test. We hope to take such problems in hand at an early
rays is so important that duplication and amplification of such date.
INDUSTRIAL AND AGRICULTURAL CHLMI5TRY IN THL BRITISH
WL5T INDILS. WITH SOML ACCOUNT OF THL WORK OF 5IR
FRANCIS WATTS, IMPLRIALCOMMISSIONLR OF AGRICULTURL
By C. A. Browne
X. V Sugar Trade Laboratory, 80 South St., Nsw V.
Received October 5, 1920
The casual traveler, who makes his first voyage among the
West Indian Islands and views from his steamer the crumbling
walls of old fortresses, or the remains of stone mansions, acquires
at the outset the feeling of a departed civilization. This first
impression is intensified by the ruined walls and towers of ancient
muscovado sugar works, which, according to the lines of Grainger,
the poet of St. Kitts, were once lit up at night by "far-seen
flames bursting through many a chimney." It is only when
the vessel steams past these scenes of desolation into the harbor
of Basseterre, the former home of this poet, and the smoking
stacks of a modern sugar factory come into view that the im-
pressions of decadent or vanished industries are dispelled.
The present paper is an effort to tell briefly the story of this
change from an old to a new order of things, in which transition
the efforts of a distinguished member of the American Chem-
ical Society have played a prominent part.
With the abolition of slavery in the British West Indies in
1834, the old industrial system of these islands came to an end.
The production of sugar, which had always been the chief source
of wealth, began to decline, partly from lack of labor and partly
from unequal competition with the more scientifically conducted
beet-sugar industry of Europe, which marked its phenomenal
rise from the date of the abolition of slave labor in the colonies.
The inequality of this conflict was later enhanced by the favoring
export bounties which beet sugar received, and had it not been
for the high prices of sugar, which existed for 20 years
after the outbreak of the American Civil War, the declining
sugar industry of the West Indies would have completely dis-
appeared.
The over-stimulation of the beet-sugar industry by bounties
and premiums soon had, however, its inevitable effect, and
between 1882 and 1892 the price of muscovado fell from 7.3
cents to 2.8 cents per pound. The industrial condition of the
British islands was becoming hopeless, and appeals were made
for assistance to the mother country, which for the 50 years
following the abolition of slavery had shown a strange indifference
to its West Indian possessions. This neglect had in fact become
so marked that many planters believed their only hope to consist
in political union with the United States. It was only with the
growing development of the Panama Canal enterprise in the
late eighties and the dawning sense of the future strategic and
economic importance of the island approaches to this gateway
of the Pacific that Great Britain began to take a renewed in-
terest in her tropical colonies. From that time until the present,
increasing efforts have been made to improve the industrial,
economic, and educational life of the British West Inches.
Botanic gardens, experiment stations, and other scientific
institutions were established, among the earliest of these being
the government laboratory in the island of Antigua, which
began its work on Jan. 1, 1889, and of which Dr. (now Sir)
Francis Watts, a graduate of Mason College, Birmingham,
assumed charge as analytical chemist.
IMPROVEMENTS IX SUGAR MANUFACTURE
One of the first investigations which Dr. Watts instituted on
beginning his new duties was a thorough examination of the
field and factory methods of the sugar industry. His chemical
training convinced him that if the cane sugar of the West Indies
had to compete with the more scientifically manufactured beet
sugar of Europe, the wasteful antiquated processes of the little
muscovado factories must disappear.
In a little work, entitled a "Manual for Sugar Growers,"
and in various reports, Dr. Watts opened the eyes of the West
Indian planters to the enormous losses which their small factory
system involved, and as a remedy suggested the erection of large
scientifically managed central factories. The idea was favorably
received but opinions were divided as to whether such factories
should be under government or private control. After much
discussion a working scheme was evolved, whereby a group of
British capitalists negotiated contracts with certain estate owners
in Antigua under which the latter undertook to supply, during
a period of 15 years, the sugar canes grown on certain stipulated
areas at a price based on the current market price of sugar,
coupled with a share in the profits of the factory and, ulti-
mately, a share in the ownership of the factory itself to the extent
of one-half. The capitalists formed a company with a capital
of some $200,000, including a sum of $72,000, subscribed by
the government. With this a small central sugar factory
HI
jJHj
ifePr
laliiP
Old Muscovado Sugar Factory, British West Indies
capable of making about 3000 tons of sugar in a season, was
erected at Gunthorpes, Antigua. The success of the new enter-
prise was immediate, and the Antigua factory has now grown
from a capacity of 3000 to 10,000 tons of sugar per season.
In 1919, at the end of the 15 years' agreement, the government
cancelled its $72,000 subscription, its own income from the
enterprise in the form of excess profits and exports taxes having
exceeded $300,000. The contracting planters received during
this time an average of 20 per cent annually on their original
investment, and at the end of the 15 years had turned over to
j£
1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
79
them shares representing $250,000 and approximately $90,000
to their credit on the company's books.
The belief that the Antigua central factory would be a pioneer
object lesson for sugar planters in other islands was so well
vindicated that a second cooperative factory was soon estab-
lished at Basseterre in the island of St. Kitts, and others in
Barbados, Trinidad, and Jamaica. The success of these central
factories has naturally had a most favorable influence upon the
welfare of the islands, the laborers receiving the benefit in in-
creased wages and the small farmers in the increased price for
their canes. All this prosperity has resulted from the simple
fact that with the economies of the chemically controlled central
system only about 9 tons of sugar cane are needed to make a
ton of sugar, while with the primitive muscovado process 14 to
15 tons of cane were required.
The results of the Antigua factory for the years of its operation
are summarized in Table I.
Table I — Results of the Antigua Sugar Factory
1905-7 1908-10 1911-13 1914-16 1917-19
3 Yrs. 3 Yrs. 3 Yrs. 3 Yrs. 3 Yrs.
Average Average Average Average Average
Cane ground, tons 27,106 42,888 61,612 92,302 85,690
Sugar made, tons 2,737 4,693 6.349 9.970 9,586
Sucrose in cane, per cent 14.17 14.37 13.74 12.67 12.79
Sucrose in bagasse, per
cent 7.33 6.07 4.61 3.22 2.63
Purity of juice, per cent 87.60 85.38 83.70 83.90 83.83
Recovery of sucrose, per
cent 68.43 73.10 72.18 82.06 84.15
Yield of sugar, per cent.. 10.03 10.93 10.32 10.78 11.20
Price of sugar, per ton... $49.68 556.42 $53.66 $69.60 $103.68
The results show that while there has been a marked increase
from year to year in factory efficiency, as shown by the rising
recovery of sucrose and the diminishing loss of sugar in bagasse,
this gain has been offset by a progressive decrease in the sucrose
content and purity of juice in the cane. The latter circumstance
has given rise to the fear that the cane of Antigua might be
undergoing a degeneration like that of the Bourbon cane in
the West Indies about 1890 and of the Cheribon cane in Ar-
gentina in 1916. The probabilities, however, are that the
diminishing sucrose content of the sugar cane in Antigua is due
to certain defects of the central system, especially in times of
shortage and ascending prices, whereby cane cutters and plant-
ers, from being paid by quantity instead of by quality, send to
the factory a large amount of cane that is unripe, diseased,
trashy, or otherwise unfit for milling. The spoiling of cane by
fermentation, as a result of delays between cutting and milling,
is also no doubt responsible for much of the trouble,1 a supposi-
tion which is confirmed by the fact that the fiber content of the
cane at the time of grinding has increased from its original value
of 15 per cent in 1905 to 17 per cent. The excess of fiber in
the sugar cane of Antigua, while insuring an extra sufficiency of
bagasse for fuel, has its objection in that the difficulties of milling
are vastly increased. This factor in an island of insufficient
rainfall and inadequate water supply, such as Antigua, where
maceration must be curtailed, necessarily impairs the recovery.
The central factories of Antigua and St. Kitts were visited
by the writer during the campaign of 1919. Both establish-
ments are thoroughly modern in their equipment and the con-
trast between them and the few remaining muscovado factories,
that were still in operation, was most striking.
CANE SIRUP
Closely connected with the sugar industry of the British
West Indies is the manufacture of cane sirup or, as it is locally
termed, fancy molasses. The process is generally carried out
in the old muscovado factories, the primitive equipment of
which is well adapted to the making of sirups. The steps of
manufacture are in fact very similar to the operations of making
1 The deterioration in quality of cane supplied to the factory has also
been noted in St. Kitts and other West Indian islands. For a full discussion
of the question see papers by Sir Francis Watts in the West Indian Bulletin,
16, 96, and 17, 183; also the paper by L. I. Henzell in the Louisiana Planter,
62 (1919). 395.
muscovado, the only difference being that precautions are taken
to invert a part of the sucrose in order to prevent its crystalliza-
tion in the container. The process, as the writer saw it carried
out in Barbados, is briefly as follows:
The canes are crushed by means of wind power between three
vertical rollers, the juice from the mill flowing by gravity into
a clarifying tank where it is heated with a little milk of lime, in-
sufficient to neutralize the natural acidity. The limed juice
after heating is allowed to settle, and the clarified liquid drawn
off into a train of copper evaporating kettles, called tayches,
heated by burning sun-dried bagasse. In the first evaporator
the juice is treated with a bucket of cane juice that has under-
gone an acid fermentation, in order to invert a part of the sucrose.
The boiling liquid is skimmed to remove impurities and during
concentration is ladled from tayche to tayche until it finally
reaches a density of about 36° Be. hot, when it is run into a
cooler. The product when cold has a density of 42 ° Be., is
of a clear wine color, and has a most agreeable flavor.
The composition of several grades of "Fancy Molasses"
according to analyses made in the Antigua laboratory by Dr.
H. A. Tempany1 is as follows:
Table II — Composition of "Fancy Molasses"
I II III IV V
Water 22.4 19.7 19.8 27.1 21.9
Sucrose 46.3 42.1 43.0 44.2 51.0
Reducing sugars 27.3 32.8 30.7 24.4 20.0
Ash 1.3 1.9 1.5 3.3 1.8
Non-sugars 2.7 3.5 5.0 1.0 5.3
Total 100.00 100.00 100.00 100.00 100.00
Direct polarization. . . 39.9 35.0 35.1 36.2 47.5
Degrees Be 41.5 41.2 39.0 41.0
In Sample IV the evaporation was not carried to the proper
degree, and in Sample V the inversion was not sufficient to
prevent crystallization. A sirup of the so-called "two forties"
standard (that is, having a direct polarization of 40 and a density
of 40° Be.) will keep without crystallization, and this is the general
aim of the manufacturer.
It is unfortunate that so little of the pure cane sirup manu-
factured in the West Indies finds its way directly to the table.
A large part of it is used by blenders for mixing with low-grade
molasses, a good product being thus adulterated to improve
an inferior one. It is the opinion of many West Indian pro-
ducers that the only effective means of getting their sirup to
the consumer in a pure recognizable form is to can the product
at the factory in sealed tins, upon which the name of the brand
is stamped in raised letters.
The activities of the government laboratory in Antigua have
been directed to the improvement of other industries besides
those of sugar and sirup. The great dissimilarity between the
different West Indian islands in soil, rainfall, and other climatic
conditions has necessitated a careful study of the adaptability
of each island to special crops and industries. The precarious
condition of sugar manufacture in the islands, where the central
system is not feasible, has also led to the encouragement of other
agricultural industries. Of these we can mention only cacao,
citric acid, essential oils, and rubber.
CACAO
Next to sugar the most important agricultural enterprise
of the British West Indies is the growing of cacao.
The cacao tree becomes productive when about 5 years of
age and, if in a healthy condition, will continue to bear from 40
to 50 years. Isolated trees may attain a height of 30 to 40
ft., although in cultivated orchards the maximum is not allowed
usually to exceed 15 to 20 ft. The fruit consists of an elongated
pod, containing from 20 to 50 or more beans or seeds, embedded
in a pink colored pulp. When ripe the seeds with the adhering
pulp are removed from the fruit and, after undergoing a process
of curing or fermenting, are cleaned, dried, and packed for the
market.
1 West Indian Bulletin, 13, S24
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol.
No.
Courtesy of the
Vacuum Pans and Multiple Effects, Gunthorpes Sugar Factorv, Antigua
Iii the process of curing, as observed by the writer in Do-
minica, the pulp-covered seeds are placed under cover in boxes,
where they are turned over once or twice a day. The tempera-
ture of the mass begins to rise and in a few days attains a maxi-
mum of about 45° C. The heating of the beans is the result
of a fermentation of the adhering mucilage, the sour liquid or
sweatings," which drain from the mass, being allowed to escape.
Kmployment of this waste for vinegar making and other pur-
poses has been proposed, but so far no successful method of
utilization has been devised. After fermenting, which lasts
from 3 to 7 days, the seeds are dried in the sun on large trays
which can be wheeled on tracks under shelter in case of rain.
As a result of the fermenting process the cacao seeds are not
only freed from pulp, but a number of important chemical
changes take place which improve the character of the product.
The beans take on a brown-mahogany color, agreeable aromatic
odors and flavors are developed, and the astringent tannin sub-
stances, which give the uncured beans a bitter taste, are modified
or removed. The subsequent drying in the sun appears to
promote the changes begun in the curing house, an effect which
artificial drying by machine does not seem to accomplish. Arti-
ficial drying is necessary, however, in rainy localities in order
to prevent the beans from becoming moldy and mildewed.
The product must be dried slowly at not too high a temperature;
fans must also be used to insure circulation of air. Artificial
drying1 is most successful when the conditions of sun drying
are imitated as closely as possible.
The chemistry of cacao curing and the conditions of obtaining
the most desirable aroma and flavor are at present very im-
perfectly understood. As Knapp2 has recently pointed out,
an important and most attractive field of chemical research here
awaits investigation.
Experiments to determine the chemical conditions of soil
necessary for securing the most favorable yields of cacao were
instituted by Dr. Watts, in association with the officers of the
Agricultural Departments, in Dominica, in 1901, and the results
of this work, which have been continued for nearly 20 years,
throw a great deal of light upon the fertilizer requirements of
this particular crop. These experiments, as summarized by
Tempany,8 show that by far the best yields under Dominican
conditions are obtained from soils which have been mulched
with a nitrogenous dressing of legumes, the decomposition of
the organic matter thus supplied rendering available the natural
reserves of potash and phosphoric acid already existing in the
soil. From 3 to 5 years are required for cacao trees to acquire
1 G. Whitfield Smith, "Artificial Drying of Cacao," West Indian Bul-
letin, 2, 171.
s "Application of Science to Cacao Production." /. Sac. Chem. Ind ,
37 (1918), 468.
3 "A Study of the Results of the Manurial Experiments with Cacao
Conducted at the Botanic Station, Dominica." West Indian Bulletin, 14, 81.
Jan., 1921
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
%i
the maximum productivity occasioned by any particular method
of manurial treatment.
CITRIC ACID
The citric acid produced in the British West Indies is derived
entirely from limes, the industry being confined mostly to the
islands of Dominica, Montserrat, and St. Lucia. Dominica
leads in lime production, and the exportation of lime juice,
calcium citrate, and the essential oil of limes from this island is
summarized in Table III, which is taken from statistics supplied
by Dr. Watts.1
Table III — Average Annual Exportation of Lime Products from
i-Year Period
1895-1899
1900-1904
1905-1909
1910-1914
1915-1919
127.960
249,849
208,26.5
348,108
600,720
Dominica
Concentrated
58,486
90,295
124,643
148,571
154.185
1816
4995
2718
Oil of
Limes
Gal.
2707
3983
4761
6166
6343
Ordinarily one barrel of approximately 1200 limes yields 8
gal. of raw juice (containing about 12 oz. of citric acid per
gallon) and 1 gal. of concentrated juice (containing about 6 lbs.
of citric acid per gal.). One gallon of raw lime juice yields
approximately 1 lb. of commercial calcium citrate.
In the ordinary crude process of concentration, the expressed
lime juice, after straining to remove floating impurities, is
first heated in a copper still to recover the essential oil. The
juice, after settling, is boiled down over an open fire in a train
of copper tayches, similar to those employed in the manufac-
ture of sirup or muscovado. The course of the lime juice is,
however, opposite to that followed in concentrating cane juice,
the strike being taken from the kettle furthest from the fire,
as greater losses from decomposition of citric acid occur when
the final concentration is made directly over the flame. The
degree of economical concentration is from about 9 volumes to
1 , the loss of acid becoming considerable if a higher concentration
is attempted. The final product is a thick black liquid, which
after cooling is run into 54-gal. casks for shipment. The loss of
citric acid by open-fire concentration varies from 6 to 16 per
cent.
In order to reduce the loss from destruction of citric acid, an
improvement has been made by concentrating the lime juice
in jacketed steam-heated pans. The loss of citric acid by this
method is said to be reduced to less than 3 per cent. In some
localities use is also made of wooden vats heated by steam coils.
Metal coils of tinned copper or of block tin are recommended
as the most suitable, as they are less subject to attack by the
hot concentrated acid. It has also been found that the use of
granite rollers, in place of iron, for crushing the limes, gives a
brighter, purer juice.
The objections to concentrated lime juice, due to destruction
of acid, expense for casks, leakage, freight, etc., induced Dr.
Watts2 in 1902 to discuss the manufacture of citrate of calcium.
After considerable experimenting he published a process for
manufacturing citrate from lime juice. As a result of this work,
the manufacture and exportation of citrate of calcium was
started in Dominica in 1906.
In the manufacture of citrate of calcium, as observed in
Dominica by the writer, the juice is removed from the crushed
limes by powerful presses. The expressed juice is then heated
in a still to recover the essential oil, the latter being collected
from the distillate in a Florentine receiver. After removing
the volatile oil, the hot juice is discharged into a settling tank
to deposit albumin, pectin, and other impurities. The clear
liquid, together with that obtained from the filtered settlings,
is neutralized with chalk and heated nearly to boiling, which
1 "The Development of Dominica," West Indian Bulletin, 16, 198.
""Citrate of Lime and Concentrated Lime Juice," Ibid., 2, 308; 7,
331; 9, 193.
causes the citrate of calcium to become crystalline and to settle
quickly. The clear, yellow, mother liquor is drawn off; the
precipitated citrate is washed several times in hot water, and
then pressed or separated in a centrifugal, after which it is
dried in a current of air between 150° and 2000 F. The moisture
content of the citrate should be reduced below 10 per cent, as
otherwise there is danger of destructive fermentation. The
commercial citrate of calcium thus prepared contains about
65 per cent citric acid. The losses of citric acid by this process
are reduced to about 2 per cent. The expense for chalk and the
cost of drying nullify, however, certain advantages which the
citrate industry has over concentrated lime juice, and large
quantities of the latter still continue to be manufactured.
The lime juice and calcium citrate manufactured in the West
Indies are exported to the United States and Great Britain,
where they are used for manufacturing citric acid for calico
printing, for making beverages and medicinal preparations,
and for various other purposes.
ESSENTIAL OILS
ESSENCE OF LIMES — The principal essential oil manufactured
in the British West Indies is essence of limes, which is prepared
in two forms, the attar of limes or hand-pressed oil, and the
distilled oil, which is a by-product in the manufacture of con-
centrated lime juice or calcium citrate. The attar of limes,
which is the more fragrant and valuable, is removed from the
fruit by an implement called from its French name an ecuelle
(meaning porringer). The latter consists of a shallow copper
dish with blunt projections on the inner surface and with a
hollow receptacle in the handle at the bottom. The limes are
rapidly rotated by hand across the projections, the essential
oil escaping from the ruptured cells of the skin and running down
into the receptacle. An expert native woman can extract over
30 oz. of oil a day by this process. The oil, after pouring from
the receptacle of the ecuelle, is separated from the underlying
watery fluid and filtered to remove cellular matter and other
impurities. A barrel of limes yields from 3 to 5 oz. of attar by
the ecuelle process, while the juice from a barrel of limes will
yield from 4 to 6 oz. of the distilled oil.
Analyses of West Indian hand-pressed and distilled oils,
made in the Antigua laboratory by Tempany and Greenhalgh,'
showed the following results;
Table IV — Properties of West Indian Lime Oils
Hand-Pressed Oil Distilled Oil
(Antigua, Montserrat, Dominica) (Dominica)
Specific gravity, 30° C . 0. 8659-0. 88593 0.854O-O.8858
Angular rotation, 31°, 100
mm. tube +31.38°- +33.43° +33.09°- +34.89°
Refractive index at 32° C. 1.4789- 1.4836 1.4702- 1.4713
Citral, per cent 2.2- 6.6 1.2- 2.0
Acid number 1.35- 2.8 0.76- 1.3
The distilled oil is distinguished chemically from the hand-
pressed oil by its lower percentage of citral, this aldehyde being
partially destroyed during the boiling of the acid lime juice.
bay oil — -The distillation of bay oil from the leaves of the
West Indian bay tree (Pimento, acris) is an industry of some
importance in several of the West Indian islands. One of the
earliest studies upon the production and chemical composition
of bay oil was made by Watts and Tempany2 in the Antigua
laboratory in 1910. Later experiments have been conducted
in the island of Montserrat to determine whether it might not
be more profitable to obtain bay oil from carefully selected
and cultivated stock rather than from the wild native trees
scattered through the woods. The results by Tempany and
Robson3 in Table V show, in fact, a wide difference in the yield
and character of the oil from different trees.
1 "Notes on Expressed and Distilled West Indian Lime Oils," West
Indian Bulletin, 12, 498.
= West Indian Bulletin, 9, 271.
» "Bay Oil and the Cultivation of the Bay Tree as a Crop Plant."
Ibid., 16, 176.
82
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Table V — Yields and Properties of Bay Oil from Different Trees
Yield of Oil
per 1 00 Lbs.
Green Leaves
Fluid Ounces
12.6
6.2
18.4
17.3
24.7
19.2
Specific
Gravity
0.9822 at 29.5°
1.0051 at 30°
0.9610 at 29.5°
0.9850 at 29.5°
0.9890 at 29.5°
0.9814 at 29°
Phenol
Content
Per cent
Rotation in
100 Mm. Tube
— 1.60 at 28°
— 1.35 at 29°
—2.05 at 29°
— 1.49 at 28°
Refrac-
tive
Index
1.5155
1.5187
1.5121
1.5163
1.5161
1.5152
According to these results the selection of seed for planting
purposes, on the basis of yield and quality of oil, has a prom-
ising outlook.
Owing to the complex composition of bay oil the haphazard
methods of distillation practiced by the natives may lead to
products of widely different character. The first fraction ob-
tained by steam distillation of the leaves consists mostly of the
lighter more volatile constituents, myrcene and phellandrene,
which float upon the waste water in the receiver. As distilla-
tion proceeds, mixtures of oils come over that have the same
density as water, and from which unaided they separate with
difficulty. The later fractions consist mostly of eugenol, with
small amounts of chavicol and other phenols, which, being
heavier than water, settle to the bottom of the receiver. The
lighter oils in rising and the heavier oils in sinking dissolve and
carry with them the portions in aqueous suspension. The
mixture of the surface and bottom fractions, when distillation
is complete, constitutes the normal bay oil of commerce. Should
the receiver be changed at the wrong time, the separation of the
oil suspended in the waste water may not be perfect. The
losses from this cause and from incomplete distillation not only
diminish the yield but give rise to products of abnormal com-
position.
■ JM
.". -
.}
jELyjfe '^Vrr '"'"7 5fcffiV«r
■^Mm
N^Mi^K^M^
Headquarters of Imperial Department of Agriculture,
Barbados, British West Indies
Experiments conducted by Dr. Tempany in the Antigua
laboratory upon the changes in bay oil during storage show that
the phenol content remains unchanged but that the specific
gravity tends to rise considerably. The latter fact is explained
by the polymerization of the myrcene, a reaction that proceeds
more rapidly in the air. For this reason it is important that
vessels used for containing bay oil should be tightly closed.
thymol — At the time of the writer's visit to the Antigua
laboratory in 1919, considerable attention was being given by
the acting government chemist, A. E. Collens, to the possibility
of producing thymol1 from horse mint {Monarda punctata) and
ajowan seed (Carum copticum). Air-dried ajowan seed grown
in Montserrat gave on distillation a yield of 3 per cent of an
oil, which yielded a recovery of 43.5 per cent thymol crystals.
1 "Notes on Thymol Content of Horse Mint and Ajowan Seed,"
West Indian Bulletin, 17, 50.
The calculated yield per acre was about 35 lbs. of ajowan oil,
which, on a basis of 40 per cent recovery, would indicate a yield
of 14 lbs. of thymol per acre. This at present prices of the drug
was considered profitable.
The field and laboratory researches of the Imperial Depart-
ment of Agriculture all indicate that the essential oil industry
in the British West Indies has a most promising future.1
While the exportation of rubber from the British West Indies
has not attained a leading economic importance, a large amount
of investigation has been conducted by the Imperial Department
of Agriculture concerning the adaptability of the various rubber-
producing trees to the climatic conditions of the different islands.
In localities which have an evenly distributed rainfall of over
75 in. per year and a minimum temperature of not less than
65 ° F., such as obtain in parts of Trinidad, Dominica, and
Tobago, the Para rubber tree (Hevea brasiliensis) thrives well,
giving on properly cultivated plantations an average yield of
200 lbs. of rubber per acre. The Castilloa rubber tree grows
better in districts with a moderate rainfall, but the yield of
rubber per acre is much less than with Hevea. With the latter
tree there is a steady flow of latex nearly all the year, while with
Castilloa there is but little wound response and the trees must
be tapped at frequent intervals. The problems of tapping the
Castilloa and dealing with its latex give difficulty and have not
been perfectly solved.
Probably over three-fourths of the plantation rubber made
in the British West Indies is coagulated from the latex by means
of acetic acid ; lime juice is also extensively employed. According
to Collens,2 the cheapest and most efficient coagulating agent is
a 5 per cent solution of sulfuric acid, in the proportion of 10
drops to 100 cc. of latex. The rubber coagulated by this means
was found to be of excellent quality and showed no signs of
deterioration.
In the process employed on plantations, the clotted cream,
which rises to the surface of the coagulated latex, is gently
washed, pressed, and then allowed to dry for a day. The "bis-
cuits" of rubber thus prepared are then smoked for 3 or 4 days
until they become transparent, during which interval they take
on an amber color and acquire a characteristic smoky smell.
The chief obstacle to the development of plantation rubber
in the British West Indies is the scarcity of cheap labor; for
this reason it is doubtful if the industry there will ever achieve
the same degree of success as it has gained in Ceylon and the
Malay States.
Limitations of space prevent the description of other tropical
industries such as those of the starches, vegetable oils, tanning
materials, dyewoods, and copra, in which there is much of
chemical interest both general and special. The extensive
chemical investigations of the Antigua laboratory upon water
supplies, soils, mineral deposits, and matters pertaining to the
public health, as well as the important researches of Dr. Watts
and Dr. Tempany in improving methods of analysis, must also
be passed over in order that a few words may be said about the
development and future of scientific research in the British West
Indies.
THE WORK OF SIR FRANCIS WATTS
The early work of the Antigua laboratory, when Dr. Watts
assumed charge in 1889, was begun in great isolation and under
enormous difficulties. The laboratory appliances were meager,
there was no gas, the library consisted of only a few general
works and there was no consulting staff of scientific co-workers;
yet this lack of equipment, denoting as it did the complete
> For the almost unlimited possibilities in this field see article by J. H.
Hart, "Preparation of Essential Oils in the West Indies," West Indian
Bulletin, 3, 171.
« "Rubber Experiments in Trinidad and Tobago," Ibid., IS, 219.
Jan., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
83
absence of any predetermined governmental policies, left the
laboratory free to develop along natural lines and to take up
the industrial and agricultural problems of most immediate
and pressing importance. The great benefit of the laboratory
was quickly felt and the scope of its work was widened when,
Sir Francis Watts, K.C.M.G., D.Sc.
Imperial Commissioner of Agriculture for the West Indies
with the establishment of the Imperial Department of Agri-
culture for the West Indies in 1898, the local Antigua laboratory
became a federal institution, with its field enlarged to comprise
St. Kitts, Nevis, Montserrat, and the Virgin Islands. Imme-
diately preceding this. Dr. Watts occupied for about a year the
position of chemist to the government of Jamaica, but re-
linquished this post after the creation of the Imperial Depart-
ment, to accept in 1899 the appointment of government chemist
and superintendent of agriculture for the Leeward Islands.
He retained this position until January 1909, when he was ap-
pointed to his present office of Imperial Commissioner of Agri-
culture for the West Indies.
From the beginning of his scientific career in the West Indies,
Dr. Watts has maintained a close contact between the chemical
laboratory and the Agricultural and Botanic Experiment Sta-
tions, and he has continued this policy of scientific cooperation
in all his subsequent administrative work. The effect of this
has been most beneficial, as results were secured which could
not have been accomplished had chemical, agricultural, botanical,
and industrial research proceeded along separate unassociated
lines.
The training of young students for the varied needs of indus-
trial life in the tropics is a subject to which the Imperial De-
partment of Agriculture has given much attention and a con-
siderable amount of Dr. Watt's time in late years has been de-
voted to questions of education. In addition to their usefulness
as centers of research, the experiment stations and laboratories
have been made to serve as training places where young students
may acquire practical first-hand knowledge of the subjects
taught in the elementary and secondary schools.
With the recent rapid growth which has taken place in de-
veloping the resources of the British West Indies a strong need
has been felt for a central higher institution of learning where
advanced students could obtain a complete theoretical and
practical training in the production of sugar, cacao, rubber,
and other agricultural commodities. The new Tropical Col-
lege, for which Sir Francis Watts has so long been working
and which is soon to be established in the island of Trinidad,
will remedy this need. Trinidad is an ideal location for the
new institution, for not only is it conveniently situated with
reference to the colonies in the West Indies and British Guiana,
but with its varied industries of sugar, cacao, rubber, limes, and
copra, as well as of asphalt and petroleum, it offers the student
almost unlimited natural facilities for study and research.
This college will be of much benefit to the Empire as a whole,
as well as to the colonies most immediately concerned, for up
to the present time the graduates of English universities who take
up scientific work in the tropics have lacked facilities for ac-
quainting themselves with the requirements of their new
duties.
The committee who have the matter in charge regard it as
desirable that an intimate relationship should exist between the
Tropical College and the Imperial Department of Agriculture,
and have recommended that the first president of the new in-
stitution should be the Imperial Commissioner of Agriculture.
The wide experience of Sir Francis Watts in the agricultural,
industrial, and educational life of the West Indies is sufficient
proof of the wisdom of this recommendation. While the ad-
ministrative duties of Sir Francis have obliged him to withdraw
from active work in -the laboratory, his original interest in
chemistry has continued unabated, and it is safe to predict
that under his leadership chemical research, as a means of
developing the industrial and agricultural resources of the trop-
ics, will find an important place in the curriculum of the new
college.
Sir Francis Watts by visits and by correspondence has always
kept in close touch with the work of his scientific confreres in
the United States, as well as in other parts of the world. He
has been a visitor at the Chemists' Club in New York, and those
who have met him there recall with pleasure his charming cordial
personality. His fellow members of the American Chemical
1 Society not only congratulate him for his enduring accomplish-
f ments but extend to him their best wishes for long years of
^.helpful activity to come.
RESEARCH PROBLEMS IN COLLOID CHEMISTRY
By Wilder D. Bancroft
rnell University, Ithaca, N.
Received November 5, 1920
The following list of problems was compiled at the request
of Prof. H. N. Holmes, Chairman of the Committee on the
Chemistry of Colloids of the Division of Chemistry and Chemical
Technology of the National Research Council. I have received
valuable assistance in preparing this list from Messrs. Holmes
and Weiser.
The arrangement is somewhat arbitrary because almost any
one of the problems could have been entered under at least two
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
heads, depending upon the particular aspect of the problem
that interested one; but a poor classification is distinctly better
than none at all. It is hoped that the publication of this list
will stimulate research in colloid chemistry. The committee
will be glad to receive suggestions as to additional problems.
In order to keep in touch with what is being done in this country
and in order to prevent unnecessary duplication of effort, the
committee will appreciate it if anybody who starts work on
any of these problems will send word to that effect to Prof.
H. N. Holmes, Oberlin, Ohio, who will furnish additional in-
formation, if desired, and who will also have copies of the list
for distribution.
ADSORPTION OF GAS OR VAPOR BY SOLID
(i) PRESSURE-CONCENTRATION ADSORPTION CURVES FOR HIGH
PRESSURES — It is believed that the adsorption isotherm for gases
has the same general form as the adsorption isotherm for solu-
tions and that at high pressures the adsorption varies very little
with increasing pressure. Dewar1 claims to have obtained an
isotherm of this type with hydrogen in charcoal at — 185°;
but he finds an adsorption of 156, 149, 145, and 138 cc. per gram
for pressures of 10, 15, 20, and 25 atmospheres, respectively,
and these adsorptions are not strikingly constant. At ordinary
temperatures and pressures the adsorption isotherm for hydrogen
in charcoal is nearly a straight line.2 Richardson3 gets approxi-
mately the theoretical curve for ammonia in charcoal at • — 64 °
and nearly a straight line at +1750. While there is no doubt
but that the nearly linear curves bend round at higher pressures,
this should be proved experimentally.
(2) ADSORPTION ISOTHERM FOR CO2 ABOVE AND BELOW THE
critical temperature — Mitscherlich4 calculated that, when
carbon dioxide at atmospheric pressure and 12° is adsorbed by
boxwood charcoal, the carbon dioxide occupies only one fifty-
sixth of its original volume. Since this is a lesser volume than
the same amount of carbon dioxide can occupy as a gas at this
temperature it is usually assumed that part has liquefied. This
assumption is the more probable because the heat of adsorption
of a gas or vapor is always somewhat larger than its heat of
liquefaction* It has been pointed out, however, by Mr. Johns-
ton that an adsorbed gas may be in such a state that it does not
liquefy even when compressed into a volume which it could not
occupy as gas in the free state. It is difficult to account for the
heat of adsorption on this view. The best way to test this
hypothesis would seem to be to determine adsorption isotherms
for carbon dioxide at temperatures above and below its critical
temperature, and at pressures up to those at which it would
liquefy in absence of charcoal. It is quite possible that these
experiments would throw some light on the form of the adsorp-
tion isotherm as discussed in No. 1. If Richardson's results
with carbon dioxide were plotted on a different scale, they might
answer the question.
(3) DATA TO SHOW THAT THE ORDER OF ADSORPTION OF GASES
AND VAPORS IS NOT NECESSARILY THAT OF THE BOILING POINTS —
It is often stated as a first approximation that a gas or vapor is
adsorbed more readily the higher its boiling point. Thus, helium
is adsorbed by charcoal much less than hydrogen, and hydrogen
again is adsorbed to a much less extent than nitrogen or oxygen.
Carbon dioxide is adsorbed less readily than ammonia, so these
substances follow the empirical rule. Argon, however, is ad-
sorbed less completely by charcoal than is nitrogen, while car-
bon monoxide is adsorbed to a greater extent at o° than either
argon or oxygen, though this is not according to the rule. Nitrous
oxide is adsorbed less strongly than ethylene, and nitric oxide
' Proc. Roy. Inst., 18 (1906), 437.
» Titoff, Z. physik. Chem., 74 (1910), 641.
» J. Am. Chem. Soc, 38 (1917), 1828.
< Sits. Akad. Wiss. Berlin, 1841, 376.
'Favre, Ann. chim. phys., [5] 1 (1874), 209; Lamb and Coolidge,
J. Am. Chem. Soc., 43 (1920), 1146.
more strongly than methane, which is not according to the boiling
points. Ethane, ethylene, and acetylene are adsorbed more
at +200 than is carbon dioxide, though the last is the most
readily condensable gas of the four. The difference between
carbon dioxide and hydrogen sulfide is in the right direction,
but seems out of all proportion to the difference in boiling points.
Hydrogen sulfide is adsorbed more than ammonia, although the
two boiling points are practically identical. Cyanogen is ad-
sorbed more than ammonia at 70° and less at 0°. In the case
of vapors there is no apparent relation between boiling point
and adsorption by charcoal. Going from higher to lower boiling
points, we have the order: water, benzene, ethyl alcohol, carbon
tetrachloride, methanol, chloroform, ether, and acetaldehyde.
The order from greater to lesser adsorption is: ethyl alcohol,
methanol, acetaldehyde, ether, benzene, water, chloroform and
carbon tetrachloride.1 There should be a systematic study of
the relations so that comparisons could be made at corresponding
temperatures and pressures. At temperatures below the critical
temperature, the limiting adsorption depends only on the pore
space and on the amount of contraction which the adsorbed
liquid undergoes.
(4) REPETITION OF HUNTER'S EXPERIMENTS ON THE ADSORP-
TION OF GASES BY DIFFERENT CHARCOALS AFTER TREATMENT
with steam AT 250° — Hunter2 found that charcoals made from
different woods behaved differently. The coconut charcoal had
the greatest adsorbing power of all. Of the others, charcoal
from logwood was the best with ammonia, charcoal from fustic
the best with carbon dioxide, and charcoal from ebony the
best with cyanogen. These results should be checked to make
sure that they are correct. The varying relative adsorption of
different gases by different charcoals is probably due at least
in part to the presence of different adsorbed impurities which
affect the different gases differently. The different charcoals
should be treated with steam at 250 ° to 300 ° in order to remove
as much as possible of the adsorbed impurities, and should then
be tested again.
(5) THE ADSORPTION OF AMMONIA BY AMMONIUM HYDRO-
sulFide — Magnusson3 found that the adsorption of ammonia
by ammonium hydrosulfide was sufficient to introduce a serious
error into the determination of the equilibrium relations for
ammonia and hydrogen sulfide. The problem should now be
reversed and a study made of the adsorption of ammonia by a
porous mass of ammonium hydrosulfide.
(6) study of vapor pressure curves of adsorbed water — ■
We get rather curious results if we apply Hatschek's view4 on
viscosity to Bingham's experiments5 on zero fluidity. If we
make the assumption that plastic flow is reached when the sur-
faces of adsorbed water are in contact, and if we make the further
assumption that we are dealing with spheres in open piling, the
voids will then be 48 per cent of the whole, and in the case of
graphite, for instance, the amount of water adsorbed by the
graphite must be 94.5 ■ — 48 = 47.5 volume per cent, or each
volume of graphite must adsorb about nine volumes of water.
If we assume close piling or different sizes of graphite powder,
the voids will be less and the amount of water to be adsorbed
will be greater. Since the volumes of two spheres are propor-
tional to the cubes of the radii, one volume of graphite will
hold seven volumes of water if the thickness of the water film
is equal to the radius of the graphite particles. If the thickness
of the water film is 1.2 times the radius, the graphite will hold
eleven volumes of water. This is the same type of calculation
'Hunter, Phil. Mag., [4] 26 (1863), 364; J. Chem. Soc, 18 (18651,
285; 20 (1867), 160; 21 (1868), 186; 23 (1870), 73; 24 (1871), 76; 26 (1872),
649; Dewar, Proc. Roy. Soc, 74 (1904), 124; Hempel and Vater, Z. Elek-
trochem., 18 (1912), 724.
' Phil. Mag., [41 26 (1863), 364.
3 J. Phys. Chem., 11 (1907), 21.
« Z. Kolloidchem., 11 (1912), 280.
> J. Frank. Inst., 181 (1916), 845.
Jan., 1921
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
$S
that Hatschek made, and it shows that it is theoretically possible
on this assumption to account for zero fluidity in a graphite-
water mixture containing 5.5 per cent graphite. It has not been
shown, however, that the adsorbed films of water on the graphite
particles are of the desired thickness, nor has it been shown
that 47 per cent of the water in the mixture is in a different
state from the rest of the water. It might be possible to do
this last by measuring the vapor pressure curve for graphite-
water mixtures and determining the point at which the vapor
pressure became that of pure water.
(7) APPARENT VOLUME OF POWDERS IN A VACUUM — As little
as 5 per cent of the apparent volume of a mass of carbon black
may be due to the solid,1 and a liter of carbon black may contain
2.5 liters of air.2 If the adsorbed air were all pumped out, the
apparent volume of the carbon black would undoubtedly be
very much less; but nobody has actually proved it. An experi-
ment to prove this would be interesting because it would furnish
a new proof of the existence of the film of adsorbed air. It
is also important to know the true voids in a mass of carbon
black or other substance, because this value plays an important
part in the theory of viscous and plastic flow as developed by
Bingham.3 Still more striking results could probably be ob-
tained by working in an atmosphere of carbon dioxide or of
ammonia, especially if powdered charcoal were substituted for
carbon black.
When indigo is reduced to a very fine powder by means of a
disintegrator,4 the single particles appear to be separated one
from another by an envelope of air, so that the dry powder occu-
pies only 20 per cent of the apparent volume. Cushman and
Coggeshall' found that cement rock powder which would pass
through a 200-mesh sieve surged like a liquid because of the film
of adsorbed air. When poured into a vessel the fine powder
filled only 46 per cent of the space, while a coarser powder filled
more. Finely ground phosphate rock also flows like a liquid. In
all these cases pumping out the adsorbed air would undoubtedly
make the powders pack more closely, but this has not yet been
proved experimentally.
(8) EFFECT OF COMPRESSING POWDERS IN PRESENCE OF AD-
SORBED gas — Platinum black takes up a great deal more hydrogen
than does platinum foil. If the hydrogen were dissolved in the
platinum the equilibrium concentrations would be the same in
both cases. While it is probable that some hydrogen is dissolved
in the platinum, it is difficult to tell how much because of the
slowness in reaching equilibrium. IPwe start with a platinum
black saturated with hydrogen, and burnish the platinum black
without removing it from the hydrogen, any hydrogen which is
set free will be adsorbed hydrogen, and a measurement of the
amount will give some clue as to the relative amounts of dis-
solved and adsorbed hydrogen in the platinum. Similar ex-
periments should also be made with palladium and hydrogen.
If powdered alumina or other material is compressed to a
solid mass in presence of an adsorbed gas, much of the adsorbed
gas will be set free and none of the dissolved gas in case any is
present.
(9) ADSORPTION ISOTHERMS FOR MIXTURES OF GASES — In
many cases the adsorption of one gas by a solid decreases the
amount of a second gas which can be adsorbed ; but there are no
satisfactory quantitative measurements to show this.* Ad-
sorption isotherms should be determined, showing the relative
amounts of two gases in the vapor phase and in the charcoal
phase when in equilibrium at constant pressure.
(10) BEHAVIOR OF MIXTURES OF CARBON BISULFIDE AND
illuminating gas with coconut charcoal — According to
1 Cabot, 8th Inlernat. Congr. Applied Chemistry, 12 (1912), 18.
* Sabin, "Technology of Paint and Varnish," 1917, p. 201.
' Am. Chem. J., 46 (1911), 278; J. Frank. Inst., 181 (1916), 845.
' J. Soc. Dyers Colourists, 17 (1901), 294.
'J. Frank. Inst., 174 (1912), 672.
J Hempel and Vatcr, Z. Eleklrochem., 18 (1912), 724
Matwin1 charcoal will take carbon bisulfide and carbonyl sul-
fide out of illuminating gas, one kilogram of charcoal cutting the
sulfur content of 10 cubic meters of gas to 2.92 g. Porous
charcoals are the best, such as pine and linden. Bone-black
takes up almost no carbon bisulfide, and coconut charcoal is
said to be even less effective. This seems very remarkable be-
cause coconut charcoal adsorbs carbon bisulfide strongly. If
the statement is correct, the illuminating gas must cut down the
adsorption of carbon bisulfide very much. If carbon bisulfide
and illuminating gas were adsorbed in the same ratio in which
they occur in the mixture, an analysis of the gas coming through
would show an apparent purification2 even though the total
adsorption were very large.
(il). DOES THE EFFECT OF A TEMPERATURE GRADIENT ON THE
MOVEMENT OF SMOKE PARTICLES DEPEND ON THE NATURE OF
THE SMOKE PARTICLES AND OF THE SURROUNDING GAS? —
Aitken3 has shown that a suspended smoke particle moves along
a temperature gradient from the hotter to the colder portion.
If this is due to the presence of an adsorbed gas film around
the smoke particles, the phenomenon must vary quantitatively
with the nature and physical state of the smoke particle and
with the nature of the gas. As yet there are no experiments to
prove this.
(12) DO ELECTRICAL WAVES OR STRESSES HAVE A MEASURABLE
EFFECT ON the adsorption of gases? — Schuster4 pointed out
that some of the most puzzling facts of the disruptive discharge
admit of explanation if we assume the existence in contact with
the electrode of a surface layer of condensed gas having a large
inductive capacity. If the layer of adsorbed gas offers an in-
creased resistance to the passage of an electrical discharge, it
follows from the theorem of LeChatelier that an electrical
stress will tend to remove the film of adsorbed gas. This enables
us to account for many apparently unrelated facts in connec-
tion with over-voltage, with colliding drops, and with the elec-
trolytic detector, the crystal detector, and the coherer as used
in wireless telegraphy.6 While this point of view has proved
useful, its accuracy has never been demonstrated experimentally.
It is very desirable that we should have experimental proof that
electrical waves or stresses do decrease the adsorption of gases.
(13) decomposition of sodium amalgam — Fernekes6 found
that alcohol and many other organic substances increased the
rate of reaction between sodium amalgam and water. He
accounts for the phenomenon by assuming the intermediate
formation of hypothetical compounds between solvent and
solute which are extremely unstable towards sodium amalgam
and, therefore, react very rapidly with it. While this explana-
tion may be right, it has not proved helpful and is, therefore,
useless, at any rate for the present. It seems probable that
certain organic substances lower the over-voltage at mercury,
and consequently make, the sodium amalgam unstable. This
hypothesis is susceptible of proof by direct experiment. While
there are no measurements as yet made under conditions strictly
comparable to those in Fernekes' experiments, Carrara7 has
shown that the over-Voltages are quite different in methanol
and in ethyl alcohol from what they are in water. I have
often wondered whether the reason that nobody has ever pre-
pared, electrolytically, a sodium alloy using a cathode of fused
Wood's alloy, might be because the over-voltage is not sufficient
in this case.
(14) fixation OF oxygen by carbon — Rhead and Wheeler8
discuss the adsorption of oxygen by carbon as follows:
■ J. Gasbel., 62 (1909), 602.
* Cf. Leighton, J. Phys. Chem., 20 (1916), 32.
' Trans. Roy.. Soc. Edinburgh, 32 (1884), 239; Bancroft, J. Phys.
Chem., 24 (1920), 421.
« Phil. Mag., [51 29 (1880), 197.
« Bancroft, J. Phys. Che,m., 20 (1916), 18, 402, 503.
'Ibid., 7 (1903), 611.
' Z. physik. Chem., 69 (1909), 75.
•/. Chem. Soc, 103 (1913), 462.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
The experiments show that carbon, at all temperatures up
to 900 ° and probably above that temperature, has the power
of pertinaciously retaining oxygen. This oxygen cannot be
removed by exhaustion alone, but only by increasing the tem-
perature of the carbon during exhaustion. When quickly re-
leased in this manner it appears, not as oxygen, but as carbon
dioxide and carbon monoxide. The proportions in which it
appears in these two oxides when completely removed depend
on the temperature at which the carbon has been heated during
oxygen fixation. No physical explanation alone can account
for this fixation of oxygen; but, in all probability, it is the out-
come of a physicochemical attraction between oxygen and car-
bon. Physical, inasmuch as it seems hardly possible to assign
any definite molecular formula to the complex formed, which,
indeed, shows progressive variation in composition; chemical,
in that no isolation of the complex can be effected by physical
means. Decomposition of the complex by heat pioduces carbon
dioxide and carbon monoxide. At a given temperature of de-
composition these oxides make their appearance in a given ratio.
Further, when a rapid stream of air at a given temperature is
passed over carbon (which has previously been "saturated"
with oxygen at that temperature) carbon dioxide and carbon
monoxide appear in the products of combustion in nearly the
same ratio as they do in the products of decomposition of the
complex at that temperature. Our hypothesis is that the first
product of combustion of carbon is a loosely formed physico-
chemical complex, which can be regarded as an unstable com-
pound of carbon and oxygen of an at present unknown formula,
CjOy. It is probable that no definite formula can be assigned
to this complex.
It is perfectly possible that the mysterious oxide is a definite
compound which is adsorbed by the charcoal and which, there-
fore, has a decomposition pressure1 which varies with varying
temperature. On this hypothesis the pure compound, possibly
CisO«, or a decomposition product,8 perhaps a compound3
C»0, would behave in one way when heated by itself and quite
differently when adsorbed by charcoal. Decomposition pres-
sures and compositions should be determined for mellitic acid,
the oxide C12O1, and any other compound, oxalic acid for instance,
which might conceivably break down to form a compound having
the properties described by Rhead and Wheeler. First-class
charcoal should then be impregnated with these substances and
the experiments repeated. It is not necessary to assume that
the compound breaks down in different ways at different tem-
peratures. There is always an excess of carbon present, and,
on slow heating, one would probably always come very close
to the equilibrium ratio for carbon dioxide, carbon monoxide,
and carbon for the temperature in question. If a current of an
inert gas were passed rapidly through the system so as to sweep
out the decomposition products as fast as formed, it ought to
be possible to approximate to the decomposition products which
the compound would give if heated by itself.
(15) oxidation temperature for carbon — The experiments
of Manville* on the oxidation of carbon were undoubtedly vitiated
by the presence of hydrocarbons. These experiments should be
repeated with charcoal which has been freed from hydrocarbons
by treatment with steam.
(16) synthesis of mellitic acid — The experiments of Meyer6
seem to show that pure carbon cannot be oxidized to mellitic
acid and that the mellitic acid obtained by the oxidation of
ordinary wood charcoal is due to the oxidation of some hydro-
carbon. To make the proof conclusive, it ought to be shown
what hydrocarbons oxidize to mellitic acid under the conditions
of the experiment. With our modern technique, this should not
be difficult.
(17) determination of heats of adsorption — We have
1 Bancroft, /. Phys. Client., 24 (1920), 220.
2 Diels and Wolf, Ber., 39 (1906), 689; Diels and Meyerheim, Ibid.. 40
(1907), 355; Meyer and Steiner, Ibid., 46 (1913), 813; Armstrong and Cole-
gate, J. Soc Chem. Ind., 32 (1913), 396.
» Lowry and Hulett, J. Am. Chem. Soc, 42 (1920), 1408.
* J. Mm. phys., 6 (1907), 297; Duhem, Van Bemmelen Cedenkboek,
1910, 1; Lowry and Hulett, J. Am. Chem. Soc, 42 (1920), 1408.
» Monatsh., 35 (1914), 163.
very few measurements on the heats of adsorption of gases,1
and some of these are not very accurate. The subject is an
important one2 and measurements should be made with great
accuracy. The heats of adsorption of hydriodic acid and of
hydrobromic acid by charcoal are several times the latent
heat of vaporization, and we do not know at all why the molecu-
lar heat of adsorption of hydrogen should be 18,000 calories
with palladium and about 46,000 calories with platinum.
contact catalysis
(18) effect of co adsorption, etc., on adsorption op
hydrogen, ethylene, ETC. — We know that carbon monoxide
cuts down the catalytic action of platinum8 on hydrogen and
ethylene, and we believe that this is because it cuts down the
adsorption of these gases; but there are no satisfactory quanti-
tative measurements on the adsorption by platinum of mixtures
of CO with hydrogen or ethylene. Maxted* has made some
measurements on hydrogen sulfide and hydrogen with palladium.
(19) ADSORPTION BY, COLLOIDAL PLATINUM OF SUBSTANCES
which poison hydrogen peroxide — While we are quite certain
that the poisoning of the platinum catalysis of hydrogen peroxide4
is due to the adsorption of the so-called poisons, there are not
even qualitative experiments to prove this. Platinum black
should be shaken with solutions of the different poisons and ad-
sorption isotherms determined.
(20) behavior of potassium cyanide solution with col-
loidal PLATINUM, PLATINUM BLACK, AND MASSIVE PLATINUM —
Bredig6 points out that when colloidal platinum is allowed to
stand in contact with hydrogen peroxide and concentrated
potassium cyanide, the platinum flocculates and precipitates.
The agglomerated platinum causes the hydrogen peroxide to
decompose, thus showing that the cyanide does not poison pre-
cipitated platinum black. There seem to be only two possible
explanations. One is that the adsorption of potassium cyanide
by platinum falls off very much more rapidly with increasing
size of the platinum particles than the adsorption of hydrogen
peroxide by platinum. The other explanation is that, through
oxidation or otherwise, there is formed what might be called
an anti-body, which cuts down the adsorption of the cyanide.
Neither hypothesis is very satisfactory and there is no experi-
mental evidence for either. This point should be cleared up.
Kastle and Loevenhart7 point out that prussic acid accelerates
the decomposition of the hydrogen peroxide by iron and copper.
There is no theory in regard to this.
(2 I ) APPARENT EQUILIBRIUM BETWEEN PHOSGENE AND AQUEOUS
hydrochloric acid — Phosgene reacts with water to give
carbon dioxide and hydrochloric acid:
COCh + H20 = CO2 4- 2HCI
So far as we know, this reaction is not reversible, and it ac-
tually runs to an end in presence of an excess of water. In
presence of concentrated hydrochloric acid the rate of hydrolysis
is practically negligible. The only way that I can see to ac-
count for this is by assuming that water and phosgene do not
react by themselves and that the reaction takes place solely
in contact with the walls of the containing vessel. When these
are coated with a film of hydrochloric acid of sufficient concen-
tration, no phosgene is adsorbed to speak of, and no reaction
takes place. The hydrolysis should be studied with different
concentrations of acid and with a varying ratio of wall surface
to mass of solution.
1 Favre, Ann. chim. phys., [5] 1 (1874), 209; Masson, Proc. Roy. Soc,
74 (1904), 209; Dewar, Proc. Roy. Inst., 18 (1905), 183.
* Lamb and Coolidge, /. Am. Chem. Soc, 42 (1920), 1146.
« Lunge and Harbeck, Z. anorg. Chem., 16 (1898), 50.
« J. Chem. Soc, 118 (1919), 1020.
» Bredig and von Berneck, Z. physik. Chem., 31 (1899), 258; Bredig
and Ikeda, Ibid., 37 (1901), 1.
« Z physik. Chem., 31 (1899), 332.
' Am. Chem. J., 29 (1903), 397.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
87
(22) EFFECT OF OSCILLATING TEMPERATURES ON THE AP-
PARENT EQUILIBRIUM OF ETHYL BUTYRATE WITH LIPASE — Tri-
chloromethyl chloroformate, CICO2CCI3, or superpalite as it
has been called, decomposes to carbon tetrachloride and carbon
dioxide in presence of alumina,
C1C02CC1S = C02 + CCU,
and to phosgene in presence of ferric oxide,
C1C02CC13 = 2COCI2.
The reverse reaction has never been made to take place to
any measurable extent. Some superpalite and ferric oxide were
placed in a glass tube connected with a closed manometer.
There was rapid decomposition at first, as shown by the in-
crease in pressure; but, before long, the reaction came apparently
to an end. On raising the temperature the reaction went a
little farther and did not reverse when the temperature was
brought back to its original value. This experiment was not
checked sufficiently to make me willing to guarantee the results ;
but it looks as though the ferric oxide was poisoned and that
when the temperature changed, more superpalite came in con-
tact with the catalytic agent and was decomposed. If this is
the true explanation, it suggests one interesting line of experi-
mentation. When ethyl butyrate is treated with a small amount
of enzyme, the decomposition proceeds only a little way.1 It
seems probable that with an oscillating temperature it might
be possible to carry the reaction much farther with the same
amount of enzyme.
(23) ACTION OF PLATINUM BLACK ON ACETIC ACID — Reiset
and Millon2 state that acetic acid can be boiled with pumice
without decomposition; but that it is decomposed completely
if distilled from platinum black. They do not state what the de-
composition products are. At first there might be enough oxygen
in the platinum black to cause an oxidation of the acetic acid;
but that would soon come to an end. We are not absolutely
certain that platinum black does decompose acetic acid catalyt-
ically at the boiling point of the latter. If that does happen,
we can only guess at the reaction products.
(24) CATALYSIS OF ETHYL ACETATE IN PRESENCE OF HYDROGEN
— If a mixture of ethyl acetate vapor and hydrogen is passed
over pulverulent nickel, it is probable that some or all of the
initial products will be reduced before they have time to react
in the normal way. A study of the reaction products should,
therefore, throw light on the probable mechanism of the reaction
which occurs in the absence of hydrogen. If methane and ethyl
formate are the products, that would indicate that the original
break had been into -CH3 and -CO2C2H5. If acetic acid and
ethane are found, they would probably be reduction products
of CH3CO2- and -CH2CH3. If the reaction products are me-
thane, ethane, and either carbon dioxide or some of its reduc-
tion products, it would seem certain that ethyl acetate splits
simultaneously into -CH3, -CH2CH3, and C02.
(25) catalysis OF ETHER by nickel — If ether is passed over
pulverulent nickel, one stage in the reaction will probably
be to CH3CH2O- and -CH2CH3 or to C2H6OC2H4- and -H. In
the first case the final products will be ethylene and water just
as with alumina. In the second case they are likely to be
acetaldehyde, ethylene, and hydrogen, though the ethylene and
hydrogen may combine more or less completely to form ethane.
A study of this reaction should, therefore, throw light on the
catalytic decomposition of alcohol by nickel.
(26) CATALYSIS OF METHYL FORMATE BY ALUMINA AND FERRIC
oxide — We have data for the catalytic decomposition of tri-
chloromethyl chloroformate by alumina and by ferric oxide. As
soon as we get the corresponding data for methyl formate, we
shall be in a position to tell whether the substitution of hydrogen
by chlorine changes the type of the reaction.
' Kastle and Loevenhart, Am. Chem. J., 21 (1900), 491.
2 Compt. rend., 16 (1843), 1190.
(27) catalytic action of ferrous oxide — Since alumina is
very transparent and ferrous oxide very opaque to infra-red
radiations, ferrous oxide should be much superior to alumina as
a catalytic agent, according to the radiation theory of W. C.
McLewis, in all cases where the formation of metallic iron or
of another oxide did not interfere with its activity.
(28) gum Arabic as catalytic agent— According to Tyndall,1
gum arabic is practically opaque to infra-red rays. If this is so,
it must emit infra-red rays and should, according to the radia-
tion theory, be a powerful catalytic agent for methyl acetate
solutions. This would seem to be a crucial experiment.
(29) ARSENIC POISONING OF THE GRILLO-SCHROEDER CONTACT
mass — The Grillo-Schroeder catalyst for the contact sulfuric
acid process consists of platinum black precipitated in a certain
way on magnesium sulfate. This contact mass is poisoned by
arsenic just as is the platinized asbestos. It has been stated,
however, that the Grillo-Schroeder catalyst can be regenerated
by boiling with hydrochloric acid. It was supposed that the
arsenic was removed as trichloride ; but analysis showed that the
regenerated contact mass contained a great deal of arsenic. The
amount was said to be 3 per cent, but I do not know whether
this was 3 per cent of the amount of platinum or of the contact
mass. This arsenic must either have agglomerated, so that it
no longer coated the platinum, or it must have reacted with the
magnesium sulfate. It might be very difficult to tell from a
microscopic examination what had happened, so that it probably
would be better to study first the behavior of arsenic with porous
magnesium sulfate in the absence of platinum.
(30) SPONTANEOUS COMBUSTION OF OILED RAGS — It is known
that oiled rags will take fire spontaneously, and there is some litera-
ture on the subject.2 In view of the number of fires which seem
to be due to this cause, somebody ought to develop a really
first-class lecture or laboratory experiment tc illustrate this, and
the experiment should be included in every introductory course
in chemistry.
(31) IGNITION TEMPERATURE OF GAS MIXTURES — When gas
mixtures are exploded by an incandescent wire or by a spark,3
it seems probable that the nature of the wire or of the electrode
has a catalytic effect, at any rate at the outset. If this is the
case, it should be possible to poison the wire to some extent.
Presence of carbon monoxide might perhaps change the apparent
ignition temperature for oxyhydrogen gas. Something of this
sort might account for the change in temperature when the
mixture is diluted with one of the constituents and for the effect
of sparks which do not cause explosion.
(32) DECOMPOSITION OF VERMILION BY COPPER — De la Rue4
states that electroplated copper blocks cause vermilion to blacken,
while cast copper does not. If this is true, the difference must
be due to the greater porosity of the electroplated copper. The
matter should be tested, so that we may know the facts.
ADSORPTION OF VAPOR BY LIQUID
(33) COALESCENCE OF COLLIDING DROPS OF DIFFERENT
Liquids — -Lord Rayleigh6 has shown that colliding drops or
jets of water do not necessarily unite. This is because of a
film of adsorbed air which prevents the drops from coming ac-
tually in contact. This phenomenon must be general, and must
be most marked the greater the adsorption of gas by the liquid
drops. Experiments should, therefore, be made with drops of
nonaqueous liquids and in different atmospheres. It has also
1 "Fragments of Science," "Radiant Heat and Its Relations."
2 Galletly, Chem. Zentr., 1873, 543; Coleman, J. Chem. Soc, 31 (1878),
259; Kissling, Z. angew. Chem., 1896, 44; Lippert, Ibid., 1897, 434.
* Roszkowski, Z. physik. Chem., 7 (1896), 485; Coward, Cooper and
Warburton, J. Chem. Soc., 101 (1912), 2278; Parker, Ibid., 106 (1914), 1002;
Sartry, Ibid., 109 (1916), 523; McDavid, Ibid., Ill (1917), 1003; White
and Price, Ibid., 116 (1919), 1462; Thornton, Proc. Roy. Soc., 90A (1914),
272; 91A (1914), 17; 92A (1915), 9, 381; Phil. Mag., [6] 38 (1919), 613.
* Mem. Chem. Soc, 2 (1845), 305.
« Proc. Roy. Soc, 28, 406; 29 (1879), 71; 31 (1882), 130: Bancroft,
J. Phys. Chem., 20 (1916), 1.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
been shown by Lord Rayleigh1 and others* that an applied po-
tential difference of about two volts will cause colliding drops
to coalesce; but this value has not been determined accurately,
and we do not know how it woidd vary, if at all, with solutions
instead of so-called pure water. Both these matters should be
studied.
(34) STUDY OF ORNDORFF AND CARRELL'S EXPERIMENTS ON AIR-
BUBBLING — In some experiments with the air-bubbling method
of determining molecular weights, Orndorff and Carrell3 found
that with urethane solutions approximately theoretical values
were obtained even when the rate of bubbling was varied a
great deal. With urea solutions there is a distinct tendency for
the apparent molecular weight to go up as the rate of bubbling
is increased. With phenol the apparent molecular weights were
low at all rates of bubbling and did not vary much with the rate
of bubbling. The experiments of Campbell4 make it probable
that some of the errors in the air-bubbling method are due to the
presence of an adsorbed gas film on the surface of the liquid.
The experiments of Orndorff and Carrell should be repeated,
amplified, and studied with special reference to the work of
Campbell. These same solutions might well be tried in No. 33.
(35) EFFECT OF POWDERS IN MAKING DROPS COALESCE — Lord
Rayleigh5 found that dry powders had a marked effect in causing
colliding drops or jets of water to coalesce, whereas most of
the powders were ineffective when wetted. No explanation
was^ given for the phenomenon and yet one should be found.
It is possible that the electrification of the powders may be a
factor. Hardy6 has noticed that powders floating on a liquid
sometimes move in the opposite direction from the same
powders when submerged.
ADSORPTION OF LIQUID BY SOLID
HNORMAL DENSITY OF POWDERS IN LIQUIDS — Rose7
claims that platinum in the state of foil has a specific gravity
of 21 to 22, while a value of about 26 was obtained for platinum
sponge precipitated from the chloride by sodium carbonate and
sugar. This can be accounted for if we assume that the powder9
is not weighed alone in water, but in conjunction with a film
of condensed water. Similar, though less extreme differences
were obtained with gold, silver, and barium sulfate. These
experiments should be repeated and extended.
(37) SYSTEMATIC STUDY OF RELATIVE WETTING, WITH SPECIAL
REFERENCE TO FLOTATION AND TO ZERO FLUIDITY — No System-
atic study of the selective adsorption of liquids by solids
seems to have been made. There are a few scattered data.
We know that kerosene will displace water in contact with metals,
and that water will displace kerosene in contact with quartz.9
while alcohol will displace oil in contact with metal,10 and linseed
oil11 will displace water in contact with white lead. When
making lithographic inks, oil is added to the wet paste and the
water is ground out. There are only a few quantitative measure-
ments15 on the selective adsorption of a liquid by a solid. A
careful systematic study of the phenomenon should be made.
It is the determining factor in ore flotation. If we get zero
fluidity15 when the voids in a powder are just filled with liquid,
' Proe. Roy. Soc, 29 (18791. 7 1 .
= Newall, Phil. Mag., [5] 20 (1885), 31; Burton and Wiegand, Ibid.,
23 (1912). 14S.
' J. Phys. Chcm., 1 (1897), 753.
' Trans. Faraday Soc, 10 (1915), 197.
' Proc. Roy. Soc, 31 (1882), 130; Bancroft, J. Phys. Chem., 20 (1916), 14.
Joe, 86A (1912). 609.
I Pogg Auk., 73 (1848), 1; J. Chem. Snc, 1 (1849). 182.
s See, however, Johnston and Adams, /. Am. Chan. Soc, 31 (1912),
563.
' Hofmann, Z. physik. Chcm., 83 (1913), 385.
"> Pockels, Wild. Ann., 67 (1899), 669.
II Cruickshank Smith, "The Manufacture of Paint," 1916, p. 92.
'-Graham. J. Chem. Soc, 20 (1867), 275; Mathers, Trans. Am. Elec-
trochem. Soc, 31 (1917), 271.
" Bingham, ,4m. Chem J., 46 (1911), 278; J. Frank. Inst., 181 (1916),
845.
the extra liquid is present as an adsorbed film and the determina-
tion of the amount is very important.
(38) BEHAVIOR OF GUM ARABIC WITH ALCOHOL AND WATER — ■
It is not very easy to peptize gum arabic by grinding with water
because the water does not displace the air readily from the gum.
If the gum is ground for a moment with alcohol, water then
wets it readily. This is surprising because water peptizes the
gum and alcohol does not; one would consequently have ex-
pected the water to be adsorbed more strongly than the alcohol.
By shaking the gum arabic with aqueous alcohol, it should be
an easy matter to tell whether the alcohol or the water is ad-
sorbed the more strongly. It is possible that there may be a
film of grease on the gum which is removed by the alcohol.
It is possible that alcohol displaces the air more rapidly because
it adsorbs the air more strongly than does water. If that is
the case, alcohol should show a special behavior as colliding
drops in No. 33. Experiments should be made with acetone,
acetic acid, glycerol, etc., so as to see to what extent the phe-
nomenon is general or to what extent it is peculiar to
alcohol.
We are always working up to the problem of why concen-
trated sulfuric acid wets sulfur trioxide more readily than water
does.
(39) BEHAVIOR OF MERCURY IN GLASS CAPILLARY AS AIR IS
removed — Mercury does not wet glass because air is adsorbed
more strongly than mercury by glass. According to this point
of view, mercury should wet glass if the air is removed com-
pletely. There are experiments by Hulett and others to show
that this is true; but the problem has never been handled in
a clear-cut manner. One would like to see mercury made to
rise in an evacuated glass capillary.
(40) carrying OF MERCURY on iron gauze — Lord Rayleigh1
pressed a piece of iron gauze down on the flat bottom of a glass
vessel holding a shallow layer of mercury, and found that the
gauze remained on the bottom of the vessel and did not rise
through the mercury. The reason for this is that the mercury
does not wet the iron. A corollary from this, which has not
been tested experimentally, is that one should be able to carry
mercury in an iron sieve just as one can carry water in an oiled
sieve.2 Since sodium amalgam wets iron,3 a dilute sodium amal-
gam should run through an iron sieve which would stop pure
mercury. Also Rayleigh's experiment should not succeed if
a sodium amalgam were substituted for mercury. All these
predictions should be confirmed or disproved experimentally.
(41) pressures due to selective wetting— When water
displaces air at the surface of a solid, one wonders how much
pressure might be developed. Jamin4 has made some prelim-
inary experiments along this line. A hole was bored in a piece
of dried chalk. Into this hole was dipped one end of a manometer,
and the hole was then closed. When the chalk was placed in
water, the air was displaced from the pores and a pressure of
3 to 4 atmospheres was obtained. This is not the maximum
pressure because the amount of dead space in the manometer,
was large. A better method would be to determine the pressure
necessary for the air to force the water out of the pores of the
chalk. It would also be interesting to substitute alcohol and
other liquids for water. By filling a porous block of silica with
kerosene and placing it in water, or by filling a porous block of
lead or zinc sulfide with water and putting it in oil, one could
measure pressures which might be of distinct interest in their
bearing on flotation and on oil deposits near the sea.
(42) constant-temperature baths — Mcintosh and Edson5
have frozen aqueous salt solutions in a mixture of ether and
1 Scientific Papers, i (1903), 430.
1 Chwolson, "Traite de Physique," 1, III (1907). 613.
> J. Chem. Soc, 26 (1873), 418.
< Chwolson, "Traite de Phj-sique." 1, III (1907), 622
' J Am. Chem Soc. 38 (1916). 613.
Jail.-, ^21
THE ThMRNAL of industrial and ENGINEERING CHEMISTRY
soM carbon dioxide. Trie solid mass is said to melt at a constant
temperature, that of the initial freezing point of the solution.
At present there is no theoretical explanation for this.
(43) THEORY OF adhEsives — The whole theory of adhesives
depends in part on the fact that the cementing material adheres
strongly to the two surfaces and hardens there. It is therefore
possible that one agglutinant may be useful for a number of
different materials, such as wood, glass, metal, ivory, etc.,
while others give good results only with special materials. Since
the books give different recipes for cements for glass, cements
for metals, cements for metals and glass, etc., the differences
in adsorption are real ones, though no one has ever made a
careful study of agglutinants from this point of view. Some-
body should study the different adhesives from this point of view.
(44) vegetable glues — There is practically no literature
on the vegetable glues outside of a few patents. We need
published research on the whole subject with special reference
to peptization, viscosity, and adsorption.
(45) waterproof GLUES — A waterproof glue of indefinite
life is needed. Our large timber is disappearing fast and, before
long, we shall be compelled to build up large pieces by gluing
together what we can get from small stuff. At present the
best waterproof glues weaken In time, no doubt because of the
action of water on the protein material. A glue should be made
that will not take up moisture after it has once dried.
(To be continued)
5CILNTIFIC 50CILTIL5
J
CROP PROTECTION INSTITUTE DISCUSSES WAR
ON BOLL-WEEVIL
A meeting of the Crop Protection Institute, recently organized
under the National Research Council and made up of growers,
scientists, and business men, was held at Rumford Hall, New
York City, on Monday, December 6, 1920.
The principal topic for discussion was the control of the
boll-weevil by the application of calcium arsenate. Cotton
growers have suffered great losses in recent years due to the rav-
ages of the boll-weevil, and although the Department of Agricul-
ture has worked out careful methods for combating this pest
by the use of calcium arsenate, the results have not always been
satisfactory owing to faulty technique in the application of this
chemical.
The attendance was made up of representatives of insecticide
manufacturers and of manufacturers of spraying machinery,
as well as the regular membership of the Institute.
Prof. B. C. Coad of the U. S. Agricultural Experiment Station
at Tallulah, La., who has done a great deal of work on the
control of the boll-weevil, presented a two-reel moving picture
entitled "Goodbye, Boll-Weevil" which demonstrated the com-
plete control that can be won over the insect by the proper use
of calcium arsenate with the right kind of machinery.
Professor Coad stated very plainly that there had been con-
siderable failure in the application of calcium arsenate in the
hands of persons who had been improperly informed on the
method of using it. He summed up the causes of failure as being
due to laxness in carrying out definitive instructions, bad chem-
icals, and misinformation passed on to the farmer by ignorant
salesmen. He also commented on the fact that many of the
dusting machines sold to users were inefficient.
In 1920, 10,000,000 lbs. of calcium arsenate had been sold
to the South, said Dr. Coad, but probably 5,000,000 lbs. re-
mained unused, owing to lack of results in many cases.
At one of the meetings of the scientists connected with the
Institute the problems involved in the production and use of
calcium arsenate were discussed at some length. The general
feeling was that a standard for total arsenic in commercial
calcium arsenate be prescribed and adhered to. The standard
which seemed most desirable was 40 to 42 per cent total arsenic.
In the discussion it was brought out that from five to seven times
the present annual consumption of arsenic in the United
States would be required for the control of the boll-weevil
alone.
The fact that about 115 scientific men and 23 commercial
concerns have already joined the Crop Protection Institute
and that the first real business meeting was so well attended
augurs well for its future. It was disappointing, however,
to the organizers to be informed by Dr. L. O. Howard in his ad-
dress that the scientists of the Federal Government did not
see their way clear to become members of the Institute evert
though they sympathized with its purposes. Although the
constitution provides for the control of the Institute by the
scientist members only, the government men feel that it would not
be proper to become actively identified with an organization,
the funds of which come largely from commercial sources.
AMERICAN INSTITUTE OF CHEMICAL ENGINEERS
The Thirteenth Annual Meeting of the American Institute
of Chemical Engineers was held in New Orleans, December
6 to 9, 1920. The meeting was held in New Orleans in order
to give opportunity to make a study of the characteristic in-
dustries of this section of the South. The program provided
for a stay of two and one-half days in New Orleans, a two-day
trip through the sulfur, salt, rice, and sugar region of the state
of Louisiana, and stops on the return trip at Chattanooga,
Tenn., Roanoke, Va., and Luray, Va. Arrangements had been
made at ail points visited for inspection of the local industries.
The program of papers contained several which were descriptive
of the local chemical industries.
Dr. R. F. Bacon presented a paper on "Recent Advances in
the American Sulfur Industry" in which he discussed the diffi-
culty encountered in burning Louisiana sulfur on account of
the presence of small amounts of petroleum.
Lezin A. Becnel presented a paper on "Operating Variations
in Sugar Production as Indicated by Some Plantation Data,"
in which the author gave the results of a study of the produc-
tion of sugar and sirup during a period of some 40 yrs.,
and contended that the greatest profits would be made by pro-
ducing either sugar or sirup, or both, according to the market
for each product. The paper was discussed by Professors
Chas. S. Williamson, Jr., of Tulane University, and Chas. E.
Coates, dean of the Audubon Sugar School.
A very interesting talk on the "Resources of the State of
Louisiana" was given by Mr. N. L. Alexander, chief of the State
Conservation Commission. Motion pictures of the extensive
state game preserves were shown. Mr. Alexander also described
very successful experiments in reforestation. It has been
demonstrated that timber suitable for wood pulp can be grown
in Louisiana in 15 yrs.
George G. Earle, chief engineer and superintendent of the
Sewerage and Water Board, described the sewage, water puri-
fication, and drainage systems of New Orleans. Particular
interest was shown in the low lift pumps used to raise the
storm waters and sewage of New Orleans to the level of the
water courses used for drainage.
The other papers presented were of a general chemical engi-
neering character. Most of them were fully illustrated by
lantern slides and were very fully discussed. They included:
90
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
E. R. Weidlein. The Conservation of Heat Losses as Applied to
Power and Heating Systems. (Lantern slides)
James R. Withrow and F. C. Vilbrandt. The Sulfuric Acid Fume
Problem.
A. G. Peterkin. Costs — A Short Study of Factory Economics.
(Lantern slides)
Maximilian Toch. Lubrication of Concrete. (Lantern slides)
E. Bartow. The Treatment of Sewage by Aeration in the Presence
of Activated Sludge. (Lantern slides)
James R. Withrow. The Federated American Engineering Societies
and the Institute.
C. B. Morey. The Salvaging of Sag Paste.
W. L. Badger. Studies in Evaporator Design. IV — Some Data
from the Horizontal Tube Evaporator.
During the stay in New Orleans a visit was made to the plant
of the U. S. Industrial Alcohol Company where molasses is
diluted and fermented, and 95 per cent alcohol distilled out.
On the same afternoon the water purification plant of the city
of New Orleans was visited.
The plants of Pennick and Ford, as well as that of the
Southern Cotton Oil Co., were not visited as originally
planned on account of a very severe rain storm and also on ac-
count of lack of time. The docks and port facilities were in-
spected during a river trip tendered by the Board of Commis-
sioners of the Port of New Orleans.
On Tuesday evening the party left New Orleans by a special
train for the visits to the sulfur, salt, and sugar region. The
first stop was made at Lake Charles where the train was met
by members of the Chamber of Commerce. After a compli-
mentary breakfast, the party visited the mines of the Union
Sulphur Co., where the entire process of sulfur recovery was
shown, including the drilling of the well and inspection of the
sulfur bearing limestone. The party watched with greatest
interest the stream of molten sulfur coming direct from one of
the wells, as well as the centrifugal pumps and pipe lines by
which the molten sulfur was transported.
The next stop of the Institute Special was at New Iberia
where the train was backed out to the salt mines. After being
lowered 525 ft. in the mine elevator the party had the unique
experience of standing in chambers some 50 to 60 ft. high and
fully as wide, hewn out of a solid block of salt several thousand
feet thick and nearly a mile square. Any doubts as to the
purity of the glistening crystals were removed by an examination
of the clear, transparent samples to be found almost at random
in the mine.
On Thursday morning a stop was made at Franklin. After
a complimentary breakfast the party was taken by autos to the
Stirling sugar factory which was producing raw sugar from sugar-
cane. This is one of the largest cane sugar factories in Louisiana,
having a capacity of 1900 tons of cane daily. After seeing this
factory the near-by cane fields were visited where the gathering
and transportation of the cane was in progress. Most of the cane
was transported from the field to the factory in wagons, as
numerous small sugar factories are located in this region.
From Franklin the Institute Special returned to New Orleans,
and at 7 : 40 p. m. Thursday the party left New Orleans for
Chattanooga, Tenn., where arrangements had been made for
visits to Wilson & Co., a by-product coke plant and a ferro-
silicon plant, as well as a trip to Lookout and Signal Mountains.
The train was 6 hrs.' late, and therefore the Chattanooga pro-
gram was canceled.
At the next stop at Roanoke, Va., the blast furnaces of the
Virginia Iron, Coal and Coke Company were visited, as well
as a near-by pyrites plant where pyrites cinder is treated with
acid to remove the copper and sulfur, then sintered and sent
to the blast furnace for the production of pig iron.
At 5 : 45 P. m. a stop was made at Luray, Va., where the
last visit of the meeting was made to the wonderful caverns of
Luray. The natural statuary, convoluted stalactites and music
produced from the stalactites were quite as interesting as the
scientific aspects of these magnificent calcareous formations.
During the business sessions at New Orleans, resolutions
were adopted and wired to Washington urging the passage of
the Nolan bill, without the rider authorizing the exploitation
of patents by government employees, also the passage of the
Longworth dye bill.
President David Wesson was reelected for another year, as
were the secretary, John C. Olsen, the treasurer, F. W. Frerichs,
and the auditor, Chas. F. McKeuna. In the place of the three
retiring directors, F. M. de Beers, A. C. Langmuir, and T. B.
Wagner, there were elected F. E. Dodge, A. H. Hooker, and
Wm. D. Richardson.
The membership of the Society is now 454, the net increase
for the year being 89.
The attendance at the meeting was excellent both by out-of-
town members and by the local chemists and chemical engi-
neers. The meeting as a whole was very successful and en-
joyable, particularly on account of the generous hospitality ex-
tended at every place visited.
Brooklyn Polytechnic Institote J- C. OLSEN, Secretary
Brooklyn, N. Y.
ASSOCIATION OF OFFICIAL AGRICULTURAL CHEMISTS
The Thirty-Seventh Annual Convention of the Association of
Official Agricultural Chemists was held at the New Willard
Hotel, Washington, D. C, November 15 to 17, 1920. Over 300
members and visitors were present.
The usual reports of referees, associate referees, and com-
mittees were presented, and a number of special papers were
read. Interesting papers on the determination of borax in
fertilizers were presented. Papers on the present official method
and on a proposed method for insoluble phosphoric acid in
dicalcium phosphate resulted in lengthy discussion in which
many members participated. A paper dealing with the prep-
aration of neutral ammonium citrate was of special importance.
Honorable Edwin T. Meredith, Secretary of Agriculture,
spoke a few words of encouragement. Addresses were de-
livered by the president. Dr. H. C. Lythgoe, State Board of
Health, Boston, Mass., on "The Application of the
Theory of Probability to the Interpretation of Milk Analyses,"
and by the honorary president, Dr. Harvey W. Wiley, Wash-
ington, D. C, on "The Importance and Value of Agricultural
Research."
The following committee was appointed to cooperate with the
American Society for Testing Materials in the preparation of
specifications and testing for lime: W. H. Mclntire, Agri-
cultural Experiment Station, Knoxville, Tenn., chairman; Wm.
Frear, State College, Pa. ; and F. P. Veitch, Bureau of Chemistry,
Washington, D. C.
The following officers were appointed for the ensuing year:
President: W. F. Hand, Agricultural Collegt, Agricultural College,
Miss.
Vice President: F. P. Veitch, Bureau of Chemistry, Washington, D. C.
Secretary-Treasurer: C. L. Alsberg, Bureau of Chemistry, Wajk-
ington, D. C.
Additional members of the Executive Committee are:
A. J. Patten, Agricultural Experiment Station, East Lansing, Mich.
H. D. Haskins, Agricultural Experiment Station, Amherst, Mali.
The names of members of committees and of referees appointed
may be secured through the secretary, C. L. Alsberg, Bureau of
Chemistry, Washington, D. C.
CALENDAR OF MEETINGS
American Ceramic Society — Annual Meeting, Deschler Hotel,
Columbus, Ohio, February 21 to 24, 1921.
American Electrochemical Society — Spring Meeting, Hotel
Chalfonte, Atlantic City, N. J., April 21 to 23, 1921.
American Chemical Society — Sixty-first Meeting, Rochester,
N. Y., April 26 to 29, 192 1.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
91
PERKEN MEDAL AWARD
Announcement is made by the Committee of Award that the
Perkin Medal for 192 1 has been awarded by the American Sec-
tion of the Society of Chemical Industry to Dr. Willis R.
Whitney, Research Director of the General Electric Company,
in recognition of his distinguished work in the chemical field.
The presentation of the medal to Dr. Whitney will be made
at the regular meeting of the American Section of the Society of
Chemical Industry, in Rumford Hall, Chemists' Club, New
York, N. Y., on January 14, 1921.
CORPORATION MEMBERS OF THE AM ERICAN CHEMICAL SOCIETY
Abbott Laboratories Co., The
Amalgamated Dyestuff & Chemical Works. Iue.
Agricultural Chemical Co.
1 Cellulose & Chemical Mfg. Co . Ltd.
C li.<
1 Co., In
American Optical Co.
American Trona Corporation
American Zinc, Lead & Smelting Co.
Anaconda Copper Mining Co.
Antiseptol Liquid Soap Co. t
Arbuckle Brothers
Arkell Safety Bag Co.
Arlington Mills
Armour Glue Works
Arnold Print Works
Baker, H. J. & Bro.
Barrett Co., The
Bausch & Lomb Optical Co.
Beaver Board Companies, The
Binalbagan Estate, Inc.
Bishop & Co., J., Platinum Works
Bour Refractories Co., L. J., Inc.
Braender Rubber & Tire Co.
Brown Co., The
Bush & Co., W. J., Inc.
Calco Chemical Co.
California & Hawaiian Sugar Refining Co.
Cambridge Color & Chemical Co.
Carnotite Reduction Co.
Chemical Catalog Co., Inc.
Chemical Company of America, Inc.
Coal Tar Products, Inc.
Coca Cola Co.
Colgate & Co.
Commonwealth Chemical Corporation
Campagnie National de Matieres
Colorantes & de Produits Chimiques
Compagnie des Forges de Chatillon Commentry
et Neuves-Maisons
Consolidation Coal Co.
Contact Process Co.
Davison Chemical Co., The
Dearborn Chemical Co.
Diamond Alkali Co.
Dow Chemical Co
Drakenfeld & Co., B. F., Inc.
Drying Systems, Inc.,
Eastern Malleable Iron Co.
Electric Heating Apparatus Co.
Electro Bleaching Gas Co.
Eli Lilly & Co., The
Everlasting Valve Co.
Fairbank Co., N. K., The
Falls Manufacturing Co., The
Fels & Co.
Fisk Rubber Co., The
Garrigue & Co., William, Inc.
General Briquetting Co.
General Chemical Co.
General Tire & Rubber Co.
Gillette Rubber Co.
Gleason-Tiebout Glass Co.
Glidden Varnish Co.
Globe Soap Co., The
Grasselli Chemical Co.
Great Atlantic & Pacific Tea Co.
Great Western Sugar Co.
Hamilton & Sons, W. C.
Hammermill Paper Co.
Heath & Milligan Mfg. Co.
Heinze Co., H. J.
Herrick-Voigt Chemical Corporation
Heyden Chemical Works
Hommel Co., O.. The
Horween Leather Co.
Humboldt Mfg. Co.
Imperial Varnish & Color Co., Ltd., The
India Refining Co.
Interocean Oil Co.
Jeffrey Mfg. Co., The
Kelly-Springfield Tire Co
Kendall Mfg. Co.
Kewaunee Mfg. Co.
Kidde & Co., Walter, Inc.
Kimble Glass Co.
Kirk & Co., James S.
Kistler, Lesh & Co.
Knight, Maurice A.
Koppers Co., The
Krebs Pigment & Chemical Co., The
Lennig & Co., Charles
Lindsay Light Co.
Little, Inc., Arthur D.
Mallinckrodt Chemical Works
Merck & Co.
Merrell Co., Wm. S., The
Metal & Thermit Corporation
Midland Linseed Products Co.
Miehle Printing Press & Mfg. Co.
Milwaukee Coke & Gas Co.
Minnesota & Ontario Power Co.
Miranda Sugar Co.
Moorman Mfg. Co.
Morrill & Co., Geo. H.
Morris & Co.
Muralo Co.
National Aniline & Chemical Co., Inc.
Natural Products Refining Co.
New Jersey Zinc Co.
Newport Co., The
Niagara Alkali Co.
Nichols Copper Co.,
Norwich Pharmacal Co.
Noyes Bros. & Cutler, Inc.
Oakland Chemical Co.
O'Brien Varnish Co.
Onyx Oil & Chemical Co.
Patent Cereals Co.
Pennsylvania Rubber Co.
Peoples Gas Light & Coke Co.
Peterson & Co., Leonard, Inc.
Pfaudler Co., The
Philadelphia Quartz Co.
Pittsburgh Plate Glass Co.
Powers- Weigh tman-Rosengarten Co.
Procter & Gamble Co., The
Providence Dyeing, Bleaching & Calendering Co.
Rahr Sons Co., William
Raymond Bros. Impact Pulverizer Co.
Republic Chemical Co., Inc.
Riordon Pulp & Paper Co., Ltd.
Riverside Acid Works
Robeson Process Co.
Roessler & Hasslacher Chemical Co
Rohm & Haas
Rome Soap Mfg. Co.
Royal Crown Soaps, Ltd., The
Schoenhofen Co.
Sears, Roebuck & Co.
Sharpies Specialty Co., The
Shell Company of California
Sherwin-Williams Co., The
Singer Mfg. Co., The
Society Anonyme de Produits Chimiques de
Droogenbosch
Solvay Process Co.
Southern Cotton Oil Co.
Sowers Mfg. Co.
Special Chemicals Co.
Squibb & Sons, E. R.
Standard Parts Co.
Standard Ultramarine Co., The
Stanley, John T.
Steel Brothers & Co., Ltd.
Steere Engineering Co.
Swan Mfg. Co.
Swift & Co.
Talbot Dyewood & Chemical Co.
Tar Products Corporation
Thomas Co., Arthur H.
Thorkildsen- Mather Co.
Titanium Pigment Co., Inc.
Union Carbide & Carbon Corporation
Union Oil Company of California
United States Rubber Co.
Universal Oil Products Co.
Universal Portland Cement Co.
Valentine & Co.
Vanadium Corporation of America
Vulcan Detinning Co.
Wallace & Tiernan Co., Inc.
Welsbach Co.
Western Paper Makers Chemical Co
Whitall Tatum Co.
White Tar Co.
Whitmore Mfg. Co.
Will Corporation, The
Will & Baumer Co , The
Winkler & Bro. Co., Isaac, The
Wisconsin Steel Works
NOTES AND CORRESPONDENCE
PURE PHTHALIC ANHYDRIDE
Editor of the Journal of Industrial and Engineering Chemistry:
A United States patent1 has been granted to C. A. Andrews,
which claims as an article of manufacture "phthalic anhydride
in the form of colorless, needle-like crystals substantially chem-
ically pure and having a melting point above 130° C, corrected."
' U. S. Patent 1,336,182; filed Oct. 14, 1919; granted April 6, 1920.
In a recent article by H. D. Gibbs1 the fallacy of this claim has
been shown by reference to previous publications in chemical and
patent literature.
We are in position to substantiate Gibbs' statement with some
additional evidence. Pure phthalic anhydride in the form of
colorless, needle-like crystals and having a melting point above
1300 C. has not only been prepared previously in various labora-
1 This Journal, 12 (1920), 1017.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. No. 1
tories but has been for many years a product of regular manu-
facture. It is true that organic handbooks, etc., give the melt-
ing point of phthalic anhydride as 1280 C, but it has been
known for some time by makers and users of this product that
the figure given in the chemical reference literature is about 3°
too low.
Prior to 1915 we imported phthalic anhydride during 6 or
7 yrs. from German and Austrian sources, and our analytical
records show that this product usually was of a very high de-
gree of purity and quite often had a melting point above 1300 C.
The melting point was determined on an average sample of
each shipment in the usual manner. In some cases the crystal-
lizing or solidification point was determined with 100 g. of the
product representing a composite sample from each of the
barrels of a shipment, and this crystallizing point also was
frequently found to be above 130° C. Comparative tests have
shown the melting point determined in a capillary tube to be
at least 0.5 ° higher than the crystallizing point determined as
described above.
Cryst. Pt. on
100-G. Sample
Date Bbls. ° C. Appearance
4/14/13 27 129.7 Short needles
5/16/13 4 130.3 Colorless needles
7/15/13 10 130.3 Colorless needles
7/14/14 10 130.7 Colorless needles
Melting Point in
Capillary Tube
4/1/14 8 131.5 Colorless needles
fi/20/14 4 130.5 Colorless needles
9/11/14 1 130-131 Colorless needles
The quality of the products of our own manufacture furnishes
additional evidence for the correctness of our contention. Prior
to the filing date of the Andrews patent we produced quantities
of phthalic anhydride in regular manufacture with a melting
point above 13 1° C, as shown by the following data taken from
our analytical records:
Cryst. Pt. on
100-G. Sample
Date Lbs. • C. Appearance
7/1/19 154 131.0 Colorless needles
7/8/19 367 131.1 Colorless needles
7/28/19 300 131.0 Colorless needles
8/14/19 175 131.0 Colorless needles
8/20/19 475 131.0 Colorless needles
9/5/19 400 131.0 Colorless needles
9/22/19 1405 131.0 Colorless needles
9/30/19 1075 131.0 Colorless needles
10/4/19 700 131.0 Colorless needles
In view of these facts it is evident that phthalic anhydride
having a melting point above 130° C. is not a new product and,
therefore, not patentable.
Monsanto Chemical Works JULES P.EBIE
St. Louis, Missouri
November 2a, 1920
STANDARDIZATION OF INDUSTRIAL LABORATORY
APPARATUS
Through the efforts of certain apparatus manufacturers, there
met informally at the Chemists' Club, New York City, on August
2, representatives of the following companies to discuss the
advisability of drawing up standard specifications for laboratory
apparatus to be used in their industrial research and works
control laboratories: Barrett Company, General Chemical
Company, Atmospheric Nitrogen Corporation, Grasselli Chemi-
cal Company, National Aniline & Chemical Company, New
Jersey Zinc Company, Solvay Process Company, Standard
Oil Company of New Jersey, and E. I. du Pont de Nemours
& Company.
Since most of these companies are members of the Manufac-
turing Chemists' Association of the United States, a committee
composed of these members was appointed by the Association
to pass on the proposals of the informal committee and to
recommend the adoption of the specifications resulting from the
informal committee's work as standard for the members of the
Manufacturing Chemists' Association.
Arrangements have been made for full cooperation with the
Committee on Guaranteed Reagents and Standard Apparatus
of the American Chemical Society, and also with the Committee
on Standards of the Association of Scientific Apparatus Makers
of the United States of America. These specifications will be
considered carefully by committees of these three societies, and
it is expected that they will then be published as tentative for
a period of 6 mo. in order to give time for general criticism.
At the end of that time the specifications will be adopted as
final.
In carrying on this work an effort will be made to obtain speci-
fications which will insure the cheapest mode of manufacture
of a given instrument consistent with the duties that it must
perform.
The committee desires to cooperate fully with all industries,
and any communications should be forwarded to the chairman,
Dr. E. C. Lathrop, E. I. du Pont de Nemours & Co.,
Wilmington, Delaware.
AMERICAN INSTITUTE OF BAKING, RESEARCH
FELLOWSHIPS
Arrangements have recently been made by the American
Institute of Baking by which the work done by its research
fellows at the University of Minnesota may be applied toward
the doctor's degree at that institution.
THE NOLAN BILL
Relief for the U. S. Patent Office, .although long delayed, is
apparently a prospect of the near future. The House has sent
the Nolan Patent Office reorganization bill to conference. The
bill was passed by the House last session and sent to the Senate.
There, during the closing hours of the session, Senator Norris of
Nebraska, chairman of the Senate Committee on Patents, was
forced to accept amendments so vitally changing the bill as
passed by the House that if enacted into law the result would
be a reduction in even the present force of the Patent Office.
The amendments were accepted, however, in order to assure
passage by the Senate during the last session, thus advancing
its parliamentary status.
Representative Nolan of California, chairman of the House
Committee on Patents, succeeded in having a special rule pro-
viding for sending the measure to conference between the House
and Senate by the end of the first week of the present session.
That all members of Congress are not supporters of the measure
is indicated by the opposition expressed on the floor of the
House. Representative Black of Texas made an effort to have
the House concur in the Senate amendments. The effect of
this would ba to enact the bill into law in the shape it passed
the Senate. This motion, however, was snowed under by a
vote of 210 to 154, and the measure sent to conference with
the House disagreeing to the Senate amendments
Representatives Nolan of California, Lampert of Wisconsin,
ranking Republican of the House Patents Committee, and Davis
of Tennessee, Democrat, were named as the House conferees,
while Senators Norris of Nebraska and Brandegee of Connec-
ticut, Republicans, and Senator Kirby of Arkansas, Democrat,
wort' named Senate conferees.
Attached to the Patent Office reorganization bill proper as
one of the Senate amendments is the measure providing for
acceptance and administration by the Federal Trade Commis-
sion of patents worked out by government scientists and tech-
nical experts. Senate conferees are desirous of keeping this
provision in the bill. House members, however, anxious that
the situation in which the Patent Office now finds itself be re-
lieved, fear that inclusion of this provision may be the cause
of the defeat of the entire bill, and will make a fight in confer-
ence to have it stricken out. Senator Norris is in favor of hav-
ing the provision remain in the bill. Other Senate conferees
also feel that the provision should be retained, and it is on this
question that the principal fight will ensue. There is no dis-
Jan., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
position on the part of the Senate conferees, Senator Norris said,
to insist on the Senate amendments reducing the salaries and
the working force of the Patent Office as provided in the bill
passed by the House. It is certain that they will readily agree
to increases both in the number of employees and remuneration
provided.
Meetings of the conferees are not expected much before
Christmas, and it is probable that no report will be made by
the committee until after the Christmas holidays. Final action
on a measure that will benefit the Patent Office within the near
future seems assured, however, both Senator Norris and Repre-
sentative Nolan being determined to press the measure.
the dye bill
Congress has swung into the second week of the third and
last session of the 66th Congress, and the fate of the dye bill is
still in question. The hearty promises that it would be imme-
diately pressed for action have begun to appear to even the most
hopeful of its supporters like the far-famed mirages of the
desert. At the present time there appears little probability
that action will be taken on either the dye or the several other
tariff measures pending in the Senate. Perhaps the most in-
teresting development in the dye situation has been the recent
frankness of Senator Moses of New Hampshire, who has waged
such a determined fight against the licensing feature of the bill
"because it violates principles I espouse."
Upon his return to Washington prior to the opening of this
session, Senator Watson of Indiana, in charge of the bill, declared
his intention of pressing the bill for action. He deemed it im-
possible, he said, to secure enactment of the measure with the
licensing feature embodied in it and consequently intended to
abandon that in favor of a system of tariff protection for the indus-
try. During a recent meeting of the Senate Finance Committee
the various tariff bills were discussed. Senator Watson said that
he did not think it would be possible to obtain passage of the dye
bill if it was to be amended by tacking on other tariff legisla-
tion for the purpose of using the dye bill as the vehicle to carry
through measures which otherwise would not be acted upon.
Senator Thomas of Colorado, Democrat, who distinguished him-
self last session by occupying the Senate floor for a week in
filibuster against the bill, said that he saw no reason why the
dye bill should not be amended so as to include the tungsten,
magnesite, "and in fact all the other tariff measures we have
here."
Senator Moses heretofore has been emphatic in his declara-
tion that his opposition was solely to the licensing feature of
the bill. The Senator possibly still holds that position. Never-
theless, in the face of declarations by Senator Watson that he
would abandon the licensing provision in favor of tariff protec-
tion, the New Hampshire Senator declared that if the dye bill
was to be acted on at this session he saw no reason why he
should not propose several amendments himself affording pro-
tection to textile machinery. This attitude of Senator Moses
can hardly be explained in view of his previous declaration.
WOOD CHEMICAL INDUSTRY CONFERENCES
The general business depression now existing, the lack of an
export market, and competition from Canada are the outstand-
ing problems facing the American wood chemical industry. Dis-
cussions at conferences held by the U. S. Tariff Commission
in Detroit December 7, and in Buffalo December 9 and 10,
■ 1920, with manufacturers, including representatives of the
Canadian industry, centered upon these obstacles. The Com-
mission was represented at these hearings by Commissioner
Edward P. Costigan and C. R. DeLong of the staff of chemical
experts of the Commission. Eight manufacturers were present
at the meeting in Detroit. At Buffalo the commission repre-
sentatives went over the situation at a conference with approx-
imately fifty, domestic manufacturers, on December 9, attending
a meeting of the National Wood Chemical Association. Two
Canadian representatives of the wood-distillation industry con-
ferred with Commissioner Costigan and Mr. DeLong the fol-
lowing day. One of . these represented the Canadian Electro
Products Company of Shawinigan Falls, Quebec, manufacturers
of synthetic acetic acid. Cooperation with the Commission in
its efforts to ascertain pertinent facts is understood to have
been promised by the Canadians.
The general business depression which now holds the business
of the nation for the most part in its grip, the decline — perhaps
to be expected to some extent — in the foreign sales, and the
competition that is being felt from the production in Canada of
synthetic acetic acid have left most American manufacturers
discouraged and depressed.
GERMAN COMPETITION IN THE DYE INDUSTRY
Congress and perhaps the country generally, inclined to dis-
count as extravagant the pictures of the probable competition to
be expected from Germany's dye trust painted by the proponents
93
of adequate protection for the American industry, is having the
enormous power of that country impressed upon it by the repre-
sentatives of many other American industries. Testifying before
the House Ways and Means Committee, urging adoption of
legislation that would equalize foreign exchange for the purpose
of assessing import duties, Franklin W. Hobbs, president of the
Arlington Mills, told the committee that "in dyestuffs for in-
stance, unless something is done we will be unable to meet the
competition and there will be no business left in this country.
Our industries will be wiped out." Mr. Hobbs was speaking in
favor of enactment of legislation that would protect the wool
manufacturer.
While perhaps there may be little to cause excitement in the '
mere announcement appearing recently in press dispatches from
Germany of the intention to establish in the United States and
m England German plants for the production of nitrate, advo-
cates of an American dye industry are inclined to see beneath
the surface the entering wedge of dangerous competition. It
is important to know whether the plant which it is proposed to
establish in this country will make ammonia or ammonium
sulfate, used for fertilizers, or go a step farther and produce
nitric acid, thus opening the way to the manufacture of aniline
and dye intermediates. It is significant that it is proposed to
establish such plants only in England and in the United States.
While our dye industry has, according to the best information
available, outstripped the development of the British industry,
these two promise the two sources of real competition to the
German industry. With Germany's past history of commercial
penetration in mind, one is inclined to view askance this newest
development and wonder if it is not another example of German
efficiency preparing to forestall the enactment of legislation ade-
quately protecting our industry and its proper development.
TARIFF REVISION
Desirous of having the new Republican revision of the tariff
on the statute books as soon as possible, the House Ways and
Means Committee has decided to begin tariff hearings on gen-
eral revision January 5. The Committee plans to go through
the present law schedules in alphabetical order, and on that
date proposes to take up Schedules A dealing with chemicals.
FOREIGN TRADE STATISTICS
Enlarged detail of import and export statistics, which has been
planned by the Bureau of Foreign and Domestic Commerce of
the Department of Commerce to be put into effect January 1,
may be delayed because of the failure of Congress to grant the
funds necessary. Plans worked out some time ago provide for
a very great extension of the import and export classifications
now contained in published foreign trade statistics. At the
present time these statistics are compiled by the customs divi-
sion of the Treasury at the various ports of entry and exit,
and the totals each month are forwarded here for publication
by the Bureau of Foreign and Domestic Commerce. In order
to simplify and coordinate the work of compilation, collection,
and publication of the statistics, it is proposed to transfer the
entire task to the Bureau of Foreign and Domestic Commerce.
This plan has met with the approval of both the Secretary of
the Treasury and the Secretary of Commerce.
In response to the numerous demands from the business in-
terests of the country, the Bureau of Foreign and Domestic
Commerce has prepared new classifications which it had hoped
to put in effect on January 1, coincident with the change from
the fiscal to the calendar year basis of publication of statistics.
It is estimated that this work will require $400,000 annually,
and provision for this sum is made in the estimates for the special
urgent deficiency bill now before the House Appropriations Com-
mittee. Whether or not the plan will go through will depend
upon Congress. The appropriations requested, it is to be re-
membered, are not in addition to funds already used, but include
funds now used by the Commerce and Treasury departments
separately for the carrying on of their parts of the work which
it is proposed to coordinate.
Hearings are expected to be held sometime within the next
2 wks. Officials of the Bureau of Foreign and Domistic
Commerce are anxious to put into effect the new schedules with
the beginning of the new year, and if a favorable report is made
by the House Appropriations Committee they will consider that
it is the intention of Congress to grant the funds necessary,
and proceed. It will be necessary, however, that Congress take
affirmative action before the last 2 wks. of January, as other-
wise it will be impossible to put the new classifications into effect
for that month.
The chemical industries are particularly interested in these
new classifications, inasmuch as they involve considerable ex-
tension of detailed figures as to imports and exports of dyes and
other chemicals.
December 14, 1920
94
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
PARI5 LETTER
By Charles Lormand, 4 Avenue de l'Observatoire, Paris. France
As I told you in my preceding letter, petroleum researches
in France are being actively pushed, and certain districts, where
it is thought petroleum will be found, remind me, in their ani-
mation, of those of Fort Worth and Dallas, which I visited at
the beginning of 1919-
Up to the present time the only positive result obtained is the
boring of Puy de Crouelle, 5 kilometers from Clermont-Ferrand.
For a long time this district of Limagne has been considered
by French geologists as likely to contain petroleum; and in 191 8
Dr. Hamor, chief of the Petroleum Division of the U. S. Bureau
of Mines, told me he thought petroleum researches should be
pursued in that district. His predictions were right, since the
present boring yields oil. The trial boring, which is 550 meters
deep, yielded 25 bbls. This oil is rather heavy, and contains
a rather high percentage of sulfur compounds (hydrogen sul-
fide and sulfur). It is supposed that it comes from the top part
of the deposit and that this part is somewhat oxidized, but that
at a greater depth lighter oils will be obtained.
The borings are made for the French government, and also,
in this same region by a Franco-Belgian company. Professor
Glangeaud, of the Faculty of Sciences of Clermont, is in charge
of the geological side of the work.
Another layer has also been reported in the Landes Depart-
ment, west from Saint-Sever. In that district the boring is
far less advanced, although geologists think that this layer
extends to the Lower Pyrenees. There also exist in this dis-
trict bituminous layers which are already being exploited.
Finally another layer is reported in the Alpine distiict, be-
tween the Rhone valley and that of the little river, Le Feir.
At the opening meeting of the Societe de Chimie Industrielle
on November 25, Professor Gentil, of the Faculty of Sciences
of the University of Paris, gave a summary of the present state
of geological information on petroleum prospecting. The contro-
versies between partisans of the mineral volcanic theory and
those of the organic theory are violent for, according to the point
of view, prospecting may be directed along very different lines.
A partial state monopoly is considered, but that project does
not seem to have great chance of succeeding, as the majority
of Parliament stands strongly against it.
THE DYESTUFF SITUATION
We are beginning to derive benefit from our efforts, made dur-
ing the war and since the armistice, not to be tributary to Ger-
many as regards dyestuff materials.
The "Compagnie Nationale des Matieres Colorantes" and the
"Soci£t6 des Produits Chimiques et Colorants Francais" were
amalgamated at the beginning of this year. These two companies
control about 70 per cent of the production, the remainder
being controlled by the "Societe de Saint-Denis," the "Societe
Alsacienne de Produits Chimiques de Thann et Mulhouse,"
the "Compagnie Francaise de Produits Chimiques et de
Matures Colorantes du Rhone," etc. German companies which
had factories in France are working under sequestration and
under the management of the "Compagnie Nationale."
The total output of all the manufactures, during the war and the
initial period, was 100 tons, jumped to 176 in June 1919, to 470
tons in January 1920, and finally to 764 tons in August 1920.
The monthly capacity of the French market is about 1000 tons.
The coloring materials we are lacking are specially alizarins,
certain basic dyes, and vat dyes.
The manufacture of intermediates has been partly ensured
by the transformation of munition factories.
INTERNATIONAL PATENTS
The French government has just agreed to the international
arrangement for the creation, in Belgium, of a central bureau of
patents. About 12 other nations have also agreed.
This Bureau, set up in Brussels, is to be an organ of docu-
mentation and of centralization as regards patents, from both
the legal and technical point of view. It has charge of the
international registration of applications for patents, and of
the transmission to the administrations of the adhering coun-
tries of applications for patents in one or several countries.
Furthermore, it will examine the applications and will proceed
to the necessary investigations regarding priorities.
Mr. J. C. Pennie's suggestions, made at the International
Chemical Conference in 1919, have been taken into considera-
tion. This is the first step towards the creation of an interna-
tional patent, which, although giving to the inventors the bene-
fit of legislation in their respective countries, will at the same
time safeguard their interests in foreign countries.
The French representative in Brussels is M. Drouet.
INDUSTRIAL CRISIS
The industrial crisis which I reported is becoming more and
more intense and the market of chemical products is under-
going a real crash. Little by little stocks are disappearing,
and in spite of the high price of certain raw materials tributary
to the rate of exchange, the drop in prices approaches 50 per
cent of those of 1919. A consequent general decrease in the
cost of living is expected.
"LA CHIMIE ET LA GUERRE"
M. Moureu, the president of the "Union Internationale de
Chimie," has just published a book, "La Chimie et la Guerre,"
which is a record of all services rendered by chemists and chemical
industries of all the allied nations. This little book covers
more than the limits of the French speaking public. Besides
indicating all that has been accomplished by chemists for the
war, it contains a great number of general ideas on the making
of chemists and the part played by chemistry in the life of
modern societies.
THE BASSET PROCESS
In one of my previous letters, I spoke about a new process
for the manufacture of steel — the "Basset process" for the
direct production of steel without using blast furnaces. This
process is more and more discussed, and it does not yet seem to
be out of the trial period. The big metallurgical firms look on
the process with reserve.
December 3, 1920
LONDON LETTER
By STBPBBN Miau., 28, Belsize Grove, Hampstead, N. W. 3, England
THE DYE BILL
Within the next few weeks Parliament must make a decision
as to the future of the dye industry in this country. Not only
is a great chemical industry essential to our future prosperity
but we cannot rely, as we have in the past, almost exclusively
on the manufacture of heavy chemicals, we must also have a
flourishing industry in the manufacture of aniline dyes, pharma-
ceuticals, and other synthetic organic compounds. The few
manufacturers of dyestuffs over here were occupied during the
war in the manufacture of poison gas and explosives, and toluene
was required for TNT rather than for toluidine; since the war
some progress has been made, but the present rate of the ex-
change between England and Germany enables Germany to
undersell the British manufacturers by a veiy considerable
margin. The government proposes to allow the German dye-
stuffs to be imported only by special license, and such license
would be refused when the British manufacturers can make the
dyestuff of good quality and sell it at a reasonable price. This
proposal, if carried, will give the British manufacturers the time
necessary for their gradual development, and though it will
be vigorously opposed by a number of the free traders over here,
it is generally expected that the government will be both wise
enough and strong enough to carry the measure through suc-
cessfully. By the time this letter reaches you the fate of the
bill will be pretty well known.
(The dye bill passed the House of Commons on December 18,
1920. — Editor)
the brunner, mond & company suit
We have been much interested in a law case recently. One
of the shareholders of Brunner, Mond & Co., Ltd., brought an
action to restrain the company from making a gift of £100,000
for educational purposes, on the ground that the company ought
not to spend its money except for its own benefit, and as the
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
95
proposed gift would necessarily benefit quite a lot of the other
people the proposal was ultra vires. The action was dismissed
by the judge, and I have not heard that the plaintiff has any
inclination to appeal. Had the decision been the other way,
the case would probably have been taken up to the House of
Lords, and if such a gift had there been held to be illegal there
was talk of introducing a bill in Parliament to make all such
gifts lawful. Indeed, the Federal Council for Pure and Applied
Chemistry had already sounded a few members of Parliament
to secure their assistance. An adverse decision would have been
a very serious blow to British chemistry, for our universities
cannot train sufficient chemists without such generous donations,
and private individuals in this country are, since the war, not
so comfortably situated as to find the necessary funds themselves.
CONFERENCE ON BRITISH PERIODICAL CHEMICAL LITERATURE
The Federal Council has within the last few days invited the
Chemical Society and the Society of Chemical Industry to ap-
point delegates to a joint conference on the periodical chemical
literature in this country. In many of the principal countries
this problem has already been successfully solved. America,
Holland, Italy, and some others come into one's mind, but in
France and Britain there is hardly any cooperation between the
societies who publish the transactions and abstracts of pure
chemistry and those who make public the new results of indus-
trial chemistry. In Britain the problem is both acute and com-
plex. Both the Societies are troubled by the high cost of print-
ing and paper and by exchequers largely depleted; each has its
own clientele, traditions, and staff; neither can afford to run
any risk of a reduced circulation and a corresponding loss of
revenue from advertisements, and the joint conference will have
to consider very carefully whether some species of cooperation
can be evolved which will effect economy in publication without
loss of revenue. Your experience in America, I am sure, will
be a valuable guide to the British committee, and if their delibera-
tions are not concluded before the summer we may learn a great
deal from you in a quiet talk round a bottle of any sustaining
fluid which the ingenuity of man may devise and procure for the
purpose. Water's the best of drinks, they say, and all the poets
sing, but who am I, that I should have the best of anything!
INTERNATIONAL LABOR ORGANIZATION
We are now seeing the first fruits of the International Labor
Conference which was held in Washington in November 1919.
This conference was presided over by a distinguished Ameiican,
but your country did not in any other respect take a conspicuous
part in the deliberations of that assembly. The conference dealt
with a variety of subjects, including diseases of occupation such
as anthrax and lead poisoning, and a recommendation was finally
adopted to prevent the employment of women and young per-
sons in processes likely to produce lead poisoning. Those of
us who attended the conference found we had plenty of work to
do, and the discussions were the more difficult in that they were
usually bilingual. ^When we came to translate the Washington
recommendation into the Act of Parliament we found it no easy
task to make the terms of the recommendation fit in with our
existing legislation and our special industrial conditions, and the
House of Lords has had to listen to details as to solubility of
lead compounds, the manufacture of lead silicates, and the de-
termination of lead in solution by precipitation and estimation
as lead monoxide. I believe all of us who have been through this
experience realize how much time and how much attention to
detail is necessary for the proper application of such general
ideas as may appear to be feasible, and how important it is
that the international labor organization shall consider such
highly technical matters as injurious processes in a detailed and
leisurely manner impossible in a hurried conference.
FUEL ECONOMY
Fuel economy has been before the public ever since I can
remember, and the number of schemes to enable us to save 10
or more per cent of our coal or money is almost infinite. The
advocates of high-temperature carbonization, of low-temperature
carbonization, of dry carbonizing and wet carbonizing have been
busy in the press and on the Stock Exchange. It is an extraor-
dinary thing that for power purposes nothing seems to be
cheaper than a well-conducted boiler of the old-fashioned type
heated by ordinary coal. Its elasticity and simplicity seem to
counterbalance and even more than counterbalance the waste
of benzene, toluene, ammonia, and phenol. Powdered fuel,
colloidal fuel, gas, and oil are still in an experimental stage. I do
not know whether all the permutations and combinations of
solid, liquid, and gaseous fuel have yet been investigated, but
a good many are still under discussion. After many years of
doubt and disaster I am now informed that low-temperature
carbonization has been got to work satisfactorily. The diffi-
culties in the past have been largely mechanical and seem to
have been surmounted. It seems that the new plant at Barnsley
in Yorkshire is working well and that there is a reasonable chance
that the patience of the shareholders will ultimately be justified.
All the metals seem to be having a race as to which can reach
the bottom first, and as no one cares to buy on a falling market
the trade in inorganic compounds is extremely limited. I
imagine that this phenomenon must be very prominent on your
side of the Atlantic as well as this, and it is hard to say whether
the outbreak of war or the outbreak of peace has been the more
disastrous.
The visit of the Society of Chemical Industry to Canada and
the United States next September already causes much interest
over here and the program, so far as it is known, is most attrac-
tive. In the future no nation can be a great industrial nation
unless it is a great chemical nation, and we have much to learn
from the well-organized chemical industries in these two coun-
tries and from the chemists whom too few of us know personally.
December 6, 1920
PERSONAL NOILS
Mr. Regis Chauvenet, president emeritus of the Colorado
School of Mines, chemist and metallurgist, died in Denver
recently at thejagejof seventy-eight.
Dr. Elijah P. Harris, emeritus professor of chemistry at
Amherst College, died recently at Warsaw, N. Y , at the age
of ..eighty-eight. Dr. Harris retired as professor of chemistry
at Amherst in 1907 and became emeritus professor on the Car-
negieJFoundation. He was the author of a book on "Qualita-
tive Analysis" which went through ten editions.
Mr. Harry W. Eberly, acid assistant in charge of nitric acid
at the Forcite Works of the Atlas Powder Co., Landing, N. J.,
and a member of the American Chemical Society, died last
October at the Dover General Hospital from the effect of nitric
acid fumes received from a spill in the nitric acid house of which
he was in charge.
Mr. Isaac Neuwirth is now associated with Dr. Israel S.
Kleiner, as instructor in physiological chemistry at the New York
Homeopathic Medical College and Flower Hospital, New York
City.
Mr. Sherman Leavitt, formerly with the Illinois State Water
Survey Division at the University of Illinois, has been appointed
instructor in food chemistry and technical analysis at the Uni-
versity of Minnesota, Minneapolis, Minn.
Mr. Robert A. Miller, Jr., formerly with the Stillwell & Glad-
ding Co., of New York, is at present engineering research chem-
ist with the Rubber Regenerating Co., of Naugatuck, Conn.
Mr. H. O. Bernstrom, until recently with the Lignol Chemical
Co., Irvington, N. J., where he was working on hardwood oils,
is now attached to the chemical and research division at Edge-
wood Arsenal, Edgewood, Md.
Mr. H. E. Brown, of New York City, has been appointed
engineer of the plant of the Bartholomay Co., Inc., at Rochester,
N. Y. This plant was formerly the Genesee Brewery, and the
Bartholomay Company has let a contract for converting it into
a vegetable oil refinery, using the Brown-Baskerville process.
Mr. Floyd E. Rowland, assistant professor of chemistry at the
University of Kansas last year, has been elected head of the
department of chemical engineering at the Oregon Agricultural
College, Corvallis, Ore.
Mr. E. G. Gross has resigned as instructor of agricultural
chemistry at the University of Wisconsin, and is holding a
fellowship in the Yale Graduate School in the department of
physiological chemistry with Dr. Mendel.
Mr. John Gore, formerly assistant superintendent of the
Russ Gelatin Co., Westfield, Mass., has become chemical en-
gineer for the Beech-Nut Packing Co., Canajoharie, N. Y.
Mr. C. G. Smith, who has been connected with the Dow
Chemical Co., Midland, Mich., for the past five years, in
the capacity of experimental chemist and engineer, resigned
last spring because of ill health, and is at the present time teach-
ing science in the Canon City High School, Canon City, Colo-
rado.
96
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Drs. Frederic C. Lee and E. Hyatt Wight have formed a part-
nership under the firm name of Lee & Wight, and have opened
a consulting and analytical laboratory in Baltimore, Md.
Mr. Ellery L. Priest, formerly with the W. S. Merrell Chemical
Co., Cincinnati, Ohio, has joined the firm of the Western Chem-
ical Co., Hutchinson, Minn., where he is assistant chemist.
Mr. Charles A. Fort has left the General Electric Co., of
Pittsfield, Mass., where he was employed as research chemist
on insulating materials, and has become chief chemist for the
Forest Products Chemical Co., of Memphis, Tenn. His new
work consists mainly of research on hard-wood tar products.
Mr. Louis Mittelman resigned his position with the Sun Com-
pany at their Toledo refinery to accept a position as chemist
with the Associated Oil Co., at Gaviota, Cal.
Mr. Jesse E. Day severed his connections this past summer
as assistant professor of general chemistry at Ohio State Uni-
versity, Columbus, O., to become assistant professor of general
chemistrv for engineers at the University of Wisconsin, Madison,
Wis.
Mr. K. V. Froude, who for the last two years has been assis-
tant chemist in the laboratory of the Bettendorf Steel Works,
Bettendorf, Iowa, has been promoted to the position of chief
chemist_for the same company.
Mr. A. E. Plumb, until recently chief chemist for F. J. May-
wald, consulting rubber technologist of Newark, N. J., with
laboratory at Nutley, N. J., now holds a similar position with
Hodgman Rubber Co., of Tuckahoe, N. Y.
Dr. Irene C. Diner, previously attached to the division of in-
dustrial chemistry at New York University, New York City,
has become associated with the research division of the Chem-
ical Warfare Service, in the capacity of associate chemist work-
ing on rubber problems.
Dr. C. B. Clevenger resigned an instructorship in the depart-
ment of chemistry, University of Wisconsin, Madison, Wis.,
to accept a professorship of agricultural chemistry and head of
the department of chemistry of the Manitoba Agricultural Col-
lege, Winnipeg, Canada.
Mr. Isador W. Mendelsohn, chemist and state sanitary engi-
neer of the State Board of Health of North Dakota for the past
two years, has become assistant sanitary engineer of the Bureau
of the Public Health Service, detailed at Washington, D. C.
Mr. C. W. Leggett is at present employed by the McCall
Cotton & Oil Co., Phoenix, Ariz., as superintendent and
chemist.
Mr. C. K. Jones has resigned from the Van Camp Packing
Company in order to accept the position as chief chemist for
the Whitman Candy Co., Philadelphia, Pa.
Mr. A. E. Koenig, who was assistant professor of chemistry
at the University of Wisconsin, Madison, Wis., has resigned
from that position and is now at the State School of Mines,
Butte, Mont., as associate professor.
Mr. Joseph V. Meigs, formerly connected with the New
Jersey Testing Laboratories, Montclair, N. J., as research chem-
ist, is chief chemist for the Massachusetts Oil Refining Co., at
East Braintree, Mass.
Mr. Rolla N. Harger has resigned as assistant biochemist,
Soil Fertility Investigations, Bureau of Plant Industry, Wash-
ington, D. C., to accept one of the National Research Council
fellowships in chemistry. Mr. Harger's work will be on a prob-
lem in organic chemistry and will be done at Yale University,
New Haven, Conn.
Mr. R. H. Currie has left the du Pont Company of Wilming-
ton, Del., where he was attached to the main office chemical staff,
and is at present with the Acheson Graphite Co., Niagara
Falls, N. Y., as assistant superintendent.
Mr. Harold J. Barrett has been appointed instructor in chem-
istry at Iowa State College, having come there from West Vir-
ginia University, Morgantown, W. Va.
Mr. Phil G. Horton has recently resigned his position as chem-
ist in the research laboratory, film section, of E. I. du Pont de
Nemours & Co., Parlin, N. J., and is taking a postgraduate
course in chemistry at Ohio State University.
Mr. J. Irving Prest, formerly chemist at the Pacific-Northwest
Experiment Station of the U. S. Bureau of Mines, Seattle,
Wash., has joined the forces of the International Harvester Co.,
Chicago, 111.
Dr. S. A. Mahood, who has been in charge of investigations on
wood cellulose and essential oils at the U. S. Forest Products
Laboratory, Madison, Wis., for the past three years, has be-
come associate professor in charge of organic chemistry at Tu-
lane University, New Orleans, La.
Miss Mary V. Buell, who taught nutrition in the home eco-
nomics department of the University of Wisconsin, Madison,
Wis., last year, is at present teaching chemical dietetics and phys-
iological chemistry in the home economics department of the
University of Iowa, with headquarters at the University Hos-
pital of the State University of Iowa, and is also cooperating
with the medical staff in their metabolism work and research.
Dr. Ernest Anderson, for the past three years professor of
agricultural chemistry in the University of South Africa, has
been appointed professor of general chemistry in the University
of Nebraska, Lincoln, Neb.
Mr. Frank Bachmann resigned his position as chief chemist,
Industrial Waste Board, Connecticut State Department of
Health, to accept a position in the sanitary engineering depart-
ment of the Dorr Company of New York City.
Mr. Floyd A. Bosworth, formerly junior chemist in the United
States Food and Drug Inspection Station at Buffalo, N. Y., is
now employed in the research and analytical department of the
United Drug Company at Boston, Mass.
Mr. Henry Ward Banks, 3d, formerly research chemist with
the Harriman Laboratory and the National Biscuit Co., and
Mr. Robert Hall Craig, formerly with the office of the Surgeon
General of the Army, Washington, D. C, and later with the con-
struction division of the Army, have formed a partnership under
the name of Banks and Craig, consulting engineers and chem-
ists, in New York City. Dr. D. D. Jackson, of Columbia Uni-
versity, is associated with the firm in the capacity of consulting
sanitary engineer.
The following have become members of the staff of the de-
partment of chemistry of the College of the Citv of New York:
W. McG. Billing, H. P. Coats, Alexander Cohen, A. C. Glennie,
Nathan Hecht, and F. D. SneU.
Mr. C. B. Wiltrout, formerly chief chemist for the Continental
Sugar Co., Toledo, Ohio, has been engaged as chief chemist by
the raw sugar refining interests of the Independent Sugar Co.,
Marine City, Mich.
Mr. J. S. Staudt has become associate professor of electrical
engineering at Texas A. & M. College, College Station, Texas.
He was formerly in the government employ at the Old Hickory
Powder Plant near Nashville, Tenn.
Mr. Hugo H. Sommer has resigned as chemist for the Northern
California Milk Producers Association, Sacramento, Cal., to be-
come assistant professor of dairy husbandry in the dairy depart-
ment of the University of Wisconsin, Madison, Wis.
Dr. Frederick E. Breithut has entered the employ of the Calco
Chemical Company, Bound Brook, N. J.
Dr. William C. Moore, until recently associated with the
School of Hygiene and Public Health of Johns Hopkins Uni-
versity, is now on the research staff of the United States In-
dustrial Alcohol Co., Baltimore, Md.
Dr. Frederick W. Lane, for the past three years instructor
in chemistry at Yale University, has become organic chemist
in the petroleum division of the Pittsburgh Station, U. S. Bureau
of Mines, Pittsburgh, Pa.
Dr. M. E. Holmes, formerly research engineer for the Na-
tional Carbon Co., Cleveland, Ohio, has been appointed manager
of the chemical department of the National Lime Association,
Washington, D. C.
Mr. Bartholomew O'Brien, formerly with the Synfleur Scien-
tific Laboratories of Monticello, N. Y, has joined the staff of
the Grasselli Chemical Co., Albany, N. Y.
Mr. Kirby E. Jackson, head of the science department at the
Marion County High School, Jasper, Tenn., has been appointed
professor of chemistry at the Daniel Baker College, Brownwood,
Texas.
Miss Martha G. Barr, who was instructor in chemistry at
Iowa State College, Ames, Iowa, from 1918 to 1920, now has
charge of the chemical laboratory of the Lane Cotton Mills of
New Orleans, La.
A recent acquisition to the engineering staff of the John
Johnson Co., Brooklyn, N. Y., is announced in the per-
son of Capt. Wilkinson Stark, late of the Army Ordnance De-
partment. Prior to his service in the Army, Captain Stark was
employed by the du Pont Company, who released him at the
beginning of the war to supervise the design, installation, and
operation of the Army's caustic recovery and cotton purifica-
tion, bleaching, and drying divisions at Explosives Plant "C,"
Nitro, W. Va.
Dr. Edward Schramm, formerly research chemist with the
Bridgeport Brass Co., Bridgeport, Conn., is now with the
Onondaga Pottery Co., Syracuse, N. Y., as research chemist.
Jan., 1021
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
Q7
GOVERNMENT PUBLICATIONS
By Nellie A. Parkinson, Bureau of Chemistry, Washington, D. C.
NOTICE — Publications for which price is indicated can be
purchased from the Superintendent of Documents, Government
Printing Office, Washington, D. C. Other publications can
usually be supplied from the Bureau or Department from which
they originate. Commerce Reports are received by all large
libraries and may be consulted there, or single numbers can be
secured by application to the Bureau of Foreign and Domestic
Commerce, Department of Commerce, Washington. The regu-
lar subscription rate for these Commerce Reports mailed daily
is $2.50 per year, payable in advance, to the Superintendent of
Documents.
DEPARTMENT OF LABOR
Employment of Women in Hazardous Industries in the
United States. Summary of State and Federal Laws Regulating
the Employment of Women in Hazardous Occupations, 1919.
Bulletin 6 (Reprint). 8 pp. 1920.
NATIONAL ADVISORY COMMITTEE FOR AERONAUTICS
Comparison of Alcogas Aviation Fuel with Export Aviation
Gasoline. V. R. Gage, S. W. Sparrow and D. R. Harper, 3d.
14 pp. Report 89. Paper, 5 cents. 1920.
Comparison of Hector Fuel with Export Aviation Gasoline.
H. C. Dickinson, V. R. Gage and S. W. Sparrow. Report 90.
10 pp Paper, 5 cents. 1920.
NAVY DEPARTMENT
Instructions for Care and Operation of Fuel Oil-Burning
Installations. Revised edition, 1920. 90 pp.
WAR DEPARTMENT
Aviation Gasoline, Specifications and Methods of Testing.
Prepared by Material Section of Air Service. Air Service
Information Circular, Heavier-than-Air, Vol. 1, No. 46, Aug.
30, 1920. 8 pp.
Report of Tests of Metals and Other Materials Made in
Ordnance Laboratory at Watertown Arsenal, Mass., Fiscal
Year 1918. War Department Document 901, 338 pp. Paper,
80 cents. (In many cases one side of the leaf only is paged,
the unnumbered side usually bearing illustrations, although
in some cases it is blank.)
BUREAU OF FOREIGN AND DOMESTIC COMMERCE
Hides and Leather in France. Norman Hertz. Special
Agents Series, No. 200. 159 pp. Paper, 20 cents. 1920. The book
includes an introduction, general survey of conditions, a descrip-
tion of market requirements for leather, the domestic tanning
industry, foreign trade in leather, customs tariff, leather mer-
chandising, foreign trade in hides and skins, domestic hides and
skins and tanning materials, and an appendix. The conclusion
is drawn that while American tanners cannot expect to continue
the volume of business in France that was transacted during the
war and immediately after, the outlook for continued sales
of many kinds of leather, especially upper leather, is very
good, provided American manufacturers keep constantly in mind
the fact that it is better to keep a customer satisfied than to
make a few large sales.
PUBLIC HEALTH SERVICE
An Outbreak of Botulism at St. Anthony's Hospital, Oakland,
Cal., in pctober 1920. Public Health Reports, 35, 2858-60.
There was a total of six cases, two of which could be considered
mild and four severe. Of these latter, three died. Unfortunately,
none of these cases was recognized as botulism until the third
day of illness, and therefore they were not immediately reported.
BUREAU OF MINES
Monthly Statement of Coal-Mine Fatalities in the United
States, August 1920. W. W. Adams. 8pp. Paper, 5 cents.
October 1920.
Monthly Statement of Coal-Mine Fatalities in the United
States, September 1920. W. W. Adams. 8 pp. Paper, 5 cents.
Norember 1920.
BUREAU OF STANDARDS
Sodium Oxalate as a Standard in Volumetric Analysis.
Circular 40, 3d ed. 13 pp. Paper, 5 cents. 1920. This
circular is not issued for the purpose of publishing any new
information or of entering into a critical discussion of volumetric
standards, but rather to give a resume of the work done at the
Bureau of Standards and elsewhere which has led to the selection
of the sodium oxalate as a primary standard. This third edition
has been revised with special reference to the methods employed
and the results obtained in the testing of the second preparation
of sodium oxalate which is now issued as Standard Sample No.
40a.
!■ Recommended Specification for Composite Thinner for Thinning
Semipaste Paints when the Use of Straight Linseed Oil Is
Not Justified. Prepared and Recommended by the United States
Interdepartmental Committee on Paint Specification Standard-
ization, September 27, 1920. Circular 102. 5 pp. Paper, 5
cents. Issued October 18, 1920. This specification covers a
composite thinner which contains in one liquid drying oil. drier,
and volatile thinner. General specifications are given, and
methods of sampling, laboratory examination, and the reagent
employed are described.
Recommended Specification for Spar Varnish. Prepared and
Recommended by the United States Interdepartmental Commit-
tee on Paint Specification Standardization, September 27, 1920.
Circular 103. 5 pp. Paper, 5 cents. Issued October 18, 1920.
The specification provides that the varnish shall be the best long oil
varnish, resistant to air, light, and water. The manufacturer
is given the wide latitude in the selection of raw materials and pro-
cesses of manufacture, so that he may produce a varnish of the
highest quality. It must, however, comply with certain require-
ments, which are outlined. Methods of sampling and a descrip-
tion of the laboratory examination are described.
Recommended Specification for Asphalt Varnish. Prepared
and Recommended by the United States Interdepartmental
Committee on Paint Specification Standardization, September
27, 1920. Circular 104. 6 pp. Paper, 5 cents. Issued October
18, 1 920. The varnish must be composed of a high grade of
asphalt fluxed and blended with properly treated drying oil
and thinned to the proper consistency with a volatile solvent.
It must be resistant to air, light, lubricating oil, water, and min-
eral acids of the concentration specified, and must meet certain
requirements, which are outlined. Methods of sampling and
laboratory examination are also described.
A Study of the Relation between the Brinell Hardness and the
Grain Size of the Annealed Carbon Steels. H. S. Rawdon
and Emilio Jimeno-Gil. Scientific Paper 397. 37 pp. Paper,
10 cents. 1920.
Sulfur in Petroleum Oils. C. E. Waters. Technologic
Paper 177. 26 pp. Paper, 5 cents. October 20, 1920. Short
accounts are given of theories concerning the origin of the
sulfur and sulfur compounds which are found in crude petroleum.
The forms of combination in which the element occurs, their
identification, and significance are briefly discussed. Tests for
the detection of sulfur are described, and the copper test is shown
to be one of great delicacy. Various methods that have been
used for the determination of sulfur in oils, and finally a new
procedure, are described. Data obtained by the analysis of
certain oils by the new and other methods are given.
DEPARTMENT OF AGRICULTURE
Milk Plant Equipment. Ernest Kelly and C. E. Clement
Department Bulletin 890. 42 pp. Paper, 15 cents. Issued
October 1920. This bulletin points out some of the more im-
portant economic and sanitary problems in the handling and
distribution of milk.
Manual of Design and Installation of Forest Service Water
Spray Dry Kiln. L. V. Teesdale. Department Bulletin
894. 47 pp. Paper, 10 cents. Issued October 18, 1920.
Describes a kiln in which the temperature, humidity, and circu-
lation can be regulated independently of the others.
Weight Variation of Package Goods. H. Runkel. Depart-
ment Bulletin 897. 20 pp. Issued November 15, 1920.
Fumigation of Citrus Plants with Hydrocyanic Acid: Condi-
tions Influencing Injury. R. S. Woglum. Department Bulle-
tin 907. 43 pp. Paper. 15 cents. Issued October 20, 1920.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
Toxicity of Barium Carbonate to Rats. E. W. Schwartze.
Department Bulletin 915. 11 pp. Paper, 5 cents. Issued
November 12, 1920.
Cooperative. Cane-Sirup Canning: Producing Sirup of Uni-
form Quality. * J. K. Dale. Department Circular 149. 19 pp.
Issued November 1920. At present the cane-sirup industry is
handicapped by a lack of uniformity in the sirup offered for sale
by the individual farmer. This condition may be remedied by
the adoption of new and ^improved methods of manufacture
and by cooperative canning.
* Report of the Chemist. C. L. Alsberg. 30 pp. Issued
December 1920. This publication is a report of the work of
the Bureau of Chemistry for the fiscal year ended June 30, 1920.
Articles from Journal of Agricultural Research
Investigations of the Germicidal Value of Some of the Chlorine
Disinfectants. F. W.'Tuaey. 20 (October 15, 1920), 85-110.
Studies in Mustard Seeds and Substitutes: I— Chinese
Colza {Brassica campestris chinoleifera Viehoever). Arno
Veshoever, J. F. Clevenger and C. O. Ewing. 20 (October
15, 1920), 111-15.
Study of Some Poultry Feed Mixtures with Reference to
Their Potential Acidity and Their Potential Alkalinity. B. F.
Kaupp and J. E. Ivey. 20 (October 15, 1920), 141-9.
The Influence of Cold in Stimulating the Growth of Plants.
F. V. CovellE. 20 (October 15, 1920), 151-60.
COMMERCE REPOETS— NOVEMBER 1020
The Government laboratory of Jamaica has been conducting
experiments for the production of pimento-leaf oil from pimento
leaves. Pimento leaves yield about 1.8 per cent of eugenol,
from which isoeugenol and vanillin can successfully be obtained.
If a market can be found, Jamaica can produce 100,000 lbs.
of pimento-leaf oil per annum from materials at present wasted.
(P. 500)
An important financial group, representing English, French,
and Rumanian interests, has purchased the control of one of
the great oil producing companies of Rumania. So far as Great
Britain is concerned, more than £2,000,000 are involved in the
matter. (P. 501)
A process for the manufacture of flax-straw waste on a commer-
cial scale has been developed in Argentina. The product of
this new process is reported to be equal or even superior in color,
elasticity, length of fiber, and resistance to fibers retted by the
old methods, which required many days' time, as compared with
less than half an hour by the new process. (Pp. 520-1) _
The outlook for the Swedish iron industry is unfavorable.
(P. 53i) . -_
A good market is reported for American laundry soap in Bul-
garia. The soap must contain fats to the extent of at least 70
per cent. (P. 541)
The German process for artificial wool has proved unsuccess-
ful, as it was impossible to put the wool into solution without
a resultant decomposition. The application for a patent has
been abandoned. (P. 549)
The United States at present furnishes very nearly all the
dyes used in the district for which Tientsin is the distributing
center, and if American manufacturers are willing to meet the
requirements of the trade they will be in the market perma-
nently. (P. 553)
The great milling wealth of the Kongo is being rapidly devel-
oped, and the production of gold, copper, and diamonds is con-
stantly increasing. The war acted as a great stimulus on the
copper-mining industry. (P. 556)
It is reported that detailed research is shortly to be under-
taken in India with a view to determining the practicability
of producing power alcohol on a commercial scale. Meanwhile,
Great Britain is trying to make possible the ready use of such
substitute fuel whenever.it becomes available in sufficient quan-
tity. (P. 57i)
The Finnish Government is erecting a superphosphate factory
in Kotka and a sulfuric acid factory in Vilmanstrand. It is
estimated that the production of the former will amount to 20,000
tons, which will be sufficient to satisfy all domestic requirements
and probably leave a small surplus for export. The products
of4the sulfuric acid factory will be used for the most part in the
manufacture of superphosphate. (P. 578)
Remarkable success has attended the manufacture of linseed
oil in South Australia. (P. 582)
Samples of flax-straw fiber and waste made from flax straw
from Argentina are available for examination at the Bureau of
Foreign and Domestic Commerce. (P. 592)
There is a shortage of brass and copper in Switzerland which
would appear to offer quite a market for American copper.
(P. 594)
Remarkable results are being obtained in Germany from the
manufacture of yarn from grasses, plants, leaves, etc. (Pp.
595-7)
A market for industrial drugs and chemicals is reported in
Argentina. Tabular statements are given showing the principal
chemical products used in Argentina, the typical industries
using such products, and a price list of one Argentine dealer in
chemicals. (Pp. 630-3)
A translation is given of a decree relative to the exploitation
of petroleum mines in Salvador. (P. 649)
A Japanese government oil monopoly is being proposed
largely in order to guarantee supplies for the navy. (P. 658)
British prohibition of the importation of synthetic dyestuffs,
except under license, is proposed in order to foster the domestic
industry. (P. 673)
A decrease of 30 per cent is reported in the production of
olive oil in the Malaga district for the season 1920-2 1 as compared
with 1919-20. (Pp. 678-9)
The Bureau of Foreign and Domestic Commerce has ready
for distribution a list of importers and dealers in paints and
varnishes in China. (P. 680)
Rubber estates in Java are reported to have had a satisfactory
first half year. (P. 693)
A market is reported in France for American leathers. Ger-
many is in no position to make deliveries, and the United King-
dom is said to have no advantages over American tanners.
(P. 696)
The rubber market in the Straits Settlements has been marked
by a steady decrease in price from $0.50 per pound in January
1920 to about $0.23 in September. (P. 708)
Statistics are given showing the quantities of coal-tar dyes and
intermediates imported into the United Kingdom during the
first nine months of the current year. Comparative figures are
also given for finished dyes not only for the current year but
for the same period in 19 13 and 19 19, and the value of these
imports, converted into American currency, is also given. (Pp.
71 i-3)
Fifteen years ago Malaya produced over 60 per cent of the
world's tin; to-day the figure stands at less than 40 per cent.
Although the percentage comparison of Malayan output with
the world's total has fallen, owing to greater production elsewhere,
the actual outturn has considerably increased. (P. 715)
About 10,000 tons of citrate of lime and about 300 metric
tons of citric acid are held in Italy. (P. 737)
A market for sodium and potassium is reported in Argentina.
Sodium, in various forms, is employed in practically every
industry, large and small. Neither hydrate, carbonate, nor
silicate of sodium are made in Argentina on a commercial scale.
(Pp. 745-7)
The discovery of extensive deposits of pyrites a short distance
from Prague, Czechoslovakia, has caused considerable stir in
the industrial circles of that republic. (P. 747)
An agreement has been reached whereby the production of
rubber will be curtailed 25 per cent until December 1921. (P.
766)
Sulfur ores in Mexico are now available for shipment to the
United States. (P. 772)
Paints and varnishes are required by the Peking-Hankow
Railway and bids are called for these materials at quarterly
intervals. (Pp. 776-7)
The manufacture of acids in Argentina is described, as wall
as the uses to which other chemicals are put. (Pp. 779-82)
A note from Manitoba is to the effect that crude oil from
Texas wells is to be imported and refined and distributed in
Western Canada. (P. 792)
The production of yacca gum in South Australia, its use,
chemical reactions and destinations of exports are described.
(Pp. 796-7)
A new paper pulp industry has come into existence in Argentina.
A species of bog grass called "paja brava" is the raw product
employed. This grass grows during the whole year and is so
abundant in the swampy places that it has been considered a
nuisance. (P. 799)
A list of importers and dealers in chemicals in Australia may
be obtained upon request of the Bureau of Foreign and Domestic
Commerce. (P. 800)
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
99
The great depressi^ in the Amsterdam rubber market still
continues. (P. 817)
The proposed petrc^im law in Peru sets forth the conditions
under which concessjons of petroleum land will be made, the
maximum term of cc.ntracts being placed at 75 yrs. (P. 819)
The Bureau of Foregn and Domestic Commerce has ready
for distribution a list i>f oil mills and exporters of vegetable
oils in India. (P. 8:>o)
An American comoanV has secured a "gusher" in Trinidad
which has a daily production of about 1000 bbls. This will
probably prove to be the best oil ever drilled in Trinidad. (P. 825)
A shortage of fuel oil is reported in Vancouver. (P. 835)
The Japanese chemical market is still unsteady, sales decreas-
ing while holdings are being readjusted. (P. 836)
Recent advices state that the Japanese dyestuff industry can-
not successfully compete with the American or German manufac-
tures, even with the new import duty of 35 per cent. (P. 851)
The leather situation in Palestine is reviewed. (Pp. 857-8)
The wood-pulp market in Finland has been steady, but while
the cellulose market was exceedingly brisk in the spring, export-
ers are somewhat pessimistic about the future. (Pp. 869-72)
Statistics are given showing the output of the government
oil reserves at Comodoro Rivadavia, Argentina, from 1907 to
1918, inclusive. (P. 873)
The Chinese summer indigo crop is reported to have been
normal, though it suffered somewhat from floods. (P. 874)
A large Australian company has under consideration the ex-
tension of its manufacturing processes to substances not pre-
viously made in Australia and from which the chief by-product
will be chlorine. (P. 884)
The Canadian starch and glucose industry is reviewed.
(Pp. 885-6)
The German factory of Adler & Oppenheimer, considered
the largest leather factory in Europe, has being sold to a group
of French and Alsatian interests, and it is intimated that special
attention will be given to exporting the products of the factory.
(P. 903)
The Argentine market for calcium carbide, chloride of lime,
glycerol, glucose, and cryolite, barium, copper, iron, and mag-
nesium sulfates is described. (Pp. 906-7)
New import duties in Peru are announced for the following
materials: chemicals, drugs, dyes, and medicines (increased);
paints, pigments, colors, and varnishes (increased) ; and paraffin
(decreased). (Pp. 919-21)
Statistics are given on the imports for consumption and
domestic exports of vegetable oil and vegetable-oil material
by British Dominions and Protectorates in Africa during the
three latest years for which statistics are available. Photostat
copies of detailed statistics showing countries of shipment of
imports and of destination of exports may be obtained from
the Bureau of Foreign and Domestic Commerce for 15 cents a
page. (Pp. 925-9)
The production of tar, rosin, and turpentine in Finland is de-
scribed. (P. 937)
The market for paraffin wax, stearic acid, and rosin in Argen-
tina is reviewed. (Pp. 940-1)
The discovery of new fire clay, copper, and salt mines is re-
ported in Azerbaijan. (P. 941)
Asphalt, which is reported to be very similar to the asphalt
deposits in Trinidad, has been discovered in Manitoba Province.
(P- 948)
Polish regulations relative to prices of crude oil and oil prod-
ucts are given. (P. 953)
The bauxite concessions in British Guiana have commenced
to produce a considerable supply of this mineral. (P. 956)
Special Supplements Issued in November
Finland — 6<j Spain — 1 8c
Portugal — 146 China — 55<f
Caucasus — 166 Japan— 58c
Canada — 266
Statistics op Exports to the United States
Belgium — (Pp. 518,
590)
Hides and skins
Wax
Copper
Minerals (unclassified)
Rubber
Resinous products
Chemicals
Bahia— (P. 583)
Hides and skins
Chrome ore
Manganese ore
Castor oil
Rubber
Medicinal roots and
Brazil— (Pp. 815,852)
Crude rubber
Bauxite
Great Britain — (P.
808)
Salt (not table)
Hides (undressed)
Skins
Cement, calcareous
Iron and steel
Lead
1 sulfate
Bleaching powder
Leather
Rubber, crude
South Australia —
(P. 797)
Yacca gum
London — (P. 853)
Rubber
Leather
Tin
Drugs and chemicals.
Gums
Lead
Aluminium
Ferromanganese
Creosote oil
Copper
Linseed oil
Scrap metal
Rubber
Naples-
Copper
Sulfur oi
(P. 773)
BOOK RE.VILW5
Application of Dyestuffs. By J. Merritt Matthews, xvi + 768
pp. John Wiley & Sons, Inc., New York, 1920. Price, $10.00.
The introduction of this work shows that it represents a
development and expansion of an earlier textbook for students
into a work of instruction and reference for those directly con-
cerned with the use of dyestuffs. In order to understand the
scope of this work it should be stated that it is definitely not
a book about the manufacture, constitution, or chemical classi-
fication of dyestuffs. These things are dealt with only as they
immediately concern the subject matter.
The book deals first with the effect of acids, alkalies, chemicals,
etc., on the textile fibers, and then with the methods of cleaning
and bleaching them, covering these matters fully, so far at least
as knowledge regarding them is likely to be valuable to the user
of dyes.
It then proceeds, after a relatively short and elementary
discussion of the classification of dyes, to its real subject, and
takes up fully their application by the usual methods to the
several textile fibers, and their construction. This occupies the
major part of the book, and is succeeded by a chapter on the
theory of dyeing, containing a most interesting presentation
and discussion of the current views on this subject. Then follows
consideration of fastness tests and chapters devoted to special
materials, not textile, such as straw, leather, paper, etc., and to
lakes and inks. The remainder of the book takes up testing of
dyestuffs, and their chemical reactions, the analysis of textile
fabrics, and such data and tables as are likely to be useful,
ending with a bibliography of value to those who wish to follow
up the literature of the subject. Along with the text are copious
footnotes, which carry a surprising amount of most valuable
information.
The development of this work from a textbook for students
has brought about the presence of a very desirable feature from
the point of view of the chemist of limited textile experience.
We refer to the general illustration of the important points by
very definitely described experiments. These are attractive
both to the beginner and to anyone who wants to have at hand
directions for demonstrating clearly in a laboratory what he
may already know.
It is difficult to criticize a book which is filled with such a deal
of information, but perhaps a few suggestions might be offered.
The writer of this review is particularly interested in the dyeing
of men's wear, and would have been glad to see a larger place
given to the merits and difficulties of the several classes of fast
chrome and mordant colors, and those auxiliary colors which
are used with them. For the man who has to deal with modern
schemes of piece dyeing, a treatment of resist work on woolen
or worsted yarn, and a discussion of silk dyeing in fast colors
for fulling and cross dyeing in men's wear would have been useful.
But perhaps Dr. Matthews felt that a limit must be placed
even in a work as broad as he has given us.
W. D. Livermore
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 1
The Chemists' Year Book, 1920. By F. W. Atack, M.Sc. Tech.
(Manch.), B.Sc. (London); Fellow of the Institute of Chem-
istry. Assisted by L. Winyates, A.M.C.T., A.I.C. 5th
Ed., 1 136 pp. in two volumes. Illustrated. Sherratt and
Hughes, London; Longmans, Green & Co., New York, 1920.
Price, $7.00 net.
These little volumes have been issued yearly since January
1915. They constitute another of the many illustrations of
British thoroughness and ability to finish the job that have been
given to us since the "contemptible little army" crossed the
channel a few months before the first issue of this Year Book
was forced by the cutting off of the supply of the well-known
German Chemiker Kalendar. Five years of success and im-
provement since then should constitute the work a permanent,
ready-reference landmark with its information in a handy
and easily accessible form.
This fifth edition, besides the usual general revisions and those
of the section on dairy products and carbohydrates, presents
its principal alteration in the complete recasting of the "Physical
Chemistry Constants" section by Dr. G. Barr of the National
Physical Laboratory.
The first volume is the smaller, 422 pages, and in general
embraces sections on atomic weights, with useful tables of
multiples, formula weights and their logarithms. Then comes
a very practical qualitative analysis section of 57 pages, in-
cluding treatment of some of the rarer elements. There are
sections on reagents, gravimetric analysis, volumetric, gas,
ultimate organic, electro- and spectrum analysis, invaluable
tables of general properties of inorganic and of organic sub-
stances, conversion tables of measurements, five-place loga-
rithms, and various mathematical constants.
The second volume of 714 pages embraces 180 pages of physical
constants, followed by an excellent illustrated section on crystal-
lography. The illustrations throughout are up-to-date and
helpful. Then follows a section on mineral properties, and a
long series of sections on technical analysis and control, including
water, fuel, efficiency of boiler plant, clays, cement, chemical
manufacture, oils, paint, agricultural chemistry, sugar, tanning,
textiles, dyes, intermediates, pharmaceuticals, trade names,
and constitution of synthetic drugs, rubber, and others. The
various special sections are written by specialists.
It is perhaps too much to expect from a "Chemists' Year
Book" many data on the engineering side of chemical production,
though the volumes are obviously intended for the industrial
chemist.
The usefulness of the many specific gravity-composition of solu-
tion tables is obvious. It is not so obvious, however, that our use
of them involves grave danger when unacquainted with the in-
dustrial status of the solution. The table of strength of formalde-
hyde solutions, for instance, would be very satisfactory if such
solutions did not always contain methanol as a preserva-
tive. Under the circumstances, the table is commercially
useless.
Some few things are a little hard to understand, such as the
fact that the sole reference to an original in the section on electro-
analysis is to a German publication, when the best work in the
field appears in our own journals as the work of Provost E. F.
Smith. That rotating electrodes will give more rapid results
is mentioned, but all data given are for stationary electrodes.
The use of warm hydrochloric acid to remove manganese dioxide
from platinum seems to demand care on the part of the nascent
chlorine liberated.
Citation of references to authority is not so frequent as might
have been. Omissions are sometimes glaring, as when a
brief table is cited from Colman for toluene evaluation (p. 957),
followed without any credit at all by two tables (pp. 959, 960),
which are precisely identical with those of F. E. Dodge in Rogers'
"Industrial Chemistry," with the exception of the typographical
error (p. 960) of 2 per cent at 1290 inste A of 1 per cent on the
20 to 80 "toluene-xylene" mixture. Ne Ve'theless, the work is
remarkably free from typographical error
The authors have done well in elimina jni: the needless diaiy-
calendar feature of the old Chemiker Kaiendar. The electro-
analysis section is more practical. In th'. ureful table of organic
compounds the use of the heading "formula weight" is to be
commended, but there is a little too much space taken up with
structural formulas, and the omission of the column of color,
crystal form, etc., to insert one of empirical formulas is a blunder.
Anyone can add up the empirical formula of a compound whose
structural formula is given, but not even an organic chemist
can imagine the crystal form and color of an unfamiliar com-
pound.
The work is not only well edited, but as a piece of book making
it is a model. The paper is good, and the print and make-up
are clean-cut and refreshing. James R. Withrow
The Microbiology and Microanalysis of Foods. By Albert
Schneider. 8vo x + 262 pp. 131 illustrations. P. Blak-
iston's Son & Co., Philadelphia, Pa. Price, $>3-50 net.
The author states in the preface: "This volume is intended
as a guide to the study of microbiological decomposition changes
in foods. It also presents a practical working basis for as-
certaining the decomposition limits of foods suitable for human
consumption, by means of the direct methods of microanalysis,
***** The text is addressed to army dietitians and food
examiners." Although the title of the book is given as "The
Microbiology and Microanalysis of Foods," the bulk of its
pages are devoted to what may be called food hygiene. Where,
however, the author treats of "microanalytic" methods, he
does so clearly and concisely, and all food analysts will welcome
this contribution to our knowledge of an intricate and puzzling
field which is sadly lacking in text and reference books.
If we are to accept the author's standards qualifying a man
to call himself properly trained to undertake investigations in
food and drug microscopy we must conclude that there prob-
ably does not exist a single individual in the United States who
can meet the requirements, for we are told that in addition to a
university training or its equivalent,
He must have made careful microscopical examinations of
all substances which may be so examined and that includes prac-
tically everything of a material nature. Skilled microanalysts
are rare. There are, indeed, many students who have been
taught certain things about the microscope and who have ex-
amined and reported upon certain microscopic objects and there
are many bacteriologists, biologists, chemists, and other in-
vestigators who make occasional use of the compound micro-
scope but these are not microanalysts in the true sense of the
term. The army microanalyst must be able to recognize at a
single glance all of the objects which may appear within any
field of the compound microscope.
It is no doubt in substantiation of the idea that microanalysts
must have studied "practically everything of a material nature"
that the author has introduced illustrations and diagrams which
are wholly irrelevant and to which no references are made in
the text, thus cutting down valuable space which might have
been used to good advantage in elaborating topics which had to
be discussed with but slight consideration.
The first six chapters or sections, comprising 68 pages, are
devoted to food hygiene, microbiology, and food decomposition,
and the statements of facts are as brief as it has been possible
to make them, and are, on the whole, correct. Reference to
authorities are unfortunately wholly omitted.
Chapter VIII (70 pages) is devoted to "General and Special
Microanalytical Methods." This chapter is a direct and valu-
able contribution to our literature of the microscopy of foods,
and will prove most acceptable to all microscopists who have
occasion to make microbiological examinations or who are re-
quired to undertake microscopic quantitative analyses. The
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
various methods which have been suggested for direct bacterial
counts in food and beverages are outlined, and the principles
underlying microscopic quantitative analyses are discussed at
length, together with the basis for the interpretation of the
results obtained.
The author devotes some 64 pages (Chapter IX) to the dis-
cussion of the interpretation of the results obtained by micro-
scopic examinations and states his views relative to the "Mi-
croanalytical Rating of Food Products." With many of these
ratings few analysts will agree, tb is being especially true of both the
methods for the examination and the ratingsof water and of gelatin.
It is to be regretted that the author in giving his ratings does
not state that under certain conditions the ratings given are
rather ideal and may prove impracticable of enforcement.
As a further guide to assist the analyst in passing upon the purity
of food, a compilation has been made in Chapter X of the legal
standards of purity of foods.
The typography and the general arrangement of the book are
excellent. The cuts are for the most part clear, and those which
have a direct bearing upon the subject matter of the text are
well chosen. E. M. Chamot
Fuel Oil in Industry. By Stephen O. Andros. 274 pp. The
Shaw Publishing Co., 910 So. Michigan Boulevard, Chicago,
111., 1920. Price, $3.75.
This is a comprehensive treatise, embracing the storage of
fuel oil, heating, straining, pumping, regulating, boiler furnace
arrangement, types of fuel-oil burners, fuel oil in steam naviga-
tion, oil-burning locomotives, use of oil in the iron and steel
industries, in heat treating furnaces, in the production of elec-
tricity, in the sugar, glass, and ceramic industries, the heating
of public buildings, hotels, and residences, and the use of oil in
gas making. In view of the enormous size of the fuel-oil industry,
there is no question but what there is place for a treatise on fuel
oil such as this book presents.
Because of the threatened shortage of petroleum, it is re-
grettable that so much of our petroleum is turned into fuel oil
instead of the more valuable products — gasoline, kerosene,
lubricating oils, wax, etc., but when, as the author says, with
equivalent bunker space, the use of oil over coal increases the
radius of action of ships over 80 per cent, and the M. K. and
T. R. R. in 1920 saved one-fourth of its fuel bill by using oil
instead of coal, the national and commercial reasons for using
oil as fuel are understood.
A chapter is devoted to colloidal fuel ; in the author's definition,
a combination of liquid hydrocarbons with pulverized carbona-
ceous substances (coal), the components so combined and so
treated as to form a stable fuel capable of being atomized and
burned in a furnace. As the author states, the title is not
scientific, since much of the solid component is not reduced
to colloidal dimensions. A reader naturally looks in the book
for a critical survey of the commercial status of colloidal fuel,
but does not find it, presumably because the substance has
scarcely passed the experimental stage. Eight pages are de-
voted to a description of the substance and to tests conducted
largely by Messrs. Dow and Smith, chemical engineers of New
York City. They made the interesting observation that in
some of the material 2.6 per cent of the particles became de-
stabilized (settled out) in 5 mo.' time. The author states
that 40 per cent by weight of coal can be suspended with 60
per cent by weight of oil, that the coal should be reduced so
95 per cent passes through a 100-mesh screen and 85 per cent
through a 200-mesh screen, and that the calorific value of the
fuel may be greater per unit volume than that of straight oil,
in some cases 15 per cent greater.
From a chemist's standpoint, the first chapter on principles
of fuel-oil combustion is not couched in language always scien-
tific, although clear and readable and perhaps well understood
by engineers who are not chemists. For instance, the author
states that copper wire is placed in cuprous chloride Orsat
pipets to reenergize the solutions if they become weakened.
The second chapter is devoted to properties and chemical
and physical tests of fuel oil. The tests are well selected and
described.
In the third chapter is found a comprehensive comparison
of fuel oil and coal. Analyses of coals are shown, also combus-
tion tests, costs of pulverizing coal, comparative efficiencies,
all well selected data, and finally a page and a half on advan-
tages and disadvantages of liquid fuel. One can find no fault
with this comparison.
A chapter on distribution and storage of fuel oil covers the
storage of fuel in ships, in locomotives, and on land, and above
and below ground. Concrete and steel construction are dis-
cussed. Regulations of the National Fire Protective Association
and the cities of New York and Chicago are included. A rule
of the New York City regulations provides that the fuel oil
must not be over 20° Be. This shuts out Mexican fuel oil.
The reviewer protested against this when the regulations went
into effect, but he could not discover the particular motive
behind it. However, there has been such an urgent demand from
other sources for Mexican fuel oil that apparently the producer
does not care.
The succeeding chapters, including one on heating, straining,
pumping, and regulating, are devoted tc appliances such as
boilers, burners, and locomotives, and to the use of fuel oil in
the various industries.
The chapter on the use of gas oil in gas making was probably
written before the gas makers of the country were thrown into
a near panic because of the recent big advance in gas oil prices,
else the author might have included some cost data.
There is no question that the book is a good treatise on the
subject and fills a much-needed want on up-to-date practice.
It should be in demand. George A. Burreu,
Analysis of Paint Vehicles, Japans, and Varnishes. By Clif-
ford Dyer HollEY. ix -f- 203 pp. John Wiley & Sons,
Inc., New York; Chapman and Hall, London, England, 1920.
Price, $2.50 postpaid, or 13s. 6d. net.
Professor Holley has written a singularly useful and needed
book, dealing with volatile thinners, paint oils, dryers, water in
paints, and the effect of storage, and containing chapters on
baking japans and varnishes which are remarkable, in the litera-
ture of the subject, for common-sense and practical value.
It is a compendium of the standard methods of analysis, where
there are any, and, lacking these, of what appears to the author
the best, though perhaps imperfect, methods available; written
with clearness and sufficient detail, and generally accompanied
with intelligible discussions of the problems involved. Prac-
tical experience in making paints is the only foundation for a
reasonable and just valuation of the various questions, and the
analyst who has this book on his desk will find many of his
troubles simplified, while the factory superintendent who is also
a chemist — the number is increasing— will get help in under-
standing what he is doing.
The book is particularly valuable for its numerous tables,
most of which are not new, but from widely scattered sources;
and, while there are plenty of references to original papers,
it is not needful to look them up, because their methods are
given in full, except in the case of some U. S. Government publica-
tions, which may be secured without cost, in cases where an
elaborate description is wanted.
One may not agree with Professor Holley about everything,
but there is no question of his sincerity and thoroughness, and
the book is most satisfactory. It is admirably printed, and
free, so far as this reviewer has discovered, from errors.
A. H. Sarin
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. i3> No. i
NLW PUBLICATIONS
Chemistry: La Chimie et la Guerre: Science et Avenir. Charles Moureu.
384 pp. Price, 10 fr. Masson & Cie., Paris.
Chemistry and Civilization. Allerton S. Cushman. 151 pp. Price,
$2.50. Richard G. Badger, Boston.
Colloids: Les Colloides. J. Duclaux. 288 pp. Gauthier-Villars & Cie.,
Paris.
Dictionary of Chemical Terms. James F. Couch. 214 pp. Price, $2.50.
D. Van Nostrand Co., New York.
Eminent Chemists of Our Time. Benjamin Harrow. 248 pp. Price,
$2.50. D. Van Nostrand Co., New York.
Handbook of Industrial Oil Engineering. John Rome Battle. 1131 pp.
h Illustrated. J. B. Lippincott Co., Philadelphia.
Logarithmic and Trigonometric Tables. Earle Raymond Hedrick. Re-
vised edition. 143 pp. Price, $1.40. The Macmillan Co., New York.
Lubricants: American Lubricants from the Standpoint of the Consumer.
L. B. Lockhart. 2nd edition, revised and enlarged. 341 pp. Price,
$4.00. The Chemical Publishing Co., Easton, Pa.
Oils: The Manufacture, Refining and Analysis of Animal and Vegetable
Oils, Fats and Waxes, Including the Manufacture of Candles, Margarine,
and Butter. Geoffrey Martin. 200 pp. Price, I2s. 6d. net. Crosby,
Lockwood & Son, London.
Organic Chemistry: Laboratory Experiments in Organic Chemistry. E. P.
Cook. 83 pp. Price, $1.00. P. Blakiston's Son & Co., Philadelphia.
Organic Chemistry: Theoretical Organic Chemistry. Julius B. Cohen.
New Ed. 604 pp. Price, $2.50. The Macmillan Co., New York.
Paint: Papers on Paint and Varnish and the Materials Used in Their Manu-
facture. Henry A. Gardner. 501 pp. Illustrated. Price, $10.00
net. P. H. Butler, 1845 B St., N. W., Washington, D. C.
Rubber: Plantation Rubber and the Testing of Rubber. G. Stafford
Whitby. (Monographs on Industrial Chemistry.) 559 pp. Price,
$9.50. Longmans, Green & Co., New York.
NEW JOURNAL
The Glass Industry. Published monthly by Glas
Co., Inc., 19 Liberty St., New York City. Price,
Industry Publishing
2.00 a year.
RECENT JOURNAL ARTICLES
Alcohol Distillation from Molasses. George M. Appell. Sugar, Vol. 22
(1920), No. 12, pp. 703-705.
Autoclaves: The Use of Autoclaves in Chemical Processes. Thomas
Callan. The Chemical Age (London), Vol. 3 (1920), No. 73, pp. 502-
503.
Blast Furnace: Heat Supplied to the Blast Furnace. W. W. Hollings.
The Blast Furnace and Steel Plant, Vol. 8 (1920), No. 12, pp. 651-655.
Brass: Investigation of Brass Foundry Flux. C. W. Hnx, T. B. Thomas
and W. B. Vietz. The Metal Industry, Vol. 18 (1920), No. 11, pp. 498-
502.
Chemical Standard Samples. C. O. Bannister. Journal of the Society
of Chemical Industry, Vol. 39 (1920), No. 20, pp. 351r-352r.
Chemicals: Safeguarding the Purchase of Chemicals. F. W. RussE.
Textile World Journal, Vol. 58 (1920), No. 24, pp. 41-43.
Coal: How to Test the Fitness of Coals for Coking. G. H. Elmore. Coal
Age, Vol. 18 (1920), No. 23, pp. 1130-1134.
Colloidal Fuel: The Case for Colloidal Fuel. Lindon W. Bates. The
Chemical Age (London), Vol. 3 (1920), No. 75, pp. 558-559.
Combustion: Killing Combustion Losses. Robert June. Combustion,
Vol. 3 (1920), No. 6, pp. 32-36.
Copper Losses in Slags. Frank E. Lathe. Engineering and Mining
Journal, Vol. HO (1920), No. 23, pp. 1076-1080.
Cost Accounting in the Rubber Industry. Ferd G. Kirby. India Rubber
World, Vol. 63 (1920), No. 3, pp. 155-157.
Cost Accounting: Relationship of Cost Accounting to Business Management
in Chemical Manufacture. William B. Ferguson. Chemical Age,
Vol. 28 (1920), No. 11, pp. 413-415.
Dyes and the Varnish Industry. George H. Priest. American Dyestuff
Reporter, Vol. 7 (1920), No. 23, pp. 19, 20.
Dyes: Tartar Emetic in the Dye House. Elton R. Darling. Textile
World Journal, Vol. 58 (1920), No. 22 pp. 47-49.
Dyestuff Industry in Relation to National Economics. L. W. Alwyn-
Schmidt. Color Trade Journal, Vol. 7 (1920), No. 6, pp. 167-170.
Electrolytic Zinc Methods. Herbert R. Hanley. Mining and Scientific
Press, Vol. 121 (1920), No. 23, pp. 795-804.
Explosives: Commercial Explosives and Their Uses. A. J. Strane. The
Coal Industry, Vol. 3 (1920), No. 11, pp. 526-528.
Fertilizers: The Determination of Borax in Fertilizers and Fertilizer Ma-
terials. William H. Ross. The American Fertilizer, Vol. 53 (1920),
No. 12, pp. 64-66.
Fertilizers: The Distillation Method for Estimating Borax in Mixed Fer-
tilizers. J. M. Bartlett. The American Fertilizer, Vol. 53 (1920),
No. 12, pp. 68-71.
Flotation: A Resume of Literature on the Theory of Flotation, with Critical
Notes. H. R. Adam. Mining and Scientific Press, Vol. 121 (1920),
No. 22, pp. 765-770. Reprinted from the Journal of the Chemical,
Metallurgical and Mining Society of South Africa.
Furnaces: Electric vs. Combustion Furnaces for Low Temperatures.
Frank W. Brooke and George P. Mills. Chemical and Metallurgical
Engineering, Vol. 23 (1920), No. 21, pp. 1008-1010.
Glass: The Annealing of Glass. L. H. Adams and E. D. Williamson.
Journal of the Franklin Institute, Vol. 190 (1920), No. 5, pp. 597-631.
Glass: The Composition of Lead Glasses. Robert J. Montgomery
Journal of the American Ceramic Society, Vol. 3 (1920), No. 11, pp. 900-912.
Glass: The Importance of Technical Control in the Glass Industry. Alex-
ander Silverman. The Glass Industry, Vol. 1 (1920), No. 1, pp. 1-3.
Glass: Some Developments in the Study of Glass Technology in the Year
1919-1920. W. E. S. Turner. Journal of the Society of Glass Tech-
nology, Vol. 4 (1920), No 15, pp. 287-296.
Glass: Some Principles in Glass Pot Manufacture. C. H. Kerr. The
Glass Industry, Vol. 1 (1920), No. 1, pp 3-6.
Leather: Hide Substance. G. L. Terrasse. Journal of the American
Leather Chemists' Association, Vol. 15 (1920), No. 11, pp. 608-620.
Leather: Rapid Estimation of Chromium in Chrome Liquor by Use of the
Immersion Refractometer, Arthur W. Thomas and Margaret W.
Kelly. Journal of the American Leather Chemists' Association, Vol. 15
(1920), No. 12, pp. 665-668.
Lime Treatment for Soil Acidity. A. T. Wiancko. Sugar, Vol. 22 (1920),
No. 11, pp. 650-651.
Mathematics: Le Role des Math6matiques en Chimie. E. Flburent.
Chimie et Industrie, Vol. 4 (1920), No. 4, pp. 525-528.
Medicinals: Les Medicaments Allemands. Augusts Lumiere. Chimie
et Industrie, Vol. 4 (1920), No. 4, pp. 435-442.
Metallurgy from the Colloid Chemical Standpoint. Clifford W. Nash.
Chemical Engineering and Mining Review, Vol. 13 (1920), No. 1 45, pp. 1 1-13.
Oil: A World View of the Oil Supply. George Otis Smith. Engineering
and Mining Journal, Vol. 110 (1920), No. 22, pp. 1047-1049.
Oils: L'Hydrogenation des Huiles. M. Frejacqub. Chimie et Industrie,
Vol. 4 (1920), No. 4, pp. 443-456.
Optical Glass: Certain Relations between Chemical Composition and Re-
fractivity in Optical Glasses. Fred. E. Wright. Journal of the Ameri-
can Ceramic Society, Vol. 3 (1920), No. 10, pp. 783-832.
Paper: Utilization of Reed in Paper Manufacture. Enn. Heuser. Paper,
Vol. 17 (1920), No. 9, pp. 23, 32.
Petroleum: Refining Problems of the Petroleum Industry. H. H. Hill.
Chemical Age, Vol. 28 (1920), No. 11, pp. 425-427.
Photography: The Measurement of Graininess in Photographic Deposits.
Loyd A. Jones and Noel Deisch. Journal of the Franklin Institute,
Vol. 190 (1920), No. 5. pp. 657-683.
Photo-Micrographs in the Textile Industry. W. F. Edwards. Textile
World Journal, Vol. 43 (1920), No. 20, pp. 43-47.
Rubber: Determination of Antimony in Rubber Goods. S. Collier, M.
Levin and J. A. Scherrer. The Rubber Age, Voi. 8 (1920), No. 3, pp.
104-105.
Rubber: Notes on Rubber Analysis. A. R. Pearson. The Analyst,
Vol. 45 (1920), No. 536, pp. 405-409.
Soap: The Surface Tension of Certain Soap Solutions and Their Emulsifying
Powers. Mollis G. White and J. W. Marden. Journal of Physical
Chemistry, Vol. 24 (1920), No. 8, pp. 617-629.
Steel: The Heat Treatment of Automobile Steels. Robert R. Abbot.
American Drop Forger, Vol. 6 (1920), No. 11, pp. 536-539.
Steel: Some Notes on the Effect of Nitrogen on Steel. O. A. Knight and-
H. B. Northrup. Chemical and Metallurgical Engineering, Vol. 23 (1920),
No. 23, pp 1107-1111.
Steel for Valves of Combustion Motors. G. Gabriel. The Iron Age, Vol.
106 (1920), No. 20, pp. 1249-1251; No. 23, pp. 1465-1469. Translated
from La Technique Automobile et Aerienne.
Steel: Study of the Testing of Welds. S. W. Mn.LER. American Drop-
Forger, Vol. 6 (1920), No 11, pp. 549-554.
Sugar: A New System of Cane juice Clarification. I. H. Morse. Louisi-
ana Planter and Sugar Manufacturer, Vol. 45 (1920), No. 19, pp. 301-302;
No. 20, pp. 315-317.
Sugar: On the Settling of Precipitates in General and of Cane Juice Pre-
cipitates in Particular. Noel Deerr. The International Sugar Journal,
Vol. 22 (1920), No. 623, pp. 618-624.
Textile Research: Modifying Influences in Textile Respaich. Louis A.
Olney. American Dyestuff Reporter, Vol. 7 (1920), No. 19, Section 2,
pp. 11-12.
Vitamines: A Quantitative Method for the Determination of Vitamine in.
Connection with Determinations of Vitamins in Glandular and Other
Tissues. Frederick K. Swoboda. Journal of Biological Chemistry,
Vol. 44 (1920), No. 2, pp. 531-551.
Zinc: Idrometallurgia dei Mineral! di Zinco. G. Aichino. Giornale di
Chimica Industriale ed Applicala, Vol 2 (1920), No. 10, pp. 566-572.
Jan., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
MARKET REPORT— DECEMBER, 1920
FIRST-HAND PRICES FOR GOODS IN ORIGINAL PACKAGES PREVAILING IN THE NEW YORK MARKET
INORGANIC CHEMICALS
Acid, Boric, cryst., bbls lb.
Hydrochloric, com'l, 22° lb.
Hydriodic oz.
Nitric, 42° lb.
Phosphoric, 50% tech lb.
Sulfuric. C. P lb.
Chamber, 66° ton
Oleum 20% ton
Alum, ammonia, lump lb.
Aluminium Sulfate (iron-free) lb.
Ammonium Carbonate, pwd lb.
Ammonium Chloride, gran lb.
Ammonia Water, carboys, 26°. . . .lb.
Arsenic, white lb.
Barium Chloride ton
Nitrate lb.
Barytes, white ton
Bleaching Powd., 35%, Works, 100 lbs.
Borax, cryst., bbls lb.
Bromine, tech lb.
Calcium Chloride, fused ton
Chalk, precipitated, light lb.
China Clay, imported ton
Copper Sulfate 100 lbs.
Feldspar ton
Fuller's Earth 100 lbs.
Iodine, resublimed lb.
Lead Acetate, white crystals lb.
Nitrate lb.
Red American 100 lbs.
White American 100 lbs.
Lime Acetate 100 lbt.
Lithium Carbonate lb.
Magnesium Carbonate. Tech lb.
Magnesite ton
Mercury flask American 75 lbs.
Phosphorus, yellow lb.
Plaster of Paris 100 lbs.
Potassium Bichromate lb.
Bromide, Cryst lb.
Carbonate, calc, 80-85% lb.
Chlorate, cryst lb.
Hydroxide, 88-92% lb.
Iodide, bulk lb.
Nitrate lb.
Permanganate, U. S. P lb.
Salt Cake, Bulk ton
Silver Nitrate oz.
Soapstone, in bags ton
Soda Ash, 58%, bags 100 lbs.
Caustic, 76% 100 lbs.
Sodium Acetate lb.
Bicarbonate 100 lbs.
Bichromate lb.
Chlorate lb.
Cyanide lb.
Fluoride, technical lb.
Hyposulfite, bbls 106 lbs.
Nitrate, 95% 100 lbs.
Silicate, 40° lb.
Sulfide lb.
Bisulfite, powdered lb.
Strontium Nitrate lb.
Sulfur, Sowers 100 lbs.
Crude long ton
Talc, American, white ton
Tin Bichloride lb.
Oxide lb.
Zinc Chloride, U. S. P lb.
Oxide, bbls lb.
.01'/,
.19
.07»A
.22
.07
20.00
23.00
• 04«/4
■ 04>/i
.16
.111/,
30.00
4.00
.08i/i
.53
33.50
.05
18.00
7.00
8.00
1.00
4.00
.16
.15
.12>/i
.lOVl
2.50
1.50
72.00
55.00
.35
1.50
.22
.30
.18
3.00
.12
.60
30.00
.51
12.00
1.90
3.80
4.00
2.90
.Oli/i
.08
.07
.15
4.00
20.00
20.00
.19Vi
.50
.40
ORGANIC CHEMICALS
Acetanilide lb.
Acid, Acetic, 28 p. c 100 lbs.
Glacial lb.
Acetylsalicylic lb.
Benzoic, U. S. P., ex -toluene., lb.
Carbolic, cryst., U. S. P., drs. . .lb.
50- to 110-lb tins lb.
Citric, crystals, bbls lb.
.15
.01'/.
.07«/«
20.00
23.00
.04«/«
• ll'/s
75.00
18
.00
6
.50
8
.00
1
.00
4
.00
.16
.15
.12'/.
lO'/i
2
.00
1
.50
.12
72
.00
50
.00
.55
30.00
.46
12.00
1.80
3.70
.08 'A
3.00
.10
.10
.24
.16
4.00
2.85
.Oli/i
.08
.07
4.00
20.00
20.00
. 19'/.
.50
.40
3.25
.10>/l
Acid {Concluded)
Oxalic, cryst., bbls lb.
Pyrogallic, resublimed lb.
Salicylic, bulk, U. S. P lb.
Tartaric, crystals, U. S. P lb.
Trichloroacetic, U. S. P lb.
Acetone, drums lb.
Alcohol, denatured, 190 proof. . . .gal.
Ethyl, 190 proof gal.
Wood, Pure gal.
Amyl Acetate gal.
Camphor, Jap. refined lb.
Carbon Bisulfide lb.
Tetrachloride lb.
Chloroform, U. S. P lb.
Creosote, U. S. P lb.
Cresol, U. S. P lb.
Dextrin, corn lb.
Imported Potato lb.
Ether. U. S. P., cone, 100 lbs lb.
Formaldehyde lb.
Glycerol, dynamite, drums lb.
Pyridine gal.
Starch, corn 100 lbs.
Potato, Jap lb.
Rice lb.
Sago lb.
Dec. 1
2.35
2.35
.35
.35
.48
.45
4.40
4.40
.16
.13>/i
.90
.80
5.50
5.25
2.30
2.30
4.00
3.75
1.10
.90
.041/4
2.75
3.18
.06 Vi
OILS, WAXES, ETC.
Beeswax, pure, white lb.
Black Mineral Oil, 29 gravity gal.
Castor Oil, No. 3 lb.
Ceresin, yellow lb.
Corn Oil, crude lb.
Cottonseed Oil, crude, f. o. b. mill. .lb.
Menhaden Oil, crude (southern), .gal.
Neat's-foot Oil, 20' gal.
Paraffin, 128-130 m. p., ref lb.
Paraffin Oil, high viscosity gal.
Rosin, "F" Grade, 280 lbs bbl.
Rosin Oil, first run gal.
Shellac. T. N lb.
Spermaceti, cake lb.
Sperm Oil, bleached winter, 38°. . .gal.
Stearic Acid, double-pressed lb.
Tallow Oil, acidless gal.
Tar Oil, distilled gal.
Turpentine, spirits of gal.
Aluminium, No. 1, ingots lb.
Antimony, ordinary 100 lbs.
Bismuth lb.
Copper, electrolytic lb.
Lake lb.
Lead, N. Y lb.
Nickel, electrolytic lb.
Platinum, refined, soft oz.
Quicksilver, flask Amer 75 lbs ea.
Silver oz.
Tin lb.
Tungsten Wolframite per unit
Zinc, N. Y 100 lbs.
5.50
2.72
.13V.
.14
.051/j
.45
85.00
55.00
.74
.33 V.
6.50
5.75
FERTILIZER MATERIALS
Ammonium Sulfate export. . . 100 lbs.
Blood, dried, f. o. b. N. Y unit
Bone, 3 and 50, ground, raw ton
Calcium Cyanamide, unit of Am-
monia
Fish Scrap, domestic, dried, f. o. b.
works unit
Phosphate Rock, f. o. b. mine:
Florida Pebble, 68% ton
Tennessee, 78-80% ton
Potassium Muriate, 80% unit
Pyrites, furnace size, imported. . . . unit
Tankage, high-grade, f. o. b.
Chicago unit
4.00
5.10
45.00
6.85
11.00
2.00
1.65
.10V2
5.25
2.72
. 13>/.
85.00
50.00
6.50
5.75
4
.00
5
.00
6
.85
II
.00
2
.00
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
COAL-TAR CHEMICALS
Crudes
Anthracene, 80-85% lb
Benzene, Pure gal
Ccesol, U. S. P lb
Cresylic Acid, 97-99% gal
Naphthalene, flake lb
Phenol, drums lb
Toluene, Pure gal
Xylene, 2 deg. dist. range gal
Intermediates
Acids:
Anthranilic lb.
B lb.
Benzoic lb.
Broenner's lb.
Cleve's lb.
Gamma lb.
H.
,1b.
Metanilic lb.
Monosulfonic P lb.
Napthionic. crude lb
Nevile & Winther's lb.
Phthalic lb.
Picric lb.
Sulfanilic lb.
Tobias lb.
Aminoazo benzene lb.
Aniline Oil lb
For Red lb.
Aniline Salt lb.
Anthraquinone lb.
Benzaldehyde, tech lb.
U. S. P.
lb.
Benzidine (Base) lb.
Benzidine Sulfate lb.
Diaminophenol lb.
Dianisidine lb.
' p-Dichlorobenzene lb.
Diethylaniline lb.
Dimethylaniline , .lb.
Dinitrobenzene lb.
Dinitrotoluene lb.
Diphenylamine lb.
GSalt lb.
Hydroquinol lb.
Metol (Rhodol) lb
Monochlorobenzene lb.
Monoethylaniline lb.
a-Naphthylamine lb.
6-Naphthylamine (Sublimed) lb.
f>-Naphthol, dist lb.
m-Nitroaniline lb.
0-NitroaniIine lb.
Nitrobenzene, crude lb.
Rectified (Oil Mirbane) lb.
P-Nitrophenol lb.
P^Nitrosodimethylaniline lb.
o-Nltrotoluene lb.
0-Nitrotoluene lb.
m-Phenylenediamine lb.
p-Phenylenediamine lb.
Phthalic Anhydride lb.
Primuline (Base) lb.
RSalt lb.
Resorcinol. tech lb.
U. S. P lb.
Schaeffer Salt lb.
Sodium Naphthionate lb.
Tuiocar b anilide lb.
Tolidine (Base) lb.
Toluidine, mixed lb.
o-Toluidine lb.
m-Toluylenediamine lb.
0-Toluidine lb.
Xylidine, crude lb.
2.20
2.25
.70
1.75
2.00
3.75
1.65
1.70
3.25
.85
1.75
2.00
6.75
2.25
.42
.4?
COAL-TAR COLORS
Acid Colon
Black lb. 1.00
Blue lb. 2.00
2.20
2.25
.70
1.7.5
2.00
3.75
1.60
1.70
3.25
2.25
1.25
2.50
2.50
.45
.45
1.00
1.(10
1.00
1.00
.80
.80
5.50
5.5J
8.00
8.00
1.90
6.75
2.90
2.90
.25
.25
1.50
1.50
1.30
1.30
2.30
2.30
2.00
2.00
2.75
2.50
.75
.75
1.10
1.10
.60
.60
1.75
1.75
.44
.44
.33
.33
1.50
1.50
1.75
1.75
1.00
2.00
Acid Colors (Concluded)
Fuchsin lb.
Orange III lb.
Red lb.
Violet 10B lb.
Alkali Blue, domestic lb.
Imported lb.
Azo Carmine lb.
Azo Yellow lb.
Ery throsin lb.
Indigotin, cone lb.
Paste lb.
Naphthol Green lb.
Ponceau lb.
Scarlet 2R lb.
Direct Colors
Black lb.
Blue 2B lb.
Brown R lb.
Fast Red lb.
Yellow lb.
Violet, cone lb.
Chrysophenine, domestic lb.
Congo Red, 4B Type lb.
Primuline, domestic lb.
Oil Colors
Black lb.
Blue lb.
Orange lb.
Red III lb.
Scarlet lb.
Yellow lb.
Ntgrosine Oil. soluble lb.
Sulfur Colors
Black lb.
Blue, domestic lb.
Brown lb .
Green lb.
Yellow lb.
Chrome Colors
Alizarin Blue, bright lb.
Alizarin Red, 20% Paste lb.
Alizarin Yellow G lb.
Chrome Black, domestic lb.
Imported lb.
Chrome Blue lb.
Chrome Green, domestic lb.
Chrome Red lb.
Gallocyanin lb.
Basic Colors
Auramine, O, domestic lb.
Auramine, OO lb.
Bismarck Brown R lb.
Bismarck Brown G lb.
Chrysoidine R lb.
Chrysoidine Y lb.
Green Crystals, Brilliant lb.
Indigo, 20 p. c. paste lb.
Fuchsin Crystals, domestic lb.
Imported lb.
Magenta Acid, domestic lb.
Malachite Green, crystals lb.
Methylene Blue, tech lb
Methyl Violet 3 B lb
Nigrosine, spts. sol lb.
Water sol., blue lb.
Jet lb.
Phosphine G., domestic lb.
Rhodamine B, extra cone lb.
Victoria Blue, base, domestic lb .
Victoria Green lb
Victoria Red lb.
Victoria Yellow lb.
STRY
Vol. 13, No
Dec. 1
Dec. 15
2.50
2.50
.60
.60
1.30
1.30
6.50
6.50
S.50
5.50
8.00
8.00
4.00
4.00
2.00
2.00
12.00
12.00
3.00
3.00
1.50
1.50
1.95
1.95
1.25
1.25
1.00
1.00
1.00
1 .00
.70
.70
1.65
1.65
3.50
3.50
2.00
2.00
2.20
2.20
2.25
2.25
.70
.7C>
1.65
1.65
1.40
1 .40
1.65
1 .65
1.75
1 .75
1.70
1.70
7.75
7.75
1 .10
1.10
1.00
1 .00
1.25
1.25
2.20
2.20
2.50
2.50
2.00
2.00
2.00
2.00
2 80
2.80
2.50
2.50
4.15
4.15
6.00
6.00
12.00
12.00
4.25
4.25
4.50
4.50
2.75
2.75
3.50
3.50
.85
.85
.70
.70
.90
.90
7.00
7.00
40.00
40.00
6.00
6.00
6.00
6.00
7.00
7.00
7.00
7.00
^dfiQ c/ournal oP
INDUSTRIAL
& ENGINEERING
CHEMISTRY
'Published Monthly by The American Chemical Society
Editor: CHAS. H. HERTY
Assistant Editor: Lois W. Woodford
Advisory Board: H. E. Barnard
Chas. L. Reese
Editorial Offices:
One Madison Avenue, Room 343
New York City
Telephone: Gramercy 0613-0614
J. W. Beckman A. D. Little A. V. H. Mory
Geo. D. Rosengarten T. B. Wagner
Cable Address: JIECHEM
Advertising Dbpartmbnt:
170 Metropolitan Tower
New York City
Telephone: Gramercy 3880
Volume 13
FEBRUARY 1, 1921
No. 2
CONTENTS
The Society's President for 1921.
100
Editorials:
Elementary Economics 107
The Road to Demoralization 108
Thoughts Translated into Deeds 10S
Sowing Good Seed 109
The Race Is Not Always to the Swift 109
Original Papers:
Measurement of Vapor Pressures of Certain Potas-
sium Compounds. Daniel D. Jackson and Jerome
J. Morgan 110
Rubber Energy. Win. B. Wiegand 1 IS
Reactions of Accelerators during Vulcanization.
II — A Theory of Accelerators Based on the Forma-
tion of Polysulfides during Vulcanization. Win-
field Scott and C. W. Bedford 125
The Action of Certain Organic Accelerators in the
Vulcanization of Rubber — III. G. D. Kratz,
A. H. Flower and B. J. Shapiro 128
Cellulose Mucilage. Jessie E. Minor 131
The Preparation and Technical Uses of Furfural.
K. P. Monroe 133
Further Studies on Phenolic Hexamethylenetetra-
mine Compounds. Mortimer Harvey and L. H.
Baekeland 135
Studies on Bast Fibers. II — Cellulose in Bast Fibers.
Yoshisuke Uyeda 141
Laboratory and Plant:
Gasoline from Natural Gas. V — Hydrometer for
Small Amounts of Gasoline. R. P. Anderson and
C. E. Hinckley 144
A Cold Test Apparatus for Oils. G. H. P. Licht-
hardt 145
Titration Bench. W. A. Van Winkle 140
Addresses and Contributed Articles:
Refining Raw Sugars without Bone-Black. C E-
Coates 147
Research Problems in Colloid Chemistry. W. D.
Bancroft 153
Pekin Medal Award:
Willis R. Whitney. A. D. Little 158
Presentation Address. Charles F. Chandler 160
The Biggest Things in Chemistry. Willis R. Whitney. 161
Scientific Societies:
Plans for the Spring Meeting; Centenary of the
Founding of the Sciences of Electromagnetism and
Electrodynamics; Dr. Henry A. Bumstead; Nichols
Medal Award; John Scott Medal Award; Rumford
Medal Presentation; President Smith Addresses
Joint Meeting; Calendar of Meetings 166
Notes and Correspondence:
History of the Preparation and Properties of Pure
Phthalic Anhydride; The Ignition of Fire Engine
Hose when in Use; Repairing Iron Leaching Vats;
Vapor Composition of Alcohol- Water Mixtures;
The British Dye Bill; European Relief Council 107
Washington Letter 169
Paris Letter 171
Industrial Notes ■ 172
Personal Notes 17.3
Government Publications 175
Book Reviews 1 79
New Publications 182
Market Report 183
Subscription to non-members, $7.50; single copy, 75 cents, to members, 60 cents. Foreign postage, 75 cents, Canada, Cuba and Mexico excepted
Entered as Second-class Matter December 19, 1908, at the Post Office at Easton, Pa., under the Act of March 3, 1879.
Acceptance for mailing at special rate of postage provided for in Section 1103, Act of October 3, 1917, authorized July 13, 1918.
Subscriptions and claims for lost copies should be referred to Charles L. Parsons, Secretary. 1709 G Street, N. W.. Washington, D. C.
106
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
THE SOCIETY'S PRESIDENT FOR 192
EDGAR FAHS SMITH
Forty-five years ago the American Chemical Society
was founded, and just a quarter of a century has passed
since Edgar Fahs Smith was its president. The So-
ciety gives expression to its appreciation of his labors
by choosing him once more for the highest office in its
gift, and in doing so it places in tried and worthy hands
the leadership of its fortunes.
Few remain now who can recall the struggles and
discouragements of those early years. So faint was
the breathing at
times that it seemed
almost as if the
patient was at his
last gasp. There
were chemists scat-
tered here and there
over the land, but
most of them were
kept too busy to give
time to investiga-
tion. The teacher
had little assistance
with his classes, and
the practical side of
building up our in-
fant industries was
all-absorbing. Be-
sides, the Society's
Journal had to enter
the field of publica-
tion with first one,
then two other jour-
nals. All honor,
then; to those who
had heart of hope
and, with vision of
the future, kept up
the struggle. In
these days of leader-
ship in many fields
of investigation it
is well to pause a
while and think of
the sturdy pioneers
who blazed the way
and made this prog-
ress possible.
Among these pioneers none stands higher than our
new president, and no one has such a host of friends
nor is so well-beloved. A kindlier soul has never
walked among us. Counselor and friend to all who
needed him. lover of the truth whether it lay hidden
in the nature around him or in his fellow man, with
deep, abiding faith in all that was fine and noble and
true, he has stood throughout the years four-square
to every wind that blew. His friendship has been an
inspiration and a blessing to many.
It might seem unnecessary to recount the contribu-
tions of Dr. Smith in the building up of our science
but, perhaps, there are some among our thousands
of members who do not realize how much his labors
have meant to all of us and how they have strengthened
chemistry in America and kept fresh the story of its
beginnings.
It is a somewhat striking coincidence that Dr. Smith
began his life work as a teacher of chemistry in the
University of Pennsylvania in 1876, the same year in
which our Society
was founded. Life-
long contemporaries
they have been in
the work. Starting
as an instructor, he
rose through the
various grades to
head of the depart-
ment of chemistry,
then vice provost,
and lastly provost
of the University
retaining through-
out his devotion to
his science and faith-
fully answering to
the limits of his
strength the calls
that were made upon
him. It is difficult
to measure such an
influence as he has
exerted. The story is
known to those who
had the good for-
tune to study under
him. They admire
him, they love him,
and happy are they
if they pattern after
him. In all these
years he has been
a wise and helpful
counselor in the af-
fairs of the Society,
and has done much to
Edgar Fabs Smith, President American Cbemicau Societv promote its interests.
As a teacher, he has been helpful in introducing new
methods and in providing excellent textbooks. At
first these were translations from the most widely ac-
cepted foreign authors — as witness his several editions
of Richter's "Organic Chemistry," and the "Electro-
chemistry" of Oettel. In this line he was one of the
first to have a well-equipped electrochemical laboratory
and to drill his students in this increasingly important
branch, issuing several valuable guides and textbooks
of his own. He devised new methods of analysis and
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
107
greatly aided in introducing this valuable adjunct to
the laboratory practice of the day. All of which was
fitting on the part of one who held the chair of Robert
Hare, who constructed the first American electric
furnace.
The long list of his investigations helps to fill the
pages of our Journal and need not be detailed here.
Suffice it to say that his interests and his work lie in
many fields. Chief among them are electrochemistry,
the complex inorganic acids, the rare earths, and the
revision of those constants, if constants they be, the
atomic weights. In this latter field he has covered
about one-fourth of the known elements, and his work
ranks high. This is a monumental work in itself.
His latest work on the atomic weights of boron and
fluorine is a fine example of how such work should be
done.
The many-sided interests of this man are shown by
the caretaking, accurate, and very valuable work which
he has done as a historian. His activities in this line
may have been aroused by the fact that he occupied
the chair which had been held by Benjamin Rush, the
first professor of chemistry in America, and lives in
the historic city of Philadelphia, where in 1792 was
"instituted" the first chemical society in the world,
antedating by a half century the London Chemical
Society, the first to be established in Europe. Also, he
is a member and for some years was president of the
American Philosophical Society, which was founded
by Benjamin Franklin.
Surrounded by such historic memories he has made
the past live over again in a series of books for which
those of us who do honor to the men who paved the
way for our feet cannot be too grateful. Hare per-
forms over again for us his surprising experiments
with the oxyhydrogen blowpipe which he invented,
and Woodhouse, Cooper, and others tell of their dis-
couragements and achievements. And now in the
account of Priestley in America, which he has just
published, we catch an insight into the character of
that great discoverer, his limitations offset by his sur-
prising vision, which some of us who have read much
about him had never gained before.
To such tried and approved leadership we intrust
the reputation and future of the Society.
Chapel Hiu., N. C. FRANCIS P. VENABLE
EDITORIALS
ELEMENTARY ECONOMICS
Some are arguing that duty-free importation of
scientific apparatus by educational institutions will
mean a great saving in dollars and cents. But to
discuss the economic aspect of this question it is
necessary to shake one's self loose from memories of
pre-war conditions and remember that to-day we are
dwelling in a very much changed world. Before the war
Germany, thanks to an abundance of cheap, highly
skilled labor, placed upon the market chemical wares
at prices with which American manufacturers could
not compete. To-day Germany is faced with
the obligation of paying off during the next twenty-
five or thirty years an enormous reparations debt.
To do this Germany will sell goods in compe-
tition at absurdly low figures in order to destroy
war-born industries in other lands, while charging
exorbitant prices wherever she has a monopoly.
There is abundant evidence of the correctness
of this statement. In Science, November 26, 1920,
page 511, Professor James Lewis Howe complains
that the file of a journal which had been offered
him less than a year before for 3,000 marks has now
risen in price to 25,000 marks (though the exchange
value of the mark had meanwhile depreciated only 50
percent). Monopoly: — exorbitant charge! But Pro-
fessor Howe explains the situation in this same com-
munication, for he quotes from a German firm's letter
to an American customer:
"A word about prices. I take it from your name and con-
nections that you are of German family and am therefore pre-
pared to make most liberal terms. As you doubtless know, it
has been generally agreed in commercial circles here that all
articles sold to uitlanders, and especially to Americans, shall
be priced considerably higher than the same thing sold to our
fellow-citizens, the idea being to in this way recuperate to some
extent from our late overwhelming losses and to make our recent
enemies aid us in paying our most outrageous and crushing war
debt.
"This policy has been adopted en bloc by our associated. . . .
since some time. But as a fellow German, I am prepared to
let you have these goods at the Berlin price, this of course being
in all confidence, my most dear sir."
No camouflage about that — as long as it is in the
family.
Now take the other side of the picture. England
developed during the war a chemical glassware indus-
try:— competition! The London Morning Post of No-
vember 24, 1920, quotes the following conditions of
the British market at that time:
(Price to
Retailer)
1 ,000-cc. separating funnel 4s. Od.
400-cc. flat bottom flask Os. 6.5d.
500-cc. graduated flask 0s. 5d.
15-cc. bulb pipet Is. 3.5d.
Potash bulb Is. 9d.
Aneroid barometer 7s. 6d.
Chemical thermometer for testing acids. ... Is. 2d.
Clinical thermometer Os. 8.5d.
British
(Cost to
Jan«facturt
17s. 7d.
Os. 11.5d.
6s. 6d.
3s. 9d.
is. 6d.
20s. Od.
3s. Od.
2s. 4d.
Destructive competition! Do you believe those
German prices will stand after the British industry is
destroyed, say, four or five years, with that great
reparation debt still having twenty or twenty-five
years to run? We would be the veriest financial
babes-in-the-woods if we deliberately shut our eyes to
such a situation.
As further evidence, if it be needed, we quote from
The Chemical Age (London), December 25, 1920, in
summarizing the report of the Subcommittee on
Chemical Glassware appointed by the Standing Com-
mittee on Trusts:
"The nature of the foreign competition they have to meet
may be gathered from the fact that, favoured by exchange rates
108
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
and other conditions, goods of the kind now being made in this
country are being supplied by Continental manufacturers at
prices less than the actual cost of manufacture here, whereas
for goods that are nol yet being manufactured here prices are being
charged by the Continental makers which mean to the consumer
approximately five times the pre-war price of such goods.'' — [Italics
ours. ]
The U. S. Tariff Commission gives a new slant to
the whole question. In its report on chemical glass-
ware just submitted to the Ways and Means Com-
mittee (Tariff Information Surveys, Scientific Instru-
ments and Apparatus, page 59), it says:
"The great durability of domestic glassware makes it the
cheapest in the final analysis. Institutions which sell at actual
cost will no doubt find it to their advantage to use this material
regardless of the price of foreign ware, because, although the
first cost is high, the replacement cost is low and smaller reserve
stocks can be carried. Those institutions, on the other hand,
which plan on obtaining a profit from the sale of glassware to
students will find it to their advantage to use the fragile foreign
material. In this case heavy breakage increases the turnover
and therefore the profit."
The Tariff Commission is not disposed to joke, nor
to make charges without facts on which to base them.
Foster the American industry, then see that it plays
the game fair!
THE ROAD TO DEMORALIZATION
Two German dye" chemists, Dr. Otto Runger and
Dr. Joseph Flachslander, were officially released from
Ellis Island and admitted into this country on Janu-
ary 5, 1921. This action followed a thorough investi-
gation by the authorities of the port of New York
based, according to press accounts, upon a protest
from Germany. We don't blame Germany for pro-
testing, but with this side of the matter we have no
concern. The herrschaflen proceeded immediately to
Wilmington, Delaware, to take positions in the re-
search laboratories of the du Pont Company. Ac-
cording to the newspapers, $25,000 each is the salary
of these newcomers. Rumor has it that the amount
is much larger. A high official of the Company in-
forms us that these reports are greatly exaggerated.
However, that matter is not important. But the
changed policy of this Company, hitherto always
considered 100 per cent American in every respect, is
important, and unfortunate from whatever angle viewed.
An economic battle for the possession of the Ameri-
can market is in progress between the American and
the German dye industry. In war information is
obtained as far as possible from captured opponents,
but renegades are not placed in positions of high com-
mand. Whatever tends to demoralization in the
American ranks is a matter of national concern,
and the gravest feature of this new policy is the
lowered morale of the du Pont research staff which
will result therefrom.
It is not difficult to imagine the feelings of American
chemists who must take direction from men who
a short while ago were busy in those plants whence
came high explosives and poison gases, the latter ac-
counting for a full third of our hospital casualties.
Temperamentally that research staff now becomes a
conglomeration of incompatibles, a hybrid mixture
which has in it the elements of failure. At the outset
of the building of the dye industry there were many
laboratories where such a mixture was found to be
thoroughly bad, and where the weeding-out process
was put into operation and the staffs Americanized
with consequent fine results.
It is easy to understand the feeling of discourage-
ment which must possess the officials of the du Pont,
as of every other American dye manufacturing com-
pany, over the failure of Congress to enact definite
and adequate protective legislation. However, the
pressure from consumers for a wider variety of dyes
has been materially lessened through the constant
licensing of imports by the War Trade Board and by
the decreased demand for dyes during the present
general industrial slump. Now is the time for de-
veloping an efficient research staff from among our
ablest American chemists.
It is not too late to repair the damage. There are
eastward-bound steamers constantly traveling across the
Atlantic. Whatever the ability of these two chem-
ists, however intimate their knowledge of special lines
of manufacture may be — send them home and let the
American industry proceed to its full development
in an American way and by the force of American
brains.
THOUGHTS TRANSLATED INTO DEEDS
Often we discuss, and plan, and build great air
castles, and develop momentary boundless enthusiasm
— and then, with the peak of the curve reached, enthusi-
asm wanes, interest subsides or becomes diverted to
other matters, and the result is nothing. Happily for
progress this is not always the case.
At the meetings of the Interallied Conference of
Pure and Applied Chemistry which met in London
and Brussels, in July 1919, it was determined seriously
and comprehensively to set about the task of better-
ment of chemical literature. The American Chemical
Society undertook for its share of this work the prep-
aration and publication of two series of monographs,
scientific and technologic, on chemical subjects. The
announcement of the issuance of the first of the scien-
tific series "The Chemistry of Enzyme Actions" by
Dr. K. George Falk is an earnest that the American"
Chemical Society proposes to carry out promptly
and to the full its part of this undertaking.
Congratulations to the three trustees. Drs. Charles
L. Parsons, John E. Teeple, and Gellert Alleman, who
so quickly finished the business arrangements con-
nected with these publications; to the editors, Drs.
W. A. Noyes and John Johnston, who already have
announced progress in the preparation or printing of
eleven other monographs; and to the Chemical Catalog
Company, Inc., which has so excellently carried out the
publication of this first of the series.
Clear a new space on your book shelves, there is a
lot of fine material on the way to you!
Feb., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
109
SOWING GOOD SEED
There have been strange doings in Washington. In
spite of the sentiment in Congress that the Chemical
Warfare Service should be developed to the fullest
extent, orders issued by high officials of the War De-
partment have tended to restrict its activities, to cripple
development, to prevent the training of troops in the
methods of gas warfare, in short, to limit the Chemical
Warfare Service solely to research.
Fortunately we are building for the future on better
lines, and in this work the American Chemical So-
ciety is doing a fine part through the annual lectures
given by distinguished members of the Society at the
United States Military and Naval Academies. The
first set of those lectures was given last winter, and
it will interest all to learn that of the graduating class
this year at West Point, 25 members requested as-
signment to the Chemical Warfare Service. The
second series of lectures is now in progress.
Recently we asked for frank opinions of the value
of these lectures. The Superintendent of the Military
Academy, Brigadier General MacArthur, wrote in
reply:
Through the courteous cooperation of the American Chemical
Society, following suggestions advanced in an editorial in the
Journal of Industrial and Engineering Chemistry for March 1919.
there were given last winter to the senior class of the Corps of
Cadets of the U. S. Military Academy a series of lectures on
important chemical processes. The lecturers and their subjects
were :
Dr. W. H. Nichols, "Sulfuric Acid, the Pig Iron of Chemistry"
Dr. C. L. Parsons, "The Fixation of Atmospheric Nitrogen"
Dr. W. H. Walker, "The Manufacture of Toxic Gases"
Dr. C. L. Reese, "Smokeless Powders and High Explosives"
Other lectures were planned but had to be omitted owing to
reduction in time made necessary by the war-time schedule
then being followed. These gentlemen, whose services were
entirely voluntary, placed their subjects before the class in an
extremely vivid, lucid and interesting manner, giving that
personal touch not to be found in textbooks and arousing the
keenest interest in their auditors, both by the subject matter
and by the manner in which it was presented.
The obvious benefit of these lectures has led to a continuation
of the policy and in the coming spring a second series will be
delivered, the lecturers and their proposed subjects being:
Dr. John Johnston, of Yale, "Industrial Research," March 23, 1921
Professor William McPherson, of Ohio State University, "Large
Scale Production of Munitions," March 30, 1921
Dr. G. A. Richter, of Berlin, N. H., "Rockets and Flares," April 6,
1921
Dr. G. W. Gray, of New York, N. Y., "Fuel. Motor and Lubricating
Oils," April 13. 1921
Dr. W. Lee Lewis, of Northwestern University, "Toxic Gases," April
20, 1921
Rear Admiral Scales, Superintendent of the Naval
Academy, was equally enthusiastic in his reply:
The suggestion for a series of lectures to be given at the
Naval Academy by members of the American Chemical So-
ciety first received public attention in an editorial entitled
"The Soldier, the Sailor and the Chemist" which appeared in
the Journal of Industrial and Engineering Chemistry for March
1919. The attention directed to this very important matter
aroused the interest of all concerned. The cordial offer of the
American Chemical Society, tendered by the President, Dr.
William H. Nichols, to arrange for a series of lectures was much
appreciated and the opportunity gladly made use of.
During the academic year 1919-20, eight lectures in the general
field of chemical engineering were delivered at Annapolis by
members of the American Chemical Society. All of these
lectures were heard by student officers attending the Naval
Postgraduate School and four of them by the First (senior)
Class of midshipmen. During the academic year 1920-21 a
series of six lectures has been arranged, all of them to be heard
by the student officers of the Postgraduate School and four of
them by the First Class of midshipmen. The lecturers for the
current session are:
Dr. John Johnston, "Industrial Research," December 4, 1920
Dr. A. S. Cushman, "Preservation of Iron and Steel," January 8, 1921
Dr. G. W. Gray, "Fuel, Motor and Lubricating Oils," Februarv 4
and 5, 1921
Dr. Wilder D. Bancroft, "Organized Research," March 4 and 5, 1921
Dr. W. Lee Lewis, "Toxic Gases," April 1 and 2, 1921
Dr. Charles L. Reese, "Explosives," April 29 and 30, 1921
The series of lectures of last year, and the current series, are
proving both interesting and profitable to all who have the op-
portunity of hearing them, as they gain at least a perspective
of what the profession of chemical engineering has done, and
can do, in furnishing indispensable assistance to our military
and naval forces in preparation for, and in conduct of, active
operations calculated to carry into effect the requirements of
our national views and aims.
It is clear to us that the purpose contained in the original
editorial suggestion is being accomplished. The ultimate
benefits of the cordial cooperation of the American Chemical
Society cannot be given a definite value, but it is certain that
the movement now under way cannot fail to be productive
of much good to the naval service.
Surely no more patriotic and fruitful work than
the delivery of these lectures could be done by the
members of the Society.
THE RACE IS NOT ALWAYS TO THE SWIFT
We hustling Americans are apt sometimes to poke
good-natured fun at the slowness of the Britisher.
But sometimes the shoe is on the other foot, witness
the following chronological history of the British
ten-year dye license bill in Parliament:
December 2, 1920
December 3, 1920
December 7, 1920
December 7, 1920
December 8-15, 1920
December 17, 1920
December 17, 1920
(midnight)
December 21, 1920
December 22, 1920
December 23. 1920
December 23, 1920
(midnight)
January 15, 1921
Bill introduced in House of Co
reading, ordered printed.
Bill printed, distributed and received endorse-
ment of Colour Users Association
London Times in a leading editorial said:
"Attack is threatened from irreconcilable Free
Traders [our Senator Thomas], out-and-out Pro-
tectionists [modified to straight-tarifl-proteetionists.
our Senator Moses], and a section of the textile
trade [our Mr. John P. Wood and his adherents]."
Continuing, the Times said in comparing with
other key industries: "There is justification for
giving the dye industry preference on the ground
that it is essential both from the economic and the
military standpoints."
Bill moved to second reading. While a member
was speaking in opposition, at eleven o'clock the
closure was moved and carried by 280 votes to 74.
The second reading was agreed to.
Bill considered in Committee.
Third reading of the bill and passage by 118
votes to 25.
First reading in the House of Lords.
Second reading, passed 83 to 36.
Passed Committee consideration.
Bill passed third reading in the House of Lords.
Bill received the royat assent.
Law became effective.
Nearly two years have elapsed since the Longworth
bill was introduced in Congress. It is still there.
What's the matter with us, anyhow?
Our correspondence basket is overflowing with a fine
crop of "Tell-it-to-Herty" communications. Indi-
vidual acknowledgment will eventually be made, mean-
while things are moving.
110
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
ORIGINAL PAPERS
NOTICE TO AUTHORS: All drawings should be made with
India ink, preferably on tracing cloth. If coordinate paper is
used, blue must be chosen, as all other colors blur on re-
duction. The larger squares, curves, etc., which will show in
the finished cut, are to be inked in.
Blue prints and photostats are not suitable for reproduction.
Lettering should be even, and large enough to reproduce
well when the drawing is reduced to the width of a single column
of This Journal, or less frequently to double column width.
Authors are requested to follow the Society's spellings on
drawings, e. g., sulfur, per cent, gage, etc.
MEASUREMENT OF VAPOR PRESSURES OF CERTAIN
POTASSIUM COMPOUNDS1
By Daniel D. Jackson and Jerome J. Morgan
Columbia University, New York, N. Y.
Received December 9, 1920
Anderson and Nestell,1*^ a report on "The Volatiliza-
tion of Potash from Cement Materials," give the pre-
dominating factors affecting the recovery of potash in
the furnace gases beyond the furnace, as follows:
(1) The temperature prevailing in the kiln; (2) volume of
gas passing; (3) the intimacy of contact between the furnace
gases and the cement mix; (4) the vapor pressure of the potash
salt or salts formed; (5) the possibility of dissociation under
certain furnace conditions (oxidizing, neutral, or reducing atmos-
phere or changing temperature) to components of greater or
less volatility than the original salt; (6) the degree of saturation
of the gas in contact with the cement material; (7) the rate of
diffusion both of the salt vaporizing in the interstices of the
cement mix to the surface of contact with the gas stream, and
of the saturated gas at the surface to the leaner gas areas beyond.
Of these seven factors, all may be more or less va-
ried at will except the fourth, namely, the vapor pressure
of the potash salt or salts formed. It was decided, there-
fore, that the fundamental thing in a study of the
volatilization of potash is the determination of the
vapor pressure of the potassium compounds involved.
In the present work results of vapor pressure measure-
ments are given for three natural silicates, leucite,
orthoclase feldspar, and glauconite, which are suffi-
ciently abundant to serve as sources of potash, and for
four other potassium compounds, the chloride, car-
bonate, hydroxide, and sulfate, which are of particular
interest on account of their connection with the recovery
of potash from cement mill flue dust. The knowledge
acquired in these vapor pressure measurements will
later be applied to the study of the volatilization of
potash from mixtures of silicates with releasing and
volatilizing agents.
PREVIOUS WORK
In I860, Bunsen2 determined the relative volatility
of certain salts by heating a centigram bead of the
salt on a platinum wire in the hottest part of a Bunsen
flame and measuring the time required for the salt to
volatilize. In 1897, Norton and Roth3 repeated and
1 Part of a thesis presented in partial fulfilment of the requirement for
the degree of Doctor of Philosophy in the Faculty of Pure Science, Columbia
University, New York, N. Y.
* Numbers refer to references at end of paper.
extended the work of Bunsen. The volatility of sodium
chloride thus measured in each case was taken as
unity. The results of these investigators, as far as
they relate to potassium compounds, are given in
Table I.
Table I — Volatility of Potassium Compounds, Taking the Volatility
of Sodium Chloride as Unity
Results of Results of
Compound Bunsen Norton and Roth
Iodide 2.828 2.362
Bromide 2.055 1.860
Chloride 1.288 1.083
Fluoride 0.329
Carbonate 0.310 0.277
Sulfate 0.127 0.149
Bergstrom,4 in 1915, found the boiling points of the
potassium halides to be as follows: potassium chloride
1500°, potassium bromide 1435°, and potassium iodide
1420°. Niggli5 found that a mixture of potassium
carbonate and silica heated for 60 hrs. at 900° to 1000°
lost 15 mg. of K20. In addition, many of the recent
articles dealing with processes for recovering potash
from silicates contain statements as to the relative
volatility of certain potassium compounds, but, with
the exception of the work of Anderson and Nestell,1
it is believed that there has been no previous quanti-
tative study on the volatilization of potassium com-
pounds.
METHOD OF VAPOR PRESSURE DETERMINATION
On account of the difficulty of finding a gastight
material which would withstand the corrosive action
of potassium compounds at high temperatures, and of
measuring small pressures at these temperatures, it
seemed useless to attempt to employ a static method
for measuring the vapor pressure. Hence the dynamic
method of von Wartenberg6 was chosen.
In this method a measured volume of gas is passed
over a weighed quantity of the substance whose vapor
pressure is to be determined at the desired temper-
ature. The amount volatilized is found by the loss
of weight, and the partial pressure is calculated from
the relation:
Moles of substance X total pressure
Pressure of substance = :
Moles of gas + moles of substance
This partial pressure of the volatilized substance repre-
sents its vapor pressure only if the gas passed over
the heated substance is saturated with the vapor of
the substance at the given temperature, a condition
which is never realized experimentally. However, the
degree of saturation of the gas stream is inversely
proportional to its speed. Hence by determining these
partial pressures at three or more speeds of the gas
stream, and plotting the partial pressures against the
speeds, it is possible to obtain the slope of the line
which shows the relation between partial pressures of
the volatilized substance and speed of the gas stream.
If this line is extended to zero speed it gives the par-
tial pressure at saturation, which is the vapor pressure
of the volatilized substance.
The application of this method presupposes a knowl-
edge of the molecular weight in the gaseous state of
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
both the substance volatilized and the gas used, in
order that the number of moles of each may be cal-
culated. The number of moles of nitrogen, the gas
passed through the reaction chamber, was easily found
by weighing the water displaced by the nitrogen at
a given temperature and pressure. In the case of the
potassium compounds volatilized, the density in the
gaseous state has been determined for only one of the
compounds studied. Nernst7 has shown that the molec-
ular weight of potassium chloride at high temperatures
corresponds to the simple formula KC1. In calculat-
ing the vapor pressures of the other compounds it was
necessary to make certain assumptions regarding the
molecular weight of the compound volatilized. The
details of these assumptions are given under the dis-
cussion of the results for each compound. It can be
pointed out here, however, that should later work
show that the assumed molecular weight in any case
is wrong, it will simply necessitate recalculation of
the results and will not impair the usefulness of the
experimental data. Furthermore, a vapor pressure
here given, used in connection with the assumed molec-
ular weight, will give practically the same result in
calculation of the amount of potash necessary to sat-
urate a given volume of gas at a given temperature
and pressure as would a corrected molecular weight
used with the recalculated vapor pressure. Never-
theless, to avoid misunderstanding special attention
is called to the fact that, with the exception of the
value for potassium chloride, the vapor pressures
herein reported are based upon assumed molecular
weights.
VAPOR PRESSURE APPARATUS
A general sketch of the apparatus is given in Fig. 1.
It consisted of the gas container A, the purifying
train B, the vapor pressure tube C, which was heated
in an electric furnace, F, the absorbing train D, and
the gas measuring apparatus E.
GENERAL SKETCH
OF
VAPOR PRESSURE APPARATUS
The gas, nitrogen, which was to be passed through
the vapor pressure tube was contained over water in
a large bottle, A, which was connected by a syphon
with another bottle, A', containing a supply of water.
This second bottle was suspended from a screw ele-
vator so that the pressure of the gas in the apparatus
could be kept constant within one centimeter of water
pressure during the course of an experiment. A small
manometer, M, filled with water showed the pressure
in the apparatus.
After leaving the gas container and before entering
the vapor pressure tube the gas was freed from any car-
bon dioxide which might be present by passing through
the soda lime tube b', and dried by passing through
the calcium chloride tube b" , of the purifying train B.
After leaving the vapor pressure tube the gas passed
through the absorbing train D, which consisted of
three U-tubes filled as follows: d\ granular anhydrous
calcium chloride; d", soda lime in the first leg and bend
and calcium chloride in the second leg; d"' , calcium
chloride. The object of this purifying train was to
prevent moisture from diffusing back into the vapor
pressure tube and to absorb for weighing carbon di-
oxide set free by heating potassium carbonate in the
determination of its vapor pressure.
The speed at which the gas was passed through the
vapor pressure tube was regulated by the size of the
capillary in the tip g, through which water was allowed
to flow from the bottle E, and the volume of gas
passed through the vapor pressure tube was determined
by weighing the water displaced. By using a bottle
with large cross-section and extending the outlet tube
/, 2 liters of gas could be drawn into the measuring
apparatus with a loss of only about 3 in. in a total
head of 40 in. This is a change of 7.5 per cent, but
experiments with different sizes of capillary tips showed
an extreme variation of about 6 per cent in the speed
of the water flowing during the first minute and during
the last minute. The speed of the gas stream, there-
fore, varied during the course of an experiment not
more than 3 per cent from the mean speed. The tube
h, connected with the outlet tube, was open at the top
and allowed the pressure in the measuring apparatus
to be read upon the scale i. The rubber stopper of
the bottle E had four holes and carried, besides the
inlet tube shown in the figure, a tube by which water
could be introduced and two thermometers, one to
show the temperature of the gas and the other that of
the water. In order to give as small variation as pos-
sible in the speed of the gas stream, before beginning
an experiment a weighed quantity of water was run
out and the level of the water brought below the shoul-
der of the bottle. The temperature of the gas at the
beginning and end of the experiment was noted and
correction made whenever necessary for the change of
volume due to change of temperature.
A longitudinal section of the vapor pressure tube
C is shown in Fig. 2. The tube was made of "Im-
pervite" porcelain, 24 in. long and 1 in. bore, with
walls about three-sixteenths inch thick. It was glazed
on the outside and was found to be gastight at the
temperatures employed. Into this tube was cemented
with a grout of impervite body the fixed plug of im-
pervite which was perforated with a one-sixteenth inch
hole and had a recess for the Pt — Pt + Ir thermo-
couple as shown. The loosely fitting plug was also
of impervite body, unglazed, and had embedded in it
a piece of platinum wire by which it could be with-
drawn from the tube. The diameter of this plug was
about one-sixteenth inch less than the internal diam-
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
Fig. 2 — Longitudinal Section op Central Portion of Vapor
Pressure Tubb
eter of the tube. Gas flowing through the vapor
pressure tube was heated by passing through the
space between the loosely fitting plug and the walls
of the tube, and after passing over the substance con-
tained in the platinum boat and taking up its load of
vapor left the reaction chamber by the one-sixteenth
inch hole in the fixed plug. The entrance end of the
tube, which projected about 7 in. from the furnace,
was closed by a rubber stopper carrying a glass tube
through which the gas was introduced. The exit end
of the vapor pressure tube, which projected from the
furnace only about 1 in., was closed by a special
stopper molded of a mixture of portland cement and
asbestos. This was doubly perforated and carried an
exit tube for the gas and a double-bored porcelain pro-
tecting tube for the platinum-iridium thermocouple.
It was cemented into the tube by a mixture of sodium
silicate and barium sulfate, and the joints were made
gastight by coating with Bakelite varnish. At the
higher temperatures. the ends of the vapor pressure
tube were cooled by strips of wet filter paper so that
there was no decomposition of the rubber stopper or
of the Bakelite varnish.
The vapor pressure tube was heated in a molyb-
denum-wound electric furnace, details of which are
given in Fig. 3. The position of the tube in the fur-
nace was such that the reaction chamber was in the
central evenly heated portion of the furnace. Evidence
that the reaction chamber was evenly heated is given
by the fact that when the loosely fitting plug was with-
drawn it was only after a few seconds that the out-
lines of the platinum boat became visible.
The temperature of the furnace was regulated by
suitable resistances and was controlled by means of
a platinum-iridium thermocouple connected with a
Siemens and Halske millivoltmeter. The hot junc-
tion of the thermocouple was located in the recess in
the fixed plug as shown in Figs. 2 and 3. The cold
junction connections of the couple wires with the cop-
per leads of the millivoltmeter were made in mercury,
which was kept at a constant temperature by a water
bath. The temperatures in the reaction chamber cor-
responding to readings on the millivoltmeter were de-
termined at the beginning of each set of experiments
by a platinum-rhodium couple and a Leeds and North-
rup service potentiometer.
By substituting for the regular loosely fitting plug
a perforated plug of the same size, the hot junction of
the platinum-rhodium couple was supported over the
empty platinum boat in the position indicated in Fig.
2. Gas was then run through the vapor pressure tube
just as in a regular experiment. The cold junction
connections of the platinum-rhodium couple with the
leads of the service potentiometer were silver soldered
and kept at 0° C. in a vacuum bottle packed with ice.
The temperature was calculated from the electro-
motive force read on the potentiometer by Holman's
formula,
e = wT",
using the values m = 0.00275 and n = 1.18, which were
obtained for this particular thermocouple by calibra-
tion against the freezing points of zinc, antimony, and
copper, by Mr. Roland P. Soule in the physics depart-
ment of Columbia University. It is thought that
these temperatures are correct within ±10° C., and
the variation of the temperature during the course of
an experiment was always well within these limits.
PROCEDURE
When the temperature in the tube, as shown by the
platinum-iridium couple, had become constant at the
required point, and a constant pressure of about 2
cm. of water showed that there was no leak in the
system, the loosely fitting plug was withdrawn, a
platinum boat containing a weighed amount of potas-
sium salt was introduced, the plug quickly replaced,
and the gas stream through the tube started by allow-
ing water to run from the capillary tip g (Fig. 1)
into a weighed container. The temperature in the
tube was read at 3- to 5-min. intervals, and kept con-
stant within =*=5°; the pressure in the system was
kept constant within ±0.5 cm. of water by raising
the syphon bottle of the gas container. After about
2 liters of gas had been drawn through the tube the
gas stream was interrupted and the boat containing
the potassium salt quickly removed.
*__ „ „ __J
3^
I ,rurT»ce S»«l of '/e'Srrf
Fig. 3 — Section op Molybdenum- Wound Electric Furnace
A — Alundum Core, 10' X 2" Bore, Wound with 27 Ft. 0.028" Molyb-
denum Wire
Core, 12" X 5" Bore S — Electric Connector ol «/«"
Steel Rod
— No. 10, Copper Feed Wire
E — Alundu
K — Alundum Cement Rings
X — Rings of l/i" Asbestos Wood
P— Asbestos Fire Felt. '/<" Thick
R — Leads of Molybdenum Wrire,
4 Ply
U— Glass "T" Tube
V — Porcelain Insulating Tube
X— Rubber Tubing
The time between starting and stopping the gas
stream was noted, as well as the temperature of the
gas in the measuring apparatus and the pressure in
the apparatus. The volume of gas at this temperature
and pressure and saturated with water vapor was
found by weighing the water displaced, its volume
under standard conditions and dry was calculated,
and from this the number of moles of gas passed through
the vapor pressure tube was determined. The amount
of potassium compound volatilized was found either
by loss of weight or by analysis. All weighings were
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
113
corrected to actual grams mass, and the total pres-
sure, as read from the water manometer and a barom-
eter, was reduced to millimeters of mercury at 0° C.
PROBABLE ERRORS
The sources and magnitudes of the errors in the
vapor pressures of potassium chloride determined by
this method may be classified as follows:
(1) Errors in measuring and controlling the temperature in
the vapor pressure tube. It is believed that the temperature in
the vapor pressure tube was determined correctly within ±10°,
and that the variation of temperature during the course of an
experiment was well within these limits. The maximum magni-
tude of these errors, therefore, varies from 9 per cent at 1044 °,
where a change of 10° in temperature makes a difference of 2.14
mm. in a total vapor pressure of 24.1 mm. of mercury, to 13
per cent at 801°, where a variation of 10° changes the vapor
pressure 0.205 mm. in a total of 1.54 mm.
(2) Errors in determining the volume of gas passed through
the vapor pressure tube. These errors may be due to (a) leaks
in the system, (b) changes in temperature and pressure during
the experiment, (c) inaccuracy in finding the amount of water
displaced. The errors due to leaks in the system were carefully
guarded against and are believed to be absent or at least negli-
gible. Those due to changes in temperature of the gas in the
measuring apparatus were always less than 0.5 per cent, and
those due to changes in pressure not more than 0.2 per cent.
The error in weighing the water displaced was 0.1 per cent, or
less.
(3) Errors in determining the amount of potassium chloride
volatilized varied from less than 0.2 per cent at 1044°, where
the error was not more than 0.1 or 0.2 mg. in weighing and the
amount lost by volatilization was from 110.0 to 131.3 mg., to
3 or 4 per cent at 801°, where the amount volatilized was 5.4 to
7.8 mg.
(4) Errors due to volatilization of the potassium compound
while the boat was being placed in and removed from the tube.
This error was never greater than the error in weighing, for
whenever it was evident that a weighable amount of the potas-
sium salt was being lost in this manner the amount was
found by blank determinations and a correction applied. Hence
this error is included in the errors in weighing.
(5) Excess volatilization of the potassium compound due to
back diffusion of the vapor against the gas stream and condensa-
tion on cooler portions of the tube and plug in front of the vapor
pressure chamber. The magnitude of this error is hard to esti-
mate. It was kept small by having the loosely fitting plug fit
as tightly as possible and still allow for rapid removal and re-
placement, and by increasing the velocity of the gas stream
whenever it became evident that the back diffusion was causing
material error. It is this error which limits the application
of the method to vapor pressures under 25 or 30 mm., on account
of the difficulty of working with gas-stream speeds above 200
cc. per minute. It is believed that the amount of this error is
never greater than the extreme variation of a single determina-
tion from the mean straight line used in extrapolating, whjch
is never over 5 per cent.
(6) Low volatilization due to partial saturation of the gas
with potassium compounds volatilized from condensations in
the tube during previous experiments. To avoid this error as
far as possible, air was passed through the tube for some time
between experiments. If allowed to accumulate, these condensa-
tions became a serious source of error, and when it became
evident that they were seriously interfering, the tube was flushed
out with air while heated at a temperature considerably higher
than that at which the experiments were to be run, or else a
new tube and new plugs were used. Owing to these precautions
and the fact that this error is somewhat compensated for by the
back diffusion mentioned in (5), it is thought that the magni-
tude of this error is never over 5 per cent.
(7) Errors due to uneven distribution of the vapor of the
potassium compound in the gas stream over the boat. The
direction and magnitude of these errors is difficult to estimate.
Their presence was shown in some of the preliminary work on
potassium chloride, where it was found impossible to get dupli-
cates that checked using two different platinum boats, one of
which happened to be deeper and narrower at the top than the
other. The results using the narrow boat were invariably lower
than those with the wider boat, due to the fact that a pocket of
stagnant saturated gas was formed in the top of the narrow
boat and hindered evaporation of the potassium compound.
In the determinations reported, shallow wide boats were used and
closely agreeing duplicates were obtained. It is believed that
under these conditions the errors of this class are not serious.
(S) Errors due to reaction of the potassium chloride vapors
with the impervite tube and plugs. Undoubtedly there was
some reaction between the vapors and the material of which the
tube and plugs were made, and this would tend to absorb the
potassium chloride vapors and give high results. However, on
account of the rapidity of the gas stream and the very small
amount of vapor present in the gas, it is thought that the error
due to this cause is entirely negligible.
(9) Errors in extrapolation. The partial pressures were
plotted against the speeds of the gas stream on coordinate paper,
and the straight line which agreed with the greatest number of
points was extended to zero speed. To check the accuracy
of this graphic method, the equations for the lines through pairs
of mean results for different speeds were written and solved
for the pressure (x) at zero speed (y = 0). The mean of the
pressures thus found, which agreed very closely with the pres-
sure found by the graphic method, was taken as the vapor pres-
sure at the temperature in question. The extreme variation of
the pressure values thus calculated from the mean value was
about * 10 per cent, and it is believed that the vapor pressures
here reported are reliable within these limits.
VAPOR PRESSURE OF POTASSIUM CHLORIDE
It has been shown by Nernst7 that the vapor density
of potassium chloride corresponds to the simple for-
mula KC1. Hence in determining the vapor pressure
of this compound the amount volatilized can be found
directly by loss of weight. The salt used was from a
2-lb. bottle of J. T. Baker Chemical Company's C. P.
Analyzed Potassium Chloride. According to the label
it contained 0.001 per cent or less of each of the follow-
ing impurities: iron, calcium oxide, magnesium oxide,
and sulfuric anhydride, and also a trace of sodium.
Qualitative tests for the above impurities showed that
they were present only in extremely minute quan-
tities. To expel moisture and avoid mechanical loss
from decrepitation, the salt before being weighed for
analysis or for use in a vapor pressure determination
was fused in a weighed platinum boat. The total
potassium present was determined both by the per-
chloric acid method, which separates any sodium
which might be present, and by evaporating a weighed
portion of the fused chloride with an excess of sulfuric
acid in a platinum dish, igniting to constant weight
and weighing as potassium sulfate. The results cal-
culated as potassium chloride by the perchlorate
method were 100.10 and 100.05 per cent, and by the
sulfate method, 99.98 and 99.94 percent. It is safe to
conclude, therefore, that the fused salt is practically
pure KC1. Analyses of the residues from the plat-
14
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
inum boat after vapor pressure determinations showed
that these also were pure potassium chloride. The
potassium chloride left in the boat after Expts. 58 to
63, inclusive, weighed 0.2040 g., and yielded 0.2387 g.
of potassium sulfate, which is equivalent to 0.2042 g.
KC1; the residue from Expts. 67 to 71, weighing 0.5980 g. ,
gave 0.6990 g. of K2S04, equivalent to 0.5981 g. of KC1.
The results of the experiments with potassium chlo-
ride at three temperatures are given in Table II. In
Fig. 4 these results are plotted, using the partial pres-
sures of potassium chloride as abscissas and the speed
of the gas stream in cubic centimeters per minute as
ordinates. The values for the vapor pressures ob-
tained by reading the partial pressures at zero speed
are: 1.54 mm. at 801°, 8.33 mm. at 948°, and 24.1 mm.
at 1044°.
Table II — Vapor Pressure op Potassium Chloride
Nitrogen Partial
Expt. Cc. per Min- Milli- .— KC1 Volatilized^ Pressure
No. Minute utes moles Grams Millimoles Mm. Hg ° C
78.2
77.9
100.1
99.8
108.8
118.6
118.7
119.9
119.7
132.2
132.9
153.0
153.5
184.3
183.0
152.9
154.0
135.9
134.2
80.0
80.5
80.1
77.7
79.4
79.5
80.2
80.2
82.7
77.1
75.1
75.4
82.3
81.6
75.0
82.5
78.8
77.9
0.0074
0.0078
0.0068
0.0065
0.0059
0.0054
0.0054
0.0337
0.0338
0.0318
0.0297
0.0244
0.0239
0. 1146
0.1110
0.1162
0.1268
0.1313
0.1285
0.099
0.105
0.091
0.087
0.079
0.072
0.072
0.452
0.453
0.426
0.398
0.327
0.321
1.54
1.49
1.56
1.70
1.76
1.72
0.93
0.99
0.85
0.82
0.77
0.69
0.69
4.24'
4.25>
3.88
3.89
3.28
3.21
13.9
13.6
15.5
15.3
16.6
16.4
801
803
800
800
802
945
945
948
949
948
947
1040
1046
1045
1042
1044
1046
plotting the line to determine the vapor pressure, the values 4.36
' corresponding to the temperature 948° were used.
VAPOR PRESSURE OF KC1
V
9
48"
C.
^
v
—
—
„>
IM
It
44
"C
-ISO
#
—
•in
—
Millimeters of Mercury
60 80 I M t!0 140 160 30 40 SO 60 70 80 12 14 16 I) 20 Tl 24
Fig. 4
To extend the usefulness of the data obtained, the
vapor pressure curve for potassium chloride from 800°
to 1500°, the boiling point determined by Borgstrom,4
was constructed. Using the values for P found at
801° and 1044°, together with the boiling point, 1500°,
the values of the constants in the empirical and approx-
imate formula of Nernst8
Xo
LogP
+ 1.75 log T-
T + C
4.571 T ' 4.571
were calculated. The simplified formula thus found
for potassium chloride is:
—5326
T
1000 1100 1200 1300 1400
Temperature °C.
Table III — Vapor Pressures
- — Temperatu
•C.
801
948
1044
1100
1150
1200
1250
1300
1350
1400
1450
1500
1 Abs.
1074
1221
1319
1373
1423
1473
1523
1573
1623
1673
1723
1773
' Potassium Chloride :
1500° C.
^— Pressure-
Calculated C
Mm. Hg ]
1.54
9.06
24.1
40.4
62.5
94.4
139.0
202.0
288.0
404.0
558.0
760.0 7
ETWEEN 80(1°
The points on the vapor pressure curve calculated
by this formula are given in Table III. The curve
drawn through these points is shown in Fig. 5.
An approximate value for the latent heat of evap-
oration of potassium chloride can also be calculated
from its vapor pressures by means of the van't Hoff
equation written in the form:9
P, P, X / 1 1 \
Logp?r;-log£T; = 4-571 vt7~t:J
The results of these calculations are given in Table I V .
Table IV — Latent Heat of Evaporation op Potassium Chloridk
Calculated from van't Hoff's Equation
Molecular Heat
Temperati
°C.
801
948
1044
1500
res Pressures
Mm. Hg
1.54
8.33
24. 1
760.0
Mean Value
of Evaporation
X
—27,600
—32,800
—32 000
—30,800
LogP =
+ 1.75 log T + 0.000511 T — 0.7004
VAPOR PRESSURE OF POTASSIUM CARBONATE
Potassium carbonate was the salt used in the first
vapor pressure determinations made because it was
Feb., 192 1
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
115
thought that the conditions of volatilization of potash
from potassium carbonate most nearly approach the
condition of volatilization of potash from a cement
mixture to which no special volatilizing or releasing
reagent has been added. The salt used was a special
grade of chemically pure potassium carbonate. When
kept in a glass-stoppered bottle, which was nearly full
and which was opened only as much as was necessary
in removing the portions used, it did not seem to
change in composition. The portions used for anal-
ysis or in the vapor pressure determinations were
quickly transferred to a platinum boat and this at
once placed in a glass-stoppered weighing bottle. The
sample weighed in this manner gave on analysis by
evaporating in platinum with an excess of sulfuric
acid, heating over a M6ker burner, and weighing as
potassium sulfate, the following results:
> — ■ Per cent .
KiO K2CO3
(a) 65.17 95.61
(i>) 65.31 95.83
(<0 65.19 95.65
(d) 65.21 95.69
Mean 65.22 95.70
The results by the perchlorate method which would
separate any sodium present were:
> Per cent
K2O KsCOj
(e) 65.22 95.70
(.0 65.15 95.59
Mean 65.19 95.65
The sample, therefore, is practically free from sodium,
and qualitative tests showed it to be free from appre-
ciable amounts of other impurities, except moisture and
possibly bicarbonate. On account of the absence of
nonvolatile impurities the amount of potassium oxide
remaining after a vapor pressure determination was
found by dissolving the residue from the platinum boat
in a platinum dish, evaporating with an excess of
sulfuric acid, and weighing the potassium sulfate
formed.
After numerous unsuccessful attempts to obtain
constant weight and constant composition by drying
the salt at temperatures from 120° to 900° C, it was
decided to use the sample as analyzed above. Atten-
tion is therefore called to the fact that the sample
used contained about 4 per cent of moisture, and to
the probability of the results as reported being slightly
higher than the true vapor pressures of anhydrous
potassium carbonate, due to the formation of a small
amount of potassium hydroxide in heating the undried
salt.
To calculate the partial pressure of the vapor of
the potassium salt it is necessary to make an assump-
tion regarding the molecular weight in the vapor state.
In these experiments the amount of carbon dioxide
absorbed by soda lime in the absorbing train agrees
roughly with the amount of potassium oxide lost by
volatilization. It seems probable, therefore, that potas-
sium carbonate on volatilizing decomposes as follows:
K2C03 — > K20 + COa
Hence the vapor pressures were calculated for K20,
using the assumed molecular weight of 94.2. In the
calculations the number of millimoles of carbon di-
oxide was included in the total number of millimoles
whenever the amount of carbon dioxide evolved was
sufficient to affect materially the final results.
The data and results of the experiments at two tem-
peratures are given in Table V, and the plots of the
results giving the vapor pressures at these temperatures
are shown in Fig. 6. The vapor pressures thus ob-
tained are: 1.68 mm. at 970° and 5.0 mm. at 1130° C.
Table V — Vapor Pressure of Potassium Oxide
Carbonate
Cc. ,— K!0 Lost-^
Expt. per Min- ^Millimoles of — . Milli-
No Min. utes N2 COi HiO Grams moles
n Potassium
Partial
Pressure
of EiO
Mm. Hg °C.
4 78 23 79.4 0.1 1.0 0.0068 0.072 0.68 970
5 79 22 76.8 0.1 0.9 0.0083 0.088 0.86 970
6 51 37 83.6 0.1 1.5 0.0109 0.116 1.03 970
7 51 36 81.6 0.1 1.1 0.0103 0.109 1.01 970
10 35 50 77.3 0.1 1.0 0.0119 0.126 1.21 970
11 35 50 77.7 0.1 0.7 0.0122 0.130 1.25 970
15 51 35 78.4 0.5 0.9 0.0390 0.414 3.9 1130
16 51 35 78.4 0.5 1.1 0.0471 0.500 4.7 1130
17 80 23 80.0 0.4 1.1 0.0311 0.330 3.1 1130
18 80 22 77.7 0.4 1.0 0.0309 0.328 3.1 1130
19 102 16 71.8 0.4 1.1 0.0243 0.258 2.7 1130
THE VAPOR. PRESSURE OF K,0 IN K, CO,
970°C
\
II30°C.
100
\
\
\
100
80
\
\
\
\
80 ^
35
S
\
i
.$ 60
v
\
en §
s.
\
b 40
\
\
AT, cT
1
40
5.
\
or, "-->
<o ia
\
20 (j
\
\
0.6 1.0 1.4 1 1.8 :o ! 40 1 6.0 1 1
OS 1.2 16 30 5.0
M///imeters /ig.
Fig. 6
VAPOR PRESSURE OF POTASSIUM SULFATE
On account of the impossibility of obtaining correct
results in the determination of either the potassium
or the sulfate radical in potassium sulfate by the or-
dinary methods of quantitative analysis, the salt used
in these vapor pressure measurements was prepared by
treating some of the same potassium chloride as was
used in the vapor pressure determinations of that salt
with pure sulfuric acid in a platinum dish, and heat-
ing the resulting potassium sulfate over a M6ker burner
to constant weight. Since this temperature was
not high enough to melt the potassium sulfate, before
using it in a determination it was melted in a platinum
boat by being placed for 2 or 3 min. in the vapor pres-
sure tube. It was found that no loss of weight re-
sulted. An examination of the residue after a series
of vapor pressure determinations by evaporating it in
platinum with an excess of sulfuric acid and heating
to constant weight showed that the residue also was
pure potassium sulfate. Hence as there was no evi-
dence of dissociation on heating and since the vapor
density of potassium sulfate has never been deter-
mined, the assumption was made that the vapor cor-
responds to the formula K2S04, molecular weight 174.4.
The partial pressures of potassium sulfate were cal-
culated on the basis of this assumption.
116
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
Table VI — Vapor Pressure op Potassium Sulfate
Milli-
-— KsSOi Lost->
Partial
Min-
moles
Milli-
Milli-
Pressure
utes
Ni
grams
moles
Mm. Hg
0 C.
48
79.4
5.2
0.030
0.29
1129
48
79.6
6.7
0.038
0.36
1129
38
78.0
4.9
0.028
0.27
1127
27
78.5
3.5
0.020
0.19
1129
23
78.1
2.6
0.015
0.15
1127
23
77.5
2.5
0.014
0.14
1126
38
82.6
4.1
0.024
0.22
1131
The results of the experiments with potassium sul-
fate are given in Table VI, and the plot showing the
vapor pressure is given in Fig. 7.
THE VAPOR PRESSURE OF K0SO4
1130° C
100— - *"' - — 100
0 0.10 Q20 0.30 040 050 0.60
Millimeters Hg.
Fig. 7
VAPOR PRESSURE OF POTASSIUM HYDROXIDE
An exact determination of the vapor pressure of
potassium hydroxide presents many difficulties on ac-
count of the extreme chemical activity of this com-
pound. First, it is difficult to prepare a 100 per cent
pure sample to use, and it is perhaps even more diffi-
cult to preserve it and to handle it for use in the ex-
periments. It is also quite a problem to find a con-
tainer made of material which is not attacked by the
hot liquid, and of such shape that it will allow free
evaporation and at the same time prevent loss of the
liquid, which shows an unusual tendency to creep out
of the container. Again there is undoubtedly some
action between the vapors and the walls of the tube
and ends of the plugs in the apparatus, and finally
the composition and molecular weight of the vapor
is not known. In view of the other uncertainties it
did not seem to be worth while to spend a large amount
of time preparing a special grade of pure hydroxide
for the determinations, and it was thought that results
which would give much light on the question of the
commercial volatilization of potash could be obtained
by use of a sample of chemically pure potassium hy-
droxide from a reliable dealer in chemicals. The ma-
terial used, therefore, was from a newly opened bottle
of chemically pure potassium hydroxide, purified by
alcohol and cast into sticks. A stick of this material
was rapidly crushed in a mortar into pieces weighing
from 0.3 to 0.6 g., and these pieces were quickly placed
in separate glass-stoppered weighing bottles and
weighed as soon as possible. Some of the weighed
pieces were used in the vapor pressure determinations
and others were analyzed. The analyses by the per-
chloric acid method gave for the total potassium cal-
culated as hydroxide: 84.67, 84.35, 84.80, 84.45, and
83.98, an average of 84.45 per cent for all of the de-
terminations made. The main impurities, water and
carbonic acid, should not materially interfere with
the volatilization.
In solving the question of containers, both platinum
and nickel were tried before silver was finally selected.
In the final experiments a weighed piece of potassium
hydroxide was contained in a boat of pure silver foil.
This inner silver boat was placed in an outer boat
also of silver foil, and slightly longer, wider, and shal-
lower. The outer boat in turn was set into a larger
nickel boat which served as a support in placing the
charge in and removing it from the vapor pressure
tube. The object of the outer silver boat was to catch
the liquid potassium hydroxide which creeps over the
sides of the inner silver boat and thus prevent its loss
or its action on the nickel boat. This it did success-
fully, for in no case was there evidence that the liquid
had reached the outside of the second silver boat.
The upper edges of the nickel boat after an experiment
were found slightly attacked, evidently by the vapors,
which formed a little dark, greenish gray powder. The
residue in the silver boats was almost colorless to light
gray, effervesced only very slightly with water, and gave
no odor of free chlorine when the water solution was
made acid with hydrochloric acid. The silver of the
two boats after removal of the residue with water and
hydrochloric acid was bright and showed no evidence
of having been attacked. The hydrochloric acid solu-
tion was perfectly clear, proving that no silver had
gone into solution. This hydrochloric acid solution
was evaporated with an excess of perchloric acid, and
the total potassium weighed as potassium perchlorate
and calculated to potassium hydroxide. The loss of
potassium hydroxide by volatilization was then ob-
tained by difference.
Since the formula and molecular weight of the vapors
at the temperature of the experiments were not known,
it was necessary to assume a molecular weight for the
vapors in order to calculate the results as partial pres-
sures. The statement of Roscoe and Schorlemmer,10
evidently based upon the work of Deville, that the
vapors of potassium hydroxide decompose at a white
heat into potassium, hydrogen, and oxygen, needs qual-
ifying, for this decomposition, according to Deville's
own report,11 takes place in the presence of incandes-
cent iron. Moreover, according to Deville in the same
report, the decomposition ceases if the temperature is
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
I [',
lowered below a white heat. Further, according to
Watts,12 who does not give the authority for the state-
ment, potassium hydroxide when heated alone does not
decompose at any temperature. Since the tempera-
ture of the experiments here reported, 795° C, is far
below a white heat, it is not probable that dissociation
takes place to an appreciable extent. Hence it was
most simple and seemed entirely justifiable to assume
that the vapors given off were KOH with a molecular
weight of 56.1.
THE VAPOR PRESSURE OF KOH AT 795°C.
The data of the experiments, together with the re-
sults calculated on this basis, are given in Table VII,
Table VII— Vapor Pressure of
Potassium Hydroxide
Cc.
Milli-
KOH Volatilized
Partial
Jxpt
per
Min-
moles
Milli-
Milli-
Pressure
No.
Min.
utes
Nt
grams
moles
Mm. Hg
" C
127
182
10
81.2
32.5
0.58
5.4
794
129
158
11
77.9
27.2
0.48
4.6
795
180
158
11
77.8
31.4
0.56
5.4
790
LSI
151
12
80.8
35.3
0.63
5.9
793
IK-'
150
12
80.4
34.4
0.61
5.7
795
lK.f
133
13
77.4
34.7
0.62
6.0
794
184
133
13
77.2
41.3
0.73
7.1
795
185
121
15
81.2
44.0
0.78
7.2
794
186
118
15
78.7
38.5
0.69
6.6
795
and these results are plotted and extrapolated in Fig.
8. On account of the possibility of variation in the
composition of the pieces of the sample used in the
different experiments, which variation probably ex-
plains the fact that three of the nine points are at slight
variance with the mean straight line, a high degree of
accuracy is not claimed for the vapor pressure found,
namely, 8 mm. at 795° C. It is believed, however,
that this result is not in error more than 25 per cent,
and that the result plainly shows that the vapor pres-
sure of potassium hydroxide at 800° C. is almost as
large as that of potassium chloride at 950° C, and con-
siderably larger than the vapor pressure of potassium
oxide in potassium carbonate at 1130° C.
VAPOR PRESSURE OF POTASSIUM OXIDE IN NATURAL
SILICATES
In the attempt to determine the vapor pressure of
potassium oxide in natural silicates, three samples were
used, each of which was ground in agate to pass a 200-
mesh sieve.
(1) Leucite — This consisted of portions of two large
tetragonal trisoctahedron crystals. The original crys-
tals were about 0.75 in. in diameter, colored gray on
the outside, and glassy, almost transparent, inside. The
sample after grinding was pure white, and analyzed
19.05, 19.10, 18.97, and 19.04; mean, 19.04 per cent
K20.
(2) Feldspar — This sample was part of a crystal of
orthoclase, with angles of 90°, very light gray in color,
with a slight tinge of red and a glassy luster. The
powder was almost pure white with a slight gray tint.
Duplicate analyses gave 13.90 and 13.97 per cent of
K20.
(3) Glauconite — The sample was furnished by the
Coplay Cement Company. According to their anal-
ysis it contained:
Silica 40 . 56
Alumina and ferric oxide 30.40
Calcium oxide 9 . 58
Magnesium oxide 2 . 09
Potassium oxide 6.06
Loss on ignition 10.52
It was found to contain iron equivalent to 20.85 per
cent of ferric oxide, and analysis gave 6.10, 6.04, 6.07,
6.03, and 6.00; mean, 6.05 per cent of K20.
In the experiments a weighed portion of about 0.5
g. was heated for 48 min. in a platinum boat in the
vapor pressure tube, while dry nitrogen was passed
through at a speed of 35 to 37 cc. per minute. Within
the limit of accuracy of the analyses (about 0.0005 g.
of K20 in a 0.5 g. sample) there was no loss of potas-
sium in any of the silicates at 1335° C. or lower.
Hence the vapor pressure of potassium oxide in these
three natural silicates when heated alone at temper-
atures under 1350° C. is entirely negligible.
The results of experiments with the three silicates,
showing loss of weight and change of state at three
temperatures, are given in Table VIII.
Table VIII — Results of Heating Potassium-Bearing Silicates for
48 to 50 Min.
Loss of
Weight
Expt. Temp. Silicate Per Loss of Residue,
No. ° C. Used cent KiO Appearance, etc.
25 1130 Leucite 0.60 None White, no sintering
28 1245 Leucite 0.73 None White, trace of sintering
32 1335 Leucite 0.74 None White, slightly sintered
24 1130 Feldspar 0.00 None Pale gray, no sintering
27 1245 Feldspar 0.04 None Pale gray, slightly sintered
31 1335 Feldspar 0.08 None Nearly all fused to a
colorless glass
23 1130 Glauconite 11.59 None Reddish brown, sintered
29 1245 Glauconite 12.13 None Dark red, fused
30 1335 Glauconite 12.47 None Dark greenish glass
SUMMARY
I — The vapor pressure method of von Wartenberg
has been adapted to the study of the vapor pressures
of potassium compounds and the vapor pressures shown
in the following table have been determined.
118
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
Vapor Pressures i
° C. Hydroxide Chloride
795 8
801
948
970
1044
1130
1335
II — From the results of the vapor pressure measure-
ments with potassium chloride at 801° and 1044° C,
together with the boiling point of this compound as
given by Borgstrom, the Nernst vapor pressure for-
mula for potassium chloride has been calculated to be:
—5326
Log P = — f- 1.75 log T + 0.000511 T —0.7064
By means of this formula the vapor pressure curve for
potassium chloride from 800° to 1500° C. has been
constructed.
Ill — It has been established by these vapor pressure
measurements that the order of volatility of those
potassium compounds which are most important in
the recovery of potash from cement or other silicate
mixtures is as follows: Hydroxide, chloride, oxide
from carbonate, sulfate, and natural silicates.
REFERENCES
I— J. Ind. Eng. Chem., 9 (1917). 253.
2— Ann., 138, 263; Jahresb., 1866, 770.
3—/. Am. Chem. Soc, 19 (1897), 155.
4 — Med. Finska Kemistsamfundet (Swedish), 24 (1915), 2; through
Chem. Abs., 9 (1915), 2361.
5— Z. anorg. Chem., 85, 234; J. Am. Chem. Soc, 36 (1913), 1693.
6— Z. Elektrochem., 19 (1913), 482; Z. anorg. Chem., 79 (1912). 76.
7—Nachr. kgl. Ges. Gottingen, 1903, 75; through Zenlr., 1903, Vol. II,
17.
8 — Nernst. W., "Theoretical Chemistry." 1911, p. 719.
9—Z. Elektrochem.. 19 (1913), 484.
10 — Roscoe and Schorlemmer. "Treatise on Chemistry," Vol II,
"The Metals," 1907, p. 321.
11— Compl. rend., 16 (1857), 857.
12 — Watts, "Dictionary of Chemistry," 1868, Vol. IV. p. 702
RUBBER ENERGY1
By Wm. B. Wiegand
Rubber Section, Ames Holden McCready, Ltd. , Montreal. Canada
It is proposed to discuss very briefly and nonmath-
ematically some of the many interesting energy rela-
tionships of vulcanized rubber.
ENERGY STORAGE CAPACITY
In the accompanying table is shown what is known
as the "proof resilience" of the chief structural ma-
terials. This is defined as the number of foot pounds
of energy stored in each pound of the material when
it is stretched to its elastic limit. You will observe
that tempered spring steel has less than one one-hun-
dredth the resilience of vulcanized rubber, and that
even hickory wood, its nearest rival, also shows less
than one per cent of the resilience of rubber.
This property of course is directly made use of in
aeroplane shock absorbers, etc., but our present ref-
erence to it is made with a view to discussion, first, of
the character of this stored energy and its transforma-
tion into thermal energy of two kinds; and, second,
the modification and in fact remarkable increases in
• Presented before the Rubber Division at the 60th Meeting of the
American Chemical Society, Chicago. 111.. September 6 to 10, 1920
energy storage capacity made possible through the
admixture of suitable compounding ingredients.
Table I — Proof Resilience
Ft. Lbs. per
Material Cu. In.
Gray cast iron 0.373
Extra soft steel 3 . 07
Rail steel 14.1
Tempered spring steel 95.3
Structural nickel steel 14.7
Rolled aluminium 7.56
Phosphor bronze 4 . OjB
Hickory wood 122.5
Rubber 14.600.00
THERMAL EFFECTS
What happens to the mechanical work done on a
rubber sample when it is stretched to any given point?
Is it in the form of potential energy of strain, as in
the case of a steel spring? The answer is, "No."
Has it all been irrecoverably lost in the form of heat.
as when a lump of putty is flattened out? No. Or
lastly, as when a perfect gas is isothermally compressed,
has the work done on the sample been turned into an
equivalent amount of heat which is, however, con-
vertible back into work during retraction? Here
again the answer is, "No."
The fact is that rubber has all three properties com-
bined. When you stretch a rubber band, some of the
energy is stored as potential energy of strain, exactly
as when you stretch a steel spring. Another fraction
of the energy input is turned into what may be called
reversible heat. You can easily feel this heat on
stretching a rubber thread and touching it to your
lips. The rest of the energy input or work done on
the rubber appears in the form of frictional heat.
RETRACTION
We will suppose that the extension was made rap-
idly (». e., adiabatically) and consider what happens
on the retraction journey, which we will assume to
take place rapidly and immediately. First of all, the
potential energy of strain will nearly all be returned
in the form of useful work, exactly as in the case of
the steel spring. Secondly, the reversible heat which
on the outward journey acted to increase the tem-
perature of the sample will be re-absorbed, transformed
into useful work, and therefore cause no energy loss.
Finally, the frictional heat developed during extension
will be increased by a further amount on retraction,
at the expense of the potential energy of the stretched
sample.
Thus, when the rubber has been stretched and al-
lowed to return to substantially its original length, it
will differ from its original state only by the total
amount of frictional heat developed. By the law of
conservation of energy, we can at once say that this
frictional heat is exactly represented by the difference
between the mechanical energy input and output of
our system. This phenomenon is, of course, known
as hysteresis, and is exhibited by all structural mate-
rials. The fact that in the case of rubber the energy
storage capacity is several hundred times greater than
in the case, say, of steel, explains why hysteresis phe-
nomena become relatively of such cardinal importance
to rubber technologists.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
119
REVERSIBLE HEAT AND THE JOULE EFFECT
Suppose we extend a rubber sample and allow the
reversible heat thus generated to disappear. In other
words, we stretch it isothermally. We are then deal-
ing with a system substantially in equilibrium. The
two factors governing this equilibrium are, first, the
load on the rubber, and, second, the thermal condition.
Any change in the equilibrium requires a change in
these two factors. Conversely, a change in either of
these factors will shift the equilibrium. Now one of
the fundamental properties of any equilibrium is that
when any factor is changed the equilibrium will be
shifted in such a way as to offset the change in the
factor. Thus, if the load is increased, the sample will
stretch and become stiffer so as to resist the increased
load. Similarly, if the temperature of the sample is
increased, the rubber will contract, since in so doing
heat is used up and in this way the disturbance min-
imized.
This contraction on heating was predicted by Lord
Kelvin, after Joule had discovered, or rather redis-
covered, the development of heat during extension.
Metals and most other rigid bodies behave, of course,
in a totally different fashion. Instead of generating
heat on extension they consume heat and become
cooler, with the result that the application of heat to
a stretched metal wire causes it to expand instead of
contract, as in the case of rubber.
The Joule effect has been subjected to many misin-
terpretations, such, for example, as attributing it to a
huge negative temperature coefficient of expansion,
which is, of course, incorrect, since rubber has in fact
a large positive coefficient. Others have attempted
to explain the phenomenon by assuming an increase
in Young's modulus. Bouasse, the French investigator,
who has done sdch masterly work on the elastic
properties of rubber, disproved this hypothesis, how-
ever, and showed in fact that Young's modulus grew
smaller with increased temperature.
The writer has not done any experimental work on
the reversible heat which governs the Joule effect,
but there can be no doubt as to its technical impor-
tance. Thus, for example, the internal state of a solid
tire tread as well as breaker conditions in large pneu-
matics is clearly bound up with the reversible thermal
effect as well as with the frictional thermal effect.
Every time the tire tread impacts upon the road sur-
face each part of the rubber stock traverses a stress-
strain cycle. Even if we admit that the reversible
heat generated during extension is reabsorbed during
contraction, we have to consider the gradual building
up of internal temperatures due to accumulation of
frictional heat. This increase in temperature, acting
through the Joule effect, will lessen the extensibility
of the heated rubber as compared with adjacent re-
gions at lower temperatures, thus setting up strains
which doubtless play a role in breaker separation, the
bane of large-size pneumatics. It is therefore highly
desirable to work out rubber compounds which will
develop not only minimum frictional heat, but also
minimum reversible heat. Quantitative measurements
of the Joule effect with different compounds and
different cures would serve as an index to this quan-
tity.
MECHANICAL PICTURE OF RUBBER
The diagram in Fig. 1, which was first suggested by
a former colleague, Dr. F. M. G. Johnson, of McGill.
helps clarify one's mental picture of the thermody-
namical phenomena associated with rubber strains.
Fig. 1 — Mechanical Picture of Rubber
Rubber may be viewed as a combination of a cylinder
of gas, a steel spring, and a friction member. Follow-
ing this picture, extension of the rubber is accompanied
in the first instance by compression of the gas, thus
generating the reversible heat, Qr. In the second
place, the steel spring is compressed, thus generating
the increase in potential energy of strain, E. Lastly,
the friction element operates through the extension,
generating nonreversible heat, Qf. When the rubber
retracts, the gas expands, the spring retracts, and the
friction element contributes another increment to the
nonreversible heat.
Suppose now the sample is extended and we apply
heat to the system. The gas in the chamber will ex-
pand so as to use up heat, raising the weight W, thus
shortening the rubber and so constituting the Joule
effect.
FRICTIONAL HEAT OR HYSTERESIS
Although the reversible heat has doubtless a decided
technical significance, by far the most important
energy transformation is that of useful work into heat
through hysteresis, and a short account will now be
IS
TEE JOURS AL OF IXDUSTRIAL AXD EXGIXEERIXG CHEMISTRY Vol. 1
carried out under the
ippel.
:"nod consisted in ger.
recording
:3n up to vai
tions.
sis loop was readings cal-
:t pounds of ene- I to one cubic
In order to obviate the ir.::
: ensile machines, and for other reasons of
a special machine was devised, the prin-
cipal features of which were the alignment of a helical
steel spring with the sample and the use of extremely
light and nicely fitting parts. The rubber sample was
a standard test piece about 0.1 in. in thick-
ness, 0.25 2 en shoulders. The
ends of the test piece were secured in special light
weight clamps designed practically entirely to obviate
creeping. The spring extension measured fr-
aud the separation of the clamps, the strains.
Through the use of this special machine it was pos-
sible to generate stress-strain cycles both under rapid,
or adiabatic, a*d slow, or isothermal, conditions.
ISOTHERMAL CYCLES ADOPTED It is of COUTSe ob-
vious that the size and char the hysteresis
cycles will depend on whether they are generated
.callyoris:" Under the former con-
ditions, the c iriational heat developed
on the extension journey are only slightly dissipated.
and so act to incr: aness of the sample and
alter the trend of the curves. Owing to the difficulties
was not found possible to generate adia-
batic loops at speeds sufficient to allow of concordant
results. The method finally adopted was to generate
the cycles at low speed? le, 20 in. per min-
rmal conditions.
preliminary extensions — It is of course well
known that the area of 1 loop is
i so on. In most
cases, however, the third loop differs only very slightly
from the succeeding loops, and so in our work when
it was the intention to generate the hysteresis loop up
to an elongation of 300 per cei I piece which
had not been otherwise handled after cutting from
the molded slab was put through two preliminary
cycles up to 300 per cent, and then clamped into the
machine, an a -is loop graphically recorded.
In taking a succession of loops at increasing elonga-
tions the same test piece was used and two preliminary
loops made at each elongation. The initial length
upon which the cycles were based was the length
measured a:: preliminary extensions had
eer. raaae.
e or compounds used — The experimental re-
-
compounds used in tire construction. They thus in-
cluded practically -. :tion compounds, lightly
loaded breaker compounds, and more heavily loaded
tread stock. The; naixed in the
ander standard conditions, and given laboratory
I
each case up to cures 275 per cent over the optimum
in some cases.
Hysteresis loops were generated at elongations rang-
ing from 100 to 500 per cent. There is considerable
. :e in opinion as to whether in measuring hys-
teresis one should work toward reaching a fixed per-
centage of the breaking load, irrespective of the elonga-
tion, or work to a definite elongation, irrespective of
the load required. The latter method seems to the
writer the only correct one from the technical stand-
point, in view of the fact that the strains incurred, for
example, by the skim coat, breaker, and tread of a
pneumatic tire are arbitrarily fixed by the inflation
pressure and the load.
RELATION BETWEEN HYSTERESIS LOSS AND CYCLIC
elongation — Fig. 2 illustrates the results obtained
with a typical pure gum, high-grade tire friction with
a breaking elongation of upwards of 900 per cent. This
particular compound contained 5 lbs. of sulfur to 100
lbs. of rubber, of which 60 were first latex rubber and
the other 40 a soft-cured wild rubber. The or.',
ingredients were a small percentage of thiocarbanilide
and 5 lbs. of zinc as activator. The energy units are
expressed as one-hundredths of a foot pound calcu-
lated to a cubic inch of rubber. The relationship is
of the character of a rectangular hyperbola, and the
hysteresis increases very sharply for elongations ex-
ceeding 300 per cent. Viewing hysteresis as frictional
is natural to expect sharply increased friction
to accompany the rapidly increasing lateral compres-
sions in the test piece. Following our mechanical pic-
ture, it is analogous to contraction of the friction
element upon the moving arm.
CYCLIC
1
ELONGATION
VS.
HYSTERESIS LOSS
-
-
1
y
: ELONGATK
Fig. 2
adopiion of standard loop — For comparison of
at compounds and for different cures it was
decided to adopt a standard cyclic elongation, and in
" " reduce experimental error it was of course
desirable to select an elongation lower than 300 per
- lying on the flat portion of the curve. For
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
121
o
J 300
va
at 200
tfl 150
UN
s8er
CURE
VS.
HYSTERESIS
OPT
1QP r-r.iso
OVER
PERCENT CURE
higher elongations the energy loss changes so rapidly
with slight changes in the elongation as to make con-
cordant results difficult. Moreover, a brief calcula-
tion of the strains set up, for example, in the skim coat
of a pneumatic casing run under service conditions
shows that under conditions of standard factory prac-
tice the rubber is strained to an elongation of not much
more than 200 per cent each time the tire flattens
against the road. For comparative purposes we there-
fore adopted a standard cycle of 200 per cent elongation.
RELATION BETWEEN STATE OF CURE AND HYSTERESIS
LOSS
It is commonly held by tire technologists that the
state of cure of the friction and skim coat of the car-
cass has a lot to do with the early or late occurrence of
ply separation.
Fig. 3 does in fact show that the state of cure has an
influence on hysteresis. What is shown as the normal
cure on this chart is the optimum cure as determined
by the tensile product. An under-cure of 50 per cent,
for example, means that if the optimum curing time
is 90 min. at 40 lbs. of steam pressure, the sample was
cured for 45 min. Similarly with over-cures. Curves
A and B are typical skim coat compounds. Curve C
is a breaker compound. It will be observed that min-
imum hysteresis occurs in the over-cured region. It
must, of course, be kept in mind that these data apply
only to cycles of 200 per cent elongation, whereas the
rubber stock in question has an ultimate elongation
of over 900 per cent. Attention must also be called
to the danger of assuming that a slight over-cure is
therefore desirable. Aging conditions must be taken
into consideration, and the writer is of the personal
opinion that the optimum cure or, in many cases, an
even shorter cure is the correct condition. It is also
noteworthy that the actual magnitude of the hys-
teresis values characteristic of high-grade, pure gum
frictions is very low, and that we must look elsewhere
for the true cause of ply separation.
lOOO
900
800
700
1 1
VOLUME OF FILLER
VS.
HYSTERESIS
~B JO R~
VOLS. OF ACTIVE PIGMENT
20 25
MIXED WITH
100 VOLS OF
Fig. 4
RUBBER
THE EFFECT OF COMPOUNDING INGREDIENTS
This presents an enormous field of research, and
reference will be confined to a brief outline of the
basic facts.
Fig. 4 shows hysteresis plotted against the volume
percentage of active pigment associated with 100 parts
of rubber. The first point on the curve shows a pure
gum compound, the second, a lightly loaded breaker
compound containing about 4.5 parts by volume of
active pigment. The third point represents a very
high-grade tread compound containing about 15 vol-
umes of active pigment: the last, another tread stock
containing nearly 24 volumes. By active pigment is
meant a pigment which definitely increases the energy
storage capacity of the compound and includes pig-
ments such as carbon black, lampblack, zinc oxide,
the finer clays, etc. It will be noted that for the par-
ticular stocks used there is a linear relationship be-
tween the amount of hysteresis and the amount of such
pigment present. It is also important to note that
the effect of the addition of a highly dispersed phase
upon hysteresis is much greater than moderate changes
in the state of cure of a compound. It is unnecessary
to emphasize the importance of this result from the
standpoint of practical compounding.
Here again, however, one must use caution not to
overlook the importance of heat conductivity, and it
is entirely within the realm of possibility that a pig-
ment, although markedly increasing the hysteresis and
so also the frictional heat, may at the same time com-
pensate for this by a greatly enhanced heat conduc-
tivity. Thus, for example, carbon black not only
causes high frictional heats, but is also a bad conduc-
tor, whereas zinc oxide, although producing similarly
high hysteresis values, has a very much better heat
conductance.
It may be of some interest to indicate roughly the
actual percentages of energy which are degraded into
heat in these various types of rubber compounds. A
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
pure gum friction or skim coat stock when led through
a hysteresis loop to an elongation of 200 per cent de-
grades about 4 per cent of the total energy into heat.
TIRE PENDULUM
A stock containing about 5 volumes of zinc oxide de-
grades about 8 per cent, whereas a tread stock con-
taining, say, 20 volumes of zinc oxide degrades in the
neighborhood of 14 per cent of the total energy input
in each cycle.
FABRIC ENERGY LOSSES
We have dealt thus far with the degradation of en-
ergy into frictional losses in and by the rubber sub-
stance itself. These are of paramount importance in
the case of solid tires, for example. However, in the
case of pneumatic tires, which consist primarily of
layers of fabric held together and waterproofed by
rubber, we have to consider the extent to which fric-
tional heat is developed by the carcass fabric itself.
It is true that the hysteresis loss of an inflated casing
taken as a whole can be accurately determined by the
electric dynamometer. This, however, is an expensive
machine, and has the further disadvantage of not
being able to determine in what proportion the various
constituent parts of the casing contribute to the in-
tegral result. The writer has therefore applied the
principle of the damped pendulum to the study of
casing energy losses. Briefly, the method consists in
inserting a 1-in. carcass section in the arm of a pen-
dulum which is allowed to swing from a fixed position
until it comes to rest. The more perfectly resilient
the carcass wall, the longer will such a pendulum
swing. In order to analyze the elastic properties of
the various structural components of the carcass, it
is necessary merely to strip off the tread and breaker
and repeat the series of vibrations with the carcass
alone. In order to ascertain the effect of the number
of plies of fabric the carcass is stripped down ply by
ply and the total period of the pendulum redetermined
in each case.
Fig. 5 shows the simplicity of the set-up. The
inch section is gripped by two clamps, the upper one
rigidly fastened to the wall, the lower attached to the
pendulum arm, consisting of thick piano wire about
2 ft. long, weighted down by a cylindrical bob of con-
venient mass, say 0.5 lb. Time will not permit de-
scription of the minute experimental details, some of
which are of considerable importance to the accuracy
of the results obtained, but, briefly, the practice was to
start the pendulum from a position, say, 60° from the
vertical, and take shadow readings on an arc back-
ground by means of a fine needle axially inserted in
the bob. The "total period" of the pendulum is the
number of seconds required for the amplitude to fall
from the fixed arbitrary value, say, when the shadow
of the needle reaches the point C until the shadow
reaches the point D, which is preferably a small dis-
tance removed from the position of rest. The length
of the carcass strip between the clamps may be varied
at will, but is preferably about 2 in.
significance of total period — The total period,
viz., the time required for the pendulum to damp down
from the position C to the position D is clearly a mea-
sure of the time required for the potential energy of
the pendulum system to fall from that corresponding
to the height of its center of gravity when the pointer
is at C to that corresponding to D. It is therefore in-
versely proportional to the rate of generation of fric-
tional heat through the various internal energy losses
in the casing section. If the tire were of theoretically
perfect resilience the pendulum would keep on swing-
ing forever, except, of course, for external losses due to-
air resistance, etc.
A typical series of determinations will serve to fix
our ideas. A 3.5-in. plain casing gave a total period
of 6 min. 42 sec. After removing the band ply of the
carcass, the period increased to 7 min. 37 sec; after
*u
1 1 1
TIRE PENDULUM
m
TP-I
V1^
20
ir>
10
o
1
s
> ;
J
1-
) t
> <
r a
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
123
removing the second ply, to 8 min.; after removing the
third ply, to 10 min. 55 sec. When all the carcass plies
had been removed and the tread and breaker inserted,
the pendulum swung for 21 min. 4 sec. As a matter of
fact, it was found in many hundreds of tests that the
total period of the pendulum when plotted against
the number of plies of fabric in the carcass lay on a
smooth curve, shown in Fig. 6.
This curve is of the exponential type, the equation
of which is
TP = K, X K>N,
where TP is the total period, Ki and K5 are empirical
constants, and N is the number of plies of fabric. An
interesting deduction from this curve is that the fric-
tional losses in a casing are not a linear function of
the number of plies of fabric. As a matter of fact,
the total period for a 5-ply carcass bears the same
ratio to that of a 4-ply carcass, as that of a 4-ply
carcass bears to that for a 3-ply carcass. In other
words, as the number of plies of fabric is increased
the frictional heat increases not in arithmetic but in
geometric progression. This constant ratio we have
called the "ply factor," and its value in a typical
square fabric casing lies very close to 0.7 for ranges
of from 2 to 7 plies. If the total period for a 6-ply
section is 100 min., that for a 7-ply section will be 70
min. If there were no fabric friction, this factor would
of course become unity, except for the small losses due
to the skim coat between the plies.
INFLUENCE OF GUM STOCKS ON CASING ENERGY
losses — It was at first thought that the condition of
the skim coat and friction between the plies of fabric
might profoundly influence the casing energy losses,
and a series of tire sections was therefore prepared of
various degrees of under- and over-cure. To our great
surprise the effect of these exaggerated under- and
over-cures upon the total period of swing was entirely
negligible in every case.
effect of tread and breaker — Our results, fur-
thermore, showed that, for example, in the case of a
3.5-in. 4-ply casing, the total period of swing for the
complete section was almost exactly the same as that
for a 4-in. 5-ply casing, stripped of its tread and breaker.
We thus see that the entire tread and breaker of a
casing contribute no more to the energy losses than
does a single ply of carcass fabric.
cord construction — These remarkable results made
it at once desirable to ascertain the effect of cord con-
struction, the advantages of which, from the stand-
point of internal chafing, seemed obvious. Our ex-
periments fully bore out this idea, and in fact we found
that a 5-in. cord carcass swings almost exactly three
times as long as a square fabric carcass of the same
size. Cord fabric is therefore three times as efficient
as a transmitter of energy as square fabric. Our pur-
pose in thus briefly describing the pendulum method
of investigation is not to expound the behavior of the
various structural elements of a casing, but rather to
illustrate the usefulness of a simple, convenient, cheap,
and yet accurate physical apparatus in helping to
solve the pressing problems of our industry.
effect of pigments on energy storage capacity
So much for the transformations of rubber energy
and in particular its degradation into frictional heat
through hysteresis.
Of equal interest, however, is the study of the total
energy storage capacity of vulcanized rubber and the
profound changes in this quantity which can be in-
duced through the. admixture of suitable ingredients.
The experimental details of this work have been pub-
lished elsewhere.1 The fundamental facts are as fol-
lows:
1 — A pure gum stock is totally unsuitable for some of the most
important technical applications of rubber by reason of its
inability to stand abrasive wear.
2 — The addition in suitable amounts of certain compounding
ingredients enormously improves the wear-resisting power of
rubber. Our investigation as to the reasons underlying these
facts naturally began with a quantitative study of the effect of
the various compounding ingredients upon the mechanical
properties of the stock. These properties are very largely
expressed by the stress-strain curve, and on selecting a suitable
basic mix and adding to it regularly spaced increments by
volume of the most important inorganic compounding in-
gredients, it was at once discovered that profound changes in the
character of the stress-strain curve were thereby induced.
These changes may be divided into two classes.
One class comprises merely a foreshortening of the curve.
Thus, for example, the addition to the basic mixing of increasing
percentages by volume of barytes produces a stock which, when
gradually stressed to the failure point, preserves the same values
of elongation and load as in the case of the pure mixing. The
only difference is that failure occurs earlier. In other words,
this pigment simply dilutes or attenuates the mechanical
properties of the mixing. It plays a passive role.
In the other class the stress-strain relationships are pro-
foundly altered. Thus, for example, if glue or zinc oxide or
one of the blacks be added to the basic mix in increasing amount,
the mechanical properties of the resultant vulcanisate show the
following changes:
First, the curvature of the stress-strain curve is diminished
and at suitable pigment concentrations actually disappears.
That is to say, rubber can be so compounded as to display the
same kind of stress-strain relationship as in the case of steel
and the other rigid structural materials, i. e., Hooke's law ob-
tains. Again, certain of these same pigments, if not added in
excessive amounts, produce compounds, the tensile strength of
which at rupture remains undiminished or even increased over
large compounding ranges. In these cases the final elongation
is, however, markedly reduced. In the other cases, although
linear stress-strain relationships are induced, both tensile
strength and elongation fall off more or less equally
It has been thought justifiable in view of these striking
differences in behavior to call pigments of the second class
active pigments and those of the former class inert pigments.
In Table II are brought together, along with the
energy storage capacities which are here designated
the total energy of resilience, the dispersoid charac-
teristics of the pigments in question, and also the in-
crease in total volume of the compounded rubber when
stressed to 200 per cent elongation. These volume in-
creases, for the details of which you are referred to a
recent paper2 by my colleague, Mr. Schippel, prove
i Can. Chem. J.. 1 (1920), 160: see also abstract in India Rubber World,
63 (1920), 18. Both references give curves illustrating the effect of various
pigments on the energy storage capacity of the rubber.
s This Journal, 12 (1920), 33.
124
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
Table II
Displace- Total
ment of Energy Volu
Apparent S. S. of Incre
Pigment Surface Curve Resilience at 200% El.
Carbon black .. . 1,905.000 42 640 1.46
Lampblack 1.524,000 41 480 1.76
China clay 304 , 800 38 405
Red oxide 152.400 29 355 1 9
Zinc oxide 152,400 25 530 0.8
Glue 152,400 23 344
Lithopone 101,600
Whiting 60,390 17 410 4.6
Fossil flour 50,800 14 365 3.5
Barytes 30,480 8 360 13.3
Base
450
beyond any doubt that particularly in the case of the
inert pigments the application of stress causes a par-
tial separation of the pigment from the rubber with
resultant development of vacua at the poles. In the
active pigments, those which show a positive effect
upon the energy storage capacity, this separation from
the rubber matrix is very slight. Column 2, which
gives the sq. in. of surface per cu. in. of pigment, indi-
cates that the extraordinary differences in behavior are
without doubt attributable to differences in surface
energy. When a stock containing one of the active
pigments is stressed to rupture, the energy required
to do so goes partly towards distorting the rubber
phase and partly towards tearing apart the rubber
from the pigment particle.
Again, the fact that in the case of the active pig-
ments the rubber remains more nearly adhesive to each
particle means more uniform stress on the rubber phase,
and so enhanced tensile properties and energy capacity.
Surface energy has, of course, two factors. The
capacity factor is represented by the specific surface,
and it is the variations in this factor which appear to
predominate in the behavior of the various pigments.
The other factor, the intensity factor, which is repre-
sented by the interfacial surface tension, is also doubt-
less of importance, as is shown by the fact that zinc
oxide occupies a somewhat anomalous position in the
energy column. It is, namely, a more active pigment
than would be indicated by its developed surface.
Briefly, any pigment of a degree of subdivision cor-
responding to a surface development of over 150,000
sq. in. per cu. in. may be expected to belong to the
active class. It must of course be remembered that
the activity of a pigment depends entirely upon the
percentage present in the mixing. Maximum activity
is developed for volume percentages lying between 5
and 25. Inert pigments of course develop no activity
no matter how much or how little is added.
THE STRUCTURE OF COMPOUNDED RUBBER
In view of the important role played by surface
energy in the properties of compounded rubber, and
also in view of the recently demonstrated fact of the
physical separation of the constituent particles from
their rubber matrix under conditions of strain, it is
clearly of importance that we should know something
about the spacial distribution of the component par-
ticles of a mixing. Thus, for example, how much
barytes may one add to a compound before the par-
ticles actually touch each other? How far apart are
the particles of zinc oxide in a tread compound con-
taining, say, 20 volumes of this pigment?
These interparticle distances are of theoretical im-
portance, not only for the proper calculation of the
forces acting upon the rubber phase occupying the
interstices, but also in connection with the influence,
if any, of electrostatic charges upon the pigment par-
ticles during mixing.
Let us first assume that sufficient pigment has been
added to cause actual contact between the particles.
Now it is not at all a simple matter to calculate what
percentage must be added to bring about this condi-
tion. The question involves a study of the theory of
piling. Thus, for example, if we fill a quart measure
with marbles, the number we can get into the measure
depends upon the character of the piling which they
assume. If, after laying in the first layer we place suc-
ceeding layers in such a way that each marble lies ver-
tically over and touching the one beneath, we obtain
what is known as cubical or loose piling* If, however,
we shake the marbles down until they lie together as
closely as possible, the piling assumes a totally different
character, known as normal, close, or tetrahedral piling.
This question of cubical or tetrahedral piling is im-
portant in all studies of granular bodies. Thus, for
example, the rigidity of mortar under the trowel, or
the firmness under the foot of the wet sand on the
seashore are both due to the fact that the granules are
in a condition of close or normal piling, the distur-
bance of which by an external force requires an increase
in the over-all volume, which in turn is resisted by the
vacua which tend to be formed.
If a test tube be loosely filled with sand and sub-
sequently gently tapped, the sand will settle down a
considerable distance in the tube. The sand was orig-
inally more or less loosely piled. It was certainly
not piled in the most loose manner possible, namely, cubi-
cally, but occupied some intermediate position. On
gently tapping the tube the particles are freed, and,
attracted downward by the force of gravity, assume a
spacial arrangement more nearly normal or tetrahedral.
THE PILING OF COMPOUNDING INGREDIENTS We have
now to consider what happens when a pigment is
worked into the rubber in a plastic state on our mix
mills. Owing to the high viscosity of the gum the
force of gravity is not free to act as it did in the case
of the sand in the test tube or the marbles in the
quart measure. Taking first a case where so much
pigment is added that the particles are compelled to
touch each other, it is possible to calculate the amount
of pigment required on the assumption, first, that the
particles are arranged cubically or loosely, and, sec-
ond, tetrahedrally or closely.
On the former assumption, irrespective of the size
of the particles (which are, however, assumed to be
uniformly spherical), the amount required would be
52.4 per cent of the total by volume. On the second
assumption, the figure comes out at 74.1 per cent.
Now it is a well-known fact in mill practice that a
compound containing 50 per cent by volume of pig-
ment is almost unmanageable on the mill. We there-
fore deduce that with the customary amount of mill-
ing the pigment particles probably exist in a condition
more closely approximating the loose or cubical piling
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
125
than the close or tetrahedral piling. The writer has,
however, observed that in working with extremely
heavily loaded stocks it is possible, by continued mill-
ing, to bring about a more or less sharply defined in-
crease in plasticity with the possibility of working in
an additional amount of pigment. With due regard
to the breaking down of the rubber owing to this ex-
cessive milling, it still remains highly probable that
the additional mastication has caused a more even
distribution of the rubber phase throughout the mass,
which is equivalent to saying that the particles have
been rearranged to more nearly normal piling. The
writer has in fact succeeded in milling in over 60 per
cent by volume of pigment in this way (*. e., 60 vol-
umes pigment to 40 volumes rubber).
20 JO 40 50 60 70
Fig. 7 — Interparticle Distance vs. Volume Per cent Pigment
SPACIAL ARRANGEMENT WHEN NOT IN CONTACT Fig.
7 shows interparticle distances for percentages of pig-
ment ranging all the way from 0 to 80 per cent. The
ordinate D shows the distance between the particles
referred to their radius as unity. The upper curve
shows conditions when the particles are tetrahedrally
disposed. Under working conditions in the factory
very few compounds contain more than 35 per cent
by volume of pigment. Taking, for example, a typical
tire tread compound containing, say, 20 per cent of
pigment by volume and assuming tetrahedral arrange-
ments, the particles will be distant from each other by
a little over their own radius. Assuming cubical ar-
rangement they would be closer together, namely, dis-
tant by about three-quarters of their radius. This of
course presupposes spherical shape. In actual prac-
tice, the pigment particles are by no means spherical,
but on the average they are more nearly spherical
than of any other definite geometrical shape, and the
error due to assuming sphericity will not be large.
The question as to whether in such cases where the
particles are not in actual contact one ought to as-
sume a tetrahedral or a cubical space arrangement is
(at least to the writer) very difficult to answer by
mathematical analysis. It should be quite possible,
however, to reach an approximate solution by numer-
ous direct microscopic measurements on thin sections
by transmitted light, and we hope to secure results of
this kind in the near future. In any case, the values
shown on this chart represent the extremes between
which the true values must lie, and we are of the opinion,
as intimated above, that the action during milling is
that the rubber phase will tend to become as evenly
distributed as possible, and that therefore the tetra-
hedral arrangement is the more nearly in accordance
with actual conditions.
The writer fully realizes that the foregoing analysis
hardly even scratches the surface of the problem of
the structure of compounded rubber. Of cardinal im-
portance are, for example, the direct measurement of
the surface tension between zinc oxide and rubber,
carbon blacks made .under different conditions and
rubber, and so on. When these values are once de-
termined the capacity factor of the surface energy as
measured by the average degree of dispersion of any
given pigment can in our opinion be most accurately
measured by its admixture under standard conditions
in a rubber compound, and the determination of the
decrease or increase in energy storage capacity as com-
pared with other samples of the same pigment. This
would seem to be of particular value in the case of the
finer pigments, such as the blacks, the individual par-
ticles of which are beyond the resolving power of our
microscopes.
Reverting to the title, "Rubber Energy," we see
that along with its already distracting array of prop-
erties chemical, rubber provides the thermodynamician
with plenty of nuts to crack. The interrelationships
of its thermal, mechanical, and surface energies make
up a field of research which has lain fallow long enough
and which should be zealously cultivated.
REACTIONS OF ACCELERATORS DURING VULCANIZA-
TION. II— A THEORY OF ACCELERATORS BASED
ON THE FORMATION OF POLYSULFIDES
DURING VULCANIZATION1
By Winfield Scott and C. W. Bedford
Goodvear Tire and Rubber Co., Akron, Ohio, and Quaker City
Rubber Co., Philadelphia, Pa.
The investigation of organic accelerators, as shown
by the literature of the past five or six years, appears
to be confined largely to a search for new compounds
or a combination of compounds to catalyze the ad-
dition of sulfur to rubber. It has been shown that
these accelerators are almost entirely organic nitrogen
compounds, and as a result nearly all classes of ni-
trogen-containing substances have been tried. Fur-
thermore, it has been shown that the nitrogen of such
compounds is basic or becomes basic during vulcani-
zation by the action of heat, sulfur, or hydrogen
sulfide.
It has been previously proposed that a sulfur re-
action of the accelerator is necessary, and certain re-
action products in some way make sulfur available
for vulcanization. In some cases a sulfur reaction is
doubtless necessary to form the true accelerator, which
is a polysulfide.
Ostromuislenski2 attributes the activation of sulfur
by aliphatic amines to the formation of thiozonides
of the type R-NH-S-S-S-NHR, which readily
■ Presented before the Rubber Division at the 60th Meeting of the
American Chemical Society, Chicago, III., September 6 to 10, 1920.
' Chem. Abs., 10 (1916), 1944.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
give up their sulfur to the rubber. The formation of
thiozonides is illustrated by the following equation:
2R-NH2 + 4S
R-NH-S-S-S-NH-R + H2S
RNH2 + H:S
By this scheme, the true accelerator is produced to-
gether with hydrogen sulfide by the reaction of the
amine and sulfur. Such an explanation necessarily
excludes the tertiary amines, since they have no hy-
drogen attached to the nitrogen, and it is also limited
to those amines that react with sulfur at curing tem-
peratures. In the formation of thiozonides, hydrogen
sulfide is a by-product and does not function directl)
in producing a true accelerator.
Andre Dubosc1 states that a part of the curing
action of accelerators is due to the polymerizing effect
of thiocyanic acid produced by a sulfur reaction on the
accelerator. He illustrates these reactions by means
of equations, but makes no statement that such re-
action products were determined experimentally. As
an example of these reactions, it is stated that aniline
reacts with sulfur at 140°, in this manner:
C6H6NH2 + 4S >■ HCNS + 2HC=CH + CS, + H2S
The writers have been unable to duplicate these re-
sults, and no reference to any such reaction could be.
found in the literature on the subject. Dubosc at-
tributes the activation of sulfur entirely to the reac-
tion between hydrogen sulfide and sulfur dioxide.
It is known that vulcanization takes place if these
two gases are allowed to react in the presence of rub-
ber. Since the publication of the above-mentioned
article by Dubosc, a patent2 has been granted to
S. J. Peachey, covering the process. While there are
accelerators, such as />-nitrosodimethylaniline, which
generate both hydrogen sulfide and sulfur dioxide
during the cure, certainly the great majority of ac-
celerators do not activate sulfur in this way, since they
function in rubber stocks that are practically oxygen-
free.
The latest theory for the action of accelerators dur-
ing vulcanization is that of Kratz, Flower and Cool-
idgc.3 These writers attribute the accelerating action
of amines, such as aniline, to the formation of an un-
stable addition product of aniline and sulfur, in which
the sulfur is temporarily attached to the nitrogen,
making it pentavalent:
CtH[NH, + S
C6HSN
Z5
-H,
The compound thus formed gives up its sulfur to the
rubber and is then regenerated by a further reaction
with sulfur.
The writers believe that the mechanism of the ac-
tion of amines is represented differently from that
given by the above investigators, and that hydrogen
sulfide is one of the important factors in acceleration.
It is believed that, in general, amines catalyze the
addition of sulfur to rubber in the following manner:
• India Rubber World, 39 (1919), 5.
- Brit. Patent 129.826.
i This Journal, 12 (1920) 317.
SH
H
H
1
LNH2 + *S —
I
1
-> RNHj
1
SH
SH
Sx
As a specific example, dimethylamine, with hydrogen
sulfide and sulfur, forms a derivative of ammonium
polysulfide as follows:
(CH,)2NH + H,S > (CHii.XH.SH
(CH3)2NH2SH 4- xS > (CH:,12NH,SH
Polysulfide compounds similar to the above are con-
sidered to be the true accelerators that furnish the
sulfur necessary for vulcanization. That this type
of sulfur is available for vulcanization has been shown
by Ignaz Block,1 who states that hydrogen polysulfides
(H2S2 and H2S3) will cure rubber at ordinary tem-
peratures. C. O. Weber2 quotes Gerard and his work
showing that alkali polysulfides in concentrated solu-
tion will also vulcanize rubber.
ORGANIC ACCELERATORS
All organic accelerators do not function in the same
manner as the bases, and for this reason the writers
choose to divide accelerators into two classes.
I. Hydrogen Sulfide Polysulfide Accelerators — In this class be-
long those bases which form polysulfides similar to yellow
ammonium sulfide.
II. Carbo-sulfhydryl Polysulfide Accelerators — This includes
all accelerators that contain the grouping =C-SH, such as
the thioureas, dithiocarbamates, thiurams, mercaptans or the
disulfides which may be formed from them by oxidation or by
reaction with sulfur.3
To the first class belong all basic organic accelerators
or such compounds as produce basic accelerators un-
der curing conditions. Certain inorganic accelerators
may also be included. These will be discussed later
in the paper.
The second class also includes certain of the Schiff
bases4 which form thiourea derivatives by a sulfur
reaction during the cure. Further discussion of this
class will be reserved for a later paper. s
' D. R. P. 219.525.
."Chemistry of India Rubber," p. 47.
J Although the term polysulfide is applied to each elass of accelerators,
it should be noted that they are distinct types. In Class I. the polysulfide
sulfur is related to a sulfhydryl group attached to nitrogen, while in Class
II the polysulfide sulfur is held by a sulfhydryl group attached to carbon.
In the so-called disulfides and their higher sulfides, the hydrogen of the
sulfhydryl group is considered as having been eliminated in hydrogen sulfide.
« Bedford and Scott, This Journal. 12 (1920), 31 .
6 The reaction of carbon disulfide on amines to form thioureas and
hydrogen sulfide is reversible, and it is entirely possible that by the action
of hydrogen sulfide during vulcanization the thioureas are changed to the
more powerful dithiocarbamates which are intermediate to the complete
transformation to amine and carbon disulfide. It is also possible that the
thioureas may form polythio compounds direct, through the carbo-sulf-
hydryl gToup.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
The phenylated guanidines belong to both classes,
since at curing temperatures they easily react with
hydrogen sulfide to form thioureas and free amines.
Diphenylguanidine, for example, gives thiocarbanilide
and ammonia.
The difference in behavior of the two above-men-
tioned classes of accelerators was well illustrated by
the following experiment: A rubber cement contain-
ing rubber, sulfur, and zinc oxide was divided into two
portions. To the first portion was added piperidyl
ammonium poly sulfide; there was no apparent change
after standing for 2 mo. To the second portion
was added an amount of piperidine equivalent to that
which was used in the first sample, and a small amount
of carbon disulfide was stirred into the mixture. This
cement jelled in less than 24 hrs., showing the well-
known higher curing power of the dithiocarbamates
as compared with basic amines and imines.
The present paper will deal with the first-mentioned
class of accelerators, i. e., with those accelerators which,
in the presence of hydrogen sulfide under curing con-
ditions, form polysulfides analogous to those of sodium
and ammonium.
The structural relationships of the polysulfides of
the nitrogen bases and the more positive metals are
not clearly understood at present, although it is known
that some of the sulfur is held in a more or less loose
form of chemical combination. This is evidenced by
the precipitation of sulfur from concentrated solutions
on dilution, and the generation of heat when sulfur
dissolves in sulfide or hydrosulfide solutions. It is
certain that the sulfur of polysulfides is quite different
from rhombic or a-sulfur, and that the aggregate
Sg is changed to the sulfur of polysulfides by the com-
bined action of hydrogen sulfide and basic accelerators.
It is a well-known fact that sulfur will react with
rubber resins and proteins at temperatures near 140°
with the formation of hydrogen sulfide. This hydrogen
sulfide in the presence of basic accelerators forms hy-
drosulfides which in turn take up sulfur to form poly-
sulfides. These polysulfides pass on part of their
sulfur to the rubber and constitute the true curing
agents. Such a mechanism applies also to the curing
action of alkali and alkaline-earth hydroxides. The
fact that basic magnesium carbonate will react with
hydrogen sulfide and sulfur in water suspension to
form polysulfide solutions no doubt accounts for its
mild accelerating power. Lime and magnesia do not
function well in deresinated rubbers where much of
the hydrogen sulfide producing materials have been
removed. The sulfides and polysulfides of the alkali
and alkaline-earth metals should function in deresin-
ated or synthetic rubbers.
The Bayer Company patent1 on basic organic acceler-
ators contains a broad claim covering all bases with a dis-
sociation constant greater than 1 X 10"8. This claim
covers those bases which readily react with hydrogen
sulfide and sulfur to form polysulfides at ordinary or
at curing temperatures. Weak bases such as aniline
cannot be expected to form polysulfides to the same
extent as strong bases like dimethylamine, since the
1 U. S. Patent 1,149.580.
formation of polysulfides is in some way dependent
upon basicity. It has been found that weak bases
such as aniline, />-toluidine, and quinoline, dissolve
more sulfur at 100° in the presence of hydrogen sulfide
than when it is absent. Aniline will dissolve about
1 per cent more sulfur at 100° and about 4 per cent
more at 130°.
The relative accelerating power of the organic bases
is dependent upon the facility with which they form
polysulfides and the extent to which they are able to
activate sulfur and make it available for the rubber.
This will, in some measure, be dependent upon the
basicity. In a previous paper by the writers1 it was
stated that at least a part of the accelerating action
of hexamethylenetetramine is due to the fact that
during the cure there are produced, among other
products, ammonia and carbon disulfide which, alone
or with basic products present in the rubber, form
dithiocarbamates. It may be added that "Hexn"
also forms hydrogen sulfide by sulfur reaction, which
with the ammonia undoubtedly forms ammonium
polysulfides. This accelerator may, therefore, be
classed under both types since it is both a hydrogen
sulfide and a carbo-sulfhydryl polysulfide accelerator.
Aldehyde ammonia, by the action of heat alone,
forms ammonia, while with sulfur it also gives hydrogen
sulfide. Heat also produces other bases such as the
alkyl pyridines or collidines. This material appears
to be solely a hydrogen sulfide polysulfide accelerator.
The ammonia condensation products of other aliphatic
aldehydes behave in a similar manner.
^-Phenylenediamine is an accelerator that is much
more active than would be assumed from its basicity.
At curing temperatures, this accelerator reacts with
sulfur to form large amounts of ammonia and hydrogen
sulfide together with certain weaker bases. If the
reaction be carried out under a cold reflux, the con-
denser will frequently become clogged with the white
solid compounds of ammonia and hydrogen sulfide
which are described by Roscoe and Schorlemmer.
The action of />-phenylenediamine in the cure is en-
tirely that of a hydrogen sulfide polysulfide accelerator.
The three above-mentioned accelerators are not
dependent on the rubber resins or proteins for their
supply of hydrogen sulfide, since this is one of their
sulfur reaction products. It is to be expected that
these accelerators will function in a deresinated or a
synthetic rubber, and the Bayer patents state that
this is true. It is also known that piperidine will cure
in a nitrogen-free rubber. Here we have a strong
base acting apparently without the aid of hydrogen
sulfide. Piperidine, however, reacts with sulfur at
temperatures lower than those used in vulcanization,
with the formation of hydrogen sulfide. Both the
sulfur reaction product and the unchanged piperidine
may then use this hydrogen sulfide to form polysulfides
with sulfur.
INORGANIC ACCELERATORS
Inorganic accelerators that function in the cure by
the removal of hydrogen sulfide the writers choose
to term "secondary accelerators," while those that
' hoe. cit.
128
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
function in the same manner as the organic polysulfide
accelerators may be classed with them as "primary
accelerators." A third class consists of those com-
pounds that are both primary and secondary accel-
erators.
I. Secondary Accelerators — Litharge, zinc oxide, etc., seem to
act no further than to form the corresponding sulfides, in con-
nection with hydrogen sulfide polysulfides.
II. Primary Accelerators — To this class belong the sulfides
and hydrosulfides of the alkali and alkaline-earth metals.
III. Accelerators That Are Both Primary and Secondary — In-
organic oxides and hydroxides function first as secondary accelera-
tors forming sulfides or hydrosulfides which then take up sulfur
and act as primary accelerators. Such accelerators are sodium
and calcium hydroxides, magnesium oxide and basic carbonate, etc.
Secondary accelerators are believed to function as
aids to organic polysulfides by breaking them up into
colloidal sulfur and the original nitrogen base. This
may be illustrated by the decolorization of polysulfide
solutions by litharge or zinc oxide. Ferric oxide does
not act as a secondary accelerator, and neither does
it readily decompose the polysulfide solutions. The
solubility of organic accelerators in sulfur and rubber
gives them much more intimate contact with hydrogen
sulfide at the time of its formation than is the case
with the comparatively large particles of litharge or
zinc oxide. Hydrogen sulfide is therefore available
for the formation of organic polysulfides before being
taken up by the. secondary accelerators. The de-
composition of a polysulfide by a secondary accelerator
regenerates the free base, which with more hydrogen
sulfide and sulfur re-forms the polysulfide. Secondary
accelerators do not act as true catalysts; once formed
into sulfides they do not react again with hydrogen
sulfide.
SUMMARY
1 — All organic accelerators are believed to function
through the formation of some type of polysulfide.
2 — Organic bases and compounds that form bases
during vulcanization are believed to form polysulfides
through the aid of hydrogen sulfide. These are termed
"hydrogen sulfide polysulfide accelerators."
3 — Thioureas, dithiocarbamates, thiurams, and
mercaptan compounds are believed to form polysul-
fides directly, or by first forming disulfides, and are
termed "carbo-sulfhydryl polysulfide accelerators."
4 — It is proposed that the function of such com-
pounds as litharge and zinc oxide may lie in the de-
composition of polysulfides into colloidal sulfur and
amines.
5 — Such inorganic compounds as sodium hydrox-
ide, calcium hydroxide and magnesium oxide are be-
lieved to function as "primary accelerators" through
the formation of inorganic polysulfides.
THE ACTION OF CERTAIN ORGANIC ACCELERATORS IN
THE VULCANIZATION OF RUBBER— III1
By G. D. Kratz, A. H. Flower and B. J. Shapiro
Falls Rubber Co., Cuyahoga Falls, Ohio
It has for some time been generally recognized that
although aniline is effective as an accelerator in the
1 Presented before the Rubber Division at the 60th Meeting of the
American Chemical Society, Chicago, 111., September 6 to 10, 1920.
absence of zinc oxide, diphenylthiourea functions but
mildly in the absence of, and strongly in the presence
of this substance. Reference to this effect has already
been made indirectly in the literature several times,
and recently Twiss1 has given curves for physical test
results which demonstrate quite clearly the effective-
ness of diphenylthiourea as an accelerator in the pres-
ence of zinc oxide. His statement that diphenyl-
thiourea is practically inert in the absence of zinc
oxide is, however, not in accord with our findings.
In a previous paper of this series2 we have shown
that in the acceleration of the vulcanization of a rubber-
sulfur mixture, the activity of one molecular part of
diphenylthiourea is less than that of an equimolecular
quantity of aniline, but equal to that of one molecular
part of aniline and one molecular part of phenyl mus-
tard oil.
Our former experiments, however, were confined to
the determination of sulfur coefficients at one cure
only. In the present instance, we desired to compare
the relative effects of aniline and diphenylthiourea
over a series of cures, and to effect this comparison
both by means of the sulfur coefficients and the physical
properties of the various mixtures and cures. Further,
it was desired to compare mixtures which contained
zinc oxide, as well as the rubber-sulfur mixtures
previously employed.
In the experimental part of this paper we have given
results obtained with six different mixtures, as follows
a rubber-sulfur control, a control which contained zinc
oxide, and similar mixtures which contained either one
molecular part of aniline or diphenylthiourea. All
of the mixtures were vulcanized for various intervals
over a wide range of time. After vulcanization, com-
parisons of sulfur coefficients and physical properties
were made.
Summarizing these results briefly, we found that, in
a rubber-sulfur mixture, the accelerating effect of
aniline is considerably greater than that of diphenyl-
thiourea, when judged" either by sulfur coefficients or
on the basis of the physical properties of the vulcanized
mixtures. In mixtures which contained zinc oxide,
however, the reverse was found to be true, and di-
phenylthiourea was more active than aniline when
judged by either of the above criteria. It was also
evident that in the case of the mixtures which con-
tained zinc oxide, although the tensile strength of the
mixture which was accelerated by diphenylthiourea
increased more rapidly than in the case of the mixture
accelerated by aniline, the same maximum tensile
strength was attained by each. The sulfur coefficients
at their respective maxima were practically identical.
While the maximum tensile strength of the rubber-
sulfur mixture which was accelerated by aniline was
the same as that obtained when zinc oxide was present
in the mixture, it was attained only at a much higher
sulfur coefficient. Lastly, it was also found that the
tensile strengths of the mixtures that contained zinc
oxide and which were accelerated by either aniline
or diphenylthiourea, particularly the latter, were in-
i J. Soc. Chem. Ind., 39 (1920), 1251.
' This Journal, 12 (1920), 317.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
129
creased tremendously during the first part of the vul-
canization, and at very low sulfur coefficients. This
would indicate the possibility of certain substances
(accelerators) increasing the physical properties of
a vulcanized mixture without greatly affecting the
sulfur coefficient.
This point is of interest as it already has been noted
by ourselves,1 Cranor,2 and others, that with mixtures
which contain zinc oxide and a strong organic acceler-
ator, the correct (or optimum) cure is obtained at
abnormally low sulfur coefficients when compared
with those obtained for unaccelerated mixtures. No
explanation has been offered for this phenomenon.
Bedford and Scott,3 however, regard diphenylthiourea
as the aniline salt of phenyldithiocarbamic acid after
H2S has been liberated. This salt is extremely un-
stable, owing to the weakly basic properties of aniline,
and in this respect, according to Krulla,4 is unlike the
metallic salts of the same acid. In this connection,
it is particularly pertinent to note that Bruni5 has
recently found the zinc salts of the mono and disub-
stituted dithiocarbamic acids to be violent accelerators.
It is quite possible, then, that such a salt may be formed
during the vulcanization process in mixtures which
contain both diphenylthiourea and zinc oxide;6 and
that, irrespective of its action as an accelerator, the
zinc portion of such a salt may be responsible for the
physical improvement imparted to the mixture.
Our present results, moreover, particularly when
interpreted with the assistance of the excess sulfur
coefficients obtained for the various mixtures at differ-
ent times of cure, show that when aniline is employed
as the accelerator in the presence of zinc oxide, the
effect of the latter substance is manifested almost en-
tirely in the physical properties of the mixture. When
aniline is replaced by diphenylthiourea the reverse is
true, and the activity of the original substance as an
accelerator is greatly increased when measured by
either the sulfur coefficients or physical properties.
In the latter instance, then, the zinc oxide most proba-
bly either assists in the decomposition of the diphenyl-
thiourea to a more active substance, or combines with
the decomposition or alteration products of the original
substance with the formation of a zinc salt, which is
responsible for the increase both in the sulfur coefficients
and tensile strength of the mixture. Our results with
aniline as the accelerator, however, do not indicate
the formation of such a salt.
Thus, in the presence of zinc oxide, the activity of
aniline and diphenylthiourea as accelerators appears
to be of a different nature. Evidently, an acid sub-
stance, probably a thiocarbamic acid, capable of re-
acting with zinc oxide, is formed as one of the de-
composition products of diphenylthiourea. The ex-
cess accelerating activity is attributed to this zinc salt.
' This Journal. 11 (1919), 30; Cliem. &■ Met. Eng., 20 (1919). 418.
'India Rubier World. 61 (1919), 137.
' This Journal, 12 (1920), 31.
' Ber., 46, 2669.
« Brit. Patents 140,387 and 140,388.
8 The action of diphenylthiourea with zinc oxide is apparently similar
to the action of the natural accelerator with magnesium oxide, as pointed
out in a previous paper (This Journal, 12 (1920), 971], In both cases the
oxide serves in a contributory capacity rather than as a primary accelerator.
It is obvious that no one oxide will activate all accelerators equally well
When aniline is employed as the accelerator, there is
no evidence of such salt formation.
EXPERIMENTAL PART
The present experiments were designed to effect a
comparison of the sulfur coefficients and physical
properties of representative mixtures when accelerated
by 0.01 gram-molecular quantities of either aniline or
diphenylthiourea. The six following mixtures were
employed for this purpose, and each was vulcanized
for a series of cures:
A — Rubber-sulfur control
B— Rubber, sulfur, and aniline
B-I — Rubber, sulfur, and diphenylthiourea
C — Rubber, sulfur, and zinc oxide control
D— Rubber, sulfur, zinc oxide, and aniline
D-I — Rubber, sulfur, zinc oxide, and diphenylthiourea
The quantities of each substance employed in these
mixtures are shown in Table I. The amounts of
Table I
Mix- Mix- Mix- Mix- Mix- Mix-
ture ture ture ture ture ture
Ingredient A B C D B I D-I
Rubber 100.00 100.00 100.00 100.00 100.00 100.00
Zinc oxide ... 100.00 100 00 ... 100.00
Sulfur 8.1 8.1 8.1 8.1 8.1 8.1
Aniline 0.93 ... 0.93
Diphenylthiourea ... ... ... 2.28 2.28
aniline or diphenylthiourea added to these respective
mixtures represent 0.01 gram-molecule of the acceler-
ator for each 100 g. of rubber in the mixture. Other-
wise, the same general method of procedure was adopted
in the course of this work as in that previously reported
in Part I.1
The rubber used was of good quality, first latex,
pale crepe, a different sample of the lot used in our
former experiments. The various mixtures were mixed
on the mill, vulcanized, and tested in the same manner
as before. The physical properties of the vulcanized
samples were determined on a Scott testing machine
of the vertical type, with the jaws opening at the rate
of 20 in. per min. A recovery period of 48 hrs. was
allowed before physical tests were made. Combined
sulfur was estimated by our method previously re-
ported in detail.2
The various mixtures were vulcanized at 141.5° C.
for different intervals of time up to 240 min.3 The
sulfur coefficients and physical properties of the dif-
ferent cures for each mixture were determined. These
results are given in detail in Table II and shown graph-
ically in Fig. 1. Generally speaking, the results ob-
tained were in good agreement, and fairly smooth
curves for physical properties were obtained.4
For brevity and clearness, the results obtained for
each mixture have been considered separately.
mixture a — This mixture of rubber and sulfur
served as a control only.
mixture b — Comparing Curves A and B, aniline
not only acts as an accelerator, but also slightly in-
creases the physical properties of a rubber-sulfur mix-
ture after vulcanization.
i This Journal, 12 (1920). 317.
'India Rubber World 61 (1920). 356.
1 In the experiments described in Parts I and II vulcanization was
carried on at a temperature of 148° C.
* Satisfactory physical test results for representation graphically are
obtainable with considerable difficulty. We have found it necessary, par.
ticularly when seeking results for stress-strain diagrams, to employ three
men, one to operate the machine and two to take readings.
li'.O
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
-Mixture A — n
Table II
: Vulcanized at 141.5°
. — Mixture B — .
-Mixture D — .
-—Mixture B-I^
, — Mixture D-I^
£-
-J
w
a*.
E
30 0.794 .. .. 1.126 545 1180 1.005
45 0.856 279 1250 1.317 1019 1170 1.055 306
60 1.038 .. .. 1.583 1228 1120 1.207 592
75 1.090 494 1220 1.898
90 1.531 709 1150 2.482 1621 1060 1.558 1041
120 2.089 871 1180 3.351 2046 1100 1.765 1815
150 2.236 1159 1130 4.033 2410 1100 2.237 1950
180 2.470 1521 1130 4.939 2670 1030 2.620 2032
210 3.179 1842 1100 5.264 2566 970 3.340 2184
240 3.751 2124 1060 6.268 2131 910 3.615 1978
1 Test pieces did not break.
mixture c — The inclusion of zinc oxide in Mixture
C was found to have little or no effect upon the sulfur co-
efficients when compared with the results obtained for A.
mixture r> — The sulfur coefficients obtained for this
mixture were found to be uniformly lower than the cor-
responding cures of B. Moreover, the maximum tensile
strength of D was attained at a much lower sulfur co-
efficient than in the case of B, although this maximum
tensile strength was almost the same in both instances.
30 60 90 /20 /SO /SO ZIO Z40
T/ME OF VULCANIZATION IN MINUTES
Fig. 1
mixture b-i — From the curves it is seen that in a
mixture of rubber and sulfur the activity of diphenyl-
thiourea is much less than that of aniline, when judged
by either sulfur coefficients or physical properties.
In fact, both the tensile strengths and final lengths
1.434
540
710
0.913
(')
1210
1.603
2210
8?0
680
1.490
1366
770
1.063
{*>
1360
1.912
2381
780
750
1.838
1819
770
1.335
<>1
1260
2.297
2442
790
1968
750
1,609
533
1230
2.623
760
2.382
2350
720
1.953
789
1230
2.962
2730
830
780
2.801
2808
780
2.496
1053
1210
3.755
2699
7 711
760
3.266
2721
770
3.109
1303
1150
4.521
2619
750
750
4.226
2663
740
4.027
1779
1110
5.357
2020
691)
760
4.806
2245
700
4.730
2021
1080
6.379
1118
5 10
730
5.564
1837
660
5.624
2362
1050
7.079
754
440
of B-f are practically the same as those of its control
mixture, A. The sulfur coefficients of B-I, however,
were decidedly higher than those of A, and, contrary
to the statement of Twiss,1 we cannot regard diphenyl-
thiourea as practically inert as an accelerator in a
mixture of rubber and sulfur only.
mixture d-i — The sulfur coefficients for D-I were
considerably higher than those of any of the other
mixtures; although the maximum tensile strength was
of the same magnitude, it was reached in shorter time.
The curves showing the comparison of the final
lengths are given in Fig. 1. It is obvious that the
physical manifestations, especially in Mixtures D and
D-I, are found in the tensile strength, rather than in
the final lengths, of the vulcanized mixtures. Con-
sequently, the tensile strengths of such mixtures, par-
ticularly until maximum tensile strength was reached,
are better indications of the point known as the "op-
timum cure" than are the loads required to effect a
given extension.2
The effect of the two accelerators, aniline and di-
phenylthiourea, have been summarized in Fig. 2,
wherein with Mixtures A and C as controls, the excess
sulfur coefficients were plotted against their times of
vulcanization. A comparison of the curves for B
and D show that, when judged by sulfur coefficients
only, the activity of aniline as an accelerator is in-
creased in the absence of zinc oxide.3 On the other
hand, a comparison of B-I and D-I shows that di-
phenylthiourea is approximately twice as active in the
presence of zinc oxide than when this substance is
absent from the mixture. In fact, the difference be-
tween the curves for B-I and D-I is so great that our
results indicate the formation of a new and more ac-
tive accelerator than the original diphenylthiourea,
or its decomposition products. It is not impossible
that the decomposition products of diphenylthiourea
react with the zinc oxide in the presence of sulfur to
form varying amounts of a zinc salt of a dithiocarbamic
acid. Salts of the latter type have already been men-
tioned as violent accelerators. On the other hand,
1 hoc. cit.
5 As Whitby has stated ("Plantation Rubber and the Testing of Rub-
ber," 1920, p. 395, Longmans, New York), complete stress-strain diagrams
are probably required for an accurate determination of this point.
3 The sulfur coefficients and physical properties of Mixture D were less
concordant than those of any of the other mixtures.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
131
the fact that the curve for Mixture D, which contains
aniline and zinc oxide, falls below that of B, which
contains aniline but no zinc oxide, argues against the
formation of diphenylthiourea (and the subsequent
formation of the zinc salt of its decomposition or con-
version products) from the aniline originally present
in the mixture.
S\
,
T
**
>'
i
,-
,
""f
i
■ -
5
r"
^
>
K'
k
-*•
■ —
M-l
*
f'
<1
r
p
^
3-
" <
5
^
J«-
Fie. 2
The preceding observations are probably applicable
to mixtures of the same general type and composition
as employed in the course of this work only.
CONCLUSIONS
(1) In a rubber-sulfur mixture, the activity of
aniline in the acceleration of vulcanization is much
greater than that of a molecularly equivalent quantity
of diphenylthiourea.
(2) In mixtures which contain zinc oxide, diphenyl-
thiourea is more active than aniline.
(3) In mixtures accelerated by aniline, either with
or without zinc oxide, the same maximum tensile
strength is obtained, accompanied by a higher sulfur
coefficient in the absence of zinc oxide than when this
substance is present.
(4) Mixtures which contain zinc oxide, and which
are accelerated by either aniline or diphenylthiourea,
show large increases in tensile strength in the early
stages of the vulcanization.
(.5) Mixtures which contain zinc oxide and which
are accelerated by either aniline or diphenylthiourea,
attain the same maximum tensile strength at ap-
proximately the same sulfur coefficients.
(6) There is apparently no general relation between
the physical properties and sulfur coefficients of ac-
celerated mixtures.
CELLULOSE MUCILAGE'
By Jessie E. Minor
Emerson Laboratory, Springfield, Massachusetts
During the past year, Schwalbe and Becker2 have
published some very interesting conclusions as to
the exact chemical changes which occur in the making
of paper from wood and cotton, based on laboratory
experiments, and some practical applications of these
1 Presented at the Cellulose Symposium of the Division of Industrial
and Engineering Chemistry at the 60th Meeting of the American Chem-
ical Society, Chicago, 111., September 6 to 10, 1920.
= Z angew. Chem., 33 (1920), 14, 57, 58.
facts. These conclusions seemed to be in such com-
plete accord with conclusions reached earlier by the
author that it was deemed worth while to present this
summary of both lines of work.
Schwalbe and Becker have assumed that the first
step of the decomposition of cellulose consists in the
formation of an insoluble hydrocellulose or oxycellulose
which has properties very similar to the hemicellu-
loses of wood incrustation, in that it reduces Fehling's
solution and is in general unstable and reactive. De-
composition of this hydrocellulose or oxycellulose or
of the hemicellulose produces a mucilaginous sub-
stance which has a higher copper number than the
hydro-, oxy-, or hemicellulose from which it was made,
and which constitutes the cementing material of the
parchment paper. If the decomposition is carried
too far, the mucilage is decomposed and we get sugars
or acids.
In our previous publications we have assumed that
pure cellulose exercises a marked positive residvial
valence by means of which it strongly adsorbs hy-
droxyl ions from the solution, the adsorption being
greatly aided by mechanical treatment. These
hydroxyl ions, by means of their close proximity to the
cellulose, are able to hydrolyze the cellulose molecule
with increasing velocity into a series of products of
which the earlier ones are insoluble and mucilaginous,
the latter ones soluble dextrins or acids. Hauser and
Herzfeld have shown that the first product, which
Schwalbe and Becker call hydrocellulose, is a mix-
ture of cellulose with more or less easily soluble dex-
trins, for if the pulp is thoroughly washed with hot
water the dextrin is washed away, the copper number
is reduced, and the development of mucilage is re-
tarded.
If these reactive dextrins were adsorbed by pure
cellulose, they would without doubt catalyze the de-
composition of the cellulose, giving an adequate ex-
planation for the increase in reaction velocity as de-
composition proceeds. The first evidence of the pres-
ence of these dextrins would be merely the increased
reactivity of the cellulose but, since they are muci-
laginous by nature, we should gradually get the in-
creased slowness of the pulp and the turbidity of the
solution due to aggregates of cellulose and dextrin.
When the insoluble cellulose became completely
changed to soluble dextrin or sugar, the solution would
lose its turbidity, but this would not occur until after
all the fiber structure had been destroyed. Schwalbe
and Becker say that when a mucilage is formed by
beating, a reducible substance must be present in
the original material. In other words, the earlier
decomposition reaction must be so catalyzed by the
adsorbed dextrins disseminated throughout the pulp
mass as to occasion a rapid formation and an accumula-
tion of mucilage at the time when, by drying, reac-
tion ceases.
Another evidence for this adsorption theory is in
the colloidal properties of the mucilaginous product.
If this mucilage is allowed to dry slowly in the air,
one obtains a horny, rather viscous mass which swells
quite decidedly in water-saturated air, much more
132
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
than ordinary cellulose. This is probably related to
the larger surface exposed to adsorption when in the
colloidal state. If the mucilage is excessively dried,
then the power to take up water goes back to the
normal value for cellulose, and if it is then pressed,
as hard ironed or pleated cloth or calendered paper,
then the adsorption is still further decreased.
Further interesting evidence of the variation in
the nature of these decomposition reactions is shown
by the effects of cold and hot water upon cellulose.
When a wood pulp lies in cold water, the slowly formed
dextrins are firmly adsorbed by the cellulose, thus
forming the insoluble, reactive aggregate which gives
slowness to the stock. Mechanical beating increases
the velocity of the reaction to such an extent that the
increase in copper number is quite apparent, but
washing decreases the copper number by slowly re-
moving the more rapidly formed and, therefore, less
firmly adsorbed soluble products. Hot water treat-
ment so hastens hydrolysis and weakens adsorption
that mucilaginous products are destroyed more rapidly
than made. An interesting experiment w hich bears
on this point was recently made in our laboratory. A
part of a sample of good parchment pulp, which had
been merely disintegrated in a beater, was triturated
in a mortar for 1.5 hrs., then the triturated and the
nontriturated portions were washed with water
which was neutral to methyl red in filter papers which
had also been washed neutral to methyl red. The
triturated pulp was decidedly more alkaline than the
original sample and, when washed with hot, neutral
water, the alkalinity increased. On washing later
with cold, neutral water, both pulps became acid to
the indicator, but on again washing with hot water,
more alkalinity was developed. This alternating of
acidity and alkalinity could be continued for some
time. Apparently, hot water developed hydration
enough more rapidly than it could be washed out
through a filter paper to have its alkalinity apparent
to this sensitive indicator, whereas the more slowly
formed hydrate of the cold water is washed out as
quickly as formed. Incidentally, since, after triturat-
ing for 1 . s hrs., the pulp tested more alkaline than
before, and this in the presence of an indicator which
can easily detect the excess alkalinity of hydration in
hot water, it would seem reasonably certain that
acids are not developed by beating except in the pres-
ence of an oxidizing agent like bleach.
Schwalbe and Becker showed that, if pulp is allowed
to remain in hot water, 100° C, for 24 hrs., pulp
degradation will proceed so far that, after subsequent
beating, the copper number is decreased and the
strength of the paper made from the pulp very much
lessened. The making of paper from wood or cotton
would then consist in so controlling the decomposi-
tion reactions as to get the minimum of soluble sugars
and acids, which constitute a complete loss of ma-
terial, and such a ratio between mucilage and unde-
composed fiber as will give the maximum strength
and all other desired physical properties to the fin-
ished paper. For a plain paper, the maximum fiber
length and strength and just enough mucilage to hold
the fibers together are desired, whereas for a parch-
ment it is essential that the mucilage be sufficient in
quantity to give grease-proof qualities to the paper,
and, with this amount of mucilage, it is possible to
sacrifice considerable fiber strength and still main-
tain paper strength.
Schwalbe and Becker note that pulps with a high
copper number, that is, pulps containing a large per
cent of reactive material, beat to mucilage more
easily than those with a low copper number. They
were able to show that pulps, which in practice are
known to make good parchment papers, always con-
tain a relatively high copper number, whereas the
softer wood pulps, from which the incrustation has
been removed, and cotton, neither of which make
good parchment paper, have a relatively low copper
number. If the cementing mucilage must be made
at the expense of the pure cellulose of the fiber, it
would be impossible by beating ever to obtain enough
to make a grease-proof sheet, since its degradation
occurs probably as rapidly as its formation. There-
fore, for parchment making, the papermaker chooses
a pulp which is rich in the reactive hemicelluloses,
that is, one in which the wood fiber incrustation has
been attacked just sufficiently to cause it to yield easily
to the beating process, but not sufficiently to make it
soluble, then beats it until he has obtained the maxi-
mum mucilage formation consistent with the maximum
fiber disintegration allowable. In experiments per-
formed in the laboratory by Schwalbe and Becker
and in our laboratory, it has been shown that parch-
ment quality can be developed in a pulp of low copper
number by treating it with acid or an acid-forming
salt previous to beating, so that the hydrocellulose
formation is accelerated and the subsequent mucilage
formation increased. In an experiment with a sul-
fite pulp of low copper number, the time required to
reach a standard slowness was reduced by acid soft-
ening from 3.75 hrs. to 20 min. Under the same
treatment a parchment pulp with a high copper num-
ber required 2 hrs. 10 min. to reach the same
slowness. Mullen pop tests upon hand sheets made
from this acid-treated pulp show a decided increase in
strength over those made from the same pulp, not
acid treated, and the blistering quality of the paper is
decidedly developed by this treatment. So far as
known, this treatment has not been tried on a com-
mercial scale and the engineering details have not
been worked out, but it would seem that it would
make it quite possible to make good, blistering, grease-
proof, parchment paper from such pulps as that re-
covered from old paper. The practical difficulties
are in the standardization of the exact conditions for
the acid treatment, since excessive acid hydrolysis
would also accelerate mucilage destruction.
A German patent has been issued for a process of
treating waste papers with chlorine and water, enough
partially to decompose the cellulose, then grinding
under water and incorporating this mass with paper
pulp to make a close, strong sheet of paper. It would
seem as if a similar mixture would also be satisfactory
to use as a waterproof coating for papers.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
133
According to Schwalbe and Becker, another evi-
dence for the colloidal nature of cellulose mucilage is
in its ready splitting of metal salts and adsorption of
the base. This is to be expected from the more strongly
negative residual valence of the hydrolyzed product.
The accumulation of residual valence over the surface
of the molecule very largely favors the colloidal state
by its repulsion of its own particles carrying like
charges. Particles carrying opposite charges, like
metal ions, are readily adsorbed, and the rate of ad-
sorption would increase with increased hydration and
hydrolysis. A practical application of this is found
in the partial conversion of the cloth of gas mantles
into a hydrolyzed product before impregnation with
metals, a treatment which, because of increased adsorp-
tion, causes a better retention of metal.
When a pulp is treated with alum, the liquid very
quickly becomes acid, but the acidity is very readily
washed out, leaving an alkaline pulp. This is due to
a splitting of the salt and an adsorption of the free
base by the fiber, leaving the free acid in the solution.
The power of splitting salts and adsorbing their bases
increases as the amount of mucilage in the pulp is
increased, and this is further evidenced by the in-
crease in the colloidal properties of the cellulose on
hydrolysis.
This theory would also explain why, when mor-
danting with the salt of a weak acid like an acetate,
the presence of some strong acid, like sulfuric, which
aids the hydrolysis of the fibers, gives a better coloring.
The adsorption of metal very markedly weakens
the strength of the paper made from it, no doubt by
diverting some of the intermolecular affinities to
the holding of the metal. By means of this loss of
strength, Schwalbe and Becker were able to deter-
mine that papers impregnated with as little as 0.25
per cent of magnesium chloride and hung in an
air which was partially saturated with moisture, were
able to split the salt and adsorb the metal, and that
the amount of metal adsorbed depends on the amount
of moisture present. The greatest effect was with an
air which contained decidedly less moisture than
enough to saturate it. The function of the air is, no
doubt, to aid hydrolysis of both salt and fiber.
Through this theory of the easy hydrolysis of salt
and fiber in moist air, one can explain the fact that
loose piles of freshly colored, unwashed fibers take on
a deeper color than do fibers not so spread out. The
loss of weight experienced in dyeing cotton goods may
be attributed to the further fiber hydrolysis forming
some soluble products. In steaming under pressure
with basic dyes, we find not only the possible forma-
tion of a dye-fixing hydrocellulose arising from the
hydrochloric acid of the dye, but also oxidation through
atmospheric oxygen in the steam, which would give
reactive oxycellulose.
Although acid presence aids mucilage formation
and dyeing, it must always be used with care, inasmuch
as excess causes loss of strength of the finished product.
Looking at the matter from a purely theoretic stand-
point, it would seem as if it would be much safer not
to attempt acid treatment on the fiber, the strength
of which it is desired to preserve, but to impregnate
such a product with a mucilage which has been sepa-
rately prepared, possibly using it as a part of the size.
SUMMARY
In the foregoing the author has attempted to de-
velop the following propositions:
(1) The first step in the decomposition of cellulose
forms a mucilaginous soluble dextrin which easily
reduces Fehling's solution. These dextrins, as soon
as formed, are adsorbed by pure cellulose, thus form-
ing a reactive insoluble aggregate, called hydrocellulose.
(2) Mucilage differs from hydrocellulose in the
larger per cent of soluble adsorbed dextrins present.
(3) These adsorbed dextrins serve to catalyze the
hydrolysis of cellulose.
(4) Complete hydrolysis leaves only soluble dextrins.
(5) Mucilage, possibly through its colloidal nature,
has a greater power of adsorbing water than has pure
cellulose.
(6) Cold water immersion causes a slow hydrolysis.
Hot water hastens hydrolysis and weakens adsorption,
so that mucilaginous products are destroyed as rapidly
as formed.
(7) With methyl red as an indicator, it is possible
to detect the increase in the alkalinity of the hydra-
tion of pulp.
(8) Pulps with an original high copper number
beat to mucilage more easily than those with a low
copper number, owing to the larger amount of catalyst
present.
(9) The copper number of bleached pulp can be
increased by a careful acid treatment prior to beating.
(10) Cellulose mucilage will split a salt and adsorb
the metal ion more easily than pure cellulose, owing to
the more colloidal state.
(11) Moisture or acid treatment aids dyeing by
forming mucilage.
THE PREPARATION AND TECHNICAL USES OF
FURFURAL1
By K. P. Monroe
Color Investigation Laboratory, U. S. Bureau of Chemistry,
Washington. D. C.
Although it has long been known that furfural (2-fur-
aldehyde)
HC CH
(4) II II (3)
HC C— CHO
(5) \/(2)
O
(1)
may be prepared by distillation of pentose or pentosan
containing substances2 with acid, and this has indeed
1 Presented before the Dye Section at the 59th Meeting of the Ameri-
can Chemical Society, St. Louis, Mo., April 14, 1920.
* Dobereiner, Ann., 3 (1832), 141; Stenhouse, Ibid., 35 (1840), 301;
Fownes, Ibid., 54 (1845), 52; v. Babo, Ibid., 85 (1853), 100, Volckel, Ibid.,
86 (1853), 65; Schwanert, /«</., 116 (1860), 258; Stenhouse, Ibid., 166 (1870),
199; Gudkow, Z. Client., 1870, 360; Williams, Jahresb., 1872, 770; Heill,
Ber„ 10 (1877), 936; v. Meyer, Ibid., 11 (1878), 1870; Hill, Am. Chem. J.,
3 (1881), 36; Stone and Tollens, Ann., 249 (1888), 227; Gunther, de Chal-
mot and Tollens, Btr., 26 (1892), 2569; Gross, Bevan and Smith, Ibid.,
28 (1895), 1940; Tollens, Ann., 286 (1895), 301; Kruger and Tollens, Z.
angew. Chem., 9 (1896), 44; Semmler, Ber., 39 (1906), 731; Erdmann and
Schafer, Ibid., 43 (1910), 2401; Gildemeister and Hoffmann, "Die aterischen
Ole," Leipzig, 1910, p. 448.
134
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
been the basis for quantitative estimation of pentosans ,*
the published methods2 seem highly unsatisfactory on
account of the low yields obtained, and on account of
the tedious processes involved in extraction of the
aldehyde from its dilute aqueous solution by immis-
cible solvents.3 The potential value of furfural in
chemical industry, which will be discussed later, led
to the present investigation of corncob pentosan4'5
as a promising source and to the following method,
which yields as pure furaldehydc approximately 26
per cent of the weight of the solids contained in corn-
cob adhesive, and involves very simple and economical
operations for the production and subsequent separa-
tion of the aldehyde from dilute aqueous solution:
Five hundred grams of corncob adhesive, prepared
according to the method of La Forge and Hudson, *■'
and consisting of a concentrated aqueous suspension
of gums rich in pentosan, were thoroughly mixed in
a 3-liter round bottom flask with a solution of sulfuric
acid prepared by mixing 150 cc. of concentrated sul-
furic acid (sp. gr. 1.84) and .500 cc. of water. To
prevent foaming during the subsequent heating opera-
tion, a lump of paraffin was added and the liquid
heated to boiling. Since preliminary experiments had
indicated the desirability of removing furfural from
the reaction mixture as rapidly as it is formed, a vig-
orous current of steam was passed through the mix-
ture; the rate of steaming and the flame under the
flask were so adjusted that the volume of liquid in the
flask remained approximately constant while the dis-
tillate was collected at the rate of 15 to 20 cc. per
minute. After five 800-cc. portions of distillate had
been obtained the operation was suspended. In the
meanwhile the portions of distillate were filtered to
remove traces of paraffin and fractionally distilled
from a flask provided with an efficient fractionating
1 Brown, "Handbook of Sugar Analysis," Wiley and Sons, 1912,
p. 372.
* For example, the directions given in Beilstein. "Organische Chemie,"
3, 3rd Ed., and by Emil Fischer, "Anleitung zur Darstellung organischer
Praparate," Braunschweig, 1908. Bran is the source of pentosan; the
yields reported are 3 and 2.5 per cent, respectively.
3 European patents have been issued on the technical preparation
of furfural by treatment of cellulosic material with steam and acid at
temperatures below 150°. This process has been operated in France and
Germany (Meunier, and Beckmann and Dehn. hoc. cit). The price quoted
on French technical furfural is 20 francs per kilo, and two French firms
have stated in private communications to the author that furaldehyde is
available in any quantity desired.
Fr. Patent 446,871, Dec. 17, 1912, process for simultaneous prepara-
tion of methylene and furfural from cellulosic material, issued to V. Raisin;
Swedish Patent 40,482, Dec. 16, 1913. process for production of furfural from
cellulosic material, issued to H. O. V. Bergstrom; Fr. Patent 464.608, March
26, 1914, process for the separation and recovery of volatile acids, methylated
products and furane derivatives from cellulosic material, issued to A. and E.
I.ederer; Fr. Patent 485.967, Feb. 26, 1918, improvements on the method of
manufacturing pure furfural from cellulosic material, issued to E. Ricard.
4 Corncobs have long been known to be rich in xylan, and consequently
have been utilized for the preparation of xylose. Stone and Lotz, Am,
Chem. J., 13 (1891), 348; Hudson and Harding, J. Am. Chem. Sue, 40
(1918), 1601; La Forge and Hudson, This Journal, 10 (1918), 925; Mon-
roe, J. Am. Chem. Soc, 41 (1919), 1002.
6 Another agricultural waste product which suggests itself as a promis-
ing source is cottonseed hulls, which are known to be rich in xylan. Hudson
and Harding, J. Am. Chem. Soc. 39 (1917). 1038.
« hoc. cit.; La Forge, U. S. Patent 1,285,247. This method involves
the separation and partial hydrolysis of pentosans contained in the cobs
by extraction with water at 150°. The aqueous solution of gums so obtained
is then evaporated to the desired concentration.
7 The author wishes to ejrpress his gratitude to Dr. La Forge for kindly
furnishing the corncob adhesive.
column.1 It is a somewhat anomalous fact in view
of the high boiling point of furfural (162°) that, by
careful fractionation of the very dilute solution which
constitutes the original distillate, nearly all the alde-
hyde is obtained in the first 100 cc. of distillate, boiling
between 97.5° and 100°. After fractionation, the
furfural phase (20 cc.) in the combined distillates was
separated from the supernatant saturated aqueous
solution,2 which was returned to the flask for re-
fractionation. The combined portions of the furfural
phase were then fractionated from a small distilling
flask. After rejection of the first 2 or 3 cc. of distillate.
which contained water, the thermometer rose rapidly
to 161.5°, and the remainder boiled between 161. 5C
and 162 °,3 which indicated a very satisfactory degree
of purity. An average yield of 53 g. (or 26 per cent
of the solid material contained in the adhesive) of
pure furaldehyde was so obtained.
While furfural has hitherto chiefly been known as
a rare organic chemical, on account of difficulties of
preparation and the consequent high price, numbers
of uses are already known, and the future field for de-
velopment seems very promising if it becomes avail-
able in quantity and at less cost. An interesting
portion of this field is the one concerning the dye in-
dustry, since at least two useful and promising direct
dyes may be obtained by simple interaction of fural-
dehyde with alkali sulfides and hydroxides.4,5'6 Hard
resins similar to the well-known Bakelite and Conden-
site may be obtained by the condensation of furfural
1 The ready separation of furfural from dilute aqueous solution by
column distillation is mentioned in the European patents fLoc. cit.). This
method is not given in any of the hitherto published directions for labora-
tory preparation although it has evidently been recognized that simple
distillation from aqueous or saturated salt solution concentrates the alde-
hyde in the first portions of distillate. On the laboratory scale the effi-
ciency of a bare column in fractionation of relatively low boiling mixtures
is known to be low on account of the comparatively small heat loss to the
surrounding air; this was partially compensated by substitution of an in-
verted Allihn condenser with bulbs loosely packed by broken glass. A
rapid current of air was drawn through the jacket in a direction counter
to that of the stream of vapor.
2 The mutual solubility of water and furfural has been investigated
by Rothmund, Z. physik. Chem., 26 (1898), 454. By interpolation of these
data, the saturated aqueous phase at room temperature (25°) is seen to
contain approximately 8 per cent furfural, while the saturated furfural
phase contains approximately 5 per cent water.
'Compare Schiff, Ann., 220 (1883), 103; Bruhl, Ibid., 236 (1886), 7.
The freezing point of pure furfural is given by Walden, Z. physik. Chem..
73 (1910), 261, as —36.5".
* Austrian Patent 72,235, August 15, 1915, process for manufacture
of a dyestuff from furfural, issued to A. and E Lederer. One dye obtained
according to the specifications of this patent by interaction of furfural and
sodium sulfide is a direct dye, fast to wool and silk, and very readily gives
shades ranging from light terra cotta to deep seal-brown. The dye
obtained by interaction of furfural with ammonium hydrosulfide is claimed
by the produced patentees to be fast to wool, silk, and cotton.
s D. R. P. 264.915, March 15, 1913. process for the preparation of baths
which dye animal and vegetable fabrics direct orange or reddish brown,
issued to A. and E. Lederer. These dyes are obtained by interaction of
furfural and alkalies. Cotton absorbs the dye very slowly; yellow shades
may be obtained by after-treatment in an acid bath.
6 Unfortunately the analog of malachite green which is obtained by
condensation of furfural and dimethylaniline has litue promise as a dye
stuff, since it is not fast to light. Other interesting color bases have been
prepared by condensation of furfural with aromatic amines: Stenhouse.
Ann., 156 (1870), 199; Schiff, "Ueber Farbstoffbasen aus Furfurol," Ibid.,
201 (1880), 355; 239 (1887), 349; de Chalmot, Ibid., 271 (1892), 11; Ehrhardt.
Ber , 30 (1897), 2012; Knovenagel, Ibid., 31 (1898), 2613; Zincke and Muhl-
hausen, Ibid., 38 (1905), 3824; Dieckmann and Beck, Ibid., 38 (1905), 4122;
J. prakt. Chem., [2] 72 (1905), 555; Carletti, Zentr., II, 1906, 825, Konig.
J. prakt. Chem., (2) 88 (1913), 193.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
135
with phenols.1 By interaction of furfural with aniline
alone or with acetone in the presence of alkalies, soluble
resins are obtained which may prove useful in the var-
nish industry.2 Furfural has also found use as a
solvent and insecticide.
FURTHER STUDIES ON PHENOLIC HEXAMETHYLENE-
TETRAMINE COMPOUNDS'
By Mortimer Harvey and L. H. Baekeland
Laboratory of the Department of Chemical Engineering,
Columbia University, New York, N. Y.
Received May 12, 1920
The production of resins or resinoid substances of
the Bakelite type4 by the interaction of phenols with
compounds containing an active methylene group
has, of late, acquired considerable importance in the
industry of coal-tar derivatives. The increasing num-
ber of applications of these products in the most
diversified fields is stimulating research in many
directions. That this industry was born and de-
veloped in the United States, which to-day is still
the leader in this branch of chemical industry, adds
interest to any subject of research which directly
or indirectly may throw light on the unusually com-
plicated chemistry of this subject.
The theoretical interpretation of the different phases
of the Bakelite reaction is not by any means an easy
one, and considerable additional research work will
be required before permitting ourselves to do much
beyond guessing at what really happens. In the
meantime, the careful study of the formation of
intermediate products can render us considerable
help in this subject. Among these intermediate
products, the further advances are amorphous mix-
tures which are not amenable to the usual methods
of chemical purification or isolation. Therefore, it is
more natural to start first with the intermediates
which are well-defined crystalline bodies of which
the chemical composition can be determined by well-
established methods. The present research work
was, therefore, confined to some of the first phases
of the reaction, and more particularly to such bodies
as are liable to form when ammonia is used in the
process, either as such or in the shape of hexamethylene-
tetramine.
In the formation of these products of the Bakelite
type the methylene-containing body may be com-
mercial formaldehyde solution — known as formalin,
formol, etc. This commercial product is practically
a mixture of several bodies containing active methylene
groups, as, for instance, methylal, formaldehyde, the
polymers of formaldehyde, their hydrates, etc. The
reaction is favored by the addition of so-called con-
densing agents, or catalysts — whatever that may
mean. Acids, salts, and alkalies have been used for
this purpose. In some cases where particular effects
' Beckmann and Dehn, Silzb. Akad. Wiss., Berlin, 1918, 1201; Clum.
Abs., 14 (1920), 642.
2 Meunier, "Application du Furfurol a la fabrication de resines a ver-
nis," Mai. grasses, 9 (1916), 4516.
3 Submitted by one of authors in partial fulfilment of the requirement
for the degree of Doctor of Philosophy in the Faculty of Pure Science,
Columbia University, New York. N. Y.
• These substances are also known under other trade names, as for
nstanee, Coadens ite, Resinit, Sipilite, Redmanol, etc.
have to be obtained, ammonia is preferable. If
ammonia is added to formaldehyde or to mixtures
of phenol and formaldehyde, the ammonia disappears
immediately and becomes hexamethylenetetramine:
N
/
CH2
./
./
\
/
CH2
\.
CH2
\
CH,
so that all these reactions wherein formaldehyde and
ammonia are used conjointly can be repeated by the
direct use of hexamethylenetetramine. But in pres-
ence of phenol, the hexamethylenetetramine does not
remain as such. It combines with the phenol in the
proportion of three molecules of phenol to one molecule
of hexamethylenetetramine and produces a well-
defined crystalline product, hexamethylenetetramine
triphenol, which has been described by Moschatos
and Tollens.1
In 1909, Lebach2 pointed out that whenever am-
monia is used in the Bakelite reaction, hexamethyl-
enetetramine triphenol is formed in the first stages
of the process. Under the action of heat, this product
undergoes a further decomposition and resinifies,
emitting ammonia.3
Contrary to the results of Moschatos and Tollens,
who were unable to prepare addition products of
hexamethylenetetramine with any of the three cresols
or with carvacrol or thymol, Baekeland had suc-
ceeded in his laboratory in preparing a corresponding
crystalline cresol derivative, but inasmuch as this work
had not been carried out with each one of the com-
pletely purified cresols and studied by itself, it seemed
desirable that each one of the three homologs should
be studied separately as to its individual behavior.
This research was also extended to carvacrol and the
results obtained thus far are set forth. Similar
compounds obtained from other phenolic bodies are
now under study. In the meantime, the observa-
tions concerning the new cresol derivatives are submitted
in the present paper.
The reason of the non-success of Moschatos and
Tollens in making the cresol derivatives of hexamethyl-
enetetramine is, mainly, that the isolation of these
substances is incomparably more difficult than in
the case of phenol. The hexamethylenetetramine
triphenol forms rapidly and visibly under almost
all circumstances, and crystallizes very well from
aqueous solutions or even from solutions when a
considerable excess of one of the constituents is used.
This is not the case with some of the cresol derivatives.
' Ann., 272 (1892), 271.
2 Z. angew. Chem., 22 (1909), 1600; J. Soc. Chem. Ind„ 32 (1913), 559.
3 A resume of the literature on this subject is given by L. H. Baekeland,
in "The Chemical Constitution of Resinous Phenolic Condensation Prod-
ucts," This Journal, 6 (1913), 506.
136
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol 13, No. 2
The temperature at which they form lies in some
cases so close to the temperature at which they de-
compose that their formation is almost sure to be
overlooked if proper precautions are not taken.
Furthermore, some of those products have a tendency
to remain liquid in the presence of an excess of some
of the reacting products or impurities. That such
products exist has been established beyond doubt
by the present investigation.
In this work data were determined for the relation-
ship of certain of the phenolic condensation products.
The results are appended.
HEXAMETHYLENETETRAMINE TRIPHENOL
Moschatos and Tollens made the easily prepared
hexamethylenetetramine triphenol by mixing 6 g.
of a concentrated water solution of hexamethylene-
tetramine with a concentrated solution containing
6 g. of phenol. The product isolated had the following
composition:
Calculated for . Found by M. and T. .
CtHitNUCeHiOH 12 3 4
Per cent Per cent
C-1 68.25 68.4° 68.09
Hio 7.11 7.34 7.44
N< 13.27 ... ... 13.65 13.77
All the phenols do not react with hexamethylene-
tetramine to form an addition product in which there
are one mole of hexamethylenetetramine and three
moles of the phenol. The various groupings about
the benzene ring seem to determine the extent to
which the addition -takes place. The three cresols
whose structural formulas are nearly identical with
that of ordinary phenol and whose properties are
somewhat similar to the latter should form addition
compounds the same as does phenol.
HEXAMETHYLENETETRAMINE DI-WI-CRESOL
The m-cresol addition product is the most easily
obtainable. At first ordinary m-cresol was used
in both dilute and concentrated alcoholic solutions;
but the expected crystalline intermediate addition
products did not appear. The alcoholic solutions
were refluxed several hours and the concentrated
solutions allowed to stand several weeks to see if
the compound would crystallize out. No crystalline
product was obtained in this case. There must
have been some impurity in the cresol that hindered
the formation, for with cresol purified according to
Pox and Barker1 the product crystallized out in 40
min.
A mixture of 315 g. of ;»-cresol and 136 g. of hexa-
methylenetetramine was heated for an hour in 80
cc. of a 60 per cent (60 parts by volume of alcohol and
40 parts by volume of water) alcoholic solution.
Too much heating caused the addition product to
decompose and pass over into the noncrystallizing
resinous material. By withdrawing portions of the
mixture from time to time, and cooling slightly, it
could be observed, by the formation of crystals,
when the most favorable point was reached before
resinification set in. On stopping the heating, crystals
appeared even in the hot solution. The crystals were
filtered off and pressed on a porous tile to get rid of
' J. Soc. Chem. Ind., 37 (1918), 260.
the adhering sirupy material. The product was then
dissolved in hot 95 per cent alcohol. On cooling,
long, fine, needle- like crystals separated out.
Analysis showed that the substance was not formed
on a 1:3 basis as is the case with the ordinary hexa-
methylenetetramine triphenol, but was an addition
product of 1 mole of hexamethylenetetramine and
2 moles of w-cresol.
Calculated for - Found .
CcHi2N..2C«H<OH.CH3 12 3 4 Av.
Per cent Per cent
do 67.40 67.45 67.23 67.34
H;i 7.87 8.03 7.80 ... ... 7.96
N. 15.73 15.59 15.80 15.69
Hexamethylenetetramine di-w-cresol has not a
true melting point, since when the substance is held
at a temperature around its point of liquefaction,
90° C, it undergoes decomposition, passing over
into the irreversible resinous stage. The compound
is very soluble in hot 95 per cent alcohol, the solu-
bility increasing with the temperature. A charac-
teristic feature is that when it is placed in a sufficient
amount of water or ether there is a very decided
tendency towards a splitting of the product. In
water the solubility of the hexamethylenetetramine
shows up predominantly, as it is dissolved by the
water leaving insoluble cresol as an oil. In ether
the solubility of the w-cresol predominates, and the com-
pound breaks up leaving the insoluble hexamethyl-
enetetramine as a precipitate. The solubility in
benzene is moderate, but increases with the tempera-
ture. Acetone has the same effect on the substance
as has ether, that is, breaking up the structure by dis-
solving out the soluble cresol and leaving the insoluble
hexamethylenetetramine.
HEXAMETHYLENETETRAMINE DI-/>-CRESOL
Pure ^-cresol was first made from ^>-toluidine.
When it was found that an addition product was
formed with hexamethylenetetramine, a larger quan-
tity of the material was made by the method given
by Fox and Barker.1
A mixture of 385 g. of /»-cresol and 167 g. of hexa-
methylenetetramine in 150 cc. of 95 per cent alcohol
was heated on a steam bath for 1.5 hrs. The same
precaution must be observed here as in the case of
the formation of the w-cresol compound. On allowing
the liquid to stand at room temperature, crystals
separate out. The compound was recrystallized from
50 per cent alcohol.
The addition product has no melting point, but
begins to resinify at the temperature of liquefaction,
87.0° C. The decomposition is shown when the
substance turns brown and partially resinifies upon
heating in a sealed glass tube for 3 hrs. at a temper-
ature of 90° to 100°.
Analysis shows that it has the same proportion of
the two constituents as the wj-compound, namely,
1 mole of hexamethylenetetramine and 2 moles
of ^-cresol.
Calculated for Found ■
C.HnN.^CtH.OH.CHs 12 3 4 Av.
Per cent * Per cent
C-o 67.40 67.18 67.35 ... ... 67.27
His 7.87 8.20 8.01 ... ... 8.10
N. 15.73 ... ... 15.82 15.71 15.76
• Loc. cit., p. 268.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
137
The same qualitative solubilities as applied to the
w-cresol product apply to the ^-cresol compound.
HEX AMETHYLENETETR AMINE MONO-0-CRES0L
Pure o-cresol was made according to the method
of Fox and Barker.1
A mixture of 475 g. of o-cresol and 205 g. of hexa-
methylenetetramine in 100 cc. of 95 per cent alcohol
was heated on a water bath for 2.5 hrs. On allowing
to cool at room temperature, crystals separated out.
These were recrystallized from 95 per cent alcohol.
The compound behaves somewhat differently from
the p- and w-cresol addition products, since on heating
there was no sharp melting point to the liquid stage,
followed by a final passing over to the resinous ma-
terial. A small portion seemed to soften on heating
and show signs of melting, but most of the substance
either sublimed or charred.
Analysis showed that the proportion of hexamethyl-
enetetramine to o-cresol was 1:1.
Calculated for . Found — ■*
CsHisNt.OH.OH.CH, 12 3 4
Per cent Per cent
C,j 62.90 63.12 63.20
Hi, 8.07 8.07 7.94
Ni 22.55 ... ... 22.74 22.69
It was thought that it might be possible to isolate
a compound of o-cresol which would have the same
proportions of the two constituents as have the p-
and the jw-cresol intermediates. The crystals of
hexamethylenetetramine were dissolved directly in the
o-cresol. and with portions of this solution various runs
were made in which the time factor of heating was
the variable. Heating was accomplished on a water
bath, the time varying from 2 to 10 hrs. For the
runs with a small amount of heating the solution
was clear, while with the runs extending over 10 hrs.
the solution was dark brown, showing that a reaction
had set in with the formation of the resinous material.
After allowing the solutions to stand several days
the crystals were filtered off, pressed on porous tile,
and recrystallized from alcohol. In all cases analysis
of the crystals showed that the product was a com-
pound with a 1: 1 proportion of hexamethylenetetra-
mine and o-cresol.
Crystals obtained after 8 hrs.' heating showed the
following composition:
Calculated for
CiHuNi.CeH.OH.CHs Found
Per cent Per cent
Ci! 62.90 63.04
H,o 8.07 8.22
N( 22 55 22.70
From this it appears that there is but one addition
product of o-cresol and hexamethylenetetramine, and
that is with one mole of each of the two constituents
present.
HEXAMETHYLENETETRAMINE HYDROQUINOL
Moschatos and Tollens2 give for the preparation
of this compound 4 g. of hexamethylenetetramine
in 5 g. of water mixed with 33 g. of hydroquinol in
4 g. of water. The product, purified by washing
with water and with ether, and drying over sulfuric
acid, analyzed as follows:
1 Loc. cit.
' Ann., 272 (1892-3), 287
Calculated for ^Found by M. and T. — -
CiHaN,.C.Hi(OH)i 1 2 3
Per cent
Cia 57.60 57.20
Hi, 7.20 7.77
Ni :... 22.40 ... 22.57 22.47
This was checked up as follows: 5 g. CeH^OH^
in 9 cc. of water were mixed with a solution of 6 g.
of hexamethylenetetramine in 10 cc. of water. The
solution was heated on a water bath for 30 min., then
allowed to stand over night. Crystals washed with
water, then ether, and dried over sulfuric acid. Anal-
ysis showed:
Calculated for
C«Hi2N4.CtH)(OH)2 Found
Per cent Per cent
Cu 57.60 57.35
His 7.20 7.11
Ni 22.40 22.46
On heating, part of the compound sublimed and
part charred with very little melting. This behavior
is similar to that of the hexamethylenetetramine
o-cresol compound.
HEXAMETHYLENETETRAMINE RESORCINOL
Moschatos and Tollens formed the compound by
heating a mixture of 2 g. of hexamethylenetetramine
dissolved in 3 g. of water and 3 g. of resorcinol dis-
solved in 3 g. of water. The composition of the
compound was found by Moschatos and Tollens to
be as follows:
Calculated for Found by M. and T. .
CiH,!N(.C«H,(OH), 12 3 4
Per cent Per cent
C12 57.60 57.14 57.35
Hi, 7.20 7.43 7.42
Ni 22.40 ... ... 22.09 22.32
By following the same order of procedure as outlined
above, a precipitate was easily obtained. On analysis
the composition was found to be the same as that
represented by Moschatos and Tollens:
Calculated Found
Per cent Per cent
Ci> 57.60 57.39
H„ 7.20 7. 10
Ni 22.40 22.34
This compound also shows no melting point, which
is similar to the hydroquinol and the o-cresol inter-
mediates. It seems to be a characteristic feature of
the hitherto observed phenol hexamethylenetetramine
compounds that it is necessary that there be at least
2 moles of the phenol to 1 of the hexamethylene-
tetramine in order that there be a well-defined point
of liquefaction.
HEXAMETHYLENETETRAMINE CARVACROL
The carvacrol obtained for use in this work was
made from cymene.1 It ran 93 per cent pure, the
other constituents being approximately 6 per cent
thymol and 1 per cent thiophenols. The product
was purified according to the method developed by
Mr. Allan Leerburger:
A very stiff paste of the carvacrol and lead acetate was al-
lowed to stand at room temperature for 30 hrs. The mass
was broken up and the phenols extracted with petroleum ether.
The carvacrol-lead acetate compound is soluble in the petroleum
ether, whereas the thymol-lead acetate is insoluble in the ether,
giving a means of separating the two phenols. After allowing
the petroleum ether to evaporate, the liquid was washed with
1 Hbtson and McKee, This Journal, 10 (1918), 982
138
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
a normal solution of mercuric chloride (using as the solvent
50 parts by volume of water and 50 parts by volume of alcohol).
This removes the thiophenols, leaving the carvacrol as the oil.
The carvacrol then distilled in a 4-bulb fractionating column,
the portion boiling between 237° and 239° C. being taken.
One mole of hexamethylenetetramine in just suffi-
cient 95 per cent alcohol to dissolve the crystals was
mixed with 3 moles of the purified carvacrol. The
mixture was heated on a water bath for 40 hrs., then
allowed to stand at room temperature for 1 wk.
The uncrystallized mass was dissolved out by mixing
with kerosene. The fine precipitate was filtered,
and the crystals dissolved in hot 95 per cent alcohol.
On cooling the alcoholic solution the compound
crystallized out readily. Further purification was
made by repeating the crystallization from hot 95
per cent alcohol.
The compound shows a point of liquefaction at
148° C, at which point it resinifies quickly. It is
very soluble in hot 95 per cent alcohol, but insoluble
in the cold alcohol. An important point is that it is
very soluble in ether and acetone. Some of the
cresol compounds, as has been stated, may be broken
up in water, ether, and acetone, the two latter sol-
vents dissolving out the easily soluble cresols and
leaving the insoluble hexamethylenetetramine as a
precipitate. This difference in solubility between
the carvacrol and cresol compounds may be due to
the difference in Unkings of different phenols with the
hexamethylenetetramine.
Analysis showed that the compound was not of
the same order of addition as were cresol and phenol
products, which were in the proportion of 1 mole
of hexamethylenetetramine to 2 moles of the m-
or />-cresol, and 3 moles of phenol to 1 mole of hexa-
methylenetetramine. The composition was found to
be as follows:
Run 1 Run 2 Average
Per cent Per cent Per cent
Carbon 76.95 77.10 77.02
Hydrogen 9.20 9.27 9.23
Nitrogen 4.92 4.99 4.96
From the table below it is clearly seen that the
hexamethylenetetramine is not directly added to the
carvacrol as it is in the case of the cresols and phenols.
C6Hi:N..CioHi,0 C«H1JN<.2C,iiHi,0 CtHi!N..3C,oH,(0 Found
Carbon 66.25 71.00 73.25 77.02
Nitrogen 19.35 12.75 9.50 4.96
Hydrogen 8.96 9.10 9.16 9.23
The percentages found do not correspond to any
simple proportion of addition, as was shown in the
case of the other phenols mentioned. However,
if we assume that a nitrogen is broken out of the
structure of the hexamethylenetetramine to form am-
monia with hydrogens of the hydroxyls of 3 moles of
carvacrol. and further that 2 moles are taken up
additively by one or two of the other nitrogens, the
percentages of carbon, hydrogen, and nitrogen corre-
spond exactly with the percentages as found. The
smell of ammonia toward the end of the heating in
the formation of this compound seems to bear out
this point that ammonia is split out, but no quan-
titative determination has thus far been undertaken.
The diagrams, in which R represents the radical
part of the carvacrol structure, illustrate possible
arrangements.
H
I
N— OR
^N-CH,-OR y |\ch,-or
CH2 CH2 or CH2 CH2
/I I \
ROH— N— CHa— N— CH2— OR RO— N— CHj— N— CHz— OR
/ \ l\
ROH CH2— OR H CHr— OR
It is to be pointed out that although the interpreta-
tion of the structure of hexamethylenetetramine is
thus far rather arbitrary, and although the correct
one may be found to be quite different from the above,
the percentages of elements will in all cases be the
same for the theoretical carvacrol compound.
Calculated from
Above Structure Found Deviatiou
Per cent Per cent Per cent
Carbon 76.95 77.02 0.07
Nitrogen 4.84 4.96 0.12
Hydrogen 9.10 9.23 0.13
All this becomes rather easy of interpretation if in
the formation of the hexamethylenetetramine car-
vacrol compound there has been 1 mole of ammonia
split out and there have been 2 moles of carvacrol
added to one of the nitrogen.
ENERGY RELATIONSHIP OF PHENOLIC HEXAHETH YLENE
COMPOUNDS
apparatus — For the heat of combustion of the
phenol, hexamethylenetetramine, and hexamethylene-
tetramine triphenol, an Emerson adiabatic bomb
calorimeter provided with a proper stirrer and a
Beckmann thermometer graduated to give an estimated
reading of 0.001° were used For the heat of solution
the bomb was eliminated and the metal can for the
water replaced by a glass container. The substance
whose heat was to be determined was held in a glass-
stoppered weighing bottle, the cover of which was
removed by small wires passing through the third
hole in the top of the calorimeter jacket.
data — The water equivalent of the calorimeter
was determined in the ordinary way by burning a
material whose heat of combustion was known. Naph-
thalene from the U. S. Bureau of Standards laboratory
was used. By weighing the separate parts of the
bomb and accessories, the water equivalent of the
bomb was found to be 453 g.; without the bomb it was
found to be 70 g. The error in the first number was
±2 g., and that in the second number was ±5 g.
Checking these values against other standard sub-
stances, 6320 was obtained for benzoic acid, whereas
the Bureau of Standards gives 6329 cal. per g. as the
correct result. The second value was used in finding
the heat of solution of as pure sodium hydroxide as
could be made without wasting too much time. The
following shows a comparison of the heat of solution
of sodium hydroxide as determined by Thomsen, and
by Berthelot, and as obtained in this study:
Kg. Cat.
Thomsen 9.94
Berthelot 9.78
Present work 9 . 85
The errors here would seem to be due to the varied
purity of the NaOH used, rather than to the manipu-
lation of the apparatus.
Feb., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY 139
(a) Heal of solution of hexamethylenetetramine. Therefore the heat of formation of hexamethylene-
Kg. Cat. tetramine = — 43.18 Cal.
Run 2 4 896 (e) Heat of formation of phenol — Berthelot1 gives
the heat of combustion of phenol at constant pressure
Average 4.899' (where 1 Cal. = 1000 small calories) and jgo q as 736 0fJ Qal_ per mole
1 Delepine (Bull., [3] IS, 1200) gives the heat of solution of hexa- . c/-tt\ i /,-vn o ti ^> i ^ ,
methylenetetramine at 15° C. as 4.8 Cal. Required : 6(C) + 6(H) + (O) = C$H60 4- X Cal.
,,,„,,,,. , ., , Found: C6H60 + 14(0) = 60 02 + 3H50 + 736.00 Cal.
(b) Beat of solution of phenol.
K Cal We know that:
Run l —2.92 6(C) + 12(0) = 60 02 + 96.98 Cal. (1)
Run 2 — 2.87 3Ha + 30 = 3H2q + gg g6 x g Ca, (2)
Average — 2.89> Substituting Equations 1 and 2 in the found equa-
1 Landolt and Bornstein, 3rd Ed., p. 419, give for the heat of solution tion We obtain
of phenol — 2.6 Cal.
6(C) + 6(H) + O = C6H60 + 50.96 Cal.
(c) Heat of reaction of phenol and hexamcthvleiic- , ,.,,,, , , ,. , , .
. , ,. T ,, . , .. Accordingly the heat of formation of phenol is o0.9i>
tetramine in an aqueous solution — In this observation _, . , ^, • , ,■„
±, , , c . , , , , ., ,. ... Cal. per mole. ihis value is different from the one
the phenol was first added to the water, then solid _ ., , . . „ , , ., , . ,
, ,, , . ..,.,. . , Berthelot gives- because he uses the heat of formation
hexamethylenetetramine added in the manner stated , __ ° , „„ _ , , _ „
. _;, , . . , , ,. , of C02 as 94.30 Cal. and the heat of formation of
above. The excess of rise of temperature above that .
, ,/, , i, , . , . . , water as 09.00 Cal. Ihese values are not considered
given by the hexamethylenetetramine would be due , , , ,.,,,.
, . ,. r ,, . , ,, , , ~. . correct and better values are used in the calculations
to the reaction of the amine and the phenol. This . , _.. , _„„ _„ _, , , . .
. ,, , . , , ,. . ., , . , f . . ., above.3 The value 736.00 Cal. per mole for the heat
is the weak point of this method of determining the , , . .... , f ,
. , ,. r , „ . . . . of combustion of phenol is used here because it repre-
heat of formation of hexamethylenetetramine tri- , , ,.,.,.
, . . .. . ..„. ,. , , : . t . ., sents the value obtained in this research.
phenol, since it is difficult to obtain accurately the
amounts of amine and phenol that have combined (/) Heai °J solution of hexamethylenetetramine tri-
in solution. After the reaction the hexamethylene- phenol.
tetramine solution was distilled to obtain the phenol, Average value obtained was— 10.671 kg. Cal.
the amount of which was determined by the tribromo- (g) Heat of formation of hexamethylenetetramine tri-
phenol method.1 The error in this way would be in phenol.
the dissociation of the triphenol compound on dis- The heat of combustion of hexamethylenetetramine
filiation of the phenol. It was found that the energy triphenol at constant pressure was found to be 3228.30
reaction was Cal. per mole.
(CH^eN^q. + 3C6H6OAq. = (CH2)6N,.3C6H6O.Aq. + 3.739 Cal. Required: 24(C) + 30(H) + 3(0) + 4(N) =
ij\ Ti , t t ,■ ti ,11,4 ■ (CH>)6N.i.3C„H60 + x Cal.
(o) Heat of formation of hexamethylenetetramine.
Heat of combustion of commercial hexamethylenetetramine: Found: (CH^eN^SCeHeO + 30.73(0) =
Run 1-7.380 Cal. per g. at constant volume 24C02 + 14.71H20 + 1.71NS + 0.58HNO3 + 3228.30 Cal.
Heat of combustion of hexamethylenetetramine resublimed in labora-
tory: We know:
Run 2 7.397 Cal. per g. at constant volume 24(C) + 48(0) = 24(C02) + 96.98 X 24 Cal. (1)
Run 3 7 399
29.42(H) + 14.71 (O) = 14.71H20 + 68.357 X 14.71 Cal. (2)
Average 7.398 0.58(H) + 0.58(N) + 1.74(0) =
By means of the Hempel gas apparatus and freshly 58 HN°s + 41-60 x °-58 Cal- (3)
prepared solutions of sodium hydroxide and pyrogallol, Substituting these three equations in the above found
the following results on the products of combustion equation and solving, we obtain the required equation:
were obtained: 24(C) + 30(H) + 3(0) + 4(N) =
Actual Result Theoretical Result (CH2)6N4.3C«H60 + 128.76 Cal. per mole
Products Grams Grams
N, 0.40 o.38 The heat of formation of hexamethylenetetramine
hno* o.ii9 0.112 triphenol, starting with crystals of phenol and amine,
CO* 1.80 1.88 . , ,,
is as follows:
To represent the above results we can write the equation Required: Hexamethylenetetramine + 3 phenol =
(CH2)oN< + 18.55(0) = 6C02 = H.T.P. + x Cal.
5.89H.O + 1.89N, + 0.22 HN03 + 0.1036.9 Cal. or (CH2)6N1(crys.) + 3C6H60(crys.) =
We know that (CH2)cN4.3C6H60(crys.) X Cal.
6(C) + 12(0) = 6C02 + 6 X 96.98 Cal. (1) We know:
(Land, and Born., 4th Ed., p. 855) 6(c) + 12(H) + 4(N) = (CH2)6N, — 43.18 Cal. (1)
11.78(H) + 5.89(0) = 5.89H.O + 68.357 X 5.89 Cal. (2) ]g(c) + 18(H) + 3(0) = 3C6h6o + 3 X 50.96 Cal. (2)
(Land, and Bom., 4th Ed., p. 850) + M(H) + 3(Q) + 4(N) =
0.22(H) + 0.22(N) + 0.66(01 = 0.22HNO3 + 41.60 Cal. (3) (CHOeN^CH.O + 128.76 Cal. (3)
(Land, and Born., 4th Ed., p. 854) _ ,, .. ... , ,„. , ,„. ,. .
Subtracting (1) and (2) from (3) we obtain:
Substituting these three equations in the found equa- (CH.)6N,3CeH60 = (CH2)6N1.3C,H,0 + 19.06 Cal.
tion above, we have:
6(C) + 12(H) + 4(N) = (CH,).N, - 43.18 Cal. \ ^ t^T ' ^ ' ^ ^
1 AUen's "Commercial Organic Analysis," 8th Ed.. Vol. 3, p. 307. • Landolt and Bornstein, 4th Ed., p. 855.
140
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
(/;) Heat of combustion of hex amethylenetttr amine
di-p-cresol.
At Constant Volume, 20° C.
Cal. per G.
Run 1 8.024
Run 2 7.992
Average 8.008
(i) Heat of combustion of hexamethyleneletr amine
di-m-cresol.
At constant volume and 20° C. =» 8.010 Cal. per gram
(J) Heat of combustion of hexamethyleneletr amine
mono-res or cinol.
At Constant Volume and 20" C.
Cal. per G.
Run 1 6.730
Run 2 6.700
Average 6.715
In the addition reactions of hexamethylenetetra-
mine with a phenol thus far investigated there does
not seem to be any definite rule by which one is en-
abled to determine the number of moles of phenol
that will combine with the hexamethylenetetramine.
Falk and Nelson1 have assumed that in catalytic
reactions there are binary and ternary compounds
formed. Kendall2 has called attention to the impor-
tant general rule that stable addition compounds
are formed when there is a marked chemical con-
trast (acidic and basic) between the two reacting
components. Thus in the additive compound formed
between organic acids and phenols, the stability is
very much greater wThen the organic acid is strong
and the phenol weak, or vice versa, than in the case
in which both substances exhibit the same degree of
acidity. A similar generalization holds for the addi-
tion compounds between two acids, or between an
acid and a ketone, or an acid and an aldehyde.
In the case of the addition compounds formed in
this work we have the phenol acting as the acid and
the hexamethylenetetramine as the base. It might
be assumed from this and from Kendall's generaliza-
tion that the greater the chemical contrast the greater
the stability of the compounds formed, and the greater
the number of moles of phenol combining with the
basic hexamethylenetetramine. This is not the case,
however, in this instance. The degree of acidity
seems to have very little to do with the extent of the
reaction. Ordinary phenol, which is a weaker acid
than o-cresol, combines in the proportion of three
moles of phenol to one of hexamethylenetetramine,
whereas the cresol combines in the proportion of
1: 1. Nitric acid, a very strong acid in comparison
with the phenol combines only in the proportion of
1 mole of hexamethylenetetramine to 2 moles of
acid. Hence we cannot apply the generalization
stated above to the case of phenol addition products.
Again, the three cresols have practically the same
order of hydrogen-ion concentration,3 but with the
p- and »«-compounds there are 2 moles adding,
whereas with the o-cresol there is only 1 mole adding
to the hexamethylenetetramine.
> /. Am. Chem. Soc, 37 (1915), 1732.
'Ibid.. 36 (1914). 2498.
3 Scudder, "Conductivity and Ionization Constants."
Since the activity of phenol is greatly diminished
in the case of the cresols, by the presence of a methyl
group, it might be said that the more negative the
benzene ring is made with negative groups (nitro
and hydroxy) the greater the activity and the greater
the number of moles uniting. With hydroquinol
and resorcinol, where there are two hydroxy groups,
the opposite is true. They react slowly with hexa-
methylenetetramine, and then only in the proportion
of one mole of the phenol to one of the amine. Picric
acid, which contains three nitro groups and one
hydroxy group, should represent a substance in which
the benzene ring has practically the maximum of
negative groups, and hence should have high combining
properties. Moschatos and Tollens found that the
proportion was only 1:1. As yet no rule can be
laid down connecting the acidity, or the degree to
which the benzene ring is made negative by negative
groupings, with the additive properties of phenols
and hexamethylenetetramine.
Why should two moles of p- and wz-cresol unite
with one mole of hexamethylenetetramine, while only
one mole of o-cresol unites with one mole of amine?
One difference lies in the structure assumed for the
three cresols. The hydroxy group of the p- and m-
cresols has on each side of it a hydrogen, while the
hydroxy group of o-cresol has a hydrogen on but one
side. From this it would seem that the extent of
addition depends upon the number and activity of
the hydrogens adjacent to the reacting hydroxy group.
The structure of hexamethylenetetramine as given by
/
CH2
N
CH2 CH2
N
/ \
/
\
CH
\
\
does not seem to represent all the facts as presented
by the addition products with phenols. Here the
four nitrogens are all tertiary in character and we
should expect that hexamethylenetetramine would
add four moles of an alkyl halide. A. Wohl1 found
that but one mole of methyl iodide was taken up
additively. In all the phenol addition compounds
that have been isolated there is not one case where
the number of moles of phenol combining with one
mole of hexamethylenetetramine is greater than
three. In the carvacrol compound found in this
investigation there is strong evidence that one
nitrogen is more reactive than the others. This is
shown by the fact that ammonia has been split out
with one of the nitrogens before one of the other
three has added any phenol.
» Bcr., 19 (1886), 1840
Feb., 1921
THE JOURNAL OP INDUSTRIAL AND ENGINEERING CHEMISTRY
Hexamethylenetetramine is formed from ammonia
and formaldehyde. Tertiary amines are formed from
ammonia and an alcohol. Alcohol is a lower oxida-
tion product than is the aldehyde. Again, amides
are formed from ammonia and an acid, the latter being
of a higher oxidation than the aldehyde. From this
we might expect that hexamethylenetetramine should
not be represented wholly as a tertiary amine, but
should exhibit a character midway between the tertiary
amine and an amide.
It does not seem from these considerations that the
structure of hexamethylenetetramine is properly repre-
sented when written in the above manner.
STUDIES ON BAST FIBERS. II— CELLULOSE IN BAST
FIBERS
By Yoshisuke Uyeda
Laboratory of Agricultural Chemistry, University op California
Agricultural Experiment Station, Berkeley, Cal.
Received June 9, 1920
In a previous paper,1 the proximate analysis of
Korean bast fibers, according to the modified methods
proposed by Dore,2 for the analysis of wood, was dis-
cussed from the standpoint of textile chemistry.
The scheme of analysis proposed by Dore was found
to be well applicable to cellulose material other than
wood.
Generally speaking, our knowledge of the nature
of the substances which make up the structure of the
materials belonging to so-called compound cellulose,
and of the forms in which these substances are present,
as well as their special functions in the plant, is still
very limited. One of the chief reasons for this is that
no accurate method for the analysis of cellulose-
containing material has been established, and conse-
quently the results obtained by the various investi-
gators have not been directly comparable. From this
point of view, the analytical studies recently made by
Dore may be regarded as a forward step in cellulose
chemistry.
Cellulose is the chief constituent of the bast fibers,
and the amount of it in the fiber is, to a great extent,
a measure of its industrial importance. For instance,
the full bleached textile goods of the bast fibers may
be considered chiefly composed of cellulose itself. In
determining the cellulose content of the bast fibers by
the chlorination method, the alkali treatments before
chlorination were found to have an important effect
on the yields of cellulose as reported in the previous
paper.
In the present paper, the effects of various prelim-
inary treatments before chlorination on the yields of
cellulose are presented, and the properties of the cellu-
lose thus obtained are studied and discussed from
the standpoints of cellulose and textile chemistry.
SCOPE OF THE WORK
The original method of Cross and Bevan3 for the
determination of cellulose is taken as a starting point
of the work. Renker4 published a critical study of
1 This Journal, IS (1920), 573-
! Ibid.. 11 (1919), 556.
""Cellulose," 2nd Ed., p. 95.
* "Bestimmungsmethoden der Cellulose," Berlin, 1910.
the determination of cellulose in various cellulose
materials; and in his method the material was di-
rectly subjected to chlorination by the Cross and
Bevan method without the preliminary alkali treat-
ment. Schorger1 also confirmed the method of Renker
by his experiments with woods. Johnsen and Hovey2
proposed a new method of hydrolysis, using a mix-
ture of glacial acetic acid and glycerol before chlorina-
tion in the cellulose determination. Recently Dore*
compared these three methods of treatment in the
case of wood and decided in favor of the Renker pro-
cedure.
Now, it is of much interest to determine whether
the relation which was found by Dore is applicable
to bast fibers. The bast fibers, which belong to the
so-called pectocelluloses, differ much in composition
from woods, which are classified as lignocelluloses,
and contain substances which are easily converted
into soluble forms by the action of alkali.
In the present work, the same three methods are
used. After preparation by (i) no preliminary hy-
drolysis, (2) alkali hydrolysis, and (3) acid hydrolysis,
the materials are subjected to chlorination, according
to the improved method of Johnsen and Hovey, which
was also recommended by Dore. But it is very
obvious that the yields of cellulose obtained by these
three methods are not directly comparable. Whether
a smaller yield may indicate a purer cellulose or may
signify a partial destruction of the cellulose itself is
very questionable. It is, therefore, very necessary
to standardize the purity of the cellulose thus ob-
tained. In this work two methods are available for
this requirement. One is to determine the quantity
of a- or normal cellulose in the residue of the various
cellulose processes by using the mercerization test of
Cross and Bevan,4 as recommended by Dore,6 of this
laboratory, and the other is to estimate the furfural
yield by Tollens and Kroeber's method.6
EXPERIMENTAL
The Korean hemp fiber whose proximate composition
was given in the previous paper7 is taken as the sample
material for this investigation. The fiber is cut into
small pieces, having an average length of 1 cm., and
preserved in a Mason fruit jar throughout the experi-
ment. Portions of one gram each are weighed and
dried for 16 hrs. in a constant temperature electric
oven kept at 100° C, extracted for 6 hrs. with ben-
zene, then for 6 hrs. with Q5 per cent alcohol, as de-
scribed in the previous paper. After this treatment,
the cellulose estimations are made in three ways, as
described in the paper published by Dore.8 Results
are given in Table I.
From Table I it will be seen that the results for yield
of cellulose by Method 1 are in good agreement, but
those from Methods 2 and 3 vary considerably be-
> This Journal, 9 (1917), 561.
2 Paper, 21 (1918), No 23, 36.
» This Journal, 12 (1920), 264.
• "Paper Making," 1918, p. 97
s This Journal, 11 (1919), 556.
• J. Land-w , 48 (1900), 357.
7 Uyeda, Loc. cit.
'This Journal, 12 (1920), 266.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
tween individuals. In other words, absence of hy-
drolysis before chlorination gives a better result than
any hydrolytic treatment preceding chlorination,
from the standpoint of analytical chemistry.
Table I — Weights of Residue by Various Hydrolytic Processes,
and Comparison of Cellulose Obtained by the Three Methods
(Percentage on Air-dry Basis — 8.83 Per cent Moisture)
Residue after
. Hydrolysis . Cellulose
Treatment Individual Average Individual Average
1 — Renker's modification o( ) 71.08
Cross and Bevan's I 71.14
method, no hydrolysis | 70.80
I 88.05' 70.44 70.81
2 — Original Cross and Bevan 1 67.92 63.28
method, treated for 30 I 68.97 64.66
min. with 1 per cent f 70.90 65.82
NaOH I 69.80 69.39 65.99 64.93
3 — Johnsen and Hovey's -\ 76.42 67.60
method, treated for 4 I 75.34 67.16
hrs. with acetic acid [77.80 70.02
and glycerol > 77.02 76.64 69.54 68.58
1 Loss on drying 8.83
Loss on extraction with benzene 1 .92
Loss on extraction with alcohol 1 . 20
Total.: 11.95
Average residue by difference 88 . 05
Next, the a- or normal cellulose in the total cellulose
residues thus obtained by various methods is determined
by means of the Cross and Bevan mercerization test.
The dry material in the Gooch crucible is transferred
as completely as possible to a small beaker, 50 cc.
of cold 17.5 per cent NaOH solution are added, and
allowed to stand just half an hour. At the end of
that period it is diluted with 50 cc. of cold water,
filtered off on the original Gooch crucible, and washed
with about one liter of .cold water, then with acetic acid
several times, and finally with sufficient cold water.
It is dried for 16 hrs. at ioo° C, and weighed. The
results are tabulated in Table II.
Table II — <»-Cellulose from Total Cellulose Obtained by Three
Methods
(Percentage on Air-dry Basis — 8.83 Per cent Moisture)
Ratio
o-Cellu-
Total Cellulose a-Cellulose lose:
. . . ■ . Total
Treatment Individual Av. Individual Av. Cellulose
1— Renker's method ) 71.08 63.98
J 70.44 70.76 62.44 63.21 0.89
2 — Original Cross and) 64.66 59.79
Bevan method J 65.99 65.32 61.22 60.50 0.92
3— Johnsen and ) 70.02 61.30
Hovey's method j 69.54 69.78 62.68 61.99 0.88
If the yield of a-cellulose from the total cellulose
be considered as a basis of standardization of the
cellulose obtained, it will be seen that the cellulose
obtained by the original Cross and Bevan method
shows the highest purity of the three, and the other
two indicate about the same degree.
Table III — Furfural Yields of the Cellulose
(Percentage on Air-dry Basis — 8.83 Per cent Moisture)
Ratio of
Furfural
from
a-Cellu-
lose to
Furfural from Furfural from Furfural
Total Cellulose or-Cellulose from
. ■ . . ■ . Total
Treatment Individual Av. Individual Av. Cellulose
1 — Renker's method 1 1.35 1.12
) 1.98 1.66 1.14 1.13 0.68
2 — Original Cross and I 1.40 0.78
Bevan method } 2.09 1.74 0.78 0.78 0.44
3 — Johnsen and 1 1.06 0.56
Hovey's method ) 0.83 0.94 0.57 0.56 0.59
Determinations of the furfural yields of the total
and a-cellulose obtained by the three processes are
made by subjecting the material to distillation with
12 per cent hydrochloric acid and precipitating the
furfural in the distillate with phloroglucinol solution
as furfural phloroglucide. A Gooch crucible with an
asbestos filter is conveniently used, and the results
are expressed in terms of furfural calculated from the
phloroglucide obtained (Table III).
The total cellulose, as well as a-cellulose, by the
Johnsen and Hovey method yields the least quantity
of furfural of the three methods used. In determining
the furfural yield, the coloration taking place when
the phloroglucinol solution is added to the distillate
is to be noted.
In the case of total cellulose obtained by Renker's
method and by Cross and Bevan's method, the solu-
tion first becomes deep brown, but changes into green-
ish, and on standing, to a deep dark green, and the
black precipitate of phloroglucide is obtained. In the
case of the total cellulose obtained by Johnsen and
Hovey's method, both the solution and the precipi-
tate remain brown, as does the a-cellulose by all three
methods. The solution is bright brown and the pre-
cipitate has the same color.
DISCUSSION OF RESULTS
It is desirable to discuss the results obtained by
the three methods from the standpoint of cellulose
chemistry, especially as applied to the textile industry.
The physical properties of the cellulose obtained by
Renker's method are very different from those of the
product by the original Cross and Bevan method.
While the latter is entirely separated into individual
fibers like cotton fiber, that by Renker's modification
retains the form of the original vascular bundle, and is
somewhat viscous, apparently due to gummy sub-
stance (probably pectin) remaining in it. As Renker,
Schorger, and recently Dore, have brought out with
the lignified materials, the cellulose free from lignin
may be obtained by Sieber and Walter's modifica-
tion of the Cross and Bevan chlorination method.
But, in the course of the chlorination of the bast
fibers, the present author observed that the alkali-
treated fiber is more easily bleached to pure white by
the chlorination than the other two methods. Some-
times it is found scarcely possible to bleach white by
the four periods of successive chlorinations in Sieber
and Walter's treatment, especially in the case of the
Renker method. Now the physical nature of cellu-
lose obtained by Johnsen and Hovey's method is some-
what similar to that by Renker's method. From these
facts it may be concluded that the pectin substance is
satisfactorily removed only by alkali treatment, and
the cellulose free from pectin in some degree can be
obtained only by the original Cross and Bevan method.
Therefore, this is the nearest to the true cellulose or
normal cellulose of the three obtained. But, as Renker
pointed out, it is questionable whether or not the cellu-
lose itself is attacked by the alkali treatment.
Let us now consider these yields of cellulose from
the standpoint of textile chemistry. The problem is
very important in the bleaching process of the hemp
fabrics. In the practice of the bleaching process,
dilute alkali treatment, bleaching by hypochlorite
(termed "chemicking"), and the exposure to direct
sunlight (termed "sun-bleaching") are combined and
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
143
repeated. The object is to bleach as white as possi-
ble without weakening the strength of the fiber.
Alkali treatment before chemicking is, of course, very
effective in bleaching, and this fact is in good agree-
ment with the observation which is made on the original
Cross and Bevan method. There is, however, danger
of impairing the strength of the fiber if the alkali
treatment is overdone. One of the important reasons
for the weakening of the fiber is, in the author's opinion,
that the alkali dissolves the pectin substance or the
binding material between the individual fibers which
make up the bast fiber. If the bleaching operation
be carried out ideally, we may expect to find the
bleached fabrics of the hemp fibers in the condition of
pure cellulose, something similar to the cellulose ob-
tained by Renker's method. As far as these three
methods are concerned from the standpoint of textile
chemistry, it seems to the author that Renker's method
has a most important suggestion as to yield of cellu-
lose.
The chemical nature of the cellulose obtained by
these three methods should next be discussed. The
mercerization test proposed by Cross and Bevan is
very important for the cellulose process, especially in
the case of the textile fibers. Not only does it serve
as a means of determining the purity of the cellulose
itself, but also it shows the chemical behavior of the
fiber toward the alkaline reagents, and the latter fact
should be duly considered in the practices of the tex-
tile industry. Pectin substance which is retained in
the cellulose obtained by Renker's and by Johnsen's
method may be partly removed by the alkali in the
mercerization test, so that the a-cellulose obtained
is in the condition of separated individual fibers like
cotton.
The determination of furfural yields of the celluloses
obtained serve, no doubt, as an indication of the de-
gree of the chemical purity of the cellulose. Johnsen
and Hovey's1 claim as to the purity of cellulose ob-
tained by their proposed method holds true, in some
points, in the case of the bast fibers as shown in the
present work. Now, the question is as to the mother
substance of the furfural yield. As to the chemical
composition of the pectin substance, it is very ob-
scure, but several contributions are available by
Ehrlich,2 von Fellenberg,3 Schwalbe and Becker,4
and Cross and Bevan.5 Taking the views of these
various investigators into consideration, we may re-
gard the pectin in the bast fibers as partly dissolved
during the mercerization tests, and the a-cellulose ob-
tained by the three methods as accordingly yielding
less furfural than the total cellulose. We now see that
the pectin substance present in the bast fiber is one
of the mother substances which give furfural. The
furfural-yielding mother substances are designated as
"furfural yielding complex" by Cross and Bevan6 or
' Paper, 21 (1918). No. 23, 36.
i Ehrlich, Chem.-Ztg., 41 (1917), 197.
' Biochem. Z., 85 (1918), 118; Chem. Abs., 12 (1918), 2196; Sckweiz.
Milllg. Lebenzm. Hyg., 6 (1914), 256; Chem. Abs., 9 (1915), 448; Sckweiz.
MMlg. Lebenzm. Hyg., 7 (1916), 42; Chem. Abs., 10 (1916), 2772.
1 Z. angew. Chem., 32 (1919), 126, 229.
6 "Cellulose," p. 217.
« Ibid., p. 99.
may be shortened to "furfurose" or "furfurosan."
According to Tollens and his pupils, pentosan (araban,
xylan, etc.) and methyl pentosan are considered as
the chief substances which give the furfural. Pentosan
is estimated by Tollens and Kroeber's method,1 while
methyl pentosan can be determined by that of Ellet
and Tollens.2 But. recently, it has been ascertained
that besides these carbohydrates belonging to the
pentosans, hexosans also yield oxymethylfurfural.
Cross and Bevan3 have assigned to wood cellulose an
oxycellulose structure which gives considerable amount
of furfural. Cross and Bevan4 classify the bast fibers
in the same group from the point of view of chemical
constitution, that is, those of maximum resistance to
hydrolytic action and containing no directly active
carbonyl group. The present author is of the opinion
that the bast fibers, especially hemp fiber, have, in
some points, a composition related to wood cellulose;
and the cellulose of the hemp itself may have an oxy-
cellulose structure in some degree. The fact that the
cellulose obtained from hemp has a much larger af-
finity towards basic dyestuff than that of cotton may
be looked upon as suggesting this view. From these
considerations it seems to the present author that when
the cellulose, as well as the a-cellulose derived from it,
is subjected to distillation with hydrochloric acid by
Tollens and Kroeber's method, it gives a mixture of
furfural, methylfurfural, and oxymethylfurfural, which,
however, is simply expressed in terms of furfural in
the present work. While the furfural phloroglucide
has a greenish black coloration, methylfurfural phloro-
glucide is brown.6 This phenomenon was clearly ob-
served in the present work, in that the a-cellulose
gave a brown phloroglucide, consisting chiefly of
methylfurfural and oxymethylfurfural. Further study
is planned from the standpoint of carbohydrate chem-
istry.
SUMMARY
i — The estimation of cellulose in bast fibers is made
by the three methods proposed, *. e., Renker's modifica-
tion of Cross and Bevan's method, the original Cross
and Bevan method, and Johnsen and Hovey's method,
according to the scheme of Dore.
2 — The chemical behavior of the cellulose obtained
is studied from the standpoint of cellulose chemistry.
3 — Renker's modification of Cross and Bevan's
method is suggested as the most practical method for
the estimation of cellulose in bast fibers from the
textile chemistry point of view.
4 — The function of pectin substance in bast fibers is
discussed.
5 — It is suggested that the cellulose of the hemp
fiber has, in some degree, an oxycellulose structure.
ACKNOWLEDGMENT
I wish to express my thanks to Mr. W. H. Dore, whose
valuable suggestions and direction have made the
present work possible.
1 Loo. cil.
"- J. Landw., 53 (1905), 20.
:"Cellulose," p. 82.
1 Ibid., p. 78.
i Oshima and Tollens, Bet., 34 (1901), 1425.
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
LABORATORY AND PLANT
100
°Be'
80
SO
GASOLINE FROM NATURAL GAS. V— HYDROMETER
FOR SMALL AMOUNTS OF GASOLINE
By R. P. Anderson and C. E. Hinckley
Unitbd Natural Gas Co., Oil City, Pennsylvania
Received October 15, 1920
In testing natural gas for gasoline it is important
to determine the gravity of the gasoline obtained.
When the quantity of gasoline is insufficient to float
the extremely small hydrometers that are available
for this purpose, it is convenient to possess an instru-
ment which requires but 4 cc. of gasoline for a gravity
determination. Such an instrument is
shown in Fig. 1. It is a modification of
hydrometers Nos. 4060 and 4072 of Eimer
and Amend's 19 13 catalog, and may be
ordered from this firm.
The instrument is designed for immersion
in water at 6o° F., and when the bulb B
is filled to the mark with gasoline at 60°
F. the gravity of the gasoline is obtained
directly from the position of the hydrom-
eter in the water, the stem being cali-
brated from 6o° to ioo° B6.
A study of the effect of temperatures
other than 60° F. upon the reading of the
instrument discloses the fact that the tem-
perature correction is small as compared
with that necessary in the case of the
ordinary hydrometer. This is because the
contraction or expansion of the gasoline
with change of temperature is partially
compensated for by the corresponding con-
traction or expansioninthe water in which the
hydrometer is immersed. The relationship
between the contraction (or expansion) of
the gasoline and that of the water is shown
graphically in Fig. 2. The three, straight,
diagonal lines picture the change in weight
of 4 cc. of gasoline of three different temper-
V J atures.1 The curved lines show the change
^w"^ in weight of 23 cc. and 47 cc. of water for
f the same temperature range.2 Twenty-
HV three cc. represent the proper volume of
» the hydrometer up to the 8o° B6. mark in
FlG' ' order that the most complete temperature
compensation may be obtained between 50° and 700
F., and 47 cc. represent a hydrometer volume which
gives excellent compensation at the temperature of the
maximum, density of water.
The actual error in hydrometer reading resulting
from incomplete compensation may be computed for
any given conditions of temperature, gravity of gaso-
line, and hydrometer volume as shown in Table I. The
effect of the expansion or contraction of the hydrom-
gasoline for
'. is taken ai
. of 100° Be
1 The change in weight of 1 cc. of 60°
0.00045 g.; for 1 cc. of 80° Be\ gasoline. 0.0005 g.; and for 1 i
gasoline, 0.00055 g. See This Journal, 12 (1920), 1011.
a Data on change of density of water with change of temperature taken
from Smithsonian Tables, "Handbook of Chemistry and Physics." 7th Ed.,
p. 322.
eter with change of temperature upon the degree of
compensation is too small to need consideration in
this connection.
Table I — Hydrometer Compensation
(Hydrometer Volume 23 Cc, Gravity of Gasoline 80° Be.)
Change in Weight
-ol
Gasoline W:iter
(4 Cc.) (23 Cc.)
4-0.0200 +0.01587
+0.0100 +0.00890
—0.0100 — 0.01109
— 0.0200 — 0.02401
Uncompensated Change
' Weight s
Per Cc.
—0.32
—0.08
—0.08
—0.31
Computations of the sort illustrated in Table I have
been made for three grades of gasoline (6o°, 8o°, and
ioo° Be\),for temperatures from 32° to 70° F.,and for
hydrometer volumes of 23 and 47 cc, and the results
are shown in graphical form in Fig. 3. An error of
+ i° B6. as used in this figure means that i° B6.
must be subtracted from the observed hydrometer
reading to obtain the gravity at 6o° F., and with an
error of — 1° B6., i° Be\ must be added. Fig. 3
may thus be used in correcting observed Baume'
gravities to a temperature basis of 60 ° F.
/
'
/
<
/
1
v
-0
1
/
1
'
1
'
'
'
/
/
/
„
/
4
'
,'
*>
-
\*
/
$
p
,
f
*
?i
X d
?
to
*c
#
&
v.
■■
/
•
1
0
loEM
ERAr
JRE "F.
6O
7
0
It will be noted from the figure that the hydrometer
with a 23-cc. volume may be used for gravities from
6o° to 100° Be\, over a temperature range from 50°
to 70° F., with a maximum correction of o.6° Be\
This portion of the figure is ruled to i° F. and 0.1°
Be\ for convenience in applying corrections.
In the case of the hydrometer with a 47-cc. volume,
the most desirable temperature range is from 36° to
40° F. It may be used from 37° to 40° F. with a
maximum correction of =<=o.6° Be\ At 35.7° F., the
correction is zero for 60 ° Be. gasoline; for 80 ° Bi.
gasoline the temperature for zero correction is 37.7°
F., and for ioo° Bi. gasoline, 39.7° F. The 47-cc.
hydrometer is the desirable one to employ in obtain-
Feb.. 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
'
•
'.
<
\
'
\
^ \
•
'.
,
-
-v
pv
---
--
60-
'
'
^
/
/
1
^
•■■
■ll
TEMP.T
:
\
i
\
/
> i
50-
'
'
v
«(
Sf
nC
/
P
r
w
M^s
v
/
7
7
tth
<&y<
■K
y
40-
W\
Pv
y
A
S-
'
L c
\|0
u
+
/J\(A^
->
Jo
y
' Jte
&
"\,
^
ERROR- DEGREES BAUHE
ing the gravity of gasoline condensed and collected
at temperatures not much above 320 F., since, under
these conditions, warming to 6o° F. would involve a
considerable change in gravity as a result of evapora-
tion of the more volatile constituents. It will be
noted also that the 47-cc. hydrometer may be em-
ployed between 36 ° and 66° F. with a maximum cor-
rection of ±1.0° Be\
SUMMARY
1 — A hydrometer has been described which makes
possible the rapid and fairly accurate determination of
the gravity of gasoline when the quantity is insuffi-
cient to float the usual type of hydrometer. Only 4
cc. of liquid are necessary.
2 — The magnitude of the corrections necessary to
change observed gravities to a 60 ° F. basis depends
upon the volume of the hydrometer. A chart has been
prepared to be used in making corrections for hydrom-
eter volumes of 23 and 47 cc. The desirable range
of temperature for the hydrometer with a volume of
23 cc. is from 500 to 700 F., and for the hydrometer
with a volume of 47 cc. from 37 ° to 40 ° F. The
maximum error for the 47-cc. hydrometer over a range
from 36 ° to 66° F. is ±i° B6., and consequently, for
approximate work, the correction may be omitted
entirely.
A COLD TEST APPARATUS FOR OILS
By G. H. P. Lichthardt
Southern Pacific Railroad Co., Sacrambnto, California
Received September 27, 1920
The apparatus herein described for making the
cold test is the result of an attempt to eliminate, as
far as possible, the personal equation in this useful
test which has long been used to show, in a compara-
tive manner at least, certain qualities and character-
istics of fixed oils. That the test is unsatisfactory
has long been recognized by various observers, and to
do away with this error, Martens, in a paper which was
abstracted in the Journal of the Society of Chemical
Industry in 1890, recommended that a U-tube be used
in a freezing mixture and connected with air pressure,
the temperature at which the air begins to flow under
these conditions being taken as the cold test of the
oil under investigation.
In an attempt to improve the application of methods
which would show the lowest temperature at which
oils will flow, many of the suggested schemes were
tried. Since the one described by Martens seemed
to be the most promising, the apparatus which is the
subject of this paper was devised.
Results can be obtained within 0.250 F. or less, de-
pending upon the thermometer, and the personal error
is to all intents and purposes nil.
The apparatus consists of a refrigerator tank, B,
containing nine tubes of glass, 0.3 in. inside diameter,
which are bent at one end and are connected with
the air supply H. The cooling box is of galvanized iron
and square in shape, the dimensions being 6X6X6
in., and contains the freezing mixture which consists
of acetone and carbon dioxide snow. The mechanical
stirrer C, operated by the motor D, insures uniform
temperatures throughout. The readings are taken
from a low-temperature thermometer, F, and the air
pressure is regulated by the glass tube inserted in the
water contained in the jar A.
The test is applied by placing enough of the oil
under investigation in the tube to occupy 6 in.
of the tube length, after which the freezing mixture
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, So. 2
is added, circulation being maintained by the mechani-
cal stirrer. When the oil becomes solid and does not
move under an air pressure of 16 in. of water, the
temperature is noted and then allowed to rise, which
it does very slowly. Readings are taken every quarter
or half minute, as the case may be, the appearance of
the oil in the straight part of the tube protruding
from the box being taken as the "cold test."
TITRATION BENCH
By W. A. Van Winkle
409 East Buttles St., Midland, Mii
Received November 15, 1920
For making evening titrations1 under working con-
ditions approximating very good daylight the titra-
tion bench herein described and illustrated has proved
very satisfactory.
5.5 in., is placed back of the burets, as shown by the
end view, j-k, in Fig. 2. Each buret is held by two
spring-brass hooks, which turn upon screws, which
may be adjusted so as to hold the burets firmly, yet
loosely enough to permit easy raising and lowering
during titration. The wooden frame is grooved where
it comes in contact with the burets.
Placed directly back of and set snugly up against
the entire rear of the bench is a portable lighting com-
partment, an end view of which is shown in Fig. 3.
Two 100-watt, nitrogen-filled, blue glass for daylight)
lamps are used, each one being in a line (front view)
with a buret. A conveniently placed switch turns
the lamps on and off. This rear compartment con-
sists of a wooden frame, mounted upon a wooden base.
The three sides and the top are of asbestos board.
The base is also covered with asbestos board, and the
The base is made of one-inch board, 26.5 X 11 in.,
and has inlaid upon its surface, and placed flush with
the border, a glass plate 25 X 10 in., the under side
of which has three coats of white (lithopone) paint.
(See heavy lines in Figs. 1 and 2.) Mounted upon this
base is a hardwood frame, made of 5/s X Vs in- strips,
which holds two triangular ground-glass sides and
rectangular ground-glass back in position. One of the
triangular plates is indicated by e, /, and g, in Fig. 2;
the rectangular plate by a, b, c, and d in Fig. 1. These
three plates are held securely in position by having
the wooden frame slotted or sawed to fit the edges of
the plates. The vertical edges of the two sides must be
butted snugly up against the back, as shown by h in Fig.
2. To protect the eyes of the operator from the light
a special rectangular screen of ground glass, 23.25 X
' J. Am. Chem. Soc, 43 (1920), 337.
surface of the latter should lie in the same plane as
that of the inlaid glass plate lying below the burets;
then no interfering shadow will be cast upon this
plate. Asbestos board is used to insure against fire
and also because its roughened, dull white surface
gives a fairly uniform diffusion of the light. For ven-
tilation a hole should be cut in the rear wall up near
the top; also one in each side, near the base. Unless
this is done the temperature may mount quite high.
All wooden parts are painted a dull white. An
electric lamp (not shown) placed on the top of the
lighting compartment and on a line midway between
the two burets facilitates the reading of the latter.
The ground-glass plates are ground upon one side
only and the smooth surface should be placed toward
the burets, otherwise difficulty will be experienced in
cleaning the plates from spatterings.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
ADDRESSES AND CONTRIBUTED ARTICLES
REFINING RAW SUGARS WITHOUT BONE-BLACK1
By C. E. Coates
Louisiana State University, Baton Rouge, Louisiana
The following is a general discussion of a condition which
has risen somewhat suddenly in the Louisiana sugar industry,
and is of necessity both informal and incomplete. In particular,
it is specifically not a discussion of the various methods of re-
fining raw sugar used at present in sugar refineries devoted en-
tirely to that purpose.
Off and on for a good many years there have been sporadic
attempts to buy raw sugars in the tropics and to take advantage
of the idle equipment in the Louisiana sugar houses by refining
this sugar between seasons without the use of bone-black.
Every now and then a few bags of raws were slipped into the
regular routine during the sugar season, but in the main the crop
was ground in the usual way and the house cleaned up before
melting began. The ventures were largely experimental, the
most exhaustive experiments having been carried on about
10 yrs. ago in a sugar house which ran all summer and turned
out a large quantity of a good grade of granulated sugar. It
was understood, however, that the results were not particularly
satisfactory financially, owing to the small margin then existing
between 96 test and granulated sugar. In the nature of things,
the bone-black refinery is slightly more efficient than the sugar
house in melting raws and can exist when the margin between
raws and granulated is so small that the sugar house would be
losing money. Just what this margin is it is almost impossible
to say at the present time, but when 96 test sugar was selling
for 4 cents it was estimated that 80 cents per hundred margin
was about an even break, and anything above this showed a
slight profit. With margins running from $1.80 up, the propo-
sition looked, on the face of it, very attractive to a good many
planters, and they went into it without thinking much about
equipment or yield, and without knowing much about the process.
Superficially, it looks like a pretty easy thing to melt raw
sugars, and turn out granulated. Practically, it is not in the
least simple, and differs at every point from the ordinary sugar-
house practice. Here we have a raw material of high cost,
which must be manufactured and sold as a perfect finished
product. Profits are determined in ordinary times by the
quality of the product, but leaving this out of consideration the
margin between raws and granulated even when large is rarely
large enough to stand much loss in process, as can be seen from
the following rough estimate.
One hundred lbs. of 96 test sugar, sold in bags and delivered
at 18 cents a lb., will yield with good refinery practice 93 lbs.
of granulated sugar and 7 lbs. of molasses with practically 1
per cent of loss in process The 93 lbs. of granulated selling at
20 cents per lb. give us $18.60. Add 20 cents for the molasses,
which is liberal, making $18.80 or 80 cents gross profit. The
raw sugar is bought in bags costing about 12 cents per hundred
lbs. sugar and sold in barrels costing about 40 cents per hundred.
The net loss for cooperage is 25 cents per hundred lbs. Sub-
tracting this from 80 cents we get 55 cents, which must cover
both cost of manufacture and profit. If, on the other hand, raw
sugar is selling at 4 cents and granulated at 5 cents, 93 lbs.
of raws give $4.65. Add 10 cents for molasses and subtract
20 cents per hundred cooperage less rebate on bags. This
leaves 55 cents for gross profit, which must include cost of process
and profit. Assuming cost of process for 4-cent sugar to have
been 35 cents, this gives about 20 cents per hundred margin
for net profit for 4-cent sugar. With 18-cent sugar, however,
1 Presented before the Section of Sugar Chemistry at the 60th Meeting
of the American Chemical Society, Chicago, 111 , September 6 to 10, 1920.
the cost of process is certainly double. Probably it does not
miss 70 cents by very much, which would show a loss of 15 cents
per hundred instead of a profit, even though the margin in one
case is 100 points and in the other case 200 points. But that
is not the worst of it. With 4-cent sugar, if the yield is not
93 lbs. but 91 lbs., this reduces its profits by 10 cents. With
18-cent sugar a yield of only 91 lbs. adds 40 cents to the deficit.
It would hardly pay to melt 18-cent sugar on a plantation at
less than 300 points, as can be seen from the following: A
very good yield is 90 lbs. and about 8 lbs. of molasses. 90 X 21
cents is $18.90, plus value of molasses 20 cents, making $19.10.
gross profit $1.10. Calling the cost of process 70 cents and
cooperage 25 cents, this leaves 15 cents profit, which is little
enough. 'The purpose of these calculations is merely to show
that a margin which pays with 4-cent sugar would mean bank-
ruptcy with 18-cent sugar. It is well to impress this point
on the planter, because otherwise when he sees the refiner getting
2 cents margin he may overestimate the refiner's profit and try
it himself with somewhat disastrous results.
With the above as a foreword let us now cover briefly certain
of the points which the sugar planter must meet when he melts
raws.
BUYING RAWS
In buying raws there would be considerable choice if the
planter could choose. At present he takes what he can get,
but ordinarily he might be able to buy a specific lot of raw sugar
on quality. Polarization is, of course, the prime factor in valuing
raws, but in addition to this, raws with hard, fairly large grains
give better yields than soft, small-grained sugars, losing less
on washing and giving washed sugar of a higher purity.
Light colored raws give better yields than dark raws. Raw sugars
also have a tendency to deteriorate in storage, due to the solu-
tion of the sucrose grain in the molasses film and its inversion
by bacteria. The smaller the grain the greater the surface
exposed to this action, and hence the greater the loss in storage.
It is quite simple to argue out a good deal for one's self about
raw sugars, keeping in mind just what a grain of raw sugar is
like. It consists practically of fairly pure sucrose of over 99
purity, which has separated from a mother liquor of molasses,
which has a purity of approximately 45. The molasses film
of raw sugar is, of course, not the final molasses, but is the run
off from a massecuite of perhaps 65 purity. This molasses will
have an apparent Brix of about 79, and real total solids of about
76. Molasses of such a density is subject to fermentation.
If the Brix of the run-off had been 83, the molasses would have
been so dense that it would hardly ferment. Sugar of this type,
therefore, would keep better than sugar from a lighter massecuite
of the same polarization, which accounts for the fact that if the
raw sugar be much washed its keeping qualities may be im-
paired. The deterioration of raw sugar is much more consider-
able and more rapid on occasions than one would suspect. It is,
therefore, well for the planter to be prepared to work up his
raws as soon as possible and to keep them in storage as short a
time as possible.
YIELDS
In buying raws refineries have taken 96 test sugar as a stand-
ard. Before the war, when sugar sold at about 4 cents, the re-
fineries gave a premium of about one-twelfth of a cent a pound for
every degree of polarization above 96 test, and imposed a penalty
of about one-eighth of a cent per pound for every degree of polariza-
tion below 96 test. These figures differed at different times. It
was generally considered that the premium was too low and the
penalty too high. Be this as it may, the whole system was
clumsy and illogical and became increasingly absurd as the
148
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
price of raw sugars advanced. Some time ago, therefore, the
buyers and sellers in New York agreed upon a new sliding scale,
which is used at the present time and is presumably fair to both
sides, though the latter point is doubtful.
In Louisiana there has been considerable refining on toll.
One sugar company some years ago, when sugar sold at 4.5 cents,
received 96 test raws in bags and delivered 93 lbs. granulated in
barrels, charging 60 cents toll per hundred raws and keeping
the molasses, which at that time was worth about 5 cents. The
rebate on the bags would not quite cover the cooperage. Possibly
the molasses would have about offset this, leaving the net toll
60 cents. This was considered a satisfactory charge by the
refiner at that time, but, of course, it would not apply at the
present time. There is no bone-black house refining on toll
at present in Louisiana. If there were it would probably be
necessary to double the previous toll and add about 25 cents
for increased cost of cooperage, the total rate depending upon
the cost of raws
When sugar was refined on the toll basis the deliveries in
granulated per 100 lbs. raw were based on polarization, according
to Table I. These figures represent perfect refinery practice
and are the results of a number of years of practical work.
The basis of this table is calculated on the following formula
which is mathematically correct :
Percentage of granulated sugar on total solids in raws =
Purity of raws — Purity of molasses
Purity of granulated sugar — Purity of molasses
Ninety-six test sugar is assumed to carry 1 per cent of moisture
(=99 total solids) and to be of 97 purity. Molasses is sup-
posed to be of 40 purity, and granulated sugar of 100. One
pound of sugar is allowed as a reasonable loss in refining. Substi-
tuting these figures we get
97 — 40
= 0.95 lbs. on 100 lbs.
100 — 40
Total solids in raws 0.95 X 99 = 94
94—1 = 93 lbs.
of granulated sugar recovered per 100 lbs. of 96 test melted,
with 6 lbs. of molasses of 40 purity and 1 lb. of sucrose lost in
process. The table has been modified to fit actual results.
Table I — Yields of Granulated per 100 Lbs. Raws
Polarization Raw Sugar Granulated
Degrees Lbs.
98.0 95.0
97.5 94.5
97 .0 94.0
96.5 95.5
96.0 95.0 (standard)
95.5 92.1
95.0 91.25
94.5 90.4
94.0 89.5
93.5 88.2
93.0 87.7
92.5 86.9
92.0 86.0
The premiums for over-polarization are 1 lb. of granulated for
every degree. Penalties for under-polarization are 1.8 lbs.
granulated for every degree. One per cent of non-sugars is
assumed to prevent 1 per cent of sucrose from crystallizing.
That this table, though empirical, is not far wrong may be seen
from the following figures obtained recently by an exceedingly
well-equipped bone-black refinery: Polarization, 95.7; yield
granulated, 92.46 lbs., molasses 7.37 lbs.; loss of sucrose in process
0.804 lb. The above table would also give 92.46. In refining
sugar by bone-black 3.5 to 4 gal. of oil were burned per 100
lbs. raws mel'.ed.
It must not be forgotten, however, that raws of the same polar-
ization and different qualities give different yields. A soft,
small-grain raw of 95 test with gummy molasses and high ash
would yield considerably less sugar to the refinery than a hard,
large-grain sugar carrying normal molasses of low ash. This
fact is well understood by the refiners, but it is practically im-
possible to allow for it in buying raws. For this reason the
planter should have it clearly mentioned in the contract on what
basis sugar, polarizing above or below 96 test, shall be adjusted
to a 96 test basis. This refinery table is certainly fair to the
seller and should be used until something better can be suggested.
It must be kept in mind also that these are bone-black refinery
figures, which show probably 2 to 4 lbs. more recovery of granu-
lated than can be obtained in any Louisiana sugar house with
its present equipment. Whereas this equipment varies so
greatly in different sugar houses that it would be impossible to
lay down a hard and fast rule for recovery to be expected, the
writer is inclined to think that if 2.5 lbs. of sugar were deducted
from the above table and 3.5 lbs. of molasses added it would
be about the best which could be expected at present, though
there is no reason why. as far as yield goes, a sugar house cannot-
do as well as a refinery.
WEIGHING AND SAMPLING
Raw sugar is always received in bags and when received must,
of course, be stored immediately. Many sugar houses are not
equipped for handling and storing raw sugar, but this equipment
is neither expensive nor difficult to obtain, and has been installed
in several places. In making this installation it is particularly
necessary to instal scales. For many reasons, which need not be
particularized, the sugar house should know exactly the number
of pounds of raws entering the house, and should take these
weights itself. The usual tare for bags is accurate enough.
In sampling raw sugar at the present time it is exceedingly
difficult to get a fair sample. The old 96 test sugar was usually
washed a little, but many Cuban raws at present seem not to
be washed at all for the most part, and seem purposely made to
carry all the molasses they will hold. If this sugar is allowed
to stand in the bag the molasses will slowly drain to the bottom.
Sugar from the top may polarize 96°, and sugar from the bottom
92° or less. Neither is it possible for an inexperienced man to
take a fair sample of the sugar — nor the experienced, for that
matter It might be thought that a trier run from top to bottom
would give a fair sample, but if the bag has had its position
changed during the shipment and is standing on its end instead
of lying on its side, the drainage of the molasses might change
the nature of the sample completely. While the usual method
of sampling may be fair enough for duty purposes where the bags
in the cargo have not been moved for some time, the problem
at the sugar house is by no means easy. In fact, I am inclined
to believe that errors in polarization due to sampling are re-
sponsible for some of the apparent inefficiency in process. These
samples should be taken with the greatest of care by the chief
chemist or some trained man.
The raw sugars after dumping are carried by a conveyor to
a mingler. In some places an extemporized mingler has been
made out of a wooden trough, and a screw conveyor. This is
not a mingler and does not accomplish its purposes. A mingler
is a semicircular trough through which runs a shaft provided
with arms which churn up the sugar and segments of a screw
which gives the mass a slight forward motion. The violent
agitation of the mass is necessary to break up the lumps of sugar
and is particularly important with the low-grade molasses sugars
we are getting at present. In the mingler the sugar is mixed
intimately with about 15 per cent by weight of wash. From the
mingler it falls into an ordinary mixer which keeps the mass
stirred up while it is being fed to the centrifugals. In spinning,
the first run-off, called greens or wash sirup or affination liquor,
may be separated from the wash proper, but this does not pay
unless large quantities are melted. The wash sirup will be about
15 per cent by weight on the raws melted and has a purity of
about 85. The washing is continued until the sugar has a purity
of about 98.5 to 99. Higher than this it is not desirable to go,
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
149
for economic reasons. From 1 to 3 gals, of water in a 40-in.
machine is all that is required. This wash may go into a separate
tank and part of it be used in affmating new raw sugars. If
there is an excess the remainder goes in with the washed sugars
for melting. It is obvious, therefore, that the wash water used
should be but little more than that necessary to make enough
wash for affiliation purposes. In most sugar houses there is no
separation of affination liquor and wash, and the raw sugar is
mingled with pure water or with the mixed wash sirup, the sep-
aration of wash not being thought worth the trouble.
MELTING
In nearly all Louisiana sugar houses the washed sugars are
melted with wash water from the presses and from the bags.
This is considered bad practice by refineries. The object is
to keep the purity of the dissolved washed sugars as high as
possible. Press wash and bag wash, while valuable, are usually
of lower purity than the melted sugars. While this is true and
under ideal conditions would be used as a basis for practice in
Louisiana houses, the improvement brought about by substi-
tuting pure water for press and bag wash is not great and might
not be advisable where the cost of evaporation is high. This
cost must always be high where only single-effect evaporation is
practiced, as is often the case at the present time. Early in the
year the raws were melted to about 20 Brix in order to facilitate
filtration. The density was gradually raised until at about 30
Brix it was found possible to cut the effects out completely and
do all the evaporation in the pan. This was convenient, but
being single-effect evaporation it is, as just said, quite expensive.
All water used for washing and for melting should be as pure as
possible, and if necessary it should be filtered. This detail is
important but is sometimes overlooked.
DEFECATION
The liquor obtained by melting raw sugars is turbid and dark
in color. Any sirup suitable for making white sugar must be
reasonably light in color and above all things must be bright and
free from suspended particles. In raw sugars these particles
consist of bagacillio, wax, silica, calcium salts, and ordinary
dirt, together with yeasts, molds, pectin, and albumins. If
boiled the albumin precipitate is coagulated, but the coagulum
is not large. After boiling, most of the turbidity can be removed
by nitration through ordinary filter paper, though the particles
are so fine that simple filtration has so far not proved successful
commercially. The problem, however, indicates purely me-
chanical filtration, but as this was formerly not thought prac-
ticable it was customary to add certain chemicals to the sirup
to produce a gelatinous precipitate which would carry down the
suspended impurities and, if possible, some of the impurities in
solution.
PHOSPHATATION
The commonest defecation is by means of phosphoric acid
and lime. The phosphoric acid was formerly made in the bone-
black houses by treating the spent char or the char dust with
either hydrochloric or sulfuric acid. At the present time it is
largely sold already made up in pure form, and is so used in
Louisiana. The amount to be added depends upon whether or
not the soluble monocalcium phosphate or pure phosphoric
acid is used. The usual size for defecating tanks is 2500 gals.,
which at 55 Brix means about 15,000 lbs. raws for the tank.
At the beginning of the season 0.25 lb. of P2C>6 per 1000 lbs. of
sugar was generally added, though this amount varied some-
what with the type of sugar melted. This, with the residual
acidity of the raws, gives an acidity of about 0.6 cc. 0.1 N for
10 cc. of liquor, using phenolphthalein as an indicator. If to
this solution we add about 0.25 lb. of CaO per 1000 raws we
get a residual acidity of about 0.35 cc. Inasmuch as commercial
preparations of lime and of phosphoric acid are not of constant
composition, it is advisable to control the defecation by de-
termining acidities. The final acidity of 0.35 cc. to phenol-
phthalein is practically neutral to litmus. In phosphatation,
to the melted sugar, heated to about 195° to 200° F., there is
added, first the phosphoric acid and then immediately the lime,
and the mixture is blown up for about 10 min. The defecated
liquor is next sent to the bag filters. None of the Louisiana
houses were provided with any other kind of filter than the bag.
The Greenwood type with movable head gave considerably better
satisfaction than the old type of Taylor filter. One house
ordered Daneks for secondary filtration; another house tried
out the Williamson aerating defecator, which works admirably
on these liquors; still others ordered the Sweetland type of leaf
press, and the Martel type which works on the same principle,
but this'.- installations were not finished before melting stopped.
In refinery practice this first liquor goes direct to the char
filter. In Louisiana, no char filters are used, so it is considered
good practice to sulfur to 0.8 cc. before sending to the pan.
This sulfuriug is thought to give better molasses. Towards
the end of the season several houses had modified the above
procedure. The acidity was brought to 0.6 cc. with phosphoric
acid and then limed back to an alkalinity of 0. 1 cc. After passing
through the bags this liquor usually showed 0.1 cc. acidity, due
to the acetic acidity of the bags after they had been washed and
allowed to stand for a few hours. It was then sulfured a very
little, to about 0.2 cc. acidity. With this procedure there was
absolutely no rise in glucose ratio and the yield of granulated
sugar was better, with no gain in color.
CARBONATION
Several years ago quite a quantity of raw sugar was refined
at one factory by a carbonation process which was as follows:
The washed raws were melted to 28° Be. and cooled to 35° C.
At this point hydrated lime was added, 2 per cent Ca(OH)j
on weight of sugar, the sirup carbonated cold to phenolphthalein
neutrality, heated to 93° C, carbonated again, and filtered.
It was claimed for the process that it was about 10 cents per
hundred cheaper than the bone-black process and gave nearly
a pound more sugar. The sugar actually produced was of fairly
good quality, but the cost of the process was not satisfactory to
the company, and it was abandoned at the end of a few months.
Probably, however, defecation, adding lime, first to the cold
juice, following with carbon dioxide and finishing up with a little
sulfur dioxide, that is, the so-called sulfo-carbonation process,
might prove both cheap and effective This latter defecation
was practiced for many years at Belle Alliance, Louisiana, and
gave good results.
SULFATATION
A third process tried out this season at several places was the
substitution of sulfur dioxide for phosphoric acid, the acidities
ranging about as for phosphatation. This process has given
excellent results in some hands and not so good in others. The
author would suggest the following procedure: The clear liquor
is heated to 70° and forced hot at fairly high speed through a
pipe emptying into the blow-up tank. A few feet away from
this tank a pipe introducing sulfur dioxide under pressure is
led into the juice pipe. Along beside it another pipe enters,
introducing milk of lime. The amount of both the lime and the
sullur can be thus regulated with exactness. When the sulfite
of calcium is formed at advanced temperature, it filters more
readily and is more effective as a defecating agent. Sulfurous
acid has the advantage over phosphoric acid that is not cumula-
tive, and will give better molasses. The sugar also is generally
whiter.
The foregoing methods employ the three commonest and
cheapest acids which will give insoluble precipitates with lime,
that is, phosphoric, carbonic, and sulfurous. In so far as the
writer has been able to see, there is little difference in the quality
of the products. The cost of the acid used per 100 lbs. raws is.
150
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
of course, negligible. The remaining processes, however, are
based on an entirely different principle, that is, on purely me-
chanical filtration.
KIESELGUHR
It has been known for a long time that if a melted raw sugar
liquor be passed through a high-speed centrifuge, it can be sep-
arated into a clear liquid and a precipitate which contains not
only most of the particles held in suspension, but also most of the
germs present and some of the gums. A few years ago the eastern
refineries began to filter their juices through kieselguhr. Kiesel-
guhr is a thin, porous, fossil shell of microscopic size, shaped
like a shallow boat or disk and composed mainly of silica. It
is in consequence exceedingly light and exposes a great surface
in filtration. Previous to the war this could be bought f. o. b.
New Orleans for about $22 per ton. At present the price is
about $50. This increase in price may affect its use in the sugar
industry, but at a reasonable figure it has unquestionably a
part to play. It was found that if a leaf press was precoated
with kieselguhr the filtered liquor was practically clear and the
leaves could be sweetened off and washed with great ease.
Filtration is rather slow, but if kieselguhr is added to the melted
sugars at the rate of about 12 to 16 lbs. to the ton of raws and
this fed properly to the precoated press, filtration is exceedingly
rapid and the nitrate bright. This system of clarification was
tried out at several sugar houses in Louisiana with varying suc-
cess. It has been materially improved, however, by a very
simple change of procedure. The washed sugar is dropped from
the centrifugal to a conveyor which carries it to a mingler.
In this mingler a slurry of kieselguhr and water of about 12° Be.
is added at the rate of 12 to 16 lbs. of kieselguhr per ton of raw.
This brings the kieselguhr into intimate contact with the molasses
film on the sugars. The mingler discharges into the melters,
where the sugar is melted, preferably with pure water. Filtered
river water answers admirably. The melt then goes to the filter
press or the bags, and the result is excellent in every respect.
First liquors clarified in this way are practically as bright and as
light in color as these clarified by phosphoric acid and lime, and
the molasses of course has considerably less ash. For this reason
a better grade of product is obtained all the way down to the
final molasses, and the yield seems to be increased about 0.3
lb. Whereas in refineries this liquor goes to the char filter,
in sugar-house practice it can go straight to the pan in a usual
way, but the writer is inclined to think a brighter sugar would
be obtained if it were sulfured slightly, say, to about 0.2 cc.
This would serve to reduce any ferric iron which might be present,
and to give a brighter granulated product.
The cost of the kieselguhr at 2.5 cents per pound is about
30 cents per ton. This can be cut down greatly by recovering
the kieselguhr. The cake consists mainly of organic matter,
a little silica, a little calcium carbonate, and the unaltered kiesel-
guhr. This can be burned at a low temperature for less than
$5 per ton, we estimate, and the ash is nearly as good a filter aid
as the original. We have recovered it five times and could notice
no difference in the filtering effect. The ash is washed by de-
cantation and does not have to be reground. We tried digesting
it with dilute hydrochloric acid, but noticed no good effect.
It is not necessary to burn off all the carbon, as what remains is
also a good filter aid, though it seems to have no decolorizing
power. Burned in a closed retort, the ash carried considerable
carbon. It filtered well, but showed no decolorizing power.
This recovering process we intend trying next fall on cane juice
by heating the cake in a closed retort, in the hope that the carbon
thus made may also show decolorizing power. In this process
the tubes of the heaters are scoured bright, and but little scale
forms on the tubes either of the effects or the pan. The filtra-
tion, however, presents certain mechanical difficulties which
have not yet been completely overcome.
ACTIVATED CHARS
A fourth method of defecation which is now attracting wide-
spread attention is by the use of activated carbons. These
carbons have from 50 to 70 times the decolorizing power of
ordinary bone-black. They are made by various processes from
wood, peat, and other organic materials. Four of these carbons,
which may be referred to here as A, B, C, and D, have been
tried in Louisiana.
A — On one of these, A, or rice hull carbon the patents an:
still in litigation. The Louisiana Sugar Experiment Station
has secured patents on this product and has dedicated them to
the public. These patents are contested at present by several
other claimants. This is quite unfortunate, in my opinion, for
the rice hull carbon is fully equal in quality to any other and
would probably be cheaper to prepare. As matters stand there
is none of it on the market, but a company is now being organized
to make it.
B — The most exhaustive exper ments have been made with the
use of B. These indeed may fairly be said to be no longer ex-
periments, though the procedure is doubtless still open to im-
provement.
C — Certain large-scale experiments recently made with C
seem to show it slightly superior in decolorizing power to B
and slightly inferior in filtering qualities. C is much heavier
than A and finer grained. Its filtering qualities would probably
be improved by making the grain somewhat larger and this I
judge would make it about equal to B.
D — This char is lighter than B, but not quite so good either
in decolorizing or in filtering qualities.
Different samples of each of these chars differed considerably.
Using total decolorizing power alone as the standard, B ranged
from 75 to 90 per cent; C from 70 to 95 per cent; D from 50 to 80
per cent. This would indicate that the processes of manu-
facture are not quite standardized as yet. If all were made
under equally careful supervision, there would probably be little
difference between them. Many other activated chars, equal or
in some cases far superior to any of the above, have been prepared
in the laboratories of the Louisiana State University and the
Sugar Experiment Station, but these have not been made on a
commercial scale. Other commercial activated chars have not
yet reached Louisiana.
The melted sugars are best first clarified with kieselguhr as
just described. This is not necessary', but it prolongs the life
of the char.
Several processes were used in applying these chars separately,
some quite elaborate and expensive, others very simple, and
installed at a minimum cost. The latter type seemed to work
as well as the former, as far as yields were concerned, while the
quality of the product was in all cases uniformly excellent. The
following process is, in the main, that carried out in one of the
less elaborate installations, modified by the writer to accord
with his experience in various other plants.
The melted raws, without defecation of any sort, are brought
to an average concentration of 20° Be.
Twenty-two hundred gallons of the liquor containing 8673
lbs. of solids are run into a 2600-gal. tank, and 400 lbs. of char
added. The amount of char depends somewhat on the character
of the raws, but runs between 4 and 5 per cent. The char is
first mixed in a closed trough by screw conveyor with some liquor
into a magma which is fed to the tanks by compressed air. Some
trouble was experienced at first in getting a good mixture, as it
tended to float on the surface. This could doubtless be over-
come by steaming the char before adding it. It is then blown
up thoroughly and circulated between the tank and the heater
and back for about 5 min. until the temperature is about 200° F.,
then passed to the receiving tank and pumping station for the
press. From here it is sent at about 8 lbs. pressure to the plate
and frame press. This pressure is subsequently increased slowly
to maintain about a constant rate of flow. Char filtration is
very rapid, owing to the decreased viscosity of the filtrate. The
filtered liquor is water-white and absolutely clear, but inasmuch
as the presses may occasionally leak, for safety's sake it is sent
through a second plate and frame press which catches any char
which may have leaked through the first. This second press
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
151
may be run for several days, if desired, without cleaning. It
might advantageously be replaced by a leaf type press, which
should give thoroughly satisfactory results. This liquor goes
to the charging tanks for the effects or the pan.
The press cake, without washing, is dropped and sent back to
a second melted sugar tank, where it is used again. This may
be repeated from 3 to 5 times, the number depending upon the
weight of char used, and partly upon the quality of the sugars
melted. Before returning to the tank, the cake passes through a
mingler where about 10 per cent of fresh char are added, and the
mass reduced to a magma. When the filtrate begins to run
yellow the char is washed to zero Brix, dropped, and sent to the
revivifying tank. Here it is treated in 800-lb. batches. To
each batch 500 gal. of 4 per cent hydrochloric acid are added in
a wooden tank provided with a perforated copper coil, and di-
gested with live steam for about 1 hr. It then passes to the acid
press, is washed to neutrality, and cut down into another wooden
cistern, with 500 gal. of 5 per cent solution of caustic soda, di-
gested with live steam for 1 hr., sent to the alkali press, and
washed to neutrality. The char is then made into a magma
with melted raws made faintly acid, and returned to process.
The cycle takes about 18 hrs. After the first revivifying the
char is used three times, again revivified and used two times,
making a total use without burning of between 9 and 10 times
for each pound of char. Special char kilns were installed in
several sugar houses, but proved of much too small capacity,
so the exhausted char was placed in piles for storage. It will
be noted that these chars serve both as a filtering medium and
as a decolorant. For this reason the following experiment was
tried, and seemed thoroughly successful. The greens or affina-
tion liquor from the washed sugar are dark in color and turbid.
They should undoubtedly be defecated before being taken back
into the process, but owing to lack of filtering capacity this was
not done in Louisiana sugar houses. This liquor was brought
to 60 Brix, boiled up with about 10 per cent of the exhausted
char, and sent through a plate and frame press. The filtrate
was found to have lost 60 per cent of its color, and was perfectly
bright. The char had lost all of its decolorizing properties. The
filtrate worked well in process. Towards the last of the season
the following method of using the char was tried out with satis-
factory results. Five per cent of char on sugar melted was added
in the blow-ups, and heated for about 5 min. This went to the
press and was followed by successive portions of filtered clear
liquor until the color was not materially changed. The char
was then dropped and sent to the kiln. This simulated the
ordinary bone-black process, the partly decolorized liquor going
back to the blow-ups and being treated with fresh char. No
acids or alkalies were used, and good results were claimed,
the yields being considerably higher than before. Data on
this procedure were not sufficient, and the process may be re-
garded as tentative only.
Owing to conditions which are well known, the difficulties of
installing new machinery delayed the installations of the elabo-
rate char plants. The quality of the product is beyond criticism
and fully equal in every respect to standard granulated. Yields,
however, seem to be no better than those obtained by phos-
phoric acid and lime or by sulfurous acid and lime. The cost
of operation seems to be higher than that of a bone-black plant.
The author sees no reason why the process cannot be made fully
the equal of bone-black in yield and cost of operation, as soon
as the usual chemical and mechanical difficulties attending
a new sugar-house process have been overcome. It has been
claimed that there was loss by inversion. This was true at the
beginning of the season, but when the acidities were kept at
the points previously indicated, of about 0.2 to 0.3 cc, the most
careful tests showed no rise in glucose ratio whatsoever.
Activated chars cost at present from 15 to 25 cents per pound.
Possibly rice hull carbon could be put on the market at 10
cents a pound, but in any case it should be kept in mind that we
are dealing with an expensive reagent in char and an expensive
raw product in sugar. This means that the process should be
under the control of the best man available. It is easy to lose
at least 1 per cent in yield. If 400,000 lbs. of raws are melted
a day, 1 per cent is 4000 lbs., which, at 10 cents a pound, is
$400.00. $400.00 a day for a few days will go quite a distance
towards paying the salary of a high-grade man, and in our opinion
no other type of men should touch the process at all. In fact,
the writer believes that many of the best qualities of activated
chars will be developed after they have been used for several
years under expert management.
BOILING
The boiling systems in Louisiana differ in each house. Melted
sugar is much less viscous and boils much more freely than cane
sirup. It is necessary to grain high in the pan in order to give
a hard, small, even grain to the sugar, but a pan which ordinarily
would boil in 4.5 hrs. with cane sirup will be finished in 1.5
hrs. with melted sugars. This means a very considerable in-
crease in the velocity of vapors through the catchall, and there
has been unquestionably a loss of sugar by entrainment. It
would seem that this loss is greatest for a short interval of time
just before graining. In order to prevent this, new systems of
baffles have been installed in the catchalls and the top coil has
been cut out in some cases.
Entrainment has thus been largely overcome, but in handling
the pans there are several things which raw sugar boilers have
had to learn Even the slightest leak in an exposed coil will
cause the sirup to stick and caramelize. This will darken the
molasses and also the sugar. The valves should be carefully
inspected to guard against this danger. In addition, when the
strike is finished and the massecuite is being discharged, any
leak whatsoever in any of the coils will have a tendency to
caramelize more sugar. For this reason it is not a bad idea to
instal a master valve and cut the pan out completely, this in
addition to the separate coil valves.
The massecuite ordinarily falls into a mixer. A crystallizer is
not practicable for the first massecuites, which would get too
stiff to be handled, for which reason they are spun as quickly as
possible. It is at this point that the equipment of most Louisiana
sugar houses fails. Rarely have there been enough centrifugals
to handle the house, when it runs at full capacity, and in conse-
quence the boiling system must be adjusted to suit the centrifugal
capacity which is. to say the least, unfortunate.
The run-off must be carefully separated from the wash, which,
being very high in purity, is returned to the first liquor. Most
centrifugal crews are careless in the matter of separating wash
from run-off. Steam is not used at all in washing, but the author
believes it could be advantageously employed and would give
a brighter sugar.
The washed sugar which generally carries about 1.5 per cent
moisture goes to the granulator, of which there are three makes
in the state, the Hersey, the Harry, and the Louisville, all working
on what is practically the old Hersey principle, and all doing
efficient work when run right. It is quite easy to get them too
hot, however, and scorch the sugar, and this is difficult to avoid
when a steam drum is used in the cooler. The newer machines
have no steam drum in the cooler, but in some of the older
machines as much as 20 lbs. of steam are occasionally carried
on this drum. The manufacturers used to call for 5 lbs. and are
now cutting it out altogether. The sugar is weighed auto-
matically into 100-lb. bags which are also sewed automatically.
These machines do their work admirably.
The first massecuite has a purity of about 99 or even higher,
the melted raws with 98.5 purity rising over 0.5 per cent during
defecation. The run-off from the first massecuite, therefore,
together with the wash, is grained a second time, the massecuite
having a purity of about 97, and the run-off from this, with a
152
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
purity of about 93 or 94, is grained a third time. These three
sugars are mixed in the granulator and are practically indis-
tinguishable from one another. The run-off from the third
massecuite has a purity of about S8 to 90. On occasions this
also may be grained and give a merchantable sugar, but ordi-
narily the sugar is light yellow and is remelted. The wash from
the bags, the presses, and all other sources goes to a blow-up
tank, where it is sometimes defecated and sometimes mixed
with the greens and grained for 96 test sugar. Massecuites of
about 60 to 65 purity are grained and go to the crystallizers
where they stay from 4S to 72 hrs. The run-offs from these
crystallizer massecuites should show about 38 to 40 purity in
ordinary sugar-house practice, but as a rule in melting raws
the purity is closer to 43. This is not so much difference,
however, as might be imagined, for the true purities of the run-
off from raw sugar crystallizer massecuites are about three to
four points higher than the apparent purities, which is not the
case with melted sugar. This should be borne in mind in making
compari ons. Sometimes the final molasses shows a purity of
about 50, in which case it is boiled to string proof and sent to the
magma tanks with the idea that it will yield a third sugar and
a run-off of about 28 to 30. The only figure we have for molasses
of this type shows a purity of 30, but with present prices for
high purity molasses the procedure is of doubtful financial value.
Yields in all cases have been lower than were anticipated.
Table II
Yield in Loss
Average Granu- Yield Sucrose
Polar- lated in Total Pounds Purity Per cent
No. ization Process Bagged 2nds Yield Mol. Mol. Raws
1 95.7 SO* 85.75 3.48 89.23 9.4 45 2.36
2 95.7 Kiesclguhr 85 3.0 88 11.8 30 4.16
3 95.2 P20« 85.5 3.7 89.1 10 43 1.7
4 95.5 PiOi 88 1.3 89.3 8 43 3.06
5 95.8 P:0. 90 0.8 90.8 7.8 43 1.65
6 95.6 P;Oi 87.5 2.1 89.6 8.3 46.7 3.4
7 95.4 Act. Char 86 3.9 89.9 9 40 1.9
8 95.8 Act. Char 89.6 .. 89.6 7.9 41.5 3.03
9 95.9 Act. Char 85.6 3.00 88.6 11.5 34.3 3.4
The figures in Table II represent the results obtained by
different sugar houses or, in one case, by different processes at the
same sugar house. In all cases they include a small quantity of
estimated sugar and an average purity for final molasses. In
some cases the sugar house was hardly equipped to obtain ac-
curate measurements. They are, therefore, only nearly cor-
rect, but they represent a fair average of the results obtained
during the season. In No. 3 yields in seconds and in molasses
were figured rather too high, and the loss in sucrose would
probably have been nearly 1 per cent more. No. 5 gives the
figures for a special run, and in the calculations there were items
of doubtful accuracy. On the whole, one may say that where
all seconds were melted back into granulated, as in No. 8, the
amount of granulated actually bagged would be close to 89
lbs. with from 8 to 8.5 gal. of molasses, and about 3 lbs. of sucrose
lost in process. The differences in individual cases may some-
times be ascribed to errors in taking stock, or to incorrect as-
sumptions as to final purities, but, in spite of this, and making
possible allowances, there seems to be about 3 lbs. loss of sucrose,
whereas in good refinery practice the loss unaccounted for ranges
from 0.8 to 1.2, of which a great portion is known to be due to
the action of bone-black. On the face of things, there should
be a smaller loss of solids in sugar-house practice than in the
bone-black refinery, but as a matter of fact the loss is about 2
lbs. greater, and the yield in granulated sugar about 3 lbs. less.
Inasmuch as the figures available are neither accurate nor com-
plete, it is impossible to explain these facts with absolute as-
surance, but the discrepancy may be due to any or all of the
following causes:
1 — Shortage of weight in the raw sugars received. If the
original shipping weights only are used, the sugar house cannot
be certain that no error has been made, and nothing lost in
transit. In one case where this error was checked up by re-
weighing, a considerable deficit in sugars received was noticed.
and the apparent yield rose accordingly.
2 — The quality of the raw sugar received this year was such
as to make accurate sampling difficult. Moreover, it was stored
under such conditions as to make deteriorations probable and
considerable. Ninety-six test sugar has on occasions dropped
two points by the time it reached New York and two more by
the time it reached the manufacturer or refinery.
3 — There can be little doubt that a sugar boiler accustomed
to boiling cane sirup will have to readjust himself considerably
in boiling melted raws. The viscosity is so small, the sirup
boils so freely, and the grain must be struck so high in the pan
that there is danger of the rapid bubbles bursting into small
particles practically like a fog and being carried away by the
high velocity of the vapor. This point has already been dis-
cussed. It is always a danger point, and in refineries it is guarded
against in several different ways. The usual sugar-house method
of analyzing the condenser water is not satisfactory, first, be-
cause of the great dilution, and, second, because it is essential to
know at what stage, if any, entrainment takes place. As a
matter of fact entrainment in well-run refineries has been re-
duced practically to zero. In the newer types of condenser
where a surface condenser is interposed between the catchall
and the ordinary condenser, the surface condenser takes out
most of the vapor and at the same time acts as a catchall itself.
This water can be caught separately and analyzed whenever
necessary, but there is no such condenser as this installed in
any of the Louisiana sugar houses at present. If entrainment
occurs it would naturally be most rapid at the moment of maxi-
mum viscosity, which would be the period of maximum super-
saturation just before graining. At the beginning of the season
it was thought that most of the loss went down the water leg of
the condenser. Some sugar is lost this way of course, but the
writer doubts that it is a 'dominant factor in houses which en-
deavor to prevent it.
4 — On the other hand, mechanical loss seemed to have been
pretty well guarded against, but here again eternal vigilance
proved to be necessary. Good press work was the exception
rather than the rule, particularly with activated chars, which
showed a strong disposition to channel in washing. In one
case a char cake showed 20 per cent sucrose in one portion, and
0.5 in another.
5 — Whenever a sugar solution is boiled there is, of course,
inversion, but this inversion is small. With the acidities used
in lime-phosphoric acid defecation there should be negligibly
little inversion. The same thing is true of defecation with lime
and sulfur dioxide. Where only kieselguhr is used one can see
no reason why any inversion at all should take place. Where
activated chars are used there may be a slight loss of sucrose,
and if the char be not carefully washed there may be also slight
inversion brought about by the hydrochloric acid retained in the
pores of the char. Inversion was tested for repeatedly. In
a few cases there were found slight increases in the glucose ratio,
but in most tests this had not changed. Under any circumstances
we do not believe the amount lost by inversion would be material.
On the other hand, there might be a loss by fermentation, but
this should not exist in a clean house. Some years ago, it was
known to make a difference of over 1 lb. in yield.
6 — Some of the loss may well be due to errors in calculation
and, therefore, only apparent. These losses should be elim-
inated when the house is cleaned up at the end of the season.
They may consist in improper weights of molasses and in the
improper purities of product.
7 — In most cases the ordinary sugar-house equipment was not
properly balanced for melting raws. Many more centrifugals
were needed in order to instal double purging where possible
for economy's sake. Better filtering devices were needed in all
cases, and greater steam economy in most. About twice the
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
153
amount of fuel was used that the refiner requires; about 6.5 gal.
of oil compared with 3.5 gal. per 100 lbs. raws melted. On the
whole, however, no difficulties have been encountered which
cannot be overcome. Processes have been fairly well standard-
ized, and are improving, so it may be said that both the cane-
sugar house and the beet-sugar house can be utilized profitably
during the off season in refining raw sugars whenever the margin
between raws and granulated passes a certain well-defined point.
RESEARCH PROBLEMS IN COLLOID CHEMISTRY
(Continued)
ADSORPTION OF SOLID BY SOLID
(46) analysis OF oxide on passive iron — It has been shown
by Bennett and Burnham1 that passive iron owes its properties
to an adsorbed and stabilized oxide of iron containing more
oxygen than ferric oxide; but they could not tell whether it
was FeC>2 or FeOa. Miiller and Spitzer2 appear to have found
that platinum stabilizes the higher oxide because they precipitate
a higher oxide of iron on a platinum anode from a strongly alkaline
ferric tartrate solution. An analysis of this precipitate would
probably settle the question. Owing to the small amount of
the precipitate such an analysis would be extremely difficult
but probably not beyond the skill of an expert analyst. It Is
possible that better results could be obtained by using a platinized
anode. It is also possible that one might precipitate a very
thin film of iron on a platinum cathode and then oxidize it com-
pletely with nitrogen peroxide.
(47) STUDY RELATION BETWEEN SIZE OF PARTICLES AND
TEMPERATURE DIFFERENCE SUFFICIENT TO CAUSE HOT PARTICLES
TO stick TO A cold rod — When a fine powder is added to a
coarser one, the former tends to coat the latter3 instead of going
into the voids. A glass rod can be considered as an extreme
case of a coarse powder and consequently it is not surprising
that a very fine powder will stick to a glass rod even when both
are at the same temperature. Coarser particles fall off when
the powder and rod are at the same temperature; but may ad-
here when the powder is hotter than the rod.4 No experiments
have yet been made to determine the relation between the
size of particles and the temperature difference necessary to
cause adherence. It is probable that the nature and pressure
of the gas enveloping the rod and the particles are factors, but
these points have not been worked out.
(48) Portland cement and gypsum — The addition of small
amounts of gypsum to cement increases the setting time. It
has been suggested that the portland cement grains become
coated with a film of gypsum; but Kiihl and Knothe6 rule this
explanation out on the ground that no such coating can possibly
be formed either during grinding or on addition of water. Since
gypsum is softer than clinker, it is probable that the gypsum
particles are distinctly finer than the cement particles. The
work of Fink6 and of Briggs7 proves that under these condi-
tions the fine gypsum particles would coat the coarser cement
particles. It is, therefore, a question of fact whether this
happens or not, and the modern microscopist ought to be able
to answer this question one way or the other.
Lime and barium carbonate powders are said to stick to char-
coal while calcium carbonate and barium sulfate do not. This
should be confirmed or disproved and experiments should be
made to determine how far the chemical nature of the powders
is a factor, and to formulate the laws.
' J. Phys. Chem., 21 (1917), 107.
2 Z. anorg. Chem., 50 (1906), 351.
» Fink, J. Phys. Chem., 21 (1917), 32; Briggs, Ibid., 22 (1918), 216.
« Aitken, Trans. Roy. Soc Edinburgh, 32 (1884), 239; Tammann,
Drude's Ann., 18 (1905), 865.
'"Die Chemie der hydraulischen Bindemittel," 1915, p. 252.
• J. Phys. Chem., 21 (1917), 32.
' Ibid., 22 (1918), 216.
By Wilder D. Bancroft
Cornell University, Ithaca, N. Y.
Received November 5, 1920
(49) BEHAVIOR OF FINE AND COARSE POWDERS IN LIQUIDS —
When fine and coarse powders are shaken up together in a liquid,
do the fine powders tend to coat the coarser ones? There is
some evidence to show that when a colloidal solution is pre-
cipitated1 the finer particles attach themselves to the coarser
ones. Owens2 showed that a dilute suspension of whiting leaves
the supernatant liquid cloudy as it settles, whereas a more con-
centrated one leaves the supernatant liquid clear. Free3 has
obtained similar results with kaolin in water. It has been shown
by Deane* that clear settling occurs when the coarse particles
are so numerous that they sweep down the finer particles with
them. In the case of clear settling, each apparent grain should
really be an agglomeration of finer grains. While this is un-
doubtedly true, it has not yet been confirmed by direct observa-
tion.5
(50) aggregation OF small particles — Hilgard8 has de-
scribed the coagulation of fine suspended particles in a current
of water, the resulting flakes consisting of twenty or thirty of
the original particles agglomerated together. Hilgard says that
the tendency towards agglomeration varies inversely with the
size of the particles and the temperature. Alcohol, ether, caustic
or carbonated alkalies tend to retard agglomeration, while neutral
salts and acids tend to promote it. These experiments should
be repeated and extended, and then interpreted from the view-
point of the colloid chemist.
adsorption of solid by liquid
(51) reversibility of calomel electrode — It is usually
assumed that the calomel electrode is reversible, but there is
no experimental proof of this. When mercury is made anode
in a potassium chloride or hydrochloric acid solution, the mer-
cury becomes coated with a black film, possibly of oxychloride,7
which offers a high resistance to the passage of the current.
When the mercury anode is covered with mercurous chloride,
the black precipitate is not formed, and the mercurous chloride
is converted into mercuric chloride which reacts slowly with
mercury to regenerate mercurous chloride. It is quite probable
that a platinum electrode coated with mercurous chloride would
show the same anode decomposition voltage as the calomel
electrode.
adsorption from solution by solid
(52) adsorption and abnormal density — When making
density determinations8 by weighing a solid in a solution, an
error may be introduced because of the solid adsorbing some of
the salt. This error is likely to be larger the finer the particles
of the solid, because the ratio of surface to mass increases with
increasing subdivision. With grains of quartz or glass varying
in diameter from 0.015 mm. to 0.9 mm., placed in solution of
iodides, the specific gravity of the latter can be adjusted so
that the smaller particles will sink while the larger will float.
1 Burton, "The Physical Properties of Colloidal Solutions," 1916, p. 160.
" Geographical J., 37 (191 1), 71.
» Eng. Mining J., 101 (1916), 684.
< Trans. Am. Elcctrochem. Soc, 37 (1920).
« See, however, Hilgard, J. Chem. Soc, 40 (1881), 970.
'Ibid., 40 (1881), 970.
' Cf. Hittorf, Fogg. Ann., 106 (1859), 344; Paschen, Wied. Ann., 34.
(1890), 62.
• Thoulet Compt. rend., 99 (1884), 1072; J. Chem. Soc , 48 (1835) 176
154
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
Marble is so porous that its surface is almost proportional to
its volume, and consequently grains of marble do not show this
phenomenon.
It would be instructive to determine the amount of error
which would be introduced if instead of weighing in water one
were to weigh in a solution of which one component was known
to be adsorbed strongly. A distinctly interesting case would
be to do such experiments with charcoal and the solutions studied
by Osaka.1
(53) ADSORPTION OF IODINE BY RED PHOSPHORUS— Sestini2
states that red phosphorus will decolorize a solution of
iodine in carbon bisulfide or of aniline red in ether. It
would be interesting to determine adsorption isotherms in these
two cases. Since the apparent density of red phosphorus varies
with the temperature to which it has been heated, it is probable
that a whole series of results could be obtained.
(54) ADSORPTION OF IODINE FROM DIFFERENT SOLVENTS BY
silver iodide — Carey Lea' has shown that silver iodide ad-
sorbs iodine strongly. This adsorption should be studied with
iodine dissolved in different solvents, so that the results could
be compared with those of Davis' on the adsorption of iodine
by charcoal.
(55) adsorption by charcoal from different solvents
OF SOLUTES other than iodine — Davis6 found that the order
of adsorption of iodine from different liquids was not the same
with different kinds of charcoal. With animal charcoal there
was decreasing adsorption in the order: chloroform, alcohol,
ethyl acetate, benzene, and toluene; with sugar charcoal the
adsorption decreased in the order: chloroform, toluene, ethyl
acetate, benzene, and alcohol; whereas for coconut charcoal,
the order was toluene, chloroform, benzene, alcohol, and ethyl
acetate. There are at least two factors governing the effect
of the solvent. The more soluble the dissolved substance is
in a given solvent, the less readily will it be adsorbed, provided
we can neglect the adsorption of the solvent itself by the solid.
There are many illustrations, but one will suffice. Charcoal
will decolorize aqueous solutions of iodine or of methyl violet,
but alcohol will extract the color from the charcoal. The solu-
bility cannot be the sole factor, however, because then the solvents
could always be arranged in the same order for the same solute,
regardless of the nature of the adsorbing agent. This is dis-
proved absolutely by the experiments of Davis. One other
factor is the adsorption of the solvent by the adsorbing agent.
This factor was not taken into account at all by Davis, whose
data are, therefore, not sufficient to enable us to tell whether
there are other factors to be considered. In order to check
these results, isotherms should be determined with solutes other
than iodine. It is possible that the different impurities in the
two charcoals account wholly or in part for the different results.
(56) quantitative adsorption of dyes by alumina, stannic
acid, etc., with special reference to hydrogen-ion con-
CENTRATION— All the work on dyes should be repeated, paying
close attention to the actual hydrogen-ion concentration. This
is more important than ever in view of the recent experiments
by Jacques Loeb.
(57) COMPARATIVE STUDY OF ADSORPTION BY ALUMINA, SILICA,
KAOLIN, FULLER'S EARTH, AND THE SO-CALLED ALUMINIUM
silicates made in THE WET way — As a help to the study of
the constitution of the silicates we ought to have comparative
measurements on adsorption by alumina-silica substances,
paying attention to impurities such as iron. While the abso-
lute value will vary very much with the structure, it seems prob-
able that a study of the relative values would be very helpful.
1 Mem. Coll. Sci. Kyoto Imp. Univ., 1 (1912), 257.
' Cazz. chim. Hal., 1 (1871), 266.
« Am. J. Sci., [3] 33 (1887), 492.
« See No. 55.
» J. Chem. Soc, 91 (1907), 1682.
(58) EFFECT OF HEAT TREATMENT ON THE ADSORPTION BY
THE preceding MATERIALS — Heating fuller's earth to about
600 ° will destroy most of its adsorbing power. The experiments
under No. 57 should be repeated with the same materials after
they have undergone a definite heat treatment.
(59) EFFECT OF HYDROCHLORIC ACID ON FILTER PAPER Miss
Murray1 found that the adsorption of hydrochloric acid by filter
paper was practically the same at the end of 3 days as at the
end of one hour. When the filter paper was left for 10 days
in contact with the acid, there was a marked change, the ad-
sorption dropping to less than half the previous value. This
should be repeated so as to determine what physical or chemical
change the paper undergoes.
(60) MATHEMATICAL TREATMENT OF WATER-RINGS — Various
people have commented on the sharpness of the water-ring
when a drop of a colored solution spreads in a piece of filter
paper. Since the water-ring is due to adsorption, the changes
in concentration as the solution passes out from the center
must correspond to an adsorption isotherm; but nobody has
ever shown that one can deduce the phenomena of the water-
rings quantitatively from the adsorption isotherm. It seems
reasonably certain that it is merely a very sudden adsorption
of color ; but this has not been proved.
(61) THEORY OF CONDITIONS UNDER WHICH ALUMINA ADSORBS
bases preferentially — Alumina is usually considered to ad-
sorb acid dyes rather than basic dyes; but Weber2 states that the
reverse is true, and Pelet-Jolivet3 says that alumina adsorbs
methylene blue and not crystal ponceau. This is said to be
due to a difference in the adsorbed ions. This matter should be
cleared up.
(62) QUANTITATIVE STUDY OF DECOMPOSITION OF SALTS BY
charcoal, ETC. — If we knew the adsorption of a base, an acid,
and the undissociated salt by charcoal, it would be possible to
calculate the amount of decomposition which should be caused
by the action of charcoal on an aqueous solution of a salt. The
first two can be determined readily; but we have no way at
present to determine the adsorption of the undissociated salt,
though one could probably make a guess at it from coagulation
experiments.4 It would be possible to measure the decomposi-
tion6 and calculate the adsorption of the undissociated salt.
At present we have no comparable quantitative data on the
adsorption of acid and base or on the percentage decomposition.
Results could certainly be obtained with aniline acetate* or
benzoate and charcoal with organic solvents.
(63) behavior OF calcium stearate — Those who believe
that acid soils are due to organic acids postulate the existence
of an insoluble acid which forms insoluble salts. Instead of
working with ill-defined substances, the thing to do is to take
solid stearic acid and treat it with varying concentrations of
barium, calcium, and sodium hydroxides and barium, calcium,
or sodium salts, making careful quantitative determination of
what happens.
(64) dyeing with mineral colors — It is probable that the
dyeing with Prussian blue, chrome yellow, iron buff, and man-
ganese brown is due to adsorption and is something more than
a mechanical precipitation of the pigment on the fiber. This
could be tested by seeing whether the fiber will adsorb Prussian
blue from a colloidal solution of this substance.
(6o) quantitative experiments on dyeing WITH mordants
— Adsorption isotherms should be determined for a number of
typical dyes with the mordants which can be used with them.
1 J. Phys. Chem., 20 (1916), 621.
» Dingier' s polyleck. J., 283 (1892), 158.
1 "Die Theorie des Farbeprozesses," 1910, pp. 61, 138.
' Weiser and Sherrick, J. Phys. Chem., 23 (1919), 305; Weiser and
Middleton, Ibid., 24 (1920), 30.
* Liebermann. Silzb. Akad. Wiss., Wicn., 74 (1876), 331;Skraup, Z.
Kolloidchem., 6 (1910), 253.
• Freundlich and Masius, "Van Bemmelen Gedenkboek," 1910, p. 100.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
155
We do not know whether the adsorption of the mordant by the
fiber results in a somewhat decreased adsorption of the dye by
the mordant. More brilliant colors are obtained with a stannic
oxide mordant1 than with an alumina mordant. We do not
know whether this is a question of transparency, of refractive
index, or of both.
(66) EFFECT OF TEMPERATURE ON ADSORPTION OF ARSENIOUS
acid — Lockemann and Paucke2 find that more arsenic is carried
down by hydrous aluminium oxide when precipitated by am-
monia from a hot solution than from a cold one. While this
is probably due to the form in which the alumina precipitates,
this has not been shown. The matter could be tested by pre-
cipitating the alumina separately hot and cold and then shaking
the resulting precipitates with the solution of arsenious acid.
(67) decolorizing action of bone-black — Patterson8 be-
lieves that the efficiency of bone-black is due in large part to
the presence of nitrogenous compounds, and he claims to have
extracted substances having 16 to 40 times as much decolorizing
action on a standard caramel solution as an equal weight of
good bone-black. This work has never been repeated. This
should be done. If Patterson's results are confirmed, the pep-
tized material should be precipitated on wood charcoal to see
what kind of a product that would give. It would be interesting
also to precipitate the peptized material or gelatin on porous
calcium phosphate, both with and without the addition of col-
loidal carbon.4
(68) adsorption by charcoal from sugar solutions—
"Bone-black is said to adsorb lime from sugar solutions,6 and
lime salts equally well if an alkali be present. Potash salts are
easily adsorbed, especially in presence of lime." This does not
seem clear, and experiments should be made to show why alkali
increases the adsorption of lime salts and why lime increases the
adsorption of potash salts.
(69) adsorption and chemical potential — If alcohol is
added to an unsaturated solution of a salt which is not soluble
in alcohol, the chemical potential of the salt is raised, as is shown
by the fact that addition of enough alcohol will cause the pre-
cipitation of the salt.* The experiments of Osaka7 on the ad-
sorption of salts by charcoal should be repeated after adding
organic liquids to the solutions. A correction would have to
be made in case there were marked adsorption of the organic
liquid.
(70) action of hydrochloric acid on hide powder — ■
Kubelka8 found that the amount of hydrochloric acid taken up
by hide powder was 0.74 milli-equivalent of hydrochloric acid
per gram of dry hide powder, regardless of the concentration in
the solution, at least from 0.01 N HC1 up. This should mean
that a definite chloride or hydrochloride is formed which shows
no appreciable hydrolysis or dissociation when in contact with
0.01 N HC1. This might be true; but Kubelka says that it is
obvious that hide powder will fix more acid in presence of sodium
chloride. When he takes a 10 per cent sodium chloride plus
hydrochloric acid he finds that the amount of acid fixed is inde-
pendent of the concentration of the acid as before, and that the
total amount is now 0.97 milli-equivalent of hydrochloric acid
per gram of dry hide powder. As a matter of fact, there is no
reason why addition of sodium chloride should increase the
amount of hydrochloric acid fixed by hide powder for the case
where there is only one compound and it is not appreciably
dissociated or hydrolyzed. Kubelka's results are, therefore,
contradictory and must be repeated. To make matters worse,
» Herzfeld, "Das Farben und Bleichen des Textilfasern," 1 (1900), 73.
2 Z. Kolloidchem., 8 (1911), 273.
• J. Soc Chem. Ind., 22 (1903), 608.
' Bancroft, J. Phys. Chem., 24 (1920), 211, 348.
> Pellet, /. Chem. Soc, 38 (1880), 834.
« Miller, J. Phys. Chem., 1 (1897), 633.
' Mem. Coll. Sci., Kyoto Imp. Univ., 1 (1912), 257.
»Z. Kolloidchem., 23 (1918). 57.
Kubelka finds that, with a 20 per ceDt sodium chloride solution,
the amount of acid taken up increases with the concentration of
the acid.
(71) adsorption of liquids from binary and ternary
systems — With two liquids miscible in all proportions, it is not
possible to determine directly which displaces the other in con-
tact with a solid. Results can be obtained by measuring ad-
sorption from binary or ternary solutions just as we are in the
habit of doing when studying adsorption from salt solutions by
charcoal, etc. There has been almost no work1 done along
this line.
SURFACE TENSION
(72) SURFACE TENSION OF MERCURY BY DYNAMIC METHODS —
Rapid measurements of the surface tension of mercury in the
presence of gases give higher values than do slower methods,
while the same values are obtained by both methods for mercury
in a vacuum.2 This is qualitatively what one would expect if
the mercury adsorbed the gas; but unfortunately the rapid
readings are higher than the readings in a vacuum and the slow
readings are about equal to the vacuum readings. Lenard*
has brought up a point which may have a bearing on this. If
we have a partially polymerized liquid such as water, the modi-
fication having the lower surface tension will concentrate in
the surface. If we form a new surface suddenly, we shall then
get a higher concentration, temporarily, of the higher modifica-
tion having the higher surface tension. If equilibrium is reached
relatively slowly, the dynamic method will give a higher value
for the surface tension than the static methods. If equilibrium
is reached instantaneously, there will be no difference. We
can account for the facts observed with mercury if we make the
assumption that mercury is a partially polymerized liquid, that
equilibrium between the modifications is reached practically
instantaneously in a vacuum, and that equilibrium is reached
relatively slowly in presence of gases. The difficulty with this
is that we have no independent proof of these assumptions. The
specific heat of mercury decreases with rising temperature and
so does that of water, at any rate up to about 30 °; but we do not
know that this is because both liquids are polymerized, nor is
it known whether all polymerized liquids show the same phe-
nomenon over some temperature range.
Another hypothetical explanation becomes possible, if we
assume that there is no sharp discontinuity at the surface be-
tween liquid and vapor. The Laplace theory of surface ten-
sion assumes that there is a perfectly sharp line of demarca-
tion between the two media bounding the surface, for instance,*
between liquid and air, while van der Waals postulates a con-
tinuous transition.
According to the latter way of looking at things, mercury in
a vacuum adsorbs its own vapor, forming a thin transition layer
varying from the density of vapor at one side to the density of
mercury at the other side. If this transition film forms instan-
taneously in a vacuum and relatively slowly in presence of a
gas, the surface tension of a fresh surface of mercury in presence
of a gas will be higher than the equilibrium surface tension of
mercury in a vacuum, and this higher surface tension thus
measured will decrease, if the surface is not renewed, down to
the equilibrium surface tension of mercury in a vacuum, or
below it if the gas is adsorbed markedly at the mercury surface.
This explanation seems somewhat more plausible than that of
Lenard ; but it is open to the same objection that there is as yet
no independent proof of the assumptions involved. The whole
problem calls for further study.
> Mathers, Trans. Am. Electrochem. Soc, 31 (1917), 271.
2 Stockle, Wicd. Ann., 66 (1898), 49; Meyer, Ibid., 66 (1898), 523.
« Cf. Aganin, Drude's Ann., 46 (1914), 1020.
'Willows and Hatschek, "Surface Tension and Surface Energy,"
1915, p. 33; Hulshof, Drude's Ann., 1 (1901), 165; Lewis, Z. Kolloidchem., 7
(1910), 197.
156
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
(73) SURFACE TENSION PHENOMENA IN TERNARY SYSTEMS—
Worley1 has discovered an interesting fact. Although sodium
chloride increases the surface tension of water, the addition of
salt to a solution of aniline in water decreases the surface ten-
sion. The sodium chloride decreases the solubility of aniline
in water and, therefore, increases the partial pressure of the ani-
line vapor. The vapor pressures, therefore, correspond to
solutions richer in aniline than that actually present, and the
surface tension relations run approximately parallel with the
vapor pressures. Worley noticed another curious thing in re-
gard to change of surface tensions of solutions with rising tem-
perature. Since liquid and vapor are identical at the critical
temperature, the surface tension becomes zero at the critical
point, and the surface tension of pure liquids, therefore, de-
creases with rising temperature. One might reasonably have
expected that the surface tension curves for solution would run
somewhere near parallel to the corresponding curves for the
pure constituents, but this is not the case for mixtures of water
with aniline or phenol. The surface tensions of the phenol-
rich solutions vary relatively little with rising temperature,
while the corresponding aniline solutions actually show an in-
crease of surface tension with rising temperature. The explana-
tion seems to be that the ratio of water to aniline or phenol in
the vapor increases with rising temperature, and that the solu-
tions, therefore, show surface tensions corresponding to what
one might expect of solutions richer in water than they actually
are. It is a pity that Worley did not also study some such case
as ether and water, where the partially miscible liquid with the
lower surface tension has the higher vapor pressure.
These experiments of Worley's should be extended and taken
up systematically for a number of cases, such as salt, phenol,
and water,5 and others in which two of the components are
practically nonmiscible at the temperature of the experiment.
(74) SURFACE TENSION OF GELATIN AND GUM ARABIC SOLS — ■
Zlobicki3 states that addition of gelatin to water lowers the
surface tension until the concentration reaches 0.5 to 0.8 g.
per 100 cc, after which it remains practically constant. If
this observation is correct, this limiting concentration must
have some physical significance, such as true solubility of gelatin
or something. The experiments should be repeated with care-
fully purified, ash-free gelatin. It is quite possible that the
results obtained by Zlobicki really depend on peptization of the
gelatin by some of the impurities.
Zlobicki* also found that small additions of gum arabic raise
the surface tension of water, after which further additions have
no effect. This seems very improbable and the experiments
should be repeated. It would be desirable to check the results
by rapid methods of measuring the surface tension of fresh sur-
faces.
(75) molecular weights OF liquids — So many liquids have
given "normal" values for the temperature coefficient of the
molecular surface energy that we have come to consider the
surface tension method a satisfactory one for determining molecu-
lar weights. On the other hand, there are a number of liquids
which give abnormally high temperature coefficients running
above three. Since it seems impossible that these liquids should
be dissociated to the extent necessary to make the temperature
coefficients normal, Walden5 rejects the whole method. This
does not seem reasonable and it is more probable that some factor
» /. Ckem. Soc, 105 (1914). 260, 273.
» Miller, J. Pkys. Ckem.. 24 (1920), 562; Steubing, Ibid., 1 (1897), 643;
Kablukow, Solomonow and Galine, Z. pkysik. Ckem., 46 (1903), 399; Rozsa,
Ibid.. 24 (1897), 13; Z. Eleklrockem.. 17 (1911), 934; Mcintosh, /. Phys.
Chem., 1 (1897), 474; Waddell, Ibid., 3 (1899), 160; Osaka, Z. physik. Chem.,
41 (1902), 560, Roth, Ibid., 43 (1903), 539.
» Bull. acad\ set. Cracovie, 1906, 497.
4 Loe. cit.
« Walden, Z. pkysik. Ckem., 75 (1910), 555; Walden and Swinne. Ibid.,
79 (1912), 700; 82 (1913), 271.
has been overlooked which becomes important in some cases.1
We know that the van't Hoff-Raoult formula gives abnormal
results whenever the heat of dilution is large; but that does not
worry us because the formula is deduced explicitly on the as-
sumption that the heat of dilution is negligible. Any discus-
sion of the Ramsay-Eotvos formula should take into account the
paper by Schames.2 He believes that the molecular weights of
the "normal" liquids are twice the formula weight, which makes
the true value for the temperature coefficient 3.36. This would
make the abnormal cases, studied by Walden, the normal ones,
an interesting possibility for which there is no independent proof
at present.
(76) rate OF evaporation — Schall and Kossakowsky* have
studied the rate of evaporation of different liquids under com-
parable conditions and get comparable results for sixteen esters,
benzene, toluene, xylene, ethylene chloride, chloroform, carbon
tetrachloride, acetone, and ether; but water and ethyl alcohol
evaporate about half as rapidly as they should, and methanol
less than one-fifth as rapidly. These variations are evidently
a result of the polymerization of these liquids; but no attempt
has been made to express the disturbing factors quantitatively.
(77) CAPILLARY ACTION IN VERY NARROW TUBES — Thomson4
has deduced a formula for the change of vapor pressure of a drop
with changing diameter; but he states explicitly that he does not
consider the formula accurate when the radius of curvature is
less than 1.2 u. He considers that the formula is not applicable
to the vapor pressure of water adsorbed by such substances as
cotton cloth and oatmeal at temperatures far above the dew-
point of the surrounding atmosphere. He believes, however,
that the difference is one of degree and not of principle ; that the
adsorption of water vapor by fibrous and cellular organic struc-
tures is a property of matter continuous with the adsorption of
vapor into a capillary tube.
It seems probable that the formula for the rise of a liquid
in a capillary tube can hold accurately only so long as the radius
of the tube is distinctly larger than the thickness of the adsorbed
film. Since it is a common practice nowadays to calculate pore
diameters from the lowering of the vapor pressure, it is very
desirable that some mathematical physicist should go over the
whole question and determine if possible at what point the for-
mulas become untrustworthy.
(78) CRYSTALLIZATION OF GRAPE SUGAR AS AN ADSORPTION
phenomenon — According to Seyberlich and Trampedach,6
grape sugar crystallizes in interlacing needles from acid solution
and in smooth plates from an alkaline solution. This differ-
ence must be due in some way to a difference in adsorption and
the problem should be studied from this point of view.
(79) CRYSTALLIZATION OF SODIUM CHLORIDE IN CUBES AND
octahedra — Sodium chloride crystallizes in cubes from pure
water and in octahedra6 from solutions of urea, boric acid, caustic
soda, etc. This should be studied as a case of adsorption.
browxian movements
(80) distribution of colloidal particles under the in-
FLUENCE OF gravity — Perrin7 found that, with gamboge particles
a little over 0.4^ in diameter, each rise of 30/1 caused the equi-
librium concentration to fall to one-half its previous value,
while a difference of 6u produced the same effect when the
gamboge particles were about 1.0/1 in diameter. On this basis
the concentration at the top of a beaker 6 cm. high would be
only V12000 of that at the bottom in the case of the fine particles.
This does not harmonize at all with the fact that the color of a
1 Cf. Harkins, Proc. Nat. Acad. Sci., 6 (1919), 539.
J Drude's Ann., 38 (1912), 830.
• Z. pkysik. Ckem., 8 (1891), 158, 241.
4 Pkil. Mas., 14] 42 (1871), 448.
4 J. Soc. Ckem. Ind., 6 (1887), 46.
4 Dammer's "Handbuch der anorganischen Chemie," [21 2 (1894), 127.
' "Brownian Movements and Molecular Reality," 1910, p. 43.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
157
•colloidal gold solution is nearly uniform over the whole height.
Either the gold solution will settle in time, or there is something
wrong with Perrin's mathematics. Professor Burton, of Toronto
University, suggests that perhaps the concentration increases
under the influence of gravity as lower levels are reached in the
beaker, up to a certain value, after which the concentration re-
mains practically uniform. It is very desirable that the actual
facts should be determined and that the mathematical theory
should be revised in case it proves to be wrong.
Since this was written, Professor Burton, of Toronto, has found
an explanation for the discrepancy. More experiments will
be needed to give a broader experimental foundation to Professor
Burton's theory.
(81) DETERMINE CHANGE IN EINSTEIN'S FORMULA FOR THE
BROWNIAN MOVEMENTS DUE TO THE ADSORBED LIQUID FILM — ■
Einstein1 has made a study of the so-called movements of col-
loidal particles suspended in a liquid and has deduced formulas
that lead to a very interesting set of relations, which are ap-
parently confirmed fairly well by the experiments. He has not
considered the possibility of an adsorbed film on the particles,
and it seems very desirable that some mathematician or mathe-
matical physicist should go over his work and see to what ex-
tent the assumption of an adsorbed film of some definite thickness
would modify the conclusions reached. The error was so serious
in the case of the formula for the viscosity that it is not safe to
assume that it will be negligible in the equations for the Brownian
movements.
COALESCENCE OF SOLIDS
(82) COALESCENCE OF RUBBER — Since two surfaces of raw
rubber unite readily and vulcanized rubber acts differently,
it should follow that vulcanized rubber adsorbs air more strongly
than raw rubber; but this lacks experimental confirmation.
(83) adhesion OF clay To STEEL — Rice2 reports that certain
clays, one of them containing 76.8 per cent silica, stick very
firmly to steel; but there is nothing to show what it is in the clay
which produces this result. This should be determined.
(84) synthetic hardpan — It is known that sodium salts
promote the formation of hardpan.3 This should be studied
more in detail as it might be possible and desirable to produce
synthetic hardpan as a sub-base for roads.
plasticity
(85) study of relation between apparent voids and point
of ZERO Fluidity — Bingham4 has made a preliminary study of
the concentration at which plasticity begins or ends. If a finely
powdered solid is added to a liquid, the viscosity of the liquid
is increased or the fluidity, which is the reciprocal of the vis-
cosity, is decreased. The fluidity was calculated from the rate
•of flow of the liquid through a viscosimeter. At temperatures
between 25 ° and 60 ° the fluidity dropped to zero at the same
concentration, so that the concentration of zero fluidity is inde-
pendent of the temperature over the range studied. With in-
fusorial earth in water, zero fluidity was reached at a volume
concentration of about 87 per cent water; with China clay at
about 96 per cent; with the graphite used in Acheson's aquadag
zero fluidity was reached at a volume concentration of about
94.5 per cent water; and with an unspecified clay at about 80.5
per cent. With infusorial earth in alcohol the zero fluidity was
reached at a volume concentration of about 88 per cent alcohol.
The mixtures having zero fluidity are not stiff and will not main-
tain their shape At higher concentrations there is a change
from viscous flow to plastic flow. The distinction made by
Bingham is that with viscous flow any shearing force — no matter
> Drude's Ann., 17 (1905), 549; 19 (1906), 280, 371; see also Smoluchow-
ski. Ibid., 21 (1906), 756.
* Trans. Am. Ceram. Soc, 14 (1912), 610.
• Hilgard, "Soils," 1906, p. 62; Ehrenberg, "Die Bodenkolloide," 1915, p.
293.
1 Am. Chem. J., 46 (1911), 278; /. Frank. Inst., 181 (1916), 845.
how small — will produce permanent deformation, whereas in
the case of plastic flow, it is necessary to use a shearing force of
finite magnitude in order to produce a permanent deformation.
It seems reasonable to assume that we reach zero fluidity when
liquid enough is added to the solid to begin to scatter the par-
ticks, in other words, when about enough liquid is added to
fill the voids. This is true in the one case studied by Bingham.
The clay referred to contained 81.6 per cent voids and required
80.5 volume per cent of water to bring it to zero fluidity. Of
course this very important generalization of Bingham's must
be tested in more cases before it can be considered as definitely
established; but it is so obvious, after it has been pointed out,
that it must be approximately true. This discovery of Bingham's
may be of distinct importance in the paint industry. The oil
requirement for a given pigment is a very arbitrary amount and
experts often differ widely in their values. Reproducible figures
could be obtained if in each case there was determined the amount
of oil necessary to give zero fluidity. Since this is more oil than
painters wish to use, it might be advisable to adopt as the
standard some definite fraction of the amount of oil necessary
to produce zero fluidity.
(86) fondant — If the grain of powdered sugar is as fine as
that of fondant, as I have been told it is, it should be possible
to make fondant without any cooking, by adding a glucose
sirup to powdered sugar.
(87) ARE sand ripples in close piling or not? — We know
that the wet sand on the sea beach is in close piling because the
pressure of the foot causes it to dilate and appear dry. We also
know that a retreating wave leaves sand ripples on the beach;
but the people who have been interested in ripples were not
interested in close piling and there seems to be no statement
whether the sand in the ripples is or is not in close piling. When
a steam roller is sent over a macadam road before the road is
dried out sufficiently, transverse ripples or ridges are formed.
It would be interesting to know whether any portion of such a
road is in open piling.
(88) THE theory OF quicksands — -It seems to be quite cer-
tain that a quicksand is a mixture of sand and water in which
the sand is in open piling and in which the sand grains are
sufficiently small or sufficiently lubricated so that the frictional
resistance to displacement is not too great. Unfortunately
this has not yet been proved experimentally to the satisfaction
of anybody.
(89) TO WHAT EXTENT IS MAXIMUM DENSITY BENEFICIAL TO
plasticity? — Some experimental studies by Professor E. B.
Mathews, of the Johns Hopkins University, seem' to indicate
that plastic clays contain particles of different sizes in about the
proportions to give maximum density. It is not unreasonable
to assume that such a mixture would give zero fluidity with less
water than any other. This matter should receive further study.
TYPES OF PRECIPITATES
(90) production OF crystals — Geologists have prepared
certain substances in distinct crystals by arranging for the slow
diffusion of dilute solutions of two salts which form the desired
substance by metathetical reaction. Johnston1 has improved
on the technique by allowing the two solutions to diffuse into
a large vessel containing water, causing a further dilution.
Dreaper2 obtained distinct crystals by letting solutions diffuse
through sand, the rate of diffusion being relatively ^low on ac-
count of the capillary spaces. Holmes3 obtained crystals of
silver bichromate in flat needles one centimeter long by this
method, substituting aluminium powder for sand. He also
filled a small test tube full of 0.1 N potassium iodide, covered
the mouth of the tube with gold-beater's skin, and immersed
' J. Am. Chem. Soc, 36 (1914), 16.
2 /. Soc. Chem. Ind.. 32 (1913), 678.
» J. Phys. Chem.. 21 (1917), 709.
158
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
the tube in a small beaker containing a saturated lead acetate
solution. At once an almost amorphous precipitate of lead
iodide appeared on the under side of the membrane and in less
than a minute crystals of lead iodide fell in a gleaming shower
to the bottom of the test tube. If the same solutions are mixed
in a test tube without using a membrane, a yellow powder is
obtained and no easily recognized crystals. This method as
developed by Holmes seems the most promising of any because
it appears to give results with more concentrated solutions and
would presumably work even better with more dilute solutions.
This method of Holmes should be tested in a number of ca-es
so as to see whether it really is as effective as it seems to be.
Perhaps by some modification of the process it might be possible
to make dolomite synthetically.
(91) EFFECT OF TEMPERATURE ON CRYSTAL SIZE — In general
a precipitate like barium sulfate comes down more coarsely
crystalline at higher temperatures than at lower temperatures.
This is due in part to the increased solubility at higher tem-
peratures. If this is the sole factor, mixing hot solutions of caustic
soda and sulfuric acid, so as to give a precipitate of sodium sulfate,
should give finer crystals than mixing the same solutions so that
precipitation occurs just above 33 °. This has never been tested.
(92) PRECIPITATION OF ALUMINA AT DIFFERENT TEMPERATURES
— Since precipitates are less gelatinous and more crystalline the
higher the temperature of formation, a series should be run on
the precipitation of alumina at different temperatures. The
results might be of distinct importance in their bearing on the
precipitation of rare earth oxides.
(93) THE PHYSICAL CHARACTER OF MAGNESIUM AMMONIUM
phosphate — The conversion of magnesium ammonium phos-
phate to pyrophosphat : sometimes is and sometimes is not ac-
companied by incandescence. The pyrophosphate formed with
incandescence is gray to black, while that formed without in-
candescence is white.1 It is suggested that the incandescence
on ignition is most marked the smaller the crystal size, which
in turn is determined by the conditions of precipitation. If
this is true, rapid precipitation in the cold in the presence of ex-
cess of strongly adsorbed phosphate ion2 should favor incan-
de=cence. The darkening of the pyrophosphate formed with
incandescence may possibly be traced to impurities adsorbed
by very finely divided magnesium ammonium phosphate.*
(To be continued)
1 Karaoglanov and Dinitrov, Z. anal. Chem., 57 (1918), 353.
2 See Weiser's discussion of the effect of adsorption on crystal siie,
J. Phys. Chem., 21 (1917), 314.
' Cf. Weiser, Ibid., 20 (1916), 640.
PLRKIN MLDAL AWARD
The Perkin Medal, well characterized as the "Badge of Knight-
hood in American Chemistry," was awarded to Dr. Willis R.
Whitney of Schenectady, N. Y., at a meeting of the American
Section of the Society of Chemical Industry held Friday eve-
ning, January 14, 1921, in Rumford Hall at the Chemists' Club
of New York City.
Dr. Whitney was the fourteenth recipient of this high honor,
and the applause which greeted him as he accepted the medal
from the hand of Dr. Charles F. Chandler, dean of American
chemists and senior past president of the American Section of
the Society of Chemical Industry, fully demonstrated the
unanimous feeling of the assembled chemists that the award was
richly deserved and that Whitney the man, as well as Whitney
the scientist, was being honored on this occasion.
In opening the meeting, Mr. S. R. Church, chairman of the
Section, spoke briefly of the history of the Perkin Medal Award,
and then called upon Dr. Allen Rogers to explain certain changes
in the manner of making the award which had been adopted
recently.
Briefly these changes provide that the medal committee which
selects the recipient shall be organized as follows: The chair-
man, secretary, and treasurer of the American Section of the
Society of Chemical Industry shall act as chairman, secretary,
and treasurer, respectivel}-, of the medal committee. The mem-
bers of the committee in addition to the above shall include all
past presidents of the Society of Chemical Industry residing in
the United States; all past chairmen of the American Section
of the Society of Chemical Industry; the vice chairman of the
American Section of the Society of Chemical Industry; the
presidents, vice presidents and secretaries of the American
Chemical Society, of the American Electrochemical Society, of
the American Institute of Chemical Engineers, and of the
American Section of the Societe de Chimie Industrielle, respec-
tively. Any of these members who are unable to attend the
meeting may be represented by a proxy. The call for nominees
to receive the award is to be sent out to the various societies in
April in place of October, thus giving more time for considera-
tion by the committee and preparation by the recipient.
Those attending the meeting of the committee shall constitute
a quorum, but no member on the committee shall represent
more than one society, except in the case of ex-officio, when he
shall indicate the society he desires to represent.
The effect of these changes is to make the committee of award
more nearly a national body, rather than one consisting largely
of residents of New York City or vicinity.
Before introducing the speakers of the evening, Mr. Church
referred to the unanimity of opinion on the part of the medal
committee in selecting Dr. Whitney for the honor to be con-
ferred and the universal approval with which this selection has
been received.
Prof. Elihu Thomson, who has been intimately connected with
the development of many of Dr. Whitney's researches, was called
upon by the chairman, and gave a detailed account of Dr. Whit-
ney's career as a scientist and investigator. He paid a splendid
tribute to the medalist's organizing ability and his early concep-
tion of the value of pure research in solving the problems of
commerce and everyday life. Dr. Thomson predicted that we
are on the threshold of great developments in thermionic engi-
neering, due largely to the pioneer work of Dr. Whitney and his
co-workers. Dr. Thomson also referred feelingly to the un-
selfish attitude which Dr. Whitney always displayed toward
the workers in his organization, his integrity of purpose, his
modesty, his ability to inspire young men, and his willingness
at all times to lend a helping hand.
Following Professor Thomson, Dr. A. D. Little reviewed some
of Dr. Whitney's achievements, touching upon many personal
phases of his career. Dr. Little's presentation, in substance,
follows.
WILLIS R. WHITNEY
By A. D. Little
Cambridge, Massachusetts
The career of Dr. Willis R. Whitney, his contributions to
science, and his influence upon research and industry have been
set forth so adequately and with such sympathy and under-
standing by the speakers who have preceded me, that I can
hardly hope to do more than review them briefly from what is
perhaps another angle and a more directly personal one.
Someone has said that an institution is the elongated shadow
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
159
of a man. Never was this more true than in the case of the
General Electric Laboratory. Its achievements have been
itemized with authority by Professor Thomson. They are the
work of many men to whom they have brought deserved dis-
tinction. None the less, the laboratory, as the entity and organ-
ization which has made this a chievement possible, is a projection
of the personality of Willis R. Whitney, and in this sense its
achievements are his achievements.
Whitney returned from Europe in 1S96 with a Ph.D. from
Leipzig. He had left home a good American and he came back
a better one. He had absorbed in Germany what were then ad-
vanced and difficult theories in chemistry and physics, and to
their application to the solution of chemical and industrial
problems he now brought vision and a contagious inspiration.
To him a problem was an opportunity, and his reaction to it
was as reflex and im-
mediate as a knee jerk.
I remember that he once
told me after a pleasant
dinner in Syracuse, when the
conversation had reached
the eternal verities, that
he didn't want to go to
Heaven unless there were
problems there.
Naturally, therefore, he
began at once the brilliant
experimental work which
has added much to our
knowledge of solubility,
colloids, and the corrosion
of metals. His funda-
mental research demon-
strated the effect of the
positive and negative ions
on the precipitation of
colloids. He found that
the corrosion of metals
was an electrochemical
process and he was, per-
haps, the first to focus
public attention upon the
great economic wastes re-
sulting from preventable
corrosion.
Whitney is a pragmatic
scientist, and the essential
and innate practicality of
his mental processes found
early expression in the suc-
cessful method which he
developed in association with Dr. A. A. Noyes for the re-
covery of ether and alcohol from collodion, a process which
assured the commercial position of the photographic film.
One very conspicuous element in Whitney's character is the
sincerity of his indifference to monetary rewards. It is the
more striking because of the clarity with which he visualizes
the economic aspects of research results.
I happen to know, for I had the honor of making the bid,
that prior to 1900 he refused a doubled salary and remained an
instructor at Technology, because he "would rather teach than
be President." At the time I thought it an extraordinary ex-
ample of devoted self-denial, but since then I have seen what
happens to our Presidents and I would, without self-adulation,
take the same position myself, much as I hate teaching.
He went to the General Electric Company, as I confidently
believe, not for money, but because it offered an environment
and opportunity for broader and more effective service. I am
Willis Rodney Whitney, Perkin Medalist, 1921
no less confident that he would return to "Tech" to-morrow and
readjust his expenditure within the narrow boundaries of a
professor's salary if he felt that there he could do a better
job.
I wonder how many of you have realized how closely in appear-
ance Whitney resembles Liszt. One expects of him — and is
not disappointed — the same fire and enthusiasm, a kindred
brilliancy of performance, a similar exothermic quality. Whit-
ney can talk to a man three minutes and inject into him
enough enthusiasm to last three months. He can recognize
genius, and he is big enough to allow the man of genius to de-
velop at his side. He has no wish and makes no effort to domi-
nate. He scrupulously apportions credit where it belongs. Jeal-
ousy is alien to his nature. These are the characteristics
of the ideal director of research, and it is because they are
possessed in superlative
measure by Willis R.
Whitney that we are pres-
ent here to-night.
Willis R. Whitney is a
great scientist, but he is not
the scientist of fiction or of
the stage. He is an in-
tensely human individual.
He is extremely fond of
out-door life, and it keeps
him sane and wholesome.
He is a farmer, not a
gentleman farmer, but a
dirt farmer who knows
hog cholera and manure,
and what to do when
his hens have the pip. He
has hobbies and rides
them. He can tell you
more about arrowheads
than an Algonquin Indian
ever knew, and if neces-
sary he can make them.
He usually prefers to pick
them up in Central Park
or Longacre Square, or at
church. He can find them
anywhere. He enjoys the
lighter things of life and
has even been known to
side-step a meeting of the
American Academy of Arts
and Sciences, and go to a
girl-and-music show in-
stead. Biological subjects
(and I am not now referring to those just mentioned in association
with music) interest him keenly. He raises flies and kills them
with X-rays to cure their cancer. Some day he may kill the
cancer first. He is a serious student of heredity and knows ex-
actly how much red hair is required to tint a large family unto
the third and fourth generation. But do not let me convey the
impression that Whitney approaches these avocational inter-
ests in the spirit of the dilettante. His knowledge of them is
not broad and thin: it is both broad and deep. When he cul-
tivates a subject, he does it intensively with all the energy in
him. Better than all this, however, Whitney has a genius for
friendship. He values it and holds it. He knows you but likes
you.
With this interest in his fellowmen so dominant and charac-
teristic, it is not surprising that Whitney should have proved an
ideal teacher or that no later absorption has turned his thought
from education. Ho inspires whole departments in the Massa-
160
THE JOURNAL OF INDUSTRIAL AND ENGINEERING^CHEMISTRY Vol. 13, No. 2
chusetts Institute of Technology; he is the prime mover of
Albany Medical College, and as trustee of Union College at
Schenectady has so tied his laboratory to the college that they
constitute a joint educational institution.
In a very striking way and more nearly, as it seems to me,
than any of his contemporaries, Whitney has the mental atti-
tude and scientific breadth of an earlier generation in the scien-
tific world, the ability to correlate and integrate observations
and deductions in wide and different fields.
In 1909 Whitney was honored by election to the presidency
of the American Chemical Society, then, as now, the largest
organization of chemists in the world. Under his administra-
tion the Society enjoyed a year of continued growth and success.
Several new divisions were organized and four new sections.
Many of the sections were visited by the president and always
with a gain to their enthusiasm and esprit. Two years later
he was similarly distinguished by the American Electrochemical
Society. For its Toronto meeting he organized a notable sym-
posium on electric furnaces and for the Boston meeting another
on electrical conduction, the subject of his presidential address
in which he brought out many interesting points. He directed
attention to the fact that whereas the resistance of pure metals
disappears at absolute zero, that of alloys does not; that we
cannot predict at all the conductivity of definite compounds
such as Cu3Sn; that no poor conductor is ductile; that if elec-
trical apparatus were made with copper having only 2 per cent
higher resistance, it would involve, on the 1912 basis of con-
sumption, about $2,500,000 added cost for power; that in the
arc the consumption of the positive electrode is apparently sec-
ondary, and that we know nothing about the theory of mag-
netism.
During the war Whitney was ubiquitous and untiring as a
member of the Naval Advisory Board, where perhaps his most
important contribution was a method for the detection of sub-
marines.
The Perkin Medal is the badge of knighthood in American
chemistry. It has never been more worthily bestowed. Its
latest recipient has inspired numberless young men; he has
brought distinction to a great corporation and proved to finan-
ciers that research pays; he has added new luster to American
chemistry. The spirit of research has laid her hands upon him,
and the spirit of youth as well.
PRESENTATION ADDRESS
By Charles F. Chandler
New York. N. Y.
It is my privilege and very pleasant duty as Senior Past
President of the Society of Chemical Industry, residing in this
country, to present to Willis R. Whitney, B.S. and Ph.D., the
fourteenth impression of the Perkin Medal, in recognition of
his most original and valuable work in applied chemistry.
Dr. Willis R. Whitney was born in Jamestown, N. Y., August
22, 1868, and was the son of John and Agnes (Reynolds) Whit-
ney. He was graduated from the Massachusetts Institute of
Technology with the degree of S.B. in 1890, and in 1896 received
the degree of Ph.D. from Leipzig.
He held the following positions at the Institute of Technology
following his graduation: Assistant, Sanitary Chemistry, 1890 to
1892; Instructor, Sanitary Chemistry, 1892 to 1894; Instructor,
Theoretical Chemistry and Proximate Analysis, 1898 to 1901;
Assistant Professor, Theoretical Chemistry, 1901 to 1904; Non-
resident Associate Professor, Theoretical Chemistry, 1904 to
1908; Non-resident Professor, Chemical Research 1908 — .
Since 1900 Dr. Whitney has been Director of the Research
Laboratory of the General Electric Company at Schenectady,
N. Y.
Among his early work, Dr. Whitney, in conjunction with
Professor A. A. Noyes, successfully developed a recovery pro-
cess for alcohol and ether from collodion which insured the com-
mercial practicability of the present photographic film.
His most notable achievement has been the creation and
development of the Research Laboratory of the General Electric
Company at Schenectady. This laboratory, one of the earliest
of its kind in this country, the embodiment of the application
of science to industry, has gained a world-wide reputation by
the quality of its work and the importance of its results. These
results speak for themselves, but only those associated in the
laboratory with Dr. Whitney can realize to what extent they
are due to him personally, or how truly the story of the lab-
oratory, from its inception with a small staff, to its present
development with 275 people on its payroll, has been the story
of his personal achievement. Its growth has followed naturally
from the value of its accomplishment, but its accomplishment
has been due primarily to him. His broad scientific knowledge,
his ability as a chemist, his resourcefulness in experiment, his
energy, enthusiasm, and optimism, combined with a clear sense
of proportionate values, laid the foundation for, and guided and
inspired all the work of the laboratory, while his democratic
and magnetic personality created an esprit de corps in his staff
which has been a powerful factor for success. It is necessary
to realize this fully in order that his personal achievements
may be justly appraised in considering the successes of the lab-
oratory.
These successes have often been recited specifically, to prove
the value of the application of organized research to industry.
In electric lighting, the first radical improvement in the carbon
incandescent filament, since Edison first produced it, was due
to Dr. Whitney's personal work. The "metalized" filament,
or "GEM" lamp, which he developed, and which embodied a
new form of carbon, gave 25 per cent more light for the same
wattage than the standard carbon filament lamp. Millions of
these new lamps were sold in a single year. A little later the
laboratory made a still greater contribution to electric lighting
by solving the problem of mechanically working tungsten, and
taught the world how to make the drawn wire which has given
the tungsten lamp its universal application. The latest achieve-
ment of the laboratory in incandescent lighting is the gas-filled
or half-watt lamp, which, in its larger sizes, has twice the effi-
ciency of the vacuum lamp, and nearly equals the most efficient
arcs. In arc lighting, the laboratory developed the magnetite
electrode, and thereby produced the most successful arc lamp
of to-day.
The laboratory has produced many new and useful forms of
insulations and molded compounds, many new alloys, for resis-
tance units and other purposes, new processes, like "Calorizing,"
for giving metals protective coatings, new articles of manufac-
ture like "sheath wire," with its core of resistance alloy, its
mineral insulation, and its metal sheath, adapted for heating
devices, new materials like "water japan" and "Genelite," new
electric furnace products, like boron carbide, useful as a flux for
casting copper, and titanium carbide for arc lamp electrodes,
new laboratory tools, such as the Arsem vacuum furnace, the
tungsten tube furnace, and the Langmuir condensation vacuum
pump, high resistance units for lightning arresters, improved
carbon and graphite brushes, and brushes of new and special
composition, such as "Metite."
The development of wrought tungsten has been followed by
several important applications worked out entirely in the lab-
oratory. Tungsten contacts have practically replaced platinum
in spark coils, magnetos, and relays, and tungsten targets have
replaced platinum in X-ray tubes.
As a result of a study of high vacuum, the laboratory devised
means and methods for producing much higher vacua than before
obtained, and the study of the phenomenon of electron discharge
in high vacuum has produced a number of new types of vacuum
tubes which have revolutionized more than one art. The
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
161
Coolidge X-ray tube was the earliest result of this investigation
and has practically displaced all other types of X-ray tubes.
It has made possible many results not otherwise obtainable, as,
for instance, the development of a truly portable X-ray outfit.
Another result was the pliotron, the first real power tube suit-
able for radio transmission. The pliotron practically created
radiotelephony, and has revolutionized radiotelegraphy. Other
types of these tubes resulting from this investigation are the
dynatron, magnetron, pliodynatron, etc.
The contributions of the laboratory to pure science have been
numerous, varied, and important, as is indicated by the titles
taken from the list of laboratory publications:
Factors Affecting Relation between Photo-electric Current and Illumina-
tion
Structure of the Atom
Theory and Use of the Molecular Gage
Theory of Unimolecular Reaction Velocities
Absorption and Scattering of X-Rays
New Method of X-Ray Chemical Analysis
New Method of X-Ray Crystal Analysis
Roentgen-Ray Spectra
High Frequency Spectrum of Tungsten
Arrangement of Electron in Atoms and Molecules
Chemical Reactions at Low Pressures
Constitution and Fundamental Properties of Solids and Liquids
Dissociation of Hydrogen into Atoms
Effect of Space Charge and Residual Gases on Thermionic Currents in
High Vacuum
Evaporation, Condensation, and Reflection of Gas Molecules
Fundamental Phenomena in Electron Tubes Having Tungsten Cathodes
Isomorphism, Isosterism, and Covalence
Mechanism of the Surface Phenomena of Flotation
Octet Theory of Valence and Its Applications with Special Reference to
the Organic Nitrogen Compounds
Properties of the Electron as Derived from the Chemical Properties of the
Elements
Structure of the Helium Atom
Structure of the Hydrogen Molecule and the Hydrogen Ion
Dr. Whitney is a trustee of the Albany Medical College and
of Union College, and a member of the Corporation of Massachu-
setts Institute of Technology. He is a member of the U. S.
Naval Consulting Board, National Research Council, American
Chemical Society (president in 1910), American Electrochem-
ical Society (president in 1911), American Institute of Mining
and Metallurgical Engineers, American Institute of Electrical
Engineers, American Association for the Advancement of Science,
American Academy of Arts and Sciences, American Physical
Society, and British Institute of Metals. He received the Wil-
ted Gibbs Medal in 1916 and the Chandler Medal in 1920.
Dr. Whitney's translation of Le Blanc's textbook of electro-
chemistry is well known.
Among the papers which he has personally published are the
following:
1 — "The Rate of Solution of Solid Substances in Their Own Solu-
tions" (with A. A. Noyes). J. Am.Chem. Soc, 19 (1897), 930.
2 — "The Nature of the Change from Violet to Green in Solutions of
Chromium Salts." J. Am. Chem. Soc, 21 (1899), 1075.
3 — "The Precipitation of Colloids by Electrolytes" (with J. E. Ober).
J. Am. Chem. Soc, 23 (1901), 842.
4 — "An Investigation of Ammonio-Silver Compounds in Solution"
(with A. C. Melcher). /. Am. Chem. Soc, 25 (1903), 69.
5— "The Corrosion of Iron." J. Am. Chem. Soc, 25 (1903), 394.
6— "Electrolysis of Water." J. Phys. Chem., 7 (1903), 190.
7— "The Migration of Colloids" (with J. C. Blake). J. Am. Chem.
Soc, 26 (1904). 1339.
8— "Colloids." Trans. Am. Electrochem. Soc, 7 (1905), 225.
9— "Arcs." Trans. Am. Electrochem. Soc, 7 (1905), 291.
10— "Suspensions in Dilute Alkaline Solutions" (with Alonzo Straw).
J. Am. Chem. Soc, 29 (1907), 325.
11 — "Organization of Industrial Research." J. Am. Chem. Soc, 32
(1910), 71.
12 — "Some Chemistry of Light" (Presidential Address, American
Chemical Society, Dec. 29, 1909). J Am. Chem. Soc. 32 (1910), 147.
13 — -"Alloys." Am. Foundrymen's Assoc, 1910.
14 — "Chemistry of Luminous Sources." Johns Hopkins Univ., 1910.
Lectures onjlluminating Engineering, Vol. 2.
15 — "Research as a Financial Asset" (Congress of Technology).
Elec World. 57 (1911), 828; J.Ind.Eng. Chem., 3 (1911), 429; Science,
33 (1911), 673.
16 — "Mental Catalysis" (Opening Chemists' Building. N. Y.). Mel.
&■ Chem. Eng.. 9 (1911), 179.
17 — "Theory of the Mercury Arc Rectifier." G. E. Review, 14 (1911),
619.
18— "Carbon Brushes." J. Ind. Eng. Chem., 4 (1912), 242; J. Frank.
Inst., 176 (1912). 239.
19 — "Electrical Conduction" (Presidential Address, American Electro-
chemical Society, April 19, 1912). Trans. Am. Electrochem. Soc, 21
(1912), 19.
20 — "Some Uses of Metals." TV. E. L. A. 35th Convention, 1,
(1912), 336. Publications of the Research Laboratory, Vol. 1.
21— "Vacua." Trans. Am. Inst. Elcc. Eng., 11] 31 (1912), 1207. Pub-
lications of the Research Laboratory, Vol. 1.
22 — "Phenomena of Catalysis." Science Conspectus, 3 (1913), 84.
23— "Light." G. E. Review, 17 (1914), 171.
24 — "Relation of Research to the Progress of Manufacturing Indus-
tries." Annals Am. Acad. Political and Social Science, 870 (1915).
25— "Research." G. E. Review, 18 (1915), 1012.
26— "The Corporation." Trans. Am. Electrochem. Soc, 29 (1916), 36.
27— "Preparedness." J. Ind. Eng. Chem., 8 (1916), 298.
28 — "Water Power and Defense." Amer. Inst. Elec Eng. (Advance
Paper). 1916.
29 — Two untitled papers. One was published in American Defense.
30 — "The Call for Research." National Defense Digest, 1916.
31 — "Research and the Newlands Bill." Met. & Chem. Eng., 14
(1916), 565.
32— "Research as a National Duty." Science, 43 (1916), 629; J. Ind.
Eng. Chem., 8 (1916). 533.
33 — "Incidents of Applied Research" (Willard Gibbs Medal Address).
J. Ind. Eng. Chem., 8 (1916), 560.
34 — "Research Organization." G. E. Review, 19 (1916), 572.
35 — "The Newlands Bill and National Research." Met. cf Chem.
Eng., 14 (1916), 621.
36 — "Practical Significance of Pure Research." Paper for American
Mining Congress, Chicago, November 1916.
37 — "The Undeveloped Powers of the South." Manufacturers Record,
70 (1916). 58.
38 — "The Great Need of Promoting Research in America." Elec,
World. 69 (1917), 12.
39 — "Research" (Address at Alumni Dinner of Massachusetts Insti-
tute of Technology, Jan. 6, 1917). G. E. Review, 20 (1917), 114.
40 — "National Need of Scientific Research." Yale Review, April 1917.
41 — "American Engineering Research." Proc. Am. Inst. Elec. Eng.
37 (1918), 115.
42 — "Patent Renewal Fees," J. Ind. Eng. Chem., 11 (1919), 936.
43 — "What Is Needed to Develop Good Research Workers." Elec.
World, 75 (1920), 151.
44 — "The Littlest Things in Chemistry" (Chandler Medal Address).
J. Ind. Eng. Chem., 12 (1920), 599.
CONFERRING OF THE MEDAL
Willis R. Whitney, Bachelor of Science and Doctor of Phil-
osophy:
It gives me the greatest pleasure, as the representative of the
Affiliated Chemical and Electrochemical Societies of America,
to place in your hands this beautiful Perkin Medal, as a token
of the appreciation and affection of your fellow-chemists.
THE BIGGEST THINGS IN CHEMISTRY
By Willis R. Whitney
General Electric Company, Schenectady, N. Y.
If I were to try to justify my receiving the Perkin Medal, I
think I would begin by assuming that now good intentions are
being rewarded. As the aim of the award is to promote or stimu-
late research, I must find the ways by which I can most directly
do so, and so I ought to say something about the biggest things
in chemistry. No matter how irrelevant some of my remarks
may seem, I hope you will believe that they are aimed with that
high intent. While it is a great honor, it is also a wonderful
opportunity to write something which may be read by 15,000
or more American chemists.
In America, patents are granted to individuals for their new
disclosures. Such patents are not granted to organizations, to
companies, or even to laboratories. This is really an antique
limitation, for discoveries are often the result of combined
165
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
efforts. And so I look at the Perkin Medal, in my case, as an
award directed to me, but belonging to the Research Labora-
tory to which I belong, it having not yet become customary to
award such medals to laboratories. In any case, I heartily
thank the various men and organizations which made this
Medal possible, and the Committee of Award who have chosen
that my name shall stand on that honor list headed by Perkin.
I am not going to tell of the specific researches in which I
may have cooperated, nor of the good fellows who have carried
them out in our laboratory, though I should like to do so. One
reason is that this is, to a considerable extent, being done all
the time, through our laboratory system. We have always fol-
lowed the plan of individual publication as completely as seemed
desirable from the scientific point of view and as rapidly as con-
sistent with fair commercial conditions. Moreover, I, being
almost the only man in our laboratory who does not often
personally carry through separate researches, have already sum-
marized the work of others until it is overdone.
What I have to say oscillates about a central point. This
point I see so well that I am surprised that every one does not
see it too, and make more use of it. I am also at a loss to know
why so many men go through college keeping their eyes mainly
on a ball of some kind or other, when the world is so full of
greater interest. Perkin's life contains all the data which we
need in analyzing scientific research, and shows at once what I
shall repeat throughout this paper, that our great advances
are usually made by men who are trained in their particular
line of work and are working diligently just beyond the bounda-
ries of the known.
Perkin was a student of chemistry in one of the best col-
lege laboratories in England, under a great teacher (Hofmann),
who was so imbued with the chemical research spirit that he
tried to keep Perkin from stopping to develop technically his
discovery of mauve. He actually left such an impression on
this young man's mind that, after years of commercial success,
Perkin returned to pure scientific research and enjoyed it for the
rest of his life.
The essentials appear to be: first, the teacher, enthusiastic
pioneer, hunting, and fishing along that ever-expanding outer
rim of knowledge; then the laboratory and equipment, supported
by some far-sighted government, individual, or organization;
and then the school boy, with shining morning face. Don't
say it can't be done, and that Perkins, Faradays, and Pasteurs
are born, not made, for the process is entirely standardized. We
in our schools have not realized the proper sequence, because we
have used so much of our energy in bringing large numbers of
men part of the way only.
On receiving the first Perkin Medal at the time of the Jubilee
Celebration, Sir William Perkin said that he had all his life in-
sisted on the importance of research, and that this medal would
accomplish a valuable result if it helped to encourage and stimu-
late activity in that direction. He then proceeded to tell the
interesting story of his subsequent discoveries. Such a story
is the strongest force he could have used to support his wish to
promote research, and it is true that, although it would have
been more agreeable to him if some one else could have told the
story, everyone who heard it, and the countless chemists who
live to read it, are glad that no one else did tell it.
PERSONAL EXPERIENCE
No greater satisfaction in connection with my own life's work
could come to me than to contribute to the encouragement and
stimulation of research. If I can help it to an appreciable extent
by telling any unpublished portions of my own story, I will
willingly disregard for a few moments a natural reluctance to
talk about myself.
I learned that Professor Perkin became a chemist through
the influence of an Englishman named Hall, with whom he
came into contact when under 15 yrs. of age, and, moreover, an
event which increased his desire to become a chemist was seeing
an experiment showing the growth of certain crystals. I have
the honor to have started as a chemist in this identical manner,
and I will tell a little more about it, because I have always
wished I had some way of expressing my gratitude to my par-
ticular Mr. Hall. When I was about 15 yrs. old, an English
mill owner and one of the leading citizens of my home town, Mr.
William C. J. Hall, assisted in establishing a Young Men's
Christian Association. He had also long been interested in
the microscope, and was a scientist such as we seldom find among
business men to-day. He formed a free evening class for about
half a dozen boys — all that could work together around the rotat-
ing table on which he placed his immense microscope. This
was so arranged that specimen, instrument and illuminating
system did not have to be disturbed as they passed from one
boy to another for observation. He did not merely show his
specimens, of which he had thousands, but taught us how to
prepare them in all the various ways now more or less common.
They were all wonderful to me, and still are. My mother gave
me some money which, combined with that of one of the other
boys, purchased a small microtome, and my father gave me
$75.00 for a microscope. Under Mr. Hall's guidance I bought
the instrument, with the understanding that whenever I wanted
a better one, the old one would be taken back at the original
price. I later procured one for §250 which, throughout 35
yrs., I have used almost daily. One of the first experiments I
tried with the microscope was to precipitate metallic silver from
silver nitrate solution onto a speck of copper filings. Anyone
who has watched these beautiful crystals grow knows that they
are surpassingly wonderful. They constituted my first chem-
istry. It was those little bottles of salts and bugs in alcohol
that led someone to call me a chemist, and it apparently deter-
mined my future work. It does not seem now as though any-
one else ever enjoyed a tenth of the pleasures my old microscope
introduced to me. I find them inseparably interwoven with
about everything I know. Even the barren North Pole re-
minds me of Andree and Amundsen and microscopic algae which
drifted across the polar circle from the Lena delta. The equally
barren Sahara reminds me of Darwin and De Vries and the
diatoms which were carried by the wind from central Africa and
fell on the deck of the Beagle, hundreds of miles away.
In trying to put the truthful personal and human element
into these notes, as previous Terkin medalists have done for the
help of would-be research men, I find I cannot lay valid claim to
the insurmountable difficulties or to especially commendable
early struggles which have helped so many others. Perhaps
even this admission, however, may have its place for the encour-
agement of some research man. I was early taught that a dollar
a day was a fair wage and that frequently this was unearned,
and I quit worrying about pay so long ago that the date is not
important. I once asked the president of a large technical
school for a salary increase of $75 a year and was shown that it
could not be done. Perhaps that wise president convinced me
that financial rewards are not the main thing. At any rate,
I believe it.
In mapping milestones not mentioned before, I want to ex-
press my indebtedness to Professor A. A. Noyes, who showed
me some of the interesting things in the science of chemistry.
He let me work with him on some physicochemical researches,
and this work was responsible for my later spending two years
with Ostwald in Leipzig, and a summer with Friedel in Paris.
Work with these men gave me a feeling of surety in chemistry
that no mere talk could ever have done. I ought to say that
one of our first joint researches, so far as publication was con-
cerned, had the peculiar effect of freeing me forever from the
wiles of college football, and if that is a defect, make the most
of it! Dr. Noyes and I conceived an idea on sodium aluminate
solutions on the morning of the day of a Princeton-Harvard
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
163
game (as I recall it) that we had planned to attend. It looked
as though a few days' work on freezing-point determinations and
electrical conductivities would answer the question. We could
not wait, so we gave up the game and stayed in the laboratory.
Our experiments were successful. I think that this was the
last game I have ever cared about seeing. I mention this as a
warning, because this immunity might attack anyone. I find
that I still complainingly wonder at the present position of
football in American education.
BIGGER THINGS
I would prefer now to talk about the biggest things in chem-
istry, not so that I may be facetious, nor yet to form a companion
piece to a talk on the "Littlest Things." Far from it. In fact,
so far from it that after having some of my thoughts in pre-
liminary notes for years, with a conviction that they ought to
be expressed, I have always deferred it. I feared that I was not
just the man to say it.
We are all interested in the detailed and specific advances
which constitute our science. We know that it is from these
little things that the largest ones grow. We see a certain simi-
larity between the history of Professor Perkin's mauve, with its
subsequent enormous development of the dye, medicine, and ex-
plosive industries, and the development of the living acorn into
the spreading oak tree. But we should sometimes look at the
forests from the plains, without obstructions. And we want to
know our chemistry, too, in its relation to the general landscape.
Some kind of an inner man advises us not to think exclusively of
the littlest things, the parts of some whole, but sometimes to
give constructive thought to the ultimate objects, to our aims
at large, our chief pretensions, our real ambitions, our main
direction of motion. Are these consistent with, or independent
of, our temporary and apparently vacillating movements?
I know from experiment (as we usually say) that no two
chemists would agree at first as to what constitute the most im-
portant things of chemistry. I have found, however, that if we
say that the "possibilities" are the biggest things, then to-day
there is some agreement between experts.
TESTED laws — Chemistry is one of those branches of human
knowledge which has built itself upon methods and instruments
by which truth can presumably be determined. It has sur-
vived and grown because all its precepts and principles can be
re-tested at any time and anywhere. So long as it remained the
mysterious alchemy by which a few devotees, by devious and
dubious means, presumed to change baser metals into gold, it
did not flourish, but when it dealt with the fact that 56 g. of fine
iron, when heated with 32 g. of flowers of sulfur, generated extra
heat and gave exactly 88 g. of an entirely new substance, then
additional steps could be taken by anyone. Scientific research
in chemistry, since the birth of the balance and the thermome-
ter, has been a steady growth of test and observation. It has
disclosed a finite number of elementary reagents composing an
infinite universe, and it is devoted to their interreaction for the
benefit of mankind. The rate of this advance in chemistry is
in our day almost incredibly great.
Mark Twain's little history game has given me a view of our
rate of development, and particularly of modern as compared
with ancient affairs, that I want to pass along to you. Possi-
bly some of you have thought of the rate of mental develop-
ment, of material development, and of power developments as
involving only a fairly uniform change through all time. This
is not so at all. But to shorten this story: I started from a
certain point in the woods with a measuring tape and marking
tools, and laid out a winding path 1000 ft. long. I cut smooth
marking places on all trees along the way and on some large
rocks. I appropriated one foot length of this patch for each
year's history since William the Conqueror (the year 1000),
and spent the rest of my time properly locating prominent
events along the path, down to 1920 ft. I was impressed by
the 45-ft. length of Queen Elizabeth's reign, near the middle of
the way, and such a short distance from Columbus and the dis-
covery of America. Stockings and pins and sugar (except as
medicine) came into the path about there. But of interest to
us particularly is that all the great chemists began to arrive to-
gether near the 1850-ft. point. This seemed very recent. It
meant that most of the superstitions about matter began to
disappear only about 250 ft. back, so to speak. You all know
the story, but for 75 or 80 per cent of my measured path, and for
the interminable portion representing all time prior to 1000
A. D. (which I let wind, without construction or destruction, back
the mile or more which might still have been historically illus-
trated), there had been no need for more than four supposed ele-
ments : earth, air, fire, and water. It was not the old facts, but
the dimensions which impressed me. While a foot is ample
space in which to erect monuments to everything we know about
any year chosen in the fifteenth century, and a single tree could
be sign-post for all the cards on events for any century a little
earlier, there was great lack of space for descriptive matter
beyond the 1800-ft. point. All down the line, to within a stone's
throw of the end, individual man-power had been the important
energy, and then, as power, it almost disappeared. Within
200 ft. of the end, which stood for the present day, steam had
been put to use, and there came in turn the myriads of machines
which multiplied a thousand-fold the previous constant and
limited muscular power of man. No one can accurately de-
termine the added spread of effort, due to this substitution of
coal for human strength, and then of machines, one for an-
other.
Within 30 ft. of the end of the path, a score of new chemis-
tries had grown into activity, and every single one seems more
promising than the original stem: physical, colloidal, subatomic
and radio, metabolic, biologic, enzymic, piezo, therapeutic —
all growing infants. Thus the time seems almost near when,
to quote Carnegie, "the mind, like the body, can be moved
from the shade into the sunshine."
This interesting game of Mark Twain's actually chokes
itself off mechanically when one tries to post modern chemical
work at one foot per year. New facts now take about that
space when posted edgewise in abstract journals, a dozen items
per page. What this game, applied to chemistry, has done
for me is to show me the almost inconceivably great strides in
countless lines which constitute our modern chemistry, and it
leaves me with the feeling that no one in the world has ever
had such possibilities open to him as the present-day student
of chemistry.
Perkin was a well-prepared research chemist when he made
his discoveries. He was just the kind of man of which we
produce too few Only a very small number of our students
get so far in the science as he went under Professor Hofmann,
and nowadays, in order to go so far, one must go much farther,
for, as Wendell Phillips said, "to be as good as our fathers were,
we must be a good deal better." The process Perkin followed
is the same one which has led to most of our discoveries. It is
the encouragement of natural inquisitiveuess under the best
conditions. It is using the newest knowledge and best tools
in exacting pieces of work. No short-cut and easy process
would have produced dyes from tar. Such efforts could not
even find a way to make tar acceptable for road material.
One of the biggest things in chemistry for us to-day is to
learn how to bring about the productive teaching of chemis-
try. The desirable qualities are illustrated by the life of Wohler,
who prepared the first organic compound, when the consensus
of opinion (and infinite argument) favored the theory that
organic compounds were producible only through a mysterious
vital force. Pasteur's work is another case of a trained research
chemist, and every American should learn his ways. What
such explorers seek are not imaginary points on a drifting field
164
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
of perpetual ice in an uninhabitable world, but something
which may possibly help every individual who lives after them.
We might have similar results developing in chemistry to-
day, but they call for the good teachers and the highly trained
observer, with well-backed faith. These two, high training
and faith, are an uncommon pair with us They seldom grow
within the same Yankee.
inorganic chemistry — I need not repeat what is known
about the many disclosures of inorganic chemistry. How,
within the past few years, chemical science has at least doubled
the number of available metals, and so raised to the ?ith power
the possible alloys. All these new metals are gradually com-
ing into use, as you know.
I am often reminded of metallic calcium in this connection,
because it is really still being born, but the process is the old one.
It was produced by high-grade electrochemical research, and
the discoverer, in describing the process, said, "We do not know
now of any use for this new metal, but when its properties and
production are understood, it will probably find its place." It
is almost useless to think otherwise. Here is a chemical element
the compounds of which are as numerous and whose ores are
as rich as those of any element known. The isolation of the
metal is not so simple as in the case of zinc, copper, iron, or tin,
and its properties are different, but, as usual, it is differing
properties which determine the new use. It is worth telling in
passing that, during the war, we made this metallic calcium
and found two widely different uses for it. One was as a suit-
able generator of hydrogen to maintain very high pressure of
this gas inside certain deep-sea sound detecting devices, where
the sea water itself was the other reagent. The reaction was
slow and well suited for this work. The other use is as a con-
tinuously reacting purifier for argon in the tungar rectifier.
This latter is now the basis of a considerable manufacturing
business. It is interesting, from the chemical research stand-
point, because it consists of a bulb made of a special new glass,
a tungsten wire spiral, an artificial graphite electrode, a little
argon gas, and some metallic calcium. Within the spread of my
brief experience, there was a time when any part of this combina-
tion would have been an impossibility from lack of every one
of these chemical materials. And so I note such researches as
Professor Lehner's, on selenium oxychloride, and I say to myself,
"Watch it grow." To add such a liquid to our little category-
will prove an ever-growing utility.
organic chemistry — We ask ourselves: Can there be greater
fields of new organic chemical research than that which met
Perkin as a student? Is not tar the last big raw material ? The
answer is simple. New fields are greater in number because the
territory- of chemical knowledge is so greatly broadened and the
new tools are so numerous. The results will depend solely on
mentality — not tar. Is it not within reason that another as
great a field as dyestuffs will be developed directly from car-
bon itself, for example? The entering gates to organic chem-
istry, reached by the shortest road, were apparently opened
when calcium carbide was first made. Thus, starting with two
of our most abundant mineral products, coal and limestone,
and adding water alone, we are supplied with the endothermic
gas, acetylene. From this point, almost anything organic
seems possible. When we realize that the manufacture of
acetone, alcohol, etc., has been thus made possible from these
inorganic raw materials, we might as well expect, by the same
road, useful food as certainly as medicaments.
I am repeatedly pointing to need in our country for the high-
est class of chemical preparation. It is not enough to talk of the
importance of fuel, of the conservation of coal, of the possible
use of benzene or alcohol in our motors. Such have already
become engineering problems, and we have a hundred thousand
engineers in the country capable of solving them. Some of
these men have already carried out the manufacture and use of
hexahydrobenzene in motors, for example, but the chemistry
itself, as a science, though still infinitely promising, is relatively
neglected.
agriculture — Possibly one of the biggest things in chcmistry
lies in agriculture, but it would be futile for me to treat of its
research by the modern truthful, but standardized, method. It
is admitted that we need more and better fertilizers. We now
use nearly $200,000,000 worth annually. It is true that we
have recently spent many million dollars on nitrate plants. We
also think we need half a million tons of potash annually, and of
this we can see how to produce locally only about 10 per cent.
We want synthetic ammonia and we can get it, because, during
the war, we were forced to adopt production methods derived
from foreign chemical research.
I do not need to go further with agriculture in order to prove
that I am not a real farmer, but I insist on doing so because I
want to make clear the thought that possibly our troubles in
genera! with Nature are sometimes due to our personal limita-
tions, not to the limitations of Nature.
It looks to me as though possibly man had developed most
of the cultivated fruits of the field along the line of maximum
human exertion and immunized them to everything else. I
draw this hasty conclusion from a single experiment of my own.
Last year I procured some special high-grade seed corn and
treated portions of it in widely different ways. In one case the
kernels were planted, properly spaced, through holes in large
sheets of paper placed on new ground which had had its grass
killed by a year's covering with gravel, w'hich was then removed.
The paper was to discourage the weeds and make hoeing un-
necessary. Other hills were planted without the paper, and
still others in which the soil was taken up, softened, and re-
placed. None of these new-type gardens was disturbed during
the summer. Less radical experiments, including nothing at
all but muscular effort, were tried on other hills in an old-type
garden. Knowing how corn had been produced through thou-
sands of years of applied work, the results could have been fore-
seen. All that grown on new soil, protected by paper from
weeds and from evaporating winds, took the whole summer
to grow about a foot high. It looked very mature, but didn't
bother to produce any ears. That which had been about buried
in modern artificial fertilizer, and well hoed, pulled through some-
how, and that which had been manured and most energetically
hoed did the best and gava a normal corn crop.
The growing of corn and grain is an older process than making
wire nails, and cannot so easily be improved. It has developed
with no fair regard to human labor, and will take more novelty
of effort to change it than was employed in freeing manual
labor from nail, screw, and bolt making, or from the production
of artificial indigo or synthetic camphor.
■When one reads of the experiments of Loeb on the rate of
growth of bryophyllum shoots as influenced by various schemes
of cutting leaf from stem, etc., one can hardly doubt that new
truth, learned for itself alone, in some such way, may at least
rearrange some parts of future agricultural research. Any-
one who has annually tried to kill a burdock by any means
short of complete eradication, or who has watched the persis-
tency with which a lot of wild chicory will grow to maturity in
the almost imaginary crack between a reinforced concrete road-
bed and the adjoining separate curbstone, will appreciate the
thought that some time, somehow, man may successfully di-
rect his researches towards the growth of useful vegetation
with reduced, not increased, human labor.
medical research — Many biggest things in chemistry are
coming from chemical research in the field of life and health.
When I recall the Rockefeller Institute for Medical Research
and think of the international character of its men and work, I
incline to the belief that, through such researches in chemistry
and allied sciences, the countries of our world may be more
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
165
certainly finally allied than by the system of countless peace-
ful words coupled with increasing arguments. There I have
seen Carrel, French scientist of the purest type, keeping chicken
tissues growing on microscope slides for nearly a decade, in
order that he may carry out those quantitative experiments
which lead to exact medical science. In such an institution a
class of refined and exhaustive work can be done whose results
stand as foundation stones on which doctors and surgeons of all
lands may build at once. The diplomacy of such institutions
leaves room for no international spies. The results, as soon as
verified, are published to all quarters of the globe. Jacques
Loeb, studying the amphoteric properties of gelatin or the tem-
perature coefficient of the life-reactions of fruit flies, is putting
permanent points of observation on the graph of human knowl-
edge where all may see, confirm, and use them. The little
Jap, Noguchi, a most attractive enthusiast and a co-worker of
Dr. Flexner's for nearly 20 yrs., is now all wrapped up in yellow
fever work. He has isolated the germ and prepared the pre-
ventive vaccine and the immunizing sera. Thus he adds
some of the finishing touches to that story of a fight which has
been under way since 1900, when Dr. Lazear knowingly risked
and lost his life by letting a certain mosquito bite him.
brain — If we think of the brain as the workshop of the mind
and then look back over the history of the growth of brains, we
find that this workshop first appeared as a relatively very small
portion of the mass of the early animals. All the prodigious
vertebrates of the mesozoic period had exceedingly small brains
in proportion to their bodies. The brain size in comparison to
the size of the animal has always been on the increase. In man
and his forerunners this is also well known. But it is significant
that, even with man, there is no continuing brain growth when
he is kept from doing or thinking something new. The Egyp-
tian fellaheen, who were kept at unchanging labor for many
centuries, possessed the same size brain cavity at the end as at
the beginning of that period. But the diameters of the brain
cavities of the early man-forms after the chimpanzee (the Trinil,
Piltdown, and Neanderthal men) stand to man as at present in
about the relation of the numbers 12, 13, 14, and 15.
And yet, in this most modern workshop, the energy which is
consumed is so small, when compared to the work done by other
organs of the body, that it cannot be measured as energy at all.
It is easy to measure the work done by the little finger and ex-
press it in calories consumed from the food eaten. The most
extensive mental exercise is much more economical of energy.
In other words, we have not yet taxed the mind's workshop from
the energy or work point of view. All this means that, follow-
ing the direction of natural development, there need be no lack
of that brain power or mentality which is needed to handle all
that he may wish to know and think.
mind — The biggest thing of all in research is the mental effect,
the projecting of a beam of light into the infinite and the growth
of man's appreciation. I can scarcely touch the many connec-
tions here. But in delicacy and sensitiveness, the mind far
transcends the wireless receivers which yet read, half around
the world, a message sent by a few watts of energy. And I
need say nothing about its possibilities as a power producer or
controller. In cooperative work, minds multiply, instead of
adding together, and growth of mind depends on the experi-
ments or the reactions with things. Whether mind is a polar-
ized energy, or merely a long habit, may still be in doubt, but
there can be little doubt as to what expands it.
Not very long ago it was safer to conceal new truths than to
disclose them. If a man wished to die by some horribly in-
genious method, he had but to discover something like the
rotundity or mobility of the earth and insist on it. For advo-
cating justification by faith alone, he would be burned alive.
Dabbling with intangible matters which led only to disputa-
tion was gradually replaced by increased attention to imme-
diate surroundings.
Is it too much to say that, through research into materials,
the main advances in physical and mental welfare take place?
Where do we meet contradiction if we say that, except for re-
search, or experimental study of matter, we stand still or mil!
about in circles filled with superstitions? Particular attributes
of the human mind may well have reached higher altitudes in
some previous age, as is usually claimed. In specific lines of
human undertaking we can but accept this as true. We have
no Homer among our poets, no Cellini nor Angelo nor De Vinci
among our artists. Plato and Aristotle and many others ages
ago equaled our present-day logicians. Such are the nuggets
of truth which the seeker for values in history is apt to dig up.
As architects or sculptors or hewers of stone we may be retro-
gressing, and in any selected development we may have passed
the zenith, but all the time the knowledge of the universe and of
each atom of it, from the tiny flower of the crannied wall to the
sun which brings it forth, and the stars which so immensely
exceed this, has been rapidly increasing. The only perpetual
motion is the growth of truth. Possibly faith, hope, and love
are not at a maximum in our age, but they may be, and through
all ages there seems to run Tennyson's one "increasing purpose."
Only one sure line of continuing increments can be traced. It is
not the line of the search for waters of eternal youth. It is
not the series of philosopher-stone experiments, though a few
of them contributed to the steady growth of our horizon. It
is not the line of ascetism, stoicism, religious tolerance, or in-
tolerance of any form, nor yet the political systems of the widest
variety. They are now useless except as they added to the ac-
cumulating mass of truth. Appreciation of environment has
always increased.
religion — The natural desire for religious truth has been
responsible for most colleges and universities. They served
first to encourage learning and prepare religious teachers, but
only recently has it become the recognized duty of universities
to seek truth by investigations of material things. Goldwin
Smith wrote of Oxford in the early days that :
For the real university students, the dominant study was that
of the school of philosophy, logical and philosophical, with its
strange jargon; an immense attempt to extract knowledge from
consciousness by syllogistic reasoning instead of gathering it
from observation, experience, and research, mocking by its
barrenness of fruit the faith of the enthusiastic student. * *
The great instrument of high education was disputation, often
repeated, and conducted with the most elaborate forms in the
tournament of the schools, which might beget readiness of wit
and promptness of elocution, but could hardly beget habits of
calm investigation or paramount love of truth.
The uptrending curve of recognized facts might be called
Nature's appreciation curve, or the growth of mind. While
cattle eat, drink, and die with no more appreciative attitude
towards their surroundings than shown in previous ages, man-
kind has accumulated, by experiment, everything that dis-
tinguishes him. But certainly the end of this growth is far away
and still out of sight When men can talk so glibly about their
closeness to a Creator and yet uniformly show, by destructive
warfare, their extreme remoteness, surely the great undertaking
whatever it means, is not nearly complete. We have much
to learn.
May it not be possible that the human urge for new truth,
the world trend for clearness of vision in material things, will
be justified? Can there be a better way of appreciating the
wonders of creation than by looking into them, uncovering,
understanding, and appreciating them?
I should identify all search for scientific truth with the high-
est religious aim, no matter what the cult. I would point out
here that our inactivity and inappreciation in the presence of
infinite, undeveloped truth is the most inexcusable type of error
166
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
and unfaithfulness. It is intense faithlessness, no matter what
conception of a Creator we adopt.
There is no better (perhaps no other) way of going forward
in the new paths which instinctively attract us than by using
new material knowledge.. Is it not possible that words of af-
fection, of sympathy and promise of all kinds, helpful, heart-
felt, and beautiful as they may be, are only the paper money of
our transactions, and that, behind them, there should be gold of
service, in which to pay the promises?
I do not look at this as crass materialism. We all know that
the mere chemical reactions of the brain are not the whole
story. A measuring machine, repeating automatically all the
motions of the scientist, would not interest us at all. Apprecia-
tion of the infinite is not mechanical, but truth is necessary for
appreciation. John Burroughs has said:
Every day is a Sabbath day to me. All pure water is Holy
Water, and this earth is a celestial abode. It has not entered
into the mind of any man to see and feel the wonders and mys-
teries and the heavenly character of this world.
Yet most of what even John Burroughs sees and appreciates
is outside of the infinitely beautiful and orderly realm of modern
chemistry. When we are first old enough to ask ourselves ques-
tions, we are so mature that we seem already surrounded by an
infinitely complex and interesting environment. A persistent
and age-old instinct makes us want to wander
Into regions yet untrod
And read what is still unread
In the manuscripts of God.
And it has developed that in no other way may we hope to un-
derstand and appreciate. Chemists should naturally be the
first and greatest appreciators. Research is appreciation.
SCIENTIFIC SOCIETIES
PLANS FOR THE SPRING MEETING
Preliminary plans for the big Spring Meeting of the American
Chemical Society to be held in Rochester, N. Y., from April
26 to 29, 1921, are already under way.
The Council Meeting, on the day previous to the regular
meeting, will be held at the Rochester Club. The General
Meeting is to utilize the Central Presbyterian Church in order
to give room for the large crowds. At this time the
address of welcome will be given by a man whose name is on
every tongue, but whose identity we are not now allowed to
divulge.
The various Sectional meetings will be held at Mechanics
Institute, where there will be hung charts illustrative of the
methods and productions of all our most important home indus-
tries. Parallel to this, there is to be a series of personally con-
ducted trips through the following large manufacturing plants:
Eastman Kodak, Pfaudler, Bausch & Lomb, Taylor Instru-
ment, and Vacuum Oil Companies.
It is also planned that during the Sectional meetings a master
of ceremonies will be in instant communication with all Sec-
tions through an intricate system of intercommunicating tele-
phones. Thus any hitches in the program which usually occur
will be at once alleviated.
• The piece de resistance will be the banquet, free to members,
to be held at Bausch & Lomb's, after which this company will
furnish a high-class entertainment. At this banquet it is hoped
much of the formality will be dispensed with, and the ladies
will be in evidence.
CELLULOSE SECTION
At the Cellulose Symposium held by the Industrial Division
at the meeting in Chicago it was voted to form a permanent
Cellulose Section. The necessary steps for organization were
taken, and President Noyes appointed Professor Harold Hib-
bert of Yale University, chairman of the new Section, with
Gustavus J. Esselen, Jr., secretary. One of the objects of the
Section is to provide an opportunity for those interested in the
practical applications of cellulose to get together with those
concerned with the more strictly scientific aspects of cellulose
chemistry, thus affording an opportunity for discussion which
should prove mutually helpful.
An interesting program is being arranged for the first meeting
of the new Section in connection with the Spring Meeting. Those
having papers which they would like to present before the Sec-
tion are requested to send title and abstract before April 1,
1921, to the secretary, G. J. Esselen, Jr., care Arthur D.
Little, Inc., 30 Charles River Road, Cambridge, 39, Massa-
chusetts.
CENTENARY OF THE FOUNDING OF THE SCLENCES
OF ELECTROMAGNETISM AND ELECTRODYNAMICS
On December 4, 1920, electrical engineers, chemists, and
men of affairs gathered at Ampere, New Jersey, on the invi-
tation of the Crocker-Wheeler Company, to do honor to the
memorable discoveries of Andre Marie Ampere.
The meeting was not held on September 18, the exact date
of the anniversary of Ampere's first memoir to the Academie
des Sciences, on account of Ambassador Jusserand's absence
abroad. Although back in this country, diplomatic matters
prevented his unveiling the bronze wreath placed above the
tablet bearing Ampere's features, which he had unveiled in
October 1908. However, his Charge d'Affaires, Prince de
Beam, made a felicitous address, and later unveiled the wreath.
Dr. Schuyler Skaats Wheeler, president of the Crocker-
Wheeler Company, introduced the speakers and welcomed the
guests.
Dr. M. I. Pupin spoke of Ampere, "The Man and Genius."
His account of the philosopher's life, his struggles against ad-
versities, his remarkable mathematical gifts, and wide acquain-
tance with all departments of learning was brought to a close
by a glowing peroration in which he eulogized Ampere as typical
of France, now emerging from imminent disaster to win the
plaudits of the world.
Dr. C. O. Mailloux, officially representing the Academie des
Sciences, devoted a part of his address to a description of the
rapidity with which Ampere developed the basic principles
upon which our electrical knowledge and engineering depend,
and then gracefully thanked the donors of the wreath in the
name of the Academie.
A series of letters by eminent scientists reprinted in pamphlet
form, from the Electrical World of September 18, and October 9,
1920, was distributed to the guests. The short genealogical
trees, drawn up by Prof. R. A. Millikan of the Ryerson Physical
Laboratory of the University of Chicago, illustrate admirably
the relationship of Ampere's work, founded on the experiments
of Oersted, to our present electrical developments:
"Electronic Amplification — De Forest, Richardson, Thomson,
Roentgen, Lenard, Hertz, Maxwell, Faraday, Ampere, Oersted.
Relativity — Einstein, Lorenz, Becquerel, Roentgen, Lenard, Hertz,
Maxwell, Faraday, Ampere, Oersted.
Radiotherapy — Rutherford, Curie, Roentgen, Ampere, Oersted.
Subatomic Structure — Sommerfield, Bohr, Rutherford, Thompson,
Roentgen, Lenard, Hertz, Maxwell, Faraday, Ampere, Oersted.
"These are merely illustrative of what might be done presuma-
bly in scores of other fields. They illustrate also the immeasur-
able value to mankind of the work of the pure scientist and the
imperative necessity of stimulating and supporting him. With
one single exception all of the foregoing names belong to men
who devoted their whole lives to pure science."
Charles A. Doremus
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
167
DR. HENRY A. BUMSTEAD
The following resolution on the death of Dr. Bumstead was
adopted at a special meeting of the Interim Committee of the
National Research Council, January 3, 1921.
Resolved, That the National Research Council learns of the
death of Dr. Henry A. Bumstead, Chairman of the Council,
with great sorrow and profound sense of loss. Dr. Bumstead
in his association with the Council had revealed to its officers
and members not only a high capacity for administration, and
a most loyal fidelity to the aims and work of the Council, but
also a sweetness of disposition and personal attractiveness which
had won for him the devoted and affectionate regard of all of
his colleagues in the Council. In his death the Council and the
scientific world lose a man of most eminent attainments, highest
character, and lovable personality.
The National Research Council extends to the bereaved wife
and family its deepest sympathy and condolence and wishes to
express to them its full appreciation of the great value of the
services which Dr. Bumstead rendered it in the period of his
association with it and the great loss which it suffers by his
untimely death. But may we all remember that "that life is
long that answers life's great ends."
recommendation of the Franklin Institute. The award was
made for special researches on the structure of photograph
images, which form part of the systematic investigation of
photographic theory undertaken by the research laboratory of
the Eastman Kodak Co., of which Dr. Mees is director.
RUMFORD MEDAL PRESENTATION
The Rumford Medal of the American Academy of Arts and
Sciences was presented on Wednesday, January 12, 1921, to Dr.
Irving Langmuir, of the General Electric Research Laboratory.
NICHOLS MEDAL AWARD
The William H. Nichols Medal for 1920 has been awarded
to Dr. Gilbert N. Lewis, of the University of California, for
his paper on the "Third Law of Thermodynamics and the
Entropy of Solutions and of Liquids," published in the Journal
ofth-e American Chemical Society, 42 (1920), 1529.
The presentation of the medal will take place at the meeting
of the New York Section of the Society, in Rumford Hall,
Chemists' Club, New York City, May 6, 1921.
PRESIDENT SMITH ADDRESSES JOINT MEETING
President Edgar Fahs Smith, of the American Chemical
Society, will deliver an address at the joint meeting of the New
York Section of the American Electrochemical Society with
the New York Sections of the American Chemical Society and
the Societe de Chimie Industrielle and the American Section of
the Society of Chemical Industry, to be held in Rumford Hall,
Chemists' Club, New York City, on February 11, 1921.
JOHN SCOTT MEDAL AWARD
Dr. C. E. Kenneth Mees has recently been awarded a John
ScottMedal and Premium by the City of Philadelphia, on the
CALENDAR OF MEETINGS
American Ceramic Society — Annual Meeting, Deschler Hotel,
Columbus, Ohio, February 21 to 24, 1921.
American Paper and Pulp Association — Annual Meeting, Waldorf-
Astoria and Hotel Astor, New York, N. Y., April 11 to 15,
1921.
American Electrochemical Society — Spring Meeting, Hotel
Chalfonte, Atlantic City, N. J., April 21 to 23, 1921.
American Chemical Society — Sixty-first Meeting, Rochester,
N. Y., April 26 to 29, 1921.
NOTES AND CORRESPONDENCE
HISTORY OF THE PREPARATION AND PROPERTIES OF
PURE PHTHALIC ANHYDRIDE
Editor of the Journal of Industrial and Engineering Chemistry:
An article on this subject was published in This Journal, 12
(1920), 1017, by H. D. Gibbs of E. I. du Pont de Nemours
& Company. As this article adds nothing to scientific knowl-
edge and also varies somewhat from being an accurate state-
ment of the facts, it was thought appropriate to present the fol-
lowing correction in order that a proper understanding might be
reached.
The matter under discussion is U. S. Patent 1,336,182, which
claims as an article of manufacture, "phthalic anhydride being
substantially chemically pure and having a melting point above
130° C. (corrected)" and "phthalic anhydride in the form of
colorless needle -like crystals substantially chemically pure and
having a melting point above 130° C. (corrected)."
It is pointed out by Gibbs that Monroe1 prepared and de-
scribed phthalic anhydride of a degree of purity which un-
doubtedly exceeds that of the product described in this patent
in 1919 prior to the date of filing of this patent. Monroe2
states in this article that "the resublimed phthalic anhydride
produced by the air oxidation process was of a high degree of
purity but it was determined to subject it to a more rigorous
purification." He found the equilibrium temperature of liquid
and crystals when this especially purified material was used to
be 130.84°. Quoting from his article, "A melting point identical
within experimental error was obtained under similar conditions
for the original anhydride which was the source of the care-
■ This Journal, 11 (1919), 1116
' Loc. cit.
fully purified material confirming the previous conclusion that
no more than traces of impurities were contained in this."
It can be definitely proved that this original anhydride was a
sample of the anhydride produced as described in the patent
under discussion (U. S. Patent 1,336,182) and was sent to the
Color Investigation Laboratory of the Bureau of Chemistry for
investigational purposes. From this there would seem to be no
doubt about the priority of the product described in the patent.
It seems quite probable that the anhydride described in this
patent is a new commercial article of manufacture. Monroe1
investigated samples of Kahlbaum's "Phthalsaure Anhydrid"
and found the equilibrium point of solid and liquid to be 129.6°.
When this material was subjected to purification, as in the case
of the product obtained by air oxidation, he obtained a constant
freezing point of 130.8°, which is the same as obtained from the
latter material. He suggests that the original samples obtained
contained a considerable admixture of phthalic acid. Certainly
the material put on the market by Kahlbaum must have been
as good as that sold in commercial quantities.
Gibbs states that "a process of manufacture by air oxidation
(using vanadium and molybdenum oxides as catalysts) which
yields a product in the form of 'long, colorless, glistening
needles' substantially chemically pure and having a melting
point above 130° C. (corrected) has been described and patented"
by himself and C. Conover. The patents referred to are U. S.
Patents 1,285,117 and 1,284,888. The essential claim of both
of these patents is as follows: "A process for the manufacture
of phthalic anhydride, phthalic acid, benzoic acid, and naphtho-
quinones, which process consists in subjecting naphthalene in
< Loc. dt.
168
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. No. 2
the gaseous state and mixed with an oxygen-containing gas
mixture, to the action of vanadium (molybdenum) oxides heated
to temperatures ranging from 250° to 650° C. When the
process is carried out according to the above claims either on a
laboratory or commercial scale, phthalic anhydride is produced
which may consist of long, glistening needles, but it is always far
from colorless and anything but substantially chemically pure,
and having a melting point above 130° C. (corrected). The
color ranges from a light yellow to black and the melting point
never is as high as 130° C. There is no mention made in either
of the Gibbs-Conover patents as to the purity of the product,
but Gibbs bases the disclosure of the remarkable purity of the
product on Monroe's work and an article published by him.1
It has been shown that Monroe carried out his work with ma-
terial made according to U. S. Patent 1,336,182, which is the
one under discussion. The article entitled "Phthalic Anhydride.
I — Introduction," just mentioned, was received for publication
August 19, 1919, which was approximately two months earlier
than the filing date of U. S. Patent 1,336,182. It will be evident
to those who have had charge of similar problems that two
months is a very short time for the development of a manu-
facturing process for the product in question. In addition to
this it can be definitely proved that this product was pro-
duced according to the claims of the patent in large quantities
at a much earlier date than either of these disclosures.
It is evident also that Gibbs has neglected to consider the
judgment reached by the examiners of the Patent Office after a
very careful search of the Patent Office records as well as the
literature on the subject.
In view of the above facts it does not seem impossible to con-
ceive the grounds upon which such a patent was granted.
ThuSeiden Company - C. E. ANDREWS
Pittsburgh, Pa.
November 15, 1920
THE IGNITION OF FIRE ENGINE HOSE WHEN IN USE
Editor of the Journal of Industrial and Engineering Chemistry:
Boston papers of November last had a most astonishing tale
of the spontaneous ignition of fire hose when in service. The
facts in the case are as follows:
It was a new 50-ft. length of the usual 2.5-in. hose consisting
of a simple rubber lining inside a heavy cotton jacket. Out-
side this was drawn a similar cotton jacket. The hose was used
in a test made on the new pumping engines, and the stream
was throttled down about 45 per cent, discharging about 250
gal. per min. Notwithstanding the fact that this quantity of
cold water from the Charles River was used, the hose took fire
between the cotton jackets. A spot 2 in. long by 1.12 in. wide was
burned clear through each. Careful examination reveals the
fact that on each side of the burned hole the inner casings or
jackets are very severely chafed. This chafing coming from
the vibration produced in the hose by the pump was in my
opinion, sufficient to produce great heat and finally active com-
bustion. I found also a similar state of things in another sam-
ple of hose used at a later test. The chemical composition of
the rubber, in my opinion, had nothing to do with the case.
I am of the opinion that the occurrence was due to excessive
friction between the cotton casings produced by the vibration
of the hose in service.
It is interesting to note that these results have been con-
firmed by Mr. J. S. Caldwell, chief engineer of the N. E. In-
surance Exchange, with three different types of engines and
three different makes of high-grade, standard hose. The ex-
periments were made in Portland, New Bedford, and Boston,
and in some cases the cotton was charred in about 15 min.
Massachusetts Institute op Technology A. H. GlLL
Cambridge, Massachusetts
January 13, 1921
1 This Journai., 11 (1919), 1031.
REPAIRING IRON LEACHING VATS
Editor of the Journal of Industrial and Engineering Chemistry:
Herewith I should like to communicate an experience in re-
pairing leaching vats which may be helpful to others.
The bottom of a 5.5 ft. by 22 ft. circular cyanide leaching
vat contained numerous holes, and some parts were so badly
worn out that a needle could be passed through without effort.
At first the leaks were calked with coal-tar soaked cotton
waste. This method proved to be inefficient. Then a 2-in.
cement bottom was laid on the inside of the tank, but pressure
variations during charge and discharge, causing various bendings
of the bottom, broke the cement layer in no time. This observa-
tion led to the construction of a more flexible bottom, built as
follows:
Over the whole defective bottom was laid a 0.25-in. asphalt
layer, covered with a layer of canvas (in our case old filter
leaves). Care was taken that the canvas was pressed on the
asphalt while the latter was still hot, in order to secure a close
contact. Finally the canvas was covered with asphalt 0.25 in.
thick.
After 24 hrs. the tank was filled with water, held under water
pressure for 72 hrs., discharged, filled again, and held under
pressure again for 72 hrs. During this experiment not the
slightest leaking could be observed.
The total repair cost amounted to approximately $92, whereas
a new tank was quoted at $750. To put a new iron bottom in
was impossible, owing to the fact that the bottom ends of the
mantel-pieces would not stand a new riveting.
As your Journal, which I receive as a member of the American
Chemical Society, often gives me helpful suggestions, I should
like to help someone who is in trouble.
French Mines C. FlURV
Taiyudong, Korea, Japan
October 13. 1920
VAPOR COMPOSITION OF ALCOHOL- WATER MIXTURES
Editor of the Journal of Industrial and Engineering Chemistry:
Under the above heading in This Journal, 12 (1920), 296
W. K. Lewis disposes of the writer's earlier results on the
same subject [This Journal, 8 (1916), 261] with the statement
that "The work of Evans is obviously unreliable in view of the
fact that he finds the composition of vapor and liquid identical
at 92 per cent by weight."
This statement of Lewis is incorrect, as the writer's experi-
ments did not extend beyond 91 .1 per cent in the liquid, which
corresponded to 91 .8 per cent in the vapor. In correspondence
Lewis says that he obtained the "92 per cent" by slightly ex-
tending the writer's curves beyond the experimental region —
graphic extrapolation. In view of the admitted experimental
error of possibly 1 per cent and the absence of evidence of the
character of the curves beyond this region, this is manifestly
unjustified, especially as the writer expressly accepted 96 per
cent alcohol by weight, as found by others, as the constant
boiling mixture.
Lewis' results are not experimentally obtained by him, but
are graphically extrapolated (again) by him from experimental
results of Wrewsky, the extrapolation being for as much as 25°
beyond the actual observations ! Surely experimental confirma-
tion of results obtained in this way might be expected, and would
be more convincing than Lewis' belief that they are "by far the
most accurate available."
A comparison of the curves obtained from Lewis' extrapolated
and the writer's experimental results, plotting alcohol per cent
against boiling point, leaves the probability in favor of the writer,
as judged from the form of the curves, especially for boiling
points between 90° and 97°, where they most diverge, Lewis'
curve showing an improbable bulge in this region.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
169
In correspondence with the writer, Lewis claims that means
should have been adopted to prevent any condensation in the
top of the distilling flask and also to prevent any superheating
of the vapor — a difficult matter. The conditions were inten-
tionally those usually obtaining in a distilling flask in which a
slow distillation of a considerable quantity of the mixture is
taking place, and therefore easily duplicated in practice, and it
is to such usual conditions that the results are still believed to
apply within the limits of error originally stated.
Purdub University P. N. EvANS
Lafayette. Indiana
October 23, 1920
Editor of the Journal of Industrial and Engineering Chemistry:
Professor Evans desires experimental confirmation of the
data as to vapor compositions of alcohol-water mixtures calcu-
lated by the writer. He will find such confirmation in the direct
experimental determinations of Lord Rayleigh,1 to which refer-
ence should have been made originally. The average differ-
ence between the twelve determinations of vapor composition
reported by Lord Rayleigh and the curves of the writer (based
•on the data of Wrewsky) is 2 per cent. Excluding two points,
the deviations of which are 6 and 7 per cent, respectively, the
average difference between Lord Rayleigh's results and the curves
is less than 1 per cent. The average difference between the
results of Professor Evans and the curves is 3.6 per cent.
The admitted failure of Professor Evans to provide against
partial condensation of vapor in the top of the flask is probably
the major source of error. This is especially serious in dilute
liquids. Thus for liquids of less than 5 per cent alcohol, the
average difference between the vapor compositions determined
by Professor Evans and those read from the curve is over 9
per cent, while the deviations of the results of Lord Rayleigh
from the curve within this same range average less than 1 per
cent. Moreover, with the exception of two points in forty-
two, all vapor compositions determined by Professor Evans are
higher than those read from the curves. This is to be expected
where partial cooling of the vapors occurs in the top of the flask.
On the other hand, ten of the twelve points of Lord Rayleigh
fall below the curve.
The data of Wrewsky were used because they seemed accurate,
and especially because no other data gave information on the
important questions of change of vapor composition and of
vapor pressure with change in temperature. When more ac-
curate data become available, it is not improbable that the
vapor-composition curve calculated from Wrewsky will be
found too high rather than too low.
W. K. Lewis
Department of Chemical Engineering
Massachusetts Institute of Technology
Cambridge, Massachusetts
January 9, 1921
Phil. Mag., [6] 4. (1902), 529.
THE BRITISH DYE BILL
A Bill to Regulate the Importation of Dyestuff s
Be it enacted by the King's most Excellent Majesty, by and
with the advice and consent of the Lords Spiritual and Tem-
poral, and Co'mmons, in this present Parliament assembled,
and by the authority of the same, as follows:
1 — (1) With a view to the safe-guarding of the dye-making
industry, the importation into the United Kingdom of the follow-
ing goods, that is to say, all synthetic organic dyestuffs, colours
and colouring matters, and all organic intermediate products
used in the manufacture of any such dyestuffs, colours, or colour-
ing matters shall be prohibited.
(2) Goods prohibited to be imported by virtue of this Act
shall be deemed to be included among the goods enumerated
and described in the Table of Prohibitions and Restrictions In-
wards contained in section forty-two of the Customs Consolida-
tion Act, 1876, and the provisions of that Act and of any Act
amending or extending that Act shall apply accordingly.
2 — (1) The Board of Trade have power by licence to authorise,
either generally or in any particular case, the importation of
any of the goods, or any class or description of the goods, pro-
hibited to be imported by virtue of this Act.
(2) For the purpose of advising them with respect to the
granting of licences the Board shall constitute a committee con-
sisting of five persons concerned in the trades in which goods
of the class prohibited to be imported by this Act are used, three
persons concerned in the manufacture of such goods, and three
other persons not directly concerned as aforesaid.
Such one of the three last-mentioned persons as the Board
shall appoint shall be chairman of the committee.
(3) For the purpose of providing for the expenses incurred by
the Board in carrying this Act into execution, the Board may
charge in respect of a licence a fee not exceeding five pounds.
3 — Subject to compliance with such conditions as to security
for the re-exportation of the goods as the Commissioners of
Customs and Excise may impose, this Act shall not apply to
goods imported for exportation after transit through the United
Kingdom or by way of transhipment.
4 — Anything authorised under this Act to be done by the
Board of Trade may be done by the President or a secretary
or Assistant Secretary of the Board or by any person authorised
in that behalf by the President of the Board.
5 — (1) The provisions of this Act shall continue in force for a
period of ten years from the commencement thereof and no longer.
(2) This Act may be cited as the Dyestuffs (Import Regula-
tion) Act, 1920.
EUROPEAN RELIEF COUNCIL
Everybody in the country by this time knows of the work
of the European Relief Council headed by Mr. Hoover, and
the "Invisible Guests" which they are struggling to entertain
until the next harvest. I am sure that everyone of the mem-
bers of the American Chemical Society wants to take part
in this splendid work, but some may be so situated that they
do not know where to send their contribution. In case no local
committee is functioning, such contributions may be sent to
me at 61 Broadway, New York, N. Y. At Mr. Hoover's request,
I am acting as chairman of the Chemicals Division in this city,
and all such contributions would naturally be credited to the
chemical industry. A word should be sufficient to bring a prompt
response from any who have not already contributed to this
magnificent work.
January 20, 1921
Wm. H. Nichols
WASHINGTON LETTER
the fordney tariff bill
Washington has been concerned of late with the amusing
and not too difficult task of muddying the waters It is easy to
muddy the waters, and who is to reprove a senator for doing so,
especially if he has handy a semi-plausible excuse?
E^There has been much fuss and feathers flung round the Ford-
ney emergency tariff measure by various members of the Senate,
both Democrats and Republicans, and that measure has been
dignified with a favorable report from the Senate Finance Com-
mittee, the members of which sat for several days hearing pil-
grims gathered to the Mecca tell of their dire straits brought
about by the squeezing pincers of economic forces.
f^There was not any doubt that the bill would pass the House
when it was reported from the House Ways and Means Com-
mittee, but in the Senate the situation is different, and there
are few members of the Finance Committee who expect the bill
to be enacted into law.
The bowing of the representatives of powerful manufacturing
districts to what they believe to be the dictate of the voting farmer
is par excellence an example of the psychology of the lawmakers
of the great United States. They know not wisdom, and prin-
ciple is a word they wot not of. Force — the fear of defeat and
the threat of defeat in votes — is understood. That is heeded.
And the Senate committee throws to the American farmer the
sop of a measure that it knows full well will never be enacted into
law.
170
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
There has been some talk of attaching the dye bill as an
amendment to the emergency tariff measure, but that would
avail little and will not seriously be attempted. Senator Pat
Harrison, Democrat, of Mississippi, has succeeded in having
attached to the emergency tariff measure as an amendment
irrelevant laws that alone will take the reading clerk of the
Senate a week to read.
Chairman Fordney's denunciation of a licensing system for the
protection of the dyestuffs industry and championing of an em-
bargo for potash when the Longworth bill was passed by the
House is recalled by Senator Smoot, of Utah. The old saw to
the effect that it depends upon whose ox is gored is perhaps
apropos. The wool growers of the West have been hard hit
by the disappearance of their market. This was evidently well
impressed upon Senator Smoot during the time he spent in Utah
when elections were uppermost in the minds of senators, for
immediately upon his return to Washington he announced that
nothing less than an absolute embargo against all importations
of wool would save the great wool and cattle industries of the
Nation. Unfortunately, perhaps, there are no manufacturers
of dyestuffs among Senator Smoot's constituents.
The dye bill
Careful survey of the situation in the Senate has convinced
friends of the vital dyestuffs industry that there is practically
no hope for enactment of a licensing bill protecting the industry
at this session. This is due to the determined opposition of
Senators Moses and Thomas and the apathy existing in the ranks
of the Republicans who profess their desire to see the measure
enacted into law. Behind this apathy upon the part of the
Republicans there is to be found a peculiar chain of reasoning.
With protection the by-word of their party, Republican senators
are anxious that it be understood that protection is spelled in
only one way, viz., tariff. If a tariff is insufficient to protect
a vital industry, that is too bad, but — let's try it anyhow; the
embargo is a Democratic measure.
Tear camouflage and political pretense aside, and in the last
analysis the secret lies in the fact that the Republican leaders
in the Senate are convinced that whatever they give to the
American dye industry it must be content and lend their party
support, because the industry cannot expect to get as much from
the Democratic party.
Because of the existing situation it is understood that a mea-
sure providing a system of tariffs for protection of the dye
industry may be introduced in the near future by a member of
the Finance Committee who is friendly to the Longworth bill.
Such a measure will, of course, not be opposed by the dye pro-
ducers. The attitude of the dye men. so far as can be ascer-
tained, has not changed. The smaller manufacturers are par-
ticulaily insistent that more than a tariff is needed for their
protection. The measure, which is understood to be under
preparation by Senator Knox, of Pennsylvania, will be built
along the general lines of the Moses amendment. Such a
measure may enable the assembling of solid Republican support
for passage at this session. Senator Thomas, Democrat, has
been absent from the Senate because of the illness of his wife,
but now is back in his seat. Such a measure as outlined will
certainly not meet with his approval, however, and he probably
will be joined by a considerable number of other Democratic
senators who would vote for the Longworth bill.
Unless the improbable occurs and some measure protecting
the dye industry is passed this session, an effort will be made to
extend the life of the War Trade Board Section of the Depart-
ment of State. Funds for carrying on the work of this organiza-
tion also are needed.
THE NITRATE BILL
Assailed as a socialist measure, the nitrate bill has been passed
by the Senate by a vote of 34 to 29 and sent to the House, where
there will be made another determined effort on the part of
Republican members to kill it. The bill as passed by the Senate
provides for a federal corporation, capitalized at $12,500,000,
to develop the nitrate plant erected at Muscle Shoals, Alabama.
Expenditure of $140,000,000 for water-power development is
also authorized by the measure.
Passage of the bill by the Senate followed lengthy and bitter
debate, with opponents just falling short by a few votes in their
efforts to defeat or emasculate it. Opponents of the measure
object to it as an entering wedge for the entry of the Government
into a field that should be left to business. Supporters declare
that the need for the product of the plant is great, but business
has not seen fit to undertake the work of supplying the needs of
the country.
Senator Wadsworth, of New York, succeeded in having several
amendments of a technical nature accepted, and several important
changes in the provisions of the measure were made as a result
of the efforts of the New York senator. An effort was made to
attach the measure as an amendment to the sundry civil appro-
priation bill early in January, but this was defeated. The fight
on the bill developed along party lines, with several Republican
senators supposed to be opposed to it absent and not paired when
the vote came. Senator Poindexter, Republican, of Washing-
ton, made a last effort to have the bill sent to the Military
Affairs Committee, but was unable to carry his motion. Senator
Smoot was particularly active against the measure and de-
clared that it was not in reality a proposition for the production
of fertilizer, but was "for the development of power in the in-
terest of utilities."
THE NOLAN BILL
The Nolan patent office reorganization bill is still in con-
ference between House and Senate, and apparently an agree-
ment on a report back from conference is not a prospect of the
next few days. The conferees have held generally to their lines
of difference previously outlined, and the section of the Senate
bill providing for the turning of patents over to the Federal
Trade Commission is the principal bone of contention. There
seems to be little question but that there will be material amend-
ments to the Senate bill, and increased personnel and pay will
be granted the Patent Office by the measure which eventually
will come from the conference.
An agreement has been reached for a vote on the bill regulating
the meat packers. This vote is to be taken on January 24,
and debate is to be held on the measure. Senator Penrose,
chairman of the Finance Committee, has declared that he wants
to make the emergency tariff measure the unfinished business of
the Senate, and the Senate still has to consider many appropria-
tion bills that are to come from the House.
CHEMICAL WARFARE SERVICE
Hampered continually by the General Staff controlled by
General March, Chief of Staff of the Army, General Amos A.
Fries, Chief of the Chemical Warfare Service, has made public
a statement in which he outlined the difficulties that have been
placed in the way of proper development of the Service by the
Chief of Staff. General Fries, it will be recalled, was hardly
back in the United States from France where he was in charge
of the Chemical Warfare Service of the American Expeditionary
Forces when he was reduced to his pre-war rank of Lieutenant
Colonel. General March and Secretary of War Baker strongly
opposed creation of the Chemical Warfare Service as a separate
department of the Army, and endeavored to have it submerged
under another department. This, however, was defeated when
the army reorganization bill, fathered by Senator Wadsworth
and Representative Kahn, of California, was passed by Congress.
The opposition in Congress to Secretary Baker and General
March perhaps resulted in Congress taking a more favorable
attitude toward the Service as a separate branch than if they had
supported such a proposal.
General Fries charged that the development of the Service
was being continually hampered and restricted by General
March, and that plans worked out by the officers in charge
of the work had been interfered with and could not be carried
out. Training of proper personnel, which will be needed, was
not permitted, he charged, and activities were limited practically
to the limited training of an insufficient number of officers with-
out the necessary enlisted personnel.
CENSUS OF DYES
The census of dyes and coal-tar chemicals for 1919, which has
been under preparation for some time by the United States
Tariff Commission, has now been published. In its report the
Commission has this to say with regard to the quality of American
dyestuffs:
As has been pointed out in earlier reports of the Commission, during
1915 and 1916 the new American dye industry naturally sought the line of
least resistance by making dyes which were easiest to make, and the con-
sumers used whatever dyes they could get instead of the varieties they
preferred. As a result there were many cases of enforced substitutions
of both German dyes (available from stocks) and American dyes This
substitution in early years of the war materially damaged the reputation of
American dyes. During the succeeding years there has been a steady and
progressive improvement in the situation. Although consumers were better
supplied with the particular dyes they desired in 1919 than they were in
1918. there were still needed certain types of dyes which could not be sup-
plied from American sources in the quantity desired. Thus in 1919 there
was an insufficient domestic output of vat dyes which, on account of their
extreme fastness and beauty of shade, are important for cotton shirtings,
ginghams, and calicoes. Considerable progress has been made, however,
toward supplying these much needed colors. There is also a demand for
many individual dyes of other classes which are not yet available at all or
only in inadequate amounts. This is particularly true of alizarin derivativet
and of certain other specialties.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
171
Commenting upon the exportation of certain American dyes
during the year, the Commission declares that:
In estimating the significance of this achievement of the domestic
industry in the exportation of dyes it should be remembered that domestic
manufacturers during 1919 and 1920 have met little competition in foreign
markets from German dyes. It should also be pointed out that any de-
ductions as to the competitive strength of the domestic industry which are
based on exports of dyes do not take into consideration the fact that the
domestic industry is still deficient in the important group of vat and alizarin
dyes.
Discussing the condition of the German dye industry, the re-
port says that:
During February 1920, the quantity of dyes reserved by German
plants totaled 876,449 lbs., indicating a total output of over 3,500,000
lbs. for that month. A progressive increase is shown in each succeeding
month to a maximum of 3,026,247 lbs. in August, which indicates a total
output of over 12,000,000 lbs. monthly. Since August there has been a
slight decline in reserved stocks to 2,779,132 lbs. in October. The rate of
production from July to October, inclusive, is only about one-third of Ger-
many's pre-war output.
One of the most important features of the report is the detailed
table it contains giving figures on dye imports into this country
during the fiscal year 1920. This is carried out in detail and gives
the same figures in general as were contained in the Norton report
early in the war.
TARIFF REVISION
Hearings on general revision of the tariff were begun by the
House Ways and Means Committee early this month. Taking
up the tariff by schedules in alphabetical order, the committee
devoted three days, beginning January 6, to Schedule A (chem-
icals). Coal-tar chemicals already provided for in the Long-
worth bill were not touched upon.
There will be, of course, no effort to begin consideration in the
House itself of the new tariff law the Republicans propose in
place of the Underwood act, now in effect. It is planned to
finish hearings on the entire law by the Ways and Means Com-
mittee before adjournment of this session of Congress, and to
have a new tariff bill ready for introduction in the House early
in the next Congress, which will be called in extra session early
in April, as Chairman Fordney has announced after a conference
with President-elect Harding at Marion, Ohio.
Germany looms as the ghost feared by those seeking tariff
protection, although great emphasis is also laid by several in-
dustries upon the competition that is to be expected from
Japan.
Considerable sentiment exists among Republican members of
the committee in favor of temporarily laying aside the new
tariff in favor of revenue revision. It is impossible at the
present time, they point out, to work out a scientific tariff based
upon the difference in costs of production in the United States
and abroad. Chairman Fordney, however, has refused to change
his plans for continuing hearings on the tariff.
Elimination of the ad valorem in favor of the specific rates of
duty has been advocated by Representative Longworth, of
Ohio, and this, too, is favored by Chairman Fordney. The ques-
tion of exchange must necessarily enter into the discussion and
several plans have been advanced, none of which so far, however,
has been received with any great kindness by the committee.
Chairman Fordney has declared that all duties should be assessed
upon the American valuation of imported goods. This has been
ridiculed by the Democrats as impracticable and described as a
camouflage designed to enable the enactment of rates consider-
ably higher than would otherwise be possible. Several Republi-
can members of the committee also are opposed to this
scheme.
Hearings on Schedule A were completed within the allotted
three days, Chairman Fordney cutting witnesses short at the
expiration of their allotted few minutes, and granting permission
to file supplemental briefs. Earthenware and glassware rep-
resentatives were heard by the committee, following the con-
clusion of hearings on the chemical schedule.
The exchange situation and efforts to ascertain the industrial
and commercial conditions in Germany and Japan evidently will
be features throughout the hearings.
January 17, 1921
PARI5 LETTER
By Charles Lormand, 4 Avenue de l'Observatoire, Paris, France
THE PAPER SITUATION
The crisis in the chemical industries to which I called atten-
tion in my previous letter still continues, more especially in the
paper trade: factories are being compelled to dismiss their em-
ployees. The Darblay factory at Corbeil-Essonnes, the Etienne
factory at Aries, the Papeterie de l'Ouest at Chatenay are cases
in point. Scandinavian competition is particularly felt in this
industry and the price of wood pulp, the raw material, plays
a very important part.
In order to rid ourselves as completely as possible of the neces-
sity of obtaining wood pulp from Scandinavia, we are at present
studying its industrial production, on a large scale, from alfa,
a product which is very abundant in Morocco and Algeria. The
Societe des Produits chimiques dAlais and Camargue, les
Papeteries de Rives, les Etablissements Berges, Outhenin-
Chalandre, etc., have had a study made at Seveux (Haute
Saone) of all points concerning the manufacture of alfa paper.
A factory is to be set up on the banks of the Rhone, near Avig-
non, in a former gunpowder arsenal which is now lying idle.
This factory is to be equipped to treat 30,000 tons, and it is
hoped to start work in 6 mos.' time.
The high cost of paper considerably hampers editors and
printers, and scientific publications are even threatened with
suspension. To avoid this difficulty the Confederation des
Societes scientifiques francaises, of which the Union Nationale
de la Chimie pure et appliquee forms part, has decided to estab-
lish a printing and publishing company for scientific works, as
well as for the sale of French and foreign books. A special de-
partment would keep the French public acquainted with English
scientific publications.
THE ALSATIAN POTASH INDUSTRY
At the last meeting of the Societe de Chimie Industrielle,
Professor Matignon made an important statement on the pres-
ent situation of the potash industry in Alsace.
The administrative and financial situation of the Alsatian
potash mines is not yet settled. A sequestration administrator
is controlling them at present. However, the process for ex-
traction and methods of work now adopted by French engineers
are different from those formerly employed, and the present re-
turns are greater than those obtained prior to 1914.
The scheme of operation consists in the extraction of salt,
leaving pillars, and filling up afterwards. This filling is done
with the lime salts left in the residues from manufacture. The
potash obtained as chloride is remarkably pure and does not con-
tain magnesium salts.
LIGHT MINERALS
At the same meeting Mr. Bigot opened a discussion on light
minerals. Under this heading he described as natural products
pumice stone and infusorial silicas or kieselguhr.
Mr. Bigot compared the light pumice stones, obtained in
California, with French pumice stones. Their quality is nearly
the same. From pumice, pulverized and then agglomerated
with silicates, it has been possible to build a new type of furnace
for glass works, the radiation of which is very slight, and which
consequently allows work to be carried out quite close to the
furnace itself, thus reducing the amount of labor necessary.
Following the same line of ideas, Mr. Bigot has obtained, by
pyrogenic methods from slate and slaty schists, an extremely
light and porous mineral, which is compact and offers the same
advantages as the natural pumice stones.
INVAR METAL
Mr. Guillaume, director of the Bureau of Weights and Mea-
sures, is continuing his studies of invar metal. He has examined
samples of that metal manufactured about 10 yrs. ago, and has
discovered small variations in length of about 0.01 mm. per
meter. This slight instability of invar he ascribes to the pres-
ence of carbon, or rather of the ferrocarbon compound called
cementite.
He proposes the addition of chromium or tungsten-vanadium
to rectify the invar, and the results obtained show that, thus
modified, invar can be used without the necessity of corrective
calculations.
THE AGE OF PAINTINGS AS SHOWN BY X-RAYS
Although rather foreign to the sphere of chemistry, a question
which is now absorbing the attention of the French scientific
world is the diagnosis of the age of pictures by X-rays.
172
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
For instance, the artists of the 17th century almost exclusively
used mineral colors impervious to X-rays. The modern paint-
ing, however, done almost exclusively in colors of organic or
vegetable origin, is permeable to X-rays.
The great French physician, Lippmann, has been able, by
this method, to determine the age of a picture and ultimately
expose to view any superimpositions or fakes. This application
of science to an art where, up till now, technical examinations
were solely the work of art critics, is of extreme interest.
In my previous letter, I spoke of the petroleum question. I
can now inform you of the bringing forward, by the government,
of a bill, the principle of which is government-controlled freedom.
In order to compete with the Claude process (fixation of air)
a certain number of French banks and factories have acquired
the Badische process (Haber patent) and are going to attempt
its exploitation in France.
January 7, 1921
INDUSTRIAL NOTL5
At a meeting of the directors of The Barrett Company, held
December 17, 1920, Eversley Childs, chairman of the Board,
and William Hamlin Childs, president, offered their resignations.
William N. Mcllravy was elected chairman, and Thomas M.
Rainhard, president. William Hamlin Childs was elected chair-
man of the Executive Committee. The following directors pre-
sented their resignations: Harry W. Croft, J. H. Fulton, Wil-
liam S. Gray, Alexander C. Humphreys, Isaac B. Johnson,
Powell Stackhouse, Hamilton Stewart, J. Harry Staats, H. D.
Walbridge, and Horace S. Wilkinson. The following directors
were elected: E. L-. Pierce, president, Solvay Process Company;
W. H. Nichols, Jr., president, General Chemical Company;
Orlando F. Weber, president. National Aniline and Chemical
Company; Walter B. Harris, sales manager, The Barrett Com-
pany; M. H. Phillips, New York manager, The Barrett Com-
pany; D. W. Jayne, manager chemical department, The Barrett
Company; Clark McKercher, general counsel, The Barrett Com-
pany; E. J. Steer, secretary and treasurer, The Barrett Com-
pany.
The United States Supreme Court on December 6, 1920,
handed down an important decision in favor of the defendant,
in the "Hydrogenated Oil Case," of Procter & Gamble vs. The
Brown Company (formerly Berlin Mills Co.), reversing the Court
of Appeals and holding with the District Court that Claims
1 and 2 of the Burchenal Patent No. 1,135,351 assigned to the
Procter & Gamble Company are invalid. Procter & Gamble
brought suit against the Berlin Mills Company in 1915 for al-
leged infringement of a product made under the Burchenal
patent. The decision of the Supreme Court is based almost
exclusively on the belief of the Court that the prior art, especially
Normann's British Patent of 1903, described the products ob-
tained sufficiently well so that an oil chemist would understand
that they could be used in any of the usual ways that fats are
used. Burchenal's contribution "did not rise to the dignity of
invention." Both sides were represented by eminent counsel
and well-known experts, and the case attracted a great deal of
interest on account of the prominence of the litigants and the
importance of the decision when it should be rendered.
The following associations of manufacturers have been formed
in England to conduct industrial and scientific research in the
fields of their industries, and have been given governmental
assistance:
British Boot, Shoe, and Allied Trades Research Association
British Cotton Industry Research Association
British Empire Sugar Research Association
British Iron Manufacturers' Research Association
British Photographic Research Association
Research Association of British Motor and Allied Manufacturers
British Portland Cement Research Association
British Research Association for the Woolen and Worsted Industries
British Scientific Instrument Research Association
Research Association of British Rubber and Tire Manufacturers
Linen Industry Research Association
British Nonferrous Metals Research Association
Glass Research Association
British Association of Research for Cocoa, Chocolate, Sugar, Confec-
tionery, and Jam Trades
British Ri fractories Research Association
Scottish Shale Oil Scientific and Industrial Research Association
Various other research organizations are under consideration for
approval, or in process of organization.
Experimental camphor groves which have been planted in
Florida are expected to attain commercial importance within
a few years. These groves, together with the synthetic camphor
now being manufactured in the United States, are expected
to make the United States the leading producer of natural and
synthetic camphor, and to render it independent of the former
sources of supply in China, Japan, and Formosa.
The committee in charge of the consolidation of the General
Chemical Co., the Solvay Process Co., the Semet-Solvay Co.,
The Barrett Co., and the National Aniline and Chemical Company
has announced that the new merger plan has become operative,
and was carried into effect as of January 1, 1921.
The President of Uruguay has submitted to the National
Administration Council a bill providing for the establishment
of several government industries under control of the Institute
of Industrial Chemistry, with a view to the development of
the industry so as to take care of the domestic needs of the country
in peace or war. Among the factories to be established are a
sulfuric acid factory with a daily production of 25,000 kilos,
all of which is expected to be required for domestic use as soon
as the country begins production of superphosphates from
bones now exported. Raw material for the sulfuric acid can
probably be obtained from important iron pyrites deposits
which are said to exist. It is planned also to build factories for
the production of nitric acid; crude benzene, toluene, xylene,
and carbolic acid; electrolytic caustic soda; alcohol and sulfuric
ether; acetic acid; glycerol; powder and explosives. The total
cost of these works is estimated at 2,180,000 pesos, to be secured
through the imposition of an import tax of 1 per cent. 25,000
pesos yearly is to be set aside for the engagement of five foreign
technical experts under three-year contracts, at the end of
which time it is expected that native experts will be able to take
their places.
The Tariff Commission of Canada is to take up the question
of a tariff against German dyes which has been laid before the
Minister of Finance by British dyestuff manufacturers, five of
whom are represented in Canada. Some German firms are
already underbidding the British dyers for Canadian business.
The United States Civil Service Commission has announced
an examination for laboratory assistants to fill vacancies in the
Bureau of Mines at Pittsburgh, Pa., and elsewhere. Salaries
are as follows: Senior Grade, $1320 to S1500; Intermediate
Grade, $1200 to $1320; Junior Grade, $1080 to $1200. Papers
will be rated as received and certification made as the needs of
the service require. Applicants will be rated on general
education and special training and experience. Applications
will be received until the hour of closing, April 5, 1921.
Examinations have also been announced for Associate Chemist
at $2500 to $3600 a year; Assistant Chemist at $1800 to $2500
a year; and Junior Chemist at $1200 to $1800 a year. Appli-
cants will be rated on (1) education, training, and experience,
and (2; publications or thesis, to be filed with application, and
must qualify in one of the following subjects: advanced inorganic,
analytical, biological, dairy, explosives, food, fuel, metallurgical,
organic, pharmaceutical, physical, soil, petroleum, gas, or ceramic
chemistry. Applications will be rated as received until further
notice.
Examinations have been announced for Associate Engineer
at $2000 to $2800 a year and Assistant Engineer at $1400 to
$1800 a year, to fill vacancies in the Bureau of Standards and
elsewhere. Applicants must qualify in one of the following
subjects: electrical, mechanical, civil, chemical, or ceramic
engineering, and will be rated on (1) education in general physics,
chemistry, and mathematics, (2j special education and ex-
perience in the optional subject; and (3) general education,
experience, and fitness. The duties of appointees will be in
connection with original investigations in some field of the
Bureau's work. Detailed information should be given in ap-
plying. Applications will be rated as received until further notice.
The Commission has also announced an examination for
Assistant Examiner, Patent Office, at $1500 a year, with $20
monthly increase to appointees who perform satisfactory service.
Competitors will be rated on (1) French or German, (2) mechan-
ical drawing, (3) technics, covering the general field of me-
chanics, mechanic arts, industrial arts and processes, and ap-
plied chemistry. In addition, applicants must select two of
the following optional subjects: chemistry, civil, electrical, or
mechanical engineering, mathematics, physics, experience.
Examinations will be given February 9 to 11, 1921, at places
named by the Commission. Details concerning the examinations
may be obtained from the Civil Service Commission. No
credit is given for student work in school or college.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
173
The French Commission in the United States has published
information regarding the reconstruction of the French chemical
industry. The chemical plants located in the devastated de-
partments, 17 per cent of all chemical plants in France, were
almost totally destroyed. On October 1, 1920, 78.1 per cent
had resumed operation in whole or in part. On October 1, 1919,
only 18.7 per cent of the 1914 personnel were occupied at produc-
tion, while on October 1, 1920, 54.2 per cent were occupied. The
1914 production of chemical plants was 850,000 tons; the
present production is between 200,000 and 300,000 tons.
A new standard sample of electric steel No. 51, 1.2 per cent
carbon, and a new standard sample of cast bronze No. 52 (ap-
proximate composition: Copper 8S per cent, tin 8 per cent,
zinc 2 per cent, lead 1.5 per cent, antimony 0.15 per cent, iron
0.10 per cent and nickel 0.10 per cent) have recently been pre-
pared by the Bureau of Standards, Washington, D. C, and
are now ready for distribution with provisional certificates.
Standard Sample No. 23a, a renewal of the exhausted Sample
No. 23, Bessemer Steel, 0 8 carbon, has also been prepared and
is now ready for distribution with a provisional certificate.
The Acetate Products, Ltd., has purchased the plant of the
Liverpool Cannery at South Westminster, B. C, and will begin
installation of an up-to-date methanol plant at once. This is
the first methanol plant to be erected on the Canadian Pacific
coast, and will produce in addition to methanol, acetate of lime,
charcoal, and wood-tar products.
Investigations by the Forest Service of the Department of
Agriculture show that the use of wood preservatives has in-
creased to a large extent in this country. In 1919 there were
used 65,556,247 gal. of creosote, 2,412,592 gal. of paving oil,
101,011 gal. of miscellaneous preservatives, and 43,482,000 lbs.
of zinc chloride. Over 6,000,000 gal. of creosote were imported,
practically all from England and Canada. The total amount
of wood treated amounted to 139,878,845 ft., covering opera-
tions at 108 plants, 17,265,694 ft. more than in 1918.
At a meeting of the Board of Directors of the National Aniline
& Chemical Co., Inc., on December 21, 1920, Mr. O. F.
Weber offered his resignation as president, and Mr. J. W. New-
lean was elected president in his stead. Mr. Weber continues
as chairman of the Board of Directors of the National Aniline &
Chemical Co., Inc., and has accepted the presidency of the Allied
Chemical and Dye Corporation. Mr. F. M. Peters resigned
from the Board, and Mr. E. L. Pierce, president of the Solvay
Process Co., was elected a director. Mr. B. A. Ludwig,
Mr. O. F. Weber, and Dr. L. H. Cone were elected vice presi-
dents.
The Canadian government has withdrawn from sale, lease,
or settlement approximately 55,000 acres of land along the Atha-
basca River in Alberta, subject to leases already issued under
the petroleum and natural gas regulation. It is expected that
a successful process will soon be evolved for the extraction from
the tar sands of oil, bitumen, and other hydrocarbons in com-
mercial quantity. The nearest estimate of tar sands available
for reduction runs into billions of tons. The drawback to de-
velopment is the scarcity of fuel to withdraw the oils, but it is
hoped that this may be overcome by finding natural gas.
On December 10, 1920, 500 shares of stock of the J. P. Devine
Company, together with letters patent of the United States
subject to the right of the company and all interests in an agree-
ment between the company and Joseph P. Devine and Emil
Passberg of Berlin, were sold at public sale by the Alien Prop-
erty Custodian. Mr. J. P. Devine was the highest bidder.
The sale, however, has not yet been confirmed by the Alien
Property Custodian.
The $4,000,000 by-product plant of the Domestic Coke Cor-
poration, Fairmont, W. Va., has recently begun operations.
When running at full capacity, the plant will consume 1100
tons of coal a day. At present only 24-hr. coke is being pro-
duced, but when sufficient coal is on hand to assure steady opera-
tion, the coke will be produced in fiom 14 to 15 hrs.
PLR50NAL NOTL5
Dr. Ira Remsen, for twelve years president of Johns Hopkins
University, former professor of chemistry at the institution,
discoverer of saccharine and other products, and one of the fore-
most men in his special field of science in the country, has ac-
cepted an offer from the Standard Oil Company to act as consulting
chemist for the corporation. Dr. Remsen was associated with
Johns Hopkins University since its foundation in 1875. He
resigned both the presidency and the chair of chemistry in 1913
to return to private life, and now holds the title of professor
emeritus. On December 13, 1920, Dr. Remsen gave, under the
auspices of Eta Chapter of Phi Lambda Upsilon at Ohio State
University, a lecture on "What Chemists Were Thinking About
50 Years Ago."
Dr. F. G. Cottrell resigned December 31 as director of the
U. S. Bureau of Mines, and Mr. H. Foster Bain, of California,
has been named his successor. Dr. Cottrell left the Bureau in
order to take up his duties as chairman of the Division of Chem-
istry and Chemical Technology of the National Research Council.
Dr. Henry A. Bumstead, professor of physics at Yale Uni-
versity, who had been on leave serving as chairman of the
National Research Council, died recently on a train from Chicago
to Washington. He was graduated from Johns Hopkins Uni-
versity in 1891, and later received his doctor's degree from
Yale.
Mr. J. Russell Marble, a native of Smithfield, and prominently
identified with the business life of Worcester, died last October
at his home in Worcester. Mr. Marble was associated with the
Northeastern Section of the American Chemical Society.
Dr. Hugh C. Muldoon has left the position of professor of
chemistry at the Albany College of Pharmacy and has accepted
the deanship and professorship of chemistry in the School of
Pharmacy, Valparaiso University, Valparaiso, Ind.
Mr. James R. Owens has severed his connection with E. I.
du Pont de Nemours & Co., and is at present holding an operat-
ing position in the wood distillation plant of the Mid-Continent
Iron Co., Midco, Carter Co., Missouri.
Mr. Charles Horvath, research chemist for the International
Motor Co., New Brunswick, N. J., resigned some months ago
from that firm to become chief chemist for the National Metal
Reduction Company of Newark, N. J., and the Atlantic Smelting
& Refining Works, of New York City, the plants of both firms
being located in Newark, N. J.
Mr. William D. Hatfield resigned as assistant professor of
chemistry at the Montana State College of Agriculture and
Mechanic Arts to accept the position of superintendent of the
new water filtration plant at Highland Park, Mich.
Mr. H. L. Lentz has resigned from the U. S. Bureau of Mines,
Pittsburgh, Pa., in order to accept the position as chief chemist
for the Robinson Milling Co., at Salina, Kan.
Mr. Walter J. Geldard recently resigned as chief of the ana-
lytical section, Fixed Nitrogen Research Laboratory, and has
accepted a similar position with the International Coal Products
Corp., of Newark, N. J.
Mr. Edwin Androvic, formerly with the Cudahy Packing Com-
pany of Omaha, Neb., is now taking some special courses
in chemical engineering at Johns Hopkins University, Balti-
more, Md., and is at the same time working with some oil
refining and hydrogenating problems.
Dr. Arnold H. Smith, secretary of the rubber division of the
American Chemical Society, resigned his position as research
chemist with the Goodyear Tire & Rubber Company to assume the
position of chief chemist with the Thermoid Rubber Co., Trenton,
N.J.
Mr. Thomas M. Rector, formerly in charge of the division of
food technology of the Institute of Industrial Research, Wash-
ington, D. C, has been appointed director of the department
of industrial chemistry of the Pease Laboratories, Inc., New
York City.
Mr. L. J. Waldbauer has left the employ of the Redpath
Laboratory of E. I. du Pont de Nemours & Co., and is at pres-
ent instructor in chemistry at the University of Maine, Orono,
Me.
Mr. B. E. Long, who was engaged as sugar factory chemist
and superintendent in Cuba and Puerto Rico, now holds a simi-
lar position with a new company, the Binalbagan Estates, Inc.,
Philippine Islands.
Mr. G. H. Cartledge resigned last June as chief for the Island
Refining Corp., of New York City, to become associate profes-
sor in chemistry at Johns Hopkins University, Baltimore, Md.
Mr. I. E. Cooper, a recent graduate of the University of Illi-
nois, has accepted a position with the Apollo Metal Works, La
Salle, 111., as chemist in charge of the research department and
control laboratory.
174
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
Mr. Hiller Zobel recently left Death Valley, Cal., where he
was engaged in metallurgical and chemical research for the
Pacific Coast Borax Co., to assume duties as research chemical
engineer at the Bayonne, N. J., plant of the same company.
Mr. Marvin J. Udy was recently transferred to the research
department of the Electro Metallurgical Co., at Niagara Falls,
N. Y., upon the closing down of the cobalt mines of the Haynes
Stellite Co., at Leesburg, Idaho, where he was mine manager.
Mr. J. Howard Roop, formerly chemist for the Noblesville
Milling Co., at NoblesvUle, Ind., has accepted a position as chief
chemist for the American Stores Co., at Philadelphia, Pa.
Mr. L. T. Bryson has temporarily left the El Salvador Silver
Mines Co., Ltd., and is engaged in analytical research work
with the Dearborn Chemical Co., of Chicago, 111.
Prof. Hermon C. Cooper has been granted leave of absence
from the College of the City of New York for the present aca-
demic year and is acting as factory manager of the Acids Manu-
facturing Corp., of New York City.
Dr. E. P. Deatrick, formerly instructor at the Pennsylvania
State Forestry Academy, Franklin County, Pa., is at present
instructor in the department of soil technology at the College of
Agriculture, Ithaca, N. Y.
Mr. J. W. Ziegler, who graduated last June in chemical
engineering at the University of Illinois, Champaign, 111., has
entered the employ of the Como Chemical Co., Kokomo, Ind.,
as foreman of one of their departments.
Mr. Donald E. Cablei has become research chemist in the
Agricultural Experiment Station of the University of Wyoming,
after having spent two years as assistant chemist and engineer
at the Forest Products Laboratory, Madison, Wis.
Mr. Bert Russell, who left the Patent Office about a year
ago, after extended service in its various chemical divisions, to
accept a position with Prindle, Wright & Small, of New
York City, is now leaving the latter firm in order to accept
employment in the office of Mr. Roy F. Steward, chemist and
patent attorney, Washington, D. C.
Mr. Joseph WertheimeT, formerly with the American Borish
Co., of Cleveland, Ohio, has been appointed to the position
of assistant professor of metallurgy at the University of Kansas,
and Mr. Henry Werner, formerly with the H. K. Mulford Chem-
ical Co., of Philadelphia, has been made assistant professor of
chemistry at the same university.
Mr. James H. Aldred has joined the forces of the Smith Rub-
ber & Tire Co., Inc., of Garfield, N. J., as general superintendent.
Mr. Aldred was previously chemist for the Industrial Supervi-
sion Company of New York City.
Mr. L. W. Briggs is instructor of inorganic chemistry at
Wooster College, Wooster, Ohio. He formerly held a graduate
scholarship at the State University of Iowa, Ames, Iowa, for the
year 1919 to 1920.
Mr. Carl E. Frick, formerly chemist for the Philadelphia
Rubber Works Co., Akron, Ohio, has been made instructor in
general chemistry at the University of Wisconsin, Madison, Wis.
Mr. Charles H. Spayd has left the Modoc Company of Pennsyl-
vania, soap powder, cleanser, and boiler composition manufac-
turers, where he was secretary-treasurer and manager, to reenter
the printing ink manufacturing business with the California Ink
Co., of San Francisco, Cal.
Mr. John H. Culver has accepted the position of textile expert
and chemist for the Firth Carpet Co., of Firthcliffe, N. Y.
Mr. R. R. Bryan until recently engaged with the Sunnyside
Mining & Milling Co., at Eureka, Col., as metallurgist, recently
went into business as consulting engineer, with offices at Den-
ver, Col.
Mr. C. H. Kerr, research manager of the American Optical Co.,
Southbridge, Mass., is now associated with Mr. H. L. De Zeng
in the management of the De Zeng-Standard Co., Camden, N. J.
Mr. S. M. Oppenheim, formerly connected with the engineer-
ing department of the Board of Commissioners of the Port of
New Orleans, has returned to the Miles Planting & Manufactur-
ing Co., as superintendent-of-manufacture of their two sugar
factories in Louisiana.
Dr. L. A. Mikeska has accepted a position on the staff of the
Rockefeller Institute, New York City, having left the Color
Laboratory of the Bureau of Chemistry in Washington, D. C,
where he was working on photosensitizing dyes.
Mr. Bernard L. Peables, who was associated with the Boston
Consolidated Gas Co., as chief inspector in field for the chemical
control section, has joined the forces of the Pawtucket Gas
Works, for the broadening and intensifying of the chemical control.
Mr. S. H. Champlin is now chemist with the Cape Cod Preserv-
ing Corp., at Onset, Mass., his previous position being that of
assistant and research chemist with the Loose-Wiles Biscuit Co.,
of Long Island City.
Mr. George R. Greenbank, formerly employed by the Good-
year Tire & Rubber Company as chemical engineer, is at present
acting in the same capacity at Edgewood Arsenal for the Chem-
ical Warfare Service.
Dr. George Borrowman, recently returned from chemical
investigations in Europe, has resigned from research work
in the laboratory of Dr. J. E. Teeple, and opened his own labo-
ratory in Chicago, 111.
Mr. Alger L. Ward, who was employed for the past five
years as a research chemist by E. I. du Pont de Nemours & Co.,
has accepted a position as an organic research chemist with the
United Gas Improvement Co., and is connected with their
laboratories in Philadelphia, Pa.
Mr. G. N. Prentiss has been appointed engineer of tests of
the Chicago, Milwaukee & St. Paul Railway Co., with head-
quarters at Milwaukee Shops, Wis., vice Mr. H. K. Fox, resigned.
Mr. John L. Parsons, formerly instructor in chemistry at
Boston University, has been released in order that he may take
up industrial research for the Hammermill Paper Co., Erie, Pa.
Mr. George F. Lull has severed his business connections in
the East and has been made president of the Trinity Paper
Mills with headquarters at Dallas, Texas.
Mr. D. M. Bates, following his resignation last March as
agent of the Lewiston Bleachery & Dye Works, Lewiston, Me.,
became vice president of Day & Zimmermann, Inc., of Phila-
delphia, Pa.
Mr. Philip A. Kober, formerly with E. R. Squibb & Sons, of
New York, is now president for the Kober Chemical Co., Inc.,
Hastings-on-Hudson, N. Y., which firm intends to manufacture
chemically pure arsphenamines, Dakin's chloramines, and
dialyzing, ultrafiltering and perevaporation membranes.
Mr. William W. Coblentz, physicist in the Bureau of Standards,
Washington, D. C, has been awarded the Janssen Medal by the
Academy of Science, for discoveries in connection with rays
emanating from the earth and stars.
Mr. Carl Bloess has left the St. Louis branch of the American
Cotton Oil Co., which branch has been discontinued, and has
become chemist for the Crown Margarin Co., of the same city.
Prof. A. F. Gilman, Ph.D., who has been professor of chemistry
at Illinois Wesleyan University, Bloomington, 111., for the past
two years, has been elected head of the chemistry department
at Carroll College, Waukesha, Wis.
Dr. J. E. Zanetti, assistant professor of chemistry at Columbia
University, has had conferred upon him by the King of Italy
the Order of the Crown with the rank of officer, for services ren-
dered during the war as Lieutenant-Colonel in the Chemical War-
fare Service. He has also received from the French government
the Legion of Honor and from the British government the
Distinguished Service Order.
Dr. J. C. Witt, assistant professor of analytical chemistry in
the University of Pittsburgh, has resigned to become chief
research chemist for the Portland Cement Association with
headquarters in Chicago. Dr. Witt has been succeeded in his
former position by Dr. C. J. Engelder, of Hornell, N. Y.
Mr. Harry E. Wently, formerly with Brown & Co., Inc.,
Pittsburgh, Pa., is at present associated with the Latrobe Elec-
tric Steel Co., Latrobe, Pa.
Mr. W. L. Moyer, while in Youngstown, O., was a chemist in
the by-product coke plant of the Youngstown Sheet & Tube Co.,
and is at present associated with the Pittsburgh Crucible Steel
Co., as heater foreman in their coke plant at Midland, Pa.
Mr. Franklin B. Furber, for several years chemist with the
U. S. Bureau of Mines and the U. S. Bureau of Chemistry, has
resigned from the position of assistant director of the Pease
Laboratories, Inc., to become associated with the Research
Laboratories, Inc., of New York City.
Mr. N. D. Doane, formerly with the Goodyear Tire & Rubber
Co., of Akron, Ohio, is now engaged in chemical and sanitary
engineering work for Mr. Charles H. Hurd, consulting engineer,
of Indianapolis, Ind.
Mr. Lloyd Platzker, formerly with the American Sugar Re-
fining Co., of Jersey City, is now associated as a chemist with
Messrs. Bendiner & Schlessinger, of New York City.
Mr. Lewis O. Bernhagen, until recently a sanitary engineer
for the Texas State Board of Health, has accepted the position
of director of sanitation for the city of Beaumont, Texas.
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
175
GOVERNMENT PUBLICATIONS
By Nellie A. Parkinson, Bureau of Chemistry, Washington, D. C.
NOTICE — Publications for which price is indicated can be The Importance of Tellurium as a Health Hazard in Indus-
purchased from the Superintendent of Documents, Government £y- AFI^m}Baxy £e,p,0rt" TTM; ,D. Shie and F. E. Deeds.
r>_: . /~>ce tt7 t_- n /-> sv.< , , • Reprint 5P0 from Public Health Reports. 18 pp. Paper
Printing Office, Washington, D. C. Other publications can 5 cents_ ig2o. _--•_--.,
usually be supplied from the Bureau or Department from which Studies of Reconstructed Milk. A. F. Stevenson, G. C.
they originate. Commerce Reports are received by all large Peck and C. P. Riiynos. Reprint 60S from Public Health
libraries and may be consulted there, or single numbers can be Reports. 37 pp. Paper, 5 cents. 1920.
secured by application to the Bureau of Foreign and Domestic Effect of Shaking Alkalinized Aqueous Solutions of Arsphen-
Commerce, Department of Commerce, Washington. The regu- amine ?nd Aqueous Solutions of Neoarsphenamine in the Pres-
, . .„.. . , .. „ -> __ -, j j •, ence of Alr- G- B- Roth. Reprint 612 from Public Health
lar subscription rate for these Commerce Reports mailed daily Reports. 7 pp. Paper, 5 cents. 1920.
is $2.50 per year, payable in advance, to the Superintendent of Municipal Wastes. Their Character-Collection-Disposal.
Documents. H. R. CrohursT. Public Health Bulletin 107. 98 pp. Paper,
20 cents
NATIONAL ADVISORY COMMITTEE FOR AERONAUTICS _. _ . _ _. . . , TT . , _,
■B-tix. a 1 t> l . Ttr l- 1 « j • ^ -^ 1 Digest of Comments on Pharmacopeia of the United States of
Fifth Annual Report of National Advisory Committee for *-„£„ (oth Decenniai Revision), and National Formulary
Aeronautics, Fiscal Year igio. 870 pp. Paper, $1.50. 1920. Uth editi(mJ) Calendar Year 1017. A. G. Du Mez. Bulletin
GOVERNMENT PRINTING OFFICE 125 of the Hygienic Laboratory. 340 pp. Paper, 25 cents.
4 . ,, , „. _. . tji_siaii.it. ^ Also issued as H. Doc. 856, 66th Congress, 3rd Session.
Agricultural Chemistry, Industrial Alcohol, Preservatives: T _ . .. . , _ . . _. „ ' _.
List of PubUcations for Sale by Superintendent of Documents. -, L Trinitrotoluene Poiso ning— Its Nature, Diagnosis, and
9 pp. Price List 40, 12th edition. 1920. Prevention Carl Voegtlin, C. W Hooper and J. M.
Johnson. H. The Toxic Action of "Parazol." Carl Voegt-
GENERAL LAND office Lin, A. E. Livingston and C. W. Hooper. III. Mercury
Regulations Concerning Oil and Gas Permits and Leases Fulminate as a Skin Irritant. A. E. Livingston. Bulletin
(Including Relief Measures) and Rights of Way for Oil and 12^ of the Hygienic Laboratory. 216 pp. Paper, 20 cents.
Gas Pipe Lines, Authorized by Act of February 25, 1Q20 (Public 1920.
146); approved March 11, 1920. 1920 Reprint as Amended GEOLOGICAL SURVEY
to October 29, 1920. 57 pp. Circular 672. Surface Water Supply of the United States, 1917. Part HI.
eM,-n0n«,.»i«c._,---,«„ 0mo River Basin. N. C. Grover, A. H. Horton and W. E.
SMITHSONIAN INSTITUTION Hall Prepared m Cooperation with the states of Illinois and
Analyses and Optical Properties of Amesite and Corun- Kentucky. Water-Supply Paper 453. 173 pp. Paper, 15
dophilite from Chester, Mass., and of Chromium-Bearing cents 1920
Chlorites from California and Wyoming E V. Shannon. Marble Resources of Southeastern Alaska. E. F. Burchard.
LPSf o?Iom ,PrTo°n mgS ° * Nat,onal Museum- Volume With _ Section on the Geography and Geology. TheodorB
OS, JNo. _.34_. 19_0. Chapin. Bulletin 682. 118 pp. Paper, 30 cents. 1920.
Some Minerals from Old Tungsten Mine at Long Hill in -,,.-., -. - . _<*• ■ ±t- ^ ± ox *
Trumbull, Conn. E. V. Shannon. 14 pp. From Proceed- . Gold> Sliver> Copper, Lead, and Zinc in the Eastern States
ings of the National Museum, Volume 58, No. 2348. "\ 'P1?- J- ,P- Dum°*- Separate from Mineral Resources
of the United States, 1919. Part I. 10 pp. Published No-
TARIFF COMMISSION vember 8, 1920.
Industrial Readjustments of Certain Mineral Industries The total value of the gold, silver, copper, lead and zinc
Affected by the War, Antimony, Chromite, Graphite, Mag- mined and sold m the Eastern States m 1919 was $25,110,186,
nesite, Manganese, Potash, Pyrites, Sulfur, Quicksilver, Tung- a d^creas? °f. about, 9 p^ cent from *h^.5°7?sp^ding,»Y?Lu£-on
sten (with Bibliographies). Tariff Information Series 21. 1918- £f this tota , gold represented $, ,052 silver $ 117,253,
320 pp. 9 maps. Paper, 65 cents. 1920. c°PPer $3,0S6,8tK), lead $232 034, and zinc $21,666 957.
The output of all metals decreased, though the decreases in
WAR DEPARTMENT quantity of copper, lead, and zinc were comparatively small.
Report of Tests of Metals and Other Materials Made in The decrease in total value of the metals was caused mainly
Ordnance Laboratory at Watertown Arsenal, Mass., Fiscal by the lower price m 1919 for copper, lead, and zinc The high
Year 1918. War Department Document 901. 338 pp. Paper, Pnce of ?llver caused lts value to increase, notwithstanding a
80 cents. In many cases one side of the leaf only is paged, decrease in quantity.
the unnumbered side usually bearing illustrations, although MmF- Production of Gold. Silver, Copper, Lead and Zinc in tub
...... J ° ° Appalachian States, 19 IS and 1919
m some cases it is blank. ,_,._ ,.,_ Decrease
PUBLIC HEALTH SERVICE Ore sold or treated, short tons 2'3?,S-,6?| 1,93i)'ns7 42|'?no
Gold, dollars 14,352 7,052 t ,300
Recent Experiments in the Control of Air Dustiness. O. M. silver, fine ounces 106,585 104. 69n 1,895
SpPNCFR Pnhlic Hfnlth Rpnorts 35 2Q07-14 The follow- Copper, pounds 17,858,535 16,596,182 1,262,353
aPENCER. ±-unnc neaitn Keports, 35, zau/ i<*._ ine iouow gg pounds 5,158,329 4,378.000 780.329
mg conclusions are reached as a result of these investigations: z'ine 'pounds 248 563 i<)2 243,558.000 5,005,192
(1) The necessity for establishing a "standard dust table" of Total value, dollars".".'. '.'.'.'.'.'.'. 27.'517,'48S 25]ll0,l86 2,407,302
the number of dust particles of a certain size permissible in all Preliminary Report on the Deposits of Manganese Ore in
d^st';reatmg .°r ,.dust-hazardous processes and occupations; fhe BatesviUe District, Arkansas. H. D. MisER. Bulletin
(2) The necessity for checking the efficiency of all dust-removmg -j-_G Separate from Contributions to Economic Geology,
systems or devices at regular intervals by an actual dust count 192Q part - 32 Published November 15, 1920. The
at the place of work and m the workroom, which count must m 'nese ores may be grouped according to composition
come r within the limits prescribed by the standard dust table intQ ,___ general classes— high-grade ores and low-grade or fer-
for that particular process. ruginous manganese ores. Most of the high-grade ores contain
Sanitary Disposal of Sewage through a Septic Tank. A 45 to 52 per cent of manganese, generally from 3 to 8 per cent
System of Simple Construction and Inexpensive Operation of iron, 0.15 to 0.30 per cent of phosphorus, and 2 to 8 per cent
for Isolated Dwellings. H. R. Crohurst. Public Health 0f siHca. Most of the low-grade ores contain 20 to 35 per cent
Reports, 35, 2959-64. of manganese, 8 to 20 per cent of iron, and 5 to 26 per cent of
Supreme Court of the United States Construes Section 2 of silica. The phosphorus content is about the same as that of the
the Harrison Antinarcotic Act. Public Health Reports, 35, high-grade ores. The ore from this district has been used for
3077-9. The Supreme Court of the United States has decided making ferromanganese, spiegeleisen, and high-manganese pig
that the issuance of a prescription for a habit-forming drug iron. Very little, if any, of it has been found suitable for chemical
by a physician not "in the course of his professional practice uses because the amount of manganese dioxide is, as a rule, less
only" is a sale of the drug and a violation of Section 2 of the than 80 per cent, and it is not likely that commercial quantities
Harrison Antinarcotic Act. of chemical ore will be discovered.
176
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
Sodium Compounds in 1919. R. G. WELLS. Separate from
Mineral Resources of the United States, 1919, Part II. 30 pp.
Published November 16, 1920. Nearly all the compounds of
sodium consumed in the United States except common salt
are manufactured products. Even the salts that occur naturally
are usually refined before they are used. As the natural salts,
however, form only a small part of the annual production, this
report deals almost entirely with the manufactured products.
The following table summarizes the production of sodium and
sodium compounds reported in 1918 and 1919:
Sodium and Sodium Compounds Produced in the United States in
1918 and 1919
. 1918 . . 1919 .
Quantity Quantity
Short Tons Value Short Tons Value
Sodium (metal) 264 $153,437 (') (')
Sodium acetate 2,622 460,783 2,426 $311,175
Sodium henzoate 203 886.0SS 126 230,224
Sodium bicarbonate 118,535 3,293,153 134.962 3,486.635
Sodium bichromate 28,334 9,868,118 26,526 6,233,566
Sodium bisulfite and so-
dium sulfite 16,362 478,482 11,846 687,750
Sodium bromide 574 438,730 499 493,3 1 9
Sodium carbonate:
Soda ash 1,390,628 35,635,520 981.054 29,895,343
Monohydrate and ses-
□uicarbonate 22,678 482,958 30,796 710,748
Sal soda 82,465 2,020,271 80,090 2,229,994
Sodium chlorate and so-
dium perborate 2,413 1,004,250 1,210 62,980
Sodium chloride:2
Salt in brine 2,830.600 1,245,265 2,809,000)
Rock salt 1.683,941 5,684,661 1,637.300 t 27,296,000
Evaporated salt 2,724,203 20,0 1 0,435 2,6 1 8,200 )
Sodium citrate, tartrate
and bitartrate (>) (') 33 58,128
Sodium cyanide, peroxide,
and iodate 9,077 5,361,000 9.148 4,515,106
Sodium ferrocyanide 4,525 2,690,110 3,437 1,346,285
Sodium fluoride, acid sodium
fluoride, and sodium fluo-
silicate (silicofluoride).. . 1,879 387,224 811 150,404
Sodium hydroxide (caustic
soda) 513,363 31,854.470 355,466 22,196,898
Sodium iodide (') (') 12 86,985
Sodium nitrate (refined)... ... ... 8,040 816,647
Sodium nitrite 1,701 609,779 676 151.621
Sodium phosphate (incl.
all sodium phosphates).. 15,620 1.427,947 14,760 1,733.996
Sodium silicate 317,161 5,870,973 300,138 5,879,628
Sodium sulfate:
Salt cake 141,054 2,844,897 134,685 2,035.543
Glauber's salt 50,715 1,041.070 42,087 860,977
Nitercake 143,155 595,660 83,402 271,424
Sodium sulfide 43,490 2,293,304 45,448 2,645,181
Sodium tetraborate (borax) 26,673 3,909,565 28,518 4,351,891
Sodium thiosulfate (hypo-
sulfitej 26,868 1,051,623 32,212 1,709,223
Miscellaneous sodium com-
pounds 390 1,188,792 841 756,548
Total 10,199,493 142,788,535 9,393,749 121,204,219
1 Included under "Miscellaneous sodium compounds."
2 Herbert Insley, "Salt, bromine, and calcium chloride." U. S. Geol.
Survey Mineral Resources, 1919, pt. 2 (in preparation).
Natural-Gas Resources Available to Dallas and Other Cities
of Central North Texas. E. W. Shaw and P. L. Ports. Bul-
letin 716-D. Separate from Contributions to Economic Geology,
1920, Part II. 31 pp. Published November 17, 1920. It
seems probable that with rigid economy and scientific conserva-
tion the present available supply of natural gas in the region
around Dallas may be depended upon to suffice for 6 to 10 yrs.,
though there will be shortages nearly every winter. Little can
be certainly predicted for future developments.
Forty-First Annual Report of the Director of the United
States Geological Survey to the Secretary of the Interior for
the Fiscal Year Ended June 30, 1920. 180 pp. 1920.
Structure and Oil and Gas Resources of the Osage Reserva-
tion, Oklahoma. T. 28 N., RS. 11 and 12 E. M. I. Gold-
man and H. M. Robinson. Bulletin 686-Y. 36 pp. 1920.
Contributions to Economic Geology (Short Papers and Pre-
liminary Reports) 1919. Part 1. Metals and Nonmetals ex-
cept Fuels. F. L. Ransome and E. F. Burchard. Bulletin
710. 248 pp. 1920. The bulletin contains an introduction
and the following special papers which have previously been
reviewed in This Journal: A Reconnaissance of the Pine Creek
District, Idaho, by E. L. Jones, Jr. (published August 27, 1919);
deposits of manganese ore in New Mexico, by E. L. Jones, Jr.
(published October 21, 1919); deposits of manganese ore in
Costa Rica, by J. D. Sears (published December 30, 1919);
deposits of manganese ore near Boqueron River, Panama, by
J. D. Sears (published December 30, 1919); deposits of man-
ganese ore in Arizona, by E. L. Jones, Jr., and F. L. Ransome
(published January 29, 1920) ; deposits of manganese ore in
southeastern California, by E. L. Jones, Jr. (published Decem-
ber 30, 1919); deposits of manganese ore in Nevada, by J. T.
Pardee and E. L. Jones, Jr. (published February 20, 1920).
The Lance Creek Oil and Gas Field, Niobrara County, Wy-
oming. E T. Hancock. Bulletin 716-E. Contributions to
Economic Geology, 1920, Part II. 32 pp. Published December
13, 1920.
Coal in Eastern Idaho. G. R. Mansfield. Bulletin 716-F.
Contributions to Economic Geology, 1920, Part II. 31 pp.
Published December 14, 1920. The results of the examination
are disappointing. The only part of the Teton Basin that is
producing coal at the present time is the Horseshoe district.
Though conditions in this district are such that large-scale
development is probably impracticable, work now in progress
will doubtless make possible a somewhat greater yield than
that of previous seasons. During the examination of the Teton
Basin several reported occurrences of oil were investigated,
but these do not indicate the presence of oil in paying quantities.
Potash in 1919. W. B. Hicks and M. R. Nourse. Separate
from Mineral Resources of the United States, 1919, Part II.
18 pp. Published December 8, 1920. The potash industry
of the United States was at a critical period of its history at the
beginning of 1919. Developments had progressed under the
high war prices until the annual productive capacity of the
plants in operation or about ready to operate was estimated
at 100,000 short tons of potash, and the capital invested in
these plants was reported to be about $25,000,000. Com-
paratively few of the larger plants had been fully paid for, and
many were still under construction or had been operated only
a short time. About one-third of the production of 1918 was
still in the hands of the producers, prices had dropped about
half, and the market for domestic potash was dull even at that
price, because lower priced potash was expected from Alsace
and Germany. As a result, most of the producers closed their
plants, and some of them went out of business. Foreign mines
were in a poor state of repair, however, and imports were small,
so that a ready market was found for the domestic output.
The quantity of potash produced in 1919 fell far short of the
production in 1918, and hardly equaled that of 1917, as is shown
by the following table:
Domestic Potash Produced and Sold in the United States in
1915 to 1919
. — Production-^ , — -Sales .
Available Available
Content of Content of
Crude Potash Crude Potash
No. Potash (K2O) Potash (KiO)
of Short Short Short Short
Year Plants Tons Tons Tons Tons Value
1915 5 4,374 1,090 4,374 1,090 $342,000
1916 70 35,739 9,720 35,739 9,720 4,242,730
1917 95 126,961 32.573 126,961 32,573 13,980.577
1918 128 207,686 54,803 140.343 38,580 15,839,618
1919> 77 110,243 30,845 173,786 46,732 11,370,445
1 Production for 1919 includes a quantity of material either utilized
by producer or reported as not marketed; sales for 1919 include material
produced in 1918 but sold in 1919.
Strontium in 1919. G. W. StosE. Separate from Mineral
Resources of the United States, 1919, Part II. 4 pp. Pub-
lished December 9, 1920. No domestic strontium ore was
mined or sold in the United States in 1919. Crude ore was
imported from England by manufacturers of strontium salts,
and some manufactured salts were also imported. Strontium
nitrate and strontium carbonate were the chief chemicals made.
Crude Domestic Strontium Ores Produced and Marketed in the
United States, 1916 to 1919
, 1916 . 1917 , 1918 . . 1919 .
Quan- Quan- Quan- Quan-
tity tity tity tity
Short Short Short Short
Mineral Tons Value Tons Value Tons Value Tons Value
Celestite 240 (') 3,630 $72,285 0 0 0 0
Strontianite 10 (') 405 15,415 400 $20,000 0 0
Total 250 $3,650 4,035 87,700 400 20,000 0 0
1 Figures not available.
Gypsum in 1919. R. W. Stone. Separate from Mineral
Resources of the United States, 1919, Part II. 15 pp. Pub-
lished December 28, 1920.
Gypsum was mined in the United States in almost contin-
uously increasing quantity for many years up to 1917, when
there began a decrease in production that amounted to three-
fourths of a million tons in 2 yrs., the production in 1918 being
the lowest recorded since 1908. In 1919, however, the quantity
mined was 2,420,163 short tons, an increase of 18 per cent over
the output in 1918. A similar increase in 1920 would make the
production of crude material greater than in any preceding year.
Crude Gypsum Mined in the United States, 1908-1919, in Short Tons
1908 1.721,829 1912 2,500,757 1916 2,757.730
1909 2.252,785 1913 2,599,508 1917 2,696,226
1910 2,379,057 1914 2.476,465 1918 2,057.015
1911 2,323,970 1915 2.447,611 1919 2,420,163
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
177
BUREAU OF MINES
Fees for Testing Explosives and Conditions and Requirements
under Which Explosives Are Tested. Schedule 1-A. 13 pp.
Paper, 5 cents. 1920. Authorization for the work is cited,
permissible explosives are defined, and tests of coal mining
explosives, conditions under which tests will be made, test
requirements of explosives for admittance to permissible list,
prescribed conditions for use of permissible explosives, condi-
tions under which an otherwise permissible explosive is not
permissible, explosives not to be considered permanently per-
missible, manner of making remittances, tests of explosives
used in metal mines, tunnels, quarries, and other engineering
operations, conditions under which tests will be made, and
test requirements of explosives used in metal mines, quarries,
and other engineering operations are described.
Stenches for Detecting Leakage of Blue Water Gas and
Natural Gas. S. H. Katz and V. C. Allison. Technical
Paper 267. 22 pp. Paper, 5 cents. 1920. The impregna-
tion of natural gas or blue water gas with a stench-imparting
chemical provides a means for reducing loss from leakage and
for eliminating accidental poisoning and explosions. Stenches
that possess a disagreeable odor serve best as warnings. Of
those examined, amyl thioether, ethyl mercaptan, phenyl
isocyanide, and pyridine present the best possibilities. None
of the stenches that contain sulfur, if added to gas in amounts
to produce strong odors, would carry sufficient sulfur to inhibit
commercial use of the gas.
Miners' Safety and Health Almanac 192 1. Published in
Cooperation with the United States Public Health Service for
the Use of Miners. Compiled by R. C. Williams. 48 pp. 1920.
Tenth Annual Report of the Director of the Bureau of Mines
to the Secretary of the Interior for the Fiscal Year Ended June
30, 1920. 149 pp. Paper, 15 cents. Issued December 1920.
Structure in Paleozoic Bituminous Coals. Reinhardt
Thiessen. Bulletin 117. 296 pp. Paper, 80 cents.
BUREAU OF STANDARDS
Effects of Cal as an Accelerator of the Hardening of Port-
land Cement Mixtures. R. N. Young. Technologic Paper
174. 24 pp. Paper, 5 cents. 1920. Cal is obtained by pul-
verizing the dried or undried product resulting from a mixture
of either quicklime or hydrated lime, calcium chloride, and
water. It is much more convenient to handle and use in
making concrete than calcium chloride, either fused or in con-
centrated solution. The general effect of Cal on portland
cement mixtures is the same as might be expected from the
use of equivalent amounts of hydrated lime and calcium chloride.
The 3-yr. tests by the Bureau of Standards on concrete gaged
with a solution of calcium chloride are sufficient grounds for
believing that the addition of Cal will not injuriously affect
the ultimate strength and integrity of portland cement concrete.
Slushing Oils. P. H. Walker and L. L. Steele. Tech-
nologic Paper 176. 23 pp. Paper, 5 cents. 1920. This
paper was published to answer inquiries requesting information
as to methods of protecting from corrosion metal in storage for
rather long periods. The investigations were confined to a
consideration of protective coatings which remain in a soft
condition so that they can be easily removed at any time.
Pouring and Pressure Tests of Concrete. W. A. Slater
and A. T. Goldbeck. Technologic Paper 175. 13 pp. Paper,
5 cents. 1920. These tests suggest the desirability of con-
ducting further tests to determine (1) the relation between
the pressure on the forms and the rate of increase in the head
of the concrete, and (2) the influence of hardening of the con-
crete upon the pressure under increasing head.
DEPARTMENT OF AGRICULTURE
The Bureau of Chemistry of the United States Department of
Agriculture. Organization, Enforcement of Food and Drugs
Act, Enforcement of Tea Act, Research Work. Department
Circular 137. 23 pp. Issued 1921.
Peanut Oil. H. C. Thompson and H. S. Bailey. Farmers'
Bulletin 751. Revised December 1920. 18 pp.
The Care of Leather. F. P. Veitch and H. P. Holman.
Farmers' Bulletin 1183. 18 pp. Issued December 1920. The
supply of leather in this country can be made to go much further
than is now the case if everyone selects with discrimination and
properly cares for their boots and shoes, harness, and machine
belts. Not only can personal budgets be cut down in this way,
but prices can be brought down to a lower level by giving the
supply a chance to catch up with the demand. This bulletin
contains suggestions for a judicious selection of articles made
from leather and tells how to care for them in order to secure
the maximum amount of service.
Articles from Journal of Agricultural Research
Some Changes in Florida Grapefruit in Storage. L. A.
Hawrins and J. R. Magness. 20 (December 1, 1920), 357-73.
A Bacteriological Study of Canned Ripe Olives. S. A. Koser.
20 (December 1, 1920), 375-9.
Relation of the Soil Solution to the Soil Extract. D. R.
Hoagland, J. C. Martin and G. R. Stewart. 20 (December
1, 1920), 381-95.
Effect of Season and Crop Growth on the Physical State of
the Soil. D. R. Hoagland and J. C. Martin. 20 (December
1, 1920), 397^04.
BUREAU OF FOREIGN AND DOMESTIC COMMERCE
Import and Export Schedules of Spain. Miscellaneous
Series No. 87. 60 pp. Paper, 10 cents. 1920. This bulletin
is a translation of the import and export schedules of Spain.
Among other things, import schedules are given for mineral
fuel, ores, gold, silver and platinum, unmanufactured iron and
steel, copper and alloys thereof, other metals and alloys thereof,
simple drugs, colors, dyes and varnishes, mineral fertilizers,
chemical and pharmaceutical products, and paper pulp. Export
schedules are given for minerals, mineral ores, gold and silver,
iron and steel, copper and alloys thereof, other metals, simple
drugs, coloring materials, chemical products, and oils.
Industrial Machinery in France and Belgium (with Bibliog-
raphy). C. P. Wood. Special Agents Series 204. 61 pp.
Paper, 10 cents. 1920.
COMMERCE REPORTS — DECEMBER 192O
Recent experiments of the British Department of Scientific
and Industrial Research prove that, provided certain precau-
tions are taken, beef can be frozen in such a way as to preserve
completely the physical and chemical qualities of the fresh
meat. The experiments were carried out with small pieces of
beef, and the committee states that subsequent attempts to
repeat them on a commercial scale have so far failed for lack
of adequate apparatus. (P. 970)
As a result of experiments at Bruenn-Koenigsfeld, turf treated
by a special patented process furnishes a material for insula-
tion and building purposes that is said to be, in most respects,
not inferior, and in some, superior, to cork. (P. 978)
Considerable uncertainty exists in Holland as to the future
of the dye trade. (P. 982)
The kauri-gum industry in New Zealand is taking on new
impetus since the closing of the war. (Pp. 984-5)
The Argentine market for drugs and veterinary remedies
is reviewed. (Pp. 990-2)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by the former German
colonies in Africa during the three latest years for which sta-
tistics are available. (P. 1004)
A Portuguese decree has been issued removing the license
requirements for the exportation of leather. (P. 1009)
The oil, medicinal products, chemical and pharmaceutical
products market in Argentine is reviewed. (Pp. 1031-3)
Recent experiments of the British Department of Scientific
and Industrial Research show that strawberries, when picked
ripe, may be held in cold storage (temperature 1° to 2° C.) in a
good marketable condition for 6 to 7 days. Unripe strawberries
do not ripen normally in cold storage, neither do they ripen
when transferred to normal temperatures after a period of cold
storage. (P. 1035)
The yield of a good quality of crude oil from English shales
by means of treatment in specially designed retorts is reported
to be satisfactory. (Pp. 1038-9)
Although the production of rosin in Spain was less during the
fiscal year ended June 30, 1920, than in the preceding year,
sales were greater and the profit was the largest that the Union
Resinera Espafiola has had in its 22 yrs. of existence. (Pp.
1046-7)
A law of the Dominican Republic provides that all patent
and proprietary remedies must be analyzed and approved by
the department of sanitation before being offered for sale in the
republic. (P. 1047)
Statistics are given showing the imports and exports of vege-
table oil and vegetable oil material by Australia during the
fiscal years ended June 30, 1916, 1917, 1918, and, when possible,
1919. (Pp. 1054-5)
According to preliminary figures issued by the Tunisian
government, the regency's olive oil yield for 1920 is given at
40,000,000 kilos, compared with 12,000,000 to 16,000,000 kilos
in 1919 and 40,000,000 kilos in 1918. (P. 1064)
178
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. Xo. 2
An American-owned manganese mine, situated on the Gulf
of California, is now operating and shipping 200 tons of high-
grade ore monthly. The ore extracted averages about 48 per
cent manganese. (P. 1066)
A company has been formed in Mexico to develop the oil
wells in the districts of Bravos, Iturbide, and Camargo. This
field, it is said, should prove to be one of the world's great oil
fields. (Pp. 1066-7)
Although the imports of oil into Czechoslovakia have been
large, the domestic production of oil has been appreciable. In
Slovakia the finding of rich, new oil wells is reported near
Trencin. (P. 1076)
The peanut and peanut oil industry of China is reviewed.
(Pp. 1083-5)
The production of cacao for 1920 in Tabasco is estimated
at 3,300,000 lbs., the largest, crop since 1913. Mexican cacao,
besides being of superior quality, is far less bitter than other
varieties, and hence requires less sugar in the manufacture of
chocolates and bonbons. As it is richer in fats and oils, it should
be profitable for American manufacturers to import it. (P. 1088)
Australian dehydrated vegetables have attained prominence
on the local market, as well as abroad. (P. 1096)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by the Philippine Islands
during 1917, 1918, and 1919. (P. 1097)
The mineral resources of Slovakia are reviewed. In addition
to iron, coal, and oil, the following minerals are of considerable
importance in manufacturing and the arts: calciferous rocks,
sand, porcelain earth and kaolin, common salt, antimony,
copper, manganese, cobalt, nickel, cinnabar, and pvrite. (Pp.
1098-1100)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by Spanish colonies and
by the Belgian Kongo during the only years for which statistics
are available. (P. 1102)
The Sicilian sumac crop is from one-half to two-thirds of
last year's production, which was about 20,000 tons. (P. 1103)
Manila is making plans for greatly enlarging its water system.
For the purpose of carrying out the improvements, the metropoli-
tan water district has been organized. Two or three experienced
engineers have been procured in continental United States
for the work, which will probably take 7 yrs. (P. 1116)
One of the most interesting contributions to the chemistry
section of the British Association during its annual' conference
at Cardiff was that which opened up a discussion on the subject
of industrial alcohol. (Pp. 1118-9)
It is estimated that the 1920 Chinese peanut oil for export
will be about 84,000 tons. (P. 1121)
A group of German textile manufacturers has established a
new company in Prague for the manufacture of artificial silk.
(P. 1132)
As a result of a general conference of those interested in
Czechoslovak mineral waters, resolutions were prepared
petitioning the government to favor the mineral-water trade
by a thorough revision of freight rates, special rates for the
return of empty bottles, export premiums, arrangements with
foreign countries for the importation of Czecho-Slovak mineral
waters under more favorable tariff arrangements, and the like.
(P. 1136)
During September, the Argentine government oil wells
at Comodoro Rivadavia produced the largest amount of petro-
leum for any month up to this date. (P. 1146)
In order to intensify production in the state oil fields of
Argentina, the Ministry of Agriculture in that republic has
under consideration a plan bv which it is expected to secure
the following production: 1920, 210,000 cubic meters; 1921, 330,000
cubic meters; 1922. 480,000 cubic meters; 1923, 600,000 cubic
meters; 1924, 700,000 cubic meters. (P. 1147)
The production of salt in Japan is reported to be short of the
country's requirements. Government help is being solicited
for the protection of the industry. (P. 1150)
The Japanese allotment of camphor for the fourth quarter
of 1920 gives to the United States the same amount as that of
the last quarter. (P
The cacao growers in Bahia, Brazil, have formed a syndicate
for the purpose of fostering the industry. (P. 1163)
The Rubber Producers' Association of Malaya has issued a
circular letter to its members in British Malaya urging them
to reduce the normal output of rubber by 25 per cent because
of the depressed condition of the rubber market at the present
time. :Pp. 1166-7)
The present condition of the Alsatian potash mines is de-
scribed, and it is claimed that the German salts of Stassfurt
are on the average less rich in potash than the Alsatian. (Pp.
1173-5)
Announcement comes from Greece that the Patras consular
district is in the market for about 55 tons of dyestuffs. (Pp.
1180-1)
Conditions in the German paper industry showed a slight
improvement during September 1920. (P. 1190)
Analyses of petroleum gas at Roma, Queensland, show it to
be considerably richer than the gas from most petroleum wells.
(P. 1191)
Imports of oilseeds, oil nuts, and kernels into the United
Kingdom in October aggregated 129,290 tons, as compared
with 197,525 tons in October 1919, a decrease of 68,235 tons.
(P. 1197)
The greater number of Germany's chemical plants are located
in Leipzig, Cologne, Berlin, and the Hambur districts. There
were 15,204 plants in operation in 1918, while the total has
fallen to 15,(369 in 1919, a decrease of 1.95 per cent. This
decrease is due chiefly to the fact that the chemical plants in
Alsace-Lorraine were eliminated from consideration in 1919.
(Pp. 1210-1)
The lime industry in Finland is considerably handicapped
at the present time by having to use wood in place of coal.
(P. 1211)
A plant for producing benzine and industrial oils is under
construction at Belgrade, Serbia. A chemical factory is also
to be built on the banks of the Danube near there. A plant
for the manufacture of chemical products and perfumery is
being built at Bjelovatz, Slavonia, and a new tannery is being
organized at Vissoko, Bosnia. It is believed that the alcohol
distilleries at Zagreb, Croatia, will soon be completed, and that
distillation will begin prior to May 1921. (P. 1213)
Licenses for the creation of alcohol distilleries will be granted
by the Minister of Finance of Jugoslavia in agreement with
the Minister of Agriculture. Preparations will be made to
abolish, by legal methods, the alcohol monopoly existing in
Serbia and in Montenegro, and everything will be done to
facilitate the development of alcohol industries in these provinces.
(P. 1215)
The vegetable oil industry in Marseille, France, is described.
During the last 5 mo. the industry was seriously affected
by the fluctuations of the oilseed market. There has been
a slight improvement of late, and the outlook for the winter
months is fairly promising. (Pp. 1222-7)
Report comes from Bradford, England, that a machine has
been designed to ascertain the contraction of a cloth due to shrink-
age. The value of the machine may be judged by the results
shown in the following tests, which cover a range of cloths
varying in shrinkage :
Average
Calculated Actual
Shrinkage Shrinkage
Cloths Tested Per cent Per cent
Worsted costume cloth (loose setting) 18.7 18.7
Milled Austrian rug 29.8 31.0
Woolen costume cloth 19.3 19.5
Honeycomb vesting 20 . 0 19.0
Mixture coating 14.3 14.7
Mixture worsted coating 21.3 23.6
(Pp. 1228-9)
The Chinese soap market is described, including native soap
substitutes. (Pp. 1229-31)
Statistics are given showing the imports and exports of vege-
table oil and vegetable oil material by Straits Settlements
during the three latest years for which statistics are available.
(P. 1238)
The following table shows the output of minerals in Mexico
during the first 6 mo. of 1920 compared with the corresponding
period in 1919:
Minerals
Antimony
Arsenic
Commercial copper. .
Tin
Amorphous graphite.
Manganese
Mercury
Molybdenum
Gold
Silver
Commercial lead
Tungsten
First 6 mo. of 1919
Kilos Total Value
4.148 S3. 434
1,358.860 898,206
21.405,829 17,424,345
1,588 4,535
3.686,563 405.522
First 6 mo. of 1920
Kilos Total Value
577,723 $381,875
770,797 309.860
23,914,011 19,466.005
1.437. 495
52,094
1,563
343,561
262,970
14.891
10.343 13,790.663
954.333 69,666,309
30,918.282 10,821,399
1,389 11.633
4.4S5.U5 1,323,109
2,441,240 390,598
31.509 7,531
42.505 220.218
648 6.173
11,775 15,699.996
,029,940 75,824,183
"^8.902 17,465,673
4,471 37,445
543,132 3,434.339
(P. 1247)
41.
Feb., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
179
The new Swedish regulations regarding the uses of artificial
leather in shoes become effective immediately. (P. 1255)
Statistics are given showing the imports and exports of vege-
table oil and vegetable oil material by Hongkong during the
two years for which statistics are available. (P. 1258)
There is reported to be an active demand in Greece for pe-
troleum products. (P. 1262)
About 20 tons of benzidine are used annually in the Athens
consular district. Benzidine has been imported in the past
from American and German firms. (P. 1263)
_ The Italian restrictions on the importation and sale of mineral
oils, including gasoline, kerosene, and fuel oils, will be removed
on or about January 1, 1921. (P. 1265)
The text of the proposed British law for restrictions on the
importation of dyestuffs into Great Britain, is quoted. (Pp.
1297-8)
The Japanese government is soon to appoint a committee for
the disposition of Germany's reparation dyes arriving in Japan.
Approximately 88 tons of German dyes are in warehouses in
Kobe. (P. 1302)
A sample of tungsten ore from Argentina has been examined
by the Bureau of Mines and found to contain 64.46 per cent
wolfram, 10.95 per cent silica plus insoluble matter, and con-
siderable calcium carbonate. (P. 1318)
Statistics are given showing the imports and exports of vege-
table oil and vegetable oil material by French Colonies and
Protectorates in Africa during the three latest years for which
statistics are available. (Pp. 1319-26)
Indications of oil in various parts of Uruguay have been
reported. (P. 1343)
The date on which the new British Dyestuffs Act is to become
effective has not yet been decided. There is said to be a reason-
able probability that a bill for the restriction of inorganic chemi-
cals and pharmaceuticals will be introduced after New Year's
Day. (P. 1345)
T Announcement is made of the discovery of lignite and iron
ore in Poland. (P. 1348)
A new process has been discovered for drying turf for fuel in
Finland. (P. 1359)
The output of the oil fields at Assam, India, is said to be
increasing, and many Indian engineers and chemists are em-
ployed under European supervision. (Pp. 1368-9)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by Portuguese colonies
in Africa during the three latest years for which statistics are
available. Photostat copies of detailed statistics, showing
countries of shipment of imports and destination of exports
from Mozambique may be obtained from the Bureau of Foreign
and Domestic Commerce for 15 cents a page. (Pp. 1372-3)
Special Supplements Issued
Belgium — 2a
France— 7c
Greece — 9a
Wales — 22h
Dublin — 22t
British West Indies-
Canada — 26c
Costa Rica — 276
Dominican Republic-
Panama — 38a
Brazil — 436
Ceylon — 54a
China— 55e
China, Shanghai — 55/
Dutch East Indies — 566
M esopotamia — 62a
Australia — 636
Australia — 63c
Statistics of Exports to the United States
Brazil (Pp. 1087, 1345) Algeria— (Pp. 1306-7)
Crude rubber Oil, geranium
Iron ore
BOOK RLVILW5
Soil Alkali. By Franklin Stewart Harris, Ph.D., Director
and Agronomist, Utah Agricultural Experiment Station.
xvi 4- 258 pp. John Wiley & Sons., Inc., New York, 1920.
Price, $2.50, net.
This book is issued in answer to the continued demand for a
volume containing a resume of the important information con-
cerning the subject. An enormous amount of work has been
done on "soil alkali" but this is the first effort to correlate it.
The term "soil alkali," is perhaps a misnomer, although it is now
definitely fixed as applying to any accumulation in the soil of
soluble salts in sufficient quantity to be injurious to plant growth.
Most of the "alkalies" are salts, namely, chlorides, sulfates,
carbonates, and nitrates of sodium, potassium, and magnesium,
and the chlorides and nitrates of calcium. Naturally, the
accumulation of alkali occurs in arid regions, or under conditions
which do not readily admit of the removal of soluble salts from
the soil.
The author points out that most of the desirable land of the
world has been taken up and about one-half of the area of the
earth is in arid regions where drought and alkali are encountered.
In the United States about 13 per cent of the irrigated area,
or about 9,000,000 acres, contains sufficient alkali to be harmful.
The volume discusses the geographical distribution of alkali
soils of the world and the causes leading to the formation or
accumulation of alkali. The discussion of alkali soils leads into
many of the sciences related to agriculture. Not only are
geographical and geological features discussed, but the range
covers biology as related to plant and seed injury, native vege-
tation as indicative of alkali, and the biological conditions of the
soil; chemistry, as in the methods employed in determining
alkali and the theory of antagonism; physics, as affecting the
physical condition of the soil, and the movement of water in the
soil; engineering as related to drainage and irrigation of the
soil; and crop adaptation for lands containing alkali.
The book seems to have been painstakingly and carefully
prepared, and the author has included the fundamental facts
concerning soil alkali as published in many places throughout
the world, as well as drawing largely from his own experience
in dealing with the problem. The bibliography, while not ex-
haustive, is comprehensive, and no important work seems to
have been overlooked. The book fills a long-felt want by workers
in this field, and should find wide use, as the author believes,
by both students and agriculturalists dealing with alkali soils.
R. O. E. Datis
The Modern Electroplater. By Kenneth M. Coggeshau,.
300 pp. Norman W. Henley Publishing Co., New York,
1920. Price, $3.00.
There is to-day in the electroplating industry a great need
for a modern American text which will explain clearly the
chemical and physical principles of electrodeposition, and their
application to commercial processes. Such a book would be of
great value not alone to progressive electroplaters, but also
to those chemists who are now being brought into contact with
the electroplating departments of large factories.
It is with a distinct sense of disappointment that one realizes
that the author of this new book has not even attempted to
meet that need. In his own words, "The aim of this book is not
scientific, but practical." Indeed the author has followed so
literally this policy that even in the statement of practical
methods he has often failed to be accurate, much less scientific.
How can we expect a practical plater to gain any correct con-
ception of an ampere when he is told that "the gallon and the
ampere, then, are both units of quantity measurement" (p. 30),
although subsequently (p. 37) the author correctly defines a
coulomb as the quantity of electricity? Even if the plater is
willing to continue the use of the Baume hydrometer, he should
not be encouraged to believe that the reading of this or of any
hydrometer is an indication of the metal content of a nickel
plating solution containing various compounds other than
nickel salts (p. 183). In spite of the fact that all progressive
platers have learned to estimate at least roughly the current
180
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
density employed in their plating operations, the author is
content to define the desired rate of deposition by the voltage,
giving always a wide latitude, as, for example, "from two to six"
volts (p. 1 88). Although practically all nickel anodes now used
commercially contain not more than 95 to 97 per cent nickel,
and frequently less, the author refers to 99 per cent nickel anodes
as if they were a regular article of commerce.
The above examples suffice to show that the book cannot
be of real service to either the plater or the chemist. Its chief
value or interest lies in the description of the mechanical equip-
ment used in plating, with modern illustrations derived from
numerous catalogs. William Blum
Technical Gas and Fuel Analysis. By Alfred H. White.
Second Edition, Revised and Enlarged. 319 pages, 59 figures,
and 13 tables. McGraw-Hill Book Co., Inc., New York, 1920.
Price $3.00.
The second edition of this excellent textbook has been revised
and enlarged to include the progress made in technical gas and
fuel analysis in the seven years intervening since the publication
of the first edition.
The greater part of the book, Chapters I to XII, inclusive, deals
with the analysis and testing of gases, fuel and illuminating
gases primarily. The difficulties involved in collecting and
storing a representative gas sample are discussed in detail,
special emphasis being laid on changes in composition produced
by the solubility of gases in the confining fluid and in rubber
connecting tubes. Methods for continuous and intermittent
sampling are described, although no mention is made of constant
flow mercury sampling tubes which can be used to good advantage
where average samples of gases of greatly varying composition
must be sampled.
The Hempel method of gas analysis is carefully described, with
many valuable details of manipulation that are too often omitted
from the average textbook. The excellent discussion on absorp-
tion methods for various constituents contains much new ma-
terial available only within the last two years.
Explosion, fractional, and complete slow combustion methods
for determining combustible constituents are described, with
especial attention to the more generally used explosion method.
A little more attention should have been given to the slow com-
bustion method of Dennis and Hopkins, which is extensively
used in miscellaneous gas analyses where the proportion of com-
bustible constituents varies widely. In the opinion of the re-
viewer this method when carried out properly gives more accurate
results than the explosion method.
On page 61 it is stated that as little as 0.005 Per cent of carbon
monoxide can be detected by the green color produced in a
mixture of iodic anhydride with fuming sulfuric acid on pumice.
This statement should read 0.05 to 0.1 per cent carbon monoxide.
Methods of exact gas analysis are discussed in connection
with the author's bulbed and compensated gas buret. At-
tention is called to errors from oxidation of nitrogen in both
slow combustion and explosion methods, the author giving
data from his own experiments.
Other forms of gas analysis apparatus than the Hempel are
briefly described, especially those which first embodied valuable
principles, such as Schlosing and Rolland's apparatus, Orsat's
apparatus, Bunte's buret, and Chollar tubes. With the ex-
ception of the po. table Orsat apparatus for chimney gas analysis,
no attempt is made to discuss the modern forms of these ap-
paratus, such as the Burrell-Orsat for complete gas analysis,
and the water-jacketed forms of the Bunte buret, as used in the
Elliott and the Morehead apparatus.
Heating value and candle power determinations are treated
in two comprehensive chapters, replete with important details
on apparatus and accuracy of methods.
Chapter IX is devoted to the difficult problem of estimating
suspended particles in gases. Methods of sampling are critically
analyzed, and the available methods for collecting these particles
are briefly described, perhaps a little too briefly for the un-
suspecting technical chemist who has never tried to determine a
mixture of tar, soot, and ash in chimney gases.
The chapters on chimney gases and producer gas will be ap-
preciated by both student and technical chemist. The applica-
tion and interpretation of such analyses are clearly explained.
Sampling, analysis, and special tests for illuminating gas are
fully described. Natural gas is treated more briefly, yet with
references to recent work on separation of the hydrocarbons
and the determination of gasoline in natural gas.
Chapter XIII on liquid fuels describes briefly the principal
tests for evaluating liquid fuels, such as heating value, specific
gravity, moisture, suspended solids, flash point, and distilla-
tion tests. No mention is made of calculating the heating value
of petroleum products to within 1 or 2 per cent from constants
more easily determinable than the calorific value, or the de-
termination of sulfur in the bomb calorimeter. The need of
standardization and development of methods for testing and
analyzing liquid fuels is apparent from the limited scope of this
chapter.
The chapters on sampling and analysis of coal and coke are
quite complete, giving in detail the standard methods of the
American Society for Testing Materials, with numerous com-
ments from the authors and references to recent work on the
subject appearing in the literature. The importance of proper
sampling is especially emphasized.
Chapters XVI and XVII contain an unusually complete dis-
cussion of calorimetric determination of heating value. Pro-
cedures and descriptions of various forms of calorimeters are
given in detail, including a special monel metal bomb used in the
calorimeter laboratory of the University of Michigan.
Thirteen tables, very useful in gas calculations, are included
in the appendix.
The second edition of Professor White's excellent book should
continue to find favor as a text on technical gas and fuel analysis,
on account of the concise presentation of the essential principals
of fuel analysis together with the necessary details of manipula-
tion and the precautions required to obtain reliable results.
The technical chemist will appreciate the up-to-date refer-
ences and new material in the revised edition.
A C. FlELDNER
The Nature of Animal Light. By E. Newton Harvey. Mono-
graphs on Experimental Biology edited by Jacques Loeb,
T. H. Morgan and W. J. V. Osterhout. viii + 178 pp. J.
B. Lippincott Co., Philadelphia and London, 1920.
Price, $2.50.
This fascinating topic has been admirably treated by the
author in a clear, concise, and very readable manner. The
book is so planned, by devoting two of the seven chapters to a
summary of the general physics of light production, that even
the layman can appreciate the relative significance of this par-
ticular branch of the science.
Two chapters describe the various forms of light-giving organ-
isms and the structure of their luminous organs, and the remain-
ing three are devoted to the chemistry of light production and
the dynamics of luminescence.
A comprehensive bibliography is appended.
The subject is considered from the experimental standpoint,
and a large number of facts and observations are made avail-
able for those who wish either to pursue the investigation further,
or to correlate the phenomena with the general theory of radia-
tion and molecular structure.
The conclusion is reached that luminescence, in at least
three groups of luminous animals, is due to the interaction of
two substances, luciferin and luciferase, in the presence of
Feb., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
181
water and oxygen, as suggested by Dubois (18S7). Lueiferase
is unquestionably a protein, heat-sensitive and nondialyzable.
Though used up in causing the oxidation of large quantities of
luciferin, it behaves in many ways like an enzyme. Luciferin
has many properties in common with the proteoses and peptones,
is heat-resistant and dialyzable, and oxidizes with production
of light in the presence of lueiferase.
Unfortunately there appears to be some confusion in the dis-
cussion of luminous efficiencies in Chapter III. The definitions
on page 48 should be more precisely stated, and one for "total
luminous efficiency" included. The data in Table 6, on page
60, giving the comparative efficiencies of different illuminants,
are those computed by Ives for total luminous efficiency, while
the text indicates them as "visible radiation X visual sensi-
bility -5- total radiation." The divisor should be "total energy
input." The efficiency of the firefly as given, 0.96, refers to
radiant luminous efficiency since the total energy input is un-
known, and hence it should not be included in this table.. Though
the radiant luminous efficiency may be very nearly the same as
the total luminous efficiency in the case of an incandescent fila-
ment, when a source such as the incandescent gas burner is con-
sidered, there is a great difference. Here while the radiant
luminous efficiency is 0.012, the total luminous efficiency is
only 0.0019. From the approximate calculation of McDermott
and Ives (Lighting Journal, 2 (1914), 61) and Karrer (/. Frank.
Inst., 185 (1918), 775) the total luminous efficiency of the fire-
fly would appear to be only about 25 per cent. Even this figure,
however, is sufficiently above our best attainments in practice
to warrant a search for the mechanism of the reaction which
the firefly has evolved.
The book, as a whole, is a very interesting summary of the
work which has been done in this field. It will be useful both
to the general reader and the specialist.
G. M. J. Mackay
Margarine. By William Clayton, M.Sc, Member British
Assoc. Com. on "Colloid Chemistry and Its General and In-
dustrial Applications." xi 4- 186 pp., 12 halftone plates and 12
illustrations. Longmans, Green and Co., London, New York,
Bombay, Calcutta, and Madras, 1920. Price, J54.75.
Another of the excellent monographs on industrial chemistry
edited by Sir Edward Thorpe makes its appearance. "A
succinct account of the modern processes of manufacture of
margarine" is the first of its kind in any language. The text,
incomplete to be sure, but rich with references to the literature
and patents (foreign, as well as British), though compact, yet
with a very full bibliography on all phases of margarine technology,
deals not alone with the constituents, the finished product,
keeping qualities, the methods of their analysis, and their
compounding. Butter, renovated butter, lard compounds, and
the "denaturing" of margarine are separately treated in a
pleasing way.
Margarine is one of the worth-while things that have quickly
developed out of the exigencies of war. In 1870 Mege-Mouries,
the French chemist, working on the problem of the production
of synthetic butter, prior to the Franco-Prussian War, con-
verted his researches into the invention of oleomargarine.
The margarine industry acquired preeminence during the World
War, and its importance has been established for all time,
manipulated fats constituting an essential in the regimen of
thickly populated communities.
The author deals with the prejudices, abuses, correctives,
advances, etc., of what has developed into a large, decent in-
dustry. He cleverly classifies the progress made under two
heads, the advances being indicated by four steps in each.
From a purely scientific point of view the noteworthy advances
were (1) the use of commercial lactic acid cultures to impart a
butter flavor; (2) the introduction of vegetable oils and fats
to produce "Nuts and Milk Margarine;" (3) introduction of
hydrogenated oils; and (4) the use of artificial milk, which is
pasteurized, soured, and emulsified.
From a practical standpoint the striking improvements have
been: (1) the use of a spray of ice-cold water to solidify the
margarine emulsion; (2) the introduction of the brine-cooled
rolling drum; (3) employment of a continuous churning ap-
paratus; and (4) the use of butter- working tables, blenders, and
other devices for kneading the margarines.
Each of these forward steps receives due attention, but all of
them were involved in the production of a material of proper
physical texture, which was attained by rapidly cooling a perfect
emulsion. An altogether delightful chapter on the "Theory of
Emulsification" directs attention to an ample field for research
and ends as follows: "So far, practically no work has been
done on solid emulsions, of which butter and margarines are
interesting, if complex, cases."
The nutritional value of margarines receives judicial treat-
ment. The importance of vitamines, or advitants, as Forster
insists they should be called, is fully set forth, and their absence
from certain margarines noted. While butter is urged for
children, adults, "with their stronger digestive powers, may with
absolute impunity replace butter by either oleo- or vegetable-
margarine; provided they consume sufficient amounts of the
vegetative green parts of plants, since these furnish an ample
supply of all three vitamines."
Charles Baskervillb
Industrial Gases. By Harold Cecil Greenwood, xvii 4-
371 pp. D. Van Nostrand Co., New York, 1920. Price,
$5.00, net.
The author has admirably attained his purpose in giving a
comprehensive review of most of the industrial gases, their
properties, and manufacture. The viewpoint is chemical rather
than engineering, and the theory underlying each process is
treated in a clear, readable manner. Particular attention is
paid to the historical development of the various methods, and
the description of important patents is included. The processes
of manufacture are tabulated so that one may easily compare
efficiency, cost (on a pre-war basis), and convenience in storage
and transportation.
The introduction, besides treating well-known gas laws
and their applicability, includes thermodynamical principles,
factors influencing catalytic reactions, theory and general methods
of testing gases for density, viscosity, and purity. Emphasis
is laid on safety precautions in compressing gases for storage
and transportation. Deviations from the theoretical volumes
under various pressures are tabulated, as are also the relations
between degree of filling and pressure developed in cylinders
containing liquefied gases. A table of physical constants of the
gases and a comprehensive bibliography are valuable additions.
The specific gases dealt with are air, oxygen, nitrogen, rare
gases and ozone, hydrogen, carbon monoxide, carbon dioxide,
sulfur dioxide, and nitrous oxide. Three sections of interest are
on asphyxiating gases, hydrogen for military purposes, and
gaseous fuels. The treatment of each gas includes its occur-
rence, physical and chemical properties, manufacture, and ap-
plications. Methods of preparation for laboratory use as well
as production on a commercial scale are included. Such gases
as ammonia and hydrogen chloride which are omitted are to be
treated in another volume of the same series of texts on industrial
chemistry. One omission which is noticeable is the class of
dissolved gases, a very prominent example of which is acetylene
in acetone.
The book recommends itself by its unusually clear correlation
of theory and practice. It is of value to both the student seeking
general information and the chemical engineer interested in
concrete application. HELEN C. Gillette
182
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
NEW PUBLICATIONS
Carbohydrates and Alcohol. Samuel Rideal. Price, 12s. 6d. net. Ball-
iere Tindall & Cox, London.
Cement: Fabrication du Ciment. J. Fritsch. 2d edition, revised. 559 pp.
186 figures, ISO illustrations. Price, $6. 00. D. Van Nostrand Co., New
York.
Chemical Engineering: A Textbook of Chemical Engineering. Ed-
ward Hart. 211 pp. 200 illustrations. Price, $4.00. Chemical
Publishing Co., Easton, Pa.
Chemistry: Introduction to General Chemistry. H. Copaux. Trans-
lated by Henrt Leffmann. 195 pp. 30 illustrations. Price, $2.00.
P. Blakiston's Son & Co., Philadelphia.
Drugs: Analysis of Drugs and Medicines. Henry C. Fuller. 1072 pp.
Illustrated. Price, 110.00, net. John Wiley & Sons, Inc., New York.
Enzymes: The Chemistry of Enzyme Actions. K. George Falk.
(American Chemical Society Monographs.) 140 pp. Price, $2.50.
The Chemical Catalog Co., Inc., New York.
Fuel Production and Utilization. Hugh S Taylor. 296 pp. Price,
£4.00. D. Van Nostrand Co., New York.
Fuel: Low Grade and Waste Fuels for Power Generation. John B. C.
Kershaw. 202 pp. 30 illustrations. Price, $4.00. D. Van Nostrand
Co., New York.
Fuel: Powdered Coal as a Fuel. C. F. Herington. 2d edition, revised
and enlarged. 338 pp. 124 illustrations. Price, $4.50. D. Van
Nostrand Co., New York.
Medicinals: The Qualitative Analysis of Medicinal Preparations. H. C.
Fuller. 2d edition, rewritten. 191 pp. Price, $2.25. John Wiley &
Sons, Inc , New York.
Petroleum: The Technical Examination of Crude Petroleum, Petroleum
Products, and Natural Gas. William A. Hamor and Fred Warde
Padgett. 591 pp. 144 illustrations. Price, $6.00. McGraw-Hill Book
Co., Inc., New York.
Priestley in America. 1794-1804. Edgar Fahs Smith. 173 pp. Price,
$2 00. P. Blakiston's Son & Co., Philadelphia.
Shale Oil Industry. Victor C. Alderson. 186 pp. 15 illustrations.
Price, $4.50. D. Van Nostrand Co., New York.
Water Softening and Treatment, Condensing Plant, Feed Pumps and
Heaters for Steam Users and Manufacturers. Wn.LiAM H. Booth.
2d edition, 324 pp. 92 illustrations. Price, $3.50. D. Van Nostrand
Co., New York.
RECENT JOURNAL ARTICLES
Ammonium Sulfate: Discoloration of Sulfate of Ammonia: Cause and
Remedy. The Chemical Age (London), Vol. 3, No. 79, pp. 678-680.
Analytical Chemistry: The Position of Analytical Chemistry in France. L.
Cofman. The Analyst, Vol. 45, No. 537, pp. 440-444.
Catalysts in Bleaching and Dyeing. A. J. Hall. Textile Colorist, Vol. 43,
No. 505, pp. 33-34.
Chemical Disarmament. V. Lefebure. Chemical and Metallurgical
Engineering, Vol. 24, No. 1, pp. 5-7.
Coal: Low-Temperature Coking of Utah Coals. Osborn Monnett.
Chemical and Metallurgical Engineering, Vol. 23, No. 26, pp. 1246-1249.
Coal: Thrift in Coal. George Otis Smith. Combustion, Vol. 4, No. 1,
pp. 22-27, 38.
Copper and Brass. J. F. Springer. Brass World, Vol. 16, No. 12, pp.
357-360.
Copper: Thermal Expansion of Copper and Its Important Industrial Alloys.
PBTER Hidnert. Mining and Metallurgy, No. 169, pp. 27-28.
Destructive Distillation of Bitumens. George McD. Johns. Combus-
tion, Vol. 3, No. 6, pp. 23-26.
Drugs: A General Method for Making Quantitative Microanalyses of
Vegetable Drugs and Related Substances. Albert Schneider. Journal
of the American Pharmaceutical Association, Vol. 9, No. 12, pp. 1140-
1153.
Drugs: Recherches sur les Hypnotiques. M. Puyal and MllE. Mon-
TagnE. Bulletin de la Societe Chimique de France, Vol. 27, No. 23, pp.
857-862.
Dyes: The International Policies of the American Dyestuff Industry. L.
W. Alwyn-Schmidt. Color Trade Journal, Vol. 8, No. 1, pp. 1-3.
Dyes: Organization and Construction of Dyehouses. A. W. Benoit.
Textile Wcrld Journal, Vol. 58, No. 26, pp. 43-47.
Dyes: Testing the Fastness of Dyed Colors to Light. H. B. Gordon.
Textile Colorist, Vol. 43, No. 505, pp. 29-33.
Dyes: The Dyestuff Industry. Herbert Levinstein. Journal of the
Society of Chemical Industry, Vol. 39, No. 23, pp. 317/-3221.
Enamels: A Classification of Enamels for Sheet Steel. R. R Danielson.
Journal of the American Ceramic Society, Vol. 3, No. 12, pp. 961-970.
Explosives, Composition, Uses and Care. John Rusen. The Coal Indus-
try, Vol. 3, No. 12, pp. 577-579.
Explosives: Initiation of Military Explosives. William A. Corley. Jour-
nal of the Franklin Institute, Vol. 191, No. 1, pp. 87-119.
Filter Paper: The Testing of Filter Paper. J. Rigaud Monin. Paper,
Vol. 27, No. 16, pp. 12. 31. Translated from La Papelerie, Vol. 42, 818.
Flotation: Surface Energies in Flotation. Frederick G. Moses. Engi-
neering and Minimi Journal, Vol. 3, No. 1, pp. 7-11.
Fuel: Modern Development of Pulverized Fuel. C. L. Bohannan. Com-
bustion, Vol. 4, No. 1, pp. 32-36.
Gas: The Facts Regarding Gas Standards. J. B. Klumpp. The Gas Age,
Vol. 66, No. 12, pp. 506-512.
Gas: Rough Cleaning Blast Furnace Gas. A. Hutchinson and E. Bury.
Blast Furnace and Steel Plant, Vol. 9, No. 1, pp. 25-28.
Glass: The Occurrence of Crust or Scum on Continuous Bottle Tank Fur-
naces. Wilbur F. Brown. The Class Industry, Vol. 1, No. 2, pp
29-30.
Glass: Use of Light Soda Ash in the Production of Flint Bottle Glass.
C. A. Cole. The Class Industry, Vol. 1, No. 2, pp. 34-38.
Gypsum: Results of Testing Gypsum Products. W. E. Emley and C F.
Faxon. Journal of the American Ceramic Society, Vol. 3, No. 12, pp.
984-993
Health Hazards in the Rubber Industry. Charles F. Horan. The
Rubber Age, Vol. 8, No. 6, pp. 229-230.
Helium: The History of Helium and Its Production. R. T. Elw3rthy.
Canadian Chemistry and Metallurgy, Vol. 5, No. 1, pp. 7-9.
Hydrocyanic Acid: The Determination of Hydrocyanic Acid. R. Leitch
Morris. American Journal of Pharmacy, Vol. 92, No. 12, pp. 908-
916. Reprinted from The Pharmaceutical Journal and Pharmacist.
Industrial Alcohol: The Future of Industrial Alcohol. H. I. Peffer.
Paint, Oil and Chemical Review, Vol. 70, No. 26, pp. 6, 7, 18, 20, 21.
International Cooperation in Science. R. F. Ruttan. Canadian Chemis-
try and Metallurgy, Vol. 5, No. 1, pp. 17-19.
Iron: Testing Hardness of Bearings and Journals. C H. Bierbaum,
J. A. Capp and H. Diederichs. The Iron Age, Vol. 106, No. 27, pp.
1727-1730.
Lubricating Oils: Methods of Examination of Lubricating Oils. G. F.
Robertshaw. Journal of the Institution of Petroleum Technologists,
Vol. 6, No. 24, pp. 324-378.
Microorganisms and Their Industrial Uses. A. Chaston Chapman. The
Chemical Trade Journal and Chemical Engineer, Vol. 67, No. 1752, pp.
802-803.
Open Hearth Practice Cause and Effect. N. E. MacCallum. Blast Fur-
nace and Steel Plant, Vol. 9, No. 1, pp. 36-38.
Ore Analysis: The Gravimetric Estimation of Bismuth as Phosphate and
Its Application in Ore Analysis. W. R. Schoeller and E. F. Watee-
housE. The Analyst, Vol. 45, No. 537, pp. 435-439.
Paper: Analysis of Sulphur Burner Gases and Sulphite Acid. A. Sander.
Paper, Vol. 27, No. 14, pp. 17-18, 32.
Patents: Utilization of the Patentable Discoveries of Government Technical
Research for the Benefit of Industry. F. G. Cottrell. Chemical Age,
Vol. 28, No 12, pp. 447-450.
Porcelain: Time and Temperature of Burning as Factors Influencing the
Constitution and Microstructure of a Porcelain Body. A. A. Klein.
Journal of the American Ceramic Society, Vol. 3, No. 12. pp. 978-983.
Precipitation: Notes on the Influence of Soluble Silica and Calcium Salts on
Precipitation. J. Hayward Johnson. Journal of the Chemical Metal-
lurgical and Mining Society of South Africa, Vol. 21, No. 4, pp.
58-62.
Rubber: The Action of Light on Rubber. B. D. Porrett. The India-
Rubber Journal, Vol. 60, No. 23, pp. 21-24.
Standardization: Relation of Standardization to Mine Management.
Chas. A. Mitke. Canadian Mining Journal, Vol. 61, No. 49, pp. 1019-
1022.
Steel: Review of Iron and Steel Literature, 1920. E. H. McClelland.
The Blast Furnace and Steel Plant, Vol. 9, No. 1, pp. 6-8.
Sulfate Cellulose: A Rapid Method of Control Analysis of the Liquor in
the Manufacture of Sulfate Cellulose. G. K. Bergman. Pulp and
Paper Magazine of Canada, Vol. 19, No. 1, pp. 11-12. Translated from
Finsk Pappers-Och Travarutidskrift.
Stresses: Determining Stresses by Polarized Light. George Weed Hall
and Arthur L. Kimoall, Jr. Scientific American Monthly, Vol. 3,
No. 1, pp. 49-53.
Tartaric Acid: Sulla Determinazione dell' Acido Tartarico per Via Polari-
metrica. Angelo Coppadoro. Ciornale di Chimica Induslriale td
Applicala, Vol. 2, No. 11, pp. 613-616.
Training Foremen for the Chemical Industries. Allen Rogers. Chem-
ical Age, Vol. 28, No. 12, pp. 461-463.
Varnish: Sur les Vernis au Furfurol. Ch. Coffignisr. Bulletin de la
Sociefe Chimique de France, Vol. 27, No. 23, pp. 865-867.
Wood Pulp: Progress in Study of Wood and Wood-Pulp Infection and
Decay. Otto Kress and C. J. Humphrey. Paper, Vol. 27, No. 12. pp.
22-25. 52.
Feb., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
MARKET
FIRST-HAND PRICES FOR GOODS
INORGANIC CHEMICALS
Jan. 1
Acid, Boric, cryst., bbls lb. .15
Hydrochloric, com'l, 20" lb. .01>/i
Hydriodic oz. . 19
Nitric, 42° lb. .07«/«
Phosphoric, 50% tech lb. .20
Sulfuric, C. P lb. .07
Chamber, 66° ton 20.00
Oleum 20% ton 23 . 00
Alum, ammonia, lump lb. .041/4
Aluminium Sulfate (iron-free) lb. .031/,
Ammonium Carbonate, pwd lb. .16
Ammonium Chloride, gran lb. . 101/,
Ammonia Water, carboys, 26°. . . .lb. .11
Arsenic, white lb. .12
Barium Chloride ton 75 . 00
Nitrate lb. .14
Barytes, white ton 30.00
Bleaching Powd., 35%, Works, 100 lbs. 3 . 50
Borax, cryst., bbls lb. .07i/2
Bromine, tech lb. .53
Calcium Chloride, fused ton 28 . 75
Chalk, precipitated, light lb. .05
China Clay, imported ton 1 8 . 00
Copper Sulfate 100 lbs. 6.50
Feldspar ton 8.00
Fuller's Earth 100 lbs. 1 .00
Iodine, resublimed lb. 4.00
Lead Acetate, white crystals lb. .16
Nitrate lb. .15
Red American 100 lbs. . 121/4
White American 100 lbs. . 101/,
Lime Acetate 100 lbs. 2.00
Lithium Carbonate lb. 1.50
Magnesium Carbonate. Tech lb. .12
Magnesite ton 72.00
Mercury flask American 75 lbs. 45 . 00
Phosphorus, yellow lb. .35
Plaster of Paris 100 lbs. 1 . 50
Potassium Bichromate lb. .17
Bromide, Cryst lb .25
Carbonate, calc., 80-85% lb. . 141/,
Chlorate, cryst lb. .10
Hydroxide, 88-92% lb. .14
Iodide, bulk lb. 3.00
Nitrate lb. .12
Permanganate, U. S. P lb. .55
Salt Cake, Bulk ton 30.00
Silver Nitrate oz. .43
Soapstone, in bags ton 12.00
Soda Ash. 58%, bags 100 lbs. 1 .80
Caustic, 76% 100 lbs. 3.80
Sodium Acetate lb. .081/2
Bicarbonate 100 lbs. 2.00
Bichromate lb. . 10
Chlorate lb. .10
Cyanide lb. .24
Fluoride, technical lb. .16
Hyposulfite, bbls 108 lbs. 4 . 00
Nitrate, 95% 100 lbs. 2.85
Silicate, 40" lb. .OU/,
Sulfide lb. .08
Bisulfite, powdered lb. .07
Strontium Nitrate lb. .15
3ulf nr, flowers 100 lbs. 4 . 00
Crude long ton 20.00
rale, American, white ton 20.00
rin Bichloride lb. .19</i
Oxide lb. .50
51nc Chloride, U. S. P lb. .40
Oxide, bbls lb. .10
ORGANIC CHEMICALS
Icetanilide lb. .25
Ldd, Acetic, 28 p. c 100 lbs. 3.25
Glacial lb . IOV2
Acetylsalicylic lb. .70
Benzoic, U. S. P., ex-toluene.. lb. .70
Carbolic, cryst., U. S. P., drs. . .lb. .11
50- to 110-lb. tins lb. .23
Citric, crystals, bbls lb. .50
REPORT-JANUARY, 1921
IN ORIGINAL PACKAGES PREVAILING IN THE NEW YORK MARKET
Jan. 1
Acid {Concluded)
Oxalic, cryst., bbls lb. .18
'' Pyrogallic. resublimed lb. 2.35
•°JV« Salicylic, bulk, U. S. P lb. .35
Tartaric, crystals, U. S. P lb. .40
.07V« Trichloroacetic, U. S. P lb. 4.40
Acetone, drums lb. J31A
07 Alcohol, denatured, 190 proof gal. .75
™'nn Ethyl, 190 proof gal. 5.25
Z6.UU Wood, Pure gal. 1.95
"nil/ Amyl Acetate gal. 3.75
.1)3 /s Camphor. Jap. refined lb. .90
Carbon Bisulfide lb. .08
°9''4 Tetrachloride lb. .11
•" Chloroform, U. S. P lb. .40
•12 Creosote, U. S. P lb. .60
75.00 Cresol, U. S. P lb. .18
Dextrin, corn lb 04i/»
Imported Potato lb. .08
3'n°./ Ether.U. S.P.,conc, lOOlbs lb. .23
• 07/2 Formaldehyde lb. .18
"„ Glycerol, dynamite, drums lb. .17
2875 Pyridine gal. 2.75
m'nn Starch, corn 100 lbs. 2.93
*•"" Potato,Jap lb. .06V,
?:" Sago ib-
4°° OILS, WAXES, ETC.
■J* Beeswax, pure, white lb. .55
now Black Mineral Oil, 29 gravity gal. .22
°V* Castor Oil, No. 3 lb. .10i/2
200 Ceresin, yellow lb. .13
1,5° Corn Oil, crude lb. .09i/i
' ' Cottonseed Oil, crude, f . o. b. mill . . lb. . 06
' Menhaden Oil, crude (southern), .gal. .30
50'°° Neat's-foot Oil, 20» gal. 1.65
•^ Paraffin, 128-130 m. p., ref lb. .08
Paraffin Oil, high viscosity gal. .45
■'7 Rosin, "F" Grade, 280 lbs bbl. 8.50
Rosin Oil, first run gal. .61
141/2 SheUac, T. N lb. .70
Spermaceti, cake lb. .30
"'* Sperm Oil, bleached winter, 38°. . .gal. 1.80
Stearic Acid, double-pressed lb. . 131/j
'2 Tallow Oil. acidless gaL 1.25
■" Tar Oil, distilled gal. .60
3000 Turpentine, spirits of gal. .76
.45
12/°° METALS
2.05
3.80 Aluminium, No. 1, ingots lb. .24'/a
.08'A Antimony, ordinary 100 lbs. 5.25
2.00 Bismuth lb. 2.72
.10 Copper, electrolytic lb. .13
.10 Lake lb. .13»/«
.24 Lead. N Y Ib. .041/2
.16 Nickel, electrolytic lb. .45
4.00 Platinum, refined, soft oz. 70.00
2.75 Quicksilver, flask Amer 75 lbs ea. 45 . 00
.OP/, Silver oz. .64
.08 Tin lb. .32'/s
.07 Tungsten Wolframite per unit 6.50
.15 Zinc, N. Y 100 lbs. 6.00
4.00
2° ' °° FERTILIZES MATERIALS
•19'/i Ammonium Sulfate export... 100 lbs. 3.35
•50 Blood, dried, f. o. b. N. Y unit 5.10
• *° Bone, 3 and 50, ground, raw ton 45 . 00
• ° Calcium Cyanamide, unit of Am-
monia 4 . 50
Fish Scrap, domestic, dried, f. o. b.
.25 works unit 5.00
3.25 Phosphate Rock, f. o. b. mine:
.10'/i Florida Pebble, 68% ton 6. 85
.70 Tennessee, 78-80% ton 11.00
.70 Potassium Muriate. 80% unit 1.85
.11 Pyrites, furnace size, imported.. . .unit .18
.21 Tankage, high-grade, f. o. b.
.48 Chicago unit 4.00
4.40
13>/i
.67
5.25
1.65
3.75
.87
.08
.11
.40
.23
.18
.16
2.75
2.93
.06i/i
.25
.05
.22
.10V.
.13
.09Vs
.06i/j
.30
1.65
.08
.45
1.80
. 13V,
5.25
2.72
.13
.131/2
.04«/«
.45
60.00
50.00
.65
• 38V>
6.50
5.90
6.85
11.00
1.70
184
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 2
COAL-TAR CHEMICALS
Jan. 1
Crudes
Anthracene, 80-85% lb. .75
Benzene, Pure gal. .30
Cresol. U S. P lb. .18
Cresylic Acid, 97-99% gal. . 90
Naphthalene, flake lb. .08
Phenol, drums lb. .10
Toluene, Pure gal. .30
Xylene, 2 deg. dist. range gal. .60
Intermediates
Acids:
Anthranilic lb. 2 . 20
B lb. 2.25
Benzoic lb. .70
Broenner's lb. 1.75
Cleve's lb. 2.00
Gamma lb. 3.75
H lb. 1.35
Metanilic lb. 1.70
Monosulfonic F lb. 3.25
Napthionic. crude lb. .85
Nevile St Winther's lb. 1.75
Phthalic lb. .60
Picric lb. .25
Sullanilic lb. .33
Tobias lb. 2.25
Ami noazo benzene lb. 1 . 25
Aniline Oil lb .20'/s
For Red lb. .42
Aniline Salt lb. .33
Anthraquinone lb. 2 .50
Benzaldehyde, tech lb. .45
U. S. P lb 1.00
Benzidine (Base) lb. 1.00
Benzidine Sulfate lb. .80
Diaminophenol » lb. 5.50
Dianisidine lb 8 .00
p-Dichlorobenzene lb. .15
Diethylamide lb 1.40
Dimethylaniline lb. .60
Dinitrobenzene lb. .25
Dinitrotoluene lb. .28
Diphenylamine lb. .70
G Salt lb .80
Hydroquinol lb. 1 .90
Metol (Rhodol) lb 6.75
Monochlorobenzene lb. . 14
Monoethylaniline lb. 2.15
a-Naphthylamine lb. .45
6-Naphthylamine (Sublimed) lb. 2.25
6-Naphthol, dist lb. .36
m-Nitroaniline lb. .90
0-Nitroaniiine lb. 1.00
Nitrobenzene, crude lb. .14
Rectified (Oil Mirbane) lb. .16
<>-Nitrophenol lb. .80
p-Nitrosodimethylaniline lb. 2 . 90
o-Nitrotoluene lb. .25
0-Nitrotoluene lb. 1 .25
m-Phenylenediamine lb. 1 . 30
P-Phenylenediamine lb. 2.30
Phthalic Anhydride lb. .65
Primuline (Base) lb 3.00
R Salt lb. .85
Resorcinol, tech lb. 2 . 00
U. S. P lb. 2.50
Schaeffer Salt lb. .75
Sodium Naphthionate lb. 1.10
Thiocaibanilide lb. .60
Tolidine (Base) lb. 1.75
Toluidine, mixed lb. .44
o-Toluidine lb. .33
m-Toluylenediamine lb. 1 .50
p Toluidine lb. 1.75
Xylidine, crude lb. .45
COAL-TAR COLORS
Acid Colon
Black lb. 1 .00
Blue lb. 1.50
2.20
2.25
.70
1.75
2.00
3.75
1.35
1.70
3.25
.85
1.75
.60
.25
.33
2.25
1.25
■ 201/2
2.50
.45
1.00
1.00
.80
5.50
8.00
.28
.70
.80
1.80
6.75
.14
2.15
.45
2.25
1.25
1.30
2.30
2.00
2.50
.75
1.10
.60
1.75
1.50
1.75
1.00
1.50
Acid Colors (Concluded)
Fuchsin lb.
Orange III lb.
Red lb.
Violet 10B lb.
Alkali Blue, domestic lb.
Imported lb.
Azo Carmine lb.
Azo Yellow lb.
Erythrosin lb.
Indigotin, cone lb.
Paste lb.
Naphthol Green lb.
Ponceau lb.
Scarlet 2R lb.
Direct Colors
Black lb.
Blue 2B lb.
Brown K lb.
Fast Red , lb.
Yellow lb.
Violet, cone lb.
Chrysophenine, domestic lb.
Congo Red, 4B Type lb.
Primuline, domestic lb.
Oil Colors
Black. lb.
Blue lb.
Orange lb.
Red III lb.
Scarlet lb.
Yellow lb.
Nigrosine Oil. soluble lb.
Sulfur Colors
Black lb.
Blue, domestic lb.
Brown lb.
Green lb.
Yellow lb.
Chrome Colors
Alizarin Blue, bright lb.
Alizarin Red, 20% Paste lb.
Alizarin Yellow G lb.
Chrome Black, domestic lb.
Imported lb.
Chrome Blue lb.
Chrome Green, domestic lb.
Chrome Red lb.
Gallocyanin lb.
Basic Colors
Auramine, O, domestic lb.
Auramine, OO lb.
Bismarck Brown R lb.
Bismarck Brown G lb.
Chrysoidine R lb.
Chrysoidine Y lb.
Green Crystals, Brilliant lb.
Indigo, 20 p. c. paste lb.
Fuchsin Crystals, domestic lb.
Imported lb.
Magenta Acid, domestic lb.
Malachite Green, crystals lb.
Methylene Blue, tech lb
Methyl Violet 3 B lb.
Nigrosine, spts. sol lb.
Water sol., blue lb.
Jet lb.
Phosphine G. , domestic lb.
Rhodamine B. extra cone lb.
Victoria Blue, base, domestic lb.
Victoria Green lb.
Victoria Red lb.
Victoria Yellow lb.
2.50
2.50
.60
.60
1.30
1.30
6.50
6.50
6.00
6.00
8.00
8.00
4.00
4.00
2.00
2.00
7.50
7.50
2.50
2.50
1.50
1.50
1.95
1.95
1.00
1.00
2.35
2.35
2.00
2. CO
1.10
1.10
2.00
2.00
.70
.70
1.25
1.25
1.40
1 .40
1.65
1.65
1.00
1 .00
1.25
1.25
5.00
5.00
1.10
1 .10
1 .00
1.00
1.25
1.25
2.20
2.20
1.00
1.00
1.50
1.50
2.00
2.00
2 80
2.80
2.50
2.50
4.15
4.15
4.50
4.50
12.00
12.00
4.25
4.25
3.25
3.25
2.75
2.75
2.75
2.75
.85
.85
.70
.70
.90
.90
7.00
7.00
17.00
17.00
6.00
6.00
2.50
2.50
7.00
7.00
7.00
7.00
TAe Journal o£
Published Monthly by The American Gnomical Society
Editor: CHAS. H. HERTY
Assistant Editor: Lois W. Woodford
Advisory Board: H. E. Barnard
Chas. L. Reese
vditorial Offices:
One Madison Avenue, Room 343
New York City
Telephone: Gramercy 0613-0614
J. W. Beckman
Geo. D. Rosengarten
A. D. Little A. V. H. Mory
T. B. Wagner
Advertising Department:
170 Metropolitan Tower
New Yotk City
Telephonb: Gramercy 3880
/olume 13
MARCH 1, 1921
No. 3
iDITORIALS:
Thinking It Through 186
Vicarious Punishment 187
Your Brother's Keeper 187
Aftermath 187
A Special Problem 188
Appreciations 188
I"he Chemical Industry and Trade of England. O. P.
Hopkins 189
Driginal Papers:
The Cryoscopy of Milk. Julius Hortvet 198
The Formation of Anthracene from Benzene and Ethyl-
ene. J. E. Zanetti and M. Kandell 208
Fermentation Process for the Production of Acetic
and Lactic Acids from Corncobs. E. B. Fred and
W. H. Peterson 211
Recovering Newsprint. Charles Baskerville and Res-
ton Stevenson 213
Regenerating Bookstock. Charles Baskerville and C.
M. Joyce 214
A New Crystalline Form of Potassium Chlorate. E. R.
Wolcott 215
A Test for Annatto in Fats and Oils. W. Brinsmaid. . 216
Benzyl Succinate: Preliminary Report on Its Composi-
tion, Manufacture, Properties, and Probable Thera-
peutic Uses. Mortimer Bye 217
Atropine Sulfate from Datura Stramonium. H. W.
Rhodehamel and E. H. Stuart 218
An Investigation of the U. S. P. Assay for Phosphoric
Acid and Soluble Phosphates. A. E. Steam, H. V.
Farr and N. P. Knowlton 220
New Method for the Determination of Potassium in
Silicates. Jerome J. Morgan 225
Centrifugal Method for Determining Potash. Elmer
Sherrill 227
Rapid Iodometric Method for Determination of Chro-
mium in Chromite. Ernest Little and Joseph Costa. 228
A Rapid Volumetric Method for Determining Alcohol.
Arthur Lachman 230
CONTENTS
Laboratory and Plant:
A Comparative Study of Vibration Absorbers. H. C.
Howard 2.31
Water Softening for the Manufacture of Raw Water Ice.
A. S. Behrman 235
Note on Partial and Total Immersion Thermometers.
C. W. Waidner and E. F. Mueller 237
Laboratory Thermometers. W. D. Collins 240
The Dayton Process. F. C. Binnall 242
Addresses and Contributed Articles:
Phthalic Anhydride Derivatives. A Partial Collection
of Names and References. Max Phillips 247
The American Potash Industry and Its Problems. John
E. Teeple 249
Spare Time. H. W. Jordan 253
President Smith Addresses the New York Chemical
Societies 254
Studies on the Chemistry of Cellulose. I — The Con-
stitution of Cellulose. Harold Hibbert 256
Research Problems in Colloid Chemistry. Wilder D.
Bancroft 260
Notes and Correspondence:
The Action of Ultraviolet Rays on the Saccharomy-
cetes; Low-Temperature Carbonization and Its Ap-
plication to High Oxygen Coals — Correction 265
Scientific Societies:
Advisory Committee Resolution on the Chemical War-
fare Service; Rochester Meeting, American Chemical
Society; Anniversary Celebration at the Chemists'
Club; Calendar of Meetings 266
Washington Letter 268
Paris Letter 269
Personal Notes 270
Government Publications 271
Book Reviews 274
New Publications 278
Market Report 279
Subscription to □
Subscript!!
-members, $7.50; single copy, 75 cents, to members. 60 cents. Foreign postage, 75 cents, Canada, Cuba and Mexico excepted,
i and claims for lost copies should be referred to Charles L. Parsons, Secretary, 1709 G Street, N. W., Washington, D. C.
186
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. No. 3
EDITORIALS
THINKING IT THROUGH
Germany has to-day the greatest and most active
dyestuff industry in the world, as evidenced by the
production in January, 1921, of 12,000 tons of dyes,
750 tons more than the average pre-war monthly
output. From these dye plants came all of the poison
gases and most of the high explosives used by Germany
throughout the world war. Bolshevist Russia has
to-day the largest standing army in the world —
1,500,000 men. If these two agencies of destruction
are ever fully combined, the world will face a new
struggle incomparably more tragic than that through
which it has just passed. Already that union
has begun, for it is known that in their successes
against the forces of General Wrangel the Bolshevist
armies were largely aided by poison gas — and Russia
has now no chemical industry. Moreover, according
to the London Times, December 30, 1920, the program
of the German, Hungarian and Russian reactionaries,
prepared in Budapest on June 22, embraced this
significant feature: "the manufacture of new forms
of arms and ammunition will be undertaken, Ger-
many providing the machinery, raw materials and
personnel."
What can be done.? Talk of disarmament is world-
wide at the present time, but the feature which is em-
phasized is relief from the burdens of taxation which
accompany the race for supremacy in battleships and
big guns. If real peace is being sought, then we cannot
ignore the most striking developments of the war — ■
aviation and gas warfare.
All are agreed that the first step in disarmament is
the stripping of war-making power from that nation
which brought about the war and which to-day shows
no sign of contrition, though defeated. Sections 168
and 169 of the peace treaty give ample power for
bringing about the chemical disarmament of Germany
through destruction of her surplus dye plants. When
in Paris in 1919 as a member of the conference on
Reparation Dyes, we asked why this had not already
been done. The reply came, "Europe wished to
do so, but American influence was against it — and
prevailed." This statement has been confirmed by
Americans present during the formulation of the peace
treaty.
The basis of this unfortunate American attitude was
the insistence that these dye plants produced products
useful in peace and should, therefore, be preserved.
Exactly the same view prevailed concerning the Ger-
man plants for fixation of atmospheric nitrogen.
But the rest of the world has determined to be in-
dependent of Germany in dye manufacture and ni-
trogen fixation. A great over-productive world ca-
pacity in these lines exists to-day. The peace-product
argument has fallen down. These surplus German
plants stand to-day as a sure incitant of future com-
mercial war, in which contest Germany has all the ad-
vantage of experience, of geographical distribution
and of governmental sanction of unification — an
economic policy abhorrent to American ideals of
healthy industrial conditions. Unneeded in peace,
these plants represent, in terms of chemical warfare,
borne out by the facts of war history, infinite possi-
bilities of war making.
Fortunately new forces are now moving. In London
a great interallied conference is now being held.
American influence is not present. The question
of chemical disarmament should there be settled
right. In our own country, within a few weeks
there is to be a complete change in government circles.
Peace will be made with Germany by a new Adminis-
tration. Possibly a world conference on disarma-
ment will be called. In any case, the new Administra-
tion has a distinct share of the responsibility of effec-
tuating the chemical disarmament of Germany, so
that she may not again embroil the world in war.
If there be those who feel that the destruction of
the enemy's battleships, forts, and guns is ample pro-
tection, then they are not aware of the fact that the
whole tendency of most recent developments in gas
warfare is to get away from former methods of pro-
jection— and we are just on the borderland of these
new developments.
General Mitchell is right when he speaks of the
enormous possibilities of destruction by aeroplanes
distributing toxic materials, whether by bombs or
by other means. He emphasizes the point that
this practice was not resorted to in the last war
because the opponents were too evenly matched and
each feared to begin.
Senator New proposes, in his bill now before Congress,
that obsolete ships be allotted to the air service for
testing the effectiveness of high explosive bombs
dropped from aeroplanes. If the bill passes, these
ships should be filled with pestilence-breeding rats
and the effect of toxic material dropped from aero-
planes studied, before the vessels are blown up by high
explosives.
And think of the possibilities of the toxic smoke
candle, dropped from aeroplanes or released by sub-
marines, surrounding and filling a battleship for hours
with an atmosphere of poison gas.
Men's minds must not work in the old channels.
Obvious developments must not be overlooked. The
League of Nations, at its Geneva sitting, took no
action against gas warfare. Our national conscious-
ness has grasped clearly the thought that dye plants
are "potential arsenals," but the thought is static
— not dynamic. We have failed to think it through.
But the time is soon coming when a grave error will
be committed if we then have still failed to think it
through. In the formulation of our peace treaty with
Germany, President Harding and his advisers should
give this question, shot through with danger to world
peace, most serious consideration.
Think it through! There is only one answer!
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
187
VICARIOUS PUNISHMENT
In the enactment of the National Prohibition Act,
Congress differentiated clearly between alcohol as a
beverage on the one hand, and as a chemical reagent
on the other. Ample provision was made for pro-
hibiting its use as an intoxicant, and equal emphasis
was laid upon the encouragement of manufacture and
facilitation of its use in the chemical industries. In
carrying out the former policy the Internal Revenue
Bureau has been extremely active; but only with diffi-
culty, and to this day inadequately, has it been roused
to its duties in carrying out the good will of Congress
toward the chemical industries.
While we clearly appreciate the tremendous obstacles
thrown in the path of prohibition enforcement by forces
of evil, nevertheless the fact stands that through
inadequate policing great abuses in securing permits
for withdrawal of alcohol have occurred. In the en-
deavor to stiffen up this side, a ruling of the Attorney
General, as to distribution of alcohol being confined
to manufacturers and wholesale druggists only, has
led to a decision to make industrial alcohol suffer,
and by this we do not mean denatured alcohol.
If these new regulations prevail, the facilitation of
the distribution of alcohol for industrial purposes as
intended by Congress will be seriously interfered with.
Another encroachment of prohibition alcohol into the
domain of industrial alcohol will have been accomplished.
These matters are now under active discussion in
Washington. Manufacturers of industrial alcohol have
joined in a vigorous protest to the Commissioner of
Internal Revenue. It is to be hoped that before these
new regulations are issued, the Secretary of the Trea-
sury, the Commissioner of Internal Revenue, and per-
haps the Attorney General, will give more generous
consideration to the needs of the chemical industries.
These industries are performing a service of high use-
fulness to the nation, and as they grow the use of in-
dustrial alcohol in their operations will constantly in-
crease. The chemical industries should not be dealt
a vicarious punishment because of the shortcomings of
prohibition enforcement.
YOUR BROTHER'S KEEPER
The day's work is not over when our desks are cleared
or when routine matters have been disposed of. To
those in positions of responsibility and power, there
are always problems connected with the material
welfare, and with the healthy development, in mind
and spirit, of those who tread the path of daily routine.
One of the broad-seeing and deep-feeling men in the
chemical industry who has given much thought to these
problems is Dr. H. W. Jordan of Syracuse, N. Y. We
reproduce with pleasure (page 253) an article contrib-
uted by Dr. Jordan which, while written in a facetious
vein, nevertheless sets forth a fundamental social prin-
ciple that requires serious attention from the industries.
It is hoped that this article may catalyze a mass of
discussion on this and related lines. We should like
to devote a special section of This Journal to such
communications.
AFTERMATH
Correspondence on file in this office is reproduced
herewith:
E. LEITZ, Inc.
New York
December 24, 1920.
Mr. Chas. H. Hertz, [sic]
Editor of The Journal of Industrial and Engineering Chemistry,
1 Madison Ave.,
New York, N. Y.
Dear Sir:
In the December issue of your Journal appeared an editorial
"playing their game" and inasmuch as no signature is given
we look towards you as being responsible for same.
This editorial links our firm with a "pink sheet" and states
that your representative, by telephone, received from some one
of our establishment an admission that we are responsible for
the writing and printing of the circular in question.
We inform you that this statement is a rigid falsehood since
you cannot advance the slightest proof substantiating your
ascertion [sic]. For one reason or other the accusation has
been instituted to cause injury to our business.
What means do you intend to persue [sic] to correct this state-
ment? If the desired satisfaction cannot be obtained by us we will
have to place this matter into our attorney's hands for further
action as may be necessary and advisable.
Yours faithfully,
E. Leitz, Inc.
per — (Signed) A. Traeger,
Pres. & Gen. Mgr.
January 13, 1921.
E. Leitz, Inc.,
60 E. 10th St.,
New York City.
Gentlemen :
On my return from a vacation trip I find your letter of De-
cember 24th, 1920. In reply I beg to say that the editorial,
"Playing Their Game," to which you refer, was written by
me as Editor of This Journal.
Letters and memoranda which are on file in this office con-
firm the statements made in that editorial regarding the writing
and distribution of the pink sheet signed "Friends of Science,
interested in its development." The editorial in question was
written in the light of the evidence, which includes acknowledg-
ment on two separate occasions by a representative of your firm
at your place of business that the leaflet was written in your
office.
Referring to the last paragraph in your letter, we shall be
glad to give space in This Journal to any statement which
you may wish to make regarding the facts in this case.
Very truly yours,
(Signed) Chas. H. Hertv,
Editor
Some six weeks have elapsed since our letter to E.
Leitz, Inc., was mailed. Our letter has not been
returned by the Post Office, so we assume it was de-
livered. Nor have we received any visit or communica-
tion from any attorney representing the firm. We
infer therefore that "the desired satisfaction" has
been "obtained" by E. Leitz, Inc. It is difficult, how-
ever, to understand in what way, for our letter
of January 13, 1921, contains practically nothing
more than was printed in the original editorial.
However, as the charge that our "statement is a
rigid falsehood" has not been withdrawn, we re-
produce below the evidence in substantiation of
our statement.
Our representative reported to us orally on the re-
sult of the investigation as to the origin of the "Friends
of Science" leaflet, and upon this report the editorial
was written. Later we asked that this report be
placed in the form of a written memorandum, and still
later asked that it be sworn to:
188
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
January 6, 1921
As nearly as I can remember at this date the conversation
which took place on the 22nd of November in the office of E.
Leitz, Inc., 60 East 10th Street, New York, was along the follow-
ing lines: —
(To the Telephone Operator) "Your firm is distributing a
circular on 'Duties on Imported Industrial Instruments' — it is
salmon colored and I am interested in obtaining a few copies."
She in turn called a young man from the rear of the salesroom
and told him to attend to me. I repeated my request. He said
he knew what I meant and went upstairs to get me a copy.
He returned with one copy and when asked if I could get any
more for some other folks interested in this information, he said
it depended upon how many I needed, for they only had a
limited number left. I then asked if he could tell me where I
could get about fifty of them, and he replied he guessed that the
circular itself would tell me, and upon examining it he suggested
that possibly I could get a lot in Washington. I thanked him
and left.
About three o'clock that afternoon I telephoned, claiming
to be the Information Bureau of a Statistical Library. I tried
at first to be connected with the man who wrote the circular,
then with the advertising department, and after much delay
and conversation at the other end of the wire, I was again
switched on to the young man of the morning, who immediately
recognized my voice. I told him I needed more circulars, and
explained that they couldn't be obtained in Washington because
that was only the place to write after you had read the circular,
if you agreed with it. I then asked if they weren't written in
his own office and he admitted that they were. I asked if he
couldn't possibly spare me about twenty more copies and he
said "Yes, if I'd call for them."
I called next morning and was handed the copies. I inquired
then if he knew what company printed them, and he replied
negatively. I asked again "But you people wrote them?" and
he said yes.
(Signed) Anne M. Golden
Sworn to before me
this 28th day of January 1921
(Signed) G. H. Sykes; Notary Public
[Seal]
But after all it was felt that it would be more satis-
factory to get some direct information from the printer
himself. This was quickly and easily done, as is shown
in the following:
•SS:
State of New York 1 „
County of New York j
Louis R. Lord, being duly sworn, deposes and says; that he
resides at No. 599 Mott Avenue, in the Borough of the Bronx,
County of the Bronx, City and State of New York; that on the
morning of February 1, 1921, he telephoned to the office of E.
Leitz, Inc. (telephone number Stuyvesant 4242) and inquired
for the name of the concern which did the printing for E. Leitz,
Inc., which information was refused both by the telephone opera-
tor and by the man to whom the telephone operator had re-
ferred him. Deponent further says that the man to whom he
spoke on the telephone understood that he was a Professor at
Columbia College and suggested that he call upon him to apply
for the information in person. Deponent further says that
thereafter on the same day, he called at the office of E. Leitz,
Inc. at No. 60 East 10th Street, in the Borough of Manhattan,
City of New York, and was referred to a Mr. Treager, who
apparently was in charge of the office. He conferred with Mr.
Treager for some time and endeavored to secure from him the
name of the person, firm or corporation who did their printing,
but Mr. Treager refused to give him such information. De-
ponent further says that while in conversation with Mr. Treager,
he observed a bundle of printed matter bearing the name of
"Brieger Press, Inc." and assumed that that was the name of
the printing concern which did the work for E. Leitz, Inc.
He thereafter went to the office of Brieger Press, Inc. at No.
409 Pearl Street, in the Borough of Manhattan, City of New
York and interviewed a man who told him that he was Mr.
Brieger of that concern and that his firm, namely, Brieger Press,
Inc. did the printing for E. Leitz, Inc. of No. 6 East 10th
Street, in the Borough of Manhattan, City of New York and
had printed for Mr. Treager of E. Leitz, Inc. a circular bearing
the caption "Why should the Tariff Duty on scientific instru-
ments be increased" which said circular was signed "Friends of
Science, interested in its development." Deponent further
says that Mr. Brieger offered to give him a copy of the circular
hereinbefore referred to and Mr. Brieger thereupon took one
from his files and handed it to him. A copy of the circular so
handed to deponent by Mr. Brieger is hereto attached and made
aVpart hereof and for identification bears the date "Dec. 23,
1920," and endorsed by deponent to identify it as being the
circular which was handed to him by Mr. Brieger as hereinbefore
stated. Deponent further says that at the time Mr. Brieger
handed the aforesaid circular to him he stated that the date
"Dec. 23, 1920" endorsed thereon was the date upon which said
circular was printed and ready for delivery to Mr. Treager of
E. Leitz, Inc.
(Signed) Louis R. Lord
Sworn to before me
this 2nd day of February, 1921
(Signed) Loretto T. Conroy
[Seal] Notary Public
From the date marked on the circular furnished by
the printer there would seem to have been at least
two printings of the circular, for the leaflet is identical
in color, texture, water-mark, typography, and sub-
ject-matter with the original copy furnished us in
November.
A SPECIAL PROBLEM
A correspondent writes of a need which is so evident
that we reproduce his statements textually, in the hope
that the thoughts of chemists interested in develop-
ments in photography may be brought to bear upon
this interesting proposition.
The advent of gas light papers worked a revolution in the
photographic business and printing out papers have been rele-
gated to a secondary place, being used largely where certain quali-
ties are required which have not yet been developed in gas light
papers. There is, however, a field in industrial work which is
not suitably taken care of either by printing out papers or by gas
light papers.
There would be a considerable application for a paper which
had something approaching the speed of gas light paper and at
the same time would show a visible image without development.
Such a paper could be largely used for various recording devices
where it is desirable to examine the record during the progress
of its making, and which could be developed and fixed later for
a permanent record. It is needless to say that if such a paper
were developed with characteristics satisfactory for general
photographic work, it would be useful not only for the above
purposes, but would be more satisfactory, at least for general
amateur work, than the present gas light papers since the depth
of printing could be judged without development.
It may be said, therefore, that the inventor of such a paper
could undoubtedly reap a very material benefit from his in-
vention.
APPRECIATIONS
In the midst of the trials and tribulations of picking
a safe and at the same time progressive course in de-
veloping publicity for chemical matters, it helps a lot
to receive occasionally such hearty appreciation as the
following excerpts convey:
The News Service of the American Chemical Society is like-
wise a priceless possession to the chemical industries in general,
and while the process of education is slow, the leaven is working,
and its efforts will inevitably lead to a much wider understanding
of the functions of the chemists which is so necessary to our
welfare nowadays. The articles sent out by the organization
possess the merit of being authoritative, and at the same time
couched in terms which will interest the average newspaper
reader. One might almost say that his suspicions are first lulled
and his interest awakened, after which the educational hypo-
dermic is slipped in so expertly as to be practically painless. —
American Dyestuff Reporter.
From what I have been able to observe, the American Chemi-
cal Society has probably done more useful work in establishing
respect for the chemist as a'business adviser and industrial builder
than any other organization in America. — Waldemar Kaempf-
fert. Editor, Popular Science Monthly.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
189
THE CHEMICAL INDUSTRY AND TRADE OF ENGLAND
By O. P. Hopkins
1824 Belmont Road, Washington, D. C.
England's predicament when the outbreak of hos-
tilities cut off the German supply of fine chemicals re-
sembled that of practically all other countries not
associated with Germany in the war, and her efforts to
free herself from fvtture dependence on that source of
supply differ in no important respect from those put
forth by other nations. What the ultimate result of
these efforts will be no one can say, but the recent very
favorable action of the government in placing the im-
ports of dyes under a license control for 10 yrs. is
looked upon in England with intense satisfaction by
chemical manufacturers, and optimism as to the future
has replaced the pessimism that has been so notice-
able since the armistice was signed.
England is an industrial nation, the birthplace of the
modern factory system. Her prosperity is the result
of her ability to manufacture in excess of her own
needs and to sell the surplus in foreign markets in
competition with able rivals. In the chemical in-
dustry this has held good in the past for only one
branch — heavy chemicals. There are no recent statis-
tics to show the extent to which the various com-
modities included under this heading are produced,
but as a basis for arriving at some idea of the situation
at the time the war began, the following figures from
the 1907 census will be useful. The first table shows
the gross value of production for the principal sub-
divisions of the chemical industry.
Production in 1907
Trades Value
Chemicals, drugs, and perfumery $116,917, 663
Oil-seed crushing 63,074,707
Oil and tallow, excluding seed crushing 32, 133,500
Fertilizer, glue, sheep-dip, and disinfectants 28,522,557
Soap and candles 59,458,897
Paints, colors, and varnishes 41, 666 , 973
Explosives 19,208,076
Matches 4, 160,858
The table that follows shows the gross value of the
products included under the first group in the fore-
going table:
Products Value
$ 6,837,433
1 ,051,164
2.564,646
16,964,619
1,815,205
12,526,371
569,381
1,567,013
8,735,368
1,844,404
7,513,876
1,469.683
Acids, except carbolic
Aluminous sulfates, including alum
Bleaching materials
Coal-tar products, except dyes
Coal-tar dyes
Drugs
Essential oils
Extracts for tanners, printers, and dyers.
Fine and pharmaceutical chemicals
Finishing materials for textile trades.. . . .
Patent medicines
Perfumed spirits.
Perfumery and toilet preparations, except spirits and soap. 2,978,298
Photographic plates, paper, and films 4,423,649
Prepared food for infants and invalids 3,046,429
Soda compounds 16,497,435
It is impossible to estimate accurately the effect of
the war on most of the chemical industries, but a cen-
sus of manufactures is now being taken, and as our
own census will shortly be completed, a comparative
study will soon be possible.
HEAVY CHEMICALS
Britain's pre-war position in the heavy chemical
trade was preeminent. Her leadership in that line
was almost as evident as that of Germany in fine
chemicals. There are no recent official statistics to
show what the actual production was or is in the
various lines, but the export returns show that the
largest business abroad was done in sodas, bleaching
powder, cyanides, aluminium sulfate, glycerol, sulfate
of ammonia, creosote and other heavy coal-tar prod-
ucts, copper sulfate and other agricultural poisons,
and superphosphates.
The latest figures (1919) show that the shipments
of a number of these commodities are much below the
pre-war averages, and it would be a difficult matter
to present all the factors that have contributed to this
result for each article. Some markets have been
affected by the growth of domestic production, in
some cases there is an inability to buy, while in still
others the English market itself is strong enough to
absorb the output for the time being. The exports
of soda bicarbonate, ash, chromate, and bichromate
were larger in 1919 than in 1913, whereas the sales of
caustic soda and salt cake decreased (see the table of
exports at end of article). The foreign sales of bleach-
ing powder and of copper sulfate were cut in two,
while the cyanides and aluminium sulfate held up
fairly well.
British manufacturers are naturally much concerned
for the future of the trade in these important staples,
but there is no way of forecasting the final outcome.
The consensus of opinion in England seems to be that
as soon as the present general business depression passes
there will be a recovery in most of the heavy chem-
icals and that England will regain much or most of
the trade that has been lost.
SULFURIC ACID
In the absence of recent statistics of production for
the various chemical industries, some interest attaches
to figures on the sulfuric acid industry contained in a
report made during the war by a committee appointed
"to consider and report on the position of the sulfuric
acid and fertilizer trades as affected by the new acid
plants which have been erected during the war by the
Ministry of Munitions for the government." The
production of sulfuric acid before the war was about
1,000,000 tons, expressed in terms of 100 per cent
acid (equal to 1,500,000 tons chamber acid). The
principal consuming industries were:
Industries 100 Per cent Acid
Tons
Superphosphates 300,000
Sulfate of ammonia 280,000
Bleaching powder, hydrochloric acid, alkali, and alum 186,000
Iron pickling 70,000
Explosives 30,000
Copper sulfate 25,000
Dyeing and bleaching 25 , 000
Oil refining 20,000
Grease recovery, textile trade 20,000
The committee estimated that, owing to the great
expansion of plant capacity to meet war needs, the
post-war production would be about 653,000 tons of
190
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
100 per cent acid in excess of the pre-war output, not
including the additional production that would result
from the roasting and smelting of Australian zinc con-
centrates, which was formerly done on the Continent.
There was naturally a desire to save as much of the
newly created plant as possible, but seemingly the only
definite recommendation of the committee was that
an effort be made to increase the consumption of
superphosphate in agriculture. The acid as such is
not much handled in foreign trade, and the sale of
superphosphate to many of the pre-war consumers is
more likely to decrease than expand. The committee
called attention to the possibility of increased sales of
superphosphate in Australia, South Africa, India,
Russia, and Rumania.
Before the war the principal raw materials used in
the manufacture of the acid were Spanish and Nor-
wegian pyrites and spent oxide. During the war con-
siderable sulfur was also used. Should the effort to
divert the handling of colonial zinc concentrates to
England be successful, the demand for pyrites will
probably be lessened.
FERTILIZERS
England is not nearly self-sufficient in the matter of
artificial fertilizers; in fact, except for large quantities
of sulfate of ammonia and some basic slag, there is no
important domestic supply. There was the usual
search for domestic sources of potash during the war,
and considerable effort is still directed at the produc-
tion of air nitrates, but assertions that results in either
direction are more than promising are not well founded.
The manufacture of superphosphates from the imported
raw material is an industry of some size.
For potash, dependence has in the past been placed
on Germany, the soda nitrate came from Chile, and
the phosphates from Africa and the United States.
Since the war the imports have remained much below
those of pre-war days, although phosphates have been
purchased on a large scale from Africa rather than from
the United States.
In the export trade England has always been a
heavy shipper of sulfate of ammonia, which is manu-
factured extensively in connection with the coke in-
dustry and the distillation of shale. The average pre-
war production may be placed at about 360,000 tons,
of which 300,000 tons were exported. The industry
was unsettled during the war by the demand for am-
monia in the manufacture of munitions, and since the
war a tendency to use the fertilizer at home as a sub-
stitute for Chile nitrate, together with unsettled mar-
ket conditions abroad, have almost wiped out the ex-
port trade (judging from 1919 statistics). The exports
of superphosphates are also much below the pre-war
figures, a fact attributed in part to the growing manu-
facture of this fertilizer in a number of countries that
formerly depended upon imports.
VEGETABLE OILS
Although dependent upon outside sources for oil-
bearing materials, England has come to be one of the
principal producers of vegetable oils, the industry being
centered at Hull, now said to lead all other European
cities in this field. The bulk of oil produced is con-
sumed at home, and a favorable factor in maintaining
the industry is the domestic demand for the cake as
cattle feed, created by a long-sustained campaign of
education among the cattle growers. Much of the oil-
bearing material formerly going to Hamburg has been
diverted to Hull.
The industry was under rigid government control
during the war and was not freed from restrictions
until March 1919, after which there was a rapid re-
covery, as the following figures indicate:
1918 1919
Imports:
Seeds, nuts, kernels $155,000,000 $269,000,000
Oils 56,000,000 105,000,000
Reexports:
Seeds, nuts, kernels 33,000 3,500.000
Oils 948,000 12,000,000
Exports:
Oils 8,000,000 49.000,000
Oil cake is also imported in considerable quantity,
the value of such imports for 1919 reaching $28,000,000,
of which $20,000,000 went for cottonseed cake and
$8,000,000 for linseed cake. During the last year of
the war these imports amounted to only a million
dollars.
A soap-manufacturing industry of great proportions
has grown up in connection with the oil business, and
English soap finds its way into almost all countries.
Nevertheless, American soap, especially a hard soap
for wool scouring, together with some toilet soap, finds
a market in England.
The paint and varnish industry, also related to the
oil business, is another that finds it possible to market
a large surplus abroad. Linseed oil was exported in
1919 to the extent of $32,000,000, although this trade
was practically nonexistent in 1918.
FINE CHEMICALS
Second to none in the manufacture of heavy chem-
icals before the war, England was dependent upon
Germany for fine chemicals, as were all other coun-
tries, and for similar reasons. Although the names of
Englishmen are identified with the discovery of many of
the chemicals so commonly used to-day, the commercial
development was usually left to the Germans, a fact
that was bitterly realized after hostilities began. The
efforts to recover the lost ground parallel in a general
way those made in other countries, and it is impossible
to estimate just what has been accomplished and what
future developments will be.
England was not handicapped, as was France, by
the actual loss of chemical plants at the outbreak of
the war, but, on the other hand, she was obliged to
make a start in the face of mobilization and the other
disturbing factors of a state of war, in which respect
both England and France were at a disadvantage as
compared with the United States. Definite informa-
tion as to actual results is lacking, but it seems safe
to assume that much has been accomplished in the
manufacture of dyes, medicinals, photographic chem-
icals, research chemicals, analytical reagents, and other
fine chemicals, and that, given suitable backing by
the government, England will eventually become self-
sufficient and even a factor in the foreign trade in such
specialties.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
191
The support asked from the government has not
been readily granted, but the Dyestuffs Act is now an
accomplished fact and there is some reason to suppose
that it will serve, as its opponents charged, as the
entering wedge in opening the way to protection in some
form for other "key" industries. In particular, the
chemical manufacturers seem to be on solid ground in
urging that if the dye industry is to be saved, it will
be necessary to support also the closely allied branches
engaged in the manufacture of by-products which will
insure profits from the dyes themselves. The indus-
try is hopeful that the anti-dumping bill promised in
the near future will provide for the control desired for
certain other fine chemicals. It is an interesting fact
that English manufacturers are not asking for pro-
tection in the shape of duties, but are united in their
demand for license control.
THE DYESTUFF INDUSTRY
Before the war England imported from Germany
about 80 per cent of the dyes she used, and when this
supply was cut off her experiences in establishing a
domestic industry were similar to those of many other
countries not allied with Germany. The government
considered many plans for supporting the industry,
and in 1915 supplied capital for a company known as
British Dyes, Ltd., which was expanded upon a small
company already in operation. Many users of dyes
also supported this company. Levinstein, Ltd., a
purely private concern, also began to expand about
this time, and these two companies continued a rapid,
and, under the circumstances, a rather satisfactory,
development until 1919, when a holding company
was organized for their amalgamation. This is a
£10,000,000 organization, known as the British Dye-
stuffs Corporation, Ltd., in which the government is in-
terested to the extent of £1,700,000, and it is upon this
company that the country is placing its chief reliance
for an independent industry. There are in addition
a half dozen or so small companies with a limited out-
put of specialties. Particular emphasis has at all times
been placed upon the necessity for research facilities.
It is not possible to give an estimate of dye produc-
tion, but the following figures from a dyestuff census
patterned after our own Norton census show the extent
to which dyes were imported in 1913:
Colors Weight, Lbs.
Direct cotton colors 6,976, 435
Union colors .* 1 1 5 . 794
Acid wool colors 5,223,101
Chrome and mordant colors 6,477,065
Alizarin 2,467,489
Basic colors 1 ,599,074
Sulfide colors 3,923,483
Synthetic indigo 3,830,483
Vat colors 588,445
Oil, spirit, and wax colors 42,253
Lake colors 1,082,079
Intermediate products 7 ,467 ,795
Unclassified 277,872
Since the armistice there have been considerable
imports of dyes from Germany, reparation and other,
and rather heavy purchases have been made in Switzer-
land and the United States. A rough estimate based
upon official British figures for the first nine months
of the year places the total imports of finished dyes
for the whole calendar year 1920 at 17,000,000 lbs.,
valued at $24,000,000. Of this value, Switzerland sup-
plied about 35 per cent, Germany 27 per cent, the
Netherlands 20 per cent, the United States 10 per
cent, and Belgium 6 per cent. As it is reasonable to
suppose, however, that the dyes credited to the Nether-
lands and Belgium had their origin in Germany, the
German share of the total may safely be put at more
than 50 per cent. The importation of intermediates
can be estimated at approximately 4,500,000 lbs.,
valued at somewhat less than $3,000,000, the
United States supplying almost the entire amount.
During the war, and for some time after, the imports
of dyes were controlled under a loose construction of
an act of 1876, and it was with something like dismay
that the supporters of the industry received the de-
cision of Justice Sankey in December 1919, that this
act did not apply and that the control of imports under
it was illegal. Following this decision, German agents
began to take orders at prices the English manufac-
turer could not meet. Although the actual importa-
tions of dyes based on these orders were not extraor-
dinarily heavy, it soon became evident that German
manufacturers could undermine the English industry
unless the government took steps to protect it. The
consequent agitation finally led to the passage of the
Dyestuffs Import Regulation Act of 1920 which pro-
vided for licensing imports without the imposition of a
duty. Exports of dyes in 1920 amounted to 34,000,000
lbs., valued at $17,000.000 — an increase over 1913 of
45 per cent in quantity and 1000 per cent in value.
The increase was entirely in coal-tar dyes, which
represented two-thirds of the quantity and nine-tenths
of the value of the dyes exported last year.
THE DYESTUFFS ACT
Thanks to this act the British dyestuff industry is
now protected by a license control of imports that
will continue for 10 yrs.
The passage of such an act in England has a sig-
nificance that should be appreciated by all Americans
who are in any way concerned with or responsible for
the future of the industry in this country. England
is by tradition a free-trade country and the bill aroused
much more opposition on that basis than could be
expected in similar circumstances in this country.
England is also a leading factor in the textile trade of
the world and her textile manufacturers were deeply
concerned at the possibility of being denied access to
any important source of colors. That there are grounds
for such apprehension may as well be conceded, for the
British textile industry has been built up on the basis
of an infinite variety of patterns. It specializes on
small lots made up to suit the tastes of a great variety
of consumers, and requires a corresponding variety of
colors. This is in contrast with the usual American
plan of producing a smaller number of patterns on a
quantity basis, and would seem to give the English
dye user a stronger argument against dyestuff control
by licensing.
In spite of the strength of the opposition, however,
the government decided that a synthetic dyestuff in-
dustry is an absolute necessity in any modern scheme
of national defense, and accordingly, in keeping with
promises made some two years earlier, introduced the
192
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
bill that was subsequently passed by both branches
of Parliament by decisive majorities. The argument
in favor of the bill as a military measure carried every-
thing before it.
It is the acknowledged intention of the supporters
of the industry to develop it to the point where it
will not only supply the needs of the Empire but even-
tually become a factor in foreign markets. This is of
special interest to France, which at present has a license
control over German products only, and to the United
States, where sole reliance at this writing is placed upon
a war-time power that will become ineffective when
peace is formally declared. Not that there is an im-
mediate prospect of extensive imports of English-made
dyes (it being generally admitted that greater progress
has been made to date in this country), but the fact
should be borne in mind that the English manufac-
turer has a splendid market upon which to build at
home and in the colonies. Practically all of the col-
onies have already taken steps to exclude non-British
dyes, although in some cases, notably India, the ex-
clusion acts have been suspended, presumably until
English manufacturers can actually supply the dyes
needed. Eventually, with such support from the gov-
ernment and such an assured market, the English
dye manufacturer must become a formidable opponent
in the struggle that is now pending.
THE IMPORT TRADE
The following table, based upon official British re-
turns, will make possible a study of the effect of the
war on the importation of chemicals (the latest de-
tailed statistics available are those for 1919). A strik-
ing feature is the increased reliance upon the United
States for many products. For the large class of
chemicals designated "not elsewhere specified," the
imports from America increased from a negligible share
of the total of $7,000,000 in 1913 to nearly half of the
$15,000,000 worth imported in 1919. (Trade with
"Russia" in 1919 is probably trade with Finland.
Some of the trade with the Netherlands in 1919 should
be considered as trade with Germany.)
Imports of Chemicals and Allied Products
Chemicals:
Acetate of calcium. .
United States
Acetone
Austria-Hungary .
Canada
United States
Acids:
Acetic (other than for table
use)
Belgium
Netherlands
Canada
United States
Ste
Belgium
Argentina
Australia
United States...
Sulfuric
Belgium
United States...
Tartaric
Germany
Italy
Ammonium chloride.
Belgium
Germany
United States
Bleaching materials:
Bleaching powder.
United States. . .
Other
1913
1916
1919
Pounds
Pounds
Pounds
11 .153.184
7.631,008
6,789,440
6,980.8+8
511,616
4,422.768
3.045,392
6,225,520
2,235.856
5,197,584
5.748,288
8.354,080
1,523.200
876,960
504,336
2,596.608
1,783,488
5,243,952
5.756,576
8.414,336
6,594,672
8,386,448
2.066,960
3,583,888
188,832
560
86.016
2,921,072
2,118.144
6.069.056
5,430,544
9,249.968
6,399,120
6.926,640
3.921,232
1,681,456
1,842,512
2,120.384
1.123.696
1,714.832
3,125,920
1,276,912
15.854,496
640.864
112
15,489,264
112
5,144,832
3,794.816
1,908,816
2,830.688
896
10,976
1,980,384
3,514,448
1,712,256
837,648
87.584
5,712
108.976
666,848
8,064
87.360
2.975,168
565,600
521,584
48,160
936,768
8,960
231,056
Imports op Chemicals and Allied Products (Continued)
1913 1916 1919
Pounds Pounds Pounds
Chemicals (Continued):
Calcium:
Borate 40,566,064
Chile 37,233,392
United States 2,658,768
Carbide 57.545,264
Italy 16,507.456
Norway 29,552,992
Sweden 10,781,456
Canada
Chemicals, n. e. s $7,241 ,517
Belgium 485,205
Chile 962,165
France 677.675
Germany 2,989,840
Italy 454,444
Japan 446,443
Canada 144,589
United States 221.573
Pounds
Chloral hydrate 23,501
Germany 19.994
Switzerland 2 . 295
United States
Chloroform 1 , 366
United States 712
Ounces
Cocaine and cocaine salts. . . 55.346
Peru 19,277
United States 300
Coal-tar products: Pounds
Dyes:
Alizarin and anthracene 6,811,056
Germany 6,755,280
Aniline and naphthalene 3 1 , 699 . 024
Germany 28,966,448
Switzerland 2,479.792
United States
Indigo, synthetic 2 , 675 , 568
Germany 2,675,456
Switzerland
Other dyes, n. e. s 17,360
Germany 16, 484
Other products, n. e. s 13,429,808
France 1,166,256
Germany 6,087,872
United States 440.832
British Possessions 3,740,016
Saccharin and mixtures Ounces
containing saccharin. . 1,242,213
France
Germany 1,126,376
Netherlands 79,415
Switzerland 35,680
United States 113
Ether: Pounds
Acetic 3,769
Gallons
Butyric 265
Sulfuric 616
Ethyl halides: Pounds
Bromide 59
Gallons
Chloride 114
France 64
Iodide 4
Glycerol: Pounds
Crude 9,845.696
Belgium 1,474,704
France 2,860,032
Germany 955,472
Australia 836,976
United States
Distilled 2,472,512
Germany 794,528
Netherlands 1,166,032
United States
Lactarine ?409 ,925
Magnesite powder 120.918
Gallons
Methanol 741 ,848
Germany 112.230
Canada 195,209
United States 357.338
Ounces
Morphine and its salts 52
Potassium: Pounds
Nitrate 26,642,560
Belgium 2.852,528
Germany 16.797,200
British India 6,720,672
Salts, n. e. s $3,067,034
France 277.950
Germany 2.148.248
Russia 284.685
United States 14.337
Ounces
Quinine and its salts 2. 422, 944
Germany 908.986
Netherlands 1,009.970
Java 390,400
United' States 110,000
Sodium: Pounds
Bicarbonate 83,888
38,192,352
27,664,112
22,285,872
18.914,336
12,439,840
5,433,008
54,855.920
55.394,528
1,830,192
38,571,904
32.654,048
5,079.648
15,008
9,145,248
22,725.136
1(36,498,862
$14,907,734
40,625
25,950,728
3,155,482
687,724
538,342
5.158
97 , 1 25
1 ,712.395
1.454,388
374.862
191,540
310.916
314,444
3,802,313
6.565.239
Pounds
Pounds
60,550
17.683
7.932
224
52,614
17,140
1.048
1.447
1,048
1.408
Ounces
Ounces
55,914
23,388
28.890
22.080
11.314
Pounds
Pounds
2,352
351.232
6.852,720
6,559,392
2,576
11,872
5.445,440
5,200,832
150,864
515,312
517,216
276,192
456,176
276,192
12,432
58,128
3,813.488
4,380,320
25,312
57,680
88,480
4,480
2,203,600
755,328
1,151,360
2,614.864
Ounces
Ounces
356,354
1,143,872
9,561
72,327
30,632
263,695
7.003
1,071.019
Pounds
Pounds
166
100
Gallons
Gallons
286
844
2
19
Pounds
Pounds
Gallons
Gallons
143
10
119
5
Pounds
Pounds
3.628,016
4,565,008
24,640
3,104.080
1,229,312
171,920
157,584
2,440,144
2,572,640
87,808
2.324,224
36.512
117.376
22.400
$794,339
Si. 694, 953
370,010
1 ,047.986
Gallons
Gallons
752,951
689.360
266,892
429.124
486.059
260,236
Ounces
Ounces
48,158
4,384
Pounds
Pounds
49,197,456
15,646,736
12,768
49,184,688
15,646,736
$3,090,373
$3,085,171
->06 , 233
266,163
1,129
608.809
1,276,123
515.971
789,444
328,099
Ounces
Ounces
3.727,022
5,764.943
3.561,683
236,040
5,496,705
26,104
Pounds
7.504
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
193
RTS
Chemicals (Concluded) :
Sodium (Concluded) :
Carbonate:
Crystals
Belgium
Germany
Soda ash
Belgium
Caustic soda
Germany
United States
Tetraborate, or borax.
France
Germany
United States
Salts, n. e. s
France.
tjermany
Norway
United States
Tartar, cream of
France
Germany
Italy
United States
Spain
Drugs and Medicines:
Drugs, n. e. s., containing
no dutiable ingredient
(including medicinal
preparations)
France
Germany
Norway
British India
Japan ». . .
United States
Dyeing and Tanning Mate-
rials:
Dyeing materials, n. e. s. . . .
France
Italy
Spain
British India
United States
Extracts for dyeing
France
British West Indies
United States
Extracts for tanning
Argentina
Austria-Hungary
France
Germany
Italy
United States
Indigo, natural. . . .
British India. . . .
Java
Salvador
United States...
Tanning materials,
British India. . . .
Germany
Cordite and other smokeless
propellants
Canada
United States
Dynamite and other high ex-
plosives
Germany
Gunpowder
Belgium
Germany
Fertilizers:
Nitrate of soda.
Chile
Phosphate rock.
Algeria
Tun
United States
Slag, basic
Belgium
Other (except bones
guano)
Germany
Netherlands
Norway
Argentina
ILS, Vecetable:
Fixed:
Ul
efined.
Germany
British India. .
Ceylon
United States.
Refined
France
Germany
Netherlands. . .
United States.
Allied Products (Conli
191? 1916
Pounds Pounds
3,672.368
3,418,912
239,008
418,768
193,760
805 , 504
94.080
397,376
1 .897,280
1,641.248
201,936
336
15,157.184
1.982,064
1.886,976
9,816.240
550,368
361,760
8,926,400
3,489,248
4,025.728
564.480
mid)
1919
Pounds
42,000
228 [368
5.139,680
2.030.112
1,126,608
897,904
10,951 .808
10.080
1,261.680
66,304
1.528,464
6.974.240
4,113,984
2,339,456
3.804,864
4.510.464
601,216
743,456
20,832
441,952
2.014,208
2.675,344
1,348,704
2,464
$6,340,368
444,633
1,617,936
436,243
221 ,606
412,139
1.356,152
Pounds
15,243,088
3,247,216
4.034,128
4,822.272
1,453.312
1,104,096
43,008
306,992
351,008
60,928
750,176
514,041,025 $17,515,307
1,271,032 1,170,987
8,239 24.770
618,561
2,407,054
1 , 040 , 604
5,440,470
$625,039
253.515
53,789
256,086
$4,489,833
813,659
283,522
2,092,039
125,298
428,481
223,995
Pounds
467,488
408,352
6,608
35,728
429.420
1,774,764
942,729
4,887,796
Pounds
23,111,872
3,894,912
1,721,328
7,390,768
4,492.768
169.456
$3,265,709
453,465
1,923.752
794,456
£16, 106,460
10.115.750
Pounds
23,202,704
5,921 ,664
3,373,776
4,237,184
3,483,760
81,424
$3,341,164
282,909
2,437,766
543,476
$14,021 ,170
6,340,719
1,739,749 1,657,160
3,823,380
Pounds
3,419,024
3.279.472
104.048
9,856
Pounds
414,512
319.984
3,688,720
893 , 200
557,312
49 . 840
6,384
3,429,440
615,776
21,679,168
9,826.320
11 .850,384
1
,541,680
30.128
1
,511 .552
535,696
16,688
392,448
141,120
Tons
Tons
Tons
140,926
20,896
24,485
136,340
20,807
24.452
539.016
333,421
355,758
44,996
81,876
48.496
189,555
174.640
243.883
177,330
61,828
47,807
51,133
1,697
47,077
172,877
16.605
25,627
143,506
242
5,394
11,600
8,883
9.726
250
6,838
2,855
296
Pounds
Pounds
Pounds
3
1
,133,760
.057,280
761,600
12
.770,240
1 1 , 200
792,960
743,680
11
,784.640
566,720
69
,753,712
47
,312,720
117
,862,192
44
,465,792
?
,249,968
9
,973.712
37
,066,848
15
,766,352
28
,680,736
43
9
,666.672
.018,128
61
,235,104
17
,353.616
52
,987,088
71
.790,272
7
,804,832
379.680
23
,587,648
1
,994.384
19
29
.792,416
,856,960
Imports of Chemical
Oils, Vegetable (Concluded):
Fixed (Concluded):
Cottonseed:
Unrefined
China
United States
Refined
Netherlands
United States
and Allied Products (Continued)
1913 1916 1919
Pounds Pounds Pounds
inseed:
Pure
Belgium
Netherlands. . ,
United States.
Not pure
Unrefined.
Italy
Spain...
Refined. . .
France . .
Italy
Spain . . .
Palm:
Unrefined
Nigeria
Refined1
Germany
Netherlands
Palm kernel, unrefined.
Nigeria
United States
Rapeseed
2,396,800
1,464,960
907 , 200
37,152,640
1,220.800
34,733,440
26.579,840
5,333,440
6,820.800
11,928,000
49.280
Gallons
871.749
119.480
221 .416
1,864,187
420,146
620.993
467,332
Pounds
174,966,736
148,507,968
6,521,760
6,254,976
Belg
Netherlands. .
Japan
Soy-bean2
China
Japan
United States.
Other seed oils. .
Belgium
Germany
Netherlands. .
China
Japan
United States.
Volatile:
Natural
17,021,760
4,220.160
2,022.720
6.240,640
Germany
Italy
British India. .
Ceylon
Japan
Java
United States.
Artificial
France
Germany
Switzerland. . .
United States.
Paints. Pigments, Varnishes:
Barytes
Belgium
Netherlands. . .
United States.
Spain
Lead:
Red
Germany. . .
Netherlands
United State
White
Belgium
Netherlands. . .
United States.
Nickel oxide
Canada
United States
45 , 65 1 , 200
9,728.320
7,723.520
10.942,400
1,225.280
7,663,040
468,160
2.323.348
241,225
193,043
303.063
177,260
140,710
761,459
168.634
9,809
102,612
260,638
38,387
191,610
20.918
4.057
122,376,640
24,455,200
90,222,608
4,820,368
231.056
6,832,672
6.383,440
406,000
35,988,176
9,305,296
15,646.512
1 ,328.880
9.425,024
2,012,080
Varnishes, nonalcoholi<
France
Germany
United States
Zinc oxide
Belgium
France
Germany
Netherlands. . .
United States .
All other
Belgium
France
Germany
Netherlands. . .
Spain
Canada
United States.
2,012,080
Gallons
478,500
15,474
33,222
394,175
Pounds
41.316,576
6,425,552
1,680,896
15,308,944
.4,712,736
13.050,800
104,059,312
6.997,984
8,966,384
42.551,488
12.357.744
10.279.808
282,128
12,275,200
1.594.880 6,852,160
741,440 2,410,240
224.000 2.912.000
22,619.520 57,211.840
8,926.400
22,113,280 46,002.880
13,440 2,105.600
528,640
1,126,720
6,720 107,520
6,720 80,640
Gallons Gallons
1,625,531 673,724
48,698 86,509
1,560,498 562,617
1,566,850 1,218,996
242,589 293,104
290,079 68,058
1,027,829 833,334
Pounds Pounds
139,278,272 208,499.200
116,184,432 175,162,176
9,565,472
'..'.'.'. 8, 847^440
3,468.080
1.977.360
1,337,280
17,895,360 11,204.080
'.'.'.'.'. 4 . 309 \ 760
14.414,400 6,867.840
66,489,920
7,898.240
40.962,880
14,056,000
109,695,040 16.647,680
421,120
6,1 53^ 280 952 \ 000
14,327.040 4.032,000
73,512,320 1.314,830
1,267,840 1.749,440
461,335
267,722
102,854
307,559
233,045
249,140
344,865
221,243
14,751
350
20.845
155,637
20,686,848
607,518
228,715
194.316
299,108
506,859
128,238
309,874
52,606
15,359
45,698,576
2,214,576
1,784,720
2,003,344
18,780,832
19,839,232
1,410.304
3,248
8,736
971,040
17,943.408
34,720
17.306.912
2,457.280
264,992
Gallons
234,479
11,220
219.434
Pounds
30,901 ,024
2,654,512
1,861 .888
7,840
10.485.664
15.617,952
63.688.464
58,240
7,684,992
84,224
24,624.432
10,140.704
635.152
16,296,112
88,368
82,320
11,754,176
1,626,016
565.600
1,060,416
Gallons
141,490
719
140^371
Pounds
14,862,960
1,905,120
93,520
49.616
2,981.776
9.360,176
52,343,984
182,560
3.357,312
955,360
8,085.616
7,560.336
759.920
28,074,704
194
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
Imports op Chemicals
Perfumery and Cosmetics:
Perfumed spirits:
In casks
France
In bottles
France
Germany
United States
Allied Products {Continued)
1913 1916 1919
Gallons Gallons Gallons
Perfumery, and articles used
in the manufacture
thereof (except perfumed
spirits and essential oils)
France
Germany
Netherlands
Switzerland
United States
Soap:
Toilet
France
Germany
United States
Transparent (alcoholic) . . .
Other Products:
Blacking and polishes con-
taining spirits or sweet-
ening matter
Germany
United States
Blacking, solid, containing
sugar or other sweeten-
ing matter
Candles
Germany
Netherlands
British Possessions
Dextrin
United States
Germany
Netherlands
Glucose
United States
Glue, size, and gelatin not
containing added sugar.
Austria-Hungary
Belgium
France
Germany
Italy
Netherlands
United States
Ink, printers'
3,320
3.071
44,522
11,266
28,939
2.750
1,580,259
588,503
136,875
4,082
4,153
777,512
1,281
1,265
13,037
11,060
1,785
1,486
10,392
9,625
2,563,681
619,598
4,535
27,648
49,037
1.797,071
2,788
23,994
1,160,614
2,237,536 1,440,320 1,983,744
418,992 205,408 43,008
366,912 336
1,330,112 1,117,984 1,270,640
24.937 3,220
4,509.792
2,653,504
1,366,512
33,264
906,640
338,240
72,800
400,736
11,643,744
4,065,712
2,728,880
164,048,640
161,213,920
28,925,232
2,307.312
7,405,664
7,077,280
8,402,240
Isinglass
Japan
British India
Straits Settlements..
Brazil
United States
Paper and pulp:
Printing or writing:
On reels
Germany
Norway
Russia
Sweden
Canada
Newfoundland. .
United States . . .
Not on reels
Belgium
Germany
Norway
Sweden
United States
Packing or wrapping.
Belgium
Germany
Norway
Ru
Sweden
Canada
United States
Wood pulp :
Chemical
Germany
Norway
Russia
Sweden
United States
Canada
Mechanical
Norway
Sweden
Canada
Newfoundland
Rosin
Belgium
France
Spain
United States
Soap, not containing sweet-
ening matter:
Household and laundry, in
bars or tablets
France
Italy
United States
96,333,776
4,683,616
112,245,616
10.854,816
33,795,328
39,038,496
15,860,880
5,041.680
458,113,152
31,447,584
99,958.096
118,608.560
29.433,488
153,048,784
1,243.984
Tons
411.803
40,972
61,848
41,628
254,097
1,098
24
565,954
312.051
128,256
69,090
50.659
Pounds
196.903.504
6,190,016
21,665,280
10,210.256
148,066.912
7.252.336
3,329,760
15,792
1,5S7,136
57,680
23,296
961,744
14,724,752
10,358.880
7.142,016
67,648
3,687,712
6,944
1,032,976
18,591,216
15,776,320
3,624,656
139,845,440
139,762,672
1,149,008
156,518.656
154,107,072
13,931,680 6,786,864
$112,635
Pounds
1,134,000
160,160
366,688
216,496
160,944
12,544
294,433,328
19,354,272
98,571.424
8,884,512
46,727,744
4,704,112
1,456
3,070,816
1.903.552
2,768,416
$379,626
Pounds
1.108,800
427,392
193,648
176,176
176,400
25,984
112
698,656
254,464
1,997,408
$107,842
Pounds
731,584
98,336
241,472
25.760
106,960
49,952
181,422,416 252,448,448
29,469,664
24,443,664
6,481,216
101,548,384
10,268,944
56,284,704
1,557,584
21,616
19.090.176
10,554,544
14,128,016
345,474,528
8,432,368
281.568
116.218,592
62,384
169,210,048
9,606,688
23,881,536
Tons
198,765
31,203,984
36,468,320
33,096,448
34,135,024
105,723.632
7,684,320
31 ,717,056
483,952
37.184
16,709,952
4,432,960
3,684,016
195,508,096
2,634,800
189,168
73,167,808
11,002,320
84.454,944
11,682,496
6,026,048
Tons
409,698
116,989
44
23.148
17,552
25,544
459,317
339,471
77.717
27.457
14.672
Pounds
224.203,280
32. 659! 648
15,775.648
169,668,912
75,797
6,763
278,152
5,299
36,297
528,522
305,132
99,923
98,576
16,890
Pounds
199,407,600
47, 437^376
13.606,208
124.898,032
18,165,056 9,313,472 11.820,928
3,314,976 837,984 111,664
2,082,640 129,472 115.696
12,387,264 7.468.608 6,555,248
Imports op Chemicals and Allied Products (Concluded)
1913 1916 1919
Other Products (Concluded): Pounds Pounds Pounds
Soap (Concluded):
Polishing and scouring.. . . 540,400
United States 297.360
Soap powder 6,249,488
Germany 59,920
United States 6,013.280
Soft soap 489 , 1 04
United States 286 , 272
All other, including cotton-
seed-oil soap 16,234,400
Italy 433,664
United States 15.672.496
Sugar: Tons
Refined 922,545
Austria-Hungary 198,064
Belgium 49,764
Germany 465,453
Java 178,567
Mauritius 273
Canada 6
United States 385
Unrefined 1 , 046 , 7 15
Austria-Hungary 160,858
Germany 472,026
Java 99
Mauritius 20,075
British West Indies 29.364
Cuba 224,227
Peru 27,487
Tar (other than coal tar) . . . 14,333
Russia 12,106
Sweden 1,133
United States 829
Pounds
Turpentine oil 62,756.960
France 3.769,472
Russia 3.656,576
United States 53,356,800
THE EXPORT TRADE
The next table affords a comparison of the export
trade in chemicals before and after the war. It should
be borne in mind that the pronounced boom in the
general export trade which was so evident during the
latter part of 1919 and the first few months of 1920
probably extended to the chemical trade, and that the
depression which set in toward the close of 1920 like-
wise affected that trade. The figures for 1919 are the
latest showing the countries of destination.
243.600
904,736
238,000
903,728
2
.811,200
598,416
2
,700,992
506,240
84,224
92,400
62.160
74,480
11
,588.080
69,440
16,397.360
11
462,976
16,383,920
Tons
Tons
410.390
462,134
990
5,532
65
253
94,615
117,060
27,959
23.452
14,788
52,651
267,048
222,082
1
122,969
1,142.323
281,676
172,838
80,629
153,682
59.740
92,490
554.453
587,252
55.613
77,577
5,782
9,338
3,001
2.397
206
2,324
2,504
3,143
Pounds
Pounds
48
,247,360
51,053,968
585,648
4,109.056
68.656
41
280,400
42.686.784
Chemicals:
Acids:
Hydrochloric. . .
Sulfuric
British India.
British Pos
Exports of Chemicals and Allied
1913
Me
Persia ....
Norway. .
Tartaric ....
Germany.
Japan
Australia.
477,792
19,096,336
8,153,824
3,052,672
1.957.872
4,998,112
Products
1916
Pounds
453,376
1,161,664
14,000
203,168
5,651,408
136,640
British Poss
Argentina
United States
luminium sulfates, includ-
ing alum
Belgium
France
Norway
British India
Argentina
Canada
United States
1,836,912
210,896
136,640
461,440
256,928
545,328
78,400
431.872
95,312
58,240
39.913,328 42,223,664
British Possessions .
Japan
United States
Chloride
France
Italy
British India
Japan
United States
Arsenic and its oxides. . .
British Possessions. . . .
United States
Brazil
Bleaching powder 81,355,680
France 1,232
Netherlands 2,656.192
Norway 1,000.496
Russia 3.036,096
10,528
1,551,536
13,069,392
2,295.552
8,639,456
3,557,120
8,703,184
2,093,392
1.998.976
694,176
484,288
241,248
10,691,632
287.168
649.488
982,912
722,736
4,299,232
1,514,912
163.296
947,184
,550,912
,202,912
,044.768
,570,000
,261,728
712,768
,832,416
921,536
757,120
288.960
,212,672
,068,144
949,536
,113.840
,682,464
,682,576
,617,392
229,264
1,568
301,952
,386.304
911,232
,184,400
,620,128
,005,088
498,400
1,904
162,848
35,159,264
1,876,896
6,677,664
3,003,840
10,497,872
1,174,656
1,393,168
354,704
6,224.176
"ii464
759,472
1,213.856
150,192
12,513.760
2.151,520
921,200
1,917,328
1.023,792
2.037,728
2.025,184
277,648
4,144
S49.808
39,075,232
9,797,312
2,279,088
2,122,960
5,488
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
195
Exports of Chemicals and Allied Products (.Continued)
1913 1916 1919
Chemicals (Continued): Pounds Pounds Pounds
Bleaching powder (Conc'd) :
Spain
Sweden 10,110,464
British India 5 , 998 , 048
Brazil 1,842,624
Canada 3,800,608
United States 44.470.720
Calcium carbide 212, 688
Chemicals, n. e. s $6,492,841
France 386,921
Germany 710,236
Italy 110.883
Netherlands 258,474
Norway 253,671
Russia 185,652
Sweden 342 ,908
Australia 705 ,141
British India 470,138
British South Africa 334 , 440
Japan 254,241
Argentina 187,292
Brazil 94,580
Canada 313,247
United States 478,260
Coal-tar products: Pounds
Products other than dyes:
Aniline oil and toluidine 1.350,678
British Possessions. . . 56,589
United States 699,631
France
Switzerland
Anthracene 564,372
Gallons
Benzene and toluene 7,987,636
France 7,585,390
Germany 132,050
United States 34 , 056
Russia 112,010
Pounds
Carbolic acid 18,915,008
France 1,130,752
Germany 2 , 657 , 536
Italy 297,696
Netherlands 6.717,536
Japan 284,144
United States 4,894,960
Russia
Coal tar, crude 9,850,288
Russia 3,118,080
British India 1.116,528
Coal tar, refined, and Gallons
varnish 3,686,700
British India 1,509,239
British Possessions,
other 1.479.618
Naphtha 618,635
France 557,774
British Possessions. . . 37, 1 15
Pounds
Naphthalene 9,637,936
Netherlands 1,621,648
Russia 2,601,872
British Possessions. . . 1 , 283 , 856
United States 2,004,016
France
Tons
Pitch 486,568
Belgium 130,632
France 206,743
Germany 10,642
Italy 60,696
Spain 27,112
China 9,003
United States 354
British Possessions. . .
Ounces
Saccharin 21,278
Gallons
Tar oil, creosote oil 44,121,113
France 337,523
Germany 346.182
Russia 219,631
Sweden 377,182
Canada 310.994
United States 40.605.650
Italy
Pounds
Other products 78,874,880
Belgium 1,313,760
France 5,657,344
Germany 6,369,552
Italy 2,828.336
Netherlands 1.949,472
Norway 17,778,544
Russia 855,904
British India 17,256,624
United States 3,870,720
Coal-tar dyes 5,451,376
France 88,480
Germany 400,288
Italy 620,032 622,496 758,240
British India 1,208,032 1,019,872 3,107,104
Australia 63,616 295.904 375.200
Japan 236,880 336 245,952
Canada 210.672 520,464 908,432
United States 1,778,336 753,648 658,560
Switzerland 50.288 2,747.584 2.327,808
Ounces Ounces Ounces
Cocaine and cocaine salts. . . 3,354 7,647 4,485
Exports
Chemicals
Allied Products (Continued)
129,136
921,424
6.987,008
1,105,328
136,640
1,250,816
731,920
$13,008,529
1,454,694
520J46
440,890
564,198
2.075,280
353,785
1,187,801
1,223,024
607,830
821,689
251,106
220,686
327,311
500.063
Pounds
2.177,492
37.552
10,860
135,079
1,777,000
2,813,700
Gallons
14,567,574
12,956,042
373,075
Pounds
12,817,168
631,680
66 i | 696
28,112
26,880
5,996,144
3,853,920
1,347,584
300,160
167,552
Gallons
4,129,128
1,236,584
1.672,808
644,071
615,789
5,627
Pounds
14,103,926
2,407!i04
1,388,352
3,333,008
4,292,400
Tons
268,116
179i328
7,983
Ounces
15,458
Gallons
40,166,356
1,469,850
88,205
16,634
35,622,185
52,833
Pounds
56.614,544
8, 994^384
I . 1 i5 ]672
630,560
22,402,800
571,760
11 ,231,696
2.208,080
6,564,992
161,504
622i496
1,019,872
295,904
336
520,464
753,648
2,747.584
Ounces
7,647
3,162,544
5,140,128
7,798,112
1,257,648
151,088
116,480
991,872
$12,951,971
2,108,207
289,858
554,173
733,902
562,217
238,789
485,735
879,016
970.414
463,437
554,051
233,933
232,098
400,309
890.764
Pounds
780,242
401,915
1,456,905
Gallons
1,175,567
555,759
Pounds
14.977,872
355.488
1,473;472
108,976
3,011,680
7,544,992
160,944
3,401,104
833,280
545.216
Gallons
3,973,033
715,711
1,801,893
683,235
658 , 240
4,248
Pounds
7.894,544
12.432
76,608
2,297,456
1,828,064
1,989,680
Tons
651,282
227.543
232.505
Ounces
208,571
Gallons
6,480,463
1,498,706
112,298
19,618
9,892,263
1,562,467
Pounds
26,196,352
605,136
8,795,136
2,1681208
316,064
588.672
43,456
4,158,448
1,527,792
12,200,160
932,960
Chemicals (Continued):
Copper sulfate
France
Greece
Italy
Portugal
Russia
Spain
Algeria
Glycerol:
■ Crude
Belgium
Germany
Netherlands
British South Africa. . . .
Canada
United States
Distilled
Italy
Norway
Japan
British South Africa. . . .
Canada
United States
Lactarine
Methanol
France
British Possessions
Switzerland
Morphine and morphine salts
France
Russia
Japan
Canada
United States
Potassium:
Chromate and bichromate
Belgium
France
Germany
Netherlands
British East Indies
Canada
Cyanide, and cyanide of
sodium
Mexico
Portuguese East Africa.
Australia
New Zealand
British South Africa
Canada
Salvador
United States
Nitrate
Italy
Portugal
Australia.
Argentina
Brazil
United States
France
Other salts
Germany
Russia
Japan
Brazil
Canada
United States
Quinine and its salts
Russia
Turkey
British India
Ceylon
China
United States
Italy
Sodium:
Bicarbonate
Italy
Australia
New Zealand
British India
China
Japan
Argentina
Brazil
Canada
Carbonate :
Crystals
Netherlands
British India
Argentina
Chile
Canada
United States
Soda ash
Italy
Netherlands
Norway
Sweden
Australia
British India
China
Japan
Argentina
Brazil
Canada
United States
1913
Pounds
169,417,920
48,758,080
5,884,480
60,766,720
9.965,760
6,668,480
11,121,600
920,640
16,324,560
222,992
375,424
4.504,416
336
117,712
11,037,152
10,786,272
18,368
246,288
1.281,168
6,142,304
1,950,368
302,512
Gallons
299,157
243,912
21,410
Pounds
6,254,752
427,168
1,184,400
2,593.024
342.048
284,928
193,872
15,732,864
860,160
1,601,600
1,462,496
3,734.976
714,000
3,508,512
912,464
132,272
367,696
3,798,816
223 \ 664
653,296
21,280
1,654.912
468,944
$637^317
66.672
112,538
71.153
37,292
35,711
116,874
Ounces
1,374,328
19,447
99,062
696,015
90,271
71,564
5,326
4,727
Pounds
55,947,584
3,921,456
8,703,184
1,867,824
8,728,048
1,312,528
9,528.400
4,526,816
1,100,176
5,553,184
30,176,720
1,130,304
1,971,760
9,834,384
4,461.408
4,011,504
675.808
349.977,264
18,745,552
6,757,184
3,771,824
4,717,440
21,083,552
43,509,648
52,867.248
70,691,488
23,812,620
16,153,648
38,541,888
3.376,128
1916
Pounds
87,178,560
48,778,240
17,920
8,915,200
3,252,480
15.523,200
100.800
5,953,920
5,452,944
948.640
6.787.088
1,232
Gallons
141,916
131,084
4,748
Ounces
225,611
49,W
41,409
116,116
14,659
89
27,337,296
2,013,760
428,960
130,368
2,945,936
953.568
13,209.280
2,103,024
446,096
69,552
2,117,136
265,776
273,168
146,944
241,360
365.792
$410,450
34i4i6
82,322
2,983
Ounces
1,659,030
208,244
250
480,180
116,659
76.032
26.426
324,157
Pounds
74,099,760
8,444,352
10,988,544
4,049,136
10,789,856
1,805,328
10.138.912
1,647,744
901,600
5,882,464
25,150.272
2,132,032
1,965,712
6,341,552
808,752
3,447.360
140,672
351,472,912
30,908,416
29,416,912
32,983,664
3,377,696
25,225,200
50,922,592
28,893,648
63,296,688
15,850,352
8,872,304
23,178,736
123.872
1919
Pounds
78,554,560
36,973,440
5,111,680
6,339,200
2,856,000
9,985,920
103,040
2,051,840
857,136
290,640
6.013,952
2.240
563,584
991,648
1,051,008
112
224
$556,486
Gallons
28,274
"l .975
16,420
Ounces
322,970
140,873
4,745
18^501
121,474
Pounds
1,360,912
116,144
132,496
159,264
118,496
56.448
43,568
12,240,480
1,167,712
2,501,744
54,992
1,121,904
231,952
2,620,240
908,544
224,000
1,306.368
6,353.984
15,680
214,032
41.664
92,624
2,525,600
3,163
62,646
61.274
18,522
13,573
Ounces
1,722,191
10,167
22,080
332,241
48.824
20,094
97,406
621,718
Pounds
58,832,816
4,191,376
3.368,736
2,221,744
11,332,384
2,799,328
10.281,712
1,190,672
969,808
3,279,584
21,947.632
10,316,768
1,179,920
2,303,056
286,496
11,984
377.925!296
13,078,128
12,307,904
18,506,432
12,662,608
16,612,288
51,294,880
72.321,312
86,553,712
17,634,736
3.802.400
5,067.888
1,951,712
196
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. .7
Exports of Chemicals and Allied Products {Continued)
1913 1916 1919
Pounds Pounds Pounds
Chemicals {Concluded) :
Sodium (.Concluded):
Chromate and bichromate
France
Germany
Netherlands
Australia
Canada
British Possessions, n. e. s
Italy
Caustic soda
Italy
Netherlands
Norway
Portugal
Rumania
Sweden
Australia
British India
Japan
Argentina
Brazil
5,435.024
1 ,415,008
2,511,600
472,080
23,968
333,312
67,424
ii.hIj
Me
United States...
Sulfate (salt cake) .
Belgium
Norway
Ru
Sweden
British Possessions.
Other salts
France
Italy
Portugal
Australia
British East Indies.
Argentina
Brazil
Canada
Me
United States
Drugs and Medicines:
Disinfectants, insecticides,
weed killers, sheep and
cattle dressings (except
tobacco offal)
Australia
British East Indies
British South Africa
New Zealand
Portuguese East Africa. . .
Argentina
Brazil
Chile
Uruguay
United States
Medicines and drugs, n. e. s.,
including medicinal
preparations
Belgium
France
Germany
Italy
Netherlands
Portugal
Russia
Spain
Australia
New Zealand
British India
British South Africa
British West Africa
Straits Settlements
China
Argentina
Brazil
Chile
Canada
United States
Dyes and Dyestuffs (not
coal-tar)
Belgium
France
Germany
Italy
Sweden
Australia
British India
Norway
Canada
United States
Egypt
Explosives:
Cordite and other smokeless
propellants
Belgium
France
Italy
Dynamite and other high ex-
plosives
France
Italy
Russia
Australia
New Zealand
British India
British South Africa
British West Africa
Japan
Portuguese Africa
6,391,168
1,115.120
1,478,400
540,960
804.720
1,714.608
1,065,456
167,792,240
20,945,008
1,793,792
1,417,136
4.009,040
4,925,648
3.496,976
11,078,368
10,647,728
24.455,200
13,908.496
15,759,856
7.007,504
178,976
1.192.240
148,3i;8,688
28,190.176
19,589,456
23,140,432
54.782,896
7,645,792
56,171,584
131,936
6.373,136
2,717,120
4,133.136
2,067,520
10,262,560
1.720,432
1,828,400
3.858.064
4,074,896
Pounds
43,816,080
3,429,888
2.647.344
7.762,496
3,677.296
1,230,992
13,941,536
188.832
1,775,984
894,096
991,984
$10,085,091
179,953
385.656
393,169
242,522
90,994
14.497
72,195
109,598
1,577,933
388,118
1,928.871
873.824
202,276
151,363
281.668
\V, ,497
288.890
122.587
648,807
336.236
Pounds
16,592.352
1.000.944
1,667,456
746.032
495,376
1,186,416
2,449,776
589.232
129.696
1.081 .024
750.960
4.887,904
14,550.592
22,176
21,686,784
2 , 853 , 200
62,294,400
854,112
13.383,888
2,954,112
6,817,216
3,253,712
6,703,760
2,526,720
975.296
28,560
2.063,712
Pounds
49,792.400
3,176,208
4 . 440 . 240
8,065.232
5,546,912
1,303,680
15,196.832
1,218,672
1,604,064
705,040
1,219,792
519,025,348
92
894,945
692,230
247.675
99,875
5.443.239
187,915
1,791.495
489.964
2.438.214
1.225,983
368,457
227,037
437.085
195.312
539.987
122.928
674.988
542.478
Pounds
13.756,280
194.656
634,704
1,888.320
103.040
1,787,408
418.768
187,264
1,446.368
1.196,496
2,353,456
18,440,800
1,232,448
1,943,088
4.108.048
5,351,360
1.109,248
1,587,376
340,256
876,512
216,272
885,136
414.512
1.085.840
33,264
65,387,840
11,687,648
4,760.000
3.522.736
921,200
145,488
8,650.880
3,927,952
2,460,192
3,533,488
6,276.592
18.032
45.808
90.944
54.146,064
347 , 200
19,600
524,496
1,121,120
117,132,288
12,524,512
5,238,016
1,074,864
2.952.880
800.800
4.749,024
7,064,176
9,756.880
21.304.416
2,676,800
8,051,792
8,400
548.912
13.552
57,781,360
9,285,136
14,890.512
1.164.800
20,704.320
5.211.696
69,195,280
10,230.528
11.198.656
2,711,296
4,069,968
2,416.512
9.116.912
2.343.600
1.175,664
1.341.984
3.605.952
Pounds
52,523.744
3,258.192
3,626,224
8,849,344
4,688.096
1.480,192
18.637.136
1,479,296
1,673,952
895,888
823 , 200
$17,772,249
440,438
1,282,420
529,855
314,634
136,116
614,210
301.027
] ,459,770
496.622
2.867.006
1,433.773
455.650
309,407
666,092
417.594
768,839
204.130
706,478
573.853
Pounds
927.024
826,112
194,320
261 .744
250.432
435,456
54.320
319,760
44 . 240
424.928
480,144
11,760
833 , 840
242,592
489,104
Exports of Chemical:
Explosives {Concluded) :
Dynamite, etc. {Concluded):
Argentina
Brazil
Chile
United States
Gunpowder
Australia
New Zealand
British India
British West Africa
Argentina
Canada
FERTILIZERS:
Ammonium sulfate
Belgium
France
Germany
Italy
Netherlands
Norway
Portugal
Spain
British East Africa. . .
British Guiana
Dutch East Indies
Japan
Canary Islands
Cuba
Hawaii
United States
Slag, basic
Denmark
France
Italy
Russia
Sweden
British Possessions, n.
New Zealand
Canada
United States
Norway
Superphosphates
Denmark
Russia
Spain
Canary Islands
Australia
New Zealand
British South Africa. .
Other
Belgium
France
Germany
Netherlands
Portugal
Channel Islands
United States
Oils Vegetable:
Fixed:
Castor
Belgium
France
Germany
Netherlands
Canada
United States
Coconut :
Unrefined
Russia
United States
Refined
Denmark
Italy
Netherlands
Sweden
Australia
Canada
Cottonseed:
Unrefined
Netherlands
British South Africa.
Refined
Belgium
France
Netherlands
French West Africa.
United States
Pure
Belgium
France
Germany
Australia
New Zealand. .
Brazil
United States.
Not pure
Belgium
France
Egypt
Brazil
Cuba
United States.
Olive:
Unrefined
Refined
Australia
Canada
United States.
and Allied Products {Continued)
1913 1916 1919
Pounds Pounds Pounds
307,440
1,386,672
1,581,104
672
7,543,424
3,289.664
493.472
387 . 296
874,608
816,368
335.216
Tons
323,054
5,169
8.874
9,388
5,822
2,872
3.507
52,357
4.926
7,725
37,119
114,583
8,495
4.249
7.143
38.919
165.100
10,787
26,995
18.234
27,159
13,632
5,764
19,793
4.277
6.774
9.392
63.480
12.040
4,801
6,585
4,105
7,321
12,522
2,373
152,437
11,304
27,399
31,816
1,702
7,706
8.073
32,208
Pounds
14.976,640
3.996,160
1,001.280
6.951.504
5,761,392
6,598,256
540,512
774.928
1,553.104
1.076.208
531,664
684,880
1.169.280
40,320
528,640
56,029,120
7,282,240
7,199.360
16,885,120
3,498,880
4,818,240
75.040
,104.080
568,512
390,320
216,160
647.920
161,728
1,456
Tons
259,290
287
24.896
7,658
82,928
9,155
5,865
2.525
21.901
7,891
313
5,028
1,570
6.481
15.592
6,908.160
1,8961560
60,480
1,120,000
916,160
1,515,248
112,000
1,034,768
4.400.816
207.312
430,304
44.800
86,352
577,024
909.104
383,040
313,600
4,480
5,391,680
1.619.520
880.320
678.720
59,893,120 52,306,240
19,904.640
792,960
13,704.320
4 , 695 , 040
8.348.480
309.120
7.107,520
920,640
1.274,560
629,440
33.600
Gallons
6,050
91,954
14,216
11.192
14.216
4.836,160
2,157,120
3.781.120
76.160
3.232.320
365 ! 120
555,520
598,080
264.320
Gallons
1,492
63,218
12,099
3.932
3,327
45,024
119,168
1,125,264
3,859,744
902,720
216,272
618,800
795,424
345,072
Tons
92.866
3,667
17,593
2.279
12,854
39,668
3,299
624
1,000
1,655
2,967
2,696
250
609
40,782
294
13.546
3,146
1,108
7,045
8,217
6,247.360
770,560
887,040
6.065.920
1.238.720
2.542.400
990,080
4.480
157.996,160
25.986.240
29.021,440
52,254,720
725,760
506.240
2,524,480
9.853,760
10.008.320
4.338,880
1,937,600
134,400
421,120
183,680
573,440
Gallons
605
20,266
5,747
3.025
Mar., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
197
Oils, Vegetable [Concluded):
Fixed (Concluded):
Palm:
Unrefined
Italy
Netherlands
British Possessions. . .
United States
Refined
France
Italy
Netherlands
British Possessions. . .
United States
Palm kernel:
Unrefined
•Netherlands
Refined
Netherlands
Rapeseed
Belgium
Germany
Netherlands
British Possessions
United States
Soy-bean
France.
Germany
Italy
United States
Other seed oils
Belgium
Netherlands
Sweden
United States
Volatile
Belgium
France
Germany
Switzerland
Japan
Australia
United States
Paints, Pigments, Varnishes:
Barytes
France
Germany
Ru
United States.
France
Spain
Turkey
Australia
British West Africa .
Argentina
Brazil
Canada.
United States.
White lead
Belgium
France
Russia
British India .
Australia
New Zealand. .
Argentina
United States.
Zinc oxide
France
Italy
British India. .
Brazil.
Chile.
Canada
Painters' colors
rials, n. e. s.
France
Germany
Netherlands
British India
British South Africa
Australia
Argentina
Brazil
Canada
United States
Perfumery and Cosmetics:
Perfumery (except spirits,
perfumed in bond, and
essential oils):
Perfumery containing
spirits
Japan
British India
British South Africa
British West Africa
Australia
Other sorts
Belgium
France
Russia
British India
British South Africa. . . .
British West Africa ....
Australia
United States
Toilet soap .
Belgium..
France. . .
Allied Products (Continued)
1913 1916 1919
Pounds Pounds Pounds
550,704
1,446,368
1 ,698,816
619,472
75 ^ 152
13,079^360
1,214.080
8,507,520
21,033,600
185,920
3.113.600
10,176.320
1,167,040
5,122,880
1,001,280
35.840
2,983,680
228.480
363,787
16,936
73,582
47,382
9,063
65,928
31,614
50,615
12,849,872
57.904
6,912,976
2,014,208
2,073,456
5,286.624
92,512
348.096
468,048
219.184
910.336
487,760
346,752
41,199,872
8,624
2.252,880
3 , 5 1 5 , 1 20
15,457,904
5,099,584
3,965,808
325.920
5,577,712
182,560
Not shown separately; incl
587,328
269,472
758.576
909,328
216,420,400
8,121,344
6,100,752
14,396,592
6,977,600
26,800,928
12,032,272
17,793.214
6,730,080
7,534,016
11,025,616
14,028,784
$819,549
42,674
135.834
48,670
30,644
86,682
$993,472
23,096
31.107
43,380
152,594
96,542
37,579
162,337
32.270
Pounds
9,591 ,344
113,568
348.432
ided with pain
6,809,488
356.272
627,984
3.488.240
2,049,600
3,385.984
44.800
315,952
5,600
500,528
1,534,736
(')
8,825 ! 600
65.555
133,928
40,279
23,898
855,904
2.292.752
7,575,568
179.424
16.800
11,872
639,072
737,520
1,339,072
490,000
548,464
231,168
29.372.000
1.520,400
3,555,104
3,604,048
9.721,152
3,428,432
1,121 ,792
98 , 784
6,101.760
1,041.936
40,880
679,392
1,459,584
285,936
133,280
69,726,256
5,150i096
3,050,208
26,282,928
13,681,248
14,374,752
6,016,976
5,785,920
2,907,072
8.494,640
$918,844
67,017
132,354
71,732
143,902
95,709
$1,840,300
1,942
29,072
116,459
248,094
157.786
204.832
232,385
57,176
Pounds
13.550,768
8,624
922,096
oil.
931.280
15.680
431.984
2,240
124,096
1,174.208
252,448
51.520
511,280
22,400
678,720
604 . 800
2,549.120
10,200.960
627,200
11,306,848
11,094,160
297,696
241,472
32.755,520
6,796,160
6,124,160
14,775,040
508,480
143,360
2,327.360
952,000
7,138,880
3,628^800
273,280
1,330,560
246,400
94,080
536.482
3,678,080
244.160
2,959,040
35,840
599,036
24,073
95,581
63,491
51,746
30,159
66,236
4,480
112.224
8,946,336
443,072
437,136
286,384
441,728
472,528
1 ,254.512
706,608
495,936
382,928
16.229,920
2.400.048
4,462,864
285,376
5.073,040
570,304
746,480
751,184
39,872
2,930,032
916,384
278,768
199,248
395,584
94,976
10,416
127.844,416
9,161,600
10,130,736
170,688
3,185,728
18,997,328
7,205,520
6,092,912
4,829.888
3.641.680
1.000.048
3.777,760
$1 ,449,793
130,982
294,860
140,320
85,066
93,641
$2,613,383
125.473
154.609
9.976
415,336
242,065
176,201
249.058
37,297
Pounds
14.626,976
2,796,304
1.250,704
Exports of Chemicals
Perfumery, Etc. (Concluded):
Toilet soap (Concluded):
<d Allied Products (Concluded)
1913 1916 1919
Pounds Pounds Pou nds
British India
British South Afrii
United States
Other Products:
Blacking and polishes, con-
taining no sweetening
matter
Belgium
France
Germany
Netherlands
British India
British South Africa
Argentina
United States
Blacking, containing sugar
or other sweetening mat-
ter:
Liquid
Solid
Candles
Belgium
Germany
France
British India
New Zealand
Morocco
Argentina
Ecuador
Dextrin
Glucose
France
Norway
Switzerland
Glue, size, and gelatin.
Belgium
Denmark
France
Germany
British East Indies. .
22S.680
268,912
,112,256
607,936
38.476,592
1 ,273,232
5,452,608
2,199,792
2,573.648
2.860.144
2,100,560
3,153,136
3,753.904
21,392
233,296
29,220.464
602 , 896
Clin
Japan
Canada
United States
Norway
Sweden
Netherlands
Paper and paper-making mi
terials:
Paper:
Writing
France
Japan
British India
Australia
New Zealand
United States
Printing
Belgium
France
Japan
British India
Australia
New Zealand
Canada
United States
Packing and wrapping.
Java
British East Indies. .
Canada
United States
Paper-making materials.
Belgium
France
Canada
United States
Household and laundry,
bars or tablets
Belgium
Germany
Italy
Netherlands
Ru
riu,
Dutch East Indies. . .
Egypt
Morocco
British West Africa. .
British West Indies. .
Polishing and scouring.
Soap powder.
New Zealand
Soft soap
Belgium
France
Norway
Sugar, refined, and candy.
Channel Islands
Denmark
Netherlands
Norway
Canada
42,560
1,781.136
1 ,230,208
8,375,920
3,032,512
1,360,576
547,344
866,992
1,571,360
562,800
2,501,968
757,008
394.128
3.363,808
3.617.040
4.885,664
3,324.160
1,534,736
24.469,312
585,648
764,624
3,111,136
8,675,184
2,576,224
243.152
210,304,752
4,762.912
13,721,456
16,937,200
30.786,672
65,894,528
13,784,064
13,624.688
3.506,384
101,410.624
11,193,168
61.369.168
2,037.616
820.960
Tons
201,754
26,035
53,763
9.596
88,970
Pounds
177,404,192
2,681 ,056
34,458.144
16,658,880
6,940,192
1,847.664
2.799,104
16,419,088
11,125,856
1.042,272
2,815.120
1.164.576
4,372,816
16.464
4,407
3.389
2.450
2.720
1,397,312
1,289,232 349,888
3.980,032 2,344,496
740,880 235,424
345,520 110,208
29,159,312
5,376
2,143,792
1,221.808
3,915,520
2,779.616
1,757.616
2,414.608
12,320
188,944
34,053.824
162,176
5,472,432
1,020.320
1 ,030.512
9.433.200
3,243.968
2,152,752
813,680
7,409,472
5,602,464
32,928
1,304.688
12.521 ,712
1.591,184
821,184
2,085,664
1,367,856
733,712
141,792
166.208
1.565,424
30,363,568
1,058,624
999.376
6.422,080
9,646,000
3,879,904
170.800
175.999,600
14,774.144
14,308,672
20,756.960
63,405,216
12.654.992
2,007,712
2,613,856
26,918,640
1 ,909,040
10.724,672
992,992
1,026,144
Tons
54,411
11,054
1 ,603
40,110
Pounds
218,624,672
52,752
11.574,416
5.353.824
24,693,984
1,077,328
599,648
36,262,128
13,149,472
15.876,448
6.078.800
6,726,496
14,576,800
10,042,368
983,360
2,962,624
1.150,016
6,749,232
81,200
4.023,376
Tons
4,475
744
25,121,712
2,015.328
1,848,784
1 ,139]264
3,078,656
2,497,152
1 ,199,632
1 ,433.040
7.168
488, 6S6
26,362,000
5.662,384
1,919,792
792,288
198,464
57,456
8,343,776
1,248,464
760,256
373,296
1,448,832
385,392
450,800
11 . 183J424
1,161,888
604.464
610.512
665.616
610,848
689,808
1,858,304
7 1 7 . 360
240,576
379,456
161,504
1,327.536
15,412.432
4,063,136
1,013,600
3,287,648
1,420.608
394 , 240
60,816
40,943,168
6,798,848
9.553.264
1 ,983,408
4.966.640
1,875.664
899,472
71.680
571,872
25.329,360
303,408
17,794.896
136,752
1.042.720
Tons
47,460
3,892
6,578
3,512
32,103
Pounds
241.486,336
52,236,352
16,590,896
16.500,960
10.348,688
4,021 ,360
4,702,768
7.119,616
21,111,552
7,043,456
6,503,392
9,472,176
4,894,512
9,843,008
8.198,288
753,424
2,897,216
142.016
10,637.648
4.777,920
1 ,726,592
1,432,256
Tons
1 , 259
1 ,156
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
ORIGINAL PAPLR5
NOTICE TO AUTHORS: All drawings should be made with
India ink, preferably on tracing cloth. If coordinate paper is
used, blue must be chosen, as all other colors blur on re-
duction. The larger squares, curves, etc., which will show in
the finished cut, are to be inked in.
Blue prints and photostats are not suitable for reproduction.
Lettering should be even, and large enough to reproduce
well when the drawing is reduced to the width of a single column
of This Journal, or less frequently to double column width.
Authors are requested to follow the SOCIETY'S spellings on
drawings, e. %., sulfur, per cent, gage, etc.
THE CRYOSCOPY OF MILK '
By Julius Hortvet
Dairy and Food Commission, State of Minnesota, St. Paul, Minn.
Received January 24, 1921
In 1896, as a result of numerous cryoscopic in-
vestigations on organic liquids, including serums pre-
pared from blood, bile, gastric juice, milk, etc., Winter-
announced the general conclusion that the serums of
blood and milk have the same freezing temperature
and that this temperature is a physiological constant.
This fact was fully verified by investigations carried
out on numerous species of animals. Stoecklin3 states
that milk is isotonic with blood and in consequence
that the freezing point of the two fluids will range from
— 0.550° to ■ — 0.560° C. This conclusion, with certain
restrictions, was confirmed by many exact determina-
tions. The prediction on the part of Atkins4 that the
freezing point of milk would never lie below that of
the blood of the animal producing it was borne out
by the examination of a hundred samples extending
over a period of 2 mo. References relative to the
freezing point of cow's blood are inadequate, but
various investigators give figures ranging from — 0.550°
to — 0.590° C. Pliester6 cites an instance of serum
prepared from blood of a sick cow as having a freezing
point of — 0.601°, while Atkins gives the freezing
point of normal cow's blood at — 0.620°. The freezing-
point figure is commonly cited as a gage of osmotic
pressure, and the cryoscopic determination is a well-
known convenient method of measurement. A general
conception regarding the various factors entering into
the freezing point of a sample of milk may be ob-
tained by inspection of the following classification
given by Alexander:6
Constituents of Milk — Colloid Chemical Classification
r- . ii j j- „„• ( Salts (such as NaCl, etc.)
Crystalloid dispersion { Sugar\lactose)
r* iia:j«i ^:ba»«ia« f Casein — an unstable or irreversible colloid
Colloidal dispersion j Lactaibumin_a stable or reversib.e cUdd
In suspension Milk fat
It will appear from the above outline that the
osmotic pressure of milk is due chiefly to the sugar
1 Based on report submitted as Referee on Dairy Products at Conven-
tion of Association of Official Agricultural Chemists, Washington, D. C,
November 16, 1920.
2 Arch. gen. Physiol., 8.
J Ann.fais., i, 232.
' Chem. Kens, 97, 241.
6 Chem. Wcekblad, 12, 354.
! "Colloid Chemistry," P. 57.
(lactose) and soluble salts which it contains. The
fat has no effect and the influence of the proteins is
either negligible or too small for cryoscopic measure-
ment. It can be seen that variations in the pro-
portion of one of the soluble constituents, for example,
the lactose, will be accompanied by such corresponding
variations in the soluble salts as will be necessary to
maintain a proper osmotic pressure. In other words,
an increase in the amount of lactose will be accom-
panied by a decrease in the total number of salt mole-
cules and ions which are normally present in milk.
It is also apparent that the alkali chlorides, on account
of their relatively low molecular weights and highly
dissociated state, contribute very largely to the total
osmotic pressure. Coste and Shelbourne1 have illus-
trated the osmotic pressure of average milk as fol-
lows:
Osmotic Pressure of Avi,k\..i: Milk
Osmotic
Per- Pressure
Constituents centage Atmospheres A
Lactose 4.7 3.03 0.250°
Alkali chlorides ! x'a'or K ions " ' 1 ° ■' '-33 0.110°
Other salts and ions 2.42 0.200°
Total 6.78 0.560°
Following these general considerations various ques-
tions naturally arise. What is the freezing point of
milk? Is the freezing-point figure fairly constant or
does it vary within certain maximum and minimum
extremes? What are the conditions giving rise to
these variations? Is it possible to lay down a safe
rule to serve as a guide in judging a sample of milk on
the basis of a freezing-point determination? Among
the twenty-five or more investigators who have pub-
lished articles on this subject there appears to be a
considerable diversity as regards conclusions. A few
individuals seem inclined to lay down hard-and-fast
rules, while others attempt broad generalizations, such
as we find expressed by Stoecklin,2 somewhat as fol-
lows: Milk, freshly drawn, from any variety of cow,
whether of high or low breed, from whatever region
of the country, from animals in stable or in pasture,
w-hether poorly or substantially fed, whether drawn
during a period near or remote from parturition, in
winter or in summer, morning or evening, and whether
the yield be scant or abundant, has a definite freezing
point which varies but little around — 0.550°, al-
though under various influences the chemical com-
position changes in enormous proportions.
One single condition is indispensable — that the
animal must be healthy, that the pathological condi-
tions of milk secretion must be in equilibrium with the
osmotic properties of the body fluids which in conse-
quence modify the freezing point.
Stoecklin states as a result of tests applied on 2500 samples
in 4 yrs. that under all conditions milk does not vary in freezing
point outside the limits of — 0.545° and —0.565°. Other writers
have expressed similar conclusions regarding the comparatively
' Analyst, 44, 158.
2 hoc. cit.. p. 234
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
199
larrow range in freezing-point variations on samples of normal
nilk.
Henderson and Meston1 give the extreme variations at — 0.540°
:o — 0.560° for the mixed milk of herds with an average' on all
:amples of —0.550°, but make no definite statement regarding
he number and character of samples tested by themselves.
MacLaurin,2 as a result of examination of 270 authenticated
;amples obtained from individual cows and herds, places the
'xtremes at ■ — 0.545° and — 0.565°, with an average of — 0.550°.
Forty-nine samples tested by Winter,3 and representing in-
lividual cows and herds, yielded results ranging from — 0.540°
:o — 0.570°, with a general average of — 0.555°. Winter and
Parmentier state that the extremes are the exceptions, whereas
he intermediate results constitute the general rule.
Ducrose and Imbert4 give results on a number (not stated)
}f samples yielding values from — 0.533° to — 0.575°. It is,
towever, explained that the lowest extreme ( — 0.533°) was
obtained on milk drawn probably from a sick cow and that the
highest value (• — 0.575°) occurred in the case of only two samples,
one being 2 days old and the other thickened.
Gooren6 concludes that, as a rule, whole milk will not give
a freezing point higher than — 0.540°; that a higher freezing
point indicates an abnormal milk, citing as an instance a sample
testing — 0.515°. Regarding the 20 samples tested by Gooren,
in the absence of any direct statement as to their origin, we are
left to infer that all were of known purity.
Hummelinck6 gives, as a result of investigations covering
several years on a number of samples, variations in freezing
point from —0.542° to —0.570°.
Van Raalte7 reports a freezing-point range of — 0.540° to
—0.570° on 155 known-genuine milks. A like general range is
given by Filippo8 and by Bomstein.'
Keister10 tabulates analyses of 31 authentic samples obtained
rom complete milkings, including one sample of herd milk,
showing freezing-point figures from — 0.541° to — 0.574°.
Similar maximum and minimum variations are reported by
Reicher11 and by Lam.12
As compared with these results, Atkins13 and Monier-Williams14
report exceptional extremes, but; owing to the unusual character
of the values published by these investigators, it will be neces-
sary to discuss them separately in sections dealing with apparatus
ind methods.
Attention is directed to the paragraph given by Leach16 on
the determination of the freezing point of milk. In spite of the
fact that there are safely anywhere from twenty-five to thirty
important references available in the literature on the cryoscopy
of milk, we find in this paragraph citations from only six authors,
is follows: Beckmann,16 Griiner,17 Pins/'Stutterheim,10 Gooren,20
ind Keister.21 It has not been possible to obtain access to the
original publications of Griiner and Pins, but an explanation
should be made with reference to the remainder of the refer-
1 Ckem. News, 110, 259, 275, 283.
2 Dominion Laboratory, New Zealand, 47th Annual Report, 1914,
» Rev. gen. Lait, 3, 193, 217, 241, 268; 4, 505.
< Bull. sci. Pharmacol., 7, 65.
« Cenlr. Bakl., Parasitenk., 36, 641.
• Chem. WeekUad, 11, 207.
' Ibid., 11, 206.
• Ibid., 11, 204.
• Russki Vrach, 3, 90.
"> This Journal, 9 (1917), 862.
■' Chem. WeekUad, 11, 323.
1! Ibid., 11, 84.
■• Chem. News, 97, 241.
■< Analyst, 97, 241.
■« "Food Inspection and Analysis," 4th Edition, 1920, 153.
'• Milch Ztg., 23, 202.
» Ann. Inst. Agric, 6, 27.
18 Inaugural Dissertation, Leipzig. 1910.
'• Pharm. WeekUad, 64, 458.
«• Cenlr. Bakl., Parasitenk., 36, II, 625.
» This Journal. 9 (1917), 862
ences cited. It is true that while Beckmann does not report a
very wide range in results, his values do not tend in the main to
indicate any very low freezing points. Also, there should be
borne in mind the fact that Beckmann advocated certain cor-
rection formulas which in recent years have been under contro-
versy, chiefly on the part of Dekhuyzen and Lam. The results
reported by Stutterheim were obtained on only eight cows, which
appear to have been selected for investigation owing to the fact
that they were known to be sick or poorly fed. The conclusion,
based on results which range from — 0.520° to — 0.560°, that
8 per cent or less of added water cannot be detected, is manifestly
unwarranted. The results of Gooren's investigations have
already been alluded to and on proper interpretation are favor-
able toward the acceptance of a narrow range in freezing-point
values. However, these investigations covered only a limited
number of samples, concerning which no definite claim was made
as to purity. It is further stated in the paragraph that Gooren
finds that homogenizing, pasteurizing, and sterilizing have the
effect of lowering the freezing point. As relates to pasteurizing,
this statement is not based on the actual results. The conclu-
sion was to the effect that pasteurizing sometimes changes the
freezing point and sometimes does not. Attention is also called
to the expression which occurs in the second sentence of the
paragraph, that — "most of the later investigators find — 0.580°
is none too high for the minimum limit." This statement is
not justified, owing to the fact that only one or two investigators
have reported freezing-point depressions as low as — 0.580°
and that these results are liable to obvious criticisms. Also
the further statement, "Mixed herd milks appear seldom to fall
outside the limits of — 0.570° to — 0.530°," while entirely un-
founded, is nevertheless more closely in conformity with facts
The actual variations reported for herd milks occur within much
narrower limits.
It is apparent from the foregoing discussion that
there has doubtless been a lack of uniformity as re-
gards the conditions under which freezing-point de-
terminations have been carried out. While it is true
in the main that these conditions have not been over-
looked and in a number of instances have been given
serious and painstaking attention, nevertheless many
investigators have published articles of more or less
importance which fail to take into account the essential
factors which determine a freezing-point result.
Broadly speaking, the various conditions which are
recognized as being vital in a freezing-point determina-
tion may be covered by the following headings:
1 — Freezing-point apparatus — cryoscopes
2 — Thermometers
3 — Methods of procedure
FREEZING-POINT APPARATUS — CRYOSCOPES
The apparatus employed by most investigators in making
freezing-point determinations appears to be modeled generally
on the principle of the Beckmann cryoscope. There are, how-
ever, a number of modifications, as may be judged from the com-
paratively limited number of adequate descriptions which have
been published. Very few writers seem to be satisfied with the
original Beckmann apparatus and have attempted modifica-
tions for the purpose of correcting manifest experimental errors.
The simplest device which has been employed in milk testing
is the one described by Henderson and Meston.1 This model
hardly embodies many of the features of the typical Beckmann
apparatus. There is a well-insulated cooling bath, but no ar-
rangement for maintaining a uniform freezing mixture, no con-
trol thermometer, and only a single test tube in which is held
the sample to be frozen. The authors do not appear to place
1 Chem. News, 110, 283.
200
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 3
any great emphasis upon details of construction, and appear
only to have in mind an elementary form of apparatus that can
be conveniently manipulated.
Bordas' makes severe criticisms of the Beckmann apparatus
and calls particular attention to the imperfect contact of freez-
ing mixture with milk test tube, liability of test tube to breakage
while being inserted in the freezing mixture, loss of time involved
in manipulation, and the necessity of frequently changing the
mixture of crushed ice and salt. The writer states further that
it is difficult to maintain a refrigerating mixture of ice and salt
at a relatively constant temperature, and that the warming of
the mass by conduction and radiation limits the number of opera-
tions and necessitates undue haste in making observations.
Attention is also directed to the great discrepancies among re-
sults obtained by different authors. He proposes the use of a
d'Arsonval-Dewar flask as an insulating container for a cooling
mixture consisting of acetone reduced in temperature by means
of carbon dioxide snow.
A number of investigators, notably Winter and Parmentier,*
appear to Use an apparatus modeled on the Beckmann principle,
including a mechanical stirring device, but use only the single
test tube holding the sample.
Stoecklin3 appears not to be satisfied with the construction
of the customary Beckmann apparatus and devises a special
make of cryoscope, using for the purpose a Dewar flask in which
is prepared the freezing mixture of ice and salt. He employs
a special kind of stirring device and gives much attention to the
importance of using a double test tube, but does not appear to
use a control thermometer.
Dekhuyzen4 describes a cryoscope of his own design, including
among other features a Dewar tube, but uses a freezing mixture
of ice and salt and provides special arrangements for avoiding
the effects of conduction and radiation; and Schoorl6 considers
it important that the temperature of the freezing bath be even
throughout and that the surface of the milk sample be a number
of centimeters below that of the freezing mixture.
There is a marked tendency toward the increased application
of the Dewar flask (known to some investigators as the d'Arson-
val) as a substitute for the various insulating devices which have
been attempted by way of improvement of the Beckmann ap-
paratus. A number of cryoscopes, in fact, have been designed
on this principle, using as a refrigerating medium either a mix-
ture of ice and salt or other compound, or in some instances a
volatile refrigerating fluid, such as ether or acetone, either with
or without addition of solidified carbon dioxide.
Atkins6 claims to have used an ordinary type of Raoult
cryoscope, but gives no description of the apparatus. Monier-
Williams7 gives a description of an elaborately constructed cryo-
scope based on the original principle of Raoult, but uses a Dewar
flask for holding the refrigerating fluid. The plan of this ap-
paratus appears to have in view chiefly the purpose of obtaining
freezing-point results under conditions approximately ideal,
that is to say, by eliminating as far as practicable well-known
sources of experimental error, chief among which are the tem-
perature of the cooling bath and the consequent supercooling
of the sample under test.
The discrepancies noted among the results published by a
good many collaborators may doubtless be explained on ac-
count of the various freezing-point arrangements which have
been employed. There does not appear to be any fairly de-
fined uniformity in respect to design and construction of ap-
paratus, and even in cases in which the ordinary Beckmann
i Ann.fals., 4, 301.
2 Rev. gen. Lait, 3, 193.
" Ann. fats.,*, 232.
* Chem. Weekblad, 11, 126.
» Ibid., 12, 220.
« Chem. News, 97, 241.
' Analyst, 40, 258.
cryoscope has been used, there are notable differences as regards
the conditions under which the determinations are carried out.
THERMOMETERS
The special Beckmann type of thermometer has been in
general use. Various modifications have been described, but
there is lacking in the literature the necessary descriptive matter
relating to the construction of thermometers.
Henderson and Meston1 first used a thermometer constructed
on the Beckmann principle. They mention the trouble of
having occasionally to readjust the column of mercury, and in
order to avoid this inconvenience recommend the use of a special
type of instrument graduated to 0.01°, each degree covering
8.5 cm. on the stem.
Stoecklin2 uses a thermometer of special design, with scale
+3° to — 2° C, each degree about 7 cm. in length and divided
into 0.01°. Monier-Williams3 describes the special make of
thermometer employed by him as having a total range of about
1° C, divided into intervals of 0.005°, and each 0.005° division
about 0.4 mm. in length. With this instrument, it is stated,
the correct reading was reached in less than one minute, and the
observed freezing point remained constant for an indefinite
period, provided that the bath temperature and the speed of
the stirrer did not alter.
Schoorl4 emphasizes the requirement that every thermometer
be standardized and states that not all thermometers are reliable
on account of thermic changes in the glass. Gooren5 expresses
the same general opinion, and in order to insure reliability recom-
mends that all thermometers be tested at the Physikalisch-
Technischen Reichsanstalt; and Dekhuyzen6 devotes a good deal
of attention to various details relative to their standardization
and calibration.
Aside from the authors who have been mentioned, there are
only a few who appear to lay any great emphasis upon the im-
portance of accurately constructed thermometers, and there is
little in the literature on the cryoscopy of milk which has to
do with proper methods of standardizing.
METHODS OF PROCEDURE
Obviously, of primary importance is the method according
to which a freezing-point determination is carried out. While
a number of investigators undoubtedly base their procedure on
well-established rules, there are many, on the other hand, who
appear to ignore or neglect certain first principles underlying
the subject of cryoscopy. The conditions which are considered
essential in a proper cryoscopic procedure may be comprised
under the following headings:
1 — Temperature of the cooling bath
2 — Convergence temperature — supercooling
3 — Volume of the sample to be tested
4 — Rate of manipulation of the stirring device
5 — Method of adjusting and observing the position of the
mercury column
The cryoscopic method described in the Codex-Alimentarius,
and which for some time has been in use in Holland, prescribes
a cooling-bath temperature ranging from — 2° to — 4° C,
and a supercooling of sample not less than 1° and not over 1.5°.
Filippo7 criticises this cooling-bath temperature and proposes
a range from — 2.5° to — 3.5°; Reicher8 concludes in favor of
a bath temperature of — 2.8° and a supercooling of ±1°; Dek-
huyzen9 urges thai the cooling bath must have a constant tem-
perature at not lower than — 2.5°, and does not favor more than
' Chem. News, 110, 284.
2 Lot. cit.
» Analyst, 40, 261.
• Chem. Weekblad, 12, 220.
» Centr. Bakt., Parasilenk., 36, II, 641.
« Chem. Weekblad, 11, 91.
' Ibid., 11, 204.
» Ibid., 11, 323.
>Ibid., 11, 91.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
201
1° supercooling. A committee of investigators composed of
Van Eck, Filippo, Lam, Van der Loan, Van Raalte and Reicher1
recommends a bath temperature of- — 2° to — 3° and a super-
cooling of 0.8° to 1.3°.
Other investigators who do not base their procedure upon the
Codex method show differences of opinion regarding the tempera-
ture of the cooling bath. Hummelinck supercools 1 ° and carries
out his tests in a bath temperature of — 4°; Atkins employs
a bath temperature of — 5° to — 6°, implies a general caution
against too great an extent of supercooling, and makes all mea-
surements on a rising column of mercury; Stoecklin mentions
— 4° to — 5° as the cooling-bath temperature, and supercools
about 0.5° ; Keister makes no definite mention of bath temperature
but leaves an inference favoring — 4°, and advocates a super-
cooling from 1° to 1.2°; Monier-Williams endeavors to carry
out his determinations with bath and supercooling temperatures
very close to the final freezing point of the sample, ranging
somewhere within 0.25° to 0.5° C, the aim being apparently
to obtain results under supposedly ideal conditions and thus
avoid the necessity of corrections which have been much under
controversy. Winter and Parmentier make no mention of
bath temperature and apparently give no attention to super-
cooling, and the same statement is apparently true regarding
the procedure adopted by Henderson and Meston, Gooren, and
others.
Great variations are noted regarding the quantity of sample
to be used in carrying out the test, ranging all the way from 12
cc. to 60 cc. Many investigators advocate a 50-cc. sample,
chiefly on the ground that a comparatively large volume con-
tributes somewhat toward diminishing experimental errors.
The rate of stirring is also given considerable attention, some
persons advocating a very low rate of 10 or 12 strokes per minute,
others a rapid rate of 1 to 2 per second. Monier-Williams
sets a constant speed of about 1300 r. p. m. as the rate of move-
ment for the mechanically operated, spiral, glass stirrer employed
by him.
Dekhuyzen displays not only critical skill in the construction
of his apparatus as well as in the arrangement of conditions for
carrying out his tests, but also adds a number of refinements in
the way of correction factors based largely on the ideas of Beck-
mann. A controversy was carried on, chiefly during the years
1911 to 1912, between Dekhuyzen and Lam, owing to differ-
ences in views regarding practical methods of cryoscopic ex-
amination and the application of correction factors. Results
reported by Dekhuyzen were obtained after the application of
corrections, whereas Lam, on the other hand, was disposed so to
arrange conditions that corrections would be practically elim-
inated. Schoorl and Spanjaard2 were able to show that the
corrections applied by Dekhuyzen and others were in fact er-
roneous under various conditions of supercooling.
Several investigators have endeavored to devise apparatus
and methods which, when practically applied, would obviate the
necessity for corrections. The method of Winter and Par-
mentier involves a number of details having this object in view
and is therefore peculiar in a number of respects. The sample
taken is from 40 to 50 cc. The bath temperature is lowered
well below the freezing point of the sample until it is stationary
(temperature lowering immaterial), then the frozen sample
withdrawn and warmed in the hand, in the meantime stirring
until the greater portion of the ice crystals melt. The tube is
then inserted in the freezing bath and the observation made on a
falling column of mercury, the lowest depression of the mercury
being read off as the true freezing point. Henderson and Meston
cool the sample in the freezing tube until crystal formations are
well developed, then remove the tube and warm in the hand
until a rise of about 0.2° is observed. The frozen mass is stirred
1 Chem. Weekblad, 12, 108.
2 Ibid., 11, 648.
and the reading taken when the mercury falls and becomes
stationary for about 2 min. Monier-Williams employs a 60-
cc. sample, lowers the temperature of the freezing bath by means
of a current of air drawn through the apparatus, which, as
previously stated, is constructed on the Raoult principle. The
apparatus is so manipulated as to maintain a relatively high
temperature of cooling bath (not above — 0.25°) with a super-
cooling initially at 0.5° and ultimately approximating that of
the bath. The question may be raised in criticism of the above
modes of procedure as to whether there does not repeatedly
arise a confusion as regards the actual condition or phase of
the sample which is under test; that is to say, whether at the
time of the freezing-point observation there exists a predominat-
ing crystal formation or the reverse change from the crystalline
to the liquid phase.
For practical purposes, Monier-Williams proposes to simplify
the freezing-point procedure by dispensing with the determina-
tion of the 0 point given by distilled water, and, instead, comparing
the freezing point of the milk sample with that of a solution of
9.495 g. of pure sucrose in 100 g. of water, which solution is
said to freeze at "exactly — 0.5345° C." Therefore, if the two
determinations, viz., the freezing point of the sucrose solution
and the freezing point of the sample of milk, are determined in
precisely the same manner, the "difference between the two re-
sults will indicate fairly accurately the true freezing point"
of the sample. It is stated that the bath may be of ice and salt
and the temperature as low as — 5° C., the important point
being that the temperature be kept approximately the same in
both determinations, and that the degree of supercooling, rate
and manner of stirring, etc., be maintained alike. Whether
the results reported by Monier-Williams on 141 samples of
genuine milk were all obtained by means of the above procedure
or by means of the method described in the preceding para-
graph of his article is not stated. At any rate, the values
found, ranging from — 0.558° to — 0.514°, are said to have been
subjected to "all the necessary corrections," which corrections
were doubtless embodied mainly in the following formula at-
tributed to Raoult:
C' — C
K = ,
cs
where C' is the observed depression of the freezing point, C the
true depression, S the degrees of supercooling, and K a constant,
which for milk is 0.017. Attention is also given to the correc-
tion for the emergent column of mercury, and mention is made
of other sources of error arising chiefly from the mechanical
production of heat by the stirrer and too low a temperature of
the freezing bath. It is stated, however, that these errors
"may be eliminated if the temperature of the bath be so regulated
that the freezing point of the solution coincides with the so-
called temperature of convergence, i. e., the point at which the
solution is at exact heat-equilibrium with its surroundings, the
amount of heat abstracted from the solution in unit of time by
the freezing bath being exactly equal to the heat imparted by
the stirrer, by radiation from the outside, etc."
Obviously, the results reported by Monier-Williams must be
interpreted in the light not only of the apparatus and method
employed by him, but also after making allowances for correc-
tions which were doubtless applied in all cases. Whatever
criticisms may be raised in regard to these results and the methods
whereby they were obtained, the fact remains to be noted that
the writer regards the freezing point as "the most constant of
any of the properties exhibited by milk," and one that "may,
in certain circumstances, be applied with advantage, as a con-
firmatory test, to the detection of added water and to the ap-
proximate estimation of the amount present." The qualified
doubt expressed in conclusion as to whether the freezing-point
method is capable of general application for purposes of milk
control may well be anticipated, owing largely to the obvious
202
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
experimental difficulties involved in the apparatus and plan of
procedure employed by the writer in making his investigations.
Such meager details as are available relating to the apparatus
and method employed by Atkins have already been given. It
may, however, be pointed out that results of tests made on sam-
ples "bought daily from various Dublin dairies" and including
"daily morning and evening milks from the same cows," lead
to the conclusion that:
The mean freezing point of cow's milk is — 0.55° C, and the
value does not usually vary by more than — 0.03° C. above
or below. Occasionally it may fall to — 0.61° C. but not below
— 0.62° C, the freezing point of cow's blood; the extreme varia-
tion on the other side met with was ■ — 0.49° C., which is 0.06° C.
above the mean, just as much as the lower limit observed differs
from it.
Nevertheless, in spite of these exceptionally and unaccountably
wide limits, Atkins concludes that:
The determinations of the freezing point and specific gravity of
a sample of milk are sufficient to show, on the one hand, whether
it has been diluted with water, and, on the other, whether the
fat has been removed * * * With a little practice the freezing-
point determination can be carried out very rapidly; four samples
were examined in 50 min. on one occasion, two of the determina-
tions being repeated a second time.
It follows from the foregoing summary of the litera-
ture that there is a demand for uniformity in regard
to the essential conditions involved in the cryoscopic
method as applied to the testing of milk. Aside from
the Codex-Alimentarius method and modifications
based thereon, there appears to be nowhere anything
approximating the objects which have been pointed
out. Whether it is- possible to unify these conditions
by means of various designs of cryoscopes may
seriously be questioned, but most important of all is
uniformity regarding the method of procedure. There
have been for many years certain well-established meth-
ods which will be found described in standard texts on
practical physical chemistry, but these methods appear
to have been given little or no attention on the part
of many individuals who have attempted cryoscopic
investigations on samples of milk.
As stated by Findlay,1 the conditions affecting the
temperature of the liquid in the freezing-point tube
are the following:
1 — Abstraction of heat by the cooling bath.
2 — Addition of heat from outside by conduction through stirrer,
thermometer, etc.
3 — Addition of heat (latent heat of fusion) by the solidifying
solvent.
The resultant of (1) and (2) is the convergence tem-
perature or its equivalent degree of supercooling' below
the freezing point of the liquid. When solidification
(freezing) takes place, latent heat of fusion is added
to the liquid with a resultant rise of temperature.
Hence, the observed temperature will not be the true
freezing point, being a resultant of factors which may
be summarized as follows:
1 — Rate at which heat is withdrawn from the liquid, depend-
ing on difference between observed temperature and convergence
temperature.
2 — Rate at which heat is given to the liquid, depending on
latent heat of fusion and velocity of crystallization.
These important factors are embodied in the fol-
lowing formula:
1 "Practical Physical Chemistry," p. 124.
I+Jtf-
f),
where T equals the true freezing point, t the observed
freezing point, t' the convergence temperature, k a
constant depending on rate of heat abstraction, and
K a constant depending on rate of addition of latent
heat.
The velocity of crystallization being proportional
to the degree of supercooling, it is apparent that the
factor (/ — t') should be made small in order to
diminish the correction k/K (I — /')•
Combined with practical considerations, the con-
clusions derived from the foregoing formula are stated
by Findlay as follows:
1 — The temperature of the cooling bath must not be too low.
It should not exceed 3° below the freezing point of the liquid.
2 — The amount of supercooling should not exceed 0.3° to
0.5°.
3 — The stirring should not be too rapid and should be as uni-
form as possible. A rate of about once per second is regarded
as sufficient.
4 — The thermometer should be tapped repeatedly before
taking a reading.
Only one practical exception may be made to the
conditions above stated, viz., the amount of super-
cooling, especially in testing a sample of milk. It
will be recalled that Keister recommends a super-
cooling of 1° to 1.2°, while others place the super-
cooling temperature in the neighborhood of 1°. For
practical reasons these conclusions seem to be right.
Unless a much lower supercooling than 0.5° is secured,
it will be found that in the testing of milk the rise
of the mercury column immediately after the freezing
has been initiated is not sufficiently pronounced, and
that there is more or less uncertain wavering and often-
times difficulty in deciding upon the exact point at
which the top of the column becomes stationary. In
order to satisfy practical requirements, an attempt
has been made to unify the conditions which have been
outlined by giving attention chiefly, first, to the con-
struction of a suitable cryoscope and thermometer,
and, second, to the method of manipulation. The
cryoscope which has been designed to serve the pur-
poses under discussion is described as follows:
CRYOSCOPE
A cylindrical-shaped Dewar flask of 1 liter capacity
and 28 cm. internal depth, surrounded by a metal
casing, is tightly closed by means of a large cork of
about 4 cm. thickness. Through the center of the
cork is tightly fitted a medium thin-walled glass tube,
250 mm. in length by 33 mm. outside diameter. At
one side of the cork is inserted a narrow metal inlet
tube, the lower end of which is formed into a per-
forated loop near the bottom of the flask. At the
opposite side is a metal tube of T-shape construction
and 6-mm. internal diameter, intended to afford escape
for vapors, and also for introducing volatile fluid into
the apparatus. At the back portion of the cork is
fitted a control thermometer having a scale range of
+ 20° to — 30° C, and with bulb extending nearly
to the bottom of the flask. The freezing test tube is
of thin glass, about 240 mm. in length by 30 mm.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
203
outside diameter, and fits closely into the larger tube
which is sealed into the cork. In the rubber stopper
of the freezing tube is fitted the standard thermometer.
The thermometer is constructed of such length as to
enable insertion of the bulb to near the bottom of the
freezing test tube and at the same time allow complete
exposure of the scale above the stopper. At the right
side of the thermometer a stirring device made of non-
corrodible low conductivity metal is fitted into the
stopper through a short section of thin-walled metal
tubing. The lower end extends to near the bottom
of the test tube and is provided with a loop, around the
outside of which are a number of pointed projections.
At the left of the thermometer is a freezing-starter
attachment inserted through an opening in the stopper
formed by means of a short section of metal tubing.
The Hortvet Cryoscope
This device consists of a noncorrodible metal rod,
at the lower end of which is a 10-mm. length opening
for the purpose of carrying a small fragment of ice.
At one side of the cryoscope is installed an air-drying
arrangement which consists of a Folin absorption
bulb inserted through a tightly fitting stopper and ex-
tending to near the bottom of a large-sized test tube.
A short section of glass tubing is inserted through a
second opening in the stopper and is connected to the
vaporizing tube which enters the cryoscope. Sul-
furic acid is poured into the drying tube to a level
slightly above the inner bulb. At the opposite side
of the apparatus is arranged a drain tube for the
purpose of conducting vapors away from the operator.
By means of a pressure and suction pump dry air may
be forced into the apparatus at a suitable rate and the
mixed vapors conducted out through the base of the
drain tube into the sink. An adjustable lens is mounted
in a suitable position in front of the thermometer for
the purpose of magnifying the scale.
THERMOMETER
The standard thermometer designed especially for
testing milk is a solid-stem instrument measuring a
total length of 58 cm., with a scale portion measuring
30 cm. The total scale range is 3° C, from +1° to
— 2°, each degree division subdivided into tenths and
hundredths. The length of a degree division approxi-
mates to one decimeter, thus making the smallest sub-
divisions of such magnitudes as to enable easy ob-
servation and readings estimated to 0.001°. The
thermometer should be carefully standardized and
calibrated in comparison with a U. S. Bureau of
Standards tested instrument.
The control thermometer should be tested in a bath
of melting crushed ice for the purpose of determining
whether the 0 mark on the scale is fairly correct to,
within a small fraction of a degree.
PROCEDURE
Insert a small caliber funnel-tube into the vertical
portion of the T-tube at one side of the apparatus and
pour in 400 cc. of ether previously cooled to 10° C. or
lower. Close the vertical tube by means of a small
cork and connect the pressure pump to the inlet tube
of the air drying attachment. Adjust the pump so
as to pass air through the apparatus at a moderate
rate as may be judged by the agitation of the sulfuric
acid in the drying tube Continuous vaporization of
the ether will cause a lowering of the temperature in
the flask, from ordinary room temperature to 0° C.
in about 8 min. Continue the temperature lowering
until the control thermometer registers near — 3° C.
At this stage, by lowering a narrow-gage, graduated
glass tube into the ether bath, then closing the top by
means of the forefinger and raising to a suitable height,
an estimate can be made as to the amount of ether
necessary to pour in for the purpose of restoring the
400-cc. volume. When the apparatus has once been
cooled down to the proper temperature an additional
10 to 15 cc. of ether is on an average sufficient for each
succeeding determination. Measure into the freezing
test tube 30 to 35 cc. of boiled distilled water, cooled
to 10° C. or lower. Enough water should be measured
in fairly to submerge the thermometer bulb. Insert
the thermometer together with the stirrer and lower
the test tube into the larger tube. A small quantity
of alcohol, sufficient to fill the space between the two
test tubes, will serve to complete the conducting
medium between the interior of the apparatus and the
liquid to be tested. A sufficiently tight connection
between the inner and outer tubes is afforded by means
of a narrow section of thin-walled rubber tubing.
Keep the stirrer in steady up-and-down motion at a
rate of approximately one stroke each 2 or 3 sec, or
even at a slower rate, providing the cooling proceeds
satisfactorily. Maintain passage of air through the
apparatus until the temperature of the cooling bath
reaches — 2.5° C, at which time the top of the mercury
204
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
thread in the standard thermometer usually recedes
to a position in the neighborhood of the probable
freezing point of water. Maintain the temperature
of the cooling bath at — 2.5° C, and continue the
manipulation of the stirrer until a supercooling of
sample of 1.2° is observed. As a rule, by this time the
liquid will begin to freeze, as may be noted by the
rapid rise of the mercury thread. Manipulate the
stirrer slowly and carefully three or four times as the
mercury column approaches its highest point. By
means of a suitable light-weight cork mallet tap the
upper end of the thermometer cautiously a number of
times, until the top of the mercury column remains
stationary a couple of minutes. Taking necessary
precautions to avoid parallax, observe the exact read-
ing on the thermometer scale and estimate to 0.001° C.
When the observation has been satisfactorily com-
pleted, make a duplicate determination, then remove
the thermometer and stirrer and empty the water from
the freezing tube.
Rinse out the test tube with about 25 cc. of the
sample of milk, previously cooled to 10° or lower,
measure into the tube 35 cc. of the milk, or enough
fairly to submerge the thermometer bulb, and insert
the tube into the apparatus. Maintain the tem-
perature of the cooling bath at 2.5° below the probable
freezing point of the sample. Make the determina-
tion on the milk, following the same procedure as that
employed in determining the freezing point of water.
As a rule, however, it is necessary to start the freezing
action in the sample of milk by inserting the freezing
starter, carrying a fragment of ice, at the time when
the mercury column has receded to 1.2° below the
probable freezing point. A rapid rise of the mercury
column results almost immediately. Manipulate the
stirrer slowly and carefully two or three times while
the mercury column approaches its highest point.
Complete the adjustment of the mercury column in the
same manner as in the preceding determination, then,
avoiding parallax, observe the exact reading on the
thermometer scale and estimate to 0.001°. The
algebraic difference between the reading obtained on
the sample of water and the reading obtained on the
sample of milk represents the freezing-point de-
pression of the milk.
For deducing the percentage of added water from
the determined freezing point, use Winter's table,1 or
use the scale accompanying the cryoscope. The per-
centage of added water (W) may also be calculated as
follows:
100(T - T
W = —- .
T
where T represents the freezing point of normal milk
(average — 0.550°) and T' the observed freezing
point on the given sample.
As stated by Keister2 it is essential that the
cryoscopic test be applied only to reasonably fresh
milk, owing to the fact that the development of acidity
to the extent of 0.10 per cent beyond normal for fresh
milk (0.15 per cent) lowers the freezing point about
i Chem. News, 110, 28.1.
• This Journal. 9 (1917), 8(j->.
0.25 to 0.30 per cent. Therefore, a sample of milk in
which a considerable amount of acidity has developed
should not be subjected to test. The correction factor
proposed by Keister (0.003° for each 0.01 per cent
increase in acidity) appears to be about as practical
as any that has so far been suggested, but owing to
insufficient investigations regarding this point, it is
not deemed advisable, excepting in extreme cases,
to test samples when it is apparent that a correction
factor will be necessary. In actual practice, as a rule,
by applying the above correction, results have turned
out substantially as would be anticipated from the
other analytical figures. There is, however, very
seldom any real occasion for applying a correction,
owing to the fact that it is entirely practicable to
obtain fresh samples, put up in proper condition, and
get them to the laboratory in time to avoid a marked
development of acidity.
PRACTICAL APPLICATIONS
During the years 1919 to 1920 analyses were made
of seventy-five samples of known-genuine milks taken
from individual cows and from herds. A general
summary of the results of these analyses is given in
Table I.
Table I — Summary of Results on Known-Gbnuine Milks, 1919 to 1920
Freezing
Sp. Gr. Fat S-N-F point
60° F. % % —0° C.
Known-Genuine Milks — Individual Cows
Minn. State Farm and State Fair. 1919-1920 — 18 Samples
Maximum 1.0346 7.30 9.83 0.560
Minimum 1.0285 3.20 8.00 0.535
Average 1.0320 4.01 8.95 0.544
Local Dairy Farms, 1919-1920 — 17 Samples
Maximum 1.0350 6.70 10.15 0.561
Minimum 1.0287 3.25 8.31 0.535
Average 1.0322 4.41 9.10 0.549
Hohtein-Friesian Guaranty Sale, June 1920 — 25 Samples
Maximum 1.0343 4.70 9.39 0.562
Minimum 1.0262 2.80 7.37 0.534
Average 1.0317 3.57 8.72 0.547
Known-Genuine Herd Milks
Local Dairy Farms, 1919-1920—15 Samples _
Maximum 1.0330 5.50 9.27 0.562
Minimum 1.0305 3.10 8.48 0.545
Average 1.0319 4.15 8.95 0.551
All Samples — 75
Maximum 1.0350 7.30 10.15 0.562
Minimum 1.0262 2.20 7.37 0.534
Gen. average... 1.0319 4.03 8.93 0.548
It will be observed that these tabulated results
comprise milks exhibiting a very wide range in com-
position. No information of special value would be
added by tabulating the analytical results on all
samples in full. The table includes samples represent-
ing any imaginable type of milk, ranging anywhere
from 2.20 to 7.30 per cent in fat, and from 7.37 to
10.15 per cent in fat-free solids. At the same time,
the freezing-point figures are seen to vary over a
narrow range, from — 0.534° to — 0.562°. Also, as
may be expected, the general range for herd milks
is within much narrower limits than the range shown
for milks drawn from individual cows, being in the
case of the former — 0.545° to — 0.562°, and in the
case of the latter from 0.534° to — 0.562°. It may
further be pointed out that cryoscopic tests have also
been applied to a large number of samples which,
while not strictly vouched for as genuine or un-
adulterated, could nevertheless for practical purposes
be safely classed with samples of known purity.
Mar., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
205
These samples were obtained from producers and
distributors concerning whom there was little or no
reason for suspicion and whose products throughout
a long period of time have customarily tested normal.
There have been subjected to cryoscopic tests some-
what over 1300 samples during the past 2 yrs., beginning
in February 1919. This number includes all samples,
viz., samples purchased from distributors, producers'
samples (many of which were of safely assumed
known-genuine grade), and the seventy-five authentic
samples included in the foregoing tabulation. While
it is true that a large proportion of these samples were
diluted by means of added water as indicated by freez-
ing-point elevations (that is, results above — 0.535°),
it is a significant fact that in no case has there been
found a sample having normal acidity (near 0.15 per
cent) and testing lower than — 0.562°. Care has been
exercised in all cases before applying the cryoscopic
test to ascertain whether the sample was "off" in
acidity, and the above statements do not cover samples
which were distinctly soured or shown to be abnormal
by the customary lactic acid titration. Owing to the
observed natural variations in freezing points of
genuine milk obtained from healthy cows, properly
fed and kept, it has been deemed advisable to adopt a
3 per cent tolerance in passing judgment on market
samples. This tolerance figure is plainly very liberal
owing to the fact that the high freezing-test results
( — 0.534° and — 0.535°) were obtained on milks from
individual cows, while the range noted in the case of
milks from herds is much narrower and includes no
results higher than — 0.545°.
During the past 20 yrs. much attention has been
given in various state and federal food control labora-
tories to the development of methods of examination
of the milk serum as a means of detecting adultera-
tion with water. The analyst of the Massachusetts
State Board of Health1 gives the following statement
relative to these methods:
The detection of added water in milk depends upon being
able to show abnormal chemical or physical constants, which
can be explained only by the addition of water, there being no
test which will distinguish between the water which may be
added to the milk and the water naturally present. It is in-
cumbent, therefore, upon persons engaged in the chemical ex-
amination of milk to become familiar with the chemical and
physical properties of milk of known purity * * * If we depend
upon the solids, fat or proteins to indicate added water, it is
evident that considerable adulterated milk will escape detec-
tion, but if a minimum figure is employed for ash, solids not fat
or sugar, more adulterated milk will be discovered. The most
successful methods for the detection of added water are based
upon the milk sugar content, and for this purpose it is usual to
prepare a milk serum, because the most variable constituents
(the fat and the proteins) remain in the curd, while the serum will
contain the sugar and the ash, which are the least variable.
Based on results obtained on the copper serums
prepared from samples of milk systematically watered,
also on results of examination of a large number of
samples of known purity, the analyst states the fol-
lowing conclusion:
1 Report upon Food and Drug Inspection, year ending November 30,
1910, pp. 18-44.
A study of the above table shows that each 5 per cent of added
water lowers the refraction by one scale division, and, there-
fore, in order to detect 10 per cent of added water in milk the
milk before watering must give a serum refracting below 38.
The question now arises as to what are the probabilities of this
happening. Of 221 samples of known purity milk, 124, or 56
per cent, gave sera refracting below 38, and of these samples
107, or 48 per cent, were below 12.78 per cent in total solids, and
114, or 51 per cent, were below 8.77 per cent in solids not fat.
The average of the samples of milk collected by the State Board
of Health in 1909, exclusive of samples which could be declared
skimmed, watered or cream, was 12.78 per cent in solids and 8.77
per cent in solids not fat. It is fair to presume from these figures
that the average of the 1909 collection of milk in Massachusetts
would refract below 38, and, therefore, 10 per cent of water
could be detected if it were added to the average milk sold in
this state. Probably 40 per cent of the samples collected would
have given sera refracting above 38, and in these cases 15 per
cent of added water could have been detected if the sample
had been adulterated to that extent.
As stated by Nurenberg,1 a comparative study of
methods of examination of milk serum leads to the
following conclusions:
There is no relation between the refraction of the sour serum
and the sour serum ash, since these figures depend upon differ-
ent milk constituents. When both of these figures fall below
the lowest limits established for pure milk (38.3 and 0.730)
it is absolute proof of the presence of added water, and all possi-
bility of the sample being abnormal milk from a sick cow is
removed * * * In all doubtful cases the sour serum ash has
served as a court of last resort.
The following limits are applied in interpreting
results obtained on various serums prepared from
milk:
acetic serum — A refractometer reading below 39
indicates added water; between 39 and 40, the addi-
tion of water is suspected. An ash result below 0.715
g. per 100 cc. indicates added water.
sour serum — A refractometer reading below 38.3
and an ash result below 0.730 g. per 100 cc. indicate
added water.
copper serum — A refractometer reading below 30
indicates added water.
comparative study of methods
During the summer of 1920 a study was made of the
cryoscopic method as compared with the refractometer
method when applied to samples of known-genuine
milk and to mixtures of milk containing known per-
centages of added water. The known pure samples
selected for the investigation were of representative
types, two obtained from individual cows and three
from mixed milk of herds. Each sample was used as
the basis for a series of mixtures containing added
water in definite proportions, beginning with 6 per
cent and continuing at 2 per cent intervals up to 14
per cent. For reasons which will be apparent, the
fifth series of mixtures includes an additional sample
watered up to 16 per cent.
Sample 18-S was taken from a 5 yr. old registered
Holstein cow, well fed and kept, with a recorded good
daily yield of average-test milk.
' J. Assoc. Official Agri. Chemists, II. 159.
206
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol 13, No.
18-S
Holstein
Added water
Per cent
14
309-P
Guernsey
A dded water
Per cent
Sl-S
100 Cows,
Common
Added watei
Per cent
Table II — Milks Containing Known Percentages Added Water
Immersion Refractometer Readings 20° C - — Acetic Serum—
S-N-F Added Ash
Per Sour Acetic Copper Water G. in Sp Gr
cent Serum Serum Serum Indicated 100 Cc. 15°C
• — Cryoscopic Examination^
. Added Water .
Freezing Per cent Per cent
Point rT-T')100 (0.550-1") 100
—0° C T 0,550
1.0286
1.0284
1.0275
1.0265
1 .0265
1.0310
1 .0308
1.0303
1.0296
1.0285
Samples
from Jnd'n
'idual Cows
8.37
39.20
40.53
36.34
None
0.7560
1.0278
0.535
None
2.72
7.95
7.88
7.66
7.39
7.37
37.90
37.23
36.50
35.83
35.20
38.50
38.00
37.64
37.14
36.40
35.05
34.75
34.44
34.19
33.80
Present
Present
Present
Present
Present
0.6948
0.6760
1 .0265
1.0257
1 . 0244
1.0241
1.0237
0.503
0.492
0.478
0.468
0.459
5.98
8.00
10.65
12.52
14.20
8.54
10.54
13.09
14.91
16.54
4.80
4.62
4.50
4.40
4.35
8.85
8.75
8.62
8.42
8.13
41.33
40.73
40.11
39.47
38.86
37.35
36.93
36.50
35.99
35.60
None
None
None
0.7600
1.0306
0.519
5.97
5.63
0.7476
1.0300
0.509
7.79
7.45
0.7354
1.0293
0.494
10.50
10.18
1.0285
0.486
11.95
11.64
1.0280
0.474
14.13
13.82
Samples from Herds
6
:
1.0305
4.50
8.67
39.39
40.00
36.55
None
0.7404 1
.0288
0.527
5.72
4.18
8
:
1.0299
4.39
8.50
38.75
39.47
36.15
None
0.7268 1
.0280
0.514
8.05
6.54
10
:
1.0294
4.23
8.34
38.42
38.95
35.69
Probable
0.7145 1
.0274
0.502
10.20
8.73
12
:
1.0285
4.12
8.10
37.72
38.39
35.33
Present
0.7022 1
.0263
0.491
12.16
10.72
14
:
1 .0278
4.04
7.91
37.17
37.75
34.93
Present
0.6920 1
.0252
0.481
13.95
12.54
100-S
)
44 Cows,
[
1.0305
3.90
8.55
39.69
40.22
36.32
None
0.7972 1
.0283
0.562
None
None
Grade
s
Added water
Per cent
6
1.0290
3.62
8.12
38.22
38.67
35.12
Probable
0.7500 1
.0262
0.528
6.05
4.00
8
1.0283
3.58
7.93
37.70
38.17
34.81
Present
0.7340 1
.0255
0.515
8.36
6.36
10
■
1.0279
3.53
7.83
37.22
37 . 65
34 . 40
Present
0.7160 1
.0252
0.502
10.67
8.73
12
1.0274
3.45
7.68
36.77
37.12
34.02
Present
0.6988 1
.0248
0.492
12.45
10.54
14
■
1.0268
3.40
7.53
36.15
36.62
33.67
Present
0.6828 1
.0242
0.482
14.23
12.36
184-S
11 Cows,
I
6 Guernsey,
\ 1
.0321 "
S.50
9.27
42.96
43.87
38.22
None
0 . 8060 1
.0310
0.559
None
None
5 Jersey
)
Added water
Per cent
6
1.0302
5.19
8.73
41.20
42.09
37.00
None
0.7760 1
.0295
0.523
6.44
4.91
8
1.0296
5.10
8.56
40.50
41.43
36 . 65
None
0.7480 1
.0290
0.511
8.58
7.09
10
1.0291
5.00
8.41
39.95
40.56
36.17
None
0.7268 1
.0285
0.501
10.37
8.91
12
1 .0284
4.90
8.22
39.38
40.17
35.72
None
0.7060 1
.0275
0.491
12.16
10.72
14
1.0280
4.79
8.10
38.61
39.55
35.34
Probable
0.6888 1
.0265
0.480
14.13
12.73
It
1.0271
4.68
7.86
37.96
38.80
34.96
Present
0.6700 1
.0260
0.468
16.27
14.91
T«m I?
Ill
' — MlLKS Containing AnnRn
Water — Ma
rket Samples
,-Ch
YOSCOPIC
Examination-
Immersion Refractometer Readings 20° C.
. — Acetic Serums
Added Water
Labora-
Added
Ash
Freezing
Per cent
tory Sp. Gr.
Fat
S-N-F
Sour
Acetic
Copper
Water
G. in
Sp
>. Gr.
Point
(0.550-1") 100
Number 15.6° C.
Per cent
Per cent
Serum
Serum
Serum
Indicated
100 Cc.
15" C.
—0° C
0.550
4431 1
.0315
3.50
8.
7 2
40
.40
41.50
37.40
None
0.527
4.2
4432 1
.0303
3.90
8.
50
38
.40
40.00
37.20
None
0.502
8.7
4502 1
.0305
3.00
8.
3S
.'7
.25
39.13
35.45
Present
0.6888
1
.0263
0.490
10.9
4602 1
.0282
3.00
7.
7S
38
.52
35.78
Present
0.6976
1
.0230
0.477
13.3
4612 1
.0290
3.30
8.
05
39.48
35.92
None
0.500
9.1
4644 1
.0307
3.30
8.
47
il
!52
39.76
35.75
None
0.7520
1
.0280
0.506
8.0
4663 1
.0294
4.40
8.
38
38
.18
40.41
36.52
None
0.7696
1
.0280
0.523
4.9
4714 1
.0304
3.25
8.
40
39
.53
40.27
36.00
None
0.7488
1
.0275
0.506
8.0
4747 1
.0300
2.60
8.
16
37
.57
38.34
35.48
Present
0.7308
.0270
0.481
12.5
4752 1
.0279
4.30
7.
<JK
37
.95
38.46
35.43
Present
0.6928
1
.0255
0.485
11.8
4766 1
.0306
3.40
8.47
41.67
37.75
None
0.7320
1
.0282
0.519
5.6
Sample 309-P was taken from a 3 yr. old Guernsey
cow, well fed and kept, with recorded large daily
yield of rich milk.
Sample 51-S is representative of mixed milk from a
herd of 100 cows of common grade, well kept and fed
under good pasturage conditions.
Sample 100-S is representative of a milking from 44
common-grade cows, poorly kept and fed under poor
pasturage conditions.
Sample 184-S is representative of milk from a small
group of 11 cows, including 6 Guernseys and 5 Jerseys,
all kept under excellent conditions and scientifically
fed.
The plan of investigation included the routine de-
terminations of specific gravity, fat and solids, im-
mersion refractometer readings on serums prepared
in various ways, ash and specific gravity determina-
tions on the acetic serums, and cryoscopic examina-
tion of all samples. The specific gravity results on
the whole and mixed samples were obtained by means
of an accurate Quevenne lactometer; fat was de-
termined by the Babcock method, the measurements
being estimated closely to the second decimal, al-
though fully realizing the limits of accuracy inherent
in the method; solids were calculated from the results
for specific gravity and fat; and the specific gravity
of the acetic serums was determined by means of a
Westphal balance. The serums were prepared and
examined, following closely in all details the A. 0. A. C.
Methods of Analysis.1 The freezing-point determina-
tions were made by means of the apparatus and pro-
' A. O. A. C, 21 (1920), 16.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
207
eedure described in this paper. For the efficient work
done in carrying out the determinations above out-
lined, the writer wishes to express his appreciation
to the assistant chemists in the Minnesota Dairy and
Food Department Laboratory — to Mr. Henry Hoff-
mann, who handled the cryoscopic determinations,
many of which were made in duplicate and involved
much painstaking checking of thermometers and
careful control of conditions; to Mr. Otto Kueffner,
who prepared the accurately mixed samples and made
all determinations of specific gravity, fat and solids;
and to Mr. Donald F. Mitchell, who handled the
refractometric work and the serum ash determina-
tions. The chemists' results are included in Table
II and are submitted for careful examination and
study. Also, there follows (Table III) a tabulation
showing results obtained on a number of market
milks purchased during August and September 1920.
DISCUSSION OF RESULTS
Samples 18-S and 100-S are similar as regards
general composition. Following the accepted rules
of interpretation of results of immersion refractometer
readings, it will be seen that the added water indica-
tions are similar in both series based on these samples.
It will be noted, however, that the two series fail to
yield any resemblances on the basis of the sour serum
refractometer readings and the acetic serum ash re-
sults. Results of the cryoscopic tests applied to both
series yield consistent and uniformly agreeing results
and indicate conclusively adulteration with water
from the lowest percentage to the highest. Owing
to the fact that the freezing-point result on Sample
18-S is near the maximum so far obtained on an
authentic sample of milk, a discrepancy is shown, as
may be expected, between the results tabulated in the
last two columns. Results calculated on the basis
of the known freezing point correspond closely with
the actual percentages of added water, whereas results
calculated on the basis of the average freezing point
of pure milk ( — 0.550°) involve a discrepancy amount-
ing to 2.72 per cent throughout the entire series.
Samples 309-P and 184-S are also very similar as
regards general composition. The immersion refrac-
tometer readings taken in conjunction with the ash
results on the acetic serum fail to indicate added water
as high as 12 per cent in both series, while the con-
clusion is doubtful at the 14 per cent limit, and in the
case of Sample 184-S is positive at only 16 per cent.
On the other hand, freezing-point results afford positive
indications of added water throughout both series,
and are concordant, and show fairly uniform gradations
throughout. However, in the case of Sample 184-S,
owing to the comparatively low freezing-point result,
the added water calculations shown in the last column
involve a discrepancy amounting to approximately
1.5 per cent as compared with results calculated on the
basis of the known freezing point of the sample. The
general contrasts between the series headed 18-S and
' 100-S on the one hand, and the series headed 184-S
and 309-P on the other, may be anticipated after an
inspection of the results for fat-free solids in the four
unmixed samples, which in the former two are low
(8.37 and 8.55, respectively) and in the latter two
are high (9.34 and 9.27, respectively). It may be
assumed that corresponding relationships would also
have been revealed by a determination of lactose on all
samples.
Sample 51-S is intermediate as regards general
characteristics. Results obtained on the various
serums fail to indicate, conclusively, added water under
10 per cent. At the 10 per cent limit the indication
is probable, followed with positive indications at the
higher limits. On the other hand, freezing-point tests
yield results which afford conclusive indications of
added water, which, when calculated on the basis of
the known freezing point of the authentic sample, are
in close agreement with the actual known amounts
added. Results calculated on the basis of the average
freezing point for pure milk involve, however, a dis-
crepancy amounting to approximately 1.5 per cent.
CONCLUSIONS
1 — A large majority of investigators publish freez-
ing-point results which range approximately from
— 0.540° to — 0.570°; a small number report lower
results in the neighborhood of - — 0.575°; and the very
few results reported outside of the above limits may
probably be accounted for by taking into considera-
tion peculiarities or defects as regards apparatus and
methods employed, or by noting the application of
correction factors.
2 — There is revealed a great want of uniformity in
respect to the construction of cryoscopes. The
principal designs range in general from various modifica-
tions of the Beckmann apparatus to a few models
suggested by the apparatus originated by Raoult.
3 — There exists also a great diversity regarding
design and use of thermometers. In many instances
there is found no definite statement descriptive of the
thermometer employed, and many investigators give
little or no attention to standardization and calibra-
tion.
4 — There are also noted radical differences regard-
ing the procedure followed in making freezing-point
tests. Attention to essential conditions appears to
be given by only a minority of investigators, and very
great differences are noted in actual practice in the
observance of such essential conditions as tempera-
ture of cooling bath, supercooling, amount of sample,
rate of stirring, etc.
5 — It is conclusively shown that the cryoscopic
method as applied to the examination of milk is in
need of being standardized; in other words, it is neces-
sary that uniformity be secured respecting conditions
involved, chiefly in the following, viz., the construction
of the cryoscope, methods of testing the thermometer,
and the method of procedure.
6 — The application of correction factors may for all
practical purposes be avoided by means of a carefully
standardized method of procedure.
7 — Results so far obtained by means of the ap-
paratus and procedure described in this paper indicate
a narrow range of freezing-point values as a charac-
teristic property of milk.
208
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
8 — The cryoscopic test is reliable as a method for
the determination of added water in amounts far be-
low 10 per cent. When the freezing point of the
original whole milk is known, results are obtainable to
within an error not far from 0.5 per cent, and when
the freezing point of the original milk (e. g., a herd
milk) is unknown, the addition of water may safely
be reported in an amount as low as 3 per cent.
THE FORMATION OF ANTHRACENE FROM BENZENE
AND ETHYLENE
[PRELIMINARY PAPER]
By J. E. Zanetti and M. Kandell
Havemeyer Laboratory, Columbia University, New York, N. Y.
Received December 16, 1920
In his classic researches on pyrogenetic reactions
Berthelot1 found that when benzene and ethylene
are passed through "red hot tubes," anthracene is
one of the products obtained. He stated that the
reaction takes place in two steps:
+
CH,
-CH
+ H2
H
H2
The ethylene combines with one volume of benzene
vapor to form styrolene, which in turn combines with
another volume of benzene to form anthracene. No
indication of the yield of anthracene available is given
by the author. He found that the main product of
the reaction which distilled at 270° to 280° C. was
diphenyl.
Graebe2 treated toluene similarly and obtained
anthracene among other products. His main reaction
product was also diphenyl.
Van Dorp3 passed o-benzyltoluene through a tube
heated to incipient red heat. He filtered the con-
densed liquid and treated the residue with glacial
acetic acid, from which he obtained yellow crystals
of anthracene, melting at 213° C. The presence of
anthracene was confirmed by the formation of the
characteristic crystals of anthracene picrate by treat-
ment with picric acid.
A careful search of the literature fails to show any
other work that has been done on the formation of
anthracene by the pyrogenetic reaction of hydrocar-
bons. In connection with other work undertaken in
this laboratory on pyrogenetic relations of hydrocar-
bons, it seemed of interest to study the anthracene
formation from a quantitative standpoint and to
study the temperature relations of this reaction.
THEORETICAL
The formation of anthracene from benzene and
ethylene is an endothermic reaction:
> Ann. chim. phys., Hi, 254.
' Ber., 7, 48.
» Ibid., S, 1070.
2C6H, + C,H2 > CuH.o + 2H2 — 5.2 Cal.1
This value represents, however, only a minimum
value, since the heat of formation of anthracene is
known only to the solid phase, and no data exist as
to its latent heat of fusion and heat of vaporization
which would make such a correction possible.
We can at best obtain an approximation to this
value by using Trouton's rule, according to which .
the molecular latent heat of evaporation is approxi-
mately 21 times the absolute boiling temperature.
Since anthracene boils at 351° the molecular heat
of evaporation lies in the neighborhood of 13.1. This
would make the heat of formation 18.3 Cal. + X,
where X is the latent heat of fusion and has of course
a negative value. The reaction is therefore strongly
endothermic and should be favored by high tempera-
tures. As, however, all hydrocarbons become ex-
tremely unstable at temperatures in the neighborhood
of 1000°, the decomposing tendency begins to mani-
fest itself and the decomposition to carbon and gas
becomes so rapid that there can no longer be any an-
thracene formed. The formation of anthracene from
hydrocarbons by pyrogenic reactions can at best give
only small yields, for it will not form at low tempera-
tures and it will decompose above 900°.
90
80
70
-(JO
Q
<J50
No
30
1
20
10
1
/
/
/
/
>
/
/
•'
>"^
00 825 850 875 900 925 950 975
Temperature °C.
Fig. 1 — Actual Benzene on Basis of Total Benzene
1000
These conclusions are, as far as this work has pro-
ceeded, fully confirmed by our results and likewise
by the occurrence of anthracene in coal tar in only
very slight amounts, since coal distillation takes place
below even the optimum temperature for the forma-
tion of anthracene.
1 Calculated from the following data of Berthelot:
C. + H. — >■ C.H«— 22.6.2C + 2H. — >■ C.H«— 14.6, and Ch + Hm —>■
C10H11 — 42.4. ("Thermochimie," Vol. II, pp. 403, 416, 436.)
Mar., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
209
y
» — «
\
y
> <
'
\
s
\
\
\
\
\
i
\
15
14
13
12
I I
10
^ 9
^ ft
5
4
3
2
800 825 850 875 900 925 950 975 1000
Temperature V.
Fig. 2 — Tar on Basis of Actual Benzene
EXPERIMENTAL
The plan of the work was as follows: Ethylene
was allowed to bubble through benzene which was
kept just boiling. The resulting gaseous mixture was
passed through a quartz tube which was kept at a
fixed temperature. The condensation products were
distilled and the amount of anthracene in the residue
(tar) was determined.
material — The benzene used was pure thiophene-
free benzene. It boiled at 80.5° C. and had a specific
gravity of 0.881 at 15.5° C. The ethylene was com-
mercial ethylene sold in tanks under 1200 lbs. pressure.
Upon analysis the gas showed 99.5 per cent ethylene.
apparatus — The heating apparatus was an elec-
tric furnace of the resistor type, in the center
of which was a quartz tube 1 in. in diameter and 2 ft.
long. The temperature was controlled by means of
a rheostat and was measured by a pyrometer having
a base metal thermocouple. It was possible to main-
tain the temperature constant within 5° C. without
any difficulty. The pyod was placed outside the
quartz tube in order to avoid any catalytic effect which
might have been obtained if the pyod were placed in
contact with the hot gases.
The gases were cooled by a copper coil condenser
which was surrounded by ice. The "fog" that col-
lected in the receiver was precipitated electrically.
In principle the method is identical with the Cottrell
form of precipitation and has been fully described by
one of us.1
procedure — The furnace was rapidly brought up
to temperature and maintained constant for at least
half an hour. The benzene was then carefully heated
with a very small flame until a temperature of 80° C.
1 This Journal, 8 (1916), 674.
15
14
13
12
I I
10
*! 8
6
5
4
3
2
800 825 850 875 900 925 950 975 1000
Temperature °C.
Fig. 3 — Tar on Basis of Total Benzene
was reached. The ethylene was turned on and allowed
to bubble through at the rate of 0.2 cu. ft. per hr.
This slow rate was chosen in order to insure a complete
mixing of the gases and their subsequent reaction in
the furnace. Although the ratio of benzene vapor to
ethylene was not controlled, there was no difficulty,
after a few trials and with careful heating, in obtaining
a ratio somewhat above the theoretical, i. e., 2: 1.
The ratio of benzene to ethylene for each run is given
in Table I.
If
/
/
/-
/
/
\
/
<
>
/
/
>
r
~l
-'
/
Volume of
Temp, of Run
Cc
of Benzene
Benzene Vapor
Ratio of Benze
°C.
Evaporated per Hr.
C
i. Ft. per Hr.
to
Ethylene
800
49.7
0.44
2.2
1
825
46.8
0.42
2.1
1
850
45.5
0.40
2.0
1
875
45.7
0.48
2.4
1
900
53.4
0.47
2.4
925
43.8
0.39
2.0
1
950
45.0
0.40
2.0
1
1000
47.0
0.42
2.1
1
At the end of each run, which was made for a period
of 1.5 to 2 hrs., the condenser was thoroughly washed
with a measured amount of benzene in order to re-
cover any tar adhering to the condenser wall. This
washing was added to the original tar and the entire
solution was distilled in a 250-cc. distilling flask. Dis-
tillation was carried on up to 300° C, and the residue
(tar) was analyzed for anthracene. It is interesting
to note that only two fractions came over. The first
distilled at 80° to 85° C. (benzene), and the second
at 250° to 275° C. (diphenyl).
extraction of tar — From 2 to 3 g. of the tar were
weighed into a 150-cc. tall type beaker and covered
with 50 cc. of glacial acetic acid. The solution was
digested on a steam bath for one hour.
An extraction cup was fitted into a filter thimble
and the whole set in the neck of a 1-liter round-bottom
flask. The digested solution was filtered into the
210 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
07 , 1 , , , , , , , 0.7
/
>
■ • —
/
/
/
1
Ji
/
06
05
C;0.4
(J
O5 0.3
<*»
0.2
0.1
800 825 850 875 900 925 950 975 KXW
Temperature "C.
Fig. 4 — Anthracene on Basis of Total Benzene
flask, the insoluble material being removed from the
beaker with a small steel spatula, and stiff hairbrush,
and by washing with glacial acetic acid. The thimble
was then adjusted in -the flask which carried a reflux
condenser. The material was extracted by re-
flux condensation until the acid filtered through
colorless. This occurred in about 4 hrs., but it was
found convenient to allow boiling to continue over
night. After removing the flame, the cup was allowed
to drain for half an hour. The caked residue was
taken out, crushed in an agate mortar, and returned
for further extraction. It took about another half
hour for the acid to filter through colorless. The cup
was removed from the flask and the amount of an-
thracene in the solution was determined.
determination of anthracene — The method used
is based on Hochst's test1 as modified by The Barrett
Company laboratories. The acetic acid solution was
transferred hot to a 500-cc. round-bottom flask pro-
vided with a connecting tube and reflux condenser.
To this solution, which was kept boiling, was added,
drop by drop, a solution of 15 g. of chromic oxide
in 10 cc. of glacial acetic acid, and 10 cc. of water.
The addition of chromic acid occupied 2 hrs., after
which the liquid was kept boiling for 2 hrs. longer.
The solution was allowed to stand for 12 hrs., after
which it was mixed with 400 cc. of cold water and
allowed to stand for another 3 hrs. The precipitated
anthraquinone was collected on a filter and washed,
first with pure water, then with 200 cc. of a 0.1 per
cent boiling solution of sodium hydroxide, and finally
with hot distilled water. The precipitate was washed
from the filter into a porcelain dish and dried at 100° C.
It was then mixed with 10 cc. of fuming sulfuric acid
(containing 10 per cent of free SO3) and heated to
100° C. for 10 min. on a water bath. The resulting
' Lunge, "Coal Tar and A
0£
0.5
c;o.4
^0.3
q;
■
800 825 850 875 900 925 950 975 1000
Temperature "C.
Fig. 5 — Anthracene on Basis of Actual Benzene
solution was kept for 12 hrs. in a damp place to ab-
sorb moisture, 200 cc. of water were then added, and
the precipitated anthraquinone was collected on a
filter. It was washed first with pure water, then with
boiling dilute alkaline solution, and finally with hot
distilled water. The precipitate was washed from the
filter into a beaker and was collected in a Gooch cru-
cible. The crucible was dried at 105° C, and weighed,
the anthraquinone was sublimed off, and the crucible
was reweighed. The difference in weight, multiplied
by 0.8558 and divided by the weight of tar taken,
gave the per cent of anthracene present in the tar.
DISCUSSION OF DATA
The results are given in Table II. No data could
be obtained at 1000° C. since carbonization was com-
plete, as evidenced by the formation of a core of carbon
which choked up the tube. No material was found
in the receiver. The yield of tar (Figs. 2 and 3) is
small but appreciable at 800° C, and increases, at
first slowly, then rapidly to 925° C.
Table II
Tar
. — Anthracene — .
From
Anthra-
From
Decomposed
Total
Actual
cene
Total
Actual
nip.
Benzene
Benzene
in Tar
Benzene
Benzene
c.
Per cent
Per cent
Per cent
Per cent
Per cent
Per cent
800
23.6
2.95
12.55
0.08
0.002
0.010
X'S
26.6
3.69
13.80
0.28
0.010
0.040
8S0
30.0
4.06
13.60
1.23
0.046
0. 167
875
39.8
5.72
14.80
2.84
0. 162
0.421
90(1
58.8
8.90
15.10
4.46
0.397
0.607
s>:>.s
100.0
15.15
15.15
4.45
0.675
0.675
".SO
100.0
7.86
7.86
3.83
0.300
0.300
0(10
100.0
0.00
0.00
0.00
0.000
0.000
Above this temperature the yield decreases and reaches
0 at 1000° C. From Fig. 2 we see that the tar on the
basis of actual benzene (total benzene minus recovered
benzene) also increases, but its increase is small as
compared with the above. However, the same maxi-
mum value is reached at the same temperature as in
Fig. 3. This may be accounted for by the following
considerations:
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
211
1 — Zanetti and Egloff1 have shown that with in-
crease in temperature above 800° C. the formation
of tar from benzene increases at the expense of the
diphenyl. This explains why the yield of tar in-
creased at all, since the products of the reaction were
mainly diphenyl and tar.
2 — From Fig. 1 we see that the per cent of de-
composed benzene increases with the temperature and
becomes unity at 925° C, the temperature at
which maximum yield occurs. In other words, the
increase in tar formation is accompanied by an increase
in decomposed benzene which becomes the total ben-
zene at 925° C.
The variation of tar at once indicates an increase
in the yield of anthracene with increase in temperature.
This is well supported by the facts, as shown in Figs.
4 and 5. The formation of anthracene is negligible
below 850° C, but increases quite rapidly until 925° C,
and then drops sharply owing to the rapidly increasing
predominance of the carbonization reaction. Owing to
the striking similarity between Figs. 3 and 4 it
can be stated that the conditions which favor the for-
mation of tar also favor the synthesis of anthracene.
5 i-
Is
I -
1
/
\
/
\
1
^^,t
1
/
i
1
>
/
1
/
825 850 875 900 925 950 975 1000
Temperature °C.
At 925° C. the amount of diphenyl which distilled
over was much less than that obtained in the preceding
run, and the formation of carbon was similarly smaller
than that obtained in the following run. This would
seem to indicate that at the optimum temperature
the sum of the yields of diphenyl and carbon is a
minimum.
It is interesting to note that the increase in yield of
anthracene was not only due to the increased tar yield,
but also to the fact that the actual per cent of anthra-
cene in the tar increased with rise in temperature up
to 925° C. (Fig. 6). Moreover, it was noticed that
the reaction products varied from a light, red liquid
1 This Journal, 9 (1917), 350.
to a heavy, greenish brown, fluorescent oil, and finally
to a black, viscous tar. At 925° C, the tar had ac-
quired an appearance and viscosity that was very sim-
ilar to that of natural coke-oven tar.
There are numerous other compounds formed in
this reaction which have not been investigated but
which will form the subject of a further communication.
SUMMARY
1 — The formation of anthracene from ethylene and
benzene has been studied at temperatures varying
from 800° to 1000° C, and at atmospheric pressure.
2 — The optimum temperature has been found to
be 925° C. Above that temperature the formation
of carbon occurs very rapidly. This optimum seems
to be at the point at which the sum of the yields of
diphenyl and carbon is a minimum.
3 — Conditions favoring the formation of tar probably
affect the synthesis of anthracene similarly.
FERMENTATION PROCESS FOR THE PRODUCTION OF
ACETIC AND LACTIC ACIDS FROM CORNCOBS'
By E. B. Fred and W. H. Peterson
Departments or Agricultu ral Bacteriology and Agricultural Chrm
istrv. University of Wisconsin, Madison, Wisconsin
Received October 4, 1920
The commercial utilization of corncobs as a source
of organic acids is a possibility which deserves careful
investigation. When partially hydrolyzed and in-
oculated with certain bacteria, Lactobacillus pento-
aceticus n. sp., the extract of corncobs ferments readily
and yields almost equal quantities of acetic and lactic
acids. If the yields on a commercial scale should
prove equal to what has been obtained in the labora-
tory, it is estimated that every ton of corncobs would
be capable of yielding more than 300 lbs. of acetic
acid and about 320 lbs. of lactic acid. The develop-
ment of this process on a commercial scale would in-
volve numerous chemical and technological prob-
lems, but the possibility of producing chemicals in
this way was successfully accomplished during the
war; more than 5,000,000 lbs. of acetone were obtained
by a fermentation process.2 The organism, Lacto-
bacillus pentoacelicus n. sp., has certain characteristics
that make it especially suitable for a commercial pro-
cess. It grows fapidly, produces large amounts of
acid, and is able to compete successfully with other
organisms.3 Some idea of the possible value of corn-
cobs may be gathered from the fact that there are
produced in the United States alone more than 20,000,-
000 tons of corncobs annually. A small amount of
this material is used in the various stock feeds, but
in general the cobs are discarded or used for fuel.
In 1918 LaForge and Hudson4 pointed out that
adhesive gum, acetic acid, crystalline xylose, and
crystalline glucose could be obtained on hydrolysis of
corncobs with sulfuric acid under suitable conditions,
the yields of these different products constituting
1 Published with the permission of the Director of the Wisconsin Agri
cultural Experiment Station.
' J. Biol. Chem.. 41 (1920), 320.
9 Unpublished data.
This Journal. 10 (1918), 925.
212
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
approximately the following percentages of the weight
of the dry cobs:
Product Pbr cent
Adhesive gum 30
Crystalline xylose 5
Acetic acid 2.5 to 3
Crystalline glucose 37
In a later paper LaForge1 discussed in detail the
production and use of this adhesive and other products
obtained from corncobs. Hudson and Harding2 re-
ported a yield of from 10 to 12 per cent of crystalline
xylose from corncobs, instead of 5 per cent.
This higher yield obtained by Hudson and Harding
represents, however, less than half of the total xylose
content of the cobs. Stone3 obtained 22 per cent of
furfural, equivalent to 38 per cent of xylose from the
cobs which he used in the preparation of xylan and
xylose. The corncobs used in the experiments re-
ported in this paper gave on analysis 39 per cent of
furfural-yielding substances, calculated as xylose.
In their paper LaForge and Hudson pointed out
the difficulty of finding a direct use for xylose. In
a recent paper we have shown4 that xylose can be
readily fermented by certain bacteria with the pro-
duction of acetic and lactic acids. This fermentation
proceeds rapidly (10 to 12 days), and results in about
90 per cent of the xylose appearing as the above end
products. The fermentation closely approximates
the following theoretical equation:
Xylose Acetic Acid Lactic Acid
C6HI0O5 = " C*JL02 + C3H6Os ,
150 60 90
where the acetic acid comprises about 40 per cent of
the products and the lactic acid 60 per cent of the
products. In our work we obtained a ratio of about
43 per cent acetic acid to 57 per cent lactic acid.
If the fermentation of xylose is to be of value from
a commercial standpoint, it would be much more
profitable to ferment the xylose sirup directly rather
than the purified xylose. Moreover, the corncob
sirup contains a much larger amount of xylose than
can be obtained in the crystalline form. It was found
experimentally that the pentose-fermenting bacteria
would ferment the crude xylose sirup, yielding the
same products, acetic and lactic acids, as were ob-
tained by the fermentation of pure xylose.
FERMENTATION OF CORNCOB EXTRACTS
Several fermentation experiments were made with
the untreated corncobs and with hydrolyzed corn-
cobs. It was found that the unhydrolyzed corncobs
can be fermented directly, but the yield of acetic and
lactic acids is small — about 1 g. of each acid from
100 g. of cobs — in comparison with the amount secured
by fermenting the acid extract of the corncobs.
The hydrolysis of corncobs can be brought about
very readily, and results in a large amount of fer-
mentable sugar. The degree of acidity, the time re-
quired, and the quantity of sugar produced are given
in Table I. In every case the cobs were hydrolyzed
in an autoclave at 15 lbs. steam pressure or about
'CAern. Age, 28 (1920), 332.
» J. Am. Chem. Soc, 39 (1917). 1038.
' Ber., 23 (1890), 3796
« J. Biol. Chem., 39 (1919), 347.
Table I — Reducing Sugars Obtained prom Hydrolysis of Corncobs
Reducing
Extracting Sugars
Solution Time as Xylose
Materials Percent Minutes Percent'
Untreated cobs Water 90 2.9
Untreated cobs 0.5 Sulfuric Acid 10 7.7
Residue from water-extracted cobs. 2.0 Sulfuric Acid 10 10.3
Untreated cobs 2.0 Sulfuric Acid 20 19.6
Untreated cobs, first extract 2.0 Sulfuric Acid 60 24.5
Residue from first extract 2.0 Sulfuric Acid 120 12.0
Residue from second extract 2.0 Sulfuric Acid 120 2.4
Total for all 3 extractions ... 38.9
Untreated cobs 2.0 Sulfuric Acid 120 28.5
Untreated cobs 2.0 Sulfuric Acid 240 31.4
1 Air-dry basis.
121° C. An examination of the figures of this table
shows that, with 2.0 per cent sulfuric acid, from 25
to 30 per cent of xylose can be obtained from cobs by
heating for 1 to 2 hrs. Sirups prepared from the
concentrated solutions were diluted with yeast water
until the concentration of xylose was about 3.0 per cent.
These solutions were then inoculated with pure cul-
tures of bacteria and allowed to incubate for 2 wks.
or more at 30° C. At the end of "this time the cul-
tures were analyzed, with the results given in Table
II. It is clear that a very complete fermentation has
Table II — Fermentation of the Products of Hydrolyzed Corncobs
Sugar Volatile Nonvolatile Sugar Ratio of
Expressed Acid as Acid as Represented Acetic to
Culture as Xylose Acetic Lactic by Acids Lactic
Number Grams Grams Grams Per cent Acids
41-11 3.0 1.0962 1.4004 83 44:56
55-9 3.0 1.1484 1.4040 85 45:55
69-19 3.0 1.1032 1.3248 81 45:55
118-8 3.0 1.0944 1.3158 80 45:55
taken place, since more than 82 per cent of the sugar
is accounted for by the two products, acetic and lactic
acids. The extent of this fermentation is practically
equal to that obtained by us with crystalline xylose,
and clearly demonstrates the practicability of fer-
menting the sirup directly.
That the volatile and nonvolatile acids found are,
respectively, acetic and lactic is established by the
data in Table III, where the results of the analysis of
Table III — Analysis of Barium Salts of Acids Formed in Process of
Fermentation
Weight of
Barium Salt Weight of Barium Sulfate
Culture Taken Found Calculated
Number Kind of Acid Gram Gram Gram
41-11 Volatile 0.2890 0.2630 0.2640
55-9 Volatile 0.2428 0.2198 0.2229
41-11 Nonvolatile 0.2968 0.2152 0.2196
55-9 Nonvolatile 0.2496 0.1800 0.1847
the barium salts of these acids are given. In the case
of the two cultures examined the agreement between
the found and calculated values is very good. Since
it is evident that these organisms will ferment the acid
extract of corncobs with the production of acetic and
lactic acids, attention was directed to the maximum
amount of acids obtained from 100 g. of corncobs.
Three successive hydrolyses on the same material
were carried out. The first hydrolysis, in which 0.5
per cent sulfuric acid was used for 10 min., gave 2.2 g.
of sugar; the second with 2.0 per cent sulfuric acid for
1 hr. gave 18.5 g., and the third with the same con-
centration of acid and for the same length of time as
in the second hydrolysis gave 10.2 g. There was thus
obtained by the three hydrolyses a total of 30.9 g. of
sugar calculated as xylose. Culture media were made
up with yeast water so that the concentration of sugar
in the three cases was 1.76, 2.0, and 2.0 per cent, re-
Mar., 1921
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
213
spectively. The results obtained on analyzing the
fermented cultures are given in detail in Table IV.
Table IV — Fermentation of Successive Acid Extracts of Corncobs
(Products per 100 g. of Air-Dry Cobs)
Total Volatile Volatile Total Non- Nonvolatile
Acid as Acid from volatile Acid Acid from
Culture Extract Acetic Fermentation as Lactic Fermentation
Number Number Grams Grams Grams Grams
Control First 0.2100 .... 0.3600
118-8 First 1.0020 0.7920 1.2150 0.8550
Control Second 1 .9647 1 .5525
41-11 Second 8.9002 6.9355 9.8235 8.2710
118-8 Second 9.0021 7.0374 9.4738 7.9213
118-8 Second 9.1853 7.2206 10.1366 8.5841
Average 9.0292 7.0645 9.8113 8.2588
Control Third 1.0282 .... 0.6426
41-11 Third 4.6573 3.6291 5.4625 4.8195
118-8 Third 4.8838 3.8556
118-8 Third 4.8654 3.8373 5.2418 4.5992
Average 4.8022 3.7740 5.3520 4.7094
Total of Three
Extracts 14.8334 12.6315 16.3783 13.8232
The total acetic acid obtained is 14.8 g., of which
12.6 g. were produced by the pentose fermenters. In
the case of the lactic acid the total amount is 16.4 g.,
of which 13.8 g. result from fermentation processes.
Of the total sugar present, about 86 per cent is ac-
counted for by these two products. Analysis of the
fermented solutions shows only slight traces (0.1 to
0.2 g.) of unfermented xylose, and strengthens the evi-
dence for almost quantitative conversion of the sugar
into these two products.
Although this fermentation process has not yet been
tested on a large scale, it apparently offers a profitable
means of utilizing corncobs.
SUMMARY
Corncobs offer a promising raw material for the
commercial production of acetic acid and lactic acid.
These acids are obtained by fermenting a sirup made
from corncobs hydrolyzed with dilute sulfuric acid.
This hydrolysis is easily brought about and yields
from 30 to 40 per cent of xylose.
Crude xylose sirup is rapidly fermented by certain
microorganisms, for instance, Lactobacillus pentoacet-
icus n. sp., with the production of the above acids.
The fermentation is almost quantitative, since 85 to 90
per cent of the xylose can be accounted for by the two
acids.
During the month of January 1921, thirty-two chemical
concerns with an authorized capital of $50,000 or greater were
organized, with a total investment of $22,295,000. Three
concerns had an authorized capital of more than $1,000,000:
the Oselda Corporation, the American Chemical & Drug
Co., and Breinig Brothers, as compared with two companies
of such capitalization in December, two in November, and
one in October.
The following table shows the authorized capital of new
chemical, drug, and dye companies organized since 1915:
1915 $ 65,565,000
1916 99.314,000
1917 146, 160,000
1918 73,403,000
1919 112,173,000
1920 487,148.900
The New York Central Lines have made a series of tests on
corrosion of tie plates and the best method of reducing the amount
of corrosion. The tests have been made over a period of six
years on special steel, Bessemer steel, high carbon Bessemer
steel, open-hearth steel, pure iron, and malleable iron, and it has
been shown that the corrosion is least with a steel containing
0.25 per cent copper.
RECOVERING NEWSPRINT'-
By Charles Baskerville and Reston Stevenson
College of the City of New Yore, New York, N. Y.
The patent literature and a recent book3 on
waste paper recovery describe processes for de-inking
paper without discriminating between newsprint
stock and bookstock. The known processes which
give satisfactory results for bookstock are not neces-
sarily applicable to old newspapers, primarily on
account of the notable proportion of ground wood
present in newsprint stock.
This communication presents a process by which
the ink and binder and oil are removed from old
newspapers with minimum injury to the fiber, and
the pulp is furnished ready for use again for news-
print.
In our experiments we used a laboratory pulper with
electrically driven propeller, a wooden box with
brass gauze bottom as washer, a brass disk-maker
with brass gauze bottom, a book press, and air dry-
ing. This was according to the practice familiar to a
paper mill laboratory. The following conclusions
give the result of about seven hundred experiments.
When printed papers, e. g., old newspapers, are
mixed with water, and pulped and washed, the ink
is partly removed. The greater part of the ink re-
mains, because:
(i) The binder of the ink is not removed
(2) The carbon of the ink is entrapped in the pulp
(3) The carbon of the ink adheres to the pulp
A well-known method for bringing the binder into
solution or emulsion, or at least removing it from
the fiber, is to treat the pulped paper with a water
solution of an alkali. Too little alkali does not en-
tirely dissolve or emulsify the binder, nor does it
liberate completely the pigment of the ink; on the
other hand, too much alkali is harmful in that it
yellows wood pulp, which is a prominent constituent
in newspaper stock. Also, too excessive alkali tends
to mercerize the fiber, and too much alkali makes
the carbon remain in the pulp in such a condition
that it does not wash out.
We have determined that 60 lbs. of caustic soda
per ton of old newspapers is the optimum concentra-
tion of alkali. We have found that 200 lbs. of soda
ash per ton of old newspapers gives as good, if not
better, results, especially in regard to the yellowing
of the paper. The soda ash is much more easily
handled. „
The use of alkali alone is not sufficient to liberate
the ink so that it can be washed away. We have
worked out a method which completely frees the
pulp from the ink, binder, oil, and pigment. It con-
sists essentially in the addition to the alkaline solu-
tion of American fuller's earth, which remains in
suspension or in colloidal solution. We have found
that approximately 100 lbs. of this earth to a ton
1 Presented before the Division of Industrial and Engineering Chem-
istry at the 60th Meeting of the American Chemical Society, Chicago,
111., September 6 to 10, 1920.
3 Patent applied for.
3 Strachan, "The Recovery and Re-manufacture of Waste Paper,"
The Albany Press, Aberdeen, 1918.
214
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
of old newspapers is sufficient, but if used in greater
proportion, the effect is slightly better.
The effect of the suspended material appears to
be a double one: it removes the oils of the binder,
and it attracts the carbon away from the pulp and
holds it. Upon subsequent washing with water the
pulp may be retained by a gauze or screen, and the
minute particles of suspended material which hold
the finely dispersed carbon and some oil are washed
away.
The best temperature for the procedure is about
50° C. The less the concentration of the pulp, while
the ratio of chemicals to old papers remains constant,
the greater is the de-inking effect. For practical
reasons, a pulp is rarely less than 2 per cent. The
alkali and suspended material should be placed in
the pulping machine with the water and heated to
500 C. before the addition of the old newspapers.
The paper must be perfectly pulped, which may be
accomplished by various machines within a period of
less than one hour. The pulp must be thoroughly
washed, requiring about one-fourth less water than
for bookstock.
The resulting product is free from carbon and oil,
and has only a faint yellow coloration. It is ready
for immediate use for making newspaper.
The product obtained described in the last para-
graph may be bleached by treatment with a solution
of sulfur dioxide, which gives a product as white, if
not whiter, than the original unprinted paper. In
practice the bleaching has been accomplished in 15
min. by the use of 20 lbs. of sulfur dioxide in cold
water, per ton of old papers.
The United States Civil Service Commission has announced
examinations for metallurgists at $3000 to $3600 per year and
assistant metallurgists at $2000 to $3000 per year, to fill vacan-
cies in the Bureau of Mines at Pittsburgh, Pa., and elsewhere.
Candidates will be rated on (1) education, training and expe-
rience, and (2) writings (to be filed with the application). Appli-
cations will be received until the hour of closing business on
April 5, 1921.
An examination has also been announced for laboratory as-
sistants to fill vacancies in the Bureau of Standards at $1200
to $1380 per year. Competitors will be rated in the following
optional subjects: advanced general physics, electrical engineer-
ing, civil and mechanical engineering, chemical engineering,
paper technology, textile technology, ceramics, physical metal-
lurgy, physics, and chemistry, and w7ill be rated on (1) elemen-
tary physics, chemistry, and mathematics, (2) optional subjects,
and (6) general education, experience, and fitness. Applications
will be received until further notice.
Examinations will also be given for laboratory assistant,
junior grade, at $1000, and senior aid at $900, to fill vacancies
in the Bureau of Standards. Competitors will be rated on (1)
physics and chemistry, (2) mathematics, (3) mechanical draw-
ing, and (4) general education and experience. Applications
will be received until further notice.
Examinations have also been announced for microanalysis
to fill vacancies in the Bureau of Chemistry at $1200 to $1800
a year. Competitors will be rated on (1) education, training,
and experience, and (2) thesis, reports or publications to be filed
with application. Applications must be filed with the Civil
Service Commission, Washington, D. C, by the hour of closing
business on March 1">. 1921.
REGENERATING BOOKSTOCK1
By Charles Baskerville and CM. Joyce
College of the City of New York, New York, N. Y.
The enormously increasing output of magazine.--
and trade journals, and a somewhat less large, but
growing, production of books have created greater
demands for book and magazine paper, which herein
is collectively designated "bookstock."
With the exception of the cheaper grades of maga-
zines, sulfite, soda, or sulfate pulp constitutes the
larger portion of the cellulosic basis of the paper used.
Some mechanical pulp is used in the cheap grades
of magazines and light reading matter. Bookstock
carries more or less filler and sizing, very variable in
character and quantity. Other cellulose fibers, cot-
ton, linen rags, esparto, etc., enter into book paper,
which may become a part of an assemblage of waste
paper. Inks of various compositions and colors have
been used on the collected waste.
The economies involved in "Recovery and Re
manufacture of Waste Paper"2 are interestingly
brought out by Strachan, although he does not deal
with an important phase of the subject particularly
of concern in the United States. The reworking of
waste paper for the manufacture of box-board, roof-
ing, etc., has developed to a considerable industry in
the United States, and the demand for such promises
increasing growth. A marked differential for box-
board, of immaterial color, and sheets for printing
will undoubtedly always obtain, but whether it will
economically carry the burden of regeneration is a
question debated, but as yet unsettled, for a genera!
policy in national conservation by some of the largest
paper producers in this country. However, at this
particular time and for some years to come, the re-
generation of bookstock means conservation and
profit.
Various processes, either mechanical or chemicai
in nature, or both, have been proposed for special
papers (photographic, waxed, etc.) and some of them
are in practical use to a limited extent. Many of the
processes, when tried on a commercial scale with the
general run of waste paper, fail to give the superior
pulp desired for book paper. The failure is due in
some instances to the fact that in the mechanical
pulping of the stock the ink pigments are driven
into the fibers, necessitating drastic treatment for
separation, which shortens and weakens the fibers,
as well as incurring (uneconomical) losses in washing
the pulp. To secure the best results mechanically,
the fibers require to be loosened and then drawn,
not torn, from the matte. Devices have been con-
structed to meet the mechanical difficulty, but they
involve time and power factors with mounting costs
of operation.
Normally bookstock is a cellulosic fiber which has
had severe chemical treatment. On the principle
that the binder of printing ink was a saponifiable oil,
caustic solutions have been and are used to "lift" the
1 Presented before the Division of Industrial and Engineering Chem-
istry at the 60th Meeting of the American Chemical Society, Chicago
111., September 6 to 10, 1920.
« James Strachan, 1918.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
!15
pigment from the fiber, which, if ground wood pulp
be absent, and if the concentration of the caustic be
regulated, and if the temperature be not too high,
serves to remove a large proportion of carbon ink.
Too great a concentration may bring about some
mercerization. More weakly alkaline solutions, for
example, sodium silicate, sodium phosphate, borax,
soap, etc., also lift the ink in part and do little damage
to the fiber. However, the detergent effect calls for
scouring or rubbing, which so embeds the carbon in
the fiber as to make it almost impossible to separate
the two.
Certain solvents, as kerosene or gasoline, tend to
loosen the ink by dissolving the binder. This may
be combined with an alkaline solution, for example,
a borax or a soap solution. During agitation the
suds or skim, which forms on the surface of the water
and entangles the carbon particles, may be washed
away.
Rosin is extensively used as a filler and binder for
the fibers of the paper, which have a "surface." As
mentioned, some of the cheaper magazine papers
contain wood pulp, which retains natural gums and
resins. They serve in part as binders for the ink
pigments. Pine oil is one of the normal solvents for
rosin, gums, and resins, so its addition to the old
printed matter helps materially to lift the ink.
In practice in reclaiming bookstock, we have there-
fore used borax (10 lbs.), soap (10 lbs.), kerosene (2
gal.), and pine oil (2 gal.) to 2000 lbs. of bookstock
in water to make a 3 to 6 per cent pulp. The stock
is soaked and gently pulled apart in a beater or other
device, thus reducing the mechanical injury to the
fibers to the minimum. Time is saved by heating
the mixture up to 75° to 90° C. by introducing live
steam. After pulping, which requires one hour or
less, depending upon the machine used, the ink and
chemicals are washed away by one of several well-
known washers. The pulp may then be bleached or
tinted as desired. A selected combination of the
chemicals may be used instead of all four with se-
lected lots of waste paper when the composition (in-
cluding ink and the binder) is known.
A superior product of desired strength, length of
liber and cleanliness has been obtained by the process.1
The City of New York, through the Board of Education and
Bureau of Vocational Activities, has established a textile school
under the direction of William H. Dooley, who has had con-
siderable experience in the textile industry and in the establish-
ment of similar schools in other cities. Day courses extending
over two years are offered in marketing of textiles, costume
design, general textiles, applied textile design, chemistry and
dyeing, textile manufacturing and engineering, and knitting
and sweater course. Evening courses open only to those engaged
in the trade include woolens and worsteds, cotton converting,
general cotton, textile chemistry, experimental dyeing, loom-
fixing, fabric analysis, costume design, draping costume design,
garment design, operating sweater and knitting machinery,
general knitting, and applied textile design. A complete experi-
mental dye laboratory has been donated by H. A. Metz & Co.
U. S. Patent, 1,351,092.
A NEW CRYSTALLINE FORM OF POTASSIUM
CHLORATE'
By E. R. Wolcott
Laboratories of Western Precipitation Co., Los Angeles, California
Received December 13, 1920
Crystals of potassium chlorate having along, fibrous,
silky appearance, as distinguished from the plates
of the ordinary form, have been prepared by dissolving
the latter in water and adding thereto an aqueous
solution of hydrocarbons such as is obtained by treat-
ing crude petroleum (California) with concentrated
sulfuric acid and slowly concentrating this mixture
as on a water bath, until the potassium chlorate crys-
tallizes out. In the presence of an excess of the water-
soluble hydrocarbon, the potassium chlorate appears
in the form of long silky fibers, as shown in the ac-
companying illustration. These crystals do not always
separate out in parallel groups as shown, but may,
under certain conditions, separate out radially from
various nuclei.
The crystalline form of these crystals has been in-
vestigated by Dr. E. T. Wherry, who reported as
follows:
The essential optical properties of these crystals are in every
respect identical with those of a typical commercial sample
("analyzed reagent") of the salt. The refractive indices are:
a, 1.440; ft 1.515; y, 1.525, making the double refraction 0.080.
The optical axial angle 2 E is 45°, and the sign negative. The
same exact numerical values are given by both samples. The
two substances must, therefore, be identical, in so far as crystal
system is concerned, and the difference lies merely in the habit
of relative development of different forms. Ordinary potassjum
chlorate is crystallized tabular parallel to the base, c, 001,
the plates being bounded chiefly by faces of a prism, m, 110.
In parallel polarized light, nicols crossed, the extinction angle
of such crystals, with reference to this prism, is 38°; with refer-
ence to the faces of a side dome sometimes present, the extinc-
tion angle is parallel (straight). The sample in question shows,
however, long rod-shaped crystals, most of them with an ex-
1 Published by permission of the National Research Council.
These crystals were first produced in the laboratory of the Western
Precipitation Company, Los Angeles, Cal. Production and tests were con-
tinued under the direction of Dr. Charles E. Munroe, chairman of the
Committee of Explosives Investigations of the National Research Council.
216
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
tinction angle of 42°. Consideration of the optical orientation,
which is: obtuse bisectrix = axis b and acute bisectrix emerges
through the base, making an angle of about 60° with the vertical
crystallographic axis c; this leads to the conclusion that these
crystals are elongated parallel to the prism m, i. e., that the
habit is prismatic (instead of tabular, as more usual).
The following is a specific example of the method
of procedure in obtaining these crystals:
Equal parts of California crude oil, about 20° Be\,
and fuming sulfuric acid were mixed and agitated for
1 hr., the acid being preferably added gradually so
as not to heat the mixture above room temperature.
The mixture was then allowed to stand for several
hours, until a solid tar-like material had separated
out on top, the residual acid being in the bottom of
the beaker. This acid, which amounted to about one-
third the total bulk, was drawn off, and the tar-like
material (probably due to the sulfonation of the un-
saturated hydrocarbons of the oil) was then dissolved
in hot water to form a solution of specific gravity
1.066, or about 6 per cent strength.
To a saturated solution of 200 g. of ordinary po-
tassium chlorate were added 10 cc. of the above
solution of water-soluble hydrocarbon, and the whole
diluted with water to a volume of 800 cc. The solu-
tion was brought to a boil, filtered, and the filtrate
allowed to crystallize. The resulting crystals were
removed from the mother liquor, dried, redissolved
in water, and recrystallized.
As will be apparent, the amount of this water-
soluble hydrocarbon compound in the above example
is very small, being less than one-third of one per cent
of the amount of the original chlorate present. Even
smaller amounts may be used to produce a like result.
In some cases, particularly when concentration is
effected by boiling the solution, some oxidation of the
hydrocarbon occurs, and then more of the latter is
necessary to alter the habit of crystallization.
The above procedure may be widely varied. Thus,
for the manufacture of the water-soluble hydrocarbons,
instead of fuming sulfuric acid, concentrated sulfuric
acid or liquid sulfur dioxide may be used, the amount
of acid needed varying through wide limits, as does
the temperature at which the reaction may be effected.
The tests have shown that all grades of California
oil, from the residuum of topping plants to the very
light oils found in some fields, may be used to pro-
duce the soluble hydrocarbons above referred to.
These crystals were also produced from neutral solu-
tions of the soluble hydrocarbons, as when neutralized
by caustic soda or ammonia.
Various stages in the transformation of the crystals
from plates to fibers have been obtained by using an
insufficient amount of the hydrocarbon, or some which
had been partially oxidized.
Preliminary tests of these crystals as to explosion
by friction were made by grinding them with sulfur in
a wooden mortar with a wooden pestle, and the results
seemed to indicate less sensitiveness, but further tests
made with the frictional pendulum at the Bureau of
Alines showed no essential difference under standard
conditions. It is possible, however, that these crystals
might be better adapted to being coated with a pro-
tecting film, which would make them less sensitive.
It was originally planned to use the water-soluble
hydrocarbon for this purpose. However, the tests
were discontinued at the signing of the armistice, and
these possibilities were not investigated.
A TEST FOR ANNATTO IN FATS AND OILS1
By W. Brinsmaid
Illinois Department of Agriculture, 1410 Kimball Bldg.,
Chicago, Illinois
The usual test for annatto in butter, oleomargarine,
and other fatty foods, in which the clarified fats are
mixed with sodium hydroxide solution, the mix-
ture of the two allowed to pass through filter paper,
and the dried paper tested for annatto with stannous
chloride solution, is somewhat unsatisfactory. This is
due to the fact that the paper becomes saturated with
the fat and oftentimes so large an amount of fat re-
mains in the paper that the sodium hydroxide solution
with the annatto does not get an opportunity to come
in contact with greaseless paper fiber so that it may
be properly absorbed. Consequently, when the stan-
nous chloride solution is dropped on the dry filter
paper, the pink color is oftentimes faint or obscure,
even when there is plenty of annatto present in the
sample to give a positive test.
The above test being at times quite unsatisfactory,
the writer tried some modifications in the endeavor
to render it more positive and consequently more satis-
factory. The method described below has been in
use for some time, and has proved quite satisfactory
for the identification of annatto in butter, oleomar-
garine, cream, ice cream, and some other food ma-
terials. The procedure is quite simple and does not
consume much time or material. The annatto is
removed from the fat, and subsequent manipulation is
free from the general messiness of oil and fat deter-
minations. Small amounts of annatto that might
easily escape identification by the older method are
easily and positively identified.
METHOD
Have ready some paper pulp made by disintegrate
ing a fair grade of filter paper in water. The ordinary
grade of Munktell Swedish paper answers very well-
Too coarse a paper makes a lumpy pulp.
Prepare a solution of sodium hydroxide by dissolv-
ing 5 g- of sodium hydroxide in 95 cc. of water.
Prepare a stannous chloride solution as follows:
Saturate concentrated hydrochloric acid with tin, di-
lute with an equal volume of water, and from time to-
time add a slight excess of acid. Keep pieces of tin
in the reagent bottle.2
In a large test tube holding at least 60 cc. place
15 cc. of the melted and filtered fat, free from moisture,
salt, and curd. Add to the fat 1 5 cc. of chloroform and
mix well. Add 15 cc. sodium hydroxide solution,
cork the test tube, and shake thoroughly for a few
1 Presented by title before the Division of Agricultural and Food
Chemistry at the 60th Meeting of the American Chemical Society, Chicago,.
111., September 6 to 10, 1920.
2 Leach, "Food Inspection and Analysis," 3rd Edition, p. 32.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
217
moments. The cork must be held tightly in the test
tube while shaking.
Remove the cork and immerse the tube nearly its
full length in a bath of water at 50 ° to 60 ° C.
Allow the tube to remain in the hot water until
the emulsion is pretty well broken up or until no fat
drops can be seen dropping from the bottom of the
soap froth when the tube is given a slight shake. If
there is a large amount of annatto present it will not
all be in the soap froth, though there will be plenty
for a test.
Remove the soap froth from the tube to a small
beaker with a spatula or small spoon, add 10 cc. of
water and 2 cc. of the sodium hydroxide solution.
Then add enough of the paper pulp to make a thin
felt in a Gooch crucible. Let stand on the steam bath
for about one-half hour with frequent stirring and the
annatto will be absorbed by the paper pulp. If the
quantity of annatto is small, it is well to leave the
beaker on the steam bath until the liquid has concen-
trated to about one-third its original volume. In this
way a more positive test is obtained with a small
quantity of annatto.
Filter with light suction on a Gooch crucible contain-
ing a small disk of filter paper. When the liquid has
passed through, if annatto is present, the paper pulp
will have an orange color. At once drop a few drops
of stannous chloride solution on the paper and again
suck dry. If annatto is present the paper pulp will
be colored pink. Reverse the crucible and blow the
felt out in the palm of the hand. The mat may then
be dried if it is to be preserved. In case the available
sample is small the quantities used in the test may be
reduced.
One author recommends 5 per cent citric acid in
place of stannous chloride and this was found to work
well.1 Boric, tartaric, acelic, sulfuric, hydrochloric,
and nitric acids of from 3 to 5 per cent also give satis-
factory results. Even so dilute an acid as that ob-
tained by blowing one's breath through water for a
few minutes may be used, but its action is slower
than with stronger acids. The stannous chloride solu-
tion, however, gives better results than anything else
tried.
There is an aqueous solution of annatto on the mar-
ket that is used by ice cream manufacturers. A few
drops of this may be added to 15 cc. of colorless oleo-
margarine freed from moisture, salt, and curd, and the
test run as described. We have used the test in this
way on some food materials after extracting the an-
natto from the bulk of the material.
An easier way to handle an aqueous solution of
annatto is to dilute the solution and make slightly
acid with hydrochloric acid. The annatto will pre-
cipitate in a form resembling ferric hydroxide. Filter
this on a soft Munktell paper about the size of a silver
dollar. Wash once with water and place paper and
precipitate in a small beaker with 10 cc. of water and
2 cc. of the sodium hydroxide solution, and proceed
as usual. The small filter paper can be disintegrated
1 Bolton and Rev-is. "Fatty Foods, Their Practical Examination," p. 113.
with the help of a glass rod and will furnish the neces-
sary paper pulp.
After the soap froth has been removed from a butter
or oleomargarine determination it will sometimes be
noticed that the sodium hydroxide layer over the
chloroform-fat mixture still has a deep color. This
is the case when the annatto is present in large amounts.
If desired, this sodium hydroxide layer may be pipetted
off and annatto tested for as in an aqueous solution.
The acidification of the solution should be carefully
done and the solution placed on the water bath so
that the fine precipitate may collect. It will then
filter quite easily.
BENZYL SUCCINATE: PRELIMINARY REPORT ON ITS
COMPOSITION, MANUFACTURE, PROPERTIES, AND
PROBABLE THERAPEUTIC USES'
By Mortimer Bye
Scientific Laboratories, Frederick Stearns & Co., Detroit, Michigan
The extremely important pharmacological studies
of Macht have recently led to the clinical application
of benzyl esters — especially benzyl benzoate — in the
treatment of cases of excessive peristalsis, or excessive
spasm of smooth muscle, with surprisingly gratifying
results. However, certain objections to the use of
benzyl benzoate have arisen which make desirable
the finding of less objectionable substitutes. The
benzoate is a fluid of disagreeable taste and odor,
practically insoluble in water. It is highly objection-
able to most patients, and cannot be tolerated by
some. By the mouth, it must be administered in a
flavored solution of alcohol, or as a flavored emulsion.
It may cause vomiting, or may develop severe gastric
disturbances if used in large amounts or over a con-
siderable period of time. Gelatin capsules contain-
ing the benzoate dissolved in oil are also given, but are
open to one or more of the preceding objections.
With these facts in mind, and being especially in-
terested in the production of various compounds of
succinic acid, the writer was prompted to take up the
study of benzyl succinate.
This substance was prepared, with certain modifica-
tions, according to the method of Bischoff and von
Hedenstrom, by heating succinic acid with benzyl
alcohol. The succinate was obtained in the form of
beautiful snow-white crystals, with a very slight aro-
matic "benzyl" taste, and with practically no odor.
The percentage of benzyl group in benzyl succinate is
61.0S, or considerably greater than that present in
benzyl benzoate (42.89 per cent).
Investigations so far show that benzyl succinate
may be administered by the mouth in powdered, tablet,
or capsule form, without fear of nausea or other in-
testinal disturbances, even when given in large doses
or over considerable periods of time.
Exhaustive preliminary experiments have demon-
strated that this product is practically nontoxic.
Guinea pigs inoculated subcutaneously with as much
as 4 cc. of a 12. 5 per cent alcoholic solution of benzyl
succinate became perfectly normal after several
1 Presented before the Division of Medicinal Products Chemistry
at the 60th Meeting of the American Chemical Society, Chicago, 111.,
September 6 to 10, 1920.
21 S
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
hours of lassitude. A rabbit weighing about 2 kg.
was fed 2 g. of the pure product in a bread paste and
24 hrs. later received a subcutaneous injection of 6
cc. of 12.5 per cent alcoholic solution of the drug.
Beyond a sedative action, this high dosage of the
benzyl succinate had no apparent effect. The animal
was kept under observation for 2 wks. and developed
no untoward symptoms.
Feeding tests upon guinea pigs and rabbits have
demonstrated the surprising fact that a guinea pig
may eat at least 10 g. of benzyl succinate per kilogram
of body weight without harm and that rabbits may
eat at least 6 g. per kilogram of body weight and show
no bad results. Comparative subcutaneous injec-
tions of the benzyl succinate and the benzyl benzoate
show the former to be less toxic than the latter, and
inasmuch as the benzyl group — which is recognized
as the significant groups-makes up a far greater por-
tion of the molecule, the succinate should prove to
be a valuable therapeutic agent.
B}' analogy, for any condition where benzyl benzoate
is indicated, benzyl succinate should prove applica-
ble, with the added advantages of ease of administra-
tion, safety of retention, freedom from nausea and
after-intestinal disturbances, and greater benzyl
strength.
Many clinical cases are proving the truth of the above
statement daily. The writer has compiled a number
of such cases which it is hoped will prove the basis
of a future paper on the subject.
ATROPINE SULFATE FROM DATURA STRAMONIUM1
By H. W. Rhodehamel and E. H. Stuart
Research Department Eli Lilly & Co., Indianapolis, Indiana
Datura stramonium, commonly known as Jimson
weed, grows in almost all parts of the United States
and Europe.
Atropine was first isolated from this plant in 1833
by Geiger and Hesse,2 but hyoscyamine is the chief
alkaloidal constituent. The latter is isomeric with
atropine, and is converted into it during the process
of extraction and purification. The percentage of
total alkaloids varies from 0.15 to 0.6 per cent in the
dried plant, the variation depending mainly on the
age and vigor of growth of the piant. The moisture
content of- the whole plant is from 75 to 85 per cent.
Assays made of the plant in flower showed the dis-
tribution of alkaloid to be as follows:
Per cent
Stems below the first fork 0.054
Stems above the first fork 0.069
Seed pods without seeds 0.054
Seeds 0.45
Leaves 0.414
The comparatively small amount of alkaloids oc-
curring in Datura stramonium made their commercial
extraction impracticable until the discovery in 1913
by J. U. Lloyd that under certain conditions fuller's
earth would adsorb alkaloids from dilute solutions of
1 Presented before the Division of Medicinal Products Chemistry
at the 60th Meeting of the American Chemical Society, Chicago, III.,
September 6 to 13, 1920.
" Ann.. 5. 43; 6, 44; 7, 269
their salts. The entire green plant was ground, per-
colated with acidulated water, and to the percolate
Lloyd's reagent was added. After drying, the Lloyd's
reagent contained by assay from 2 to 2.5 per cent
alkaloidal material. In this manner a considerable
concentration of the alkaloids was effected.
COMMERCIAL EXTRACTION OF THE ALKALOID
The stramonium plant was harvested from about
the middle of July to the first hard frost, which usually
occurred during October. The entire plant, except
the roots, was ground in the green state, packed in
large wooden tanks, and percolated with water con-
taining 0.2 per cent sulfuric acid and 0.5 per cent
formaldehyde. Maceration was allowed to continue 3
days, and the rate of percolation controlled so that about
300 gal. each day were obtained from a 4000-gal. tank.
Fifteen hundred gallons of the dilute atropine sulfate
solution were treated at one time with Lloyd's re-
agent. The minimum amount of the latter necessary
for maximum adsorption was controlled by assay of
the percolate prior to its addition. To insure adequate
agitation, air was blown into the mixture for about
20 min. It required about 12 to 14 hrs. for the Lloyd's
reagent to settle, after which the exhausted percolate
was decanted, and the precipitate drained and thor-
oughly dried at a temperature of about 50° C.
Percentage
Alkaloidal Alkaloidal of Total Lloyd's
Percolate Material Materia] Alkaloidal Reagent
Collected per 100 Cc. in Percolate Material Added
Portion Gallons Grams Pounds Removed Pounds
Tank 1'
1 1266 0.0123 1.30 10.75 60
2 1500 0.0107 1.34 11.08 60
3 1500 0.0075 0.94 7.77 45
4 1500 0.0042 0.53 4.38 20
Total 4.11 33.98 185
Assay of extracted drug gave 0.07 per cent alkaloid.
Tank 2'
1 1600 0.03676 4.91 59.28 230
2 900 0.0319 2.40 28.98 110
3 1500 0.0028 0.35 4.23 16
4 950 0.0006 0.05 0.57 3
Total 7.71 93.06 359
Assay of extracted drug gave 0.024 per cent alkaloid.
Tank J'
1 1500 0.0251 3.14 25.99 150
2 1500 0.0143 1.79 14.81 90
3 1500 0.0071 0.89 7.35 45
4 1500 0.0018 0.23 1.36 12
Total 6.05 50.01 297
Assay of extracted drug gave 0.054 per cent alkaloid.
Average Percentage of
No. of Tanks Packed in Alkaloid Present
10 Tuly 40.69
11 August 69.03
8 September 58.89
7 October 39 . 02
Average for the year 51.9 per cent
1 Packed July 15 with 26,000 lbs. of green stramonium. Moisture
85 per cent. Assay of dried sample gave 0.31 per cent alkaloidal material
From the assay the tank contained 12.09 lbs alkaloidal material.
2 Packed August 23 with 15,500 lbs. of green stramonium. Moisture
85 per cent. Assay of dried sample gave 0.356 per cent alkaloidal material
From the assay the tank contained 8.28 lbs. alkaloidal material.
3 Packed October 4 with 26,000 lbs. of green stramonium. Moisture
85 per cent. Assay of dried sample gave 0.31 per cent alkaloidal material
From the assay the tank contained 12.09 lbs alkaloidal material.
Results obtained on a great number of tanks would
be of no especial interest. The percolation records of
three tanks have therefore been selected to show, first,
the poor adsorption obtained when using young drug
harvested in July; second, the best adsorption from
August drug; and third, the decrease in adsorption in
October drug.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
219
DETERMINATION OF ADSORBED ALKALOID
The adsorbed alkaloidal material was determined
as follows: Two grams of the Lloyd's reagent con-
taining the alkaloid were placed in a glass-stoppered
bottle, and 40 cc. ether and 3 to 5 cc. 16 per cent ammonia
water were added. The contents were thoroughly-
agitated, and after settling the ether was decanted.
The ether extraction was repeated six times, and the ex-
tracts combined, filtered, and evaporated to dryness.
Ten cc. 0.05 N sulfuric acid were added, and the ex-
cess acid titrated with 0.02 N sodium hydroxide solu-
tion, using cochineal as the indicator.
Determination of the alkaloid remaining in the
Lloyd's reagent after extraction was made in the same
way, except that a larger sample was used. The
reagent after extraction always contained about 0.2
per cent alkaloidal material which coitld not be eco-
nomically removed.
Percentage
Per- Alkaloidal Alkaloidal of Total Lloyd's
colate Material Material in Alkaloidal Reagent
Gal- per 100 Cc. Percolate Material Added
Portion Ions Grams Pounds Removed Pounds
Barrel i1
1 36 0.01721 0.0517 41.87 2.6
2 36 0.0085 0.0255 20.68 1.3
3 36 0.0046 0.0138 11.18 0.7
Total 0.0910 73.73 4.6
Assay of exhausted drug gave 0 02 per cent alkaloid. 4,6 lbs. Lloyd's
reagent recovered. Assay 1.99 per cent. 74.09 per cent of the alkaloidal
material was removed by the Lloyd's reagent.
Barrel 2'
1 36 0.01336 0.0401 32.50 2.0
2 36 0.0087 0.0261 21.16 1.3
-3 36 0.0060 0.0180 14.60 0.9
ToTAI. 0.0842 68.26 4.2
Assay of exhausted drug gave 0.048 per cent alkaloid. 4.2 lbs. Lloyd's
reagent recovered. Assay 1.97 per cent. 67.00 per cent of the alkaloidal
material was removed by the Lloyd's reagent.
Barrel 33
1 36 0.0148 0.0445 36.05 2.25
2 36 0.0077 0.0231 18.73 1.15
3 36 0.0028 0.0084 6.81 0.4
Total 0.0760 61.59 3.8
Assay of exhausted drug gave 0.036 per cent alkaloid. 3.9 lbs. Lloyd's
-eagent recovered. Assay 2.05 per cent. 64.74 per cent of the alkaloidal
material was removed by the Lloyd's reagent.
Barrel 4>
1 36 0.0127 0.0381 30.89 1.9
2 36 0.0048 0.0144 11.68 0.72
3 36 0.0034 0.0102 8.27 0.80
Total 0.0672 50.84 3.12
Assay of exhausted drug gave 0.032 per cent alkaloid. 3.25 lbs.
Lloyd's reagent recovered. Assay 1.97 per cent. 51.84 per cent of the
alkaloidal material was removed by the Lloyd's reagent.
1 The menstruum was water containing 25 g. of bleaching powder and
10 cc. of sulfuric acid per gallon.
2 The menstruum was water containing 8 cc. of cresol and 7 cc. of
sulfuric acid per gallon.
3 The menstruum was water containing 30 cc. of 40 per cent solution
of sodium bisulfite and 10 cc. sulfuric acid per gallon.
* The menstruum was water containing 18 cc. formaldehyde solution
ind 7 cc. sulfuric acid per gallon.
Differences in age of the plant and condition in
growth caused some variations in the extraction of
the alkaloidal material. The plants harvested in July
were about 2 ft. high and just beginning to flower.
The alkaloidal content of the young plants was 0.1
per cent higher than those gathered in August, and
considering this, the July plants should have yielded
more atropine per pound of drug than did the August
plants. This, however, was not the case. Taking
into consideration the amount of alkaloid obtained
and the amount actually present in the plant, the
average yield for July was 28.5 per cent lower than
that obtained in August. Since the drug after ex-
traction showed only negligible amounts of alkaloid,
it was assumed that a considerable proportion of
alkaloid was decomposed during percolation. Exam-
ination of the exhausted drug showed no evidence of
decomposition resulting from bacteria or molds. Pos-
sibly the loss was due to an enzymic action, although
this point was not gone into.
A considerable number of small experiments were
made with the attempt to increase the yield of alka-
loid. A menstruum containing acetic hydrochloric
or sulfuric acid in various concentrations gave no bet-
ter results and showed no marked difference. Some-
what better results were obtained, however, when
other preservatives were substituted for the formalde-
hyde. Results on four of these experiments are given
below. With the usual formaldehyde preservative
50.84 per cent of the total alkaloidal material was
extracted; with sodium bisulfite as the preservative
61.59 per cent; with cresol 68.26 per cent; with bleach-
ing powder 73.73 per cent.
A number of barrels were packed September 20
with green stramonium, each containing 260 lbs.
Moisture 80.8 per cent. Assay of dried sample gave
0.24 per cent alkaloidal material. Accordingly, the
drug in each barrel contained 0.1235 lb. of alkaloidal
material. Percolated at the rate of 12 gal. per day.
EXTRACTION OF THE ALKALOID FROM LLOYD'S REAGENT
In a general way the alkaloidal material was ob-
tained from the Lloyd's reagent by first adding
water, then making the mixture alkaline, and sub-
sequently extracting with an organic solvent. It was
very essential to make the mixture alkaline with a
base that would not decompose the alkaloid. Am-
monia and lime water were found to be the best for
this purpose. Three methods were used for the ex-
traction. First, ammonia water and ether; second,
lime water and ether; and third, lime and alcohol.
The extractions were made in a revolving drum.
method 1 — To 300 lbs. of Lloyd's reagent containing
the alkaloid, 35 gal. of 16 per cent ammonia were added.
This gave a rather thick paste, and on revolving the
drum the material was carried part way up the sides,
then fell back, and in this way was thoroughly mixed
with the ether. Each extraction was continued for
45 min. The results were as follows:
Alkaloidal
Ether Material
Used Removed
Extraction Gal Oz.
1 200 13.5
2 130 7.1
3 120 9.4
4 120 8.2
5 1 20 5.3
6 150 8.0
7 140 6.1
8 12(1 4.9
9 120 4.1
10 120 3.8
An assay of the extracted Lloyd's reagent gave 0.45
per cent alkaloid, showing that 22.5 per cent of the
alkaloidal material still remained in it.
method 2 — Same as Method 1, except that in place
of 16 per cent NH3 40 lbs. of CaO in 35 gal. of water
were added.
An assay of the extracted Lloyd's reagent gave 0.29
per cent alkaloid, showing that 13 per cent of the
alkaloidal material still remained in it.
220
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
Alkaloidal
Ether Material
Used Removed
Extraction Gal. Oz.
1 160 14.22
2 140 9.41
3 145 8.62
4 160 7.66
5 150 5.80
6 150 5.80
7 150 5.44
8 150 2.89
9 150 5.33
10 150 4.41
method 3 — To 300 lbs. Lloyd's reagent (assay 2.36
per cent) 40 lbs. CaO were added and the mixture ex-
tracted for about 3 hrs. with the following volumes of
80 per cent alcohol:
80 Per cent Alkaloidal
Alcohol Used Material Removed
Gal. Oz.
175 45.44
150 17.61
150 13.68
150 8.92
150 7.42
An assay of the extracted Lloyd's reagent gave 0.18
per cent alkaloid, showing that 7.6 per cent of the
alkaloidal material still remained in it.
The following is of interest in connection with the
alcohol extraction of the alkaloidal material from
Lloyd's reagent.
A mixture of 10 g. of Lloyd's reagent with 1.3 g. of
slaked lime was extracted for 14 hrs. with 50 cc. of
alcohol of the following strengths:
Alkaloidal
Strength of Alcohol Material Removed
Per cent . Per cent
100 0.00
90 25.42
80 41.25
70 41.25
60 33.82
50 23.50
The volume of 80 per cent alcohol was varied as
follows:
Alkaloidal
Alcohol Used Material Removed
Cc. Per cent
20 26.8
30 32.6
40 35.0
50 41.25
80 43.6
100 47.0
PURIFICATION OF THE CRUDE ATROPINE
The alkaloidal material was extracted from the
Lloyd's reagent with 95 per cent alcohol, using lime
to obtain the proper alkalinity. The extractions were
acidulated with acetic acid and the solution concen-
trated first to 12 per cent, and then tinder diminished
pressure to 2 per cent of its original volume. This
procedure was sufficient to convert all the hyoscyamine
into atropine. After neutralization with ammonia,
the solution was allowed to stand over night and fil-
tered. A test portion of the filtrate was shaken
with ether. If an emulsion resulted, the solution was
diluted about one-fourth and returned to the vacuum
still. Distilling the neutral liquid, and again filtering,
usually prevented the troublesome emulsion with ether.
Ammonia was added until the solution was alkaline
and the atropine alkaloid extracted with ether. After
evaporation of the ether, the alkaloid was carefully
dried at about 35° C.
The dried alkaloid was dissolved in ethyl alcohol in
the proportion of one ounce of alkaloid to two fluid
ounces of solvent, and the solution almost neutralized
with sulfuric acid, using cochineal as indicator. After
filtering it was evaporated on the water bath to a
thin sirup, and to this sirup, while still warm, acetone
was added almost to the point of precipitation of the
atropine sulfate.
On cooling, the atropine sulfate crystallized. If not
sufficiently pure the crystals were dissolved in alcohol
and recrystallized as outlined above.
The acetone was evaporated from the mother liquor,
and the alcoholic solution of atropine sulfate poured
into a large volume of water. From this the alkaloid
was extracted with ether, and if not of sufficient
purity the process already outlined was repeated.
AN INVESTIGATION OF THE U. S. P. ASSAY FOR PHOS-
PHORIC ACID AND SOLUBLE PHOSPHATES'
By A. E. Steam, H. V. Farr and N. P. Knowlton
MAU.INCKRODT CHEMICAL WORKS, ST. LOUIS, MISSOURI
In routine analysis of samples of phosphoric acid in
this laboratory, it was noted that, although aliquots
from the same solution when assayed according to
the directions given in the U. S. Pharmacopeia2
gave concordant checks, it was difficult to obtain check
results when two different samples were weighed out
and made up to volume, unless the size of the sample
happened to be nearly the same in both cases. Briefly,
the method is to transform the acid to the disodium
salt by neutralizing with NaOH to a phenolphthalein
end-point, precipitate with an excess of standard
silver nitrate solution, bring the solution to neutrality
to litmus with ZnO, and determine the excess AgN03.
Calculations were made of the error introduced by
the actual volume occupied by the precipitate. This
error, assuming a specific gravity of i for the precipi-
tate (the value is given as between 7 and 8), adsorption
of water to the extent of one mole per mole of phos-
phate, the presence of the equivalent of 50 cc. o. 1 N
salt, and an equal volume occupied by the excess of
ZnO added, was shown to have a maximum possible
value of 0.5 per cent, and more reasonable assump-
tions reduced this error to 0.08 per cent on a 90 per
cent sample. This small error by no means explained
the large discrepancies of 5 to 10 per cent met with at
times. A few preliminary experiments seemed to
indicate that the results were influenced very markedly
by the size of the sample. The larger the amount of
sample, the lower were the results obtained. In the
filtrates, after the Ag3P04 had been filtered off, a test
with ammonium molybdate showed the presence of
significant quantities of phosphate which the silver,
though present in considerable excess, had failed to
carry down.
The importance of this particular method may be
realized when we recall that it forms the basis for the
assay not only of phosphoric acid and the alkali phos-
phates, but also of many hypophosphites, such as
those of Ca, Na, K, Mn, NH4, etc. The method is
not confined to the U. S. P., but is found in the N. F.
and even in the "New and Non-official Remedies."
1 Presented before the Division of Medicinal Products Chemistry, at
the 60th Meeting of the American Chemical Society, Chicago. 111., Sep-
tember 6 to 10, 1920.
2 Ninth Revision, p. 21.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
221
It was therefore well worth while to investigate the
cause of these phenomena, confirm them, and deter-
mine, if possible, a reliable procedure, or at least a
size of sample which would give fair results in routine
work.
ROUTINE ANALYSIS OF STOCK PHOSPHORIC ACID
The effect of varying the size of sample was first
studied in the case of a stock solution of the acid
taken from the laboratory shelf. A solution was
made up of approximately 10 to n g. per liter, and
analyses of different aliquots were made. The pro-
cedure was as nearly as possible that of rapid routine
work. Room temperature was considered sufficiently
constant (though on warm days the solution was
cooled to the temperature at which it was made up)..
Cc Solution in Sample
Fig. 1 — Showing Effect of Size of Sample of H3PO4 on Per cent of
HjPO« Obtained. U. S. P. Method
Table I gives the results so obtained. These data are
also plotted in Fig. 1, the number of cc. of acid solu-
tion in the sample being plotted as abscissae, while the
per cents of H3PO4 found are plotted as ordinates.
The phosphate in the filtrate was determined by pre-
cipitation as phosphomolybdate and titration of the
precipitate with standard alkali. This method is
sufficiently accurate for the small quantities in the
filtrate, though it was found unsatisfactory as a check
method on the total H3PO4. The method actually
used as reference was the standard pyrophosphate
method, results of which are also given for comparison.
["ABLE 1-
—Analysis of
a Solution
of 23.362
a
Phosphoric Acid Made
Up to
2 Liters
Total
0.1 N
HjPCu
Total
HiPO.
AgNOj
H3PO1
Recoveree
HjPO<
Present (Pyro-
Sample
Consumed
Found
rom Filtrate
Found
phosphate)
Cc.
Cc.
Per cent
Per cent
Per cent
Per cent
1
3.20
89.56
89.56
86.7
3
9.58
89.37
89.37
5
15.75
88. 15
88.15
7
21.98
87.87
87.87
10
30.97
86.66
trace
86.66
12
37.20
86.75
0.1
86.85
15
43.90
81.90
3.7
85.6
17.5
49.95
78.29
8.35
86.63
10 cc
gave 0.1151 g
Mg2P207 or 86.76 per
cent HsPCu
0.1150
86 . 69 per
cent
Av., 86
7
Each value given represents the average of at least two titrations which
in the case of samples up to 10 cc. checked to the drop, and in practically
all other cases checked within one drop. The same is true of data pre-
sented in the other tables.
ANALYSIS OF DISODIUM PHOSPHATE
In order to ascertain whether the rapidity and in-
accuracies of routine work were responsible for the dis-
crepancies shown in Table I, a sample of C. P. sodium
phosphate was recrystallized twice, centrifuged, and
dried to constant weight at no0, where it was com-
pletely exsiccated. Practically the same procedure
was followed as in the case of the phosphoric acid, ex-
cept that all the accuracy which time and precautions
could give was added. The solution was made up
at 250 C. and maintained within o.i° of that tem-
perature; the volumes of the standard solutions were
in all cases corrected for even slight changes in tem-
perature, and great care was exercised in making the
solution neutral to litmus, after precipitation with
AgN03. It was not sufficient to take a drop and touch
it to litmus paper, or even to float pieces of red and
blue litmus on the surface. The acidity was regulated
more by means of dilute NaOH than by ZnO, though
this was added. It was manipulated until pieces of
red and blue litmus, after vigorous shaking in the solu-
tion, kept their respective colors side by side.
Pol
4^
A= Pyrophospha
O U.S. P. Volue
7^~
— 2-_
A
o
e?3
'2.5
(6.75
25
Cc Aliquot Take.
Fig. 2 — Showing Effect of Size of Sample of Na2HPO« of Per cent of
Na2HPO< Obtained. U. S. P. Method
The results of this series of experiments are given
in Table II, and the data plotted in Fig. 2. In Column
5 are found data upon which the size of the points in
Fig. 2 is based, this size representing the error intro-
duced into the position of the point by an error of one
drop (0.0445 cc. in the buret used) in titration. In a
certain sense the size of a point represents its accuracy
from a manipulative point of view. This does not-
mean, however, that the points can be considered
significant only to the extent of their respective areas,
Table II — Analyses
■ to
Litmus
Neutral
Neutral
Neutral
Neutral
Neutral
Neutral
1?
5
Neutral
15
Neutral
15
Very si. acid
17
5
Neutral
20
70
Neutral
SI. acid
20
Very si. alk.
T?
5
Neutral
22
.S
Neutral
■S
Neutral
25
Neutral
7.5
Neutral
75
Neutral
25
Very si. alk.
15
. gave 0. 1195
15
. gave 0.1195
-o
0
2.21
4.41
6.51
10.76
15.05
21.36
(4 det.)
26.77
31.97
31.47
37.26
42.53
40.86
42.94
46.11
46.15
45.13
49.85
50.00
50.80
53.50
t. Mg.P207
5. Mg2P2Oj
103.01
102.78
101. 15
100.31
100.22
99.59
99.82
99.34
98.78
98.22
99.12
95.23
100.07
95.52
95.59
93.49
92.95
93.23
94.72
99.75
or 100.
or 100.
2.10
1.05
0.70
0.42
0.30
0.21
0.16
0.13
0.13
0.10
0.10
0. 10
0. 10
0.10
0. 10
0.10
0.10
0.10
0.10
0.10
10.158 G. Made Up to
H
103.01
102.78
101.15
100.31
100.22
99.59
99.82
99.34
98.84-
98.22
99.12
95.234-
100.07
95.52
95.59
95.27
95.40
96.73
2.15 96.87
99.75
cent Na2HPOi
cent Na-HPOi Av.,
si. ppt.
si. ppt.
1.92
2.45
3.50
for an error of two drops is more likely on the portion
of the curve where the points are small than that of half
a drop where they are large.
In Fig. 2 the same tendency as in Fig. 1 will be
222
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
noted, though to a less marked degree. The column
representing "Reaction" is given because this condi-
tion was found to be a source of error which outweighed
all others. It will be noted (in the case of one of the
20-cc. samples) that very slight acidity gives low re-
sults, while very slight alkalinity gives seemingly
high results, a distinctly alkaline solution precipitating
Ag20, and the back titration showing too little AgNC>3.
For this reason phenolphthalein cannot be used as an
indicator. Berthelot1 suggests neutrality to phenol-
phthalein for complete precipitation of phosphate
with silver; and if the result looked for is merely the
complete precipitation of the P04 ion this is all right,
but if the excess of the silver is to be determined it
will not work. The solubility of Ag20 is o.oooioS
mole per liter at '25°. Silver oxide in solution is
practically completely hydrated and is a compara-
tively strong base, so that we have the following
equilibrium:
Ag20 + H20 ~7~^ 2AgOH 7~^" 2Ag+ 4- 2OH-
At 25° we have in solution in one liter 0.0001 mole
Ag20 or 0.0002 g. ions each of Ag+ and OH-, so that
its solubility product is of the order of
(0.0002) ' = 1.6 X io~15.
In ordinary assays we have an excess of 20 cc. o. 1 AT
AgN03 per 100 cc, or 0.02 equivalent per liter. For
a red reaction to phenolphthalein the OH" concen-
tration is approximately io"s. Thus
(0.02)* X (o.ooooi)2 = 4 X io~".
This value exceeds by some thirty times the solubility
product of silver hydroxide, so that a considerable
quantity of Ag20 would come down. On the other
hand, Ag3P04 is soluble in acid solutions forming the
acid phosphates.
DISCUSSION
Referring to the standard pyrophosphate values, it
will be noted that in both series of experiments very
small samples gave abnormally high values; the sam-
ple recommended in the U. S. P. gave fair to good re-
sults, and large samples gave very low results, though
in these cases it is difficult to obtain checking dupli-
cates, and different determinations even on the same
size of sample vary widely.
Several factors affect the first-mentioned case. The
inaccuracy of measuring such small volumes seems to
the writer to play an important part, as does also the
inaccuracy of titration where one drop of o. 1 N solu-
tion corresponds to over 2 per cent in the result. It
must be borne in mind, however, that the titration is a
back titration, and that an overtitration would cause
the error to throw the results low instead of high, so
that the high results seem difficult of explanation at
the present time.
The fact that results go from much too high grad-
ually to much too low as the sample is increased shows
that it must cross the line of a true result at a certain
point or with a certain size of sample. It is this size,
whether accidentally or not, which happens to be given
in the U. S. P. The results obtained at this point
' Ann. chim. fhys., (7] 26 (1902), 160.
are probably due to the accidental compensation of a
number of errors at that particular concentration.
At first thought, from a theoretical point of view,
neglecting the possible influence of any mechanical
occlusion of either Na2HP04 or AgNO.; in the precipi-
tate, the method should work over the entire range
studied. The idea of mechanical occlusion, which
was formerly overworked in many cases where dis-
crepancies were thought to have been noted, has given
place largely to the idea of higher order compounds,1
or to that of intermediate compounds in the case of
polyvalent substances." Some light on the present
case can be obtained from the studies of two men,
Berthelot and Y. Osaka,3 who state:
According to Berthelot, in the action of sodium phosphate
on silver nitrate, the precipitate of trisilver phosphate retains
a certain amount of the disilver phosphate, and, under certain
conditions, of a silver-sodium phosphate. The quantities of
these substances vary with the composition of the supernatant
liquor with which it is in equilibrium. This equilibrium has
been studied by Osaka.
Upon precipitating Na2HP04 with three equivalents
of AgN03, Berthelot found by analysis of the precipi-
tate and of the filtrate that equilibrium conditions
were expressed very satisfactorily by the equation:
3AgN03 + Na.HPO, = 2NaNOa +
o.78AgN03 4- o.2HN03 + o.6 Ag3P04 + o^AgH^PO.
These conditions are fairly represented by the larger
samples in Tables I and II, where the excess of silver
is quite small. The solubility of Ag3P04 in a solution
of AgN03 is very small itself if the solution is not acid.
Much acid tends to form the acid salts Ag2HP04 and
AgH2P04. In the present study we are interested in
two equilibria. We have always an excess of AgN03
present and we remove the HN03, so that our condi-
tions after the precipitation of silver phosphate are:
AgH2P04 + AgN03 7"" Ag2HPO< + HNOj
+
NaOH (or ZnO) (i)
NaN03 + HOH
AgsHPOi + AgNOj ^1 Ag3P04 4- HNOs
+
NaOH(orZnO) (2)
w
NaNOs + HUH
In the case of Equation 1 we have a salt highly
acid to litmus, and NaOH is added, shifting the equi-
librium far to the right and transforming most of the
salt into the nearly alkaline Ag2HP04. In pure water
this is said to hydrolyze readily into Ag3P04 and
H3P04. This hydrolysis would be greatly retarded
by the presence of the neutral salts which are in solu-
tion,4 and of the trace of HN03. In the case of Equa-
tion 2 we have a condition with only a very small
change in H+-ion concentration for relatively large ad-
ditions of alkali. In other words, the conditions ex-
' G. McP. Smith, J. Am. Chem. Sac. 39 (1917). 1152.
2 Berthelot, Loc. cit.
' Mem. Coll. Set., Kyoto Imp. Univ., 1 (1904-5), 18S.
* Compare Treadwell-Hall, "Analytical Chemistry," 2, 587.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
223
pressed by Equations i and 2 seem to represent con-
ditions which not only give a pronounced "buffer"
action, but which seem to be practically neutral to
litmus over a wide range. Thus there would seem to
be a good deal of uncertainty as to when the equilibrium
was completed to the right. On the other hand, the
addition of a just sufficient quantity of NaOH should
theoretically shift the equilibrium completely to the
right and precipitate all of the phosphate, since under
no conditions would NaN03 be hydrolyzed to the same
extent as Ag^HPOj. With this in mind, calculations
were made as to the theoretical amount of HNO3
which would be liberated from a 25-00. sample of the
sodium phosphate solution (Table II). This was
found to be equivalent to 3.58 cc. of 0.5 N alkali.
Two samples were taken and into one were put 3 . 50
cc. 0.5 N alkali, while into the other were put 3.60 cc.
0.5 JV alkali, and the phosphate was precipitated.
The results are given in Table III.
imple
Cc.
0.5 N
Alkali
Added
■ Ce.
0.5 N
AgNOj
Required
Cc.
Table
NasHPOi
Found
Per cent
III
NaiHPO.
NajHPOi by
in Filtrate Pyrophosphate
(Molybdate) Per cent
25
3.50
53.27
99.88
SI. but distinct yel-
low coloration
25
3.60
53.67
100.07
No color 100.06
Compare Table II, Lines 13 and 20.
These figures seem a very significant confirmation
of the above-mentioned buffer action when viewed in
the light of three facts:
(1) Referring to Table II, it will be noted that when the solu-
tion containing a 20-cc. sample was made very slightly on the
alkaline side of neutrality to litmus, a result of 100.07 per cent
was obtained, and the same treatment of a 25-cc. sample yielded
99-75 Per cent, while the ordinary determinations on the same
sized samples were running up to some 8 per cent lower.
(2) When the first point at which the solution reacts neutral
is taken as the point of complete precipitation, increasingly
low results are obtained with increase of sample since the smaller
the excess of AgN03, the greater the concentration of acid salts
formed in the original mixture, and the wider the range of the
buffer action.
(3) With increasingly large samples it becomes increasingly
difficult to determine this "first point of neutrality," so that,
although fair checks are often obtained on duplicates run side
by side and treated almost exactly the same, it will be noted in
Table II that it is increasingly difficult to get two sets of de-
terminations with like-sized samples to check. In other words,
it is harder to strike the same point on the wider buffer range
every time.
This fact, coupled with the striking results in Table
III, suggested that reliable results might be obtained if
we should have present in solution just enough sodium
hydroxide to take up all the nitric acid as fast as it
was liberated in the precipitation of the Ag3PO<.
Such a method would seem to have several advan-
tages over neutralization with zinc oxide. Thus all
of the nitric acid which can be liberated is taken care
of by an excess of sodium hydroxide already present,
and the acid salts AgH2P04 and Ag2HP04 are pre-
vented from forming by the distinct alkalinity of the
solutions during the precipitation.
So long as there is any phosphate present no silver
will be precipitated as oxide, owing to the greater in-
solubility of the phosphate. The solubility of Ag20
at 20° is 0.00009 mole per liter, while that of Ag3PO<
is 0.000015 mole per liter. Thus no Ag20 will be
precipitated until the concentration of the POj ion
is reduced to 0.000015 mole per liter even in an alka-
line solution, provided there is an excess of AgNOj.
In case there is not an excess it can be easily shown
that at equilibrium there will be only 0.003 times
as much P04 in solution as there is OH.1
An apparent -disadvantage may suggest itself in
overtitration of the phosphoric acid and consequent ex-
cessive addition of alkali in taking care of the nitric
acid to be liberated. As a matter of fact, the hy-
drolysis of the Na2HPOi, which is distinctly alkaline
to phenolphthalein, takes care of this. Indeed, the
hydrolysis occurs to such an extent that if the titration
be made on a plain acid solution at room tempera-
ture the excess alkali will be significantly deficient for
neutralization of the nitric acid liberated during
the precipitation. This hydrolysis is inhibited by
having the solution ice cold and by the presence of a
neutral salt. Treadwell-Hall recommends sodium
chloride. This, of course, cannot be used here, but
sodium nitrate can be introduced. The difference in
titration of phosphoric acid with and without these
precautions is shown by the following figures:
Cc.
Ice cold, with NaCl 20.75
Room temperature, without NaCl 20.45
Ice cold, with NaCl 17.00
Room temperature, without NaCl 16. 70
Ice cold, with NaNOi1 47.20
Room temperature, without NaN03 46.35
1 The NaNOa was tested and found to react neutral.
A small overtitration affects results much less than
it might at first seem. In the first place, the error
throws the results high and tends to compensate for
the slight error introduced by the volume occupied
by the precipitate. One drop overtitration of o. i N
NaOH, even if the alkali were completely precipitated
as Ag20, would amount to 0.045/30.0, or 0.15 per
cent, since a representative sample consumes 30 cc. of
o. 1 N AgN03. In Table IV are given the results of a
Table IV
0. 1 AT Alkali Added Amount of NajHPO) Found
Run Cc. Overtitration Per cent
1 10.75 0.0 100.49
2 10.85 0.1 100.75
3 10.95 0.2 101.12
4 11.05 0.3 101.43
5 11.15 0.4 101.74
6 11.25 0.5 102.05
7 11.35 0.6 102.24
8 11.45 0.7 102.49
9 11.75 1.0 103.48
series of determinations upon the effect of overtitra-
tion. The solution of specially purified Na2HPO<
was used so that there was no question about the end-
point. The assay of somewhat over 100 per cent in
the first figure is probably due to the fact that the solu-
tion, which had assayed 100.06 by the pyrophosphate
■For example: Ag* X (OH)j = 1.6 X 10"" (1)
In same way Ag* X (POO =5 X 10" (2)
Cubing (1) Ag< X (OH)« = 4.1 X 10~« (3)
Squaring (2) Ag» X (PO()' = 25 X 10"" (4)
Dividing (3) by (4) —~r% = 1/6 X 10 ' or PO« - 770 (OH)'
Taking any definite value for PO*, such as 0.0001, and solving for (OH)
we obtain the relation:
OH = 300 POi (5)
224
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
method and 100.07 by this method, had been stand-
ing with a loose cork stopper and had become slightly
more concentrated, since this experiment was made
some time after the rest of the work had been finished.
The theoretical amount of alkali to be added is 10. 75
cc. o. 1 iV to a 15-cc. charge.
In these titrations the average number of cc. of
0.1 N AgN03 Consumed was 33. The error per one
cc. overtitration, then, should be 1/33 X 100, or 3 per
cent. Glancing at the results of Runs 1 and 9, we find
103.48 to 100.49, giving an error of 3 per cent.
There is in practice, however, very little danger of
overtitration with alkali, on account of the aforemen-
tioned hydrolysis.
PROCEDURE SUGGESTED FOR THE ASSAY OF PHOSPHORIC
ACID
In the light of the foregoing the following procedure
is suggested for the assay of phosphoric acid. Weigh
out about 10 g. of the acid and make up to 1000 cc.
Introduce 10 cc. into a 100-cc. standard flask. Add
3 to 5 g. C. P. NaNC>3, cool in an ice bath, and titrate
with NaOH, using phenolphthalein as indicator. Take
the number, of cc. of standard alkali required, divide
it by two, and add this quantity in excess to the sample.
Add 50 cc. o. 1 N AgN03, make up to the mark, mix,
filter through a dry filter, rejecting the first 20 cc. of
the filtrate. To 50 cc. of this filtrate add 5 cc. concen-
trated, HNOs, and titrate with 0.1 N sulfocyanate.
Table V gives the results of a series of determina-
tions made according to the above procedure. The
method has also been used by the writer as well as
by others on a number of samples to be tested, and its
use was attended with apparent satisfaction. On
various occasions it has been checked up very favora-
bly with pyrophosphate determinations on the same
sample.
Table \
— Analysis of a Solution op 11.447 G
op Phosphoric Acii
Made
Up to One Liter
H3PO.
H3PO< HaPO.
0.1 N
0.1 N Calc. from
Calc. from Pyro-
NaOH
NaOH
AgNOa NaOH
AgNOa phosphate
Sample
Titer
Added
Consumed Titration
Consumed Method
Cc.
Cc.
Cc.
Cc. Per cent
Per cent Per cent
1
2.08
3.10
3.20 89.11
91.38 91.3
2
4.25
6.37
6.40 91.04
91.40
5
10.50
15.75
16.00 89.96
91.38
7
14.60
21.90
22.35 89.60
91.20
10
21.00
31.50
31.90 90.00
91.10
10'
20.80
31.20
31.80 89.15
90.81
12
25.40
38.10
38.40 90.68
91.38
15
31.90
47.85
47.85 91.10
91.10
10 cc.
gave 0.
188 g. Mg;P;Oj or 91 .38 per cent H3PO1
0.
186
91 .23 per cent
Av„ 91.3
1 At
room temperature.
Column 5 furnishes an answer to the question as to
whether it would not be just as well to calculate the
strength of the acid from the NaOH titration as to go
on through the entire procedure. The results in this
column vary over a range of 2 per cent, while in the
next column the variation is confined to only 0.3 per
cent. It will be noted that, in the case of one of the
determinations on a 10-cc. sample, significantly low
results were obtained by not titrating the solution ice
cold.
A word as to the use of zinc oxide as a neutralizing
agent may be in place. The solubility of zinc oxide
at room temperature is 0.00005 mole per liter. The
solubility product (Zn) X (OH)2 = 0.00005 X
0 0
I I
1 0 1 J
A= Pyrophosphate Value®
w^ — '
0= Modified U.S.P Value
x= Value from NaOH Ti
s^
ration
£*
5?
es£-
Cc. Aliquot Taken
Fig. 3 — Upper Curve: Showing Per cent HaPO« Obtained as a Func-
tion op Size op Sample. Modified U. S. P. Method. Lower Curve:
Showing Variable Results op NaOH Titration of H1PO1
Co.oooi)2 = 5.2 X io"13. A representative sample
of phosphoric acid (0.1 g.) liberates 0.001 mole of
HNO3 in 100 cc. The zinc oxide going into solution
to neutralize this acquires a concentration of o . 00 1 / 2 X
10 or 0.005. The maximum OH- concentration at
the final point of neutrality then should be
h-2 X 10-'3
or 10^.
0.005
Obviously, this is a sufficiently alkaline solution.
Yet a few facts may be pointed out in this connection.
The concentration of the OH ion in a saturated solu-
tion of ZnO, assuming complete hydration with solu-
tion, is 0.0001, and yet even after boiling a suspension
of ZnO it requires some hours for it slowly to turn red
litmus blue. This indicates that, even though hydra-
tion is probably complete with solution, its rate is ex-
tremely slow in a solution approaching neutrality; thus
the neutralization process in the H3PO4 assay would
be very slow even with the last traces of free HNO3,
but when precipitation takes place in acid solution
we have not free HN03 finally, but the acid phos-
phates of silver, which it is doubtful if the zinc oxide
would ever neutralize. Conditions approaching good
working conditions might possibly be obtained by in-
troducing the zinc oxide first and then adding the
AgN03 very slowly, thus neutralizing the free acid
as it is formed, if not formed too rapidly. This pro-
cedure is not practicable, however, and the one out-
lined above has all the advantages of this last sugges-
tion.
SUGGESTED PROCEDURE FOR ASSAY OF Na2HPO.) AND
Na2HP04.i2H20
As an outgrowth of the above-suggested procedure
for the assay of phosphoric acid, a simple modifica-
tion for the assay of the salts has been tried with suc-
cess. In the case of the exsiccated salt which will run
99 to 100 per cent Na2HPO.i there will be, for every
molecule of salt, one molecule of HNO3 liberated by
the silver precipitation. On the assumption of a
99 per cent or a 100 per cent material it is easy to
calculate the quantity of alkali necessary to neutralize
this acid, as follows:
Weigh out 15 g. of dried sample and make up to
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
225
1000 cc. To 10 cc. of this solution add, for every
0.15 g. of the salt, 10.50 cc. 0.1 N alkali. (This is
one drop overtitration for a 99 per cent salt and one
drop undertitration for a 100 per cent salt.) Add 50
■cc. 0.1 iV AgN03, make up to volume in a 100-cc.
standard flask, mix, filter through a dry filter, and
titrate 50 cc. of the filtrate with o. 1 N sulfocyanate.
The crystals NaiHPOj.i 2H2O might be treated the
same way, adding 10.50 cc. alkali per 0.378 g. of the
salt. Here, however, the method falls down, as any
appreciable efflorescence would cause the calculated
amount of alkali to be too small and the results would
he low. It would be better to exsiccate the salt at
no°, determine the moisture, and then analyze the
dried salt as above.
SUMMARY
1 — The U. S. P. method for the assay of phosphoric
acid is incapable of yielding true results except at one
specific concentration, namely. 6.2 mg. per cc. The
error varies from about + 3 per cent at a concentra-
tion of 0.62 mg. per cc. to — 8 per cent at a concentra-
tion of 11 mg. per cc.
2 — This is probably due to the formation of acid
phosphates of silver which are slightly soluble, the
amount formed increasing rapidly as the phosphate
concentration is increased and the excess of silver
nitrate is simultaneously decreased.
3 — The fair results obtained at the specific concen-
tration given in the U. Si P. is probably due to the
accidental compensation of a number of errors at that
particular concentration.
4 — By modifying the method to the extent of trans-
forming the acid to the tri-sodium salt, results are ob-
tained which coincide with the results yielded by
the pyrophosphate method, and which are independent
of the concentration of the phosphate.
The Corn Products Refining Company is said to have concluded
negotiations for the taking over of plants in England, Germany,
and France, after negotiations extending over several months.
The company, capitalized at 880,000,000, intends to manufac-
ture and distribute its goods in Europe, and has worked out a
plan on a large scale in order to overcome the high duties col-
lected on business transactions between the United States and
European nations. The German plants are to be located at
Hallem, Steutz, Grafenhainichen, and Nierstein.
Reports of the glass industry in West Virginia show that a
majority of the glasshouses in the state have shut down, only
the largest ones which have big contracts going ahead with the
completion of their orders. Plants which are in operation have
their forces cut down sometimes as much as 75 per cent. Belgian
glass is said to be selling at two dollars per box less than the
American price.
Lever Brothers Company, of Cambridge, Mass., the American
auxiliary of the British company of the same name, has in-
creased its capitalization to $lf>0,000,000, preliminary to taking
over the American Linseed Company. During the past 12
mo. the company has taken over by purchase wholly or in part
the capital stock of a majority of the British oil mills and
refineries and has consummated a gigantic combination of the
industry.
NEW METHOD FOR THE DETERMINATION OF POTAS-
SIUM IN SILICATES'
By Jerome J. Morgan
Columbia University, New York, N. Y.
Received December 9, 1920
The usual methods of determining potassium in
silicates, particularly in fused residues, have been
found to present numerous difficulties. In some work2
on the volatilization of potassium oxide from natural
silicates, a combination of the J. Lawrence Smith
method and the perchloric acid method was used in
determining the amount of potassium in the residues
from an experiment, whenever that residue was in
such form that it could be removed from the platinum
boat in which the experiment was made, and ground
to a powder. In many cases the residue had fused,
and to remove it from the boat it was necessary to
dissolve it with hydrofluoric acid. In such cases a
combination of the hydrofluoric acid method of Krish-
nayya3 and the perchloric acid method was employed.
While it was possible by either of these methods to
obtain results in duplicate that agreed fairly well, the
results by one method did not agree with those by
the other, and both methods were tedious and time-
consuming. It was therefore evident that if much
work was to be done on the volatilization of potassium
salts from silicate mixtures, it would be necessary to
find a more rapid and more reliable method for the
determination of potassium in silicates.
In order that the method might be applicable to
residues which had been melted and solidified in a
platinum boat, it was necessary to decompose the sili-
cate with hydrofluoric acid, and hence it was decided
to get rid of the fluorine by evaporating with per-
chloric acid instead of with sulfuric acid. This was
found to work very satisfactorily. Only in mixtures
containing considerable calcium is it necessary to re-
peat the evaporation after taking up with hot water
and adding more perchloric acid to transform the fluor-
ides completely to perchlorates. This procedure offers
an additional advantage, since the perchlorates of all
of the bases, except potassium, commonly found in
silicates, are soluble in the alcohol wash used in the
regular perchlorate method.4 Hence the residue after
evaporation can be treated at once with alcohol wash,
and the insoluble potassium perchlorate transferred
from the dish in which the silicate is dissolved directly
to the Gooch crucible in which it is weighed. The
only common substances likely to interfere in the
analysis are ammonium and sulfur compounds. The
ammonium compounds can be removed by preliminary
heating, and some experiments, which will be mentioned
later, seem to show that any interference of the sulfur
compounds can be estimated and a correction applied.
The method has been used on a large number of mix-
tures of feldspar and glauconite with sodium chloride,
calcium chloride, calcium carbonate, and limestone,
' Part of a thesis submitted in partial fulfilment of the requirement for
the degree of Doctor of Philosophy in the Faculty of Pure Science, Columbia
University, New York, N. Y.
2 Jackson and Morgan, This Journal, 13 (1921), 110.
' Chem. News, 107 (1913), 100.
< Scholl, J. Am. Chem. Soc., 36 (1914), 2085.
226
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
and there was no interference from sulfur compounds. interference of sulfur compounds
This was demonstrated by the facts that the water The materials analyzed by the above method were
solution of the weighed perchlorate precipitate was free from sulfur compounds in amounts sufficient to
found in every case to be free from soluble sulfates, interfere with the method, as was shown by the ab-
and that the weight of the Gooch crucible after each sence 0f sulfates in the weighed potassium perchlorate.
determination showed the absence of insoluble sul- a few experiments were made, however, to show what
fates, might be the interference of sulfur, and the suggestions
In the method finally used, after the silicate was from these experiments are of interest. The weight
decomposed the excess of hydrofluoric acid was ex- 0f potassium perchlorate obtained from equal vol-
pelled by evaporating at a low heat on a sand bath, umes 0f a potassium chloride solution, both with and
and the residue was dissolved by warming with 3 N without addition of 2 cc. of 0.1 N sulfuric acid, showed
hydrochloric acid. This gave an opportunity to see jn the presence of an excess of perchloric acid no potas-
that the decomposition of the silicate had been com- sium suifate was formed, and a test of the solution of
plete, and admitted of the removal of the platinum the weighed perchlorate in water proved that it con-
boat, tained no sulfate.
details of method If suifur is present in the silicate analyzed it will
From 0.3 to 0.6 g. of the silicate is decomposed by either be volatilized during the evaporations with
digesting at room temperature with an excess of hydro- hydrofluoric and perchloric acids or else will remain
fluoric acid, and this excess is removed by evaporating in the final residue as a sulfate. To interfere with
to dryness at low temperature on a sand bath. About the determination of potassium as perchlorate, the
25 cc. of 3 N hydrochloric acid are added, and the sulfate radical must be combined with a base whose
mixture warmed until all except a small amount of sulfate is insoluble in alcohol containing perchloric
calcium fluoride is dissolved. An excess, about 10 cc, acid. Of the bases usually present in silicates, es-
of 10 per cent perchloric acid is added, and evaporation pecially the silicates used in cement making, the sul-
continued on a sand bath until dense white fumes of fates of ferric iron, aluminium, manganese, and mag-
perchloric acid are obtained. At this point the resi- nesium are soluble in alcohol. On the other hand,
due may be allowed to go to dryness over night on an those of barium and strontium are so insoluble in
electrically heated sand bath designed for this purpose water that they will be left on the asbestos felt when
and regulated so that the heat is not high enough to the residue is dissolved in hot water, and can be cor-
decompose the perchlorates in the residue. rected for in weight. Since potassium sulfate is not
The residue is then taken up with hot water, in which formed in the presence of an excess of perchloric acid,
all except a small amount of calcium fluoride should this leaves only calcium sulfate and sodium sulfate,
be soluble, 1 or 2 cc. of 10 per cent perchloric acid are which are insoluble in alcohol but soluble in water,
added, and the evaporation to dense white fumes and hence may be weighed as potassium perchlorate
repeated. If the residue from the first evaporation is in the method given.
not completely soluble in hot water plus perchloric Sulfates in the Potassium Perchlorate Precipitate
acid, the residue from the second evaporation is dis- Jo u -S al § gZ a Z
solved in hot water, a little more perchloric acid is -| .2 ■< fc° £ +s ° «
added, and the liquid again evaporated to white fumes. 2 ,-S ^ ac ^1 <5~S ^" '
The evaporation in every case is repeated once after Expt. of-1 w< ^o o,° <gO ^am u*. v-
the residue is completely soluble in hot water. Usually a' 10 0.1849 0.1849 0.0995
it is necessary to evaporate only twice. J J° ^ ■■ ° 'i856 " " oils* 00999
The residue from the final evaporation is allowed to J.V.V.-.V::: 10 2 !. o:>859 q . ^ q ..^ o:,859 oliooo
cool thoroughly. It is then treated with about 20 cc. f 10 2 2 0.2006 0.0239 0.0149 0.1857 0.0999
of alcohol wash (97 to 98 per cent alcohol containing both^STnd suifat^dtca0" ^lllV^^V^tl Z™£ £
1 cc. of 60 per cent perchloric acid per 300 cc.) and this m<=th°d-
allowed to digest with frequent stirring for at least Two experiments with the potassium chloride solu-
15 min. The alcohol solution must be cold when tion mentioned above, to which both sulfuric acid and
filtered. The solution is finally decanted through as- calcium chloride were added before it wTas evaporated
bestos in a Gooch crucible, and the potassium per- with perchloric acid, showed that all of the sulfate
chlorate washed by decantation and also in the cru- radical added was present as a calcium salt in the per-
cible with small portions of the alcohol wash. The chlorate precipitate. The residue, after weighing, was
precipitate is particularly satisfactory to work with, dissolved in water, hydrochloric acid was added, and
showing no tendency to creep or stick to the platinum the sulfate determined as barium sulfate. If the
dish, and the washing can be made complete with a amount of calcium sulfate, 2CaS04.H20, equivalent to
total volume of filtrate and washings of 50 to 75 cc. the barium sulfate found, is deducted from the weight
The precipitate is dried at least 30 min. at about 130° of the perchlorate precipitate, the amount of potassium
C. Its composition is KCIO4, the factors of which perchlorate in this case agrees remarkably well with
are 0.340 for K20 and 0.538 for KC1. The weighed the amount found for the same volume of potassium
salt is dissolved from the asbestos felt with hot water, chloride solution in the other experiments. The tabu-
and the crucible, after drying, is then ready for the lation of these results is given in the accompanying
next determination. table. No experiments have yet been made on the
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
227
interference of sulfates in the presence of other bases,
but it is believed that with the bases usually found
in cement materials, where there is a great excess of
calcium, any sulfate in the perchlorate precipitate will
be present as 2CaS04.H20, or if not all combined
with calcium, the rest will be combined as anhydrous
sodium sulfate whose molecular weight, 142, is so
close to the weight of CaS04 + V2H20, 145, that no
serious error is introduced by correcting for a small
amount of sulfate in the way indicated.
SUMMARY
It is believed that for the determination of potassium
alone in silicate materials which are free from appre-
ciable amounts of sulfur compounds the method here
given is the simplest and most accurate yet devised.
It has the following advantages:
1 — It is not necessary to have the material finely
ground.
2 — There is no chance for loss of potassium by vol-
atilization, as is the case in other methods where the
salts, usually chlorides, are heated to decompose the
silicate or to remove ammonium compounds.
3 — All separations of other elements by precipita-
tion which might cause loss of potassium salts by ad-
sorption, formation of double salts, etc., are avoided.
4 — The only time-consuming operations are the
evaporations, which may be carried on with very little
attention, especially on an electrically heated sand
bath, as there is absolutely no tendency to spatter
when a moderate heat is used.
5 — The potassium compound which is filtered and
weighed is, under the conditions of the method, the
most insoluble of any used in the determination of
potassium, and is absolutely constant in composition.
THE ALSATIAN POTASH INDUSTRY
Discussing the Alsatian potash situation before the Societe de
Chimie Industrielle, in December 1920, M. Matignon pointed out
the remarkable progress made under adverse conditions since
the war, and the wide possibilities of future development.
In 1913 Alsace produced 50,000 tons of potash (K20). In
spite of transportation difficulties and strikes, the 1919 produc-
tion reached 90,000 tons. The potash sold in 1920 will amount
to 200,000 tons, or almost one-fifth of the world's pre-war pro-
duction. It is hoped that in 5 yrs., with a sufficient operating
force, the production may approach 600,000 tons.
The resumption of work since the war has involved the re-
placement of a German directing personnel by a French or Alsa-
tian staff, and also the adoption of a more modern and econom-
ical mining system than was followed by the German operators.
The deposit should guarantee the world's 1913 consumption
for 250 to 300 years. The purification of the Alsatian products is
much simpler than that of those from the German deposits, owing
to the low content of magnesium salts. Common 12 to 16 per cent
sylvite (a mixture of common salt and potassium chloride) and
sylvite containing 20 to 22 per cent pure potash, both of which
are in demand for agriculture, are easily obtained from the crude
product. From a sylvite brine, a 90 per cent KC1 is obtained,
which is easily converted to a 98 per cent chloride. Three fac-
tories are at present producing 300 tons of rich chloride daily.
At the Reichland mine, from 1000 tons extracted, 600 tons are
removed as common and rich sylvite, the remaining 400 tons pass-
ing through the factory and yielding 100 to 120 tons of chloride.
CENTRIFUGAL METHOD FOR DETERMINING
POTASH
By Elmer Sherrill
Huntington Beach Laboratory, The Holly Sugar Corporation,
Huntington Beach, California
Received August 31, 1920
The ever-increasing production and consumption
of potash in this country and the efforts to discover
and develop new sources make the need of an accurate,
economical, and rapid method of analysis keenly
felt. Also in potash producing and consuming fac-
tories it is desirable to exercise chemical control over
operations, heretofore a difficult if not an impossible
procedure.
The object of this article is to describe a method
which can be depended upon to furnish the desired
results, practically reducing the time element from
hours to minutes and the cost for chemicals per de-
termination from dollars to cents, and which in its
simple form is capable of wide application.
OUTLINE OF METHOD
Five cc. of an approximately 1 per cent K20 solution
of the sample are transferred to a potash centrifuge
tube containing 17 cc. of specially prepared sodium
cobaltic nitrite solution. To a similar tube add 5 cc.
of a standard 1 per cent potash (K20) solution. Centri-
fuge both at once in a Babcock milk test hand centri-
fuge at 1000 r. p. m. for 1 min. Observe each tube,
tap gently with the finger to level the surface of the
precipitate, and centrifuge again for 15 sec. Calculate
results by the formula:
Cc. to which sample is diluted X reading of sample
Gram of sample in above solution X reading of standard
per cent K20
STANDARD POTASH (K20) SOLUTION Dissolve 15.83
g. of highest purity potassium chloride in distilled
water in a liter volumetric flask, add 8 or 10 drops of
C. P. glacial acetic acid, dilute to the mark, and mix
thoroughly.
SODIUM COBALTIC NITRITE To 450 g. of C. P.
sodium nitrite in a large wide-mouth bottle add 800
cc. of distilled water. Let stand over night, or longer,
with occasional stirring. In a similar manner treat
250 g. of C. P. cobalt acetate with 800 cc. of distilled
water. As soon as the sodium nitrite is all dissolved
pour it into the cobalt acetate solution. Mix well
and dilute to 2 liters. This solution keeps well for
months.
To prepare the solution for use add 65 cc. of water
and 5 cc. of glacial acetic acid to 100 cc. of stock solu-
tion, mix, and let stand over night before using. It
does not keep well, and a new solution should be pre-
pared every 3 or 4 days.
sodium hydroxide solution — Prepare 500 cc. of
10 N solution. A saturated solution of sodium car-
bonate is sometimes used instead.
potash centrifuge tubes — These are manufac-
tured specially for potash determinations. If a
Babcock milk test bottle were inverted, the stem sealed
and the bottom cut out, it would be nearly the same
size and shape as a potash centrifuge tube, which has
228
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
comparatively a much smaller stem and finer gradua-
tions. They should be calibrated with mercury be-
fore using, in which case a long drawn capillary tube
is useful in filling and emptying. It is also .useful in
washing out precipitates after a potash determination.
Linings for the centrifuge tube shields can be made from
large corks to prevent breakage of the potash tubes.
NOTES ON METHOD
The solution of the sample should contain ap-
proximately 1 g. of the K20 per 100 cc. Before di-
luting to the mark, it should be rendered alkaline with
sodium hydroxide and acidified with glacial acetic
acid, using phenolphthalein as indicator. If it contains
insoluble matter, filter through a dry paper, and centri-
fuge 5 cc. of the clear filtrate. Samples containing
ammonium salts should be weighed and ignited be-
fore bringing into solution. The stem of the tube
should be full of water before adding the nitrite solu-
tion. The temperature at which the determination
is made is 22° C. or above. The precipitate reading
of the sample should not be over five small divisions
above or ten below that of the standard, which should
be about 10.5. A 4-tube head centrifuge allows three
samples to be run with the one standard.
APPLICATIONS OF METHOD
The ease with which samples are prepared for anal-
ysis, the rapidity of. obtaining reliable results, and the
minimum costs of chemicals per sample make the
method ideal. Samples that used to take the most
time are now determined quickest. For instance,
the KoO in molasses is determined as follows: Trans-
fer 26 g. more or less to a 100-cc. volumetric flask by
aid of hot water, render alkaline with sodium hydroxide,
acidify with acetic acid, cool, fill to the mark with
water, and mix. Centrifuge 5 cc. and calculate the
per cent K20. This requires 12 min. in all. Dis-
tillery and sugar factory wastes can be determined in
from 4 to 8 min.
Altogether over 1700 determinations have been
made in this laboratory by the method, about 60 of
them being on 50-ton car shipments of crude potash.
The results obtained on twelve car samples by the
centrifugal method, in comparison with those of a well-
known public analyst and in the case of disputed
samples those of an umpire chemist in New York,
are given below:
al Method
Public Analyst AnaJysi
s Umpire An.il>
cent
Per cent
Per cent
Moisture
KiO Moisture
32.68 5 '.<
34 .12 3 . 95
KjO
33.74 4.11
3S'. 65
(K98
26 . 36 1 . 1 1
1.45
S0.92 1.47
1 . 30
29.76 1.58
1.59
28.10 2.20
1.36
28.38 1.53
29! 38
1.65
37.28 1.32
0.73
39.44 1.01
0.83
41.30
0.82
40.80
The results given by the centrifugal method were
those obtained the first time run, not averages of two
or more determinations, and not over 25 min. were
required for any result. In each case they were just
one of several samples run during the day.
RAPID IODOMETR1C METHOD FOR DETERMINATION
OF CHROMIUM IN CHROMITE
By Ernest Little and Joseph Costa
Rutgers College. New Brunswick. X. J.
Received October 2, 1920
The determination of chromium after oxidation to
sodium chromate immediately suggests the rapid
accurate method of iodometry. Because of the
analogous action of the dichromate and ferric ions on
the iodide ion, however, the analysis of chromite by
this method presents a problem, and our purpose here
is to present a method whereby an iodometric de-
termination of chromium may be effected with its
usual rapidity and accuracy without time-consuming,
intermediate procedures for the elimination of iron.
Practically all the methods in use for the analysis
of chromite prescribe that the ore be fused with sodium
peroxide, or sodium peroxide and sodium carbonate,
in a spun iron crucible. The methods differ after the
extraction of the melt and are of two classes: first,
those in which the iron is removed as ferric hydroxide
by filtration, and the filtrate of sodium chromate is
analyzed by any of the usual methods, including an
iodometric method;1 and second, those in which the
chromium is determined in the presence of iron in an
acid solution. The objection to the methods of the first
class is that the filtration of a solution containing in
suspension a voluminous precipitate of ferric hydroxide
is a tedious operation and quite likely not to give
quantitative results on the first filtration; three ni-
trations and subsequent reprecipitation are very often
necessary.2 In methods of the second class, the ex-
tract is acidified with either hydrochloric or sulfuric
acid, a weighed excess of Mohr's salt or ferrous sulfate
is added, and the excess titrated with standard per-
manganate or dichromate. The shortcomings or in-
conveniences of these methods are well known. In
the case of the potassium permanganate, when the
titration is carried out in a moderately small volume,
the end-point is obscured by the bright blue-green
color of the chromic ion; when larger volumes are used
in order to overcome the above-mentioned difficulty,
blank tests on the water are necessary. Furthermore,
permanganate is rather unstable in solution, and fre-
quent restandardizations are necessary. When di-
chromate is used, an outside indicator with its in-
conveniences is imperative. The use of an outside
indicator is especially difficult in this analysis, owing
to the high concentration of chromic ion, the color
of which makes the end-point more difficult to deter-
mine.
An iodometric method has not been considered pos-
sible here on account of the presence of the ferric ion.
A method has been outlined in which the interference
of the ferric ion is claimed to have been removed by
the addition of a solution of phosphoric acid, in the
presence of which iron forms a very slightly ionized
ferric acid phosphate.3 This method, however, has
not been tried in the presence of large excesses of iron,
' Brunn. Z. anal. Chem., 52, 401.
2 Schorlemmer, Collegium, 1918, 145.
! O. L. Barnebey, /. Am. Cham. .>u. . 39 (1917), 604.
ar.,
1921
THE JOURNAL C
)F INDl
c Method —
Grams
Cr-Os
0.3581
0.3569
.'ST RIAL
AND ENGINEERING CHEMISTRY
wt.
Sample
0.9600
0.9600
■ N<
Cc.
Used
114.46
114.11
Per cent
Cr203
37.30
37.19
Reagent
Used
KMnO.
Weight
Mohr's
Salt
6.0072
s salt Keduction AletHod ;
Equiv. 0.1 N
Cc. 0.1 .V Ox. Reagt.
Mohr's Used Grams
Salt Cc. Cr2Oa
153.19 13.09 0.3549
'
No.
1
Normality
0.1235
0.1235
Per cent
Cr.Oj
36.97
2
3
4
0.9600
0.9600
0.9600
0.4100
0.4100
115.40
92.96
92.63
52. 45
52.31
0.1235
0.1235
0.1235
0.1235
0.1235
0.3610
0.2909
0.2898
0.1641
0.1637
37.61
30.30
30.19
40.02
39.91
KMnO,
KMnO.
KiCr^O;
KMnO,
5.7863
5.8816
4.7770
4.9339
2.6000
145.25
145.99
121.82
1 25 . 82
66.30
3.31
7.32
7.62
11.94
1.79
0.3595
0.3614
0.2893
0.2985
0.1634
37.45
37.65
30.13
30.05
39.86
5
0.4100
0.4100
45.17
45.40
0.1235
0.1235 •
0.1413
0.1409
34.47
34.37
KMnO)
2.3913
60.98
5.02
0.1417
34.56
6
0.4100
0.4100
52.50
52.44
0.1235
0.1235
0.1643
0.1641
40.05
40.01
KMnO,
2.7300
69.62
5.10
0.1634
39.86
7
0.4100
0.4100
75.12
75.00
0.1030
0.1030
0.1960
0.1957
47.79
47.72
KMnO*
3.3830
3.2099
86.27
81.85
8.77
4.66
0.1963
0.1955
47.88
47.70
8
0.4100
68.31
0.1030
0.1782
43.47
KMnOi
3.0554
77.92
7.58
0.1782
43.46
9
0.4100
0.4100
84.42
84.44
0.1030
0.1030
0.2203
0.2206
53.72
53.80
K?Cr202
3.6632
93.42
6.59
0.2199
53.65
10
0.4100
S3. 53
0.1030
0.2180
53.16
K-CrO:
3.59S1
3 . 7024
91.76
94.42
5.89
8.68
0.2175
0.2172
53,05
52.97
11
0.4100
0.4100
91.20
91.37
0.1030
0.1030
0 . 2380
0.2384
58.04
58.16
K^Cr-O?
3.9214
3.9217
100.00
100.00
6.13
6.21
0.2378
0.2376
38.00
57.95
12
0.4100
0.4100
96.80
96.47
0.1023
0.1023
0.2509
0.2500
61.09
60.98
K:Cr:0;
3.9214
3.9214
100.00
100.00
1 .60
1.46
0.2492
0.2496
60.811
60-86
13
0.4100
0.4100
98.05
97.81
0.1023
0.1023
0.2541
0.2535
61.95
61.82
KjCrsOj
4.4850
114.37
13.88
0.2546
62.09
229
and the data given are hardly sufficient to warrant its
acceptance at this time.
FERRIC-FLUORIDE COMPLEX
It is known that when the fluoride ion is added to
a solution containing the ferric ion, a very slightly
ionized, but fairly soluble complex is formed, probably
FeF6-. The very low ionization of this complex is
well demonstrated by the fact that such a slightly
soluble substance as ferric hydroxide will dissolve quite
readily in the presence of the fluoride ion. Also if
potassium iodide and starch paste are added to a solu-
tion containing the ferric fluoride, no blue color is
produced. The theoretical considerations in the re-
action of the Fe+++, F~, and I- ions will not be en-
tered into here, as they have already been fully pre-
sented.1 The ferric-fluoride complex is, however,
broken up by large excesses of either acid or alkali,
but is stable in acid concentrations such as are suitable
for the chromite analysis. In the case of the analyses
here outlined, twice the amount of acid prescribed had
to be added before trivalent iron from the complex
reacted with the iodide. If less acid is used, the
oxidizing potential of the dichromate is too low, and
the titration is greatly retarded. A faise end-point
may appear, the blue color returning after a few sec-
onds. This leads to no inaccuracy, however; the
solution may be allowed to stand a few minutes longer,
or 2 to 3 cc. more acid added, and the titration com-
pleted. The ferric-fluoride complex is, of course, least
ionized in the presence of an excess of the fluoride ion.
but a large excess is not necessary. From 1 to 4 g.
excess ammonium fluoride were used, and the results
were identical in each case. While spot tests with
potassium ferrocyanide were used to insure the absence
of the ferric ion, this is hardly necessary. Ammonium
fluoride was used in most cases, but the results with
potassium fluoride, as would be expected, were found
to be identical. Hydrofluoric acid was used in a few
instances, and found satisfactory but inconvenient.
When very large amounts of iron are present, the
ferric fluoride is precipitated, giving an opaque white
i Little and Hulls, This Journal, 12 (1920), 270.
character to the solution. The formation of this pre-
cipitate interferes in no way, but rather aids the end-
point, which goes sharply from the usual deep blue
to an opaque white, instead of to the transparent, bluish
green chromic solution.
SUGGESTED METHOD
Four-tenths of a gram of chromite were mixed
thoroughly in a 25-cc. iron crucible with 3 g of sodium
peroxide, and covered with 2 g. more. This mixture
was heated at a low heat for about 5 min., and then
fused for 15 min. at a higher temperature. The cru-
cible was allowed to cool completely, and placed in a
beaker containing 150 cc. water. After ebullition had
ceased, the crucible was thoroughly washed, and re-
moved. A half gram of peroxide was then added to
the solution to insure complete oxidation, and the ex-
cess peroxide driven off by boiling. The solution was
cooled and hydrochloric acid added until the ferric
hydroxide dissolved, when 5 cc. excess concentrated
acid were added for each 100 cc of solution. Am-
monium fluoride was now added until the solution no
longer reacted for ferric ion with potassium ferro-
cyanide on a spot plate, and 1 g. in excess used. Three
grams of potassium iodide were then added, the solu-
tion allowed to stand 3 min. and titrated against a
standard thiosulfate solution, using starch solution as
an indicator.
The crucibles used in the fusion weighed about 25 g.
and lost in each fusion an average of 0.5 g. in weight.
It is evident, therefore, that the determinations were
carried out in the presence of large excesses of iron.
The above table shows the results obtained by
this method in the analysis of thirteen typical chromite
ores, compared with the results of analyses made by
reducing the chromate with Mohr's salt and titrating
the excess reducing agent with either standard per-
manganate or potassium dichromate.
CONCLUSION'S
1 — An iodomctric titration for dichromic acid may
be easily carried out in the presence of large excesses
of iron by means of the formation of the ferric-fluoride
complex.
230
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
2 — This method has been found to be rapid, accurate,
and highly satisfactory with chrome iron ores, and
should adapt itself for use in control work, in the
analysis of such ores.
A RAPID VOLUMETRIC METHOD FOR DETERMINING
ALCOHOL
By Arthur Lachman
143 Fourteenth Avenue, San Francisco, California
Received October 25, 1920
The accurate estimation of alcohol by means of the
density of water-alcohol mixtures requires great care,
especially in regard to temperature control. The
tables of the Bureau of Standards are carried out to
five figures, with alcohol values in terms of hundredths
of per cents; but such accuracy requires a temperature
adjustment of about 0.01°. Atmospheric changes may
introduce fluctuations of more than 0.15 per cent,
involving reduction of weights to vacuum. The
tables of the Bureau have been compiled with all
possible care, as have those of the German Normal-
Aichungs-Amt; yet these two tables differ in parts by
as much as 0.10 per cent, or more than ten times the
limit of accuracy postulated in the tables themselves.
The method herein briefly described gives a high
degree of accuracy, and is exceedingly rapid. It is
based on the determination of the critical point of an
equilibrium of the -third order. A fixed weight of
aniline (25.00 g.) is pipetted into a definite volume
(50.00 cc.) of the alcohol-water mixture whose strength
is to be determined. If the aniline does not dissolve
completely, some convenient fixed volume, such as
25.00 cc. of strong alcohol of known strength, is added
until solution occurs. Water is run into the clear
solution from a buret until a permanent turbidity
occurs. The end-point is exceedingly sharp; a single
drop of water converts the perfectly clear, or slightly
opalescent, liquid into a milky suspension that cannot
possibly be mistaken. If the end-point is overshot,
the vessel is slightly warmed in the hand, and a drop
or two of water added again. When the end-point
is reached, the temperature of the mixture is noted to
0.1° C. The operation is then complete, requiring
merely 2 or 3 min. From the known volume of sample,
of added alcohol, and of added water, the percentage
of alcohol in the sample can be calculated. The
following tabulation shows the character of the results
obtained:
Voluj
^Determined by — *
Density Titration
tE Per cent
- — Determined by — ■
Density Titration
20.10
20.04
20.02
20.04
32.54
32.57
32.58
22.94
22.91
22.95
22.91
50.63
50.60
50.59
50.62
50.66
23.76
23.72
23.76
23.82
23.76
23.78
96.03
96.04
96.07
96.08
96.07
25.15
25.12
25.12
99.84
99.86
99.83
of the volume of contained alcohol. If a number of
points on the curve are determined, the intermediate
values may be obtained by graphic interpolation
without serious error. In the following condensed
table are given the total solvent volume and the
corresponding alcohol volumes. By deducting the
known volume of added, alcohol, we find the volume
of alcohol in the sample:
Relation between Total Volume op Solvent and Volume or Con-
TAINBD
Alcohol
(For 25.00 G.
Anil
ine at 15.6° C.)
Total
Total
Solvent
Alcohol
Solvent
Alcohol
50
22.28
100
37.41
60
25.38
110
40.30
70
28.40
120
43.05
80
31.43
130
45.80
90
34.42
140
146
48.50
50.00
Several corrections must be made before the final
result is obtained. Tables for these have been calcu-
lated, but owing to lack of space they cannot be given
here, and a brief enumeration must suffice.
The total solvent volume given above holds only
for the normal alcohol temperature of 15.6°. The
temperature coefficient happens to be almost exactly
1 per cent of the total solvent volume per degree, for
a range of 2° or 3° in both directions. The tem-
perature during titration may be kept close to the
normal by immersing the flask occasionally in cold
wTater.
The temperature of the sample and of the added
alcohol may be kept between 14° and 17° without ap-
preciable effect upon the results; larger deviations
require correction. The volume of water added from
the buret may require correction if the room tem-
perature differs by more than 5° from normal.
The most troublesome correction is caused by the
contraction of volume which has previously taken
place in the sample. It may be ascertained by making
an approximation value, then computing the con-
traction, and recalculating. Tables have been worked
out for this correction, but cannot be given here.
The above method has been used in commercial
control work over a period of nearly 10 yrs. Where
routine work is done over a comparatively limited
range of strength, it is possible to condense all calcula-
tions into one set of tables, and to obtain percentages
of alcohol directly from the buret readings.
The calculation depends upon the experimentally
established fact that the total volume of solvent
(alcohol plus water) is a nearly strictly linear function
The anti-trust suit of the Federal Government against the
Eastman Kodak Company was settled February 1, 1921, with
the filing of a decree in the U. S. District Court in Buffalo,
requiring the company to dispose of approximately $4,000,000
of its assets, which total $90,000,000. Among other things the
decree orders the sale of the Premo factory and the Century-
Folmer and Schwing factory in Rochester and the Aristo plant
in Jamestown, N. Y., plants which were acquired from competi-
tors, and not developed as part of the industry built up by George
Eastman. It is stated that the decree will result in no substantial
disruption of the organization, since a radical move for dissolu-
tion has practically been stopped, and the company will carry
on its activities with renewed confidence. Notice of appeal
was withdrawn after a conference of the company's representa-
tive with the Attorney General in Washington.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
231
LABORATORY AND PLANT
A COMPARATIVE STUDY OF VIBRATION ABSORBERS'
By H. C. Howard
Research Laboratories, B. F. Goodrich Company, Akron, Ohio
Vibrations in laboratories always cause great annoy-
ance, and frequently either prevent the employment
of sensitive instruments altogether or necessitate the
installation of elaborate and mechanically unstable
suspensions.
The purpose of this study was to work out a method
for determining the relative value of different devices
and materials in absorbing vibration.
A review of the available literature showed that
very little had been published on vibration in build-
ings. Some very careful and valuable work has been
done by Prof. E. E. Hall,2 of the University of Cal-
ifornia, in buildings in San Francisco and Berkeley.
-Knife Edae
■ Standard
^P^l Pivoted Bearing
:
Recording f/eedle
Fig. 1 — Simple Pendulum for Recording Horizontal Vibrations
Deutsch3 has done work in New York City, and a few-
descriptions of instruments for measuring vibration
have appeared in the engineering magazines.4 With
few exceptions the instruments which have been de-
scribed for the measurement of vibration are con-
structed on the principle of the seismograph.6 A pen-
dulum of some type constitutes the fixed mass in the
measurement of the horizontal component of the vibra-
tion and a weighted helical spring in the measurement
of the vertical.
The apparatus which was used for obtaining records
of horizontal vibration is shown in Fig. i. It con-
sisted of a simple pendulum weighing about 25 lbs.,
and having a period of vibration of approximately
one second. A very light aluminium recording needle
1 Presented before the Division of Industrial and Engineering Chem-
istry at the 60th Meeting of the American Chemical Society, Chicago,
111., September 6 to 10, 1920.
» Eng. News, 68 (1912), 198; Elec. World, July 29, 1912; Dec. 15, 1915.
We are also indebted to Prof. Hall for a personal communication describing
his apparatus in detail.
> Eng. Record, 61 (1911), 630.
*lbid., 55 (1907), 735; Sci. American, 96 (1907), 129; 97 (1907), 470;
110 (1914), 176; Sci. American, Supfl., 60 (1905), 24688; 63 (1907),
26018; 78 (1914), 364; 82 (1916), 188; Eng. Mag., SO (1906), 433.
»G. W. Walker, "Modern Seismology," 1913; H. F. Reid, Report
California Earthquake Commission, published by Carnegie Inst., Wash-
ington, 1910; C. F. Marvin, "Universal Seismograph," Monthly Weather
Review, November 1907; D. Grunmach, "Experimental Untersuchung tur
Messung von Erderschutterungen," Leonard Simion, Berlin, 1913.
-Sprinq
Pivoted Bearing
Fig. 2 — Instr
for Recording Vertical Vibration
was connected to this pendulum in such a way as to
give about a 20-fold magnification on the record sheet.
For vertical vibration we used the apparatus shown
in Fig. 2, consisting of a helical steel spring, No. 14
wire, about three-fourths inch in diameter and 12 in.
long when unstretched, and loaded with a lead bob
weighing about 3 lbs. The bob was constrained to
movement in one vertical plane by knife edges. Ver-
tical motion relative to the bob was transformed into
horizontal by a system of very light aluminium levers
Q Q Q Q.
(a)
n n Q n
O O O O
C\
p>
(di
Fig.
working in slots. Simultaneous records of vertical
vibration, horizontal vibration in one direction, and
time were made on smoked, glazed paper carried by a
kymograph.
232
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
1 — vertical Vibration.
2-KVMOGRAPH RECORD IN SECONDS. 3-HORIZONTAl VIBRATION
Mar , 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
233
H zj
3
L 2i
All of the measurements were made on the sixth
floor of a modern steel and concrete building in which
the vibrations were due to the operation of heavy
machinery on the first floor and were very distinctly
felt throughout the building. The instrument was set
up on a soapstone slab which weighed approximately
200 lbs., and records were made with this slab sup-
ported by the device to be tested. At frequent intervals
records were made with the slab resting directly on the
desk, thus furnishing a reference curve and enabling
us, when comparing curves, to take into account va-
riations in the vibration of the building at different
periods of the day.
Vibration records were obtained with apparatus sup-
ported by the following devices:
I — Air bags inflated to various pressures. These bags when
uninflated were about 26 in. long and 5 in. wide. Inflated to
10 lbs. pressure they were nearly circular in cross section, while
at 1.5 lbs. they were almost flat.
II — Rubber balls filled with air at 40 lbs. pressure. External
diameter of balls, 2 in. Thickness of wall seven-thirty-seconds
inch. These balls were arranged in various ways as follows:
(a) Held between strips of wood, as in Fig. 3a.
(b) Separated by a frame, as in Fig. 36.
(c) Piled in a section of a pipe supported by a flange, as in
Fig. $c.
(d) Piled in the form of a tetrahedron, the three base balls
being held in place by a triangular wooden frame. See Fig. 3d.
Four of these were used under each slab.
ord in Seconds. 3 — Horizontal Vibration
III — Slabs of sponge rubber built up to a thickness of 4 in.
IV — Slabs of cork about 3 in. thick.
V — Layers of felt built up to a thickness of 3 in.
DESCRIPTION OP CURVES
Curves A were selected as typical from among a great num-
ber made directly on the laboratory desk. The frequencies
average from eight to ten per second, and there are also present,
impressed upon these high frequency displacements, much more
regular vibrations of very long period (in some cases as long as
,S sec.) which presumably correspond to the movement of the
building as a whole.
Curves B were made with the device which we consider best
for absorbing vibration. Note the marked decrease in fre-
quency and the improvement of the curve in respect to smooth-
ness and regularity. These curves were made with the tetra-
hedral arrangement of balls as shown in Fig. 3d. It is, of course,
not possible to absorb the long period vibrations corresponding
to the movement of the building as a whole, so that these appear
as before.
Curves C, D, K. and F were made with air bags inflated to
1 -5. 2-5. 5. and 10 lbs. pressure, respectively. These curves show
the best results with 2.5 and 5 lbs. inflations. In the case of the
10 lbs. inflation the resiliency is so high that the amplitude of
the vibrations is actually increased.
Curve G was made with the balls arranged as in Fig. 36.
This is a very effective arrangement, and as the balls flatten
considerably under the weight it is quite stable.
Curve H was made with the balls held as in Fig. 3a. The
curves show that this arrangement is relatively ineffective. It
is very stable.
234
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
Q
3\
1 — Vertical Vibration. 2 — Kymograph Record in Seconds. J — Horizontal Vibration
Curve I was made with the balls arranged as in Fig. 3c, and
shows that this system is of no value.
Curve J was made with the same arrangement as in B, but to
increase the stability balls held in wooden frames were brought
to bear against the edges of the slab. As is to be expected, the
curves obtained under these conditions showed considerable
increase in horizontal vibration.
Curves K and L were made with the slab placed directly on
the desk when no machines were running and there was no per-
ceptible vibration in the laboratory. The disturbances at the
beginning and end of the curve were produced by the operator
pounding on the desk.
Curves M and N are of interest because a switch engine passed
along the tracks near the building while they were being made.
Curve M was made with bags inflated to 5 lbs. pressure, while
Curve N was made with arrangement of rubber balls, Fig. 3a.
It will be observed that the air bags have increased the periods
from a little over 1 sec. to about 5 sec.
Only qualitative comparisons, consisting of observations on
the degree of agitation of a mercury surface, were made on sponge
rubber, felt, and cork, but it is certain that these materials are
much inferior to air bags or rubber balls as vibration absorbers.
SUSPENSION DEVICE
It will be noticed that our attempts to develop
devices for eliminating vibration have been directed
solely toward supporting systems. This was done
because of the manifest advantage of supports over
suspensions, such as greater mechanical stability, port-
ability, and absence of wires or springs in the working
space above the table. For purposes of comparison,
however, since suspensions have long been employed
to eliminate vibrations,1 some measurements were
made on a spring suspension. This consisted of a
heavy rectangular wooden frame supported from each
of the four corners by two helical springs, which were
one inch in diameter and 6 ft. long when loaded. The
diameter of wire was three-thirty-seconds inch. The
vibration recorder was placed on the frame, the record-
ing needles were adjusted, and the apparatus left un-
touched for a period of one hour. The drum of the
• W.H.Julius, Wild. Ann., 66 (1895), 151 ; Z. Instrumentenk., 16 (1896).
267, W. P. White. Phys. Rev., 19 (1904), 323.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
235
kymograph was started by means of an electromag-
netic device, so that the only contact of the suspension
with the building (other than its overhead supports)
was through a spiral of fine copper wire. The curves
obtained are shown in 0 and P. A comparison of
these curves with the others shows that a spring sus-
pension is markedly superior to any of the support-
ing devices developed. Considerable vertical vibra-
tion is still present, however, and a photomicrographic
apparatus mounted on this suspension did not give
uniformly satisfactory results, even at low magnifica-
tions. The results obtained with a combination of the
supporting device (Fig. 3d) and the suspension, i. «.,
tetrahedra placed under the vibration instrument on
the framework of the suspension, are shown in Curve
Q. This curve shows considerable improvement, and
the arrangement is very little more unstable and awk-
ward than the suspension alone.
In conclusion, we wish to point out that every lab-
oratory vibration problem must be solved indepen-
dently, because freedom from vibration and great
stability are not reconcilable. The determining factor
is, of course, the degree of freedom from vibration
that is required, and this being once fixed determines
the amount of stability possible. That is, a mounting
of great stability can be constructed which would be
entirely satisfactory for a quantitative balance, but
for high-power microscopic work greater freedom from
vibration is required and hence less stability can be
obtained. For very sensitive instruments such as
galvanometers, where the greatest freedom from vibra-
tion is required, lack of stability must be accepted as a
necessary evil.
The devices which have been found effective in
absorbing vibration may be arranged in the order of
their merit as follows:
1 — Spring suspension
2 — Tetrahedron arrangement of rubber balls
3 — Balls separated and held by a wooden frame
4 — Air bags inflated at from 2 to 5 lbs. pressure
The second of these has been used in this laboratory
with complete success as a support for a Leeds and
Northrup reflecting galvanometer, type 2420, quan-
titative balances, and high-power microscopes.
SUMMARY
A simple apparatus for making comparative measure-
ments of vibration has been constructed.
The results of measurements of the vibration ab-
sorbing capacities of various devices are presented.
Certain arrangements of rubber balls have been
found very effective.
The Federal Trade Commission has cited the United States
Refining Company of Cleveland, Ohio, in complaint of unfair
competition in the manufacture and sale of paints and other
products. The complaint alleges false and deceptive advertising.
At a recent meeting of the Gypsum Industries Association,
six to eight fellowships were provided for, each with a stipend
of $1000 to $1500 a year, to be located at various agricultural
colleges in the eastern United States, for the purpose of investi -
gating the use of gypsum in crop production and for making
a fundamental study of the relation of sulfur to crop nutrition
and growth.
WATER SOFTENING FOR THE MANUFACTURE OF RAW
WATER ICE1
By A. S. Behrman
International Filter Co., Chicago, Illinois
The manufacture of ice from distilled water is rapidly
being replaced by the production of ice from raw water
— or, more strictly speaking, from undistilled water.
The two agencies principally responsible for this de-
velopment are cheap, dependable power and applied
chemistry, in the form of water softening.
The requisite characteristics of first-quality ice are
clearness, firmness, and freedom from discoloration.
These qualities are possessed by ice made from pure
water, free from dissolved solids and gases, such as
the reboiled distilled water which has, until com-
paratively recently, been almost exclusively used in
the artificial ice industry. Ice frozen from impure
water is opaque, discolored, or brittle, depending on
the nature of the impurities.
Freezing water is, in many respects, much like boil-
ing and evaporating it, in that by far the greatest part
of the substances dissolved in the water freeze out
in the ice made from it. The most effective purifica-
tion of raw water for ice making is, therefore, that
which reduces the objectionable impurities in the
water to a minimum. It is now generally recognized
that this most effective purification is accomplished
by lime-soda softening, followed by sand filtration.
METHOD OF MANUFACTURE OF RAW WATER ICE
In the process of manufacturing ice from raw water,
cans of the water are surrounded by a sodium or
calcium chloride brine having a temperature usually
12° to 18° F. Air, under either high pressure (15 to
25 lbs.) or low pressure (3 to 5 lbs.), is bubbled through
the water as it freezes, the high-pressure air being in
general more effective. The first ice formed around
the sides of a can is usually relatively pure. The
dissolved solid and gaseous impurities in the water
are frozen out and begin to deposit on the face of the
ice; but the currents of water set up by air agitation
wash these impurities off the surface of the ice and
carry them towards the center of the can. The im-
purities in the raw water thus become concentrated
in the unfrozen water in the middle of the can. If
these impurities are insoluble, their accumulation in
this unfrozen water usually becomes so heavy that
eventually the currents of water set up by the air
agitation are not powerful enough to keep the par-
ticles in suspension. As a result, these white or col-
ored particles begin to deposit in the ice before the
cake is frozen solid, or, if the impurities are soluble,
such as sodium salts, their concentration may become
so great that freezing is materially retarded. In
either case this concentrated impure water, or "core
water," as it is termed, is generally removed, usually
with a suction pump, and replaced with fresh water.
The solids and gases left in the core water, or intro-
duced in the fresh water replacing it, appear as white
1 Presented before the Division of Water, Sewage, and Sanitation at
the 60th Meeting of the American Chemical Society, Chicago, 111., Sep-
tember 6 to 10, 1920.
236
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
or colored deposits, and as air needles in the core of the
ice when the cake is frozen solid.
OBJECTIONABLE IMPURITIES
The most objectionable impurities in raw water
for ice making are the compounds of magnesium,
calcium and iron, organic matter, silica and alumina,
and sodium salts. A word about each will be in order.
CALCIUM AND MAGNESIUM COMPOUNDS— The most
common, and at the same time most undesirable class
of calcium and magnesium compounds are those
causing temporary hardness — that is, the bicarbonates.
Just as heating a water of this nature causes precipi-
tation of the normal carbonates, ■ so will freezing it
drive off the loosely held "half-bound" carbon dioxide
and cause a precipitation in the ice of the normal
• carbonates, arid possibly of magnesium hydrate.
With air agitation, these precipitated compounds will
be carried more or less completely to the center of
the can. Here they will accumulate until it becomes
necessary to pump out the heavily laden water and
replace it with fresh water. Frequently this ac-
cumulation takes place so rapidly that two, and some-
times even three, core pumpings are required. Even
with good air agitation, however, the removal of the
precipitated compounds to the middle of the can is
often not complete, and milky white dots, bubbles,
.and patches are found distributed throughout the
clear portion of the ice. Frequently, also, a wlnte
opaque shell of the precipitated carbonates will be
found around the lower portion of the cake, where
freezing is most rapid. When ice containing the pre-
cipitated carbonates melts, it leaves this objection-
able sediment.
Softening with lime removes the bicarbonates
•effectively and cheaply, and leaves in the treated
water no products of the reaction beyond the 2.5 to
4 grains per gallon of calcium carbonate and magnesium
hydrate generally considered the limit of the lime re-
action in the cold.
The removal of permanent hardness is far less im-
portant for ice making than temporary hardness.
Investigations now under way indicate that in a great
many cases, possibly all, permanent hardness need
not be removed, provided that the magnesium, which
always tends to make white ice, is removed from such
compounds and replaced with calcium. This is ac-
complished, of course, in the treatment with lime.
The calcium sulfate and chloride left in the water as
a result of the lime treatment appear to be no more
detrimental, and in some cases even less so, than the
sodium salts which would result from the removal of
the permanent hardness with soda ash. In a number
of cases with waters of widely varying nature, we have
discontinued the use of soda ash. In practically
every instance, ice made with the plain lime treatment
is equally good or better than when soda is used.
In addition, sedimentation in the softening tanks is
more complete, reducing the load on the filters. Fur-
ther, when no soda is employed, the carbonate ions
in the treated water are lessened, and. as the ice freezes,
a much greater concentration in the unfrozen water
is required before the ion-product constant is exceeded.
As a result, the unfrozen water remains clear much
longer, free from particles of the precipitated carbonate
that would tend to deposit in the ice; consequently,
core pumping can be delayed, lessening the amount
of water and refrigeration thus wasted.
IRON, SILICA, ALUMINA, AND ORGANIC MATTER As
little as 0.2 p. p. m. of iron may cause "red ice" — that
is, ice colored red-brown, chiefly in the core. Silica
and alumina are deposited in the core of the ice cake,
imparting a muddy appearance to it; when this ice
melts, a gray, slimy sediment remains. Organic mat-
ter is frequently found in objectionable quantity in
surface waters, particularly in warm weather. It
usually colors the core of the ice a muddy or bright yel-
low, which is sometimes so objectionable that the ice
is difficultly salable, even though otherwise of good
quality.
Lime-soda softening of the raw water, followed by
sand filtration aided by the use of a coagulant, ef-
fectively removes the iron, reduces the silica and
alumina usually by a half to three-fourths, and greatly
lessens the amount of objectionable organic matter.
In removing organic matter, we have in some cases
found helpful the use of bleaching powder, applied
with the softening chemicals.
sodium salts — The chief objection to sodium (and.
of course, potassium) salts is that they accumulate
in the core water, retarding freezing, and are finally
deposited as white solids in the ice. If considerable
sodium salts are present, the lengthening of the freez-
ing period may be so serious that several core pump-
ings and fillings with fresh water may be necessary.
In addition to this general objection, certain sodium
compounds have specific undesirable effects. Sodium
bicarbonate in considerable amount tends to cause
brittleness and cracking. Large quantities of sodium
sulfate tend towards the formation of a white shell
on the outside of the ice, giving the entire cake an
opaque appearance even though the interior portion
is quite clear.
Treatment with lime converts the bicarbonate of
soda to the normal carbonate and decreases some-
what the tendency towards brittleness. Softening
has no other beneficial effect on sodium salts. The
only practical way to remove them, of course, is by
distillation.
CORE PUMPING
Core pumping involves a number of very serious
losses. There is the expense of refrigerating the fresh
water, the decreased plant capacity due to the extra
time necessary for freezing this fresh water through
the excellent insulation of the surrounding ice, the
labor required, and the cost of pumping, and of the
water itself. These combined losses are so heavy
that, in many cases, if competition for trade is not
keen, the ice maker will not pump cores when they
really should be pumped, and will produce a cake of
ice having a heavy white or discolored center, instead
of a thin, colorless, tasteless, ' and practically trans-
parent one.
From the standpoint of core pumping, the most
objectionable impurities in raw water are those causing
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
237
temporary hardness, due to the heavy, gritty sedi-
ment formed by freezing out the half-bound carbon
dioxide. When, as is frequently the case, the im-
purities in a raw water are chiefly of this nature,
softening with lime reduces the offending substances
so much that it is often possible to produce first quality
ice without core pumping, provided the air agitation
is not stopped too soon.
Even when the presence of large amounts of impuri-
ties other than temporary hardness, or when improper
air agitation prevents entire elimination of core pump-
ing, lime-soda softening reduces the quantity of water
that must be pumped. Usually one small core pump-
ing is all that is required. This effects a very ma-
terial saving in water and refrigeration, and, in a large
plant, of labor. The freezing time is also shortened,
increasing the plant's output.
CHECKING AND CRACKING
A very unwelcome and expensive phenomenon in
an ice plant is the tendency of the ice to crack and
shatter, particularly when low brine temperatures are
employed. There has been no satisfactory explana-
tion advanced for this tendency, beyond that the ice
is evidently frozen under an internal strain.
It would appear to be quite possible that the pres-
ence of bicarbonates in the water is chiefly responsible
for this strain. During the freezing process, while the
half-bound carbon dioxide is trying to escape, the ice
continues to crystallize, entrapping bubbles of gas and
particles of the precipitated compounds, which are
readily visible. The ice thus formed is comparable
to a metal casting full of blowholes and impurities,
and is in consequence inherently weak and brittle.
Some weight is given this hypothesis by the general
experience that removing the bicarbonates of calcium
and magnesium from a water by treatment with lime
results in the production of much clearer and firmer
ice, and frequently permits the use of lower brine
temperatures. Further, in a recent series of ex-
periments, ice was frozen from water to which had
been added varying amounts of sodium bicarbonate.
In all cases except the lowest concentration (10 grains
per gal.) the ice formed was quite brittle, cracked
readily, and showed considerable evidence of a bubbly
■structure. Analysis of the melted core ice showed
the conversion of the bicarbonate to the normal car-
bonate in all cases to the extent that the normal car-
bonate alkalinity averaged 35 per cent of the bicar-
bonate alkalinity.
ZEOLITE SOFTENING
It is this relation of bicarbonate alkalinity to brittle
and bubbly ice which is probably partially responsible
for the unsuccessful application of zeolite softening
to the manufacture of raw water ice. Contrasted
with the actual removal of the bicarbonates of calcium
and magnesium that is effected by softening with lime,
the zeolite or base exchange process leaves in the
treated water the slightly greater equivalent weight
of sodium bicarbonate. Calcium and magnesium sul-
fate are converted to sodium sulfate, which has the
•disadvantages already discussed. Iron, silica, alumina,
and organic matter are not eliminated or reduced by
zeolite softening.
LIMITING SALT CONCENTRATIONS
Finally, the question arises as to the limiting quan-
tities of the various impurities that a raw water can
carry and still make first-quality ice. We do not know
exactly as yet, in all instances. Obviously, in the
cases of the bicarbonates of calcium, magnesium, and
iron, the limiting concentrations are their own solu-
bilities, since softening with lime leaves the same
residual content regardless of the initial concentration.
It is also probable that the permissible maximum of
silica and alumina is not exceeded in natural waters,
if treatment with lime is employed.
With regard to sodium salts, and to calcium sulfate
and chloride, investigations are now under way as to
the limiting concentrations possible, and the results
will be published when completed. Tentatively, it
would appear that when the total soluble salt content
of a raw water exceeds 30 to 40 grains per gal.,
exclusive of the temporary hardness, first-quality raw
water ice cannot be made even with softening and high-
pressure air agitation.
NOTE ON PARTIAL AND TOTAL IMMERSION
THERMOMETERS1
By C. W. Waidner and E. F. Mueller
Bureau of Standards. Department op Commerce,
Washington, D. C.
Received December 13. 1920
To avoid the necessity of applying the correction for
the emergent stem, so-called partial immersion ther-
mometers are made, which are pointed and calibrated
to read, as nearly as possible, correct temperatures
when immersed to a definite mark on the scale, e. g.,
8 cm. above the bottom of the bulb. The indications
of such thermometers are obviously influenced to some
extent by the temperature distribution above the
bath; for example, if the thermometer were used in a
bath, the top of which was insulated, the indications
would be somewhat different from those obtained in
an open bath where the emergent stem would be
heated by convection currents. The difference would
be still more marked if the thermometer were used in
a small bath heated by a gas flame.
Such thermometers should be marked ".... cm.
immersion" or its equivalent, and should be provided
with a mark on the stem to indicate the depth of
immersion. The reliability of the corrections certified
as applicable to partial immersion thermometers is
necessarily somewhat less than that of the corrections
certified for total immersion thermometers, but this
does not by any means imply that, if both thermom-
eters are used with partial immersion, more accurate
results will necessarily be obtained with the total im-
mersion thermometer.
RELATIVE ACCURACY OF PARTIAL AND TOTAL
IMMERSION THERMOMETERS
For general laboratory use the partial immersion
thermometer has some very evident advantages. In
l Published by permission of the Director of the Bureau of Standards
238
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
choosing the type to be preferred for any one kind of
measurement it is necessary to decide whether the pos-
sible errors incident to the use of a partial immersion
thermometer are larger than are permissible, and
whether it is worth while to use a total immersion
thermometer under conditions approximating total im-
mersion or, if the total immersion thermometer must
be used with a considerable portion of the stem emer-
gent, to make an accurate determination of the stem
correction. The magnitude of the possible error due
to the use of a partial immersion thermometer is best
illustrated by an example.
PARTIAL IMMERSION THERMOMETER AT 300°— Sup-
pose a partial immersion thermometer to have been
standardized in a certain type of bath so that, for a
bath temperature of 300° C, the average temperature
of the 300 "-length of emergent stem was 40° and that
it is later used to measure the temperature of another
bath at 300°. Under the most markedly different
conditions the average stem temperature could hardly
differ by more than 50° from that which prevailed
during the standardization of the thermometer. For
this possible difference in mean stem temperatures in
the two cases the resulting difference in the indications
of the thermometer (error as used) would be:
0.00016 X 300 (50) = 2.4°
Except under very unusual conditions the error under
consideration would be hardly more than half that
calculated above, or, in round numbers, about 1°.
total immersion thermometer at 300° — Consider
next the accuracy attainable by the use of a total im-
mersion thermometer likewise used with 300° of the
mercury column emergent from the bath. If the
average stem temperature is actually 40° as before,
the total stem correction is
0.00016 X 300 (300-40) = 12.5°.
It is at once evident that totally neglecting this
stem correction, as is now the practice in many stand-
ardized commercial tests, will introduce an error many
times as large as could possibly result from the use of
a partial immersion thermometer. If, on the other
hand, the necessary care is taken to determine accu-
rately the large stem correction, under the above con-
ditions of use of the total immersion thermometer, this
stem correction could be determined to an accuracy
of at least 0.5°, corresponding to an accuracy of about
10° in determining the average stem temperature, and
in that case a somewhat higher accuracy could be
attained with the use of the total immersion thermom-
eter. If, however, the stem temperature were deter-
mined by hanging an auxiliary thermometer beside
the stem, the reading of this thermometer might differ
considerably more than 10° from the average tem-
perature of the stem, and the resulting error in the
determination of the stem correction might exceed 1°,
which is comparable with the error incident to the
use of a partial immersion thermometer. Obviously,
if the auxiliary thermometer were hung with its bulb
a short distance above the bath, it would indicate a
temperature considerably in excess of the average tem-
perature of the stem, and if placed with its bulb too
near the top of the emergent column, it would indicate
too low a temperature. To determine the average
stem temperature accurately, it is necessary to use a
suitable capillary ("faden") thermometer, which is a
thermometer with a long capillary bulb, and which
serves to measure the average temperature of the
portion of the stem beside it. This is a very special
device that is very rarely used outside of a thermometer
standardizing laboratory.
accuracy at lower temperatures — In the above
illustration a bath temperature of 300° was assumed.
At lower temperatures the case is slightly less favor-
able to the partial immersion thermometer, because of
the fact that a large part of the possible error in its
use is due to differences in the temperature of the
laboratory at different seasons. As an example, sup-
pose a partial immersion thermometer is used to
measure the temperature of a bath at 90°, with 90°
of the column emergent; a difference of stem tem-
perature of 30° under different circumstances is pos-
sible, corresponding to a difference in reading of 0.4°,
but except under unusual conditions the difference
should not exceed 0.2°. For a total immersion ther-
mometer, with 90° emergent and an average stem
temperature of 25°, the stem correction would be
about 0.9°. If, as seems reasonable, the average stem
temperature could easily be determined within 5° or
10°, the stem correction would be determined to about
0.1°, so that in this case somewhat more accurate re-
sults could be obtained with the total immersion ther-
mometer, even if the stem correction were merely de-
termined in the usual manner.
GRADUATION INTERVALS
The above considerations apply primarily to ther-
mometers graduated in 1° or 2° intervals. For ther-
mometers which are graduated in smaller intervals,
and particularly for thermometers graduated in 0.1°
or 0.2°, in the use of which an accuracy of a few hun-
dredths of a degree is desired, the situation is not the
same, as may be shown by an example.
Suppose a temperature of 70° C. is to be measured
with a thermometer graduated from 0° to 100° in 0.2°.
If a total immersion thermometer with 70° of the mer-
cury column emergent from the bath is used, it may
reasonably be supposed that the average temperature
of the emergent stem can be determined with an error
not exceeding 5° by the use of an ordinary auxiliary
thermometer, or within 1° by the use of a capillary
thermometer. The error in the computed stem cor-
rection, due to an error of 5° in the average tempera-
ture of the stem, is
0.00016 X 70 (5) = 0.06°.
A partial immersion thermometer may be used at
one time in a room at 15° C. and at another time in
a room at 35° C. (usual range at the Bureau of Stand-
ards). If the same temperature (70°) were measured
with the partial immersion thermometer under the
two extreme conditions, the results obtained would
differ by
0.00016 X 70 (20) = 0.22°,
or more than one whole scale division. The compar-
Mar., 1921
THE JOURS AL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
239
ison is less favorable to the partial immersion ther-
mometer at temperatures lower and more favorable at
temperatures higher than the one considered.
From the above considerations it will be seen that
increased accuracy in the use of partial immersion
thermometers cannot be had by using finer graduation
intervals, such as 0.1° or 0.2°, nor can it be had by
the use of total immersion thermometers graduated
into such intervals, when a total immersion ther-
mometer is actually used with a long emergent col-
umn, unless the average stem temperature is accu-
rately determined. It seems, therefore, inadvisable to
resort to such fine graduation intervals in all cases
where the thermometer must be used with a long
■emergent column.' Finely divided thermometers are
presumably intended to yield accurate temperature
measurements, and hence such thermometers should,
in general, always be graduated as total immersion
thermometers, and should be used, as nearly as pos-
sible, under conditions of total immersion; or, if that
is not possible, the average stem temperature should
be determined with the required accuracy. Otherwise,
the increased accuracy which one would naturally ex-
pect is not attainable. The only excuse for resorting
to such fine graduations in the case of a thermometer
that has to be used with a long emergent column is the
somewhat greater ease of reading by an inexperienced
observer. It is very easy with a little practice to train
anyone with moderate intelligence to estimate 0.1 of
a graduation interval, so that there is no very strong
reason for graduating thermometers to be used with
a long emergent column finer than 1°, although, of
course, this is admittedly a matter of personal prefer-
ence, and depends somewhat upon how entirely un-
trustworthy are those to whom the reading of ther-
mometers is entrusted. It has always seemed to the
writers that laboratory assistants who could be relied
upon to carry out most standardized chemical tests
could equally well be expected to possess sufficient
intelligence to learn quickly how to estimate ther-
mometer readings to 0.1 of the smallest graduation
interval.
The custom of some manufacturers of marking cer-
tain thermometers for "bulb immersion" is open to
serious objection, first, because the term is indefinite,
and, second, because the top of the bulb must be at a
sufficient distance below the surface of the bath so
that the entire bulb shall be at the bath temperature,
as otherwise very erratic results would be obtained.
The minimum immersion of a partial immersion ther-
mometer in a liquid bath should be 0.5 in. (13 mm.)
above the top of the bulb, and the intended depth of
immersion should be marked on the stem as already
noted.
Thermometers of the industrial type are very gen-
erally graduated and used as partial immersion ther-
mometers. Where the requirements of their use are
such that the thermometer is very long and the grad-
uated part of the scale is at a considerable distance
from the bulb, the two parts may be joined by ther-
mometer tubing having a much finer capillary bore
than is used in the upper portion of the stem where
the mercury must be easily seen and read. This con-
struction minimizes the effect of temperature varia-
tions of the stem on the indications of the thermometer.
TOLERANCES AND ACCURACY OF PARTIAL IMMERSION
thermometers — -It will be noted that somewhat larger
tolerances must be allowed for partial immersion than
for total immersion thermometers, and also that the
certified corrections, resulting from an ordinary routine
test, are reliable to a lower order of accuracy. This
is due to the fact that for total immersion thermometers
the temperature of the mercury column is completely
specified, while for partial immersion thermometers the
stem temperature is, in the nature of the case, incom-
pletely specified, as illustrated in the examples given
above. However, if a high-temperature partial immer-
sion thermometer were used under the exact conditions
prevailing during its standardization (including room
temperature) the reliability of the measurements would
not be much less than of those for a total immersion
thermometer actually used under conditions of total
immersion.
Attention should be called to the fact that standard-
ized methods and apparatus are used in most routine
tests, and that the accuracy with which the testing
laboratory can duplicate its corrections for a partial
immersion thermometer is in excess of the accuracy
to which the users can determine actual temperatures,
where the conditions prevailing in the use of the in-
strument are very different from those prevailing in
the test. The error due to this difference could, of
course, be made very small if, for the standardized
test in question, a determination were made of the
correction necessary to take into account the difference
in conditions prevailing during the standardization of
the thermometer and during its subsequent use in the
standard test.
Another procedure which might possibly receive the
consideration of committees preparing standardized
testing specifications is the continuance of the use of
total immersion thermometers and the determination,
for each such test, of the appropriate stem correction
that should be applied to the reading of the thermom-
eter at various temperatures. Such a stem correc-
tion could be determined once for all, so that it could
be applied directly by the user, just as he applies the
ordinary corrections taken from a certificate, provided,
of course, the apparatus, including the thermometer,
were standardized as to its dimensions. Obviously, the
same stem correction would not apply if the ther-
mometers differed much in their dimensions or if they
were used under markedly different conditions of im-
mersion. This procedure would take care of stand-
ardized tests, yielding results of substantially the same
accuracy as would be obtained with partial immersion
thermometers, but the fact would still remain that in
the ordinary everyday use of thermometers in the
laboratory, where stem corrections are almost always
neglected, the user would, in general, get a higher
accuracy by the use of partial immersion thermometers.
In considering the preparation of standard specifica-
tions for chemical thermometers for general laboratory
uses, the question has arisen whether such ther-
240
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
mometers should be graduated as total or partial im-
mersion thermometers. For the ordinary everyday
use of a thermometer it seems to be quite customary
to immerse it a few inches in the bath or medium, the
temperature of which is to be measured. It also seems
to be quite customary to neglect the stem correction.
If these are the usual conditions of use it will be seen
that more accurate results would be obtained by using
partial immersion thermometers, and about as accurate
results would be obtained by such usage as would be
obtained with total immersion thermometers, even
when the stem correction was applied, unless due care
were taken to determine the stem correction with
sufficient accuracy.
CONCLUSIONS
The above considerations may be summarized in
the statement that in all cases where the application
of stem corrections is neglected, which includes a vast
majority of ordinary routine laboratory temperature
measurements, more accurate temperature measure-
ments would be attained by the use of thermometers
graduated as partial immersion thermometers; the
same statement would apply for measurements at the
higher temperatures (above 200° C. or thereabouts).
even if stem corrections are applied, when the ordinary
method of estimating average stem temperature is
used instead of the more accurate capillary thermom-
eter method. At the lower temperatures, on the
other hand, a slight -advantage rests with the total
immersion thermometer, if the stem correction is de-
termined and applied in the usual manner, i. e., by
the intelligent use of an auxiliary thermometer to
determine the average stem temperature. Thermom-
eters graduated in intervals smaller than 0.5° C.
should not, in general, be graduated as partial immer-
sion thermometers, if the accuracy of which they are
capable is desired, unless such finer graduation be
deemed of sufficient importance solely from the stand-
point of convenience in reading.
LABORATORY THERMOMETERS
By W. D. Collins1
The Albany Chemical Company has been ordered by Federal
Judge Dietrich to withdraw all applications for a trade-mark
of the word "aspirin." The Company was cited by the Federal
Trade Commission in complaint of unfair competition, being
charged with falsely advertising that no other person or corpora-
tion has a right to the use of the word "aspirin." Upon expira-
tion of the patent on the word, it became a descriptive name
and not the property of anyone.
The Journal of Commerce reports that by the amalgamation
of Aniline Dyes & Chemicals, Inc., with the Swiss Society for
Chemical Industry, an amalgamation of the three Swiss firms,
the Geigy Co., Ltd., The Chemical Works formerly Sandoz),
and the Society for Chemical Industry, with the two American
firms of Ault & Wiborg and Aniline Dyes & Chemicals, is ac-
complished, since the recent sale of Ault & Wiborg to the Geigy
Company was really a sale to the Swiss amalgamation.
A car containing 49,494 lbs. of sodium peroxide manufac-
tured by the Niagara Klectro-Chemical Company, at Niagara
Falls, N. Y., recently exploded while standing on the tracks in
the freight yard. No reason for the disaster has been an-
nounced.
Received January 10, 1921
In the following discussion "thermometer" means
the usual mercury-in-glass thermometer with engraved
stem. The type with enclosed glass scale is much
superior for many operations, but in the ranges regu-
larly used is not yet produced sufficiently generally in
the United States to make possible its adoption as
stock apparatus.
The mercury thermometer at its best is not an in-
strument of extreme precision. At its worst it may
be very misleading. The large errors which are occa-
sionally found are due to carelessness in manufacture,
usually in the process of pointing. Excessive depres-
sion of the zero point after heating to a high tem-
perature does not occur unless the maker has failed
to use proper glass for the bulb. Irregularities in the
bore rarely have any serious effect on the accuracy
if the distances between reference points are not too
great. If reasonable care in annealing or aging has
been exercised the readings do not change much with
time. Slight errors due to all these causes will be
found in any thermometer and cannot be allowed for
with great precision. On the other hand, a well-made,
carefully pointed thermometer is as accurate and
reliable as many of the other features of regular chem-
ical work in which it is used.
The discussion by Waidner and Mueller in the pre-
ceding article covers the question of the accuracy of
thermometers made to be used with total immersion
or partial immersion. It is well know-n that a large
proportion of the temperature measurements in regular
chemical laboratory work arc made with a greater or
less length of emergent mercury column without cor-
rection.
It has been objected that errors may result from
introduction of partial immersion thermometers into
laboratories where those pointed for total immersion
have been in use. It does not seem likely that anyone
careful enough to correct for the emergent stem on a
total immersion thermometer would fail to use prop-
erly one marked for partial immersion. The others
would all gain in accuracy.
The specifications given below were prepared by
Mr. E. P.' Mueller of the Bureau of Standards to
include certain features which had been suggested by
various members of the Committee on Guaranteed
Reagents and Standard Apparatus, and had been
discussed at a conference of members of the committee
with Dr. Waidner and Mr. Mueller. It was felt that
the three thermometers described furnish a good work-
ing set for general laboratory use.
The thermometer with a range from — 20° to 150'
C. in single degrees is much more useful than one with
the widely used range from — 10° or — 5° to 100° or
110° C, and the cost need not be much greater. The
length of the degree divisions is better than on a 0°
to 100° thermometer of the same length for subdivi-
1 Chairman, Committee on Guaranteed Reagents and Standard Ap-
paratus, American Chemical Society.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
241
sion by the eye by those without special practice in
such reading.
The — 10° to 360° thermometer covers as nearly as
seems practicable the whole range of temperatures
measured in regular chemical laboratory work. It
was felt that the danger of breakage in handling and
use would be increased more than proportionally by
additional length, while a shorter thermometer with
this range would have the degree divisions too small.
For the sake of added strength the diameter limits
have been raised from those for the 150° thermometer.
Thermometer 3 has been added to provide for the
more accurate measurement of temperature up to 100°.
As explained by Waidner and Mueller, the graduation
in 0.2° divisions makes it out of the question to point
and use this as a partial . immersion thermometer.
The uncertainty of the reading may amount to one
or two divisions, making the recording of fractions of
divisions absurd. Despite the greater length, the
diameter has been specified smaller than the 360°
thermometer, because it will probably be used more
carefully, and it is felt that a small diameter is an
advantage except for strength.
The specifications call for accuracy which should be
obtainable without excessive cost. If much greater
accuracy is desired it is better obtained by careful
comparison with standard thermometers and the use
of the corrections so determined, rather than by at-
tempting to secure a thermometer which can be used
without correction for the more exacting work.
Tests and certificates of corrections for thermometers
can be secured from the Bureau of Standards, but
the expense and time required are justified for only
a small proportion of thermometers used in chemical
work. A laboratory may do very well, especially with
partial immersion thermometers, by having one or
two of each range tested at the Bureau of Standards
and comparing all others with them. Serious errors can
be detected easily in any laboratory without such
standardized thermometers. The zero point can be
tested by placing the thermometer up to the immer-
sion point or to the top of the mercury in melting
finely cracked ice, keeping the thermometer wet with-
out an excess of water. The 100° point can be tested
by placing the thermometer up to the immersion
point in steam, applying any necessary correction for
departure of atmospheric pressure from 760 mm. Mr.
R. M. Wilhelm has suggested1 the use of naphthalene
and anthracene for checking the points 218° and 340°,
respectively. He states that the boiling points in-
crease 0.05° and 0.07°, respectively, per mm. of mer-
cury increase in pressure.
The requirements in the General Supply Committee
Schedule for purchases by the government laboratories
in Washington during the fiscal year 1922 are based
on the specifications given below. If other labora-
tories use these specifications there should be a con-
centration of production on these items which will
bring down the price and improve the quality of ther-
mometers for chemical laboratory work.
1 "Emergent Stem Corrects
Distillation Flasks." U. S. Bur
(1915), 16.
for Thermometers in Creosote Oi!
of Standards, Technologic Paper, 49
Specification No. 1
Thermometer: — 20° to 150" C. in 1° intervals; 8 era. immer-
sion. Total length 30 to 31 cm. (approximately 12 in.); diam-
eter of stem 5.5 to 6.5 mm.
Bulb, cylindrical; not larger than stem and not over 2 cm.
long. Bulb and stem to be of suitable thermometric glass;
enamel-backed thermometer tubing; diameter of capillary must
be at least 0.1 mm.
Thermometer to be graduated for 8 cm. immersion, a mark
being etched on the stem 8 cm. above the lower end of the
bulb to indicate this depth of immersion. The — 20° gradua-
tion must be above the 8 cm. mark. The length of the graduated
scale from — 20° to +150° must be at least 15 cm. If above
specifications are complied with, it is permissible to continue
graduations below — 20° or above 150°. Every fifth line, be-
ginning at — 20°, to be longer than the intermediate lines; num-
bering at 10° intervals; error at any point not to exceed 1°.
The space above the mercury may be evacuated or gas-filled.
The reservoir at the top of the capillary shall be large enough
to permit heating of the thermometer to 200° C. without danger
of breakage due to the heating.
The thermometer shall be marked "8 cm. immersion," and shall
also be marked with the manufacturer's name or trade-mark
and a serial identification number.
The thermometer shall be made with a small glass ring or
loop at the top.
Suitable material and good workmanship shall be employed
throughout to produce a usable thermometer. The thermometer
is to be supplied in a suitable case.
Specification No. 2
Thermometer: — 10° to 360° C. in 1° intervals; 8 cm. immer-
sion. Total length 37 to 38 cm. (approximately 15 in.); diam-
eter of stem 6 to 7 mm.
Bulb, cylindrical; not larger than stem and not over 2 cm.
long; bulb and stem to be of suitable thermometric glass; enamel-
backed thermometer tubing; diameter of capillary must be at
least 0.1 mm.
Thermometer to be graduated for 8 cm. immersion, a mark
being etched on the stem 8 cm. above the lower end of the bulb
to indicate this depth of immersion. The length of the grad-
uated scale from — 10° to +360° must be at least 26 cm. If
above specifications are complied with, it is permissible to
continue graduations below — 10° or above 360°. It will be
necessary to allow a portion of the scale to extend below the
8 cm. mark. Every fifth line, beginning at — 10°, to be longer
than the intermediate lines; numbering at 10° intervals.
The thermometer must be suitably annealed; error at any
point up to 150° not to exceed 1°; at higher points, up to 300°,
not to exceed 1.5°; above 300°, not to exceed 2°.
The spaces above the mercury must be filled with a dry inert
gas at a pressure sufficient to prevent separation of the column at
any temperature of the scale. The volume of the space above the
360 ° graduation must be large enough to permit heating the ther-
mometer to 400 ° C. without danger of breakage due to the heating.
The thermometer shall be marked "8 cm. immersion," and
shall also be marked with the manufacturer's name . or trade-
mark and a serial identification number.
Suitable material and good workmanship shall be employed
throughout to produce a usable thermometer. The thermometer
is to be supplied in a suitable case.
Specification No. 3
Thermometer: — 5° to 105° C. in 0.2° intervals. Total im-
mersion. Total length 45 to 46 cm. (approximately 18 in.) ;
diameter of stem 5.7 to 6.7 mm.
Bulb, cylindrical, not larger than stem and not over 3 cm.
long; bulb and stem to be of suitable thermometric glass; enamel-
backed thermometer tubing; diameter of capillary must be at
least 0.1 mm.
The length of the graduated scale from — 5° to +105° must be
at least 33 cm. If above specifications are complied with, it
is permissible to continue graduations below — 5° or above
105°. Each degree mark is to be longer than the intermediate
marks; numbering at 2° intervals. The error at any point
must not exceed 0.3 °.
The space above the mercury may be evacuated or filled
with dry inert gas. The reservoir at the top of the capillary
shall be large enough to permit heating of the thermometer to
140 ° C. without danger of breakage due to the heating.
The thermometer shall be marked with the manufacturer's
name or trade-mark and a serial identification number.
The thermometer shall be made with a small glass ring or
loop at the top.
Suitable material and good workmanship shall be employed
throughout to produce a usable thermometer. The thermometer
hall be supplied in a suitable case.
242
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
THE DAYTON PROCESS1.2
By F. C. Binnall
General On. Gas Corporation, 511 Fifth Ave., New York, N. Y.
The Dayton process of gas manufacture is essen-
tially an air-oil gas process in which partial combus-
tion of certain constituents of the oil takes place
within the retort or reaction chamber itself, thus
supplying internally all the heat necessary for the
thermal decomposition of the hydrocarbons. Thermo-
dynamically, internal combustion gives the highest
heat efficiency in furnishing the requisite energy for
oil-gas production. This method then becomes the
most economical of all oil-gas processes. Over 88
per cent of the heat in the oil is obtained in a usable
form as gas or tar. The fact that no external heating
is required distinguishes this from all other methods
of artificial gas making.
The only raw material necessary is a liquid hydro-
carbon such as gas oil or fuel oil, which is atomized
and mixed with preheated air in predetermined and
automatically maintained proportions, and fed con-
tinuously into suitable retorts or reaction chambers
located within properly insulated settings. Within
the retorts partial combustion of the carbon and
hydrogen takes place with the oxygen of the air,
generating sufficient heat to maintain the reaction
temperature continuously, and to take care of heat
lost through radiation and combustion, and the sensible
heat carried out in the hot gases. This partial com-
bustion is sufficient to carry out as carbon monoxide
or carbon dioxide that portion of carbon which would
otherwise be deposited as lampblack. By this method
of production there is delivered as a combustible
practically all the carbon of the oil, the loss of which
in ordinary destructive distillation and carbureting
processes produces a lowering of efficiency. As the
lampblack carbon is burned within the retort, there
can be no clogging and therefore no troublesome
shutdowns.
HEAT UNIT RANGE OF GAS PRODUCED
The process provides a substantial and simple
apparatus for the manufacture of gas which is easily
controllable within the heat unit range of commercial
uses. The gas-make is continuous, uniform, and
automatic, except for nominal control, irrespective
of the gas-make per unit of time. The oil and air
settings on the atomizer are initially made for the
particular grade of gas desired, and when once ad-
justed, the ratio of air to oil cannot vary. Thus the
maintenance of this fixed ratio insures a continuous
production of the grade of gas desired. If the ratio
of air to oil is varied, the temperature of the retort,
and the quality of the gas will vary; for if more air
is added, the partial combustion of the hydrocarbons
will be more complete, thus generating more heat
per unit of time, resulting in higher temperatures
in the retort. The higher temperatures result in a
disturbance of the equilibrium and thus bring about
a change in the quality of the gas. On this basis,
1 Chapter in "American Fuels" by Hamor and Bacon.
8 Presented before the Pittsburgh Section of the American Chemical
Society. December 16, 1920.
it is obvious that the production of a very lean gas
will bring about prohibitive retort temperatures
and inefficient operating conditions. On the other
hand, the upper limit of gas B. t. u. possible is repre-
sented by that ratio of air to oil which will bring
about sufficient incomplete combustion for mainte-
nance of proper temperatures. Within these limits,
which approximate a 300 to 560 B. t. u. gas, any
grade of gas can be produced continuously, and varied
at will. Above 560 B. t. u. per cu. ft. some external
heating is necessary, as the air supplied for this heat
content does not permit of enough partial combustion
to liberate sufficient heat to sustain the reaction.
The production of 450 to 500 B. t. u. gas produces
a maximum efficiency thermally and allows the maxi-
mum production per unit of time. Also, conditions
which bring about the production of such a gas pro-
duce by-products in suitable quantity and quality.
Fig. 1 — Section through Standard Gas Generator Unit
The process is founded on correct chemical and
physical principles, so applied as to promote the
highest heat and gas-make efficiency under all rates
of make per unit of time. The air supplied for the
partial combustion during the gas-make stage is pre-
heated by the hot gases leaving the retort. This
preheated air is intimately mixed with the oil at the
atomizer, and is supplied through a pipe together
with the oil into the center of the retort. Thus
complete vaporization of oil and admixture with the
air is insured before entering the hot zone, and there
is no decomposition of the oil in the liquid phase to
augment carbon deposition. By this method of
prevaporization the maximum surface of the oil
particles is exposed in the reaction chamber, insuring
an efficient gas-make state. Lowering of partial pres-
sure is known to promote the formation of unsaturated
hydrocarbons in the gaseous phase. In this process
the large percentage of inert nitrogen present in the
air supplied for partial combustion brings about a
lowering of the partial pressure of the hydrocarbons
in the gaseous state, acting as though an actual vacuum
had been applied on the hydrocarbon system. Thus
in the cracking or gas-make stage the conditions
are proper for the formation of the maximum produc-
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
243
tion of unsaturated compounds which possess a very
high heating value. It follows, then, that the process
is capable of producing a high healing value gas with a
high nitrogen content.
Fig. 2 — Typical Plan of Generating Unit op Eicbt Retorts.
Capacity 600.000 Cu. Ft. per Day
Since the surface and pressure on the gas-make
system (approximately atmospheric) are constant,
and the concentration, time, and temperature are
under control for any predetermined condition, it
follows that when once started the process will deliver
continuously and automatically the grade of gas
desired.
PURITY OF GAS
The gas produced is free from sulfur compounds
and mechanical impurities, such as dust particles, and
no purification is necessary. The gas is clean because
the only raw materials used in its production — oil
and air — are free from impurities. The fact that the
sulfur in the oil are oxidized to the dioxide during the
gas-make stage brings about a practically sulfur-free
gas, as the sulfur dioxide passes out with the waste
water from the hydraulic main and water scrubber.
In producing 100 cu. ft. of gas in commercial installa-
tions from a quantity of oil carrying 310 grains of
sulfur, there are present in the unpurified gas only
1.34 grains of sulfur. Since, under most statutes,
purified illuminating gas is permitted to carry 30
grains or more of sulfur per 100 cu. ft., the statement
that Dayton gas is free from sulfur is warranted.
It obviously follows that when using any of the com-
mercially obtainable oils no purification for sulfur
will be required.
No costly and cumbersome gas holder is necessary
with the process, as with systems where the gas-make
is intermittent, or where wide variations in the quality
of the gas require an "averaging up." Only a small
regulator gasometer of about 300-cu. ft. capacity
is required. If there is a sudden decrease in con-
sumption, or the demand for gas is curtailed, the
apparatus instantly adjusts the gas-make to this
condition by reducing the air pressure on the air
and oil feed system to a point where the make equals
the demand. The make is correspondingly auto-
matically increased when the demand increases.
During these automatic changes the B. t. u. of the
gas will not vary, owing to the maintenance of the
constant ratio of air to oil at the atomizer under all
conditions.
The apparatus is quickly started by heating the
retorts externally to the reaction temperature. Less
than one hour is required to bring a cold retort to
operating efficiency. Where the load factor is such
that a portion of the plant is in operation over the
full 24 hrs. of the day, the entire plant is always
ready to deliver its maximum output instantaneously,
for the reaction temperatures are constantly main-
tained in the balance of the settings. However,
where the plant is entirely shut down over night or
Sunday, the settings are so insulated that the burner
provided need be operated less than 0.75 hr. to
obtain the necessary retort temperatures. In case
consumption is curtailed for 2 or 3 hrs., the heats
in the retorts are maintained by the insulation, and
gas making can be started instantaneously without the
application of external heat.
No external heating is necessary when once the
proper retort temperatures are obtained. The partial
combustion during the gas-make stage is sufficient
to furnish enough heat always to maintain the proper
temperatures for continuous gas making. As these
temperatures are always maintained irrespective of
the gas-make per unit of time, it is then independent
of an external source of heat.
The complete installation is small and compact.
Only 1500 sq. ft. of floor space are required for a plant
with a production of 1,000,000 cu. ft. per day. This
is in direct contrast to the space required for a pro-
ducer-, coal-, or water-gas set. In addition, there is
required no auxiliary steam generating or purifying
equipment, thus making the process simple and self-
contained.
The labor required is small. One man per shift
is sufficient to operate a plant of 1,000,000 cu. ft.
capacity per day. His duties are only nominal and
supervisory; for when once started the process is
continuous and automatic. His main responsibility
is to see that the oil supply tanks are filled, and that
244
THE JOURNAL OF INDUSTRIAL AXD ENGINEERING CHEMISTRY Vol. 13, No. 3
Fig. 4 — Diagrammatic Ki.evation of
the compressor is properly lubricated. There are
no raw materials to be conveyed or handled as in an
ordinary gas plant.
Approximately 4.00 gal of fuel or gas oil are required
for the production of 1000 cu. ft. of 450 B. t. u. gas.
From this there is recovered 0.28 gal. of tar As the
tar is equal to. or greater in value (see data below)
than an equivalent quantity of the oil used, for com-
parison purposes. 4.00 — 0.28 = 3.72 gal. of oil
actually consumed per 1000 cu. ft. of 450 B. t. u. gas.
r Heat Balance for Production of 450 B. T. v. Gas
Oil Used 4.00 gal.
Tar Recovered 0 . 28 gal.
Oil Consumed 3.72 gal.
Heat Supplied:
4.00 gal. Oil @ 136,000 B. t. u. per gal 544.000 B. t. u.
Heat Recovered:
1000 cu. ft. Gas @ 450 B. t. u. per
cu. ft 450.000 B. t. u.
0.28'gal. Tar <3» 136,000 B. t. u. per gal. 38.080 B t u
Total Heat Recovered 488.080 B. t. u.
Heat Loss 55,920 B, t. u.
»~*°"-!nSjj- 82.72percent
HeatinTar - s-|L2jj? - 7.00percent
59 9^0
HeatL°St " 544J055 " 10.28 per cent
Total 100.00 per cent
Physical Characteristics of 450 B. T. u. Gas
Specific Gravity 1 . 02
Chemical Characteristics of 450 B. T. u. Gas
Per cent
by Volume
CO: 6.1
Unsaturated Hydrocarbons 14. 7
O, 0.9
CO 5.6
Saturated Hydrocarbons 7.8
Hj 1.7
Ns 63.2
Total Sulfur 1 to 2 grains per 100 cu. ft.
Flame Temperature (theoretical) 3700° F.
Comparison of Nitrogen Content in Mixtures of 100 Cu. Ft. or
450 B. T. u. Dayton Gas and 630 B. T. u. City Gas with Air
Ready to Burn
Air required per cu. ft. Dayton Gas 3 . 60 vol.
Air required per cu. ft. City Gas 5.58 vol.
Dayton Gas Illuminating Gas
450 B. t. u. 630 B. t. u.
Nitrogen in 100 cu. ft. gas 63.2 6.8
Nitrogen from air 292. 2 (3.60 vol.) 442.0 (5.58 vol.)
Nitrogen in mixture 355.4 cu. ft. 448.8 cu. ft.
Combustion Data (Per 100 lbs. Gas Burned)
Illuminating
Dayton Gas Gas
450 B. t. u. 630 B. t. u.
B. t. u. per cu. ft. of combustible mix-
ture 97.50 95.8
Water vapor formed 28.75 lbs. 169.5 lbs.
Total weight combustion products... 478.00 lbs. 1291.0 lbs.
Convection efficiency 49.75 per cent 46.3 per cent
Theoretically it has been found, and under practical
conditions of industrial operation proved, that Day-
ton gas of 450 B. t. u. per cu. ft. is required in no
greater volume than illuminating gas of 630 B. t. u.
per cu. ft. for the same work. This is due to the
higher flame temperature; to the smaller weight
of combustion products per cu. ft. of gas burned.
thus less heat lost in the waste gases; and to the smaller
difference between the high and low heating values
of the gas, as evidenced by the difference in weight
of water formed during the combustion of the two
gases.
From each 1000 cu. ft. of 450 B. t. u. gas produced
there is recovered 0.2S gal. of valuable tar, the charac-
teristics of which are given in Table I. By com-
pression to only 30 lbs. per sq. in. and cooling to 32°
F., it is also possible to recover 0.35 gal. of light oil
which distils completely below 170° C. (see Table
II). The removal of this light oil produces a lowering
of the B. t. u. in the gas of less than 4 per cent.
.Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
j££cL&aubtac
Dayton Process" Oil Gas Apparatus
Table I — Tar-Distillation Test
A B
Specific Gravity 0.986 0.988
First Drop 85° C. 83" C.
Per cent Per cent
Fraction up to 80° C None None
Fraction 80-170° C 13.8 10.2
Fraction 170-230° C 26.8 26.8
Fraction 230-270° C 15.2 18.4
Fraction 270-360° C 32.6 31.0
Pitch 11.3 12.7
Water 0.6 0.6
Loss 0.7 0.7
Table II — Light Oil — Distillation Test
C D
First Drop 35° C. 35° C.
Per cent Per cent
Water None 0.2
Light Naphtha up to 80° C 14.0 9.8
Crude Benzene 80-100° C 37.2 54.4
Crude Toluene 100-120° C 20.0 16.4
Crude Xylene 120-145° C 14.0 8.8
Solvent Naphtha 145-170° C 9.6 9.0
Residue, above 170° C 4.4 1.4
Distillation Loss 0.8 1.4
The various fractions of light oil, purified by treat-
ment with sulfuric acid and caustic soda, gave on
redistillation:
Table III
C D
Per cent Per cent
Light Naphtha up to 80° C 14.0 9.8
Purified Benzene 80-100° C 26.0 43.7
Purified Toluene 100-120° C 12.7 15.8
Purified Xylene 120-145° C 12.7 1.6
Solvent Naphtha 145-170° C 8.8 7.5
Residue, above 170°C 4.4 1.4
Removed by sulfuric acid 21.4 20 . 2
Paraffins in fractions 80-145° C None None
It is interesting to note that the total yield of aro-
matic compounds of the benzene series is greater
than the yield obtained by so-called high tempera-
ture and high-pressure processes. In addition these
compounds are produced free from saturated ali -
phatic compounds, thus making their purification
possible.
COST PER THOUSAND CUBIC FEET
Based on results commercially obtained, the cost
of production of 1000 cu. ft of 450 B. t. u. gas in a
plant producing 1,000,000 cu. ft. of gas daily with the
labor of one man per shift becomes:
Cost of Production 450 B. T. u. Gas
Cents
Oil. 4.0 gal. @ 8 cents per gal 32.00
Power, Vs kw.-hr. per M. of gas @ 1.5 cents per lcw.-hr 0.90
Water, 8 cu. ft. @ 30 cents per M. cu. ft 0.24
Labor, 1 man per shift at 55 cents per hour 1 .32
Plant Maintenance @ 3 cents per M. gas 3.00
Total Gross Cost 37 . 46
Credit 0.28 gal. Tar <§) 8 cents per gal 2.24
Net Cost 35.22
No account is taken of the light oils obtainable as
by-products referred to above.
DESCRIPTION OF APPARATUS
Fig. 4 gives the complete diagrammatic elevation
of the apparatus. A single motor, A, is the sole motive
power for the air B, and oil, C, fed to the generator
D, and for the exhauster E, on the finished gas system.
Thus, as all units are synchronous, all factors are
maintained in their predetermined ratios. The air
feed system is connected directly to the service oil
tank F, and to an air regulating valve, G, on the
gasometer H. Thus if the gas-make is greater than
the gas consumption, the gasometer will rise, release
the air regulator valve, and decrease the air pressure
on the air feed line, and on the oil service tank. As
the pressures on the air and oil supply have decreased
the same amount, the ratio of feed at the retort has
decreased substantially in the same ratio. Vice
versa, should the consumption be greater than the
make, the gasometer falls, the air regulating valve
246
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
closes, and the air pressure on the air and oil systems
increases thus increasing the oil and air entering the
retort in the same constant ratio, increasing the gas-
make. This constant ratio air-oil feed is the basic
controlling principle of the successful operation of the
process.
The hot gases and vapors from the retort pass
through a heat interchanger, I, giving up a portion
of their heat content to the incoming air, thence into
the hydraulic main J, where they are initially cooled
and part of the vapors removed. From there they
pass to the water scrubber K, where they are further
cooled, and more vapors removed; and then directly
to the regulating holder. From the regulating holder
they pass through a tar extractor, L, to an exhauster
which supplies the gas main. In case the gas is
delivered from the exhauster in greater quantities
than is consumed, it is returned to the hot gas line
entering the scrubber through a check valve, M, thus
building up the gasometer which automatically operates
the air regulating valve on the air supply to the system.
The water from the scrubber and hydraulic main
is removed by way of the separator N, where the
tar separates and passes into the primary storage
0, and the water passes to the sewer through the over-
flow. The tar from the extractor L is recovered
in the primary tar tank P and then is transferred to
the tar storage tanks.
Fig. 1 shows a cross section of the retort or generator
with the details of the necessary auxiliaries, together
with the burner Q which is used in heating the retort
up to the reaction temperature in starting.
The retort or reaction chamber is well built, strong,
and durable under the temperature used. It operates
under low pressures, never exceeding 1 lb. per sq. in.
gage pressure at a maximum. It is a section of a
sphere and is approximately 24 in. in diameter, and
forms a chamber which is internally 4 in. in breadth.
The actual volume barely exceeds 0.5 cu. ft. for a
retort with a daily output of 80,000 cu. ft. of gas.
They are assembled in units of two and multiples of
the same up to any desired number needed. The
construction is such that any one or more of the
retorts may be cut out without interfering with, or
affecting, the remainder of the set. Thus the failure
of a single unit will not interrupt gas making or seriously
curtail the output of any commercial-sized installa-
tion. An unusually safe feature of the apparatus
is that the retorts can be changed by two men within
an hour. The life of a retort compares well with the
life of an ordinary water-gas generator.
Fig. 2 shows a plan view of a multiple generator
set of eight retorts, together with the atomizers, air
preheaters, and hydraulic main.
Fig. 3 shows a typical layout of a plant of 1,000,000'
cu. ft. capacity per day. This shows the plant
complete with all the necessary auxiliaries, housed
in a building 30 ft. X 53 ft. with 18 ft. of headroom.
Fig. 5 shows a front view of three units installed
in a large industrial plant, producing 500,000 cu. ft.
of gas a day.
APPLICATIONS OF THE GAS
In its application this gas can economically replace
natural gas and displace illuminating gas and the
direct burning of oil in all industrial operations. It
can also be used for admixture with the ever-decreasing
supply of natural gas or for admixture with coal gas
for all industrial and domestic purposes. In addi-
tion, it can also be used for gas undertakings of cities
and towns, as well as in gas engine installations for
industrial power development in which it will effect
a very considerable saving.
SUMMARY
The principle points of difference between the Day-
ton process and other types of artificial gas genera-
tors are as follows:
1 — The process herein described is independent of
intermittent and external heating.
2 — The process is automatic, continuous, and self-
sustaining.
3 — The B. t. u. value desired can be selected, and
when the apparatus is once adjusted this heat content
is automatically maintained without variation.
4 — The only raw material necessary for the pro-
duction of 1000 cu. ft. of 450 to 500 B. t. u. gas is
4.0 gal. of residuum or fuel oil.
5 — The gas produced is clean and free from sulfur,
thus requiring no purification, regardless of the sulfur
content of the oil used.
6 — The equipment is compact and requires little
floor space. A plant with a capacity of 1,000,000
cu. ft. per day of 450 to 500 B. t. u. gas can be housed
in a room 30 ft. X 50 ft.
7 — No gas storage is required, the gas-make being
automatically regulated by the demand
8 — The labor requirements are but one man per
shift for a plant of 1,000,000 cu. ft. capacity per day.
9 — After a complete shutdown for 24 hrs. or longer,
the equipment can be brought to capacity in less thant
0.75 hr.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
247
ADDRL55E5 AND CONTRIBUTED ARTICLL5
PHTHALIC ANHYDRIDE DERIVATIVES1
A PARTIAL COLLECTION OF NAMES AND REFERENCES
By Max Phillips
Color Laboratory, Bureau of Chemistry, Department op Agriculture, Washington, D. C.
Received June 28, 1920
In connection with some work on the new process for making
phthalic anhydride developed in this laboratoryi it became
necessary to know the number and kind of compounds that
can be made from it. Accordingly the following list was com-
piled, and although it does not pretend to include every com-
pound that was ever made from phthalic anhydride, it is, never-
theless, published here in the hope that it may be of some bene-
fit to those working along this line.
3-Acetaminophthalic anhydride
/. Am. Chem. Soc, 31 (1909), 483
3-Acetaminophthalimide
J. Am. Chem. Soc, 31 (1909), 483
3-AcetaminophthaIphenylhvdrazine
J. Am. Chem. Soc, 31 (1909), 483
3-Acetaminophthal-o-tolil
/. Am. Chem. Soc, 31 (1909), 483
Acetonylphthalimide
Ber., 21 (1888), 2684
Ber., 26 (1893), 2198
Acetylphthalimide
Ber., 19 (1886), 1400
Allvlphthalimide
Ber., 23 (1890), 999
Ber., 26 (1893), 2850
w-Aminobenzaldehvdephthalanil
J. prakt. Chem., (2] 88 (1913), 810
^-Aminobenzaldehydephthalanil
J. prakt. Chem , 88 (1913), 810
3-Amino-4-phthalic acid
/. Am. Chem. Soc, 31 (1909), 483
3-Arainophthalic anhydride
/. Am. Chem. Soc, 31 (1909), 483
Anhydrophthalylbisdiketohydrindene
Gazz. chim. Hal., 37 [III (1907), 303
Benzenylazoxime-benzenyl-o-carboxylic acid
Ber., 18 (1885), 2463
o-Benzoylaminoacetalcarboxylic acid
Ber., 27 (1894), 3103
Benzoytresorcinolphthalein
Ber., 14 (1881), 1864
Benzylphthalimide
Ber., 20 (1887), 2227
Biphthalimide
.4nn.,228 (1885), 137
Biphthalyl
Arm., 164 (1872), 230
Biphthalyl chloride
Ann., 228 (1885), 133
o-(CarboxyethylbenzovI)-3-£-toIylcrotonlactone
Ber., 47 (1914), 2708
#-Chlorofluorescein
Ann., 233 (1886), 239
0-Chloronaphthanthraquinone
U. S. Patent 941,320
^-Chlorophthalanil
Ber., 11 (1878), 2260
Chloroquinophthalone (sulfonated)
U. S. Patent 890,588
Chloro-o-xylylphthalimide
Ber., 21 (1888), 580
Compound C1H1N3O3
Am. Chem. J., 9 (1887), 220
Compound (addition) of KOH and phthalic
anhydride
J. Am. Chem. Soc, 39 (1917), 2646
Condensation product of phthalimide and for-
maldehyde
Ber., 31 (1898), 3230
Condensation product of phthalimide and for-
maldehyde
Ber., 31 (1898), 2732
Condensation product (resin)
U. S. Patent 1,108,329
Condensation product (resin)
TJ. S. Patent 1,108,330
Condensation product (resin)
U. S. Patent 1,108.331
Condensation product containing nitrogen
D. R. P. 202,354
Chem. Abs., 3 (1909), 492
•-Cresolphthalein
Ber., 12 (1879), 237
Ann., 202 (1880), 153
/J-Cresolphthalein anhydride
Ann., 212 (1882), 340
Cresorcinolphthalein
Ann., 215 (1882), 95
P-Cresoxvethylphthalamide
Ber., 24 (1891), 191
Cyanobenzylphthalimide
Ber., 20 (1887), 2231
3-riiacetaminophthalimide
J. Am. Chem. Soc, 31 (1909), 483
Diacetylphthalhydrazide
J. prakt. Chem., [2] 61 (1895), 382
Diallylphthalide
J. Russ. Pkys. Chem. Soc, 44 (1912), 1868
Diamidofluorescein
Ann., 183 (1876), 35
/»-Diaminobenzylsulfidephthalide
Ber., 29 (1895), 1339
Dibromodimethvlanilinephthalein
Ber., 10 (1877), 1623
Dibromodinitrofluorescein
Ann., 133 (1876), 61
3,4-Dichloro-5,6-diiodo-phthalic anhydride
J. Am. Chem. Soc, 40 (1918), 214
3,6-Dichloro-4,5-diiodo-phthalic anhydride
J. Am. Chem. Soc, 40 (1918), 214
4,5-Dichloro-3,6-diiodo-phthaIic anhydride
J. Am. Chem. Soc, 40 (1918), 214
DichloromethyIanthraquinone(2,3)
U. S. Patent 902,895
Diethyldisulfidediphthalamide
Ber., 24 (1891), 2131
Diethylditoluylphthalamide
Ann., 227 (1885), 188
Diethyleosine
Ann., 183 (1876), 50
6,6'-DihydroxynaphthoIfluorane
Ber., 47 (1914), 1076
3,4-Diiodo-phthalic anhydride
J. Am. Chem. Soc, 40 (1918), 214
3,6-Diiodo-phthalic anhydride
J. Am. Chem. Soc, 40 (1918), 214
Diisopropyl phthalate
Cazz. chim. Hal., 28 [II] (1898), 50
2,4-Dimethyl-3-acetyIpyrroIenephthalide
Z. physiol. Chem., 82 (1912), 266
Dimethyl-3-aminophthalic acid hydrochloride
J. Am. Chem. Soc, 31 (1909), 483
3,6-DimethyIfluorane
Ber., 46 (1913), 1484
Dinitrofluorescein
Ann., 183 (1876), 30
Di-o-diphenylenephthalamic acid
Monatsh., 28 (1907), 411
Diphenylene-oxide-keto-benzoic acid
Monatsh., 28 (1907), 411
Diphenylphthalamide
Ann., 227 (1885), 190
Diphthalethylenediimide
Cazz. chim. ital., 24 [I] (1894), 405
Diphthalsuccinanilide
Ber., 18 (1885), 3123
Diphthalsuccinidehydranilide
Ber., 18 (1885), 3123
Diphthalyl-2,5-diaminohydroquino!
Gazz. chim. ital., 16 (1886), 254
Diphthalyllactone
Ber., 46 (1913), 1484
Diphthalyl-o-phenvlenediamine
Monatsh., 39 (1918), 873
olphthalein
13 (1880), 1654
nide
Ethylenediphthalamide
Ber.. 21 (1888), 2670
Ethylenediphthalimide
Ber., 20 (1887), 2225
Ethylenephthalamide
Gazz. chim. ital., 24 [I] (1894), 405
Ethyleosine
Ann., 183 (1876), 15
Ethyl ester of phthalglycine
Ann., 242 (1887), 5
Ethvlphenolphthalein
Ber., 17 (1884), 669
Ethylphenvlphthalamide
Ann.. 227 (1885), 185
Ethylphthalimide
Ber., 10 (1877), 1645
Ethyl a-phthaliminopropionate
Ber., 33 (1900), 980
Ethvlsulfonediphthalamide
Ber., 24 (1891), 3103
Fluorescein carboxylic acid
Ber., 11 (1878), 3103
Wien. akad. Ber., [2[ 77, 224
Hematoxylinphthalein
Ber., 12 (1879), 1651
Hydrobiphthalyl
Ber., 17 (1884), 2180
Hydroquinolphthalein
Ber., 6 (1873), 506
Ber., 11 (1878), 713
Hydroxy biphthalyl
Ann., 233 (1886), 244
0-Hydroxyethvlphthalamide hydrochloride
Ber., 21 (1888), 572
Hydroxy phthalamide
Ann., 206 (1880), 306
Hvdroxyphthalanil
Ber., 9 (1876), 1528
0-Hydroxytrimethylenediphthalimide
Ber., 21 (1888), 2690
Isoamylphthalamide
Ber., 23 (1890), 998
TY-Isopropylene-aminophthalimide
Ber., 27 (1894), 691
Isopropylphthalide
Gazz. chim. ital., 28 [II] (1898), 501
l-Methyl-3-aminophth3lic acid hydrochloride
J. Am. Chem. Soc, 31 (1909), 483
TV-Methylcarbazole-S^-diphthalaldehydic acid
Monatsh., 32 (1911), 1103
jV-Methylcarbazole-3-phthaldehydic acid
Monatsh.. 32 (1911), 1103
Methylenediphthalimide
Ber., 23 (1890), 1002
Methylenephthalamide
Ber., 26 (1893), 957
Methyleosine
Mon. set., 20 (1878), 1171
Methylphthalhydrazine
J. prakt. Chem , [2] 61 (1895), 382
Methylphthalimide
Ann., 247 (1888), 302
2-Methyl-4-quinazolone-5-carboxylic acid
J. Am. Chem. Soc, 31 (1909), 484
Monomethyltetrabromofluorescein (methylery-
thrin)
Ann., 183 (1876), 50
Naphthylphthalimide
Gazz. chim. ital.. 15 (1885), 346, 480
Nitrobenzylphthaliniide
Ber., 20 (1887), 2227
ch the standard American Chemical Society abbreviations ;
1 In addition to the well-known journals,
eluded, with abbreviations as noted:
"Beitrage zur Chemischen Physiologie und Pathologie," by Franz Hofmeister: Beitr. chem. physiol. (Ho/.).
"Fortschritte der Theerfarbenfabrikation und verwandter Industriezweige," by F. Friedlander: Friedl.
"Handbuch der Firberei der Spinnfassen," by Knecht, Rawson and Lowenthal, 2nd Ed. (Berlin. 1900): Handb.
"Farbstofltabellen," by G. Schultz, 5th Ed. (Berlin, 1914): Schultz.
"Wiener akademisches Berichte:" Wien. akad. Ber.
"Zusammenstellung der Patente auf dem Gebiete der organischen Chemie," 1877 to 1904, by Adolf Winther: Winth
d, the following publications £
24S
THE JOURNAL OF INDUSTRIAL AXD ENGINEERING CHEMISTRY Vol. i:;. No.
Nitrophthalanil
Ber., 28 (1895), 1120
Nitrophthalanilide
Ber., 28 (1895), 1120
4-Nitrophthalic acid
.•Inn., 208 (1881). 224
Ber., 18 (1885), 3448
Nitrofluorescein
Bull. soc. chim., 12] 30 (1S78), 531
Orcinolphthalein
Ber., 7 (1874), 2314
.Inn., 183 (1870), 63
Phenolphthalein anhydride
.Inn., 212 (1882), 347
Phenoxyethylphthalamide
Ber., 22 (1889), 3255
Phenvlenediethvlacetone
Ann., 133 (18"65), 259
Ber., 4 (1871), 658
Ber., 9 (1876), 1230
.In »., 202 (1880), 68
Phenylphthalamide
Jahresber.. 1847-48, 605
Phenylphthalanilurethane
Gazz. chim. Hal., 16 (1886), 253
.Y-Phenylphthalimide (phthananil)
Ann., 210 (1881), 267
5-Phenvluraminophthalimide
J. Am. Chem. Soc, 31 (1909), 483
Phthalallvlpseudocumidoamide
Ber., 17 (1884), 1808
Phthalaminothiophenol
Ber., 13 (1880), 1233
Phthalamide
Am. Chem. J., 3 (1881-1882), 29
Phthalanil-o-carboxylic acid
Ber., 29 (1896), 2679
Phthalcarboxylic acid
Ber., 31 (1898), 369
Phthalchloride
D. R. P. 139,553
l'hthaldinitromesidil
Ber., 15 (1882), 1017
I'hthalglycine
J. prakl. Chem., [21 27 (1883). 41S
Phthalhydrazide
J. prakt. Chem., [2] 61 (1895), 396
1'hthalhvdrazideacetic acid
J. prakt. Chem., [21 61 (1895), 383
I'hthalic acid
■Inn., 75 (1850), 1
1 • Phthalidene-3-Ji-methoxystyrylcrotonolactor
Ber., 47 (1914). 2708
l-Phthalidene-3-phenvlerotonolactone
Ber., 47 (1914), 2708
l'hthalimide
[«n., 41 US42), 98
Ber., 31 (1898), 2732
m-Phthalimidobenzoie acid
Ber., 16 (1883). 1320
o-Phthalimidobenzoic acid
Ber., 11 (1878), 2261
l-Phthalimido-2-nitro-£-tolunitrile
Ber., 27 (1894), 2165
Phthalimidosulfonic acid
Ann., 233 (1886). 226
a-Phthalimino-.V-ethyl butyrate
Ber., S3 (1900). 980
Phthalisocymidide
Ann., 221 (1883), 169
Phthalmesidil
Ber., 15 (18S2), 1017
Phthalnitroisocymidide
Ann., 221 (1883), 169
Phthalnitxomesidil
Ber., 15 (1882), 1017
Phthaloxime
lm. Chem. .'.. 47 .1912). 89
Phthalpseudocumidide
17 (1884), 1802
Phthalpseudocumidoamide
17 (1884), 1802
Phtualpseudocumidomethylamide
Ber., 17 (1884), 1808
Phthalureide
Ann.. 214 (1882), 23
Phthaluric acid
Ann., 214 (1882), 19
Phthalyl-^-aminobenzoic acid
Ber., 10 (1877), 579
Phthalyl-.V-aminobutvronitrile
Ber., 22 (1889), 3337
Pbthalvlarainocapric acid
.4n»:, 242 (1887), 9
Phthalyl-o-aminodiphenvlmethane
Ber.l 27 (1894), 2786
Phthalyl-p-aminophenol
Arch. Pharm., 234 (1896), 620
Phthalyl-fi-aminophenol acetate
Arch. Pharm., 234 (1896), 620
Phthalyl-£-aminophenol benzoate
Arch. Pharm., 234 (1896), 620
Phthalyl-/>-aminophenol butyrate
Arch. Pharm.. 234 (1896), 620
Phthalvl-/>-aminophenol propionate
Arch. Pharm., 234 (1896), 620
Phthalylasparagineaminobenzoic acid
Gazz. chim. Hal., 16 (1886), 7
Phthalylasparaginephenvlimide
Gazz. chim. Hal., 16 (1886). 7
Phthalylasparaginic acid
Gaze. chim. ital., 16 (1886), 2
Phthalylchloride
Ber., 19 (1886), 1187
1'lithalylcyanacetylene
J. prakt. Chem., [2] 39 (1889), 275
Phthalvldiaminoacetal
Ber., 21 (1894), 3102
Phthalyldicreatinine
Beitr. chem. physiol. (Ho/.), 9, 183
Phthalvldisarcosine
Ber. ,'21 (1888), 278
Phthalvldiphenvlasparagine
Gazz'. chim. ital., 16 (1886), 10
Phthalylguanidine
J. prakt. Chem.. [2] 49 (1894), 42
I'hthalvlhvdroxylamine
.4nii., 205 (1880). 295
Styrvlphthalamide
Ber., 26 (1893), 1857
Stvrylphthalimide
Ber., 26 (1893), 1857
Sulfoamidophthalic acid
.4ii«., 233 (1886), 229
3-Sulfophthalic acid
Inn., 233 (1886), 220
4-Sulfophthalic acid
.4 mi.. 143 (1867), 257
4-Sulfophthalic acid monochloride
.Inn., 233 (1886), 228
4-Sulfophthalic acid trichloride
Ann., 233 (1886), 228
Tetrachlorophthalic anhydride
U. S. Patent 322,368
Tetramethyl-3-azo-phthalate
J. Am. Chem. Soc, 31 (1909), 483
Tetraphenylphthalamide
Ber., 16 "(1882). 830
Ann., 227 (1885), 192
o-2-Thenovlbenzoic acid
.4 mi., 407 (1915), 94
Thiophthalic anhydride
Ber., 17 (1884), 1176
Thiophthalic naphthoquinone
U. S. Patent 852,158
3-4-6-Triiodophthalic anhydride
J. Am. Chem. Soc, 40 (1918), 214
Triphthah'lpicramide
Gazz. cliim. ital., 16 (1886), 253
,-Xvlylenephthalimide
Ber., 21 (1888), 579
Ber., 26 (1893), 2213
Xvlylphthalimide
Ber., 21 (1888), 576
X.istHEse Dyes
Alky! ester of dialkyl-homo-rhodamine
I S. Patent 516,585
Aureosin (chlorofluorescein)
D. R. P. 2618
Chrysoline
Sri., [3] 7 (1887), 860
Jahresber., 1887, 1233
Heumann. 1, 463
Handb. (2nd ed.), 765
Cerulein paste A
Ber., 4 (1871), 556
Cerulein B, BR, BW in paste, BWR in powder
Inn.. 183 (1876), 28
Schultz, 204
Cerulein S in paste; Cerulein SW in paste;
Cerulein MS; Alizarin green; Anthracene
green
.4iiii. .209 (1881), 272
Dingler's polytech. J., 229 (1878), 178
Schultz, 205
Handb. (2nd ed.), 1062
Cvanosine (ale. sol.)
'Handb.. 7(.K
Schultz, 201
Cyanosine B (J)
Schultz, 203
Diethyleosine
.Inn., 183 (1876), 50
Diethylrhodamine
U. S. Patent 456,081
Dimethyldicthvlrhodamine
U. S. Patent 576,222
Dirnethylmethylrhodamine (not esterified)
U. S. Patent 578,578
Diphenyldichlororhodamine
U. S. Patent 413,049
Diphenylrhodamine
U. S. Patent 413,048
Diphenyltetrachlororhodamiue
U. S. Patent 413.050
Hosine BN; Nopalin G; Safrosin J
Ann., 183 (1876), 61
Inn., 202 (1880), 68
Heumann, 1, 483
Eosine G; Eosine 3 J; Eosine S; Eosii
Eosine MP
Ber., 7 (1874), 1753
Ber., 8 (1875). 62. 1147
.Inn.. 183 (1S76), 2
Dingler's polytech. J., 263 (1887), 49
Dingler's polytech. J., 284 (1892), 21. 4'.
Chem.-Ztg., 16 (1892), 1956
Ber., 28 (1895). 312
Heumann, 1, 468
B
Erythrosin D
Heumann, 1, 489
Hrythrosin (extra blue)
Dingler's polytech. J., 263 (1887), 66
Dingler's polytech. J., 283 (1892), 258
Erythrosin R (J); Erythrosin (extra yellow)
Handb., 767
Gallein, Alizarin violet; Anthracene violet
Ber., 4 (1871), 457, 555, 663
Ann., 209 (1881), 49
D. R. P. 30,648
Methyleosine J
Ann., 183 (1876), 53
Chem.-Ztg., 16 (1892), 1956
Monomethyltetrabromofluorescein (meUi> I
erythrin)
.Inn., 183 (1876), 50
Phloxin P. New Pink; Erythrosin BB
British Patent 44,779
Chem. Ind., 3 (1880), 59
Handb., 768
Schultz, 201
Phloxin N, BB; Eosine blue; Cyanosine [DHL
Eosine 10 B
Schultz, 202
Handb. (2nd ed.), 768
Phthal green
.Inn.. 206 (1880), 112
Compt. rend., 126 (1897), 221
Primrose, Eosine ale. sol.
Ann.. 183 (1876), 46
Dingler's polytech. J., 263 (1887), 49. 99
Dingler's polytech. J.. 283 (1892), 210
Rhodamine B; Rhodamine O; Safraniline
Brit. Patent 15,374; 96.000
U. S. Patent. 377,349; 377,350
D. R. P. 44.002; 48,367
Fr. Patent 186,697
Chem.-Ztg., 16 (1892), 1056
J. Soc. Chem. Ind., 12 (1893). 513
Rhodamine 3 B; Anisoline
D. R. P. 66.238; 71,490; 73.451
U S. Patent 499, 927
Bull.. 7 (1892), 523
-Z<e.. 16 (1892), 1956
Schultz, 192
Rhodamine G
D. R. P. 63.325
U. S. Patent 516.588
Fr. Patent 215,700
Friedl., 3, 175
Winlher, 2, 192
Rose bengal 2 B; Rose bengal B; Bengal rose 2 B
Handb., 768
Schultz, 203
A sulfonated amiuo-oxvphthalein or toluylrhodal
U. S. Patent 609,997
Mar.. 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
249
Jranine; Fluorescein
Bet., 4 (1871). 558, 662
Her., 8 (187.S1 . 14(.
Ann., 183 (1876), 2
-\nn., 212 (1882), 547
Her., 7 (1874), 1211
.'. Soc. Chem. lnd., 6 (1887), 283
J. Soc. Chem. hid., 11 (1892), 675
hem.-Ztg., 16 (1892). 1956
./. Soc. Chem. lnd., 12 (1893), 513
Ber., 21 (1888), 3376
Her., 24 (1891 I, 1412
Her., 25 (1892), 1385, 2118, 3586
Her., 28 (1895), 28
Ber., 44 (I'M n, .',[2. 396, 128
Quinolinb Dyes
Quinaldine yellow
U. S. Patent 290,585
Brit. Patent 136,283
Schullz, 210
Winther, 2, 786
Ber., 16 (1883), 297, 878, 513, 1082
Quinoline yellow (water sol.)
D. R. P. 23,188
Ouinophthaloue
U. S. Patent 290,585
Brit. Patent 136,283
Ber., 16 (1883), 297, 298
Ber., 16 (1883), 513, 1082
Ann., 315 (1901), 303
Anthraquinone Dyes
Alizarin brown R, N, G, F, II, VVR
llandb. (2nd ed), 1046
Schullz, 270
Anthracene brown W, WR, WG
Ber., 10 (1877), 38
Indigo Dyes
Indigo
Literature extensive — sec Schullz, 297-298
Unnamed Dyes
U. S. Patent 929,422
U. S. Patent 1.196,127
- U. S. Patent 968,533
U. S. Patent 688,885
V. S. Patent 633,883
U. S. Patent 540,564
U. S. Patent 990,224
U. S. Patent 675,216
U. S. Patent 188,217
I S. Patent 211,180
D. R. P. 275,670
THE AMERICAN POTASH INDUSTRY AND ITS
PROBLEMS1
By John E. Teeple
50 Kast 41st Street, New York, N. Y.
Economic conditions growing out of the war left two chemical
foundlings on our shores. One was the dye industry and the
other the potash industry. The first proved to be a noisy one,
.ind we have been kept rather well informed of its progress, its
possibilities, its hopes, and particularly its needs. The potash
industry has been far less noisy, although we have been kept
informed from time to time that we have such an industry. But
when we ask, "How much of a potash industry have we?"
— "Is it a permanent one?" and "Can it either now or in the
future compete with the German potash industry, or must it
temporarily or always receive protection as an infant industry
in order to exist?" we find a considerable divergence of opinion.
I want to discuss some things regarding the progress
and problems of this American potash industry, its present posi-
tion, and its hopes.
POTASH IN THE UNITED STATES
This is primarily an agricultural country. It normally con-
sumes 250,000 tons K;0 per year, which is equivalent to 400,000
tons of 100 per cent KC1 (potassium chloride). This figure, of
course, includes all grades of potassium salts brought into this
country, and over 90 per cent of the total is used on the land as
fertilizer. Before the war we produced no potassium salts at
all in this country, with the exception of an infinitesimal amount
• i potash leached from wood ashes. Even the caustic potash
made in this country was made from imported potassium chloride.
When the war shut off commerce with Germany and the country
awoke to the fact that it had no potash and that it must have
it to produce the large crops that were needed, our Government
sent out urgent requests to hasten the discovery and the pro-
duction of potash from every possible source. These urgent
requests, together with the high price which could be obtained
for any salts containing potassium, resulted in the installation
of plants to work the natural brines of Nebraska, California,
and Utah; the dust from cement kilns and blast furnaces; the
waste liquors from distilleries and beet-sugar factories; the alunite
deposits of Utah; the leucite deposits of Wyoming; the kelp fields
of the Pacific coast; the wood ashes of Michigan; and even the
i,reensand of New Jersey. In all we find a total of over 100
different plants built to produce potash from these sources.
In 1918, the banner year, 123 different plants operated, giving
a total production of over 54,000 tons KsO. In 1919, with the
fall of the price of potash, this production dropped to about
30,000 tons; and, while the figures are not yet available for 1920,
the production will be probably in the same neighborhood —
that is, something like one-eighth of the country's requirement.
1 Based on addresses given before the Rochester and Cornell Sections
of the American Chemical Society, January 24 and 25, 1921,
Out of the 128 plants reported as producing in 1918, only 43
were reported as producing in 1920. With the price of potash
in 1921 still lower than it was in 1920 we may expect a still
greater falling off in the number of producing plants, and possibly
in the total output.
Up to the present time probably 70 per cent of the total pro-
duction of potash in this country has come from natural brines.
These natural brines include a whole series of lakes in Nebraska,
the Salduro Marsh in Utah, and Searles Lake in California
There are eight plants working on the Nebraska brines, one on
the Salduro Marsh, and three on Searles Lake. Just now, of
the eight Nebraska plants five are closed down and only one of
the three plants on Searles Lake is in regular operation.
SEARI.ES LAKE POTASH
The oldest and largest of the plants working on Searles Lake
and also the largest producer of potash in the United States
is the American Trona Corporation. In 1918, the year during
which the United States produced more potash than it has ever
done before or since, this one plant was responsible for about
one-seventh of the entire production of the country. To-day
this one plant is probably responsible for about 30 per cent of
the production of the United States, and as it seems to be making
more progress and spending more money in studying its prob-
lems than any other potash organization, a study of its diffi-
culties encountered and results achieved should give us some
basis for predicting the future. I hope that a study of these
difficulties will be interesting from a chemical and engineering
point of view, and at the same time it will show us why the in-
dustry has not progressed faster than it has, why potash is not
yet as cheap as it was before the war, and why we may expect
that with moderately good fortune a permanent potash indus-
try can be founded here.
When I first assumed responsibility for the operations of this
concern about a year and a half ago, I found a going plant which
represented an investment not far from $10,000,000, but which
still did not seem particularly well adapted to the purpose for
which it was built. It was producing at that time only a mod-
erate tonnage of potassium chloride, averaging less than 70 per
cent in purity, and its production costs were high. Many differ-
ent processes had been tried at this plant in a desultory manner,
many millions of dollars had been spent, not always wisely,
and even with such a brief history behind it the plant was being
run on tradition rather than on information. This is not said
in a spirit of petty criticism, for we all realize that pioneer work
when done under pressure for production is not usually ac-
companied by careful, painstaking work, calm judgment, and
economical operation. The whole spirit under such conditions
is one of snap judgment and lavish expenditure, and a certain
amount of both is excusable and unavoidable. In any case, by
the middle of 1919 the plant had passed the pioneer stage and
the press for production where such modes of operation could be
excused, and was entering on a period where an entirely different
250
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
method of handling the problems was necessary if the plant was
to live. Two essential lines of work seemed to offer themselves
for me to undertake at this stage. One was to study the ex-
isting plant and put it into a position to produce as much ma-
terial as possible of the best quality and at the cheapest price
consistent with the minimum expenditure of money for plant
extensions and changes. The second line of work was to make
a complete study of Searles Lake brine so as to know definitely
how it should be handled in the existing plant, or in any other
plant that might take its place. Both these lines of work have
been of intense interest to me, and I hope as I report progress
of them to you they will have some measure of interest to you.
THE SEARLES LAKE DEPOSIT
Searles Lake is a bed of crystallized salts about 11 or 12 sq.
mi. in area and 60 to 70 ft. in depth. The salts are permeated
throughout with brine that has come to equilibrium with the
salt deposit. The lake is fed continually by underground streams
which enter the salt bed probably from below, come to equilibrium
with the salts, and evaporate their excess water at the surface
or furnish brine for the potash plants located on the shores of
the lake. In summer evaporation keeps the brine an inch or
so below the surface of the salt body so that the whole lake be-
comes a level and luxurious automobile course. In winter when
evaporation is slower the brine stands an inch or so above the
surface of the salt. The salt crystals consist of:
Halite (NaCl)
Mirabilite (NaiSOi.lOHiO)
Thenardite (NaiS04)
Trona (NaiCOi.NaHCOs.2HjO)
Tinkal (Na2B<O7.10HiO)
Hanksite (9NaiS04.2NaiCOi.KCl)
Glaserite (NaiS0«.3KsS04)
This list of salts comprises practically the entire crystal body.
Neither KC1 nor Na^COj exists as such in the salt body, nor do
calcium or magnesium salts. But below the salt body itself
we find insoluble salts of calcium and magnesium where they
are apparently precipitated before the inflowing water reaches
the salt bed. The brine which permeates the whole salt body is
naturally kept in equilibrium with the salts by solution and
precipitation. Since the temperature of the brine taken at
a point below the surface is fairly uniform at 23° C. summer and
winter, it follows that the brine drawn out for use in the plant
is of uniform composition.
The lake is probably the finest natural situation to study
and plot equilibria that a chemist ever had. The large body of
salts and brine serves as an insulator or heat reservoir. The
varying evaporation provides a thermostat, and centuries of
time have passed since the whole mass reached a static condition.
The composition of the brine as it is drawn from the middle of
the lake, probably 50 ft. below the surface, is as follows, when
expressed in conventional symbols:
Per cent
NaCl 16.54
KC1 4.82
NaiCOi 4.17
NaHCOj 0.52
NaiB.Oi 0.85
NaiBiO. 0.85
NaiSOi 7.16
HiO 65.09
This composition does not vary more than a few hundredths of
a per cent at any time throughout the year. There are a few
minor annoyances, like sodium sulfarsenite, sodium bromide,
sodium iodide, organic matter, etc., but they need not be con-
sidered now.
The quantity of this brine is appalling. It has been esti-
mated to contain over 12,000,000 tons of potassium chloride,
and the salt body itself probably contains more than twice as
much more undissolved potassium, computed as potassium
chloride.
EQUILIBRIUM DIAGRAMS
Looking back at the brine analyses you will note that figures
are given for the content of bicarbonate and metaborate. These
figures were arrived at by Mr. W. E. Burke, of our research
department, after a complicated calculation based on certain
assumptions. We do not guarantee their accuracy, but they
are the best approximation we have been able to make. We
know that bicarbonate is present because the brine is in equi-
librium with trona, and we know metaborate is present because
borax in the presence of sodium carbonate is known to form
metaborate. Up to the present, however, we have found no
direct and reliable method of determining metaborate and bi-
carbonate in the presence of borax and carbonate.
Looking again at the brine analyses it is obvious that the
two most valuable constituents, potassium chloride and borax,
are present in relatively small amounts, and hence that we must
concentrate them to make them marketable. How shall this
be done? We could, of course, evaporate off all the water. This
would leave a salt containing nearly 14 per cent KC1 and so
corresponding to the German carnallite, but as this salt would
also contain nearly 5 per cent Na2B40; it would not be market-
able. In the case of Nebraska brines, however, where the borax
content is negligible, this method is actually in use, and most
of the Nebraska potash that has heretofore come on the market
has been subjected to no other operation than simple evapora-
tion, or evaporation and drying. In our case this is impossible.
We must concentrate both potash and borax in some manner,
and since neither can be precipitated to advantage we must turn
our attention to the removal of the undesired salts at the same
time that we evaporate the water. To do this we can consider
evaporation in solar ponds, in spray ponds, in spray towers,
or in vacuum pans, or we can consider refrigeration. We have
tried all these methods. At present we are evaporating in triple-
effect vacuum pans, because this was the equipment we found
in the plant. What we shall do ultimately is still an open ques-
tion. In this question of concentration we find our equilibrium
diagrams of supreme importance. It would be a prolonged
task to plot the equilibria, taking into consideration all the brine
constituents, so we undertook to plot simply the system of
sodium and potassium as chloride, sulfate, and carbonate, at
various temperatures between 0° and 100°, and for all possible
saturation concentrations. This work is now well under way.
So far, including double salts, we have located 7 quadruple
points, 14 triple points, 10 double points, and 8 single points.
I do not know how many more there are; possibly a combination
of a mathematician and a physical chemist could figure it out.
This equilibrium work has been done chiefly by Mr. Harold
de Ropp, of our research department, and as it has progressed
it has proved most useful in enabling us to understand what
we were doing, and hence in permitting us to improve intelli-
gently on our practice. It is proving still more valuable in
helping us to avoid useless experimentation. When the equi-
librium work is completed we should be able to predict just
what would happen in any suggested operation or "process."
This work will all be published at the proper time and should
prove a valuable contribution. It will be noticed that in this
equilibrium study we eliminated borax, metaborate, and bi-
carbonate for the sake of simplicity. Even physical chemists
have their limitations. While they handle the fourth dimension
with impunity they sometimes hesitate to undertake an equi-
librium model requiring the use of a fifth, sixth, or seventh
dimension. We are seeing what can be done with these neglected
salts in a separate study.
DOUBLE SALTS
The bete noir in concentrating Searles Lake brine and similar
brines for potash is the formation of double salts, particularly
glaserite or aphthitalite (Na^Oi.SKoSOiL Given a solution
containing KC1 and NaCl, the separation is fairly easy. Evap-
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
251
oration by boiling precipitates NaCl and enriches the KC1
in solution. Cooling then precipitates KC1. Given KC1 and
NasSOi, however, the picture is entirely different. We may
imagine a reaction equation as follows:
6KC1 + 4Na2SO« + water -T^ai^SO, Np.SD, + 6NaCl 4- water
The transition point for glaserite is just about 3° C, so if we
evaporate at a temperature above 3° C. the solid phase is glas-
erite and NaCl. If we evaporate below 3° C. the solid phase
is Glauber's salt and KC1. In neither case have we made any
real concentration. In order to avoid this precipitation of
potassium as glaserite at any temperature we must keep the
concentration of NajSGi below the point where it would be in
equilibrium with glaserite at that temperature. This did not
seem an easy thing to do, but Mr. Burke discovered the remedial
agent in the form of another double salt, Na»C03.2NajSO<.
This double salt has not previously been described in the litera-
ture. We have accordingly called it "burkeite" and it will be
described in detail in a separate paper. It forms well-defined
crystals of very high luster and definite composition. Its transi-
tion point is about 24° C. Below this temperature it does not
seem to exist. As the temperature rises its solubility decreases.
This, in fact, led to its discovery. In July 1919 my attention
was called to a beaker of brine which was being gently warmed
far below evaporation temperature, and which was forming
beautiful crystals of a salt. Various suggestions were made
that these were crystals of sodium chloride, sodium sulfate,
sodium carbonate, or mixtures, and, while I suggested that it
might be well to do a little analytical work and find out just
what they were, it made no particular impression on me or any-
one else, because our brines are so thoroughly saturated at all
stages that something is always separating out of them, whether
we cool them or warm them or evaporate them or merely look
at them. Later, Mr. Burke's analyses showed that we had to
deal with a true double salt. Now, the discovery of this double
salt, together with a study of our equilibrium diagrams, showed
us how by proper manipulation of our sodium carbonate concen-
tration we could always keep the concentration at which sodium
sulfate was in equilibrium with burkeite below the concentra-
tion necessary to form glaserite. In other words, the sodium
sulfate present could be made to separate from the solution as
burkeite and not as glaserite, so the potash could be kept in
solution and concentrated to saturation. It was necessary only
to mix the raw brine with other liquors rich in carbonates and
evaporate the mixture in triple-effect vacuum pans, keeping the
carbonate always at proper concentration,1 to depress the sul-
fate below the point of glaserite formation. Under these con-
ditions sodium chloride and burkeite separate continuously
until we arrive at a hot concentrated liquor which contains
more potassium chloride and borax than it does all other salts
combined, and which on cooling to 30° deposits essentially only
potassium chloride and borax.
SEPARATION OP POTASSIUM CHLORIDE AND BORAX
Unfortunately, no one wants a mixture of potassium chloride
and borax. During the war under government urgings for
production, such mixtures were sold more or less regardless of
their borax content and were used in fertilizers, and the experts
are still arguing whether the borax did or did not harm certain
crops. In any case, it seemed more profitable to separate the
borax from the potassium chloride and sell it independently
for other purposes than for fertilizer. This separation proved
a difficulty for some time, but the laziness of borax finally came
to our assistance. It was found that by cooling the hot solution
rapidly and quietly to about 30° a crop of potassium chloride
separated without a crystal of borax in it.1 The mother liquor
from this crop without further cooling but with agitation, or
with time, deposited a good crop of borax with very little potas-
1 This is the subject of patent application.
sium chloride, and this little was easily removed. It was not
simple to design a cooler that would act promptly and effectively,
but a new one recently installed according to ideas worked out
by Mr. H. S. Emlaw, the general manager of the plant, seems to
meet all requirements and furnishes a borax which is uniformly
over 99.5 per cent in purity, and a potassium chloride which at
present averages over 92 per cent KC1 with less than 0.5 per
cent borax, and which we expect in the near future to average
96 or 98 per cent KC1 with still lower borax content. In fact
carloads of potassium chloride shipped now, taken at random,
very frequently run 97 or 98 per cent purity. One carload, the
analysis of which I noticed recently, ran 99.78 per cent KC1.
The impurities present are, of course, chiefly sodium chloride
with a little sodium sulfate, sodium carbonate, and borax. In
the matter of purity, these products at present leave little to
be desired, and their quality is still being improved. When com-
pared with the German potash furnished to this country in pre-
vious years they represent an enormous advance in purity.
FOAMING
Now that we have seen our way through the operation of pro-
ducing potash and borax from these brines, which is after all an
amazingly simple one of evaporation and crystallization, let
us go back to a few of the other troubles. One very serious
trouble has been the foaming of the brines during evaporation.
As soon as boiling in the vacuum pans was well under way
a voluminous, persistent, pernicious foam, like soapsuds, would
rise from the brine and pass over with the vapors to the calandria
of the next effect, or to the condenser, causing serious losses of
the products we were trying to save, and slowing down the opera-
tion materially. A synthetic brine containing all the known
inorganic constituents of the natural lake brine did not foam
seriously, in fact, it boiled as quietly as a tea kettle, so we in-
ferred that the foam producer was organic. On this assumption
we tried oxidation, reduction, chlorination, electrolysis, all the
usual remedies, with no satisfactory result. We did find, how-
ever, that the foam producer could be entirely removed from the
brines by treating them with decolorizing carbon, or bone-black,
or in some cases with clays, but all these methods were expensive
both in installation and in use. We found further that any
slight coating of oil on the surface of the brine, whether the oil
was animal, vegetable, or mineral, completely stopped the foam-
ing so long as a film of oil stayed on the surface; and this would
have been the natural and complete remedy for foaming had it
not been for one unfortunate and unexpected cause of trouble.
Any oil that was used attached itself to the burkeite crystals
and acted as a flotation agent, keeping the burkeite suspended
instead of allowing it to settle, and the oil itself being thus con-
tinually removed from the surface had to be as continually re-
placed. This definitely eliminated the possibility of using oil.
Centrifugal foam separators were, of course, installed, and various
mechanical devices tried. These were necessary but not suffi-
cient. Various methods of operation were likewise attempted,
such as carrying the liquor at a low level in the evaporator tubes.
This absolutely prevents foaming, but on the other hand it
causes the tubes to salt up rapidly and put the evaporator out of
commission.
Things being in this unsatisfactory condition, then, it seemed
wise to determine, if possible, what this organic material was
and whence it came. To answer the last question a short study
of the watershed was made to learn what organic matter might
be at hand in this desert region of so potent a quality that 2 to
4 in. of annual rainfall could bring it into the lake in quantities
sufficient to cause such a disturbance. The only vegetation
occurring in considerable quantity seemed to be the desert
sage, the cactus, and the creosote bush. The creosote bush
[Larrea mexicana) was found to be the offender. The leaves
of this bush appear to be heavily varnished, and an extract of
the leaves and branches when added to synthetic brine causes
252
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
it to foam just as the natural brine does. Investigation of the
creosote bush showed that the foam-producing constituents
were certain resins composing this varnish, and certain saponins,
particularly acid saponin, which were easily extracted from the
plant. With this as a basis a careful study was made of the
whole question of foams, and quite a large number of materials
were found which would stop the foam when added in almost
infinitesimal amounts.1 For example, while ethyl alcohol
increases the amount of foam in natural brine, caprylic alcohol
decreases it; and if we go to still higher alcohols, like cholesterol,
an exceedingly small amount — say 10 p. p. m. — has a very marked
effect in stopping the foam. Gum arabic increases the foam, and
a colloid gum of unknown origin decreases it. Certain esters,
like amyl valerianate, check the foam, as well as do certain
organic acids, sulfonic acids, and their salts. This field is still
being investigated for different classes of materials, like phenols,
amines, etc. As far as we can see at the moment, it is either a
surface-tension phenomenon or a precipitation phenomenon
by a colloid of opposite sign, or both. In any case, our troubles
at the plant from this cause are apparently entirely in the past.
A considerable part of the early work on this subject was done
by Mr. Frederic Vieweg, the assistant manager, and the later
work by Mr. Burke and Mr. Clark M. Dennis of the research
department. Credit for suggesting and working out the details
of the means now actually in use goes to Mr. Russell W. Mum-
ford, in charge of research and development work at the plant,
and this will all be reported on in detail at the proper
time.
VACUUM DISTILLATION
One interesting feature of this problem of foam, which was
first called to our attention by Mr. A. L. Webre, was the fact
that the boiling temperature of the liquor in our vacuum pans
did not agree with the boiling temperature of the same brine
obtained in the laboratory at the same pressure. The discrep-
ancy was found to be due to the fact that in the plant the foam
passing through the vapor lines from the vacuum pans caused
so much friction, and hence back pressure, that the vacuum
which we read in the vapor lines was not the actual vacuum in
the pans, and this difference was sufficient to cause 12° F.
rise in the boiling point of the brine. Now that the foaming is
stopped this difference no longer exists.
OTHER PROBLEMS
We have mentioned above a few of the problems that have
been solved. Anyone familiar with this kind of work will
realize at once that the solution of these few problems in a going
plant represented a very large amount of work by a considerable
organization. We have succeeded in improving the quality of
the product to a point where we can satisfy the requirement of
almost any buyer no matter what his specifications are. We
have succeeded in cutting the cost of production very materially
below what it was in previous years, and this has been done even
in the face of rising costs of fuel, labor, and supplies. But it
will be realized at once that there are many other problems still
under investigation whose solution will be necessary before the
work can be considered finished. For example, in our evaporators
we have never yet succeeded in getting the capacity, i. e., the
pounds of water evaporated per square foot of heating surface
per hour, anywhere near up to the point where it should be
and where we hope to get it. We use iron tubes in the evapora-
tors, and we must in some way increase the coefficient of heat
transmission through the iron. Investigation has already shown
that we can get this increase by giving a proper circulatin g motion
to the brine, but how to give this proper circulating motion
through some 30,000 tubes of our evaporators is an engineering
problem still in course of study. We should like to use copper
1 This is the subject of patent applications.
tubes in the evaporators because its coefficient of heat trans-
mission is considerably higher than that of iron, but our brine?
are alkaline and contain small amounts of ammonia which ren-
ders the use of copper impossible on account of corrosion. The
brines contain some sulfur which seems to be given off as hy-
drogen sulfide or volatile sulfides. This attacks the iron on
the steam side of the tubes, converting it into iron sulfide and
ultimately making replacement necessary. We know how much
water a pound of fuel oil or a pound of steam should evaporate
from our brines in triple-effect evaporators. We are as yet
unable to approach this figure, and even after making due al-
lowance for the heat of solution of the salts that separate, and
the specific heat of the salts themselves, there is a very consid-
erable unexplained discrepancy. If we make 100 per cent re-
covery of all the potassium chloride in the brine it will be seen
that we must evaporate about 1-1 lbs. of water for every pound
of potassium chloride produced. Our recoveries are still a very
long distance from 100 per cent. We have made very good
progress in improving the per cent recovered, but we still have
a long way to go. Consequently, at present we still must evap-
orate a good deal more than 14 lbs. of water to produce 1 lb.
of KC1, and, being located as we are, in a place where the only
fuel available is rather expensive fuel oil, it becomes obviou-
that the cost of fuel and the cost of steam production in general
is one of our largest items of expense and one of the places where
we can still make the largest saving. I consider the problem ol
chasing the elusive B. t. u. one of the most important problems
now facing us, and this work is under way. We have not yet
reached a point where our cost of production is as low as lo
cents per unit K2O, which was about the minimum selling price
of German potash before the war, but we are beginning to see
where we may get within shooting distance of it. It will prob-
ably take two or three years yet to work out this problem to
the point where we are producing potash at Searles Lake in
large quantities as cheaply as it can be produced there. When
this point is reached I do not think we need seriously fear Ger-
man or any other competition.
TEMPORARY PROTECTION
The two largest items of cost in production we have at the
present moment are fuel and freight, and if we can get any kind
of ultimate cooperation from the oil producers and from the rail-
roads we shall be able to supply a large part of this country-
need of potash without any protection. Do we need protection
until this work is finished? It is probable that we do. Ger-
many's need of money and goods is a most serious need. There
will be great temptation for her to convert some of her supplier
of potash into immediate cash. Probably no potash plant in
America could sell its product to-day at $1.00 per unit and
cover its cost of production. If this industry can be coddled
for about 3 yrs., until investigation and development work are
finished, it is probable that we shall have a very considerable
production in the United States on a sound basis and at a fairly
cheap price. If it is not coddled the chances are that production
will almost cease, and our experience shows that where produc-
tion ceases there is little incentive to keep expending money on
research and development work. Prices of potash during thf
past year have averaged close to $150 per ton of KC1. On the
basis of our average consumption this represents close to (60,-
000,000. Before the war this would have represented around
$20,000,000, The size of either figure makes it well worth while
to encourage the growth of such an industry in this country,
since it apparently has every prospect of being able to live alone
and do its own fighting once its development period is over
We have discussed only the problems of one single plant. All
the other plants have their own problems which they are working
out in their own way, and in very many cases they will no doubt
arrive at as favorable a conclusion as wre ourselves hope to reach.
if they are permitted to have this period of development.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
253
SPARE TIME
By H. W. Jordan
Syracose, New York
Received February 7, 1921
"Do married men live longer, or does it only seem longer?"
Charles A. Dana used to ask in the New York Sun. A similar
query confronts us. Is life easier, or do we only think it easier?
Are we growing more versatile, now that power driven machinery
does the work we used to do with our muscles? Are we putting
more into life than we take out, and building a reserve of interests
to draw upon after the age of fifty? Electric power and lighting
have added one day a week to our spare time. Are we using
those hours to gain superior skill of mind and of senses?
The easiest way is not always the best. Some well-meaning
but misguided persons feel sorry for animals. They put sweaters
on dogs and feed them mushy food instead of cheap, tough meat
and bones, and they fix soft pillows for them to sleep on along-
side the radiator. It doesn't help the dog. When he falls afoul
of a real dog that has led a dog's life, the dog with the sweater
usually returns home looking like a shredded wheat biscuit, if
he returns at all. Even though he escape that swift fate, we
know that he will lose his teeth, grow blind, and die several
years earlier than if he were to run at large on a farm, eat bones,
and sleep in the haymow I once saw the keeper throw a loaf
of hard Vienna bread to a bear that had been raised in the Bronx
Park Zoo. He broke it open, scooped out the soft inside, ate it,
and threw the rest away. That is what civilization does to
bears. It is becoming a serious question if the same thing is
not happening to us, through a law. of evolution that has begun
destructive action.
This law of evolution is, that increasing specialization and
peculiar fitness for any special condition of life mean unfitness
for other and different conditions. When specialization in any
one direction goes so far as to unfit us for other and general
conditions, then the chances for survival are greatly reduced.
Sooner or later the narrow, specialized species becomes extinct
or returns to a more generalized type.
That is happening in America. Most of the work now done
in factories by machinery used to be done by hand at home.
Soap, clothing, tablecloths, sheets, and all else were made at
home. Every ounce of food was cooked or preserved there,
and cooking was a household art. To-day, if we lost our can
opeuers we would starve. We used to do any job that came
our way, do it right the first time, and do it alone.
Electricity and the gasoline engine brought widely distrib-
uted, finely subdivided light, transportation and power, and
highly specialized work. In Chicago, forty-one men join in
the job of killing a steer. Forty-one years ago, one man killed
a steer. What is more, he raised the steer. In raising him, he
gained far more experience in real life than any of the forty-
one can possibly accumulate to-day. Raising cattle takes mus-
cle and time, but it builds character, foresight, and self-reliance.
It is generalized work.
The specialized work of the forty-one has set our law of
evolution in action, namely, that when specialization goes so
far that it fits us to do only one thing, we lose our self-reliance
and tend to become extinct, or we return to our generalized life.
Proof of this is the rapidly increasing demand that the govern-
ment organize and do everything. We insist that the state
legislature pass laws to run the cities, and we implore Congress
to regulate the price of wheat and peanuts. # The more govern-
ment does, the more we want it to do. Like the pet dog in the
pink sweater, we refuse to eat, unless it be brought to us and we
be coaxed to eat sweetened food that we don't need to chew.
We do not realize how quickly we lose valuable powers of hand,
eye, and ear, that have taken ages to acquire. Our New York and
New England forefathers got most of their meat by hunting for
it in the woods, instead of by telephoning to have it delivered
at the house and charged on the bill. They could track game
for miles, as a hound does a fox. The hunter's sense of trailing
is lost to us city dwellers. Many other keen faculties of ear,
eye or hand that we were forced to use before we got our easy
jobs on automatic machines are fading away. We are so thor-
oughly contented with our power driven, short hour work that
we have not taken the trouble to think up new, personal, im-
proving activities to keep our hands and heads busy through
that extra day a week that electricity has given us.
We have lazily given up individual pursuits and have fallen
victims of commercialized amusement and crowd habits that
steadily drag us deeper into passive life. We sit in crowds on
bleachers or in dark rooms, to watch small groups of active
people, paid to exercise for us, some of whom are only photo-
graphic images, that do not require even the exertion of applause.
Our second generation of automatic machine people, born the
past thirty years, know nothing of the self-reliant life of their
American grandparents. They have become far more passive
than their parents. They know only one or two kinds of work,
and if those stop, many of them think they cannot earn a living
at anything else. The law of evolution begins to act.
This rapid, broadspread decline in the personal resourceful-
ness of our people, their tendency to lean on crowds and the gov-
ernment, is a serious social condition. If we allow it to grow,,
the end is the inevitable one of evolution. Either we shall be-
come a weak, inferior nation with a declining birthrate ending
in extinction, or we shall be conquered by a more virile and
versatile people of generalized type, who will come in, round us
up, and put us on reservations.
Our best national defense is that we each be versatile in many
lines outside the day's work. If we bowl, play in the band or
take part in a minstrel show, let us put our every ounce of energy
and brain into it. If it be checkers, or whist, get the best books
on the subject, study the play, and learn it to its depths. When
that is conquered, take up other subjects and become master of
each, in its turn. "Hit the line hard," said Roosevelt, who
made himself an expert in everything he undertook.
The highly specialized life that we limit to the day's work ami
to passive spare time makes us narrow, selfish, and intolerant.
It benumbs our intellectual and social senses. "Specialists are
more or less indifferent to intellectual acquirements and gifts
that lie outside their specialty. When they air their ideas upon
social or philosophic topics, they utterly astound one by their
primitive and rustic conceptions."
When we consider that several great civilizations have be-
come completely extinct in Asia, the Greek Islands, Egypt,
Yucatan, and Peru, we must not be too sure of the endurance
of American civilization, if we disregard evolution by wasting
our spare time. City life does not permit strenuous, outdoor,
muscular action, but it offers a wide range of keenly entertain-
ing, personal interests that compel skilful use of the hands, and
force us to see straight, hear straight, and think straight. We
need, each, to be an amateur expert in many interesting, personal
things, that we do for the love — the amour — of the working.
A splendid feature of the war was the prolonged session of
knitting that brought back the nimbleness of fingers and atten-
tion to color and design that our grandmothers had in patch-
work quilt days. Until we try it, we cannot realize the joy,
health and friendship that spring from amateur music, amateur
drama or gardening, and from social subjects studied alone or
in classes to stimulate discussion and public speaking. Alt
these keep our bodies young and our minds clear, so that we put
more into life than we take out of it. One of the youngest
citizens of Syracuse is a clergyman of some seventy years, whose
ardent love of roses keeps him in such splendid condition that
he swims a mile or more at a time in summer, for the love of
the swimming.
Life, like a business enterprise, fails and dies if it does not
grow. In the easy satisfaction that arose from the flood of talk-
254
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
ing machines and other semi-automatic pleasure-giving devices
that burst upon us about 1890, we have been like a child in the
week after Christmas. But the New Year is at hand. Some
of our toys are getting worn and commonplace. Even moving
pictures cannot be endured yesterday, to-day, and forever. So
we must find substantial, individual spare-time interests that
build personal character, and a strong nation. If we don't,
somebody will be accepting a mandate over us.
PRESIDENT SMITH ADDRESSES THE NEW YORK
CHEMICAL SOCIETIES
At the joint meeting of the New York chemical societies held
under the auspices of the New York Section of the American
Electrochemical Society in Rumford Hall, Chemists' Club, on
Friday evening, February 11, 1921, Dr. Charles A. Doremus
introduced President Edgar Fahs Smith of the American Chem-
ical Society as the speaker of the evening.
In the course of his remarks. Dr. Doremus presented to the
Chemists' Club a picture of Robert Hare, together with pictures
•of apparatus which he used in his experiments.
In replying to Dr. Doremus' remarks. Dr. Smith paid tribute
to Robert Hare, James Woodhouse, and those other early
American chemists who established chemistry in America on a
firm basis.
In the course of reminiscences over the twenty-five years
since his former presidency, Dr. Smith referred especially to the
remarkable development of the Society's journals from the strug-
gling early days of the Journal of the A merican Chemical Society
until, as he said, they have arrived "at such a stage that the
world respects them, the world looks to them, the world says
America is doing something that is worth while in the various
fields of chemistry."
Referring to his years of executive and administrative work,
Dr. Smith said, "I have often wondered why these institutions
of learning have dropped down upon quite a number of chemists
and made them their executive officers. And you know I have
reached the conclusion that chemists are a pretty patient sort
•of people. Perhaps the experimental work makes them patient.
When we want to hurry things, and when we do, we spoil them.
*»« But I fancy that it is not only patience we acquire, a good
deal of patience, but we respect details, and if you quizzed all
men who have been chemists in their day and have been college
presidents, you would find that the people about them would
say, 'We put him there because he is a good detail man.' " Dr.
Smith also warned the young man, "No matter how alluring the
invitation may be to assume the president's chair, tell them there
is something in the laboratory that you love better."
Coming to the subject of research, Dr. Smith said:
RESEARCH
There isn't anything particularly new in research that I am
capable of elaborating, for it is a subject which has been widely
and intimately discussed many times. This fact, however, that
it has been a subject of frequent debate, makes it interesting
apart from every other consideration. The mere mention of
research puts in motion in every one of us, a vast multitude of
thoughts which, if we were to utter, would provoke animated,
perhaps acrimonious and endless discussion, at the close of
which, very likely, few of us would be in sweet harmony. Yet
the frailty of our nature continues to prompt us to prolong the
discussion in spite of the certain disagreements upon which we
shall come.
Because I've been a teacher of our science for forty-four years,
I shall make bold to present to you one or two thoughts which
I've carried about with me for a long time.
After a basal training in the old classical curriculum with a
great deal of extra time in chemistry and allied subjects, I was
plunged, early in the seventies, into a German laboratory atmos-
phere, where one heard little else than research. It wasn't
strange that in due course I acquired the tendencies and the
language of my surroundings, and that I was soon heard chanting
eins, zwei, drei — am Hydroxyl forbei, and that my conception of
research in large measure consisted of studies of the position of
substituents in the benzene nucleus with an accompanying skill
in representing, on a flat surface, the most astounding changes
in the benzene hexagon — even extending as far as the erection
of Luft schlosserl These fanciful things were most attractive;
and delighted, indeed, was I, when I could draw for my own de-
lectation and that of my indulgent friends, the most involved,
intricate, and architecturally attractive figures which un-
consciously led me to think of the molecules upon which I was
engaged as possessing some such alluring internal arrangement.
Yes, I soared aloft, elated beyond expression; for I was actually
engaged in research. The quantitative determination of a few
elements, such as carbon, nitrogen, hydrogen, the halogens, etc.,
didn't signify in the least. All that was easy, despite my blind
stumbling along this road. There was one, and only one, re-
spectable field in which a chemist could do research and that
was in the organic field (so I thought). All other chemical fields
were exhausted, and should I say it — they were not the fields in
which real doctors could afford to waste time and thought. I
had become a researcher — an investigator — and my field was the
single field deserving consideration. What poor unfortunate
simpletons were they who wrestled with problems in inorganic,
analytical, agricultural, applied, and physical chemistry ! They
had my commiseration!
And there soon came to my attention that chemists were of
two breeds — pure and impure. The pure were those who oc-
cupied themselves with the profoundest problems, while the
impure were they who spent their days and nights in works,
never reading papers or entering into discussions; just hanging
around at chemical society meetings, hoping to pick up the
crumbs which fell here and there from the tables of the savants.
The Annalen and the Berichle seemed the only worth-while
journals.
But disillusionment was on its way. Fate placed monazite
sands in my hands for careful analytical study. Just one year
and a half of time from the precious organic field with daily
baffling experiences with monazite! New elements appeared.
Never before had I met them outside of textbooks. My intro-
duction to them was jerky and awkward. Mutely, I strove to
understand. Night after night I lay awake cogitating! At
last I humbly confessed (to myself) a profound ignorance as to
the nature of my new acquaintances. But I did not turn my
back upon them — not at all. I doggedly pushed in upon them
and made them tell me their stories, so that eventually I emerged
from an eighteen months' enthrallment quite prepared to ac-
knowledge that there were other elements than carbon and that
they — each one of them — had their own migrations and experi-
ences to narrate. All this broadened the horizon and outlook
of this particular researcher! It also caused him to extend his
acquaintance to other elements until he was at last able to say
that he had been introduced to every element known at the time
of his Wanderjahr. It was a delightful experience in every
particular. There were, of course, many anxious periods; but,
these passed, the "going was good." There were naturally dis-
couragements and strong temptations to turn aside and even to
go back to those alluring compounds with the sesqui-pedaliaa
names, but something within said, "go on." This was sternly
said, and acted like a spur.
Not to weary you, this researcher came out of his journey
deeply humbled in spirit, but quite certain that he was now be-
coming a real chemist. He modestly thought that he had got
beyond his a, b, c's, could actually spell and put words together.
Yes, he had acquired a respect for analysis, learned to use the
spectroscope with ease and confidence, determined specific heats
Mar., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
255
with pleasure, refractive indices with accuracy, vapor densities
by those classic methods of Dumas and Hofmann, and even
built up an outfit by means of which he could carry out Bunsen's
"gasometrische methoden." In short, his adventures would
have filled a good, stout volume. He forgot altogether that he
was a researcher, who had loftily and with contempt viewed the
innumerable and ever-increasing hosts of Nature's chemical
products. His one absorbing desire was now to be a chemist.
Often, after searching introspection, he tremblingly asked me
whether he might think of himself as such.
Another rude awakening came to this researcher when he
began to visit those wonderful plants in which simple chemical
principles were solving world problems and inquiries — when he
saw his science contributing to the comfort, happiness and wel-
fare of his fellowman. Then he lost sight of pure and im-
pure chemists. That division took flight from his mind, for he
was again humbled. Happy was he when a brother of the guild,
giving his best talents to the solution of industrial problems,
deigned to enlighten him, and those were truly precious gifts
which he bore home to his classes. When, in his own language,
he could recite the wonders and marvels he had beheld in fac-
tories, and his own hand, once so deft in picturing the falsely
supposed internal arrangements of atoms in molecules, traced
on the blackboard sketches of plants and apparatus. Those
were ecstatic moments! To think of the elements to which
he had been introduced on his travels of penitential instruction,
actually playing (silently it is true) a part of supreme importance
to sentient beings. Why, it caused his heart to swell with pride
at the thought that he was permitted to be a quiet, earnest
helper in such a magnificent science.
At this point my good wife, to whom I read the preceding lines,
pointedly asked, "Just what are you trying to do?" "Well,"
I drawled, "isn't it plain that I desire my researcher to be
(1) Broadly trained; not running off into some narrow field
without a comprehensive knowledge of chemistry as a whole.
I'd have him know his mathematics and physics, his botany,
mineralogy, and geology — and literature, for he will need them
all. I would have him be a chemist — sometime later he may
subscribe himself an organic chemist, physical chemist, etc., etc.
That will take place naturally and unconsciously.
(2) Then it almost follows from what has already been said
that I'd have him so conversant with the various divisions of
our science that there never would occur to him such a con-
glomeration as pure and impure chemists."
All chemists should be researchers. They will become such in
time. Their love of the science will lead them into the field of
inquiry. The Almighty only now and then lays his hand upon
some one chemist's head and ordains him for the higher phil-
osophy. In this exalted station it ill becomes him to view with
contempt his humbler brother who is busily and sturdily en-
gaged in pointing the unfinished parts of the glorious structure
reared by him in his eager and sweeping flight to the heaven-
aspiring pinnacles.
Rammelsberg, whose magnificent works we older men appreci-
ated
"felt that every analysis which he could make, every substance
which he could prepare, was something new, of unknown import
and involved the exercise of new powers. To a young, ardent,
and ambitious student this in itself must have been an over-
powering impulse to energetic labor; in no life was this delight
in work better exemplified than in that of Rammelsberg. _
"He was always ready to assimilate new views and to dissem-
inate them. He ranged over the whole domain of inorganic
chemistry. His addition to the store of chemical knowledge is
amazing by its magnitude.
"Without his labours, the illuminating discovery of isomorphism
would never have excited such widespread influence."
The world somehow or other placed him not among its geniuses;
but he gave himself devotedly to things he could do, and thus
achieved a lasting remembrance.
He knew the signal and stepped on with pride
Over men's pity.
Left play for work and grappled with the world
Bent on escaping.
"What's in the scroll," quoth he,
"Thou keepest furled?"
My reference to literature calls to mind that Chaucer wrote:
Of the care and woe
That we had in our matters subliming,
And in amalgaming, and calcining
Of quicksilver, called mercury crude,
For all our sleights we cannot conclude.
And Shakespeare:
Hast thou not learned me how
To make perfumes, distil, preserve?
While Goethe sang:
Who, in his dusky workshop bending,
With proved adepts in company,
Made, from his recipies unending,
Opposing substances agree.
While Scott, Dumas, and even Dickens pay honor to our science.
I'd have my researcher glean from all fields — never turning
in lordly fashion from any helpful subject or individual. In
short, I'd have him "prove all things and hold fast to the good."
Men of genius, on their departure, leave examples of a life
which all can admire but to which few can attain; men of talent
using their powers unceasingly "contribute equally to the in-
crease of knowledge and leave an equally valuable legacy, an
example that all can emulate."
Yes, researchers go forward well armed:
The secret art of chemistry is nearer possible than impossible;
the mysteries do not reveal themselves except by force of labour
and perseverence. But what a triumph it is when man can
raise a corner of the veil which conceals the works of God!
The Nashville Industrial Corporation which purchased the
government plant at Old Hickory, Tenn., is now engaged in dis-
posing of the immense supplies of surplus materials on hand.
This includes fifteen contact sulfuric acid plants, seven nitric
acid plants, seven cotton purification plants, seven cotton dry
houses, nine nitrating houses, five mix and weigh houses, nine
boiling tub houses, nine pulping houses, nine poacher houses,
sixteen solvent lecovery houses, one diphenylamine plant, one
causticizing plant, four box factories, three chemical laboratories,
and a 3500-ton refrigerating plant. As soon as the present
stock is disposed of an intensive advertising campaign will be
inaugurated towards bringing large industries to Old Hickory.
A study is now being made by Meigs, Bassett & Slaughter, of
Philadelphia, consulting engineers, of all phases of the plant and
the uses to which the various units can be adapted.
The Great Southern Sulphur Company of New Orleans is
about to develop the natural sodium sulfate deposits in the dry
lake near Alamogordo, Dona Ana County, New Mexico. The
area of the lake is 4000 acres. Preparations are being made for
immediately erecting a plant for purifying the salts, which is
to have a capacity of 100 tons of the salt cake daily. The
quantity of sodium sulfate available in the deposit is said to be
many million tons and the depth is more than ninety feet. The
average analysis of the raw material is given as follows :
Per cent
Water of crystallization 20 . 24
Sodium sulfate 43.51
Calcium sulfate 33 . 28
Magnesium sulfate 0. 54
Sodium chloride 117
Insoluble 1.26
The company has tested apparatus utilizing the method by
refrigeration for fractionating the salts, which it announces has
produced a refined material analyzing as follows:
Per cent
Sodium sulfate 98 . 20
Calcium sulfate 0.51
Magnesium sulfate 0.41
Sodium chloride 0.30
Insoluble 0 .08
Moisture 0 . 50
256
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
STUDIES ON THE CHEMISTRY OF CELLULOSE
I— THE CONSTITUTION OF CELLULOSE1
By Harold Hibbert
Department of Chemistry. Yale University, New Haven, Conn.
In a recent pica for the scientific study of cellulose chemistry2
the writer submitted a new formula for the cellulose nucleus:
CH2OH
CH-
-CH-
CHOH— CHOH— CH
In view of the interesting results recently obtained by Denham
and Woodhouse3 on the methylation of cellulose and of those
of Pictet and co-workers4 on the distillation of pure cellulose
and starch under reduced pressure, which tend to confirm the
writer's views, a discussion of the constitution of cellulose in
the light of our previous and present knowledge appears de-
sirable.
It has long been known that cellulose is closely related to
dextrose, since it yields the latter quantitatively on hydrolysis —
a fact of fundamental importance. Some of the first work on
the subject was carried out by Braconnot6 in 1919, but the
identity of the sugar as dextrose was first established by Flechsig.6
While the fact of the "quantitative" conversion of cellulose into
dextrose has been questioned, the recent work of Willstatter
and Zechmeister,' and more especially that of Ost,3 serve to
confirm Flechsig's results and to establish beyond question the
fact that dextrose can be obtained in quantitative yield by the
hydrolysis of cellulose with acids. Thus the latter author not
only succeeded in obtaining a yield, determined polarimetrically,
of 95.3 per cent of dextrose and in isolating it as a crystalline
product, but also converted it into ethyl alcohol of which some
SO to 83 per cent of the theoretical quantity was obtained.
Furthermore, in his earlier work' on the acetylation of cellulose
lie was able to obtain a 90 per cent yield of pentacetylglucosc
'taking into account the octacetyl cellobiose formed at the same
time). These facts confirm beyond question the quantitative
relationship existing between dextrose and cellulose, notwith-
standing certain arguments to the contrary.10
PROPOSED FORMULAS FOR CELLULOSE
Of the various formulas proposed for cellulose by different
investigators, those of Tollens,11 Cross and Bevan,12 Vignon,'3
Green,14 and Barthelemy16 may be mentioned.
tollens — Tollens16 assumes that cellulose possesses the fol-
lowing structure:
1 Presented at the Cellulose Symposium, Division of Industrial and
Engineering Chemistry, at the 60th Meeting of the American Chemical
Society, Chicago, 111., September 6 to 10, 1920.
2 Chem. & Met. Eng., 22 (1920), 838.
• J. Chem. Soc, 103 (1913), 1735; 106 (1914), 2537; 111 (1917), 244.
< Helvetica Chim. Acta, 1 (1918), 87, 226, 2 (1919), 698; S (1920), 258,
640, 645, 649. See also P. Karrer, Ibid., 3 (1920), 258; Sarasin, Arch. sci.
phys. not., [IV] 46 (1918), 5.
'Ann. chim. phys., [2] 12 (1819), 172.
• Z. physiol. Chem., 7 (1882), 913.
' Ber., 46 (1913), 2401.
'Ibid., 46 (1913), 2995; Ost and Wilkening, Chem.-Zlg., 34 (1910), 461.
• Ann., 398 (1913), 323.
>» M. Cunningham, J. Chem. Soc, 113 (1918), 178; Cross and Bevan,
Ibid., 113 (1918), 182.
" "Kurzes Handbuch der Kohlenhydrate," 3rd Ed., 1914.
■« /. Chem. Soc, 79 (1901), 366; Rev. ges. mat. color., 6 (1901), 72; "Re-
searches on Cellulose," |I), p. 77; (II], p. 131; "Cellulose," p. 75; Caout-
chouc &■ gutla percha, 1917, 9327.
" Bull. soc. chim., [3] 21 (1899), 599.
» J. Chem. Soc, 81 (1906), 811; Rev. ges. mat. color., 2 (1907), 130;
Z. Farben-lnd., 3 (1904), 97, 309.
'» Caoutchouc if gutla percha, 1917, 9274, 9328; see criticism by Cross
and Bevan, Ibid., 9327; Chem. Abs., 11 (1917), 3428.
19 Loc cit., p. 564.
OHC— (CHOH)3— CH— CH,
(A) | |
O O
\/
CH— (CHOH):n
H2C CH
! I
O O
\/
HOH2C— HOHC— (HOCH)3— CH
(C) (B)
in which the oxygen of the aldehyde group of one molecule of
dextrose is assumed to have condensed with the hydrogen atoms
of the two end hydroxyl groups of a second one. In this way
any desired number of molecules may be combined, the — CHO
group (A) of the first ultimately combining with the two hy-
droxyls, B and C of the last, to form a closed ring. As is indi-
cated below, the formula is quite inadequate to explain the re-
actions of cellulose.
cross and bevan1 — According to the earlier work of these
authors the cellulose nucleus has the constitution indicated by
the formula:
CHOH— CHOH
OC<^ \CH2
CHOH— CHOH
This is assumed to be capable of polymerizing to give ring forma-
tions such as
CHOH— CHOH y CHOH— CHOH , CHOH— CHOH
OOy \cH— C(OH) \cH— C(OH) ^>CH: (1$
CHOH— CHOH \hOH-CHOH ^CHOH-CHOH
in which any desired number of single molecules may be coupled
together. On the other hand, instead of such aldol formation,
these authors assume that condensation may also take place be-
tween the CO group (hydrated) and a secondary alcohol group,
as follows:
CHOH— CHOH HO CHOH— CHOH
OC<^ ^>CH2 4- \c/ ^>CH2
CHOH— CHOH HO CHOH— CHOH
CHOH— CH O CHOH— CHOH (II)
— *- oc<^ Nch. Nc<^ ^CH*
CHOH— CHOH OH CHOH— CHOH
which may then couple up again according to Scheme I or II.
In their most recent publication2 Cross and Bevan point out that
"no purely chemical synthesis of any compound similar to cellu-
lose has been attempted; we are therefore without the essential
criterion of any general formula which might be proposed, if only
as a condensed expression of the relationship and functions of
its constituent groups."
They emphasize the following points3 as having an important
bearing on the subject:
1 — The conversion of cellulose into dextrose.
2 — Partial resolution under treatment with HC1 accom-
panied by the setting free of carbonyl groups.
3 — Complete decomposition on fusion with alkalies giving
hydrogen, carbonic, oxalic, and acetic acids. "The yield of
the latter, tending to a maximum of 30 to 35 per cent, indi-
cates that the grouping — CO — CH; is an important element
in the constitution of the unit groups."
4 — So-called "negative characteristics" more typical of sat-
urated compounds, such as resistance to alkaline hydrolysis
oxidizing agents, acetylation.
o — Synthetical reactions, such as ester formation, the
xanthate reaction, etc.
The authors assume1 that the balance of evidence is in favor
of a cyclic formula for the unit groups comprising cellulose, for
the following reasons:
1 Loc. cit.
2 "Cellulose," New Ed., 1918, 75.
' Ibid., 75.
« Ibid., 77.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
257
1 — The general differentiation of cellulose in regard to sta-
bility which points to a symmetrical formula as distinguished
from the normal chains upon which the hexoses are represented.
2 — The formation of a cellulose acetate of the composition
C6H60(OAc)4 in which only 2n carbon valencies are taken up in
"outside" combination.
3 — The simple and manifold transition of cellulose, in the
plant world, into keto-R-hexene and benzene derivatives.
The importance of Fenton and Gostling's reaction,1 viz., the
formation of w-bromomethyl furfuraldehyde by the action of
dry HBr on cellulose in presence of chloroform with a yield of
about 30 to 35 per cent (compared with the weight of cellulose
originally taken), is emphasized by Cross and Bevan,2 who state:
The reaction is therefore a main reaction and shows that cellu-
lose under these conditions breaks down, at least in large part, to
keto-hexose units.3 By these investigations the polyaldose
view of the constitution of cellulose is directly called in ques-
tion ***** On the broad and general question of
the actual constitution of cellulose there is as yet but little posi-
tive evidence.
The opinions of these authors, in view of their eminent stand-
ing in the cellulose field, have been quoted at some length,
but the writer finds it difficult to obtain from their writings any
clear mental picture of the probable structure of the cellulose
molecule, an opinion in which he is aware he does not stand alone.
With regard to the formula previously proposed by them and
to which apparently they still hold, it may be said that:
1 — The formula gives no indication of the close quantitative
relationship existing between dextrose and cellulose.
2 — There is no indication of the presence of a free carbonyl
group in the cellulose molecule.
3 — There is very little evidence in favor of their assumption
of four hydroxyl groups. The data on acetylation,4 nitration,5
methylation,6 and the action of heat under reduced pressure"
are against this view, and favor that of the presence of three,
and three only, "active hydroxyl groups."
4 — The formation of acetic and oxalic acids by the action of
fused alkali at an elevated temperature cannot be regarded
as providing evidence of the previous existence of the group-
ing — CH2 — CO. It seems more probable that they are ob-
tained as a result of secondary reactions.
5 — It seems scarcely permissible to speak of the yield of 30
per cent by weight of u-bromomethyl furfuraldehyde from
cellulose8 (equivalent to 20 per cent of that theoretically ob-
tainable) as constituting a "main reaction."
vignon — A third formula is the one put forward by Vignon :'
CHOH— CH CH2 -,
O
o
./
-CH
CHOH— CHOH-
It will be seen that the simple molecule contains three hydroxyl
groups and represents an intramolecular condensation product of
the aldehyde group of dextrose with the end hydroxyl groups.
r CHOH— cho|h|— ch2o|h -,
L CHOH— CHOH— CH|0_
CHOH— CH — CH;
L CHOH— CHOH— CH-
-O J x
+.vH,0
' J. Chan. Soc, 73 (189S), 554; 76 (1899), 423; 79 (1901), 361.
= "Cellulose," 1918, Appendix, 333.
3 The fallacy in this argument is shown by the fact that the writer, in
conjunction with Mr. H. S Hill, has recently found that various glucosides
(for example, the methyl glucosides of dextrose) also yield appreciable
quantities of oj-bromomethyl furfuraldehyde. The investigation of these
bodies is in progress.
1 Ost, Z. angew. Chan., 1906, 993; Ann., 398 (1913), 323, footnote;
Law, Chan.-Ztg., 32 (1908), 365; Green, Z. Farben-lnd., 3 (1904), 309;
Bayer & Co., D. R. P. 159,524; Vignon and Gorin, Comfl. rend., 131 (1900),
588.
* Vieille, Conipl. rend., 95 (1882), 132.
9 Denham and Woodhouse, Loc. cit.
7 Pictet and co-workers, Loc. cit.
» Fenton and Gostling, J. Chan. Sue, 79 (1901), 363.
9 Loc. cit.
It will be noted that its structure indicates the presence of a
5-, a 6-, and a 7-membered ring; further that it contains three
secondary alcohol groups.
Oxycellulose is assumed to be cellulose combined with the
following typical oxycellulose group:
OHC— (CHOH);)— CH— CO
\ /
O
From the arguments put forward below, it is apparent that
the formula, containing "three secondary alcohol groups," is
unable to account for a number of important reactions.
green — The formula put foward by Green,1
CHOH— CH— CH2
I \ \
o o
I / /
CHOH— CH— CHOH
possesses interest in view of his compilation of the icactions
which any proposed formula must be capable of explaining:
1 — The highest stage of nitration of cellulose (calculated on
the C6 formula) is the trinitrate.
2 — The highest acetylation product (contrary to the views
of Cross and Bevan) is the triacetate.
3 — Cellulose forms with concentrated sodium hydroxide a
sodium compound, which is decomposed by water, leaving the
cellulose as a hydrated product. In this latter form it is much
more readily soluble in a solution of ZnCl2 or ammoniacal cop-
per sulfate.
4 — On treatment of the sodium derivative of cellulose with
CS2 a cellulose xanthate is obtained, readily soluble in water.
This product is very unstable, and is decomposed by acids,
acid salts, ammonium chloride, or heat with regeneration of
a hydrated cellulose.
5 — Cellulose does not react with phenylhydrazine or with
hydroxylamine; therefore, apparently does not contain free
carbonyl (aldehyde or ketone) groups. On the other hand, by
subjecting it to simple hydrolysis, derivatives containing free
carbonyl groups are obtained.
0 — Cellulose yields dextrose as the end product of hydrolysis
(for example, with H2S04).
7 — Cellulose yields oj-bromomethyl furfuraldehyde on treat-
ment with HBr in ether or chloroform solution.
8 — The oxidation of cellulose gives oxycellulose, a body
of marked acid character, which yields furfuraldehyde on dis-
tillation with dilute HC1.
9 — On heating oxycellulose with calcium hydroxide, iso-
saccharic and dioxybutyric acids are formed.
10 — The nitrocelluloses when treated with dilute caustic
soda yield hydroxypyruvic acid.'2
According to Green, his formula is capable of explaining all
of the above facts. Cellulose is represented as an inner an-
hydride of dextrose. Its latent "aldehyde character" is seen in
the change
— CH, — CH,OH — CH2OH
\
O + H20
/
—CHOH
OH
-CH
\
OH
The formula is also in agreement with the formation of the tri-
nitrate and triacetyl der vatives as the highest stages of nitra-
tion and acetylation, respectively. Higher derivatives can be
obtained only by employment of the hydrated cellulose, i. e.,
after the central O group has been converted into two OH groups.
— HC— — CHOH—
\
O + H20 >
/
— HC— — CHOH—
Similarly with NaOH, we have
— HC— —CHONa—
O + 2NaOH > + H20,
— HC— —CHONa—
I Loc cit.
' Will, Ber., 24 (1891). 400.
258
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
CH =
:C— CH2
1
\ \
0 o —
CH =
/ /
C— CHOH
CH
= C— CH2Br
1
\
0
CH
/
= C— CHO
a body capable of reacting with carbon bisulfide to give a
xanthate, from which latter, on treatment with acid, a hy-
drated cellulose is obtained.
Fenton's reaction (actionof dry halhydric acids in ether or
chloroform solution) is explained as follows: Cellulose first
undergoes dehydration, and the body, formed adds on HBr,
and from this o-bromomethyl furfuraldehyde is obtained by
(he splitting-off of water:
CHOH— CH— CH-.
I \ \
O O 3
I / /
CHOH— CH— CHOH
CH = C— CH2Br
I \
O OH
I / /
CH = C— CH
\
OH
Cross and Bevan have criticised this formula1 on the ground
that it indicates the presence of only three and not four hydroxyl
','roups; further, that as a type of semialdose derivative, it should
lie easily decomposed by alkali, while the change
Cellulose * Xanthate — -> Cellulose hydrate
takes place quantitatively as a simple hydration or hydrolysis
and without further change in the molecule.
The formula undoubtedly offers a satisfactory explanation
of many of the reactions of cellulose but does not explain:
1 — Formation of the trimethyl glucose obtained by Denham
and Woodhouse by the hydrolysis of completely methylated
cellulose.
2 — Relation of cellulose to dextrose and cellobiose.
3 — Intimate nature of the relationship of dextrose to cellu-
lose both in plant synthesis and chemical decomposition, con-
sidered from the point of view of cyclic configuration.
4 — Relation of starch to cellulose.
5 — Properties of oxycellulose.
6 — Connection between the cellulose nucleus and the highly
polymerized product which we know as "cotton cellulose,"
and behavior of the latter.
7 — Formation from it of levoglucosan, a body which shows
only slight tendency towards polymerization.
barTHELEMY — This subject of the constitution of cellulose
has recently been discussed by Barthelemy,2 who concludes that
its properties are best represented by the structure:
/
\
HO— CH
CH— CH2OH
HOCH
CH
|
i>
CH
CH
o/|
j
\l
CH
CHOH
32C— CH
CHOH
\
/
C
1
The formula indicates the presence of two /3-oxidic linkiugs,
which does not agree with the properties of cellulose.
Such a product should be hydrolyzed with remarkable
ease, react readily with permanganate, and readily yield
pentacetyl derivatives, none of which properties is shown by
cellulose. It is also incapable of explaining the formation of
1,2,5-trimethyl glucose and of the intimate connection between
dextrose and cellulose.
1 "Researches on Cellulose," II, p. 133; Z. Farben-lnd., 3 (1904), 97; see
reply by Green, Ibid., 3 (1904), 309.
3 Loc cit.
bernadou, nastjukow, oddo — Apart from interesting data
by Bernadou,1 Nastjukow,2 and Oddo,8 these represent the
principal contributions to the subject, and in view of several
recent important investigations it is necessary to see how closely
the various formulas fit the new facts. The bearing of two of
these latter on the structure of cellulose will first be discussed.
constitution of dextrose and properties of hydroxy
aldehydes
It is now generally accepted that dextrose possesses the ->-oxidic
structure :4
CH.OH— CHOH— CH— CHOH— CHOH— CHOH
L o J
This tendency of hydroxy-aldehydes to assume the cyclic form
is a general characteristic of such derivatives, as iudicated in
the recent researches of Helferich5 on •y-hydroxy-valerianic and
caproic aldehydes. Both of these are shown to possess the
7-oxidic structure,
CH3— CH— CH2— CH2— CHOH and
O-
CH3— CHr-CH— CH2— CH>— CHOH
-O
respectively. In view of the close relationship existing between
-,- and o-lactones and similar derivatives, it would seem that
6-hydroxy aldehydes should also exhibit the same tendency
towards ring formation, although apparently such derivatives
have not yet been submitted to the same careful examination.
We therefore have ground for the assumption that in the case
of dextrose there also probably exists a tendency to assume the
6-oxidic form in addition to that of the y, although up to the
present apparently no isomer of this type has been isolated.6
THE METHYLATION OF CELLULOSE
By subjecting cellulose to six successive treatments with alkali
and dimethyl sulfate, respectively, and then hydrolyzing the
resulting product with acid, Denham and Woodhouse7 were
able to show that the resulting product contained a large amount
of trimethyl dextrose with only a trace of a tetramethyl deriva-
tive. From the evidence submitted it would appear that the
former has the constitution 1,2,5-trimethyl dextrose:
CH2(OCH3)— CHOH— CH— CH(OCH3)— CH(OCH3)— CHOH
I o J
The cellulose, in spite of the successive treatments to which it
was subjected, underwent relatively little disintegration. This
result has an important bearing on the question of the constitu-
tion of the cellulose molecule, for it apparently indicates that of
1 J. B. Bernadou, "Smokeless Powder, Nitrocellulose and Theory of
the Cellulose Molecule," 1901.
' J. Russ. Phys. Chem. Soc, 34 (1902), 231, 235, 505, 508.
» Cazz. chim. Hal., 49 (1919), 127; Chem. Abs., 14 (1920), 1529.
' Hudson, J. Am. Chem. Soc., 31 (1909), 66; 32 (1910), 889; Parcus and
Tollens, Ann., 257 (1890), 160; Pope and Read, J. Chem. Soc, 95 (1909),
171; Perkin, Ibid., 81 (1902), 177; Boeseken, Ber., 46 (1893). 2612; Irvine,
Fyfe and Hogg. J. Chem. Soc, 107 (1915). 524; Fischer, Ber., 47 (19141,
1980; McDonald, J. Chem. Soc, 103 (1913), 1896; Net, Ber., 47 (1914).
1980.
' Ber., 52 (1919), 1123, 1800.
8 It is of interest that the recently discovered so-called > -isomer of mono-
methyl dextrose [Fischer, Ber., 47 (1914), 1980] may possibly have the
5-oxidic structure CH:OH— CH— CHOH— CHOH— CHOH— CHOCHi.
0
although the evidence submitted by Irvine. Fyfe and Hogg [J. Chem. Soc, 107
(1915), 524] indicates that it is more probably of the 0-oxide type CHiOH —
CHOH— CHOH— CHOH— CH— CH(OCHs). Thus it is hydrolyzed with
\/
o
remarkable ease and reacts readily with permanganate, properties which
distinguish it sharply from the *>- and 5-oxides.
' Loc. cit.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
259
the three hydroxyl groups present in cellulose, two are of a sec-
ondary and one of a primary character.
In the first place, it should be pointed out that the views of
Cross and Bevan as to the presence of four hydroxyl groups in
the cellulose molecule do not appear to be warranted by the evi-
dence available. Not only does the experimental work carried
out by Green on samples of Cross and Bevan's own acetylation
product fail to confirm their view of it as a tetracetate, but the
researches of Ost and others support Green's conclusions. The
fact that, as pointed out by Cross and Bevan,' cellulose, when
treated with acetic anhydride in presence of zinc chloride, is
capable of giving a product approaching the tetracetate in com-
position should occasion no surprise and is to be attributed to
the remarkable role played by zinc chloride in connection with
oxidic linkages contained in substances of the cellulose type.
Thus it is of interest, as indicated later, that the polymerization
of ethylene oxide, and its conversion into diethylene dioxide, are
facilitated in a marked manner by the presence of traces of
zinc chloride.2
On the assumption that there are only three hydroxyl groups
in the cellulose nucleus, it is of interest to consider how closely
the formulas proposed for it by Vignon, Green, and the writer
correspond with the present state of our knowledge of the sub-
ject. A glance at these three
CHOH— CH CH,
I \ \
O O
I \ /
CHOH-CHOH— CH
Vignon
r- CHOH— CH— CH,
\ \
o o
/ /
L- CHOH— CH— CHOH-J
Green
CH,OH
I
-CH-
-O
L CHOH— CHOH— CH
Hibbert
reveals a marked similarity between those of Vignon and Iiibbert,
inasmuch as they both represent intramolecular condensation
products of the aldehyde group of dextrose with two of its hy-
droxyl groups and are true hydroxyl derivatives, while that of
Green represents a somewhat different type, namely, a hemi-
acetal.
It may possibly be of interest to trace the development of the
new formula proposed by the writer. Attention was first
directed to this subject some 7 or 8 years ago in connection
with an investigation on the condensation of aldehydes with
polyhydroxy compounds and the possible interrelation of this
type of reaction to that prevailing in the nitration of mixtures
of sugar and glycerol. Regarding the first of these, considerable
new experimental evidence was accumulated indicative of the
ease with which such condensations take place. While the for-
mation of an acetal from an aldehyde and alcohol is facilitated, in
general, by the presence of a dehydrating agent, the condensation
of the former with a polyhydric alcohol takes place readily and
completely in presence of water; in fact, as shown by Verley,3
the presence of this is a necessary factor in certain cases of this
' "Cellulose," 1918, 36.
2 It is very striking that according to their own statements, when a
trace of iodine is substituted for the zinc chloride, the reaction proceeds
quite normally and a triacetate is obtained free from by-products. A
satisfactory explanation of the role played by the iodine in dehydration
phenomena has been given by the writer in a previous communication
(J. Am. Chem. Soc, 37 (1915), 1748) and there would seem to be no ground
for assuming that it exerts any other role in the one under consideration;
it is in fact known that iodine differs radically from bromine and chlorine in
exerting no action on cellulose.
a Bull. soc. chi'm., 13] 21 (1899), 275.
type. In general, it was found that the type of condensation
represented by
HO— CH— R yO— CH— R
R.CHO + | = R.CH< | + H,0
HO— CH— R' X>— CH— R'
is best effected by the use of a small amount of iodine or of 20
per cent sulfuric acid, the yield in nearly all cases being re-
markably high. Such changes would seem to be a result of
the well-known pronounced tendency towards the formation
of 5- and 6-membered rings, especially the former. These re-
actions represent intermolecular hydroxy-aldehydo-condensa-
tions, but there is also evidence that similar condensations also
take place intramolecularly with great ease. Thus when 7,7'-
dibromovalerone is boiled with water the following changes
CH,— CH,— CHBr— CH,
I
CO
I
CH2— CH,— CHBr— CH,
CH2— C H,— CHOH— CH,
I
CO
I
CH,— CHr
-CHOH— CH,
CH,— CH2— CH— CH,
\
Os
CH2— CH2— CH— CH,
(dimethyloxetone)
iliniethyloxetone being formed.
If we now imagine the two bromine atoms to be in the 7,0-
positions to the CO group, it seems probable that a similar con-
densation might occur:2
CH,— CHBr— CHBr CH2— CHOH— CH2OH
I I
CH, — >- CH2 — >•
I I
CO— CH,— CH,— CH,— CH3 CO— CH2— CH,— CH2— CH,
CH2— CH— CH,
' CHr— CH2— CH»— CH,
Such a reaction would typify, according to the writer's views,
the mode of formation of the cellulose nucleus from dextrose:
CHOH— CHOH— CH
I /|
H— O
CHOH— CHOH— CH
CH O H— O— CH
I
CH,OH
CII--
/
O
-CH— CH2OH
' Volhard, Ann., 867 (1892), 90.
2 These bodies have not been extensively investigated but are now
being made the subject of inquiry along various lines.
In view of the apparently close relationship of such condensation
products to cellulose it would seem advisable to extend such investigations
to include a variety of bodies with similar linkings. Furthermore, bodies
of the ethylene oxide and diethylene dioxide types should be examined and
their properties, such as stability towards acids and alkali, halogens and
oxidizing agents, together with their tendency towards polymerization, in-
vestigated. The former, for example, readily polymerizes under the in-
fluence of traces of metallic salts, while the latter is remarkable for the
facility with which it unites with acids, bromine, etc., to form stable com-
pounds. Such information should be of material assistance in elucidating
the function of similar linkings in the cellulose molecule and in providing
data regarding the nature of residual affinities. See Hans Clarke, J. Chem.
Soc, 101 (1912), 1788.
2m
THE JOl AW. I/. OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
The only example in the literature of a Y,o-dihydroxy ketone
appears to be the derivative obtained by N. Prileshajew1 from
methyl heptenone by oxidation with benzoyl peroxide and treat-
ment of the resulting oxide with watei
CH— (CHsli- CO— CH3
J. Russ. Phys < hem. Sue, 43, 609; Chem. Zcnlr , 1911 (II), 268.
Healing with ."> per cent sulfuric acid is said to convert this
dihydroxy ketone into the diketone:
(CH3)S : CH . CO — CH= — CH, — CO — CH,
There is no indication, apparently, of any bridged ring forma-
tion,' and it is possible that the presence of the methyl groups
may diminish such tendency very appreciably. This behavior
would be in harmony with the general, more unstable, character
of polyhydroxy-keto-, in comparison with polyhydroxy-aldehydo-
condensation products.
(To be concluded)
1 It seems probable that such a change could be induced by the use of
a suitable condensing agent, such as iodine, phosphoric acid, etc., and these
experiments are to be carried out.
RESEARCH PROBLEMS IN COLLOID CHEMISTRY
By Wilder D. Bancroft
Cornell University, Ithaca, N. Y
Received November 5, 1920
(Continued)
PEPTIZATION
(94) WILL ANY LIQUID PEPTIZE A WETTED SOLID AT A SUFFI-
CIENTLY high temperature? — We believe that when a liquid
is adsorbed by a solid, it tends to peptize the solid. We know
that at higher temperatures the action increases and we get
gelatin peptized by water, glass1 by water, and vulcanized rubber2
by various organic liquids; but there are no experiments to show
whether this is absolutely general and whether any solid will
be peptized at a sufficiently high temperature by any liquid
which wets it.
(95) PEPTIZATION OF PRECIPITATES BY GLYCEROL, SUGAR,
^tc. — A concentrated solution of sugar in water will prevent the
precipitation of lime, calcium silicate,3 silver ehromate, silver
chloride,'' and the hydrous oxides of copper,5 uranium, and iron.6
Invert sugar is about seven times as effective as cane sugar in
holding up hydrous ferric oxide. Grimaux7 showed that glycerol
prevents the precipitation of hydrous ferric oxide by caustic
potash. We ought to get peptization of the precipitates in all
these cases under favorable conditions, but this has never been
proved experimentally. Some preliminary work has shown that
the time factor may be very important and that one may get
peptization at the end of a week or more, in cases where there
was no apparent immediate action.
(96) STUDY OF PEPTIZATION BY, AND ADSORPTION OF, UNDISSOCI-
ATED salts — There is no work at all on peptization by salts in
practically nonionizing solvents, and yet cases of this sort must
occur and will undoubtedly be found if looked for.
(97) DOES glycerol peptize iodine? — Contrary to the usual
opinion, iodine is abundantly soluble in glycerol.8 First dis-
solve the iodine in alcohol or acetone, then add glycerol and
drive off the first solvent by evaporation at a low temperature.
A solution can also be obtained by heating iodine and glycerol
in a closed vessel to 1200 to 150°. These elaborate directions
do not sound like an ordinary case of solution and make one
1 Barus, Am. J. Set., [3] 38 (1899), 408; 41 (1891), 110; [4] 6 (1898),
270; 7 (1899), 1; Phil. Mag., [5] 47 (1899), 104, 461.
1 Barus, Am. J. Set , [3] 42 (1891), 359.
» Weisberg, Bull. soc. chim., [3] 16 (1896), 1097.
• Lobry de Bruyn, Ber., 35 (1902), 3079.
> Graham, J. Chem. Soc., 15 (1862), 253.
' RilTard, Compi. rend., 77 (1873), 1103.
'Ibid., 98 (1884), 1485, 1540.
' Catillon, J. Soc. Chem. Ind., 22 (1903), 377.
wonder whether iodine perhaps forms a colloidal solution in
glycerol.
(98) THEORY OF PEPTIZATION BY MIXED SOLVENTS — There
are a number of cases where mixed solvents will peptize a solid
much better than either one alone — cellulose nitrates in ether
and alcohol, casein in pyridine and water,' and probably ein-
chouine in chloroform and alcohol,5 as well as phloretine in ether
and water.3 The theory of this has not been worked out. Cellu-
lose nitrate swells in alcohol and not in ether;' but it is not
known whether this is universal. We do not know whether
alcohol peptizes cellulose nitrate at higher temperatures. Zein
is also peptized in mixed solvents.6 Larguier des Bancels6
claims that gelatin is peptized more readily by aqueous alcohol
or aqueous acetone than by water alone.
(99) IS IODIDE ADSORBED WHEN GELATIN IS PEPTIZED BY
potassium iodide? — The experiments of Briggs and Hieber7
furnish conclusive proof that the liquefaction of gelatin by po-
tassium iodide solutions is a case of reversible peptization. As
yet, however, nobody has shown that there is marked adsorption
of potassium iodide by gelatin.
(100) colloidal calcium carbonate — Spring8 considers that,
in natural waters, calcium and magnesium carbonates, silica
and alumina are in solution, while, in green waters, they are
partly suspended through a deficiency in the carbon dioxide.
In the blue Rhone we have 785 CaC03 and 79.5 CO2, while in
the green Rhine we have 1056 CaC03 and 76 CO2. This raises
the question whether we know that calcium bicarbonate is really
dissolved in water and is not calcium carbonate peptized by
carbon dioxide. Ultrafiltration would probably settle this
point. It would also be of interest to know exactly what the
suspended material is which occasionally makes the water in
porcelain-lined swimming tanks look green.
(101) cocoa — Cocoa is a colloidal solution and the making
of cocoa should be discussed from the viewpoint of the colloid
chemist.
1 Leviles, Z. Kolloidchem., 8 (1911), 4.
! Oudemanns, J. Chem. Soc., 26 (1873), 533.
' Schiff, Z. physik. Chem., 23 (1897), 355.
1 Private communication from Professor Chamot.
s Galeotto and Giampalmo, Z. Kolloidchem., 3 (1908), 1 18.
« Compi. rend., 146 (1911), 290.
> J. Phys. Chem., 24 (1920), 74.
« J. Chem. Soc, 46 (1884), 260.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
20 1
PREPARATION OF COLLOIDS
(102) PRODUCTION OF COLLOIDAL METALS WITH CHARCOAL —
Lazowski1 states that ignited wood charcoal reduces not too
concentrated solutions of the salts of tin, copper, mercury,
silver, platinum, palladium, and gold, provided they contain
no free acid. One of the interesting things about this is that
with copper the metallic coating varies from blue to red, which
presumably means that he had colloidal copper. This should be
confirmed and the conditions worked out for getting red gold,
yellow silver, etc.
(103) colloidal copper in sulfuric acid — According to
Rasenfosse'2 colloidal copper can be obtained by the action of
alcohol on anhydrous copper sulfate and concentrated sulfuric
acid. This is not a case where the concentration of electrolyte
is low and this experiment should be repeated in order to find
out what keeps the copper particles from agglomerating. It
would also be interesting to know whether the copper particles
are charged positively or negatively.
Fischer3 has obtained a precipitate of metallic copper in the
solution by using a high current density with a copper anode in
sulfuric acid. Cuprous sulfate is formed, which breaks down to
metallic copper and cupric sulfate. This does not give colloidal
copper; but could probably be made to do so if one were to add
a suitable protecting agent.
(104) THEORY OF ORDER OF METALS IN ELECTRICAL DISIN-
TEGRATION— Svedberg4 found that the order of disintegration
of metals by an oscillatory discharge under an organic liquid was:
iron, copper, silver, aluminium, calcium, platinum, gold, zinc,
tin, cadmium, antimony, thallium, bismuth, and lead, the iron
being disintegrated the least rapidly and the lead the most
rapidly. There is no apparent relation either with the order
of the boiling points or with the order of disintegration by cathode
rays6 or by canal rays, though it must depend on some physical
properties. Svedberg points out that, in the same group of
the periodic table, the disintegration increases with the atomic
weight, though much more rapidly: copper, silver, gold; mag-
nesium, zinc, cadmium, aluminium, thallium; antimony, bis-
muth; nickel, platinum.
(105) PREPARATION OF COLLOIDAL SOLUTIONS BY ELECTRICAL
disintegration — The objection to the Svedberg method of
making colloidal solutions is that there is always some decompo-
sition of the organic liquid, though nothing like so much as with
the direct-current arc that Brcdig used. Schoop6 has developed
a process for plating metals on all sorts of materials by blowing
compressed air at about five-atmospheres pressure through a
pointed nozzle into an arc playing between wire terminals.
By making one pole of copper and the other of zinc, a deposit of
brass can be obtained. It seems possible that colloidal solutions
might be obtained with an arc in hydrogen with compressed
hydrogen blowing the metal into a well-stirred organic liquid.
By using nitrogen it might be possible to obtain colloidal solu-
tions of nitrides. By using two different terminals it might also
be possible to obtain colloidal solutions of brass, ferrosilicon, etc.
(106) colloidal metals with cored arcs — Mott7 apparently
obtained yellow rouge condensing on the electrodes when he
used a cored arc containing iron salts. Working in an atmos-
phere of hydrogen it should be possible to obtain very fine de-
posits of metals in this way.
(107) STRUCTURE OF CARBON BLACK WHEN A HYDROCARBON
IS CRACKED IN PRESENCE OF A GAS WHICH IS ADSORBED STRONGLY
by charcoal — If a solid precipitates from solution in presence
of a substance which is adsorbed strongly by it, the solid conies
1 Chem. Gaz , 1848, 43.
' J. Soc. Chem. Ind., 30 (191 1). 133.
» Z. Elektrochem., 9 (1903), 507.
* "Herstellung kolloider Losungen," 1909, 466.
' Kohlschutter, Z. Elektrochem., 14 (1908), 233.
■ Chem. Abs., IS (1919), 2640.
' Trans. Am. Eleclrochem. Soc., 34 (1918), 292.
down very finely crystalline. The same thing musi hold foi
a solid precipitated from the gaseous phase. In this specific
case of carbon black, the presence of a strongly adsorbed gas
should tend to keep the particles of a carbon black from agglom-
erating. This is not so important as it might seem, because the
adsorption is relatively small at the temperature at which
methane cracks. This objection would not be so serious with
other compounds which crack at a lower temperature. It
is certainly desirable from a scientific point of view to have this
gap in our knowledge filled. Kohlschutter' reports that elec-
trically disintegrated metals give the coarsest particles in hydro-
gen and the finest in argon.
(10S) PROTEIN-FREE colloidal Silver — For pharmaceutical
work there is needed a colloidal silver protected by a nonpro-
tein because there is always possibility of harmful effects due to
protein when the present colloidal silver is used medicinally.
ULTRAFILTRATION
(109) rapid ultrafiltration — The varying methods of
ultrafiltration- are going to be of so great importance in chemis-
try that some apparatus should be devised whereby one could
filter rapidly liters or hundreds of liters of liquid instead of cubic
centimeters.
(110) size of particles in ultrafiltration — There seems
to be a marked discrepancy between the methods of determining
the diameter of colloidal particles.3 Tests with a Chamberland
filter made it probable that the coarsest particles in a collargo!
solution were less than 170^^1 in diameter. Experiments with
a collodion filter made the particles between 2oomm and 490^,11,
while the ultramicroscopic examination made the particles
about 20/uju in diameter.
(m) are alkaline copper tartrates, etc., solutions
or colloids? — Electromotive force measurements with alkaline
copper and lead tartrate solutions4 or in presence of sugars show
that the concentration of copper or lead as ion is very low. If
we are dealing with true solutions, this means that the copper
and lead form complex salts. If we are dealing with colloidal
solutions such a conclusion is not permissible. Since we know
that sugar has been used to form colloidal solutions of hydroxides.
No. 95, it is improbable that we are dealing with complex salts
in this case.
(112) ultrafiltration of nonaqueous sols — While we
have very satisfactory ultrafilters for aqueous sols, the general
technique has not been worked out for sols in organic liquids.
This should be done.
(113) ultrafiltration of stearin in olive oil — It seems
probable that stearin forms a colloidal solution in olive oil;
but this should be proved or disproved by ultrafiltration ex-
periments. Shaking with water might also be instructive.6
(114) quantitative ultrafiltration of soap solutions —
Dilute soap solutions show a rise of boiling point and concen-
trated soap solutions practically none. Since absolute concen-
tration of ions should normally be larger in concentrated solu-
tions than in dilute ones, this abnormal result must be due to
adsorption. It should be possible to verify this assumption by
doing ultrafiltration of soap and analyzing the filtrate.
(115) ultrafiltration and dialysis — In dialysis the water
does not pass out through the diaphragm to any appreciable
extent and we are dealing chiefly with the diffusion of the dis-
solved material. In ultrafiltration the liquid is forced through
the diaphragm, carrying with it everything that is not held back
' Z. Elektrochem., 18 (1912), 428.
•■ Martin, J. Physiol., 20, 364: ./. Chem. Soc, 70, II (1896), 665, MbI-
fitano, Compt. rend., 139 (1904), 221; 140 (1905), 1245; Z. fihysik. Chem.,
68 (1909), 236; Bechhold, Ibid., 60 (1907), 257; 64 (1908), 328; van Bemmr-
len Cedenkboek, 430; Schoepf, Z. Kolloidchem., 8 (1911), SO; Foiiard, J.
Soc. Chem Ind., 30 (1911), 708.
» Bechhold, Z. physik. Chem., 64 (1908), 337.
« Kahlenberg, Ibid., 17 (1895), 577.
' Cf. Winkelblech, Z. angew. Chem., 19 (1906), 1953.
262
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
by the diaphragm. While the general relation is clear, an in-
tensive discussion of the two is desirable, because it is not clear
why some of the colloidal material should not pass through an
ultrafiltration diaphragm in case the latter is used in dialysis
experiments.
(n6) staining with auranTia — Bechhold1 states that a
collodion filter is stained more deeply by the readily diffusing
dyes such as aurantia, methylene blue, and crystal violet, the
more concentrated the collodion, while the reverse is true with
Bismarck brown and benzopurpurin, dyes which scarcely diffuse
at all. It is not clear why a more concentrated collodion filter
should dye more intensely than a dilute one, though it might
appear to do so because there is more collodion to be stained.
These experiments should be repeated to see what the cause of
the phenomenon is, in case it is not an optical illusion.
centrifugal force
(117) EFFECT of centrifugal Force — If a colloidal solution
is centrifuged it becomes less stable because this is equivalent to
increasing the force of gravity. In the separator the cream,
which is lighter, goes to the center, while the skimmed milk
is thrown to the outside. A separator does not give cream with
homogenized milk2 in which the fat particles are less than o.8/j
in diameter and which is, consequently, a more stable emulsion
than ordinary milk. There are a few experiments on the pre-
cipitation of colloidal solutions by centrifuging;8 but there has
been no systematic study of the subject to bring out the quanti-
tative relations between density, size of particles, and number
of revolutions per minute necessary to cause precipitation.
specific volume
(118) specific volume of colloidal solutions — Wintgen4
claims that the specific volume of a colloidal solution is prac-
tically a linear function of the percentage concentration by weight.
His experiments should be checked and extended, so that we
may know the degree of accuracy and the limitations of this
generalization. If the data are extrapolated to 100 per cent
colloid, the value for the specific volume comes out too low and
consequently the value for the density too high. This is prob-
ably due to the existence of a film of adsorbed water around each
particle. It would be interesting to check this by experiments
with substances for which the point of zero fluidity has been
determined.
viscosity
(119) effect of viscosity on reaction velocity — The ex-
periments of BuchbOck6 and of Raschig6 indicate that viscosity
may be an important factor affecting the reaction velocity in
cases where gas bubbles are formed. This could be tested very
satisfactorily by studying the decomposition of the diazo com-
pounds because this reaction gives good constants.7
color
(120) blue Eyes as a lecture experiment — Since the color
of blue eyes is apparently the blue of turbid media,8 Tyndall
blue, it should be possible to make an admirable lecture experi-
ment with a dark background and a film of turbid medium in front
of it. By painting a yellow color on the front of the glass, it
should be possible to duplicate the green, hazel, and brown eyes.
1 "Colloids in Biology and Medicine," 1919, 428.
2 Fleisehmann, "Lehrbuch der Mitchwirthschaft," 1906, 393.
> Franklin and Freudenberger, Trans. Am. Electrochem. Soc, 8 (1903),
29; Giolitti, Gazz. chim. Hal., 36, [II) (1906), 159; Dumanski, van Bemmelen
Cedenkboek, 1910, 421. Friedenthal, Z. Kolloidchem., 15 (1914), 75; Ayres,
Mel. & Chem. Eng., 14 (1916), 500.
« Kolloidchem. Beihefte, 7 (1915), 251.
»Z. physik. Chcm., 23 (1897), 123; 34 (1900), 229.
• Henderson, "Catalysis in Industrial Chemistry," 1919, 60.
' Hausser and Muller, Compl. rend., 114 (1892), 549, 667, 760, 1438;
Bull. soc. chim., [3] 7 (1892), 721; 9 (1893), 353; Hantzsch, Ber., 33 (1902),
2517; Cain and Nicoll, J. Chem. Soc., 81 (1902), 1412; 83 (1903), 206.
» Bancroft. J. Phys. Chem . 33 (1919), 356.
( 1 2 I ) DUPLICATION OF BLUE FEATHERS WITH SOLIDS IN GELATIN
or LACQUER — The color of the blue feather is apparently due to
the scattering of light by innumerable numbers of tiny air bubbles'
embedded in the horny mass of the feathers. It should be possi-
ble to duplicate this experimentally with powdered glass of high
refractive index or with powdered titanium oxide embedded in
a collodion lacquer or in a gelatin film.
(122) DUPLICATION OF BLUE FEATHERS WITH AIR BUBBLES
IN glass OR gelatin — Hannay* exposed glass at 2000 to oxygen
and to carbon dioxide at 200 atmospheres pressure, and allowed
the glass to cool under pressure. So much gas was taken up that
the glass passed into a foam when heated quickly. It would
undoubtedly have been possible to have regulated the pressure and
the rate of heating8 so as to have obtained such minute bubbles
in the glass as to duplicate the blue of birds' feathers. If a
film of gelatin were hardened with formaldehyde and then dried,
we should get air replacing the water, and it might be possible
to regulate the concentrations so as to obtain a satisfactory blue.
(123) OPTICAL PROPERTIES OF BLUE EYES AND BLUE FEATHERS
-Since the blue of blue eyes and blue feathers is apparently the
blue of turbid media, Tyndall blue, the blue light should be
polarized more or less completely, in which case it should be
possible to weaken or even destroy the color by suitable adjust-
ment of a nicol prism.
(124) PIGMENTAL OR STRUCTURAL COLORS WITH SULFUR —
Wolfgang Ostwald4 has shown that blue and green solutions of
sulfur are obtained in molten sodium chloride, in a borax bead,
in liquid ammonia, and in organic liquids like glycerol. It is
probable that these liquids contain colloidal sulfur; but this has
not been proved nor do we know why colloidal sulfur should be
blue. The blue may be a structural color.6
(125) COLORS OF MASSIVE SILVER BY MULTIPLE REFLECTION —
From the colors of colloidal silver, we can deduce that the sur-
face color of massive silver is yellow by multiple reflection and
red when the number of reflections is somewhat less. There is
some experimental evidence that both these assumptions are
correct, but a more adequate test of these two points should be
made.
(126) surface color OF iodine — Harrison6 believes that the
blue color of the so-called starch iodide is the color of colloidal
iodine. If this is the case, the surface color of solid iodine should
be blue. Tests should be made to determine whether or not
this is true.
(127) color of colloidal iodine — If the blue color of starch
iodide is due to colloidal iodine, it should be possible to make a
very finely divided iodine fog which would be blue by transmitted
light.
(128) LIGHT TRANSMITTED BY COLLOIDAL MAGENTA, ETC. —
The surface colors of gold, silver, and indigo are red, yellow, and
red, respectively, and colloidal solutions of these substances
transmit red, yellow, and red light, respectively, when the sus-
pended particles are extremely fine.7 This is fairly good pre-
sumptive evidence that the phenomenon is general, in which case
a colloidal solution of magenta should be green by transmitted
light. This should also be true for a magenta fog which might
be easier to prepare. The phenomenon should be tested with
a number of organic pigments which show marked surface colors.
(129) preparation OF yellow ROUGE — Andersen8 has shown
that plates of hematite are yellow by transmitted light when
they have a thickness of 0.1 p, and that the color varies with
I Bancroft, J. Phys. Chem., 33 (1919), 365.
• Proc. Roy. Soc, 33 (1881), 407.
' J. Frank. Inst., 174 (1912), 344.
'Kolloidchem. Beihefte, 2 (1911), 47; Cameron and Macallan, Proc.
Roy. Soc, 46 (1899), 13.
« Keen and Porter, Proc. Roy. Soc. 89A (1914), 370.
• Z. Kolloidchem., 9 (1911), 5.
' Bancroft, J. Phys. Chem , 23 (1919), 561.
• Am J. Sci.. [4] 40 (1915), 370.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AXD ENGINEERING CHEMISTRY
263
increasing thickness through reddish brown to deep brown-red
or blood-red. An anhydrous yellow ferric oxide is said to be
obtained by the oxidation of ferric sulfide,1 and we get yellow
bricks on burning a highly calcareous clay even though the iron
content is higher than that which would give a red clay if the
lime were not present. It seems probable that the ferric oxide
is present in these clays in such a fine state of subdivision that it
is yellow and not red.2 Mott3 has prepared both red and yellow
ferric oxide by volatilization of iron in the electric arc, the yellow
being the finer powder. Unfortunately, Mott did not analyze
his product. These experiments should be repeated and some
method devised for making yellow rouge in appreciable quanti-
ties.
(130) preparation OF blue copper oxide — Experiments
by Schenck4 on the precipitation of hydrous copper and alumin-
ium oxides make it seem probable that cupric oxide is blue
in thin films, and not black. It is possible that by drying the
mixture of copper and aluminium oxides at a low temperature,
■one could then dissolve the alumina in caustic soda, leaving be-
hind a blue powder of copper oxide. Mott obtained a brilliant
blue by volatilizing a mixture of equal parts of manganese
and copper in the electric arc, but he did not analyze the product.
(131) preparation of coral-red tellurium — In low con-
centrations tellurium colors glass coral-red to purple-red, and at
higher concentrations gives a steel-blue. A blue colloidal tel-
lurium is easy to make by reducing a dilute, boiling mixture
of sodium tellurate and protalbinate with aqueous hydroxyl-
amine hydrochloride. No coral-red tellurium seems ever to
have been made; but Berzelius6 describes a preparation which
might be that. It should not be difficult to fill in this gap in
our knowledge. In connection with this the red solution of
TeS03 should be studied.6
(132) EFFECT OF MEDIUM ON COLOR OF POWDERS — When
copper sulfate crystals are ground to a fine powder, they be-
come white owing to the scattering of light. Under the same
circumstances potassium ferricyanide changes from red to yellow.
If these powders were immersed in liquids having about the same
index of refraction as the powders, these latter should become
blue and red, respectively. The theory of this has been formu-
lated by Merwiu,7 but a few striking illustrations would be helpful.
(133) SURFACE COLOR — Wood8 implies distinctly that surface
color or selective reflection is due to resonance, the light which is
absorbed very strongly, being reemitted. If this is true the
characteristics of the apparently reflected light should be more
like those of light emitted by glowing bodies9 than like those
of ordinary reflected light. It is easy to recognize the surface
color of fuchsine and difficult to recognize that of silver. The
method of multiple reflections is crude. By a study of the lateral
emission, if any, and the polarization of the green surface color
of fuchsine, it should be possible to work out a quick and easy
method of determining the surface colors of metals and alloys.10
(134) DEFINITION OF LUSTERS — The people11 who write about
gems speak of adamantine, vitreous, oily, waxy, resinous, pearly,
silky, and metallic lusters, but there is no adequate definition
of any of these terms.12 Somebody should work out definitions
of these terms with reference to the optical properties involved.
This is the more important because in at least one case the oc-
' Diamond, J. Soc. Chem. Ind., 37 (1918), 451i?.
• Keane, J. Phys. Chem., 20 (1916), 734; Scheetz, Ibid., 21 (1917), 570.
' Trans Am. EUctrochem. Soc, 34 (1918), 292.
' J. Phys. Chem., 23 (1919), 284.
• Ann. Phys., [2] 32 (1834), 1.
•Weber, J. prakt. Chem., [2] 25 (1882), 218; Divers and Shimose,
J. Chem. Soc, 43 (1883), 329.
» Proc. Am. Soc. Testing Materials, 17, III] (1916), 494.
« "Physical Optics," 1911, 402, 409, 452, 454, 631, 636.
• MilUkan, Phys. Ret., 3 (1895), 81, 177.
'0 Cf. Michelson, Phil. Mag., 16] 21 (1911), 554.
11 Farrington, "Gems and Gem Minerals," 1903, 16
" Bancroft, J Phys. Chem., 23 (1919), 289.
currence of a resinous luster was one of the criteria of a good
technical product.
ELECTRICAL PROPERTIES
(135) ELECTRICAL ENDOSMOSE WITH SOLUTIONS WHICH ARE
adsorbed strongly by the diaphragm — In most experiments
on electrical endosmose the adsorption by the diaphragm has
been of interest only in so far as it affected the direction of the
flow. Experiments should now be made with special reference
to the adsorption, comparing chlorides, bromides and iodides,
for instance.
(136) electrical conductance without a solute — Suppose
wc have two sets of finely divided particles neither of which
adsorbs the other appreciably, and let us also suppose that one
set of particles adsorbs a given cation very strongly, while the
other set of particles adsorbs a given anion strongly. If we
take a mixture of these two sets of particles and add a small
amount of the salt of the given base and the given anion, we
shall have a colloidal solution which will conduct electricity
very well but which will contain no free ions to speak of, because,
by definition, the cations have been practically completely ad-
sorbed by one set of particles and the anions by the other set
of particles. It is not known whether these limiting conditions
can all be fulfilled simultaneously. A possible case would be
the mixing of dilute solutions of silver sulfate and lead chloride.
The lead sulfate would adsorb sulfate or lead ions strongly, and
the silver chloride would adsorb chloride or silver ions strongly.
Nobody knows what each would do to the other. It may be
necessary to add gelatin to keep the two colloids from precipi-
tating each other.
(137) CONDUCTANCE OF POTASSIUM IODIDE SOLUTION IN PRES-
ENCE of powdered charcoal — Bleininger1 has shown that if a
clay suspension is stirred, the conductance may increase be-
cause the adsorbed ions, which are carried down when the sus-
pension settles, are brought up between the electrodes. It would
be interesting to extend these experiments to cases where the
adsorption was known or could be determined, say, potassium
iodide solutions with powdered charcoal.
(138) electrical charge on colloids — While colloidal
platinum is ordinarily charged negatively in aqueous solution,
Billitzer2 reports that it is charged positively in aqueous alcohol.
This should be checked and the same thing tried with other sols
so as to see whether the effect is specific or general.
(139) negative osmosis — It seems to be established satis-
factorily that we do get negative osmosis at least temporarily
in certain cases and that this is connected with the electrical
charge on the diaphragm.4 On the other hand, the way in which
the negative osmosis takes place has been discussed in a very
sketchy and unsatisfactory manner.4 There is nothing, for
instance, to show at what point and why the negative osmosis
changes to positive osmosis, though it is recognized that this
does take place.
(140) EFFECT OF COLLOIDS ON SOURNESS — In one of the .stand
ard textbooks on physiological chemistry, there is the statement
that the hydrogen-ion concentration in currants is less than in
some of the sweeter berries. If this is true, the presence of
colloids must have masked the physiological action of hydrogen
ion on the tongue. This could easily be tested with protein
solutions of known acidity.
STABILITY
(141) precipitation OF casein by salts — While the pre-
cipitation of albumin by salts seems to be about what one might
expect, the same cannot be said for the precipitation of casein
by salts. When peptized by hydroxyl, casein is precipitated
' Trans. Am. Ceram. Soc., 16 (1913), 343.
2 Z. physik. Chem.. 46 (1903), 312.
> Bartell, J. Am. Chem. Soc., 36 (1914), 646; J. Phys. Chem., 24 (1920),
444; Loeb, J. Gen. Physiol, 2 (1920), 387, 563, 577.
« Cf. Freundlich, Z. Kolloidchem., 18 (1916), 11.
2G4
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 3
by solutions of calcium chloride, barium chloride, magnesium
sulfate, zinc sulfate, copper sulfate, and alum. In these cases
it seems probable that the negative charge is neutralized by
the readily adsorbed cations. On the other hand, when pep-
tized by hydrogen ion, salts cause precipitation in the following
order:
ZnCl2> KBr> CuCU> MnClj
There is no apparent reason for such a series and there must be
experimental error somewhere. The whole behavior of casein
in presence of salts needs careful study because the data now
available are quite unsatisfactory.
(142) STUDY OF MIXTURES OF GELATIN AND GUM ARABIC -
Tiebackx1 states that when a 0.5 per cent gelatin solution is
mixed with a 4 per cent gum arabic solution, the mixture is
precipitated readily by acids. If the acid is washed out, the
coagulum can readily be dispersed in water. Tiebackx points
out that the properties of a gelatin and gum arabic mixture are
almost those of a globulin or of casein. A systematic study
should be made of these mixtures to see how they are affected
by salts. The first thing to do is to prepare an ash-free gela-
tin and to make certain that mixtures of this with gum arabic
behave like a globulin or like casein.
(143) SPECIFIC COAGULATING ACTION OF IONS — Freundlich2
gives data for the precipitation of negatively charged mastic
sols by different cations; but only three anions are tried, and those
under conditions which are not comparable. The experiments
should be repeated with a number of univalent anions so as to
bring out the specific effect of the anions. In the precipitation
of colloidal platinum3 the change from chloride to hydroxide
has more effect than the change from sodium to barium. Ex-
periments should be made with barium hydroxide. The work
on colloidal silver4 should be supplemented by experiments with
barium hydroxide and with the sodium salts of organic acids.
One would also like to see experiments with barium acetate on
arsenic sulfide5 sols.
(144) TWO PRECIPITATION CONCENTRATIONS OF CERTAIN
colloids with CERTAIN electrolytes — Freundlich6 observed
that certain electrolytes possess two precipi+ation values for
certain colloids — one above the other with a zone of nonpre-
cipitation between. He attributes this to change in the sign
of the colloid when the electrolyte reaches a certain concentra-
tion above the first precipitation value. Weiser7 has observed
this phenomenon with colloidal ferric oxide in the presence of
hydrochloric acid, and has found that the sign of the colloid
remained unchanged. A systematic investigation of these
phenomena should be made.
(145) THE EFFECT ON THE PRECIPITATION VALUE OF HYDROLYSIS
OF A precipitating Electrolyte — From the results of certain
experiments, Freundlich* concludes that the hydrolysis of an
electrolyte has no effect on its critical coagulation concentra-
tion for a given colloid. It has been found, however, that alkali
salts with univalent organic anions usually have a very much
higher precipitating power for positive colloids than alkali
salts of monobasic inorganic acids. It is altogether probable
that this may be due as much to the formation by hydrolysis
of the strongly adsorbed hydroxyl ion as to the adsorbability
of the organic anion. The hydroxyl-ion concentration in solu-
tions of different organic salts at the coagulation concentration
should be found, and the influence of this concentration of hy-
droxyl ion on the coagulation value of neutral salts determined.
1 Z. Kolloidchem., 8 (1911), 198, 238.
s "Kapillarchemie," 1909, 367.
s Freundlich, Ibid., 1909, 352.
• Pappada, Gas:, chim Hal., 42, [I] (1912), 263.
'Freundlich, "Kapillarchemie," 1909, 351; Freundlich and Schucht,
Z. physik. Chem., 80 (1912), 564.
« Z. physik. Chem., 73 (1910), 385; 86 (1913), 641.
» J. Phys. Chem., 24 (1920), 277.
• Z. physik. Chem., 73 (1910), 385.
(146) THE EFFECT OF THE RATE OF ADDITION OF ELECTROLYTE
ox the critical coagulation concentration — It has been
found1 that the concentration of electrolyte necessary to cause
coagulation of a definite amount of colloid is greater if the elec-
trolyte is added slowly instead of all at once. Further investi-
gations should be made of the nature and cause of colloids be-
coming "acclimatized" in the presence of electrolytes.
(147) ADSORPTION OF ANIONS BY COAGULATED ALBUMIN -
Weiser and Sherrick2 found that the order of adsorption of
anions by barium sulfate is the reverse of that deduced from
Hofmeister's data on the coagulation of positively charged al-
bumin by electrolytes. A quantitative determination of the
adsorption of anions by precipitated albumin should be made 3
(148) coagulation OF clay — A suspension of clay is usually
charged negatively and should, therefore, be coagulated by
positive ions. This is practically what Hall and MonsonJ
found, though they postulated a metathetieal reaction. Roh-
Iand5 believes that the concentration of hydroxyl is the es-
sential factor in the deflocculation of clay. This was easily
disproved by Ashley6 who was, however, rather vague as to the
real relations. The work on the flocculation and deflocculation
of clays should be repeated so as to bring out clearly the part
played by each ion.
(149) WHAT IS THE STABILIZING AGENT IN NONAQUEOUS
liquids? — When metallic sols in organic liquids are prepared
by the Svedberg-Bredig method, we do not know what stabilizes
these sols. It can hardly be the liquid itself because the sol
precipitates with rising temperature. It may be an electri-
fication or it may be a decomposition product of the organic
liquid ; but we do not know definitely which, nor do we know what
the decomposition product is in case that is the important factor.
(150) PRECIPITATION OF COLLOIDAL SILVER BY CERTAIN-
ALCOHOLS — Schneider7 has made alcoholic solutions of colloidal
silver and finds that they are coagulated at once by isopropyl
alcohol, normal and secondary butyl alcohol, trimethy carbinol,
and heptyl alcohol; but not by propyl or isopropyl alcohol.
Nothing is known as to the reason for this.
(151) EFFECT OF AMYL ALCOHOL ON STABILITY OF ARSENIC
sulfide sols — Kruyt and Duin8 report that addition of amyl
alcohol or of phenol makes the arsenic sulfide sol more susceptible
to univalent and trivalent cations, and less sensitive to bivalent
and quadrivalent cations; but no explanation is offered for this
extraordinary phenomenon. The facts should be verified and
some hypothesis formulated.
(152) effect of ultraviolet light on colloidal solutions.
- -Farmer and Parker9 report that ultraviolet light coagulates
colloidal platinum. It would be interesting to know whether
ultraviolet light will coagulate all negatively charged sols, all
negatively charged metallic sols, or only particular metallic
Mils.
(To be concluded)
The Atlas Powder Co., Philadelphia, Pa., is now producing
a new explosive, which is nonfreezing and therefore specially
adapted for cold-weather blasting. It is extremely stable, re-
quiring a No. 6 blasting cap for successful detonation. A
further advantage claimed is that it does not cause headaches
among the men handling it.
The Solvay Securities Company, a war-holding company for
the Solvay Process Company stock, is to be dissolved and its
assets distributed to stockholders. The assets consist entirely
of stock in the Allied Chemical & Dye Corporation.
1 Freundlich, Z. physik. Chem., 44 (1903), 144.
■ J. Phys. Chem., 23 (1919), 20V
» Weiser and Middleton, Ibid., 24 (19201, 30.
' J. Agr. Sci., 2 (1907), 224.
« Z. anorg. Chem., 41 (1904), 325.
6 Bureau of Standards, Technologic Paper, 23 (1913), 63.
' Ber., 38 (1905), 3217.
» Kolloidchem. Beihe/le, 5 (1913), 269.
» J. Am. Chem. Soc, 38 (1913), 1524.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
205
NOTLS AND CORRESPONDENCE
THE ACTION OF ULTRAVIOLET RAYS ON THE
SACCHAROMYCETES
Editor oj the Journal of Industrial and Engineering Chemistry:
In This Journal, 12 (1020). 740, Messrs. Feuer and Tanner
state that when ordinary brewers' yeast, as well as other
species of the Saccharomycetes, were exposed to the action of
ultraviolet light they did not survive the exposure for more
than 1 min.
It is very difficult to understand this result, since it is entirely
opposed, not only to the results of my own experiments but to
those of a good many other observers. Among the latter I may
mention :
Henri and Stodel, Compl. rend., 148 (1909). 582
Henri and P. Cernovodeanu, Ibid., 150 (1910), 52
Gabriel Vallet. Ibid.. 150 (1910), 632
Maurice Lombard, Ibid.. 150 (1910), 227
Van Aubel, Ibid., 149 (1909), 983
I might also mention articles in the
Deutsche Essig Industrie. 1910. 214
Brewing Trade Review, 1915, 67
Chem. Zenlr., 1918 ,11], 51.
During the years 1915 to 1917, I carried out a long series of
observations on the differential effect of the ultraviolet rays on
the bacteria and the Saccharomycetes, and my results are pub-
lished in detail in the Annali di Chimica Applicata, 1915, 301;
1016, 221; and 1917, 93.
In my experiments I exposed brewers' yeast for 12 hrs. to the
ultraviolet rays from a 1200-candle power lamp at a distance of
20 cm. Not only was the yeast not injured by this treatment,
but its fermentative activity was actually increased. All
the bacteria present in the yeast were destroyed after a brief
exposure. In addition to this laboratory result, I may point
out that, since 191S, the Peroni Brewery in Rome (which is
perhaps the most important brewery in Italy) has installed a
plant for the freeing of yeast from bacteria by submitting it to
the action of ultraviolet rays, and the results obtained on this
large industrial scale fully confirm my own experiments.
Via Sicilia 43 ROMOLO DE Fazi
Rome (25), Italy
November 3, 1920
Editor of the Journal of Industrial and Engineering Chemistry:
We wish to point out that Fazi has indicated the subject for
discussion by selecting as the topic for his polemic "The Action
of Ultraviolet Rays on the Saccharomycetes."
Fazi states that we found the brewers' yeast, as well as other
species of Saccharomycetes, unable to endure the action of ultra-
violet rays for more than 1 min. Such is not the case, for
Fig. 1 of our paper shows that Saccharomyces of Binot lived
for 4 miu., one strain of Saccharomyces ellipsoideus for 7 min.,
and Saccharomyces marxianus for 7 miu. under the conditions
maintained in our experiment.
To anyone having any knowledge of microorganisms, it is
evident that no two strains of the same organism react in the
same manner to any unfavorable condition. The conditions
under which the endurance of microorganisms to various types
of disinfectants is tested determine the results. Our suspensions
were not heavy, merely a loop of growth in 9 cc. of water spread
out in a very thin layer and exposed to the action of the ultra-
violet rays at a distance of 25 cm. with nothing intervening.
Scharff1 has shown that disinfection by ultraviolet rays is an
orderly time process and that, consequently, if the initial num-
ber of cells is small, the point will be reached more quickly « here
' J. Inf. Dis.. 10 (1912), 305.
the unit volume will contain no living cells. Our unit was the
platinum loop, while Fazi- was a much larger one.
Unfortunately we have not had access to Fazi's original papers
in the Annali di Chimica A pplicata, but having seen abstracts
of them in the abstract journals of three languages, we feel that
we have sufficiently accurate information upon which to base
this discussion. Fazi's method consisted in exposing the yeast
cells in dextrose solution and water to the action of ultraviolet
rays emitted from a lamp of 1200 candle power operating at
110 volts and 4 amperes. The distance was 20 cm. After
exposure, the fermenting activity of the cells was determined
by measuring the amount of carbon dioxide formed. Burge1
found that the ultraviolet rays would not destroy the endoenzyme
of bacteria, for there was little difference between the amount
of gelatin liquefied by the sterile filtrate secured from crushed
cells which had been exposed to ultraviolet rays, and cells which
were in the active growing stage. Stassano and Lematte2
found this to be true for endoenzymes and also for those other
bodies so much like enzymes, the agglutinins, toxins, etc. It
is not, therefore, to be expected that the enzymes in yeasts would
be destroyed; when the exposed material such as Fazi used to
test the viability of yeasts is added to a fermentable substrate,
the formation of carbon dioxide would be expected, since the
endoenzymes responsible for fermentation would not be de-
stroyed. There is no reason to assume that the enzymes in
yeast cells are less resistant to ultraviolet rays.
The most interesting part of Fazi's discussion to us is the
imposing list of references which he cites. "Among others"
he mentions the following:
M. Lombard, "Sur les effets chimique et biologique des rayons ultra-
violets."
E. van Aubel, "Sur la production d'ozone sous ['influence de la lumi're
ultra violette."
G. Vallet, "Penetration et action bactericide des rayons ultraviolets
par rapport a la constitution chimique des mileux."
P. Cernovodeanu and V. Henri, "Etude de Taction des rayons ultra-
violets sur les microbes "
V. Henri and G. Stodel, "Sterilization du lait par les rayons ultraviolets."
From the context of Fazi's polemic, the reader is led to believe
that all of these papers support Fazi by statements or data
■indicating that the Saccharomycetes are very resistant to ultra-
violet rays. A careful reading of these papers did not reveal
even the word yeast or Saccharomycete. or any reference to the
budding fungi. In one or two of the papers there are references
to bacteria, B. coli in particular, but none with regard to the
yeasts.
Fazi also mentions articles in the Deutsche Essig Industrie,
the Brewing Trade Review, and the Chemisches Zentralblatt.
The last reference in this group is a four- or live line abstract
of one of the papers by Fazi himself. We have made no serious
effort to look up the first two papers, since they are not avail-
able in the University of Illinois Library, and more on account
of the nature of the other paper to which Fazi refers. Fazi's
imposing array of references to support his claim of the greal
enduring power of Saccharomycetes to ultraviolet rays dwindle
down to practically nothing, since every paper to which he re-
fers, with the exception of his own work, has no relation to the
topic under discussion.
It is strange that Fazi overlooks the excellent paper by
Buchta,3 in which he states:
The ultraviolet rays check the growth even with the mini-
mum exposure of 10 sec; by an exposure longer than " min ,
the cells are killed.
i Am. J. Physiol . 43 (1917), 429.
I Compt. mi,! . 152 (191
3 "tiber den Einfluss des Lichtes auf die Sprossung del HCefe," Cen
Bakt. Abt., 41, |II] (19141, 140
266
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
The data by Buchta are in absolute accord with our own. He
found that the cells of Saccharomyces cerevisiae and Saccharomyces
ludwigii could not withstand more than a 3-min. exposure to
ultraviolet rays.
Lastly in this connection, it came to our attention that one of
our colleagues in studying a case of spoilage in a carbonated
beverage, isolated two yeasts which would reproduce this spoilage.
Exposure to ultraviolet light destroyed them both in less than
1 min. They are apparently Saccharomycetes.
Anyone who has had any experience whatever with ultraviolet
rays, or who has studied the data of others, cannot help but be
impressed that this form of energy is one of the most toxic known.
Chamberlain and Vedder1 found that amebae, whether motile
or encysted, were quickly killed by ultraviolet rays. Fairhall
and Bates- state:
The abiotic power of ultraviolet rays is not restricted to
vegetative bacterial cells alone but extends to the spores, as
well as to certain molds, such as Penicillium, Aspergillus, and
Mucor.
To maintain in the light of all the work done on various micro-
' Philippine J. Sci., 1911, 2B, 383.
• J. Bad., 5 (1920), 65.
organisms, that the yeasts, the Saccharomycetaceae, are able
to endure direct continuous exposure, at a distance of 20 cm.,
to the ultraviolet rays emitted from a 1200-candle power lamp,
for from 12 to 14 hrs., is out of the question.
Bertram Feuer and P. W. Tanner
State Water Survey Division
Urbana, Illinois
December 23, 1920
LOW-TEMPERATURE CARBONIZATION AND ITS APPLI-
CATION TO HIGH OXYGEN COALS— CORRECTION
Owing to a mistake in this office the stenographer's report of
my discussion on Professor Parr's paper [This Journal, ij
(1921), 16] was submitted for publication instead of the revised
discussion.
The following corrections should be made: On line 4 sub-
stitute "evolved" for "involved;" on line 6 substitute "decom-
position" for "combustion." In the remainder of the paragraph,
substitute "carbonization" for "combustion."
Bureau op Mines Alfred R. POWELL
Pittsburgh, Pa.
[
SCIENTIFIC SOCIETIES
ADVISORY COMMITTEE RESOLUTION ON THE
CHEMICAL WARFARE SERVICE
Following the passage of the Army Appropriation Bill by the
House of Representatives on February 8, 1921, wherein General
Fries' estimate of $4,457,000 as a minimum for the needs of
the Chemical Warfare Service was cut to $1,500,000, the follow-
ing resolution was adopted by the Advisory Committee of the
American Chemical Society by telegraph and forwarded to
members of Congress:
While in complete accord with the spirit prompting the re-
strictions of appropriations by the present Congress, never-
theless the American Chemical Society's Committee on
National Policies would urge upon the Congress more favorable
provision for the Chemical Warfare Service than is contemplated
in the amount set by the House of Representatives — $1,500,000.
The carefully prepared estimates of the officers of that Ser-
vice, slightly less than $4,500,000, represent less than one and
a half per cent of the total appropriation for the Army carried
in the House bill. This amount is to care for the valuable
property of the Government at Edgewood Arsenal, to enable the
continuation of research on new lines of defense and offense,
and to provide for the training of special troops and for the in-
struction of the entire Army in all features of gas warfare.
In view of the tremendous increase in the use of gases during
the last year of the war, and of the fact that approximately
thirty per cent of the casualties of our Army in the war were
due to gas wounds, we feel that the proposed reduction to one-
third of the appropriation asked would so seriously cripple the
development of the Chemical Warfare Service as to constitute
a matter of grave national concern.
We therefore urge that the Congress appropriate the original
amount asked for the Service in the estimates submitted.
ROCHESTER MEETING, AMERICAN CHEMICAL SOCIETY
The following schedule of meetings by which Tuesday is
devoted entirely to General Meetings, and Friday to excursions,
lengthens the time devoted to Sectional Meetings by at least
one-half day, and in many cases it may be lengthened by another
half day. This plan also provides that excursions shall not
interfere with Sectional Meetings. Moreover, excursions are
so arranged that the nature of the plants visited are such that
members may not all desire to visit the same plant; thus people
desiring to go to Bausch and Lomb, which deals largely with
physical apparatus, would not necessarily be interested in
seeing Pfaudler Company's apparatus, which deals with chemical
tanks, etc., for large-scale plant manufacture.
Summary of Days of Divisional and Sectional Meetings
Extra
Wednesday Thursday Time
A. M. P. M. A. M. P. M. Day
Physical and Inorganic x x x x 0.5
Industrial and Engineering., x x x x 0.5
Biological x x x .. 0.5
Medicinal x x x .. 0.5
Organic x x x x 1
Dye xx x x 0.5
Leather Section x x x .. 0.5
Fertilizer x x x x 0.5
Agricultural x x x x 1
Rubber x x x x 0.5
Cellulose Section x x x x 0.5
Water, Sewage, Etc x x x x 1
Sugar x x x x 0.5
PROGRAM COMMITTEE
Edgar F. Smith, President, American Chemical Society
Charles L. Parsons. Secretary, American Chemical Society
CHAIRMEN OF MEETINGS
Physical and Inorganic Chemistry: H. N. Holmes
Industrial and Engineering Chemistry: H. D. Batchelor
Biological Chemistry: A. W. Dox
Chemistry of Medicinal Products: Charles E. Caspari
Organic Chemistry: Roger Adams
Dye Chemistry: A. B. Davis
Leather Chemistry: E. E. Marbaker
Fertilizer Chemistry: F. B. Carpenter
Agricultural and Food Chemistry: C E. Coates
Rubber Chemistry: W. W. Evans,
Sewage, and Sanitation Chemistry: W. P. Mason
Water, Sugar Chemistry: C. A. Browne
CHAIRMEN OF LOCAL COMMITTEES
Executive: Frank W. Lovejoy, Honorary Chairman
J. Ernest Woodland
Finance: Herbert Eisenhardt
Entertainment: Charles F. Hutchison
Registration and Information: Harry A. Carpentf.r
Program: Erle M. Billings
Transportation: Charles Markvs
Hotels: Harry LeB. Gray
Excursions: William Earle
Relation to Other Scientific Societies: Donald B. Howe
College and Fraternity Dinners: Ivar N. Hultman
Assisted by: H. T. Clarke. V. J. Chambers, F. Baxter, J. Howe, B. V.
Bush, O. 1. Chorman, Wilbur Miller, A. J. Hettel, F. Elliott, J. I. Crab-
tree, R. Salter, F. W. Lovejoy, L. Burrows, W. Line, O. Cook, Mrs. R.
Kruger, Miss G. Reissman, E. Pickard, C. Hallauer.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
267
ANNOUNCEMENTS
PLACE OF meetings — The General Meetings will be held in
the Chamber of Commerce Auditorium, 67 St. Paul Street,
Central Church, Plymouth Avenue North, and Convention
Hall, Clinton Avenue South. All Divisional Meetings will be
held at the Mechanics Institute, 55 South Plymouth Avenue.
headquarters — The Hotel Rochester, corner Main Street
and Plymouth Avenue.
abstracts — Hand a short (100 words) abstract of your
paper to the Secretary of your Division, if not sent in advance,
in order that your paper may be properly listed in Science.
Long abstracts cannot be printed.
press — The A. C. S. News Service, with the cooperation of
the Publicity Committee of the Rochester Section, will have at
the Hotel Rochester, Press Headquarters, near the entrance
to the president's and secretary's rooms. Adequate accommo-
dations will be provided for the representatives of both technical
and lay publications covering the meeting, and abstracts of
papers will be distributed. There will also be a Press Head-
quarters in the Mechanics Institute.
general program
Monday, Aprh. 25
4:00 p.m. — Council Meeting. Rochester Club, 120 East Avenue.
6:30 p.m. — Dinner to Council at Rochester Club. 120 East Avenue.
Tuesday, Aprii, 26
10:00 a.m. — General Meeting. Chamber of Commerce, 67 St. Paul Street.
Addresses of Welcome. (Program not complete.)
Response. Edgar F. Smith, President of the American
Chemical Society.
General Addresses. Hon. Nicholas Lougworth. (Program not
complete.)
2:00 p.m. — General Meeting. Convention Hall, Clinton Avenue South.
8:00 p.m. — Public Meeting. Central Church, Plymouth Avenue North.
(Program not complete.)
Wednesday, April 27
8:30 a.m. — Divisional Meetings. Mechanics Institute, 55 South Ply-
mouth Avenue.
I 2 m. — Luncheon at Hotel Rochester. Powers Hotel, Duffy Powers Cafeteria.
Phi Lambda Upsilon Luncheon. (Details later.)
1:30 p.m. — Divisional Meetings. Mechanics Institute, 55 South Plymouth
Avenue.
Good-Fellowship Meeting.
Thursday, April 28
9:00 a.m. — Divisional Meetings. Mechanics Institute, 55 South Ply-
mouth Avenue.
12:30-2:00 P.M. — Luncheon at Hotel Rochester. Powers Hotel, Duffy
Powers Cafeteria, Mechanics Institute.
Sigma Xi Luncheon. (Details later.)
2: 00 p.m. — Divisional Meetings. Mechanics Institute, 55 South Ply-
mouth Avenue.
6-30 p.m. — College and fraternity dinners will be held Thursday evening.
Members desiring to make arrangements to attend these
meetings should be prompt in filling out the necessary
blanks at the Registration Room.
Alpha Chi Sigma Dinner. (Details later.)
Friday, April 29
8:00 a.m. and 1:30 p.m. — Excursions.
SYMPOSIUM ON DRYING
The Division of Industrial and Engineering Chemistry will
hold a symposium on drying, giving particular attention to the
six points of interest to the chemical engineer. These points
have been selected as follows:
1 — Transmission and distribution of heat in drying
2 — Temperature control of material in drying
3 — Effect of atmospheric conditions in drying
4 — Economy in drying
5 — Cost of drying
6 — Solvent recovery
Papers have been secured from authorities on rotary dryers,
solvent recovery, compartment dryers, vacuum drying, and
spray drying.
The chairman of the committee organizing this symposium
is Mr. Charles O. Lavett, of the Buffalo Foundry and Machine
Co., Buffalo, N. Y.
ANNIVERSARY CELEBRATION AT THE CHEMISTS' CLTJB
March 17, 1921, will be the tenth anniversary of the opening
of the present chemists' clubhouse, and it has been designated
by the trustees as a fitting date for celebration.
The Board of Trustees has also decided to renew the former
custom of conferring of Honorary Membership upon leaders
in chemistry in a manner commensurate with its significance.
Last year the Club elected to Honorary Membership four
distinguished foreign and four distinguished American chemists:
Professor Ciamician, University of Bologna.
Professor LeChatelier. College de France.
Dr. Ernest Solvay, Brussels.
Sir Edward Thorpe, Imperial College of Science and Technology.
Dr. John Uri Lloyd, Past President. American Pharmaceutical Asso-
ciation.
Dr. W. H. Nichols, Past President, American Chemical Society,
Society of Chemical Industry, and 8th International Congress of Applied
Chemistry.
Dr. Edgar Fahs Smith, Past and Present President, American Chem-
ical Society.
Dr. Edward Weston, Physical Chemist.
They have been invited to be our guests on the evening of
March 17. A short reception will be held at 6:30 p.m. in the
Social Room, followed by a dinner in their honor, beginning
at 7 p.m. sharp. At 9 p.m. all will adjourn to Rumford Hall,
where the formal ceremony of conferring Honorary Membership
upon the above-named gentlemen will be held. This will
be followed by two addresses, one by Dr. Irving Langmuir
and one by Dr. Jacques Loeb.
Those present will then repair to the dining room for light
refreshments, where there will be an opportunity to foregather
with and hear from our new Honorary Members and the govern-
ment representatives of those from other countries who may
not be able to be present.
Inasmuch as a large attendance is anticipated and the House
Committee cannot provide for more than 130 diners within
the Club, reservations will be made in the order of their receipt;
the charges per member for the entertainment being $4.00. This
includes the dinner, and may be debited to the house account
of each one who applies.
The guest list will be suspended for the evening, and Rum-
ford Hall will be closed except to those who have made reserva-
tions beforehand. Admission will be by ticket only. Members
who apply too late to be accommodated at dinner within the
Club will receive tickets for Rumford Hall until its seating
capacity is reached, provision being made for them to dine
at a special table d'hote at a convenient hotel.
Please make your reservations promptly, and all join in
making this a memorable and happy occasion.
(Evening Dress)
Charles BaskervillE,
February 16, 1921 Chairman
CALENDAR OF MEETINGS
American Paper and Pulp Association — Annual Meeting,
Waldorf-Astoria and Hotel Astor, New York, N. Y., April
11 to 15, 1921.
American Electrochemical Society— Spring Meeting, Hotel
Chalfonte, Atlantic City, N. J., April 21 to 23, 1921.
American Chemical Society— Sixty-first Meeting, Rochester,
N. Y., April 26 to 29, 1921.
American Institute of Chemical Engineers— Spring Meeting,
Detroit, Mich., June 20 to 24, 1921.
Seventh National Exposition of Chemical Industries— Eighth
Coast Artillery Armory, New York, N. Y., September 12 to
17, 1921.
268
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
WASHINGTON LLTTLR
LAST DAYS OF THE 66TH CONGRESS
The approaching death of the 66th Congress confirms the
belief of supporters of the American dye industry that nothing
will be done this session toward passing the dye bill. As usual,
Congress finds itself faced with the task of passing numerous
supply bills on which they must work against time. Word
came to-day from President-elect Harding that appropriation
bills must be got out of the way, leaving the road clear for the
legislation planned for the new session. Republican leaders
will make an effort to obtain a vote on the Fordney Emergency
Tariff Bill before adjournment February 15. It is doubtful
if they will succeed. It is certain that they would not want to suc-
ceed if they were not confident that the measure would be ve-
toed by President Wilson. The legislative battle over the
emergency tariff bill has developed into one purely of politics,
with Democrats and Republicans alike seeking an advantage
out of which they may make political capital. It was rumored
that the dye bill might be attached as an amendment to the
emergency tariff measure. While it is not yet too late to do
this, it is certain it will not be done unless there is an entirely
unforeseen and radical change in the entire situation. The
dye bill, so far as any real chance of enactment into law this
Congress goes, is dead. That is the conviction of most of its
strong supporters. Introduction of a new measure based upon
a tariff at this session also is improbable.
The War Trade Board Section of the Department of State
has been given an appropriation of $10,000 to carry on its work
until July 1 .1921. The Board asked for $15,000, but the amount
carried in the appropriation bill will enable it to continue as
at present until the end of the current fiscal year.
Until declaration of peace, the War Trade Board has authority
to continue its present control over the importation of coal-tar
products. President-elect Harding is expected to call the next
Congress in extra session early in April. The Republican
program calls for the passage of the Knox peace resolution,
amended somewhat, immediately the Senate is able to get down
to business. There is certain to be some debate on this measure.
Passage of the resolution formally bringing peace between the
United States and Germany and its signature by Mr. Harding-
is expected by the middle of May. It is regarded as highly
improbable that Congress will be able to enact into law a measure
affording protection to the dye industry before that time. Un-
less something is done to extend the life of the War Trade Board
or to meet the emergency in some other manner, the dye indus-
try will be without protection for a time. Republican leaders
are confident, however, of their ability to meet this situation
when it arises.
With action taken to prevent a hiatus it is proposed to include
protection for the dye industry in the regular Republican tariff
measure as a part of Schedule A.
It will be interesting to see the attitude that is taken by Mr.
Harding when he enters the White House. At the beginning
of a new administration the influence of the Chief Executive
upon Congress is stronger perhaps than at any other time.
There are few members who can afford to risk presidential dis-
favor in the ladling out of "patronage." Should President-elect
Harding lend his support to an embargo measure, there is no
doubt that such a measure would prove acceptable and would
be passed by both Houses of Congress. Several senators,
however, are anxious that the embargo method of protection
be abandoned in favor of a tariff, some of them declaring that
more effective protection can be given through a tariff than an
embargo.
the Tariff law
The Ways and Means Committee of the House has practically
finished the work on the new Republican tariff law which it
had mapped out for itself. Chairman Fordney carried his
point that tariff hearings should be held this Session only over
opposition of Representative Longworth and other Republican
leaders of the House, who contended that because of the inability
of Congress to obtain information as to foreign production costs
sufficiently detailed and accurate to form the basis of a scientific
tariff which the Republican party could properly sponsor, the
subject should be laid aside temporarily in favor of revenue
legislation. There is now a recurrence of these arguments and
an effort undoubtedly will be made when the new Congress
comes into power to rush through a new revenue law. Chair-
man Fordney has denied that his committee is not unanimously
in favor of pushing the tariff. Nevertheless, if those who stress
the importance of revenue revision preceding tariff should fail
in the House, an effort that will probably be more successful
will be made in the Senate. There still is talk also among Re-
publican leaders of the plan to rush through the next Congress
a general "emergency" tariff law designed to supplant the
Underwood law immediately and fill in the gap that will elapse
before it is possible to put the regular Republican tariff law on
the statute books. These things are pertinent to the dye in-
dustry and the dye bill, because each of them will have an effect
upon the proposed legislation protecting it.
NOLAN BILL
After several weeks in conference the Nolan Patent Office
Reorganization Bill has been reported back. An effort will be
made to obtain passage in both Houses within the next fort-
night. As was expected, the Senate conferees knocked out the
Senate amendment reducing the rates of pay of Patent Office
employees as contained in the bill passed by the House. The
conference bill contains more or less the House provisions affect-
ing salaries and number of employees. Senator Norris, in
charge of the bill in the Senate, however, insisted on retention
of the Senate amendment providing for the taking over and ad-
ministration of patents by the Federal Trade Commission.
This was a foregone conclusion. The final yielding on this
point by the House conferees means that the measure will con-
tain this provision when passed. As agreed upon in committee,
the Federal Trade section of the bill was somewhat changed
from the language of the Senate. The conferees also agreed
upon inclusion of a revised Section 7. The Senate proposed to
strike this out. This section finally included in the bill reported
back from conference amended Section 4921 of the revised
statutes., dealing with patent litigations. In all probability
the revised bill will be passed in the near future.
THE MUSCLE SHOALS NITRATE BILL
Since its passage by the Senate the Muscle Shoals Nitrate
Bill has been before the House awaiting action. Those favoring
its passage in the House declare their intention of forcing it to
a vote and are confident of its passage before March 4. The
fight in the House will take in general the same lines as brought
out in the Senate. The Sundry Civil Appropriation Bill has
been made the vehicle for carrying a part, at least, of this bill
through Congress. An appropriation of $10,000,000 for the
continuation of the water-power development at Muscle Shoals
was included in this bill in the Senate. This has caused a hang
in conference between House and Senate, with the Senate con-
ferees insisting that the amendment stand.
V. S. TARIFF COMMISSI. .X
The Sundry Civil Bill also contained an appropriation of
5300,000 for the United States Tariff Commission. The Com-
mission was given $250,000 by the House. It asked for $500,000.
During the last two fiscal years it has received S300.000 annually,
and it was on the motion of Senator Smoot of Utah that the House
appropriation was increased to $300,000
The Commission plans to revise most of the tariff information
series published early this year. Desirous of placing avail-
able information in the hands of Congress at the earliest possible
moment, the Commission devoted its attention to speed. It
is planned now to re-check carefully all the figures of the series,
some of which will be changed slightly.
C. R. De Long has been made chief of the chemical division
of the Tariff Commission. Dr. Grinnell Jones will devote his
entire time to his work at Harvard University, retaining a con-
nection with the Commission in an advisory capacity. The
chemical staff of the Commission, in addition to Mr. De Long,
consists of S. D. Kirkpatrick, A. R. Willis, and W N. Watson
DUTY-FREE IMPORTATION OF SCIENTIFIC APPARATUS
The American Chemical Society already has gone on record
in opposition to the exemption from duty of scientific apparatus
imported by colleges and educational institutions.
On February 14 hearings were held by the Ways and Means
Committee on the subject of duty-free importation of scientific
apparatus. In the brief submitted by the Scientific Apparatus
Manufacturers Association of the United States there was in-
cluded a large number of statements of consumers favoring the
omission in the new tariff act of Section 573 of the Tariff Act
of 1913.
In the course of the hearing it developed that an American
manufacturer had been underbid by an importer of German
wares on a bid for supplies for a government laboratory. Im-
mediately several members of the Committee exclaimed. "That
government officer ought to be impeached."
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
269
Evidence was submitted to the Committee by Dr. Chas. H.
Herty showing how Germany was underselling on competitive
articles while charging exorbitant prices on articles on which a
monopoly still existed.
The sentiment of the Committee was so plainly favorable to
the elimination of the duty-free clause that the hearings seemed
to constitute a perfunctory formality.
THE GERMAN DYE SITUATION
An interesting development in connection with the activities
of the German chemical cartel has been brought to the atten-
tion of American officials in a confidential report recently re-
ceived. It appears that Herr von Weinberg has made an ar-
rangement with one of the Italian dyes works by which it is
agreed to furnish intermediates so that the Italian company can
eventually supply Italian dyestuff needs. This perhaps is not
nearly so surprising as is the report that Mr. Frossard, acting
for the Compagnie Nationale des Matieres Colorantes en France,
has made a similar agreement with Herr von Weinberg, and the
profits of the French company are to be divided equally with the
Germans. The French concern, however, is not to extend its
market beyond France. It seems that neither France nor Italy
would need very many dyes from the reparation commission
under this scheme.
The rushing of German dyes into Great Britain in order to
beat the effective date of the new British dyestuffs licensing bill
is shown in figures which have recently been received here. Im-
portation of German dyes, including those obtained through
the reparations commission, had increased until by December
they amounted to 1430 tons per month. Imports of German
dyes into Great Britain for the month of November, it is said,
amounted to £'2,000,000, or about 1400 tons. It is added that
the Germans apparently have steadily increased shipment of
dyes to England during the last year and apparently have en-
deavored to get a fairly large stock of German dyes into England
before they were stopped by the legislation England put on its
statute books to protect its industry.
NATIONAL RESEARCH COUNCIL — C. W S. EXHIBIT
An educational exhibit upon which considerable care has been
expended will be opened here with an address by Dr. Chas. H.
Herty, on February 21. The exhibit, to be conducted under the
joint auspices of the National Research Council and the Chem-
ical Warfare Service, is designed to show the close connection
between the coal-tar chemical industry and national defense.
WASHINGTON CHEMICAL SOCIETY
That fertilizers must contain vitamines in order to produce
good results was the theory recently proposed by Dr. Harvey W.
Wiley before the Washington Chemical Society. The Society
heard many experts discuss the fertilizer situation, including Drs.
Waggaman and Davis, of the Bureau of Soils, and Schreiner, of
the Bureau of Plant Industry, together with representatives of
potash and fertilizer producers and the Ordnance Department.
A scientific reception will be given by the Washington Chemical
Society, the Local Section of the American Chemical Society,
to Madam Curie, who is to come here in May.
Aniline dyes exported from the United States during De-
cember were valued at $1,788,170, according to figures made
public by the Bureau of Foreign and Domestic Commerce.
Exports of logwood extract were valued at §75,868, and all other
dyes and dyestuffs exported were valued at $154,415. China
was the largest consumer of American aniline dyes, exports to
that country having a value of $728,650. Exports to Hongkong
were valued at $69,290. Mexico was second with $209,729, Eng-
land third with $122,078, and British India next with $113,592.
Approximately one-third of the dyestuff manufacturers' reports
for the 1920 coal-tar chemical census of the U. S. Tariff Com-
mission are now in the hands of the Commission. Progress in
the collection of data made so far seems to assure comparatively
early publication of the 1920 census by the Commission.
February 14, 1921
PARIS LETTER
By CB
I.ORMAND, 4 AV
THE INTERNATIONAL CHEMICAL CONFERENCE
The International Chemical Conference last June decided
to hold the next conference in Poland, at the invitation of Mr.
Kowalski. At that time the situation in that country seemed
fairly settled, but since then affairs have become disturbed,
and the Council of the Union has decided that the next meeting
cannot be held in Warsaw. Dr. Parsons has extended an invita-
tion from the American Chemical Society to hold the 1921 meet-
ing in the United States, but European chemists are not in a
position to make this move. Therefore the Council has decided
to hold the next meeting at Brussels, at the end of June.
However, Mr. Paul Kestner, president of the Societe de Chimie
Industrielle, will attend the Canadian meeting of the British
Chemical Society as the French delegate, and will return by way
of the United States, where he will attend the meetings of the
American chemical societies.
COKE-OVKN GASES
The utilization of coke-oven gases, both from the point of
view of nitrogen fixation and of recover/ of hydrocarbons, is
the subject of many investigations.
Messrs. I.ebeau and Damiens have analyzed a number of such
gases, and state that the nitrogen content is from 10 to 20 per
cent, as compared with 1 per cent in illuminating gas. This
coke oven gas does not contain benzene or ethylene.
Mr. LeChatelier calls attention to the fact that the products
which would be of importance, ;'. e., ethylene for the industrial
synthesis of alcohol, and benzene for the dyestuff industries,
are destroyed in the coking furnaces, which are made of materials
capable of shrinkage, such as alumina bricks; this permits
the entrance of air, which burns the hydrocarbons and increases
the nitrogen content of the gas. He advocates the substitution
of the much less contractile silica brick for the alumina brick
now used.
AGRICULTURAL RESEARCH
Chemical research, as applied to agriculture, is assuming
great importance. The French government has just voted an
appropriation of 22 millions for scientific research dealing with
agriculture.
Before the war, nitrogen cost the French farmer about 1 fr.
50 per kilo of nitrogen. At present, the cost is 7 fr. per kilo
for nitric nitrogen, and 7 fr. 50 for ammoniacal nitrogen.
; de l'Observatoire, Paris, France
The French government plans to convert the powder mill
at Toulouse into a factory for nitrogen fixation, by the Haber
process, for the annual production of 150,000 tons of ammonium
phosphate.
The development of the Claude process, of which I have
spoken already, has delayed the initiation of this other project.
A commission is now studying the comparative value of the
two methods. The Claude process uses a larger amount of
energy, but the resultant increase in cost would be balanced
by the facts that the ammonia would be available as chloride,
and that sodium carbonate, which has a high market value,
would be a by-product. Mr. Claude, referring to the work
of Mr. Georges Ville, estimates that, for equal weights of nitrogen,
ammonium chloride has a fertilizing action absolutely identical
with that of other salts.
In Germany, at the present time, analogous discussion is
going on in the comparison of the Haber with the Franek-Caro
icyanamide) process.
The use of sulfur as a fertilizer is likewise the subject of dis-
cussion. It has inspired much investigation in America; and
the fertilizing action of sulfur in nature has been shown by Mr.
Nicolas, who has demonstrated the favorable action of this
substance in the fixation of chlorophyll, in quantities of 200
kilos per hectare. Its action upon the fixation of nitrogen
seems disputable, but this work demonstrates the importance
of this element in the fixation of the carbohydrates
A decided parasiticidal action is also claimed for sulfur.
For a long time French viticulturists have used Bordeaux mix-
ture for diseases of the vine. This lime and copper sulfate
mixture seemed to owe its action to copper salts. The work
of Mr. Villedieu has recently shown that the copper has no
specific action, and that the sulfur alone plays a part in the
parasiticidal action. As the French consumption of copper
sulfate in Bordeaux mixture is considerable, this discovery has
aroused numerous polemics.
The question of the Alsatian potash mines is now definitely
settled. The French parliament has voted an appropriation
of 75 millions for the buying in of these mines.
French science has recently lost a most distinguished scholar.
Professor Bourquelot, famous for his work in the synthesis
of the glucosides.
270
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
Before the war, manganese dioxide was supplied to France
by Russia and Japan. The difficulty of obtaining this material
for the manufacture of batteries has led to a search for another
depolarizer. Mr. Ferry uses for this purpose the oxygen of
the air. He has constructed a battery which is absolutely
constant, which does not produce creeping salts, and which
does away with manganese dioxide. This battery was used
during the entire war by the Postal Service, where it wholly
replaced the old batteries. The results of this four years' use
are extremely favorable.
Under the date of January 15, the French government has
published coefficients of increase in scale of duties. We find
there a very important list of chemical products, especially
dyestuffs and their intermediates.
Professor Beal, whose process for the synthesis of camphor
is now in general use and permits competition with the natural
Japanese camphor, has been elected a member of the Academie
de Sciences.
February 4, 1921
PERSONAL NOTL5
Prof. William T. Sedgwick, of the Massachusetts Institute of
Technology, an authority on biology and sanitation, and for a
time president rof the American Health Association, died sud-
denly at his home in Boston. Professor Sedgwick had been a
member of the faculty since 1883. He was born at West Hart-
ford, Conn., in 1855, graduated from Sheffield Scientific School
in 1877, and taught for five years at Johns Hopkins.
Mr. John H. Yocum, of Newark, N. J., died on the 27th of
January, after being ill about a week with pneumonia. Mr.
Yocum was born at Ashland, Pa., in 1870, and was graduated
from Pennsylvania State College in 1891.
The death of Dr. James Marion Pickel was recently announced
by the Department of Agriculture of North Carolina, where he
was for many years past their efficient feed chemist.
Dr. Robert P. Fischelis has recently joined the editorial staff
of This Journal. Dr. Fischelis will devote only part of his time
to this work, and will continue his connection with the National
Research Council and the various other activities in which he is
interested.
Dr. Martin H. Fischer, professor of physiology in the Uni-
versity of Cincinnati, has been granted a three month's leave
of absence in order that he may accept an invitation to lecture
in the various universities of Holland on his recent researches
in colloid chemistry.
Mr. R. E. Stephenson has resigned as soil chemist in the Ex-
periment Station at West Virginia and has accepted a position
as extension specialist in soils at the University of Kentucky,
Lexington, Ky.
Mr. Leo Roon, formerly chief of the chemical division of E.
R. Squibb & Sons, is now engaged in consulting chemical engi-
neering work in New York City.
Mr. Joseph S. Reichert, for the past two years superviser of
production in the Edible Products Department at the Ivorydale
Plant of Procter & Gamble Co., Cincinnati, O., accepted the
appointment as professor of general and industrial chemistry at
the University of Notre Dame, Notre Dame, Ind.
Mr. E. B. Clark, formerly connected with the laboratories of
the Ward Baking Co. and Hecker Jones Jewell Milling Co., of
New York City, has resigned as chief chemist of the Omaha
Flour Mills Co., Omaha, Neb., and has accepted a position as
manager of the Royal Baking Co., Oklahoma City, Okla.
Dr. J. A. Bridgman has left E. I. du Pont de Nemours & Co.,
where he was research chemist at their Jackson Laboratory,
and has become chief chemist and production manager for the
Wilbur White Chemical Co., manufacturing chemists, at Owego,
N. Y.
Mr. Arthur G. Weigel, formerly of East St. Louis, is at pres-
ent chief chemist in charge of chemical laboratory at the Ferti-
lizer Works of Swift & Co., Norfolk, Va.
Mr. E. A. Goodhue has resumed his duties as instructor of
chemistry at the University of Vermont, Burlington, Vt., after
a year as teaching fellow in chemistry at California Institute of
Technology.
Mr. E. R. Wiles, until last November in the employ of Cosden
& Co., in the capacity of assistant chemist in charge of analytical
work, has become associated with the Southern Oil Corporation
as chief chemist, and is located at their refinery at Yale, Okla.
Mr. Joseph B. Oesch has accepted the position as chief of
research of the Newport Co., leaving his post as chief chemist
of British Dyes and lecturer on color chemistry at the Uni-
versity of Leeds, England.
Dr. Milo C. Burt, formerly of the ribbon and carbon paper
factory of the Remington Typewriter Co., and the Aetna Ex-
plosives Corp., and Mr. Walter R. Hibbard, formerly of the
U. M. C. Works of the Remington Arms Co., Inc., have opened
a consulting and research laboratory in Bridgeport, Conn.,
under the firm name of Burt and Hibbard, Inc.
Col. G. A. Burrell, of New York City, has returned to the
United States after spending three months in Europe on petro-
leum business.
Mr. Robert R. Dreisbach has resigned as chemical engineer
with the Dow Chemical Co., Midland, Mich., and is now asso-
ciated with the Barrett Company at Frankford, Pa., in connec-
tion with production and development work.
Dr. H. Rossbacher has resigned as chief chemist of the Chicago
Paving Laboratory and is now connected with the Western
Electric Company in the capacity of research chemist.
Mr. H. H. Hill succeeds Mr. E. W. Wagy as superintendent
of the Petroleum Experiment Station of the U. S. Bureau of
Mines at Bartlesville, Okla., where he had been assistant super-
intendent for the past year. Mr. Wagy resigned in order to
accept a position as production engineer with the Standard Oil
Company of California.
The following lecturers on special applications of organic chem-
istry in the industries have been appointed at Yale University:
Dr. Ralph H. McKee, professor of chemical engineering, Colum-
bia University; Dr. M. L. Crossley, research chemist, Calco
Chemical Co.; Dr. P. A. Levene, biochemist. Rockefeller Insti-
tute for Medical Research; Dr. David Wesson, technical manager,
the Southern Cotton Oil Co.; Dr. Harry N. Holmes, professor
of chemistry, Oberlin College ; and Dr. Elmer V. McCollum, pro-
fessor of chemistry, School of Hygiene, Johns Hopkins University.
Dr. Michael I. Pupin, professor of electrical mechanics at
Columbia University, is this year's recipient of the Edison
Medal. Professor Pupin 's work in telephone communication was
the chief factor in securing the honor. The medal was given
at the convention of the American Institute of Electrical Engi-
neers on February 15, 1921, in the Electrical Societies Building.
Mr. H. B. Rosengarten, formerly head of the Powers- Weight-
inan-Rosengarten Co., of Philadelphia, and for many years
one of the most widely known chemical manufacturers in that
section of the country, died February 20, 1921, at the age of
eighty-four.
Mr. O. F. Stafford is on leave of absence from the University
of Oregon until the coming fall, in order to carry on some in-
dustrial researches at Kingsport, Tenn., for the Tennessee East-
man Corporation.
Mr. E. S. Porter resigned as assistant chemical superintendent
of the Arlington Works of E. I. du Pont de Nemours & Co.,
to take a position as research chemist with the Amerada Petro-
leum Corp., New York City.
Mr. John A. Montgomery has left the employ of the Structural
Materials Research Laboratory, where he was chief chemist, to
go with the Borromite Co., Chicago, 111., where he is employed
in a similar capacity.
Mr. D. Mcintosh has resigned as professor of chemistry at the
University of British Columbia, Vancouver, B. C, and has taken
a position as chemist with the Tate Textile Processes Co., Crans-
ton, R. I.
Mr. Josef J. Johnson, a former student at the California In-
stitute of Technology, specializing in laboratory technique and
apparatus design, has accepted a position in the inspection and
testing department of the Central Scientific Co., Chicago, 111.
Mr. T. B. Hine resigned as physical chemist with the U. S.
Bureau of Mines at their Southwest Experiment Station, Tucson,
Ariz., in order to accept an appointment as chief of the physical
chemistry department of the research and development division
of the Chemical Warfare Sen-ice at Edgewood Arsenal, Edge-
wood, Md.
Dr. Ellis M. Black is at present associated in a research capac-
ity with Cornell University Medical College in experimental
biochemistry. He was formerly acting head of the department
of physiology and experimental pharmacology at Tufts College
Medical School, Boston, Mass.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
271
GOVERNMENT PUBLICATIONS
j
By Nellie A. Parkinson, Bureau of Chemistry, Washington, D. C.
NOTICE — Publications for which price is indicated can be
purchased from the Superintendent of Documents, Government
Printing Office, Washington, D. C. Other publications can
usually be supplied from the Bureau or Department from which
they originate. Commerce Reports are received by all large
libraries and may be consulted there, or single numbers can be
secured by application to the Bureau of Foreign and Domestic
Commerce, Department of Commerce, Washington. The regu-
lar subscription rate for these Commerce Reports mailed daily is
$2.50 per year, payable in advance, to the Superintendent of
Documents.
CONGRESSIONAL COMMITTEES
Survey of American Cottonseed Oil Industry. Prepared by
the Tariff Commission. 26 pp. 1920. (Ways and Means
Committee.)
Survey of American Peanut Oil Industry. Prepared by the
Tariff Commission. 18 pp. 1920. (Ways and Means Com-
mittee.)
Survey of American Soy-Bean Oil Industry. Prepared by the
Tariff Commission. 22 pp. 1920. (Ways and Means Com-
mittee.)
SMITHSONIAN INSTITUTION
Discovery of Helium and What Came of It. C. G. Abbot.
Publication 2.ri 0. From Report, 1918. 6 pp.
Problem of Radioactive Lead. T. W. Richards. Publica-
tion 2557. From Report, 1918. 20 pp.
Some Problems of International Readjustment of Mineral
Supplies as Indicated in Recent Foreign Literature. E. F.
Bliss. Publication 2560. From Report, 1918. 19 pp.
PUBLIC HEALTH SERVICE
The Distribution of the Spores of B. Botulinus in Nature.
K. F. Meyer and J. C. GeigER. Public Health Reports, 36,
4-6. The conclusion is drawn that the spores of B. botulinus
may be widely distributed in nature in certain localities and that
they may be on vegetables or fruits when they are picked or
bought in the open market. Protection against botulism can be
achieved only by sterilization of the food product to be pre-
served at a temperature above boiling (under pressure) or by
cooking the contaminated food before eating, or even better, by
discarding any canned vegetables or fruit which show the
least sign of spoilage.
Report on Investigation of Typhoid Fever Epidemic at Green-
ville, Tenn. C. N. Harrub. Public Health Reports, 36,
72-80. The data collected indicated that the water supply
was the responsible agent. It was therefore recommended,
among other things, that a liquid chlorine plant be installed
immediately and that thorough disinfection of the water be
insured before delivery to the citizens.
A Preliminary Study of the Physiological Effects of High
Temperatures and High Humidities in Metal Mines. R. R.
SayrES and D. Harrington. Public Health Reports, 36,
116-29.
OEOLOOICAL SURVEY
Lead in 1918. General Report. C. E. Siebenthal.
Separate from Mineral Resources of the United States, 1918,
Part I. 35 pp. Published January 6, 1921. The following
tabular statement gives the general items regarding domestic
production and consumption of refined lead:
Summary of Statistics of Refined Lead, 1917-18, in Short Tons
Production 1917 1918
Domestic desilverized lead 303 , 679 282 , 024
Domestic soft lead 188,503 210,463
Domestic desilverized soft lead 56 , 268 47,418
Total 548,450 539,905
Foreign desilverized lead 62,319 100,290
Total refined primary Mead 610,769 640,195
Antimonial lead 18,646 18,570
Secondary' lead 93,500 97,100
Consumption2
Apparent consumption of primary lead, stocks disre-
garded 515,535 542,975
1 "Primary lead," which is produced directly from ore, is here dis-
tinguished from "secondary lead," which is obtained by refining skimmings,
drosses, and old metals. The statistics of secondary lead are given on p.
944. Wherever in this report the word "lead" is used without qualification
it means primary lead.
3 For method of calculating consumption see p. 969.
Ground Water in the Norwalk, Suffield, and Glastonbury
Areas, Conn. H. S. Palmer. Prepared in Cooperation with
the Connecticut Geological and Natural History Survey. Water
Supply Paper 470. 171 pp. Paper, 65 cents. 1920.
Contributions to Economic Geology (Short Papers and
Preliminary Reports), 1919. Part II— Mineral Fuels. Bulletin
711. David White and G. H. Ashley. 171 pp.
Sand and Gravel in 1919. K. W. Stone. Separate from
Mineral Resources of the United States, 1919, Part II. 14 pp.
Published January 5, 1921. The sand and gravel produced in
the United States in 1919 amounted to 70,576,407 short tons,
an increase of 8,751,981 tons, or 14 per cent, over the production
in 1918.
Exploratory Drilling for Water and Use of Ground Water for
Irrigation in Steptoe Valley, Nevada. W. O. Clark and C. W.
Riddell, with an Introduction by O. E. Meinzer. Water
Supply Paper 467. 70 pp.
The Iron and Associated Industries of Lorraine, the Sarre
District, Luxemburg, and Belgium. A. H. Brooks and M. F.
La Croix. Bulletin 703. 131 pp. This report in its original
form was prepared at Paris for the use of the American Com-
mission to Negotiate Peace. The purpose of the original report
was to lay before the Commission certain facts relating to the
pre-war use of Lorraine iron ore and thereby to forecast the
probable future of the metallurgic industry in Lorraine as
modified by the new national control of certain districts. In the
revision of the report an attempt was made to modify state-
ments to accord with the new conditions created by the signing
of the peace treaty, but in general the report remains as
originally prepared. Attention is called to the fact that the
American people should have full knowledge of European in-
dustries, and especially of the iron and steel industries of
Lorraine, which has been and will be the strongest competitor
with our export trade in iron and steel products.
BUREAU OF MINES
Monthly Statement of Coal-Mine Fatalities in the United
States, October 1920. W. W. Adams. 8 pp. Paper, 5 cents.
December 1920.
Monthly Statement of Coal-Mine Fatalities in the United
States, November 1920. W. W. Adams. 10 pp. Paper, 5
cents. Issued January 1921.
Chlorination of Natural Gas. G. W. Jones, V. C. Allison
and M. H. Mieghan. Technical Paper 255. Petroleum
Technology 63. 44 pp. Paper, 10 cents. Issued January
1921. The work described in this report was confined to the
effect of different catalyzers on the chlorinating reaction; also
the effect of temperature and, to a smaller extent, that of water
vapor were observed.
State Mining Laws on the Use of Electricity in and about
Coal Mines. L. C. Ilsley. 53 pp. Technical Paper 271.
Paper, 10 cents. December 1920.
Causes and Prevention of Fires and Explosions in Bituminous
Coal Mines. Edward Steidle. Miners' Circular 27. 75 pp.
117 illustrations. Paper, 20 cents.
Quality of Gasoline Marketed in the United States. H. H.
Hill and E. W. Dean. Bulletin 191. Petroleum Technology
59. 275 pp. Paper, 30 cents. The bulletin furnishes, in
addition to the analytical figures, fairly complete data on the
production, consumption, and quality of gasoline, and contains
considerable material of interest to producers and consumers
of motor fuel. The bulletin is divided into four chapters, as
follows: (1) General information on gasoline; (2) report of
the 1919 gasoline survey; (3) report of the 1917 gasoline survey;
and (4) general summary and comparison of gasolines marketed
in 1917 and 1919. The analytical figures obtained through the
analysis of some 1100 samples collected in the surveys of 1917
and 1919 appear in extensive tables which are printed as an
appendix. The important conclusions based on these figures
are summarized in briefer and more concise tables which appear
in the text, supplemented, wherever possible, with curves and
diagrams.
Treating Natural-Gas Gasoline to Meet the "Doctor Test."
D. B. Dow. Reports of Investigations. Serial No. 2191.
4 pp. December 1920. Data are submitted as a basis for the
installation of an economical treating process which will produce
a gasoline meeting the requirements of the "doctor test."
272
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol.
No. 3
Comparison of Methods o'f Gold Recovery from Black Sand.
John Gross. Reports of Investigations. Serial No. 2192.
4 pp.
Fire Hazards in Metal Mines. B. O. Pickard. Reports of
Investigations. Serial No. 2194. 2 pp.
Hazards of Handling and Transporting Volatile Petroleum
Products. C. P. Bowie. Reports of Investigations. Serial
Xo. 2195. 2 pp.
Structure in Bituminous Coal. Reinhardt Thiessen. Re-
ports of Investigations. Serial No. 2196. 4 pp.
Coal-Mine Fatalities in 1Q20. W. W. Adams. Reports of
Investigations. Serial No. 2197. 6 pp.
Recent Articles on Petroleum and Allied Products. Com-
piled by E. H. Burroughs. Reports of Investigations. Serial
No. 2198. 27 pp.
Tests of Miners' Flame Safety Lamps in Gaseous, Coal-Dust
Laden Atmospheres. L. C. Ilsley and A. B. Hooker. Re-
ports of Investigations. Serial No. 2199. 5 pp.
BUREAU OF STANDARDS
Causes and Prevention of the Formation of Noncondensable
Gases in Ammonia Absorption Refrigerator Machines. E. C.
McKelvy and Aaron Isaacs. Technologic Paper 180. 10
pp. Paper, 5 cents. As a result of investigations conducted,
the conclusion is drawn that noncondensable gases found in
ammonia absorption refrigeration machines are due to either
or both of two causes, namely, (a) leaks of air into the system,
and (b) the corrosive action of the ammonia liquor on the metal
of the plant. Methods of preventing gas formation are out-
lined.
Carbonization of Lubricating Oils. Circular 99. 44 pp.
Paper, 10 cents. The nature and effects of the deposits formed
in internal combustion engines are discussed. It is shown that
the term "carbon" is a misnomer, because the deposits consist
largely of asphaltic matter. Brief accounts are given of the
nature of petroleum oils and of the theories concerning the forma-
tion of deposits. The oxidation and cracking of petroleum are
discussed in detail. Carbonization tests which depend upon
oxidation and upon cracking are next taken up. The general
discussion gives brief summaries of certain controversial papers.
DEPARTMENT OF AGRICULTURE
Substitute for Sucrose in Curing Meats. Ralph Hoagland.
Department Bulletin 928. 28 pp. Issued January 7, 1921.
The results of the experiments in curing pork hams indicate
that the several sugar substitutes employed, viz., dextrose,
cerelose, 70 per cent corn sugar, and refiners' sirup, can be used
successfully in place of cane sugar in curing this class of meats.
The difference in the quality of the hams cured with the several
sugars was slight.
Atmospheric Nitrogen for Fertilizers. R. O. E. Davis.
Separate 893 from Yearbook of Department of Agriculture,
1919. 7 pp. Paper, 5 cents.
Fermented Pickles. Edwin Le Fevre. Farmers' Bulletin
1159. 23 pp. Issued December 1920.
The Maine Sardine Industry. F. C. Weber. With the
collaboration of H. W. Houghton and J. B. Wilson. Depart-
ment Bulletin 908. 127 pp. Paper, 50 cents. Issued January
18, 1921. The bulletin describes the methods employed in
packing sardines, the experimental work conducted, grading the
fish, standardization of the sardine pack, sanitary precautions
in packing sardines, waste in packing, and economic considera-
tions. A bibliography is also included.
Articles from Journal of Agricultural Research
Composition of Normal and Mottled Citrus Leaves. W. P.
Kelley and A. B. Cummins. 20 (November 1, 1920), 161-91.
Injury to Seed Wheat Resulting from Drying after Disinfection
with Formaldehyde. 20 (November 1, 1920), 209-44.
COMMERCE REPORTS— JANUARY 1021
High wages and the heavy cost of raw material make it im-
possible for Swiss paper manufacturers to compete with foreign
exporters. As a result of this, one large establishment has re-
cently closed and others are expected to close their factories
in the near future. (P. 5)
Experiments are being resumed in Brussels with a view to the
use of palm oil in internal combustion motors. (Pp. 10-11)
The report from the Straits Settlements is that the outlook
for the rubber industry is very gloomy for some time to come.
(P. 12)
Japanese drillers are soon to commence boring for oil in
Saghalien on an extensive scale. (P. 12)
The mining association of Britons in China has asked the
Vladivostok government for permission to work the unexploited
official oil mines in northern Karafuto. (P. 12)
Active preparations are being made to make Abadan, Persia,
one of the important oil ports of the world. (Pp. 38-9)
According to figures furnished by the German Potash Syndi-
cate, the sales of potash in 1919 were less by 192,279 tons than
those of 1917, and 298,367 tons less than the sales of 1913.
(Pp. 46-7)
Conditions in the pulp and paper industry of Norway remain
practically unchanged with a slack export demand. (P. 53)
British capital is being solicited to develop gold and copper
mines in the Le Pas district in Northern Canada. (P. 56)
The new oil refinery which the Anglo-Persian Oil Company
is erecting at Swansea is said to be practically ready to begin
operations. The initial capacity of the plant is stated to be
12,000 to 15,000 tons of oil per week. While the primary object
of the company is to refine for fuel purposes, it plans ultimately
to enter the field of high-test refining. (P. 57)
Ethyl alcohol may be brought from the United States into
Italy without any restrictions. The importer must pay, how-
ever, four separate taxes. (P. 67)
Statistics are given showing the imports and exports of
vegetable oils and vegetable oil material by Ceylon during the
years 1917, 1918, 1919. (Pp. 86-7)
There is said to be a market for tin and tinned plate in the
Mukden district. (P. 90)
The Government of Perak, one of the Federated Malay
States, is prepared to grant land, upon very favorable terms,
for the cultivation of African oil palm. (P. 109)
The South African soap industry is almost entirely dependent
upon imported raw materials, with the exception of salt and whale
oil, and because of this has been severely handicapped. At-
tention, however, is being focused on the possibility of producing
profitably some of the raw materials in the Union. (Pp. 116-7)
Petroleum and salt may now be purchased freely in all of the
stores of the Monopole in Jugoslovakia. (P. 118)
The government of Jugoslovakia has decided to construct,
near the Bor plants, a manufactory for copper sulfate. (P. 119)
The progress now being made by oil manufacturers toward
developing a process by which the oil may be extracted from the
raw coconut meat without the necessity of making it into copra
is likely soon to eliminate copra entirely from the list of Philip-
pine articles of export. (P. 121)
With respect to the British purchases of Australian zinc
concentrates during the war, announcement is made that no
concentrates have been acquired since January 1, 1920. Stocks
amounting to 503,000 tons are held in Australia by His Majesty's
government, and the whole of the spelter trade of Great Britain
has been closed down for the last three or four months for the
lack of raw material. (P. 139)
Announcement was recently made in Parliament that Great
Britain is no longer under obligation to purchase tungsten ore
from either Empire or foreign sources. (P. 139)
The exploration for oil in Great Britain is reviewed. (P. 144)
New discoveries of tin in the Kunanan district of Malaya
are said to be very extensive. (P. 158)
A shrub growing principally in the gold fields of Australia
has been found to possess properties suitable for tanning pur-
poses. Some excellent samples of fast dyes have also been
extracted from this shrub. (P. 158)
A proposition is being considered to abolish the Japanese
salt monopoly and convert it into a private enterprise. (Pp.
158-9)
Samples of fibers, woods, and other raw materials from Brazil
may be procured by addressing Admiral de Graca, 201 Decatur
St., New Orleans. (P. 160)
A depression is reported in the metal industries of South
Wales. (Pp. I i
Although the exports of Chilean nitrate exceeded the pro-
duction during the first 11 months of 1920, there is still a large
stock of finished nitrate on the coast, more than enough to
supply shipments for over half a normal year. (Pp. 174-5)
An unfavorable situation is reported in Finland's metal in-
dustries. (P. 188)
A company, called the Union Petroleum Company of Belgium,
has just been established in Ghent with a capital of 2,000,000
francs, of which at least half is owned by American companies.
P. iss,
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
27:;
The Australian government has prohibited the importation of
calcium carbide, except under written permit from the Minister
of Trade and Customs. (P. 196)
The plumbago trade of Ceylon reached a minimum in 1919,
having dropped from an exportation of over 33,000 tons in 1916
to 6671 tons in 1919. This slump in exportation has led to the
closing of the majority of the small mines. (Pp. 200-1)
The final report of the lubricants and lubrication inquiry
committee of the British Department of Scientific and In-
dustrial Research is summarized. (Pp. 211-3)
The leather industry of Finland has made considerable prog-
ress during and since the war. (P. 22 1 1
Belgian regulations for the exportation of chicory are cited.
The Belgian government apparently does not intend to dis-
criminate against export orders. (P. 224)
The situation in the Finnish tar and turpentine industries
is said to be very favorable. (P. 224)
The total value of all the minerals produced in the Union of
South Africa in September amounted to §10,455,530. (Pp.
237-8)
The French prohibition against the exportation of pure fixed
oils has been removed. (P. 242)
The depression in the Chilean nitrate market continues, with
no sign of improvement. (P. 242)
A plan has recently been initiated in the United Kingdom,
having as its objective the centralization of British chemical
research in London by means of coordinated action by the
various chemical societies and industrial firms whose processes
involve the utilization of chemical developments or the by-
products of the primary chemical industries. (P. 248)
The Mexican Secretary of the Treasury has recently issued a
circular fixing the valuations of petroleum products upon which
the 10 per cent export duty is based. (P. 234)
There is considerable demand for soda ash, bleaching soda, and
caustic soda throughout the Mukden consular district. (P.
268)
Copper for export from Mexico is free of duty when the market
value of electrolytic copper in New York City is 15 cents or less
per pound. (P. 273)
A market is desired for South African barium sulfate. (P.
281)
The peanut industry in Japan is reviewed. (Pp. 282-7)
Statistics are given showing the exports of petroleum from
Mexico for each of the first ten months of 1920. (P. 291 I
A tabular statement is given showing the grades of rubber
on the New York market with equivalents in Singapore, Batavia,
and East India grades. (P. 314
Siam's trade in soaps is described. (Pp. 316-7)
The pulp and paper industry of Canada for the calendar year
1919 is reviewed. (Pp. 327-8)
The production of alcohol in the Dutch East Indies is rapidly
assuming an important position and bids fair to exceed in 1920
the phenomenal figures of recent years. (Pp. 362-3)
The international metric system is the sole legal system of
weights and measures at Danzig. (P. 365)
Italian import duty on kerosene and gasoline has been in-
creased. (P. 385)
The chemical industries of Czechoslovakia are described, in-
cluding the fertilizer industry, pharmaceutical products, ex-
plosives, varnishes and lacquers, colors and dyes, oils and greases,
soap manufacturing, and the candle and starch industries. (Pp.
393-4)
The German soap industry is in a very dangerous condition
and unless raw materials can be procured at once factories will
have to close down. (P. 394)
A Japanese market is reported for iron, steel, and lubricating
oils. (Pp. 400-1)
Blister copper has been sent to the United States from Tas-
mania for refining because of the accumulation of this material
due to strikes. (P. 408)
A factory and plant have been erected in New South Wales
for the extraction of starch from the burrawong plant. (P.
409)
Australian regulations for the importation of dyes are cited.
(P. 417)
The tanning industry of Japan developed considerably during
the war, and at the present time large quantities of tanning ma-
terials are being used. (P. 431)
Renewed activity is shown in the manganese mines in
Argentina. This is the result of an increase in the local demand
for manganese in the glass and iron industries. (Pp. 456-7)
Export licenses for reasonable quantities of practically all
dyestuffs and intermediates, except benzene, will be granted to
British firms which actually have the material in hand. The
expectation is that by this provision trade will be opened up,
especially in alizarin. (P. 465)
The petroleum production of Egypt for the years 1918, 1919,
and 1920, respectively, was 277,300 tons, 231,180 tons, and
151,490 tons. Production in Persia for the same periods was
583,200 tons, 874,800 tons, and 918,600 tons, respectively.
(P. 465)
The Japan Chemical Industrial Co., together with other
fertilizer companies, will form a joint stock organization to
develop the production of phosphate in Hirata. (P. 472)
The manufacture of salt in Chosen during 1920 was unusually
successful because of favorable weather conditions. (P. 473)
Importers of dyestuffs must give evidence of a definite order
for the full quantity, according to the British Dyestuffs Act.
No dyes will be admitted on consignment. (P. 481)
The oil and fat trade of the Netherlands is reviewed. (Pp.
482-3)
The Barbados Islands have suspended the prohibition on the
importation of foreign dyes and dyestuffs. (P. 496)
The importation of dyestuffs being the produce or manu-
facture of Germany is prohibited in Nigeria. (P. 497)
The St. Vincent government has temporarily suspended the
prohibition against the importation of foreign dyes and dye-
stuffs. (P. 497)
Private statistics show that the crude oil production of Ger-
many reached 29,950 tons in 1920, as compared with 33,000
tons in 1919. (P. 513)
The British embargo on the exportation of coal tar, all prod-
ucts obtained therefrom and derivatives thereof suitable for use
in the manufacture of dyes or explosives, dyes and dyestuffs
from coal-tar products, and synthetic indigo, has been removed,
effective February 1, 1921. (P. 529)
The German potash industry is reported to be seriously
threatened by that of Alsace. (P. 548)
A new bamboo paper plant is to be opened in the Pegu District,
Burma. (P. 558)
A depression, due to labor difficulties, exists in the tin and
rubber markets of Burma. (P. 558)
Caps Town— (P. 13)
Lead and copper
Vanadium
Copper matte
East Indies — (P. 92)
Copra
Cinchonidine sulfate
Hides and skins
Citronella oil
Quinine sulfate
Quinine hydro-
chloride
R,ubber
Sulfate tablets
Tin
Paraffin
Italy (Palermo) —
(P. 182)
Citric acid
Tartaric acid
Licorice roots
Manna
Sumac
Crude tartar
Sulfur oil
Leather
Bergamot oil
Lemon oil
Canada (Riviere du
Loup)— (P. 187)
Wood pulp (chemi-
cal)
of Export to the Un
Czechoslovakia —
(P. 195)
Chemicals ($717,000)
Ecuador— (P. 305)
Annatto
Cinchona bark
Manganese ore
Rubber
Copra
Malaga— (P. 346)
Cuttle-fish bone
Tartar (crude)
Thymol
Sulfur oil
Oils, essential
Almond sweet oil
Edible oils
Oxide of iron
Yellow ocher
Malaga — (P. 521)
Chemicals, drugs,
etc.
Oils:
Lavender
Rosemary
Sulfur
Thyme
Olive
Paints and colors
ited States
Liverpool — (P. 388)
Ferromanganese
Minerals, crude
Palm oil
Tin ore
Chemicals, drugs ,
and dyes
Society Islands — (P.
405)
Copra
Coconut oil
Hongkong — (P. 4 20)
Antimony
Camphor
Chemicals
Peanut oil
Wood oil
Aniseed oil
Cassia oil
Bismuth
Manganese ore
Wolfram ore
Tin
Nantes — (P. 461)
Glycerol
Fertilizer
Africa, Ciiii i
486)
Copper
Tin
Wolfram
Wolfram ores
Special Supplements Issued
Bulgaria — 3a
Denmark — 56
Italy — 10a
Netherlands — 1 16
Norway — 12a
Switzerland — 206
United Kingdom — 22j
Nicaragua — 37&
Manchuria — 55g
China— 55ft
China— 55>
Japan — 58d
Japan — 5Se
Malaya— 596
British East Africa and Uganda — 68i
British South Africa — 696
British West Africa — 70a
British West Africa — 72c
274
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
BOOK REVIEWS
The Manufacture of Chemicals by Electrolysis. By Arthur
J. Hale, B.Sc, F.I.C. xi 4- 80 pp. D. Van Nostrand Co.,
New York, 1919. Price, $2.00 net.
This little monograph is one of a series on electrochemistry
edited by Bertram Blount, F.I.C. In the preface to the present
volume the author claims that he has given a complete and up-to-
date account of processes "now in use." This is not the case,
however, for the book is primarily a compendium of the patent
literature covering the preparation of the less common elec-
trolytic products. The author concedes that "descriptions in
patent specifications do not necessarily represent the process
as carried out in practice, and in some cases are drawn with that
intention; they should therefore be accepted with caution."
Bearing in mind, however, that there are practically no other
published data available regarding the "manufacture" of the
products discussed, with a few exceptions, the author is to be
congratulated for bringing together in a very readable form
the little information available. The products discussed in-
clude persalts, hydrogen peroxide, hydroxylamine, hydrosulfites,
fluorine (no mention of the new improved method for fluorine
developed during the war at the American University), lead
chromate, lead peroxide, electrolytically tanned skins, amino-
phenols, chloroanilines, hydrazobenzene, anthraquinone, sac-
charin, iodoform, chloral, azo dyes, and other organic derivatives.
There are numerous literature references appended. The little
book will be welcomed in particular by the research electro-
chemist. It contains many valuable suggestions for investi-
gations. Colin G. Fink
Science and Life. By Frederick Soddy. xii -f- 229 pp. E.
P. Dutton & Co., New York, 1920. Price, $4.00.
To one living in this land of research enthusiasm and popular
science and to one who is acquainted with Professor Soddy only
as a brilliant investigator who brought to the study of sub-
atomic phenomena that knowledge of chemistry which pointed
the way to the physicists, this book comes as a double surprise —
first, in revealing that the vindication of Science for its own
sake is yet far from complete among our British brethren, and
second, in its flow of vigorous speech which will speed that
inevitable vindication in the most benighted land. Yet lest
his attack on the "illegitimate" and "ancillary" subjects in the
standard classical education, on the "unholy combination against
science in our universities," in Scotland lead to a wiser-than-
thou attitude, let us note that with us the bachelor's degree is
still regarded as evidence of professional competence, and let it
be admitted that for each of us there is much incentive to action
as well as much lasting inspiration in these addresses of the
distressed Aberdeen professor (since gone to Oxford) who pleads
the cause of "creative, insatiable and prospective" research in a
land weighed down with "essentially imitative, self-sufficing and
retrospective" humanist education.
The title is misleadingly broad. Two of the addresses are
properly scientific, lucid interpretations of the evolution of
matter and of the conception of the chemical element. The
remaining eight are Huxleyan in tone and in their insistence
that the future belongs to science, that the ideals of the race-
can be based only on a complete knowledge of nature, that the
present communism of science is an earnest of the spirit of future
civilization, and that the barriers to progress placed by the
conservative, the priestly, the ruling-class mind are but a chal-
lenge to the vigorous and youthful mind of the common man,
who has most to gain by the emancipation through science.
The appendix serves to publish correspondence and records on
the administration of the million-pounds Carnegie Trust for
scientific research in Scottish universities. During the first
fifteen years of its existence not more than fourteen per cent of
the income was devoted to research of all kinds, including
historical, linguistic, and economic subjects. "I have formed
the deliberate opinion that it is useless for benefactors, like
Mr. Carnegie, to give money for scientific research because under
the existing system it will be diverted. * * * If science is not to
get ordinary decent fair-play in ancient educational establish-
ments it is the youth of the country who will pay again. It is
not good to be young in a country that is governed by worm-
eaten prejudices and absurd conjuring tricks with words."
Soddy admits that these are, in Scotland, his "well-known
views." They should be here. They deserve attention, per-.
haps publicity, and might even be entrusted to that Juggernaut —
propaganda — who devours all his attendants save Truth. And
this even though several of the addresses were made to branches
i jf the Labour Party and in spite of frequent paragraphs which
betray an imagination more than creative.
Gerald L. Wendt
The Natural Organic Colouring Matters. By Arthur George
PERKin, F.R.S., F.R.S.E., F.I.C, Professor of Colour Chem-
istry and Dyeing in the University of Leeds, and Arthur
Ernest Everest, D.Sc, Ph.D., F.I.C, of the Wilton Re-
search Laboratories, late Head of the Department of Coal-
Tar Colour Chemistry, Technical College, Huddersfield.
Longmans, Green and Co., London, 1918. Price, $9.00 net.
This volume is a notable contribution to the series of Mono-
graphs on Industrial Chemistry that are being published in
English under the editorship of Sir Edward Thorpe.
The experiences of English-speaking lands during the recent
war brought into high relief the need of a dyestuff literature in
English, and revealed the large usefulness in modern industry
of natural coloring matters.
Prior to the publication of this volume, only two works of
similar note have appeared. In 1874, Professor William Crookes
treated compendiously the chemistry at that time known of the
natural coloring matters, in a treatise entitled "A Practical
Handbook of Dyeing and Calico Printing." In 1900, the state
of the science was ably presented in Dr. Hans Rupe's handbook,
"Die Chemie der Natiirlichen Farbstoffe," and in 1909, owing
to the large amount of new knowledge on the subject, a second
volume was published. Dr. Rupe's volumes have not been
translated into English. A considerable mass of new data
concerning natural coloring matters having been brought to
light in the past decade, the present volume is timely.
The intimate association of the authors with the development
of the knowledge of the subjects they present, adds interest to
the perusal of the book. They state in the preface:
The intention has been to make this book of interest not only
to the student, but of value as a work of reference to the inves-
tigator * * * There is hardly a group of substances in the whole
range of organic chemistry which offers greater fascination to
the purely scientific investigator than the study of the naturally
occurring colouring matters and the elucidation of their remark-
able relationships one to another.
A general historical introduction precedes the more detailed
descriptions. The natural organic coloring matters are classified
according to their constitutional structure into eighteen groups,
each group forming the subject matter of a chapter. There is
also a chapter on "Lakes from Vegetable Colouring Matters."
The enumeration of the groups would give little idea of the
completeness with which the subjects have been treated. Nat-
ural coloring matters from all parts of the globe and from every
imaginable source are described. The chemical and physical
methods and the reasonings by which were established the con-
stitutional formulas of the chemical principles of these multi-
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
275
farious substances are expounded. The same treatment is ac-
corded the various chemical derivatives from these principles.
Physical and chemical constants, properties, and reactions are
given with exhaustive completeness.
The authors are especially interested in the attempts to utilize
the more readily accessible of the naturally occurring coloring
matters as starting points in the building up of synthetic dyes
of great value. Considerations that lead to this suggestion are
developed in the chapter on the y-pyran group, pages 2.34 to 236:
o
0
■\/\
\/\
C C—
c c-
The groups
1 II
or ||
c c—
c c
/X/
/%/
c
1
c
1
1
o
o
/\
c—
s/\
c
and
II or
II
C—
1
c
\A
vA
c
c
are of considerable interest in connection with both the arti-
ficial and naturally occurring colouring matters. They form the
basis of a number of synthetic colours that have been in com-
mercial use for many years, of which the following may be cited
as typical instances:
CI
Me*N O NMe.
c
O Br O
/
Br
C
,— ONa
H
Pyronine G
Eosin A
Et*N
MejN
o
NM
Y
e2
K,
KX
c
)
Ph
Tetramethylrosamine
CI
1
O
NEt
Y
2
OH
1 OH |
o | o
YY>
OH
KX
c
J
I
1 )
c
J
1
COOH
Rhodamine B
Coerulein
whilst related to these, but of less value, are such products as
the succineins and sacchareins.
The result of recent researches upon naturally occurring
colouring matters has been that a large number of substances,
the anthocyans, colours of great beauty and widely distributed
in nature, are now known to be derivatives of the benzopyranol
complex; indeed all the products of this group as yet investigated
are derived from the following nucleus:
CI
I
O
OH |
H
by the introduction of further hydroxyl groups.
Interest in this type of compound is increased by the fact that
compounds related to the anthocyans have been synthetically
prepared which have rather more useful tinctorial properties
than those possessed by the natural colours, and it is not im-
possible that the number of commercially useful derivatives in
which the y-pyran nucleus is present may be further increased
by work that may follow upon the recent researches in this
field.
In further substantiation of this thesis, the halogenating of
indigo has produced vat dyes of the Ciba type, which are es-
sentially faster than indigo.
The chapters on the natural yellow organic coloring matters —
the xanthone, flavone, and flavonol groups, and on brazilin and
logwood — the dihydro-pyran group — are of special historical
and chemical significance. The student of organic chemistry
will derive special pleasure and profit from reading the pages
describing the chemistry of cochineal and carminic acid.
As the volume is intended primarily for the student and scien-
tific investigator, and not as a textbook of dyeing, the authors
give almost no space to the description of the application of the
natural coloring matters in industry. They state, for example,
page 381 :
Logwood and its extracts are enormously employed for the
dyeing of blacks on silk, wool, and to a less extent, with
cotton.
Hematine paste, which plays such an important role in modern
dyeing, is simply mentioned. No account is given of the de-
velopment in the past two decades of logwood crystals and
hematine pastes and crystals for a variety of purposes in indus-
try, as the dyeing of leather, and the weighting of silk.
The authors make the prophecy — page 2 — that it is merely
a matter of time when the application of natural coloring matters
at present employed in industry will cease. The inference of
the context is that the natural coloring matters now in use will
be displaced by superior artificial dyes, or by the same products
synthetically produced. This statement is more sweeping than
present conditions would seem to warrant. It is outside the
province of this review to argue the subject at length. It may
suffice to state that in the year 1900 in the United States, there
were produced of logwood and fustic products about 50,000,000
lbs. of extract, corresponding to 25,000,000 lbs. of powder, and
to a money sale value of $6,000,000. These figures do not in-
clude the considerable quantity of quercitron bark extract and
products used in industry, nor the figures for various tannin
materials, as quebracho, oak bark, sumac, etc. All these natural
products can be supplied at an astonishingly low cost to con-
sumers, so that the task of the synthetic chemist to produce
satisfactory substitutes at a lower cost is difficult.
The volume performs a service to modern industry to which
the authors have not laid claim. The notable developments of
the use of natural dyestuffs in modern industry in recent decades,
as in wool dyeing and in the weighting and dyeing of silk, have
come from a more perfect grasp of the chemistry of the natural
coloring matters. This has enabled investigators to apply mod-
ern theoretical and scientific principles to the manufacture of
special extracts and dyewood products and to their application
on fibers and materials. The ample data of this volume will
thus perform a great service to modern industry as well as to mod-
ern science. Edward S. Chapin
27G
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 3
Industrial Organic Analysis. By Paul S. A kip, B.So, IMC.
2nd edition, revised and enlarged, xi -f- 471 pages, 2.") illus-
trations. J. & A. Churchill, London, 1020. Price, 12s. Gd. net.
Under this rather ambitious title, we have to note an excellent
little manual. The title is something of a misnomer, however.
as it covers only a portion of the field of industrial organic
chemistry. Three of its nine chapters are devoted to the subject
of the fatly oils, soaps, milk, and butter, which is the author's
special line of professional activity. While it covers coal tar
and its chief distillation products, it does not go into the ques-
tion of dye colors, and other important organic chemical indus-
tries, like the textile industries, wood-distillation products,
cellulose products, leather, paints, and varnishes, are not covered.
The first chapter is devoted to "Coal and Coke." The clas-
sification of coals is largely based, it is true, upon English coals,
and the table of analyses on pages 12 and 13 also deals mainly
with English coals. The author stales, however, that he leaves
out of his discussion imperfect coal such as lignite, on the one
hand, and highly condensed products like anthracite, on the
other, and the discussion is therefore mainly upon the classes
which are to be considered as intermediate. The author quotes
at length from the publications of the "Committee on Coal
Analysis of the American Society for Testing Materials, and
the American Chemical Society." We note also in the foot-
notes that reference is made to many articles which have ap-
peared in This Journal. In fact, the author gives very full
and abundant credit to American work in this connection.
In the chapter on "Coal Tar and Its Distillation Products,"
considerable reference is also made to the literature, and par-
ticularly to the articles by the "Committee of American Coal-tar
Chemists," under the presidency of J. M. Weiss, which appeared
in This Journal during the year 1918. Of course, considerable
reference is made also to Lunge's "Methods of Technical Anal
\-is." and to some German sources. Jn fact, we consider that
from the standpoint of the raw materials, or primary products
of the coal-tar industry, the book is very helpful in its dis-
cussion of methods.
The author interrupts what might be called a natural relation-
ship, in that he leaves the discussion of petroleum products to
a later chapter, and takes up next the "Fatty Oils and Fats."
As this is the special province of the author, it is very well
handled. In fact, it is a more connected account of the meth-
ods in this industry than we find in the larger works of Lew-
kowitsch and Hefter. We note particularly his discussion of
The Reichert-Meissl, Polenske and Kirschner Values, and his
explanation of the application of these determinations, which
is distinctly the best we have seen on this subject.
We note at the end of this section on "Fatty Oils" the im-
portant statement that "there is no certain method for detect-
ing hardened oils which have of recent years been used to some
extent in margarine." The author practically refers the detec-
tion of these fats to the expert taster, and states that while
palatability plays an important part in the valuation of these
products, it is not susceptible of chemical measurement.
The chapter on "Petroleum and Its Distillation Products"
we do not consider as satisfactory as some of the other parts
of the work. The literature used is predominantly English and
German, and the author is apparently not acquainted with
some of the best work published in this country. For instance,
under lubricating oils, no mention whatever is made of the
carbon residue test, carried out by Conradson's method, which
is always referred to in the specifications for lubricants for
automobile and other uses. In the literature references no
mention is made of the important work of Bacon and Hamor
on "The American Petroleum Industry','' and for petroleum
technologists reference should also be made to the publications
of the Kansas City Testing Laboratory, which are perhaps the
most comprehensive on this subject.
The chapter on "Milk and Butter" is of great value, because
• ii tin- author's special acquaintance with this subject. He
gives full credit to the publications of the American Associa-
tion lor official Agricultural Chemists and the methods therein
described, and of course quotes very fully from the very valu-
able English manuals, such as those of Richmond.
Tin chapter on "Starch and Allied Products" is in the main
very satisfactory. We call special attention to the author's
endorsement of the takadiastase method for hydrolyzing starch
as against the hydrochloric acid method, which is still given in
the publications of the American A in for Official Agri-
cultural Chemists, and the O'Sullivan method for using mall
diastase. The author shows very clearly the superiority of the
method which he recommends.
Under the subject of "Flour" we do not find any reference to
the test for the distinguishing of bleached flour, and the recog-
nition of nitrites in the same, which in this country, at all events.
is of importance.
The chapter on "Sugars and Alcohol" is very satisfactorily
treated. We note his reference to the work of the English
chemist, E. E. Armstrong, on the biological methods for tin
analysis of sugar mixtures, which has been recognized is ol
very great value.
The last chapter is devoted to the subject of "Preservatives
and Artificial Coloring Matters in Foods," and concerns itself
chiefly with preservatives in milk, cream, butter, and marga-
rine. The treatment of these topics is very well done, and makes
the manual of value for reference.
As before said, the manual is a very excellent, compact book
for handy reference, and on the topics chosen for discussion is,
in the main, very satisfactory. I commend it, therefore, quite
strongly to the attention of the class of chemists for whom it
is designed. Samuel P. Sadtler
The Simple Carbohydrates and the Glucosides. By E Frank
land Armstrong. [Monographs on Biochemistry edited by
R. H. A. Plimmer and F. G. HorKiNs] 3rd Edition. Royal
Svo. ix + 239 pp. Longmans, Green and Co., London.
New York, Bombay. Calcutta, and Madras. 1919. Price.
i net.
A recent article by Karrer1 records a discovery that will doubt-
less have far-reaching influence upon the future development of
the chemistry of the carbohydrates, namely, that the destruc-
tive distillation of (J-glucose at very low pressure yields levo-
glucosan. Pictet and Sarasin2 described the similar production
of levoglucosan from starch and from cellulose, but from glucose
they obtained glucosan, not levoglucosan. Karrer now clears
this matter tip by showing that levoglucosan is indeed obtained
from one form of glucose, the ^-modification, and that Pictet
and Sarasin did not obtain it because they experimented with
a-glueose. From these striking results Pictet has now deduced
the space configurations of the a- and /3-forms of glucose In
the same number of the Swiss journal, Karrer and Weidmann'
describe the synthesis of a glucoside of methyl salicylate, which
proves to be an isomer of the natural glucoside of the win
plant, gaultherin. The synthetic method that was used would
lie expected to yield a ^-glucoside, and Karrer and Weidmann
consider therefore that natural gaultherin, isomeric with their
fJ-gaultherin, must be n-gaultherin. This conclusion seems
quite doubtful to the reviewer, for the reason that both natural
gaultherin and the synthetic glucoside rotate polarized light to
the left, whereas it is to be expected from well-established princi-
ples that the a-form of gaultherin. when discovered, will rotate
■ Helvetica Chim. Ada, 3 (1920
' Ibid., 1 (19181. 87
» Ibid., 3 (1920), 649.
« Ibid . 3 (1920), 252.
Mar., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
277
strongly to the right. Indeed its expected rotation can be cal-
culated from that of the synthetic /3-gaultherin.
These observations are mentioned to draw attention to the
great progress that is being made to-day in the extension of our
knowledge of the chemistry of the carbohydrates, and also to
indicate the purpose of Dr. Armstrong's book, which presents
in logical relation the advances that have been made in this
subiect in the last 15 or 20 years. Anyone may test his knowledge
of these advances by observing whether he can grasp from the
preceding paragraph just, what Pictet and Karrer are doing.
Dr. Armstrong has brought this last edition well up to date.
He has adopted the nomenclature which Rosanoff suggested
many years ago for xylose, gulose, and several related sugars,
which simplifies considerably the study of the sugar group.
An excellent method, quite simple and conclusive, for proving
the configurations of the main members of the sugar group is
published on page 36. The work of Irvine and his students
on methylated sugars is described, leading up to Howard and
Leiteh's recent proof of the structure of milk sugar (page 107).
As Dr. Armstrong's book interests advanced students and re-
search workers particularly, it seems unfortunate that no liter-
ature references are mentioned in the body of the work. The
bibliography at the end of the volume is not correlated with the
text except in the general way of references to chapter headings.
Much of the possible value of the book to investigators is lost
by the omission of textual literature references, and in some in-
stances this lack of full precision has led Dr. Armstrong, doubtless
quite unconsciously, into omitting to give credit to authors.
On page 71 the yield of mannose from vegetable ivory should
be stated as 40 per cent, rather than 4 per cent. On page 78,
iditol, in addition to sorbitol, should be mentioned as a reduction
product of sorbose. The specific rotation of isotrehalose (p.
143) should be stated as ■ — 39. D*\ Armstrong uses the spelling
"melicitose" which has somehow crept into several recent books
on sugars; as the sugar was named by its discoverer, Berthelot,
"melezitose," from the French name of the larch tree, meleze,
where its occurrence was first noted, and only the original spelling
indicates the correct pronunciation of the name, there seems no
proper reason for changing it.
The book as a whole. is quite commendable. It is a clear and
interesting summary in fair detail of the present state of our
knowledge of the sugar group. To research workers it repre-
sents a sort of advance supply base from which they may obtain
the most useful weapons — ideas and methods — for the next
push forward. C. S. Hudson
The Manufacture of Sugar from the Cane and the Beet. By
T. H P. Heriot, F.I.C , Lecturer on Sugar Technology at
the Royal Technical College, Glasgow; Author of "Science
and Sugar Production." With illustrations, octavo, 426 pp.
Longmans, Green & Co., London and New York. L920.
Price, $8.50 net.
This new work on sugar manufacture is one of a series of
monographs on industrial chemistry edited by Sir Edward
Thorpe. These monographs are not so much concerned with
the technical minutiae of manufacture as with relations of
principle to practice, and the aim of the present work is to show
that successful practice is becoming more and more dependent
on scientific principles, which can be studied more effectively
outside the factory than inside. The author says it is worth
recording that the cane-sugar producer followed the beet-sugar
producer in adopting the following inventions and processes:
Boneblack and sulfur dioxide for bleaching the juice; the car-
bonation process for purifying and clarifying the juice; the
diffusion process for extracting sugar from the plant; the filter
press; the multiple effect evaporator in vacuo; the vacuum pan;
apparatus for crystallization-in-motion ; the use of seed grain in
the vacuum pan; the centrifugal for curing sugar; the centrifugal
machine for clarifying juice; technical schools for the study of
technology; ami chemical control of manufacturing opera-
tions.
The work is divided into ten parts, each consisting of several
chapters, in which are discussed with surprising fullness, con-
sidering the space taken, the raw materials; the extraction,
composition, and treatment of cane and beet juices; the evapora-
tion of water and crystallization of sugar; as well as the various
by-products from the cane- and beet -sugar factories, and the
processes of refining.
The text is well illustrated by numerous pictures of typical
sugar beets and cane, machinery and appliances, and by a num-
ber of diagrams and schemes illustrative of processes and methods
of operation. Throughout the book stress is laid upon tin
chemical and other scientific principles upon which the industry
is founded, and these are given in admirable detail. A marked
feature of the work is the repeated discussion of efficiency and
economy in the many operations described.
Space prevents even a reference to more than a few of the
innumerable interesting features of the book, but some of these
can be mentioned in an attempt to give one an adequate idea
of the scope of this treatise. The opening chapters give detailed
discussions of the structure of the beet from the botanical
standpoint with descriptions of new varieties, seed production,
and cultivation in general. Varieties of sugar cane and seedlings
are also discussed. In the milling of cane a description of the
various methods of saturation is included, and detailed de-
scriptions of rolls, crushers, shredders, and diffusers are all gone
into with thoroughness. Careful discussion is also given to the
various operations of beet slicing and diffusing.
The chapters on the chemistry of the sugars and of beet and
cane juice are replete with useful and comprehensive informa-
tion, including that which has been most recently developed,
and include a discussion of the chemical control of sugar fac-
tories. All the information in regard to defecation is timely
and up to date. Excellent descriptions are given of various
methods of filtration and the mechanisms employed. The
several methods of carbonation and sulfitation of beet juice are
clearly discussed.
Multiple-effect evaporation is well set forth with diagrams
and illustrations, as well as tables and formulas covering the
underlying principles as well as the specific forms of apparatus
most generally in use. Crystallization in general is next taken
up, followed by chapters on the scientific principles underlying
crystallization in the vacuum pan and out. Schemes are given
of the principal methods used in cane- and beet-sugar factories
for the recovery of sugar solutions by crystallization; and control
tests, including those by the Brasmoscope, air given in detail.
Another chapter describes several of the principle methods for
recovering sugar from beet molasses, and others deal with the
many by-products of cane- and beet-sugar factories, illustrated
by schemes, and including the production of alcohol. Finally
sugar refining is taken up in a brief historical way followed l>\
descriptions of the principal operations, accompanied by specific
figures giving the ranges within which the operations air eon
ducted. In speaking of the revivification of char, the author refers
to the nearly horizontal rotating cylinder provided with internal
shelves and heated externally as a kiln of the earlier form,
whereas the fact is that this is of comparatively recent invention
and has in many cases superseded the less satisfactory kilns <.f
the vertical type.
Taking it all together, the work is a most commendable com-
pilation of exact information regarding the very many processes
employed in this field of industry, combined with brief but clear
discussions of the scientific principles on which sugar manu-
facture depends. The book will surely find a welcome at the
hands of those interested in the industry and will be a welcome-
addition to every sugar library. W. D. Horne
278
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
NEW PUBLICATIONS
Applied Colloid Chemistry: General Theory. Wudsr D. Bancroft.
345 pp. Illustrated. Price, $3.00. McGraw-Hill Book Co., Inc., New
York.
The Atom. Albert C. Crehore. 177 pp. Illustrated. Price, $2.00.
D. Van Nostrand Co., New York.
Cellulose Esters: Les Ethers Cellulosiques. Premiere Partie. Les
Ethers Mineraux de la Cellulose. Vol. I. La Nitrocellulose et le Cellu-
loid. Andre Dubosc. 344 pp. A.-D. Cillard, Paris.
Chemical Laboratory: How to Make and Use a Small Chemical Laboratory.
R. F. Yates. 102 pp. Illustrated. Price, $0.75. D. Van Nostrand
Co.. New York.
Chemistry of Bread- Making. James Grant. 3rd Edition. 236 pp.
Illustrated. Price, $2.00. D. Van Nostrand Co., New York.
Coal in Great Britain: The Composition, Structure, and Resources of the
Coalfields, Visible and Concealed of Great Britain. Walcott Gibson.
311pp. Price, $7.50 net. Longmans, Green & Co., New York.
Concrete: The New Stone Age. H. E. Howe. 289 pp. Price, $3.00.
The Century Co., New York.
Dyes: Unification des Noms des Colorants les Plus Usuels. P. Sisley.
196 pp. Union des Producteurs et des Consommateurs pour le D6-
veloppement de l'lndustrie des Matieres Colorantes en France, 53 Rue
de Chateaudun, Paris.
Gas Analysis for Chemists. Augustus H. Gill. Reprinted from "Stand-
ard Methods of Chemical Analysis," by Wilfred W. Scott. 52 pp.
Price, $1.25. D. Van Nostrand Co., New York.
India-Rubber Goods Manufacture: A Practical Guide to the Manufacture
of Rubber Goods. "Factory Manager." 496 pp. Price, $7.75.
Maclaren & Sons, Ltd., London.
Modern Brickmaking. Alfred B. Searle. 2nd edition, revised and
enlarged. 510 pp. 310 illustrations. Price, $7.00. D. Van Nostrand
Co., New York.
Organic Chemistry: A Laboratory Course of Organic Chemistry, Including
Qualitative Organic Analysis. A. W. TitherlEY. 263 pp. Illustrated.
Price, $2.50. D. Van Nostrand Co., New York.
Organic Medicinal Chemicals. M. Barrowcliff and Francis H. Care.
(Industrial Chemical Series.) Price, 15s. net. Bailliere Tindall & Cox,
Plant Chemistry: The Chemistry of Plant Life. RoscoE W. Thatcher.
268 pp. Price, $3.00. McGraw-Hill Book Co., New York.
Plant Chemistry: An Introduction to the Chemistry of Plant Products.
Vol. I. On the Nature and Significance of the Commoner Organic Com-
pounds of Plants. Paul Haas and T. G. Hil. 3rd edition. 414 pp.
Price, $5.50. Longmans, Green & Co., New York.
Technical Chemists' Pocket Book. Robert Ensoll. 204 pp. 31 illus-
trations. Price, 8s. 6d. net. E. & F. N. Spon, Ltd., London.
NEW JOURNALS
American Journal of Hygiene. William H. Welch, Editor, School of
Hygiene and Public Health, Johns Hopkins University, Baltimore, Md.
Published bimonthly. Price, $6.00 a year.
Canadian Dyer and Color User. W. A. Lawrence, Consulting Editor.
Published monthly by the Westman Press, Ltd., 72 Queen St., W., To-
ronto, Canada. Price, $3.00 a year.
RECENT JOURNAL ARTICLES
Bacteria as Chemical Reagents. Arthur I. Kendall. Chemical and
Metallurgical Engineering, Vol. 24 (1921), No. 2, pp. 56-60.
Brass Industry in Great Britain. Paul M. Tyler. The Iron Age, Vol.
107 (1921), No. I, pp. 15-18.
Catalysis: The Influence of Lead on the Catalytic Activity of Platinum.
Edward Bradford Maxted. Journal of the Chemical Society, Vol. 117
(1920), No. 698, pp. 1501-1506.
Chemistry of the Earth's Crust. Henry S. Washington. Journal of the
Franklin Institute, Vol. 190 (1920), No. 6, pp. 757-815.
Chemistry of Sulfite Cooking. A. Chambovet. Paper, Vol. 27 (1921),
No. 21, pp. 21-24. Translated from La Papeterie.
Colloid Chemistry of Tanning. H. R. Procter. The Chemical Age
(London), Vol. 4 (1921), No. 84, pp. 94-95.
Color Standardization in the Textile Industries. Roberts Beaumont.
Textile Colorist, Vol. 43 (1921), No. 506, pp. 97-100.
Combustion and Instruments. Robert June. Combustion, Vol. 4 (1921),
No. 2, pp. 24-28.
Combustion of Lignites and High-Moisture Fuels. T. A. Marsh. Com-
bustion, Vol. 4 (1921), No. 2, pp. 39-44.
Cotton: Fundamental Research in Cotton Industry. D. E. Douty. Tex-
tile World Journal, Vol. 59 (1921), No. 6, pp. 197-198.
Cotton Cellulose: The Application to Industry of Recent Researches on Its
Viscosity. R. A. Punter. Journal of the Society of Chemical Industry,
Vol. 39 (1920), No. 24, pp. 333/-347J.
Cyanidation: Sidelights on the Cyanidation Process. Alfred James.
Engineering and Mining Journal, Vol. Ill (1921), No. 3, pp. 102-104.
Disinfection: SulT Impiego della Cloropicrina (Tricloronitrometano) nella
Disinfezione dei Cereali. A. Piutti and A. Mango. Giornale di
Chimica Industriale ed Applicala, Vol. 2 (1920), No. 12, pp. 677-682.
Drugs: Thymol and Carvacrol Problems. D. C. L. Sherk. American
Journal of Pharmacy, Vol. 93 (1921), No. 1, pp. 8-18.
Dyes: Colorations Obtenues sur Fibres au Moyen des Derives Nitroses.
Messrs. Wahl and Guindon. Revue Generate des Matieres Colorantes
de la Teinlure, de I'Impression el des Apprlls, Vol. 24 (1920), No. 288.
pp. 179-182.
Dyes: Laboratory Methods of Dyeing and Testing Cotton Dyestuffs.
P. F. Estey. American Dyesluff Reporter, Vol. 8 (1921), No. 1, Section 2,
pp. 16-20.
Electrification of Water and Osmotic Flow. Jacques Loeb. Science,
Vol. 53 (1921), No. 1361, pp. 77-84.
Enamels: A Reading List on Vitreous Enameling on Iron and Steel. Clar-
ence Jay West. Journal of the American Ceramic Society, Vol. 4 (1921),
No. 1, pp. 47-64.
Fertilizer: The Reactions Taking Place in Cyanamid when Used in Mixed
Fertilizers. W. S. Landis. The American Fertilizer, Vol. 54 (1921),
No. 2, pp. 49-55.
Fire Brick: A Study of Spalling. Raymond M. Howe and Robert F.
Ferguson. Journal of the American Ceramic Society, Vol. 4 (1921),
No. I, pp. 32-46.
Ferroalloys and Steel-Making Metals in 1920. Robert J. Anderson.
The Iron Age, Vol. 107 (1921), No. 1, pp. 73-76.
Fuel Supply of the World. L. P. Breckenridge. Coal Age, Vol. 19
(1921), No. 2, pp. 60-63.
Fuel: Instruments Essential in Saving Fuel in the Gas Industrial Plant.
F. H. Sweet. American Cas Engineering Journal, Vol. 114 (1921),
No. 3, pp. 54, 59.
Fuel Oil. A. F. Baillie. Journal of the Institute of Brewing, Vol.27 (1921),
No. 1, pp. 6-21.
Gasoline by the Charcoal Absorption Process. G. A. Burrell, G. G.
OberfELL and C. L. Voress. Chemical and Metallurgical Engineering,
Vol. 24 (1921), No. 4, pp. 156-160.
Health: Les Mesures d'Hygiene a Prendre dans les Industries du Chlore.
Paul Razous. L'lndustrie Chimique, Vol. 8 (1921), No. 84, pp. 13-14.
Hydrazines: The Preparation of Some Hydrazines. Leonard Thompson.
Journal of the Society of Dyers and Colourisls, Vol. 37 (1921), No. 1, pp.
7-1 1.
Leather: The Determination and Control of Acidity in Tan Liquors. W. R.
Atkin and F. C. Thompson. Journal of the American Leather Chemists
Association, Vol. 16 (1921), No. 1, pp. 9-20. Reprinted from Journal
of the Society of Leather Trades' Chemists, Vol. 4 (1920), 143.
Leather: Iron Tannage. Daniel D. Jackson and Te Pang Hou. Journal
of the American Leather Chemists Association, Vol. 16 (1921), No. 2, pp.
63-75.
Lime Liquors: The Caustic Alkalinity of Lime Liquors. Wtlliam R.
Atkin and John Atkin. Journal of the American Leather Chemists
Association, Vol. 16 (1921), No. 2, pp. 85-93. Reprinted from the
Journal of the Society of Leather Trades' Chemists, Vol. 4 (1920), 236.
Nickel: Black Nickel Solutions. Joseph Haas, Jr. The Metal Industry,
Vol. 19 (1921), No. 1, pp. 23-25.
Paper: Relation of Paper Manufacture to Other Industries. James
Strachan. Paper, Vol. 27 (1921), No. 18, pp. 9, 10, 32.
Pigments: Natural Earth and Chemically Made Pigments and Their Re-
spective Characteristics. E. W. Storey. Paint, Oil and Chemical Re-
view, Vol. 71 (1921), No. 4, pp. 10-11.
Poison Gas: La Produzione dei Gas Asfissianti Impiegati dai Tedeschi in
Guerra. Gino Gallo. Giornale di Chimica Industriale ed Applicate,
Vol. 2 (1920), No. 12, pp. 692-702.
Potash: The Storage and Handling of Potash. G. F. Zimmer. The
Chemical Age (London). Vol. 4 (1921), No. 82, pp. 34-37.
Research: The Organization of Research. William Morton Wheeler.
Science, Vol. 53 (1921), No. 1360, pp. 53-67.
Rock Analysis: Note on Crucibles Used in Rock Analysis. Henry S.
Washington. Journal of the Washington Academy of Sciences, Vol. 11
(1921), No. 1, pp. 9-13.
Rubber: On the Aging of Vulcanized Rubber. O. De Vries and H. J.
Hellendoorn. The India-Rubber Journal, Vol. 61 (1921), No. 2, pp.
23-26.
Sugar: The Analysis of Sugar Mixtures Containing Two Monosaccharides.
C. A. Browne. International Sugar Journal, Vol. 23 (1921), No. 265, pp.
35-38.
Sulfur: Recent Advances in the American Sulfur Industry. Raymond F.
Bacon and Harold S. Davis. Chemical Age, Vol. 29 (1921), No. 1, pp.
24-29.
Teaching Engineering Students to Write. Homer A. Watt. Mining and
Scientific Press, Vol. 122 (1920), No. 6, pp. 192-194.
Water Purification: Epuration Perfectionnee des Eaux pour Chaudieres.
G. Paris. Chimie el Industrie, Vol. 4 (1920), No. 6, pp. 722-730.
Mar., 1921 TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
MARKET REPORT— FEBRUARY, 1921
FIRST-HAND PRICES FOR GOODS IN ORIGINAL PACKAGES PREVAILING IN THE NEW YORK MARKET
279
INORGANIC CHEMICALS
Feb. 1
Acid, Boric, cryst., bbU lb.
Hydrochloric, com'l, 20° lb.
Hydriodic 01.
Nitric, 42° lb.
Phosphoric, 50% tech lb.
Sulfuric, C. P. lb.
Chamber, 66' ton
Oleum 20% ton
Alum, ammonia, lump lb.
Aluminium Sulfate (iron-free) lb.
Ammonium Carbonate, pwd lb.
Ammonium Chloride, gran lb.
Ammonia Water, carboys, 26°. . . .lb.
Arsenic, white lb.
Barium Chloride ton
Nitrate lb.
Barytes, white ton
Bleaching Powd., 35%, Works, 100 lbs
Borax, cryst., bbls lb.
Bromine, tech. lb.
Calcium Chloride, fused ton
Chalk, precipitated, light lb.
China Clay, imported ton
Copper Sulfate 100 lbs.
Feldspar ton
Fuller's Earth 100 lbs
Iodine, resublimed lb.
Lead Acetate, white crystals lb.
Nitrate lb.
Red American 100 lbs.
White American 100 lbs
Lime Acetate 100 lbs
Lithium Carbonate lb.
Magnesium Carbonate. Tech lb.
Magnesite ton
Mercury flask American 75 lbs.
Phosphorus, yellow lb.
Plaster of Paris 100 lbs
Potassium Bichromate lb.
Bromide, Cryst lb
Carbonate, calc, 80-85% lb.
Chlorate, cryst lb.
Hydroxide, 88-92% lb.
Iodide, bulk lb.
Nitrate lb.
Permanganate. U. S. P lb.
Salt Cake, Bulk ton
Silver Nitrate oz.
Soapstone, in bags ton
Soda Ash, 58%, bags 100 lbs
Caustic, 76% 100 lbs.
Sodium Acetate lb
Bicarbonate 100 lbs
Bichromate lb.
Chlorate lb.
Cyanide lb.
Fluoride, technical lb.
Hyposulfite, bbls 108 lbs
Nitrate, 95% 100 lbs
Silicate. 40° lb
Sulfide lb.
Bisulfite, powdered lb.
Strontium Nitrate lb.
Sulfur, flowers 100 lbs.
Crude long ton
Talc, American, white ton
Tin Bichloride lb.
Oxide lb
Zinc Chloride, U. S. P lb.
Oxide, bbls lb.
• 01»/i
.19
.071/.
.20
.07
20.00
23.00
■04'/,
.03'/,
.10
.10
•09s/4
.10
65.00
.14
30.00
3.50
• 07'/,
18.00
6.25
8.00
1.00
4.00
.15
.15
.11'/.
.09i/i
2.00
1.50
.11
72.00
50.00
.35
1.50
• 14'/,
.13
3.00
ORGANIC CHEMICALS
Acetanilide lb.
Add. Acetic, 28 p. c 100 lbs.
Glacial lb
Acetylsalicylic lb.
Benzoic, U. S. P., ex-toluene. .lb.
Carbolic, cryst., U. S. P., drs. . . lb
50- to 110-ib. tins lb
Citric, crystals, bbls lb.
3.25
.10'/,
.Ol'/i
.19
.07V.
.18
.07
20.00
23.00
.04'/,
.03'/,
.10
.10
30.00
3.50
.07'/,
18.00
6.25
8.00
11V.
. 09 V,
2
.00
1
.50
.10
72
.00
50
.00
.35
1
.50
.14'/:
12.00
12.00
2.05
1.90
4.00
3.80
.14'/,
.14'/,
4.00
4.00
2.85
2.75
.01V,
.01'/,
.07
.07
.06
.06
.15
.15
3.50
3.00
20.00
20.00
20.00
20.00
. 19V,
. 19V.
Acid (Concluded)
Oxalic, cryst., bbls lb.
Pyrogallic, resublimed lb.
Salicylic, bulk, U. S. P lb.
Tartaric, crystals, U. S. P lb.
Trichloroacetic, U. S. P lb.
Acetone, drums lb.
Alcohol, denatured, 190 proof gal.
Ethyl, 190 proof gal.
Amyl Acetate gal.
Camphor, Jap. refined lb.
Carbon Bisulfide lb.
Tetrachloride lb.
Chloroform, U. S. P lb.
Creosote, U. S. P lb.
Cresol, U. S. P lb.
Dextrin, corn 100 lbs.
Imported Potato lb.
Ether, U. S. P., cone, 100 lbs lb.
Formaldehyde lb.
Glycerol, dynamite, drums lb.
Methanol gal.
Pyridine gal.
Starch, corn 100 lbs.
Potato, Jap lb.
Rice lb.
Sago lb.
.37 "
.35
4.40
4.40
.13'/,
. 13'/,
.67
.63
5.00
5.00
3.75
3.75
.08'/,
.18
3.55
1.65
1.65
2.75
2.75
2.65
2. 65
OILS, WAXES, ETC.
Beeswax, pure, white lb.
Black Mineral Oil, 29 gravity gal.
Castor Oil, No. 3 lb.
Ceresin, yellow lb.
Com Oil, crude lb.
Cottonseed Oil, crude, f. o. b. mill. .lb.
Linseed Oil, raw gal.
Menhaden Oil, crude (southern), .gal.
Neat's-foot Oil, 20' gal.
ParaflBn, 128-130 m. p., ref lb.
Paraffin Oil, high viscosity gal.
Rosin, "F" Grade, 280 lbs bbl.
Rosin Oil, first run gal.
Shellac. T. N lb.
Spermaceti, cake lb.
Sperm Oil, bleached winter, 38°. . . gal.
Stearic Acid, double-pressed lb.
Tallow Oil, acidless gal.
Tar Oil, distilled gal.
Turpentine, spirits of gal.
Aluminium, No. 1, ingots lb.
Antimony, ordinary 100 lbs.
Bismuth lb.
Copper, electrolytic lb.
Lake lb.
Lead, N. Y lb.
Nickel, electrolytic lb.
Platinum, refined, soft oz.
Quicksilver, flask Amer 75 lbs ea.
Silver oz
Tin lb
Tungsten Wolframite per unit
Zinc, N. Y 100 lbs.
Ammonium Sulfate export. .. 1^0 lbs.
Blood, dried, f. o. b. N. Y unit
Bone, 3 and 50, ground, raw ton
Calcium Cyanamide, unit of Am-
monia
Fish Scrap, domestic, dried, f. o. b.
works unit
Phosphate Rock, f. o. b. mine:
Florida Pebble, 68% ton
Tennessee, 78-80% ton
Potassium Muriate, 80% unit
Pyrites, furnace size, imported. . . . unit
Tankage, high-grade, f. o b
Chicago unit
.09'/,
.05'/,
.73
.13'/,
1.73
. 12'/,
.92
.92
5.25
5.25
2.40
2.50
.13
. 13'/.
.12»/«
.13
.04>/<
,04»/<
.45
.43
65.00
65.00
50.00
50.00
.59'/,
.59'/,
.33'/,
33 V,
6.50
6.50
5.50
5.50
EBIALS
3.25
3.23
5.10
5.10
45.00
45.00
4.50
4.50
5.00
5.00
6.85
6.83
11.00
11.00
1.60
1.50
280
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 3
COAL-TAB CHEMICALS
Feb. 1
Crudea
Anthracene, 80-85% lb. .79
Benzene. Pure gal. . 30
Cresol. U S P lb. .18
Cresylic Acid, 97-99% gal. .90
Naphthalene, flake lb. .08
Phenol, drums lb. .093/<
Toluene, Pure gal. .30
Xylene, 2 deg dist. range gal. .60
Intermediates
Acids:
Anthranilic lb. 2.20
B lb 2.25
Benzoic lb. 70
Broenner's lb. 1 . 75
Cleves lb. 2.00
Gamma lb. 3.75
H lb. 1.25
Metanilic lb. 1.60
Monosulfonic F lb. 3.25
Napthionic crude lb. .85
Nevile S: Winthers lb. 1.60
Phthalic lb .60
Picric lb. .25
Sullanilic lb. .33
Tobias lb. 2.. '5
Aminoazobenzene lb. 1.25
Aniline Oil lb .21
For Red lb .42
Aniline Salt lb .28
Anthraquinone lb. 2.00
Benzaldehyde, tech lb. .45
U S P lb 1.00
Benzidine (Base) lb. 1.00
Benzidine Sulfate lb. .80
Diaminophenol lb. 5.50
Dianisidine lb 6.00
<>-Dielilorobenzene lb .15
Diethylaniline lb 1 .40
Dimethylaniline lb. .55
Dinilroben/ene lb. .25
Dinitrotoluene lb. .28
Diphenylamine lb. .60
G Salt lb .80
Hydroquinol lb. 1 .80
Metol (Ruodol) lb 6.75
Monochlorobenzene lb. .14
Monoethylaniline lb. 2. 15
fl-Naphthylamine lb .43
i-Naphthylamine (Sublimed) lb. 2.25
6-Naphthol, dist lb. .36
m-Nitroaniline lb. .90
0-Nitroaniline lb. 1 .00
Nitrobenzene, crude lb. .14
Rectified (Oil Mirbane) lb . .16
p-Nitrophenol lb. .80
0-Nitrosodimethylaniline lb. 2 . 90
o-Nitrotoluene lb. .25
0-Nitrotoluene lb. .90
m-Phenylenediamine lb. 1 . 15
P-Phenylenediamine lb. 1 . 75
Phthalic Anhydride lb. .65
Primuline (Base) lb 3.00
R Salt lb. .85
Resorcinol. tech lb. 2.00
U. S P lb. 2.25
Schaefler Salt lb. .75
Sodium Naphthionate lb. 1 . 10
Thiocarbanilide lb. .60
Tolidine (Base) lb. 1.40
Toluidine, mixed lb. .44
o-Toluidine lb. .27
m-Toluylenediamine lb. 1.15
f-Toluidine lb. 1.25
Xylidine, crude lb. .45
COAL-TAB COLOBS
Acid Colon
Black lb. 1.00
Blue lb. 1.50
.09>A
2.20
2.25
.70
1.75
2.00
3.75
1.20
1.60
3.25
.85
1 .60
2.25
1.25
.4S
l."0
1.00
.80
5.5)
6.00
IS
1.40
1.70
6.75
.14
2.15
.38
2.25
1.00
.14
.16
1.15
1.75
1. 00
1.50
Acid Colors [Concluded)
Fuchsia lb.
Orange III lb.
Red lb.
Violet I0B lb.
Alkali Blue, domestic lb.
Imported lb.
Azo Carmine lb.
Azo Yellow lb.
Ery throsin lb.
Indigotin. cone lb.
Paste lb.
Naphthol Green lb.
Ponceau lb.
Scarlet 2R lb.
Direct Colors
Black lb.
Blue ?B lb.
Brown R lb.
Fast Red lb.
Yellow lb.
Violet, cone lb.
Chrysophenine. domestic lb.
Congo Red. 4B Type lb.
Primuline, domestic lb.
Oil Colors
Black lb.
Blue lb.
Orange lb.
Kcd III lb.
Scarlet lb
Yellow lb.
Nigrosine Oil. soluble lb.
Sulfur Colors
Black lb.
Blue, domestic lb.
Brown lb
Green lb.
Yellow lb.
Chrome Colors
Alizarin Blue bright lb.
Alizarin Red 20% Paste lb.
Alizarin Yellow G lb.
Chrome Black, domestic lb.
Imported lb.
Chrome Blue lb.
Chrome Green, domestic lb.
Chrome Red lb.
Galloey.ii] in lb.
Basic Colors
Auramine, O. domestic lb.
Auramine, OO lb.
Bismarck Brown R lb.
Bismarck Brown G lb.
Chrysoidine R lb.
Chrysoidine Y lb.
Green Crystals, Brilliant lb.
Indigo. 20 p c. paste lb.
Fuchsin Crystals, domestic lb.
Imported lb.
Magenta Acid, domestic lb.
Malachite Green, crystals lb.
Methylene Blue, tech lb
Methyl Violet 3 B lb.
Nigrosine, spts. sol lb.
Water sol., blue lb.
Jet lb.
Phosphine G. , domestic lb.
Rbodamine B extra cone lb.
Victoria Blue, base, domestic lb.
Victoria Green lb
Victoria Red lb.
Victoria Yellow lb.
Feb. 1
Feb. 15
2.50
2.50
.60
.60
1.30
1.30
6.50
6.50
6.00
6.00
8.00
8.00
4.00
4.00
2.00
2.00
7.50
7.50
2.50
2.50
1.50
1.50
1.95
1.95
1.00
1.00
1.65
1 .65
2.35
2.35
2.00
2 CO
1.10
1.10
2.00
2.00
.90
.90
3.00
3.00
.70
.70
1.25
1.25
1.40
1.40
1.65
1 .65
1.00
1 00
1.25
1.25
5.00
5.00
1 .10
1 .10
1 .00
1.00
1 .25
1.25
2.20
2.20
1.00
1.00
1.50
1.50
2.00
2.00
2 80
2.80
2.50
4.15
2.50
4.15
4.50
4.50
12.00
12.00
4.25
4.25
3.25
3.25
2.75
2.75
2.75
2.75
7.00
7.00
17.00
17.00
6.00
6.00
2.50
2.50
7.00
7.00
7.00
7 00
The Journal of
Published Monthly by The American Chemical Society
Advisory Board: H. E. Barnard
Chas. L. Reese
Editorial Offices:
One Madison Avenue, Room 343
New York City
Telephone: Gramercy 0613-0614
Editor: CHAS. H. HERTY
Assistant Editor: Lois W. Woodford
J. W. Beckman A. D. Little a. V. H. Mory
Geo. D. Rosengarten T. B. Wagner
Cable Address: JIECHEM
Advertising Department:
170 Metropolitan Tower
New York City
Telephone: Gramercy 3880
Volume 13
APRIL 1, 1921
No. 4
CONTENTS
Editorials:
On to Rochester 282
Echoes from the 60th Congress 282
Specific Facts 283
Death of Lord Moulton 284
The Chemical Industry and Trade of Switzerland.
O. P. Hopkins 285
Original Papers:
An Application of the Vapor Pressures of Potassium
Compounds to the Study of the Recovery of Potash
by Volatilization. Daniel D. Jackson and Jerome
J. Morgan 292
Possible Uses of Corncob Cellulose in the Explosives
Industry. L. G. Marsh 296
Some Interpretations of the Ammonia Synthesis
Equilibrium. R. S. Tour 298
The Production of Artificially Dense Charcoal. L. F.
Hawley 301
The Melting Point of Ammonium Sulfate. James
Kendall and Arthur W. Davidson 303
Rapid Dry Combustion Method for the Simultaneous
Determination of Soil Organic Matter and Organic
Carbon. J. W. Read 305
Studies on the Nitrotoluenes. VI — The Three-Com-
ponent System: o-Nitrotoluene, ^-Nitrotoluene,
1,2,4-Dinitrotoluene. James M. Bell and Edward
B. Cordon 307
Studies on the Nitrotoluenes. VII — The Three-Com-
ponent System: ^-Nitrotoluene, o-Nitrotoluene,
1,2,4,6-Trinitrotoluene. James M. Bell and
Fletcher H. Spry 308
The Anilides of /3-Oxynaphthoic Acid. E. R. Bruns-
kill 309
The Non-Biological Oxidation of Elementary Sulfur
in Quartz Media. W. H. Maclntire, F. J. Gray and
W. M. Shaw 310
The Melting Point of Diphenylamine. Homer Rogers,
W. C. Holmes and W. L. Lindsay 314
The Activity of Phytase as Determined by the Specific
Conductivity of Phytin-Phytase Solutions. F. A.
Collatz and C. H. Bailey 317
Studies of Wheat Flour Grades. I — Electrical Con-
ductivity of Water Extracts. C. H. Bailey and F.
A. Collatz 319
The Rate of Evaporation of Ethyl Chloride from Oils.
Charles Baskerville and Myron Hirsh
Boron in Relation to the Fertilizer Industry. J. E-
Breckenridge
Determination of Chlorides in Petroleum. Ralph R.
Matthews
Laboratory and Plant:
Humidity Control by Means of Sulfuric Acid Solutions,
with Critical Compilation of Vapor Pressure Data.
Robert E. Wilson
Notes on Laboratory and Demonstration Apparatus.
Clifford D. Carpenter
Solvents for Phosgene. Charles Baskerville and P. W.
Cohen
Addresses and Contributed Articles:
Studies on the Chemistry of Cellulose. I — The Con-
stitution of Cellulose. Harold Hibbert
Combustion Smokes. Geo. A. Richter
322
324
325
326
332
333
334
343
Research Problems in Colloid Chemistry.
Bancroft
Wilder D.
352
Scientific Societies:
Rochester Ready for Chemical Cohorts; Philadelphia
College of Pharmacy Celebrates One Hundredth
Anniversary; New York Chemists' Club Confers
Honorary Membership; Colloid Development;
Calendar of Meetings
Notes and Correspondence:
Note on the Use of Potassium Permanganate in the
Determination of Nitrogen by the Kjeldahl Method;
The Formation of Anthracene from Ethylene and
Benzene — Correction; The Estimation of Cellulose
in Wood; Phthalic Anhydride Derivatives; A
Memorial of Sir William Ramsay 358
Washington Letter 364
London Letter 365
Paris Letter 366
Industrial Notes 367
Personal Notes 308
Government Publications ." ; ' ; \ »
Book Reviews 372
New Publications. 374
Market Report 375
Subscription to non-members, $7.50; single copy, 75 cents, to members, 60 cents. Foreign postage, 75 cents, Canada, Cuba and Mexico excepted.
Subscriptions and claims for lost copies should be referred to Charles L. Parsons, Secretary, 1709 G Street, N. W., Washington, D. C.
282
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. i
EDITORIALS
On to Rochester !
Those who attended the meeting of the American
Chemical Society at Rochester in 1913 have carried
with them constantly memories of a delightful week
of intellectual stimulation and charming hospitality.
That opportunity is soon to present itself again,
for the 1921 Spring Meeting will be held during the
week of April 25 to 29, with the Rochester Section
acting as host.
During the intervening eight years that Section
has increased largely in numbers and has justly earned
the reputation of being one of the most flourishing
of our Local Sections. Its members are determined
to add fresh laurels to the record of 1913 by provid-
ing a program of scientific and social activities which
insures a memorable meeting.
It is particularly appropriate that those attending
are to have the pleasure of learning to know personally
Senator James W. Wadsworth, Jr., and Congressman
Nicholas Longworth, for each of these distinguished
members of Congress has heartily worked for legisla-
tion affecting chemistry. Then, too, a treat awaits
us in the public address of that venerable youth, Dr.
Charles F. Chandler.
Even the railroads have given things a boost by
offering round trip rates at one fare and a half on the
certificate plan. (See preliminary program for details.)
Times are quiet in a business way. Let's take ad-
vantage of the opportunity to assemble for common
counsel in preparation for the active days which all
are confident lie just ahead.
Echoes from the 66th Congress
The 66th Congress has adjourned, sine die. Look-
ing back over its history a remarkable picture pre-
sents itself. With Republican majorities in both
Senate and House, that Congress stood logically
committed to the policy of protection of home indus-
tries. At its initial session bills were introduced
whose object was the effective safeguarding of a num-
ber of chemical and allied industries — dyes, chemical
glassware and porcelain, scientific instruments, pot-
ash, magnesite, tungsten, etc. As the work of the
Congress developed it was plainly evident that the
prevailing sentiment was strongly in favor of these
bills, yet not one of them was enacted into law. We
missed our guess; the Senate didn't pass the dye bill.
The unceasing opposition of Senators Moses and
Thomas to the dye bill has been discussed in these
columns at length; Senator Penrose frankly and
publicly announced his opposition to the whole group
of bills on the ground that they were "pop gun bills."
However, the record of Senator Penrose on the farmers'
emergency tariff bill suggests that in the 67th Con-
gress he owes very active and vigorous support of pro-
tective measures for the chemical and allied industries
if he believes in protection as a matter of principle
rather than of policy, and we believe he does.
The failure of one other measure must bring regret to
all interested in our industrial development, namely,
the bill providing relief for the Patent Office. Here,
again, was a case where a great majority favored the
legislation, but the bill was strangled by a rider which
incorporated the feature of giving to the Federal
Trade Commission the right to receive assignments
of patents, and the power to administer them, includ-
ing the regulation of royalties. The American
Chemical Society protested in vain against this
doubling up. The Senate refused to adopt the report
of the Conference Committee and the Patent Office
is still without relief.
In the next Congress these bills bearing on patent
questions will again be introduced, presumably as
separate bills. If so, the bill giving the Federal Trade
Commission, or any other governmental agency, the
powers above referred to should be vigorously opposed;
for it is contrary to the spirit of the times, it will result
in the gradual accumulation of two distinct classes of
patents — the one owned by individuals, the other by
the government, and in legislation over conflicting
patents endless confusion will be brought, stimulation
of individual invention will be handicapped, and the
public, which is the ultimate beneficiary under the
whole idea of our patent system, will be the loser.
There will be no difference of opinion about a bill
providing for the relief of the Patent Office. The
crippling of its staff during past years and the steady
decrease in the efficiency of the service it can render
appeal to all as justifying a prompt remedy. The
difficulties just experienced in getting this relief sug-
gest that still more fundamental legislation in its be-
half should be enacted. At present the Patent Office
occupies an anomalous position; it is a subdivision of an
executive department, whereas its functions are purely
judicial. An appeal from the decision of the Com-
missioner of Patents does not go to the Secretary of
the Interior Department, but to the courts. The
salary of the Commissioner is now determined by that
prevailing for bureau chiefs, whereas the Commissioner
should be essentially a man of judicial training, re-
ceiving the higher salary comparable with that of
other judges. From the fees paid in past years.
which go direct to the Treasury of the United States,
approximately $8,000,000 more has been received
than has been expended by Congressional appropria-
tion on the Patent Office. Why should the patentee
of a new chemical process or compound pay fees to
the Government to aid in maintaining the marines in
Haiti or decreasing the postal deficit, while he is un-
able to secure desired copies or reproductions of foreign
chemical patents because the Congressional appropria-
tion for that purpose is exhausted?
Applicants for patents desire service, the best service
obtainable. They are willing to pay for it. If neces-
sary let the fees be increased, but let them go direct
to the maintenance of the Patent Office at the highest
possible state of efficiency.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
283
Specific Facts
Much has been said, much has been written within
the last two years about the use of the dye plants of
Germany as the source of her supply of poison gas dur-
ing the war. The significance of this fact has not yet
been grasped by the average citizen. We believe this
is due to the use of only general terms in discussing
the matter. Specific information seems to be required
to drive the thought home. For this reason, there is
reproduced here a most illuminating document.1
Report of the British Mission Appointed to Visit Enemy
Chemical Factories in the Occupied Zone Engaged
in the Production of Munitions of War
Members of the British Mission:
Brig. Gen. H. Hartley. C. O. W. D
Mr. F. H. Carr.
Capt. A. C. G. Egerton.
Lieut. H. G. Greenwood.
Dr. H. Levenstein.
Mr. W. Macnab.
Mr. A. W. Tangye.
Mr. S. I. Levy, Secretary.
Delegates of allied Goi
British zone:
ts who ;
Lieut. Col. C. W. Steese, O. D„ U. S. Army.
Lieut. Col. J. F. Morris, C W. S , U. S. Army.
Maj. T. W. Sill, C. W. S., U. S. Army.
Capt. R. D. McGrath, C W. S„ U. S. Army.
Capt. J, W. Martin, Ord., U. S. Army.
Lieut. H. J. Himmelein, R. D., U. S. Army.
French —
Col. M. Marqueyrol (direction des Poudres).
Comm. M. Chaud.
Mons. T. Sordes.
Mons. N. Simon.
Italian —
Capt. C. Mazetti.
Lieut. I. Cardoso.
Lieut. M. Malvano.
Sig. M. Bonelli.
Sig. M. Piersel.
Belgian—
Capt. M. Janlet.
The usual procedure was first to have a general view of a
factory in order to get an idea of its lay-out and prewar capacity,
and of the way in which this had been utilized and extended
for war purposes. Afterwards the mission divided into three
sections in order to get details of the war productions, as follows:
Initial products (e. g., sulphuric acid, nitric acid, ammonia, chlorine,
caustic soda): Mr. Tangye, Lieut. Greenwood, Capt. Egerton.
Explosives: Mr. Macnab. Mr. Levy.
Poison gas: Mr. Levinstein, Mr. Carr.
The information obtained by each section has been embodied
in the present report.
In some cases considerable difficulty was experienced in ob-
taining accurate details of manufacture, especially as regards
substances which have a peace value, and the information must
be accepted with some reserve on this account, although it was
checked by cross-examination of the officials concerned and by
a careful examination of the plant admittedly employed for
war purposes.
As a result of its visit, the mission had obtained valuable in-
formation as to the methods of manufacture of explosives and
poison gases employed by the enemy, and of the initial prod-
ucts necessary for their production. It was also able to form a
clear impression of the military value of the German chemical
industry.
Some years before the war, a combination was formed by the
Bayer, Badische and A. G. F. A. companies and somewhat
later a second group was formed which included Meister Lucius &
1 Reprinted from the Hearings before the Committee on Ways and
Means, House of Representatives, on H. R. 2706 (the original number of
the Longworth bill for the protection of the coal-tar chemical industry),
pages 210-214.
Bruning, Casella & Kalle. During the war, these two groups
amalgamated, and the Griesheim Elektron, Weiler ter Meer,
Leonhardt, and other smaller companies, entered the combina-
tion, which is known as the I. G. It was largely owing to the
efforts of this combination that Germany was enabled to con-
tinue the war in spite of the blockade. The I. G. works pro-
duced the bulk of the synthetic ammonia and nitric acid needed
for the production of fertilizers and explosives, all the poison
gas (with the exception of some chlorine and phosgene), and a
large proportion of the high explosives.
The following are the more important works of the I. G.
which were not visited, as they are outside the occupied zone :
Factories of the Aktien Gesellschaft fur Anilinfabritation.
Factories of the Griesheim Elektron Gesellschaft
Factory of the Bayer Co. at Elberfeld.
Factory of the Badische Co. at Merseburg.
Factory of Casella & Co., Mainkur, near Frankfurt.
Factory of Leonhardt & Co., Mulheim, near Frankfurt.
A summary of the information obtained as to the war produc-
tion of the factories visited is given under the headings of "Initial
products," "Explosives and poison gases."
INITIAL PRODUCTS FOR MANUFACTURE OF EXPLOSIVES AND
POISON GAS.
The principal materials concerned are ammonia, nitric acid,
sulphuric acid, and chlorine, and it was on the output of these
that the war production of chemical munitions depended. The
expansion of output by the factories of the I. G. combination
during the war is shown by the following tables:
Ammonia (metric tons \'fh per day).
1914 1918
Oppau 25 250
Merseburg (1) 400
Total 25 650
■ Nil.
Nitric acid (metric tons 100 per
1914 1918
Leverkusen 56 180
Hochst 150 375
Oppau ? 100
Ludwigshafen 40 (?) 40
Weiler ter Meer 12 24
Total 258 719
Oppau has the power to produce now 500 tons HNO3 daily,
still retaining sufficient ammonia to supply the output at Hochst.
Sulphuric aiiJ [metric Ions 100 per cent acid per day).
1914 1918
Leverkusen 340 470
Hochst 224 280
Ludwigshafen 27o 410
Weiler ter Meer 48 00
Total S*i7 122U
Meister Lucius & Bruning have also erected a large new plant
at Hochst which has not yet started and was not examined.
The Bayer Co. has erected at Dormagen a large vitriol plant
equal to 250 tons per day.
Chlorine [metrii Ion', per day).
1914 1918
Leverkusen 7 20
Hochst I 8
Ludwigshafen 13 35
Total 37 63
Explosives. — Xo arrangements appear to have been made
prior to the outbreak of war to utilize the resources of any of
the dye factories for war purposes, and on mobilization their
chemists were called up for military service. After the battle
of the Marne the Government realized the need for expanding
the output of explosives and most of the chemical works were
producing small quantities by the end of 1914. The demands
made on them increased during 1915, but it was not until 1916
that plant was laid down to assist in the enormous production
of explosives required by the Hindenburg program. .Most of
the big extensions of the synthetic ammonia and of the nitric
and sulphuric acid plants date from this time, many chemists
being released from the army and the scientific stall' of some of
the works being augmented. Standardized plant used for the
manufacture of dyes was converted for the production of ex-
plosives with remarkable speed; for instance, at Leverkusen a
T. N. T. plant producing 250 tons per month was put into opera-
tion in six weeks.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
The following table shows the amounts produced in the fac-
tories visited:
High explosives and intermediates.
Quantities of intermediates are shown only where these were not con-
verted to finished explosives in the producing works.
[Metric tons per week.]
■a 5« -g-i
1 1! !J
■ - .5 >. * ~
H - =
E-
Factory
Leverkusen. . - 250 .. 150 40 .. .
Domagen 600
tjrdingen Wl ... 75 (=)
Hochst 500 140 ... 200 30 .. >1'A
L u d w i g s-
hafen 25 50 IS 300 35 25* ...
Oppau 200
Merseburg... (?)
Wiesdorf 120
Schlebusch.. 100 150
1 For 3 months only. 2 Small. 3 For 1 year.
Other intermediates — Ludwigshafen, sodium benzene sulphonate. 100
tons per week.
Other explosives — Schlebusch. hexanitrodiphenylsulphide, 15 tons per
week
Poison gas. — At first chlorine and phosgene were the main
requirements, but afterwards a variety of organic substances
were employed, all of which were made by the factories of the
I. G. combination. Many of these substances were new and
difficult to prepare, and rapid production was only possible
owing to the speed with which the peace organization of the dye
factories could be utilized for this purpose. When the Govern-
ment wished to introduce a new gas, a conference of the various
firms was held at Berlin to determine how the manufacture
should be subdivided in order to use existing plants to the best
advantage. For instance, the initial stages of the manufac-
ture of mustard gas were carried out at Ludwigshafen and the
final stage at Leverkusen.
The following table shows the production of gas and inter-
mediate products in the various factories visited:
Propellant explosives, detonating substances, etc,
(Metric tons per week.]
Nitro- Di-
cellu- ethyl di- Di- Nitro- Cor-
lose phenyl- phenyl glycer- dite Dyna- Tet-
Factory powder.
Urdingen
Kupperste,:
Troisdorf - i
Schlebusch
Opladen
Wiesdorf
35
(?)50
paste, mite, ryl.
41'
Ful-
min- Lead
ate. azide
Output of finished poison gases from various works.
Monthly output Total
(metric tons)1, produc-
. ■ . tion (if
Aver- Max- known). Date of
Factory age. imum. Tons, commencement.
1. Chlorine. . . . Leverkusen 600 ... .... Prior to war.
Hochst 240 Do
Ludwigshafen 860 1,261 38.600 Do.
2. Phosgene... . Leverkusen 30 Do.
Ludwigshafen 28S 621 10,682 Do.
3. Diphosgene.. Leverkusen . . . 300 June, 1915.
Hochst 139 266 3.616 September, 1918
4. Chlorpicrin.. Leverkusen . . . 200 .... July, 1916.
Hochst 45 101 1,127 August, 1916.
5. Xylyl bro-
mide Leverkusen ... 60 .... March, 1915.
6. Bromacetone do ... 20 .... July, 1916.
7. Brom ace-
tone, brom-
ethylmethyl-
ketone Hochst 19 45 685 April, 1915.
8 Phenyl car-
bylamine
chloride... do 65 124 721 March, 1917.
9. Mustard gas. Leverkusen ... 300 4.5001 Before Julv, 1917
10. Diphenvl-
chlor arsine Hochst 150 300 3.000 May, 1917.
Diphenyl-
cyano
arsine do February, 1918.
11. Ethyldichlor
arsine do 78 150 1,092 August, 1917.
12. Dichlor-
methyl.... do 26
13. Dibrom
methyl
ether do 7 29 69 April, 1917.
1 Estimated from capacity of plant. Probably the same quantity was
produced at some other factory as the output of thiodiglycol from Ludwigs-
hafen would suffice for this.
233 September, 1917
Output of Intermediate Products for Poison Gas Manufacture.
Total Destina-
output tion of
Intermediate (metric Place of intermediate
Finished gas. products. tons), production. products.
Phenylcarbylamine. . Phenyl mustard oil (') Kalle Hochst
Mustard gas Thiodiglycol 7.026 Ludwigshafen Leverkusen
and 1 other
factory.
Diphenylchlorarsine. Phenyl arsinic acid 1,600 do. Unknown.
1.200 Kalle Do
Diphenylar s e n i c
acid 4.800 Leverkusen Probablv
A. G. I"
A., Berlin.
Ethvldichlorarsine Ethvl arsenious ox-
ide 840 Ludwigshafen Hochst
1 Not obtained.
Note. — In addition Hochst produced 3,000 tons of diphenyl chlor-
and cyanarsines from own intermediates.
MILITARY IMPORTANCE OF THE GERMAN CHEMICAL INDUSTRY.
The above figures for the output of explosives and gas show
the great military value of the factories of the I. G combina-
tion. Although no arrangements had been made to mobilize
them at the outbreak of hostilities, they were rapidly converted
to war purposes, thanks to their highly trained personnel and
the great technical resources of their peace organization. In
the future it is clear that every chemical factory must be re-
garded as a potential arsenal, and other nations can not there-
fore submit to the domination of certain sections of chemical
industry which Germany exercised before the war. For mili-
tary security it is essential that each country should have its
chemical industry firmly established, and this must be secured
as one of the conditions of peace, as otherwise we are leaving
Germany in possession of a weapon which will be a permanent
menace to the peace of the world.
The key to Germany's war production of explosives was the
Haber process for the production of ammonia from atmospheric
nitrogen. It is significant that large scale production by this
process only began at the end of 1912, and that in the early part
of 1914 great pressure was put on the Badische Co. to increase
its output. During the war, owing to the extension of the Haber
plants at Oppau and Merseburg, Germany has become inde-
pendent of foreign countries for her supplies of ammonia and
nitric acid, substances indispensable for the manufacture not
only of high explosives but also of fertilizers for food produc-
tion. Without such a process Germany could not have made
the nitric acid required for her explosives programme, nor ob-
tained fertilizers for food production after the supply of Chile
saltpeter had been stopped by our blockade, and it is probable
that she could not have continued the war after 1916. In the
event of another war we might be cut off from supplies of saltpeter.
The resources of the German dye industry are of no less mili-
tary importance. Most of the gases employed toward the end
of the war were complex organic substances, none of which had
been made previously except in small quantities, and some of
which were prepared for the first time during the war. Gas
warfare will undoubtedly continue to develop in this direction,
and in the future organic substances will be employed which we
do not know to-day. The use of gas will always offer great
opportunities for surprise in military operations, and the ex-
periences of the present war has shown that rapid production
of a new gas is essential if the surprise is to be effective. Any
country without a well-developed organic chemical industry
will be severely handicapped in this respect.
H. Hartley,
Brigadier General,
On Behalf of the Members of the Mission.
London, February 26, 1919.
Death of Lord Moulton
On March 9, 1921 Lord Moulton, the head of
British Dyes, Ltd., and President of the Association
of British Chemical Manufacturers, died suddenly at
his residence, Onslow Square, London. Throughout
the critical war period he performed an inestimable
public service through his work as Chairman of the
Advisory Committee on Chemical Products and the
Committee on High Explosives. After the war his
talents were unselfishly and intensely devoted to the
permanent establishment of the British dye industry.
His guiding principle was the gospel of "work and still
more work."
Apr.. 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
285
THE CHEMICAL INDUSTRY AND TRADE OF SWITZERLAND
By O. P. Hopkins
182-1 BEUIONT Road, Washington. D. C.
The war placed Switzerland in a most trying and in Switzerland, and a fair share of the credit for the
delicate position. Always in danger of being forced development of this industry is not always given the
into the conflict, she found herself hard pressed for Swiss chemist. The early and successful start is
favors from both sides, and equally hard pressed to usually attributed to the excellent technical training
find sufficient food and fuel for her own people. Some afforded, to the steady domestic demand for high-
industries, especially those engaged on luxuries, suffered class colors, and to the fact that no patent laws affect-
from foreign import restrictions, while the great textile ing chemicals were in force in Switzerland previous to
industry was deprived of raw materials by foreign export 1908, a circumstance favoring the use of foreign patents
restrictions. She is alive to tell the tale, however, and without restriction. At any rate, the production of the
in most ways better off than her belligerent neighbors. best class of dyes increased steadily until an export trade
A number of her industries were helped by the war. of more than $5,000,000 was recorded in 1913, the
The high price of her money is at once an indication of year before the war began. As far back as 1890 the
her economic strength and a handicap in the marketing exports were valued at $2,600,000. It is understood
of her goods. Nine-tenths of the pessimism in Swiss that the exports amount to more than 80 per cent of
trade is based on this exchange difficulty. the production and that the lower-priced staple dyes
Although the majority of the inhabitants are engaged do not figure prominently in the trade,
in agricultural pursuits, Switzerland is known abroad When the German dyes were excluded from the
for its manufacturing industries, the products of which world markets the Swiss makers found it impossible
are largely exported, whereas agriculture supplies to meet the demands made upon them. They were
only a part of the country's needs. These industries n°t abIe to maintain their pre-war exports so far as
are unique in that they depend almost wholly upon quantity was concerned, as there were difficulties in
imported raw materials. The more valuable exports getting supplies of intermediates and also difficulties in
in normal times are embroideries and cotton goods, silk delivering the finished products. But prices rose rapidly
goods, watches and clocks, machinery, ready-made and the makers profited. Previous to the war the
clothing, timber, woolen goods, chemicals, cheese, con- industry relied largely upon intermediates from Ger-
densed milk, and chocolate. Swiss milk is used in the many, but these supplies were cut off, and the dye
manufacture of cheese, condensed milk, and chocolate, plants were obliged to undertake the manufacture of
some of the chemicals are based upon domestic supplies intermediates from crudes supplied by Austria, Eng
of salt, lime, and asphalt, and the timber is home land. Germany, France, and even the United States, a
grown, but the great bulk of manufactured goods is very close cooperation being worked out with the
made entirely of imported materials. They are mainly English for an exchange of crudes for finished dyes,
highly finished goods that sell on a quality basis in the The demand did not fall off when hostilities ceased,
most "competitive markets. All of which is a tribute the productive capacity has been greatly increased
to the skill of the Swiss workman, the excellence of since that time, and the deliveries of raw materials
the country's technical training, and the intelligence have been satisfactory, so that the value of the export
of the Swiss manufacturer trade has reached a rather remarkable figure. In
Whatever may have been the effects of the war on 1918, the last year of the war, the value of exports
other industries, there is no disputing the fact that the was given as $18,900,000. In 1919 the value had
chemical industries as a whole were benefited, particu- "sen to $26,000,000, although the quantity was still
larly the dye and electrochemical branches. Accord- slightly below the figure for 1913. Figures for the full
ing to the census of 1911, there were at that time 197 year 1920 are not available, but estimating the total at
enterprises engaged in the manufacture of chemicals, twice the value of the exports for the first six months,
employing 8692 workers. In 1918 there were 270 we arrive at the impressive sum of $44,500,000. The
concerns, employing 17,764 workers. Before the war quantity exported, estimated in the same manner, was
the exports of chemicals (nearly 90 percent of the pro- 25,9-77,000 lbs., an increase of 8,107,000 lbs. over 1919
duction is exported) were roughly valued at $20,000,000, a"d of 6,518,000 lbs. over 1913. The development ot
about one-fourth of which were dyes. During the the export trade in dyes has been as follows:
first six months of 1920 the value of chemical exports ar QPoundsV Value
reached the imposing total of $30,000,000, of which 1S90 5,417,000 $2,700,000
., ,f. , , ,„, , • , 1913 19,459,000 5,500,000
more than two-thirds were dyes. ( these are chemicals 1918.... .. 12,939.000 18,900,000
in the 'stricter sense of the word and do not include 1920!!!! '.'.'.'. mII^mo' ^soo.ooo'
many allied products.) Whereas the chemical ex- ' Twice the total for the 6rst six months.
ports ranked about ninth before the war, they now rank Thg increasing activity of the Swiss exporters has
third, judging from the incomplete 1920 returns. cauged nQ Hule discussion in this country. It is
the dye industry felt by some that German dyes and Swiss dyes made
Coal-tar dyes were manufactured at an early date from German or Austrian materials are coming in
286
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
from Switzerland that would be excluded by the War
Trade Board if properly described. It is rather diffi-
cult to get at the facts. That no coal is mined in
Switzerland is well known. Facilities for the distilla-
tion of coal tar recovered at gas plants have recently
been created, but no statistics of production are avail-
able. The bulk of the crudes are imported, and some of
the intermediates. In 1919, under the heading of aniline,
aniline oil, and aniline compounds for the manufacture of
dyes, the total imports were only 1,756,000 lbs., of which
84 per cent were from England, 9 per cent from Germany,
and smaller percentages from France and the United
States. (These statistics are from official Swiss
returns, which are considered reliable.) In 1918, a
war year, about 4,000,000 lbs. were imported, of which
only 7000 lbs. were attributed to Germany. The
imports of aniline intermediates for the first six months
of 1920 were much heavier, however — 4,600,000 lbs.,
or at the rate of more than 9,000,000 lbs. for the year.
Germany's share for the first six months was 172,620 lbs.
But the Swiss dye makers now rely largely upon
crudes rather than upon intermediates, and the sta-
tistics show that in 1919 the imports of such crudes,
given as "coal-tar derivatives for the manufacture of
dyes" in the Swiss statistics,1 amounted to 5,291,000
lbs., of which England supplied 29, France 28, Germany
27, Austria 15, and the United States about 1 per cent.
It is obvious, however, that the imports of crudes in 1919
are not large enough to account for the exports of nearly
18,000,000 lbs. of dyes, including indigo; so, in the
hope of shedding more light on the subject, suppose
we lump together the imports of such crudes for 1916,
1917, 1918, and 1919. The total for these years
is 49,000,000 lbs., of which Austria supplied 47 per
cent and Germany 19 per cent, the rest coming from
England, France, and the United States. The largest
imports are recorded for 1916, when Austria supplied
the bulk of the purchases. For the first six months
of 1920, the imports of such crudes were 6,808,000
lbs., or at the rate of about 14,000,000 lbs. for the year,
exceeding the average for the four years previous.
During these six months, Germany supplied 2.7 per
cent and Austria 4.2 per cent, the chief sources of
supply being England, the United States, and France.
It will be observed that Germany and Austria sup-
plied a considerable proportion of the crudes imported
over a period of four and a half years, but that this
proportion is gradually being reduced.
Another point is to be considered. Are German-
finished dyes imported into Switzerland for reexport?
According to the statistics, only to a slight extent.
In 1919, a total of 516,000 lbs. came from Germany
for consumption in Switzerland and 25,000 lbs. for re-
export. For the first six months of 1920 the imports
for consumption amounted to 649,000 lbs., practically
all of which originated in Germany, with small amounts
from Austria and Czechoslovakia. Dyes imported
for reexport during the same period are not shown.
In view of the foregoing facts, can it be assumed that
1 Under this heading in the Swiss statistics are included benzene, tolu-
ene, xylene, anthracene, naphthalene, anthracene oil, chloride of naphthalene,
nitronaphthalene, dinitrotoluene, benzoic acid, carbolic acid, etc.
dyes are coming into this country from Switzerland
that ought to be excluded? The writer hesitates to
express an opinion. There may be, but it is practically
impossible to prove it. If an importer is told that the
dyes he is importing are not made of materials of
German or Austrian origin and he makes affidavit to
that effect, how is it possible to prove that he is in
error? If identical dyes can be made from German and
English crudes and both materials are used in the same
Swiss plant, is it possible to identify the dyes made
from the German material? And if it is possible, can
the limited staff of the present War Trade Board
conduct the necessary investigations?
Turning again to the status of the Swiss dye industry,
it is interesting to note that the three big concerns
have pooled their interests for a period of fifty years
and can be assumed to be operating and marketing
their product on an efficient basis. They seem con-
fident of the future and are counting on a continuance
of their profitable new connections in such quarters
as Alsace-Lorraine and Belgium. They recognize
certain serious handicaps, chiefly the exchange rate.
Swiss money is at a high premium in most European
countries, whereas German money is very cheap. Also,
Swiss workmen have recently gained the eight-hour day
and higher pay, a fact that is cited over and over by
all Swiss writers on financial and business topics.
Nevertheless, the pessimism concerning other branches,
of the chemical industry is almost entirely missing in cur-
rent discussions of the future of the dye industry.
ELECTROCHEMICAL INDUSTRIES
The war greatly stimulated the development of
hydroelectric power in Switzerland, as there was a
serious shortage of coal from the beginning of hos-
tilities. The available waterpower is estimated at
4,000,000 horsepower, of which 500,000 horsepower
had been utilized by 1914. At the end of 1919 new
installations had raised the total to 720,000 horsepower,
an increase of nearly 50 per cent.
The carbide plants were especially active during the
war, for it was never possible to meet the demands-
from the belligerent countries. From a production
of 7500 tons in 1913 there was a continual increase
until a total of 40,000 tons was reached in 191S. Then
came the post-war slump and production fell off to
10,000 tons, with no signs of immediate recovery.
The capacity for manufacturing carbide in Europe
now exceeds the peace-time demand and the Swiss
are not hopeful of the future. As in other countries,
attention has been directed to the increased manu-
facture of cyanamide from carbide, using the air-
nitrogen facilities developed during the war, but the
Swiss peasant is rather skeptical about the value of
this fertilizer and has welcomed the return of other
artificial manures with which he was well acquainted
before the war. Owing to the small size of the country,
most of the plants that make carbide are within easy
reach of communities that are turning to electricity
for lighting and heating as the result of the long-con-
tinued coal shortage, and these plants are making the
best of the opportunity to sell current for such purposes.
They will make carbide as a side line in the future.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
287
Nevertheless, it is reported that seven of the fifteen
plants in operation in 1918 were closed in 1919.
The aluminium plants were also stimulated by the
war. They manufacture a high-grade metal and first-
class wares, and have been able to continue operations
during the post-war period. Employment was steady
in 1919, when the carbide industry was so hard hit, but
business was naturally not so good as during the war.
The exchange rate is the principal handicap.
Plants that manufactured nitric acid during the
war are turning their attention to sodium nitrate and
calcium nitrate, but the farmers are not enthusiastic
users of the latter. The electrolytic production of
caustic soda, bleaching powder, and chlorine is of some
importance and was reported active in 1919.
The manufacture of ferroalloys, especially ferro-
silicon and ferrochrome, is a promising industry, al-
though it has experienced a post-war slump almost
as serious as that affecting the carbide industry. The
output of ferrosilieon has been as high as 10,000 tons a
year. The production of abrasives in connection with
the electrochemical industry is also noteworthy.
DRUGS AND PHARMACEUTICALS
Although no longer ranking with the dye industry
in importance, the manufacture of drugs is still flourish-
ing in Switzerland. The period of greatest pros-
perity was during the war and the influenza epidemic,
but business has been fairly good since then. Com-
petition from English and American manufacturers
is felt on the Continent in some lines, and considerable
anxiety is felt on the score of the return of German
products. A full line of vegetable alkaloids is produced,
the exports amounting to over 51,000 lbs. in 1919 as
compared with 44,000 lbs. in 1913, the increase in
value, of course, being much greater. The manufac-
ture of synthetic drugs has been developed along with
the dye industry, and the products are considered to
be of fine quality. The statistics do not give details
as to the varieties of drugs exported.
PERFUMERY AND COSMETICS
The manufacture of artificial scents came into
prominence in Switzerland between 1890 and 1900,
and has grown into an important industry since.
It goes hand in hand with the dye and medicinal in-
dustries. There is also a considerable output of
natural scents. The exports of finished perfumes and
cosmetics amounted to over $1,200,000 in 1913.
The total for 1919 was somewhat below that of 1913
in quantity, but prices were up during the period of
luxury-buying that followed the armistice. It is an
industry that suffers during periods of business de-
pression such as marked the latter half of 1920.
As compared with 1913, the export trade in soaps,
both toilet and common, showed a big increase in
1919, although at best it is not comparatively a large
trade. The Swiss manufacturers were caught with
large stocks of high-priced oils on their hands when the
slump in prices came.
HEAVY CHEMICALS
Switzerland is naturally not a large producer of
heavy chemicals, as there are few domestic raw ma-
terials and the geographical position of the country
makes the cost of importing such materials prohibitive.
The only soda factory was compelled to suspend
operations for a time during the war, but was later
operated as an essential war-time institution in spite of
the high price of coal. In 1914 there was only one sul-
furic acid plant, but the great chemical plants at Basle
later established a plant for the manufacture of sulfuric
and hydrochloric acids. Domestic supplies of nitric
acid are more than adequate as a result of the de-
velopment of nitrogen fixation plants during the war.
Heavy chemicals are manufactured to some extent by
electrolytic processes, as mentioned elsewhere.
THE MARKET FOR IMPORTS
Bearing in mind the size of the country, it will be
seen in the following table that Switzerland imports
chemicals on a fairly large scale — that is, heavy chem-
icals. The source of supply has been European
rather than American, however. In normal times
dependence is placed pretty largely upon Germany
and to a lesser extent upon England. American
participation has been irregular and incidental and
confined to a comparatively few articles — a few acids,
denatured alcohol, tin salts, dyeing extracts, phosphate,
turpentine, and pharmaceuticals. A table showing the
import trade in detail follows:
of Chemicals
and Allied
Products
1913
Pounds
1916
Pounds
1919
Pounds
2,650
11)4. -150
34,170
;«,5io
33 , 730
1.9S0
440
1 , 540
;nite of iron
16,530
98.110
Acetate of:
Lead, nitrate of lead
United Kingdo:
Acetylene, liquefied under pres-
sure 6.S30
Acids:
Acetic and lactic, methanol,
crude; acetone; methyl-
ethylacetone; prepara-
tions with pyridine base. . 4,449,810
Austria-Hungary 334,250
France 19,400
Germany 1,696,020
United Kingdom 10.140
United States 695,560
Arsenic; antimony compounds,
n.e.s.; chloride of sulfur;
bisulfide of calcium; sul-
fide of arsenic 99.430
Germany 79,810
Arsenious (white arsenic);
chlorides of barium, cal-
cium, and manganese;
magnesium carbonate and
sulfate 2,169,560
Austria-Hungary 220
Germany .' 1,408,310
United States 2,200
Boric and phosphoric 69,670
France 11,240
Germany 57,540
Italy 220
United States
Citric and tartaric 351 .200
France 78,930
Germany 162,920
Italy 106,260
Hydrochloric 17,302,0110
Austria-Hungary
France 1.302,270
Germany 15,987,050
Nitric 503,090
France 41,230
Germany 425 , 270
Oxalic, oxalate of potassium . . 119,930
Germany 119,930
Sulfuric, sulfurous acid in
aqueous solution 21,189,510
Austria-Hungary
France 1,515.900
Germany 19,581.890
Italy 4S.720
Sulfuric, fuming; chlorosul-
furicacid 3, 87.'!, 300
Austria-Hungary
France 272.490
Germany 3,597.060
United Kingdom 440
4.534,020
2,079,400
610,460
182,540
66 , 800
177,910
552,260
1,026,910
949 , 530
291,010
2.202.600
253,750
17,420
15,430
15,650
15.210
4,466,120
1,146.840
119,710
111,770
1 ,078,990
1,024,710
11,680
2 , 200
231,050
214,710
146 , 390
11,240
440
6.390
61,950
106,700
29,100
378,310
122,360
106,700
50 , 270
3,310
250,450
68,560
1,569,030
2.533,110
277,780
549,610
899,700
283,520
7,500
1,650,380
648 , 820
615,090
494.940
14,110
660
587.970
545,640
366,630
.".45,640
303,360
2,677.070
5,019,480
709,230
1.289,040
1 , 936, 320
20.720
1,957,480
1.011,040
354 , 500
1,430,580
2.323,450
676,600
560.190
1,242,960
10,750
S70.390
115,960
2.SS
THE JOURNAL OF INDUSTRIAL AXD ENGINEERING CHEMISTRY Vol. 13, No. 4
Imports of Chemicals and Allied Products (Conh
1913 1916
Chemicals (Continued): Pounds Pounds
Acids {Concluded):
Tannic, gallic, gallaminic 70,550 112,440
Acids, liquid, n. e. s 16,090 9,700
Alcohol :
Amyl (fusel oil) 32.190 12,790
Denatured spirits of wine 1 5 . 5S4 , 920 9 , 648 530
Austria-Hungary 6.S70.700 16,530
Russia 8,310,990 830,700
Dutch East Indies 306 ,440
United States 7,727,'420
Methanol, pure; collodion;
organic compounds of
bromine, chlorine, iodine;
phosgene; other similar
products 3.018,790 2.956,620
Germany 2,664,730 328,050
Spain ..;..
United Kingdom 48,060 1,519,640
United States 101,190 491,850
Aluminium sulfate; hydrate of
alumina: sodium aluminate;
chloride, sesquichlorate. and
fluoride of chromium; thio-
cyanate of aluminium 8,803. 060 59.220,790
Germany S, 325, 540 57,526,090
United States 788,370
Alums 245.370 3,526,510
Germany 211,200 3,107,630
Ammonia:
In aqueous solution 1S6.070 440
Germany 1S1.440 440
Liquefied under pressure 17,640
Ammonium muriate (sal am-
moniac) 400,800 169,320
Germany 396,390 168,880
Bromine and iodine and salts. . . 131. S40 111 990
Germany 125.000 27,120
United States 49 , 820
Calcium:
Carbide 68,780 23,590
Chloride 2,648,850 1,320
France 258,380
Germany 2.358,510 1,320
Carbon sulfide S04.470 787,930
Carbonic acid, liquefied 352,520 440
Chlorates, perchlorates, persul-
fates, n. e. s 153,220 220
Chlorine, liquefied under pres-
sure 566.150 440
Chloroform, chloral 24,470 14 770
Copper sulfate and preparations 4.636,540 3.908|l30
France 2,416,040 307,540
United Kingdom 689,600 2.392,010
United States 222.230 414,030
Ether:
Acetic 10.360
Sulfuric 63,490 440
Formaldehyde, aldehyde, de-
natured 825,630 701,290
Germany S24.310 140,430
United States 355,600
Gases, liquefied, n e. s 341,050 41,000
Glycerol, glycerol lye 604.290 57,320
Hydrogen peroxide 313.280 498.460
H>pochlorites. 278,220 S9.730
Inorganic prepared auxiliary
materials, n. e s 1,123,920 767,430
France 143,300 108,470
Germany 760,370 547,410
United States 11.900 6.610
Iodoform 2 , 650 220
Iron sulfate, zinc sulfate 1,118.850 194,230
Lactarine (casein), extract of
rennet 399.920 332,240
France 306.440 239.640
United States 48.060
Lead oxide 210.710 110,010
-Magnesium chloride 0.527.890 4,412 3::"
Germany 6.432, 200 4,412 330
Milk sugar, whey powder 26.680 51,150
Peroxides of barium, lead,
sodium 749.130 895,080
Germany 609.580 719, si"
Phosphorus:
Red (amorphous) S3 . 780 28.220
White 107. S10 24 470
Potash, crude S4S.340 1.749.590
Potassium
Hvdroxides of potassium and
sodium, solid 19.635.250 18,715,260
Austria-Hungary 1 , 849 . 900
France 1,026.030 3.397,760
Germany IS, 595. 770 9.291.820
United Kingdom 220 3.114,690
United States 1,060,860
Hydroxides of potassium and
sodium, liquid (lye) 1.501,120 1,402,800
Nitrate, and nitrate of sodium
(pure) 1,653,910 1,179.250
Germany 834,230 13.230
1 nited Kingdom 1.760 579,160
United States 104,060 3,970
Prussiate, bichromate, per-
manganate, thiocyanate,
cyanide 987.670 228,180
Austria-Hungary 149.470 71.430
Germany 769.190 151 240
United States
Silicate, and silicate of so-
dium (water glass) 5,648,020 4.450.470
France 314.820 1.215.190
Germany 5,308,290 3,211,030
3,028,270
1.95S.140
2.680,600
348,990
929,030
392,640
664 . 250
23S.320
200,840
,388,030
.299.620
1,320
411,600
311 ,950
247,140
8,820
1.322,990
111.110
1.150,150
440
61,070
297.620
13,230
2,341,750
46,300
1,482,600
10,800
434,750
164,460
196,870
121,920
65,040
266 . 540
93,700
898.380
112,880
67S.140
34,170
1,100
89,510
363,540
4 . 366 . 690
16,310
54,010
3S.360
194,230
506.400
3.040.830
290.790
2,469, tOO
44,310
259,040
974,000
M,.-. ;.;,,
136.020
14.770
Imports op Chemicals and Allied Products (Conli,
1913 1916
Pounds Pounds
Chemicals (Concluded):
Potassium (Concluded):
Pyrolignite and phenate; bar-
ium nitrate; lead sulfide
iron sulfide; zinc powder.
France
Germany
United Kingdom
United States
Sodium:
Acetate, hyposulfite, fiuosili-
cate
France
Germany
United States
Arsenate, bicarbonate, sulfite,
and bisulfite
France
Germany
United Kingdom
Borate (borax)
France
Germany
United Kingdom
United States
Carbonate:
Crystals
Soda ash
France
Germany
United Kingdom
Chromate (bichromate), cyan-
ide, sulfate, sulfide
Austria-Hungary
France
Germany
United Kingdom
United States
N'itrite
Phosphate
France
Germany
United Kingdom
United States
Salts, n. e. s
France
Germany:
Italy...".
United States
Tartar:
Crude
Cream of; neutral tartrate;
tartar emetic
Tin salts
3.343.310
1.348,130
1,395.740
5,510
225,970
755,080
252,210
108.020
394.850
1,587,770
41,890
1,532,430
5,070
707.680
97.440
597 , 670
3,970
2,158.100
6.631.720
135.140
998,690
2.079.620
71.430
2.008.190
453.710
151.900
293 . 880
6.S30
United States
Zinc chloride, mother-lye of :
chloride
Germany
Coal-Tar Products:
Coal-tar dyes:
Alizarin:
Germany. . . .
Aniline.
thalei
dyes,
63,930
,849,240
.59S.570
Indigo, natural or synthetic...
Germany
Other products:
Aniline, aniline oil
France
Germany
United Kingdom. .
United States
Aniline compounds for the
nufacture of dyes
1,539,270
1,476,660
153,440
152,560
Fra
United Kingdom
United States
Benzyl chloride, nitrobenzene,
naphthol and its deriva-
tives
France
Germany
United Kingdom
United States
Coal-tar derivatives for the
manufacture of dyes
l benzene, toluene, etc.)...
Austria-Hungary
Germany
United Kingdom
United States
Phthalic acid, resorcinol
Saccharin
Salicylic acid
Tar-oi! derivatives (carbolin-
eum, creosote, creosote oil,
creolin, lvsol, etc.)
France....".
Germany
United Kingdom
United States
Dyeing and Tanning Materials:
Extracts for dyeing
France
Central America
United States
1,956.160
6,170
1,871,280
7s. 710
2,388,050
2.377.020
•K920
7,331.690
660
401.020
6 , 232 , 250
6S9 , 600
2,913.190
276,900
1,668,020
365,970
525,800
343,480
167.330
205,030
990.100
211,200
590,8411
27 , 560
.198,430
700.850
220
269,620
207,010
3.750
139,330
1.165.140
299 . 1 70
465. S40
30.640
19.340,710
1.344.160
14,820,350
803,810
2,921,560
377,210
245,370
1,161.620
904 , 560
232,810
530,870
157.630
120,370
4,190
33.070
415,350
31,090
201,720
60.410
1.203,500
K)5 78
132,000
949,750
949 , 750
17.200
17,200
280,210
4,410
199.960
42,990
Ml .280
325,180
4,410
470.020
41,670
25 038,330
16,645,560
927.920
4,708,850
2,433,460
22s. 400
32,850
880
116,840
,127,460
267,860
s27.nl 1 1
996,710
S54.730
93.260
19,840
531 ,750
1.091.950
280,870
140,390
301,590
1.100
471.130
22.050
233,910
136.470
1 . 405 , 220
264,110
756,400
179,020
604 , 290
18,960
3.300
224.210
223.990
220
560, 160
242,950
483,250
2,113,130
514,560
125.880
796.090
343,920
880
660
213,190
129.190
309.970
220
136.470
132.940
22,050
6,170
10,800
".S2.020
184,090
390,000
475.090
41,230
41,230
56.220
13,670
745. S20
17.190
142.420
727.090
i I 97 140
38 77"
240.960
803,140
152, :4o
' 870
720.030
1.494.290
1,428,160
1,509.730
89,730
107,360
11,020
168,210
23.563,450
720
21,752.350
95.900
47. IsO
1 , 1 1 1 , 790
65.480
342.380
53 080
Apr., 1921 THE JOURNAL OF INDUSTRIAL
Imports of Chemical
AND ENGINEERING CHEMISTRY
Dveing. Etc. (.Concluded): p",'V
3 . 644 , 460
Allied Products (Continued)
Fra
Italy
Argentina.
United States..'..!
Explosives:
Guncotton, pyroxylii
Dynamite and other
1.281.330
374,340
28 . 220
Fireworks an
preparations
Fertilizers:
Chile saltpeter, ammoniu
plosives,
pyrotecrinical
1916
Pounds
5,592,900
19,840
1.158,530
2,209,690
1.776,270
4,630
1919
Pounds
7.658,860
373,240
263,230
6,999,670
3.970
4,630
Metric Tons Meti
29,100
Stassfurt salts
bone meal,
Bd&t-ai
France
Germany. ......
Algeria-Tunis .,'.'
United States
Potash fertilizers
France
Germany
Potassium muriate. .
France
Germany
Slag, basic. . . .
France
Germany
Sulfuric acid, used. ..
Superphosphates and
pared fertilizers.
France
Germany
Algeria-Tunis. '...'.
United States
Medicinal
Drugs:
Alkaloids, vegetable.
Germany
Balsams, concentrated' juice's of
plants, medicinal oils
Chemical products, n e. s for
pharmaceutical use
Foods, artificial (somatose, etc )
3,328
18,885
2 us:;
1,565
2.114
3,045
8 . 882
13,241
18
pre-
1.572
5 . 793
7 , 992
7,749
1,994
20. iin.i
4,833
15,537
29,922
1.985
27,937
Preparations
Pounds
24,910
11,900
Pharmaceutical products
(pills, powders, plasters
tinctures, etc.) ....
France '_[
Germany. . .
Italy
United States. ... 1 .' '
Sera, vaccines. .
Spring salts and
Oils, Vegetable
expressed
arsh salts
Fixed <
Castor:
Crude.. .
Colorless, purified .
Coconut, palm, and other
France
Germany. ,
Italy
Dutch East Indies.'.'.'.'.'.
Africa.
United States..'.'.!
Linseed
Belgium
France
Netherlands
1.031.980
308,210
522,270
95.240
22.710
4 . 030
32,630
679,020
105,600
1.829.670
1,213,200
2.315,730
278 , 000
Pounds
6.390
3,310
534 , 620
329, SKI
78.040
78,930
1,320
2,650
48,060
14,859
329
4,832
21
7,145
2 . 530
29 336
15,361
13,945
4 . 776
4 . 68.5
41
46 . 443
32 826
9 . 337
110
Pounds
46.740
34 , 390
046.390
341 ,060
152,340
76,060
30 , 860
5,290
19.620
Imports of Chemicals ai
Oils, Vegetable (Concluded)-
Volatile or essential (Concluded)
France
Germany.
Other (cloves, lavender.' aspic
jumper; ethers with fruit
odor)
France
British India.'.'.'.'.'.'
United States
Paints, Pigments, Varnishes-
Chemical colors, dry, not pre-
pared :
Black, lampblack, bone black
Germany
United States'.*.*. '.!."!.'.'."'
Cinnabar. Prussian biue ul-
tramarine, Schweinfurt
, green, bronze colors...
Allied Produc
1913
Pounds
(Continued)
272, 'Kill
32,410
102,960
2,650
509 . (140
455,700
15,430
289,250
44,310
219,360
173,000
115,300
16.530
6,142,960
3.315,090
010.830
10,514,060
5,338,930
1,593,910
Spata™"*"*"15 2,9721930
Dutch East Indies .".*.'.'.".!."
Japan
United States...'.:.'::.''.'' ii' iin
Denatured
France. . . .
Spain
United States
Edible.
3 , 554 . 290
1.558,230
257,940
48.720
France " 1'SZS'2I2
Italy.
Spain .;:::::
United States .'
Peanut, rape, hemp, sesame
cottonseed, and other, for
industrial purposes
2.675.310
1,816,830
835,330
927,930
682,110
156,310
20,280
1,947,560
697,980
630,080
499,790
nd other sulfo-
France
Italv
United Kingdom'
Dutch East Indie
Japan
United States...'
Turkey-red oil ;
ricinoleates. .
Oils, edible, n. e. s....':
Belgium
France.
Spain....:.::::
United States '.'..'.'.
Germany. . .
Volatile or essential:
For pharmaceutical use and
perfumery (rose, violet
cajeput, nutmeg, pine-
needle, bitter-almond,
eucalyptus)
6,321,090
1,034,850
1.977,990
2,463,000
2,200
292,770
358.250
65 . 040
6,51.5,980
175,930
366:900
1 . 224 , 890
2,229,970
577,830
296,520
5.381.260
267,200
660
992,520
324,080
746.040
1.395,970
49,380
2,872.400
160,060
2,625,040
48,280
5,250.700
272,490
271,830
4,711,940
440
.731,340
50,270
39 . 900
326,720
221,790
02.8,700
. SS3 , 200
259,270
335,540
20.764,680
2.412,520
10,471,510
5, 366 i 930
1,979,970
13,132,930
5, 528 : 750
555,780
1,457,480
15,472,480
220
Fran.
Germany
^ United States ..'.'!.'" '
Color varnishes (carmine ge-
ranium, scarlet, yiridin)..
Lead:
White 539.910
Yellow 84S.690
I..^hoponeyPear, „,,„,,:: 2.069.920
Victoria green... '.'.::;;;:;;; ''Jg-gg
*BeiS™' zincolithe 1 .779.350
Germany::.:;:;::;:;- • ^?,ooo
Other (chrome yellow and
green; mineral blue; smalt
zinc green, etc.)
,-° ? °f alll;inds. prepared:' '
and other colors,
ater paste
(linseed oil and
oil, boiled,
470,420
39,240
86,860
4,850
2,704.190
2,607.030
10,360
276,680
37,700
23.5 , 670
47.5,540
67,680
108,470
440
2.504.890
2,252,680
80,910
1. SOS. 670
776,690 1,555; 140
-(.Mi, inn
Chrome t
Oil varnishes
poppyseed
fluid)
White casein
(alabastine. a
durine. etc )
White lead ..".'!.".'
Zinc white, pearl white ... '
Other prepared colors
Germany
United States. ... .
. lacs, and siccatives.
40,900
glue colors
phiboline, in-
117,250
917,120
622 , 360
452,170
362,660
2,200
- •'""»»■ . 1,722,030
Germanv 219.360
USES Kingdom"" l>°2&-2£
i-ERFUMERV AND COSMETICS:
containers weighing more
than 1 kilo
France
Germany.
United States .......
In containers weighing l' kilo' or
less ... . .
France . . "
Germany. . .
United States. ...,'.'.
Other Products:
Albumin
United States.
Blacking and polishes
In containers weighing 5 kilos
or more
In containers weighii
than 5 kilos
Germany
United Kingdom
United States..
Candles:
Ball tapers, Christina
candles, colored or
mental candles
less
tree
56.8S0
15,870
36 , 380
220
264 , 7S0
119.710
104,940
3 . .530
822,320
070,000
72,750
7,940
All othe
Dextrin
Glue:
For joiners.
plasterers ' 1 .> = •, oin
Germany ;.
Fran
United States..
Gelatin, fish glue.
Liquid or in powd
Liquid, for office u
Ink:
Printing
Writing and other.
932,330
177,030
2,420
231,050
178.130
52,030
495,160
327,380
264 , 770
1,11 0
59 , 080
1,980
13,000
302,690
258,600
220
549.610
161,380
157,190
100.970
55,340
152, 781 1
33. '.1511
109,130
1.100
262,570
160,940
81,350
3,750
426,370
250,400
79,800
31,750
783,740
102.31(1
175,490
134,920
108,09(1
37,040
539,250
106. 4S0
80,690
55,560
328.270
212,(15,1
37,920
201,910
61,290
165,790
3,310
659,400
569,230
33 , 730
800,21111
11,020
659,400
20,720
1,980
34,390
183.200
135,140
6,830
478.180
117,950
127,430
118,830
76,280
04,150
17,640
35,710
1.100
373,240
241,400
56.060
23,810
221,340
103.400
39.240
1.760
23, 1.50
1 12,01,1
United States
Paper and pulp:
Paper:
Newsprint
Germany
Other printing, writing/and
drawing paper
Germany. . . .
United States. .
Pa£kil>S '.'. 5.079,010
L.ermany 3,005, 780
*3Weden 686,740
-142.690
229,720
199.520
440
9,630,010
7,557,220
13,230
10,405,160
8,043,120
54,670
4,642,050
2,941,850
511,0'.K)
39 , 240
33,510
29,320
133,600
211,290
187.390
660
3.935,910
633,610
3.145,770
6,747,030
5,283,380
24,910
8.457,370
5.288,450
1,065,270
290
THE JOURN
II OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
Imports of CbBMICAvs an
Other Products (Concluded):
Paper and pulp (.Concluded).
Paper pulp:
Chemical
Germany
Sweden
Russia
Mechanical
Pitch, unmanufactured
Germany
> Allied Products (Concluded)
1913 1916 .191?
Metric Tons Metric Tons Metric Tons
Exports of Chemicals and Allied Products (Continued)
1013 1916
Resins, manufactured (brewers'
and shoemakers' pitch, etc.)
Rosin
France
Spain
United States
S°Common. in bulk, cases, casks;
in lumps, cakes, etc.; soft
soap
Trance
Spain
United States
Other (toilet, medicinal, special
soaps)
France
Germany
United States
Soap powder and prepara-
10.170
6,539
1,867
120
1,590
2 . 589
2,330
Pounds
768,530
6 209.520
3. 081. ISO
9,074
475.310
93.4S0
285,940
12.570
laundries J'llf'lOO
'.'.'.'.'.'■ 848! 120
Germany
Soap waste
Stirch surn.^prepiraiions '"' 1 4S: 920
2,198
1.321
989
Pounds
50.040
7,785,400
6,543.540
554,020
388,890
4,435,920
2,913, L90
149,250
91.050
9 . 700
18,960
320 . 550
319.670
43,650
9.929
1,661
1.117
22,219
18,842
Pounds
58.200
3.190,530
1.443.370
1 ,713,650
29,540
Metric Tons Metric Ton
6.195.S70
1. 082,910
4,756.690
97.220
313.060
130.290
5.290
46,520
46.960
20.720
18,740
122,580
Metric Tons
Sugar, ra
solid ....
Austria Hungary
France
Germany
Netherlands. . .
Dutch East Indu
Central America
United States .
and refined; glucose,
Tar.
117,261
74.917
7.600
33,229
Pounds
2.447,350
188,270
10.017
9.067
31.131
Turpentine, white resin ^ 259,990
Spirits of l'.835,570
France ""I 2,371,730
United States.
48.213
Pounds
173.060
66,800
3.274.970
1.953.740
ssT .".Mi
433,650
84
2,486
694
88,096
3,533
1.283
Pounds
2.998,730
6,390
3.405.040
641.330
2.491.440
272,270
THE EXPORT TRADE
The following table shows in detail the exports of
chemicals and allied products according to official figures
for 1913 1916, and 1919. In the absence of any recent
census of manufactures these figures will be a guide
in estimating production, as a very large proportion of
most manufactured chemicals are exported.
Exports „■■ Chemicals and Allied Products
Chemicals:
Acetate of: . . , .
Chromium, pyroligmte of iron
Lead, nitrate of lead . .
Acetylene, liquefied under pres-
sure
' Acetic and lactic; methanol,
crude; acetone; metnyl-
ethylacetone ; preparations
with pyridine base
Germany
Italy
Arsenic; autimony
392 . 640
2.200
5,510
5,290
. impounds,
chloride of sulfur;
bisulfide of calcium; sulfide
of arsenic : ■■
Arsenious (white arsenic);
chlorides of barium, cal-
cium, and manganese;
magnesium carbonate and
sulfate ....
France
Italy ■■ -.
Boric and phosphoric
Citric and tartaric
Hydrochloric j
1,067.040
574.080
186,510
Nil
Oxalic, oxalate of potassium .
Sulfuric, sulfurous acid n
aqueous solution
Germany ■ ■ ■ •
Sulfuric, fuming; chlorosullur
acid .- -.
Tannic, gallic, gallaminic
France
Germany
United Kingdom
Acids, liquid n.e.s
40 , 560
5,070
31.300
217.600
6.170
568,590
178,150
I. 173,740
160.720
2.604,980
2,099,680
440
520,950
35,720
294,320
46,740
22.930
423.950
416,450
81,570
440
45,860
24,250
24,250
64,370
344.360
1S5.190
nd
thio-
Chemicals {Continued):
Alcohol:
Amyl (fusel oil)
Denatured spirits of wine . . .
Methanol, pure; collodion;
organic compounds of
bromine, chlorine, iodine;
phosgene; other similar
products
France
United Kingdom •
Aluminium sulfate; hydrate o!
alumina; sodium alununate
chloride, sesquichlorate
fluoride of chromium,
cyanate of aluminium
Alums..
Ammonia:
In aqueous solution
Liquefied under pressure-
Ammonium muriat
moniac) .•••.-
Bromine and iodin
salts
Calcium
Carbide
Belgium
Germany
Netherlands
Portugal
Rumania
Chloride
147,050
95.680
1,760
362.000
68, 120
237.660
(sal
1 . 540
660
274,470
34,610
239 . 200
29,320
13.670
201.500
837.100
11.020
697,760
8,600
185.410
70 085.830 127.ss9.7lN)
a' 180.200 1.522.070
' 7S 700 22,840.990
55 144'000 101. 99il. U20
5 888.550 44.090
182.320
111.110
103,180
8,820
11.680
81.332,040
88,180
26.690.260
53.868,850
44.090
Italy
Austria-Hungary
Carbonic acid, liquefied
France
Chlorates. perchlorater
sulfates
Belgium
France
Germany
Japan
Australia
Chlorine, liquefied
300 , 490
1.980
63,710
228,620
8,820
8,820
4.911.919
451,730
316,580
678,360
1,444,910
427.700
462,970
1,336,000
1,203.280
130,070
2,650
146.170
124.340
2,462,120 1
317.450
724,000
489,870
233.470
34.170
79.150
932.340
inder pres-
14,110
70.2*0
366.190
521,390
16.760
Chloroform, chloral
Copper sulfate and preparations
Ether:
Acetic
Sulfuric ,••/■;■■.,'•
Formaldehyde, aldehyde, de- ^
natured ... . . . . ... 56,220
Gases liquefied, n. e. s
Glycerol, glycerol lye... 1-1§S"lSS
France
Germany
United Stales
Hydrogen peroxide. .
Hypochlorites
Inorganic prepared
materials, n. e. s
Austria-Hungary
France
Germany
United States
Iodoform
Iron sulfate, zinc sulfate. . .
Lactarine (casein), extract
rennet
Germany
Lead oxide
Magnesium chloride
Milk sugar,
431 ,890
24,910
5.730
440
3,300
2,650
9.200
671,300
auxiliary
281,750
150.090
7.500
52,030
„., *hey powder ....
Peroxides of barium, lead, sodium
Potash, crude
Potassium:
Hydroxides of potassium and
sodium:
Solid
Lquti (ly?) . ..
Nitrate, and nitrate of sodium
(pure)
Prussiate, bichromate, per-
manganate, thiocyanate,
cyanide ■■ • ■■■ •■
Silicate and silicate of sodium
Pyrolignite and phenatc: harium
nitrate; lead sulfide; iron
sulfides, zinc powder 1
France
Germany
Italy
Sodium: ,„ a ...
Acetate, hyposulmc, fluosili-
Arsenat'e'. bicarbonate, sulfite,
and bisulfite
Borate (borax)
Carbonate:
Crystals
Soda ash
Germany
Italy
Netherlands
Chromate (bichromate), cy-
anide, sulfate, sulfide
Germany
Italy
1,584,240
10.140
19,840
1 45S.5SO
440
5,070
675,940
7.940
3.750
16,980
232,590
1,100
8,160
1,540
403 , 070
.".1 .590
60,190
2 159, 180
466.280
1,112,230
027.210
5.070
5,510
590.400
303,360
303.140
2,200
84 . 220
21,160
5,510
52,470
24 . 250
30.200
169.770
494.710
599.430
12,120
770.960
149,470
212.300
366.410
2 732. S50
1.030.000
1 510,390
215,850
216,710
11,680
74,960
223.990
33.730
160,500
1,980
139,990
92,150
356,040
75,400
201,940
132.940
26.450
4.030
3 . 530
1.540
9 . 700
5,061 .590
176,150
4,850,610
Apr., 1921
THE JOURNAL OF INDUSTRIAL
Exports of Chemical
Chemicals {Concluded)
Sodium {Concluded):
Allied Products {Continued)
1913 1916
Pounds Pound.
Nitrite
Germany. .
Italy '"
Phosphate ' ' . '
Germany . . .
Italy
Salts p 2 2
France
Germany. ....!.'..'
Russia '
Spain
United Kingdom
Japan
United States.
Tartar:
Crude
Germany. ...
United States. '.
Cream of; neutral tartrate
■583 . 780
•407,820
50 . 930
I . 124,360
728.410
395,730
1.026,910
54.450
317.24(1
144,. S40
20 . 500
"•! 150
122,360
9.700
tartar emetic.
908.960
122.580
1 1 . 020
13.450
60.850
284.400
1 1 . 020
281,310
■457,460
■422, ISO
13,000
Pounds
162.700
10.S00
136.690
961,220
193.120
746.260
595,470
80,250
111,550
AND ENGINEERING CHEMISTRY
op Chemicals and Allied Products (Conlinu
291
185.630
55,340
1,100
6,610
alts.
mother-lye of ;
Zinc chloride
chloride. ..
Coal-Tar Products:
Coal-tar dyes:
Aniline. anthracene. naph-
thalene dyes; coal-tar
Austria-Hungary. .. '
Belgium
France .'.]
Germany. .
Italy
Fertilizers (Concluded)-
Superphosphates and other pre
_, Pared fertilizers
France
Germany. '
Italy .
MEDDrugs: PrEP*r«-"NS ' and
Alkaloids, vegetable..
France
Germany '.'.'.'.'.
Rumania. . . .
United Kir.gicm
irui™/' co"«n"aU-,l juic, oi
iruits, medicinal oils
Chemical products, n e V "for
Pharmaceutical use
France
Germany
Italy "";
Russia
Spain .
United Kingdom'
Japan . . .
United State
_ Metric Tons Metric Tons Metric^L
10,994
1,238
8.1.23
807
Pounds
44,310
660
37.040
•46.0SO
702,170
90,390
161,820
40,340
,7i)u
9.040
39 , 680
53.3 K)
16,750
15.508.S60
711 , 650
764,340
309 970
3,586,260
Netherlands::::::; 1^!:0"1
169,980
38, 300
313,720
175,050
, 188.050
British India J'n'a'HfS
China 1.09(1. ISO
Norway. .
Russia. . . .
Spain
Sweden . . .
United Kingdo
Japan .
Brazil
Canada
United States...!
Indigo, natural or s
Belgium ■
France. .
Italy ' _'
Russia
United Kingdom
China
Japan. . . .
United Stat
Other products:
Aniline compounds for the
manufacture of dves
France "
Germany ....
United States.'.
Benzyl chloride, nitrobenzene',
naphthol and its deriva
tives. .
France....'.'.'.';
Coal-tar derivative ' f™ ' li'.
Fran'
Germany
facture of dyes
toluene, etc.) ,
id, resorcinol.
Phthalic
Saccharii
Austria-Hungary
Netherlands. . .
United Kingdom
British India.
United States...
Salicylic acid
Tar-oil derivatives (carh
eum, creosote, creosote
etc.)
Dyeing and Ta
Extracts for dyeing.
Germany.
United Kii.0„
United States
Extracts for tann
France
anning Materials:
ngdom .
Germany. .
Italy...:....'.'
Rumania
United States.
589.070
767,870
91,930
144.40(1
2.815.300
3.950,240
235,890
1,100
80,250
55 . 560
2.84: -..7;:i I
H3.960
(76.860
294,980
''.-| (All
136,020
2.200
232.150
2.870
218,480
1,100
174, 160
1,980
47,020
12,330
31.970
23,810
987,230
370,160
45.420
56,440
2,902,600
612.440
838 860
26,240
6 12
3,750
1,162,720
55, 780
21.380
68 120
272,490
38 580
4,62] ,990
51,810
S4.440
132,380
211 , 120
45,190
1.507,520
1,633,850
(.ii
30.42(1
51.370
430
820
810
14.137,230
IS. 520
838,420
2,516,580
2 , 650
1 ,731,070
lll.no
18,300
85,320
348 , 330
Jin ,940
5 , 1 50 , 0(10
492,730
182.540
264,990
177,470
65,040
I 168 7_'u
3,632,340
100,090
123 860
242,070
F»^™llMlalOM|dcJ 2.71 ;;,u
Pharmaceutical products n V s ' '"'^ """
(Pdls, powders, plasters'
tinctures, etc )
Austria-Hungarv
Germany
Italv...
Netherlands
I'nited Kingdom
Argentina
United States.'.'..'
Sera; vaccines 0,510
Spring salts and 'marsh' sal
539,470
51,590
-'i>''. i.r.ii
16.541)
25,790
52,910
18,740
Vegetable:
xpressed :
34,830
440
1,100
19,620
345,020
1 . 760
Km 970
248 . 680
1.893,990
145,500
448,420
128.310
105. ICO
8,820
Oils.
Fixed (
Castor, crude."
Coconut, palm, and other "
.Austria-Hungary
Linseed. . .
Olive dsnatured
eanut, rape, hemp, sesame',
cottonseed and other, for
... "Mlustnul purposes..
4 urkey-red oil and other sul'fol
ncmoleates
Oils, edible, n "e "s'
volatile or essential
For pharmaceutical use and per-
fumery (rose, violet, etc I .
Other (cloves, lavender, aspic
jumper; ethers with fruit
s Coi ORS V
odor
Paints, Pigment
nishes:
Chemical colors, dry, in lumps
or powder, not prepared:
Back lampblack, bone black
Cinnabar. Prussian blue ultra-
marine, Schweinfurt green,
bronze colors.
Color varnish.
Lead :
Red.. .
Whitf
J.ithopone. pearl white
Zinc white, zincolithe....." '
Other (chrome yellow and
green; mineral blue; smalf
zinc green, etc. I. .
Colors of all kinds, prepared'
C hrome oxide and "other colors
n. e. s , in water paste '
Oil varnishes (linseed oil and
Poppyseed oil, boiled, fluid)
"" casein or glue colors
phiboliiie, in-
White
(alabastii.,. ..
durine. etc.) .
20.619
8,702
11,520
396
Pounds
19,620
.SMI
12 ; .ii
880
1,760
11,680
493,620
145,280
17,200
29,980
37,480
15.870
84,660
7 , 500
88 , 850
652.790
98,550
232.150
29 , 540
35.270
48,060
16 310
24.470
14,770
7.116
5,282
1,758
10
Pounds
51,370
12,350
14,990
1 . 100
1.100
19, lso
•514, 7S0
108,690
4. 630
53,130
23,810
43.210
62.170
19.400
25. 130
2,870
220
703 050
5 510
34 , S30
66,360
68,120
135.140
1-, 080
25,130
14.330
3.310
440
1.821 ,240
1.490,320
703,930
15,870
XPLOSIVES:
Dynamite and othe
92 1 Mill
Germany. ...!!!!
ireworks and pyrotechii
arations
Russia
55, 120
5 290
1.1.9(1, Oil)
181,440
437, ISO
352,520
485.020
1,100
White lead
France
Zinc white, pea, I white
i ii her prepared colors
txnishes, lacs, ;in.l siccatn
Austria Hungai y
Fran.
Germany
Perfumery i
In contain
tha
Cosmetics
weighing i
1 ,760
7,050
4,410
5.290
I'll 500
153,880
1.760
71 ,430
46,080
France
Ru
3RTILI2ERS:
Chile saltpete
Phosphates, crude: bone
Metric Tons Metr
1,500
966
280
United Kingdom'.: .'.'.'""
1 luted States
In containers weighing 1 kilo ,
less
France . . . .
Rumania
Russia
United Kingdom..
Japan
Brazil .'
United States. ... !
Other Products1
Albumin
United States..'.! : . .
203,050
20,060
15,210
55.120
18,940
340,610
20.940
660
5.07(1
6 , 830
7.720
242.070
7,940
1.760
188,320
188 320
1 16, 180
162,040
959.450
64.150
21 .600
843,710
315.700
67,900
44,310
51 , 150
26,240
151 ,020
4.400
32 850
SKI)
2,650
12.570
5.070
4,190
I in
94,800
880
1.320
1 ,540
939,390
938,730
2,870
69,450
358,690
49.S20
.Oil
259,040
204,15(1
7(1.990
440
30.420
18,520
216,710
3,970
25,790
8,600
5. 73(1
3,310
77.160
11 .C..S0
THE JOURNAL OF INDUSTRIAL A XI) ENGINEERING CHEMISTRY Vol. 13, No. I
Exports of Chemicals and Allied Products (Cont
1913
Other Products (Continued): Pounds
Blacking and polishes:
In containers weighing 5 kilos
or more 07,400
In containers weighing less
than 5 kilos 100.010
Candles:
Ball tapers. Christmas tree
candles, colored or orna-
mental candles 000
All other 58,860
Dextrin 352,080
Glue:
For joiners, house painters
plasterers 2,914,950
France 203.450
Germany 1 ,658,510
Italy 921.310
United Kingdom 19,620
United States 16,310
Gelatin, fish glue 432 . 33(1
France 18,300
United Kingdom 93 . 480
United States 100. 720
Liquid or in powder 12,350
Liquid, for office use 10. 14(1
Ink:
Printing 7,060
Writing and other 31 .1)70
Paper and pulp:
Paper:
Newsprint 23.810
Belgium
France 23,590
Italy
Other printing, writing, and
drawing paper 514 , 780
France 64,000
1916
1919
Pounds
Pounds
429,020
89 , 730
100,310
110,8511
20.500
1 ,320
209,220
33,950
1,100
11,080
,631 ."no
3,953.770
891.770
1 . 084 . 670
580.920
2,442.280
1 14,620
178,130
097,320
38,300
1 39 , 770
33,070
113,1 iii
300 , 270
88,180
• 57.980
1118,910
91,270
39.020
29,320
105.600
23,590
1,760
9,480
120,100
15.650
100.090
86,200
. 171.2511
3,771,890
446.000
,474,030
2,817,510
220
472,450
,973.140
2,735,050
,347,900
1,599,680
Exports of Chemicals and Allied Products (Condi
1913 1916
Other Products (Concluded): Pounds Pounds
Paper and Pulp (Concluded):
Germany 123,400 50,040
Italy 130.730 218,920
United States 31.750 174,380
Packing 495,600 2.875,930
Trance 199,740 2.720.000
Italy 95.6S0 20.720
Paper pulp: Metric Tons Metric Tons
Chemical 4 , 831 4 890
France 3,193 3,715
Italy 1,532 1,175
Mechanical 1.818 1.765
France 1,702 1.700
Pitch, unmanufactured. 26 534
Resins, manufactured (brewers' Pounds Pounds
and shoemakers' pitch, etc.) 23.590 436,730
Common, in bulk; in lumps.
cakes, etc.; soft soap 253,310 1.298,300
Germany 34,610 1,235,690
Russia 440
France 112,440 48,720
Other (toilet, medicinal, special
soaps) 60,410 49,160
Soap powder and preparations
for laundries 265.220 125.220
Soap waste 2.186.540 315,480
Starch gum, preparations for
sizing and finishing 97,000 117,730
Metric Tons Metric Tons
Sugar, raw and refined; glucose,
solid 101
Pounds Pounds
Tar 36,150,740 1.039.480
France 8,007,630 51.370
Germany 27.925,730 982.600
Turpentine, spirits of 69,450
2,278,700
1,427,270
01,5 ".8(1
Metric Tons
7.092
2.940
1 075
1.601.650
1,045.210
300.490
10,360
Pounds
256,620
31.970
220
ORIGINAL PAPERS
NOTICE TO AUTHORS: All drawings should be made with
India ink, preferably on tracing cloth. If coordinate paper is
used, blue must be chosen, as all other colors blur on re-
duction. The larger squares, curves, etc., which will show in
the finished cut, are to be inked in.
Blue prints and photostats are not suitable for reproduction.
Lettering should be even, and large enough to reproduce
well when the drawing is reduced to the width of a single
column of This Journal, or less frequently to double column
width.
Authors are requested to follow the SOCIETY'S spellings on
drawings, e. g., sulfur, per cent, gage, etc.
An Application of the Vapor Pressures of Potassium Compounds to the
Study of the Recovery of Potash by Volatilization1,2
By Daniel D. Jackson and Jerome J. Morgan
Columbia University, New York, N. Y.
The immense amount of work which has been done
upon the extraction of potash from complex mineral
silicates is clearly shown by a bibliography on the sub-
ject published at the beginning of 1918 by E. C.
Buck.-1 This bibliography refers to no less than one
hundred and thirty patents and fifty general articles
published in the six years, 1912 to 1917. Of the pro-
posed processes for the recovery of potassium in the
form of soluble salts from the natural potassium-bear-
ing silicates fully one-third are based upon the separa-
tion of the potassium compounds by volatilization.
In spite of this great amount of work and with the
stimulus of the inflated prices of potassium com-
pounds, only a very few of the numerous processes
proposed have been put into actual operation on a
commercial scale. It was decided, therefore, to apply
the knowledge obtained from the vapor pressure ex-
periments recorded in a previous paper4 to an inves-
tigation of the volatilization of potassium compounds
1 Received December 20, 1920.
2 Part of a thesis submitted iu partial fulfilment of the requirement
for the degree of Doctor of Philosophy in the Faculty of Pure Science,
Columbia University, New York, N. Y.
> Met. Chem. Eng., 18 (1918), 33, 90.
* Jackson and Morgan, This Journal, 13 (1921), 110.
from mixtures of silicates with releasing and volatiliz-
ing agents. It was thought that this investigation
would show the reason for the apparent failure of so many
of the proposed methods and might suggest the condi-
tions for a method which would be commercially suc-
cessful. In the light of the vapor pressure determina-
tions the methods involving the use of a chloride seemed
to be most practicable, and glauconite, or greensand.
was thought to be the most promising of the natural
silicates containing potassium. Hence the first ex-
periments were made with mixtures of greensand and
calcium chloride.
VOLATILIZATION OF POTASH FROM MIXTURES OF
GREENSAND AND CALCIUM CHLORIDE
In these experiments a carefully weighed amount of
greensand, powdered to pass a 200-mesh sieve, was
well mixed in a small platinum boat with approxi-
mately 10 per cent of its weight of powdered, anhy-
drous, C. P. calcium chloride. The boat and contents
were heated in the vapor pressure apparatus in a current
of nitrogen dried with calcium chloride, as has been de-
scribed under the determination of the vapor pressure
of potassium chloride.
Irregular results obtained at 1200° C. were thought
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
293
to be due to the temperature being too low for com-
plete fusion and rapid intermingling of the reacting
substances. At 1300° the results of duplicate deter-
minations agreed better, and the amount of potassium
chloride volatilized varied with changes in the speed of
the gas stream in such manner that it was possible to
plot the partial pressures and obtain the vapor pres-
sure of potassium chloride in the mixture. The value
of 1.6 mm. of mercury thus obtained at 1300° bore,
however, no apparent relation to the known vapor
pressure of potassium chloride or to the amount of
potassium in the mixture. The percentage of K20
volatilized at 1300° was found to be only slightly
greater than at 1200°. On account of the claim
of Spackman and Cornwell1 that the presence of
water vapor in a cement kiln aids in the formation
of soluble potassium compounds from potassium-
bearing silicates and acid-forming gases, e. g.,
chlorine from the decomposition of chlorides added
with the charge, experiments were made in which
water vapor was mixed with the nitrogen used in the
vapor pressure tube. The results of these experiments
show plainly that no advantage in the formation and
volatilization of potassium chloride is gained by the
use of water vapor with a mixture of calcium chloride
and greensand.
The figures obtained with mixtures of greensand and
calcium chloride are given in Table I.
Table I — Volatilization of Potash from Mixtures of Grhicnsand
used. The results of heating these mixtures for 11
min. at 1300° C. are shown in Table III.
Min- ature
utes ° C.
12 1204
12 1203
14 !208
14 1205
16 1201
15.5 1202
18 1303
11 1301
11 1300
18 1301
26 1302
26 1302
26 1297
26 1303
16 1298
17 1302
12 1299
12 1301
The gas used was
0.5993
0.6744
0.6153
0.5710
0.7117
0.6660
0.6364
0 . 6008
0.6086
0.6314
0.5819
0.5879
0.5541
0.5728
0.6059
0.5900
0.6235
0.6338
t mixture of
K20
Charge
0.0363
0.0408
0.0373
0 . 0346
0.0431
0.0403
0.0386
0.0364
0 . 0369
0.0383
0.0353
0.0356
0.0336
O.0347
0.0367
0.0358
0.0377
0.0384
trogeu and dry steam
0.060
0.075
0.061
0 . 064
0.072
0.066
0.065
0.061
0.061
0 . 065
0.058
0.059
0.055
0.057
0.061
0.059
0.062
0.063
R< ,i. In.
0.0320
0.0354
0.0332
0.0301
0.0385
0.0350
0.0319
0.0310
0.0313
0.0317
0.0286
0.0284
0.0281
0.027 7
0.0311
0.0306
0.0310
0.0333
Vola-
tilized
VOLATILIZATION OF POTASH FROM MIXTURES OF
SILICATES WITH LIME
The next experiments were with calcium oxide as a
releasing agent. On account of the number of ex-
periments necessary to obtain results which can be
plotted and extrapolated to vapor pressures, and on
account of the difficulty in finding any definite rela-
tion between the vapor pressures of potassium com-
pounds in the mixtures and the vapor pressures of
the pure compounds involved, it was decided to run
the experiments in duplicate. The speed of the gas
stream was varied, but the time of the experiment was
kept constant. The results were expressed in terms
of the percentage of potassium oxide volatilized. The
knowledge of the vapor pressure of the pure potas-
sium compounds involved was then used in interpret-
ing the results. In the experiments with lime as a
releasing agent the mixtures given in Table II were
l U. S. Patent 1.202.327 (1916); C. A., 11 (1917), 89.
. Per
CaO after
cent of .
Mixture Materials
Proportions
Heating
KiO in Raw
No.
I
Used
Greensand
Grams
10
Calculated
Mixture
CaC03 pptd.
22
64
1 .90
3
Greensand
30
Limestone
70
50
2.38
VI
Greensand
10
Calcium hydroxide
15
62
' 46
VIII
Greensand
6
CaC03 pptd.
9
48
2 . 4 2
VII
Greensand
6
CaCOj pptd.
6
38
3 . 03
III
Feldspar
3
CaCOj pptd.
9
65
3.50
V
Feldspar
3
Ca(OH)3
6
64
t 7ii
III— Volatilization op Potash prom Silicate
Mixtures (Heated 11 min. at 1300° C)
in
. Mg.
K.O .
Ka< p
Cc Na
Water
Weight
Vol-
per
Vapor
Charge
Per
Resi-
atil-
Min.
Mg.
Grams
cent
Charge
due
ized
1 50
0.5754
34.9
10.9
2 7
75
117
ii 5727
34.9
10.9
2.7
75
79
0.5529
35.0
10.5
2.4
77
150
i6!<3
0.5502
35.2
10.5
1 .0
91
117
7.8
0.5695
35.2
10.8
1 .1
90
80
6.0
0.5839
35.2
11.1
1 .2
89
162
0.5588
32.9
13.3
9.3
30
134
0.5390
33.0
12.8
9.8
23
163
8.2
0.5242
33.5
12.5
6.1
51
132
7.2
0.5062
33.6
12.1
5.5
55
161
0.5032
19.9
12.4
7.4
40
135
0.4971
20.0
12.2
6.6
46
161
i.vi
0.5362
20.3
13.2
5.8
55
160
0.4763
30.6
11.6
10.4
111
160
19.9
0.4732
30.7
11.4
10.0
12
160
0.4140
27.3
12.5
11 .5
8
160
5^8
0.4290
27.1
13.0
12.1
7
162
0.3100
34.0
10.9
9.9
'i
134
0.3077
34.0
10.8
9.7
10
158
7.6
0.3030
34.3
10.6
8.5
20
133
6.6
0 . 3050
34.3
10.7
8.4
22
164
0.3030
17.7
14.5
13.5
7
133
0.2992
17.8
14.3
13.1
8
160
i 2 '. 3
0.3262
18.1
15.7
13.5
14
146
11.1
0.3116
18.3
15.0
12.8
15
VIII
VIII
VII
VII
A consideration of the results of the experiments
given in Table III leads to the following conclusions:
(1) The low volatilization in the feldspar mixture fill) is due
to the fact that the vapor pressure of potassium oxide alone is
too low at 1300° C. to cause rapid and complete volatilization of
the potassium in the mixture. The vapor pressure of potassium ox-
ide from potassium carbonate has been found to be 1.68 mm. at
970° C. and 5.0 mm. at 1 130°, while the vapor pressure of potas-
sium chloride at these temperatures is 10. 1 mm. and 52.7 mm., re-
spectively. If the vapor pressure curve for potassium oxide in
potassium carbonate has the same general form as that for the
chloride, the vapor pressure of the oxide at 1300° C. would be
about 13 mm. It would seem that the vapor pressure of potas-
sium oxide in the highly limed mixture of silicate and lime is
not greater than that of potassium oxide in the carbonate, and
has probably about the same value as the vapor pressure of water
at 15° C.
(2) The explanation of the higher results in the greensand
mixture (I) lies in the fact that greensand is a hydrated silicate.
Accordingly, any K-O formed by the action of CaO upon the
greensand is formed in the presence of water vapor which is
being evolved from the silicate. This affords an excellent oppor-
tunity for the formation of potassium hydroxide, provided the
reaction
K2( I + H20 > 2KOH
is not completely reversed at 1300° C. The statements of
Deville,1 quoted by Roscoe and Schorlemmer,2 and of Watts3
i Compt. rend . 45 (1857), 857.
2 Roscoe and Schorlemmer. "Treatise on Chemistry," Vol, II, "The
Metals," 1907, 321
'Watts "Dictionary of Chemistry," Vol. IV. 1868, 702.
294
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
are contradictory on this point, but it is believed that at a tem-
perature of 1.300°, or lower, the reaction of K2O and H20 to
form potassium hydroxide must certainly take place at a speed
which is not inappreciable. Now the vapor pressure of potas-
sium hydroxide at 800° C. has been determined and found to
be about as great as that of the chloride at 950° and considerably
greater than that of the oxide from the carbonate at 1130°. At
1300° the vapor pressure of potassium chloride is 202 mm., and
at this temperature the hydroxide must be near its boiling
point. Hence it is believed that when the greensand molecule
reacts with calcium oxide at the high temperature of these ex-
periments, a considerable portion of the potassium in the green-
sand forms potassium hydroxide with the oxygen and hydrogen
which are combined in the silicate, and is thus volatilized from
the mixture. In an attempt to aid the volatilization of potas-
sium from the greensand and feldspar before the theory of the
volatilization as given above had been fully developed, some
experiments were made in which calcium hydroxide was sub-
stituted for calcium carbonate in the mixtures (V and VI).
The use of calcium hydroxide did not aid the volatilization and
it is not to be expected that it would, for this compound is dis-
sociated into calcium oxide and water vapor so rapidly at the
high temperature of the experiments and the water vapor is
so quickly carried away from the mixture by the rapid stream
of dry nitrogen used that there is little chance for the formation
of potassium hydroxide. On the other hand, the water vapor
from greensand is given off rather slowly, and since the hydrogen
and oxygen exist closely associated with the potassium in the
greensand molecule there is every chance for the formation and
volatilization of potassium hydroxide.
(3) The results of the experiments in which nitrogen carrying
a considerable amount of water vapor was used instead of dry
nitrogen confirm in a very striking manner this new theory of
the volatilization of potassium from mixtures of silicates with
lime in about the proportions used in the manufacture of port-
laud cement. According to the theory, the low volatilization of
potassium from the feldspar and lime mixtures is due to the low
vapor pressure of potassium oxide formed by interaction of the
potassium aluminium silicate and calcium oxide, and the higher
volatilization of the potassium from the greensand and lime
mixtures is on account of the high vapor pressure of potassium
hydroxide, which is formed along with potassium oxide by the
action of calcium oxide on the hydrated potassium iron silicate.
The potassium hydroxide thus formed may be dissociated at
this high temperature, possibly according to the reaction :
2KOH ^~^ K20 + H20
Hence it would be expected that a continuous and fairly large
supply of water vapor in the atmosphere of the reaction chamber
would prevent to some extent the dissociation of the potassium
hydroxide and aid in the volatilization of potassium from the
mixture. It would also be expected that the water vapor thus
supplied would react to form hydroxide with the potassium
oxide in the feldspar mixtures and increase the volatilization
of potassium from these mixtures as well. The results of the
experiments in which water vapor was used completely fulfilled
these expectations, and thus confirmed the theory of the volatil-
ization of potassium as developed above.
(4) The percentage of potassium volatilized from the mixture
(3) of greensand with limestone is lower than that obtained
when either precipitated calcium carbonate or calcium hydrox-
ide was used. This is probably due partly to the lower lime con-
tent of the mixture and partly to impurities present in the lime-
stone. Even in this mixture, however, the volatilization was
doubled by the use of water vapor.
(5) The very low volatilization of potassium in the greensand
mixtures (VII and VIII 1 is due partially to the small percent-
age of lime in the mixtures, but mainly to the fact that these
low lime mixtures at this temperature fuse completely,
forming a glass in which the potassium is probably combined
with the silica and thus dissolved in the other liquid silicates
so that it is prevented from volatilizing both by being chem-
ically combined in a rather nonvolatile compound and by being
dissolved in a viscous liquid. Undoubtedly the small amount
which was volatilized came off during the melting of the
mixture. Naturally when potassium is held in a glassy silicate,
water vapor cannot aid in its volatilization.
VOLATILIZATION OF POTASH FROM MIXTURES OF
SILICATES WITH LIME AND CALCIUM CHLORIDE
From our knowledge of the vapor pressures of the
compounds involved it might be predicted that better
results would be obtained in the volatilization of potas-
sium from silicate mixtures containing both lime and
calcium chloride, than from mixtures of silicates with
either of these compounds alone.
In the experiments to test the efficiency of calcium
chloride as a volatilizing agent when used in conjunc-
tion with lime as a releasing agent, the mixtures given
in Table IV were used. Both were made in propor-
tions which would give, after heating, a residue that
approached portland cement in composition.
Table IV — Mixtures of Silicates with Calcium Carbonate and
Calcium Chloride
Materials
Used
Proportions
Grams
Per
CaO after
Heating
Calculated
cent of
K;0 in Ra
.Mixture
Greensand
CaCOi pptd.
CaCU anhyd.
10
21
1
65
1.90
Feldspar
CaCOa pptd.
CaCl: anhyd.
10
26
2
65
3.70
The results of heating these mixtures for 11 min. at
1215° and at 1300° C. are given in Table V. The
experiments with the greensand mixture at 1300° were
made first. Since the volatilization was practically
complete at this temperature, the experiments at 1215°
were performed so as to find whether the use of water
vapor had any influence on the volatilization of pot-
ash from cement mixtures when used in connection
with a chloride.
Table V — Volatilization of
with Lime t
(Heated 11 Min. with 125 to
Potash from Mixtures of Silicat I
.nd Calcium Chloride
170 Cc. of Nitrogen Passing per Min )
Expt.
No.
Mix-
ture
No.
Tem-
pera-
ture
° C.
Water
Vapor
Mg.
Charge
Loss
Weight
Per
cent
. Mg-
Charge
K-O
Resi-
due
Per
cent
KjO
Vola-
tilized
103
10+
105
II
II
II
1300
1300
1300
0.5603
0.5618
0.5629
36.0
JS g
36.1
10.7
\i> :
10.7
0.3
0.3
0.2
97
97
98
109
110
111
II
II
II
1300
1 500
1300
10.9
12.0
8.1
0.5132
0.5551
0.5350
36.2
36.2
36.2
9.8
10.5
10.2
0.3
0.3
0.2
97
97
98
1 S2
133
II
II
1215
1215
0. 5223
0.5301
36.2
36.2
9.9
10.1
0.7
Trace
92
134
135
II
II
1215
1215
7.4
15.6
0.5301
0.5257
36.2
36.2
10.1
10.0
0.8
0.4
92
96
136
137
IV
IV
1215
1215
0.3249
0.3056
36.8
36.9
12.0
11.3
3.5
3.1
71
73
138
139
IV
IV
1215
1215
13.7
7.3
0.3021
0.3149
36.9
36.9
11.2
11 .6
2.9
3.0
74
74
The results of the experiments on mixtures of green-
sand and of feldspar with both calcium oxide and
calcium chloride in proportions to give a residue which
has about the composition of portland cement show
that:
(1) The removal of potassium by volatilization from the
greensand mixture is practically complete in 11 min. at a tem-
perature as low as 1215° C, but the volatilization of potassium
from the feldspar mixture is not as complete.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
295
(2) As might be expected, no advantage is gained by the
use of water vapor when there is present in the mixture sufficient
chlorine as chloride to form with the potassium of the silicate
the stable compound potassium chloride, whose vapor pressure,
101 mm. at 1215° C. and 202 mm. at 1300° C, is high enough
to allow of rapid evaporation.
(3) The claims made by Spackman and Corn well1 that the
presence of water vapor aids in the formation of potassium
chloride from chlorides and potassium-bearing silicates appear to
be unfounded.
VOLATILIZATION OF POTASH FROM LOW LIME SILICATE-
CHLORIDE MIXTURES
In the previous experiments we had learned: first,
that potash is volatilized at a lower temperature and
more rapidly from greensand mixtures than from feld-
spar mixtures; and, second, that the volatilization of
potash from low lime mixtures which fuse is slight.
It was surmised, however, that in the latter case the
low volatilization was due rather to the fusion of the
mixture than to the lack of lime to set free the potash
from the silicate.
A series of experiments was therefore run using mix-
tures of greensand with a chloride and with limestone
in much smaller proportions than the proportion of
limestone used in portland cement mixtures. In these
experiments the mixtures given in Table VI were used.
T
ABLE VI— LOW Li
ME GREENS!
nd-Chi
OR ID
: Mixtures
ixture
No.
Materials
Used
Proportions
Grams
Ratio of
Greensand
Limestone
. — Percentage of — *
Chloride KjO in
Added Mixture
5
Greensand
Limestone
50
50
1 :
1
None
3.85
7
Greensand
Limestone
Sodium chloride
10
10
1
1 :
1
5.0
3.67
8
Greensand
Limestone
Calcium chloride
10
10
0.9
I :
1
4.5
3 . 69
9
Greensand
Limestone
Sodium chloride
20
10
2. 1
2:
7.0
4 75
10
Greensand
Limestone
Sodium chloride
20
10
0.9
2:
3.0
4.95
The results of heating these mixtures at temperatures
just below those at which they start to fuse are given
in Table VII.
Table VII — Volatilization of Potash from Low Lime Gref.nsand-
Chi.oride-I.imestone Mixtures
(Air Passing at Rate of 100 to 150 Cc. per Min.)
Ratio Chloride - Potassium Oxide
£ 5
O
1050
60 1
1 No
ne
0.4419
25.12
17.0
17.2
1170
30 1
1 None
0.4810
25.63
18.5
17.3
1170
30 1
1 None
0.4641
25 . 45
17.9
16.9
1050
60 1
1 NaCl
5.0
0.4434
30.09
16.3
6.0
1190
15 1
1 NaCl
5.0
0.4862
3 1 . 96
17.8
0.4
1200
15 1
1 NaCl
5.0
0.4737
31 .10
17.4
1.6
1170
15 1
1 NaCl
5.0
0.4627
31.55
17.0
I .6
1170
15 1
1 CaCh
4.5
0.4767
31 .63
17.6
3.6
1170
IS 2
1 NaCl
7.0
0.4222
28.00
20.0
3.0
1170
15 2
1 NaCl
3.0
0.4260
24 25
21.1
8. 1
A consideration of the results given in Table VII
shows that:
(1) The volatilization of potash from a 1:1 mixture of green-
sand and limestone without the addition of a chloride is very
small at temperatures up to 1170° C. This is true even in the
presence of water vapor which was used in Kxpt. 163.
(2) On addition of a chloride in proportion slightly greater
than that calculated for the formation of potassium chloride,
the potash in greensand and limestone mixtures can be readily
volatilized at temperatures slightly lower than the temperatures
at which the mixtures begin to fuse. This has been shown for
mixtures containing as little as one-third limestone.
(3) Sodium chloride appears to be somewhat more efficient
than calcium chloride as a volatilizing agent, and when less
chloride is used than the amount calculated to give potassium
chloride with all of the potassium in the mixture there is a
decided decrease in the volatilization.
SUMMARY
1 — In the application of a knowledge of the vapor
pressures of potassium compounds to a study of the
volatilization of potash from silicate mixtures, a new
theory involving the high vapor pressure of potassium
hydroxide has been advanced to explain the volatiliza-
tion of potassium from silicate and lime mixtures.
Thistheory is supported by thefact that greensand which
contains the elements of water loses its potassium by
volatilization very much more readily than feldspar,
and by the fact that when water vapor is present to
aid in the formation of potassium hydroxide, the vol-
atilization of potassium from high lime mixtures is.
greatly increased in every case.
2 — Experiments on a mixture of feldspar with cal-
cium chloride and lime in the proportions necessary to
give a portland cement clinker, and on a mixture of
glauconite with lime and calcium chloride, show that
the potash is volatilized from both silicates at tem-
peratures as low as 1215° C. The potash is, however,
more readily volatilized from the glauconite than from
the feldspar.
3 — It has been shown that when a chloride is used
in the volatilization of potash no advantage is gained
by the use of water vapor. This is in accord with
what might be expected, since the chloride of potas-
sium is so much more stable at high temperatures than
the hydroxide, and is contrary to the patent claims of
Spackman and Cornwell.
4 — Experiments on mixtures of greensand with a
chloride in the proportion calculated to give potassium
chloride and limestone in proportions much lower than
those used in portland cement mixtures show that the
potash can be readily volatilized from mixtures con-
taining as little as one-third of limestone, provided the
mixture is heated at a temperature slightly below its
fusing point.
Examination for Pyrotechnic Assistant
The United States Civil Service Commission has announced
an examination for pyrotechnic assistant at S1S72 a year to
fill a vacancy at Picatinny Arsenal, Dover, N. J . and other
vacancies requiring similar qualifications. The duties of the
appointee will be to assist in the development of design, test,
and manufacture of military pyrotechnics and in addition the
duties of an observer and firer from aircraft. Competitors will
be rated on II) physical ability, 40; (2) education, experience,
and fitness, 00. Applicants must be high school graduates
and have had one year's experience along the line of pyrotechnic
material. Experience in flying and acquaintance with the
present equipment and devices of the Aircraft Divisions of the
War Department are desirable. Applications should be filed
with the United States Civil Service Commission, Washington,
D. C, prior to the hour of closing business on April .">, 1921.
296
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
Possible Uses of Corncob Cellulose in the Explosives Industry1
By L. G. Marsh
Pittsburgh Experiment Station, U. S. Bureau of Mines, Pittsburgh, Pa.
Among the many economic and industrial problems
arising out of the late war was that occasioned by the
shortage of cotton cellulose for use in the manufacture
of guncotton. The extreme importance of this prob-
lem caused a search for cotton substitutes to be in-
stituted,3 with the hope that some material could be
found suitable for use either alone or in conjunction
with cotton cellulose as a basis for cellulose nitrate
explosives.
PREVIOUS WORK ON COTTON SUBSTITUTES
Various forms of cellulose have previously been proposed for
the preparation of nitrates, in an endeavor to produce more
stable and less expensive esters, and, as early as 1859, J. Mack-
intosh and G. Rhodes4 succeeded in nitrating white pine sawdust
to a constituency suitable for use as a waterproofing ma-
terial.
In 1870, Henry Spill attempted to use esparto grass, but his
experiments were never completely successful, owing to the
difficulty encountered in the removing of the silica from the raw
product.
Ramie,6 flax, and esculapius weed6 have also been investigated,
and their nitrates have been successfully worked up into plastics
for dental plates.
Dean prepared nitrodextrin' by treating bleached cotton with
sulfuric and hydrochloric acids and nitrating in the usual
manner.
Bernstein8 made an investigation of the solid fruits, nuts, and
shells of trees of the palm spe.i s, particularly the fruit of the
Phylelephas macrocarpa (usually known as vegetable ivory) and
of several species of Maurita, and found that after being subjected
to boiling in alkaline solutions, followed by a thorough washing
in water, these materials reacted with mixtures of nitric and
sulfuric acids to form esters resembling those of cellulose
nitrate.
Dolliak0 prepared a cellulose nitrate with a nitrogen content
of 11.07 per cent and a flash point of 177° C. by boiling rye straw
for 15 hrs. in a 0.5 per cent caustic soda solution and then sub-
jecting it to the action of nitrating acids.
Cross and Bevan'0 carried out extensive investigations on jute
fiber, and successfully established the fact that it is a mixture of
cellulose and noncellulose, and yields explosive nitrates, of which
the highest is the tetra nitrate. These nitrates closely resembled
those of cotton cellulose in all essential points.
The Marsden Company'1 found that vegetable pith, such as
that of maize or cornstalk, after being separated from the wood
and fiber, could be nitrated successfully to an ester of great solu-
bility and low viscosity.
Among other materials which have at various times been in-
vestigated as possible sources for commercial cellulose are wood
' Received December 7, 1920.
2 Published by permission of the Director, U. S. Bureau of Mines.
3 This investigation was undertaken by the Explosives Chemical Labora-
tory of the Bureau of Mines, at the request of the Committee on Explosives
Investigations of the National Research Council.
< Brit. Patent 734 (1859).
' L. Dietz and B. P. Wayne, U. S. Patent 133.969 (1872).
• Bickford, Spooner and Pyroxylin Manufacturing Co., Brit. Patent
1170 (1873).
' Brit. Patent 2226 (1881).
• Brit. Patent 12,778 (1885).
» J. Soc. Chcm Ind., 4 (1885), 366.
■» J. Client. Soc, 38 (18S0), 667; 56 (1889), 202.
» Brit. Patent 6656 (1S89).
fiber,' esparto,2 hemp,3 gorse,4 the fiber of Ulex europens? wood
pulp,6 the flower stems of various species of agave,7 bamboo fiber
and certain bast fibers growing in Japan,8 and marine fiber or
Posidonia australis. With the exception of marine fiber and
wood pulp these materials have been found to be impractical for
commercial use, owing to the difficulty in purification or in ob-
taining sufficient amounts of the raw material to justify con-
tinued use.
Woodbridge in his investigation of wood pulp showed that this
product could be used commercially as a basis for nitrate explo-
sives, but the efficiency of its application was greatest when it
was used in mixtures with cotton cellulose.
Smart,9 prompted by the unsuccessful cultivation of cotton
in Australia and the attendant shortage of the raw product for
explosive use, investigated the possibilities of marine fiber
(Posidonia australis) as a successful source of cellulose for gun-
cotton. The results of this investigation have shown that a stable
guncotton can be produced from the fiber and the raw material
can be purified on a commercial scale so as to render it suitable
for nitration. Further research on a commercial scale is neces-
sary before industrial exploitation of this material should be
undertaken.
CELLULOSE FROM CORNCOBS
LaForge and Hudson10 showed that corncobs, which
have always been comparatively a waste product of
our agriculture, can be successfully utilized as a source
of raw material in the preparation of adhesive gums,
crystalline xylose, acetic acid, and crystalline glucose.
According to their procedure, crude cellulose was ob-
tained as a by-product in the manufacture of xylose
and adhesives as follows:
The coarsely broken corncobs were heated in an autoclave to
140° C, then at 160° C, for 1 hr., after which treatment the
mixture was subjected to strong pressure to separate the liquid
from the solid residue. The solution, after evaporation, con-
stituted the adhesive gum. The solid residue remaining was
heated in an autoclave with 1.75 per cent sulfuric acid at 130° C.
for 1 hr., thereby causing the liberation and solution of xylose
and acetic acid. After this treatment, the solid residue consisted
chiefly of crude cellulose, and could be separated from the acid
solution by compression.
The crude cellulose thus obtained is a rather finely
divided, short-fibered, compact substance which can
be readily purified. LaForge and Hudson utilized
it in the preparation of glucose, and in addition to its
use in the manufacture of materials necessarily char-
acterized by a cellulose base suggested the possibility
of its use as an absorbent for nitroglycerin in dyna-
mite.
' W. Ruckteschell, Brit. Patent 4349 (18S5).
' Pro:. Chcm. Soc, 1894, 89, 137; Cross and Bevan, J. Ckem.Soc, 38
(1880), 667.
' C. F. Hengst, Brit. Patent 13,656 (188S)
< A. Bouret and A. B. Verbie^e, Brit. Patent 24,768 (1898); F. G Hortcl-
oup, Fr. Patent 347.353 (1904).
»G. Horteloup, Fr. Patents 331.176 (1903); 347,533 (1904); 327,136
(1902).
6 Brit. Patent 336 (1891); Woodbridge, This Journal, 12 (1920 . 38 I
I Brit. Patent 21,505 (1905).
• N. Nishida, This Journal, 8 (1916), 1096.
• Chcm. Ens. Min. Rev. Australia, 10 (1918), 380.
■° This Journal, 10 (1918), 925.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
CORNCOB CELLULOSE AS AN ABSORBENT FOR NITRO-
GLYCERIN
The corncob cellulose used in the experiments was
furnished to the Explosives Chemical Laboratory by
the Carbohydrate Laboratory of the Bureau of Chem-
istry. It was prepared by the extraction of ground
cobs with 1 per cent caustic soda solution at 100° C,
with subsequent washing and extraction with 4 per
cent sulfuric acid at 100° C.
A portion was broken up in an agate mortar and
screened to pass 30 mesh, then dried at 90° C. for 5
hrs. To 9.2 g. were added 26.2 g. of nitroglycerin, the
mixture well kneaded and allowed to stand for 24 hrs.
Two portions of this material were then placed in
Gooch crucibles and submitted to the exudation test
by centrifuging.1
The loss in weight was noted, and the material al-
lowed to stand for an additional 24 hrs., and again
centrifuged. The second loss was noted, and the resi-
due extracted with ether in the Wiley apparatus.
This extraction showed that the cellulose held 150 per
cent of its own weight of nitroglycerin. This was
verified by making up a mixture of 1 part of the cellulose
with 1.5 parts of nitroglycerin, and testing as before.
The exudation was well within the limits of safety,
showing that this material could be used as a carbon-
aceous combustible absorbent in a dynamite.
CORNCOB CELLULOSE AS A SUBSTITUTE FOR SHORT-
FIBERED COTTON IN PRODUCTION OF CELLULOSE
NITRATES
In the nitration of cotton it is desirable to know the
relative rates at which the cotton tested will take up
the mixed acids during the nitrating process. The
rates of acid absorption are naturally dependent on
the purity of the cellulose material. Cotton which
is free from oils and natural impurities is very readily
acted upon by nitrating acids, while, in the case of the
crude material contaminated with oils and other
vegetable matter, there seems at first to be a repulsion
between the fiber and the surrounding liquids. The
absorptive power of any cellulose may be determined
by a study of its action with respect to water.
absorptive capacity for water — As a preliminary
step to the nitration of corncob cellulose, the rate of
absorption of water was determined on the material
both in its original form and after its subsequent treat-
ment with sodium carbonate solution. The method
given by Dr. C. E. Munroe2 was followed. Samples
of the material were dropped on the surface of distilled
water, and the time from the moment that the cellulose
touched the surface of the water until it became com-
pletely submerged was noted. All samples were sub-
merged in less than 12 sec.
Similar determinations were made for the cotton
to be nitrated for comparison with the corncob cellulose,
both in its original condition and after purification by
successive boilings in 5 per cent sodium carbonate-
1 Bureau of Mines, Bulletin 61, 10.
3 "Inspection of Cotton for Use in the Manufacture of Guncotton,"
J. Am Chem. Hoc, 17 (1895), 793.
1 per cent bleaching powder solution and water, fol-
lowing the identical treatment described for the puri-
fication of the corncob cellulose. The unpurified cot-
ton was not submerged in 24 hrs., while the purified
samples were submerged in 1.5 min. These results
indicate that corncob cellulose will be very readily
acted upon by nitrating acids.
nitration — The nitrating acid consisted of mixed
nitric and sulfuric acids containing 22 per cent HN03,
1 4. 2 per cent H20, and 0.1 percent N204. The cotton was
nitrated in the usual way, the excess acid wrung out,
and the cotton washed thoroughly with hot and cold
water, then cut in the beater. After this it was again
washed several times with hot and cold water until it
proved to be stable by the Abel and 135° tests. It
had a nitrogen content of 12.66 per cent and gave a
yield of 151 per cent of the dry cotton.
The corncob cellulose was nitrated in the same way,
but there was difficulty in separating the nitrated
product from the acid. The material was so fine that
it passed through the screen. It was finally separated
by gravity, using a mat of nitrated cotton. It did not
hold as much acid mechanically as nitrated cotton
filtered in the same way. It was easy to wash, as it
settled readily and the water was drawn off from the top.
The material was so fine that it was not cut in the
beater, but the purification was continued as in the
case of the nitrated cotton.
There was no apparent difference in the results of
the heat tests, as the corncob nitrocellulose met the
specifications for use in smokeless powder in this
respect.
The nitrogen content was only 12.30 per cent and
the acetone-insoluble, or unnitrated material, very
high. A sample of the nitrated cellulose was dissolved
in acetone and filtered off from the insoluble residue,
after which the soluble nitrocellulose was thrown out
of solution and nitrogen determined. This portion
ran 12.70 per cent nitrogen. On examination, the
residue was found to consist of fine, hard grains, ap-
parently little touched by the acids. Several de-
terminations were made with acids containing more
water, and with the time of nitration increased to 2
hrs.. but in every case the acetone-insoluble was much
too high. The hard nature of the residue, as well as
the excessive amount, would make it impossible to
use this nitrocellulose in the manufacture of a perfor-
ated powder.
Some experiments were conducted to overcome the
mechanical losses due to the fine material remaining
with the acid. Mixtures of equal parts of cotton and
corncob cellulose were nitrated together. The longer
fibers of cotton acted as a mat and held most of the
corncob nitrocellulose. There was little use of carrying
the work further, however, as the final product did not
meet the requirements in regard to acetone-insoluble
residue.
The yields in the corncob cellulose averaged about
130 per cent. This was accounted for by the loss of
fine material and the residue that was not nitrated,
or only partially nitrated.
298
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
Where a thin solution of the nitrocellulose was made
by dissolving the nitrated material in a solvent such
as ether-alcohol, acetone or amyl acetate, the insoluble
material settled out from a clear supernatant liquid,
indicating that it could be vised in the manufacture of
collodion and some lacquers. In these products, how-
ever, the cost of the nitrocellulose itself is of minor
importance as compared with the other costs. So
there is no advantage in using nitrated corncob cel-
lulose as long as cotton is available.
CONCLUSIONS
It appears that the only use for corncob cellulose
in the explosives industry at the present time is as a
carbonaceous absorbent for liquid ingredients, such
as nitroglycerin, in the manufacture of dynamite.
For that use it must compete with such materials as
wood pulp, sawdust, cornmeal, charcoal, peanut hulls,
rice hulls, and similar materials, all of which have
properties which are advantageous for the manufacture
of special grades of dynamite.
Some Interpretations of the Ammonia Synthesis Equilibrium1
Plant One Section, Nitrate Division. Ordnance Dept., and t
The extent to which the reaction
•ANj-f VjHj^NH,
can proceed is a function of the temperature, pressure,
and concentrations of the components of the system.
Thermodynamic considerations lead to the following
relation for concentrations at equilibrium:
Cnh, = Kc X (Cn,)'A X (Ch,)'A (1)
where Kc is the concentration equilibrium constant.
Using partial pressures instead of concentrations, the
above may be expressed as:
PiNH.) = K, X (PN!)'A X (pHJ>/> (2)
where ^(NHab (Ph«), (Pn2) are partial pressures in
atmospheres of the respective constituents and K^
is the pressure equilibrium constant. In the latter
form Haber'2 gives the following equation for the
value of Kp as a function of the absolute tempera-
ture T:
13:00
By R. S. Tour
, and the Fixed Nitrogen Resea
I.abora
Washington, D. C.
logioK. =
'IT
6.134
(3)
-If a = volume fraction of ammonia in the system at equi-
librium,
c = volume fraction of inert gases at equilibrium,
r = volume ratio of hydrogen to nitrogen at equilibrium,
P = total pressure in atmospheres,
then by simple transformations we may arrive at
the following relation:
u=^ = KPu^ (4)
where K has the same value as Kp above.
If interested in the ammonia content, the equi-
librium condition may be most simply inspected and
calculated, and the effect of different variables best
noted and determined with the help of Formula 4.
In Fig. 1 is given a set of curves showing the effect
on equilibrium ammonia content of a variation of
any one of the conditions involved when the others
are held at the arbitrary values: T = 773° A., P =
100 atmospheres, r = 3, c = 0. It is to be noted
from the equation and the curves that:
(1) The effect of temperature is very marked, especially at
the lower temperatures, the ammonia content rapidly increas-
ing with decrease in temperature, although it should be remem-
bered that reaction velocity decreases very rapidly with this
' Received November 26, 1920.
1 F. Haber. Z EUclrochtm., 21 (19151. S9.
decrease of temperature. A reduction of temperature from
500° to 485° C. is as advantageous as a rise in pressure from
100 to 120 atmospheres.
(2) Pressure does not increase the ammonia content in direct
proportion, but at a decreasing rate with increasing ammonia
content.
!
Temp/0
\
' >/?.7 1
\
. Effect of Variations from Assumed Corrffions
\
P-tOOfltm
V AfyZSXfAtstf,)
//2)Pfessvrc
\
/nerfGos*0%
/
d
/
V
/
'
* _
^
/
| _
r
/
\
£-
A
/
'
\
/
1
"
$ -
9
1
/
/
\x
J&.J31
I
t
N
s
v
V
,,, M
6
/
\
\
WOW
t
\f4)/rier/-
J
/
^(fJ&mA
Pressure (Z)
)
Temp. 4O0 20406030 500 20 40 eo go €00 20 40 6
Press O /OO ?on t.
0 °c
O
Nj/^H^) 0 S /O & 20 2* SO ** 40 4S SO SS eo A
/nert . , . 0 J 'O /s 20 2s jo js *
? %\
(3) Changes in ratio of hydrogen to nitrogen have but a small
effect over a considerable range. The maximum ammonia
content is, of course, for the theoretical proportion of INs : 3H?,
but a variation to 2N2 : 3H2 (or 0.5 N2 to 3 H-) involves a re-
duction of less than 10 per cent of the equilibrium content.
(4) The effect of inert diluents is often misunderstood and
considered as merely similar to an equal percentage drop in
pressure. It should be noted, however, that the pressure of
the diluent not only lowers the partial pressures of the reacting
gases, but also actually dilutes them as well. To show this
we may write the equilibrium expression in the form:
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
Orct/hafes
303
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
5?
I*
M
I!
«: % 5 * « « ?
~j « t - * 5 < ■>.
t 5 | 5 I l-l-
;5 J5n»
o, " TV
<' sis
IT
I 4
r
a-
or very closely
c)- [(l — o)(i — C).
= (1 — e)*KP
(1 — a)2 (l+r)»
It will he seen from Equation 5 that the effect of 10 per cent
diluents corresponds closely to a 20 per cent drop in pressure.
The frequent computation and solution of the ex-
pression
- = KP r , where log,„K = 1320° - 6 134
(1 — a — of (1 + r)» 4.571 T
is long and tedious, and families of curves are ordinarily
confusing. However, if we write the closely approxi-
mate expression (5) in the form:
log — = 2 log (1
(1— a)2
c) + log P +
■>A
+
6
(1 + n2
we may then plot each of the terms as a separate
single curve with its variable as abscissa. By adding
the ordinates for any complete set of conditions, we
may directly obtain a graphically from the curve for
log
(] — o)s
(see Fig. 2).
The figure show diagrammatically the set of curves
just described. A similar chart at present in use
carries ten times the scale divisions shown in the figure
and is accurate to 0.1 per cent NH3.
More frequently, however, the equilibrium ammonia
content is desired when only temperature and pressure
are the variables, while r is at the theoretical value
of 3.0 and c = 0. For this case the simple nomograph
shown in Fig. 3 may be constructed if the equilibrium
be expressed in the form:
2888
;P +
+ const.
7
(1 — a)2
The figure is a reproduction of a chart 12 in. X 42 in.,
which is being tised at present with great satisfaction.
It is hoped that the curves and graphical solutions
given will prove of value to laboratories working
on the problem of ammonia synthesis.
Exports of Naval Stores
During the calendar year 1920 domestic exports of naval
stores from the United States were valued at $34,545,296, more
than three times the figure for 1918, and an increase of 10 per
cent over 1919. Annual exports for 1919 and 1920 were as
follows :
. 1920 . . 1919 .
Quantity Value Quantity Value
Rosin, bbls 1,160,385 $19,781,353 1,209,627 $20.-133,970
Tar, turpentine, and
pitch, bbls 53,149 451.641 67.25S 551.793
Turpentine (spirits)
gals 9,162.607 14,312.302 10.672,102 10.448.234
Totai $35,545,296 $31,433,997
Average Annual Export Prices of Naval Stores
Tar, Pitch. Spirits of
Rosin. and Turpentine. Turpentine.
Vear per Bbl. per Bbl. per Bbl.
I'.ns $ 9.70 J7.61 $0,612
1919 16.89 S.85 0.979
1920 1705 8.50 1.562
December IPI'0 12.30 7.04 1.089
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
The Production of Artificially Dense Charcoal
Section of Derived Produ
By L. F. Hawley
Forest Products La
Late in 1917 it was called to the attention of the
Forest Products Laboratory that coconut shell for
making gas-mask charcoal was becoming scarce and
that a dense charcoal manufactured from a plentiful
domestic material would be desirable. The writer was
acquainted with the process in which the distillation
of briquetted hardwood sawdust was carried out under
slight mechanical pressure for the purpose of prevent-
ing the briquets from falling to pieces during the pro-
cess, and it was thought that by both making and dis-
tilling the briquets at much higher pressures an arti-
ficially dense charcoal could be produced.
SMALL-SCALE APPARATUS
A small ''homemade" apparatus was used to try
out this idea. The briquets were made in a mold
l15/i6 in. in diameter and 6 in. deep. By packing the
sawdust firmly into the mold by hand and then com-
pressing in a testing machine, a briquet about 1 in.
thick, with a gravity of about 1.0S, was produced.
These briquets were distilled in a 2.5-in. iron pipe,
2.5 ft. long, held in a 4-in. pipe as a jacket. The outer
pipe was heated by a row of Bunsen burners. The
pressure was furnished by a screw threaded through
the cap on the end of the outside pipe and a weight
hung over a pulley wheel on the end of the screw-shaft.
When the weight descended to the floor, the cord was
wound around the pulley again and in this way fairly
constant pressure was maintained. The briquets were
separated by thin plates of metal to prevent them from
sticking together.
With low pressures during distillation the shrinkage
in diameter of the briquet as the wood changed to
charcoal was very marked. When distilled under high
pressures, however, there was frequently very little
change in diameter, but the compression in thickness
was very marked.
It was soon found that fine sawdust (under 20-mesh)
was required for best results, and that the briquetting
pressures should be at least 15 tons per sq. in. The
pressures obtained on the briquets during distillation
were difficult to measure, since so much of the force of
the descending weight was taken up in friction. The
figures mentioned hereafter in connection with this
apparatus were computed with an allowance for fric-
tion of one-half of the total force.
Several species of wood were tried under varying
conditions of pressure before and during distillation,
and a charcoal with maximum apparent density2 of
0.57 was made from maple-wood sawdust briquetted
at 50,000 lbs. per sq. in. and distilled under 300 lbs.
per sq. in. The briquets had a density of about 1.10
when first made, but rapidly swelled until the density
was about 1.09. Apparently there is a stage during the
distillation when the wood or charcoal is slightly plas-
1 Received December 3. 1920.
2 Apparent density is an empirical figure showing the weight per cc.
of the charcoal between 8- and 14-mesh which can be poured inlo a tube
10 cm. long by 1.41 cm. in diameter under closely specified conditions.
tic and the application of the proper amount of pres-
sure at this time increases the density of the final
charcoal. If too much pressure is applied the char-
coal is shattered without increasing the density of the
granules.
Not only a high apparent density was required but
also an absorption value after activation, which value,
however, varied in general with the density of the
charcoal. The absorption value for chloropicrin1
(designated "C. P."), under standard conditions ex-
pressed in minutes, was determined for this sample
and found to be 590 min., in comparison with 900 min.
for coconut-shell charcoal activated and tested under
similar conditions. Pine woods with natural rosin
binders and hardwoods with binders of rosin, hard-
wood pitch, asphalt, etc., wTere found to give higher
gravity briquets and charcoal, but the C. P. of these
charcoals after activation was in no case so high as
that obtained from wood briquetted without a binder.
Mechanical Pkessike
A — 4-in. pipe; B — collars to hold pipe E in place; C — collar to increase
thread length through top of cap; D — screw; E — 2.5-in. pipe; K — bearing
plate: G — wheel for moving screw D; H — outlet to condenser
Further work on untreated woods with or without
binders was stopped by the discovery of a material
which was very much more promising. It was found
that the insoluble residue obtained by hydrolyzing saw-
dust with dilute acid and leaching out the sugar2 gave
a denser briquet, and a higher yield of a denser charcoal,
and that the charcoal was more absorbent after activa-
tion. The briquets made of 20-mesh dust under a
pressure of 35,000 lbs. per sq. in. had a gravity when
first made of about 1.21, but in a few hours they
swelled to about 1.18, after which there was very
little more swelling. When distilled under a pressure
of 300 lbs. per sq. in. (estimated) at a final maximum
temperature of 450° C, these briquets gave a 40 per
cent yield of charcoal with an A. D. of 0.52 and a
C. P. of 700. This charcoal resembled anthracite coal*
more than ordinary charcoal; it had a conchoidal frac-
ture, was hard and shiny, and showed no trace of the
structure of the wood from which it was made. In
fact, thin pieces under the microscope were slightly
translucent.
SF.MICOMMERCIAL APPARATUS
These results were so promising that further small-
' This Journal. 11 (1919), 519.
2 "Ethyl Alcohol from Wood Waste," Met. Chem. Ens , 16 (1910), 78.
Two plants were producing about 400 tons per day of this material and
using it for fuel.
1 It is, therefore, unnecessary to assume high pressures or long periods
of time to account for the natural formation of coal. Here is a case where
a natural carbonaceous material is made into a product resembling coal
in luster, density, and hardness with only moderate pressures and in a
very short lime.
!02
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
icale work was considered unnecessary, and attempts
were made to confirm the results in semicommercial
apparatus. The Development Division of the Chem-
ical Warfare Service finally offered to construct and
operate a larger apparatus, and the rest of the work
was carried on at the Defense Laboratory of that
Division. A retort 10 ft. long was constructed in
which 4-in. briquets could be distilled, while the pres-
sures on the briquets could be automatically regulated
at any height desired.
It was soon found that the optimum pressures as
estimated from the results with the small apparatus
were too high and that only about 125 lbs. per sq. in.
were required for the best results. It was also found
that, as might be expected, a much more careful regu-
lation of conditions was required in the larger ap-
paratus to obtain a satisfactory product. Even with
the best regulation of the temperature that could be
obtained a portion of the charcoal was unsatisfactory
in density. The end surfaces of all the briquets next
to the plate were hard and dense, but the center por-
tion of some of them was porous and soft. Since it
seemed that it was only the pressure conditions of the
small-scale work which were not reproduced very closely
in the large-scale work (except those conditions due
to the size of the units), an attempt was made to re-
produce the pressure conditions also. The pressure in
the small-scale work was known to have been very
uneven, since the weight would often remain still for
a time and then drop several inches. This effect was
simulated in the larger apparatus by adjusting the
pressure-control apparatus so that the pressure varied
over a wide range, dropping from maximum to min-
imum slowly and then rapidly running up to maximum
again. With these pressure conditions it was pos-
sible to make a much better quality of charcoal. The
best results were obtained with briquets made of
medium-sized commercial hydrolyzed sawdust (be-
tween 4- and 43-mesh), distilled slowly under pressures
varying from 80 to 130 lbs. per sq. in. It was not
possible to make this charcoal quite so hard and homog-
enous as that made on a small scale with the 2-in.
briquets, but an A. D. of 0.58 on the untreated coal
was obtained and a C. P. of 600. There are several
possible reasons for the less satisfactory results shown
by the large-scale work:
1 — The actual size of the briquets may have been too large
to allow a ready escape of the vapors from the center of the
briquet to the surface, while at the same time the pressure was
applied constantly enough to get the full effect. This might
be the cause of the ..porous centers of some of the charcoal
briquets.
2 — The raw material was coarser and not so completely
cooked through.
3 — There was no way to obtain high pressures in making the
briquets, the maximum used being only about 20,000 lbs. per
sq. in.
4 — No other study was made of special activation methods
for this charcoal except comparative tests by the same activa-
tion methods as were used for coconut-shell charcoal. The
wood charcoal having had a maximum temperature of only
about 350° C, naturally contained much more volatile matter
than the coconut shell which had been distilled at 900° C, and
this may have influenced the activation results.
SUMMARY
On a small scale, a charcoal was made from native
raw materials which had an apparent density (A. D.)
of 0.62 and an absorption value for chloropicrin (C. P.)
of 700 min., as compared with a standard coconut-shell
charcoal value of A. D. 0.63 and C. P. 900.
On a larger scale (commercial-sized unit) an A. D. of
0.58 and C. P. of 600 were the best that could be ob-
tained after incomplete experimental work.
Food Research Institute
At the suggestion of Herbert Hoover, a Food Research Insti-
tute for the study of all problems of production, distribution,
and consumption is to be established at Leland Stanford Junior
University, with an endowment of $700,000 provided by the
Carnegie Corporation. Under the terms of the agreement,
the university agrees to establish a research organization and to
appoint three men of science, to be known as directors of the
Institute, who will have authority to determine the scientific
policies of the institute and the problems to be studied. The
directors will head three separate divisions; one will be an ex-
pert in the field of physiology and chemistry of nutrition, one
in economics and food distribution, and one in the chemistry
of food manufacture and agriculture. There will also be an ad-
visory committee made up of men of national prominence
(among them being Mr. Hoover), representing agricultural, con-
sumer, economic, and other groups of the community. The
university will appoint seven members, the president of the
university and the president of the Carnegie Corporation serv-
ing ex-officio. It is the hope of the Carnegie Corporation that
eventually the new organization will be known as 'the Hoover
Institute. The institute may receive such specially qualified
students as it may be possible to instruct without disadvantage
to the primary research purposes of the organization. A small
group of fellowships will be available for graduate students.
The institute will begin its work July 1, 1921, the Carnegie
fund being provided for a period of ten years. After the insti-
tute is once established, the Carnegie Corporation will abstain
entirely from any direction or control of the work.
Classification of Coal for Export
A cooperative agreement has been effected between the Tide-
water Coal Exchange, Inc., of New York and the U. S. Bureau
of Mines for the classification of coal shipped for export through
the ports of New York, Philadelphia, and Baltimore on a basis
of accurate sampling and analysis. The agreement provides
for the establishment of limits and tolerances of quality for cer-
tain pools and for the maintenance of the quality of the pools
within the limits specified. The Bureau of Mines will direct
the work of obtaining the technical information required, col-
lecting representative samples of coal as shipped and of mine
samples when necessary and making analyses at the Pittsburgh
Experiment Station. The Tidewater Coal Exchange will make
classifications on a basis of the analyses and will assign coal to
pools within the limits and tolerances as finally published. The
general purpose of this classification is to expedite transporta-
tion and shipment and to insure the maintenance of certain
standards as representative of the quality of American coals
shipped from various districts to Europe. The pooling of coals
was resorted to in war time by a voluntary organization of coal
operators and railroads, and in view of the great saving in the
use of freight cars and maritime shipping it has been found de-
sirable to continue the arrangement.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
303
The implicit trust whi
tables of constants is unfortunately not always justi-
fied. Even for the most common chemicals, the cur-
rent data for such fundamental properties as melting
point and boiling point are often quite indefinite.
For example, the melting point of potassium iodide2
is variously given as from 614° to 723°. For the melt-
ing point of ammonium sulfate, a substance which is
produced by the ton daily, the figures fluctuate still
more widely. The lowest recorded value is 140°,
the highest 423°; truly a remarkable variation in a
simple physicochemical "constant!"
This particular case is cited by a recent writer3
as "a striking example of the neglect of physical chem-
istry in Germany;" his own efforts to furnish a solu-
tion, however, only serve to confuse the problem still
further. To enable us to escape the possible re-
proach that physical chemistry is still more flagrantly
neglected in this country, a brief discussion of the
fusion phenomena of ammonium sulfate and an explana-
tion of the discrepancies in the literature may be here
presented. For a more detailed examination of the
system: ammonium sulfate-sulfuric acid, reference
should be made to a recent article by Kendall and
Land on.4
PREVIOUS INVESTIGATIONS
The results of previous investigators may first be
summarized. Marchand6 in 1837 obtained a melting
point of 140°, which has been handed down ever since
in all the textbooks and tables as the melting point
of the neutral salt. After more than 80 years, how-
ever, it has been discovered6 that the work of Marchand,
owing to his rather misleading method of expression,
has been misinterpreted, 140° referring not to the
neutral salt, (NH4)2S04, but to the acid salt, NH4.HS04.
Hodgkinson and Bcllairs" described the use of dried
and carefully melted ammonium sulfate in 1895, but
gave no value for the melting point. The objection
was immediately raised by Smith8 that neutral am-
monium sulfate does not melt when heated, but de-
composes with loss of ammonia, leaving finally the
acid salt, which melts at 140°. This was confirmed
by Reik9 in 1902 and by Langmuir10 in 1920. Bridg-
man11 has reported that acid ammonium sulfate is
"entirely melted" at 150°, but gives no minimum value.
Kendall and Landon obtained 146.9 =*= 0.5° as the
melting point of the acid salt, but did not succeed in
melting the neutral salt in a sealed tube even at the
boiling point of sulfur. Caspar12 states that the neutral
i Received February 2. 1921
■ Kaye and Laby, -'Physical and Chemical Constants." 1911, 115.
1 Janecke, Z. angeu: Chem.. 33 (1920), 27S.
< J. Am. Chem. Soc. 42 (1920), 2131.
' Pogg. Ann.. 42 (1837), 556.
« Caspar, Bcr.. S3 (1920), 821.
' Proc. Chem. Soc, 152 (1895). 114.
* J. Sot. Chem. Ind , 14 (1895), 629.
» Monatsh., 23 (1902), 1033.
'» J. Am. Chem. Sot.. 42 (1920), 282.
ii Proc. Am. Acad. Sci., 62 (1916), 12.5.
The Melting Point of Ammonium Sulfate1
By James Kendall and Arthur W. Davidson
Chemistry Department, Columbia University, New York, N. Y.
h most chemists place
salt sinters in an open tube at about 310°, melts
at 336° to 3.39°, and decomposes at 355° with evolu-
tion of gas; in a closed tube it sinters at about 360°
and melts at 417° to 423°. Janecke,1 finally, in an
ambitious attempt to define the essential features of
the complete phase-rule diagram for the system H-S04-
NHj, claims to have obtained 251° for the melting
point of the acid salt and 357° for the simultaneous
melting and decomposition points of the neutral salt
under atmospheric pressure.
The essential source of the divergent values ob-
tained is the instability of the neutral salt. All in-
vestigators agree that the acid salt NH|.HS04 is quite
stable at its melting point; Janecke even gives it a
definite boiling point of 490°, a figure which, in view
of the dubious character of his remaining results, must
be regarded with considerable reserve. Kendall and
Landon's carefully determined value for the melting-
point of the acid salt (146.9°) is in very good agree-
ment with the results of all previous observers; how
Janecke could possibly obtain a figure more than 100°
higher (251°), unless he misread his thermometer by
100°, must remain a mystery. The neutral salt,
however, loses ammonia when heated, decomposition
being appreciable2 even at 200°. When the neutral
salt is heated in an open tube, therefore, the determina-
tion of a true melting point is impossible, since the
composition of the solid phase is changing from minute
to minute through loss of ammonia. If this ammonia
is allowed to escape freely and the experiment per-
sisted in long enough, the melting point of the acid
salt will finally be obtained. If, on the other hand,
the apparatus is so arranged that the ammonia evolved
is permitted to accumulate above the salt, decomposi-
tion will cease before the acid salt is reached. Thus,
Smith found that when dry NH3 gas was bubbled
through melted NH4.HS04 considerable absorption
took place even at temperatures as high as 420°.
The ammonia so taken up was evolved again, however,
on passing a current of air through the apparatus,
even at temperatures as low as 200°. It is obviously
futile, consequently, to speak of determining the melt-
ing point of neutral ammonium sulfate under atmos-
pheric pressure. This statement holds even if a pure
ammonia atmosphere is ensured, for while it is true
that the mixture of neutral salt and acid salt3 obtained
on heating will possess a definite vapor tension with
respect to ammonia at any fixed temperature, and at
some fixed temperature will melt, yet it could only be
by an extreme coincidence that fusion should take
place at that very temperature for which the vapor
tension just equals one atmosphere and (as will appear
below) the coincidence does not occur in practice in
this particular case. The values 336° and 357°
i Loc. rit.
•' Smith, Loe. til.
' It may be mentioned here that the existence of salts intermediate in
composition between the neutral salt (NH<)2SO< and the acid salt NH..HSO,
(see Kendall and Landon, Loc. cit.) necessitates the decomposition taking
place in stages, and not directly.
304
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
obtained by Caspar and Janecke, respectively, for
the melting point of neutral ammonium sulfate heated
in open tubes must, therefore, refer to perfectly in-
determinate mixtures, not in equilibrium with their
vapor phase. For the same reason the elaborate
phase-rule diagram presented by Janecke is hopelessly
in error, as may be seen by comparing it with the re-
sults obtained by Kendall and Landon with the use
of sealed tubes.
The actual melting point of neutral ammonium sul-
fate can, indeed, be determined only by heating the
salt in a sealed tube with practically no free air space,
to avoid appreciable loss of ammonia. It is true that
a melting point so obtained refers to a pressure in
excess of atmospheric, but the temperature of the
equilibrium solid-liquid changes in general so slightly,1
except for tremendous pressure variations,- that this
is of no practical significance.
The only definite value reported for the melting
point of neutral ammonium sulfate in a sealed tube
is that of Caspar, 417° to 423°. In view of the fact,
however, that Kendall and Landon failed to obtain
a melting point for a specimen of the salt suspended in
a sealed tube in the vapor of boiling sulfur (445°),
it' would seem that Caspar's determination is doubtful.
The most probable explanation is that considerable
■decomposition of the salt occurred before fusion, owing
to the air space in the sealed tube being too large, thus
inducing too low a value for the melting point. The
experiments described below conclusively prove that
Caspar's result is in error.
EXPERIMENTAL PART
A pure sample of the salt was obtained in the form
•of very fine crystals by rapid cooling from a concen-
trated hot aqueous solution, which was well stirred
during the precipitation. The crystals were washed
with alcohol and ether successively, and
desiccated over 99 per cent sulfuric acid.
Small glass bulbs of the type shown in
the diagram were packed with the
crystals and then sealed off at the point
A, leaving as small an air space as
possible. A sealed bulb was attached
to a nitrogen-filled thermometer (read-
ing to 560°) and suspended in a Pyrex
test tube containing powdered anhy-
drous zinc chloride. This tube was
air-jacketed with larger tubes and finally
with a beaker, the whole being sur-
rounded by sheet asbestos, with glass
windows for observation. The temper-
ature was raised very gradually by means
of a number of Bunsen burners to about
550°, the crystals thus being brought
to their fusion point in a bath of molten zinc chloride
\ The first tubes, made of thin glass, exploded before
the salt showed any signs of melting. Later attempts
were consequently conducted with bulbs made from
thick-walled capillary tubing, with better success. Two
concordant experiments gave melting points of 520° =•=
1 For the mean case, an increase of pressure of more than 30 atm. is
required to produce a change in the melting point of 1°. See Findlay,
"The Phase Rule," 1918, 71.
" Bridgman, Proc. Nat. Acad. Sci., 1 (1915), 514.
5°, but in view of the smallness of the bath and the
uncertainty in the exposed stem correction for the
thermometer, this value was regarded as only approxi-
mately accurate. The salt showed signs of softening
below 500°.
The final experiments were carried out with a much
larger bath (a one-liter Pyrex beaker, thoroughly
insulated with asbestos and provided with observa-
tion windows, containing a mixture of fused nitrates
stirred by means of a motor-driven brass stirrer)
and a calibrated platinum resistance thermometer.1
The temperature of the bath was allowed to rise ex-
ceedingly slowly (not more than 0.2° per min.) in
the neighborhood of the melting point. The salt
began to soften perceptibly at 490° and finally melted
at 513° =*= 2°. This value may, therefore, be given
as the definite melting point of neutral ammonium
sulfate, under an ammonia pressure of considerably
more than one atmosphere.2
High as this figure may appear in comparison with
the results of previous investigators, it is of interest
to note that it is still far below that recently predicted
by Langmuir.3 According to the octet theory of
valence, the melting point of ammonium sulfate should
be only a little below that of potassium sulfate (1072°);
in reality it is more than 500° lower. We have here,
indeed, the first known example of an inorganic sul-
fate with a melting point below that of the correspond-
ing chloride. Langmuir, by the use of the same method
as was employed in this work, has lately determined
the melting point of ammonium chloride as 550°,
under an estimated pressure of 66 atmospheres. The
difference between this value and that here obtained
for ammonium sulfate is not very large, but it is sig-
nificant, since all other sulfates melt at temperatures
considerably higher than the corresponding chlorides.
SUMMARY
Janecke recently pointed out the fact that the
melting point of ammonium sulfate is not accurately
known, and attempted to remedy the deficiency.
It is demonstrated in this article that Janecke's
value for the melting point of acid ammonium sulfate
(251°) is more than 100° too high, the correct figure
being 146.9° =±= 0.5°, while his value for the melting
point of neutral ammonium sulfate (359°) is more than
150° too low, the correct figure being 513° =*= 2°. The
extreme discrepancies recorded in the literature are
shown to be due essentially to the instability of the
neutral salt when heated in an open tube.
In the light of the results here obtained, it would seem
that Janecke's plea formoreinvestigations of the physical
properties of the common chemicals in everyday use
might profitably be amended to a plea for fewer in-
vestigations, of somewhat greater accuracy.
1 For the use of this apparatus we wish to express our thanks to Pro-
fessor C. D. Carpenter.
2 Since some loss of ammonia must have occurred before the salt melted.
the value here determined is, strictly speaking, only a minimum figure.
In view of the small air space left in the sealed tube, however, we feel con-
fident that any change in composition of the salt before melting, and con-
sequently any error in the melting point recorded due to this cause, cannot
be appreciable. The only factor that might introduce any significant
error is the solvent action of the partially molten
glass, which was quite noticeable, but unavoidab
experiment.
" /. Am. Chem. Soc, 42 (1920), 282.
ionium sulfate on the
der the conditions of
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
305
Rapid Dry Combustion
[ethod for the Simultaneous Determination of Soil Organic
Matter and Organic Carbon1
By J. W. Read
Chemistry, Arkansas Experiment St
In order to carry out certain investigations on the
quantitative relations of soil organic matter it became
necessary to devise an accurate and suitable procedure
for determining the percentage of carbon in the organic
matter in a large number of representative soils selected
from nearly every Experiment Station in the United
States for the purpose of making a more exact study
of the percentage relationship of the organic carbon
to the total organic matter. The methods in general
use for the total organic matter determination are (1)
the loss on ignition, and (2) the organic carbon method.
The latter involves the use of a conventional conversion
factor.
A scheme which would make it possible to determine
the organic matter and the organic carbon simultane-
ously, thereby reducing the labor to about one-third,
at the same time securing the highest accuracy, was the
chief object sought. The method described below met
these requirements the most satisfactorily. By its
use the writer was able to complete twelve combustions,
twenty-four determinations, in an ordinary day's work,
including all the necessary preliminary and final
weighings, and employing only one combustion furnace.
With the exception of several modifications and the
introduction of a new feature in the type of combustion
boat, the rapid organic combustion method as modified
and used by Levene and Bieber2 formed the basis of
the procedure adopted. The success of determining
on the same sample of soil both the organic matter
and the organic carbon simultaneously is due in the
main to the use of a special perforated-bottom com-
bustion boat3 and a specially constructed filter funnel.4
which made it possible to filter by suction in the same
manner as with the ordinary Gooch crucible. The
boat possessed suitable dimensions (97 mm. long,
18 mm. wide, 13 mm. deep) for handling the quantity
of materials required.
One-gram samples of soil (1-mm. sieve) were pre-
pared for combustion by removing the carbonates and
hydrated minerals in accordance with Method B de-
scribed by Rather.5 This preliminary preparation
may be briefly stated as follows:
A 1-g. sample of soil is- weighed into a platinum evaporating
dish and given six successive digestions, 5 min. each, on a boiling
water bath, with 30 cc. of water and 10 cc. each of 2.5 per cent
hydrochloric and hydrofluoric acids. After each digestion the
supernatant liquid is carefully decanted through the combustion
boat on to an asbestos mat. After the sixth digestion the entire
sample is transferred to the boat with a rubber policeman.
1 Presented before the Division of Agricultural and Food Chemistry
at the 59th Meeting of the American Chemical Society, St. Louis, Mo,
April 12 to 16, 1920.
' J. Am. Chem. Soc, 40 (1918), 460.
3 Made especially by the Coors Porcela
The writer sincerely thanks the company for thi
him and for the care and pains taken to produc
4 Grateful acknowledgment is made to E
construction of the special filter funnel used with the boat. (See Fig. 3.)
'Arkansas Experiment Station, Technical Bulletin 140 (1917); This
Journal, 10 (1918), 439.
Co., Golden, Colorado,
aluable cooperation given
. satisfactory boat,
er and Amend for their
The results reported by Rather indicate that the
amount of organic carbon lost in the filtrate from the
acid treatment is negligible, falling within the limit of
error in most cases at least.
APPARATUS AND REAGENTS
The combustions were made in a 100-cm. silica tube,
having an internal bore of 23 mm., and with one-half
its length made of transparent silica so that the process
of combustion and the manipulation of the boat were
under observation at all times. A 3-ttnit electric fur-
nace was used, and the combustion tube was charged
as shown in Fig. 1.
cerium oxide asbestos' and pumice — The asbestos
catalyst was prepared by suspending highly purified,
medium fibered asbestos in a saturated solution of
chemically pure cerium nitrate and evaporating prac-
tically to dryness on a boiling water bath. The as-
bestos was then heated in a glass tube in a stream of
oxygen, the escaping vapors being absorbed in dilute
alkali. The cerium dioxide pumice, 12 mesh, recom-
mended by Fisher and Wright2 as more desirable than
asbestos because of the tendency of asbestos to crumble
and "sag," was similarly prepared. Reimer3 also had
previously called attention to certain difficulties due
to the crumbling of the asbestos impregnated with
the cerium dioxide. However, no such difficulty arose
with the asbestos used in this work. On the other
hand, it remained throughout long service in the very
desirable granulated condition which it assumed in the
process of preparation.
lead peroxide — It is very important that strictly
pure peroxide be used for absorbing the nitrogen prod-
ucts. Considerable trouble was experienced at the
beginning with a supposedly high-grade reagent.4
Previous to using, the peroxide was digested three
times with boiling water, filtered, washed, and dried
on a Biichner funnel in an electric oven. In charging
the tube alternate layers of peroxide and peroxide
asbestos were lightly tamped into a fine copper gauze
container. The peroxide asbestos was prepared by
intimately mixing about equal volumes of the two
substances.
purifying apparatus — This consisted of two 8-in.
Peligot tubes filled as indicated in Fig. 1. Obviously,,
a purifying train filled in this manner will serve for a
large number of combustions. The use of the phos-
phoric anhydride as the dehydrating agent is unneces-
sary unless accurate determinations of hydrogen are
wanted.
absorption apparatus — Accuracy and speed were
the principal advantages gained in the absorption ap-
' J. Am. Chem. Soc, 40 (1918), 162
' Ibid., 40 (1918), 869.
'Ibid., 37 (1915), 1637.
« The author is greatly indebted to Dr. W. D. Collins, U. S. Bureau
of Chemistry, for furnishing him with a satisfactory peroxide manufactured
by E. R. Squibb and Sons. The Bureau's analysis of Squibb's reagent
gave 0.15 per cent soluble matter and 0 60 per cent sulfate.
306
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
| <2Sa > —4; IB Sc
H - ZSc--\' — 20cm
CfO.zed - ?5em-^
i Jin,
In
1 — Calcium chloride
2 — 12-mesh soda lime
3 — 30-mesh soda lime
1 — Contents of Tubes by Sections
4 — 30-mesh soda lime
5 — 60-mesh soda lime
0 — Calcium chloride
7 — Short fibered asbestos
.S — Phosphorus pentoxide
0 — Asbestos
paratus, shown in Fig. 2. which also illustrates the
manner of filling the apparatus. In the case of soils
one filling of the absorption bulb served for more
than several hundred determinations. The 30- and
CO- mesh soda lime carrying 5 to 10 per cent moisture
gave very efficient absorption. Xesbitt absorption
bulbs, similarly filled, were also successfully used.
icT
Fio 2 — Contents of Tubes bv Sections
10 — 12-mesh pumice moistened with H1SO1
11 — Glass wool
12 — Asbestos
13 — Phosphorus pentoxidi
14 — Glass wool
1 5 — Asbestos
16— 30-mesh soda lime
17 — 60-mesh soda lime
IS — 30-mesh soda lime
Tubes A
19 — Asbestos
20 — Phosphorus pentoxide
21 — Asbestos
22 — Asbestos
23 — Phosphorus pentoxide
24— Glass wool
25— Calcium chloride
26 — Palladious chloride solution
,nd B are filled alike
palladious chloride solutiox — Palladious chloride
solution,' prepared by adding 1 cc. of a 5 per cent solu-
tion to 200 cc. of distilled water, was used to detect
any carbon monoxide resulting from imperfect com-
bustion. No difficulty at all was experienced in this
respect.
FILTERING —Filtration through the boat was ac-
complished quite satisfactorily by placing a rectangular
piece of rubber, with a hole of the proper size and shape
cut in its center, over the top of the funnel (Fig. 3),
and then fastening the boat near each end on to the fun-
nel by ordinary rubber bands, which were made suffi-
ciently tight to secure good suction. The rectangular
piece of rubber was cut from the inner tube of a motor-
cycle.
asbestos — Baker's washed in acid and ignited, me-
dium fibered asbestos was further purified by treating.
i Fisher. "Laboratory Manual of Organic Chemistry," 1940, 245.
Wiley and Sons, Inc.
first, for several days with dilute hydrochloric acid,
washing, and then treating in a similar way with dilute
nitric acid. The asbestos was washed free of nitric
acid with hot water and ignited to constant weight at
high temperature in a muffle furnace.
WEIGHING SOIL SAMPLES
After drying in the electric oven for 16 hrs. at 99° C,
the combustion boat containing the sample was cooled
in a desiccator over phosphorus pentoxide and weighed
with counterpoise in a "piggie"' weighing tube, having
a ground glass stopper. Since the samples of soil are
very hygroscopic it is necessary to be exceedingly
careful at this point. All weighings were made on a
high-grade balance sensitive to 0.05 mg. and with a
very high-class set of weights certified by the U. S.
Bureau of Standards.
RUNNING THE COMBUSTION
The time required to begin and complete a combus-
tion, including the initial and final weighings, averaged
1 from 35 to 40 min.
/ The time required
to burn the sample
and sweep out the
tube varied from
13 to 20 min., de-
pending on the per-
centage of organic
matter present in
the soil. All the
combustions were
made in a rapid
current of air. The
bubbling was sev-
eral times faster
than could be
counted. The use
of air appeared to
remove certain difficulties in weighing the absorption
bulbs shortly after completing the determination.
The boat containing the sample was carried in and
out of the combustion tube on a platinum foil skid to
prevent its gathering any of the loose copper oxide
always present in the tube from the oxidized spiral.
The sample was introduced into the tube and Units 1
and 2 were brought to bright redness before starting
the combustion. The sample was burned by gradually
bringing Unit 1 over the entire boat. From 5 to 9
^-f1
Fio. 3— Filter Funnel for Cmmbustion Boat
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
307
min. were required to burn the sample, and 8 to 1 1 min.
more were used to sweep out the tube, during which
time the two hot units cooled sufficiently to introduce
another sample. The temperature of Unit 3, used for
heating the lead peroxide, was kept between 300° and
320° C. by means of a long stem thermometer with
its bulb placed in the center of the peroxide charge.
Much above 320° C. decomposition of the absorption
products formed with the nitrogen compounds took
place. The absorption bulbs were always handled in
duplicate under the same conditions to facilitate weigh-
ing. They were protected from the furnace heat by
a thick shield of asbestos. The absorption of the
carbon dioxide from the soil combustions never pro-
duced any perceptible change in the temperature of
the bulb taking it up. Upon detaching the bulbs for
weighing they were very carefully wiped with lens
cloth and weighed after standing a very few minutes
or just before their use another time. Two sets of
bulbs were kept in use.
DATA
The data presented herewith are quite typical of the
several hundred combustions made without recharging
the combustion tube or either the purifying or ab-
sorption trains. The determinations are given in
duplicate. The furnace was checked on a standard
sample of sucrose received from the Bureau of Stand-
ards, with the following results in percentages of car-
bon, —42.06, 42.13, 41.99. Theoretical = 42.08.
Per cent
Carbon in Or-
— Kanic Matter — ,
(li (21 Av.
54.94 54.63 54.78
46.44 46.95 46.64
50 59 50.66 50.62
47.22 47.10 47.16
55.46 55.43 55.44
56.67 56.44 56.55
17 08 47.05 47.07
26.55 26,90 26.72
22.93 22.72 22.82
52.91 52.96 52.93
42.12 42 117 12 09
27 98 28 21 28.08
49.00 49.05 49.02
12 58 42 28 12 12
The simultaneous determination of the organic
matter and the organic carbon by the above method
effects a saving in time of approximately 60 per cent.
It is believed that the data secured on the many
soils which have been investigated are more ac-
curate than could have been obtained by any previously
described method, and that the magnitude of error is
reduced to a minimum.
Regis-
Depth
tration
of
Per cent Or-
Num-
Sample
7ifr
tc Matter —
ber Type of Soil
Inches
121
Av.
2654 Lamour silty clay loam
0-20
6.17
6.20
6 is
2655 Subsoil to 2654
211-36
1 13
1.15
1.14
2656 Webster silty clay loam
0-15
3.66
3.59
3 62
2657 Subsoil to 2656
[5-36
1 23
1 21
1.22
265S Wabash silty loam
O-20
6 is
6 is
6 Is
2659 Subsoil to 2658
20-36
2.17
2.21
2.19
2672 Decatur silty loam
0-10
1 72
1.64
1.68
2673 Subsurface soil to 2672
10-20
0.076
0.074
0.075
2671 Subsoil to 2672
20-36
0.044
o ills
0.046
2675 Grundy silty loam
0-12
2.71
2.70
2.70
2676 Subsurface soil lo 2675
12-18
1 01
1 05
1.03
2677 Subsoil to 2675
11076
0.087
0.081
2792 Diablo clay
0-24
1 38
1 3B
I 38
2793 Subsoil to 2792
24-72
1.07
1.09
1.08
SUMMAKA
Studies on the Nitrotoluenes. VI — The Three-Component System: o-Nitrotoluene,
p-Nitrotoluene, 1 ,2,4-Dinitrotoluene1 ,2
By James M. Bell and Edward B. Cordon
University op North Carolina, Chapel Hill, N. C.
In a previous paper of this series by Bell and Herty,3
the cooling-curve method of obtaining the freezing
points of various three-component mixtures has been
described. The present paper contains the results
0NT-445'
refer to some of the features of this system. A fore-
going paper1 has shown the existence of two forms of
ONT, and therefore there should be two charts for this
present study: One where the component, ONT,
is in its stable form, and one where it is in its meta-
stable form. These two charts would be identical
except in the portion of the diagram where ONT
is the solid phase. Reference to the foregoing paper
MNT5/.3-
26S0"
D NT 6355-
-obtained by the same method for another three-
component system of the nitrotoluenes. We shall
not repeat the details of the method or the methods
of preparation of the pure components, but shall
Received December 21, 1920.
This paper is the sixth of a
dealing with t"he freezing points
and thermal properties of the nitrotoluenes, the investigation having been
undertaken at the request of the Division of Chemistry and Chemical
Technology of the National Research Council,
a This Journal, 11 (1919), 1128.
Freezing Point
° C.
56.01
47.85
47.75
18 82
38.66
01
27.52
26.98
2d 47
12.08
10.55
0.84
1 I Kl
2 45
—4.19
— 1.50
!0 13
19 :-,
— 13.20
—3^89
8.48
19.10
27.83
35.69
—11.82
—15.65
—5.95
7.64
17.55
27.08
34 . 25
41.32
i This Journal, 13 (1921), 59.
308
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 4
shows why we were unable to obtain points where
stable ONT was the solid phase, for neither binary
eutectic, ONT-MNT or ONT-DNT, was found in
the presence of metastable ONT. All the points in
the diagram in the top field represent liquids saturated
with respect to stable ONT.
Again we have observed the tendency for great
supercooling with respect to DNT, and therefore
we have been compelled to seed with crystals of that
substance. The approach to equilibrium after seeding
is also somewhat slow, and rather long extrapolations
have been necessary.
The position of the boundary curves has been es-
tablished by the method of the paper already cited.
The freezing points of mixtures with a constant per-
centage of one component have been plotted. The
points lie on two curves which intersect at the boun-
dary curve, and the composition and temperature
given by the plot establish one point on the boundary
curve. The complete boundary curve may be ob-
tained by finding a number of such points. The
intersection of the three boundary curves fixes the
composition of the ternary eutectic, found in this case
to be 62 per cent ONT, 19 per cent MNT, and 19 per
cent DNT.
For most of the low-temperature work we used a
bath of ice and salt, but for temperatures in the
neighborhood of the ternary eutectic a lower tem-
perature was necessary. For this purpose we used a
bath of mixed carbon tetrachloride and gasoline in
which was a coil of metal tubing connected with a tank
of liquid ammonia, tilted so as to deliver the liquid
at the control valve. The evaporation of the liquid
into the metal coil lowered the temperature sufficiently
to obtain cooling curves for the lowest freezing mixtures.
The ternary eutectic temperature was reached by
first obtaining the binary eutectic mixture, ONT-
MNT, and by adding DNT in small quantities.
Each addition lowered the temperature until no more
DNT would pass into the melt. When the liquid
is saturated with DNT also, the ternary eutectic has.
been reached, in this case at - — 20.1°.
Studies on the Nitrotoluenes. VII— The Three-Component System: p-Nitrotoluene,
o-Nitrotoluene, 1 ,2,4,6-Trinitrotoluene1,2
By James M. Bell and Fletcher H. Spry
University of North Carolina, Chapel Hill, N. C.
of the components: p
All the binary systems
nitrotoluene (MNT), o-nitrotoluene (ONT), and
1,2,4,6-trinitrotoluene (TNT) have already been de-
scribed in previous articles of this series.3 In each
case the freezing-point curves consist of two lines
intersecting in a eutectic point. There is no com-
pound of the components in any of the cases.
ONT-W
these crystals being necessary. The accompanying
table comprises only data for three-component mix-
tures, the temperatures along the sides of the triangle
having already been recorded in the articles referred
to above. The positions of the boundary curves and
of the eutectic point were determined by the method
described by Bell and Cordon.1 The diagram shows the
boundary curves with 5° isothermals. The eutectic
temperature and composition are — 19.5° and 05.5 per
cent ONT, 19.5 per cent MNT, 15 per cent TXT.
In this study we have met only the simplest condi-
tions. There are no binary and no ternary compounds.
35.r TNT 3035-
MNTsi.3-
In the study of the three-component system we
have followed the methods already outlined in these
articles. The freezing points where ONT is the solid
phase refer to the stable form (/3-ONT), seeding with
1 Received December 21, 1920.
2 This paper is the seventh of a series dealing with the freezing points
and thermal properties of the nitrotoluenes, the investigation having been
undertaken at the request of the Division of Chemistry and Chemical
Technology of the National Research Council.
» MNT-ONT and TNT-ONT. Bell, Cordon, Spry and White,
This Journal, 13 (1921), 59; MNT-TNT, Bell and Herty, Ibid., 11 (1919),
1124.
Freezing Point
37.4
32 . 2
29. l>
38.4
49.4
57.9
65.65
35. 1
29.85
23.4
28.64
38.7
13.8
27.23
38.8
47.4
18.85
10.85
12.35
26.63
37.6
7.5
—3.8
9.95
25.47
—18.5
— 12.0
8.6
—16.3
— 10.5
— 11.9
i This Journal. 13 (1921). 307
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
309
The Anilides of /3-Oxynaphthoic Acid1
By E. R. Brunskill
Cincinnati Chemical Works, Norwood, Ohio
The colors obtained by substituting /3-oxynaphthoic
acid for /3-naphthol in the ice process are brighter and
are of a somewhat greater range in shade. They do
not have the brownish appearance which /3-naphthol
colors sometimes have, and the solutions can be kept
longer and with more ease than is the case with /3-
naphthol. The /3-oxynaphthoic acid colors, however,
have the very serious fault of washing out easily, and
are not fast to rubbing. In order to overcome these
serious defects the carboxy-group has been covered
by substituted amines, the principal one of which is the
anilide, known also as Naphthol AS.
A great number of the anilides of /3-oxynaphthoic
acid are described in the patent literature, but for the
comparison to be made here only the anilide, the p-
toluidide, and the />-chloroanilide are considered.
METHOD OF PREPARATION
They were made by a process similar to those de-
scribed in the various patents.
One mole (in grams) of /3-oxynaphthoic acid, one
mole of amine, and 1400 cc. of toluene were heated to
gentle boiling under a reflux condenser. Then, with
stirring, the theoretical quantity of phosphorus tri-
chloride was slowly dropped in. The hydrochloric
acid gas evolved was absorbed over water, and the re-
action was ended when no more gas was evolved. The
time required was from 2 to 4 hrs. The mixture was
poured into water and the toluene drawn off. The
water suspension of the anilide was made slightly al-
kaline with soda ash, in which the anilide is insoluble.
The solution, containing the uncombined /3-oxynaph-
thoic acid, was filtered, and the precipitate washed with
a little water. It was then dissolved in the necessary
quantity of 1 per cent caustic soda solution at about
50° C. Upon filtration and precipitation with acid,
a very pure product was obtained.
The anilides are very slightly soluble in alcohol and
toluene, while the free acid is quite soluble. The
anilides melt with decomposition above 200° C.
They are soluble with a yellow color and without de-
composition in warm, dilute, caustic soda solution.
-METHOD OF DYEING
The ordinary methods of dyeing were tried, but owing
to the slow coupling properties of the anilides good
results were not obtained. The method adopted was
as follows:
The cotton, which had been boiled out with soap
and thoroughly rinsed, was soaked for an hour in a 2
per cent solution of the anilide in the theoretical
amount of caustic soda. In the meantime the diazo
solutions were prepared in the usual manner and made
up to a concentration of 0.1 mole in 500 cc. An ice-
cold saturated salt solution was treated with enough
soda ash to make a 3 per cent solution, and fil-
1 Presented before the Division of Dye Chemistry at the 60th Meeting
of the American Chemical Society, Chicago, 111., September 6 to 10, 1920.
tered to remove the precipitated CaC03, BaCO,, and
MgCO„.
To dye a 10-g. skein, 300 cc. of the cold salt solution
were measured into a liter beaker. The thoroughly
wrung skein of treated cotton was immersed in the salt
solution, and immediately 80 cc. of the diazo solution
were added, with constant turning of the cotton. The
cotton was turned for about an hour, then rinsed first
in cold water, then in hot soap solution, and finally
in warm water. In the developing bath a test should
show a slight excess of soda ash and diazo compound
at the finish. If not, more of the one which was lacking
should be added for another dyeing, as the best dyeings
were obtained only by adding all the materials at
once.
Dyeings were made using the following substances as
naphthols: /3-oxynaphthoic acid, the anilide, the
toluidide, and the />-chloroanilide. Each naphthol was
coupled with aniline, />-nitroaniline, />-chloroaniline-o-
sulfonic acid, />-toluidine, w-nitro-/>-toluidine, and o-
chloro-/>-toluidine sulfonic acid.
All the colors made from /3-oxynaphthoic acid washed
out and were not fast to rubbing, especially those made
from the sulfonated amines. Moreover, the colors
were not as bright as those made from the anilides.
The anilides gave colors which were fairly fast to wash-
ing and rubbing, except in the case of the sulfonated
amines.
In order to make the colors from the latter faster
to washing they were treated as follows:
The damp rinsed dyeings were dipped into a 3
per cent solution of calcium chloride and allowed to
remain with turning for a half hour at 50° C. They
were then rinsed and dried. This treatment made the
colors fast to washing and rubbing, with but very little
change in shade.
All the /3-oxynaphthoic acid colors were also treated
with calcium chloride, which made them much faster
to washing, notably in the case of ^-chloroaniline-o-
sulfonic acid.
One might expect to obtain a difference in color
between the three anilides, and as far as these dyeings
show there are some differences, but, before one could
definitely say just what effect a substituent in the
amine of the amide has upon the color, a larger number
of anilides must be studied.
It appears, however, that the />-chloroanilide, and
the />-toluidide give brighter shades than the anilide,
and that the />-chloroanilide gives a slightly brighter
shade than the /(-toluidide, except in the case where
there is a nitro group in the diazotized amine, in which
case the p-toluidide gives the brightest colors.
The effect of the nitro group can also be observed
by comparing the colors from />-nitroaniline and m-
nitro-/>-toluidine, those from the latter being in every
case the brightest, so that it seems that a nitro group
must be balanced with a methyl group in order to
obtain the best results.
310
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
The Non-Biological Oxidation of Elementary Sulfur in Quartz Media1
[PRELIMINARY REPORT]
By W. H. Maclntire, F. J. Gray and W. M. Shaw
Unxvbrsity of Tennessee, Agricultural Experiment Station, Knoxvili.e, Tennessee
The conversion of native organic sulfur into sul-
fates in soils is generally considered to be an almost
exclusively biological process. The oxidation of added
elementary sulfur is likewise usually attributed to
the action of bacteria. The native organic sulfur
phase of sulfate generation, as influenced by calcium
and magnesium materials in varying amounts, has
been under investigation at the University of Ten-
nessee Agricultural Experiment Station since July
1914. At that time, forty-six lysimeters were filled
with Cumberland loam, twenty-three tanks having
soil alone, and twenty-three having surface soil above
a 1-ft. layer of clay subsoil. Each annual aggregate
of sulfate leachings has been determined quantita-
tively. Divergent effects of calcium and magnesium
compounds upon the sulfate outgo during the first
two years were reported upon in a preliminary
paper by the writer and associates.2 The supple-
mentary study of sulfur additions to a Cherokee
sandy loam was begun in August 1917. Fifteen
tanks received sulfur additions. Each 5-tank group
received one of the three forms of sulfur: namely, iron
sulfate, iron pyrite, and flowers of sulfur, each in an
amount equivalent to 1000 lbs. of sulfur per 2,000,000
lbs. of soil. The question of the influence of lime and
magnesia upon added sulfur was also included in the
supplementary study. In this second installation,
comprising twenty-two lysimeters, the loss of sulfur,
as leached sulfates, was determined for each tank
periodically, as necessitated by the unsupplemented
rainfall. The data secured demonstrated that the
flowers of sulfur and iron pyrite were both converted
into sulfates with distinct rapidity.
It was at first assumed that the oxidation of both the
elementary sulfur and that of the pyrites was induced
in the main, if not solely, by organisms. However,
some doubt concerning this assumption was intro-
duced about 2 yrs. after the inauguration of the ex-
periment, when it was observed that a strong odor
of sulfur dioxide was given off from the reserve sam-
ple of iron pyrites, which had been kept in the dark
in an 8-oz. glass bottle, tightly stoppered with an
ordinary No. 6 cork stopper. A 10-g. charge of the
pyrites was found to yield soluble sulfate of iron,
equivalent to a determined weight of 0.4172 g. of
BaSd, as an average of seven determinations. The
same observation has been reported by Allen and
Johnston3 in 1910. These workers further reported
that an increase of 100 per cent of sulfate of iron was
caused by grinding for a period of 1 hr. They ac-
counted for the reaction by means of the equation:
FeS2 + 302 ^ FeSOi + S02
Contact of moist pulverized metallic iron and
flowers of sulfur was found to produce iron sulfide,
1 Received December 11, 1920.
>W. H. Mclntire. I.. G. Willis and W. A. Holding, Soil Set., 4 (1917), 231.
8 ''The Exact Determination of Sulfur in Pyrite and Marcasite," This
Journal, 2 (1910), 196.
a reaction which was also found to be recorded.1 These
observations suggested the possibility that the ap-
plied elementary sulfur might combine to a certain
extent with the iron of the soil, forming compounds
which, in turn, would undergo oxidation to sulfates.
It even seemed plausible to assume that the presence
of iron might be essential to the extensive conversion
of elementary sulfur into sulfates.
These observations led to a laboratory study of
the two major queries:
1 — What function, if any, does metallic iron, and what func-
tion does iron oxide, or oxides, have upon the conversion of ele-
mentary sulfur to sulfates in soils?
2 — Will the effects possibly induced by iron, or its oxides, be
independent of biological activation?
EXPERIMENTAL METHOD
It was planned to study the oxidation of elementary
sulfur in the absence of appreciable quantities of iron,
under aerobic and anaerobic conditions, with the un-
altered medium, the sterilized medium, and the medium
plus inoculation. The purest obtainable quartz was
used as the medium for sulfur additions. An un-
successful attempt was made to secure an iron-free
quartz. The finely ground New England quartzite
used ran 99.28 per cent Si02, 0.34 per cent Fe203,
and 0.0096 per cent S. The purest hydrogen-pre-
cipitated iron obtainable (0.0475 per cent sulfur)
was used as one source of iron. The other iron com-
pound used was limonite, analyzing 39.50 per cent
iron and 0.013 per cent soluble sulfate sulfur.
Five hundred-cc. Pyrex flasks were used as con-
tainers for the treated media. The very finely ground,
unleached quartz was used in the constant amount
of 250 g., with 14 per cent distilled w^ater additions
for moisture. Each medium was kept in the dark
for a period of 60 days after treatment. In addition
to the constant amount of quartz the following sin-
gle or combined constants were used: 0.1251 g. of
sulfur; 10.0806 g. of metallic iron; 25.3164 g. of
limonite; 0.5076 g. of C. P. precipitated calcium car-
bonate; 0.5000 g. of C. P. precipitated magnesium
carbonate; 0.5181 g. of 100-mesh limestone; and
0.5449 g. of 100-mesh dolomite. The calcium and
magnesium materials were chemically equivalent.
The biological conditions maintained in the original
quartz-medium experiments were:
1 — Unaltered quartz.
2 — Quartz sterilized by heat.
3 — Inoculation by soil infusion "A."
4 — Inoculation by soil infusion "B."
These four conditions were maintained under
aerobic and anaerobic conditions. The aerobic flasks,
both sterile and nonsterile, were stoppered with cot-
ton plugs. The anaerobic atmosphere was pro-
duced by a 6-hr. passage of purified carbon dioxide.
■ S. P. Sadtler and V. Coblentz, "Pharmaceutical and Medicinal
Chemistry," 3rd Ed., Vol. I, .">74.
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY 311
Table I— Summary Showing Soluble Sulfates Engendered from Contact of Flowers of Sulfur with Powdered Quartz and Various Additions
Sulfate increases expressed as lbs. of S per 2.000,000 lbs. of medium. Uniform rate of sulfur additions, equivalent to 1000 lbs per 2 000 000 lbs of
medium. Total of 118 distilled water extractions after 00 days of contact
^-Access to Atmosphere through Cotton Plugs^ . Sealed Atmosphere of CO" .
,, ,„• ■ . ,, j , .. ,. Thrice Infusion Infusion Thrice Infusion Infusion
otf, A i m . "altered Sterilized Soil Soil Average of Unaltered Sterilized Soil Soil Average of
250 O. ot Quartz Quartz Quartz A B Treatment Quartz Ouartz A B Treatment
Sulfuronly 213.1 198.1 241.0 237.7 222.5 243.2 138.3 40.7 167.0 147.3
Sulfur and CaCOa 023.0 210.0 423.0 505.5 440. S 352.4 ... 154 1 239 3 248 6
Sulfur and limestone 516.4 192.9 404.9 321.9 359.0 412 0 199 5 -'"S4 ^gn'o
Sulfur and MgCOs 774.:: 142.6 245.4 206. 1 3.57.1 34.4 o6:.3 143.7 ~MM "73 4
Sulfur and dolomite (98 I 134.4 410.4 482.6 406.5 379.8 146.4 225.7 1S2.0 233.5
Average for carbonate group 628.0 170.2 371.2 394.0 390.9 294 7 98.4 180.8 178.7 208.9
Sulfur and Fe. . 89.0 86.9 68.3 63.0 77.0 39.9 —37.7 —18.0 —23.5 — 29. S
Sulfur, CaCO,, and Fe 172 1 123.0 84.7 70.5 112.6 —27.0 —32 2 —19 1 —82 —''19
Sulfur, limestone, and Fe 167.8 170.3 78.1 129.5 136.4 39.9 —37.2 —36.6 —224 —34 0
Sulfur, MgCOs, and Fe 154.1 58 5 73.8 91.8 94.6 42 I —26 S —20 2 —16 9 26's
Sulfur, dolomite, and Fe 169.9 112.1 127.9 104 0 128.7 —29.0 — ,50.8 — 4S.6 —27^8 — 39^1
Average for iron group 150.6 110.2 86.6 92.1 109.5 —3.5.8 —36.9 —28.5 —19.8 — 30.3
Sulfur and limonite 490 7 222 0 657.9 4.53.6 4.511 0 280.3 312.6 140.2 134 9 219 3
Sulfur, CaCO., and limonite 560.1 316.8 539.9 624.1 510.2 383.6 361.7 25.1 110 4 220 2
Sulfur, limestone, and limonite 195 1 23] 7 594.6 592.4 47s 5 334 1 403.2 146.5 166 7 262 7
Sulfur, MgCOi, and limonite 680.9 270 0 341.6 356.9 412 l 185.2 145.3 154.6 139 0 1.56.3
Sulfur, dolomite, and limonite .570 2 186.9 673.8 636.1 .510 0 343.7 376.0 1.54.0 143.1 2.54'4
Average for limonite group 561.2 245.7 561.6 532.6 475.2 305.4 310. S 120.0 130.0 224 6
Grand average — showing effect of chemical
treatment given quartz 418.9 177.2 331.1 320.2 314.1 184.7 1322 92.9 10.5 1 129 6
,„.,,. t , , , , . 277.0' 218.6" 139.41 157.71 194. 4>
1 r\ot including the less-than-eheck iron group.
An additional series containing purified hydrogen vent the possible accumulation of free end-product
was also subjected to experimental treatment, but acids. These data represent the summation of a
this series is not yet ready for report. number of tables secured from the analysis of leach-
The sterilization was effected by three successive inSs after the first period of 60 days and are corrected
daily heatings in the autoclave, without contact of bv subtraction of the soluble sulfates leached initially
quartz, and the separately sterilized materials used frorn the single or combined treatments, as determined
in the several treatments. The sterile added ma- upon the separate materials. Most of the sulfates
terials were mixed throughout the dry sterile quartz leached from the second 40-day period have been
immediately before the addition of the constant determined and will be included in the more detailed
moisture content, every care being taken to insure report to be published at an early date. The data
continued sterility. All of the stoppered flasks were are given in pounds of sulfate sulfur, per 2,000,000 lbs.
put away in the dark, in a room relatively free from of quartz, recovered from the added flowers of sulfur,
fumes, for a period of 60 days. At the end of the 60- which was applied in amounts equivalent to 1000 lbs.
day period the contents of the flasks were extracted of sulfur per 2,000,000 lbs. of quartz,
by addition of cold distilled water to near-complete Some further studies involving the use of water-
volume. After 4 hrs.' shaking and standing over leached and acid-leached quartz media are also being
night, the extracts were filtered with double filters used for further study of the transformations follow-
through Buchner funnels. Each residue was then inS additions of elementary sulfur. The influence of
thoroughly mixed and returned to its original flask a combination of metallic iron and limonite is also
for an additional period of contact of 40 days, after being studied with regard to antagonism. It has
which the filtration was repeated. The filtrates were been f°und that such a combination evolves consid-
analyzed for sulfides, and, if necessary, sodium hydrox- erable amounts of heat. An effort is also being made
ide was introduced. They were then acidified and to determine whether or not the generation of sulfur
evaporated to dryness, in order to remove silica, -under the conditions maintained would have any
The engendered sulfates, as well as the sulfates of effect upon the solubility of simultaneously added
all blanks, were determined gravimetrically. Tests and intimately mixed rock phosphate,
were made to insure the fact that the precipitates discussion of results
were not barium fluoride. In addition to the eight The data of Table I show a number of consistent
series of fifteen flasks each, an additional set of twelve anci striking relationships. In the case of the flasks
flasks was run simultaneously. Three flasks con- having limited access to air, the unaltered and un-
tained inoculated quartz and nitrate nitrogen to the treated quartz shows a gain in sulfate, as do also the
extent of 10 mg. of nitrogen, one flask containing portions sterilized and inoculated. The first group
sodium nitrate, one calcium nitrate, and one magne- 0f calcium and magnesium supplementary materials.
slum nitrate. These three nitrate treatments were to be considered, in a sense, as checks, shows a dis-
duplicated with an increase of nitrate nitrogen to a tinct increase in sulfates above the gain shown by
basis of 50 mg. The six flasks above described were the quartz and sulfur alone, induced directly or in-
then duplicated as to nitrogen treatment, but with directly, in the three conditions other than sterilized,
the addition of 10. 0806 g. of metallic iron to each flask. in the metallic iron group the consistent 'lupressivc
The details of the scheme of treatment and the sum- action of iron alone is strikingly demonstrated; while
mary of available leaching data are set forth in Tables the oxidizing tendency of the supplementary car-
I and II. The calcium and magnesium materials bonate materials is shown by the excess of sulfates
were not added upon the assumption that they would where these materials are included, as contrasted
react directly with the sulfur, but in order to pre- with the iron alone.
312
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
In the third, or limonite, group there is demon-
strated an acceleration in sulfur oxidation, particularly
as contrasted with the depressive tendency exhibited
by the metallic iron group. This holds true for
limonite alone and limonite as supplemented by the
carbonate materials. On comparing the four car-
bonate-limonite additions with the four carbonate-
only treatments, it would seem that both materials
are, in part, responsible for the general tendency to-
ward increase when the combined treatments are made.
Although the heat-sterilized flasks yielded less sulfur
than did the unaltered quartz, this fact could not be
considered as positively indicating eradication of bio-
logical agencies by heat. It is possible that the re-
peated heating may have depressed the activation of
the materials able to induce chemical oxidation; for
it will be noted that the two inoculations did not in-
crease the sulfate yield above that of the original
unaltered quartz. Then, too, such repeated heat-
ings might be considered as dissipating a part, or
the whole, of any oxidizing atmosphere which may
be condensed upon the surface of the quartz parti-
cles.
Considering the anaerobic carbon dioxide series,
we find certain striking results. The elementary
sulfur in the quartz-sulfur flasks appears to have
utilized oxygen from either the carbon dioxide of the
atmosphere, water, or silica. It appears hardly con-
ceivable that silica could be considered as a source
of oxygen for the oxidation phenomenon However,
in the case of the carbonate materials, the combined
carbon dioxide may be considered as possibly having
either a direct or indirect influence upon the acquisi-
tion of oxygen by the elementary sulfur. But, since
the distilled water used to maintain a uniform mois-
ture contact was freed of gases by boiling, the oxygen
could have come from no other sources, unless it be
assumed that appreciable quantities of oxygen or air
were condensed upon the surface of the quartz parti-
cles. This hypothesis would necessarily be predicted
upon the assumption that such a condensed gas is
tenaciously held by physical attraction, but is, at the
same time, extensively available chemically for the
oxidation of the added materials under conditions
of intimate moist contact. None of the treatments
leached up to this point have been tested for an
occurrence of free hydrogen, but several have been
tested for carbon monoxide. In one case, a quantita-
tive determination gave 280 mg. of carbon monoxide
in the absence of limonite.
It appears that the magnesium carbonate has a
distinct depressive tendency upon the oxidation of
sulfur in the presence of an atmosphere of carbon
dioxide. The cause of this particular phenomenon
will not be considered at this time except to point to
the ready solubility of MgC03 in carbonated water.
It will be noticed, moreover, that this distinctive de-
pressive action of magnesium carbonate is not ob-
tained in a case of the aerobic group.
A study of the metallic iron group shows that, in
every case of the twenty treatments, we find a posi-
tive depression to the extent of being below the actual
determined blank in each instance. The depression
induced by iron was decidedly accentuated in the
anaerobic atmosphere, as compared with the aerial
atmosphere, no one treatment of which gave a re-
covery less than the corresponding blanks. It would
seem that the oxygen available, in whatever form, is
more readily attached to the metallic iron than to the
elementary sulfur. The occurrence of ferric hy-
drated oxide is readily noted when the contents of
the flasks are subjected to extraction and leaching.
Again, in noting the sulfate recovered from the
limonite group, we find that the limonite alone, and
when supplemented, is responsible for acceleration
in the formation of leachable sulfates. In this group, as
in the corresponding group under aerobic conditions,
it is difficult to differentiate quantitatively between
the results induced by the limonite and those induced
by the carbonate, when the combination treatments
were made. It is apparent, however, that both the
mineral carbonates and calcium carbonate have the
accelerative tendency exhibited by limonite in the
generation of sulfates.
Here, again, we note the same retarding tendency
exhibited by the magnesium carbonate in the pres-
ence of carbonated water that was manifested in the
case of the magnesium carbonate treatment alone,
under the anaerobic condition It is rather strikingly
demonstrated that the presence of limonite tends to
restrict, or offset, the depressive influence exhibited
by the precipitated magnesium carbonate wherein
contact with carbon dioxide was maintained, which
was so distinctly recorded in the first group of calcium
and magnesium materials alone.
Table II — Showing Influence op Iron and of Nitrate N'itkogen
upon Oxidation of Elementary Sulfur
Added at rate of 1000 lbs. per 2,000,000 lbs. of medium. Soil infusion;
CO2 atmosphere; 60-day and 40-day periods of contact
Sulfate Sulfur
Leached after
Removal of
Sulfate Sulfur Nitrate Nitro-
Leaehed. I.bs. gen. Effected
per 2,000.000 by First Extrae-
Materials Added to Lbs. of Medium tion — 40-Day
250 G of Quartz after Period of
60 Days Contact
Sulfur only 40.7 188.1
Sulfur and 10 mg. N as NaNOj 173 7 218.0
Sulfur and 10 mg. N as Ca(NOj): 132. S 167.2
Sulfur and 10 mg. N as Mg(NOj)i 253.0 222 1
Group average for 10 mg. N 1S6.5 202.5
Sulfur and 50 mg. N as NaNOs 12.5 302.2
Sulfur and 50 mg. N as CafNO.,)-, 3.2 236.0
Sulfur and 50 mg. N as Mg(NO»)» 4.4 195.3
Group average for 50 mg. N 6.7 244 .,
Sulfur, 10 mg. N as NaNOa and Fe —38.8 +8.7
Sulfur, 10 mg. N as Ca(NOi), and Fe... —35.3 4-16.4
Sulfur, 10 mg. N as Mg(NO]), and Fe.. . —33.3 4-19.1
Group average for 10 mg. N and Fe .. . —35.8 +14 .7
Sulfur, 50 mg. N as NaNOj and Fe — 12.5 +13.0
Sulfur, 50 mg. N as CalNOj). and Fe... —30.0 I -1 5 3
Sulfur, 50 mg. N as Mg(NOj)j and Fe... —34.4 +13.6
Group average for 50 mg. N and Fe. — 25.0 +14.2
The contents of Table II are from the simultaneous
supplementary experiment. In this particular instance,
the three forms of nitrate nitrogen, such as might be
found in a normal soil, were introduced along with
an infusion from a soil of known sulfofying capacity.
It is consistently shown that the presence of added
nitrate has an effect upon the generation of sulfate.
The greater depression induced by the larger amounts
Apr., 192]
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
313
of the oxygen-carrying salts indicates that the con-
centration of salts in the moisture of the medium is a
potent factor in the speed, if not ultimate extent, of
the sulfate formation. It is quite possible that this
factor of salt concentration in the moisture of the
medium may account for the depressive action ex-
hibited by magnesium carbonate in the carbon di-
oxide atmosphere, as compared with the anaerobic con-
dition, since magnesium carbonate is exceedingly
soluble in carbonated water.
The data relative to the amounts of sulfates leached
after the second exposure of 40 days, subsequent to
the removal of both added nitrate and generated sul-
fates, confirmed the point indicated by the results
from the first contact. Here, again, we find the de-
pressive tendency of metallic iron prevailing, though
nitrates were present. It is a rather striking fact
that these six determinations added to the corre-
sponding data of Table I give us twenty-six deter-
minations of remarkable consistency relative to the
influence of metallic iron upon the formation of sul-
fates. In every one of the twenty-six treatments
(excepting the one instance of an increase of but 1 . 1
lbs.), involving additions of metallic iron, the recovery
is below the amount actually determined as being
present initially in the added materials, singly and in
combination. It would appear, also, that not only
does the metallic iron preempt the available
oxygen, but it also effects a reduction of the sulfates
originally present as impurities in the several ma-
terials.
The problem of the function of surface in effecting
oxidation is one which is also being considered. The
presence of the quartz medium exerts a certain definite
increase in the end-products, within a definite time,
over the amounts found where the reaction takes place
in the absence of silica. As an example, a mixture of
quartz, sulfur, and limonite, boiled gently over night
with distilled water, gave an increase amounting to
3.2 times that obtained when the sulfur and limonite
were boiled together without quartz. It is hoped to
remove part, or all, of any condensed atmosphere
upon the quartz particles and then study the oxida-
tion induced thereafter. The fact that we have se-
cured the extensive oxidation of sulfur added to
quartz in an atmosphere of hydrogen eliminates
the assumption that the phenomenon is necessarily
induced by the oxygen of the atmosphere, or that
of the carbon dioxide gas.
It should be made plain that it is not our thesis to
prove that sulfofying organisms are not responsible
for transformation of sulfur into sulfates in the soil
mass. This is particularly true with reference to
native or added organic sulfur materials. Granting
that the transformation of added elementary sulfur
into sulfates may be, in part, a function of the bio-
logical content of the soil, nevertheless, the quartz-
medium data presented seem to point very conclu-
sively to the fact that added elementary sulfur may be
also readily and extensively transformed into sul-
fates, by independent chemical action under aerobic
and anaerobic, sterile and nonsterile conditions of
moist contact at normal temperature, when ferric
oxides and alkali-earth carbonates are present.
A detailed report of these and other studies along
the same lines will be offered shortly, together with
some consideration of the chemical explanations to
be advanced as accounting for the oxidation, with
such suggestions as the work may carry relative to
other oxidation reactions in the soil.
Annual Tables of Constants
Assembled and published by an International Commission
acting under the authority of the International Union of Pure
and Applied Chemistry.
Commissioners
Ch. Marie (France), General Sec'y Paul Dutoit (Switzerland)
G. Carrara (Italy) Alfred Egerton (England)
Ernst Cohen (Holland) E. W. Washburn (United States)
The publication of the "Annual Tables of Constants and
Numerical Data, Chemical, Physical, and Technological," which
was interrupted during the war, has now been resumed. Sub-
scriptions to Volume IV, containing all numerical data published
during the years 1913 to 1916, inclusive, will be received up to
May 31 at the special reduced rates indicated below. The edi-
tion will be limited, and the price will be raised after May 31.
Advanced Subscription Rates for Vol. IV
(Effective until June 1, 1921)
. Part I Only — . ^Parts I and 11^
Bound Unbound Bound Unbound
A. Regular $12.50 $11.00 $25.00 $22.00
B. Special (To members of
the American Chemical
Society) 9.50 S.00 19.00 16.00
Vol. IV is divided into two parts, Part I containing the con-
stants from "Compressibility" to "Electricity" (see Table of
Contents, Vol. Ill), and Part II the remaining constants. Part
I will be delivered probably early in July and Part II some
months later. Subscribers to both volumes will receive Part
I on the July delivery.
Subscribers whose payments accompany their subscriptions
will receive the volumes carriage free. To others delivery
will be made by C. O. D. express.
Orders for Volumes I, II, and III will be received at $7.20
each. Vol. I is, however, not sold separately, owing to the
limited supply.
Volume V, covering the years 1917 to 1920, inclusive, is in
preparation and will be ready for distribution late in 1922.
Orders from members of the Society should include the state-
ment: "I hereby certify that I am a member of the American
Chemical Society."
The British Dyestuffs Committee
In accordance with the provisions of the British Dyestuffs
Act of 1920, the following committee has been appointed by
the Board of Trade to advise with respect to the granting of
licenses under the Act:
Vernon Clay, Joint Managing Director, Robert Clay, Ltd.
George Welsh Currie
George Douglas, Managing Director, Bradford Dyers' Association, Ltd.
E. V. Evans, O.B.E., F.I.C, Treasurer, Society of Chemical Industry
Martin Onslow Forster, F.R.S., F.I.C, Director, Salter Institute of In-
dustrial Chemistry
C. C. Railton, Director, Calico Printers' Association, Ltd.
H. B. SHACKLETON, Messrs. Taylor, Shackleton & Co., Shipley
Thomas Taylor, Cornbrook Chemical Co., Stockport
S. A. II. WhETmore, British Dyestuffs Corporation, Ltd.
W. J. U. Woolcock, C.E.B., M.P., General Manager, Association British
Chemical Manufacturers
Pending the appointment of a permanent chairman, Mr.
Percy Ashley, C.B., Assistant Secretary, Industries and Manu-
factures Dept., Board of Trade, will act as chairman of the com-
mittee. The secretary is Mr. W. Graham, M.B.E.
314
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. Xo. 4
The Melting Point of Diphenylamine1
By Homer Rogers, W. C. Holmes and W. L. Lindsay
E. I. do Pont dk Nemours & Co., Wilmington, Delaware
Diphenylamine has become a product of very con-
siderable commercial importance, by reason of its
extensive use in the explosive and dye industries.
During the war, the specifications of the United States
Government called for diphenylamine of a melting-
point range between 52° and 54° C, thereby implying
that the latter temperature was the melting point of
the pure material. As experience had indicated that
54° was probably too high a figure for this constant,
it seemed desirable to determine the melting point of
pure diphenylamine very exactly.
The temperature generally quoted in literature as
the melting point of diphenylamine has been 54° C
the first authorities for which were Merz and Weith. -
They stated that previous to their work in 1873, the
accepted figure for diphenylamine had been 45° C,
which temperature was obtained by Hofmann3 in
1864. The purity of the product which Merz and
Weith used was tested by analysis for carbon and
hydrogen. They gave no details of their methods of
preparing their pure product or determining its melting
point.
The following reference works, which include almost
without exception the authorities to which one would
turn for dependable information on the subject, give
54° C. as the melting point:
Beilstein, "Handbuch der Organischen Chemie"
Meyer and Jacobsen, "Lehrbuch der Organischen Chemie"
Richter, "Lexikon der Kohlenstoffverbindungen"
I.andolt-Bornstein, "Physikalisch-Chemisehe Tabellen"
Watts, "Dictionary of Chemistry"
Thorpe, "Dictionary of Applied Chemistry"
Sidgwick, "Organic Chemistry of Nitrogen"
Allen, "Commercial Organic Analysis"
In addition, the figure is quoted in such generally
used textbooks of organic chemistry as those by Richter,
Bernthsen, Cohen, Holleman, and Molinari.
In spite of the impressiveness of the above list of
references, it is interesting to note that in all cases
where any authority is cited for the figure 54° C.
the reference is to Merz and Weith.
Matignon and Deligny,4 in 1897, found the melting
point to be 54.2° C. Stillman and Swain,5 in 1899,
determined the melting point as '54°.
All the published determinations since that time,
however, to the best of our knowledge, point to a
lower temperature than 54° for the melting point.
Bogojawlenski6 and Narbutt,' in 1905, by independent
determinations, found diphenylamine to melt at 52.85°
C. Olsen8 quotes this figure. Merck9 gives 53.0° C. as
the melting point.
Owing to the pressing nature of the question during
the war, the investigation of the true melting point
1 Received December 20, 1920.
"- Bar., 6 (1873), 151 I.
' Jahresb., 1864, 427
• Compt. rend., 136 (1897), 1103.
<■ Z. physik. Chem., 39 (1899), 705.
8 Chem. Zenlr., (1905), II, 945.
» Z. physik. Chem., 64 (1905), 696.
5 Van Nostrand's "Chemical Annual," 1918., 4th Ed.
8 "Chemical Reagents, Their Purity and Tests," 1914, 2nd Ed.
and freezing point of diphenylamine was taken up at
two of our research laboratories.
FREEZING POINT
While Merz and Weith mention, and apparently
determined, the melting point of diphenylamine, in
the tests carried out on diphenylamine to determine
whether it meets the specifications the melting point
is always determined by the solidification method,
and not by means of the familiar capillary tube at-
tached to the bulb of a thermometer and immersed
in a liquid bath.
While diphenylamine freezing at 52° C. and higher
was successfully manufactured on a large scale, the
care required to achieve this result, together with a
consideration of the nature of the impurities likely to
be present, led us to doubt whether absolutely pure
diphenylamine could have a freezing point as high as
54° C, especially since in a previous investigation with
a similar object the purest material obtained froze at
52. 85° C. It was, therefore, decided to undertake
the preparation of absolutely pure diphenylamine.
either by purification of the commercial product or
by some synthetic method, and to establish its true
freezing point beyond doubt. This program was not
carried to completion because of the relatively slight
importance of the subject after the signing of the
armistice, and while the work thus fell short of our
original intention of establishing the true freezing
point exactly, we have considered it worth while to
publish our conclusions as far as they go, together
with the most important data on which these conclu-
sions are based. Our conclusion is that pure diphenyl-
amine has a freezing point within a few hundredths of
a degree of 53° C. Our evidence in support of this
view is summarized briefly below.
crystallization — Our purest diphenylamine was
obtained by repeated crystallization of the commercial
product. A number of solvents were examined as
regards their suitability, including acetone, carbon
disulfide, carbon tetrachloride, ether, benzene, toluene,
xylene, aniline, and nitrobenzene, in all of which di-
phenylamine is highly soluble at room temperature;
methanol, ethyl alcohol, isopropyl alcohol, normal
butyl alcohol, dimethylaniline, and acetic acid, in
which saturation is reached at room temperature
with a diphenylamine concentration of 20 to 40 per
cent; and the paraffin hydrocarbons, most of which
dissolve less than 20 per cent at room temperature.
Water was the only liquid tried in which diphenylamine
is comparatively insoluble in either the liquid or solid
state. The preliminary experiments with these various
solvents (including ligroin, used by Merz and Weith)
indicated that methanol could be depended upon to
give at least as good results as any other, and in all
probability better results than most of the solvents
listed above. Methanol gave appreciably better and
speedier results than any of the aliphatic hydrocarbons
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
315
tried. In some experiments it was considered ad-
visable to include crystallizations from petroleum
ether in order to remove impurities which might be
more soluble in this solvent than in methanol. A
typical series of crystallizations will perhaps serve to
indicate the progress of the purification. Crude
diphenylamine, freezing at 51.7° C, was crystallized
five times from methanol, the product at this point
freezing at 52.95° C. Crystallization of this product
from petroleum ether raised the freezing point to 53° C.
Two more crystallizations from petroleum ether failed
to raise the freezing point. Crystallization from meth-
anol of the material recovered from the fifth crystal-
lization from methanol also gave material freezing
at 53° C. In another series the crude material was
distilled, then crystallized from methanol, distilled
and crystallized again, distilled and crystallized a
third time, and then crystallized four more times from
methanol. The second of these four crystallizations
brought the freezing point to 53° C, but the two subse-
quent crystallizations failed to increase it. It is of
interest also to note that the material recovered by
evaporation of the mother liquor from the last crystal-
lization froze at 52.98° C. All the temperatures
were measured with a carefully calibrated thermometer
and are corrected for stem emergence. While the
work on crystallization included many experiments, the
above results are typical of the best obtained and were
based on a considerable amount of preliminary work.
distillation — In addition to the crystallization
experiments, distillation with a column was tried as
an alternative method of purification. After many
preliminary distillations in glass, an iron column was
finally constructed. In a typical distillation with
this column, about 1G kilos of crude diphenylamine
gave fractions freezing at from 51.35° up to 52.5° C,
and then down again to 49.3° C. The fraction freezing
at 52.5° C. amounted to 600 g. (about 3.7 per cent
of the total). The temperatures were not recorded
in this run. In a typical distillation in glass, a frac-
tion freezing at 52.5° C. distilled over a range of 0.5°.
The material used in this distillation was a fraction,
freezing at 52.2° C, obtained in a previous fractiona-
tion in glass.
other methods — Various other lines of work, started
with the object of confirming the results described
above, either gave products freezing well below 53° C.
or were discontinued because of the decreasing im-
portance of the subject. Among these were attempts
to synthesize diphenylamine by unusual methods,
none of which gave a product freezing above 53° C,
even after careful crystallization, and a synthesis by
the usual aniline salt method, starting with benzene
purified with extreme care, and purifying the inter-
mediate products and reagents by the best methods
available in the literature. The crude material ob-
tained from this latter synthesis, after simple steam
distillation, froze at 52.8° C. Crystallization from
petroleum ether raised it to 52.85° C, and a second
steam distillation and crystallization from petroleum
ether to 52.95° C, at which point the work was dis-
continued.
From a consideration of the results obtained as
above, we have concluded that the freezing point of
pure diphenylamine is within a few hundredths of a
degree of 53° C. and that the results of Merz and
Weith cannot be accepted as the true freezing point
(or true melting point) of pure diphenylamine. If
the true freezing point were 54° C, our purest product
must have contained more than 1 per cent of an im-
purity with a molecular weight of not less than 100,
or more than 2 per cent of an impurity with a molecular
weight equal to that of diphenylamine. It would
require almost 3 per cent of triphenylamine to lower
the freezing point by 1° C. It seems probable that
Merz and Weith determined the melting point by
the ordinary capillary method, which is known to givfe
high results unless made with extreme care. Without
attempting to review the literature completely on the
physical constants of diphenylamine, attention may
be called to an abstract of an article by Vassilief.'
giving the melting point of diphenylamine as 53.2° C.
Unfortunately, the original article, which so far as
we know contains the most recently published data
in this connection, appeared in a Russian journal which
is not available to us.
In addition to the above data on our own prepara-
tions, freezing and melting points were determined on
various purchased samples, as follows:
. Melting Point .
Freezing Sweating Meniscus Clear
Point Point Point Point
° C. ° C. ° C. ° C.
Merck & Co 52.85 52.95 53.05 53.10
A. H. Thomas Co 52.85 ... 52.75
A. H. Thomas Co., twice crystal-
lized from methanol 52.85 ... ... ...
Kahlbaum 52.15 52.55 52.85
Eimer and Amend 51.65 52.15 52.65
All temperatures were determined with a standard
thermometer and are corrected for stem emergence.
The Kahlbaum and the Eimer and Amend samples
were too small for a freezing-point determination.
The following work was done at another laboratory.
The diphenylamine used for the tests was washed
once with distilled water, to which a small amount of
hydrochloric acid had been added. It was then thor-
oughly washed five times with hot distilled water,
crystallized five times from ethyl alcohol, and dried
by prolonged heating in a drying oven at a temperature
slightly below the melting point.
Determinations of the solidification point were made
on this material, and purity was considered to be es-
tablished when the crystals from three successive
crystallizations gave identical solidification points,
within the limits of experimental accuracy. Thi
diphenylamine to be tested was placed in a wide-
mouthed test tube, which was inserted through a
tightly fitting rubber stopper in a bottle of about 500'
cc. capacity. The bottle was then partially evacuated.
The solidification point was obtained by the usual
method of warming the diphenylamine until all was
melted, then allowing to cool, careful observation being
made of the temperature at which solidification took
place. A thermometer was immersed in the molten
diphenylamine during the cooling, and the liquid was
1 Bull. soc. Mm., 16, 182.
316
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. Xo. 4
:gorously meanwhile with a g'...
The tern: -ing the cooling
solidification began to take place, at which point the
". onary for a few minutes or
rose slightly. The ;
highest point of the rise in temperature, or at the
-
rief time, [f I perature is read at definite
le during the cooling and solidification.
1 5 or 30 sec, and the c
on a curve, temperature against : solidifica-
■
:ng as described at: following de-
stinations were made and checked for the solidifica-
point of diphenylamine, nc -eing
the material from the fifth
cion had been obtained.
Sole>:f.:
Sufu c C
: •_:-. > -
52 "c
6th Crystallization
- -taEization 52.96
7 th Mother Liquor Evap 52.96
In the determination of the solidification pec
1 in the diphenylamine to
a depth of about 3 in. As the exposed portion of
—.lometer was partly within the open test tube and
irtly unenclose ■ .nsforemer.
correction being, of c:
- r two. This same diphenylamine, on
which a solidification point of 52.96° C. had
obtained, was tested for melting point by the capillary
: method, and found to melt at the same poi:.
::rst lot of material. 53.05° C. The pure product
n color with a mild pleasant odor.
MELTIXG POINT
The material used as a starting pc:
paring pure diphenylamine was a sample of good com-
mercial product, of a light yellow color, meltir.,
>°C. The crude
hundred grams of the diphenylamir. ;
I -
the water being decantei en treatments.
The material w times from
I alcohol, the crystals being freed from the rxt I
tor each tint: .chner funnel. Tl
thoroughly dried in the air ited
temperature, and then vacuum-dried over
chloride. The • mine was
assumed to be complel
points of the dr: . tad of the residue obtained
i ;.ther liquc t
53.05 c C.
The determinatior.; ■:: the melting point
: :e capillary -
prepared by drawing out 12-cm. glass tubing. [1
led desirable illary tubes should have
an outside diameter of not more than 1.0 mm.
had been shown to be imeter in
ions experiments. As the heat of fusion c:
phenylamine is 26.3 cal. per g. it is more than usv
imp::
The individual determinations are recorded below:
Original Material
After washing with water.
-
2nd Crv>:
2nd Crvst.
3rd Crvst
3rd Crvst
4th Crvst
•:
•
I
-:
■
4th Mother Liquor Evap. .
tiler Liquor Evap..
4th Mother Liquor Evap. .
4th Mother Liquor Evap..
5)
--.
:
-
5th Crvst.
•
5th Crvst,
5th Mother Liquor Evap..
5th Mother Liquor Evap..
Rate of
Rise of Temp.
::' : It*
6 mm.
Diameter of
CapiHarv
Tubes"
Mm.
10
0.6
1.0
10
1.0
1.0
1.0
0.6
0.8
1.0
0.8
0.6
0.9
0.6
0.6
0.9
0.6
0.8
0.8
0.6
0.8
1.0
1.0
0.9
0.8
1.0
1.0
0.8
1.4
1.0
1.0
■
S2.8
53.0
53.1
53.05
53.0
53.05
53.0
53.0
53.05
52.9
-
52.85
53.05
53.1
53.05
53.05
53.0
53.05
53.05
53.0
53.05
53.05
S3.0S
The melting point was. taken at the point at which
the diphenylamine within the capillary tube became
absolutely clear and transparent, without any sus-
pended, unmelted crystals apparent. The majority
of the above determinations on the final product
showed 53.05° C. as the melting point, especially
those determinations which were carried out most
carefully.
In order to eliminate as far as possible any error
-oduced through the inaccuracy of
standard thermometer
the determination, one standardized
V. S. Bureau of Standards and the other by the
-.'.ische-Technische Reichsanstalt. These ther-
momet:: .ind to check one another exactly
p plying the corrections furnished by these
ties. The accuracy c: r.iardizations
hnation of their respec-
ons for temperature of emer-
troughout.
SUMMARY
The temperature generally quoted in the standard
referen: t the melting point of diphenylamine
is 54.0" C. All published determinations made within
the last 15 yrs., however, indicate a lower
than 54° C. for the melting p
: :1 determinations on thoroughly purified ma-
sing standardized thermometers, have shown
erial to have a melting point of 53.0° C.
- .vrate investigations of the freezing point gave
:' 52.96° and 53.00° C.
Platinum Theft
During the night of Monday, February 14. 1921. three plat-
inum crucibles were taken from the laboratory of the Pacific
Coast Steel Co., San Francisco, Cal.
Two of these crucibles were marked Baker & Company, and
weighed 12.1592 and 12.1617 g., respectively. The third was
. id 11.6668 g.
Apr... 1921
THE JOURXAL OF IXDUSTRIAL AXD EXCIXEERJXG CHEMISTRY
3 1 ;
The Activity of Phytase as Determined by the Specific Conductivity of Phytin-Phytase
Solutions1,2
By F. A. Collatz and C. H. Bailey
Division of Agricultural Biochemistry, Minnesota Agricultural Experiment Station, St. Pail, Minnesota
The activity of phytase has commonly been mea-
sured by determining the quantity of inorganic com-
pounds of phosphoric acid produced by the hydrolysis
of phytin. The early studies of this enzyme by Su-
zuki. Yoshimura, and Tokaishi3 were occasioned by
the appearance of phosphoric acid or its salts in a
mixture of rice bran and water. Vorbrodt4 studied
the activity at different temperatures of phytase
prepared from barley, and concluded that it reached a
maximum in the neighborhood of 28° C. At tem-
peratures of 58° to 60° the action was found to be
Since the principal object of these experiments was
to determine the influence of temperature upon the
activity of phytase, time and temperature were the
only variables studied. The temperatures employed
ranged by 5° intervals from 2.5° to 60° C. A water
solution of purified phytin1 was used as the substrate.
The active phytase was prepared by digesting finely
ground wheat bran with water at a temperature of
2° to 3° C, and precipitating the enzyme by filtering
into 95 per cent alcohol. The precipitate was dried,
dissolved in water, and reprecipitated with alcohol.
X -
;
/
22
'
»
f
/
'
«.
5 r"
/
/ /
/
/
•
\
f
I
— ,
//
G
>
_^C
\
Fig. 1— Graphs Showing Effect of Hydrolysis of Phytin by Phytase at Different Temperatures upon Conductivity of Solutions
slow, while boiling stopped the formation of phosphoric
acid.
Since phosphoric acid or its salts are end-products of
the hydrolysis of phytin, and are ionized more in water
solution than the original phytin, the electrolytic re-
sistance of the solution of phytin and phytase should
afford a measure of the activity of the latter.
■Received December 1, 1920.
3 Published with the approval of the Director, as Paper No. 212,
Journal Series, Minnesota Agricultural Experiment Station.
' "Uber ein Enzyme 'Phytase' das 'Anhydro-oxymethylene-ai-phos-
phorsaure' spaltet," Tokyo Imperial Univ. College of Agriculture, Bulletin
7 (1907). 503.
« "Untersuchungen fiber die phosphorverbindungen in den rflanz-
ensamen mit besonderer Bertcksichtigung des Phyiins," Bulletin lnt de
1'Acad. Sci. Cracovie, Serie AI (1910), 414.
This was repeated several times, the precipitate dried
at room temperature in vacuo, and finely pulverized
in a mortar, yielding a grayish white powder.
Solutions of phytin and of the active phytase prep-
arations were prepared by dissolving .50 mg. of each in
separate 50-cc. portions of water. These were brought
to the desired temperature, equal volumes were mixed
in a Freas conductivity cell, and the electrolytic re-
sistance determined at once, and again every 15 min.
until successive readings were alike or nearly so.
It was found that when phytin and water were mixed
in the absence of active phytase, no change o
in the electrolytic resistance of the solution when
This phytin wns kindly supplied by Dr. .1 B. Rather.
318
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
/
a
i
/ /
/
/
/
/
'///
/ /
1/
%
//
i /
y//
T/ME -MINUTES
Fig. 2 — Increase in Specific Conductivity (Calculated ti» 30^) of Phytin-Phytasb Solutions Di.-.estkd vr Dxffbrbnt Tempkratires
incubated for a time. Any decreases in the electro-
lytic resistance when phytase was present were at-
tributed to the appearance of electrolytes resulting
from the hydrolysis of phytin.
computed to a basis of the conductivity at 30°, and
the results are given in Table II. After the calcula-
tions to a common temperature basis, the increase in
specific conductivity during each 15-min. interval was
Tabi.
I — Specific Conductivity of
Phytin-Phytase
Solutions IIv-
Tabi
E 11 — Specific Conductivity of
Phytin
DROLVZBD AT VARIOUS
Temperatures
BY
Phytase
Calcu
LATED TO
30°
25°
30°
35°
40°
45" 50°
55°
60°
25°
30°
35°
40c
45° 50°
55°
60'
Time
K:, X
Kjo X
Km X
K.o X
K« X
Kjo X
Ku X
Ke. X
Time
Km X
Kjo X
Kjo X
Kjo X
Kjo X
Kjo X
Kjo X Kjo X
Min.
10 «
10 «
10 «
10"«
10-'
10-'
10-'
10-'
Min.
io-«
10-'
10-'
io-«
10-'
io-«
10-'
10"'
0
1 . 1481
1.3121
1.4416
1 . 3964
1.4551
1.4854
1.6660
1 7887
0
1 . 2679
1.3124
1.3171
1.1745
1.1338
1.0780
1.1316 1
1410
15
1.2047
1 U'-N
1.6109
1.7390
1.7719
1.9556
■1 2090
2.5933
15
1.3304
1.448S
1
4719
1.4626
1.3800
1.4193
1.5004 1
m
1.2746
1.5S71
1.7S25
1.8832
2.0921
2.3270
2.6410
2.7193
30
1.4076
1.5871
1
62S6
1 . 5S39
1 . 6301
1 . 6888
1.7939 1
-
45
1 352(1
1.6901
1.9177
2.1063
2.2212
2.4010
2.7010
2.7700
45
1.4937
1.6901
1
7522
1.7610
1 . 7307
1.7426
1.8346 1
7680
60
1.4318
1 . 750S
1 9688
2.1170
2.2506
2.4140
2.7230
2.7938
60
1.5811
1.7508
1
79S9
1 . 7806
1 . 7536
1.7520
1.8496 1
7S32
75
1.4821
1 8146
1.9872
2.1347
2 . 2592
2.4250
2 . 7360
2.8015
75
1.6367
1.8146
1
8157
1 . 7954
1 . 7603
1 . 7600
1.8584 1
7SS3
90
1.8226
1.9872
2.1424
2.2620
2.4330
2.7410
2.8271
90
1.6876
1 8226
1
8157
1.8019
1 . 7625
1.7657
1.8618 1
8043
105
1 . 5588
2.1424
2 . 43S0
2.7410
2.83S4
105
1.7214
1 s257
1.8019
1 . 7694
1.8618 1
8115
120
1.5727
1 . 8257
120
1 . 7367
1 . 8257
135
135
1.7444
150
1 . 5796
150
1 7144
In Table I are given the specific conductivities of
solutions of phytin and phytase prepared and digested
as described, while the same data are shown graphically
in Fig. 1. These are of value chiefly in showing the
rate of hydrolysis at the several temperatures, and
indicate that as the temperature is elevated the reac-
tion is accelerated and reaches completion more
quickly.
The data in Table I are of limited value, since the
conductivity in each series was determined at the tem-
perature of incubation. To make the data comparable
it was necessary to calculate the conductivity of the
several series to a common temperature basis. To this
end, a solution was digested at 55° until hydrolysis
ceased. Its conductivity was determined at 55°,
and, after cooling, was redetermined at 25°. The
difference between the two readings indicated an
increase in conductivity of 1.89 per cent for each degree
of increase in temperature. All of the data were then
computed, and in Fig. 2 these data are shown graphi-
cally. They indicate that, while the acceleration of
hydrolysis of phytin by phytase increases up to 60°
during the first 15-min. interval, after the end of IS
min. the rate diminishes when the temperature ex-
ceeds 55°. Thus the increases in the conductivity
of the mixtures digested at 50° and at 55° were greater
at the end of 30 min. than in the mixtures digested
at 60°.
SUMMARY
Changes in the specific conductivity of a water solu-
tion of phytin and phytase afford a convenient measure
of the progress of the hydrolysis of phytin. The
phytase prepared from wheat bran appeared to effect
a more complete hydrolysis of the phytin at a tempera-
ture of about 55° than at any other temperature,
although hydrolysis proceeded more rapidly at 60°
during the first 15 min. As the temperature is in-
creased the reaction reaches completion more quickly.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
319
Studies of Wheat Flour Grades. I— Electrical Conductivity of Water Extracts12
By C H. Bailey and F. A. Collatz
Division of Agricultural Biochemistry, Minnesota Agricultural Experiment Station, St. Paul, Minnesota
The ash content of wheat flour is almost universally-
employed at the present time as an index of grade.
High-grade or patent flours contain the least ash,
occasionally as low as 0.35 per cent, while the lower
or clear grades sometimes contain over 2 per cent.
These differences are due to the fact that the lower
grades contain more of the branny and embryo struc-
tures, which structures contain a higher percentage
of ash than the floury portion of the wheat kernel.
Swanson3 determined the ratio of total to water-
soluble phosphorus in different streams and grades of
commercial flours. He found that when the flour was
extracted with water at 40° there was generally a
parallelism between the percentage of phosphorus in
the water extract and that in the original flour. He
suggested that at least part of the phosphorus in the
flour extract is probably in the form of phosphates of
potassium.
In view of this observation of Swanson's, it appeared
probable that the electrical conductivity of water
extracts of flours would increase with the percentage
of ash. To ascertain whether or not such a relation
existed, a series of preliminary experiments was
conducted, and in a note by Bailey4 it was indicated
that the parallelism was apparently fairly exact.
METHOD OF STUDY
The data secured in the preliminary study were not
adequate for drawing any definite conclusions, and
recently a more comprehensive study was made of the
factors determining the conductance of such extracts.
Two samples of flour, representing a high-grade or
patent flour containing 0.43 per cent of ash, and a
clear or lower grade containing 0.92 per cent, were
extracted with conductivity water at different tem-
peratures, and for various lengths of time.
The general details of the procedure were as follows:
10 g. of the flour were weighed into a dry Jena flask,
and 100 cc. carefully prepared conductivity water
having the desired temperature were added. The
flour was suspended in the water by vigorous agitation,
care being taken that no lumps were formed. The
flask containing this mixture was partially submerged
in a water thermostat, which was maintained at the
desired temperature. The flour was kept in suspen-
sion by intermittent shaking during the extraction
period, and was then thrown out of suspension by
whirling for 5 min. in a centrifuge. The clear decan-
tate was passed through a filter to remove any floating
particles, and its electrical conductivity determined.
APPARATUS FOR CONDUCTIVITY MEASUREMENTS
A special dip electrode was employed, which was
similar to the ordinary Freas cell with the bottom cut
off. The glass walls of the cell extended far enough
■Received December 1, 1920.
' Published with the approval of the Director, as Paper No. 213,
Journal Series, Minnesota Agricultural Experiment Station.
■ This Journal, 4 (1912), 274.
'Science, 47 (1918), 645.
below the platinum electrodes to protect them from
mechanical injury. In using this cell, the extract
was placed in a glass vial and brought to temperature
(30°), and the electrodes were then immersed in the
contents of the vial. This made it possible to work
rapidly by transferring the dip electrode from one
vial to another. In actual practice it was found
advisable to place portions of the extract in at least two
vials, in the first of which the electrode was rinsed off,
while the measurements were made with the electrode
in the second of the two vials.
A constant speed, high frequency generator furnished
a current of 1000 alternations per second, which was
used with a tunable telephone receiver. A balance
was secured by means of a resistance box, and a IO-
meter wire bridge calibrated in the middle for 50 cm.
INFLUENCE OF TIME AND TEMPERATURE OF EXTRACTION
The patent and clear flours were extracted for periods
of time ranging from 15 to 960 min. at 0°, 25°, 40°,
and 60°. In Table I are given the specific conductivi-
ties of the extracts thus prepared, data which are given
graphically in Fig. 1. In the case of the patent flour
Table I — Specific Conductivity (Km X 10"*) of the Water Extracts
of Patent and Clear Flours Extracted at Different
Temperatures for Different Lengths of Time
Time of . — Temperature of Extraction .
Extraction 0° 25° 40° 60°
Min. Kjo X 10~« Kso X 10~< Kto X 10"< Kio X 10-'
Patent Flour
15 6.478 6.797 6.181
30 4.601 5.590 6 916 6.253
60 4.600 6.668 5.958 6.272
120 5.264 5 7'..8 6.110 6.347
240 5.515 6.S30 6.1S1 6.444
480 5.009 5.950 6.211 6.443
960 6.780 6.957
Clear Flour
15 8 789 9.355 9.780
30 6.477 9.167 9.880 9.872
60 6 770 9.367 10.018 9.936
120 7.378 9 999 10.260 10.182
240 8 041 10.100 10 347 10 195
480 8.890 10.401 10.680 10 474
960 9.333 10.593 10.770 10.474
the conductivity increased with time and temperature
within certain limits. At temperatures of 40° and 60°
there were slight increases in conductivity of the ex-
tract after 240 min , while at 25° equilibrium was
reached at the end of 4S0 min., and at 0° it was not
reached until after at least 900 min. Moreover,
there was a difference in the shape of the curves at the
four temperatures. As the temperature in<
the initial rise in conductivity per unit of time became
more abrupt, but equilibrium was reached much
sooner, and the curve consequently flattened out in a
shorter time.
The clear flour gav,e somewhat different results.
Equilibrium was not reached so quickly at any of the
temperatures, and what is even more significant, the
conductivities of the extracts prepared at 00° were
lower, with the exception of the one taken
of 15 min., than were extracts prepared at 40°. Thus
the values at 00° were intermediate between the 25
and 40° extracts.
The explanation of these curves is probably to be
320
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
found in the conclusions reached from observations
made on phytase activity. In the preceding paper
by Collatz and Bailey1 the progress of the hydrolysis
of phytin by phytase was discussed, and data were
presented showing much the same response to tem-
perature as is exhibited by these flours. Phytase from
wheat bran was found to have an optimum tempera-
~J
—\
;=
' —
■s^
/
__
.
Tl\t£ - MIHU7CS
Fig. 1 — Graphs Showing Effect of Time and Temperature of Ex-
traction of Patent and Clear Flours upon Specific
Conductivity of the Extracts
ture of 5-5°; the initial rate of change in conductivity
of a phytin-phytase solution increased with, the tem-
perature, and reached equilibrium more quickly at the
higher temperatures. The difference in the behavior
of the patent and the clear flours at 60° may possibly
be attributed to the ratio of substrate to enzyme in
the several grades. From the available data we
conclude that the electrolytes of the water extract of
wheat flours are chiefly phosphates which are pro-
duced as the result of hydrolysis of phytin by the
phytase in the natural tissues of the kernel. Since the
activity of phytase, and the consequent appearance of
electrolytes in the phytase-phytin solution in water,
is affected by temperature, and increases to a point of
equilibrium with lapse of time, it follows that there are
variations in the conductivity of water extracts of any
flour dependent upon the conditions of extraction.
It is necessary, therefore, to maintain uniform condi-
tions with respect to time, temperature, and ratio of
flour to water, in comparing several flours by the elec-
trical conductivity of their water extracts.
ELECTRICAL CONDUCTIVITY OF WATER EXTRACTS OF
DIFFERENT FLOUR GRADES
To afford a wide range of quality, and of percentages
of ash, the flour streams from two different mills were
secured. The series of flours from one mill, designated
as Series A, comprised four break flours, and five
middlings flours, containing from 0.44 to 1.62 per cent
of ash. That from another mill, designated as Series
B, included five break flours, a sizings, stone stock,
seven middlings, three tailings, and a dust flour, in
addition to the patent, first clear, and second clear
i This Journal, 13 (1921), 317.
flours marketed by the mill. These contained from
0.35 to 1.73 per cent of ash.
The flours in Series A and B were extracted in the
ratio of 1 part of flour to 10 parts of water at 25° for
30 min. This temperature was employed primarily
because it was easy to maintain. This being about the
mean laboratory temperature, it follows that there is
little likelihood of significant variation in the tempera-
ture of the digest resulting from exposure of the ma-
terials either before or after combining the flour and
water. The temperature of the mixture consequently
changes very slightly during the clarification and
filtration processes. It is probable that the deviation
from the means observed in the preliminary studies
reported by Bailey, in which the flours were extracted
at 0°, may be attributed to the varying rate of tem-
perature change in the mixtures from the time they
were removed from the ice bath until the clarification
was completed. Again, a small variation in the length
of the period of extraction results in less error when
the extraction is conducted for 30 min. at 25° than
when conducted for the same length of time at 0°.
Temperatures above 25° are open to the same objec-
tions as are those materially lower, namely, the diffi-
culty of maintaining the mixture at a uniform tempera-
ture throughout the operation.
Tatile II — Relation of Specific Conductivity of Water Extracts
to Ash Content of Wheat Flours
Specific Con-
ductivity of
Ash Water Extract
Grade of Flour Percent Kao X I0"«
Series A
First break 1.34 10.563
Second break 0.59 6.647
Third break 0.67 7.690
Fourth break 1.62 11.969
First middlings 0.44 5. 395
Second middlings 0.4.". 5.547
Third middlings 0.56 6.33.S
Fourth middlings 1.17 10.242
Fifth middlings 0.61 6.777
Scries B
First break 0.56 6.503
Second break 0.4S 5.971
Third break 0.58 6.838
Fourth break 0.80 8.483
Fifth break 0.96 9.167
Sizings 0.45 5.564
First middlings 0.41 5.270
Second middlings 0.3S 4.744
Third middlings 0.42 5.002
Fourth middlings 0.46 5.514
Fifth middlings 0.43 5.192
Sixth middlings 0.42 5.075
Seventh middlings 0.47 5.870
Stone stock 0.35 4.643
First fine tailings 0.73 7.624
Second fine tailings 0.92 S.650
First coarse tailings 0 . 66 7 . 450
Dust flour 1.38 10.610
Patent. 90 per cent 0.44 5.815
First clear 0.90 8.850
Second clear 1.73 12.67S
The 30-min. period was selected in order to reduce
to a minimum the time involved in completing the
determination. A method of grading flour based on
the conductivity of the water extract will be more
advantageous than the determination of ash only
in the event that the time required is materially re-
duced. If a 30-min. extraction gives comparative re-
sults, the reduced time may be more important than
increased accuracy accompanying a longer extraction
period. From the data presented in the foregoing
section it is evident that any procedure is more or less
empirical and must be scrupulously followed to afford
any basis for comparison.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
321
— =FFffFF
— =£=
■spcc/f/c comduct/wty of extract hj0 x /o"* .
Fig 2 — Relation of Ash Content to Specific Conductivity of Water
Extracts Prepared by Extracting at 25° for 30 Min.
When the extracts of the thirty flours in the two
series were prepared in the manner described, it was
found that their specific conductivities varied with the
ash content. The variation was not direct, and the
curve was not a straight line, but a simple parabola.
The ash content and specific conductivity of the flours
in Series A and B are given in Table II.
Table III — Specific Conductivity of Water Extract, Actual and
Calculated Percentage of Ash in Flours of
Series A and B
Specific
Conductivity of - Ash in Flour .
Water Extract Actual Calculated Difference
Sample K»o X 10"» Per cent Per cent Per cent
Stone stock 4.643 0.346 0.367 +0.021
Second middlings.... 4.744 0.378 0.375 — 0.003
First middlings. 5.270 0.409 0.421 +°,-°12
Sixth middlings 5.075 0.417 3 ~ °,.014
Third middlings 5.002 0.41ft 0.391 ~"
Fifth middlings 5.192 0.427 0.414 TS'SJI
Patent' 5.590 0.435 0.4o2 +0.017
First middlings' 5.395 0.442 0.433 Tn'SSS
Patent 5.815 0.442 0.474 +0.032
Second middlings'... 5.547 0.446 0.43S — S'SSS
Si/ings flour ...... 5.564 0.451 0.449 —0.002
Fourth middlings.... 5.514 0.460 0.444 Tj-g"
Seventh middlings... 5.870 0.467 0.481 +0-0
Second break 5.971 0.479 0.492 +2-2J?
Third middlings'.... 6.338 0.555 0.534 ~S'S?i
First break 6.503 0.564 0.554 "T^JS
Third break 6.838 0.579 0.597 +0.0 8
Second break- 6.647 0.585 0.572 „ni-
Fifth middlings'. .. . 6.777 0.613 0.588 t5'S??
First coarse tailings.. 7.450 0.662 0.683 +2-23 J
Third break' 7.690 0.668 0.719 +°M^
First fine tailings.... 7.624 0.726 0.709 Tn'nl-
Fourth break 8.483 0.803 0.849 +°?*5
Clear flour 8.850 0.900 0.914
S^or.a £c- tellings . 8 S5C 0 213 0 8'8 —0 041
Clear flour- 9.167 0.920 0.973 +0.053
Fifth break 9.167 0.955 0.973 ±n'2i?
Fourth middlings'... 10.242 1.171 1.198 +0.02o
First break'...!.... 10.563 1.340 1.263 ~M07,Q
Dust flour 10 610 1.383 1.274 — 0.109
Fourth break' 11.970 1.620 1.606 T^Pil
Second clear flour. . . 12.678 1.731 1.797 +0.066
1 Flours used in preliminary experiments.
' Series A.
For convenience in comparison, the flours are ar-
ranged in Table III in order of their ash content with
the specific conductivity in a parallel column. The
same arrangement is shown graphically in Fig. 2. In ad-
dition, these data have been subjected to mathematical
treatment, and the ash content calculated which cor-
responds to each unit of conductivity on a smoothed
curve. In parallel columns are given the results of
these calculated percentages, and the differences be-
tween the actual and calculated percentages of ash.
It will be observed that up to 0.80 per cent of ash the
differences are small, being in all but one instance
within the limits to be expected in ash determinations.
The ratio of conductivity to ash content is sufficiently
exact to permit of the determination of the former as
an index of flour grade.
SUMMARY
Specific conductivity of the water extracts of wheat
flour varies with the time and temperature of ex-
traction. A temperature of 00° or somewhat less
gives the highest values.
From the similarity of the response of flour extracts
to temperature changes and that of phytin-phytase
preparations, it appears that the conductivity of water
extracts of wheat flour is due chiefly to inorganic salts
of phosphoric acid, resulting from the hydrolysis of
phytin through the activity of the enzyme phytase.
When comparisons of different flours are to be made
it is necessary that a uniform procedure be followed
in the preparation of the extracts.
Specific conductivity of flour extracts parallels ash
content and can be employed as an index of flour grade.
In determining the grade of flour by this method it
has been found convenient to extract 1 part of flour
with 10 parts of water at 25° for exactly 30 min., and
measure the conductivity of the clear extract a I 30°
with a dip electrode.
Standardization of Petroleum Specifications
The Interdepartmental Committee on Standardization of
Petroleum Specifications, superseding the war-time committee
on the same subject, was organized at its first meeting at the
Bureau of Mines, Washington, D. C, February 19, 1921. The
committee gave its approval to Bulletin 5 of the previous com-
mittee, continuing in force the specifications on gasoline, kero-
sene, fuel oils, lubricating oils, signal oils, etc., and decided to
adopt the plan of adding a technical subcommittee to handle
the details of drawing up and revising specifications and meth
ods of testing. N. A. C. Smith has been appointed chairman
of the technical committee. The Committee on Standardiza-
tion consists of Dr. H. Foster Bain, Bureau of Mines, Chair-
man, representing the Department of the Interior; J. H. Vawter,
Office of the Supervising Architect, representing the Treasury
Department; Captain Wm. H. Lee, Q. M C, Office of the
Quartermaster General, representing the War Department; E.
B. Cranford, Asst. Supt, Division of Post-Office Service, repre-
senting the Post-Office Department; B. A. Andertou, Bureau of
Public Roads, representing the Department of Agriculture; Dr.
C. W. Waidner, Bureau of Standards, representing the De-
partment of Commerce; W. A. E. Doying, Inspecting Engineer,
representing the Panama Canal; M. W. Bowen, Assistant to
the Chairman, representing the Shipping Board.
322
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
The Rate of Evaporation of Ethyl Chloride from Oils1
By Charles Baskerville and Myron Hirsh5
COLLBGB OF THE ClTY OF New YORK, NEW YORK, N. Y.
The determination of the rate of evaporation of
ether from various oils3 gave the foundation of ether-
oil colonic, and later oral, anesthesia introduced by
Gwathmey,'1 and since extensively used by a number
of surgeons and specialists with gratifying success.6
In particular cases analgesia is preferred to anesthesia,
in so far as the one may be caused to prevail. Anal-
gesia is evident previous to anesthesia during induc-
tion and obtains as the patient comes out of the stage
of full anesthesia, the period of analgesia varying in
time and degree with the drug administered, rate of
administration, body saturation, and rate of elimina-
tion. Analgesia is desirable in minor short, as well as
prolonged, operations in dentistry, when recourse need
not be had to anesthesia. Analgesia, without anes-
thesia, offers opportunity for comfortable dressing of
serious wounds. Prolongation of post-anesthetic an-
algesia reduces the necessary time of anesthesia for
the sewing of the incision; and the dressing may be
done during that period.
Cocaine, stovaine, novocaine, and this general class
of drugs are most useful for such purposes, being ap-
plied in various ways, but their use is always attended
unhappily with an element of uncertain idiosyncrasy.
Ethyl chloride in quantity is about six times as
strong (this term being used for lack of a better) as
ethyl ether, and when judiciously administered pro-
duces prolonged pre- and post-anesthetic analgesia.
Furthermore, its physiological action is less accom-
panied with the variegated hallucinations always ev-
ident in patients to whom nitrous oxide is administered.
At the suggestion of Dr. J. T. Gwathmey, the senior
author's medical colleague in all his researches on
anesthesia,6 an investigation was undertaken on the
rate of evaporation of ethyl chloride from oils and
mixtures of ethyl chloride and ether from oils with
the view of using the results as a basis for inducing
analgesia, or prolonging it in conjunction with anes-
thesia, for the purposes indicated above.
The mutual solubility of ethyl chloride and oils
presented nothing novel, but the physical properties
of the former (b. p. 12.5° C.) indicated probable
marked variations in rate of evaporation from that of
ethyl ether (b. p. 34.6° C). On account of the ex-
tremely rapid evaporation of ethyl chloride at ordinary
room temperatures, all mixtures were prepared cold,
after containers and constituents had been chilled by
melting ice.
The rate of evaporation of ethyl ether from different
] Presented before the Division of Medicinal Products Chemistry at
the 60th Meeting of the American Chemical Society, Chicago, III-, Septem-
ber 6 to 10, 1920.
1 Du Pont Scholar, College of the City of New York.
> Am. J. Surgery, January 1916; Proc. Am. Phil. Soc., August 1916.
4 International Medical Congress, London, 1913; "American Year
Book of Anesthesia and Analgesia,*' 1916.
' Gwathmey and Karsner, J. Am. Med. Assoc., 70 (1918), 993; Brit.
Med. J., March 2, 1918; Ficklen, N. O. Med. J., January 1920; Lathrop,
New Orleans Meeting, A. M. A., and others.
* Gwathmey and Baskerville, "Anesthesia," D. Appleton & Co.
oils1 having been shown to be practically the same,
or parallel, only one oil was used in these experiments,
viz., neutral corn oil, which had been refined by the
process of the senior author.2 The ethyl chloride used
was "Kelene," and the ether was 97 per cent ethyl
ether and 3 per cent ethyl alcohol, purified by the
senior author's process.3
The procedure was essentially that described in a
previous paper.1 However, the rate of evaporation of
ether from oil having been shown to have a direct
ratio to the surface exposed and related to the distance
from the surface of the liquids to the top of the ves-
sels, tubes of uniform size were used.
It is recognized, of course, that results obtained by-
such experiments do not disclose the conduct of such
mixtures when in contact with the walls of the alimen-
tary canal. The glass water thermostat was stirred
by air and kept at a constant temperature of 37° C.
(±0.1° C.) by heating coils of resistance wire, a cal-
ibrated thermometer reading to hundredths being used.
Large glass tubes, all of the same diameter and with
walls of practically the same thickness, calibrated to
1 cc. from 20 cc. to 105 cc, were weighted with lead
to maintain their position in the ice bath and later
when suspended in the thermostat to within 8 cm. of
the tops.
During the first 5 min. after the tubes were placed
in the thermostat, readings were taken every minute
to determine the maximum volume expansion up to
37° C. After that, readings were made every 5 min.
for 2 or 3 hrs.
The mixtures by volume, measured at the temper-
ature of melting ice, are shown in the accompany-
ing chart, which gives a graphic representation of the
results obtained. The abscissae show the number of
cc. of ethyl chloride evaporated from the oil mixture,
and the ordinates the time of evaporation. The experi-
ments offering results of value in connection with our
particular object were verified by frequent repetition.
The mixtures containing 25 per cent or more ethyl
chloride by volume boiled vigorously during the time
the temperature rose to 37° C. The use of such mix-
tures for internal administration was obviously out of
question However, it was determined that the rate
of evaporation of ethyl chloride from oil quickly ac-
quires a definite and fairly fixed speed, which begins
when the solution has acquired a volume composition
of 13 to 14 per cent of ethyl chloride. If an original
mixture of 15 per cent be used, the uniform speed is
established within 10 min. for surface exposures ob-
taining in the experiments.
APPLICATION TO USE IN ANESTHESIA
These facts may later prove to be of moment in
ethyl chloride-oil alimentary administration, for, as
mentioned above, 5 cc. of ethyl chloride are equivalent
1 Loc. cil.
■J. Frank. Inst., June 1916.
' Baskerville and Hamor, This Journal, 3 (1911), 302.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
323
5 10 IS 20 25 30
Cubic Centimeters Evaporated
to 30 cc. of ether as an inhalation anesthetic, although
animal experimentation carried out by Drs. J. T.
Gwathmey and G. B. Wallace in the Bellevue Lab-
oratories, New York, with ethyl chloride-oil colonic
administration, have not so far been encouraging; yet
most satisfactory results have been obtained in dental
surgery by Dr. M. Ecker in cooperation with Dr.
Gwathmey. The technique is very simple. A vessel
containing an 18 per cent ethyl chloride mixture is
interposed in the train of the nitrous oxide-oxygen
mixture on its way to the patient. Just enough ethyl
chloride vapor is picked up by passing over about 5
cm. of the ethyl chloride mixture to induce analgesia
for the extraction of teeth without the patient having
experienced the excitement stage just prior to surgical
anesthesia, so noticeable in the use of nitrous oxide.
As only a few hundred cases of humans have been so
treated up to date, even though with the most grati-
fying success, it is too soon to draw conclusions.
However, sufficient data were accumulated to warrant
a study of the keeping qualities of such mixtures as
might prove to be most useful in dental surgery. The
insertion of anesthol (ether, 47.1; ethyl chloride, 17;
chloroform, 35.89 per cent) in the train has proved
most successful in about 4000 cases.
Oil solutions containing 18 to 22 per cent ethyl chlo-
ride lose one-fourth to one-half of the volatile constitu-
ents upon standing for one week at room temperature
in loosely stoppered bottles, which are occasionally
opened for a few minutes. Hence, such ethyl chloride-
oil mixtures must be tightly closed or kept in a refrig-
erator to prevent changes in proportions. In fact, it
is advisable to make up such solutions immediately
before use so that the anesthetist may know the quan-
tity of_anesthetic he is administering.
ETHYL CHLORIDE-ETHER-OIL MIXTURES
As oil-ether (usually 25: 75) has proved to be such
a valuable adjunct to the comfort of the patient in
operations and dressings, by either colonic or oral
administration,1 and as ethyl chloride exhibits such
desirable analgesic effects, a mixture of oil, ether, and
ethyl chloride was prepared and the comparative rate
of evaporation determined. For reasons already indi-
cated above, the mixture was made up of oil, 30 per
cent; ether, 65 per cent; and ethyl chloride, 5 per i en1
The curve obtained is plotted on the chart. As yet
clinical data are not available for drawing any con-
clusions.
Further studies of mixtures have been inaugurated
in this laboratory with a view of adapting them in
special fields of surgery and treatment of the more
elusive nervous and mental disturbances.
Tests on Lubricating Oils
The chemical engineering and the agricultural engineering
departments of the A. and M. College of Texas have started an
experiment to determine the properties of asphaltic base and
paraffin base lubricating oils and the qualities that recommend
them for use as lubricating oils in internal combustion engines.
Several oil manufacturers have contributed samples of their
products for experimental material, specimen automobile and
tractor motors of different makes and types have been obtained
from manufacturers, and the various kinds of oil will be subjected
to a practical test in these engines. Before and after the oils
are used the chemical engineering department will make various
tests to ascertain the physical and chemical qualities, and to
determine the relation between the laboratory tests and the actual
value of the oil.
Manufacture of Research Chemicals at the University of
Wisconsin
A summer course in the manufacture of organic chemicals is
to be given at the University of Wisconsin under the direction
of Prof. Glenn S. Skinner. It is planned to utilize the laboratory
facilities for the manufacture of such chemicals as are needed
in the various departments, and the staff have been asked to
hand in their orders for chemicals.
Kight of the most promising advanced students will be ad-
mitted to the course. They will work from nine to ten hours a day,
and will receive pay of about 40 cents an hour. The course
offers an opportunity for intensive training in practical organic
chemistry and experience in large-scale manipulation.
Sugar Production in the Philippines, 1920 to 1921
The sugar crop in the Philippine Islands for the season 1920-21
as estimated by the Philippine Bureau of Agriculture is 552,027
metric tons, an increase of 128,500 tons or 30 per cent over the
previous season.
324
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 4
Boron in Relation to the Fertilizer Industry1
By J. E. Breckenridge
American Agricultural Chemical Co., Carteret, N. J.
Owing to the lack of potash during the war, it was
produced from many new sources, among which were
materials which contained boron. In some parts of
the country unusual agricultural conditions developed.
Investigation revealed the fact that, in some cases,
boron was present in fertilizers where injury to crops
had occurred.
We find recorded experiments2 showing stimulating
effects with boron in small amounts and toxic effects
when larger amounts are used.
The author's attention was called to a case in North
Carolina where the farmer believed boron had injured
his crop. On thorough investigation and analysis of
the fertilizer used, the control officials reported boron
absent. Again, another case came to the author's
attention where an experienced farmer lost his crop of
potatoes, but here again no boron could be found in
the fertilizer used. These instances are mentioned
to show that boron is not the only cause of trouble,
and conclusions must not be drawn until a complete
and thorough investigation has been made.
Injury to corn was first reported in Indiana in 1917. 3
Later, trouble seemed to develop in the potato crop
in Maine, and the tobacco and cotton crops in the
South.
The Indiana Station4 and the U. S. Department of
Agriculture5 carried on investigations, as well as the
South Carolina Experiment Station.
The conclusions as to toxic limits which have been
reached have been rather indefinite. The toxic effect
of boron is dependent upon how the fertilizer or
fertilizer material is applied, whether broadcasted
or applied in the row, and whether or not there is a
good rainfall soon after planting.
A series of experiments was conducted in the green-
house under the writer's direction, with potatoes,
beans, and corn.
POTATOES
A 4-8-4 fertilizer was made in the laboratory. The
government quantitative method showed 0.01 per cent
borax and the qualitative method showed less than
0.01 per cent.6 The fertilizer was used at a rate of
2000 lbs. per acre, in each pot, and spread out as evenly
as possible, placing it approximately 2 to 3 in. under
the seed.
Ten pots were used and the quantity of borax was
as follows-
Lbs. per Acre
None (control)
HI
Presented before the Fertilizer Division at the 60th Meeting of the
Chemical Society, Chicago, 111., September 6 to 10, 1920.
2 Brenchley, "Inorganic Plant Poisons and Stimulants," University
Press, Cambridge.
» Purdue University, Bulletin 215.
* Bulletin 239.
« Circular 84.
< Borax, whenever stated quantitatively, means anhydrous borax.
Good root growth was observed in the control pots
and in the pots receiving 4 and G lbs. of borax per acre.
The 8- and 10-lb. borax applications showed that the
roots kept away from the fertilizer layer and developed
near the surface of the soil.
The potato plants did not suffer very much, but this
fact was probably due to the favorable condition which
could not readily be duplicated in the field.
BEANS
Three treatments were made, using 4-8-4 fertilizer
alone and with borax in the following quantities:
Lbs. per Acre
None (control)
6
10
In this case a marked injurious effect was early
noticeable on the plants in borax-containing pots.
The control plants grew very rapidly and the leaves
were of a dark green, healthy appearance. The others
showed the characteristic "gilt-edge" effect of borax;
the leaves soon became spotted with yellow, which
spread, and the leaves later dropped off. Growth, in
both cases, as compared to that of the control, was
stunted. The roots of the plants showed the effect
of the borax, the control plants having all roots at the
seed and going down into the fertilizer. The plants
in the 6-lb. per acre application had poor seed roots
and had a few at the surface.
The beans showed an even more marked recovery
than in the case of potatoes. New leaves forming had
a healthier appearance and were not so badly spotted.
CORN
The fertilizer used was 2-8-2, 2000 lbs. to the acre,
and contained less than 0.01 per cent borax. Three
treatments were made:
Lbs. per Acre
None (control)
6
10
The plants grew very slowly, and for about 3 wks.
the tips of the plants having 6 and 10 lbs. of borax
per acre became dry, and the edges of the leaves were
slightly bleached. The plants partially recovered,
however, and began to grow rapidly. The plants
having no borax showed good seed root formation;
the 6 lbs. of borax per acre, less seed roots and more
surface roots; and the 10 lbs. borax per acre, still less
seed roots and more surface roots.
CONCLUSIONS FROM THE POT EXPERIMENTS
1 — From the experiments it is evident that certain
percentages of borax are detrimental to plant growth,
but under favorable conditions such as optimum mois-
ture, good drainage, etc., rapid recovery is noticeable.
2 — Corn and beans showed borax poisoning with
6 lbs. of borax per acre, and 10 lbs. per acre showed
decided harmful results.
3 — Potatoes showed no harmful effects, but rather
stimulating, when 4 lbs. borax and even 6 lbs. borax
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
were used; 8 lbs. and 10 lbs. borax seemed to cause
less root formation at the seed and more surface roots.
4 — With optimum moisture plants seem to recover
somewhat from the toxic effect of borax when used
6 lbs. per acre, but in short seasons the recovery would
be too late for good crop results.
5 — The fact that the fertilizer having more than 6
lbs. of borax to the acre prevented seed roots and the
root system was largely near the surface, would result
in the plants being stunted and probably dying in a
dry season.
METHODS FOR DETERMINATION OF BORON
Much work has been done on the distillation method
and the government method, both qualitative and
quantitative, for determining boron.1
Ana- . — 1 — *
lyst G. D.
1 0.25 0.27 0
2 0.25 0.25 0
3 0.25 0.33 0
4 0.19 0.18 0
5 027 0.29 0
6 0.19 0.22 E
. . 0 . 20
7 0.26 ..
8 0.21 L...
9 0.21
10 RT RD
0.40 0.32
11 ( 0.05) . .
(PlusQ.) ..
0.22 0.20
3-
D.
D.
13 0.11 0.10 0.09 0.09 0.05 0.04
13 0.07 0.09 0.08 0.07 0.(12 0 05
20 0.08 0.13 0.14 0.12 0.07 0.09
13 0.09 0.08 0.07 0.08 0.04 0.06
16 0.13 0.09 0.06 0.05 0.08 0.03
0.16 0.12 E.. .. 0.08 0.04 E.
Blanks
Cc. 0.1 N
NaOH
G. D
0.4 .07
0.15 ..
0.4 1.0
0.00 1.20
0.4 0.4
0.10
0.10 ..
0.07 L. .
0.08 ..
RT
0.07 ..
0.01 PlusQ.
0.05
0.05 ..
0.04 L. .
0.01 ..
RT ..
0 . 02
0.01 Plus Q.
0.9
0.2
0.12
0.3
0.08 0.07
0.03 0.03
salts
E — Evaporating distillate to dryness and proceeding a
L — Lipscomb method — Clemson College, S. C.
RT — Results by turmeric method according to Rudnii
RD — Distillation method according to Rudnick.
Q — More than — by qualitative turmeric test — Swift.
G — Government method — Bureau of Soils.
D — Gladding method — distil with methanol.
0.35 0.35
determining
Other methods have been suggested, but are, as a
rule, modifications of these two. Jones and Anderson1
of the Vermont Station have suggested a modification
which is accurate and speedy. The South Carolina
Experiment Station has proposed a method worked
out by Lipscomb, Inman and Watkins.2
Five samples of varying percentages of borax were
prepared by the writer and analyzed by five different
chemists, and three of the samples were analyzed by
eleven different chemists. The results are given in
the accompanying table.
The borax content in Sample 1 was 0.25 per cent,
and in Sample 5 less than 0.01 per cent. The other
samples were:
Sample 2 — 0.5 No. 1 and 0.5 No 5
Sample 4—0.25 No. 1 and 0.75 No 5
Sample 3 — 0.33 No. 1 and 0.66 No. 5
Since this work has been done everyone has had
more experience with the borax determinations, and
the results as listed under Sample 5, which show from
0.01 up to 0.08 per cent by the government method,
have been reduced to 0.01 per cent and less.
CONCLUSIONS
The government method gives accurate results when
carefully carried out, but time may be saved by using
the Jones and Anderson modification.
All reagents must be free from carbonate.
Separation of the phosphates must be complete and
no precipitate should form on standing after the final
titration, which point is noted in the government
method.
Results should be confirmed by the qualitative test.
Determination of Chlorides in Petroleum2
By Ralph R. Matthews
Roxana Petroleum Corporation, Wood River, Illinois
In order to determine the corrosiveness of water in
petroleum, and the amount of soluble salts which may
be crystallized and precipitated when the oil is dis-
tilled, a determination of chlorides in the water is
generally necessary. Some light petroleums easily
give up this water, and a sample can be obtained and
readily titrated. There are oils, however, which do
not become entirely anhydrous no matter how long
they are allowed to settle, though they may eventually
reach a point where there is 0.2 to 0.4 per cent of water
and sediment. For such oils the method described
below has been evolved so that a determination of the
chlorides may be easily possible. Various other meth-
ods than the one shown have also been tried, but have
failed to give concordant results.
OUTLINE OF METHOD
The sample of oil is thoroughly mixed by shaking
the can, or other receptacle, in which it has been re-
ceived, so that whatever salt water is present may be
uniformly distributed in the oil, and 500 cc. are care-
fully measured into a 500-cc. graduated cylinder.
The oil is then drained into a 2000-cc. graduated, glass-
stoppered cylinder, and 125 cc. of acetone are mea-
1 Am. Fertilizer, March 13, 1920.
3 Received January 20, 1921.
sured in the same 500-cc. cylinder. (The U. S. P. grade
of acetone may be used, but it must be tested to be
sure no chlorides are present.) After the acetone has
been added to the oil in the 2000-cc. cylinder, the two
are thoroughly mixed by shaking for approximately 3
min. The action of the acetone appears to be two-
fold, to reduce the viscosity of the oil, and to take up
and collect the salt water. The total volume is now
brought up to 2000 cc. with 1375 cc. of distilled water,
which is also measured in the 500-cc. cylinder, thus
thoroughly cleaning out all chlorides which may have
been left in the cylinder. The distilled water, oil,
and acetone should be completely mixed for approx-
imately 5 min. Care must be taken in shaking, since
too violent an agitation has a tendency to produce a
semi-emulsion which will settle out quite slowly. This
is especially true of oil which contains much paraffin,
and extreme agitation has not been found necessary
for complete extraction of the acetone and salt water.
The contents of the cylinder are allowed to settle until
approximately 500 cc. of the water and acetone have
settled out. About 400 cc. of the acetone-water mix-
ture are next drawn off with a glass siphon. If a lit-
• Am. Fertiliser, April 10, 1920.
"■ Ibid., February 28, 1920.
326
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
tie oil comes with it, it is removed by filtering through
dry filter paper. An aliquot part, depending on the
salt content, is then concentrated for titration with a
solution of approximately 0.05 N silver nitrate, using
potassium chromate as an indicator. From these re-
sults the chlorine can be calculated, or, if previous
analysis of similar brine has shown it to consist mostly
of sodium chloride, it may be calculated as such.
We have tested the accuracy of the method by mak-
ing a re-treatment of some of the oil which had settled
out after the treatment outlined above. A mere trace
of chlorides could be found, thus furnishing good proof
that the first treatment had effected their almost com-
plete removal.
The method has been used for about a year, and the
following check results, expressed as grams of salt per
liter of oil, have been obtained:
Gravity
Water by
First
Second
of Crude
K. S. & W.
Dist.
Result
Result
° Be.
Per cent
Per cent
G.
G.
30.9
1.0
n.8
0.77
0.75
36.5
2.2
1 .6
0.49
0.50
31.3
0.6
0.5
0.72
0.75
35.8
0.9
0.8
0.35
0.37
32.3
1.6
1.1
0.60
0.59
31.4
0.8
0.6
0.67
0.68
ACKNOWLEDGMENT
Experimental work on the method was carried out
in this laboratory by Messrs. Philip A. Crosby and
John G. Campbell.
LABORATORY AND PLANT
Humidity Control by
[eans of Sulfuric Acid Solutions, with Critical Compilation
of Vapor Pressure Data1
of Applied Chem
By Robert E. Wilson
Massachusetts Institute of Technology, Cambridge, Ma
ACHUSETTS
NEED 1'OR HUMIDITY CONTROL IN LABORATORY WORK
In the course of both research and routine labora-
tory work, many occasions arise when it is desired to
maintain a definite humidity in an enclosed space or
to produce a stream of air of definite moisture content.
In studying the humidity equilibria and rate of drying
of various substances, such control is, of course, a
prime requisite. There are, however, many other
properties of materials which vary greatly with changes
in their moisture content. In order to obtain re-
producible results in any investigation which relies
upon the quantitative measurement of such properties,
it is therefore necessary either to test the materials
in an atmosphere of a definite humidity, or else, when
the time of the test is short compared with the rate of
taking up moisture, previously to equilibrate them
with a definite humidity.
In cases where only a single humidity is to be used
for such tests, this Laboratory has adopted 50 per
cent relative humidity as a standard for articles
which are to be tested under conditions approximating
those prevailing indoors, and 65 per cent humidity
to approximate those prevailing outdoors. In many
cases, however, it is necessary to make the tests under
a variety of conditions. Accurate control of tempera-
ture is generally not as important as control of hu-
midity, as the moisture content of most materials
varies but little with moderate changes in temperature,
providing the relative (not absolute) humidity is
kept constant.
The object of this article is not to suggest any
new methods of obtaining this humidity control,
but merely to present in convenient form the data
which this laboratory has compiled from the litera-
ture, or found by practical experience, writh reference
to what seems to be the most satisfactory method of
small-scale humidification, namely, the use of sulfuric
acid solutions of definite composition.
1 Received December 14, 1920.
ADVANTAGES OF SULFURIC ACID SOLUTIONS FOR
HUMIDITY CONTROL
Sulfuric acid solutions have many advantages over
other materials which might conceivably be used for
this purpose. Homogeneous solutions varying from
0 to 100 per cent water can be obtained; the vapor
pressure of these solutions has been much more ac-
curately determined than for any other concentrated
solutions; the composition, and hence the vapor pres-
sure, of the solutions can be quickly and accurately
determined by measuring their density, which varies
greatly with changes in composition; their relative
vapor pressure (per cent of that of pure water at the
same temperature) varies but little with wide changes
in temperature; they come to equilibrium rapidly
with the surrounding atmosphere; the sulfuric acid
itself exerts no appreciable vapor pressure; and finally,
material of adequate purity is cheap and readily ob-
tainable.
For the purpose of maintaining a constant humidity
in a closed chamber, sulfuric acid solutions have no
real competitor under ordinary conditions, since it is
merely necessary to place within the chamber some
acid of the proper strength with an amount of surface
exposed in general somewhat larger than that of any
other moist or hygroscopic material present.
When a fairly large stream of humidified air is to
be produced it is, of course, possible to obtain it by
mixing two streams of air, one of which has been
thoroughly dried and one of which has been bubbled
through water. By varying the relative amount of
the two streams it is possible to obtain any desired
humidity. This necessitates, however, both drying
and humidifying fairly large amounts of air, and also
the maintenance of an absolutely constant ratio be-
tween the two streams. It also requires frequent
analytical control which, at lower temperatures,
necessitates the use of an absorption method. At
higher temperatures wet and dry bulb thermometers
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
327
may be employed to determine the humidity, but this
method necessitates the rejection of that fraction of the
air which passes over the wet bulb and thereby picks
up an uncertain amount of additional moisture.
Under ordinary conditions in the laboratory this
method is much more cumbersome and expensive
than the simple procedure of bubbling the stream
through sulfuric acid of a definite composition. The
former method does, however, find some application
under certain exceptional conditions where fairly
high humidities are to be produced and there is avail-
able an air supply of reasonably constant low humidity
which does not require chemical desiccation.
Since the sulfuric acid method has thus been shown
to be remarkably well adapted for all-round purposes
as a laboratory method of humidification, this Lab-
oratory has made a careful study and compilation of
the best available data on the vapor pressure and
density of sulfuric acid solutions as dependent upon
their composition and temperature.
COMPILATION OF VAPOR PRESSURE DATA
The first step m compiling the vapor pressure data
was to plot on a large scale the results of four investi-
gators1 who have determined the vapor pressure at
25° C. of sulfuric acid solutions as a function of their
concentration. These results showed a surprisingly
good concordance throughout the middle range of
concentrations (30 to 60 per cent H2S04, or 17 to 76
per cent relative humidity), but somewhat larger
deviations at the two extremes. It therefore appeared
desirable to make use of the very careful work of
Dieterici,2 who unfortunately made his measurements
at 0° C, It is possible, however, by a simple and
surprisingly accurate thermodynamical calculation
(made as described hereinafter) to convert these re-
sults over to the corresponding values for 25° C.
The addition of this series of points left little doubt
as to the precise location of the curve except in the
range between 65 and 85 per cent H2SO4. The un-
certainty in this region might be expected on account
of the very low vapor pressures exerted by such solu-
tions at 25° C. (0.2 to 2.3 mm.), and especially at 0° C,
which makes their accurate measurement extremely
difficult.
At higher temperatures, however, these vapor pres-
sures become quite large and can be measured readily
and accurately. Fortunately, three investigators have
determined the vapor pressure of such concentrated
solutions at temperatures of 75° or 100° C, and their
data were also calculated to 25° C. by similar thermo-
dynamical calculations.
When these results were compared with those
measured at 25° C, it appeared quite certain that
Sorel's low temperature results were somewhat too
high in this range, while those of Regnault and Bron-
sted were more nearly correct. This is not surprising
in view of the fact that if Sorel's original data in the
low temperature-high concentration range are plotted,
the points vary widely from a smooth curve, and do
1 Regnault. Ann. Mm. phys., [31 IB (1845), 179, Sorel, Z. angew. Chem.,
1889, 272. Helmboltz, Wied. Ann., 27 (1886), 532; Bronsted, Z. fhytik.
Chem., 68 (1909), 693
' Dieterici, Wied. Ann . 60 (1893), 60; 62 (1897), 616.
not correspond with his own figures obtained at
higher temperatures, when they are calculated over by
thermodynamical methods.
It is thus possible to draw a vapor pressure-compo-
sition curve for sulfuric acid solutions at 25° C. (see
heavy line, Fig. 1) which is probably accurate within
0.1 mm. throughout. It will be noted that relative
vapor pressures (per cent of that of pure water at the
same temperature, thus corresponding to the relative
humidity of the air) are plotted rather than the ab-
solute values in millimeters, because the former vary
but little with temperature, and also because they
are more significant for most laboratory purposes.
The absolute vapor pressures at any temperature can
readily be calculated by reference to steam tables or
other sources of vapor pressure data for pure water.
The encircled points in Fig. 1 all correspond to actual
measurements at 25° C, while those in triangles are
points calculated to 25° from measurements made at
other temperatures. Table I presents the original
observed values and those calculated over to 25° C.
for all the latter group of points.
Table T — Calculated Values for Relative Vapor Pressure of Dilute
Sulfuric Acid at 25° C.
Calculated
Relative Relative
Vapor Vapor Vapor
H2SO4 Temp. Pressure Pressure Pressure
Investigator Per cent < ° C. Mm. at / ° C. at 25° C.
Dieterici 5.62 0 4.535 98.0 98.1
Dieterici 9.24 0 4.452 96.4 96.6
Dieterici 15.73 0 4.284 92.7 93.1
Dieterici 20.8 0 4.065 87.9 88.6
Dieterici 27.2 0 3.664 79.3 80.3
Dieterici 32.8 0 3.200 69.3 71.2
Dieterici 35.4 0 2.952 63.9 66.2
Dieterici 40.5 0 2.435 52.7 55.2
Dieterici 47.3 0 1.748 37.8 40.8
Dieterici 53.4 0 1.206 26.1 29.1
Dieterici 61.3 0 0.569 12.3 14.7
Burt 62.8 75 45.9 15.9 11.6
Dieterici 68. S 0 0.164 3.5 4.6
Burt 70.8 100 57.0 7.5 3.7
Sorel 74.0 75 12.1 4.2 2.3
Briggs 77.5 100 20.2 2.66 0.94
Sorel 78.0 75 7.0 2.4 1.14
Briggs 79.2 100 14.3 1.88 0.61
Again using thermodynamical methods, it is possible
to calculate, from the accurately located 25° C. curve,
similar curves for other temperatures at which little
or no direct experimental data are available. Such
curves (dotted) are also shown in Fig. 1 for 0°, 50°,
and 75° C. By means of these curves it is possible
to determine readily and accurately the vapor pressure
of any sulfuric acid solution at any temperature
between 0° and 100° C. In order to make possible
the reproduction of these curves on a large-scale plot,
a series of points are presented in Table II.
Table II — Best Values from Vapor Pressure Curves for Sulfuric
Acid Solutions
, Relative Vapor Pressure Values at •
H!SO. 0° C. 25° C. 50° C. 75" C.
Per cent Per cent Per cent Per cunt Per cent
0 100.0 100.0 100.0 100.0
5 98.4 98.5 98.5 98.6
10 95.9 96.1 96.3 ". 5
15 92.4 92.9 93.4 93.8
20 87.8 88.5 89.3 90.0
25 81.7 82.9 84.0 85.0
30 73.8 75.6 77.2 78.6
35 64.6 66.8 68.9 70.8
40 54.2 56.8 59.3 61 '.
45 44.0 46.8 49.5 52.0
50 33.6 36.8 39.9 42.8
55 23.5 26.8 30.0 33 0
60 14.6 17.2 20.0 22.8
65 7.8 9.8 12.0 14.2
70 3.9 5.2 6.7 8.3
75 1.6 2.3 3.2 4.4
80 0.5 0.8 1.2 1.8
It will be noted that for a temperature change of 5°
or 10° C. the relative vapor pressure of most of the
32S
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13,'No. 4
o%
v<?%.
W7,
307, 40V. £07.
6CV.
rov.
<%
7QA
■
,
^s
^i
Q
v/
?(?
IfA
1
r/
41
**f
f?
_J
=?
??
fr?
17/
/£
,^
^c>
\
- 2«D
^
V
^
.UEittn—i
I
^
}fc
A
Tfl
,F
in
LQ7 .&CZn
^
7
\n
"r<
7f-<
a
S
£
'S A rtJNG*
me
a
\\
^
1
'&
ti/
JA
V*
VI
*U2
E"
-4
'£L
J
'JO
in
ft
'5
i ri
a
y
8
K\
(
[\
Sx
\
1
\v
s
1"
v
\\
\\
&
h
\:
5
£
k
0
,\
§
?
&
^
k
^
V
\
!U
\*
V
r
V
\
\ \
/
\
s
\H
s
\
/
^
_^
3
2ts
faa
&
\
A
/
\
<7
Sj-v
f.y
0
A
\
c
•/'■j.
>•?<
t
"Q
s.
k
A
/
/
/
'j
r,
j
0
y\
\
/
/
^
^
\
\ \
/
/
b
&
*\
\
/
j
1
\
\>
^3
\ \
v \
\
Li
fc
\
vx
/
/
/
^
g
v,\
g
V
s
V
h
c?
G
V \
^
h
t
^x
M
I
3sa
*\
\
D-
c-s
«
^
\
\ >
\
£
/
.■■L\
^\
*
s
>
/
\
V
\
•4
v N
tr\
\
^
\
\'
v
f
>.•'''
^;'"
<3
\
\
Si
5)
\
V
LJ
\ v
rN
\
a3
/
<S
7^1
7/?
Y
Oi
f
nA
77"
s?
\
■\"^\
\
"■
/
rml
azlLfizi
lY-r
,'<■
Mi
\
o>
0
-./i.
«Jt
22^5 1
r-t
s"^
v
■
-,s
t>vl
-, -.
.--■
-*?™ £
Urn
AT..
rji.i
^«j
1
\
,
-3
•1
t'n'.
/--
--
,-.-" :
CA
m*
f'
'
^\
\
\
iJ
<-
"
—
n .•
T
,ff-
—
\
0
V
§
**
=-
i~J
<■■■*-
■
•cr
iTI
•>j
.. *
■•Tt
'""
1
^^
^
07.
-<*£.S
ifF.
7T,
- CI
ft:
i.
</■«*"
/f<7C7
C%
y^7?j
/^7%-
<37% -4<7Ve JSUV.
I*£J?CE7Yr JULfUKIC V7GZD
ec%
7UV*
<5fc7%
solutions is practically constant; furthermore, the
small increase which does occur with increasing tem-
perature is in the right direction to compensate for a
similar slight tendency on the part of practically all
materials whose humidity equilibria have been de-
termined.1 It is therefore not necessary when study-
1 It is planned in the near future to present values which have been
determined by this laboratory and others for the humidity equilibria of
various substances, such as wood, paper, cotton, silk, wool, jute, leather,
rubber, carbon black, etc.
ing such equilibria to attempt to maintain the system
at a temperature any more constant than that of the
average laboratory.
The information most frequently desired, however,
is not what vapor pressure is exerted by a solution of
given concentration, but what concentration of acid
should be used to obtain a given vapor pressure.
This information is conveyed in Table III, which is
also determined from Fig. 1 drawn on a large scale.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
329
64.8
55.9
50.9
43.4
36.0
30.4
18.5
Give Definite
75° C.
68.3
59.0
54.0
46.2
38 . 3
32.4
211.0
PRACTICAL USE OF THE VAPOR PRESSURE CHART
Since density determinations afford a very satis-
factory and rapid method of determining the exact
concentration of sulfuric acid solutions, Fig. 1 also
includes curves showing the variations in this property
with temperature and concentration. These are con-
structed from the very accurate data of Domke.1
To prepare a solution having a specified vapor
pressure at a given temperature, it is therefore only
necessary to refer to Fig. 1 to find the proper concen-
tration of acid, and also the density of the solution.
The temperature at which the density is determined
need not be that at which the solution is to be a ed,
providing the proper curves are used. Thus the
density curves in Fig. 1 indicate that in order to obtain
a relative humidity of 50 per cent at 25° C, 43.4
per cent H2S04 should be used, and this acid has a
density of 1.329 at the same temperature. If, how-
ever, it be desired to determine the concentration
before the solution has had time to cool after pouring
the strong acid into the water, another line shows that
the density of the acid at 50° C. is 1.311. It is unwise
to attempt to measure densities at temperatures
higher than this, but the values for intermediate
temperatures can readily be determined by interpola-
tion.
Either vapor pressure or density values at any
temperature between 0° and 100° C. can readily be
obtained by a simple inter- or extrapolation. Suffi-
ciently accurate density determinations can be made
by any properly calibrated (water at 4° C. = 1)
Westphal balance or hydrometer reading to three
decimal places, a pyenometer being more accurate
than is necessary.
RECOMMENDED METHODS OF DETERMINING HUMIDITY
EQUILIBRIA
In determining the humidity equilibrium of any
substance at a given temperature, the most satis-
factory general method is to subdivide it until the
amount of surface exposed is reasonably large, place
from 20 to 00 g. in a small straight or U-tube of known
weight, and pass a slow stream (50 to 500 cc. per min.,
using the higher rates at lower temperatures) of prop-
erly humidified air through it. In no case should
any glass wool or cotton be used in the tubes. The
tube containing the material is weighed every few
hours until constant weight is reached, after which
the moisture content may be determined, preferably
by passing through it a stream of warm air (50° to
125° C, depending on the nature of the material)
previously dried by P205, until constant weight is
reached. The loss in weight, of course, represents the
equilibrium moisture content at the temperature and
■ Z. thysik. Chen:., 43 (1905). 125; also Landolt-Bornstein, 1912, 265.
humidity in question. In order to make certain that
substantial equilibrium has been reached, in any given
case, it is always desirable to approach it from both
the dry and the moist sides.1 The simplest way to
accomplish this and to determine all the points on the
curve with a single sample is to pass fairly dry air
through at the start, and then determine in turn the
equilibrium weights at 10, 25. 50, 7"). and 90 per cent
humidity; saturated air is then passed through for a
short time and the same points redetermined in the
reverse order, finally obtaining dry weight at the ele-
vated temperature. Moisture contents should prefer-
ably be expressed as per cent of the dry weight.
In general, equilibrium can be reached from 18 to
96 hrs., and the dry weight within 2 to 6 hrs., depending
largely on the state of subdivision of the material.
Higher water contents and lower temperatures re-
quire the longer times. These rates are much more
rapid than can be obtained by the frequently used
method of exposing the sample over sulfuric acid,
where the rate of approaching equilibrium has been
found to be surprisingly slow, due to the slow rate of
diffusion in still air. If a small fan be used in the
desiccator, and a stirrer in the acid, the rate can be
made to approach that of the tube method, but this
is difficult to arrange in an ordinary desiccator. The
use of vacuum greatly increases the rate of approaching
equilibrium, but is quite likely to introduce errors on
account of the inrush of unconditioned air when the
vacuum is broken preparatory to removing and
weighing the exposed sample.
Fig. 2 — Apparat
Eouilibri.
A few precautions must be observed in conditioning
the air stream. If the rate of (low is more than aboul
100 cc. per min., some special form of bubbli
signed to give good contact between liquid and ,uas,
should be employed. A petticoat type such as that
indicated in Fig. 2 has been found to give excellent
results. The use of broken glass or beads in the acid
bottle also aids in distorting or breal ing up the bubbles
1 While the tu<> figures thus obtained will genei ree within
narrow limits, some colloidal materials which tend to hi- highly hydrated
or form gels will exhibit different apparent equilibrium values, depending
on the side from which it is approached. This appears to be due to a
hysteresis effect frequently observed in such materials, which may require
a matter of months or years to reach substantially thi an tcture when
approaching the same point from oppositt I
330
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
of air and bringing them to equilibrium. With such
bubblers, substantial equilibrium can ordinarily be
reached, even with only two bottles in series, at rates
of flow up to 2 liters per min.
In case the entering air is very far from the desired
humidity, or if the rate of flow is rather high (2 to
10 liters per min.), three bottles should be used in
series. If for any reason it is desired to humidify
larger amounts than this, either two parallel lines of
bubblers or a tower filled with glass beads, over which
acid is trickling, should be used. The recommended
size of the acid bottles varies from about 500 cc. for
the slower rates of flow to 2 liters for the higher.
They should be filled about half full of acid.
In order to determine when the acid needs to be
replaced, it has been found desirable to mark the
initial level of acid in each humidity bottle. If three
bottles are used, as is recommended for most pur-
poses, the volume of acid in the first bottle can be
allowed to change by 3 or 4 per cent before it is neces-
sary to add water or acid to restore the original con-
centration. The density of the acid in the second and
third bottles should be checked up occasionally, but
will usually be found to change but little if the con-
centration in the first bottle is properly adjusted.
If the humidity of the entering air is known to be
considerably lower than the desired value it is gen-
erally desirable to have the initial water content of
the first bottle 2 or 3 per cent higher than the true
equilibrium concentration used in the last two bottles,
and vice versa, if the entering air is too moist. This
brings the air to equilibrium more rapidly, and makes
the first bottle serve just so much longer before it
goes too far to the other side of the equilibrium con-
centration and must be renewed.
For reasons previously pointed out, it is ordinarily
not necessary to control the temperature, as varia-
tions of 5° or 10° C. in the temperature have practically
no effect upon humidity equilibria.
One important precaution to observe is the use of a
tube rather tightly packed with glass wool, or similar
material, to remove entrained particles of sulfuric
acid from the air stream lest they be deposited on
the material to be equilibrated. Quite appreciable
amounts may be carried over in this way unless this
precaution is observed.
Fig. 2 shows a typical set-up of apparatus for the
rapid and accurate determination of the humidity
equilibrium of a fibrous material such as cotton.
METHOD OF CALCULATING TEMPERATURE CORRECTIONS
Since it might be desired to extend the foregoing
data over still wider temperature ranges, probably
with some sacrifice of accuracy, it appears desirable
to present as briefly as possible the method of calcu-
lating the vapor pressure values from one temperature
to another, together with the thermochemical data on
sulfuric acid solutions which was assembled for the
purpose.
The basis of the calculations was, of course, the
approximate form of the Clausius-Clapeyron equation,
viz.,
d In ps AH_ AHi + AH2
dT ~ RT2 ~~ RT2
where AH is the heat absorbed in the evaporation of
one mole of water from a large amount of the solution
(so that there is no appreciable change in concentra-
tion). This is equal to the sum of the heat effects
involved in removing one mole of liquid water from
the solution and in evaporating it, or to AHi + AH2;
where AHi is the molal heat of vaporization of pure
water and AH2 is the heat absorbed when one mole
of water is removed from solution without change in
concentration.
Since the same equation applies to pure water, viz.,
din pw _ AH!
dr - RT2
it is possible to eliminate the large quantity, AHi,
by subtracting the second equation from the first,
and thus obtain a very accurate expression for the
ratio ps to pw, which will be called r, the relative vapor
pressure of the solution, as previously defined. This
expression,
d In r _ AH2
Hx RT2'
can be integrated on the assumption that aH2 is
independent of the temperature,1 giving the equation
used in the calculations, namely,
, I? _ AH; T; — T,
g n 2.3 R ' T2.T, '
To obtain the values of AH2 for different concen-
trations, use was made of the data of Bronsted2 on
the heat of dilution of sulfuric acid, apparently at
18° C. These appear to be better than the earlier
data of Thomson, who probably had a small amount
of water in his supposedly pure sulfuric acid. Bron-
sted gives values of Q (total heat of dilution) for the
reaction
H2S04 + n H20 — >• H2S04.n H20 + Q.
where n varies from 0 to 15.
In order to obtain similar values of Q for other
temperatures it is necessary to make use of Kopp's
Law,
dX
=ZFi— sr2,
where 2Fi and 2T2 are the heat capacities of the
reacting materials and the reaction products, respec-
tively. In comparing the results of various inves-
tigators on the heat capacities of sulfuric acid solutions,
especially Thomson,3 Berthelot,4 Marignac,6 Cat-
taneo,6 Pickering,7 and Schlesinger,8 the agreement
was not found to be highly satisfactory. Fortunately,
however, the specific heats are mere minor correction
terms for the purpose in hand, and need not be known
with great accuracy. The values used were taken
since, as noted later, the value
in between the particular Ti and
1 This involves no appreciable er
used for AH? was always that for the ;
Tj in question.
'Z physik. Chem., 68 (1909), 693.
» Pogg. Ann., [3] SO (1853), 261; also "Thermochemische Unter-
suchung," 3, 1.
' Ann. chim. fihys., [5] 4 (1875), 446.
' Arch. Soc. Phys., 39 (1870), 217; 56 (1876), 113.
6 Nuovo Cimenlo, [3] 26 (1889), 50.
' J. Chem. Soc. 67 (1890), 91.
« Physik Z. 10(1909), 210.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
331
from a smooth curve which appeared to be repre-
sentative of the more recent and better work, and which
may be reproduced from Table IV.
,ues Assumed
FOR
Spg
CM
[C Heats op Sui.
Solu
TIONS
AT
18'
' c.
cent H,PO<
Specific Heat
0
1.00
20
0.84
40
0.68
60
0.53
80
0.41
100
0.34
Using these data, the corresponding values of Q
at the desired mean temperatures were calculated
and the results are presented in Table V.
Table V — Calculated Heats as Dilution (Q) of Adding n HtO to
1 H2SC>4 at Different Temperatures
(In Calories per Mole of H-S< U)
Per cent
H2SO,
18° Cobs.)
12.5°
37. 5°
50°
62.5°
84.5
6,710
6,680
6,830
6,900
6,980
78.4
8,790
8,750
8,940
9,040
9,140
73.1
10,020
9,970
10,190
10,300
10,400
64.5
1 1 ,640
11,570
11,880
12,040
12,200
57.7
12,830
12,760
13,090
13,250
13,420
43.8
14,890
14,820
15,160
15,330
15,500
37.7
15,620
15,540
15,890
16,060
16,230
26.6
16,660
16,580
16,950
17,130
17,320
22.3
16,990
16,900
17,290
17,480
17,680
18,090
18,600
18,870
19,110
1.646
1.666
1.676
1.684
The amount of heat evolved (AH...) when one mole
of water is added to a large amount of a solution of a
definite concentration is of course equal to the rate at
which the total heat of dilution, Q, is changing at that
particular concentration. This may be determined
by plotting Q against n and determining by graphical
methods the slope of the tangent (aH2) at a given
concentration. It was found more accurate and con-
venient, however, to perform this operation analytically.
Thompsen had shown that the heat of dilution of sul-
furic acid could be expressed fairly accurately by an
equation of the form
11 + b
In order to determine the value of the coefficients a
and b, it is only necessary to substitute two values of
n and Q and solve the two equations simultaneously.1
Having obtained the equation of the curve, the values
of aH2 were readily and accurately calculated by
taking the first derivative for the proper values of
11, i. e.,
dQ _ a an
dn ~ n + b _ (» + b)1'
Tables VI and VII present values of AH2 and of
r2 : Ti ratios calculated in this way for various per-
centages of sulfuric acid. Using these ratios it is ob-
viously a simple matter to calculate an observed
vapor pressure at any one of the indicated tempera-
tures over to any other of these temperatures, or,
by interpolation, to intermediate temperatures.
Although these correction ratios appear large in the
case of the more concentrated solutions, it should be
remembered that the vapor pressures in these regions
1 Actually, in order to distribute the inaccuracies over the curve,
three pairs of values of n were taken, namely, 1 and 3, 1.5 and 4, and 2 and
7, and the three values of a and b averaged. Using these average values
of the coefficients (see Table V), it was found that the maximum deviation
of the calculated from the original observed values of Q was less than 150
cal. up to ti = 4 and less than 300 from 11 = 7 on.
AH2 =
are very low, so that the error in calculating any vapor
pressure from 25° to 75° C. certainly cannot exceed
0.4 per cent relative vapor pressure. The maximum
probable error from all sources of any of the curves
shown in Fig. 1 is about 0.6 per cent relative humidity.
Table VI — Values of Hi for Various Concentrations and Mean
Temperatures
Per cent
HiSO. » 12.5° 37.5° 50° 62.5°
20 21.8 54 56 58 59
30 12.72 145 150 153 155
40 8.18 290 320 326 330
50 5.45 593 612 624 630
60 3.63 1068 1108 1128 1152
70 2.34 1870 1940 1962 1996
80 1.36 3290 3380 3430 3460
Table VII — Factors to Be Applied to Relative Vapor Pressure
at 25° to Give Relative Vapor Pressure at
Temperatures Indicated
Per cent
HzSOi 0° 50° 75° 100°
20 0.992 1.007 1.014 1.020
30 0.978 1.020 1.038 1.054
40 0.956 1.043 1.082 1.116
50 0.912 1.084 1.163 1.236
60 0.848 1.156 1.314 1.478
70 0.749 1.289 1.608 (1.968)
80 0.601 1.556 (2.295) (3.240)
ACKNOWLEDGMENT
The writer desires to express his appreciation of the
assistance rendered by Dr. D. R. Merrill in making
the thermodynamic calculations involved in the prep-
aration of this article.
American Oil Chemists' Society
For a number of years the leading chemists of the cottonseed
oil industry have been associated in the Society of Cotton
Products Analysts. As a result of the widening of the field
of the vegetable oils which took place during the war, the Society
was reorganized at its annual meeting last May, as the Amer-
ican Oil Chemists' Society.
All persons engaged in chemical work on oils, fats, waxes, and
allied interests are eligible for active membership, provided they
have had at least five years' chemical training. The Society
publishes its transactions regularly and maintains the Chemists'
Section in The Cotton Oil Press, devoted exclusively to the edi-
ble vegetable oil industry.
The membership also includes those interested in the so-called
technical aspects of the industry. Since most of the oils dealt
with are industrially more or less interchangeable, their chem-
ical control and technological development can be properly
fostered only by intimate contact between science and industry.
Any one interested in the activities of the new organization
may obtain further information from the secretary, Mr. Thos.
B. Caldwell, Wilmington, N. C.
T. A. P. P. I. Meeting
The annual meeting of the Technical Association of the Pulp
and Paper Industry is to be held at the Waldorf-Astoria and
the Hotel Astor, New York City, April 11 to 14, 1921.
Engineering problems in the industry will be broadly con-
sidered in committee reports and in special papers. Among the
subjects considered will be a new groundwood process, prelim-
inary impregnation of wood as a means of shortening the cook-
ing time in the sulfite process, the operation of water-power
plants at maximum efficiency, the measurement of moisture in
chips for cooking, the testing of crude rosin, methods of drying
paper on paper machines, and the electrification of paper ma-
chinery. On Wednesday, April 13, a discussion, in charge of
the committee on heat, light, and power, will be conducted on
Pulverized Fuel and Steam Economy.
332
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 4
Notes on Laboratory and Demonstration Apparatus1
By Clifford D. Carpenter
Department of Chemistry. Columbia Universit
APPARATUS FOR DEMONSTRATING THE VAPOR PRESSURE
OF LIQUIDS
The apparatus herein illustrated shows five Tor-
ricelli tubes standing in a special overflow trough.
The principal feature is that the inner trough is small
and uses little mercury, and the sides are low so that
the mercury runs over into the outer trough when
too full. This gives a constant zero point at the lower
end of the tubes. The cross-section, g, gives the de-
tail. Two rods,
each 3 ft. in length,
are screwed into
the ends of the
inner trough and
are used as supports
for a crossbar by
which the tubes
are held in position.
In practice a rub-
ber band or cord is
sufficient to hold
the tubes in place
against the cross-
bar. Tube d is
fitted into a large
stopper which
closes the lower end
of a large tube used
as a jacket. This
large open tube has
an outlet, /, at its
lower end, making
it possible to
change the water
and to surround d with water at definite tempera-
tures. Tubes d and e are graduated in mm. from
the bottom upward, making it possible to read the
height of the mercury column directly.
In a demonstration all tubes are filled with mercury
and inverted, and the heights of the columns noted.
The jacket about d is filled with water at room tem-
perature. By the aid of pipets, /;, water is introduced
into d, alcohol into c, chloroform into b, and ether into
a, while e is left as a comparison tube. Attention may
then be called to the relative vapor pressures of the
different substances. If tubes d or e are not grad-
uated a meter stick may be used. The depression of
the mercury in d is measured and the temperature
noted. Water of a different temperature is then intro-
duced into the jacket around d and the depression and
temperature again noted, and the results are com-
pared with the aqueous tension tables given in the
handbooks.
true in the case of a lecture demonstration, for if each
experiment can be set out in some prominent place
while under discussion, the pupils can follow the pro-
cedure much more readily than when the experiment
is one of a long line arranged from one end of the desk
to the other. A slight alteration in the common ring-
stand makes it possible to mount the apparatus used
in many experiments, ordinarily requiring two or more
supports, upon a single support. The illustrations in
Figs. 1 and 2 show two simple alterations which have
been found very practical and useful.
Such modifications would also prove very useful to
students. Each student could be provided with a
ringstand set as follows: a base 7 in. X 10 in. and
three interchangeable rods; a straight rod 26 in. X
0.375 in. which, when mounted in the base, would give
the ordinary ringstand; a second rod 36 in. X 0.375
in. bent at right angles, so that when mounted in the
base the horizontal portion is 11 in. above the base,
as illustrated in Fig. 1; and a third rod 36 in. X 0.375
in. bent so that the two portions make an angle of 75°,
as illustrated in Fig. 2, so that when mounted the
perpendicular portion is about 18 in. in length.
A RINGSTAND SET
Mobility of apparatus after it is assembled for use
in an experiment is most desirable. This is especially
' Received December 7, 1920.
While the rods may be screwed into the base it is
not entirely satisfactory, as rusting and wear will
gradually make the interchange of rods difficult.
Moreover, the bent rods must always take the same
position with respect to the base when mounted. This
difficulty is easily overcome by using a "lock socket."
Apr., 1921 THE JOURNAL OF INDUSTRIAL AXD ENGINEERING CHEMISTRY
LABORATORY SINK
The accompanying sketch illustrates a convenient
form of sink for laboratories in elementary and gen-
eral chemistry. The main feature of the sink is its
three compartments. The two smaller compartments
drain into the larger center compartment by a 1-in.
hole, c, which can be closed by a stopper. When filled
with water it overflows into the center compartment.
These smaller compartments are intended to be used
for collecting gases. When in use it is not necessary
to stop up the whole sink and make it entirely use-
less to all other students.
The sink is designed to be used by four students,
two on either side of the desk. Three water faucets,
a, a, b, are illustrated, a and a are small and taper-
ing, making them especially adapted for attaching
rubber tubing for condensers, etc.
The sink is made of albarine stone and as illustrated
is 32 in. X 1G in. outside dimensions. The smaller
compartments are 14 in. X 5 in. X 4 in. deep on the
lower overflow side, which is 0.5 in. lower than the
top of the sink. The larger compartment is 18 in. X the large compartment and is protected
14 in. X 10 in. deep. The drain is in the middle of The size of the sink can be altered to suit
! :
by a sieve,
any space.
Solvents for Phosgene1
By Charles Baskerville and P. W. Cohen
College of the City of New York, New York, N. Y.
After the signing of the armistice, restrictions were
placed on railroad transportation of liquefied phos-
gene in' the United States. Previous to 1914 small
cylinders of the liquid were imported from Germany
to be used in producing a limited number of carbon
compounds and for research purposes. It was pro-
duced in the country on a small scale after the blockade
and before we entered the war, and was distributed in
cylinders. Immense quantities were on hand when
hostilities ceased. The greatest danger in the trans-
portation of phosgene, liquid or in solution, would
arise in case of fire or wrecks. Protection against
leaky valves is quite simple.
While the demand for phosgene for the purposes
mentioned is not great from the quantity point of
view, nevertheless it exists. Oft expressed have been
the hopes of finding more extensive uses for the poison
gases of the World War in peace times. It seemed,
therefore, worth while to endeavor to find other means
for the transportation of and other applications for
phosgene.
Among other qualifications, a liquid solvent for
phosgene should be (1) inert to carbonyl chloride, (2)
have a low vapor pressure, (3) hold notable amounts
in solution, (4) admit of easy recovery of the gas, (5)
preferably be noninflammable, and (6) involve min-
imum expense. The first and last of these qualifica-
tions are the most important, the former being pri-
marily due to the reactivity of phosgene.
As a general statement it may be said that phosgene
is soluble in ether, chloroform, liquid hydrocarbons,
1 Presented before the Division of Industrial and Engineering Chem-
istry at the 60th Meeting of the American Chemical Society, Chicago, 111.,
September 6 to 10. 1920.
carbon disulfide, and sulfur chloride, as well as in
some of the liquid metal chlorides (stannic chloride and
antimonic chloride).
The following liquids were used by us as solvents:
carbon tetrachloride, chloroform, gasoline, paraffin oil,
Russian mineral oil, benzene, toluene, glacial acetic
acid, ethyl acetate, and chlorocosane. The last sub-
stance is paraffin which has been melted and treated
with chlorine. It forms a light yellow compound, the
formula of which has not yet been determined. This
compound is used medicinally to dissolve dichlor-
amine-T.
The method of procedure was to pass the gas through
a Bowen's absorption bulb containing the solvent at
atmospheric pressure. The solution was stoppered
well in a dry test tube and allowed to stand for 2
wks. Various tests were made on each solution to
detect any evidence of reaction.
The following is a table of results for the solvents
mentioned above:
Solvent Grams
Carbon tetrachloride 79.5
Chloroform 49.4
Gasoline 37.0
Paraffin oil !4.<>
Russian mineral oil. 30.1
Benzene 43.9
Toluene 50.3
Glacial acetic acid.. 31.4
Ethyl acetate 20.5
Weight
Weight Phosgene
Solvent Absorbed
Grams COCL
Solubility
Ratio by
Weight
Chlorocosane.
25.2
Solvent Soluti)
by
lumbers
Below
All weighings were made at 20° to 21° C. The ratio values
are not given with mathematical accuracy for obvious reasons.
(1) With carbon tetrachloride no evidence of reaction was
observed. The boiling point of the solvent was the same before
and after saturation with phosgene.
334
THE JOURNAL OF I NDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
(2) and (3) In gasoline and chloroform, reactions were evi-
denced by heat of solution and change in boiling point.
(4) Paraffin oil was completely inert. No phosgene dissolved
in it.
(5) Although Russian mineral oil did not show any evidence
of reaction, it could not be used profitably because of the low
solubility of phosgene in it.
(6) Benzene maintained the same boiling point before and
after saturation. Phosgene and benzene in the presence of
anhydrous aluminium chloride react to form benzoyl chloride
and finally benzophenone. It was therefore undertaken to
prove the absence of these substances in the solution of phos-
gene in benzene. Air was passed through a drying tower con-
taining soda lime, and then through a solution of phosgene in
benzene, through several U-tubes immersed in a freezing mix-
ture, and finally through a solution of sodium hydroxide. The
clean dry air, free of carbon dioxide, removed the phosgene from
the benzene, the phosgene was liquefied in the U-tubes, and the
excess air passed through the sodium hydroxide. At the same
time if any hydrochloric acid were present in the benzene due
to reaction, it would be carried over to the sodium hydroxide
and there neutralized. The benzene free from phosgene was
tested for benzoyl chloride and benzophenone by hydrolyzing
with sodium hydroxide. A negative result was obtained.
However, the sodium hydroxide in the train of apparatus was
completely acidified, evidently due to phosgene which had been
carried over. The benzene used in these experiments was not
free from thiophene. In saturating benzene with phosgene the
solution increased in volume noticeably.
(7) Tolutne showed a change in boiling point.
(8) Phosgene reacted with glacial acetic acid. Reaction was
evidenced by heat of solution and an effervescence, also change
of boiling point. This may have been due to a small amount
of water in the acid.
(9) Ethyl acetate proved to be a solvent which closely rivaled
benzene. It formed a 49.6 per cent solution with phosgene and
was inert towards the latter.
(10) Chlorocosane was inert and a fairly good solvent. How-
ever, it was not quite so good as benzene and ethyl acetate.
The vapor pressure of the saturated solution exerted
at 20° C. was one atmosphere, while at 50° C, or the
temperature of a hot sun, a further pressure of 308
mm. mercury or about 6 lbs. to the sq. in. developed.
The problem of containers, therefore, is not serious.
On heating the solution the phosgene is readily, and
may be completely, driven off. Of the solvents tried,
the two which gave most promise are benzene and
ethyl acetate. Of these, benzene is probably the bet-
ter, because it has a lower vapor pressure and is cheaper.
The imagination allows of possibilities of practical
uses for such solutions in ridding lawns, etc., of moles,
and in "mopping up" rats and other vermin.
ADDRESSES AND CONTRIBUTED ARTICLES
Studies on the Chemistry of Cellulose. I — The Constitution of Cellulose
DBF
By Harold Hibbert
,iknt of Chemistry, Yale University. Nbw Haven. Connecticut
( Concluded)
It is also of interest that l-ehloro-2-hydroxy butyl methyl
ketone (CH2C1— CHOH— CH.— CH,— CO— CH,i when boiled
with alkali does not yield the oxide
CH2— CH— CH.— CH;— CO— CH3.!
\0/
With respect to the second point, namely, the nitration of glyc-
erol-sugar mixtures, it is known that the nitrogen content of
these nitrated products is considerably lower than that of pure
nitroglycerin. From the values customarily obtained in tech-
nical practice it would seem that the results are in general agree-
ment with the assumption of a primary dehydration of the sugar
molecule with the loss of one molecule of water, whereby two
of the hydroxyl groups disappear, the remaining three under-
going nitration.
RecenUy it has been found possible, as indicated in the second
part of the paper, to carry out some work on this subject.2 It
was found that when pure dextrose or cane sugar is dissolved in
glycerol and nitrated with the usual H2S04-HN03 glycerol
nitrating mixture, the resulting nitrated product, judged from
the nitrogen content, appears to contain only six nitrate groups,
although there were eight hydroxyls originally present, viz., five
in the dextrose and three in the glycerol molecule. The same is
true if we substitute a glycol for glycerol. In this case the
' Henry, Bull. acad. Toy. belg., [31 36 (1898), 31; Chem. Ztntr., 1598 (2).
663. No indication is given as to the nature of the bodies formed and the
subject is being investigated under the writer's direction by Mr. J. A.
Timm.
2 This work was carried out by Mr. R. R. Read at the Bureau of Mines,
Pittsburgh, and the writer wishes to express his kindness to him for the
assistance rendered; also to express his gratitude to Major Fieldner, Super-
vising Chemist, for kind permission to use the laboratory facilities.
nitrogen content corresponds to only five nitrate groups, although
the original mixture contained a total of 7 hydroxyl groups. How
can such results best be explained? There are two possibilities:
1 — The dextrose may undergo an inlermolecular condensation
with the glycol or glycerol, leaving six OH groups susceptible to
nitration:
CH2OH
CH2OH— (CHOH)4— CHO
CHOH =
I
CH,OH
/O— CH,
CH,OH— (CHOH),— CH< | 4- H20
X0— CH
I
CH2OH
2 — The dextrose may undergo, under the influence of the acid,
an intramolecular condensation, to give a product, isomeric with
CH2OH
I
-CHOH
CHOH-CHOH-CHOH
Dextrose
CH-
CH;OH
-CH O
CHOH-CHOH-CH
| HNOi 1
fHiSCh /
CHzNOj
CHN03-CHN03-CH
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
335
the cellulose nucleus, which then undergoes nitration to form
a trinitrate. In view of what has already been said with respect
to the constitution of hydroxy-aldehydes and ketones and the
ease of formation of the y- and 6-oxide types it seems possible
that the changes represented (p. 334) might occur, thus opening
up the possibility of the presence of a body isomeric, if not
identical with, the trinitrate of the cellulose nucleus.
Which of the two views is correct can be decided only by
further experimentation, and it would seem that determinations
of the lowering of the freezing point of pure nitroglycerin by
such products should enable a decision to be reached.
The transformation of the simple molecule into the highly
polymerized product may take place by means of the opening
of either a 5- or a 6-membered ring to give
.O— CH-
CH2OH
I
-CH
CHOH— CHOH— CH O—x
CH-
CH,OH
I
-CH— O x
(1)
(2)
CHOH— CHOH— CH O— x
in which x — x represent additional cellulose molecules.
As is indicated later, the balance of evidence is in favor of
Formula 2, according to which cellulose is to be regarded as a
dextrose glucoside of dextrose. It may be represented more
fully as:
CHoCH
1
CH
CHoOK _^CH -
1 -o-^|
- C!I - 0 - CH - CHOH - CHOH
CH - 0-
"
--HC -
\
CHOH
I
X0
\
0
\
CHOH
HC
H-CHOHiCH - 0 - CH-CH
HOH£C CHOH-CHOH=CH
-0
-CH -
|
CH
CH20H
Such a theory can, of necessity, be of value only if in agree-
ment with the experimental facts, and any proposed formula
for cellulose must be capable of explaining not only the reac-
tions quoted by Green,1 but also the following:
11 — Relation of cellulose to the cellulose nucleus.
12 — The formation of 1,2,5-trimethyl glucose and the absence
of a tetramethyl derivative by the action of dimethyl sulfate
and subsequent hydrolysis of the methylated product (Denham
and Woodhouse).
. 13 — The formation of dextrose and cellobiose by the hydrolysis
of cellulose acetate.
14 — The production of levoglucosan by the action of heat on
cellulose, starch, and /3-glucose under diminished pressure.
15— Formation of w-hydroxymethyl furfuraldehyde on dis-
tillation.
16 — Action of metallic salts such as zinc chloride.
17 — Formation and properties of hydrocellulose and cellu-
lose hydrates.
18 — Action of acids.
19 — Relation of cellulose to starch and dextrose and the prob-
lem of plant metabolism.
These will now be discussed in the light of the proposed new
formula.
1,2 CELLULOSE NITRATE AND ACETATE
The formula indicates that the highest nitration product should
•See Part I, This Journal, 13 (1921), 257.
be a trinitrate and the highest acetyl derivative the triacetate,
both of which facts are in agreement with the experimental
evidence, higher values than the triacetate being associated
with a partial disintegration of the cellulose molecule.
3,4 — ACTION OF ALKALIES AND XANTHATE FORMATION
It is unnecessary to assume, as Green does, that the action
of alkali on cellulose results in the opening of one of the rings,
the behavior corresponding more nearly to that of a mixture
of any alcohol with sodium hydroxide in which we have an
equilibrium of the type:
ROH -f NaOH ^ RONa + HjO
This should be capable of reacting with carbon disulfide in
a manner similar to that of any alkali, and in view of the pro-
nounced tendency of alcoholic solutions of potash to undergo
atmospheric oxidation, the increased tendency in this respect
of an alkaline solution of cellulose xanthate is only what
might be expected.
5,6 — ABSENCE OF CARBONYL GROUPS, AND HYDROLYSIS WITH
ACIDS
As already stated, the quantitative conversion of cellulose
to dextrose is now a well-established fact and is of fundamental
importance as a guide to the nature of the cellulose molecule.
The change may be represented:
CH20H ,
I H|0H
CH - 0 J- rax
CH0H-CHo0H
.^
I \ H;0H
CHOH-CHOH-CH 0;- not
rax= additional "cellulose nuclei"
7 — FORMATION OF u-BROMOMETHYL FURFURALDEHYDB
Using the new configuration (A), in which the cellulose nucleus
is assumed to have polymerized by the opening of the 6-mem-
bered ring, the changes taking place may be assumed to occur
as follows:
CH20H
CH - (
tH£0
CHOH-CHOH-CH-
::a/
CH^Br
Cl^Br
f-'ifc - chV
, ^TOH'
fj.-OH
CHOH . CH lOHf^'CH Cl -
h :oh
CHpBr
I
CH=C
l /
CH=CC_
in which the reactions arc indicated by reference to the trans-
formation of the polymerized product.
The first change is assumed to be the formation, from the
primary alcohol grouping, of a bromide and water, followed
by the addition of water and its subsequent removal, in the Im-
position, the latter being facilitated by the influence of the
bromine. A 5-membered ring thus results, which then un-
dergoes depolymerization and dehydration as indicated.
336
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 4
A reaction of this type in which the yield does not amount
to more than 26 per cent of the theory cannot be regarded as
of the same fundamental importance as one in which the yield
is quantitative, as in the case of dextrose formation.1
8 — FORMATION AND PROPERTIES OF OXYCELLULOSE
The information contained in the literature regarding the
properties of oxy cellulose is both conflicting and confusing.
Depending upon the type of oxidizing agent used and the condi-
tions employed, a widely different type of product is obtained,
the solubility of which in alkali, for example, varies within very-
wide limits. In a recent communication by Bancroft2 on the
oxidizing action of nitric acid, hypochlorites, permanganates,
and chloric acid on purified cellulose, the conclusion is reached
that there is only one oxycellulose, all the different products
described in the literature probably representing mixtures of
unchanged cellulose with oxycellulose. This view is based on
similarity of properties, and especially on the fact that further
treatment with the oxidizing agent of the product left after
extraction with alkali gives an increased yield of alkali-soluble
product.
Considered from the new structural point of view, it is evi-
dent that with three hydroxyl groups there is a considerable
number of possibilities.
In the first place it would seem that the — CH2OH group,
being a primary alcoholic group, may, on treatment with oxidiz-
ing agents, yield first an aldehyde and then an acid. Thus,
with cellulose and one class of oxidizing agent we might expect
to get both an aldehyde and an acid of the types:
CHO
I
-CH— O.
COOH
I
-CH— O *
CHOH— CHOH— CH. .O— x CHOH— CHOH— CH. . . .O—x
(I) (II)
and it is quite possible that the oxycelluloses soluble in alkali
correspond to II, while other types possibly represent mixtures
of I and II with unchanged cellulose. The golden yellow color
with alkali given by many oxycelluloses is possibly due to the
resinification of the aldehydic compound.
On the other hand, for example with Fenton's reagent (hydro-
gen peroxide and a ferrous salt), there is a possibility that only
the — CHOH groups may be oxidized and the — CH2OH left
intact. Just as tartaric acid is oxidized to dihydroxymaleic
acid by this reagent, we might expect that cellulose would un-
dergo the following changes (III, IV):
CH2OH
I
CH CH— O *
C(OH) = C(OH)— CH...O— x
(III)
CH2OH
I
CH— CH— O x
CHOH— CO— CH O-
(IV)
which would give an oxycellulose insoluble in alkali.
Finally, both types of oxidation may, and possibly do, take
place at the same time to give oxycelluloses of the types V
and VI:
i Cross and Bevan ("Cellulose," 1918, Appendix, 334) are apparently
still unreconciled to such a point of view,
s J. Phys. Chan., 19 (1915), 159.
CH-
COOH
I
-CH— O.
COOH
I
CH CH— O.
CHOH— CO— CH.
(V)
CO— CHOH— CH O-
(VI)
From the above standpoint, the view of Bancroft (p. 166) that
"it is thus clear that the so-called insoluble oxycellulose is really
unoxidized cellulose" cannot be considered as conclusively es-
tablished.
The true nature of such products can be solved only after
extensive investigation with a wide variety of reagents capable
of exercising preferential oxidation as between the — CHOH
and the — CH2OH groups.1
There is the further question as to the greater ease with which
furfuraldehyde may be obtained from oxycellulose. If we
consider Type II, hydrolysis should result in the following
changes:
COOH H!OH
(6)
COOH
(4)
CH-
\
CHOH-CHOH-CH. .O— *
CHOH-CHOH-CH.
(3) (2) (1
The carboxyl group attached to C-5 may then play the same
role as the — CH2Br group presumably does in the formation
of bromomethyl furfuraldehyde from cellulose, namely, by-
weakening the affinity of the H* atom, resulting in the formation
of a 5-membered ring which then loses water and C02:
COOH COOH
I I
CH . C^- H CHtifl"; Hfc CH=ra
/ /OH; I /
CHOH - HC . CH r* : CH=C
\f)H: ^CHO
It is, on the other hand, much more difficult to postulate any
such series of reactions with an oxycellulose in which the oxida-
tion of either of the — CHOH groups is involved. Assuming
that the latter could be oxidized, leaving the — CH2OH group
intact, we might expect to get a type of oxycellulose insoluble
in alkali and yielding practically no furfuraldehyde on treat-
ment with acids.
Presumably an investigation of the behavior of a substance
of the type
CHjOH—CHj—CHj— CHOH— CHOH— CH(OC»H
(in which the number and position of the hydroxyl groups corre-
spond to those in cellulose) toward a variety of oxidizing agents
would throw much light on the nature of the oxycelluloses.
9 — FORMATION OF DIOXYBUTVRIC AND ISOSACCHARIC ACIDS
FROM OXYCELLULOSE
Tollens and Faber,2 by the action of calcium hydrate on an
oxycellulose prepared by the use of dilute nitric acid accord-
ing to the method of Cross and Bevan,3 were able to isolate
from the mixture calcium dioxybutyrate and isosaccharate.
The former they assumed to be derived from either
l The investigation of this interesting subject is being continued at
Cornell University under the guidance of Professor Bancroft.
* Ber., 32 (1899), 2594; von Faber, Dissertation, Gottingen, 1899.
» J. Chem. Soc, 43 (1883), 22; 46 (1884), 206, 291, 897.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
337
CH,
\
CH3— CHOH— CHOH— COOH or C(OH)— COOH-
/
CH2OH
/CH2OH
the latter, from CH2OH— CHOH— CH2— C(OH)<
NCOOH
In the present state of our knowledge it is not possible to trace
the course of such reactions, but with the accumulation of further
experimental data regarding the chemical constitution of the
oxycelluloses, and assisted by the wonderful researches and
speculations of Nef1 on the saccharic acids, much light should
be shed on the nature of these changes.
10 — FORMATION OF OXYPYRUVIC ACID FROM NITROCELLULOSE
The formation of oxypyruvic acid by the action of alkali on
collodion cotton (N = 11.2 per cent) was shown by Will.2
Assuming the latter to have the constitution
CH0ONO2
CH CH O x
|\-o-x
\
CHONO2— CHOH— CH O— x
and to undergo hydrolysis according to the following scheme:
CHgOUOg
H'.OH mi - m i« *
CH - CH - 0 + --X CH0H-CH0H-CHo0N02
^^0. H/OH » ,— J (A)
I ^< Hi OH :
CH0N0„-CH0H - CH 01- x CHOIIOo-CHOH-CHO
d \ a ^ « «
the body (A) so produced would have two NO3 groups in the
•y-position to the hydroxyls attached to C-4 and C-5, so that the
latter would be very susceptible to intramolecular oxidation.
This view is supported by the fact that while 1,2-glycols are
nitrated readily with the usual glycerol nitrating acid, on the
other hand 1,3-glycols (trimethylene, butylene) show a marked
tendency towards spontaneous combustion and the operation
has to be conducted with much greater care.3 The cause of this
is in all probability the primary formation of mononitrate, in
which the NO3 group, being in the 7-position to the hydroxyl,
exercises spatially a marked influence in increasing the tendency
towards oxidation of the latter.
With the cellulose dinitrate, if we assume a similar influence
of the NO3 groups, oxidation of the 7 hydroxyls should occur,
which, together with a splitting of the ring and saponification,
should yield oxypyruvic acid:
\ 1
HO . CH— CHOH— CH. . ON02 HOOC— CO— CH2OH
._._! ,
CHONOo— CHOH— CHO CH2OH— CHOH— COOH(?)
It is not necessary to assume that hydrolysis of the cellulose
nitrate occurs prior to the oxidation process; presumably all
of these changes occur together.
The difference in the behavior towards alkalies of cellulose
nitrates on the one hand, and of the acetates on the other, would
seem to be in harmony with this point of view. In the case of
the acetates there is no tendency towards intramolecular oxida-
tion and, as is well known, the cellulose is regenerated in the
form of hydrate.
• Ann., 357 (1907), 214; 376 (1910), 1.
'Bar., 24 (1891), 400.
3 Author's unpublished researches.
11 — RELATION OF CELLULOSE TO THE CELLULOSE NUCLEUS
The nature of the linking by means of which polymerization
takes place is of the greatest importance, since the properties
of cellulose are in large measure controlled by it.
It is well known that the tendency Inward formation of 5-mem-
bered rings containing oxygen is greater than that of G-membered,
and that with similarly constituted bodies the latter are less stable
than the former. This is shown clearly in the condensation of
polyhydroxy derivatives with carbonyl compounds. Thus, when
acetone, acetaldehyde, benzaldehyde, etc., condense with
glycerol, 5- and not 6-membered rings are formed:1
CH2OH CH2OH CH2OH
I I I
CH— Ov XH3 CH— Ov CH— Ov
>C< >CH— CH, I >CH.C.H,
CH2— Ox NCH3 CH*— 0/ CHj— <Y
(I) (ID (HI)
The tendency towards polymerization is invariably related
to the outstanding residual affinity of one or more atoms in the
molecule, and with dextrose the principal seat of this is to be
found in the "aldehyde residue." The hydroxyl group asso-
ciated with this in the dextrose molecule is in a more reactive
condition than either of the other four, as seen in glucoside
formation, and it may be assumed that the plant will, therefore,
utilize this as the starting point for the next step in the synthesis
of cellulose. A consideration of the phenomena of plant life-
emphasizes the remarkable tendency towards glucosidic forma-
tion, and the simplest way in which this can be exercised in the
case of glucose would appear to be by "intramolecular glucosidic
formation" by means of condensation involving the most active
hydroxyl group, namely, that of the "aldehydic residue." The
first change from dextrose to cellulose is probably that of
CH-OH CH2OH
I I
CH CH OH CH— CH O
(I)
CHOH— CHOH— CHOH
(ID.
CHOH— CHOH— CH
II thus representing to some extent a type of intramolecular
glucosidic condensation. Whether this body is actually formed
and is capable of free existence could best be ascertained by
effecting its direct synthesis. It is possible that it may not be,
but that instead the simple molecule at once undergoes polym
erization, as indicated previously.
Cellulose is thus nothing more than a polymerized dextrose
glucoside of dextrose. Viewed from this point its reactions be-
come much more intelligible than if we assume a splitting of
the 5-mcmbered ring and a polymerization of the type:
x O— CH-
I
CH2OH
I
-CHOH O
CHOH— CHOH— CH O— *
With the former constitution the quantitative conversion into
dextrose is at once apparent, and the formation of cellobiosc,
maltose, and other derivatives admits of simpler explanation
The exact nature of the chemical forces involved in the polym-
erization process is a matter of speculation. According to
Staudinger- the same forces operate in polymerized products
as in the ordinary valence type of compound while, on the other
1 Irvine. Macdonald and Soutar, J. (hem. Soc. 107 (1915), 337; Irvine
and Patterson, Ibid., 10S (1914), 898; Peacock, Ibid., 107 [1915), 815;
Fischer, Ber., 27 (1894), 1536; 28 (1895), 1167, 2496. In a recent papei
(posthumous) by E. Fischer and E. Pfaehler [Ber., 53 (1920), 1606] it is
shown that acetone does not condense with trimethyleneglycol under simi-
lar conditions.
* Ber., 53 (1920), 1073.
338
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
hand, Hess1 is inclined to emphasize the part played by "partial
valencies" as applied in the sense of Werner's theories.
12 — NUMBER OP HYDROXYL GROUPS IN CELLULOSE AND THEIR
RELATIVE POSITION (FORMATION OP 1,2,5-TRIMETHYL
GLUCOSE)
The trimethyl glucose obtained by Denham and Woodhouse
by the action of dimethyl sulfate on cellulose appears, from the
evidence submitted, to have the constitution
CH3OCH2— CHOH— CH— CH(OCH3)— CH(OCH3)— CHOH,
I o I
i. c, 1,2,5-trimethyl glucose.
That such methylations proceed normally (namely, without
ring scission) with bodies of the type indicated by the formula
for cellulose under discussion is shown by the fact that Irvine,
MacDonald and Soutar,2 by the action of dimethyl sulfate on
isopropylidene glycerol in alkaline solution, were able to obtain
a good yield of the a-methoxy derivative, in spite of the fact
that the isopropylidene glycerol derivative is a relatively un-
stable substance.
It is somewhat improbable with such a powerful methylating
agent as dimethyl sulfate that one of the hydroxyl groups in
the cellulose molecule would remain unacted upon, and the
fact that no indication (or only the merest trace) of a tetra-
methylglucose was obtained by these authors serves to establish
the position and character as well as the number of the hydroxyl
groups, and is a fact of fundamental importance in arriving at a
decision as to the constitution of cellulose.
None of the formulas previously considered indicates the
presence of a primary alcohol group. On the other hand, the
formation of the trimethyl glucose in question is exactly what
would be predicted from a consideration of the new formula:
CHgOH
CEjOCHj
CHOH.CHOH-CH 0 - x CHtOCHj J-CHfOCHjT^CH ol- X
1
CH- CHOH - C^OCHj
CH(0CH3)-CH(0CHgT^CH0H
13 — FORMATION OF CELLOBIOSE AND DEXTROSE
When cellulose is treated with a mixture of acetic anhydride,
glacial acetic acid, and a small amount of sulfuric acid, it is
converted into a mixture of cellobiose octacetate and dextrose
pentacetate. Ost,3 as already stated, was able to obtain a com-
bined yield of both, equivalent to 90 per cent, calculated on
the assumption that cellulose is built up entirely from dextrose
molecules. The relative proportions of these two products
vary in a marked manner with the operating conditions.
It seems probable from the work of Haworth and Leitch4
that cellobiose has the formula
CH20H
CH - CH
CH - CHOH-CHOH
CHOH-CHOH-CH CH - CHOH - CH20H
i. e., it is a dextrose glucoside of dextrose, and in view of its
' Z. Elektrockem., 26 (1920), 232. In this connection see criticism by
P. Karrer, Helvetica Chim. Acta, 3 (1920), 620, and reply of Hess, Ibid, 3
(1920), 866; also discussion in appendix to this paper.
'J. Chem. Soc, 107 (1915), 337.
3 hoc. cit.
< J. Chem. Soc, 113 (1918), 188; 116 (1919), 809.
mode of formation it has been assumed that it possibly pre-
exists as such in the cellulose molecule.1 The formula under
discussion, however, represents cellulose as a polymerized dex-
trose glucoside of dextrose, so that the formation of the cello-
biose octacetate may be represented as a simple disintegration
of the acetylated cellulose molecule with subsequent acetylation:
CH - CH - 0
:rfTcHOAc-CH0Ac
CHOAc-CHOAc-CH - 0 - CH - CH i
I | ~~ 0^ H i0H
CH20Ac CHOAc-CHOAc-CH - 0--J x
Ac0CH2-CH0H-CH-CH0Ac-CH0Ac?CH-0-CH-CH-CH0Ac-CH0Ac-CHCH
^~^~ 0^ CHoOAc ^^ 0 ^
I
Ac0CH2-CH0Ao-CH-CH0Ac-CHOAc-CH-O-CH-CH-CH0Ac-CH0Ac-CH0Ac
^~^0^"^ CH20Ao ^~-~- 0 ^
The cellobiose octacetate thus formed readily undergoes sec-
ondary decomposition to give dextrose pentacetate.
14 — ACTION OF HEAT ON CELLULOSE
The recent remarkable discoveries relating to the distillation
of cellulose, starch, and glucose under reduced pressure carried
out by Pictet and co-workers2 open up a new era in the study
of cellulose chemistry, supplemented as they are by the recent
interesting paper by Karrer.2
In brief, the former investigators show that when cellulose
and starch are heated under diminished pressure (12 to 14 mm.)
to a temperature of about 210° a yield of about 40 per cent of
levoglucosan (C6Hi0O6) is obtained. It was not found possible
to ob'ain the same product by subjecting ordinary (a) g'ucose
to the same treatment. When, however, ^-glucose was so treated,
Karrer was able to show that a similar high yield of levoglucosan
is obtained.
On the other hand, Pictet and Castan3 found (in agreement
with the work of Gelis)' that a-glucose yields glucosan (CoHioOs)
on similar treatment. Both glucosan and levoglucosan have
the same empirical formula (CbHioOs), they are monomolecular,
soluble in water, and contain three hydroxyl groups but no
free carbonyl group. When levoglucosan is heated at a some-
what lower temperature (180°) in presence of platinum black,
it is converted into dextrin.
A further investigation of the properties of these two inter-
esting products6 shows that they possess Formulas I and II,
respectively :
CH CHOH-CH2 CH— CHOH— CH„OH
CHOH-CHOH-CH
Levoglucosan
(I)
CHOH-CH— CH
\/
O
Glucosan
(II)
1 If such were the case it would naturally have a very important bear-
ing on the constitution of cellulose for, as pointed out recently by Hess, a
constant ratio should be found to exist between the amounts of dextrose
and cellobiose formed on hydrolysis. The important contribution of this
author was received only after the present article had been communicated,
and a short discussion of it is included as an appendix.
» hoc. cit,
* Helvetica Chim. Acta, 3 (1920), 645.
« Compt. rend., 51 (1860), 331.
« Helvetica Chim. Acta, 3 (1920), 640, 645.
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
:>:;o
It is also of considerable interest that the most recent paper
of Pictet1 enables a decision to be reached as to the different
structure of a- and /S-glucose.
The following chart will perhaps serve to visualize the bear-
ing of these important discoveries on the constitution of cellu-
lose and their relation to the formula under discussion:
Dextrose (C6H1206)
OH OH
— °~1
7 1
OH
Lc-C-C-C-C- CHoOH
I I I I I
H H OH H H
[h OH H~ "I
Mill
LC-C-C-C-
- C . CH20H
1 < ' II
OH' H OH H H
CHOH-CHoiftCH-O.-.j
Cellulose'1
1 Picttt, Luc. cit.
1 Pictet and Castan, Luc cit.
5 Pictet and Cramer, Loc. cit.
* Pictet and Sarasin, Loc. cit.
If4we assume that starch possesses the constitution shown
(and its quantitative conversion into maltose would indicate
this to be the case), then starch must represent a polymerized
form of levoglucosan, and the ease with which the latter is con-
verted into dextrins, closely related to starch, bears out this as-
sumption.
CH CHOH-CH.
CH-
-CHOH-CH2OH
CHOH-CHOH-CHOH
Dextrose
/
\
CHOH-CHOH-CH
Levoglucosan
-CHOH— CH,OH
x O
CHOH CH-CH
\/
O
Glucosan
CH2OH
I
-CH
CHOH-CHOH-CH
Cellulose nucleus
The emphasis placed throughout the present article on the
fundamental importance of the carbouyl group thus seems to
be warranted when it is borne in mind that three of the possible
reactions into which the dextrose aldehyde group can enter are
known to occur (see bottom of preceding column).
In considering the action of heat on cellulose the first point
of attack will presumably be the most susceptible part of the
molecule, namely, the "aldehyde residue."
If scission takes place here, there arc three possibilities for
secondary ring formation:
CHgOH
CH - CH - 0
CHgOH
CH - CH - 0
CH . CHOH >CH
Apparently at the higher temperature Formula I represents
the most stable configuration, so that on further pyrolysis levo
Klucosan is obtained.
Hi OH
■OK ...
O
O
CH— — CHOH-CH2
O
CHOH-CHOH-CH CHOH-CHOH-CH
This, as shown by Pictet,roirheating with platinum black at a
somewhat lower temperature, polymerizes into dextrin:
CH-
CHOH— CHo— O x'
O
CHOH-CHOH-CH O— x'
(?)
15 — FORMATION OF OJ-HYDROXYMETHYL FURFURAl.OKHYDE BY
THE ACTION OF HEAT
It was shown by Erdmann and Schaefer1 that when cellu-
lose is subjected to dry distillation w-hydroxymethyl furfural-
dehyde is formed and may be isolated from the products of dis-
tillation.
Its formation probably takes place according to the scheme
previously outlined for the production of w-bromomethyl Tur-
in aldehyde.
CHjjOH
CH2OH
I h!oh
CH - Oi---
CHOH-CHOH-CH 0 - X
OHoOH
1
CHOH - HC
I -, / ^H
CHOH - HC - CH -1
^CfH
! H-'OH
ch;oh:--ch o- -
H 'OH
' Helvetica Chim. Ada, 3'(I920), 649.
16 — ACTION OF METALLIC SALTS (ZINC CHLORIDE, ETC.)
The solubility of cellulose in zinc chloride solutions is proba-
bly to be associated with the well-known tendency of the latter
to form addition compounds with hydroxy and carbonyl de-
rivatives:
■ Bcr., 43 (1910), 2391, 2398.
340
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
CH-
-CH-
CH;OH
I
\ CH(OZaCI)— CH— O . . . . x
O + ZaCh ->■ |
\ CHOH— CHOH— CH..O— x
\ I
CHOH-CHOH-CH. . . .O — .1 CI
Such an unstable addition compound (assuming one molecule
of zinc chloride attached to each dextrose residue) would con-
tain 21 per cent Zn, calculated as such, and according to Cross
and Bevan1 the product precipitated by water contains from
18 to 25 per cent Zn. This tendency of zinc chloride to add on
to oxygen linkings is shown in the ease with which ethylene
oxide is converted into diethylene dioxide under the influence
of a trace of this material, its catalytic action presumably being
due to the formation of a similar unstable addition compound.
CHiv CH:— OZnClCl— CH. CHr-O-CHj
2 | >0 + 2ZnCh =| | -> | | + 2ZnCl2
CH/ CH.— CI ClZn O-CH. CHs— O— CHs
The addition of water to the zinc chloride-cellulose addition
compound would presumably leave hydrated or partially hy-
drated products of the types shown below:
A
CH - CH - 0 X
CHOH-CHOH-CH 0
CHOH - CHOH - CH 0
CI^OH
CH - CH . 0—
CHOH-CHOH-CH 0 -
17 — CELLULOSE HYDRATE AND HYDROCELLULOSE
It is well known that cellulose prepared from zinc chloride
solutions represents a hydrated product which is much more
reactive than ordinary cellulose, and a consideration of the
above equilibria would appear to offer an explanation of this.
If the cellulose molecule has become hydrated — either actually,
through the exercise of full valencies, or in a latent manner
through partial valencies — evidently it should be more soluble
in various solvents, therefore more reactive, and at the same
time should give acetyl and other derivatives of a higher order
than three. That such an equilibrium mixture probably ex-
ists is supported by a consideration of the properties of alde-
hydes in general. Thus, with chloral the tendency to form a
hydrate is so pronounced that the reverse change CCI3 — CH-
(OH)2 > CCI3 — CHO + HjO scarcely comes into consid-
eration. On the other hand, with acetaldehyde we probably
have an equilibrium of the type:
,OH /OH
CH3CHO + H,0
CH3— CH<
\
CH3 — CH
OH
OH
The more negative the carbonyl group, the greater the ten-
dency for addition to take place. In the case of cellulose we
are dealing with a "latent" aldehyde group only, so that its
negative character is relatively very small and the tendency
to add on water, therefore, only slightly pronounced. It must,
nevertheless, exist, and the moisture content of ordinary cotton
cellulose is possibly to be associated not only with the hydroxyl
groups but also to some extent with this factor. In the action
of zinc chloride the character of the carbonyl group, due to the
attachment of the negative chlorine to the carbon atom, be-
comes much more emphasized, with the result that hydration
can then take place more readily.
18 — ACTION OF ACIDS
The remarkable ease with which cellulose is resolved quanti-
tatively into dextrose under the influence of highly concentrated
aqueous hydrochloric acid2 is a strong argument for the close
relationship existing between them. Its behavior falls into line
with that of any other glucoside, and to this extent supports
1 "Cellulose," p. 8.
3 Willstatter and Zechmeister, hoc. cit.
that point of view as to its structure. The difference in behavior
between concentrated sulfuric and hydrochloric acids is to be
explained by their specific action. The latter is characterized
by a greater ease of addition in general to oxygen linkings re-
sulting in a depolymerization and ring opening. The former,
on the other hand, is characterized by a greater power of dehydra-
tion; the additive power is less pronounced, so that for complete
conversion into dextrose it is necessary to use dilute acid at an
elevated temperature. The experiments of A. L. Stern1 on the
action of sulfuric acid on cellulose are interesting as indicating
a different behavior of two of the hydroxyls in the cellulose
molecule, these two, according to Cross and Bevan,2 "having a
superior basic or alcoholic function." Possibly these corre-
spond to the secondary alcohol groups in the formula under
discussion.
19 RELATION OF CELLULOSE TO S:.iRCH AND DEXTROSE AND
THE PROBLEM OF PLANT METABOLISM
There would appear to be a close relationship between glucosan,
levoglucosan, dextrose, starch, and cellulose. Glucosan is much
more readily converted into dextrose than levoglucosan, in
this way resembling starch as compared with cellulose. If
later work should show the ready convertibility of glucosan into
levoglucosan, a possible scheme of plant synthesis would in-
volve the following changes:
C02 ♦ E^O > CH20H-CH0H-CH0 '
CHOn-CHOH-CH-0-
Starch
E. Fischer, Ber., 23 (1890). 2238.
That the formation of sugar by the plant actually takes place
through the medium of such a powerful plant poison as formalde-
hyde has been disputed by Michael,3 who claims that the active
intermediate is glycollic aldehyde; also the question as to whether
starch is always formed prior to the cellulose is still a disputed
matter.4 There is, however, apparently, quite general agree-
ment that under the influence of plant life carbohydrates are
readily convertible into cellulose. This being the case, what
type of reaction could be simpler than that of an intramolecular
aldehydic condensation of the dextrose molecule as indicated
by the writer's formula?
CH,OH
I r-
CH2OH
I
-CH O
CHOH-CHOH-CH
Dextrose
+ H,0,
CHOH-CHOH-CH
Cellulose nucleus (Hibbert)
■ "Cellulose," 1918, 49.
3 "Cellulose," 1918, 51.
s /. prakl. Chem., 60 (1899), 48+; see also Fenton, /.
(1895). 780; 71 (1897), 375; 75 (1899), 575.
4 Cross and Bevan, "Cellulose," p. 73.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
It is probably safe to say that the plant will work along lines
involving the least expenditure of energy necessary to effect
the required synthesis, and this would seem to correspond with
the 7,5-dihydroxy condensation shown above. The facility
with which aldehydes and ketones condense intermolecularly
with hydroxy derivatives to form 5- and 6-membered rings
and the ease of intramolecular y- and probably ^-condensation
in the case of hydroxy-aldehydes and ketones both lend support
to this view. Dextrose admittedly possesses the 7-oxide con-
stitution and the knowledge that 1,4- and 1,5-glycols readily
split off water to form closed rings:
CH
<
CH2— CH2OH
CH2— CH2OH
CH2<
,CH2— CH;
NCH2— CHj
V> 4- H20
is further evidence of the ease with which the above intra-
molecular condensation of glucose might be expected to take
place.
The necessity for a closer scientific study of the properties
of the cellulose molecule becomes increasingly evident in view
of the present pronounced shortage of paper pulp, and it does not
seem unreasonable to assume that with a more extended knowl-
edge of its chemical constitution important material will thereby
become available for the solution of such technical problems as
the utilization of waste sulfite liquor, improvements in the yield
of wood pulp, scientific afforestation, and in the domain of vul-
canized fiber, artificial silk, explosives, celluloid, and synthetic
fuels. Up to the present our knowledge of the cellulose mole-
cule has been based on a variety of empirical reactions such as
those of hydrolysis, acetolysis, nitration, oxidation, the xan-
thate formation, etc. The time would now seem to be op-
portune when the question of direct synthesis should be under-
taken, and the writer has already made a start along the general
lines outlined below.
An examination of the new formula indicates the parent sub-
stance to be a body of Type I, while a still simpler derivative
would be that indicated by II,
CH3
I
CH — CH — O
-CH2— CH2
(I)
CH — CHj— O
CH2— CH2
(ID
and attempts (in conjunction with Mr. H. S. Hill)1 to synthesize
the latter give promise of success, the following being the method
adopted.
1 — Glycerol bromohydrin is first condensed with bromo-
acetaldehyde to give 1-bromoethylidene glycerol bromohydrin,
CH CH, O
CHO
CHOH— CH2— OH
I + I
CH2Br BrCH
CH2Br BrCH2-CH
2 — This dibromo derivative reacts very vigorously, either
alone or in presence of solvents, with zinc or magnesium, less
vigorously with sodium and silver. The nature of the products
formed is being investigated in the hope that the two bromine
atoms may have been removed with formation of a closed ring
and the body desired.
1 These results are to form the subject of a separate communication
and the writer would like to reserve this field for the present. The work is
being pushed as rapidly as the somewhat limited assistance at his disposal
permits.
CH— CH2— O
+ 2Na =
CH;Br BrCH2CH
+ 2NaBr
CH2— CH,— CH
The product may be expected to yield on hydrolysis with dilute
acids 3,4-dihydroxyvalerianic aldehyde, a fact which would be
of considerable importance in its bearing on the constitution
of cellulose.
By substituting bromoacetonc for the bromoacetaldehydc
in the above reactions, a body possibly closely related to inulin
of the type
CH— CH2 — O
CH2— CHr- C— CH3
could be synthesized, and it is hoped this suggested mode
of synthesis, namely, -y,5-hydroxy aldehydo (respectively, keto)
condensation may prove capable of wide application. It would
seem that any derivative of the type R.CHOH— CHOH— CH2—
CH. — CHO should undergo condensation to the bridged ring
type
R
I
CH — CH — O
CH2— CH2— CH
and the various aldehyde condensation products from croton-
aldehyde, acrylic aldehyde, acetaldehyde, allyl acetone, etc.,
are being investigated from this standpoint. Coincident with
such researches it would seem highly desirable, in view of our
increased knowledge, to subject to careful reexamination many
of the typical reactions of the cellulose molecule.
It cannot be too clearly indicated that the above speculations
are all concerned with the nature of a product of plant
metabolism, regarding which knowledge can be acquired
only by patient, intensive research, involving a far-reaching
study of its botanical, physical, and chemical nature. The de-
gree of polymerization may, and probably does, vary with the
nature of the plant metabolism and the reason why different
celluloses do not show much greater variations in chemical be-
havior than they do, is that the energy relations of the atoms in
two molecules, one of which is, say, (CsHwO&K, and the other
(CeHioOohoo, cannot be very different. The evidence at present
available would seem to be against the idea of the entire cellu-
lose family being representable by one large molecule (CgHioOs)x.
In the purification treatment small amounts of various deriva-
tives are removed, and such removals probably leave the mole
cule in a more active state, owing to the setting free of residual
affinities, hitherto exercised in holding them in combination.
The sensitiveness of cellulose to small changes may probably
be accounted for in this manner. In conclusion, the stlbjed
of the constitution of cellulose and the scientific principles un
derlying its industrial applications calls for an intimate co-
operation between plant physiologist, and organic and physical
chemist. The former, by the elucidation of the nature of plain
enzymes, may ultimately place the forester in the position oi
being able to improve materially the growth of trees, while from
the union of the two latter forces many technical advance
may be hoped for, not the least of which is that of obtaining a
342
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
new fuel supply to replace our fast-diminishing gasoline re-
sources. '
Since the above paper was communicated there has appeared
an interesting and valuable article on this subject by Kurt
Hess.2 The author, from various considerations, one of which
is the pronounced tendency of plants to form glucosides, ar-
rives at the conclusion that the properties of cellulose are best
explained by the formula:
,CH — 0-|-CH— CHUH— CHOH— CH— CHOH— CH2OH
CH—O-i-CH— CHOH— CHOH— CH— CHOH— CH2OH
I !L n !
CH—0-I-CH— CHOH— CHOH— CH— CHOH— CH2OH
(»
CH — O— CH— CHI )H— CHOH— CH— CHOH— CH8OH
CH2— O-'-CH— CHOH— CHOH— CH— CHOH— CH2OH
-O-
Cellulose is accordingly to be regarded (at least in so far as the
ground-structure is concerned) as a pentadextrose glucoside
of dextrose.
The principal evidence on which this is based rests on the con-
stant ratio assumed to exist between the amounts of cellobiose
octacetate and dextrose pentacetate formed when cellulose is
acetylated (under prescribed conditions) by acetic anhydride in
presence of glacial acetic acid and a powerful catalyzer and de-
hydrating agent, vis., concentrated sulfuric acid. By carefully
regulating the conditions of acetylatiou, Ost3 was able to obtain
a combined yield of 90 per cent of the theory calculated on the
assumption that cellulose is made up entirely from dextrose
molecules. The highest obtainable yield of cellobiose octace-
tate was 37.2 per cent of that theoretically obtainable (assum-
ing cellulose to consist entirely of cellobiose molecules), this
amount being found to vary considerably with the tempera-
ture, time of acetylation, amount of catalyst, etc. The values
obtained do not support the view of a constant ratio between
dextrose pentacetate and cellobiose octacetate formation.
If the conditions employed are such that no decom-
position of the cellobiose acetate into dextrose acetate may
lie assumed to have taken place, and if acetylation occurs with
scission of the molecule as outlined diagrammatically above,
thus accounting for the formation of cellobiose octacetate, viz.,
CH-
AcO . CH— CHOAc— CHOA.
I o
-CH— O—
I
CH2OAc
CH— CHOAc— CHOAc— CH— CHOAc
-O-
' CH2OAc
then four molecules of glucose pentacetate would be formed to
each one of cellobiose octacetate
Hess gives the results obtained in eight experiments by several
1 The British government is already giving serious consideration to
this subject and has appointed a special committee for this purpose. Of
interest is the fact that last year the sum of £90,000 was donated for research
on cotton alone. The Cotton Association now proposes to raise a Research
Fund of $1, 250.000.
'Z. EUktrochem., 26 (1920), 232.
» Ann., 398 (1913), 323.
investigators, and these are reproduced below. (On the above
assumption, 9.38 g. of dry cellulose should give 6.42 g. of cello-
biose octacetate and 12.51 g. dextrose pentacetate .'>
Wt. of wt. of
Cellobiose Dextrose
Expt, Octacetate Theory Pentacetate Theory
I1 5.3 6.42 6.4 12.51
II' 6.8 6.42 12.0 12.51
IIP 7.3 6.42 12.4 12.51
IV 7.08 6.42 10.4 12.51
V 2.8 6.42 17.0 12.51
VI. VII, VIII1 5.8;5.9;6.2 6.42 Not determined 12.51
' Ost, Ann, 398 (1913), 323.
* Madsen, Dissertation, Hannover, 1917.
It will be noted that there is a wide variation in the values
found for both cellobiose octacetate and dextrose pentacetate.
Of fundamental importance (in view of the eminent standing
of the author and his reiteration of the correctness of the work I
are the high values for cellobiose octacetate obtained by Ost
as indicated in Expts. II, III, and IV, and they seem to provide
strong evidence against the soundness of Hess' views. Greater
reliance is placed by the latter on Expts. VI, VII, and VIII, al-
though it is unfortunate that no values for the glucose pentacetate
are given. No explanation is vouchsafed for the remarkable course
which the hydrolysis of the cellulose molecule is supposed to
follow, and all that can be said at the moment is that the data
submitted offer the possibility of a highly interesting relation-
ship, which, if true, would necessarily have a marked bearing
on the constitution of cellulose.
Of considerable importance are the results quoted by Hess
and Wittelsbach in the same article on the acetolysis of a sam-
ple of cellulose ethyl ether (OC2H6 = 47.2 per cent). This
product was submitted to continued treatment at a low tem-
perature with a mixture of acetic anhydride, and glacial acetic and
strong sulfuric acids, and determinations made of the ethoxyl
content of the products formed after given intervals of time.
Under the conditions employed the cellulose ethyl ether was
converted partly into acetylated dextrose-, partly into acetylated
dextrin-ethyl ethers. On the theory that the latter are pro-
duced by the successive removals of dextrose residues in the
Hess molecule, with acetylation of the newly formed hydroxyl
groups, it is evident that, with each such removal, the new dex-
trin formed should contain, relatively, a lower percentage of
the ethoxyl radical. It is assumed (and appears to be the
case) that no displacement of the ethoxyl group occurs during
the process, and the values actually obtained are, in fact, con-
siderably lower, decreasing from an initial value of around 40
per cent to 26 per cent, those of the dextrose pentacetate re-
maining approximately constant. While these experiments
furnish supporting evidence they cannot be accepted as supply-
ing anything in the nature of final proof. In the first place, the
values relate to dextrin derivatives, and our knowledge of these,
as a class, is admittedly in a very hazy condition. It is to be
regretted that determinations of the "acetyl" values were not
carried out simultaneously, for this might possibly have pro-
vided strong evidence for a decision as between this formula and
the writer's.
The fact that tetramethyl glucose is not formed by the hydroly-
sis of completely methylated cellulose as shown by Denham and
Woodhouse is a strong argument against the Hess formula.
These investigators were unable to identify any trimethoxy
glucose other than the 1,2,5-derivative, although from a con-
sideration of his (Hess') formula there seems to be no logical
explanation as to why several isomeric trimethoxy deriva-
tives should not be formed simultaneously. In view of the
fact that the triethoxy cellulose used by Hess was apparently
a mixture of di- and tri-derivatives, it seems advisable to have
the work repeated with preparations made according to the
Lilienfeld process and containing the equivalent of three (OCsHs)
radicals calculated on the molecule CeHioOj.
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
Combustion Smokes1'2
By Geo. A. Richter
Research Department,
343
A new development of the late war with the Central Powers
was the use of artificial smokes for obscuring purposes. The
allied navies made early provision for smoke screens as part
of their program for eluding the wily submarine, and in the
later days used them in major offensive operations against the
submarine bases. The armies also found it economical to lay
down smoke barrages before taking the offensive. The first
devices were very crude, for little was known concerning the
physical properties of such clouds. Consequently, research
was necessary along chemical lines to improve the smoke-pro-
ducing substances themselves and also along mechanical lines to
perfect the devices in which the smoke is generated. This
paper concerns itself primarily with the chemical developments,
which are known as combustion smokes.
In general, we may classify smokes according to the method
of generation, as detonation smokes, cold reaction smokes, and
combustion smokes. The first class is represented by a bursting
shell containing oleum or sulfur trioxide, which creates a cloud
by the disintegration of the substance into a screen or mist made
up of a myriad of small particles. It takes its name from
the detonating charge of TNT or similar explosive used to
break it up. The well-known ammonium chloride smoke may
be called a cold reaction smoke, because it results from inter-
action of two gases without appreciable heat change. The com-
bustion smokes, on the other hand, involve exothermic reac-
tions, which disseminate solid material into the air in the form
of minute particles. This classification is of course artificial,
and some smokes cannot be defined by it. For instance, the
smoke produced by the detonation of phosphorus in a 3-in.
shell represents both the detonation and the combustion
types.
Combustion smokes are used to good advantage in grenades,
candles, trench mortar shell, and in navy smoke boxes, designed
to be thrown overboard. Other things being equal, the com-
bustion smoke has very decided advantages over the detonation
type. Both laboratory and field experiments have proved
that a screen secured by combustion persists for a longer time
and clings closer to the ground than a cloud realized by detona-
tion. In the case of artillery shell, however, the choice is lim-
ited to the detonating type, since a shell fired from a rifled gun
travels at enormous velocity and is apt to bury itself from 2 to
6 ft. in the ground. Under these conditions we must have an
explosive charge of sufficient power to blow shell fragments and
smoke producer from out the ground as desired. An attempt
to utilize a combustion smoke in the artillery shell would result
in a smothered combustion underground with no real screening
effect .
LABORATORY METHODS
Although field experiments are necessary to determine the
ultimate value of any substance or device as a smoke producer,
a fair determination of relative values may be made in the labora-
tory. The unit used in the laboratories of the Chemical Warfare
Service for comparing relative values of different smoke pro-
ducers is called the "total obscuring power," or, in abbreviated
form, the T.O.P. It is defined as the product of the volume of
smoke produced from a unit weight of the original mixture
and the density of the smoke. The density is the reciprocal
of the depth of smoke layer beyond which it is impossible to
distinguish clearly the filament of a 40-watt Mazda lamp. Since
the English units are employed for most field work, they are re-
tained for this purpose.
'Received February 15, 1921.
"■ Published by permission of the Chief of the Chemical Warfare Service
Brown Company, Berlin, N. H.
The chamber used for actual measurements at the American
University Experimental Station had a cubical content of 228
ft. In carrying out the determination, the mixture to be tested
was placed on the floor of the box and ignited or disintegrated
by a detonating charge. The smoke cloud was made of uni-
form density by means of an electric fan within the box. Read-
ings with a movable pilot lamp were taken over a series of short
intervals and the resulting data plotted. Such values as aver-
age of maximum T.O.P. could then be read from the curve
obtained.
In the interpretation of results, T.O.P. measurements must
be supplemented by a careful consideration of the type of device
to be used and by actual service tests. The conditions affecting
the persistency of a cloud in the open field are often very differ-
ent from those prevailing in a closed chamber. For instance,
it is still an open question whether phosphorus or sulfur trioxide
is the more efficient substance to employ in artillery smoke
shell, whereas laboratory measurements show the phosphorus
to have twice the T.O.P. of sulfur trioxide. The sulfuric an-
hydride cloud, however, is cooler and has less tendency to rise.
PRELIMINARY WORK
The theoretical basis of American research on combustion
smokes was the well-known fact that metals high in the electro-
motive series react with organic chlorides to form metallic chlo-
rides, which are sublimed by the heat evolved. A mixture of
carbon tetrachloride, zinc powder, zinc oxide, and kieselguhr
showed greatest promise and was chosen as a point of departure.
On ignition of this mixture, the exothermic reaction disseminates
zinc chloride in the air in the form of cloud of fine solid particles,
which have obscuring power. The zinc oxide and kieselguhr
prevent segregation of components and stiffen the mass. They
also serve to prolong the time of burning and to coo! the smoke.
\\
?
■
V
§
1
*
rs.
.•',■/
OT
tr,
yy {
Vi
*»'.
"I .
-••.-.
■vv
s a
y
'
/
'■■-
'a
' 3
Vr/>
AG
Of
3,~.
J>-
Mi
~ '
-if
/
I
/
'
:
\
\
k
"S
,v
L>-
S'~.
't/s-
' C.
xa
to &> jo ftt jd to ?o eo &> /oo //o /&> /jo rx> tso /so 170 ieo /so soo
Fig 1
The early mixtures of these four components, however, proved
imperfect. The amounts of zinc oxide and kieselguhr that pro-
vided for fairly efficient burning only made a thin pasty mass
Although the light gray smoke produced had good obscuring
power, the burning was very uneven and considerable residue-
was left.
THE IDEAL SMOKE MIXTURE
In order to follow a logical line of research, the following
desirable features of a combustion smoke mixture were listed :
1 — The materials must be cheap.
2 — The materials must be obtainable in large quantities.
3 — The mixture must be staple.
344
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
■, "7,
«
V
TV
.'
n
p<.
m
V£
H
1
IJ/7
r
hw
-
77
'PS
&A
ri *
£
I V
>■ '
:,
•JH
X.-/TL
//V
W
;;
*
•':
*
5
-
\
\
-.',.
r.f-j,
."
.-•■
'
:.- p.
V
or
-,1
J ■''-■
*>r
=sm
(Ti
*.-'
'JV
■>
2 3 *f 5 e
,,
S
■',.-
V?
M4
SV7AS
■■-*■-,; >£■
rcc
■■->
«
,■-
■nsja^
r-
vc/sr/S]
rr
M.?y, is y
72=
■s
---.--
1//K
rt ■-' '."'■
-
7
/■** //% If J
-0*
J
/
;•
/
'
'
|
.-■:
, VfA AGL TO P
v
.••'
■■
S/x-A
ws
OS
/y<7. Src vs
/*vf> ' ct we rwofisi/, •
r 2 3 f 5 e
'33/
o //
jS/rSi4M1if6
v.va
svxrt'.?f
ro ° C v/?v r5
AaWllt7£
ML-si/Ltrr
CO.VS7VI7
rs.
7A«f7»K
V*W><// G
'yon
\
-
AM. WS /■»
"«/
■
\
X
J-N
*** V.4<; r 7 OyP
^J -ftf.; ^ / ■*/**?£*. ■*■/: -
Fig. 2
Fig. 3
4 — The reaction rate must be subject to control, in order to
obtain a predetermined fast or slow burning substance.
5 — The smoke produced must have a high obscuring power.
6 — The smoke produced must be comparatively cool, in order
to slow down dissipation of the cloud.
The preliminary results suggested that five types of material
were necessary.
1 — A metal or metallic oxide capable of producing a readily
volatile chloride.
2 — An oxidizing agent.
3 — A cooling material.
4 — An absorbing substance.
5 — A chlorinating agent.
CHOICE OF METAL
The metals seriously considered were zinc, iron, and aluminium.
All substitutes for zinc powder proved inefficient or impractica-
ble. Reduced ircn mixtures gave a brown smoke which faded
to a white as the cloud drifted from the source. The obscuring
power did not compare with that obtained with the zinc combina-
tions. Moreover, reduced iron is not available in large quanti-
ties and at reasonable cost. Although not recommended for a
screen smoke, a reduced iron mixture was sometimes employed
as a signal smoke. Aluminium is more plentiful, but is costly.
The smoke produced by aluminium mixtures was white and of
fair obscuring power. The laboratory measurements gave no
higher T.O.P. values than those obtained with the best zinc
mixtures. On the field much less effective covering power was
realized on account of the high heat of reaction, which caused
the clouds to rise too rapidly. As the standard smoke mixture
was improved from time to time, aluminium and iron were
tried again but never with success.
SELECTION OF OXIDIZING AGENT
Since white smokes have always proved more effective as
screens, one of the criticisms of the first mixtures concerned
their color. Although perchlorates and nitrates were tested
to neutralize the carbon gray in the original components, sodium
chlorate was finally selected for economic as well as chemical
reasons. After a series of box and field experiments, a mixture
of the following composition was selected:
Parts
Carbon tetrachloride 35.0
Zinc powder 40.0
Zinc oxide 6.4
Sodium chlorate 9.0
Kieselguhr 9.0
Results with this mixture suggested the need of changing the
cooling and absorbent ingredients. The smoke produced is
white and has good obscuring power. In consequence of the
high heat of reaction, however, the cloud formed is hot and rises
rapidly. Therefore much of the theoretical T.O.P. is lost when
burned in the open. Moreover, it is very difficult to control
the time of burning due to arching over of the residues left.
CHANGE IN COOLING AGENTS
In order to cool the smoke, zinc oxide was replaced by am-
monium chloride, which absorbs considerable heat by its volatil-
ization and partial dissociation. The addition of ten parts of
chloride caused a cooler cloud and increased the time of burning.
The T.O.P. was correspondingly increased by the volatilized
ammonium chloride. The modified mixture is represented by
the following formula:
Parts
Carbon tetrachloride 41.4
Zinc 3.". 4
Sodium chlorate 9.ry
Ammonium chloride 10.0
Kieselguhr 3.7
One pound of this mixture packed in a can .3 in. in diameter
burned in 2 min. The T.O.P. was from 1200 to 1700, while
white phosphorus burned under the same conditions gave a
value ranging from 4000 to 5000. Unsuccessful attempts were
made to increase the amount of ammonium chloride.
REGULATION OF TIME OF BURNING
The substitution of ammonium chloride for zinc oxide did
not eliminate the difficulty experienced in control of time of
burning. An extensive investigation carried out with large
quantities of the mixtures showed that the factors which most
influenced the time of burning were mesh of chlorate crystals,
percentage of ammonium chloride present, and the type of ab-
sorbent used. The finer the chlorate used, the more rapid
was the burning. The curve (Fig. 1) showing the time of burn-
ing plotted against the mesh of the chlorate flattens somewhat
with crystals above 40 mesh. Inasmuch as the change of rate
between 40 and 60 mesh is less noticeable, this mesh was usually
specified. Mixtures were often calibrated by changing the
amount of chloride in the formula.
The use of kieselguhr as an absorbent proved to be the source
of many irregularities. During burning it had a tendency to
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY :;45
arch over the combustion surface, causing successive periods sium nitrate functions as satisfactorily but possesses two disad-
of slow and fast burning. Moreover, surveillance tests in the vantages: it is not so stable under surveillance tests, and its
laboratory showed a reaction between carbon tetrachloride and reaction liberates gaseous products, often with explosive vio-
z.nc This deterioration was due to the moisture from the lence and the consequent rupture of the entire container,
kieselguhr, and ammonium chloride acted as a further catalyzer.
A precipitated magnesium carbonate was fully as efficient as conclusion
kieselguhr. Its substitution for kieselguhr provided for sta- The B' M- mixturt' with certain modifications in proportions
bility under conditions encountered in transport. Its gradual has beetl used in grenades, smoke candles, Stokes bombs, Livens
decomposition by heat made for smoother burning. Mag- Projectiles, smoke boxes, and various signal devices. It pos-
nesium carbonate was employed in practically all the zinc chloride sesses greater possibilities than phosphorus, and it is possible
smoke mixtures recommended. that it might have displaced phosphorus as the most important
chlorinating agents Sm°ke produccr' if the war had continued. Several suggestions
. for its use in peace time have been made, but no active develop-
The advantages of substituting a solid chlorinating agent ment is under way.
for carbon tetrachloride were realized from the first. Silicon
and titanium tetrachlorides were found to offer no added ad-
vantage over carbon tetrachloride. Mixtures containing the Dr. Martin Fischer Tells of European Trip
silicon compound were peculiarly sensitive, a single drop of water ^. ,, .. „. ,
being sufficient to start the reaction. nf r^Sl? T I prof^Jor of Physiology at the University
ot Cincinnati, who returned from Europe early in March, gave
b. m. smoke mixture a highly interesting account of his impressions of conditions in
T. „ fl , . . .... . „ , , t,he countries which he visited, at a meeting of the Cincinnati
Ihe final mixture was called the B. M. smoke mixture, be- Section of the American Chemical SociETv, held March 9, in
cause it was perfected while the American University Experi- tne Chemical Lecture Hall of the University of Cincinnati,
mental Station was still under the Bureau of Mines. The pro- T Dr- Fischer had given a series of lectures on colloids at the
portions in the following representative formula were varied lTmversity of Amsterdam, by invitation, and in addition to his
somewhat, depending on the method and form of device in which ^any" H°"and he had a'S° visited parts of England and Ger"
He was impressed with the apparent absence of feeling re-
Parts garding the late war in both the neutral and warring countries.
zinc 3.3.4 Tlle People seem anxious to forget all about the war and turn
Carbon tetrachloride 4l.ii tneir attention to the problems of reconstruction. There is a
Sodium chlorate 9.3 marked feeling of friendliness toward the scientific men of
Ammonium chloride VI foreign countries, and American men of science are particularly
Magnesium carbonate S3 popular. They are known abroad by their works.
A change in the general attitude of people toward things of ma-
INFLUENCE OF WEATHER Conditions terial advantage was observed by Dr. Fischer. People belong-
ing to the educated group, including teachers physicians, and
T.O.P. measurements in the chamber revealed the fact that scientists in general, seem to have been hit hardest by the change
weather conditions have a marked influence on the efficiency of things since pre-war days.
of the B. M. mixture. Increasing the moisture content of the ln Holland there are many distinguished scientists who art-
air raises the T.O.P., while an increase of temperature reduces sometimes classified by Americans as natives of other countries.
,. TnD „,. ... . , because of the fact that their articles arc published in English,
the T.O.P. When both moisture content and temperature French, or German journals and also because they write their
are raised in proportions that may be ordinarily expected in scientific papers in French, English, or German rather than in
the field, the result is an increased T.O.P. value. Figs. 2, 3, and Dutch.
4 show the rate of change in T.O.P. under different conditions. Dr- Fischer ascribed the splendid development of the I lutch
In this work the T.O.P. values were taken at 7-min. intervals. PfPje to the fact that there is keen competition among them
»,, .. , • , ,, ^, • * ^ t, at all times. A nation of seven million people confined to a coni-
The curves give the changes in both the maximum T.O.P. and parativeIy small area can make as heavy an irnpress upon the
the average T.O.P. obtained over this period. The average world in general as the Dutch have made, only because o I 'keen
T.O.P. is easily calculated by integration between the fixed competition.
limits of the area under the curve. Dr. Fischer concluded his address with a plea for greater work
It is thus evident that the most efficient smoke is produced and efTort on the part of the American chemist in helping to con-
, ,-„,,. ... , , , serve our natural resources and in developing our man power
from the B. M. mixture on a cold, damp day, whereas the poorest through the accomplishment of difficult tasks. He called at-
cloud results on a warm, dry day. These observations in the tention to the laws of biology which underlie all human progress,
T.O.P. chamber were confirmed by field experiments. The and cited examples of the rise and fall of nations due to the work-
increase of obscuring power with humidity is apparently due to ings of tl}ese laws- , " we are to develop our brain power we must
, . ... ,, -j - , use our brains, and it we want to keep alive the strong men ol
absorption of water by the hygroscopic zinc chloride particles. our nation we raust give them difficult and extensive work to do.
Measurements of the efficiency of phosphorus smokes showed
similar effects of humidity and temperature.
method of ignition Lectures at the College of the City of New York
The B. M. smoke mixture may be ignited in several ways, Announcement is made of a series of lectures to be held mi
but the most simple and fool-proof consists in using a train of der the auspices of the City College Chemical Society. The
preheating agents. The operation and construction of the ^ltmtes' to be Sivfn at 4 :i0 p- "■ '<» ** Doremus Lecture
... . , . r , . Iheatre, are as follows:
smoke device in question usually determine the sequence ot this
train. Generally a delay is convenient between the ignition Mr. Ellwood Hendrick, "Beyond the Laboratory," March 7.
and the burst of smoke, in order that the operator may get away. Dr' Marston Taylor Bocert, Professor ot Chemistry, Columbia tlni-
~ . . . . . versity, "The Service of the Synthetic Dye Industry to the Stale,
The ignition may be caused by the firing of a cap, which starts March 15
the time fuse, which in turn ignites a capsule containing a mix- Dr. Charles h Macdowell, President, Armour Chemical Co., "The
ture of potassium permanganate and reduced iron. The tern- Trial of the Chemist in the Packing Industry," March 23.
perature reached by the oxidation of the reduced iron is sum- Mr- Es»bst M Sjmmbs, Hercules Powder Co., "Explosives in Wa. and
.... • t-» -ht Peace, April 8.
cient to melt through the capsule and ignite the main B. M. Dr Danik,. d. Jackson, Professor of Chemical engineering. Columbia
mixture below. A starting mixture of reduced iron and potas- University, "Chemical Evolution," April 11.
346
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
RESEARCH PROBLEMS IN COLLOID CHEMISTRY1
(Concluded)
GELATINOUS PRECIPITATES
(153) WHAT CONSTITUTES A GELATINOUS PRECIPITATE? —
No one has any difficulty in recognizing a gelatinous precipitate,
but we are not at all clear as to what gives an inorganic gelat-
inous precipitate these properties. In the case of gelatinous
ferric oxide and silica, there is every reason to suppose that none
of the water is combined to form a definite chem'cal compound.
It may be that the rouge or the sand is precipitated as a super-
cooled liquid which is in itself viscous and gelatinous. If one
objects to the distinctly arbitrary assumption that we have
viscous liquids and water in the gelatinous precipitates, one
alternative is to assume that solid particles and water behave
like a gelatinous precipitate when the solid particles are suffi-
ciently fine and provided they adsorb water sufficiently strongly.
This is apparently what Zsigmondy2 does; but he does not show
why this should be so. Another alternative is to assume that
the adsorbed ion makes the surface viscous. In the case of an
emulsion this does happen. We may have drops of oil coated
with a soap film and these may coalesce sufficiently to form a
gelatinous mass. This is not helpful because the soap is gelat-
inous in itself. It is possible, however, that there is an inter-
mediate stage between that of peptization and that of irreversible
coagulation, where there may be a surface which is gelatinous
in its properties. While something of this sort may happen,
it has not been shown to take place. The real test would be to
make a gelatinous gold precipitate without any protecting col-
loid. Until something of this sort has been done, or until we
know why it cannot be done3 we must admit that we know very
little in regard to what constitutes a gelatinous precipitate.
A possible explanation with ferric oxide is that we have grains
of oxide with a gelatinous film of instable ferric hydroxide ad-
sorbed on the surface and stabilized thereby. This would not
be inconsistent with the vapor pressure data because those
show only that ferric hydroxide does not exist in mass under the
conditions of the experiment. We know that sand can be con-
verted into gelatinous silicic acid if ground sufficiently fine and
that clay particles have a gelatinous coating. The difficulty is
that this explanation does not help us in the case of barium sulfate,
and either we must explain all gelatinous precipitates in the same
way or we must divide them into groups and be able to dis-
tinguish between the groups.
(154) CRITICAL COMPARISON OF THE PROPERTIES OF STANNIC
AND METASTANNIC ACIDS, TUNGSTIC AND METATUNGSTIC ACIDS,
ETC. — There is apparently no place where one can find a clear
statement of the exact difference between stannic and meta-
stannic acids, for instance. An exhaustive monograph on the
gelatinous oxides is needed very much.
(155) CHARACTERISTICS OF PRECIPITATED SULFUR — Oden*
found that the physical properties of sulfur precipitated from
colloidal solution varied very markedly with the electrolyte used
for precipitation. It came down as a hard precipitate with
potassium salts, fine-grained with copper sulfate, plastic with
barium salts, fluid with hydrochloric acid, and slimy with other
salts. This work should be repeated and the reasons for these
differences formulated.
(156) WHAT IS THE DIFFERENCE BETWEEN A FILM OR FILA-
MENT COMPOSED OF A VISCOUS LIQUID AND ONE COMPOSED OF
1 Received November 5, 1920.
2 "Kolloidchemie," 1912, 149.
8 It has been suggested that gold does not adsorb water
ongly to give a gelatinous precipitate.
' "Der kolloide Schwefel." 1912, 134, 157.
By Wilder D. Bancroft
Cornell University, Ithaca, N. Y.
partially coalesced viscous DROPS' — A film composed of
partially coalesced viscous drops will have holes in it, while a
liquid film will not. We need a discussion of the differences in
properties, if any, of the two types of films, together with methods
of distinguishing between them. The collodion ultrafilters
are evidently sieves and a copper ferroeyanide membrane is
probably a liquid film,1 and we know that some of the properties
of a copper ferroeyanide membrane can be duplicated with a
liquid film. What is a rubber membrane and why?
JELLIES
(i57) JELLIES IN NONAQUEOUS SOLVENTS — The formation of
jellies in organic liquids should be studied because at present
practically all our quantitative data are on aqueous jellies.
Excellent jellies can be formed with soap in mineral oils. Pyr-
oxylin solutions evaporate to jellies. Baskerville has patented
the addition of 90 cc. alcohol to 10 cc. saturated calcium acetate
solution, this procedure giving him an excellent "solid" alcohol.
(158) THE THEORY OF THE FORMATION OF HYDROUS OXIDE
JELLIES AND THE EFFECT OF CERTAIN SALTS ON THEIR FORMATION
and permanency — There is no satisfactory theory of jellies.
The most familiar hydrous oxide jellies are prepared by adding
alkali to a salt until the precipitate formed is dissolved and al-
lowing the solution to stand for a time. It has been found2
that the presence of an excess of alkali and of certain salts has
a deleterious effect on the formation and stability of jellies, while
the presence of other salts seems to favor the formation. It is
suggested that a jelly results when a highly hydrous oxide ag-
glomerates from a colloidal solution. It may be possible to
trace the effect of hydroxyl-ion concentration and the influence
of certain salts to the varying agglomerating and stabilizing
action of various ions on the colloidal oxide.3 Another form
of the same problem which calls for more systematic study is
the production of jellies by dialyzing4 out the peptizing agent.
(159) LIQUEFACTION OF A SODIUM STEARATE JELLY — Since
a one per cent sodium stearate jelly must owe its rigidity to its
structure, it ought to be possible to liquefy it by picking at it
until it was disintegrated. Similar experiments should be tried
with all sorts of jellies.
(160) theory OF swelling OF jellies — We have no satis-
factory theory of the swelling of jellies. For instance, Arisz6
finds that at 20 ° a 0.5 per cent gelatin jelly disintegrates com-
pletely in water, a 10 per cent jelly goes to a 2 per cent jelly in
4 days, a 20 per cent jelly to a 6 per cent one, a 50 per cent jelly
to a 16 per cent one, and an 80 per cent jelly to a 20 per cent one.
Although the 20 per cent jelly will take up enough water so that
its composition is equal to that of a 10 per cent jelly, the two do
not then behave alike. The jelly which has swelled until its
composition is 10 per cent will not then take up so much water
in a reasonable time as a jelly which is made up at 10 per cent.
This shows that there is probably a difference in structure and
in the way in which the water is held, although Sheppard con-
siders that these phenomena are due to changes in the shape
of the mass and to a consequent unequal distribution of water
Until we have some satisfactory theory to account for this
difference in behavior, all experiments on the swelling of gelatin
' This is disputed by Tinker, Proc. Roy. See. 92A (1916), 357: 93A
(1917), 268.
•- Cf. Bunce and Finch, J. Phys. Chem., 17 (1913). 769; 18 (1914), 26:
Nagel, Ibid., 19 (1916), 331.
' Weiser, /. Phys. Chem., 24 (1920), 277.
'Holmes and Arnold. J. Am. Chem. Soc, 40 (1918). 1014; Holmes and
Fall, IM<f., 41 (1919), 763.
« Kolloidehem. Beihefle, 1 (1915), 1.
jfficiently
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
347
jellies in solutions of salts, acids, and lusts are likely to be mis-
leading, because one does not know to what extent the electro-
lytes are causing a change in structure. That a change in struc-
ture takes place even with water is shown by the experiments of
Arisz on intermittent soaking. If two identical gelatin jellies
are placed in water and one is kept in the water 6 days, while
the other is in the water only on the first, fifth, and sixth days,
the amount of swelling will be the same in the two cases, within
the limits of experimental error. While the partially swollen
jelly is out of the water, some change in structure takes place,
such that it takes up water so much more rapidly than the other
that the total swelling is the same in the two cases, although
one jelly was soaked twice as long: as the other.
(161) WILL DRIED GELATIN JELLIES BECOME IDENTICAL ON-
LONG standing?— If dried gelatin is placed in cold water it
swells a good deal and may take up ten times its weight of water;
but there are no experiments to show that it would ever go up,
say, to an 8 per cent jelly. On the other hand, it is possible to
start with an 8 per cent jelly and dry it to a 96 per cent jelly,
after which it will take up water rapidly to an 8 per cent jelly.
This means that the structure of the gelatin plays an important
part in the rate of swelling. This is confirmed by some un-
published preliminary results by Mr. Cartledge. Gelatin
jellies were made up containing 8, 16, 24, and 32 per cent of
gelatin. These were all dried at room temperature to about
06 per cent concentration. When water was added, each
swelled rapidly to the original concentration and then took
up water slowly. If these results are accurate, it means that
the four 96 per cent jellies were all different, and that the
8 per cent gelatin did not become like the 16 per cent, -'4 per
cent, or 32 per cent gelatin while being dried. If the different
96 per cent jellies were held long enough at some temperature
below the point of obvious liquefaction, they should become
identical. This ought to be tested.
(162) SYNERESis of jellies — In the case of some inorganic
jellies, the presence of certain ions seems to be necessary either
to ensure sufficiently slow precipitation or to prevent contrac-
tion. To get chromic oxide jellies,1 acetate or sulfate must be
present. With cupric oxide jellies2 a small amount of sulfate
is necessary. The theory of this should be worked out with
special application to starch and gluten jellies because of its
probable importance in connection with stale bread.8
(163) STRUCTURE OF COPPER FERROCYANIDE JELLIES — It is
probable that it would be possible to make a copper ferrocyanide
jelly. If that were done in a sugar solution and the jelly placed
in water, the jelly might be expected to swell and disintegrate
if the sugar solution were internal phase.4 If such a jelly were
allowed to stand, it would be interesting to know whether syner-
esis would cause the exudation of pure water or of a sugar solution.
(164) CRYSTALLIZATION IN GELATIN JELLIES — If gelatin jellies
of different concentrations were made up with saturated solu-
tions of suitable salts, and were then dried, it ought to be possible
to tell something about the structure of the gelatin jellies from
the resulting structure of the crystals. If the jellies have a
sponge structure, the salt might reasonably be expected to crystal-
lize in a more or less coherent, feathery mass. If the jellies
have a honeycomb structure, one would expect to get granular
masses. It would be essential to take salts which tended to
crystallize in branching needles. If the gelatin could be hardened
with tannin or formaldehyde, the results might be even more
instructive.
(165) study of rhythmic banding— Holmes6 has shown that
colloidal gold gives three colored bands — red, purple, and blue —
■ Bunce and Finch, J. Phys. Chcm., 17 (1913), 269; Nagel, Ibid., 19
I 1915), 331.
3 Finch, Ibid., 18 (1914), 26.
' Wo. Ostwald, Z. Kolloidchem., 26 (1919), 37.
• Cf. Tinker, Proc. Roy. Soc, 92A (1917), 268.
« J. Am. Chcm Soc., 40 (1918), 1187.
before repeating. This lias not been considered in any theory
of rhythmic banding and yet it seems to offer an important clue.
(166) REPETITION OF VON SCHROEDER'S EXPERIMENTS — In
Ostwald's laboratory von Schroeder1 claimed to have found
that a gelatin jelly which is in equilibrium with saturated water
vapor will take up more water when placed in liquid water.
Wolff and Buchner2 claim that von Schroeder's results were
due to experimental er or, while Washburn3 apparently believes
that they were right, but that the effect is due to gravity. Under
the circumstances the experiments ought to be repeated. It
might be a good plan to do similar experiments with rubber and
an organic liquid.
(167) EQUILIBRIUM PRESSURES FOR RUBBER, GELATIN, ETC.,
WHEN THE AMOUNT OF LIQUID IS VERY SMALL — Posnjak* has
made some experiments on the amount of water with which
gelatin is in equilibrium under different pressures and he has
also studied the corresponding behavior of raw Para rubber in
different organic liquids. The most concentrated solutions
which he studied contained 0.92 g. water per gram of gelatin
and 2.09 g. benzene per gram of rubber, and his highest pressure
was about 5 atmospheres. These experiments should be ex-
tended to cover the more interesting range of the initial swelling.
(16S) clouding OF a silica GEL— When a silica gel dries,
it clouds at the center owing to the appearance of air bubbles,
the water apparently evaporating from the center instead of
from the outside. Zsigmondy* suggests that there is a tendency
for the water to rise to the surface of the capillaries and that
the dissolved air comes out at the center. The phenomenon
should be duplicated and studied, using a capillary tube closed
at one end.
(169) hardening of gelatin by chromic sulfate — The
experiments of Lumiere and Seyewetz5 indicate that gelatin
decomposes chromic sulfate, adsorbing the chromic oxide very
strongly and the sulfuric acid less strongly. This simultaneous
adsorption of a free base and a free acid is an unexpected phe-
nomenon and calls for careful study.
Ci7o) STUDY OF calcium SUCRATES — In view of the way in
which sugar solutions promote the formation of colloidal solu-
tions of the heavy metal hydroxides, the question arises whether
there are any calcium sucrates. Cameron and Patten7 did not
obtain any as solid phases in their work. The work on the
calcium sucrates8 should be repeated, and a study should also
be made of the conditions under which solutions set to a jelly.
(171) ACTION OF LIME ON OPTICAL ROTATION OF SUGAR
It is stated9 that the addition of lime water to a sugar solution
diminishes the rotary power of the solution though according
to no apparent law. Acetic acid restores the rotary power.
This should be discussed with reference to the existence or non-
existence of the calcium sucrates. No. 170.'
(172) chloral hydrate and camphor — According to Brown,10
a rise of temperature is observed if chloral hydrate and camphor
are rubbed together in a mortar, and a sirup is obtained which
is neutral to test papers and does not give a precipitate with
silver nitrate. On treatment with distilled water, it hardens to
a translucent white solid. The chloral hydrate can be dissolved,
leaving the camphor in crystalline grains. This should be in-
vestigated for itself and also for its bearing on the formation of
celluloid.
' Z. physik. Chem., 46 (1903), 109.
« Ibid., 89 (1915), 271.
« J. A m. Ceram. Soc, 1 (1918), 25. .
« Kolloidchem. Beihefle, 3 (1912), 417.
» "Kolloidchcmie," 1912, 160.
8 Bancroft, J. Phys. Chcm., 24 (1920), 25.
' /. Phys. Chcm., IS (19! 1), 67.
» Horsin-Deon. J. Chem. Sot , 28 (1872), 810; 26 (1873), 612; Pusclicr,
Ibid., 26 (1873), 306; Carles, Ibid., 27 (1874), 422; Latour. Ibid., 27 (1874),
423; l.oiseau, Ibid , 46 (1884), 419; Petit, Ibid., 64, I (1893). 451; Svedbcrg,
"Die Herstellung kolloider Losungen," 1909, 305
» Desor, J. Chem. Soc, 38 (1880). 834.
" J Chem Soc, 27 (1874 !3
348
THE JOURNAL OF INDUSTRIAL AXD ENGINEERING CHEMISTRY Vol. 13, No. 4
EMULSIONS
(173) adsorption OF gelatin by oil — Winkelblech1 has
shown that gelatin concentrates at the dineric interface when
organic liquids are shaken with water. Holmes and Child2
find that with kerosene-in-water emulsions, with gelatin as
emulsifying agent, there is apparently no adsorption of gelatin
at the oil-water interface.
Had there been any concentration by adsorption around the
oil droplets, the liquid below the cream should have been poorer
in gelatin than the original solution. To test this we withdrew
5 cc. from the lower layer and analyzed for nitrogen by the
Kjeldahl method. Even with the most dilute gelatins, analysis
showed a loss of only 0.008 g. which meant nothing since in
making emulsions we did not attempt accuracy beyond one
part in a thousand.
The discrepancy between the two sets of measurements should
be cleared up.
(174) EFFECT OF CONCENTRATION ON TYPE OF EMULSION —
Bhatnagar3 has used a conductivity method as a means of de-
termining whether an emulsion is oil-in-water or water-in-oil.
He seems to have found that with potassium oleate as emulsifying
agent, the emulsion changed from the oil-in-water type to water-
in-oil when the oil concentration became high enough. This
contradicts the most careful measurements that have been made
hitherto and raises the question of the accuracy of Bhatnagar 's
measurements. He did not work with a constant amount of
potassium oleate as he should have done. Instead, he used a
constant amount of potassium hydroxide and a varying amount
of oleic acid, the concentration of oleic acid in the oil being con-
stant. "The bottles were shaken for a constant time after each
addition in a powerful mechanical shaker, and the total time
of shaking was kept constant to ensure identical conditions."
Working in this way it would be practically impossible to get
the high concentrations of oil in water,4 and consequently the
most that his experiments could show would be the limiting
efficiency of the shaker. This seems to have been the case for
he says:
It is found that the water-in-oil type with kerosene oil is very
unstable. The emulsion shows no conductivity for a minute
or two, and then it gradually rises until it indicates its previous
conductivity. The drops of water, as they de-emulsify, are
visible, and are seen constantly falling to the bottom, until
the emulsion undergoes complete disintegration.
In addition to these sources of error, there is a possibility of a
special error in the case of olive oil. Olive oil is an indefinite
substance and may contain varying amounts of stearin, presum-
ably in colloidal solution. When working with small amounts of
soap and large amounts of olive oil, it is possible that a reversal
of type may have actually occurred because of the presence of
an emulsifying agent in the olive oil. It is evidently necessary
that these experiments should be repeated making use of the
best technique.
(175) EMULSIFYING AGENTS FORMING COLLOIDAL SOLUTIONS
in both liquids — In many cases emulsifying agents are used
technically which form colloidal solutions both in the oil phase
and the water phase, though more readily in one than in the
other. It is appreciably easier to form emulsions quickly under
these conditions than when the emulsifying agent forms a col-
loidal solution in only one of the liquids. The theory of this
has not been worked out. It is quite possible that in these
cases the amount of emulsifying agent may have to be larger
than in the normal cases. For instance, Winkelblech5 was
not able to coagulate gelatin in water by shaking with ether,
while Miller and McPherson6 found that arsenious sulfide dis-
' Z. angew. Chem., 19 (1906), 1953.
2 J. Am. Chcm. Soc., 42 (1920), 2049.
> J. Chem. Soc., 117 (1920). 544.
1 Briggs, J. Phys. Chem., 24 (1920), 120.
' Z. angew. Chcm., 18 (1906), 1953.
• J. Phys. Chem., 12 (1908), 706.
tributes itself between the ether and the water layer, though form-
ing a colloidal solution in both.
(176) mayonnaise — Briggs1 has shown that intermittent
shaking is much more effective than continuous shaking in pro-
ducing emulsions. These experiments throw some light on the
making of mayonnaise. Since mayonnaise is essentially an
emulsion of oil in water (vinegar) with egg as the emulsifying
agent, it ought to behave like any other emulsion, and so it does
for the experts in the Departments of Home Economics. They
can add the ingredients in any order, all at once or in separate
portions, hot or cold, and the mayonnaise always comes. On
the other hand, these same experts do not train their pupils so
that these latter can make mayonnaise every time. It seems
certain that the experts do something or other unconsciously
which they consequently do not tell to their pupils. Probably
the expert is so sure of the result that she works leisurely without
being hurried or flurried, and is practically doing intermittent
stirring. The person who is not an expert and who is uncertain
of the outcome probably goes at her task so vigorously as to de-
feat her object in many cases. While this explanation has not
been tested, one expert said that she had found that if the ma-
terials were beaten well together, and then allowed to stand for
a moment or two, a couple of swishes would make the mayon-
naise. I have been told that Bearnaise sauce is an emulsion of
melted butter in tarragon vinegar without any egg, and that it
is very easy to make. If this is so, tarragon vinegar must con-
tain a good deal more of some emulsifying material, probably
a tannin, than ordinary vinegar. A study should be made
of the different recipes for making mayonnaise and the results
accounted for.
(177) saponification of fats with lime — When caustic
soda is used to saponify fats, it is necessary to use at least the
theoretical amount if practically complete hydrolysis is to be
obtained. When working with lime in an autoclave at 12
atmospheres pressure (corresponding to a temperature of 195°),
it is possible to cut the amount of lime down to about one-
tenth of that necessary to neutralize all the acid in the fat,
0.1 per cent of lime causing practically complete hydrolysis-
It seems probable that the real hydrolyzing agent is water,
and that the lime is important because the calcium soap which
is formed causes the water to emulsify in the fat instead of the
fat in the oil. This is the more probable because magnesia
and zinc oxide act like lime. There is no direct experimental
proof, however, of this explanation of the action of lime.
(178) study OF bubbles — While a great deal of work has
been done on soap bubbles, it has been done without taking
into account the fact that soap forms a colloidal solution with
water and that the hydrolysis of the soap will change with the
varying thickness of the film. It is practically certain that a
study of the existing data from the viewpoint of the colloid
chemist would lead to the solution of some of the problems
involved.
(179) colloidal gas bubbles — It is generally believed that
natural mineral waters lose their gas more slowly than arti-
ficially charged waters. If this is true, it must be because of
colloidal material in the natural waters which keeps the bubbles
very small.3 This should be duplicated experimentally.
(180) BUBBLE FLOTATION OF CALCIUM CARBONATE, COLLOIDAL
gold, and WHITE lead — We know that calcium carbonate
goes into the oil-water interface,* while calcium sulfate does not.
We also know that colloidal gold5 goes into the oil-water interface.
■ J. Phys. Chem.. 24 (1920). 120.
■ Thorpe, "Dictionary of Applied Chemistry," 4 (1913), 639.
" Wolfgang Ostwald, Z. Kolloidchem., 25 (1919), 41.
« Hofmann. Z. physik. Chem., 83 (1913), 385; Bancroft, J. Pi:
19 (1915), 286.
» Reinders, Z. Kolloidehcm., 13 (1915), 325.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
349
More to complete the record than anything else, it should be
shown that both these substances can be floated up by the bubble
method of ore flotation. The calcium carbonate experiment is
important in its bearing on the behavior of calcareous ores.
Since white lead1 is wetted preferentially by linseed oil and
zinc oxide2 by water, a study should be made of bubble separa-
tion of these two, paying especial attention to the effect of the
relative sizes of grain.
(181) bubble flotation OF sewage— Biltz and Krohnke3
tried to remove the colloidal matter from sewage by shaking
with organic liquids, but were not successful because only about
30 per cent extraction was obtained. This is really an applica-
tion of the Elmore bulk oil method. Since this has been super-
seded in the mining world by bubble flotation, it seems de-
sirable to try bubble flotation with sewage to see whether an
improvement in yield can be obtained and, if so, how great a
one. A point which Biltz and Krohnke did not know is that
addition of any salt which decreases the stability of the colloidal
solution will increase the amount of extraction.4 The process
might be applicable to milk wastes.
(182) stabilization of foam — To get a foam the only es-
sential is that there shall be a distinct surface film, in other
words, that the concentration in the surface layer shall differ
perceptibly from that in the mass of the liquid. All true solu-
tions will, therefore, foam if there is a marked change of surface
tension with change of concentration, regardless of whether the
surface tension increases or decreases. All colloidal solutions
will foam if the colloid concentrates in the interface or if it is
driven away from the interface. To get a fairly permanent foam
the surface film must either be sufficiently viscous in itself or
must be stabilized in some way. This can be done by intro-
ducing a solid powder into the interface.
Solutions of aqueous alcohol, acetic acid, sodium chloride
and sulfuric acid all foam when shaken; but the foam is instable.
Soap solutions foam when shaken and the foam is, or may be,
quite stable owing to the viscosity of the soap film. With
saponin the surface film is even more stable. If we add to
aqueous alcohol some substance like lycopodium powder which
goes into the interface, we get a stabilized foam. We can do
the same thing with aqueous acetic acid by adding lampblack.
The presence of enough of a finely divided solid in the interface
will make the film so viscous that the foam will be quite stable.
Grease will help stabilize a foam in some cases and it has been
claimed erroneously that the foaming of sulfuric acid solutions
is due to grease.6
In 1857, Gladstone6 pointed out that aqueous solutions of
organic substances are apt to froth, and he cited beer as a then
familiar instance. He did not realize, however, that it was the
colloidal matter in the beer which caused the frothing. It
has been shown by Zeidler and Nauck7 that removing the al-
bumoses from beer destroys the foaming. Gladstone showed,
however, that the dissolved air was not essential to the frothing.
If this were pumped out in a vacuum, the liquid frothed freely
when shaken with air. Gladstone states that aqueous solutions
of the acetates of iron, copper, lead, and other metals froth
readily, especially the ferric acetate solution. As we know,
this is the one which hydrolyzes most readily, and the frothing
is due undoubtedly to the combined effect of the acetic acid
and the hydrous ferric oxide.
There has been no systematic study as yet of the stabiliza-
tion of foam. The armor-plated bubbles of the Minerals
Separation Company's process consist of air bubbles, with an
1 Holley, "Lead and Zinc Pigments," 1909, 71.
» Cruickshank Smith, "The Manufacture of Paint," 1918, 92, 103.
• Z. angew. Chem., 20 (1907), 883.
« Briggs, J. Phys. Chem., 19 (1915), 210.
' Lang, Bo-., 18 (1885), 1391.
• Phil. Mae., [41 14 (1857), 314.
' J. Soc. Chem. Ind., 20 (1909), 260.
oil film round them, in water and stabilized by adsorbed ore
particles. When these bubbles rise to the top, they form a very
stable froth. The Foamite process for fighting fire consists in
the production of a froth of carbon dioxide bubbles made stable
by a film of hydrous alumina and another substance which is
reported to be licorice or something of that sort. The technical
development of the subject has gone well ahead of the scientific
side, and it is desirable to restore the balance.
(183) destruction of foams and emulsions — There has
been a good deal of scientific work done recently on the stabiliza-
tion of emulsions and foams; but the destruction of emulsions
and foams may be quite as important technically. A number
of methods are known already and the oil companies probably
have a large amount of unpublished information, especially on
the cracking of emulsions; but no systematic study of the sub-
ject has been made. There is no certainty that better methods
may not be devised than any we now have, and there is no way
at present of telling in advance which of the known methods is
the best in any particular case.
NONAQUEOUS COLLOIDS
(184) study OF nonaqueous COLLOIDS — Most of the re-
search work on colloids has been concerned with aqueous sols
and gels. This work should be paralleled by studies of the be-
havior of colloidal solutions in alcohols, esters, hydrocarbons,
chloroform, acetone, ether, carbon tetrachloride, fats, waxes,
melted sulfur, camphor, melted salts, etc. While peptization
or stabilization by ions is relatively unimportant in most of the
cases, it may play an important part with melted salts, and may
be a minor factor with certain other nonaqueous solvents. The
study of the other types of sols is important in itself and will
probably throw light on the behavior of some of the aqueous sols.
The chemistry of the cellulose esters is a fruitful field for re-
search in colloid chemistry. These substances are peptized
by a number of liquids (so-called solvents), and can then be
converted into jellies, films, filaments, etc.
(185) behavior of mixed colloids in nonaqueous solvents
■ — When a mixture of hydrous chromic oxide and hydrous ferric
oxide is treated with caustic soda solution, the mixture is pep-
tized, giving an apparently clear green sol in case the hydrous
chromic oxide is present in sufficient excess, the hydrous chromic
oxide peptizing the ferric oxide.1 When the hydrous ferric
oxide is in excess, there is no peptization at all and the sodium
hydroxide solution remains colorless because the hydrous ferric
oxide adsorbs the chromic oxide and keeps it from being peptized.
People believed that they had pure oxycellulose because the
product did not behave like cellulose, and yet the evidence is
very strong that nobody has ever prepared pure oxycellulose.2
It seems probable that there are nothing like the number of
cellulose nitrates which the literature revels in and that people
are dealing with mixtures of perhaps not over three cellulose
nitrates which are peptized very differently and have different
apparent properties depending on the relative amounts and on
the way in which they are adsorbed. Preliminary experiments,
made before the war by Mr. M. W. Bray, indicated that this
was the case.
(186) black phosphorus — The literature on black phosphorus
is very confused3 and the subject is not mentioned in Thorpe's
"Dictionary of Applied Chemistry." Apparently mercury, ar-
senic, etc., can form colloidal solutions in phosphorus, and it
would probably be interesting to study these.
fog
(187) dry fog — -Dense fogs have been noticed around London
when the humidity was only 50 to 80 per cent. Fraukland*
believes that this is due to films of oil from coal smoke coating
' Nagel, J. Phys. Chem., 19 (1915), 331.
"■ Bancroft, Ibid., 19 (1915), 159.
8 See Dammer, "Handbuch der anorganische
* Proc. Ray. Soc. 28 (1879), 238.
Chcmie," 2, I (1894), 95.
350
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
the drops of water and retarding the evaporation. While this
explanation is probably true, we do not know under what con-
ditions a fog of oil and water gives drops of water coated with
oil or drops of oil coated with water. From our experience with
emulsions, it seems that it should be possible to make water-in-
oil fogs and oil-in-water fogs; but this has never been studied.
If we consider the case solely as oil, water, and air, only one
type will be possible, just as only one type is possible in an emul-
sion with a given emulsifying agent. If we add a fourth com-
ponent, I see no reason why we may not get a reversal. In
view of the fact that lampblack enables us to emulsify water in
oil,1 a smoky atmosphere might well be conducive to the pro-
duction of dry fogs.
(188) synthetic thunder storms — Simpson2 has developed
a theory of thunder storms which seems to be the best available,
though it is by no means accepted universally. He assumes the
existence in the center of the storm of a rapidly ascending cur-
rent of air which spreads out and loses speed above a certain
height. Large rain drops will fall through this air current until
they reach a point where they are broken into smaller drops, and
are then carried to the upper and colder levels where they grow
again and repeat the cycle. When the drops break up they be-
come charged positively, while the negative ions are carried
up more rapidly by the air and are finally caught by cloud par-
ticles at some higher level. Simpson satisfied himself that the
electricity generated by the breaking up of the falling drops might
easily account for the gradient of 30,000 volts per centimeter
necessary for lightning. If we could make a synthetic thunder
storm in the laboratory by means of a blower, it would enable
us to test Simpson's theory in a way that cannot be done now,
and it would probably be of great interest in other meteoro-
logical problems. If we change from flashes of lightning a
mile or so long to flashes an inch long, the other dimensions of the
thunder storm would be decreased considerably, though we do
not know to what extent. It is a problem in mathematical
physics to determine approximately the minimum theoretical
size of a thunder storm.
(189) THEORY OF SMOKE PRECIPITATION WITH ALTERNATING
current — Lodge3 tried the effect of electrification on a mass
of smoke. With potentials of one hundred volts very little
effect could be detected. When the potential rose to a few thou-
sand volts and a brush discharge began to be possible, the smoke
agglomerated and settled very rapidly. The theory of this has
never been worked out. In ordinary smokes about 30 per cent
of the particles are charged electrically. It may be that the
alternating current reverses the sign of the charge periodically
and that the particles agglomerate when they are electrically
neutral, or it may be that it causes the charged particles to col-
lide with the uncharged ones. In connection with this it would
be interesting to determine the effect of a high-voltage alternating
current on the stability of a suspension in a practically non-
conducting liquid.
(190) DO COARSE and fine powders attract or repel each
OTHER WHEN BOTH HAVE THE SAME ELECTRICAL CHARGE?—
Two liquid drops of the same size repel each other if they have
equal electrical charges of the same sign. When two drops
bearing unequal charges, or two unequal drops bearing equal
charges, are brought closely enough together, there are immensely
strong, increasing forces of attraction between them, and co-
alescence will surely take place if the resulting drop is not as
large as to be instable.4 Nobody seems to have discussed
whether two electrically charged solid particles, smoke for in-
' Schlaepfer, /. Chem. Soc, 113 (1918), 522; Moore, J. Am. Chem. Soc .
41 (1919), 940.
s Phil. Trans., 209A (1909), 379; Humphreys, J. Frank. Insl , 179
1914), 751; Phys. Ret.. [21 6 (1915), 516.
» Phil. Mae., (3] 17 (1884), 214; J. Soc. Chem. Ind., 6 (1886), 572.
< Burton and Wicgand. Phil. Mag., [6] 23 (1912), 148.
stance, may attract each other under suitable conditions, even
though the sign of the charge on the particles is the same.
PRECIPITATION OF SOLID
(191) formation OF mirrors — The formation of a metallic
mirror involves the precipitation of the metal in a very finely
crystalline form. It is, therefore, a problem in colloid chem-
istry, and the literature on the subject1 should be gone over and
presented from this point of view.
(192) study of filamentous precipitations — There is a
certain amount of literature on filamentous silver,2 mossy copper,'
filamentous potassium chloride,4 and on silver chloride growths*
with silver, sodium chloride, and gelatin; but there is no ade-
quate discussion on the subject from the point of view of a col-
loid chemist.
(193) COLORS OF SILVER SOLS IN DIFFERENT VESSELS If
hydrogen is passed into a saturated aqueous solution of silver
oxide containing an excess of the solid salt, silver precipitates to
some extent as crystals and in part as colloidal silver.' The
form in which the metal comes down depends on the nature of
the containing vessel. In a platinum vessel no hydrosol is
formed, and all the silver precipitates in a crystalline form on the
walls of the vessel. In vessels of quartz and of ordinary glass,
the colloidal silver is yellowish brown by transmitted light,
while it comes down red to blue in a flask made of Jena glass.
The ratio of silver hydrosol to ordinary silver is greater in the
Jena glass vessel than in the other two. At first sight one would
expect this difference in behavior to be due to differences in
material dissolved from the walls, but this is not the case.
Kohlschutter allowed water to stand in an ordinary glass flask
for a while and then poured it into the Jena glass flask. The
reduction product was red. When water which had stood in a
Jena glass flask was poured into an ordinary flask »r into a
quartz one, the silver came down yellowish brown. The phe-
nomenon is, therefore, connected with the presence and nature
of the solid. The more plausible explanation is, as suggested
by Kohlschutter, that the reaction concentrations are highest
at the surface of the platinum and lowest at the surface of quartz
and the ordinary glass, so that the silver comes down coarsest
and most crystalline in platinum vessels and finest in quartz.
This could be checked experimentally by determining the ad-
sorbing power of platinum, quartz, and Jena glass for silver oxide
and for colloidal silver. It is probable that the adsorption is
greatest with platinum and least with quartz. This behavior
of the silver may be connected with the fact that it is easier to
get a yellow stain7 of silver on a potash-lime glass than on the
hard glasses.
(194) sedimentation — Dewar8 states that if a glass rod is
cooled to the temperature of liquid air and is then brought into
the air of the room, moisture will condense on it as a sheet of
ice. If the glass rod is electrified with a piece of silk, the ice
forms as a forest of crystals and not as a sheet. The reason for
this seems to be that the ice particles are themselves electrified
and consequently precipitate as far from each other as possible.
It is possible that something of this sort may play a part in de-
termining the very different volumes which the same precipitate
may occupy, depending upon the way in which it is precipitated.*
' Cf. Wadsworth, Z. Inslrumenlenk., 16 (1895), 22; Neogi, Z. anorg.
Chem., 59 (1906), 213; Chattaway, Proc. Roy. Soc, 80A (1908), 88; Silver-
man and Neckerman. Trans. Am. Ceram. Soc, 17 (1915), 505.
2 Kohlschutter, Z. Eleklrochem., 11 (1908), 49; IS (1912), 373, 419.
Ann., 387 (1912), 86; 390 (1912), 340; 398 (1913), 47; Phillips. J. Chem
Soc, 72, II (1897), 32
' Hutchings, J. Chem. Soc, 32 (1877), 1 13.
< Warrington, Ibid., 8 (1856). 30.
s Luppo-Cramer. Z. Kolloidchem., 9 (1911), 116.
• Kohlschutter, Ibid., 14 (1908). 49.
' Rosenhain, "Glass Manufacture," 1908, 185.
' Chem. Ne-.cs. 97 (1908), 5.
• Schulze, Pogg. Ann., 129 (1866), 366.
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
351
(195) MECHANISM OF THE ACTION OF COLLOIDAL ADDITION
AGENTS IN THE ELECTRODEPOSITION OF METALS — III Order for
a colloidal addition agent to function well, it must be carried to
the cathode and be adsorbed by the precipitating metal in suit-
able amount to give the desired crystal size. Are the best re-
sults obtained with an addition agent which shows a strong
preferential adsorption for the specific ion deposited, or is this
both unnecessary and undesirable? A quantitative determina-
tion of the adsorption of lead ion, for instance, by a particularly
good addition agent and by a comparatively poor one should be
made. Quantitative determinations should also be made of the
adsorption of various addition agents during the precipitation
of colloidal metals.
(196) THE CAUSE OF THE HIGH RESULTS IN THE DETERMINA-
TION OF ZINC BY THE ELECTROANALYTICAL METHOD — In electrO-
analysis, zinc is precipitated from strongly alkaline solution and
the results obtained are uniformly high. Under these condi-
tions, the zinc is, at least in part, in colloidal solution as the
hydrous oxide which gradually agglomerates and settles out on
standing.1 It is altogether possible that the high results are
due to the separation of a part of this colloidal hydrous oxide
during the analysis, thus contaminating the deposit. This could
be determined by a careful quantitative investigation of the re-
sults under widely varying conditions.
GASES IN SOLIDS
(197) gluten in wheat — Some wheat flours require admixture
with other flours in order to ensure good bread. Work by Gort-
ner, Henderson, and others indicates that the glutens are not
chemically different and that the observed differences are due
to salt content, hydrogen-ion concentration, etc. The problem
is, therefore, one in colloid chemistry involving size and ar-
rangement of aggregates, degree of hydration, etc. It might
be possible to treat a flour with a so-called weak gluten so as to
bring it more nearly up to standard. Anybody interested in this
important problem should get in touch with Dr. H. E. Barnard,
American Baking Institute, Minneapolis, Minn.
SOLIDS IN SOLIDS
(198) DETERMINATION OF PIGMENTS IN GLASSES AND GLAZES
— Our knowledge of the chemistry of colored glasses and glazes
is extremely rudimentary.2 This is due in part to the difficulty
of manipulation and still more to the analytical difficulties.
By working with the coloring oxides dispersed in alumina, it
would be possible to work with a two-component system and
thus simplify the analytical problem. Other oxides could be
substituted for alumina and working with a borax or phosphate
bead would be much easier than working with a regular glass.
(199) COLLOIDAL SILVER IN PRESENCE OF BISMUTH OXIDE —
In enamels the addition of silver carbonate and bismuth oxide
gives an intense blue.3 One function of the bismuth oxide is
to hold the silver to the body; but it must also cause a partial
agglomeration of the silver because the lusters are blue to green
instead of yellow to brown. Experiments should be tried in
precipitating silver oxide with bismuth oxide and then reducing
the silver oxide, so as to keep the laboratory experiments in close
connection with the technical methods.
(200) ACTION OF ULTRAVIOLET LIGHT AND OF RADIUM ON GEMS
— The action of heat, ultraviolet light, and radium on the colors
of gems is very interesting and opens up a broad field for re-
search.* Pale amethysts become darker when exposed to radium,
while ultraviolet light has no effect. When heated to redness
in hydrogen or oxygen, the pale amethysts become colorless,
while they turn yellow if heated in ammonia. The decolorized
' Hantzsch, Z. anorg. Chem., 30 (1902), 289; Fischer and Herz, Ibid.,
31 (1902), 352.
J Bancroft, J. Phys. Chem., 23 (1919), 603.
■ Franchet, Ann. Mm. phys., (81 9 (1906), 37.
> Bancroft, /. Phys. Chem., 23 (1919), 642.
amethysts regain their color when treated with radium. Rose
quartz is made colorless by ultraviolet light and blackish brown
by radium. It is not changed when heated in ammonia. Smoky
quartz loses its color when heated and radium brings it back,
while hydrogen peroxide tends to make the color yellower.
Colorless topaz is made yellow to orange by radium and is de-
colorized when heated. Ultraviolet light tends to change the
orange produced by radium to lilac. Kunzite changes from lilac
to green under the influence of radium and is changed back by
ultraviolet light. It becomes colorless when heated to 400 °,
but exposure to radium brings back the blue-green color. Corun-
dum occurs as blue, green, violet, yellow, and white sapphires
and as ruby. The Oriental sapphire is said by Verneuil1 to be
colored by iron and titanium, while the clear sapphire is colored
by iron only. Blue <apphires are changed to yellow or yellowish
brown by radium, the blue-green sapphires to green, and the
white sapphires to yellow. Violet sapphires become pure red
and natural rubies lose any violet tinge. Artificial rubies and
sapphires are not changed by exposure to radium, but their
coloring matter is chromium or cobalt. Ultraviolet light makes
yellow sapphires blue and violet ones more violet. Heating
sapphires in air makes them colorless. Soddy has shown that
colorless gold glass is turned to ruby by the action of radium
emanation.2
The general result seems to be in all cases that heating makes
the gems more nearly colorless and that the action of radium
and of ultraviolet light is antagonistic. The only possible ex-
planation seems to be that radium increases the dispersity of the
colloidal particles, while ultraviolet light decreases it or vice
versa. We know that (3-rays increase the agglomeration of
sulfur and that they change a selenium hydrosol into crystalline
selenium. It should be possible to test this explanation on syn-
thetic materials, using perhaps borate glasses. For instance,
radium produces no change in pure chromic oxide but turns it
brown when the chromic oxide is dissolved in borax. Ultra-
violet light changes the brown to yellow, and when a chromium
oxide borax glass is heated in ammonia it becomes pale. Alumina
is not changed by radium but hydrous aluminium oxide sol is
turned blue by it. If cases of this sort should be studied care-
fully it would probably give us the necessary data to straighten
out the question of the colors of gems without any difficulty.
U. S. Army Examinations
A final competitive examination for appointment of second
lieutenants in the Regular Army will be held beginning April
25, 1921. Among the vacancies to be filled are thirty-two in
the Chemical Warfare Service.
Information as to the scope and details of the examination
is contained in Army Regulations No. 605-5, which may be ob-
tained by candidates at any military post or station. Applica-
tions should be submitted at once at any post or station, or at
the headquarters of the department or corps area in which the
candidate resides.
Institute for Research in Tropical America
Plans are under way for the organization of an Institute for
Research in Tropical America for the promotion of exploration
and research in the interest of natural science. The movement
was inaugurated by the division of biology and agriculture of
the National Research Council and will be primarily devoted
to biological research to promote medicine, agriculture, forestry,
fisheries, and general scientific development in Central and
South America. Research stations for experimentation will
be established in the countries investigated.
Medicinal Research on Animal Tissues
The municipal authorities of Paris have voted'a fund for the
establishment of a laboratory in connection with the city slaugh-
ter-house at La Villette for research into further medicinal
uses for extractives of animal glands and tissues.
■ Compl. rend., 161 (1910), 1053.
'Garnett, Phil. Trans., 20SA (1904), 400.
352
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
SCIENTIFIC SOCIETIES
Rochester Ready for Chemical Cohorts
Special Correspondence to The Journal of Industrial and Engin
Chemistry by John Walker Harrington
Rochester, N. Y., March 20 — Tulips soon will blaze in
the parks and spring burgeon in every square of Rochester.
Surely the lines of those who are to attend the April meeting of
the American Chemical Society will fall in pleasant places!
Scarcely is the chill of March driven from the ground in the valley
of the Genesee before Rochester becomes a smiling garden.
No more fitting place could have been chosen for the Society
to renew its youth. Here it was that in 1891, before the or-
ganization had attained its national scope, its fifth general
meeting was held, and again in 1913, it gathered here when it
had reached the 7000 mark in
membership. It is expected,
judging from the returns received
by the active local committees,
that fully 2500 of the more than
15,000 members of the Society
will be present when President
Smith taps his gavel on the
morning of April 26.
It is estimated that within
a night's travel there are fully
9000 of our members. Rochester
is easily accessible from New
York, Boston, Philadelphia,
Baltimore, and many other
cities of the Atlantic seaboard.
It can be reached readily from
Chicago, Minneapolis, St. Louis,
Cleveland, Cincinnati, and
scores of other important com-
munities. As an important rail-
road center, Rochester also
offers special advantages in
transportation to the large and
nourishing sections of the
Society on the Pacific Slope.
The announcement that all
members attending the Spring
Meeting may, upon obtaining
proper certifications, avail them-
selves of the fare and a half
rate will also have a stimulating
effect upon the attendance.
Delegations from the Middle
West are likely to be unusually
large. Dr. Gerald L. Wendt
has issued a call in the Chemical
Bulletin, urging the membership of the nine sections around
Chicago to join in a special train to Rochester. Mr. Herbert
G. Sidebottom, secretary of the New York Section, has begun
his campaign for a special car, or cars, and several other sections
are planning either to come in reserved Pullmans, or to attend
in large groups.
The veterans of the Society who knew Rochester 25 years
ago will find that industrial chemistry has had much to do with
her commercial advancement. Nearly 30,000 of her citizens,
in a population of more than a quarter of a million, gain their
livelihood from chemical industries or enterprises under chemical
control. In Kodak Park alone there are, in round numbers,
6000 men and women employed. Since the war the industries
of Rochester have made giant strides, for they have been instru-
le M. Billings
Program
Local Committee Chaibmen
mental in breaking the strangle hold of German monopoly in
such commodities as optical glass and refined chemicals. Enor-
mous quantities of chemical and other scientific apparatus are
produced here, and Rochester is doing much toward the equipping
of the laboratories of the universities and colleges, as well a<;
those of research and industry.
If time permitted, Rochester could indeed make an exposition
of' the chemical industries within her borders. The Rochester
Section, although it cannot arrange for exhibits on a large scale,
is preparing a series of charts and graphs which will illustrate
the importance of the community as a chemical headquarters,
and will also show the relationship of the industrial chemistry
practiced here to the country at large.
What Rochester does in pre-
paring the chemists of the
future for their life work is well
visualized in the University of
Rochester, under the able direc
tion of its president, Dr. Rush
Rhees. The department of
chemistry, of which Dr. Victor
John Chambers is the head, has
well maintained laboratories in
which the student may not only
obtain a general knowledge of
chemistry but in which he may
prepare himself for the career of
chemical engineer. In Eastman
Hall, which is dedicated to our
science, are well-equipped lab-
oratories, and one of its lecture
rooms is frequently the meeting
place of the Rochester Section.
The arrangements made by
the indefatigable local com-
mittees will give full play to all
the activities of the coming
meeting — scientific and social.
Those who wish full oppor-
tunity to discuss the technical
papers in academic calm will
have it in the large and airy
rooms of the Mechanics Institute
at 55 South Plymouth Avenue,
within a block of the official
headquarters. The head of the
department of chemistry there,
Dr. J. Ernest Woodland, who is
also chairman of the local Execu-
tive Committee, has arranged
Ernest Woodland
Executive
Harry LeB. Gray
Hotels
that the various divisions and sections of the Society will
have the entire use of the building during the Spring Meeting,
as no classes will be held during that period. This will place
equipment and apparatus of all kinds at the disposal of those
who are reading papers, and will create that atmosphere of both
pure and applied science which was a feature of the divisional
meetings held last autumn at the University of Chicago. As
all these gatherings are to be held under the same roof, it will
be very easy for members to go from one division to another and
to follow the papers in which they are especially interested.
Information just received from the office of Dr. Charles L.
Parsons shows that there will be no meeting this spring of the
Fertilizer Division and the newly organized Leather Sec-
tion.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
353
The large general meeting will be held at the Chamber of
Commerce, 67 St. Paul St., on Tuesday, April 26. The addresses
of welcome will be delivered by Hiram Edgerton and by V. Roy
McCanne, president of the Rochester Chamber of Commerce.
Dr. Smith will respond, as president of the Society. Representa-
tive Nicholas Longworth, author of the Longworth Bill, and Sena-
tor James W. Wadsworth, Jr., the staunch friend of the Chemical
Warfare Service, will be among the speakers. The general meet-
ing will be continued in the afternoon at Convention Hall,
Clinton Avenue, South. The evening is to be given to various
college and fraternity dinners.
The large public meeting, to which the citizens of Rochester
are especially invited, is to be held on the evening of Wednesday,
April 27, at Convention Hall, and not at the Central Church, as
originally announced. Dr. Charles F. Chandler has accepted
the invitation to make the address at this meeting. The Good
Fellowship Meeting will take place on the following evening in
the dining hall at the plant of Bausch & Lomb. The program, in
other respects, is practically as originally published.
As Rochester is in so many ways a chemical center, the popula-
tion is already deeply interested in the approaching meeting.
The newspapers have for several weeks been printing in detail
the news relating to the arrangements made by the local com-
mittees. Their interest has not only been fed but most skilfully
stimulated by Mr. Benjamin V. Bush, the chairman of the Pub-
licity Committee of the Rochester Section. There is no city
in the country where more attention is bestowed upon the ac-
tivities of the resident chemist than is given by the newspapers
of the Flower City. The indications are, therefore, that the
proceedings of the Spring Meeting will be fully and accurately
reported.
There went up a cry from ancient Egypt, from a most ingenious
people, that it could not make bricks without straw; and like-
wise it is difficult even for good reporters to make reports out of
whole cloth. The work of reporting the proceedings at Rochester
will be greatly facilitated if authors of papers which have a popular
interest will send in abstracts of them to the A. C. S. News Ser-
vice, One Madison Avenue, New York City, as far ahead of
time as they can. These abstracts of four or five hundred words
each are made into the form of bulletins, which are issued to the
news associations of the country as near ten days in advance
of the delivery of the papers as possible, subject to the usual form
of newspaper release. The principal factor in getting the work
of the Spring Meeting to the attention of the American press is
in the clearly written popular abstract prepared in time to make
its distribution nationwide. Such material should be in as
nontechnical language
as is consistent with
precision.
The Press Room
this spring will be in
the Mechanics Insti-
tute, where unusual
facilities for serving
the members of the
Fourth Estate will be
provided.
AsThis Journal goes
to press, the members
of the local committee
are making every en-
deavor to see that the
hotel accommodations
are adequate and that
everything will be in
readiness to give the
welcome of an over-
flowing hospitality to
the members of the Frank W. Lovejoy
largest scientific body IIoNORARY Chairman, Convention Executive
in the world. Committer
INITIAL MEETING OF THE PETROLEUM SECTION
The organization of a Petroleum Section has been author-
ized by the officers of the American Chemical Society, and it
is proposed to hold the initial meeting of this section at the
general meeting at Rochester. Dr. Thomas G. Delbridge, of
the Atlantic Refining Company, Philadelphia, Pa., has been
appointed chairman, and Dr. W. A. Grusc, of Mellon Institute,
354
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
A — Mechanics Institute
B — Hotel Rochester
D — Convention Hall
-Chamber of Commerce
-Rochester Club
-University
G — Bausch & Lomb
Pittsburgh, Pa., has been appointed secretary for the Roches-
ter meeting.
The purpose which this organization is expected to fulfil
may be expressed as follows:
(1) To enable chemists and technologists engaged in the
petroleum, shale-oil, and natural gas industries to meet and to
correspond, and to accumulate trustworthy information regard-
ing the geochemistry of petroleum, oil-shale, and natural gas,
the conversion of the raw materials into manufactured products,
and the characteristics and usages of these products, together
with their transport and storage.
(2) To promote the better education of persons desirous of
becoming petroleum engineers, refinery engineers, or hydrocar-
bon chemists, and to elevate the professional status of those
employed in the industries mentioned by establishing a high
standard of scientific and practical proficiency.
(3) To encourage research in hydrocarbon chemistry.
(4) To cooperate with the American Petroleum Institute
and with the National Research Council, and to collaborate
with the American Society for Testing Materials in its work on
the standardization of bituminous and petroleum products.
Fifty chemists and chemical engineers actively engaged in
the petroleum industry have pledged their support and co-
operation, and fifteen papers on the chemistry of petroleum have
been promised for the first meeting. At this meeting it is de-
sired also to take up such questions as that of the degree and
scope of the activities of the section, the form of cooperation
with other technical and scientific societies, the exact name of
the section, and other interesting points. If time permits, it is
planned to hold an informal symposium on the problems of the
petroleum and allied industries.
All members of the Society who are interested, and all other
persons who desire to become members of the section, are re-
quested to send their names to its secretary, W. A. Gruse,
Mellon Institute, Pittsburgh, Pa. A full attendance at this
organization meeting is urged and the submission of papers is
solicited.
The secretary will be glad to have any suggestions which this
announcement may call forth.
TO THE DYE CHEMISTS
On Wednesday and Thursday, April 26 and 27, the Dye
Division will assemble as a part of the 1921 Spring Meeting of
the Society.
Scientific work is, has been, and always will be the backbone
of the dye industry. These semi-annual meetings of the division
afford to the dye chemists an opportunity to participate in the
presentation of scientific work in the field of dyes, and to meet
other chemists engaged in like work. It will be worth your while
to attend regularly the Spring and Fall Meetings. For the good
of the industry keep up your membership in the division and
induce others to join (dues are $1.00 a year and are for stationery,
postage, and the like).
The Longworth Dye Bill protecting the dye industry will be
introduced again in the new Congress. Write to your Senators
and to your Representative in Congress, urging an early passage
of this bill.
Finally, plan to attend the Rochester meeting and endeavor to
present a paper before the division. Send title to the secre-
tary, R. Norris Shreve, 43 Fifth Ave., New York City.
SPECIAL RAILROAD RATES
A special one and a half fare on the certificate plan has been
granted, if 350, carrying certificates, attend the meeting. Mem-
bers must pay full fare going, taking certificates at the time
they purchase their tickets, which certificates will allow the
purchase of a return ticket over the same route at half fare.
Philadelphia College of Pharmacy Celebrates
One Hundredth Anniversary
The one hundredth anniversary of the beginning of pharma-
ceutical education in America was celebrated in Carpenter's
Hall and the Auditorium of the Philadelphia College of Phar-
macy on the afternoon and evening of February 23, 1921.
The Philadelphia College of Pharmacy and Science is the
outgrowth of the Philadelphia College of Apothecaries organized
in historic Carpenter's Hall, Philadelphia, by the pharmacists
of that city on February 23, 1821. Before that date there had
been no organized courses in pharmacy for the training of drug-
gists at any of the universities or colleges then in existence.
The pharmacists of that period, recognizing the need for educa-
tion in their profession, united to organize the Philadelphia
College of Apothecaries, which later became the Philadelphia
College of Pharmacy and has recently become, through charter
amendment, the Philadelphia College of Pharmacy and
Science.
The Founders' Day Celebration of the College took the form
of a short meeting at Carpenter's Hall on the afternoon of
February 23 in which the descendants of the founders of the
College, the present officers, faculty, and members of the college
took part. When they had assembled in the same room where
the founders of the college met. Dr. C. A. Weideman, the present
secretary of the College, read the minutes of the first three
meetings of the founders. Mr. George M. Beringer, the chair-
man of the Board of Trustees, then gave a brief resume of the
progress that has been made by the institution in the past one
hundred years. The ceremony was very impressive and was
followed in the evening by a larger meeting in the auditorium
of the College. Over six hundred officers, faculty, alumni,
students, and friends of the College gathered at the evening
meeting and listened to impressive addresses by Mayor J.
Hampton Moore of the City of Philadelphia, Dean Charles
H. La Wall of the Philadelphia College of Pharmacy and Science,
Professor H. V. Amy of the College of Pharmacy of Columbia
University, and Dr. S. P. Sadtler, Emeritus Professor of Chem-
istry of the Philadelphia College of Pharmacy and Science.
The College is planning an endowment and building fund
campaign for the purpose of enlarging the educational facilities
which have been sorely taxed in the past few years.
Apr., 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
355
New York Chemists' Club Confers Honorary
Membership
The tenth anniversary of the opening of the present club
house of the Chemists' Club, New York, was fittingly cele-
brated on the evening of March 17, 1921, by the award of honor-
ary membership in the Club to eight distinguished chemists,
four from foreign countries and four Americans, and by the
presentation of the results of two splendid researches by Dr.
Jacques Loeb and Dr. Irving Langmuir, respectively.
The fact that the Chemists' Club of New York is a national
institution and in some respects international in scope was never
more forcibly brought out than at this celebration. The
presence of representatives of the embassies of Belgium,
France, Great Britain, and Italy, who represented the scientists
of the respective countries upon whom honorary membership
was conferred, and the gathering of nonresident members from
various sections of the country with those who reside in the
Metropolitan District, bore testimony to the unique position
which this Club has attained in scientific and social circles.
Early in the evening an informal reception to those selected
for honorary membership and their representatives was held
in the social room of the Club. This was followed by a dinner
in their honor, after which adjournment was taken to Rumford
Hall, where the principal exercises of the evening were held.
In a few well-chosen words Ellwood Hendrick, president of
the Chemists' Club, stated the purpose of the gathering and
introduced Dr. Charles Baskerville, chairman of the Committee
of Arrangements, who gave a brief history of the organization
and progress of the Club. Starting with eighty-nine men in
1898, the Club has grown to a total membership of 1728, a
majority being nonresident members. Dr. C. F. Chandler,
the first president of the Club, now in his eighty-second year,
was present and was given an ovation when he was asked to
rise. Dr. Baskerville referred feelingly to the untiring efforts
of the late Morris Loeb, who contributed so much in energy,
time, and money to the launching of the present club house,
which was first occupied ten years ago.
Dr. Baskerville called attention to the fact that according
to the constitution and by-laws of the Chemists' Club, honorary
membership is limited to ten foreign and ten American scientists
and election is by the unanimous vote of the trustees. He
then announced that the following distinguished chemists
would have honorary membership conferred upon them: Pro-
fessor Giacomo Ciamician, University of Bologna; Professor
H. L. LeChatelier, College de France; Dr. Ernest Solvay, Brus-
sels; Sir Edward Thorpe, Imperial College of Science and Tech-
nology; Dr. John Uri Lloyd, Past President, American Pharma-
ceutical Association; Dr. W. H. Nichols, Past President of the
American Chemical Society and Society of Chemical Industry;
Dr. Edgar Fahs Smith, Past and Present President, American
Chemical Society; and Dr. Edward Weston, the eminent phys-
ical chemist.
PROMINENT CHEMISTS PRESENT HONORARY MEMBERS
Dr. Bernhard Hesse presented Dr. Ernest Solvay— represented
by Consul General Mali, of Belgium — as follows:
Founder of the ammonia-soda process, for three score years a pioneer
and leader in industrial chemistry, whose activities have enormously de-
veloped the production and use of sodium products over all the world,
and likewise have profoundly stimulated dependent and related industries;
a leader in the application of scientific study to industrial problems; founder
and indefatigable supporter of many institutions devoted to science, to
public health and welfare, and to the elevation of human intercourse and
relations; a source of great strength to his country in her peril, and a shin-
ing mark for the vengeance of her despoilers. The members of The Chem-
ists' Club proclaim their admiration and esteem by election to Honorary
Membership.
Professor Marston T. Bogert presented Professor Henri L.
LeChatelier — represented by Consul General Liebert — as fol-
lows:
Professor at College de France and at l'Ecole des Mines, member of
the Academie des Sciences, for over forty-six years an active, resourceful,
fruitful, daring and original investigator of the fundamental principles under-
lying chemical action and thermodynamics. He has enriched our knowledge
with countless facts and with many sound and far-reaching theories based
upon them; and he has greatly influenced and enhanced the arts of metal-
lurgy, of electrometallurgy, and of applied chemistry generally. He was
called on by his country in her time of stress to bring his profound knowl-
edge and experience to bear upon the solution of problems vital to her pres-
ervation and necessary to her progress, and on the return of peace he was
honored by her with many prizes and medals. To him the members of
The Chemists' Club tender evidence of their profound esteem by election
to Honorary Membership.
Dr. Landis presented Sir Edward Thorpe — represented by
Counsellor Broderick of the British Embassy — as follows:
Born near Manchester, a student of science at Owens College, the Uni-
versities of Heidelberg and Bonn, a brilliant teacher in several colleges in
his native land, at the age of three-quarters of a century he is Professor of
Chemistry Emeritus of the Imperial College of Science and Technology,
South Kensington. For many years director of the Government Labora-
tories in London, his accuracy of methods of analysis and clarity in their
exposition, coupled with a wisdom as to human purposes in the interpre-
tation of law, gave a model for municipal experts in caring for the welfare
of his fellow citizens. His delightful biographies of famous chemists are
examples of charming literary style for others to study and follow. His
Dictionary of Applied Chemistry is an authoritative work, turned to by all
seeking full knowledge. His researches in pure chemistry carried him to
the presidency of the Chemical Society of London; his exposition and
knowledge of technology were recognized a generation ago by a similar de-
mand on the part of the Society of Chemical Industry; and his breadth
of appreciation of all science likewise brought him the vice presidency of
the British Association for the Advancement of Science and the Royal
Society. His eminence as a scientist, technologist, and author, command-
ing several languages, for he had a large personal acquaintance with
savants of foreign tongues, burdened him with Honorary and Corresponding
Memberships in numerous scientific, literary, and philosophical academies
and societies of other lands. Many times doctored, this Fellow of the Royal
Society will long remain a teacher of power, even to many who may never
hear his voice. We honor ourselves in electing him to be one of that limited
number to whom The Chemists' Club can pay such tribute.
Professor Maximilian Toch presented Professor Giacomo
Ciamician — represented by the Italian Ambassador, Rolando
Ricci — as follows:
Senatore del Regno, professor of general chemistry at the University
of Bologna, for more than forty-two years an active, ingenious, fruitful, and
original investigator in pure organic chemistry, applying it to determine the
nature and mechanism of the origin of constituents of plants and animals,
and the influence therein of sunlight, uncovering many facts which have
finally enabled him so to correlate these phenomena that our view of them
has become greatly clarified, and much firm ground for further and beneficial
advance in this most intricate field has been created. The members of
The Chemists' Club elect him to Honorary Membership in recognition of
his eminence in science and in appreciation of an associated ally in a holy
Dr. Bloede presented Dr. John Uri Lloyd — represented by
Dr. Alfred Springer, of Cincinnati, Dr. Lloyd being ill — as
follows :
Born in New York State, a student of nature and of people, trained in
a severe school of experience in Kentucky, he rose to the professorship of
chemistry in the Cincinnati College of Pharmacy and to the presidency
of the American Pharmaceutical Association. By his investigation in
phytocheraistry, especially applied to medicine, he created new knowledge
of alkaloids, glucosides, and the physiological variations in reactions of
drugs, especially as colloids. A graceful and imaginative pen has aug-
mented his contributions to scientific literature and perpetuated his close
and accurate study of the dialect, superstition, and folklore of the Blue
Grass Country. His "String Town" alone has aroused interest in chemistry
and given pleasure to over a million people. He, with his brother, has hand-
somely housed one of the most complete libraries of botany and chemistry
in the world, permanently endowed it, and given it in pcrptlue to the city
wherein he struggled as a youth, conquered as a strong man, and now lives,
surrounded by affection and esteem. Over three score years and ten find
him still active in the laboratory and in public affairs. Numerous honors
nave come to him and are deservedly his. To them the members of 'flit
Chemists' Club take this, their best means, of adding appreciation of his
diligent and fruitful labors for human welfare and happiness.
Professor Wilder D. Bancroft presented Dr. W. H. Nichols
in person, as follows:
For more than fifty years successfully engaged in those branches ol
industrial chemistry of fundamental importance to the development of
350
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
our country, at many places and in every section of this continent; a firm
believer in the application of science to industry and always its consistent
follower in practice; a staunch and helpful leader and supporter in securely
expanding the study of chemical science, research, and application in all
branches of our educational system; far-sighted in the promotion of inter-
national understanding among chemical associations and chemists, and for
many years with rare patience and discernment creating and fostering
opportunities for scientific, technical, and social cooperation among the
chemists of the United States to the permanent benefit of all. His construc-
tive capacity carried him to the presidency of the American Chemical
Society, of which he was one of the founders. His world-wide recognition
brought the presidencies of the Society of Chemical Industry and Eighth
International Congress of Applied Chemistry. Among the numerous
honors and distinctions which have come to hira, we, the members of The
Chemists' Club, desire to include our appreciation of his great services on
behalf of Science, Business, and the Welfare of Mankind, by electing him
to Honorary Membership.
Dr. Charles Reese presented Dr. Edgar F. Smith in person,
as follows:
Again president of the American Chemical Society after a lapse of
twenty-five years; one to whom that Society owes much for devoted and
self-forgetful service in its pioneer days; connected with the University of
Pennsylvania as educator and administrator for over forty years; a scientist
whose researches have covered widely separated fields in electrochemistry,
the rare earths, and atomic weights; author of standard texts on electro-
chemistry, as well as translator of foreign texts; a historian who adds to a
charming literary style the painstaking accuracy and attention to detail
which have made him a brilliant teacher and scientist. To the innumerable
evidences of esteem and affection on the part of students, colleagues, and
citizens, we, the members of The Chemists' Club, desire to add ours by his
election to Honorary Membership.
Dr. Cottrell presented Dr. Edward Weston in person, as
follows:
Of English birth, for over fifty years an American chemist, physicist,
and inventor; a scientific investigator of absolute integrity, he has brought
to the solution of physical and electrical problems the chemist's point of
view. He has been an early worker in the electroplating field, he perfected
the dynamo for use in that art; was inventor of the recently rediscovered
flaming arc; was one of the pioneers in the development of the incandescent
lamp and filament. He is the inventor of standard electrical measuring
apparatus. This work involved detailed and long-continued researches
on alloys, and the results have led to entirely new views on the nature of
metals and non-metals. A wise counselor in the affairs of The Chemists'
Club, the members elect this friend and scientist to Honorary Membership
as an evidence of affection and esteem.
Each recipient of the certificate of honorary membership
was roundly applauded in turn, and the newly created honorary
members or their representatives took seats on the stage under
the flags of their respective nations. It was a ceremony which
should link to an even greater degree the chemists of the allied
countries with their brother chemists in America.
DR. LOEB DISCUSSES RESEARCH ON PROTEINS
The second part of the program was devoted to the presenta-
tion of two highly interesting and perhaps epoch-making inves-
tigations. Dr. Jacques Loeb, of the Rockefeller Institute,
presented an account of his researches on "The Chemical and
Physical Behavior of Protein Solutions." Dr. Loeb stated that
life is so closely linked to the chemical and physical properties
of proteins that the knowledge of their properties must precede
the attempt to unravel the dynamics of living matter.
The modern concepts of colloid chemistry have been used to
supply this knowledge, and foremost among these is the idea
that the reactions of colloids in general and proteins in par-
ticular are not determined by the purely chemical forces of
primary valency, but by the rules of adsorption; and that the
influence of electrolytes on the physical properties of proteins
is due to an alteration in the degree of dispersion or in the de-
gree of hydratation of the protein particles. From his experi-
ments Dr. Loeb has reached the conclusion that the views sum-
marized above are based on a methodical error as far as the
proteins are concerned; namely, on the failure to take into
consideration the hydrogen-ion concentration which happens
to be the chief variable in the chemistry and physical chemis-
try of proteins. When this variable is duly considered, it is
found that the laws of classical chemistry account for the chem-
ical and at least a part of the physical behavior of the proteins.
Dr. Loeb then gave an account of his experiments in detail.
He showed that proteins combine by the purely chemical forces
of primary valency and in strictly stoichiometrical proportions
with acids and alkalies. Experiments based on the measure-
ment of the hydrogen-ion concentration have led Dr. Loeb to
the conclusion that the physical properties of proteins, such as
osmotic pressure, swelling, viscosity, and potential difference,
are not affected by the nature of the ion in combination with
the protein but only by the valency. This fact finds its explana-
tion in the Donnan membrane equilibrium. Furthermore, Dr.
Loeb has shown through his experiments that the influence of
the hydrogen-ion concentration on the P. D. and on the osmotic
pressure of protein solutions can also be accounted for not only
qualitatively but quantitatively by Donnan's theory. Dr. Loeb
stated that Procter's experiments and some of his own experi-
ments which are not yet complete suggest that the influence of
the hydrogen-ion concentration and of the valency of the anion on
the swelling of gelatin-acid salts may possibly be explained in
the same way. The classical laws of general and physical
chemistry therefore furnish us with a quantitative theory not
only of the chemical behavior of proteins, but also of at least
some of their physical properties.
DR. LANGMUIR PRESENTS THEORIES ON DEDUCTIVE CHEMISTRY
Dr. Locb's address was received with great applause, and
President Hendrick then introduced Dr. Irving Langmuir, of the
Research Laboratory of the General Electric Company, who
spoke on the "Influence of Physics on Modern Chemical
Thought." Dr. Langmuir believed that the work of the physicist
will have an increasing influence on the development of chemistry
in the coming years. He referred to the new aspect in chem-
ical viewpoints that has developed in the past decade, and par-
ticularly to the new theories regarding the constitution of the
atom. He believes that when once the constitution of the atom
is definitely known, chemistry will become a deductive science.
We would not have to rely on experiments to determine the
properties of chemical compounds, for they could be accurately
deduced. The speaker reviewed some of the theories which
had been advanced regarding the condition of the electrons in
the atom and pointed to the dominating influence which atomic
structure is beginning to exercise because of the clear under-
standing it will give of chemical relationships. At the present
time, said Dr. Langmuir, the chemist bases his predictions on
a certain intuition which comes with long experimental practice,
and also on mature judgment resulting from laboratory ex-
periences. Once the structure of the atom is solved, more de-
pendable methods will be available to the chemist for deducing
the properties of compounds and probable reactions. Dr.
Langmuir then pointed to the fact that Coulomb's law supple-
menting the theory of valence almost eliminates what he calls
chemical intuition as to which compounds are stable and which
are unstable. By the same means it is possible to calculate
energy values, and Dr. Langmuir believes that with a little more
experimenting he will be able to calculate the heats of reaction
of various chemical substances.
It is very necessary for the development of chemistry, in Dr.
Langmuir's opinion, that the student should learn the new
views based on the development of the past one hundred years,
rather than crowd his mind with a study of the beginnings
of chemistry and the many progressive steps that have been
necessary to arrive at the present state of our knowledge of the
subject. He believes that once atomic structure is solved, 90
per cent of the study of chemistry will be deductive. Dr.
Langmuir felt that the goal to which we should look forward
is the prediction of chemical properties and relationships with-
out the necessity of going through a long series of experiments.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
357
More and quicker progress can be made by deduction than by
experimentation. The fundamental thing to be determined is
whether the electrons in the atoms are moving or whether they
are stationary, as this will give us the key to atomic structure.
If they are moving in orbits, the task will be very difficult; if
they are stationary, the task will be comparatively easy.
The applause which followed Dr. Langmuir's presentation
showed that those present realized that chemistry is on the
threshold of a rapid development, and that they had possibly
listened to the beginning of a new epoch of progress in the funda-
mental principles underlying the entire structure of this science.
Colloid Development
The Committee on the Chemistry of Colloids, appointed by
the National Research Council, feels that interest in colloid
chemistry is growing rapidly. No better evidence of this could
be found than the Symposium on Colloid Chemistry at the
Society's meeting in St. Louis, in April 1920. The other divi-
sions all adjourned in favor of the symposium, and eight hundred
chemists crowded into the room. Probably two hundred
stood for an hour or two. Comments on the program showed
very great interest by the audience.
In This Journal, ii (1919), 794, we offered a number
of lectures by members of the committee and others. There was
a ready response. Within a year about one hundred such lec-
tures were given before universities and sections of the Society.
New England, the South, the Middle West, California, and the
Northwest availed themselves of the offer. This method of
stimulating interest paid. More of these lectures are being
given this year at various institutions.
In response to the request of the committee, W. D. Ban-
croft has written and published a stimulating book on "Applied
Colloid Chemistry." We need more courses in the subject,
and proper texts and laboratory manuals help to make this
possible. For the same reason the chairman has nearly com-
pleted a "Laboratory Manual of Colloid Chemistry," to be pub-
lished in the near future. A classified bibliography with brief
comment is also being prepared. This will probably be issued in
a very incomplete condition in mimeograph form. Copies will
be distributed for criticism and suggested additions. The final
product will then be published in some suitable manner. In
the meantime, chemists can render valuable assistance by sending
the chairman references to their favorite colloid fields. The
comment need not exceed fifty words. This is not to be an ab-
stract of each article but a sign post to show the reader whether
or not it is worth his interest.
The list of "Research Problems in Colloid Chemistry," now
being published in This Journal by W. D. Bancroft, is another
part of our plan. No sooner had the first instalment appeared
than the chairman received decidedly interesting letters of in-
quiry.
The suggestion that the committee be made a sort of clearing
house for the colloid chemists and the manufacturers brought
out a ready response. Requests have come in for highly trained
colloid chemists, but as yet such men are few in number. More
must be trained at once. Two very great dye companies have
asked for help. A manufacturer in another line recently offered
to pay as high as $7500 for the right colloid chemist. Evidently
no missionary work was needed to convince this man of the im-
portance of colloid chemistry in the industries. Unfortunately,
the vigorous development of our subject in this country is too
recent to have created an adequate supply of the men needed.
The chairman suggested to one manufacturer asking for help
that the company select a young man equipped with his Ph.D.,
and possibly some experience, and send him to any one of three
or four institutions that might be named, for a year's training
in colloid routine and research. This should be on salary, of
course. The manufacturer, by this method, selects a man
for his fundamental training and personality and adds to this
the specialization desired. The teacher in charge of the young
man gains in having a trained research assistant. Industrial
men must face the situation squarely. If they want highly
trained colloid chemists they must help in their training.
One of our leading physical chemists urges that we publish
from time to time, revised lists of books on colloid chemistry
Such a list follows:
BRIEF BIBLIOGRAPHY
1 — Emil Hatschek: "An Introduction to the Physics and Chemistry
of Colloids." 116 pp. P. Blakiston's Son & Co., Philadelphia, 1919
Based on a course of ten lectures. A remarkably clear introduction to
colloids. Third edition. A laboratory manual has since been written by
Hatschek.
2 — Jerome Alexander: "Colloid Chemistry." 90 pp D. Van
Nostrand Co., New York City, 1919. Deals largely with the practical
applications of the science.
3 — Bayliss: "Principles of General Physiology." Longmans, Green
& Co., New York City, 1915. In pp. 74-110 is given a clearly written
introduction to the "Colloidal State."
4 — Wolfgang Ostwafd: "Theoretical and Applied Colloid Chem-
istry " Translated by Martin Fischer. 232 pp. John Wiley & Sons,
Inc., New York City, 1917. Revision of a course of five lectures given
in the United States a few years ago. A very stimulating book.
5 — W. D. Bancroft: "Applied Colloid Chemistry." 345 pp. Mc-
Graw-Hill Book Co., Inc., 1921. Written at the request of the Committee
on the Chemistry of Colloids. A delightful book, full of illuminating com-
ments on the work recorded in the literature. Especially strong in treat-
ment of adsorption. Every colloid chemist should own this book.
6 — Zsigmondy: "The Chemistry of Colloids." Translated by Spear.
288 pp. John Wiley & Sons, Inc., New York City, 1917. Probably the
most useful book of its size on the subject yet published. Contains 33
pages on the industrial applications of colloids.
7 — Freundlich: "Kapillarchemie." 591 pp. Leipzig, 1909. The
greatest classic in the literature of colloids.
8 — Wolfgang Ostwald: "Handbook of Colloid Chemistry." Trans-
lated by Martin Fischer. 278 pp. P. Blakiston's Son & Co., Philadelphia,
1915. Gives valuable references to the literature. A translation of Ost-
wald's "Grundriss der Kolloidchemie."
9 — Bechold: "Colloids in Biology and Medicine." Translated by
Bullowa from second German edition. 464 pp. D. Van Nostrand Co., New
York City, 1919. A splendid book, somewhat specialized as the title
indicates, but valuable to any student of colloids. Contains 40 pages on
"Methods of Colloidal Research," including much of the author's own work
on ultrafiltration.
10 — Taylor: "Colloids." 327 pp. Longmans, Green & Co., New
York City. Not well arranged. Contains some useful directions for the
preparation of colloids. Should be used only as a reference book on isolated
points.
11 — Burton: "Physical Properties of Colloid Solutions." 197 pp.
Longmans, Green & Co., New York City, 1916. Contains a useful bibliog-
raphy. Rather physical in treatment.
12 — The Svedberg: "Herstellung Kolloider Losungen." 507 pp.
Theodor SteinkofT, Dresden, 1909. A classic. Gives full directions for
preparing hundreds of colloids. Contains a valuable bibliography.
13 — Martin Fischer: "Oedema and Nephritis." 2nd Ed. 695 pp.
John Wiley & Sons, Inc., New York City, 1914. Outlines and defends a
treatment of disease based on the principles of colloid chemistry.
14 — First, Second and Third Reports on Colloid Chemistry and Its
General and Industrial Applications, by the British Association for the
Advancement of Science. At H. M. Stationery Office, 128 Abingdon St.,
London, S. W. 7. Each report (about 160 pp.) contains chapters on special
fields by eminent authorities. Thorough reviews, numerous references
An invaluable colloid library. Each report costs 2/6 d.
15 — A Laboratory Manual of Colloid Chemistry written by Harry
N. Holmes at the request of the Committee on Colloids will be published in
the near future by John Wiley & Sons, Inc.
16 — Martin Fischer and Marian Hooker: "Fats and Fatty Degenera-
tion." 146 pp. John Wiley & Sons, Inc., New York City, 1917. Theories
of emulsification discussed, especially in relation to body tissues.
17 — U. S. Bureau of Soils, Bulletin 52; "Absorption by Soils." 85
pp. 1908. Very useful.
18 — U. S. Bureau of Soils, Bulletin 51; "Absorption of Vapors and
Gases by Soils." 1908.
19 — Ashley: "Technical Control of the Colloidal Matter of Clays."
U. S. Bureau of Standards, Technologic I'aper 23. 115 pp. Written
in 1911.
20 — Bancroft: "Applied Colloid Chemistry." Chan. Met. Ens.,
23 (1920), 454. A brief survey of the field.
21 — W. C. McC. Lewis: "Some Technical Applications of (
and Electrocapillary Chemistry," Met. Chem. Eng., 15 (1916), 253-259;
also J. Soc. Chem. Jnd., May 31, 1916. Somewhat like the book by Alex-
ander (No. 2).
358
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
22 — Whitney and Ober: J. Am. Chem. Soc, 23 (1901), 856-863.
Gives an excellent bibliography, with brief comment, of colloid work pub-
lished before 1901. Nearly 150 references.
23 — A. Miiller: "Bibliography of Colloid Chemistry," Z. anorg.
Chem., 39 (1904), 121. 356 references grouped by subjects, without com-
ment
24 — Hober: "Physikalische Chemie der Zelle und Gewebe." Wil-
hetm Engelmann, Leipzig, 1911.
25 — Rideal and Taylor: "Catalysis in Theory and Practice." The
Macmillan Co., New York, 1919. Not primarily a colloid book but con-
tains material of value to colloid chemists. A new edition is promised.
Kolloid-Zeitschrift and its Beihefie have devoted their columns exclu-
sively to colloid research. Very important.
The Journal of Physical Chemistry contains a vast amount of
invaluable material and no student of colloid chemistry can
afford to neglect this journal. Many of the articles contain ex-
ceptionally full summaries of the work done in special fields,
and are really monographs. The results of colloid research,
however, are found in most of the great journals.
Since many chemists waste time and become discouraged by
reading the wrong book first, we urge any one of the first three
in the above list as the proper introduction to the subject.
Oberlin, Ohio Harry N. Holmes, Chairman,
Obbrlin Collbob Committee on Chemistry of Colloids
Calendar of Meetings
Technical Association of the Pulp and Paper Industry —
Spring Meeting, Waldorf-Astoria and Hotel Astor, New York,
N. Y., April 11 to 14, 1921.
American Paper and Pulp Association — Annual Meeting,
Waldorf-Astoria and Hotel Astor, New York, N. Y., April
11 to 15, 1921.
American Electrochemical Society — Spring Meeting, Hotel
Chalfonte, Atlantic City, N. J., April 21 to 23, 1921.
American Chemical Society — Sixty-first Meeting, Rochester,
N. Y., April 26 to 29, 1921.
American Oil Chemists' Society — Twelfth Annual Meeting,
Chicago, 111., May 16 to 17, 1921.
American Institute of Chemical Engineers — Spring Meeting,
Detroit, Mich., June 20 to 21, 1921.
Seventh National Exposition of Chemical Industries — Eighth
Coast Artillery Armory, New York, N. Y., September 12 to 17,
1921.
NOTES AND CORRESPONDENCE
Note on the Use of Potassium Permanganate in
the Determination of Nitrogen by the
Kjeldahl Method
Editor oj the Journal of Industrial and Engineering Chemistry:
It was for a long time the practice in this laboratory to add
potassium permanganate at the end of digestion in the deter-
mination of nitrogen. About a year ago it was decided to de-
termine whether the addition of the permanganate was neces-
sary. After making determinations for several weeks in which
permanganate was added to one of the duplicates, we concluded
that it had no effect and its use was discontinued. On that ac-
count we were surprised at the results obtained by Cochrane
(This Journal, 12 (1920), 1195]. The results of further ex-
periments lead to the conclusion that the addition of perman-
ganate is not necessary when sodium or potassium sulfate and
mercury are used with the sulfuric acid in the digestion.
It was noted that Cochrane did not use either potassium or
sodium sulfate and it seemed possible that the more uniform
results obtained when he used potassium permanganate were
due to the fact that the digestions were not complete at the end
of 2 .5 hrs. Several digestions were, therefore, made with sodium
sulfate in one duplicate and none in the other. The results
showed that the digestion is not complete within 2.5 hrs. if
the sulfate is not added.
Our results are summarized in the following table:
. Per cent of Nitrogen .
12 3 4
Na2S04 NajSO.
No. of No and and no
Deter KMnOi KMnOi KMnO. KMnOt
mina- Added Added Added Added
Substance tions Average Average Average Average
Cottonseed Meal A 2 6.993 6.822 7.043 7.043
Cottonseed Meal B 2 6.977 6. 789 7.044 7.043
Wheat Mixed Feed A 2 2.720 2.712 2.784 2.730
Wheat Mixed Feed & Sc. A 2 2.470 2.444 1.488 2.461
Comp. Feces A 2 1.342 1.394 1.344 1.400
Comp. Feces B 2 1.360 1.283 1.360 1.400
Broom Corn Silage Refuse A 2 0.472 0.492 0.459 0.499
Broom Corn Silage Refuse B 2 0.464 0.486 0.424 0.483
C. T. DOWELL AND W. G. Friedemann
Oklahoma Agricultural Experiment Station
Stillwater, Oklahoma
January 20, 1921
Editor of the Journal of Industrial and Engineering Chemistry:
I would call attention to the fact that in five out of the eight
samples analyzed, the data presented in Columns 1 and 2 of
the table support the conclusions drawn in my article.
No comparison was made in my article between the straight
Kjeldahl method and the Gunning modification, nor were any
data presented bearing on the use or non-use of permanganate
in any method where sodium or potassium sulfate is used to
raise the boiling point of the digestate.
Pennsylvania State College D. C. Cochrane
State College, Pa.
February 5, 1921
+ 2H,
The Formation of Anthracene from Ethylene
and Benzene — Correction
In our paper on the above subject [This Journal, 13 (1921),
208] several self-evident errors escaped proof reading, and we
wish to have them corrected though they do not in any way affect
our results or conclusions.
On page 208, first column, the reaction should read:
H
/Cx
^— CH
I2
H
On the same page, second column, the reaction should read:
2C,H6 + C2H4 — > CnHio + 3Hf — 5.2 Cal.
On the same page, second column, footnote, the change should be
2C, + 2H6 — > 2C6HC — 22.6 Cal.
and Ci*Hio instead of CioHM.
J. E. Zanetti and M. Kandel
Columbia University
New York, N. Y.
The Estimation of Cellulose in Wood
Editor of the Journal of Industrial and Engineering Chemistry:
With the exception of a few attempts to determine the cellu-
lose content of lignified materials by dissolving and reprecipitat-
ing the cellulose, it has been the object of all quantitative cellu-
lose determinations to isolate the cellulose by dissolving out the
noncellulose compounds. A complete removal of these com-
pounds from a highly lignified substance, such as wood, without
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
35lJ
attacking the' cellulose proper has never been accomplished.
But it is possible by careful manipulation to remove completely
some of the noncellulose substances, such as rosin, lignin, and
lower carbohydrates, from finely disintegrated wood ; and to ob-
tain a residue which does not contain decomposition products
of the cellulose originally present as such in the wood. This
residue, however, differs chemically from normal cellulose as
represented by purified cotton, in that it yields an appreciable
quantity of furfural on distillation with hydrochloric acid, proba-
bly owing to the presence of highly resistant pentosans.
Of the many methods that have been suggested for the quan-
titative determination of cellulose in wood, none have been more
widely accepted than Cross and Bevan's1 method, which is based
upon the removal of the lignin by chlorination. The method
was originally applied to jute fiber and included boiling of the
fiber for one-half hour in a 1 per cent sodium hydroxide solution,
treatment with chlorine gas for 30 to 60 min., and dissolving of
the lignin chloride in a 2 per cent solution of sodium sulfite at
boiling temperature. After washing, the fibers were finally
bleached with potassium permanganate.
In applying the method to wood fibers, several investigators
found that it was not possible to remove the lignin completely
with one single chlorination, but that if the fibers were subjected
to alternating treatments with chlorine gas and sodium sulfite,
a complete removal of the lignin compound could be effected.
Renker2 obtained from wood a residue which did not give any
of the lignin reactions, by repeating the treatment six times
with a total time of exposure to the gas of 2.75 hrs. He also
modified the original method by omitting the treatment with
sodium hydroxide previous to chlorination, stating that he thereby
obtained a considerably higher cellulose value with equal purity
of residue. It is of importance for the following discussion to
point out at this place that Renker based this statement upon the
fact that the residue did not give the qualitative lignin reactions,
while he did not analyze the residue with regard to furfural yield.
According to Renker the time of exposure to the chlorine gas
should be as short as possible, since the cellulose itself is attacked
by prolonged exposure to the gas, and he was supported by Heuser
and Sieber,3 who found that under the action of chlorine gas a
layer of lignin chloride is rapidly formed on the surface of the
fiber, preventing further penetration of the gas. It is therefore
necessary to dissolve this layer before the chlorination is con-
tinued, and in doing so it is possible to remove the lignin com-
pletely without injury to the cellulose. Sieber and Walter4
found that four chlorinations with a total exposure to the gas of
1 hr. were sufficient for the complete removal of the lignin in wood.
They also allowed the fibers to remain in the same Gooch crucible
with a stationary calico pad throughout the entire process of
purification, thereby eliminating mechanical losses, which might
occur when using Renker's method. Their method of manipula-
tion has been adopted by recent investigators with the exception
of Schorger, who used practically the same method as Renker.
The chlorination method has the advantage above other
methods of cellulose determination of being a well-studied re-
action, simple in operation and quick, and giving a residue free
from lignin and without decomposition products of the original
cellulose. But it was severely criticized by Konig and Huhn6 on
account of the high furfural yield of the residue. These investi-
gators proved that the furfural-yielding substances could be
practically completely removed from the wood fiber by hydrol-
ysis, but their method of accomplishing this, as well as the method
proposed by Tollens and Dmochowsky,6 both of which methods
include a hydrolysis with inorganic acids and both of which yield
1 "Cellulose," London. 1918, 94.
* "Bestimmungsmethoden der Cellulose," Berlin, 1910
' Z. angew. Chem., 26 (1913), SOI.
* Papier-Fabr , 11 (1913), 1179.
•"Bestimmung der Cellulose in Holzarten und Gespinnstfasern."
Berlin. 1912
a product free from lignin and practically free from furfural-
yielding substances, cannot be recommended for quantitative
estimation of cellulose, because, as I have shown, the cellulose
itself is attacked and partly dissolved in the process of purifica-
tion. It is a fact that the furfural-yielding compounds of the
wood are subject to hydrolysis, but it is equally true that even
very dilute inorganic acids attack normal cellulose.
Apparently the cellulose is much more resistant towards the
action of organic acids. In fact Schwalbe and Johnsen1 found
that cellulose heated with a mixture of glycerol and acetic acid
at 135° C. for several hours did not show any sign of attack as
indicated by reducing power, and a method of estimating the
cellulose content of commercial wood pulps which included this
treatment was developed by them. Later, Johnsen and Hovey'
suggested a method of cellulose determination in wood consisting
of a 4-hr. hydrolysis with glycerol and acetic acid at 135° C,
with a subsequent chlorination according to Sieber and Walter,
and found that by employing this method a residue of higher
purity could be obtained from wood fibers.
The subject of cellulose determination was recently discussed
by Dore,3 who arrived at the conclusion that "all processes in-
volving preliminary hydrolysis result in a diminished yield ol
cellulose as well as total cellulose and are therefore inacceptable
as accurate cellulose processes." Partly on the basis of this
statement, partly on his own observations. Mahood4 in a more
recent contribution to the subject states that "The modification
of the Cross and Bevan method proposed by Johnsen and Hovey
appears to be of doubtful value since the cellulose, as well as the
hemicelluloses and furfural-yielding constituents, are attacked."
In view of the importance of the subject under discussion, it
would seem advisable to prove such statements by convincing
experimental data. But Dore, as well as Mahood, has failed
to do so, and I hope to be able to show in this article that the
conclusions arrived at by the two investigators are based upon
insufficient analytical data and upon statements which are mis
leading and partly incorrect.
In order to facilitate the discussion of some of the experimental
results, two tables taken from Dore's publication are copied
below:
Table II — Comparison of Methods op Preliminary Hydrolysis as-
Applied to Woods
Results in percentages of air-dry wood (11.62 per cent moisture)
Ratio
..-Cel-
lulose:
Total Cellolosb o-Celluloss Total
Individual Av. Individual Av. Cel-
lulose
(1) Renker's modification of 47.93 36.04
Cross and Bevan's method. 48.46 36.02
No hydrolysis 48.97 36.71
48.77 36.84
48.91 37.09
48.27 36.76
48.24 48.51 36.99 36.64 0.75
(2) Original Cross and Bevan 45.86 35.38
method. 1 hr. with 1 per 46.28 35.49
cent sodium hydroxide at 45.85 35.25
boiling temperature 45.07 35.83
45.64 35.76
46.29 45.83 35.55 35.41 0.77
(3) Johnsen and Hovey method. 44.04 34.60
4 hrs. with acetic acid and 44.11 34.73
glycerol at 135° C. 44.37 34.70
44.49 44.25 34.53 34.64 0.78
Table III — Furfural Yield of Products
In percentages of air-dried material (11.62 per cent moisture)
From Total From a-
Cellulose Cellulose
Individual Av. Individual Av
(1) Renker's process. No hydrol- 2.66 0.52
ysis 2 . 36
2.69 0.48
2.38 2.52 0.51 0.50
(2) Cross and Bevan's process. Al- 2.67 0.31
kaline hydrolysis 2.63 2.65 0.24 0.27
(3) Johnsen and Hovey's process. 2.18 0.25
Acid hydrolysis 2.20 2.19 0.27 0.26
' Pulp Paper Mae. Can., 13 (1915), 600.
" J. Soc. Chem. Ind., 37 (1918), 132.
• This Journal, 12 (1920), 264.
• Ibid., 12 (1920), 873.
son
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 4
The determination of a-eellulose gives, of course, an excellent
indication of the purity of the residues, provided the a-cellulose
is a well-defined substance. Table II, however, shows that this
is not so, since the furfural yield of the a-eellulose obtained from
Renker's process is considerably higher than of that obtained
with Johnsen and Hovey's method. The a-cellulose from the
latter process yields 0.26 per cent furfural, which is very close
to the yield from purest cotton cellulose,1 e. g., 0.24 per cent.
With regard to furfural yield and a-cellulose content of the resi-
dues, it will also be seen from the two tables that the cellulose
resulting from Johnsen and Hovey's method is of a higher purity
than that from Renker's method (no hydrolysis), which latter
accordingly must give a higher yield. Assuming that the fur-
fural originates with highly resistant pentosans (which has never
been disproved), the difference in yield of pentosan-free a-cellulose
with the two processes was only 1.58 per cent, while the difference
in total cellulose in the two processes was 4.26 per cent, which
shows that Dore's statement that the total cellulose and the
a-cellulose "are destroyed in the same proportion" is incorrect.
The difference of 1.58 per cent in the yield of a-cellulose does
not necessarily mean that the normal cellulose is attacked in the
hydrolytic treatment. The possibility naturally exists that a
cellulose which has been exposed to acid hydrolysis is more easily
attacked by strong alkali than a cellulose which has not received
this treatment. But it is more probable that the difference in
yield is caused by the removal of carbohydrates other than
pentosans and less resistant than cellulose. Apparently Dore.
as well as Mahood, is inclined to consider as cellulose all sub-
stances in the cellulose residue which do not give furfural reac-
tion. This can hardly be accepted as correct since we must
assume the presence of hexosans of less resistance than cellulose,
and which therefore can be separated from the cellulose proper
by hydrolysis, but by a more effective hydrolysis than that ob-
tained with sodium sulfite at 100° C.
This would explain the considerably lower yield of cellulose in
the commercial wood pulp processes than the yield indicated by
the cellulose determination, since the commercial processes in-
clude hydrolysis at high temperature and pressure. It would
also explain why the yield obtained with Johnsen and Hovey's
method is lower than that of Renker's method, because the former
includes an acid hydrolysis with acetic acid in glycerol at 135° C.
Since this process removes the more resistant furfural-yielding
substances and hexosans to a larger extent than Renker's method,
the residue is more identical with the pulps obtainable in the
commercial processes. Johnsen and Hovey therefore considered
their method "very useful in the valuation of the various woods
for the commercial paper pulp processes."
Dore concludes that "the hydrolytic processes do not remove
any appreciable amount of the furfural-yielding complexes from
the product." But there are no experimental data in Dore's
article to prove this conclusion, while Johnsen and Hovey's
publication shows that with their method over 10 per cent more
of the total furfural-yielding substance is removed, or that be-
tween 22 and 25 per cent of these substances still remaining in
the residue from Renker's method are removed with their method.
In discussing the removal of these substances by acetic acid
hydrolysis, Mahood states that "approximately the same result
could be attained by a further chlorination of the sample than
usual." But this is not so, since apparently the furfural-yielding
constituents, while being comparatively easily hydrolyzed, are
very resistant to chlorination or oxidation. Furthermore, it
must be remembered that it is not permissible in a quantitative
method to continue the chlorination after the total lignin has
been removed, since this would result in an oxidation of the
cellulose proper.
Mahood's strong criticism of the Johnsen and Hovey method
is based to a very great extent upon Dore's experiments, according
1 Z. angtu. Chcm , March 5 and 12 (1918); Paper, 23 (1918), 277.
to which the normal cellulose is destroyed by hydrolysis with
acetic acid in glycerol at 135° C. For these experiments Dore
selected as normal cellulose "a piece of cotton sheeting which had
been repeatedly laundered and might therefore be considered a
residue consisting of highly resistant cellulose, mostly of the
normal type." This is fundamentally incorrect, since it is well
known that the resistance of cotton cellulose is considerably
reduced by laundering. On the other hand, Schwalbe and John-
sen have found that the hydrolysis with acetic acid in glycerol
does not attack the cellulose. Purest cotton cellulose hydrolyzed
with this mixture and subsequently treated with nitrous gases
lost only 0.12 per cent of its weight. Unfortunately this work
has not yet been published in detail, but it has been referred to
in recent publications by Johnsen1 and by Schwalbe.1
In conclusion, the writer wishes to refer to two statements in
Mahood's article, because they are in disagreement with the
results obtained by other investigators, and should therefore be
more thoroughly investigated. Mahood found that there was
an appreciable loss in weight of the fibrous filter pad used in the
Gooch crucible, owing to the action of chlorine. When using un-
purified calico Sieber and Walter recorded a loss of 0.001 g. A
purified calico pad gained 0.0002 g. in the treatment. Sieber
and Walter also found that cooling did not have any influence
upon the yield, while Mahood believes that the lower yield of
cellulose which he experiences with Sieber and Walter's modi-
fication of the method as compared with the original method is
due to the higher temperature.
Sieber and Walter's modification of Renker's method repre-
sents a decided improvement in the process in mechanical manip-
ulation, in that it eliminates mechanical losses of fiber, and the
method has therefore been adopted by most of the recent in-
vestigators and by commercial laboratories. It should therefore
be carefully investigated whether the lower yield with this pro-
cess as recorded by Mahood is due to destruction of cellulose
substance on account of excessive chlorine treatment, or whether
it is due to a less complete purification with Schorger's equip-
ment.
Hammermili, Paper Company
Erie, Pennsylvania
November 5, 1920
Bjarne Johnsen
Editor of the Journal o} Industrial and Engineering Chemistry:
Johnsen contends that my conclusions "are based upon insuffi-
cient analytical data and upon statements that are misleading
and partly incorrect." It is to be regretted that Johnsen offers
no new experimental data in support of this rather sweeping
statement.
The first point at issue concerns the definition of cellulose, and
it is stated that I (in common with Dore) am "inclined to regard
as cellulose all substances in the cellulose residue which do not
give furfural reaction." This statement is indeed misleading,
for, in regard to the cellulose obtained in the investigation under
discussion, I say that "the cellulose obtained in each case was
treated with chlorine and sodium sulfite to the point where no
color was obtained." This defines wood cellulose as well as our
present knowledge of its chemistry will permit. The residue
thus obtained is made up apparently of hexosans, pentosans, and
possibly furfural-yielding constituents other than pentosans.
Johnsen's original paper on the subject, as well as his more recent
discussion of it, is open to the criticism that he does not define
what he means by cellulose. Apparently he considers that there
is but one cellulose, and that normal or cotton cellulose. As
pointed out by Schorger, it is no more reasonable to expect cot-
ton to be the only cellulose in nature than glucose to be the only
sugar. It is probable that wood celluloses should be looked upon
as definite compounds of hexosans with varying amounts of
pentosans.
1 Loc. tit.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
361
We are not obliged to assume, as Johnsen contends, "the pres-
ence in wood of hexosans of less resistance than cellulose and
which can therefore be separated from cellulose by hydrolysis,
but by a more effective hydrolysis than that obtained by sodium
sulfite at 100° C." This assumption is very convenient for the
purpose of correlating Johnsen and Hovey's method of cellulose
determination with the wood pulping processes, but it ought to
have some experimental basis which as yet is entirely lacking.
Commercial processes are as a rule poor criteria by which to judge
analytical methods. It is generally considered that the differ-
ence between the yield of cellulose obtained from wood by the
laboratory method and that obtained by the pulping processes
is due to the more drastic treatment in the latter which destroys
some of the cellulose. Since Johnsen and Hovey's method gives
a "residue more identical with the pulps obtainable in the com-
mercial processes" it may be assumed, in the absence of experi-
mental data to the contrary, that it, too, destroys some of the
cellulose.
Johnsen objects to my statement that "approximately the
same result could be attained by a further chlorination of the
sample than usual" in reference to the residues obtained by his
method. Approximately 50 per cent of the furfural-yielding
constituents of woods are removed by the chlorination process.
It seems reasonable to suppose, therefore, that a further loss of
these constituents would result on continued chlorination (John-
sen says "this is not so," but gives nothing to show that it is not).
Since it is not permissible, as Johnsen points out, to continue
chlorination after the total lignin has been removed, as this
would result in oxidation of the cellulose, further chlorination
of the sample than usual would have the effect of reducing both
the pentosan and the pentosan-free cellulose content, and this is
the apparent effect of the digestion with glycerol and acetic acid.
Johnsen's statement that my criticism of his method is based
"to a very considerable extent on Dore's experiments" seems to
be an attempt at subterfuge. My data show that the yield of
pentosan-free cellulose as well as the pentosan content of the cellu-
lose is reduced by preliminary treatment of the wood sample with
the acetic acid-glycerol mixture. Johnsen explains this lowering
of the pentosan-free cellulose by assuming that the loss is due to
hexosans less resistant than cellulose, but there is nothing in
Johnsen's paper to warrant this assumption. On the other hand,
Dore's data corroborate mine, and although it is true that laun-
dering, beyond a certain point, reduces the resistance of cellulose,
the data still hold for the comparative purpose for which they
were intended.
Johnsen's observation that "two statements" in my article
"are in disagreement with the results of other investigators"
should be modified to include only two other investigators, i. e.,
Sieber and Walter working jointly, and it should be noted that
my statement in regard to the effect of temperature is supported
by Cross and Bevan and by the work of Renker.
The fact that my data are not in accord with those of Sieber
and Walter on the loss in weight of the fibrous pad emphasizes
this potential source of error in the procedure. I used the best
calico obtainable and subjected it to treatment with chlorine and
sodium sulfite prior to making the test runs. The loss entailed
will be determined largely by the previous history of the calico,
and since this cannot usually be determined it cannot be assumed
that the loss in weight will be negligible if accurate results are
desired. If other objections to the Sieber and Walter procedure
are overcome this potential source of error can probably be
eliminated by the use of a Willard crucible.1
Applying Johnsen's test of purity of cellulose, i. e., the amount
of furfural it yields, to the cellulose residues obtained by me with
Sieber and Walter's apparatus, they contain an average of 7.68
1 Described at the St. Louis Meeting of the American Chemical So-
ciety, April 12 to 16, 1920. The bowl of this crucible is pyrex glass, while
the bottom consists of a porous alundum disk which is fused to the glass.
per cent pentosan, while those obtained with Schorger's apparatus
contain 7.35 per cent. The purity of the residues, which Johnsen
thinks may be different, appears, therefore, to be of the same
order.
The lower yield of cellulose using Sieber and Walter's equip-
ment does not appear to be due to "excessive chlorine treatment,"
as indicated by the following data from my paper:1 "Five one-
half hour chlorinations were required for complete chlorination
following Cross and Bevan's procedure while periods of 20, 15,
15, 10, and 10 min. were required with the modified procedure."
Taking into consideration these experimental facts and also the
work of Cross and Bevan and of Renker, my statement that "the
higher yield (of cellulose) obtained using the original procedure,
notwithstanding the longer exposure to chlorine, is probably ac-
counted for by a lower concentration of chlorine and a lower
chlorination temperature" seems justified.
In the hands of competent analysts the mechanical losses in
manipulation using the method of Renker and of Schorger are
negligible. The only advantage of the Sieber and Walter method
is a shortening of the time required for the analysis. With the
use of the Willard crucible, a dilution of the stream of chlorine
or the use of a suitable cooling device or both of these, perhaps,
it may be made to give as good results as the original Cross and
Bevan procedure.
The statement by Johnsen that the Sieber and Walter method
"has been adopted by most of the recent investigators and by
commercial laboratories" is answered in part at least by the fol-
lowing from the article by Johnsen and Hovey:2 "As in recent
investigations use has not been made of this improvement, which
in our opinion is extremely valuable, the preparation of the
crucible as suggested by Sieber and Walter is described here."
Where it has been used it apparently has been adopted in the
way that Johnsen and Hovey adopted it, i. e., without determin-
ing its accuracy in comparison with the original procedure.
Johnsen's suggestion that the controverted points should be
"more thoroughly investigated" is therefore timely. In this
investigation should be included another of Sieber and Walter's
conclusions as stated by Johnsen "that four chlorinations with
a total exposure to the gas of 1 hr. was sufficient for the complete
removal of the lignin from wood." Schorger3 found the number
of chlorinations necessary to obtain lignin-free cellulose to vary
with wood from the same species as well as with wood from dif-
ferent species.
Up to the present time the Johnsen and Hovey method has
not proved to be4 "a standard method which could be recom-
mended for future investigations." In fact, with the determina-
tion of the furfural-yielding constituents as the sole test of purity
of the resulting cellulose, the treatment with the glycerol-acetic
acid mixture, in addition to being objectionable for reasons al-
ready pointed out, seems superfluous, since the percentage of
cellulose free from furfural-yielding constituents or "pure" cel-
lulose can be obtained by deducting the percentage of these
"impurities" from the cellulose values obtained by chlorination.
Such a correction is recommended by Schwalbe5 and is made
by him and Becker6 recently in the analyses of some species of
German woods. It can be applied to the results of Schorger
and others who have recorded the pentosan content of the cel-
lulose if one objects to furfural-yielding constituents as impurities
in the cellulose.
The Laboratory of Organic Chemistry S. A. MahOOD
Tulane University, New Orleans, La.
February 8, 1921
I This Journal, 12 (1920), 875.
' J Soc. Chem. Ind., 37 (1918), 1331.
i This Journal, 9 (1917), 563.
i J. Soc. Chem. Ind.. 37 (1918). 132/.
>Z. angew- Chem., 32 (1919), 125.
' Ibid., 32 (1919), 229.
362
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
Editor of the Journal of Industrial and Engineering Chemistry:
Johnsen protests against my statement that "all processes
(for the determination of cellulose in woods ) involving preliminary
hydrolysis result in a diminished yield of a-cellulose as well as
total cellulose and are therefore inacceptable as accurate cellulose
processes." This, he maintains, I have failed to prove "by con-
vincing experimental data."
The first part of the above statement is nothing more than
the verbal expression of data which Johnsen has quoted in Table
II, and may be regarded, therefore, as a fact beyond dispute if
the data be accepted as reliable. The second part of my state-
ment deals with the significance and interpretation of these facts
and it is with this part that Johnsen's criticisms are concerned.
Johnsen expresses a doubt as to whether a-cellulose is a well-
defined substance, inasmuch as that obtained from Renker's
process yields an average of 0.50 per cent furfural while that
from the Johnsen and Hovey process yields only 0.26 per cent
furfural. The differences in furfural yield do not necessarily
indicate that the a-cellulose is an ill-defined product. It is by
no means certain that the furfural obtained from the a-cellulose
residues is due to pentosans; on the contrary, the fact that the
yield is small increases the probability that it originated in other
substances, for it is well known that other carbohydrates than
pentosans are capable of yielding furfural, usually, however,
in but small amounts. Furthermore, the fact that the amount
of furfural obtained from any one substance varies according
to the conditions maintained during the analysis appears to
indicate that the furfural is obtained, not altogether from pre-
formed groups, but, at least in part, by rearrangements within
the molecule. In view of the known labile character of the cellu-
lose molecule, it is not unreasonable to regard the furfural yield
of the a-cellulose as probably resulting from such rearrangement.
The observed differences in furfural yield between the a-cellulose
residues by the two processes may be due to alterations in the
molecular arrangements during preliminary treatment. Such
changes may be assumed to take place without necessarily im-
plying that the two products are essentially different.
Since the furfural yield is subject to the influence of so many
possible factors, it would appear that the conclusion expressed
in my original article is correct and that no significance is to be
attached to the small furfural yield of the a-cellulose.
Johnsen claims that the a-cellulose by the Johnsen and Hovey
process yields an amount of furfural approximating that from
purified cotton. This claim is based upon the agreement of data
which are not properly comparable. The figures quoted in
Table III of Johnsen's article show that the residue by the John-
sen and Hovey process yields 0.26 per cent of furfural expressed
in percentage of the original air-dry wood. When recalculated
to the basis of the a-cellulose, which constitutes 34.64 per cent
of the air-dry wood, the furfural yield by the Johnsen and Hovey
process becomes 0.75 per cent. When this figure is compared
with that given by Johnsen for the furfural yield of purified
cellulose (0.24 per cent), it is clear that the residue by the Johnsen
and Hovey process yields considerably more furfural than puri-
fied cotton.
Inasmuch as it is generally recognized that substances other
than pentosans are capable of yielding furfural, we are not obliged
either to assume or disprove that the furfural yield of cellulose
residues is due to pentosans. It appears probable that the small
yields of furfural from the a-cellulose residues are largely or
wholly due to other sources; therefore Johnsen is not justified in
assuming that the furfural originates in pentosans, or in applying
a pentosan correction to the residue. He has accordingly failed
to disprove that the total cellulose and a-cellulose are "destroyed
in the same proportion."
The data in the last column of Table II, quoted by Johnsen,
show that the total cellulose by the Renker process contains an
average of 75 per cent of a-cellulose, while that by the Johnsen
and Hovey method contains an average of 78 per cent of a-cellu-
lose. In the case of cotton cellulose, the total cellulose by the
Renker process yielded 95 per cent of its weight of a-cellulose,
and that by the Johnsen and Hovey process yielded 94 per
cent of a-cellulose. This is apparent from the following data
quoted from Table IV of my original article:1
Ratio
a-Cellulose:
Total Total Cellu
Treatment Cellulose a-Cellulose lose
No hydrolysis (Renker's method) 89.90 80.32 0.95
Acetic acid and glycerol 4 hrs. at 135° C.
(Johnsen and Hovey's method) 85.91 SO. 63 0.94
My original contention, in so far as it applied to the Johnsen
and Hovey process, was that the differences between 75
and 78 per cent in one instance, and between 95 and 94 per cent
in another, are not sufficient to indicate a material improvement
in the purity of the product by the Johnsen and Hovey process
over that by the Renker process. It therefore appears correct
to ascribe the diminished yields of total cellulose and a-cellulose
to a destruction of those substances in practically the same
proportion.
Johnsen has shown that if the furfural of the a-cellulose be
calculated to pentosan and deducted, the residue by the Johnsen
and Hovey process still contains 1.58 per cent less of the pentosan-
free a-cellulose than the residue by the Renker process. This
difference, he maintains, is probably due, not to an attack on
normal cellulose, but to a removal of less resistant carbohydrates
not properly to be regarded as cellulose. However, these car
bohydrates, which Johnsen would exclude from the a-cellulose
residue as not being normal cellulose, are resistant to chlorina-
tion and sulfite treatments and the subsequent treatment with
17.5 per cent sodium hydroxide. It would seem, therefore, that
there is little or no justification for designating them as "lower
carbohydrates," or classifying them with the hemiceUuloses
when their properties are so much more closely related to those
of the true celluloses.
In my original article2 my conception of cellulose "as applied
to material derived from woods," was stated as the "residue
remaining after alternate treatments with chlorine and sodium
sulfite solution" when the process is "preceded with non-hydro-
lyzing treatments only. The residue so obtained should be
free of lignin and hemicelluloses. It may contain a-, &-, and
7-celluloses corresponding to the definitions of those substances
implied by the conditions of the mercerization test, also furfural-
yielding complexes, but should be free from easily hydrolyzable
pentosans." The quotations should render unnecessary any
speculation as to what I consider cellulose.
The definition of cellulose as a residue of processes is consistent
with the views of Cross and Bevan and those of Renker. Schor-
ger, who confirmed some of Renker's views, has given a formal
definition of cellulose as "the residue remaining after alternate
treatment with chlorine gas and sodium sulfite up to the point
where the chlorine sulfite color reaction or the Maule reaction
disappears."3 All of these authors regard cellulose as a residue
of processes. Until more complete information exists regarding
its chemical nature, it appears desirable to regard wood cellulose
as a group of substances with a similar degree of resistance to
reagents. Repeated attempts to narrow it down to a single
substance, similar to the cellulose of cotton, have been uniformly
unsuccessful, because the high resistance of the residue requires
the use of drastic reagents, which invariably attack all members
of the group.
Johnsen claims that my statement that "the hydrolytic pro
cesses do not remove any appreciable amount of the furfural-
yielding complexes from the product" is not supported by ex-
perimental data. The data quoted in Table III show that the
1 This Journal, 12 (1920), 268.
1 Loc. cil., p. 269.
» This Journal, 9 (1917), 563.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
363
total cellulose by Johnsen and Hovey's method yields only 0.33
per cent less furfural than that by Renker's process. The same
table shows a variation of 0.33 per cent between the highest and
lowest of four determinations of furfural yield on material pre-
pared by Renker's process. No significance can be attached,
therefore, to a diminution of a few tenths of 1 per cent in furfural
yield, and the results indicate that at most only a trifling re-
duction in furfural yield is accomplished by the Johnsen and
Hovey method.
It is claimed for the Johnsen and Hovey method that it gives
a residue corresponding closely to that obtained in manufacturing
wood pulp, and that it is therefore "very useful in the valuation
of woods for the commercial paper pulp processes." I do not
dispute the possible value of this method as a technical method
in pulp mill practice. The residue, however, does not conform
to any recognized conception of cellulose and should not be so
designated. Johnsen does not claim that the residue by the
Johnsen and Hovey process is "pure" in the same sense that he
regards the Renker residue as "impure." He claims that the
former is purer, but the most favorable data show that at best
it can be regarded as only slightly purer. Furthermore, the
reduced yields of total and a-cellulose by the process show that
true cellulose is partly destroyed. (This statement rests upon
the experimental data which Johnsen has quoted. It has been
questioned by him but not disproved ) It is my contention,
therefore, that however useful the Johnsen and Hovey method
may be for judging the paper-making qualities of woods, it is
unsuitable for scientific investigations on the chemical nature of
woods or other cellulosic materials.
Johnsen has taken exception to my statement that "cotton
sheeting which had been repeatedly laundered" might be con-
sidered "a residue of highly resistant cellulose mostly of the
normal type." The fact that the residue on chlorination yielded
95 per cent of a-cellulose shows both a high degree of resistance
and a high proportion of a- or normal cellulose. No claim has
been made that it was in any sense a chemically pure cellulose,
and it was not necessary that it should be such for the purpose
in mind, namely, to determine whether cellulose from an unlig-
nified source showed the same behavior as wood cellulose. The
data show that this cellulose, as well as wood cellulose, gives less
total and less a-cellulose when treated by the Johnsen and Hovey
method. The reduced yields of a-cellulose indicate that the
normal cellulose is attacked by this process.
Experiments with highly purified cellulose are undoubtedly
capable of contributing greatly to our knowledge of fundamental
cellulose chemistry. It is unfortunate that the valuable data
to which Johnsen has referred have not been published in detail,
and it is to be hoped that they soon will be made completely
available. WALTER H. Dore
University of California Experiment Station
Berkeley, California
January 31, 1921
Phthalic Anhydride Derivatives
Editor of the Journal of Industrial and Engineering Chemistry:
I noted with interest the list of phthalic anhydride derivatives
appearing in This Journal, 13 (1921), 274. I was surprised
to note that some of the commercially most important deriva-
tives have been omitted. I am listing below certain of these
products and the literature references for the same, and suggest
that these be added to the list already published.
Schultz' "Dyestuff Tables." 260. Also, under the dyestuffs should
be added the product known and sold as Sirius Yellow G, which is produced
from the above-mentioned intermediates, and is an important dyestuff
in the lake pigment industry.
Anthraqu
a-Benzoylbenzoic acid
Z. angew. Chem., 19 (1906), 669; Ber., 41 (190S), 3631
Quinizarin (1^4-Dihydroxy-anthraquinone)
Ber., 6 (1873), 508; U. S. Patent 708,142. This product is used in the
production of two very important dyestuffs, namely, Alizarin and Cyanine
Green, and Alizarin Direct Violet, also known as Alizarin Irisol
2-Methylanthraquinone
Ber., 41 (1908), 3632. This very important intermediate is used in the
manufacture of three well-known vat dyes, namely, Anthraflavone G,
Cibanone Orange R, and Cyauanthrol R and G. This last-named inter-
mediate is used in the production of other intermediates, from which are
produced other vat dyes such as, for example, Indanthrene Gold Oraage G
Hydron Yellow
D. R. P. 1,055,287
A very good reference on all the above-mentioned products
may be found in "The Manufacture of Intermediate Products
for Dyes," by J. C. Cain, 2nd Ed., Macmillan & Co., 1919.
You may see from the above list, which is by no means com-
plete, that there are some very important products among them,
from the standpoint that they are the starting points for the
manufacture of dyestuffs, a great proportion of which have not
as yet been produced in this country.
The Chemical Foundation, Inc. Arthur LlNZ
81 Fulton St., New York, N. Y.
March 5, 1921
A Memorial of Sir William Ramsay
It has just been learned that the Dean and Chapter of West-
minster Abbey have decided to place a bronze medallion in the
Abbey as a memorial of Sir William Ramsay.
The news of this tribute to the genius of the brilliant English
chemist will be received with the deepest and most sympa-
thetic interest among his many American friends, who regarded
him so highly as a scientist and loved him so truly as a man.
Federal Trade Commission Rulings
The Federal Trade Commission has denied the application
of the Meadows Oil and Chemical Corporation for license under
the Trading-with-the-Enemy Act to use trade-marks covering
ichthyol. A former application made in November 1920
was denied, but the company applied for a re-hearing, which took
place on January 25. The Commission says "it is not to the
public interest to grant the desired license." Last December
the War Trade Board called the company's attention to the
fact that a bulletin issued by the company regarding im-
portations of ichthyol had been so worded as to mislead a num-
ber of firms into thinking it an official statement of the War
Trade Board. The Meadows Company has issued a statement
explaining that this impression was not intentionally created.
According to a statement by the Board, "Information
received by the War Trade Board would tend to show that
American ammonium-ichthyol-sulfonate and other substitutes
for German ichthyol — satisfactory physically, chemically, and
therapeutically — are obtainable from domestic sources on rea-
sonable terms as to price, quality, and delivery. It is under-
stood, of course, that the American product is not derived from
the bituminous shale found in Seefeld, Tyrol, but is derived
from a somewhat similar fossiliferous rock found in Texas. Any
statements which we may make regarding the issuance of licenses
to import German ichthyol are subject to revision upon the re-
ceipt of new information which may tend to prove that the Amer-
ican product is or is not a satisfactory substitute in all respects
for the German ichthyol."
The Commission has cited the Winthrop Chemical Com-
pany, Inc., New York City, in complaint of unfair com-
petition in the drug trade. The company is charged with
falsely advertising that genuine veronal is sold exclusively by
that company. Prior to the war veronal was sold in the
United States under a German patent, and during the war three
American manufacturers, not including the Winthrop Chemical
Co., were licensed by the Federal Trade Commission to make
and sell veronal. Subsequently the Winthrop Company bought
from the Alien Property Custodian the German trade-mark with
the right to make and sell veronal. April 12, 1921, or shortly
thereafter has been set for the hearing of the complaint.
364
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. -i
WASHINGTON LETTER
By Watson Davis, 1418 Rhode Island Ave., Washington, D. C.
The new administration is now passing through its first days
of power, and these are times of conferences and meetings on
Capitol Hill, at the White House, and in the various depart-
ments. Tariff and appropriation legislation programs are being
formulated in anticipation of the convening of Congress on April
11, as President Harding announced only this afternoon.
PLANS FOR THE TARIFF BILL
Following a conference this afternoon of Republican members
of the Senate Finance Committee and the House Ways and
Means Committee with Secretary of the Treasury Mellon and
his advisors, it was decided that a permanent tariff bill will be
drafted at once and that no attempt will be made to push through
an emergency tariff. Whether tariff or revenue bills will come
first, or whether they will be considered concurrently, is still
undecided.
The dye and the chemical industries in general will be amply
protected in the complete revision of the tariff that will be made,
is the assurance of Representative Nicholas Longworth, who
will probably head the Ways and Means Subcommittee on
Schedule A, chemicals. That these essential chemical industries
should have protection from foreign dumping is the unanimous
opinion of those who will frame the necessary legislation, it is
said. The decision for a permanent tariff bill means more hear-
ings, and it may be weeks and months after the convening of
Congress before the final bill is signed. Values and rates in the
Fordney Emergency Tariff Bill that was not passed over Presi-
dent Wilson's veto will exert little influence on the new legislation.
The decision reached at to-day's conference, that an anti-
dumping bill and a measure providing for the levying of ad
valorem duties on the domestic valuation instead of on the
foreign basis of valuation, as at present, will be rushed through
both houses, is of vital interest and importance to the chemical
industry. These two measures will be designed to give emergency
protection to American industry, the former by preventing
foreign dumping of goods and products in this country at prices
below the cost of production, and the latter by eliminating the
advantage given to foreign goods by reason of the present ex-
change situation.
THE CHEMICAL WARFARE SERVICE
That the position of the Chemical Warfare Service will be
very secure and that the present administration will give favor-
able consideration to chemical warfare, is the statement of
Senator Wadsworth, chairman of the Military Affairs Committee.
While it probably will not be possible to give this branch all the
money it asks for, the fundamental and important research and
development connected with gas warfare work will be aided and
pushed, according to Senator Wadsworth. This view of the
importance of chemical warfare is in contrast to that held by the
retiring Secretary of War and Chief of Staff who opposed the
organization of that Service as a separate unit.
According to Gen. Fries, Secretary of War Weeks is very
favorable to the Service and appreciates its importance. The
Army Appropriation Bill which received a pocket-veto by Presi-
dent Wilson gave $1,500,000 to the Service, instead of the
$4,500,000 asked for, and Gen. Fries states that plans are being
made to continue the lesearch, development, and proving of
gases and masks and other material, and to cut down plant
maintenance and supplies, with the expectation that the million
and a half appropriation will be made in the new army bill.
GOVERNMENT REORGANIZATION
Government reorganization is one of the first items on the
program of President Harding and his cabinet. The Joint
Congressional Commission headed by Senator Smoot is con-
sidering this problem. The backbone of the reorganization
scheme is said to be the adoption of the national budget system,
the reorganization of the departments according to a systematic
and logical plan, and the effecting of personnel and salary
changes along the lines recommended by the joint commission
on reclassification. How the chemical and research bureaus
of the departments, and the government chemists, will fare is
problematical. It has been proposed that all of the bureaus
concerned with educational and scientific research work should
be grouped under a new department of education and science.
The Public Works plan for grouping the engineering agencies,
which has been definitely outlined in the Jones-Reavis Bill,
will receive early consideration, it is said.
The Nolan Patent Bill was not voted on in the Senate after
being in conference and was therefore defeated. It is ex-
pected that the three important portions of the bill, the
salary and reorganization features, the provision for the taking
over and administration of patents by the Federal Trade Com-
mission, and the amending of statutes dealing with patent
litigations, will be reintroduced as separate bills at the coming
session. Senator Norris, present chairman of the Patent Com-
mittee, will become chairman of the Committee on Agriculture
and will probably be succeeded by Senator Brandegee. Repre-
sentative Nolan will probably be made chairman of the House
Labor Committee, while Representative Lampert will probably
head the Patent Committee.
The appropriation of $10,000,000 for the completion of Wilson
Dam of the Muscle Shoals Power Plant was lost when the
Senate receded and passed the Sundry Civil Bill without the
amendment. When this action on the nitrate plant proposition
was taken, the Chief of Engineers instructed that all further
construction work be stopped, and there is, at present, about
$1,000,000 left, which will be sufficient for maintenance work
until such time as final decision is made as to the fate of the
entire project at Muscle Shoals.
The appointment of Herbert Hoover to be the Secretary of
Commerce in President Harding's cabinet is one of the most
important features in the change of administrations from the
standpoint of the technical man. Mr. Hoover has taken up
the task of making the Department of Commerce more bene-
ficial to the country. While he has announced that radical
changes in the scope of the department's activities will await
the general governmental reorganization, his ideas for imme-
diate activity include: Better cooperation between industry
and the foreign agents of the Bureau of Foreign and Domestic
Commerce; constructive study of transportation; power develop-
ment and labor readjustment; extension of voluntary standard-
ization of manufactured products; promotion of greater efficiency
in industry; applying idle labor to such needed projects as
housing, power plant development, waterways, and highways.
NATIONAL RESEARCH COUNCIL
The National Research Council Division of Chemistry under
Dr. F. G. Cottrell is cooperating with Prof. W. L. Badger of the
University of Michigan in his work on boiling points of saturated
solutions under various pressures. As a result, the work that
he is doing for commercial organizations, on the theory and heat
transference of evaporators, will be carried to a higher degree
of accuracy than is necessary for the primary object of the tests.
While the organization of the Alloys Research Association
is not being vigorously pushed by the National Research Council
at the present time on account of the industrial situation, a
considerable number of large metallurgical firms have joined.
DR. ALSBERG RETIRES FROM BUREAU OF CHEMISTRY
To assume directorship of the Food Research Institute that
the Carnegie Corporation will establish at Leland Stanford Junior
University, Dr. C. L. Alsberg will leave his present position as
chief of the Bureau of Chemistry of the Department of Agri-
culture about June 1. It is understood that politics will not
enter into the selection of Dr. Alsberg 's successor, but that the
best chemist obtainable for the position will be appointed.
An appropriation of $25,000 has been given the Bureau of
Chemistry to continue its investigations of explosive and in-
flammable dusts that are a menace in mills, elevators, oil-
presses, gins, and other places where dust is created. With the
idea of transferring its appropriation for fish and sea food in-
vestigation to the Bureau of Fisheries, the Bureau of Chemistry's
appropriations for this activity were cut off. However, as no
money was given the Bureau of Fisheries, these investigations
must be suspended.
A chemist and a college professor entered the Senate when
Dr. Edwin F. Ladd took his seat as a senator from North
Dakota. He has been for years president of the North Dakota
Agricultural College.
Dr. E. D. Ball, who is professor of entomology and zoology
at Iowa State College and state entomologist of Iowa, has been
reappointed Assistant Secretary of Agriculture to continue the
general direction of the department's scientific work.
March 14, 1921
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
365
LONDON LETTER
By Stephen Miali., 2S, Belsize Grove, Hampstead. N. W. 3, England
THE EXCESS PROFITS DUTY
In the dark and gloomy sky which overshadows all, a small
patch of blue has just made its appearance, the abolition of the
Excess Profits Duty.
The abolition of this obnoxious duty fills us all with hope and
gives us a certain modified confidence that the present lack of
trade is teaching us a much-needed Jesson. But it will not
do very much more than this; the causes of the present unem-
ployment are so deep seated, so varied and so interdependent
that a great lapse of time, much patience, and the wisest of coun-
sels will be required to make the necessary change. I see no
reason to think that in three, six, or twelve months trade will
be what it was a year ago. How long will it be before Russia
can again buy huge quantities of tea from India and so enable
India to buy goods from England? When will Austria and
Germany, Czechoslovakia and Poland, buy from France and
Italy? Some day Greece and Turkey will convert their swords
into ploughshares, the Sinn Fein will lie down with the Ulster-
man, and the suspicion which suggests to Britain, America, and
Japan a naval rivalry will be replaced by a desire for coopera-
tion to advance the happiness of the world. Until those days
come the world trade on which we all live will not really flourish.
But we are getting nearer to that time every day, and we have
turned the corner. Business is not quite so stagnant as it was
in December; but up to now the big firms here have weathered the
storm, so they will repair their shattered barks, untaught and
unwilling to endure poverty.
Conservation of matter, conservation of energy, have had
their day; conservation of resources is now the watchword, and
accordingly the developments in industrial chemistry are meager.
They are like the Irishman's crop of potatoes which did not
come to as much as he expected, and he never thought they
would. Although many commodities have not yet reached
their bottom price, some few seem already to have done so.
Moreover, the stocks in the hands of merchants and retailers
are slowly getting exhausted, and the orders for which we are
waiting seem to be gradually preparing to emerge from their
present obscurity.
THE DYESTUFFS BILL
The Dyestuffs Bill has, in spite of opposition and even obstruc-
tion, found a place on the Statute Book. Naturally a bill of
this description revived to a small extent the old Free Trade or
Protection controversy. The advocates of cheap goods flourish
in Lancashire and other parts of England, and they would have
been able to put up a very strenuous fight had not the circum-
stances of this bill been so unusual. Its supporters urged that
an aniline dye industry is an essential part of that chemical
trade without which no country can be a great industrial power;
that an aniline dye industry is a necessary part of our national
defense as the only industry in which poison gases of modern
type can be speedily made in large quantities; and, lastly, that
protection to the industry had been definitely promised by this
and the preceding Governments. These arguments are really
unanswerable and do not concern the question of Free Trade
or tariffs. But a determined fight was put up by the Labor
party and a band of vigorous Free Traders who feared that
expensive dyestuffs would kill the textile trade of Yorkshire
and Lancashire and urged that the Government could keep its
promise by giving a subsidy for the promotion of research on
dyestuffs and their cheaper manufacture. As to the necessity
of cheap dyestuffs, all were united, and it was argued that in the
long run it would pay to keep up some manufacture here to pre-
vent the Germans from obtaining a monopoly and then raising
the prices, as was done to a certain extent in pre-war days in
the alizarin dyes. Also the bill only proposed to restrict foreign
imports by the agency of a licensing committee on which the con-
sumers were adequately represented. The alternative of re-
stricting imports or granting a subsidy was hotly debated in
the Press and in Parliament. Many over here, including
myself, prefer in general the granting of a subsidy as being more
effective and more economical. From the point of view of the
direction of money to the place where it is needed a subsidy is
quicker, simpler, and more easily controlled. But in this especial
case the difficulties surrounding a subsidy to the dyestuff industry
were colossal. Britain, France, Belgium, and some other
European countries were receiving from Germany considerable
quantities of dyes under the treaty of peace. All these coun-
tries were receiving more than there was a demand for, and most
of them were selling their surplus in this country. The conse-
quence was that at the end of 1920 there lay in warehouses in
England nearly enough German dyes to supply the whole con-
sumption for 1921. Had the importation not been stopped,
the subsidy necessary to keep the British works progressive and
usefully employed in manufacture and research would have been
enormous.
MANUFACTURE OF FINE CHEMICALS
Similar arguments will arise again in this country pretty
shortly. There is talk of introducing a bill for the protection
of the fine chemical manufacture and, in particular, the manu-
facture of synthetic drugs. It is by no means certain that such
a bill will be so acceptable as the Dyestuffs Bill. Many of the
special arguments in support of the latter do not apply to the
manufacture of fine chemicals. Moreover, the fine-chemical
manufacturers have not hitherto made the opportunity or the
organization to render to the community services comparable
to those rendered by the dye makers. Broadly speaking, fine
chemicals have here been made by small firms with either insuffi-
cient ambition or insufficient capital to create that large enter-
prise necessary to supply this country with a wide range of
fine chemicals and research reagents of guaranteed purity.
Whether this is now the occasion and whether — assuming it to
be such — it will be seized, no one can say. The Dyestuffs Bill
is no precedent.
But our Free Trade arguments will be put to the proof in con-
nection with the German indemnity. How much we shall get
and in what shape it will come seem to me minor matters in com-
parison with the great question : Will it do us any good to get an
indemnity? I suppose Germany has a small quantity of gold, but
not enough to count where thousands of millions are involved.
Now that she has lost Alsace and Lorraine and undertaken to
send to France coal to replace the supply from the French coal-
fields so stupidly destroyed by the Germans, she has not an
enormous surplus of raw materials to export, or of foodstuffs.
We have taken her ships and incidentally caused short time in
English shipyards. So if she pays at all, it looks as if she will
pay in manufactured goods. Now, in old days, if we took
£20,000,000 of goods from Germany we paid for it by sending
out to her (or some other country) £20,000,000 of British-made
goods, and employment was not affected. If we are going to
receive, without sending anything in exchange, some huge quan-
tities of German manufactured goods, shall we not increase
the unemployment already terrible enough here? After
the Franco-Prussian war it was Prussia, not France, which had a
slump in trade. To reconcile war and its consequences, includ-
ing revolutions, indemnities, depreciation of currency, and so
on, with trade and the pursuit of money is a hopeless task and
reminds one of a schoolboy with an axe, a glue pot and some
fireworks, trying to regulate an eight-day clock. Whatever he
does he will spoil the mechanism and one must be thankful if
he comes away without the flash, bang, and sting, which are the
marks of what juvenile students consider a successful chemical
experiment.
February 14, 1921
This morning we cannot help considering the meaning of the
break in the negotiations between the Allies and Germany
and its effect on the economics of the world. It is apparently
as difficult for us to understand the German mentality and diplo-
matic methods as it is for them to understand ours. It is
singular that two peoples, each partially descended from the
same stock and speaking varieties of the same Teutonic language,
having had much intercourse both social and commercial in
the past, should in the space of a few years have drifted so much
apart that one is quite unable to understand the point of view
of the other. It will require a good deal of care to prevent the
same catastrophe from dividing the great English-speaking
nations of the two sides of the Atlantic, and that is why the
meeting of their chemists in Montreal and New York this sum-
mer is of such infinite importance. It is chiefly the trifling
matters of divergence which are so difficult to adjust, but it is
these which become of greater and greater importance. I
think I notice a tendency towards a greater divergence in our
language than existed thirty or fifty years ago; unless we are
careful we shall in time become mutually unintelligible. Can-
not we chemists take a step toward greater community of ex-
366
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
pression? It will be hard for either side to give up the little
tricks and prejudices which are our pride. But is not the
permanent community of thought worth this small sacrifice?
Is it perhaps too early in our history to suggest that to prevent
undue divergence a joint committee be appointed to consider
our scientific or at any rate our chemical language?
KEY INDUSTRIES BILL
The details of the new Key Industries Bill, which is to protect
the manufacturers of fine chemicals, optical glass, scientific
instruments, magnetos, and other things, are not yet published,
and one hears rumors that the advocates of tariffs and the advo-
cates of importation under licenses are unable to agree upon a
common policy. The makers of fine chemicals favor importa-
tion under a system of licenses such as prevails in the dyestuff
industry, but the application of this principle to all the objects
in the schedule of the Key Industries Bill would be extremely
difficult and cumbrous. Recent bye-elections here do not
point to any considerable departure from free trade.
March 8, 1921
PARIS LETTER
By Charles Lormand, 4 Avenue de l'Observatoire, Paris, France
THE CLAUDE PROCESS
The importance of the nitrogen problem leads me to report
to you each month new developments which have occurred along
this line.
Mr. Georges Claude is steadily developing his process and ex-
pects it to supersede the Haber process. He has just constructed
a hypercompressor of greatly reduced dimensions. This appara-
tus will compress 700 cubic meters of mixed nitrogen and hydro-
gen per hour, thus yielding 5 tons of anhydrous ammonia,
equivalent to 25 tons of ammonium sulfate per day.
This hypercompressor operates in two stages, the one at 100
to 300 atmospheres, the other at 300 to 900 atmospheres, the
pressure finally used. For an output of 710 cubic meters per
hour compressed from 100 to 900 atmospheres, the electric
current is 97 kw., and the mechanical power 122 h. p. The total
power from 1 to 900 atmospheres is 310 h. p.
Numerous tests have verified these figures, and in spite of
the high pressures, the total leakage is only 3 cubic meters, or
0.5 per cent.
All preliminary calculations had pointed to this result, but the
realization is now accomplished, and the process seems to be
definitely perfected. There remains only one further problem,
the feeding of the hydrogen. Mr. Claude has undertaken
the study of this question.
A company with an initial capitalization of one million, to be
increased soon to ten millions, has been formed in Italy for
the development of the Claude process. This company has been
formed with the support of the Societe de l'Air Liquide et des
Produits Chimiques de Saint Gobain.
DYE MANUFACTURES
The Compagnie Nationale des Matieres Colorantes has just
completed the development of basic dye manufacture, and is
undertaking the manufacture of alizarin dyes. These two
industries are established at the factory of Villers-St. Paul,
near Creil. The old national powder mill at Oissel has been
made over by the same company, which will make there the
entire series of azo colors.
Similar efforts in the United States and in England lead us
to hope that the dye market may soon be entirely free from
German influence, although the German companies have enor-
mously increased their capital and are trying to maintain their
old supremacy.
During the war the German chemical industries also studied a
number of industrial chemical problems for the replacement of
natural products of which their country was deprived. Thus,
they manufactured synthetic rubber, and also fat yeasts to re-
place feeding stuffs. The future of these industries seems very
doubtful.
ALCOHOL MANUFACTURE
Among these industries rising from the war, that of alcohol
derived from calcium carbide seems the only one worth con-
tinuing. At the last meeting of the Societe de Chimie In-
dustrielle, Mr. Georges Mignonac discussed this industry, which
is being conducted on a large scale only by one Swiss concern.
The acetylene from the calcium carbide is converted into
acetic acid and ethylidene acetate, then reduced to alcohol.
The cost of making the alcohol by one of the procedures em-
ployed, starting from the acetylene, would be about 0 fr. 60 per
liter. Although this price is relatively low, it seems that in
France the tendency is toward the development of fermentation
alcohol, from corn and Jerusalem artichoke, or from cassava
which is furnished in abundance by our African colonies.
on the products obtained from the vegetable kingdom. In
France we are following attentively the attempts to cultivate
camphor in -the United States. Similar plantings have been
made in the south of France and in Algeria, but the first results
have not been very encouraging. I have personally analyzed
camphor trees from the region of Antibes, and their camphor
content is nil.
The Office des matieres premieres is carrying out systematic
investigations on the culture in Algeria and Morocco, but it is
too early to learn the results. Moreover, the market for cam-
phor seems to be growing less. The celluloid industry is grow-
ing smaller, because of the manufacture in France of a large
number of products of the bakelite type. On account of their
noninflammability, these products are replacing celluloid to
a greater and greater degree.
The Bureau of Mines has recently published its report for 1920.
On the whole, there has been a marked increase in production,
in mineral fuels as well as ferrous minerals and other metals,
and especially in salts (rock salt and potash).
Mr. Matignon has made a study of the industrial preparation
of magnesium from the oxide or chloride, by reaction with cal-
cium carbide. He has obtained satisfactory results in the labora-
tory. The difficulty in the way of industrial application lies
in the use of a high temperature (1200°), a temperature at
which oxygen and nitrogen react with magnesium. The use of
an inert gas, argon for example, would solve the problem, which
thus rests on the industrial production of this rare gas.
This opens up an interesting problem which I commend to
American investigators.
The city of Paris plans to establish a radium institute, for which
it has voted the credit necessary for the purchase of a gram of
radium metal for hospital use. Madame Curie herself is about
to start for the United States, and during her visit will receive
a gift of one gram of radium for use in her research work.
Funds for this purchase are now being raised in America by
popular subscription. We are extremely proud of the welcome
which American chemists are offering to her.
I would call attention to the invention by Messrs. Bernard
and Baron of an apparatus for lighting and extinguishing gas
burners in towns. This apparatus permits lighting and extin-
guishing all the burners of a sector by turning a single cock in
the factory. From the point of view of diminution in labor
this invention is an interesting development.
March 12, 1921
There is also noticeable a tendency to investigation in the
domain of agricultural industrial chemistry, that is, research
Gift to Dermatological Research Laboratories
According to recent newspaper accounts, the sum of
$500,000 has been given by Drs. Schamberg, Kolmer, and Raiziss
to the Dermatological Research Laboratories of Philadelphia,
for the support of medical research. This sum represents
the profits received during the war from the sale of arsphen-
amine which was manufactured — first as a war-time necessity,
and later as a licensed preparation — at the Dermatological Re-
search Laboratories. Inasmuch as the drug, though manufac-
tured under war-time conditions, was sold at one-third the pre-
war price of salvarsan, the vastly greater toll collected by the
German proprietors for the sale of salvarsan may readily be
calculated.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
367
INDUSTRIAL NOTES
The Industrial Potash Corporation has been chartered at
Salt Lake City with $30,000,000 capital to develop the alunite
deposits in the Mount Baldy, Ohio, and Durkee districts.
The Federal Trade Commission has cited the International
Paint and Oil Company, of Peoria, 111., in complaint of unfair
competition in the manufacture of a coal-tar distillate called
"tar-pentine," which can be used for some of the same pur-
poses as turpentine. The complaint states that the name "tar-
pentine" so closely resembles turpentine that the public might
be deceived.
The Federal Trade Commission has cited the United Chem-
ical Products Corporation, Jersey City, N. J., in complaint of
unfair competition in the manufacture and sale of dyestuffs
and chemicals. The company is charged with paying out ap-
proximately 10 per cent of its entire yearly business in cash
commissions to dyers and other employees of its customers to
influence the purchase of its products.
In the effort to prevent the Kali Syndicate of Germany from
reestablishing a monopoly in the potash industry in the United
States, the State Department has refused to vise the passports
of the directors of the company to enter the United States,
inasmuch as the German syndicate will not agree not to attempt
to reestablish its monopoly of the potash trade by long term
contracts or by other means.
The Atlantic and Gulf Export Company, recently organized
with a capitalization of $2,000,000, has completed its organiza-
tion. Over one hundred firms are estimated to be represented.
300,000 bbls. of rosin have been pledged for export purposes,
and it is planned to send representatives to Germany, Austria,
Belgium, Italy, South America, and other countries. Business
will also be conducted in lumber, petroleum, meats, hides, and
other commodities.
Sixty-nine per cent of the world's petroleum production in
1919 came from the United States. Of the world total of
544,885,000 bbls., the American output was 377,719,000, Mexico
coming next with 87,073,000 bbls., and Russia being third
with 5 per cent of the output.
Announcement is made by the Bureau of Standards that
renewal bd of the exhausted Standard Iron Sample C and
renewal 10c of the exhausted Standard Bessemer Steel 0.4 Carbon
are now ready for distribution with provisional certificates.
The price of these standards is $2.00 per 150 g., and samples will
be shipped by parcel post C. O. D. upon application.
The question of prohibiting carbon black companies
operating in the north Louisiana gas fields from using natural
gas or of forcing them to curtail the use of gas has taken a new
turn, due to the contemplated construction of a pipe-line system
to connect New Orleans, Baton Rouge, Alexandria, and other
centers of population with the Monroe gas district, and the
proposed construction of electrical power plants near Monroe
to generate current for distribution over a wide area. The
capitalists interested in both the pipe line and the electrical
current projects are ready to begin construction if the carbon
plants are closed or curbed, but not otherwise. They contend
that the carbon mills are destroying the gas fields by the excessive
use of gas, and will hardly last for ten years, while under the
proposed plans it is said that the supply of natural gas will last
for fifty or one hundred years.
The Dow Chemical Company has announced the production
in the Midland plant of ethylene glycol and dichloroacetic acid,
which are now made for the first time in America. Both materials
are made by new processes and are of exceptional purity, since
they are not subject to the impurities which have always re-
' suited from their manufacture by the older processes involving
the use of chloral as an intermediate. Prices at present are high
on account of limited production, but are already below the
prices formerly charged for the German products and may be
still further reduced if new uses can be found, making increased
production possible.
The School of Technology of the College of the City of New
York now offers courses extending over a period of five years
and leading to degrees in chemical, civil, electrical, and me-
chanical engineering. During the first two years the work con-
sists almost entirely of prescribed collegiate science subjects;
during the third and fourth years, of strictly engineering subjects,
so arranged that the student is eligible for the degree of Bachelor
of Science; and during the fifth year, of purely advanced technical
engineering subjects. The engineering subjects are given in
identical courses in both the day and evening sessions.
Three men were injured by an explosion which wrecked
the building occupied by the Keystone Metal Reduction Com-
pany, Cheswick, Pa., on March 5, 1921. The plant is one of the
three radium-producing plants in the United States and turns
out about one gram of radium a year, valued at $120,000. The
explosion was caused by the blowing up of an autoclave. The
loss is estimated at $10,000.
At the annual meeting of the National Aniline and Chemical
Co., Inc., the following directors were elected: Wm. Hamlin
Childs, Wm. H. Nichols, Wm. H. Nichols, Jr., Edward L.
Pierce in place of C. S. Lutkins, H. Wigglesworth, T. M. Rian-
hard, F. M. Peters, and W. N. Mcllravy. The remainder of
the board was reelected.
The New York office of the Societe Commerciale des Potasses
d'Alsace has been opened at 25 W. 43rd St., New York City.
Captain F. C. Dossert is director of the American Bureau, and
will become general sales manager for the Societe on the resigna-
tion of Mr. W. B. Howe, general manager of the Nitrate Agen
cies Company.
The U. S. Department of Agriculture has decided to estab-
lish a production unit at Fitzgerald, Ga., for the manufacture
of sweet potato sirup. The process was worked out in the
Bureau of Chemistry laboratories by Dr. H. C. Gore. The
sirup is rich in sugar, of a fine brown color and highly pala-
table, and has been found valuable for baking, candy making,
and table purposes. Questions as to the cost of commercial
production and the market value as compared with cane, corn,
and other sirups have yet to be determined before the commer-
cial practicability of its manufacture can be recommended.
Production is to be begun as soon as the machinery can be in-
stalled.
The boiler house and main retort building of the Irvington
Experimental Plant of the International Coal Products Com-
pany, of Newark, N. J., was destroyed by fire on February 21,
1921, with damage estimated at $100,000. The plant is being
rebuilt as quickly as possible.
On March 3, 1921, the Bureau of Mines, resorting to a war-
time measure which gives it control over all importations of ex-
plosives, requested the customs officials to hold up all shipments
of detonators and to send samples to laboratories of the Bureau
for tests. The detonators sent here by German manufacturers
for use in ditch digging and stump blowing are said to be of such
low grade as to constitute a serious danger, and this step was
taken to prevent the Germans from flooding the country with the
low-grade detonators.
A preliminary announcement by the Bureau of Crop Esti-
mates places the aggregate production of beet and cane sugar
in the United States during 1920 at 2,605,174,000 lbs., or 1,163,-
023 long tons, approximately 53 per cent more than the 1919
production. The production of beet sugar is figured at 991,000
tons, an increase of 27 per cent over the previous record produc-
tion, which was in 1915.
The Chilean government has formulated laws which it is ex-
pected will lead to the establishment of a fine beet sugar industry.
Premiums to be paid by the government in gold are provided
for beet sugar production, extending over 10 to 15 yrs. Import
duties are established in case of a drop in price, and sugar ma-
chinery is admitted free of charge. The new law applies only
to manufacturers having their homes in Chile.
The production of German dyestuffs during the year 1920
amounted to 145,000 tons, the largest output in the history
of the industry, the average yearly production before the war
amounting to 135,000 tons. During the month of January
1921 the production reached 12,000 tons and during February
1921 reached 15,000 tons.
Discovery of what may prove to be a large deposit of
alunite has been made in Texas. There are said to be six out-
crops of the mineral, from six to twelve miles apart, the outcrop
of the higher grade variety covering approximately 20 acres and
being of better quality than any other yet discovered in the
United States. Samples have been tested by Mr. Braun, the
discoverer, and also in the El Paso School of Mines, the Univer-
sity of Texas, and the San Antonio Public Service Co., and it
has been demonstrated that the mineral is of the purest grade
obtainable and means much to the country if it exists in quanti-
ties sufficient to warrant commercial exploitation. The fact
that the alunite is found in a level country upsets the theory
heretofore held by geologists that the mineral exists only in
volcanic formation.
368
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. No. 4
PERSONAL NOTES
Dr. J. C. Cain, editor of the Journal of the Chemical Society
(London), died on January 31, 1921, in his fiftieth year. Through-
out his scientific career, Dr. Cain was closely associated with the
British dyestuff industry. During the war he served on Lord
Moulton's staff, advising as to the convertibility of chemical
factories for explosives manufacture. He later was in charge
of H. M. Factory, Hackney Wick, and still later was trans-
ferred to the Technical Committee of British Dyestuffs, Ltd.
Dr. Cain was the author of "The Synthetic Dyestuffs and In-
termediate Products," "Chemistry of the Diazo Compounds,"
and "The Manufacture of Intermediate Products for Dyes."
His revision of Roscoe and Schorlemmer's "Non-Metallic Ele-
ments" appeared only a short time before his death.
Dr. J. D. Pennock, general manager of the Solvay Process
Co., died on March 11, at Syracuse, N. Y.
Dr. Ernst J. Lederle, who was health commissioner of New
York Citv during two administrations, that of 1902 to 1904 and
from 1910 to 1914, died at Goshen, N. Y., March 7. Dr.
Lederle was one of the few health commissioners of New York
who was not a physician. He was born in Staten Island in
1865, and was graduated from the Columbia School of Mines in
1886, later receiving from the same university the degrees of
Ph.D. and Sc.D. He founded the Lederle Laboratories and
the Lederle Antitoxin Laboratories, which are now merged with
the firm of Lederle and Provost.
Mr. Jacob Hasslacher, well known in chemical circles, and
until a year ago an active member of the firm of Roessler &
Hasslacher Chemical Co., which he helped to establish in 1889,
died at his home in New York City on March 15, 1921, at the
age of 69. Mr. Hasslacher was born in Ems on-the-Lahn, Ger-
many, and became a naturalized citizen of the United States in
1899. He was the leading factor in the formation and subse-
quent development of the Niagara Electro Chemical Company
and the Perth Amboy Chemical Works, as well as other enter-
prises in which the company is interested.
Dr. John Iredelle Dillard Hinds died at Nashville, Term.,
March 4, 1921, at the age of 74 years. Dr. Hinds was for over
40 years a professor of chemistry in Cumberland University,
the University of Nashville, and Peabody College, and at the
time of his death was chemist of the Tennessee Geological Survey.
Dr. William F. Jones, a chemist who was prominent in the
development of the pyroxylin industry, died recently at his
home at Colonial Heights, Tuckahoe. Dr. Jones was born in
Hillsboro, N. C, and was educated at Wake Forest College and
Johns Hopkins L'niversity.
Dr. F. P. Dewey, chief chemist of the Mint Bureau of the
U. S. Treasury, Washington, D. C, died February 12, 1921.
Mr. Hyman Bornstein has entered the employ of Deere &
Co., Moline, 111., as metallurgical engineer, where his duties will
be in connection with metallurgical problems in the manufacture
of agricultural implements. Mr. Bornstein's previous position
was chemical engineer of the Bureau of Engineering, City of
Chicago, 111.
Mr. Philip Drinker has left the Buffalo Foundry and Machine
Co., Buffalo, N. Y., where he was employed in the sales engineer-
ing department, and is now engaged in research work in the
laboratory of applied physiology at the Harvard Medical School,
Boston, Mass.
Mr. Ralph W. Boyd has resigned as chemist of the metallurgical
research department of the Colorado School of Mines, and has
become associated with the Desert Shale Oil Corporation of
Salt Lake City.
Mr. M. A. Hurtt, formerly connected with the By-Product
Coke Works of the Illinois Steel Co., Gary, Indiana, has become
general foreman of the Bv- Product Coke Works of the Pittsburgh
Crucible Steel Co., Midland, Pa.
Mr. W. R. Holt, formerly with the chemical division of Procter
& Gamble Co., is now plant superintendent with the Harris
Soap Co., Buffalo, N. Y.
Mr. C. L. Voress, who was in charge of the experimental and
development work of the "Charcoal Absorption Process" at the
plants of the United Natural Gas Co., and the B. B. Stroud Co.,
at Bradford, Pa., has been made general manager of the newly
incorporated Gasoline Recovery Corporation, New York, and
Mr. Vernon C. Canter, formerly with Procter & Gamble Co.,
and more recently with Mr. Voress, has been given active charge
of all the experimental and development work at Bradford, Pa.
Mr. Wilson H. Low resigned as head chemist of the Cudahy
Packing Company last June, after 22 years of service in that
capacity, and has entered partnership with his former head
assistant, Mr. John H. Show, in Los Angeles, Cal.
Mr. P. B. Place, a recent graduate of New Hampshire College,
is at present employed as junior chemist at the U. S. Bureau of
Mines, Pittsburgh, Pa.
Mr. Alfred N. Finn, formerly in the research department of
the Hydraulic Steel Co., Cleveland, Ohio, has been reinstated as
associate chemist at the Bureau of Standards, Washington, D. C,
where, previous to the past year, he had been engaged for about
nine years in the chemical testing of structural materials and
miscellaneous supplies. His present assignment is in chemical
control of the manufacture of optical glass.
Mr. H. J. Nimitz resigned as manager of the feed department
of the Buckeye Cereal Co., Massillon, Ohio, in order to become
superintendent of the feed department and chemist with the
Brooks Milling Co., Minneapolis, Minn.
Dr. Lula Gaines Winston has resigned as head of the depart-
ment of chemistry at the State Normal School for Women,
Farmville, Va., and holds a similar appointment at Meredith
College, Raleigh, N. C.
Mr. G. E. Webster, who was discharged last November from
the Ordnance Department where he last served as army inspector
of ordnance, property responsibility officer, and in other capac-
ities, was reinstated as chemist at Picatinny Arsenal in De-
cember 1920.
Mr. F. P. Monoghan, for the past ten years superintendent
for the Burt Portland Cement Co., of Bellevue, Mich., is em-
ployed in a similar capacity with the Glens Falls Portland Ce-
ment Co., Glens Falls, N. Y.
Dr. Philip L. Blumenthal has left the Babcock Testing Labora-
tory of Lackawanna, N. Y., and is now with the Lacteal Ana-
lytical Laboratories, Inc., Buffalo, N. Y.
Mr. Leicester Patton resigned as chief of the Buffalo Station,
Bureau of Chemistry, and has accepted a position with the
Brocton Fruit Products Co., Brocton, N. Y., as chemist and
production manager.
Mr. Julius Gorzo has changed from his former business of
chemical engineering, and is now with the Pittsburgh Industrial
Engineering Service, Pittsburgh, Pa., where he takes charge of the
engineering and sales departments.
Mr. Arnim R. Brandt has resigned as chief chemist for the
Amazon Rubber Co., Akron, O., and is now acting in a similar
capacity for the Islewortli Rubber Co., Ltd., Isleworth, England.
Dr. A. L. Kibler has accepted the transfer from Picatinny
Arsenal, where he served as chief chemist, to the Old Hickory
Powder Plant, Jacksonville, Tenn., for the purpose of supervising
the recovery of platinum from contact mass owned by the Ord-
nance Department.
Mr. H. W. Blanchard recently severed his relations with the
chemical division of Procter & Gamble Co., Cincinnati, O.,
and at present is connected with the physics department of
Purdue University, LaFayette, Ind.
Mr. M. E. Campbell has left the United British Refineries of
Trinidad, B. W. I., and has accepted the position of chief chemist
for the Continental Mexican Petroleum Co., Tampico, Tamau-
lipas, Mexico.
An Industrial Fellowship has been established at the Uni-
versity of Pittsburgh by Mrs. Fredonia J. Pratt, of St. Louis,
Mo., as a memorial to her husband, the late Dr. David S. Pratt,
former assistant director of the Mellon Institute, for research
in that field of organic chemistry in which Dr. Pratt was espe-
cially interested.
Mr. R. L. Sibley, formerly employed as research chemist
by the Goodyear Tire & Rubber Co., Akron, O., is now con-
nected with the Intelligence Section of the Development De-
partment of the Standard Oil Company of New Jersey.
Mr. Allen E. Steam, formerly assistant professor of chemistry
in the University of West Virginia, Morgantown, W. Va., has
accepted a similar position in the University of Missouri,
Columbia, Mo., where he has charge of the work in electro- and
physical chemistry.
Mr. Martin S. Kissel, formerly of Brooklyn, N. Y., is now
connected with the Sun Cheong Milling Co. of Shanghai, China,
in the capacity of chief chemist.
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
369
GOVERNMENT PUBLICATIONS
By NbluiK A. Parkinson, Bureau of Chemistry, Washington. D. C.
NOTICE — Publications for which price is indicated can be tiary beds around the greater part of the Rock Springs uplift,
purchased from the Superintendent of Documents, Government as well as the review of some facts which indicate that the cen-
Printing Office, Washington, D. C. Other publications can tral area of the Rock Springs uplift probably contains oil and gas.
usually be supplied from the Bureau or Department from which Geography, Geology, and Mineral Resources of the Fort
they originate. Commerce Reports are received by all large Hall Indian Reservation, Idaho. G. R. Mansfield. With a
libraries and may be consulted there, or single numbers can be chapter on Water Resources by W. B. Heroy. Bulletin 713.
secured by application to the Bureau of Foreign and Domestic 152 pp. Paper, 50 cents. Under mineral resources the phos-
Commerce, Department of Commerce, Washington. The regu- pjjate and metalliferous deposits, coal prospects, volcanic ash,
lar subscription rate for these Commerce Reports mailed daily is and the soil composition are described.
$2.50 per year, payable in advance, to the Superintendent of The Future of ^^ Mining ^ ^ ^^ Minmg Jndm_
documents. ^ ^ lglg Papers bv A H. Brooks and G. C. Martin.
CONGRESSIONAL COMMITTEES Bulletin 714-A. Mineral Resources of Alaska, 1919-A. 103
Opium. Exportation of opium, hearings before subcommit- P^™?^6 S],f ? n*f°. f SfrieS °f anaUal h.^ti™ treatifg
tee on H. R. 14500, to amend Section 6 of the act approved °{u*rP7T? «<r Z V ^ tt ■ summarizing the results
January 17, 1914 (to amend) the act to prohibit the importa- ^"^1 ^? Z! £ J rl mv^st!gaf10.n ° . the mm^ral
r- '. c • r Li. ia- j- • 1 resources 01 the territory, the report includes the more lm-
^^Ihr^lT'^nq T°a^rv q",,^^ 10noai TaPrrT' f& Portant economic results °f the ^ear " contains an account of
dd 1921 the miuiug industry> including statistics of mineral production
PP' ' . . . and also preliminary statements on investigations made by the
Opium. Exportation of opium, hearings on S. 4553, to Geological Survey,
amend .Section 6 of the act approved January 17, 1914 (to amend) potash Resources of Nebraska W B Htcks Bulletin
the act to prohibit the importation and use of opium for other ^otasn Kesources ot weDrasK^ w. B. hicks Mulletm
.• • , j o u n mnn t-> _ 715-1. Contributions to Economic Geology. 1920. Part I. 15
than medicinal purposes, approved February 9, 1909; Decern- " „, ,,■ , . _. . „ 0 lno, rrU _. iC. iAX
ber 11 1120 25 nn PP' Published February 8, 1921. There are more than 100
' ' PP' known productive lakes in Nebraska, scattered over an area of
Containers. Food and drug containers, hearing on H. R. some 800 sq. mi., and covering an aggregate area of more than
10311, further to amend Section 8 of the act for preventing 6097 acres. A summary of their estimated potash content is
the manufacture, sale, or transportation of adulterated or mis- contained in the following table:
branded or poisonous or deleterious foods, drugs, medicines, and Solids Potash
liquors, and for regulating traffic therein, approved June 30, ^Area (Acres)-^ ,-Short Tons^ (KiO)
1906, and amended by the act approved March 3, 1913. 30 „ , Sub- Brine Sub- Short
1Q21 County Surface surface Short Tons Surface surface Tons
PP^ ' , , ^ . . , Sheridan 3.107 697 15,872.000 146,590 329,215 115,360
Eggs. Frozen eggs, hearings before Committees on Agricul- Garden 1,147 196 4,655.000 103,150 83,440 40,910
ture and Forestry on H. R. 9521, to prevent hoarding and de- Morrill 502 130 2,607.700 40,880 42,020 17,670
terioration of, and deception with respect to, cold storage foods, ^cherr^'.31^ 150 38 266,000 750 13,720 2,440
to regulate shipments of cold storage foods in interstate com- In doubt.'!!!!! 1,191 263 9.353.000 76,260 105,190 38,730
merce, and for other purposes. 40 pp. 1921. These hear- „ ;
ings were held at a joint meeting of the Senate Committee on ToTAt- 6'097 J'324 32.753.700 367,655 573,585 215,110
Agriculture and Forestry and the House Committee on Agri- Phosphate Rock near Maxville, Granite County, Montana,
culture. J. T. Pardee. Bulletin 715-J. Separate from Contributions
Nitrogen. Sundry civil appropriation bill (fiscal year, 1922), to Economic Geology. 1920. Part I. 5 pp. Published February
nitrate plant at Muscle Shoals, hearing before subcommittee 7, 1921. The quantity of nunable material in these deposits
on H. R. 15422. 28 pp. 1921. is at least as great as that in the known deposits near Melrose,
Garrison, and Elliston, and they are less than 6 miles from the
TARIFF COMMISSION railway.
Dyes and Dyeing. Census of dyes and coal-tar chemicals, The Divide Silver District, Nevada. Adolph Knopf. Bulle-
1919. Tariff Information Series 22. 95 pp. Paper, 20 cents. tin 715-K. Contributions to Economic Geology. 1920. Part I.
1921. 28 pp. Published February 12, 1921. The discovery of silver
BUREAU OF INTERNAL REVENUE ore that started tne great activity at this camp was made late
in 1917, wholly by chance. The chief producing mine is the
Alcohol, Denatured. Supplement to Regulations 60 relative Tonopah Divide, which yields ore averaging 25 ounces of silver
to dealing in, transportation, and use of tax-paid industrial ancj §2.50 in gold to the ton.
alcohol in original stamped packages only. Treasury Decision — , .«• ,, r»- *_: * m- ., • tt r* t>„ „ „„..
Qinn T?-„m tv„,„ £„ • • ,o xt„ ci ro r „„ inoi The Mogollon District, New Mexico. H. G. Ferguson.
310b. rrom treasury Decisions 38, T\o. 51-53. 6 pp. 1921. „ „ .. nK T * .... T, w . ^ . ,m»
J ' * K Bulletin 715-L. Contributions to Economic Geology. 1920.
WAR DEPARTMENT Part I. 34 pp. Published February 8, 1921. The ores of the
Lubricating Oils, Specifications and Method for Testing. Air district are valuable mainly for silver. Argentite, pyrite.
Service Information Circular, Heavier-than-Air, 2, No. 118, bornite, chalcopyrite, and tetrahedrite, together with small
October 20, 1920. 7 pp. amounts of horn silver and native silver, are the principal ore
minerals. The ores are principally sulfides.
INTERIOR DEPARTMENT Coaj m ^ Middle ^ Eastern Parts of San Juan County,
Petroleum. Operating regulations to govern the production jjew Mexico. C. M. Bauer and J. B. Reeside, Jr. Bulletin
of oil and gas, under the act of February 25, 1920. Public 716-G. Contributions to Economic Geology. 1920. Part II.
Document 146. 4 pp. 1921. 83 pp Published February 11, 1921. The coal is chiefly of
INDIAN AFFAIRS OFFICE subbituminous rank, but in the northern part of the field it is good
Mineral Lands. Regulations (approved November 12 and fnouSh * be raked as bituminous. The beds numbering
December 27, 1920) governing leasing for lead and zinc mining ffrom. tv,,° *° ■» att m^ '°,cal'ties' ran^ » K£^0J™1*
„_„..• „ J. ° ct-4.jTj- ij-<~i few inches to 40 ft. The thickness 01 the various beds at manv
operations and purposes, of restricted Indian lands in Quapaw , . . . f. nil.Iitv „nH character of the coal and the
Agency, Oklahoma, under the acts approved June 7, 1897, and Pla.ces. ls S™ ?' and *f e c'Han.ty and cnaracter ot tne coal ancl tne
March 3, 1909. 21 pp. 1921. inclosing strata are described.
Character of Coal in the Thomas Bed near Harrison, West
geological survey Virginia. M. R. Campbell. Bulletin 716-H. Contributions
Oil Possibilities in and around Baxter Basin, in the Rock to Economic Geology. 1920. Part II. 3 pp. Published
Springs Uplift, Sweetwater County, Wyoming. A. R. Schultz. February 18, 1921. Chemical analyses show that this coal is a
Bulletin 702. 107 pp. This preliminary report was prepared semibituminous or smokeless coal, which is rather high in ash
in order to make public certain data bearing on the presence of and contains a variable amount of sulfur.
oil in Baxter Basin, in the Rock Springs uplift, in Wyoming, Coal in 1018. Part B. Distribution and Consumption. C.
and on the occurrence of oil shale around the uplift. A brief E. Lesher. Separate from Mineral Resources of the United
summary is given of the occurrence of oil shale in the late ter- States. 1918. Part II. 78 pp. The statistics collected from
370
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
the operators of coal mines and published in this report show the
quantities of bituminous coal and lignite (1) used at the mines
for generating steam and heat, (2) sold locally or used by em-
ployees, (3) used at the mines for making coke (none of this coal
is shipped), and (4) shipped to market either by rail or by
river.
Chromite in 1919. J. S. Dlller. Separate from Mineral
Resources of the United States. 1919. Part I. 5 pp. Pub-
lished February 4, 1921. The total domestic chromite of all
grades shipped from mines in 1919 amounted to 5079 long tons,
valued at $129,302, or $25.46 a ton, a decrease of nearly 94 per
cent in quantity and nearly 97 per cent in value from the ship-
ments of 1918, although it exceeded the domestic output during
any year before the war.
Secondary Metals in 1919. J. P. Dunlop. Separate from
Mineral Resources of the United States. 1919. Part I. 35 pp.
Published January 31, 1921. The following tabular statement
shows the secondary metals of certain classes recovered in the
United States in 1918 and 1919:
1918 . , 1919 .
Quantity Quantity
Short Short
Tons Value Tons Value
Copper, including that
in alloys other than m^
brass 122,510 $'60,519,900 112,400 J41.812.800
Brass scrap remelted.. 328,800 128,696,300 249;700 75,944,100
^adutaToys::.;.;.: li.lil} 13.7ss.200 { ^:|f|} 12,942.600
Zinc as metal 27.10S1
Z^anabrI's0sySan0dthfn ^0-™° { Vol?} «-™-°°°
chemical compounds 11,082 J
ffitaEE::::::::: il:lU} «.38i.ooo } J;^} 29,868,200
Anlimon^fnaToys:::: S.lll} l-3^000 { 4.3ol} ™ -™
Aluminium as metal... 6.0501 ,~ ,,,, finn ( 6.017) 1Q nu Ann
Aluminium in alloys.. gioooj 10.113,600 } 12,674 } 12.014.600
Nickel as metal 178) ( 163)
Nickel in nonferrous [ 1,532,300 \ J- 1,829,400
alloys 1.215 i t 2,284}
Total $264,298,900 $181,841,500
Mineral Waters in 1919. A. J. Ellis. Separate from Min-
eral Resources of the United States. 1919. Part II. 35 pp.
Published January 21, 1921. The statistics in this report
refer only to domestic mineral waters that have been sold, im-
ports being excepted. Three uses of mineral waters are recog-
nized—table use, medicinal use, and use in the manufacture of
soft drinks. The reports show that as many as 81 waters are
sold in the United States for both table and medicinal purposes,
and that 22 waters are sold for table use, medicinal use, and use
in the manufacture of soft drinks.
BUREAU OF MINES
Use of the MacMichael Viscosimeter in Testing Petroleum
Products. W. H. HerschEL (Bureau of Standards) and E. W.
Dean. Reports of Investigations. Serial No. 2201. 12 pp.
Issued January 1921. The aim of the paper is to outline in a
simple manner the principles involved in the calibration and
use of the MacMichael viscosimeter and to describe a procedure
that has proved satisfactory in the respective laboratories of the
authors.
Properties of Typical Crude Oils from the Eastern Producing
Fields of the United States. E. W. Dean. Reports of In-
vestigations. Serial No. 2202. 57 pp. Issued January 1921.
Results of the laboratory analysis of 35 samples of crude petro-
leum representing the so-called Eastern fields are offered for
purposes of general information. Figures for a few samples
from Mid-Continent and the Western States are included for
the purposes of comparison. Attention is called to several
conclusions of general significance. Figures for approximate
refining yields are given for purposes of rough and ready_com-
parison.
Consumption of Reagents Used in Flotation. Thomas
VarlEy. Reports of Investigations. Serial No. 2203. 4 pp.
The Talc Industry in 1920. R. B. Ladoo. Reports of In-
vestigations. Serial No. 2204. 5 pp. Issued January 1921.
The production of talc in 1920 was probably the largest in
history, and imports of talc were larger than ever before.
Investigation of Low-Grade and Complex Ores in Colorado.
R. R. Hornor and W. H. Coghill. Reports of Investigations.
Serial No. 2206. 4 pp.
Tests of Carbon Monoxide Detector in Mines. D. Harring-
ton and B. W. Dyer. Reports of Investigations. Serial No.
2207. 3 pp. Issued January 1921.
The Value of Oxygen Breathing Apparatus in Mine Rescue
Operations. D. J. Parker. Reports of Investigations. Serial
No. 2209. Issued January 1921. 3 pp.
Recent Articles on Petroleum and Allied Substances. Com-
piled bv E. H. Burroughs. Reports of Investigations. Serial
No. 2210. 25 pp. Issued January 1921.
BUREAU OF STANDARDS
Annual Report of the Director of the Bureau of Standards to
the Secretary of Commerce for the Fiscal Year Ended June 30,
1920. Miscellaneous Publications — -No. 44. 281 pp. 1920.
Lime — Definitions and Specifications. Circular 106. 15 pp.
Paper, 5 cents.
DEPARTMENT OF AGRICULTURE
Nicotine Sulfate in a Dust Carrier against Truck-Crop In-
sects. R. E. Campbell. Department Circular 154. 15 pp.
Paper, 5 cents. Issued February 21, 1921.
Articles from Journal of Agricultural Research
Degree of Temperature to Which Soils Can Be Cooled without
Freezing. George Buoyoucos. 20 (November 15, 1920),
267-9.
Changes Taking Place in the Tempering of Wheat. E. L.
Tague. 20 (November 15, 1920), 271-5.
Carbon Dioxide Content of Barn Air. M. F. Hendry and
Alice Johnson. 20 (December 15, 1920), 405-8.
Daubentonia Longifolia (Coffee Bean), a Poisonous Plant.
C. W. Marsh and A. B. Clawson. 20 (December 15, 1920),
507-13.
Nodule Bacteria of Leguminous Plants. F. Lohnis and
Roy Hansen. 20 (January 3, 1921), 543-55.
Measurement of the Amount of Water That Seeds Cause to
Become Unfree and Their Water-Soluble Material. G. J.
Bouyoucos and M. M. McCool. 20 (January 3, 1921),
587-93.
Concentration of Potassium in Orthoclase Solutions Not a
Measure of Its Availability to Wheat Seedlings. J. F. Brea-
zeale and L. J. Briggs. 20 (January 15, 1921), 615-21.
Composition of Tubers, Skins, and Sprouts of Three Varie-
ties of Potatoes. F. C. Cook. 20 (January 15, 1921), 623-35.
Further Studies in the Deterioration of Sugars in Storage.
Nicholas Kopeloff, H. Z. E. Perkins and C. J. Welcome.
20 (January 15, 1921), 637-53.
Effect of Various Crops upon the Water Extract of a Typical
Silty Clay Loam Soil. G. R. Stewart and J. C. Martin. 20
(January 15, 1921), 663-67.
COMMERCE REPORTS— FEBRUARY 1921
The leather situation in Bulgaria is reviewed. (Pp. 609-10)
The production of olive oil in Greece is described and statistics
showing the production by districts. (Pp. 665-6)
Serious consideration is being given to the use of fuel oil in
place of coal in Italy. (Pp. 668-9)
Recent experiments indicate that indigo grown in Assam will
prove a formidable competitor of synthetic indigo. A very
large share of Indian indigo has been grown in the Province
of Bihar, but the exhaustion of the fertility of the soil has caused
a great decrease in the yield. It is believed that this situation
should open up a market for American fertilizers. (P. 684)
The following table shows the production (in kilos) of metals
and minerals in Mexico for the years 1917 to 1920, the figures
for 1920 being of a preliminary nature subject to later rectifica-
tion:
1917 1918 1919 1920
Gold 23,542 25,313 23,586 23,370
Silver 1.306,988 1,944.542 2.049,898 1,979,972
Copper 50.985,923 70.223.455 50,172.235 46.056.900
Lead 64.124,752 98,837,154 71.375.908 121.434.066
Zinc 45,180,778 20,698,990 11,559.685 14,363,057
Mercury 33.132 163,597 118,940 77,229
Antimony 2.646.544 3.27S.546 470,738 1,572,376
Graphite 420.046 6,190,849 4,023,015 2,991,529
Tungsten 187.637 149,486 21.970 34.917
Tin 9,214 13,538 1,588
Arsenic 1,284.820 1,881,011 2,246,378 1.198,806
Manganese 73.387 2.878,383 2,294,227 838,624
Molybdenum 27,371 1.767 648
(P. 709)
The Czechoslovak hide and leather industry is reviewed. (P.
718)
Business conditions were so unfavorable during 1920 that no
new graphite-producing districts were opened in Madagascar,
no new company for its exploitation was formed, and opera-
tions at a number of the old deposits ceased. (P. 720)
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
371
Statistics of Siam's imports of chemicals and drugs show the
substantial progress made by the United States in this trade
during the last seven years. (P. 733)
By a decree dated December 10, 1920, sesquisulfide of phos-
phorus is included in the section "raw materials" for use in in-
dustry, when imported into Uruguay, with a valuation of 1.50
pesos per kilo and a duty of 8 per cent of this valuation. (P.
751)
In normal years India produces well over 5,000,000 tons of
oil seeds, one-third of which is usually exported. These seeds
include cottonseed, rape seed, peanuts, sesame seed, mowra
seed, poppy seed, linseed, castor seed, as well as copra. (Pp.
772-3)
The fluospar industry is reported to be active in Germany.
Most of the fluospar is consumed at present by the German iron
industry. (P. 788)
A diminished production in the Norwegian paper industry is
reported. (P. 809)
The production, transportation, storage, composition, speci-
fications, uses, prices, and exports of wood oil in China are de-
scribed. (Pp. 812-5)
The Italian restriction on the importation of crude and re-
lined mineral oil has been removed. (P. 833)
A reward has been offered in New South Wales to the first
producer of 100,000 gallons of petroleum within the State.
(P. 840)
An industry for the supply of toilet preparations made from
talc, graphite, black oxide, many different water colors, man-
ganese, tailors' chalk, colored ochres, healing ointment, etc.,
has been started in Tasmania, and a company floated to produce
all of these articles from the raw material. (P. 840)
Picked samples from Manitoba's new nickel-copper and gold
camp have shown values of 10 per cent in nickel and 20 per
cent in copper, with considerable gold. (P. 848)
Mineral production in Canada during 1920 is estimated at
$200,000,000, compared with $176,686,390 in 1919. (P. 848)
An Italian company has developed a process for obtaining
mineral oil with an exceedingly low bituminous content from
Sicilian asphalt. (P. 852)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by Sweden during the years
1917, 1918, and 1919. (Pp. 854-5)
The Esthonian Ministry of Trade and Industry has estab-
lished factories for drying potatoes and making potato flour
along the lines employed by Germany during the war. (P. 855)
Poland has been negotiating with the Chilean government for
the purchase of 300,000 tons of nitrate a year on a credit guaran-
teed by the Chilean government. If this arrangement is ef-
fected, a large part of the present surplus stocks will be dis-
posed of. (P. 857)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by French India during the
years 1912, 1913, and 1914. (P. 861)
After thorough investigation it is stated that flavoring ex-
tracts and coloring matter are the only articles which can be
profitably sold to the Argentine candy manufacturers by the
American exporter. (P. 872)
The production and marketing of olives and olive oil in Greece
are described. (Pp. 874-5)
Advice from Alexandria, Egypt, states that there can be but
a very limited market for industrial chemicals with the excep-
tion of fertilizers, brewery supplies, etc. There is, however, a
good market for drugs and certain of the lighter chemicals. (P.
888)
In view of the almost total lack of potash fertilizers, the
agriculturists of Piedmont, Italy, are urging that the Ministry
of Finance in Rome turn over to a private concern the utiliza-
tion of the salt fields from which an enormous quantity of fer-
tilizers could be obtained. (P. 895)
Potassium salts have been recently discovered in nearly all
of the numerous salt wells in Szechwan Province, which range in
depth from 1000 to 3000 ft. The mother liquor contains about
3.5 per cent of potassium. (P. 896)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by the French Oceania dur-
ing the years 1912, 1913, and 1914. (Pp. 918-9)
f A scarcity of soda in Czechoslovakia is reported and it is stated
that the amount available will supply only about 30 per cent
of the needs of the glass factories and other concerns using that
product. (P. 934)
The Czechoslovak iron industry is reported to be suffering
from the competition of German iron producers. (Pp. 934-5)
A decrease is shown in the imports of chemicals and drugs
into Madras, India, for the year ending March 31, 1920, but a
continued expansion in the imports of dyes and colors was quite
notable. (P. 950)
The Warsaw Agricultural Syndicate has a plan whereby
farm products are to be exchanged for fertilizers in Poland.
(Pp. 957-9)
Statistics are given showing the trend of prices in the German
leather industry. (P. 967)
Statistics are given showing the production of rubber on
plantations in the Dutch East Indies during the years 1918,
1919, and 1920. This production has shown a large and steady
annual increase since 1913. (P. 971)
The British Board of Trade has prohibited the exportation of
ammonium sulfate, superphosphate, lime, basic slag, and com-
pound fertilizers containing any of these products. (P. 977)
A concern in Jaffa, Palestine, writes that it can export Arabic
gum and myrrh, and would like to get in touch with American
firms manufacturing these substances. (P. 1040)
There has been a steady reduction in the output of petroleum
in Japan since 1915, but experts believe that there will be a
gradual increase, beginning this year. (Pp. 1044-5)
The prices Of all French industrial metals dropped in 1920
because of the holding off of buyers, and prices to-day are about
equal to those at the lowest point in 1915. (P. 1045)
Unfavorable conditions are reported in the Malayan rubber
industry. (Pp. 1064-5)
A revised list of the importers and dealers in chemicals and
drugs in China, giving available information as to their rela-
tive number, nationality, and whether wholesale or retail, is
now available at the Bureau of Foreign and Domestic Commerce.
(P. 1100)
Tests extending over several months have passed the experi-
mental stage and conclusively demonstrate that peat, reduced
to powder or prepared in the form of briquets, makes an ex-
cellent substitute for coal as fuel for locomotives on Swedish
railways. (P. 1109)
Statistics are given showing the imports and exports of vege-
table oils and vegetable oil material by Federated Malay States —
Parak, Selangor, Negri Semblian, and Pahang— during the two
years for which statistics are available. (P. 1131)
Specifications for aviation petrol from Roma oil bore points,
Queensland, are much more stringent regarding the content of
the constituents for higher boiling point than those for ordinary
motor fuel. With regard to the absence of higher boiling-point
fractions the petrol is well within the limits prescribed by the
United States Fuel Administration for aviation petrol, domestic
grade, though as regards volatility the petrol is not quite up to
specifications. (P. 1132)
The production of zinc in Japan in 1915 reached 21,131 tons,
which was sufficient to cover the local demand. Consumption
steadily increased until the height of production was reached
in 1917. Since then the demand has gradually decreased, and
at present only three factories that use materials produced in
their own mines are continuing business. (P. 1156)
Special Supplements Issued
Russia— 16c
Statistics
of Exports to the United States
Japan — (P. 663)
Bahai— (Pp. S23, 8S9)
Italy— (P. 915)
Menthol crystal
Castor beans
Citrate of lime
Peppermint oil
Hides and skins
Cbrome ore
Madras — (Pp. 956-7)
Sydney, Nova Scotia —
Manganese ore
Copra
(P. 671)
Oils:
Indigo
Pulpwood
Vegetable — castor,
Monazite sand
Creosote oil
crude
Nux vomica
Sulfate of ammonia
Rubber
Oils:
Medicinal roots and
Coconut
China— (P. 727)
leaves
Lemon grass
Sesame seed
Carnauba wax
Sandalwood
Sesame oil
Ore, chrome
France— (Pp. 898, 997J
Rubber
Egypt— (P. 749)
Drugs, crude
Turmeric
Colocynth
Ammonium nitrate
Gum arabic
Chalk, crude
London— (P. 1041)
Senna
Chicory root
Leather
Oil, fuel
Chemical products
Hides
Raw hides
Tin
Naples, Italy — (P.
Gums
771)
Marseille, France—
Drugs and chemicals
Tartar
(.P. 975)
Aluminium
Chemicals
Linseed oil
British Guiana— (P.
Drugs
556)
Dyes
Greece — (P. 6U5)
Bauxite
Olive oil
Ripe olives
372
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No 4
BOOK REVIEWS
The Chemistry of Enzyme Actions. By K. George Falk.
[American Chemical Society Monograph Series. ] 136 pages.
The Chemical Catalog Co., Inc., New York, 1920. Price,
$2.50.
This monograph is the first of two series to be published under
the auspices of the American Chemical Society. Accord-
ing to the statement of the committee in charge of their prepara-
tion and publication, these monographs are to serve a dual pur-
pose. The first purpose, which must be of vital interest to every
member of the Society, is to present the knowledge available
upon the subject in a readable form, intelligible to those whose
activities may be along wholly different lines. The second pur-
pose is to promote research in the branch of science covered by
the monograph, by furnishing a well-digested survey of the
progress already made in that field and by pointing out direc-
tions in which investigation needs to be extended, together with
extended references to the literature, or at least a. critical selec-
tion of the most important papers dealing with the subject at
hand.
In the introductory chapter the general problem of enzymes
and enzyme action is outlined. Two lines of investigation are
suggested : the one a study of the kinetics of enzyme action, the
other the study of enzymes as chemical substances possessing
definite chemical structures or configurations. These two
thoughts predominate in the discussions in Chapters I and II,
and in Chapter III. where the subject of catalysis is taken up.
Enzymes are catalysts; they are not used up, neither are they de-
stroyed, but by their mere presence set in motion a reaction
between two other substances. Since the chemical reactions
whose velocities are increased by enzymes include a number of
comparatively simple reactions (as well as many complex ones)
and can be brought about also by simple chemical means, though
very much more slowly, these simple chemical changes are dis-
cussed in Chapter IV. The enzyme which accelerates the re-
action is neglected and attention is directed to the reaction itself.
The hydrolysis of sucrose by acid is discussed and the amount
of change produced is studied by:
(a) The rotation of the plane of polarized light.
(b) The change in viscosity.
(c) The reducing power of the hexoses formed upon alkaline
cupric salt solutions such as Fehling's solution and others.
The three sets of theories to account for catalytic action of acids
on the hydrolysis of sucrose are mentioned. First, the reac-
tion is considered as due entirely to hydrogen ions present in
solution; second, the dual theory assumes the action to be due
both to the hydrogen ions and to the un-ionized molecules;
third, the addition theory of chemical reactions assumes a primary
formation of an addition compound with the acid molecule and
considers that the solvent is involved as one of the main factors,
while the ionization is secondary. None of these three views
has been found completely satisfactory, but the writer sug-
gests a preference to the last mentioned. Oxidizing and re-
ducing enzymes appear even more difficult to handle from the
theoretical side than do the hydrolytic reactions due to enzyme
activity.
Chapter V considers the physical properties common to
enzyme preparations. Their colloidal character and non-
dialyzability through collodion membranes, their absorption
by other colloids, their precipitation or coagulation either by
the addition of a foreign substance to the solution, or by the re-
moval from the solution of a substance apparently essential
in holding the enzyme in solution are discussed. Mention is
also made of the importance of the reaction of the medium to
the activity of the enzyme, and tabulated data are given of the
recognized optimum hydrogen-ion concentration necessary
for best activity.
In Chapter VI the chemical properties common to all enzyme
preparations are considered. Every such preparation which
has been examined contains nitrogen, and a table is given show-
ing the nitrogen content of some of these preparations. The
inorganic elements, as well as carbon and hydrogen, are too
difficult to treat with our present knowledge. Attention is
called to the fact that no enzyme has actually been isolated
and their chemical formulas are still a matter of conjecture.
Interesting parallelisms between the behavior of indicators and
of enzymes are pointed out. The interrelation in enzymatic
activity between the three factors: temperature, hydrogen-
ion concentration, and time, is shown, as well as the fact that the
optimum pH value for the enzyme may vary for the different
substrate being acted upon. Finally, the activating and inhibit-
ing actions of certain inorganic substances are considered.
Chapter VII considers the mechanism of enzyme actions and
deals with the velocities of the chemical reactions, the factors
which influence them and the inferences which may be drawn
concerning the enzyme actions involved.
In the next chapter the author discusses the uses and applica-
tions of enzymes. Here, the chemist whose activities are along
an entirely different line gets his first introduction to what
the previous eight chapters are all about. It is shown that the
enzymes are catalysts produced by living animal and vegetable
matter, the function of which is to break down and render as-
similable food for growth and renewal of tissues or their com-
ponent cells. The actions of enzymes therefore consist in favor-
ing or accelerating those reactions which are required in the life
process and making possible its continuance.
The uses of enzymes are roughly divided into five groups:
Industrial application of enzymes
Enzymes of metabolism and catabolism
Enzymes in plant growth
Bacterial enzymes
Enzymes in laboratory work
This list does not tend to be complete. In the industrial ap-
plication mention is made of the fermentation industry, the
production of glycerol, of acetone, succinic acid, acetic acid,
formic acid, fusel oils, and esters. It is also suggested that a
new thought may be possible, viz., the synthesis of complex
molecules out of simpler ones, in contrast to the cleavage of com-
plex ones as practiced to-day.
There is a typographical error in the table on page 121, where
melibiose instead of melibiase is shown to hydrolyze melibiose
into galactose and glucose. The term sucrase in the same
table is obsolete, invertase being the name at present used for
this enzyme, and also that used by Hudson in the article men-
tioned.
In Chapter X the author sums up what has appeared in the
previous chapters, adding a discussion of the specificity of the
enzymes. An enzyme which acts upon starch cannot act upon
protein or fat, and vice versa.
Co-enzymes are taken up. Reference is made to the activa-
tion of the pancreatic lipase by the bile salts and to the activation
of pancreatic amylase by salt, etc., and the suggestion is made
that the word co-enzyme be dropped from the literature and
that an attempt be made to study the problem of activation
from a purely chemical standpoint.
In commenting upon this monograph, the first thing that
seems lacking is an extended bibliography. The references
Apr., 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
373
given are all too few, and they would have been much more
serviceable had they been properly classified at the end of the
book. On the whole, the book is well written and shows much
painstaking effort on the part of the author. For the specialist
and research worker in this and allied lines, this book will prove
of inestimable value, and it certainly deserves a place in the
library of such men. I would point out, however, the need of
pure enzymes for further research. If the studies of enzyme
action are to be pursued, it is absolutely necessary that pure
enzymes be made much purer than most at present at the dis-
posal of the workers. Much of the conflicting evidence now re-
corded may undoubtedly be traced to variations in the purity
of the enzymes under investigation. It is the reviewer's opinion
that the author did not lay sufficient stress upon this fact.
For the chemist whose activities may be along a wholly
different line, it is a question whether his interest could be held
through the discussions in the first four chapters sufficiently
for him to finish the book. Inasmuch as this is the first of the
series, it is to be hoped that the monographs to follow have an
extended bibliography in the back, properly indexed, and that
as much attention be devoted to the subject to develop it from
the practical as from the theoretical standpoint.
Howard T. Graber
The Determination of Hydrogen Ions. By W. Mansfield
Clark. 318 pp. Williams and Wilkins Co., Baltimore,
Md., 1920. Price, $5.00.
The present volume is frankly written for the biologist and the
biological chemist. Within the past decade we have awakened
to the fact that "titratable acidity" is a relatively unimportant
factor in living processes, while the actual H+-ion concentration
is of paramount importance. Originating with the epoch-
making researches of Sorensen, whose portrait very properly
"forms the frontispiece of this book, exact methods for the de-
termination of hydrogen ions have been used more and more
extensively by biological workers. Michaelis in 1914 published
"Die Wasserstoffionenkonzentration" and gave a new impetus
to the work. However, the apparatus which Sorensen and
Michaelis used appears very complicated and formidable to
those who have not been trained in the niceties of physical chem-
istry, with the result that no doubt many workers have decided
that they were not sufficiently skilled to undertake H+-ion work.
Such a fear need no longer be felt. The reviewer is proud of the
enormous advances that American manufacturers have made
in designing apparatus for the exact determination of hydrogen
ions, making the process so simple that anyone can master it
within a very few hours.
In America we have had this advantage of fine apparatus
for several years, but have of necessity been forced to depend
for guidance on Michaelis' book and on a great mass of data
scattered through many scientific journals. Now we have this
admirable work by Dr. Clark in which we can find a ready answer
to most of our perplexing questions.
The first seven chapters of the book are devoted to the colori-
metric methods of H+-ion determination. Surely no one could
write more convincingly in this field than the author, for it is
to him and his co-workers that we owe much of our present
knowledge, and are indebted for a series of new, sensitive, and
brilliant indicators.
Chapter I considers the general relations between acids and
bases, dealing primarily with dissociation constants and neu-
tralization curves. The author strongly emphasizes that we
must distinguish sharply between what "we call 'normality' in
its older sense, the quantity factor of 'acidity' and the hydrogen-
ion concentration, the intensity factor." The outline of the
colorimetric method includes an excellent color chart by means
of which H+-ion concentrations ranging from pH 1.2 to 9.8
may be roughly estimated. In discussing the theory of indica-
tors, the author rightly points out that there are still many
unknown factors in this field and that "there seems to be no
inherent reason why ionization, tautomerism, alteration in the
fields of force within the compound and light absorption should
not (all) be correlated." Under "optical aspects" he considers
among other questions those involving the psychology of the
eye, pointing out that in dealing with a dichromatic indicator
(blue and red) "the eye instinctively fixes upon the very domi-
nant red." Further chapters deal with the choice of indicators,
with standard buffer mixtures, and with the errors involved in
colorimetric determinations, including the "protein error" and
the "salt effect." Here the author frankly acknowledges that
much additional research is needed before all of the factors can
be known. He states:
We can bring to bear upon the problem no adequate explana-
tion of the "salt effects," no general theory of the "protein
errors," no comprehensive treatment of the optical difficulties,
and finally no perfectly rigid basis upon which to compare the
electrometric and colorimetric measurements. It seems wise
to leave any detailed treatment of these subjects to painstaking
research and to the resolution which will doubtless come when
the conduct of strong electrolytes is placed upon a sound basis.
What a refreshing change from the all too common practice of
stating one's pet hypothesis as actual fact! The colorimetric
method is concluded in a chapter on approximate determinations
with indicators.
The second part of the book deals with the electrometric
method, and includes a discussion of the principles of the method,
the theory of the hydrogen electrode, potential differences at
liquid junctions, hydrogen and calomel electrodes and electrode
vessels, the potentiometer, and hydrogen generators, wiring,
etc. The discussion is full and to the point. The mathematical
and physical formulas are presented concisely, but the text is
handled in such a way that the formulas are a help to the under-
standing of the method, but not a necessity. Every detail of a
successful electrometric installation is considered. In Chapter
XIV the relation of hydrogen electrode potentials to reduction
potentials is considered, and Chapter XV is devoted to sources
of error in electrometric measurements of pH. For one who is
just beginning electrometric measurements the advice found
in this chapter alone will be invaluable. Chapter XVI is
devoted to standard solutions for checking H+-ion measure-
ments, and in Chapter XVII the author considers the question
of the standardization of pH measurements. Everyone working
with the potentiometric method should read this chapter, for
the author points out that we still have no absolute unalterable
standard, due to the various methods of effecting the liquid
junction, the unknown temperature corrections, etc. He wisely
suggests that the various workers should carefully state the ex-
act conditions under which they carried out their measurements
so that corrections, which we cannot now apply for lack of knowl-
edge, may be applied in the future.
The last two chapters consider supplementary methods and
the application of H+-ion methods in the various fields of ac-
tivity. The book closes with a complete bibliographic citation
of 1234 references, giving author (arranged alphabetically),
year, title, and journal reference. An appendix containing
several useful tables, as well as a list of equipment required for
the electrometric method, closes the volume.
As stated above, the book was written for the biologist and
the biological chemist. It should, however, be equally useful
to everyone whose problems involve either quantity of acidity
or intensity of acidity. Its place is not alone on the shelf of
every chemical library, but on the working desk of every chemist
whose problems involve the determination of hydrogen ions.
Ross Aiken Gortner
374
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
NEW PUBLICATIONS
Chemistry: Inorganic Chemistry for Schools and Colleges. Jas. Lewis
Howe. 2nd edition, revised. 3d edition of "Inorganic Chemistry
According to the Periodic Law," by F. P. Venable and J. L. Howe. 448
pp. Price, $4.00. The Chemical Publishing Company, Easton, Pa.
Chemistry: Organic Chemistry for the Laboratory. W. A. Noves.
4th edition, revised. 293 pp. Illustrated. Price, $3.50. The Chem-
ical Publishing Company, Easton, Pa.
Chemistry: Treatise on Chemistry. H. E. Roscoe and C. Schorlemmer.
Vol. I. The Non-Metallic Elements. Price, $9.00. Vol. II. The
Metals. Price, $12.00. 5th edition, completely revised. 968 pp.
Illustrated. The Macmillan Co., New York.
Copper Refining. Lawrence Addick6. 206 pp. Illustrated. Price,
$3.00. McGraw-Hill Book Co., Inc., New York.
Dictionary of Chemical Solubilities — Inorganic. Arthur M. Comey and
Dorothy A. Hahn. New edition, revised. Price, $14.00. The Mac-
millan Co., New York.
Elementary Dynamics: A Textbook for Engineers. J. W. Landon.
246 pp. Cambridge University Press, Loudon.
Oils: Lubricating and Allied Oils. A Handbook for Chemists, Engineers,
and Students. Elliott A. Evans. 128 pp. Price, 9s. 6d. (The
Directly-Useful Technical Series.) Chapman & Hall, Ltd., London.
Paper: The Manufacture of Pulp and Paper. J, J. Clark. Vol. I.
Arithmetic, Elementary Applied Mathematics, How to Read Drawings,
Elements of Physics. 441pp. Illustrated. Price, $5.00. McGraw-Hill
Book Co., Inc., New York.
Poisons: Laboratory Manual for the Detection of Poisons and Powerful
Drugs. Wilhelm Autenrieth. Translated by William H. Warren.
5th American edition. 342 pp. Illustrated. Price, $3.50. P. Blakiston's
Son & Co.. Philadilphia
Properties of Steam and Thermodynamic Theory of Turbines. H. L.
Callbndar. 531 pp. Price, $14.00. Longmans, Green & Co., New York.
Vitamines: Essential Food Factors. Benjamin Harrow. 219 pp.
Price, $2.60. E. P. Dutton & Co., New York.
RECENT JOURNAL ARTICLES
Alcohol: Manufacture of Ethyl Alcohol from Wood Waste. E. C. Sher-
rard. Chemical Age, Vol. 19 (1921), No. 2, pp. 76-79.
Aluminium: Ferric Sulfate as a New Etching Reagent in the Metallog-
raphy of Aluminium. Robert J. Anderson. The Metal Industry,
Vol. 19 (1921), No. 2, pp. 69-70.
Atomic Structure: Atomi e Nuclei Atomici. Roberto Salvadori. Giornale
di Chimica Industriale ed Applicata, Vol. 3 (1921), No. 1, pp. 13-19.
Blast Furnace Gases: Electrostatic Precipitation Applied to Blast Furnace
Gases. H. J. Bush. The Chemical Age (London), Vol. 4 (1921), No.
85, pp. 116-117.
Calorizing as a Protection for Metals. Arthur V. Farr. The Iron Age,
Vol. 107 (1921), No. 4, pp 251-254.
Carbonization: Sulfur Distribution in Carbonization. U. O. Hutton
and C. C. Thomas. The Gas Age, Vol. 47 (1921), No. 3, pp. 88-94.
Charts: The Construction and Use of Alignment Charts. A. J. V. Uman-
ski. The Chemical Trade Journal and Chemical Engineer, Vol. 68 (1921),
No. 1761, pp. 233-236; No. 1762, pp. 269-272.
Chemical Engineering: Some Problems of Chemical Engineering. A. R.
Warnes. The Chemical Trade Journal and Chemical Engineer, Vol.
68 (1921), No. 1761, pp. 237-238; No. 1762, pp. 273-275.
Chemical Industry: Theory and Practice in Chemical Industry, with
Special Reference to Physical Chemistry. E. B. R. Prideaux. Journal
of the Society of Chemical Industry, Vol. 40 (1921), No. 3, pp. 40r-42r.
Chemical Methods of De-Aeration of Water or Solutions. H. A. Whits.
The Journal of the Chemical, Metallurgical and Mining Society of South
Africa, Vol. 21 (1920), No. 6, pp. 105-111.
Clay: The "Why" of Aging Clay. H. Spurrier. Journal of the Amer-
ican Ceramic Society, Vol. 4 (1921), No. 2, pp. 113-118.
Cobalt Brasses. Leon Guillet. Chemical and Metallurgical Engineering,
Vol. 24 (1921), No. 10, pp. 439-443. Translated from Revue dc Mital-
lurgie. Vol. 17, No. 7, p. 494.
Cottonseed Oil: On the Catalytic Hydrogenation of Cottonseed Oil.
Louis Kahlenberg and George J. Ritter. Journal of Physical
Chemistry, Vol. 25 (1921), No. 2, pp. 89-114.
Direct Recovery Process for Flue Dust. George B. Cramp. The Blast
Furnace and Steel Plant, Vol. 9 (1921), No. 3, pp. 198-202.
Dyes: Fastness Properties of the Principal Red Dyes. Barrington
Db Puyster. Color Trade Journal, Vol. 8 (1921), No. 3, pp. 106-114.
Dyes: Notes on the Manufacture of the Rhodamines. Raffaele San-
sons. Coior Trade Journal, Vol. 8 (1921), No. 3, pp. 84-88.
Dyes: Sur la Coloration des Indigoids. J. Martinet. Revue Generate
des Maliircs Coloranles de la Teinturc, de I Impression, et des Apprlts,
Vol. 2S (1921), No. 290, pp. 17-1S.
Dyes: Standardization of Dyestuff Intermediates. Ernest Fyleman
Journal of the Society of Dyers and Colourists, Vol. 37 (1921), No. 2. pp
37-43.
Explosives: Some Properties of Explosives. Sir Robert Robertson
Journal of the Chemical Society, Vol. 119 (1921), No. 699, pp. 1-29.
Fuel Oil: Heating by Fuel Oil for Manufacturing Processes. C. C. Her-
mann. Industrial Management, Vol. 61 (1921), No. 5, pp. 199-202.
Fuels — Their Utilization and Conservation. Charles Longbnbckbr.
The Blast Furnace and Steel Plant, Vol. 9 (1921), No. 2, pp. 144-146.
Gases: An Apparatus for Recording COs and Combustible Gases. Roland
MoELLER. Paper, Vol. 27 (1921), No. 24, pp. 24-29.
Gas Making with Cheap Oxygen. E. A. W. Jefperibs. American Gas
Engineering Journal, Vol 114 (1921), No. 9 (whole no. 3286), pp. 180-
1S4, 189; The Gas Age, Vol. 47 (1921); No. 4, pp. 145-150.
Glass: The Development of Various Types of Glass. C. J. Pbddlb.
Journal of the Society of Glass Technology, Vol. 4 (1920), No. 16, pp. 299-
366.
Glass: The Manufacture and Treatment of Glass Melting Pots. W. K.
Brownlee and A. F. Gorton. Journal of the American Ceramic So-
ciety, Vol. 4 (1921), No. 2, pp. 97-112.
Hardwood Distillation: "The Chemist and the Crude Factory" in the
Hardwood Distillation Industry. R. E. Gii.more. Canadian Chemistry
and Metallurgy, Vol. 5 (1921), No. 2, pp. 37-41.
Helium: Its History, Properties, and Commercial Development. Richard
B. Moore. Journal of the Franklin Institute, Vol. 191 (1921), No. 2,
pp. 145-197.
Hydrocarbons: The Determination of Aromatic Hydrocarbons in Mixtures
of Hydrocarbons. H. T. Tizard and A. G. Marshall. Journal of
the Society of Chemical Industry, Vol. 40 (1921), No. 3, pp. 20<-2«.
Hydrogen: Possible Developments in Hydrogen Manufacture. Eric K
Ridbal. Journal of the Society of Chemical Industry, Vol. 40 (1921).
No. 2, pp. 10/-141.
Industrial Chemistry: Taking Industrial Chemistry into Partnership.
Frederic Dannerth. Industrial Management, Vol. 61 (1921), No. 5.
pp. 151-154.
Lead Salts in the Cyanidation of Silver Ores. Ralph W. Perry. Mining
and Scientific Press, Vol. 122 (1921), No. 7, pp. 221-225.
Leather: Acid Unhairing. R. H. Marriott. Journal of the Society of
Leather Trades' Chemists, Vol. 5 (1921), No. 1, pp. 2-10.
Leather: Official Method of the American Leather Chemists' Association
for the Analysis of Vegetable Materials Containing Tannin. Journal
of the American Leather Chemists' Association, Vol. 16 (1921), No. 3, pp
113-139.
Medicinals: Les Phenomenes Chimiques en Biologie et en Medecine.
H. Schwarz. Chimie et Industrie, Vol. 25 (1921), No. 1, pp. 18-26.
Open Hearth Furnaces: Application of Waste Heat Boilers to Open
Hearth Furnaces. Thomas R Tate. The Blast Furnace and Steel
Plant, Vol. 9 (1921), No. 2, pp. 173-174.
Paper: The Compound Microscope and Its Value in the Mill. I. L.
Gartland. Paper, Vol. 27 (1921), No. 25, pp. 14-17, 36.
Pharmaceutical Research. George M. Beringer. Journal ofthe Amer-
ican Pharmaceutical Association, Vol. 10 (1921), No. 2, pp. 89-96.
Photography: Les Methodes Actuelles de Virages en Diverses Couleurs
des Papiers Photographiques aux Sels d'Argent. A. Seyewetz. Chimie
et Industrie, Vol. 5 (1921), No. 1, pp. 3-10.
Potash: Sources and Composition of American Potash. J. W. Turren-
tine. The American Fertilizer, Vol. 54 (1921), No. 5, pp. 93-104.
Radio-Activity and Some Practical Applications. C. W. Davis. Mining
and Scientific Press, Vol. 122 (1921), No. 7, pp. 229-232.
Rare Earths: The Precipitation of Some of the Rare Earths by Creams
of Insoluble Oxides and Carbonates, Based on the Principle of Hydrolysis.
Arthur C. Neish and J. W. Burns. Canadian Chemistry and Metal-
lurgy, Vol. 5 (1921), No. 3, pp. 69-74.
Research: The Value of Research in Mining and Metallurgy. Samuel
H. Dolbbar. Engineering and Mining Journal, Vol. Ill (1921), No. 9.
pp. 384-385.
Steel: Notes on the Microstructure of Annealed Soft Steel, with Special
Reference to Phosphorus in Tin Plate. George F. Comstock. Forging
and Heat Treating, Vol. 7 (1921), No. 1, pp. 60-63.
Steel: Review of Iron and Steel Literature, 1920. E. H. McClelland
Forging and Heat Treating, Vol. 7 (1921), No. 1, pp. 8-9.
Sugar: Chemistry of Clarification in Plantation White Sugar Manufacture.
J. P. Ogtlvie. Journal of the Society of Chemical Industry, VoL 40
(1921), No. 2, pp. 22r-24r.
Sugar: Clarifying Methods for Raw Sugar. C. E. Coates. Sugar, Vol
23 (1921), No. 3, pp. 149-150.
Sulfite Liquors: Analysis of Sulfite Cooking Liquors. A. Chambovet.
Paper, Vol. 27 (1921), No. 25, pp. 16-19. Translated from La Papeterie
Sulfuric Acid: Ammonia Oxidation Units for Sulfuric Acid Plants. Wil
frid Wyld. The Chemical Age (London), Vol. 4 (1921), No. 86. pp.
150-151.
Sulfuric Acid: The Chamber Process under Tropical Conditions. W. H
Mawdsley. Chemical Trade Journal and Chemical Engineer, Vol. 68
(1921), No. 1758, pp. 132-133.
pr.
1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
MARKET REPORT-MARCH, 1921
PIRST.BAND „ coo. - ««i ««- ™ - - - —^7
INORGANIC CHEMICALS
eld, Boric, cryst., bbls ^
Hydrochloric, com'l, 20
Hydriodic
Nitric, 42°
Phosphoric, 50% tech
Sulfuric, C. P
Chamber, 66°
Oleum 20%
Hum, ammonia, lump
Uuminium Sulfate (iron-free). . .
Ammonium Carbonate, pwd
Immonium Chloride, gran.. . - •
Ammonia Water, carboys, 26 . .
Arsenic, white
Barium Chloride
Nitrate
ton
100 lbs.
.15
.Ol'/i
.19
.07 V,
.20
.07
20.00
23.00
.04V«
.03»/t
.10
.10
.09»/4
30.00
3.50
.07-/,
.40
28.75
.04
18.00
5.50
8.00
1.00
3.75
.15
.15
.11'/.
.09Vi
2.00
1.50
.10V,
72.00
47.00
Barytes, white • • • " * * "
Bleaching Powd.,35%. Works, 100 lbs.
Borax, cryst., bbls "
Bromine, tech. wks ■ •
Calcium Chloride, fused ™
Chalk, precipitated, light • l ■
CWnaCUy imported.. ...... ^-^
Copper Sulfate
Feldspar
Puller's Earth
Iodine, resublimed ■"'
Lead Acetate, white crystals ».
tt^:::::::::™*
^-f-ri- ; r.
Lime Acetate
Lithium Carbonate '
Magnesium Carbonate. Tech -^
Magnesite.... £
Mercury Bask
Phosphorus, yellow
Plaster of Paris
Potassium Bichromate '" •
Bromide, Cryst • J ■
Carbonate, calc, 80-85% |b
Chlorate, cryst J
Hydroxide. 88-92% ">
Iodide, bulk Jh
Nitrate
Permanganate, U. S. P.
Salt Cake, Bulk
Silver Nitrate ^
Soapstone, in bags • ■ •
Sod;Ash.58%,bag, 00 bs.
Caustic, 76% >«> lb»
Sodium Acetate^ - ;
Bicarbonate '""
Bichromate '
Chlorate ' '
Cyanide '
Fluoride, technical ■ ">•
Hyposulfite, bbls 100 lbs.
Nitrate, 95% «» *••
Silicate, 40° °-
Sulfide ™"
Bisulfite, powdered "■
Strontium Nitrate • • •' ■
Sulfur, Bowers «» «*
Crude long ton
Talc, American, white tan
Tin Bichloride 'b-
Oxide b
Zinc Chloride, U. S. P °
Oxide, bbls Ib
OBQANIC CHEMICALS
.100 lbs
..lb.
ton
1 50
.13V.
3.00
35.00
.40
12.00
2.00
3.60
.07
2.00
.081/=
.14'/,
4.00
2.80
.01V,
.15
3.00
20.00
18.00
. 19Vl
.45
.40
.10
.lb.
Acetanllide • ■ •
Add, Acetic, 28 p. c 100 lbs.
Glacial lb
Acetylsalicylic lb'
Benzoic, U. S. P., ex-toluene.. lb.
Carbolic, cryst, U.S. P., drs... lb.
50- to 110-lb. tins lb
Citric, crystals, bbls 'b-
.25
3.00
Mar. 15
.14V,
.01V,
.19
.07 V,
.18
.07
20.00
23.00
.04«/«
.03
.08
.10
.09«/«
.08V,
65.00
Acid (Concluded)
Oxalic, cryst., bbls ">•
Pyrogallic, resublimed lb.
Salicylic, bulk, U. S. P lb.
Tartaric, crystals, U. S. P lb-
Trichloroacetic, U. S. P "».
Acetone, drums •
Alcohol, denatured, 190 proof. . . gal.
Ethyl. 190 proof *al.
Amyl Acetate g"^
Camphor. Jap. refined ">•
Carbon Bisulfide *.
Tetrachloride ,b-
Chloroform, U. S. P *
Creosote. U. S. P lb
Cresol, U. S. P ■•■■■»■
Dextrin, corn 100 "»
Imported Potato "■
Ether, U. S. P., cone, 100 lbs
Formaldehyde
Glycerol, dynamite, drum* '»■
Methanol, pure, bbls 8"-
gal.
100 lbs.
8.
00
1.
00
3.
75
15
.15
.HVl
09V.
2
.00
1
.40
.iov
72
.00
4£
i.OO
35.00
.37 V:
12.00
2.70
.01V,
.07
.06
.15
3.00
20.00
18.00
. 19V,
.40
.40
.10
2.75
.09
lb.
Pyridine
Starch, corn
Potato. Jap.
Rice
Sago
lb.
.18
2.00
.23
.32
4.40
.13V,
.58
4.90
3.50
.80
.08
.12
3.55
.09
.20
.18
.16
1.65
2.75
2.65
.05
.25
.05
Beeswax, pure, white •
Black Mineral Oil. 29 gravity g<"
Castor OU, No. 3 J°
Ceresin, yellow •
Corn Oil, crude ''"'.;,' ',K
Cottonseed Oil, crude, f. o. b. mill . .lb.
Linseed Oil, raw ".""«" 8_i
Menhaden Oil, crude (southern) . . gal
N«at's-f oot Oil. 20*
Paraffin, 128-130 m. p., ref .
Paraffin Oil, high viscosity
Rosin, "F" Grade, 280 lbs..
Rosin Oil, first run
Shellac. T. N
Spermaceti, cake • •
Sperm Oil, bleached winter, 38
Stearic Acid, double-pressed. .
Tallow Oil. acidless
Tar OS, distilled
Turpentine, spirits of
OILS, WAXES. ETC.
lb. 55
.22
gal.
Ib.
gal.
bbl.
gal.
lb.
Ib.
gal.
.lb
nal
Kal.
gal
.09 V,
.13
.07 V.
.05
.67
.30
I. IS
METALS
.lb
24
Aluminium. No. 1, ingots
Antimony, ordinary 1°° '"
Bismuth
Copper, electrolytic ^
Late lb
Lead, NY
Nickel, electrolytic ^
Platinum, refined, soft
Quicksilver, flask
Silver
Tin
Tungsten Wolframite.
Zinc, N. Y
FERTILKEB MATEHIALS
Ammonium Sulfate export. . . 100 Ita.
Blood, dried. l.ab.M.y... "^
Bone, 3 and 50, ground, raw . . . ton
Calcium Cyanamide, unit of Am-
.75 lbs ea.
. per unit
. 100 lbs.
45.00
Mar. 15
.17V,
2.00
.23
.34
4.40
.13V,
.55
4.90
3.05
.70
.08
3.55
.09
.20
.15V,
. 14V,
1.25
2.75
2.65
.05
.25
.05
monia
Fish Scrap, domestic, dried, f. o. b
works .'
Phosphate Rock, f. o. b. mine.
Florida Pebble, 68%
Tennessee, 78-80%
, Muriate, 80%
UDlt
.ton
.ton
.unit
unit
Potassiun
Pyrites, furnace size,
Tankage, high-grade, f. o. D. ^
Chicago
4.50
3.50& 10
11.00
15.00
2.75&.10
.13
.07 V,
.04V«
1.73
.11V,
5.25
5.75
1.75
1.65
.12»A
.13
.12
.12V.
.04
04Vi
.45
.45
65.00
65.00
47.00
45.00
.56V,
.57
3.25
5.10
3.25
3.50
45.00
4.50
3.50& .10
11.00
IS 00
37G
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 4
COAL-TAB CHEMICALS
Mar. 1
Crude!
Anthracene, 80-85% lb. .75
Benzene. Pure gal. .30
Cresol, U S. P lb. .18
Cresylic Acid, 97-99% gal. .90
Naphthalene, Bate lb. .08
Phenol, drums lb. .10
Toluene, Pure gal. .30
Xylene, 2 deg dist. range gal. .60
Intermediate!
Acids:
Anthranilic lb. 2.20
B lb. 2.25
Benzoic lb. .60
Broenner's lb. 1.75
Cleve's lb. 1 .50
Gamma lb. 3.75
H lb. 1.25
Metanllic lb. 1 . 60
Monosulfonic F lb. 2.75
Napthionic, crude lb. .75
Nevile & Winthers lb. 1.60
Phthalic lb. .40
Picric lb. .30
Sulfanilic lb. .33
Tobias' lb. 2.25
Aminoazobenzene lb. 1 . 25
Aniline Oil lb. .22
For Red lb. .42
Aniline Salt lb. .28
Anthraquinone lb. 2 .00
Benzaldehyde, tech lb. .45
U. S. P lb. 1.00
Benzidine (Base) lb. .90
Benzidine Sulfate lb. .75
Diaminopbenol lb. 5.50
Dianisidine lb. 6.00
p-Dichlorobenzene lb. . 15
Diethylamide lb. 1 . 40
Dimethylaniline lb. .50
Dinitrobenzene lb. .25
Dinitrotolvene lb. .28
Diphenylaiaine lb. .60
G Salt lb . .80
Hydroquinol lb. 1 .70
Metol (Rhodol) lb. 6.75
Monochlorobenzene lb. .14
Monoethylaniline lb. 2. 15
a-Naphthylamine lb. .38
o-Naphthylamlne (Sublimed) lb. 2.25
ft-Naph thol, dist lb. .34
m-Nitroaniline lb. .90
£-Nitroaniline lb. .90
Nitrobenzene, crude lb. .13
Rectified (Oil Mirbane) lb. .14V,
0-Nitrophenol lb. .80
f -Nitrosodimethylaniline lb. 2.90
o-Nitrotoluene lb. .25
l-Nitrotoliiene lb. .90
m-Phenyleaediamine lb. 1 . 15
t Phenylei ediamine lb. 1.75
Phthalic Anhydride lb. .55
Primuline (Base) lb. 3.00
RSalt lb. .80
Resorcinol. tech lb. 2.00
U.S. P lb. 2.25
Schaeffer Salt lb. .75
Sodium Naphthionate lb. 1.10
Thiocarbanilide lb. .60
Tolidine (Base) lb. 1.40
Toluidine, mixed lb. .44
o-Toluidine lb. .27
m-Toluylenediamine lb. 1.15
»-ToIuidlne lb. 1 .25
Xylidine, crude lb. .45
COAL-TAB COLOBS
Add Colon
Black lb. 1.00
Blue lb. 1 .50
.75
.30
1.80
2.25
.60
1.75
1.50
3.75
1.25
1.60
2.75
.75
1.60
2.25
1.25
5.50
6.00
1.40
.50
1.70
6.75
.80
2.90
1.15
1.75
.55
3.00
.75
2.00
2.25
.70
1.10
1.15
1.25
1.00
1.50
Acid Colon (Concluded)
Fuchsin lb.
Orange HI lb.
Red lb.
Violet 10B lb.
Alkali Blue, domestic lb.
Imported lb.
Azo Carmine lb.
Azo Yellow lb.
Erythrosio lb.
Indigotin. cone lb.
Paste lb.
Naphthol Green lb.
Ponceau lb.
Scarlet 2R lb.
Direct Colon
Black lb.
Blue 2B lb.
Brown R lb.
Fast Red lb.
Yellow lb.
Violet, cone lb.
Chrysophenine, domestic lb.
Congo Red, 4B Type lb.
Primuline, domestic lb.
Oil Colors
Black lb.
Blue lb.
Orange lb.
Red in lb
Scarlet lb.
Yellow lb.
Nigrosine Oil. soluble lb.
Sulfur Colon
Black lb.
Blue, domestic lb.
Brown lb.
Green lb.
Yellow lb.
Chrome Colon
Alizarin Blue, bright lb.
Alizarin Red, 20% Paste lb.
Alizarin Yellow G lb.
Chrome Black, domestic lb.
Imported lb.
Chrome Blue lb.
Chrome Green, domestic lb.
Chrome Red lb.
Gallocyanin lb.
Baiic Colon
Auramine, O, domestic lb.
Auramine, OO lb.
Bismarck Brown R lb.
Bismarck Brown G lb.
Chrysoidlne R lb.
Chrysoidine Y .' lb.
Green Crystals, Brilliant lb.
Indigo, 20 p. c. paste lb.
Fuchsin Crystals, domestic lb.
Imported lb.
Magenta Acid, domestic lb.
Malachite Green, crystals lb.
Methylene Blue, tech lb
Methyl Violet 3 B lb.
Nigrosine, spts. sol lb.
Water sol., blue lb.
Jet lb.
Phosphine G., domestic lb.
Rhodarcine B, extra cone lb.
Victoria Blue, base, domestic lb.
Victoria Green lb.
Victoria Red lb.
Victoria Yellow lb.
Mar. 1
Mar. 15
2.50
2.50
.60
.60
1.30
1.30
6.50
6.50
6.00
6.00
8.00
8.00
4.00
4.00
2.00
2.00
7.50
7.50
2.50
2.50
1.50
1.50
1.95
1.95
1.00
1.00
.90
.90
.70
.70
1.65
1.65
2.35
2.35
2.00
2.00
1.10
1.10
2.00
2.00
.90
.90
3.00
3.00
1.40
1.40
1.65
1.65
1.00
1 .00
1.25
1.25
5.00
5.00
1 .10
1.10
1 .00
1.00
1 .25
1.25
2.20
2.20
1.00
1.00
1.50
1.50
2.00
2.00
2 80
2.80
2.50
2.50
4.15
4.15
4.50
4.50
12.00
12.00
4.25
4.25
2.75
2.75
2.75
2.75
2.75
2.75
.70
.70
.60
.60
.90
.90
7.00
7.00
16.00
16.00
6.00
6.00
2.50
2.50
7.00
7.00
7.00
7.00
The Journal o£
Published Monthly by The American Chemical Society
Advisory Board: H. E. Barnard
Chas. L. Reese
Editorial Offices:
One Madison Avenue, Room 343
New York City
Telephone: Gratnercy 0613-0614
Editor: CHAS. H. HERTY
Assistant Editor: Lois W. Woodford
J. W. Beckman A. D. Little A. V. H. Mory
Geo. D. Rosengarten T. B. Wagner
Advertising Department:
170 Metropolitan Tower
New York City
Telephone: Gramercy 3880
Volume 13
MAY I, 1921
No. 5
CONTENTS
Rochester Meeting, American Chemical Society:
An Anomaly 378
Council Meeting 378
Story of the Week 380
Address of Welcome. E.G.Miner 380
Some Problems of National Defense. Senator James
W. Wadsworth, Jr 382
The American Chemical Industry and Its Need for En-
couragement and Protection. Hon. Nicholas Long-
worth 384
The Place of Chemistry in Business. A. D. Little 386
Chemistry in the United States. Charles F. Chandler . 391
Division and Section Meetings 398
Committee Reports 401
Convention Side Lights 404
Editorial Notes 405
Original Papers:
The Role of Acidity in the Dehydration of Sewage
Sludge. John Arthur Wilson and Henry Mills Heisig. 406
Applications of Maleic and Fumaric Acids and Their
Salts in the Textile Industry. J. H. Carpenter 410
A New Lead Number Determination in Vanilla Ex-
tracts. H. J. Wichmann 414
The Mineral Constituents of Potatoes and Potato
Flour: Effect of Process of Manufacture on Composi-
tion of the Ash of Potato Flour. C. E. Mangels 418
Notes on the Volumetric Determination of Aluminium
in Its Salts. Alfred Tingle 420
The Detection of Phenols in Water R.D.Scott 422
The Setting and Melting Points of Gelatins. S. E.
Sheppard and S. Sweet 423
The Symposium on Drying:
The Rate of Drying of Solid Materials. W. K. Lewis . . 427
The Theory of Atmospheric Evaporation — With Spe-
cial Reference to Compartment Dryers. W. H. Car-
rier •. 432
The Compartment Dryer. W. H. Carrier and A. E.
Stacey, Jr 438
The Spray Process of Drying. R. S. Fleming 447
Direct Heat Rotary Drying Apparatus. Robert G.
Merz 449
Tunnel Dryers. Grahame B. Ridley . 453
Addresses and Contributed Articles:
The Immediate Needs of Chemistry in America.
William J. Hale 460
The School of Chemical Engineering Practice of the
Massachusetts Institute of Technology. R. T.
Haslam 465
Our Anomalous Patent Office. K. P. McElroy 469
The Chemical Industry from a Tariff Viewpoint. C.
R. DeLong 470
Unit Weights for the Purchase of Reagents — II. W.
D. Collins 473
Social Industrial Relations:
Social Industrial Relations. H.W.Jordan 473
Spare Time— A Criticism. F. O. Sprague 474
A Selected Bibliography of Books, in the English
Language, Dealing with Ceramic Chemistry and
Ceramic Industries:
Chemistry and the Ceramic Industries. E. W.
Washburn 476
Clays and Clay Products. C. W. Parmelee 476
Glass and Glass Manufacture. E. W. Washburn 477
Vitreous Enamels. C. W. Parmelee 477
Refractories. E.W.Washburn 477
Cements, Limes and Plasters. R. K. Hursh 477
Notes and Correspondence:
The Industrial Fellowships of the Mellon Institute;
Food Research Institute; The Bloede and the Hoff-
mann Scholarships of the Chemists' Club; Cen-
trifugal Method for Determining Potash; Annual
Tables of Constants — Correction 478
Scientific Societies:
Sixty-first Meeting American Chemical Society,
Rochester, N. Y., April 26 to 29, 1921 ; Atlantic City
Meeting of the American Electrochemical Society;
Paper Trade and Technical Association Conven-
tions; Calendar of Meetings; American Drug Manu-
facturers Hold Tenth Annual Meeting 480
Miscellaneous :
Chandler Medal Award 422
The Reception of Madame Curie 468
Washington Letter 486
Industrial Notes 487
Personal Notes 488
Obituaries 489
Government Publications 490
Book Reviews 494
New Publications 498
Market Report 499
Subscription to non-membei
Subscriptions and cla
i. $7 50; single copy. 75 cents, to members. 60 cents. Foreign postage, 75 cents, Canada, Cuba and Mexico excepted,
ms for lost copies should be referred to Charles L. Parsons, Secretary, 1709 G Street, N. W , Washington, D. C.
378
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
ROCHESTER MEETING
AMERICAN CHEMICAL SOCIETY
An Anomaly
These are dull times, no doubt about that. Perhaps
there was never a time when our chemical industries
were at so low a stage of activity. It is the moment of
dead low tide, and many a commercial bark is strug-
gling to keep in the narrow channels of the few markets
which remain. Retrenchment is the word on all sides.
In many cases this policy has affected first of all
the chemical staffs. Especially is this true in organ-
izations where the seed of industrial research evidently
fell on very shallow ground. Consequently many
chemists are to-day seeking employment.
In contrast with this gloomy picture was the
air of buoyancy and optimism which characterized
the unusually large gathering of chemists at Rochester
for the Spring Meeting of the American Chemical
Society. The mood fascinated us and as the week
progressed we tried to analyze its meaning.
Of course a contributing factor was the splendid
work of the members of the Rochester Section who
displayed remarkable ability in executive management
and who possessed to an unusual extent that true
spirit of hospitality which is based upon the conviction
that there is more pleasure in giving than in receiving.
The full explanation of that buoyant spirit at
Rochester, as we see it, had deeper and more solid
foundation than the ephemeral joys of a few days
of good entertainment. There was genuine satisfac-
tion in the thought that in the formulation of the
general policies of the American Chemical Society,
with true American independence of thought and
firm initiative, there had been developed an organi-
zation, contrary to the traditions of other lands, in
which men of the universities and of the industries
could, to the benefit of both, rub elbows, and who
therefore would all the more readily stand shoulder
to shoulder in time of emergency; an organization
whose voice in national matters would stand as the
sentiment of American chemists. When the program
of the meeting brought out in close sequence views
of pure scientists, of industrialists, of business men, and
of statesmen, who could escape the up-lifting feeling
that the organization was fully playing its part?
It was a big week for American chemistry in its re-
lation to the national welfare, a week of recognition
all too sparingly given in the years past. Senator
Wadsworth and Congressman Longworth spoke straight
and to the point, no pussyfooting, no buncombe.
President Harding's sympathetic attitude, conveyed
through Mr. Longworth, assured support from the
highest officer in the land, and while the meeting was
in progress the author of the peace resolution, Senator
Knox, demonstrated his active support by personally
appearing before the Senate Finance Committee and
urging ad interim legislation to safeguard, for the
nation's sake, our coal-tar chemical industry.
What room was there for gloom or pessimism when
such big guns were vigorously in action? No, not
pessimism, but an optimistic spirit spread over that
meeting as the chemist saw himself revealed and ac-
knowledged as an integral part of the country's defense.
The responsibility has been placed, it is joyfully
accepted and it will be worthily met.
Council Meeting
The cordiality with which the Rochester Section,
represented by the chairman of the Entertainment
Committee and his assistants, received the members of.
the Council at the Rochester Club on Monday after-
noon, April 25, 1921, epitomized the character of the
reception accorded the members of the Society
throughout the week of the meeting. The hall of the
Club afforded pleasant surroundings for the business
meeting, and in the dining rooms respite from serious
deliberation was granted, while the members partook
of a delightful dinner, the Rochester Section acting
as hosts.
Attendance at the Council Meeting reached a total
of 113. Business was transacted with dispatch, yet
important matters were given careful consideration.
Questions of internal policy regarding Society matters
were discussed and acted upon, and the Society's opin-
ion upon matters of national concern was recorded in
formal resolutions. Likewise the governing body of
the Society heard the reports of its committees, all
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
379
of which showed that conscientious and effective
labor had been performed by these arduous workers
in the Society's behalf.
Birmingham, Alabama, was unanimously selected as
the place of meeting for the spring of 1922, the exact
date to be determined upon later by the Advisory Com-
mittee. Dr. George D. Rosengarten was reelected
a member of the Committee on National Policy (Advi-
sory Committee). With evident pleasure the Council
nominated for honorary membership in the Society
two charter members, Dr. Charles F. Chandler and
Dr. William H. Nichols. This action was unanimously
confirmed at the General Meeting of the Society the
following morning.
The following resolution was unanimously adopted:
That this Council expresses to the Directors of the Society the
hope that the Eschenbach Printing Company will be released
from any forfeits that may arise under the terms of its current
contract with the Society in connection with the impending
strike, due to the insistence upon the 44-hour week, and
That the members of this Council also express their full willing-
ness, in the event such a strike is not amicably settled, to wait
indefinitely for the publication of the journals of the Society.
At the Directors' meeting on Wednesday action in
accord with this expression of the Council was taken.
It was reported that approximately fifty per cent
of the budget for the publication of the Critical Tables
of Chemical and Physical Constants had been sub-
scribed, and continued support of this important un-
dertaking was urged.
The Council voted unanimously:
That the secretary of each Division and Section of the Society
is hereby authorized to demand submittal in advance of any
paper offered for the program of a general meeting, for
decision as to its suitability for presentation at a general meeting.
The chairman and secretary of each Division and Section, act-
ing jointly, are hereby authorized to decline acceptance of any
paper, if in their judgment the circumstances warrant such
action.
The Committee on Time for Divisional Meetings at
the General Meeting reported in favor of not less than
four half days. The Committee's recommendations
were in effect at this meeting, with excellent results.
A resolution urging upon the Congress the necessity
of ad interim protection for the American coal-tar
chemical industry was unanimously adopted, as
follows:
Whereas it appears probable that the Congress will speedily
enact legislation terminating the state of war, and
Whereas the power of the War Trade Board to control
importations of coal-tar chemicals under the Trading with
the Enemy Act automatically expires with the proclamation
of peace, and
Whereas we feel that the need of continued control of such
importations from whatever source is urgent,
Therefore be it resolved, First, that the Council of the American
Chemical Society, representative of a nation-wide membership
of fifteen thousand chemists, urge upon both the Senate and the
House of Representatives the passage of ad interim legislation
which will fully safeguard this industry until the Congress has
adopted permanent protective legislation.
Second, that this resolution be telegraphed to the Chairman
of the Finance Committee of the Senate and to the Chairman of
the Ways and Means Committee of the House of Representa-
tives.
Upon hearing the report of the Committee to Co-
operate with the Chemical Warfare Service (page 403),
the Council adopted the following resolution by a
unanimous vote:
In the light of the report of our committee to cooperate with
the Chemical Warfare Service we beg to tender to the Chief of
that Service, Brigadier General Amos A. Fries, and his associates,
military and civilian, sincerest congratulations upon the faithful
care given to government property and upon the energy and re-
sourcefulness shown in the vigorous prosecution of the work of
this unit of the War Department.
Feeling as we do from all present indications that chemical
warfare is to constitute in one form or another a growing feature
of modern warfare, and convinced that our Army and Navy
should have at their disposal, in case of emergency, the very best
means available in this field, we hereby pledge to our Govern-
ment the united support and cooperation of the American
Chemical Society, in whatever form it may be desired.
The following resolution was presented and adopted:
Whereas special knowledge is required in examining chemical
patents and in making searches relating thereto,
Therefore be it resolved that the Secretary of the American
Chemical Society be authorized to call the attention of the
Commissioner of Patents to the facts and recommend to him
that a chemically trained examiner be appointed upon his staff
of chief examiners.
The Secretary brought informally before the Council
the subject of the administration of that section of
the National Prohibition Act bearing upon the use of
alcohol in the industries. Dr. R. P. Bacon had ex-
pected to point out the handicaps under which the in-
dustries were suffering, and to urge Council action, but
was unavoidably absent. By vote of the Council, Pres-
ident Smith was requested to appoint a committee
to investigate the situation and report to the Advi-
sory Committee, which body was given power to act
in the matter. The President has named the following
committee: Dr. Martin Ittner, chairman, R. F. Bacon,
Chas. Baskerville, F. R. Eldred, E. Mallinckrodt, Jr.,
Geo. D. Rosengarten, and B. R. Tunison.
Following the presentation of reports by the Com-
mittee on Patents and Related Legislation, the Council
reaffirmed its former position in support of legislation
for the relief of the present conditions in the Patent
Office, and in addition passed the following resolution:
Moved: That the Council of the American Chemical Society
go on record as being opposed to the substance of Section IX,
380
THE JOURNAL OF INDUSTRIAL AND EXCIXEERIXG CHEMISTRY Vol. 13, No. 5
H. R. 11984, known as the Xolan Bill, 66th Congress, Third
Session.
This section of the Xolan Bill was the rider which des-
ignated the Federal Trade Commission as an agency
for the receiving and administration of patents issued
to government employees. [The Patent Office Relief
Bill has been re-introduced in the House of Represen-
tatives. 67th Congress, as the Lampert Bill, H. R. 210,
and does not contain the Federal Trade Commission
Section.]
The full report of the Council proceedings will he
printed in the May issue of the Journal of the America v.
Chemical Society. There are printed on pages 401 to 404
some of the committee reports of particular interest
to the readers of This Journal. Others will appear
in the June issue.
Story of the Week
OPENING SESSION
When J. Ernest Woodland, chairman of the Execu-
tive Committee of the local Convention Committee,
called the first session of the General Meeting of the
Society to order in the Chamber of Commerce Hall
at 10:15 a.m., Tuesday, April 26, 1921, nearly one
thousand members had assembled. After briefly wel-
coming the Society, Mr. Woodland introduced Frank
W. Lovejoy, honorary chairman of the local Executive
Committee, who presided during the welcoming ad-
dresses.
Mr. Lovejoy spoke of the growth of the city of
Rochester since the last meeting of the American
Chemical Society in 1913, and referred particularly
to the expansion of the chemical industries of the city
and the Rochester Section since that time. In behalf
of the local section he expressed the desire of its mem-
bers to do everything in their power to make the
visitors feel at home. He then introduced Mr.
Bernard J. Haggarty, secretary to the Mayor, who
extended the freedom of the city to the members of
the Society on behalf of Mayor Hiram Edgerton,
who was unable to be present. Mr. Haggarty paid
tribute to the chemical industries of Rochester for the
important part they are playing in the development
of the city. He was followed by Mr. E. G. Miner,
a past president of the Rochester Chamber of Com-
merce, a director of the United States Chamber of
Commerce, and president of the Pfaudler Company of
Rochester. Mr. Miner delivered a splendid address,
which is printed in full below:
Address of Welcome
By E. G. Miner
The City of Rochester, through its Chamber of Commerce,
bids me tell you how glad we are to have you as our guests,
and to give you a most cordial greeting. Through daily contact
with those individuals of your organization who live among us,
we have come to know and appreciate the high purposes which
animate your profession, and this knowledge not only makes
' us the more mindful of the honor you have conferred upon
us in selecting this city for your gathering, but keenly desirous,
as well, of extending you such courtesies as he within our power.
We hope, also, that you may have an opportunity during
your stay to see what has been accomplished through the co-
operation of our captains of industry and the local leaders in
your profession, in bringing within the reach of the everyday
man those things which not so long ago were cloistered in the
laboratory or the classroom.
The relation of chemistry to modern industry is one of the
most fascinating features of the last half century of our develop-
ment of modern knowledge, and to my mind, the final per-
ception on the part of the average manufacturer of the possi-
bility of the application of science to the material needs of the
world makes a long step forward in the education of mankind.
Commerce did not see it clearly at first. It took years of
hopeless effort, of prophets crying in the wilderness of industrial
ignorance, and no one heeding them — years in which those
prophets had to combat not alone the ignorance of those whom
Mb. E. G. Miner
they desired to help, but the reproaches of their associates as well,
because they turned from the highroad of purely scientific
research to the bypaths of sordid commercialism. It was a
thankless and disheartening task, but their day of triumph came
because they persevered; and great honor is due their names,
for they brought the vast body of accumulated knowledge in
their science out of the storehouse where it had been guarded
and devoted it to the increasingly pressing needs of mankind
Times have changed since the days of our fathers, so far as
we who are manufacturers are concerned. In their day condi-
tions were static. In the countinghouse and factory, men
were guided by the traditions of their business. Now, conditions
are dynamic, and in the industrial struggle in which the world
of to-day is engaged, only those succeed who are efficient, and
that efficiency is based upon scientific knowledge as it is applied
to industry.
NEED OF RESEARCH DURING PRESENT INDUSTRIAL DEPRESSION
And here, for a moment, let me sound a note of warning, in
a brief reference to the importance of continuing original re-
search work and the development of new products during the
trying times in industry through which we are now passing.
By reason of the slump in business, a number of chemical
firms are hard hit at the present moment, and, in an effort to
economize, have largely reduced their research staffs, or in some
cases have stopped laboratory work altogether. If this persists,
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
381
it is bound to have a most unfortunate influence upon the future
of American industry.
During the war many corporations made great research plans,
which at present are being abandoned. It would help materially
if we could bring ourselves to consider such expenditures, not as
expense, but as investments of capital, justified during periods
of depression, and as an insurance policy on the future.
To those who desire to share in the results of commerce,
:hemistry shows the open door; to the adequately trained
y'oung man is given the opportunity to advance knowledge,
to be of service to his fellowman, and to reap material reward.
In the vast possibilities which lie before him, those great dis-
:overies and developments yet to come, those undiscovered
:ountries in science, whose boundaries we have yet but touched
apon, there is the excitement of adventure, the chance of buried
treasure, as great as ever lured a Drake or Hawkins.
MEED OP ENCOURAGEMENT OF PURELY SCIENTIFIC RESEARCH
And yet, this is not the ideal of scientific achievement, and
1 should pay a poor tribute to your profession, if it were made to
ippear that our appreciation of your calling is based only
lpon the material benefits which accrue to us from your assistance,
in return for which we are to pay you in kind.
We know there is a higher plane, a realm which we of com-
rierce are not fitted to enter, the domain in which men think
n terms of pure science. There is the danger that, by being
:oo subservient to our needs and wishes, the scientist may be-
;ome too utilitarian, and degenerate into what corresponds to
:he "hack writer" in literature — a mere artisan. Such men can-
lot endure in the race which carries on the torch of progress,
ind for our own good, to speak selfishly, it is for us to see that
tfe aid, by all the means in our power, in assisting in the de-
velopment of the men with productive minds — men who can
see the problems before them in their largest bearings.
Already we have learned that, in general chemistry, such
amous men as Richards of Harvard, Noyes of Illinois, Remsen
)f Hopkins, and your own honored president are men who were
irst schooled in pure chemistry. In the science of nutrition,
vhich is simply chemistry applied to the needs of the human
)ody, men like Mendel, Sherman, Murlin, and McCollum
;mphasize the debt which the world owes to men of pure
icience; and if my words had any effect upon my fellow
vorkers, I would stress the importance of pure research for its
>wn sake.
America has not yet sufficiently honored these men who are
eading where we all must follow, and if we are to improve the
>pportunity in science which has been thrust upon this country
)y recent events, we must heed their teaching and admonition,
ts well as accord them the praise which is their due.
For many centuries, two opposing schools of thought have
lebated the question whether mankind should be elevated by
dlowing the individual to rise to a higher spiritual and moral
)lane through his own travail, or by attempting to lift to a
ligher plane the conditions of his material surroundings. From
the standpoint of one of the most recent amendments to the
Constitution of the United States, it would appear that the
jroponents of the latter proposition have possession of the field,
it least for the time being. Adopting this premise, it is logical
:o argue that any man who discovers a new thing, makes a
>etter thing, or anything of value in a better way, does an act
)f good that can never pass away, and whether by this applica-
:ion of the new knowledge he ministers to the needs of the body
>r to the hunger of the soul, he still has benefited mankind.
This is the process of evolution which modern society de-
iires, rather than the Bolshevistic attempt to raise a certain
portion of the race to a pretended higher level by establishing
hem upon the ruins of a finer civilization, and in the scientist
)f to-day lies the hope of the future, for pure science is simply
Jie search for truth, than which there is no nobler calling.
President Edgar Fahs Smith of the American
Chemical Society was then introduced, and responded
in a very happy vein to the welcoming addresses which
had preceded, and thanked the hosts of the Society
in behalf of the assembled membership for the splendid
arrangements that had been made for the comfort
and entertainment of the visitors. In speaking of
Rochester's chemical history he recalled that Doctor
Richardson, one of the pioneers in the use of ether for
anesthesia, as far back as 1840, had been a resident of
Rochester before moving to Boston, where he con-
tinued his experimental work along this line.
A short business session began with the election, by a
unanimous rising vote, of Dr. Charles F. Chandler and
Dr. William H. Nichols, both of New York City, to
honorary membership in the Society. These dis-
tinguished chemists are charter members and past
presidents of the American Chemical Society.
Professor E. C. Bingham, chairman of the Com-
mittee on the Metric System, was introduced, and
urged the chemists of the country to take the initiative
in making the metric system the standard of weights
and measures in the United States by putting it into
actual use in their commercial transactions as well
as in the laboratory and plant. He announced that
the directors of chemical departments in a number of
universities and colleges had agreed to place their
orders for chemicals in metric units, and that all would
be appealed to by letter to follow this procedure.
Heads of laboratories in industrial plants will likewise
be asked to encourage the use of metric weights and
measures in ordering and furnishing supplies and in
the preparation of labels and price lists. By resolu-
tion of the Council, authors are asked to use only the
metric system in preparing papers for publication,
and the editors of the Society's journals have been
authorized to convert all weights and measures units
in articles to be published into the metric system, when
it is in their opinion desirable.
Dr. Raymond F. Bacon spoke on the difficulties
confronting the chemical industries requiring alcohol
in their manufacturing processes, owing to the enforce-
ment of prohibition regulations in various communities
where apparently no distinction is made between the
illegal use of alcohol for beverage purposes and the
perfectly legal use of alcohol for industrial purposes.
He advocated a separation of the provisions for en-
forcement of the National Prohibition Act into two
sections, the first applying to the use of alcohol for
beverage purposes, to be enforced by the Department
of Justice, and the second, applying to the use of
alcohol for industrial purposes, to be administered
and enforced by a Bureau of Industrial Alcohol, to be
created. This bureau should be headed by a techni-
cally trained man who was familiar with the uses of
alcohol in the industries, assisted by a staff of field
workers who could investigate reports of the illegal use
of alcohol.
Attention was called by Dr. H. E. Howe to the
forthcoming issue of the fourth volume of the "Annual
Tables of Constants and Numerical Data, Chemical.
Physical, and Technological" which will be ready
382
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
about the first of July. Only a limited edition is to
be published.
Captain George B. Hyde of the Near East Relief
was given the privilege of the floor, and made a stir-
ring plea in behalf of the starving Christian popula-
tion of the countries of Asia Minor who are threatened
with extermination by the ruthless warfare of the
Turks and their own inability to provide for them-
selves because of lack of machinery, tools, and food.
President Smith then introduced United States
Senator James W. Wadsworth, Jr., of New York, who
delivered the following address:
Some Problems of National Defense
By Senator James W. Wadsworth, Jr.
It is very good of the gentlemen having in charge this con-
vention to ask me to come here to say a few words. I am afraid
they did not realize the chance they were taking when they
issued the invitation, because I know so little about chemistry-
it would not be worth the telling. Some of you have,
perhaps, encountered those illustrations of the skilled artisan's
work, such as the engraving of the Lord's Prayer upon a dime.
If a skilled artisan took all I know about chemistry, he could
use a pickax and get it on a shoe button. Of course, I have
a fleeting idea that the substance in this container is HjO,
about which we are learning more and more every day ; I imagine,
however, that my ignorance of chemistry is shared by a great
many people; some are in the Congress. Most men in politics
know little if anything about chemistry, although I always
except my friend Longworth, who will tell you all about it
because he has always been interested in the subject, especially
in its industrial aspects.
Dr. Parsons did me a very good turn about six weeks ago
by leaving on my desk a book entitled "Creative Chemistry."
I rather edged away from it for some time, but finally took it
up, and did not put it down until I finished it. I found it the
most fascinating and valuable volume I have encountered. I
had no idea until I read that book of what chemistry means in
the industries and in the life of the human race. We laymen
know now or may know if we take the trouble to look it up
that we could not build a great steel bridge had not chemists
told the ironmaster how to fashion steel; that this building
could never have been erected had it not been for the achieve-
ments of chemists; that railroad trains could not go at great
speed until chemists had made rails to stand the impact; and
that, indeed, the human race, or a great portion of it, would
probably starve within a generation had not chemists taught
those who till the soil how it may be renewed in its fertility and
produce and continue to provide food for human beings.
I have always envied an architect, for an architect in the
course of his profession builds something that lives after him.
When he has finished a piece of work, he can gaze upon it and
say, "I did that." I have always envied engineers because,
in like manner, when they have finished their job they can say,
"We did that and it will live after us." And now I have an
equal amount of envy for the chemist, for I believe, after all
is said and done, the architect and the engineer could not get
very far unless the chemist had pointed the way. It is the fact
that you create things that makes your profession so fascinating.
Long since you relegated to the rear analyzing things,
and now you are putting things together, and in many respects
improving upon nature, and if this great art or science, which-
ever you call it, does not continue to progress and help solve
the problems which flood this world, it will not be long before
we are much less happy than we are to-day.
As your illustrious president did, I am going to ramble (at
least I believe that is what he called it) for a few moments, for
on your program I am put down for a few remarks on the national
defense. I cannot instruct you on this, but perhaps can make
a few observations which will not be out of place on such an
occasion.
Senator James W. Wadsworth, Jr.
THE CHEMICAL WARFARE SERVICE AND ITS WORK
Three or four weeks ago, I paid a visit to the Edgewood
Arsenal, with which many of you are familiar. I could spend
only a day there, but I can assure you it was a busy day, and
gave me an idea of what that institution is doing for the
people of the LTnited States, not only in this generation but
in the generations to come. The plant is of staggering size.
I had no idea of its size until I went there. To make any
examination with thoroughness would consume a week, but
I find from experience that the only way in which to get even
a mild comprehension is to go to the place where the work is
carried on; and I want to say before this gathering of chem-
ists that the people of this country, regardless of their views
on international issues, are mighty fortunate in having in a
standby condition that great plant, and in having General
Fries in general charge of the research work of the Chemical
Warfare Service.
We have had some discussions at Washington, some of them
a year ago, as to the status of the Chemical Warfare Service.
These took place before the Committee of Military Affairs
in the Senate, of which I happen to be chairman. There were
a considerable number of people who thought that the Chemical
Warfare Service was of comparatively little importance and
that it might be combined with some other branch of the service.
The War Department itself, through its official head and the chief
of staff of the Army, contended against the creation of a separate
Chemical Warfare Service and insisted that it should be merged
— and perhaps submerged— in the Engineer Corps. The
members of the Committee had an instinctive knowledge of
what chemical warfare meant for the future and only a
groping idea as to what the real facts were, but when we
read that 30 per cent of the casualties in the A. E. F. in
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
3S3
one year of actual fighting came from gas, we made up our
minds that it would be well to create a separate Chemical
Warfare Service, and so the legislation was finally passed.
It is now on the statute books, and the men in charge are
doing their best to perfect their processes, and the perfecting
of them at Edgewood Arsenal is exceedingly interesting. I do
not envy the young men who subject themselves to the ex-
periments being made there, but I take off my hat to them
for the gallantry they are showing. They are working on
the offensive as well as the defensive tactics. 120,000 of the
latest gas masks have been made there, with 120,000 extra
canisters, and they tell us these are the best in the world.
But they are not satisfied; indeed, there are some gases already
contrived which will go through them, such as a toxic smoke
which I saw go through one of them at Edgewood Arsenal.
They are struggling, and I think they will succeed in finding a
safe mask, so that if we are ever summoned to war again, and
the enemy insists on using gas, our men will be reasonably safe.
What is there to preparedness except making our own children
as safe as possible? Uncle Sam has not all the money he wants or
would like to have for this and other work of equal importance.
Perhaps many people here were disappointed in the size of the
appropriations for the next fiscal year for the support of the
Service. I think it is safe to say that the Congress is not going
to permit that Service to perish, and will see to it that it will
go ahead as a great research laboratory experimenting and per-
fecting so that we shall not be caught as we were the last time.
THE SIZE OF THE CHEMICAL warfare SERVICE
You have heard a good deal of discussion lately about the
size of the Regular Army of the United States; there are con-
flicting views about it. For myself, I do not believe in a great
standing professional army. I believe in training the citizen
by the thousands and thousands, so that when war comes
he can defend the country and have a decent chance for his life
while he is doing it. But there is such a thing as making the
Regular Army too small. It should be a nucleus of men around
which the trained citizens may gather in time of war. It is
important as a teacher in times of peace to instruct the
citizens in the method of defense. The size of the Army
may be of some interest to you here in this Society, for the
Army basic law provides allotments of officers and men to the
different branches of the service. With an army of maximum
authorized strength the number of officers in the Chemical
Warfare Service is 100 out of 17.S00 officers in the entire Army,
and the number of enlisted men is 1200 out of 280,000. If
we reduce the Regular Army as severely and as savagely as
some people propose and as has been proposed by men who
exercise power and influence, the figure set for the whole Army
will bring the Chemical Warfare Service down to 400 men.
For one, I believe it would be a pity to reduce to 400
that body of men on whom the country must depend to
teach the citizen how to defend himself. Perhaps as you see
these discussions proceeding in the Congress and elsewhere you
will remember that there is such a thing as false economy. We
cannot spend untold millions because the tax payer cannot
stand it, but in shaping our policy we ought to remember some
of our experience during the last three or four years and make
up our minds that it will not recur.
high explosives and nitrogen fixation
Just a word about another matter in which chemists are
interested, and in which undoubtedly every citizen, man or
woman, who has an understanding of what has occurred in the
recent past and is able to measure the possibility of events to
come is interested; it is the subject of high explosives. This
book, "Creative Chemistry," tells me that high explosives are
based upon nitrates; that you must have nitrates before an army
can fight. No matter what the size of the army it must have
nitrates. Nitrates must be had before a shell can be launched
from the guns. We were dependent upon Chile almost en-
tirely before going into the war for our supply of nitrates. It is
rather a slender thread to be depending upon a country 6000
miles away; the shipping might be interfered with, and if it
were checked or shut off during war, this country would be
disarmed and helpless if it had no resources of its own. I
think we learned the truth of this during the war, and again
the chemist comes to the rescue and tells the Government,
the soldier and the sailor, and all the people how it is possible
to defend themselves with nitrates whether the commerce
with Chile is cut off or not. And so you have evolved this pro-
cess of extracting nitrogen from the air. Various proposals have
been made, all of them in the interest of the national defense
and in connection with the function of government in this
matter of the atmospheric fixation of nitrogen. I may be old-
fashioned about some of these things, but I have never read
of a great people defending itself unless it was self-reliant.
I have never read about a people defending itself if it had become
in times of peace a dependent people. If there is one thing to
be said for national defense, it is this — that the best measure of
national defense is found in that kind of defense which the
people prepare for themselves in times of peace in their industries,
in their agriculture, and in the training which men and women
receive in school, college, and technical institutions. In other
words, I do not believe the government alone can prepare a
country for defense in times of peace. I do not believe there is
any government upon the earth strong enough, wise enough,
skilful enough, and, politically speaking, pure enough to carry
on great industrial enterprises which will provide weapons
in time of war. And so it may not be out of place for
me to say that on one or two occasions I have opposed certain
proposals which have been made in the name of national
defense and preparedness which would have launched the
Government of the United States itself into a great industrial
enterprise on the theory that that was the way to prepare the
nation. I think that is the way to starve the nation of the
spirit of initiative without which it cannot defend itself any-
where at any time. After all, it is the people who fight wars,
not the government, and it is the people who must prepare
or be ready to defend themselves if they are attacked.
None of us like war. War is organized destruction. Every
sensible man and woman hates it. The world has been drenched
with misery to an extent never contemplated before. We
should be glad to be convinced that it would never overtake us
again, and I wish I could utter a conviction that the United
States will never be forced to defend itself again. But I cannot.
And I doubt if any man or woman here can entertain that con-
viction. Human nature must change a good deal before we can
reach that conviction. A lot of the passions to which human
beings are subject will have to be eliminated if we are to reach
such a happy condition in the world. Until greed and jealousy
are eliminated from the human heart, until we are sure they
are eliminated, we cannot afford to neglect the possibility
of wars in the future. I rejoice that an organization of this
kind whose work is basic in its character, which builds things
for the benefit of the human race to make people happier and
more comfortable, that an organization of this kind has a con-
cern for the future security of the Republic. And that its mem-
bers, both in and out of military service, are devoting
themselves to this work of research and experimentation, so
that if the time should come when we are in danger, there
will be at least one body of men who can turn their skill to
the defense of the best country that the sun ever shone upon.
384
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
Directors : H. P. Talbot, W. D. Bancroft, President E. F. Smith. W D. Bigelov
Secretary C. L. Parsons, G. D. Rosengarten, A. D. Little
This address was frequently interrupted by long
applause, and it was a source of great delight to those
assembled to note the Senator's keen conception of
the importance of the Chemical Warfare Service and
the chemical industries to the future welfare of the
Nation. The entire audience rose while President
Smith thanked Senator Wadsworth for his inspiring
address.
Congressman Nicholas Longworth, of Ohio, was
then introduced by the President.
The American Chemical Industry and Its Need for
Encouragement and Protection
By Hon. Nicholas Longworth
In acknowledging the great gratification I feel for your most
kindly reception, I ought perhaps to apologize for the fact that
I came here to speak to this most august and distinguished body
entirely unprepared. I made an agreement with the distinguished
Senator who has just addressed you that neither of us would
prepare any remarks so that neither would have any advantage
over the other, but his well-rounded periods have shown that
the midnight oil has been burning, and without challenging
comparison with what he has said or I am about to say, I can
only hope that my address will not be much worse.
What the Senator and I may be able to help to do for the
chemical industries of this country will lie in action in Wash-
ington and not in telling you things here that you know already.
I dropped in on Friday afternoon at a mansion known to every
American, the oldest, the most dignified official residence in the
United States, and there met a man whom I am glad to call
my friend and the friend of Senator Wadsworth, the most
influential man in the United States and in the whole world to-day,
and he said: "I hear that you and Jim are going to address
the American Chemical Society. May I suggest that what
the industry needs more than addresses is protection?" With
that sentiment I heartily agree, and I am here to tell you to-
day that you are going to get protection.
I am just as modest, and perhaps with even more reason, about
my accomplishments as a chemist as is my friend the Senator.
I attained my early education at Harvard University, and as
far as my chemical researches were concerned they were con-
fined mainly to the judicious admixture of HsO with C2HsOH. I
might say that my researches have been very much limited
since my colleague Volstead got into action. Now I find
myself the chairman of the subcommittee of the Ways and
Means Committee for framing the chemical schedule, and I
think that even you skilled chemists will admit that that is a
pretty hard job to-day in the present situation of the country
and the world, and perhaps I can best occupy a few minutes in
telling you the situation from the practical standpoint with re-
gard to the chemical schedule to be written into the tariff bill.
PROBLEMS IN ARRANGING THE CHEMICAL SCHEDULE IN THE
TARIFF BILL
In the first place, there is no human being that I have ever
met who can tell us the cost of production of chemicals in this
country and certainly not the cost of production abroad. It is
a field of guess work, and we cannot follow the old definition
carried in many Republican platforms in making duties for
competing articles, that is to say, the adjustment of the differ-
ence in cost of production here and abroad because we cannot
find out what those costs are, and we are, on the other hand, not
up on the question of what the prices are. We have come across
May, 1921
TBE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
385
instances of chemicals, well-known chemicals, whose prices have
varied in the past three years in thousands of per cent. I cannot
think of the name of the chemical now, but I know one which
has varied from ten cents to $4 a pound in the last three years.
We have a man-sized job before us.
I had hoped that in framing the program for duties on chem-
icals, as well as on every other article of international commerce,
we might be able to go back to specific duties. When you have
these, you know exactly where "you are at," and it furnishes
more effective protection to American industry than ad valorem
duties, and yet a specific duty which Dr. Herty might suggest to
me to-day three or four months from to-day might not be a
protective duty or a revenue duty, and thus we are forced in
most cases to go to ad valorem duties. Moreover, a situation faces
us which has never before faced us in this country, the question
of foreign exchange. Values expressed in terms of German
currency or Italian currency or even French currency, when
translated into an ad valorem duty based upon value, reduce
any tariff rate almost to the vanishing point.
There is one way in which we can deal with that situation.
We never tried it but once, and that more than a hundred years
ago, and that is to have it based on the wholesale price of those
products here in America. It is extremely difficult to work out,
and adds a great deal to the technical difficulties of adminis-
tration, but it is absolutely necessary if we are going to pro-
tect the American industries to-day, where we are forced to put
on ad valorem duties. Never before in the making of an Amer-
ican tariff has it happened that instead of being a debtor nation
we are a creditor nation. Europe owes us $14,000,000,000.
How are they ever going to pay us if we bar them, and yet
how are we going to permit them to come in with any regularity
when a country such as Japan will come in and monopolize our
market and that of our late allies?
This is the question facing us and one for which it is hard to
find a solution. My personal idea is to have what might be
called a "bargaining" tariff with three different rates of duty: (1)
a conventional rate to prevail against every country ; (2) a maxi-
mum rate to be used against any countries who treat us on less
favorable terms than they do other countries; and (3) a minimum
rate to be applied by the President to certain articles by an agree-
ment with another country that certain of their articles might be
admitted, under consideration of certain of our articles being
admitted in that country under particularly favorable treat-
ment. You might have certain minimum duties on perfumes,
imported from France, in consideration of similar preferential
treatment by France of imports of chemicals from America, in
which way we could keep up trade without knocking the bottom
out of American industries. So much for the matters facing us
with regard to the protective features of these various chemicals.
PROTECTION OP THE DYE INDUSTRY
But we come to one class of chemicals for which no protective
rate, however high, is in fact protective — I mean all coal-tar
products. Thousand per cent duties would not help that situation.
We have not only to put duties on some chemicals, but also to
keep some out altogether. The bill which I introduced in the last
Congress, and which passed the House but never got through the
Senate, I propose to put bodily into the chemical schedule, ex-
cept that instead of having the license feature as written in that
bill, it will be changed into a selective embargo. The proposi-
tion of the license, or the mention of the word license, as Dr.
Herty and others who have taken a great interest in the matter
well know, does not sound well to many American business men.
They don't like to have to get a license to import chemicals.
It is proposed that the Tariff Commission shall make a list of
dyes not importable under any conditions, another of those
importable under certain conditions, and another of those im-
portable under any condition. Roughly speaking, those dyes
which Germany makes and which we make here at reasonable
prices and in reasonable quantities are not to be permitted to
come into this country at all for a reasonable period ; those which
are produced here, but in limited quantities and where delivery
might not be certain, may be imported under certain conditions
and in certain quantities, and dyes not produced here may be
imported.
I am firmly convinced that Germany is simply awaiting the
day when the present restrictions against limitless import of
these products is raised, and that there will be a flood of these
products into this country which will wipe out those industries
developed here during and since the war. My impression is that
the German dye works are running full time, are larger than
they ever were before, that none of them were destroyed or
even damaged, and that their forces were not called upon to serve
in the army but required to stay in the plants and produce.
Hon. Nicholas Longworth
If we want to save this basic industry in war and in peace,
we must go to the extent of putting a flat embargo on the product,
and I have every reason to believe that this time we are going
to be successful.
There is another condition that makes this proposition even
more difficult. I have told you of the problems that we are
trying to solve with regard to a tariff. In my judgment, we
shall not get a bill through before November or December.
The War Trade Board, which now limits importation of coal-
tar products and others from enemy countries, goes out of ex-
istence the first of July, or even sooner if the Knox resolution
declaring peace with Germany is passed by the Congress. We
shall not have the bill ready in the Ways and Means Committee
very much before the first of July, and in order to make effec-
tive some sort of prohibition against these importations, we
must pass a joint resolution the very day the tariff measure
is introduced in the House, and make the provisions of that
resolution law until the President signs the bill. It is drastic
but absolutely necessary, and I think I can promise you it will
be done.
I have said this much only to try to bring before your minds
the difficulties that we amatuer chemists have in trying to
386
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
translate into legislative action what we think ought to be done.
The situation looks immensely favorable, and I believe that the
average American and every member of the Upper and Lower
House has finally got through his head the thought so ably
presented by Senator Wadsworth, that the chemical industry,
in so far as it relates to preparedness for war or defense against
war, lies in the continuance of the chemical industry, and to
have that industry effective in time of war it must be permitted
to continue to exist industrially in time of peace. That is the
whole situation in a nutshell. I think it was Edison who said
some years ago that the next war would be a war of chemicals,
and the most unfortunate war, not yet over, at least in a techni-
cal sense, was absolutely a war of chemicals. No matter how
brave your boys may be, or how powerful your guns may be, or
how many your ships, unless you have explosives you cannot
wage war, and if other nations know you have not explosives,
they will come and make war on you. What chance would any
nation not prepared with poison gases have against any other
so prepared, self-sufficient at all times, and which did not have
to depend on Chile or any country for explosives?
In thanking you for your courtesy, I close by reiterating what
Senator Wadsworth has said: If the time comes, as God forbid
it will for years to come, when we again become involved in war,
what an immense advantage will accrue to us from the existence
of the Chemical Warfare Service and a Society like this, com-
posed of men who know the technical side of the very bed-rock
necessity for war for the preservation of our country and of
American institutions.
Mr. Longworth's address was also received with
great enthusiasm, and his references to President
Harding's attitude toward the needs of the chemical
industry, as well as the Congressman's assurance that
the American dye industry shall not be permitted to
disintegrate, were heartily applauded.
Again the entire audience stood while President
Smith thanked the speaker for his splendid, reassuring
message.
The meeting adjourned shortly after the noon hour.
AFTERNOO"N SESSION
just as the first session of the General Meeting had
evoked great enthusiasm in behalf of the public and
economic aspects of chemistry, so the second session
held at Convention Hall showed the keen interest with
which members of the Society always receive the re-
sults of fundamental research in the development of
the science of chemistry. Six papers were presented
at this session, covering a wide range of subjects.
E. C. Franklin read a very interesting paper on "Am-
mono Carbonic Acids." C. E. K. Mees spoke on
"The Measurement of Color" and illustrated his re-
marks with lantern slides. "Blue Eyes and Blue
Feathers," an illustrated paper by W. D. Bancroft,
"Surface Films as Plastic Solids" by R. E. Wilson,
"The Relation between the Stability and the Structure
of Molecules" by Irving Langmuir, and the "Ionization
of Electrolytes" by G. N. Lewis completed the pro-
gram. The attendance at this second general session
was fully as great and possibly greater than that at the
General Meeting held in the morning.
layman, attendance at the Rochester Chamber of
Commerce luncheon on Wednesday, April 27, surely
dispelled it. It was a wonderfully pleasing sight to
behold the great dining hall of the Chamber of Com-
merce filled to the last available seat with members of
the Rochester Chamber of Commerce and members
of the American Chemical Society, who intermingled
and conversed as though chemists and business men
had been lifelong partners. Dr. Arthur D. Little rose
to the occasion in a masterful address which brought
home to those assembled the close relation between
chemistry and everyday life. It was a happy thought
on the part of the officers of the Rochester Chamber
of Commerce and the members of the Rochester Sec-
tion to stage this "get-together" of progressive busi-
ness men and chemists from all over the country and
to secure Dr. Little as the speaker of the meeting.
Those who were fortunate enough to attend considered
the affair one of the most pleasing incidents in the
convention program. One business man remarked
chamber of commerce luncheon
If there was any doubt on the part of anyone as to
the recognition of the importance of chemistry by the
H. E. Howe. W. D. Bancroft, President Smith, David Wesson,
and Robert F. Ruttan, Administrative Chairman of the Ad-
visory Council for Scientific and Industrial, Research
in Canada
that the inscription "Commerce carries civilization
around the world" which appears in large letters above
the rostrum of the assembly hall in the Chamber of
Commerce might well be changed to "Chemistry
carries civilization around the world." Truly, Com-
merce and Chemistry, layman and chemist, are getting
together. Dr. Little's address follows:
The Place of Chemistry in Business
By A. D. Little
In the mind of the average business man chemistry is some-
thing quite apart from business, an abstruse science that deals
with things of evil smell and unpronounceable names, something
for the laboratory or the underpaid professor, but with which
the hard-headed man of affairs has little need to concern him-
self. Yet you business men, who deal in dollars, think it well
worth your while to learn all you can about them. You want
to know where they are plentiful and where they are scarce.
You follow their purchasing power and the interest rate they
carry. You sit up nights trying to devise new ways to put
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
387
salt on the eagle's tail. You employ bookkeepers and accountants
and income tax specialists in order that you may trail these
dollars through every portion of your establishment and per-
suade the Government that a few of them really belong to you.
You study balance sheets and audits and inventories, and base
your decision upon what they tell you about dollars.
But the dollar is merely a symbol, a generic symbol of the
value of things. The values are in the things the dollars repre-
sent, not in the dollars themselves. The things behind the dollar
are materials and labor, and labor creates values only as it
works upon material. Obviously, therefore, the ways and prop-
erties of material or matter are of greater fundamental importance
to you as business men than even the properties and ways of
dollars.
Now chemistry is the science which deals with the properties
of matter and the changes which they undergo. Whether you
know it or not, chemistry is, therefore, a partner in your business
in a far more real and vital sense than the Federal Trade Com-
mission, the Interstate Commerce Commission, the Tariff
Board, the labor unions, the Federal Reserve Bank, or any
other of the man-made agencies with which you admittedly
have to reckon. As wise business men you take carefully into
account freight schedules, city ordinances, insurance regulations;
you observe the man-made laws of legislatures and of Congress.
But chemistry has some laws of its own that are not man-made :
laws beyond the power of any legislature or Congress to repeal.
What do you know about them, or how far do you take them
into account in the conduct of your business? The science of
chemistry is simply a codification of these laws and an orderly
arrangement of the innumerable facts upon which they are
based. The chemist is the counsellor-at-chemieal-law, and as.
such you need him in your business. I suggest that you make
an early reservation, as there is only one chemist to each 7000
of our population. An ounce of whiskey in 55 gallons of water
is a pretty thin mixture.
Now what have these relatively few chemists with their pred-
ecessors and associates throughout the world been able to ac-
complish for business and the nations? What contribution have
they made that bears upon your own affairs?
THE SERVICE OF CHEMISTRY IN AGRICULTURE
We are still essentially an agricultural country. Our pros-
perity comes from the soil. Just now, in fact, it seems to be
underground. Two Boston men were talking the other day
when their conversation took a theological turn — Boston is the
home of Unitarianism, you know. Finally one of them said:
"I'm a Unitarian. I don't believe in Hell and all that nonsense."
"You don't believe in Hell?" the other replied, "Where has your
business gone to?" With the same friendly interest I would
inquire of you, "Where would agriculture go without chemical
fertilizers?" But the great potash deposits of Stassfurt were
not available to the farmer until van't Hoff applied the principles
of physical chemistry to the separation of the salts. Two
hundred and fifty great plants in this country are engaged in
converting phosphate rock to acid phosphate by chemical
methods. Nitrogen is another essential plant food. The world
has derived its chief supply from the Chilean nitrate beds, but
the exhaustion of these deposits is perilously near. It is bad
enough to be tied in this way to a single far-away deposit, but
the situation became alarming to those who realized that unless
a new source of supply were found the world must make up its
mind to starve. Fortunately, the chemists recognized that on
every acre of the earth's surface the nitrogen of the atmosphere
is pressing down with a weight of 33,800 tons. They have
boldly attacked the problem of rendering available such portion
of this inexhaustible supply as the world may need. The
methods employed have been brilliant and daring in the ex-
treme and so successful that our supplies of nitrogen for agri-
Dr. A. D. Little
culture or for war are now assured, provided only our Govern-
ment stands behind the chemists.
If you were a farmer, what would you think of the business if
you had to pick potato bugs by hand? Who would get the
potatoes? My money is on the bugs. Meantime, what is the
farmer to do with the other devouring hosts — the gypsy and
brown tail moths, the inch worms, the boll weevil, the coddling
moth, the cabbage worm, and all the innumerable multitude
of insects, molds, and fungi that would feed at his expense?
Were it not for chemical sprays and insecticides, he would be as.
helpless before them as were the Egyptians before the plague of
locusts.
Chemistry puts new values on farm products by greatly ex-
tending their range of use. Kirchhoff discovered the inversion
of starch to glucose by dilute acids, and as a result of that simple
observation a single corn products plant treats 50,000 bushels
of corn a day. Not many years ago cottonseed was a nuisance.
Laws were passed forbidding the throwing of it into streams.
The chemist converted it into a perennial source of Southern
wealth and the raw material on which are based such great
enterprises as the Southern Cotton Oil Co., and the American
and Buckeye Companies. From it he derived edible oils, soap
stock, and cattle feeds. Then Sabatier supplied more chemistry,
and by his process of hydrogenation converted vegetable oils
to solid fats, which provide an adequate and satisfactory sub-
stitute for lard and butter. Again the price of cottonseed oil
went up. A single company in England treats by this process
2000 tons of coconut oil a week, and in more than one county
in the South peanuts are worth more than the cotton crop.
Few discoveries have been more far-reaching in their influence
than the observation by Schonbein in 1845 that cotton on ex-
posure to nitric acid was converted into a new and highly ex-
plosive product. For seventy years research has been focused
on that observation. It led von Lenk and Abel to guncotton;
Viele, Nobel, Abel, and Dewar to various forms of smokeless
powder. It revolutionized warfare. It led Hyatt to celluloid,
Goodwin to photographic films, du Chardonnet to artificial
silk, and is the underlying fact on which is based the manu-
388
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
facture of patent leather, artificial leather, lacquers, and a
bewildering variety of other products which are everywhere
in daily use. Hundreds of millions of feet of nitrocellulose
film, most of which comes from Rochester, carry their message
of instruction or amusement to hundreds of millions of people
in the tens of thousands of moving picture theatres throughout
the world each year.
Before we leave the farmer you will perhaps permit me to
quote from an advertisement of the laboratory with which I am
associated. It is headed, "Chemistry and the Astonished Cow,"
and proceeds: "The cow made the milk for use in the family,
her own family. She was indignant and surprised when the
farmer ran it through a separator and extracted the cream,
but she was astonished when the chemist took the skimmed milk,
which the farmer threw away, and converted it into billiard balls
and back combs, fountain pens, and a size for coated papers.
Her astonishment was shared by the farmer."
Years ago a manufacturer was making a water paint from
glue and gypsum. He had found a German product which was
better than glue for his purpose. It made the paint insoluble
when it was dry. Its analysis showed a mixture of casein and
lime for which the Germans wanted 30 cents a pound. That
was more than his product would stand. It was pointed out
to him t-hat casein was easily prepared from skimmed milk.
His factory was in a dairy country. He was shown how to
make casein. A few months later he moved to New York,
organized a large corporation, pulled down a salary of $50,000
a year, and took a house on Fifth Avenue.
THE WORK OF LOUIS PASTEUR
There are few men to whom the world stands in greater debt
than the French chemist, Pasteur. There is probably not a
man in this room who is not under heavy obligation to him, and
except for his discoveries some of you would not be here at all.
His demonstration of the germ theory of disease and the de-
velopment of the serum and antitoxin treatments have saved
more lives than the recent awful war has cost all the belligerents
combined. Such service is beyond estimate in monetary terms,
but the direct financial value of Pasteur's discoveries was years
ago appraised by Huxley as sufficient to cover the whole cost
of the war indemnity paid by France to Germany in 1870.
In 1865 a fatal epidemic among the silk worms had ruined the
silk growers of France. In June of that year Pasteur was called
to the south of France to study the disease. In September he
announced the method which proved successful for its control.
Other studies saved the French wine industry from the de-
structive ravages of phyloxera, stamped out chicken cholera
and anthrax, and for the first time put brewing and wine making
on a scientific basis. More recently they have reverted to the
status of cottage industries, and the scientific control is less in
evidence. Sufferers from gastritis who consult their physician
are commonly greeted with the observation, "I see you make
your own."
RELATION OF THE CHEMIST TO THE TRANSPORTATION PROBLEM
Perhaps the greatest domestic problem before the country
to-day is that of transportation I still guard, not as carefully
as formerly, a few shares of the New York, New Haven & Hart-
ford Railroad which I bought at 188. It was going to 200.
I doubled up at 70. It is now about 16. And yet a New
York banker had the nerve to tell the American Chemical
Society at a dinner at the Waldorf that what he required of
chemical investments was absolute security. We have lots of
things at 30 Charles River Road, Cambridge, that are lead-pipe
cinches in comparison with any bank-managed railroad that
slides from 188 to 16. I know of one poor little chemical com-
pany which started with $20,000 capital and in a few years
wrote off $750,000 in real estate and equipment.
However deeply your sympathies may be aroused, you must
not let my ownership of a hand car or a water tank on the New
Haven blind you to the fact that your business cannot go on
without the railroads. You will admit that without argument,
but what I want you to realize is that the railroads cannot go
on without chemistry. They operate on steel rails, and those
rails are cheap because of the Bessemer process of making steel.
Few even among railroad men realize how greatly the whole
community is in the debt of Dr. Dudley, whose laboratory work
went far to standardize the railroad practice of the country.
His specifications covered rails, soaps, disinfectants, oils for
signals and for lubricating, paints, steel in special forms for
every use, car wheels, cement, signal cord, and every detail of
equipment. He made the transportation of life and property
cheaper, safer, and more expeditious by reason of his applica-
tion of chemistry to the problems of railroad management.
I would ask you to consider what chance you would have of
securing cheap transportation without the Bessemer process,
or that of Thomas and Gilchrist which followed for phosphatic
ores. What without them would be the value of iron ore lands
in this country or that of coking coal? What inducement would
Germany have had to go to war if she could not smelt the phos-
phatic minette ores of Lorraine? Picture, if you will, the op-
portunities for labor which these processes have created in the
mining of coal and iron ore, in the coking of coal, in the making of
rails and structural steel and plates for ships. Shopkeepers
who never heard his name owe their prosperity to Bessemer,
and cheap Bessemer steel is the foundation of countless industries.
But modern civilization makes demands which cannot be
satisfied by Bessemer steel. So the chemist has developed
nickel steel for armor and for guns, and tungsten steel for army
helmets and for tools whose cutting power is four times that of
ordinary good tool steel. You regard the automobile and the
motor truck as among the highest expressions of mechanical
engineering. They are revolutionizing transportation. Be-
cause of them the road before your door which formerly seemed
to lead only to the village or the town is now the opening to the
highway upon which you may travel north or south or east or
west upon the continent, as you choose. But the automobile
is as truly a chemical creation as it is a mechanical product.
Chemistry enters into its every part. It supplies the alloy
steel, the aluminium, the artificial leather, plates the nickel,
vulcanizes the rubber, provides lacquers and pigments and
paints. It furnishes the gasoline and promises to develop new
types of motor fuel. Good roads of cement or bonded with
asphaltic compounds are replacing the stretches of dust on which
we used to travel.
artificial abrasives
A chance remark of Dr. George F. Kunz in 1880 on the in-
dustrial value of abrasives turned the thoughts of Acheson to
the problem of their artificial production, and led to the dis-
covery in 1891 of carborundum and its subsequent manufacture
on a small scale at Monongahela City, Pennsylvania. In 1894
Acheson laid before his directors a scheme for moving to Niagara
Falls — to quote his own words:
To build a plant for one thousand horse power, in view of the
fact that we were selling only one-half of the output from a one
hundred and thirty-four horse-power plant, was a trifle too much
for my conservative directors, and they one and all resigned.
Fortunately, I was in control of the destiny of the Carborundum
Company. I organized a new board, proceeded with my plans,
and in the year 1904, the thirteenth from the date of the dis-
covery, had a plant equipped with five-thousand electrical
horse power, and produced over 7,000,000 pounds of those specks
I had picked off the end of the electric light carbon in the spring
of 1891.
THE SULFUR INDUSTRY
Especially notable and picturesque among the triumphs of
American industrial research is that by means of which Frasch
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
389
Save to this country control of the sulfur industry of the world.
There is in Calcasieu Parish, Louisiana, a great deposit of sulfur
1000 feet below the surface, under a layer of quicksand 500
feet in thickness. An Austrian company, a French company,
and numerous American companies had tried in many ingenious
ways to work this deposit, but had invariably failed. Mis-
fortune and disaster to all connected with it had been the record
of the deposit to the time when Frasch approached its problem
in 1890. He conceived the idea of melting the sulfur in place
by superheated water forced down a boring, and pumping the
sulfur up through an inner tube. In his first trial he made use
■of twenty 150 h.-p. boilers grouped around the well, and the
titanic experiment was successful. The pumps are now dis-
carded, and the sulfur brought to the surface by com-
pressed air. A single well produces about 450 tons a day, and
their combined capacity exceeds the sulfur consumption of the
world.
OIL REFINING
An equally notable solution of a technical problem which
Tiad long baffled other investigators is the Frasch process for
refining the crude, sulfur-bearing Canadian and Ohio oils.
The essence of the invention consists in distilling the different
products of the fractional distillation of the crude oil with me-
tallic oxides, especially oxide of copper, by which the sulfur is
•completely removed, while the oils distil over as odorless and
sweet as from the best Pennsylvania oil. The copper sulfide
is roasted to regenerate the copper. The invention had im-
mense pecuniary value. It sent the production of the Ohio
fields to 90,000 barrels a day, and the price of crude Ohio oil
from 14 cents a barrel to $1.00.
THE ELECTRIC DYNAMO
The dynamo supplies the current which lights our streets
and homes and factories, drives our machinery, fires electric
furnaces, creates new products in electrolytic cells, and is our
ready and ever-willing servant responding in countless ways
to our demands. It so serves us only because Faraday, by re-
fined research, stimulated and directed by the scientific imagina-
tion at its best, developed the underlying principles on which
its operation depends. Faraday was first of all a chemist.
When he needed the science of electricity he created it as he
went along.
CHEMICAL INDUSTRIES AT NIAGARA FALLS
At no place in the world are the results of industrial research
more strikingly evident than at Niagara Falls. The electrical
■energy derived from a small fraction of that stupendous flow
produces, in its passage through electric furnaces and decompos-
ing cells, aluminium, metallic sodium, carborundum, artificial
graphite, chlorine and caustic soda, peroxides, carbide, cyanamide,
chlorates, and alundum. The story of the electrochemical
development behind these products is an epic of applied science.
It starts with the wonderful story of aluminium. Discovered.
-in Germany in 1828 by Wohler, it cost in 1855, $90 a pound.
In 1886 it had fallen to $12. The American Castner process
brought the price in 1889 to $4. Even at this figure, it was
■ obviously still a metal of luxury with few industrial applica-
tions. Simultaneously Hall in America and Heroult in Europe
discovered that cryolite, a double fluoride of sodium and alu-
minium, fused readily at a moderate temperature, and, when so
fused, dissolved alumina as boiling water dissolves sugar or
salt, and to the extent of more than 25 per cent. By electro-
lyzing the fused solution, aluminium is obtained.
On August 26, 1895, the Niagara works of the Pittsburgh
Reduction Company started at Niagara Falls the manufacture of
aluminium under the Hall patents. In 1911 the market price
• of the metal was 22 cents, and the total annual production
40,000,000 pounds.
EXTRACTION OF GOLD FROM ORES
As business men you are directly interested in gold as the
standard of values. It is not a fixed standard, and any increase
in the available supply reacts at once upon other values. Two
chemical processes, cyanide and chlorination, have had a pro-
found effect upon the volume of the world's supply of gold, and
so influence the price of everything you buy and sell. They
permit the profitable extraction of gold from low-grade ores
like those so abundant in the gold fields of South Africa.
EXPLOSIVES
Mining, the building of railroads, the great construction pro-
jects for which America is famous, like the Panama Canal and
the vast works of the Reclamation Service, are possible only
through the agency of explosives which make instantly and
locally available enormous stores of chemical energy. To
supply this energy chemistry has developed various types of
black powder, nitroglycerin, dynamite, guncotton, and other
compounds and mixtures so numerous as to require a "Dictionary
of Explosives." Nowhere has their manufacture been so highly
developed or conducted upon so vast a scale as in this country.
The war, from which we are now slowly recovering, was in a very
real sense a chemists' war, and if we have another, which God
forbid, chemistry will make it inconceivably more terrible than
the last. Fortunately for our country, the Chemical Warfare
Service, which functioned with such magnificent resource,
energy, and effect throughout the war, has had its continued ex-
istence assured as an independent though skeletonized branch
of the military service.
THE PLACE OF CHEMISTRY IN RECONSTRUCTION
The war, which has changed everything, has given a new
aspect to chemistry and a fresh impetus to research. Here-
after the nation which would live must know. Through the
wreck and peril of other peoples, Americans have learned with
them that research has something more to offer than intellectual
satisfactions or material prosperity. It has become a destructive,
as well as a creative agency, and in its sinister phase the only
weapon with which it may be fought is more research. The
organization and intensive prosecution of research has thus
become a fundamental and patriotic duty which can neither be
ignored nor set aside without imperiling our national existence.
Now we are carrying as cheerfully and hopefully as we may
the stupendous burden of the war. Chemistry, with the sym-
pathetic and understanding cooperation of business and financial
men like yourselves, can do more to lighten that burden by the
creation of new wealth in vast amounts than all the law makers
in Congress and state legislatures. And the first step is to
stop the stupid, wicked, childish waste of our basic natural
resources. The time has passed for quoting figures. They are
of astronomical proportions anyhow and make no more impres-
sion on the mind than the distances of the fixed stars in light years.
The time has come to demand action, to the end that we may pay
our bills with what we waste. Let us develop our estate. It
has potentialities vastly beyond anything we have accomplished.
A very large proportion of industrial problems are problems
in applied chemistry. Many of these so-called problems have
already been solved somewhere. The present need of industry
is not so urgent for new research and for new facts as for the
immediate and proper utilization of facts already known and
demonstrated.
A few of you may remember that in pre-prohibition days beer
commonly became cloudy when placed on the ice. It was an
objectionable tendency which the best skill of the brewers was
unable to overcome. A little research by a clever chemist proved
that the cloudiness resulted from the deposition of albuminoids
previously in solution. He remembered that pepsin digested
albumin, added a trace of pepsin to the beer, and the thing was
done. The beer remained bright at any temperature.
390
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
Not long ago a Jewish manufacturer was using a leather stain
for which he was paying eighty-five cents a gallon. It proved
to be water containing a little gum tragacanth and still less aniline
dye. He was shown how to make it at a cost of less than ten
cents a gallon. He said he began to realize where the Gentiles
get the money the Jews get from the Gentiles.
In a plant near Boston using two tons a week of special steel,
rolled very thin, their chemist was able in about two years to
reduce the cost of this material from eighty to forty cents a pound,
at the same time standardizing and greatly improving the quality
of the steel. Broken rails are more expensive than analyses,
and there are no dividends in broken trolley wires, defective
castings, spotted or tendered piece goods, or rejections in any line
of manufacture. Competition is difficult when your wastes are
your competitor's profit.
WAYS IN WHICH CHEMISTRY CAN AID THE MANUFACTURER
By way of suggestion, let me point out a few of the more
obvious ways in which chemistry can serve the manufacturer.
There is, first, the control of quality of raw materials, as in
case of steel, alloys, bearing metals, lubricants, coal, paints,
paper, cement, and practically everything else you buy.
Second, perhaps, is the problem of finding suitable substitutes
for such supplies as are unobtainable or unduly high in price.
For example, there is the use of selenium in place of gold in the
production of ruby glass, the substitution of tungsten points for
platinum in spark plugs, of silica ware for platinum dishes for
the concentration of sulfuric acid, of casein for glue, of chlorate
of soda for chlorate of potash in dyeing, of zein (derived from
corn) for the prohibited shellac for varnishing confectionery, of
specification oils for oils whose value is largely in brand names,
and of the specifically indicated chemicals in place of high-priced
boiler compounds.
Of even greater importance is the scientific control of processes
of production, control of formulas, temperatures, pressures, time
and spacing, fineness of material, moisture content, and all the
other factors which influence the quality and amount of your
daily output. Correlative with such control are the studies
having for their object the standardization of your product and
the elimination of seconds and rejections.
Wastes can be minimized and often turned to profit by well-
directed research. The waste liquor of the sulfite mills is now
a source of alcohol and of adhesives. Barker waste is an ex-
cellent raw material for certain low-grade papers. The Cottrell
process of electrical precipitation effects the recovery of values
of smelter fumes, cement dust, and many other chimney products.
In some industries, as lumbering, the potential values in the
wastes are greater than the realized values in the product.
The wholly abnormal conditions under which business every-
where is now conducted lend particular interest to another
function of industrial research, namely, that of finding new-
outlets for present products and new products for existing plants.
Bankers and capitalists should realize, as they doubtless do,
that the basis of credit for industrial enterprises has shifted.
Past earnings have lost their significance. Audits and inven-
tories and balance sheets tell the story of past performance.
What is now required is the assurance of future earning power.
That assurance can be safely based only on technical studies
covering raw material supply, the adequacy of equipment, the
relation of processes and methods to the best modern practice,
the efficiency with which energy and material are utilized, and
the status of the product in the market under the new industrial
and economic conditions. Now is the time to put our house in
order, to sweep out wastes and inefficiencies, to study and solve
our problems, to make ourselves worthy of and ready for a
sounder and broader prosperity than our country has yet known
Let us go to it.
CHEMICAL WARFARE SERVICE DINNER
About one hundred veterans and present officers of
the Chemical Warfare Service sat down to a most
enjoyable dinner held in the Rochester Hotel Wed-
nesday evening, and pledged their continued allegiance
and effort in furthering the cause of the Chemical
Warfare Service in the United States. Unfortunately,
Brigadier General A. A. Fries was detained in Wash-
ington and could not attend. However, Major E.
J. Atkisson, who is in charge of Edgewood Arsenal,
substituted for the General, and in a stirring address
called upon the members of the Society, and particu-
larly the veterans of the Chemical Warfare Service,
to continue their cooperation and whole-hearted back-
ing of the Service. Major Atkisson pictured the
Chemical Warfare Service as a pattern into which
every chemist fits naturally during time of war, and he
expressed the hope that' the chemists of the country
who really were responsible for the creation of the
Service would continue to give it their support when-
ever called upon. Dr. Chas. H. Herty, the toast-
master of the occasion, spoke enthusiastically of the
pleasing manner in which the civilian workers in the
Chemical Warfare Service and the military members
of the Service conducted their work side by side with-
out the slightest friction of any kind. The toast-
master introduced Mr. D. B. Bradner, who is in charge
of the research work at Edgewood Arsenal. Mr.
Bradner referred to the mutual benefit that had been
derived by the chemist and the Chemical Warfare
Service from the time of the inauguration of this
branch of warfare. He pointed out that more money
had been invested in the organic chemical industries
in this country since chlorine was first used by the
Germans as a war gas than in the entire previous his-
tory of chemistry in the United States. The necessity
for keeping up public interest in chemistry and driving
home the fact that chemical industries, such as the dye
industry, are not only essential for the welfare of the
nation in times of peace but will furnish the sinews of
war in time of stress was brought out very forcefully by
Mr. Bradner. He predicted that the next war would
be fought in a large measure by the Air Service and the
Chemical Warfare Service. These two services are
not only necessary for the national defense but they
are also great aids in the prevention of war, said Mr.
Bradner, because nations will think twice before open-
ing hostilities against other nations which are prepared
with an effective chemical warfare and aviation
service. The toastmaster, in referring to the increas-
ing interest of the public in chemistry and its increasing
knowledge of the importance of this science in prob-
lems of everyday life, called attention to the volume
entitled "Creative Chemistry," written by Dr. Slosson,
which is being so well received. He asked those
assembled to encourage their lay friends to read this
book, as it will undoubtedly rank among the most
important means of interesting the layman in our
science. The affair closed with short addresses by
Dr. Clowes and Professor MacPherson, who pledged
the continued loyalty of those assembled to the Chemi-
cal Warfare Service.
May, 1921
THE JOURNAL OF INDUSTRIAL
PUBLIC MEETING
A large attendance, which comfortably filled the
large Convention Hall of Rochester, greeted Dr.
Charles F. Chandler, past president of the American
Chemical Society and known more generally as the
"Dean of American Chemists," when he stepped on
the stage accompanied by President E. F. Smith, and
Past Presidents Dr. W. D. Bancroft, Dr. Arthur D.
Little, Dr. Chas. H. Herty, and Dr. W. F. Hillebrand.
The entire audience rose and applauded for several
minutes. Dr. Smith introduced the speaker in a few
well-chosen words. Dr. Chandler delivered the follow-
ing address:
Chemistry in the United States
By Charles F. Chandler
It gives me great pleasure to meet with you again. Words
are inadequate to express the interest I have always taken in the
American Chemical Society.
I wonder how many of you know how it came into existence.
Its history is a good illustration of the way one good enterprise
is sure to lead to another.
For several years in the later sixties, a monthly reprint of the
London Chemical News was printed and issued in New York
City. At the request of the New York publisher, I prepared
an American supplement, which was appended to each number.
This reprint was not a very successful venture for the publisher,
and at the end of 1869 it was discontinued.
In place of it the American Chemist was published in 1S70,
edited by my brother, Prof. William H. Chandler, of the Lehigh
University, and myself. Soon afterward we became the owners
of the journal, publishing it for seven years, until the American
Chemical Society was in condition to finance its own journal,
which was in 1877. The American Chemist was devoted to
■original articles by American chemists, and each monthly number
contained copious abstracts from foreign and American journals,
prepared by a corps of twenty-eight prominent American chem-
mists who generously volunteered their services.
THE CENTENNIAL OF CHEMISTRY — 1774-1874
Early in 1874, the editors of the American Chemist received a
letter from Prof. H. Carrington Bolton, of the School of Mines
•of Columbia College. In this letter he referred to the fact
that various centennials were now being proposed, as that of the
"Boston Tea Party," and suggested the propriety of a Cen-
tennial of Chemistry, as 1874 would be a very appropriate date.
He referred to the isolation of chlorine by Scheele, his recogni-
tion of baryta as a peculiar earth, and his masterly essay on
manganese. Lavoisier was engaged during that year in an
investigation of the cause of the increase in weight of tin when
calcined in closed vessels, a research which led him to subsequent
discoveries of immense importance. Wiegleb proved alkalies
to be true natural constituents of plants. Cadet described an
improved method of preparing sulfuric ether. Bergman showed
the presence of carbonic acid in white lead. On September 27
in this year, Comus reduced the "calces" of the six metals by
means of the electric spark, before an astonished and delighted
audience of savants. On the first of August 1774, Priestley
discovered oxygen, the immediate results of which were the
overthrow of the time-honored phlogistic theory and the foun-
dation of chemistry on its present basis.
Bolton proposed that some public recognition of this fact
should be made during the coming summer, and that American
chemists should meet at some pleasant watering place, to dis-
cuss chemical questions, especially the wonderfully rapid progress
•of chemical science in the past hundred years.
AND ENGINEERING CHEMISTRY 391
This letter was published in the American Chemist for April
1874, page 362, with a note emphasizing the "hearty approval"
of the editors. The project was very favorably received. Many
letters of approval were promptly received. Among the writers
I will mention: Prof. E. N. Hosford, S. Dana Hayes, Albert
R. Leeds, Benjamin Silliman, T. Sterry Hunt, Dr. H. Ende-
mann. Prof. E. T. Cox, S. D. Tillman, and Prof. E. O. Hovey.
Dr. Charles F. Chandler
The most important letter came from Rachel L. Bodley,
professor of chemistry at the Woman's Medical College of
Pennsylvania. In this letter she gave an account of a pilgrimage
she had made in the previous August to the grave of Priestley,
in Northumberland, Pa., where she was deeply impressed by
the locality, its associations, and its charming surroundings.
She proposed "that the centennial gathering be around this
grave, and that the meetings, other than the open-air one on the
cemetery hilltop, be in the quaint little church built by Priestley,
where might be exhibited the apparatus devised by the great
scientist, and used in his memorable experiments."
Miss Bodley also sent us the following quotation from her
valedictory address before the twenty-second graduating class
of the Woman's Medical College of Pennsylvania on March
13, 1874:
Apropos of the pleasant hours spent together in lectuie room
and laboratory, let me remind you that chemistry holds a Cen-
tennial next August beside an honored grave at the meeting of
the waters of the Susquehanna, amid the picturesque scenery
of the interior of Pennsylvania.
The hand that plunged the glowing taper into fhe primal jar
of dephlogisticated air long since crumbled into dust beneath
that simple headstone, but science will not forget, through
centuries to come, the historic receiver, burning lens, and taper,
neither will willingly let die the name of Priestley, who in August
1774 discovered oxygen.
ACTION OF THE N. Y. LYCEUM OF NATURAL HISTORY — At a
meeting of the Chemical Section of the N. Y. Lyceum of Natural
History, May 11, 1874, President J. S. Newberry, LL.D., in
the chair, the subject of a chemical centennial was discussed, and,
392
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
on motion of Dr. H. C. Bolton, the following resolutions were
adopted :
Whereas, the discovery of oxygen by Joseph Priestley on the first of
August 1774 was a momentous and significant event in the history of
chemistry, being the immediate forerunner of Lavoisier's generalizations
on which are based the principles of modern chemical science; and
Whereas, a public recognition of the one-hundredth anniversary of
this brilliant discovery is both proper and eminently desirable; and
Whereas, a social reunion of American chemists for mutual exchange
of ideas and observations would promote good fellowship in the brother-
hood of chemists; therefore
Resolved, That a committee of five be appointed Ijy the chair, whose
duty it shall be to correspond with the chemists of the country with a view
to securing the observance of a centennial anniversary of chemistry during
the year 1874.
President J. S. Newberry subsequently appointed the following
committee; Dr. H. C. Bolton, Prof. C. F. Chandler, Prof.
Henry Wurtz, Prof. A. R. Leeds, and Prof. Chas. A. Seeley.
These communications and resolutions were published in the
American Chemist for June 1874, pages 441 to 443.
By this committee the Centennial of Chemistry was organized,
and the call, signed by thirty-seven prominent chemists, was
issued to the chemists of America to meet on the thirty-first of
July, at Northumberland, Pa.
Attached to the call was a program of the meeting containing
a list of the addresses to be delivered, .and the names of the
thirty-four members of the local committee, of which Joseph
Priestley, M.D., was chairman, and H. B. Priestley was also a
member. (American Chemist, July 1874, pages 11-13.)
The meeting — On Thursday, July 30, the chemists began to
arrive, many accompanied by their wives and daughters.
Seventy-seven of the chemists registered their names, and are
recorded in the published proceedings. (American Chemist,
Aug.-Sept., p. 35, and Dec, pp. 195-209.) As nearly as I can as-
certain, of these seventy-seven, only three besides myself are
now living: A. A. Breneman, Samuel A. Goldschmidt, and
Stephen P. Sharpies.
On the morning of July 31 the public school building was
crowded, the meeting was temporarily organized, and a nominat-
ing committee appointed, with Prof. E. N. Hosford of Harvard
College, as chairman.
The officers nominated and elected were as follows :
President
Prof. Charles F. Chandler
Vice Presidents
Prof. Rachel L. BodlEy Prof. J. W. Mallet
Prof. John W. Draper Prof. S. St. John
Prof. Silas H. Douglas Prof. A. P. S. Stuart
Prof. T. G. Wormley Dr. Albert H. Gallatin
Prof. Eugene W. Hilgard Prof. Henry Wurtz
Prof. E. N. Hosford Prof. C. A. Joy
Dr. H. Carrington Bolton
Secretary
Prof. Albert R. Leeds
Treasurer
Prof. William H. Chandler
In addition to the officers, committees were appointed as
follows: Finance, Resolutions, Scientific Papers, Telegrams,
and, on motion of J. Lawrence Smith, a committee to represent
America in spirit at the unveiling of the Priestley statue on
August first at Birmingham, England.
The address of welcome was then delivered by Col. David
Taggart of Northumberland. The president replied, returning
thanks on behalf of the chemists to the citizens of Northumber-
land for their liberal hospitality. Letters and telegrams from
several absent chemists were read. A telegram was received
from "The Priestley Memorial Committee of Birmingham,"
to which an answer was sent.
An interesting discussion arose as to the advisability of found-
ing a national chemical society. The idea was proposed by
Professor Persifor Frazer and favored by William H. Chandler
and Dr. H. C. Bolton.
On the other hand. Prof. J. Lawrence Smith pointed out the
difficulties which stood in the way of such a project.
The country is too large, it would be impossible to centralize
its chemical research.*** We want all our scientific institutions
dispersed far and wide.*** We have already two great institu-
tions in the country — the American Scientific Association and
the American Academy of Sciences, which cover the ground.**
The meetings of the London Chemical Society and the French
Chemical Society are very meagerly attended, as chemists
prefer to read their papers before the Royal Society and the
French Academy.
These objections were recognized by F. W. Clarke, E. N.
Hosford, E. T. Cox, B. Silliman and Dr. Van der Weyde.
They all advocated the cooperation of the chemists as a
body with the American Scientific Association, and held that if
any national association of chemists were formed it should be
as a permanent section of that body. These views prevailed and
a committee was appointed to cooperate with that association.
An address was then given by Professor Henry H. Croft of
the University College, Toronto, on "The Life and Labors of
Doctor Joseph Priestley." This was followed by the reading
by Professors Hosford and Pynchon of fifteen letters signed
by Priestley, one dated 1775, and the rest between 1798 and 1800.
The morning session then adjourned to the mansion formerly
occupied by the son of Dr. Priestley, occupied by the hospitable
Mr. Joseph Bird.
The day being bright and clear, a number of photographs
were taken by Louis H. Laudy of the Columbia School of Mines.
There is a complete set of these photographs in a frame in Have-
meyer Hall at Columbia. They are very interesting and should
have been more generally circulated among the chemists. They
include:
1 — A copy of an engraving representing the looting of Dr. Priestley's
house in Birmingham, when he was driven out of England.
2 — A copy of a portrait of Dr. Priestley.
3 — The Priestley residence.
4 — A group picture of the assembled chemists.
5 — A collection of Priestley's physical instruments and apparatus.
6 — A collection of Priestley's chemical apparatus.
The afternoon session opened with an address by Prof. T.
Sterry Hunt on "A Century's Progress in Chemical Theory-"
After tea the chemists, in company with a large number of
visitors, were conducted to the cemetery, to the grave of Priest-
ley. Here the large audience listened to an oration by Henry
Coppet, LL.D., president of Lehigh University. (American
Chemist, August and September number.)
In the evening Prof. J. Lawrence Smith gave an address,
"A Review of the Century's Progress in Industrial Chemistry."
In presenting the "Chemical Industry of Coal" he stated that
"it was started by two individuals of practical mind, Murdock
in England and Le Bon in France, who sought to control the
gaseous products emanating from burning coal in such a manner
as to be useful for illuminating purposes. The direct effect of
this was to convert night into day, and to make the short and
obscure days of winter equal to those of summer, and to enable
those occupied with indoor pursuits to conduct their labors with
less fatigue to the eyes and more certainty of execution." He
also enlarged upon the coal-tar dyes, the first of which, mauvein,
had been discovered by Perkin eighteen years before, in 1856.
He stated that the annual production of these dyes had already
reached $10,000,000, and that the production of artificial alizarin,
but little known and of no commercial value in 1870, had during
the past year reached 1000 tons, with a standard of 10 per cent
of alizarin, worth upwards of $4,000,000, one-half of which was
produced in Germany.
THE SECOND DAY'S PROCEEDINGS. OXYGEN DAY, AUGUST 1—
Prof. J. L. Smith called attention to the claims of the Liebig
Memorial Fund. He reminded the chemists that while "Oxygen
Day" might be called the golden wedding day of general chem-
istry, the silver wedding day of organic chemistry came at about
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
393
the same time, and that the German chemists were going to
celebrate it as a Liebig Memorial Day, attributing to him the
birth of organic chemistry fifty years ago.
Prof. Hosford, a pupil of Liebig at Giessen, contributed some
interesting reminiscences of his experiences.
Subscriptions amounting to $650 were announced, to be
devoted to the monument at Giessen.
American contributions To chemistry — Professor Silliman
began to write this address, with the idea of delivering it at the
meeting at Northumberland, but he became so interested in
the subject that only the introductory portion could be read
at the meeting. He actually gave an account of every chemist
in America who had ever published books or articles, down to
the end of 1874, giving the titles, dates and journals, with the
page numbers of each. This account begins with Priestley,
Franklin, and Count Rumford, and comes down to include the
chemists at the meeting, including 184 names, and covering 60
double column pages of the American Chemist.
I cannot leave this subject of the early chemists without
mentioning the wonderful industry which has been shown by
our president, Dr. Edgar Fahs Smith, in his biographies of
distinguished pioneer chemists.
I — "Chemistry in America." 356 pages. 1914.
2 — "The Life of Robert Hare." 508 pages, 1917.
3 — "James Woodhouse— A Pioneer in Chemistry — 1770-1809. "290 pages,
1918.
4 — "Chemistry in Old Philadelphia." 106 pages. 1919.
5 — "James Cutbush — An American Chemist — 1788-1823." 94 pages,
1919.
6 — "Priestley in America — 1794-1804." 173 pages, 1920.
In addition several works on inorganic, organic, and electrochemistry.
THE AMERICAN CHEMICAL SOCIETY
Early in 1876 it was suggested in informal conversation that
this might prove to be as favorable a time as any to organize
a professional society of chemists, theoretical and practical.
A list of chemists residing in New York and its vicinity, though
by no means complete, showed that there were at least one hun-
dred chemists in this neighborhood who might properly be
admitted as members to the proposed society. This decided us
to issue the following circular:
New York, January 22, 1876.
Dear Sir: — For some time past many chemists of this city and vicinity
have felt the want, and deplored the absence of an association, such as
exist among other professions, which would lead to a better understanding
and a closer acquaintance among its members; in which scientific and
practical subjects relating to our special science might be discussed, and
means devised in the common interest of the profession
Widely scattered as the chemists in this neighborhood are, such an asso-
ciation would become the center of a pleasant personal intercourse, and of
an interchange of views, experiences, and researches which would benefit
all concerned.
The undersigned, believing the present an opportune time for estab-
lishing a "Chemical Society" in New York, respectfully invite your co-
operation, and would be pleased to receive an early expression of your views
on the subject. As soon as a sufficient number of assenting replies have
been received, it is proposed to call a meeting for the purpose of forming
a permanent organization.
Chas. F. Chandler Henry Morton
W. M. Habirshaw Isidor Walz
H. Endemann F. Hoffmann
M. Alsberg P Casamajor
In response to this circular we received about forty verbal or
written assurances of sympathy and cooperation. Gratified
by the unexpected interest shown, the committee decided to
make an attempt to form a national instead of a merely local
society; and in order to test the disposition of the chemists in
the country towards such a project, the committee invited a
further number of members of the profession to take part in its
deliberations, which resulted in issuing a second circular, dated
March 22, 1876.
This circular was accompanied by a draft of a Constitution
and By-laws which the committee prepared on the model of
those of the German and French chemical societies. This
circular was mailed to out-of-town chemists on March 28.
Favorable replies were promptly received from more than fifty
of the leading nonresident chemists in the country.
A meeting for organization was called for April 6, 1876, and
was held in my lecture room in the College of Pharmacy on
Washington Square.
There was some hesitation on the part of some of the chemists
present who feared that such a society might diminish interest
in the New York Academy of Sciences. Dr. Endemann said
that the N. Y. Academy had a fine library, but no chemical books.
Dr. Alsberg said the Chemical Section of the American Associa-
tion for the Advancement of Science did not fill the want which
we wished to supply.
William H. Nichols said that we did not come there expecting
to find a society ready formed, with a library and a fine building;
those would come in time. He thought there was enough en-
thusiasm among the chemists to give us them by-and-by. "We
have much intelligence assembled here, and that is better than
a library." He could see that much benefit would accrue to
all branches of the profession from such a society as that proposed.
"A few years ago an Association of manufacturing chemists
was started, which had not half the reasons for existence this has,
being intended for sociability only; yet it had proved valuable,
and endeared itself to all its members. Let us begin this society
small, let it do its work well, and it will undoubtedly grow."
After a little further discussion, the Constitution and By-
laws were submitted by the committee, taken up article by
article, voted on, and approved.
Thus the American Chemical Society was born and clothed,
and in its right mind. The second meeting for organization
was held on April 20.
Edward P. Eastwick was elected president pro tern. A
nominating committee submitted a list of officers to be voted
upon. The president appointed William H. Nichols and H.
Endemann as tellers. The following officers were elected unan-
imously:
President: John W. Draper.
Vice Presidents: J. Lawrence Smith, Frederick A. Genth, E. Hilgard .
J. W. Mallet, Charles F. Chandler, Henry Morton.
Corresponding Secretary: George F. Barker.
Recording Secretary: Isidor Walz.
Treasurer: W. M. Habirshaw.
Librarian: P. Casamajor.
Curators: Edward Sherer, W. H. Nichols, Frederick Hoffmann.
Committee on Papers and Publications: Albert R. Leeds, Hermann
Endemann, Elwyn Waller.
Committee on Nominations: E P. Eastwick, M. Alsberg, S. St. John,
Charles Froebel, Charles M. Stillwell.
The first regular meeting after the Society was organized
was held on May 4, 1876. At this meeting the first chemical
paper was read by Dr. H. Endemann, one of the chemists of
the Health Department, on "The Determination of the Relative
Effectiveness of Disinfectants."
During the first year, the proceedings of the Society, and
the papers read before it, were published monthly in the American
Chemist, and the columns of type were used to print off separate
additional copies in pamphlet form for the members of the
Society.
The Society continued to grow rapidly, and at the end of
April 1877 it decided to publish its own journal. As there was
no further object in publishing the American Chemist, my
brother and I decided to discontinue it.
Since that April the American Chemical Society has pros-
pered, until now it is by far the largest chemical society in the'
world, having 15,000 members. Meetings are held regularly
by fifty-five local sections throughout the United States and
Canada.
Instead of publishing one chemical journal, it now publishes
what no other society does — three distinct journals:
(1) The Journal of the American Chemical Society — Devoted
to articles on general, physical, inorganic, organic, and biological
chemistry, edited by Arthur B. Lamb and twelve associate
editors. This journal is now in its forty-third year.
394
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
(2) The Journal of Industrial and Engineering Chemistry—
Edited by Chas. H. Herty, his assistant editor, Lois W. Wood-
ford, and seven members of the Advisory Board. Published
monthly. Now in its 13th year.
(3) Chemical Abstracts — Edited by E. J. Crane, associate
editors, Elmer Hockett and Helen Game, forty-five assistant
editors and 240 abstractors.
In addition to the abstracts prepared by these workers, the
editor has made a cooperative agreement by which he receives
abstracts from the editors of the Journal of the (London) Chemical
Society, the London Journal of the Society of Chemical Industry,
and the Journal of the American Ceramic Society.
This journal is in its fifteenth year and appears twice every
month. The abstracts come from every chemical periodical
published, and include United States, British, and German
patents. Everything is classified under thirty different heads,
for ready reference.
THE CHEMISTS' CLUB
The Chemists' Club, although a New York corporation and
located in New York City, is by no means a local institution.
It is national in its scope. It aims to serve all chemists in the
United States. It was founded in 1898 with a total membership
of 89; its present membership is 1800. In the beginning it
served as a center at which all the various chemical and allied
societies in and about New York held their local and general
meetings. Its quarters were then at 108 West 55th St., and
apart from the auditorium and the social room, it possessed only
a library and reading room.
Gradually but certainly, its usefulness expanded, and the need
for larger quarters became more and more pressing. It was not
until 1911, when, through the magnanimous action of many of
its friends, and particularly the late Prof. Morris Loeb, it was
housed as at present, in the Chemists' Building. Its quarters
are most centrally located in an eleven-story fire-proof structure,
of which the Club occupies the lower five floors. The upper
six floors are let to chemists for offices and laboratories, probably
the only building in the .United States that provides for and
prefers chemists as tenants.
In addition to the large auditorium known as Rumford Hall,
with a seating capacity of 310 and equipped with ample demon-
stration and lecture-illustration facilities, there is provided a
large pleasant library, containing 24,000 volumes, including 800
journal sets.
The Club's restaurant is unsurpassed. It has also a large
social room, a delightful roof garden in the summer, and two floors
of guest rooms, which are available to members, resident and
nonresident, with the best of hotel service.
Members, resident and nonresident, may frequently obtain
the temporary use of furnished laboratories in the building, thus
assuring themselves of all the privacy and security of their own
laboratories at home. The library is accessible to members at
practically all hours of the day.
The Employment Bureau, in recent years an incorporated
body, with the Club officers as its officers, is now a licensed
employment agency. It aims not only to provide employers
with routine chemists, but to bring members of the profession,
whether recent graduates or specialists of many years' experience,
into touch with opportunities in their own branch. Positions
to the number of 50 to 100 are constantly on file with the Bureau,
and these cover the whole field of industry. From seven to
eight hundred men are always registered in the office.
In short, the Chemists' Club is a place where chemists are
made cordially welcome, and are provided, under one and the
same roof, with everything that pertains to their professional
activity, and at the same time provides them with very desirable
living quarters and the opportunity for social intercourse.
The record at the new Club House shows that nonresident
members are increasingly availing themselves of and benefiting
by these unique advantages. It confirms the judgment of those
who so generously aided in making the present quarters a reality,
namely, that the Chemists' Club is in fact a national institution
in every respect.
THE AMERICAN INSTITUTE OP CHEMICAL ENGINEERS
This society was organized at Philadelphia, June 22, 1908.
The membership is about 350, of whom about 60 reside in New
York City. The president is David Wesson of Montclair, N. J.
THE AMERICAN ELECTROCHEMICAL SOCIETY
This society was organized April 3, 1902. The membership
is about 2200, of whom the larger number reside in New York City
and Philadelphia. The president is Walter S. Landis, Beech-
hurst, Long Island, N. Y.
THE SOCIETY OF CHEMICAL INDUSTRY (LONDON, ENGLAND)
This was established in 1881. President, Sir William J. Pope.
1 — To promote and advance applied chemistry and chemical
engineering in all their branches.
2 — To afford members of the society opportunities for the inter-
change of ideas with respect to improvements in the various
chemical industries, and for the discussion of all matters bearing
upon the application of chemical science.
3 — For the publication of information connected with these
subjects.
Its journal is issued fortnightly. It contains original papers
read before the various sections, abstracts from other journals
and transactions, with British, French, German, and United
States patents classified under twenty-four heads.
The Society has eighteen sections where local meetings are
held, five Canadian, and one American, which was founded
August 30, 1894. The chairman of the American Section is
S. R. Church. The American section numbers about 850 members,
and the following Americans have been elected president of the
Society.
Charles F. Chandler 1S99-1900
Wn.LiAM H. Nichols 1904-1905
Ira Remsen 1909-1910
Marston T. Bogert 1912-1913
SOCIETE DE CHIMIE INDUSTRIELLE (PARIS, FRANCE)
The American Section was established January 8, 1918.
The Society publishes a monthly journal.
CHEMICAL EDUCATION
About the middle of the last century a movement began to
provide special instruction for young men desiring to become
chemists. The Yale Scientific School, at New Haven, and the
Lawrence Scientific School, at Harvard College, were established.
The demand for such instruction was very limited, as were
also the facilities provided.
My taste for chemistry was developed by an excellent teacher
in the New Bedford High School, a young Mr. Hemingway.
He made the subject fascinating. I turned my little workshop
into a laboratory, devoted all my spending money to the pur-
chase of apparatus and chemicals, and with two or three of
my boy companions devoted all my Saturdays and other spare
time to experimenting.
My father and mother became satisfied that this was a real
interest and desire to become a chemist, and they offered to do
what was within their means to give me the necessary oppor-
tunities. So in the autumn of 1853 I entered the Lawrence
Scientific School, where I studied under Prof. E. N. Hosford.
He was a delightful friend to the half dozen boy pupils; but the
number was so small that no lectures were given us. What was
very remarkable was that we were not permitted to attend the
chemical lectures given to the undergraduate college students. It
was apparent to us that "Scientific" students were regarded
as inferior to classical students. Prof. Hosford came to us
daily in the laboratory and directed our work. We went through
a course of laboratory work in qualitative analysis, analyzing
the 100 bottles of unknown contents. We also made a good
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
395
beginning in quantitative analysis. That was as far as we could
go.
Fortunately we boys heard of the advantages offered by the
laboratories of the German universities. Two of us went over
in 1854 to Gottingen, were warmly received by the great Wohler,
and were at once admitted to his advanced laboratory, where
twenty-five or thirty young men were at work. There was
another laboratory where about one hundred young men were
receiving instruction.
We received direct assistance daily from Wohler himself,
besides which we received six lectures a week from him in com-
pany with about two hundred other young men, besides attending
lectures by other professors on cognate subjects. There were
seven or eight other American students in the laboratory, and
at the beginning of the second term two more of our fellow stu-
dents came over from the Lawrence Scientific School.
The following year I spent in Berlin, in the private laboratory
of Heinrich Rose, attending his lectures as well as those of several
of his colleagues.
I have enlarged upon this experience because it shows that
Germany realized the importance of professional chemists,
even at that early day. There were several other German
universities to which American students desiring to become chem-
ists were attracted, as there were also several mining schools
for the education of mining engineers and metallurgists. It
was not until 1864 that the first mining engineering school
was established in the United States at Columbia University
in New York City.
THE COAL-TAR DYE INDUSTRY
We can understand from this how it happened that although
the coal-tar industry started in England in 1856, it was promptly
monopolized in Germany, where there were a host of chemists,
old and young, to devote themselves to its development. The
cost of living was low, salaries were very moderate, and there
were many well-equipped laboratories. Very soon the German
chemists began to invent new dyes and synthetic medicines,
which they distributed to other countries. They also took out
local patents in other countries to prevent the manufacture of
their products by others. Some dyes and synthetic medicines
were invented in other countries.
After the foreign patents expired, it was still very difficult or
impossible to make these products in competition with the
German inventors. The language of the German patents
was carefully selected for the protection of the inventor, and
not to instruct other chemists how to practice them. So the
manufacture of dyes and synthetic medicines did not really
flourish outside Germany.
We had in this country a few manufacturers who succeeded
in putting certain goods on the market at a profit, so there was
a modest coal-tar industry in this country when the recent war
broke out.
As the German chemical works were promptly appropriated
by their government for the manufacture of explosives and
other materials and later for making poison gases, our supply
of German goods was cut off, and our enterprising chemical
manufacturers immediately entered the field to manufacture
and supply them. They have been very successful.
The companies supplied the capital, and hundreds if not thou-
sands of chemists turned their attention to coal-tar chemistry,
with great success. The most important synthetic dyes,
such as alizarin, artificial indigo, and several hundred
other most important products are now made here of ex-
cellent quality, and supplied at reasonable prices. Many millions
of capital have been invested and some thousands of men have
been trained to the business. And the war is over.
Those numerous dye and color works which the German
government took over for war purposes, and the numerous
new chemical works that were built are no longer wanted for
war purposes. They will go back to the work of making dyes
and synthetic medicines, for which the makers must find a
foreign market, or go out of business. They can work cheaper
than English or American manufacturers can, the costs of living
are lower, and unless our Government takes some action, our
new industry will be destroyed. The Germans can undersell
us and still make a profit. But they can go further, they can
sell their goods for a time at half or a quarter of their cost, by
what we call "dumping" their goods on our market.
Suitable legislation is now before Congress, but a certain
amount of opposition has arisen against its passage from persons
who do not realize what an advantage it is to this country to
maintain this comparatively new industry.
Some persons interested in the textile industries claim that
they have a right to buy their dyes where they can get them
cheapest. They forget that the textile interests are protected
from competition by import duties of 10, 20, 30, 40, 50 and some-
times even larger percentages of import duties. Two or three
billion dollars' worth of textile goods, cotton, woolen, and silk
are manufactured in this country per year, and only a few million
dollars' worth are imported.1
Another important consideration has recently appeared in
print. The cost of dyed goods will not be materially increased by
any import duty that will be required to protect our chemical in-
dustries. Dr. Louis J. Matos has published in Drug and Chemical
Markets an article in which he shows what the actual increase
in cost would be. For a man's all-wool suit, there are required
3.75 yards of 54-in. cloth, which would weigh about 5.13 pounds,
or 82.08 ounces. To dye this black 6 or 7 per cent of dye would
be required, or 6.5 ounces. A good black dye would cost $1.35
per pound or 8.42 cents per ounce and the actual cost for the
amount of dye necessary for the suit would be 48.4 cents.
Suppose the cloth is dyed navy blue. About 3.5 per cent or
2.87 ounces of dye would be required. The cost for the chrome
blue would be about S3. 03 per pound, or 19 cents per ounce,
or 54.53 cents for the suit. Using fancy shades, 3 per cent of
dye would suffice, or 2.46 ounces at $1.25 per pound or 7.77
cents per ounce. The cost would be 19.11 cents per suit.
With worsteds the situation is about the same. A suit re-
quiring 3.75 yards of cloth, 54 inches in width, will weigh 5.81
pounds, or 92.96 ounces. To dye a good black shade would
require 6 to 7 per cent of dye, or 5.75 ounces, costing 54.75 cents.
Navy blue, with a 3.5 per cent shade, requires 3.4 ounces, cost-
ing 61.75 cents. Fancy blue shades require 3 per cent of dye
weighing 2.78 ounces, and costing 21.6 cents per suit.
It thus appears that for dyeing an average suit of woolen clothes
for a man, the actual cost of the dyestuff required for black,
navy blue, or fancy blues will vary from a minimum of about
19 cents to a maximum of about 62 cents.
Any duty that could be placed on these dyes to prevent the
destruction of the American dye business and ruin of investments,
even if it were 100 per cent, would be worth considering, for
the welfare of our country, in sustaining our coal-tar chemical
industry. But to prevent dumping of synthetic dyes, medicines,
and intermediates, below cost, to drive our manufacturers out
of business, some special regulations in addition to duties will
be required.
CHEMICAL RESEARCH
Chemical research has expanded to enormous proportions in
recent years.
The most important investigations in agricultural questions
have been conducted by the U. S. Department of Agriculture
under the direction of Harvey W. Wiley, and at the Experiment
Stations.
The work of Prof. Thomas B. Osborne on the proteins and
vitamines is monumental. Teller's work on the proteins of
the wheat kernel, Atwater's studies on the nitrogenous con-
1 See Summary of Tariff Information, 1920, Government Printing Office.
396
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
stituents of meat, and Browne's work on the butter fats are all
most comprehensive. Atwater's respiration calorimeter has
made it possible to study successfully the metabolism of energy
in the body. The study of the physiological effect of creatine
and creatinine by Prof. J. W. Mallet has thrown a new light on
physiological chemistry.
Sanitary chemistry, the treatment of sewage, and the care of
our water supplies have now been reduced to sound scientific
practice.
Research in industrial chemistry has advanced wonderfully
in the past few years.
One of the best illustrations of this progress is the work of the
Mellon Institute of Industrial Research of the University of
Pittsburgh. Its fellowship system is unique. It originated
with Dr. Robert Kennedy Duncan in 1906, and was placed in
operation at the University of Kansas in 1907, and at the Uni-
versity of Pennsylvania in 1911. In 1913 Andrew William
Mellon, now Secretary of the U. S. Treasury, and Richard
Beatty Mellon, banker of Pittsburgh, established it on a perma-
nent basis in the Mellon Institute of Industrial Research.
The number of industrial fellowships has increased from
.eleven in 1911 to forty-eight in 1920 to 1921. The number
.of Fellows has increased from twenty-four in 1911 to eighty-
three in 1920.
One hundred and sixty-five United States patents have al-
ready been issued for improvements in industrial chemistry by
these "Fellows."
There are many other such research institutions, in which
■similar investigations are being conducted, for example:
The Eastman Laboratory of Industrial and Engineering
Chemistry, in Rochester, C. E. Kenneth Mees, director; the
Laboratory of the General Electric Company at Schenectady
under the direction of Willis R. Whitney; the Food Research
Institute, founded by the Carnegie Foundation.
Then there is the Research Information Service of the National
Research Council in Washington. This is a clearing house for
-information about the mathematical, physical, and biological
■sciences and their applications in industry, commerce, and
.education. The chemical director is Charles L. Reese of
E. I. du Pont de Nemours & Company.
Among the advisory members of the Research Information
Service are some of our own members:
C. L. Alsberg, Chief, Bureau of Chemistry, Department of Agriculture.
F. G. Cottrell, Chairman, Division of Chemistry, N. R. C.
A. D. Little, President of Arthur D. Little, Inc.
V. H. Manning, Director of Research, American Petroleum Institute.
M. C. WhitakER, Consulting Chemical Engineer.
These are but a few of the more important organizations for
.encouraging and facilitating chemical research. There are
many more.
THE CHEMICAL FOUNDATION, INC.
The Chemical Foundation is a corporation organized at the
■suggestion of the Alien Property Custodian, by members of the
American Dyes Institute, the American Manufacturing Chem-
ists' Association, and other gentlemen engaged in various
branches of the chemical industries, to buy from the Alien Prop-
.erty Custodian and hold for the chemical industries and for the
country at large, the German-owned United States chemical and
allied patents taken over by the Alien Property Custodian under
■the amendment of November 4, 1918, of the "Trading with the
Enemy Act."
The company is a Delaware corporation, capitalized at
$500,000, of which $400,000 is preferred stock, and $100,000
common stock. Each of these stocks is limited so that it can
(receive no more than 6 per cent dividends.
The officers and directors of the Foundation are as follows:
President: Mr. Francis P. Garvan (Former Alien Property Custodian).
■Vice President: vCol. Douglas I. McKay (Late Colonel, General Staff,
Vice President of J. G. White & Co., and Deputy and Police Commissioner
of the City of New York, under Mayors Gaynor, Kline, and Mitchel).
Treasurer and Secretary: Mr. George J. Corbett (Assistant Secretary,
Central Union Trust Company).
These gentlemen are for the present serving without salary.
For its patent counsel the Foundation has retained Mr. Ramsay
Hoguet, of the New York firm of Emery, Varney, Blair & Hoguet,
to whom, as patent counsel for the Alien Property Custodian,
has been due the successful accomplishment of the enormous
task of finding and transferring the German patents. The
general counsel of the company is Mr. Joseph H. Choate, Jr.,
who for the past year has been entirely occupied in the chemical
part of the work of the Alien Property Custodian's Bureau of
Investigation.
The chief chemist is Prof. Samuel A. Tucker of Columbia
University, who served as war chemist at Washington during
the war.
The members of the American Dyes Institute and the Manu-
facturing Chemists' Association have placed themselves on
record as willing to take the entire capital stock of the Foundation,
and have provided in advance so much of the capital as was
required for the purchase.
To the Foundation as thus organized, the Alien Property
Custodian has sold for the sum of $250,000 substantially all of
the German dye and chemical patents, seized by him, except
those which were included in the sale of the Bayer Co., Inc., which
took place before the organization of the Foundation. The
patents cover a very wide field, the classification including
metallurgy, fertilizers, fixation of nitrogen, hydrogenation of
oils, etc., and number approximately 4500. They will be used
to encourage manufacture in this country and discourage im-
portation from Germany. The Foundation will issue non-
exclusive licenses under them, on reasonable and equal terms,
to manufacturers whose Americanism and competence are
unquestioned. It will also prosecute with all possible vigor
suits against all persons who attempt to import any infringing
product. Since many of the patents are product patents, the
Foundation should be able to exclude infringing goods from any
source whatever, and should thus be able to give partial pro-
tection to a part, at least, of the new American dye industry.
In addition to the patents, the enemy trade-marks taken over
by the Alien Property Custodian have likewise been sold to the
Foundation. A plan is being formulated under which it is hoped
that the Foundation will be able to license American manu-
facturers to use these trademarks. The intention is to issue
such licenses only when the goods to which the mark is to be at-
tached are found, on examination by the Foundation itself, to be
equal or superior to those of the original owner.
The Foundation has also purchased from the Custodian
the German copyrights covering some of the indispensable
literature of science. By this means it should be able to render
many of the necessary scientific publications vastly more acces-
sible than at present. The Foundation also has power, under
its charter, to purchase new patents, and it is hoped that this
may become an important field of its activities. It seems clear
that an immense stimulus will be offered to chemical invention
by the provision of such a disinterested and impartial possible
purchaser; at the same time, such transactions would be valua-
ble to the public at large, as all inventions thus purchased
would be available for immediate use by any suitable manu-
facturer, and could not be suppressed.
The chief usefulness of the Foundation, however, is expected
to be as a center of research. Its charter provides that after
the redemption of the preferred stock, the free net earnings of
the Corporation shall be "used and devoted to the development
and advancement of chemistry and allied sciences in the useful
arts and manufactures in the United States." If the patents
turn out to be as valuable as it is hoped, this provision should
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
397
Good Fellowship Gathering in Assembly Hall of Bausch & La
render a considerable income available for research purposes,
and for this work the Foundation is in a position of unique
advantage.
The most important subject for this meeting to consider is
how to aid in securing the passage of the Longworth Bill to pro-
tect the chemical industries of this country which is now before
you. It is absolutely indispensable to our safety.
It was difficult to realize that the distinguished
chemist who addressed this meeting with so firm and
strong a voice and youthful bearing could be old enough
to have witnessed not only the beginning of the Society,
but practically the beginning of chemistry in America.
Dr. Chandler in the eighty-four years of his life has
been one of the most active factors in the growth of
chemistry in the United States. When he concluded
his address the audience again rose, and after prolonged
applause Dr. Smith thanked Dr. Chandler on behalf
of those assembled for his splendid message and pre-
sented him with a beautifully bound copy of the thesis
which Dr. Chandler had presented for his degree of
doctor of philosophy sixty years ago.
SECTION OF HISTORICAL CHEMISTRY
Following out a happy inspiration of President E.
F. Smith and Dr. C. A. Browne, a group of men met
as an informal section on the history of chemistry,
Wednesday morning, April 27. An attendance of
twenty-five showed a decided interest in this phase of
chemistry which is now attracting renewed attention
abroad and in this country.
Dr. Smith in explaining the object of the meeting
drew only too briefly upon his great store of informa-
tion regarding the development of chemistry in America.
He showed an early chemical work in Latin bearing
the date of 1671, characterized by the unusual ending
for a scientific book, "All Honor and Glory to God,
the Keeper of the Earth."
Dr. Smith spoke also of W. W. Mather, whose paper
on the atomic weight of aluminium was the first atomic
weight work done in the United States. In concluding
his remarks. Dr. Smith showed an interesting collection
of autograph letters by Priestley, Robert Hare, Th.
Cooper, Berzelius, Chaptal, Davy, and others.
Dr. Browne mentioned that the history of chemistry
in America could be traced back to John Winthrop, Jr.,
whose collection of old works on chemistry and alchemy
in the New York Society Library is the oldest chemical
library in the United States. He gave also an account
of the life and work of Fred. Accum, a London chemist
in the early days of the last century, a man of interest
to Americans in that it was in his laboratory that
Silliman, Dana, Peck, and others received their training
in analytical chemistry. Accum was a pioneer in the
detection of the adulteration of foods, and a copy of
his book was shown with its famous frontispiece bear-
ing the legend of "Death in the Pot," a work that
awakened England to the dangers of such gross adul-
teration.
Dr. Browne favored the section with a sight of a
few of his treasures, such as a miniature of J. Priestley
of about 1780, Eaton's "Chemical Instructor," one of
the early purely American publications, and autograph
letters of Dalton, Priestley, Rumford, Parkes, Silliman,
and Davy.
Prof. F. O. Rice of N. Y. University gave a short
account of the taking by Prof. Draper of the daguerre-
otype of his sister, the first picture of a living subject.
Prof. F. B. Dains described briefly the choice old
chemical and medical library of Transylvania Univer-
sity in Lexington, Ky.
398
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
Another speaker mentioned the discovery of vana-
dium by Del Rio, a Mexican chemist of 120 years ago.
Among other speakers were Dr. E. C. Franklin, Dr.
F. J. Moore, and Father George L. Coyle. The meet-
ing was a great success, and it was agreed that, without
any formal organization, such a symposium should
be planned as one of the features of future conventions
of the Society. For the training of American chem-
ists, one of the things needed is a proper appreciation
of the historical and human side of our great science.
MEETING OF ABSTRACTORS
A dinner meeting of the editors and abstractors
comprising the staff of Chemical Abstracts was held
Wednesday evening, and was well attended. Dr. E.
J. Crane, the editor of this publication, was the chair-
man of the meeting, and after the dinner he called
upon the assistant editors and abstractors to tell some-
thing about themselves and particularly about their
work on Chemical Abstracts. G. E. Barton and L. A.
Olney, who have served faithfully as assistant editors
since the beginning of this journal in 1907, reminisced
at some length on the first years of the publication.
W. E. Henderson referred to the splendid spirit of
cooperation and service which is playing so large a
factor in making Chemical Abstracts the peer of all
scientific abstract publications. Many" valuable sug-
gestions for furthering the work of the journal were
offered during the course of the meeting.
MEETING OF CHAIRMEN AND SECRETARIES OF LOCAL
SECTIONS
A fairly well-attended meeting of the chairmen and
secretaries of local sections of the Society was held at
the Mechanics Institute Thursday, April 28, at 3 p.m.
A similar meeting had been held at the St. Louis con-
vention for the first time, and although interest seemed
to have waned in such a gathering of local section men at
the Chicago convention, it was considerably revived at
Rochester. Dr. R. H. McKee of New York acted as
the chairman of the meeting and Edgar B. Carter of
Indianapolis, as secretary. A great many topics of
interest to section officers, particularly with regard to
the arrangement of programs, etc., were discussed,
and it was the general feeling that a permanent organi-
zation of section officers should be formed. Accord-
ingly the officers of this meeting were instructed to
prepare a set of by-laws and take the necessary steps
to form this organization into a section of the parent
Society. Dr. G. N. Lewis was elected chairman for
the ensuing year and Mr. Carter was continued as
secretary. Among the topics discussed were the possi-
bility of interchange of speakers, arranging for popular
lcctures on chemistry in various cities where sections
of the A. C. S. are located, methods of interesting
college students as well as members of the Society in
the meetings of the sections, methods of promoting
discussion at meetings, and the possibility of holding
annual section outings. The expressions of those who
attended clearly indicated the value of such an inter-
change of thought and experiences on the part of those
who are charged with conducting and keeping up
interest in local sections.
ENTERTAINMENTS
In conformity with the vote of the Society at its
Chicago meeting, the Rochester Section was instructed
to reduce entertainment features to a minimum. Al-
though this request was reluctantly complied with by
the Section, they nevertheless found time for several
entertainment features which will help to make the
Rochester meeting memorable to all those who at-
tended. College, fraternity, and other group dinners
were arranged for Tuesday evening. An entertain-
ment for the ladies was given in the Ad Club rooms
of the Hotel Rochester on Tuesday afternoon. This
entertainment took the form of a tea and musical. All
of the members and friends of the Society took part
in the great "good fellowship" meeting at the Bausch &
Lomb building Thursday evening. This was one of
the most magnificent affairs ever staged by any section,
and included a wide variety of entertainment. The
evening began with a dinner served in the Bausch &
Lomb dining hall where nearly two thousand people
sat down together and enjoyed instrumental music
and selections by the University of Rochester Glee
Club while the dinner was being served. Later a
general entertainment took place in another portion of
the building, and the variety as well as the quality of
the numbers was pleasing to all. The vaudeville enter-
tainment was followed by moving pictures of unusual
interest which were shown for the first time before this
gathering. Dancing concluded the program.
EXCURSION'S
The arrangement of concentrating all of the excur-
sions in one day, thus making it possible for the mem-
bers to devote their time to section meetings without
missing any excursions, and vice versa, worked out very
successfully. Friday was set apart for the excursions,
and a majority of the members in attendance stayed
over to take part in one or more of them. The pro-
gram included trips to:
Bausch and Lomb Optical Company
Pfaudler Company-
Gas Plants— Rochester Gas and Electric Corporation
Municipal Garbage Disposal Plant
Municipal Sewage Disposal Plant
Bastian Brothers
Eastman Kodak Company, Kodak Park Works
General Excursion
Synthetic Organic Chemical Department
Taylor Instrument Companies
Laboratory Equipment
Industrial Apparatus
High Temperature Apparatus
Vacuum Oil Company
Bartholomay Company — Baskerville Refining Process
Division and Section Meetings
Two full days of the convention were given over to
Division and Section meetings of the Society. The
Fertilizer Division and the Leather Section did not
meet. Both groups are planning for interesting pro-
grams in September.
A complete list of the paperi presented is published
on pages 480 to 483 of^this issue. Short accounts of
these meetings follow:
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
399
DIVISION OF PHYSICAL AND INORGANIC CHEMISTRY
This division held two sessions on Wednesday^and Thursday,
presided over by H. N. Holmes, chairman. The program con-
tained 64 papers, and nearly all were read. One session of the
meeting was devoted to a symposium on contact catalysis under
the chairmanship of Professor W. D. Bancroft. The outcome
of several war problems on acid production and nitrogen fixation
was discussed in this symposium, including a report on "Dis-
sociation of Some Mixed Oxides" by J. C. Frazer. There was a
lively discussion on the function of adsorption in contact catalysis
and on the effect of agitation. Catalysis in the production of
water gas was dealt with by H. S. Taylor and R. N. Pease.
The general papers covered a wide range of subjects, includ-
ing analysis and atomic weight determinations, and particularly
colloid chemistry. It may be fairly said that the papers showed
definite progress in the development of quantitative methods
and conceptions in the study of colloids. The papers by G. S.
Clark and his collaborators, by R. H. Bogue and by H. B. Weiser
illustrated this, while another contribution in the same direction
was E. C. Bingham's extension of the conception of plastic flow
to the viscosity of emulsion colloids. The latter's work on the
properties of cutting fluids was of great practical interest and,
together with the discussion, showed the importance of factors
other than viscosity in the matter of lubrication. Dr. Bingham
considered that his results supported the view developed by
English investigators that groups or molecules having residual
affinity cementing them to the metal were essential, he considered,
however, that the essential property was not limited to free fatty
acids. In connection with emulsions the most spectacular ex-
hibit was that of Dr. H. N. Holmes, whose "Chromatic Emul-
sions" aroused great interest. These emulsions are produced
by emulsifying one liquid in another in which it is insoluble, the
dispersive power for light of the two being varied over certain
intervals.
A notable piece of work on the determination of atomic weights
was that of H. S. Booth, whose paper was entitled "The Atomic
Weight of Nitrogen by the Thermal Decomposition of Silver
Trinitride." The ratio N: Ag was measured from the compound
AgNs, in face of the almost insuperable difficulties involved in
dealing with a material which, while highly explosive, had to be
handled in complete darkness.
The business meeting of the Division developed certain pro.
posals for the rearrangement of the program at future meetings.
DIVISION OF ORGANIC CHEMISTRY
The program of this Division was unusually interesting and
the variety of subjects discussed was large. Out of forty-one
papers, thirty- three were delivered by the authors at the meeting.
The attendance varied from about forty to eighty.
During the business portion of the session, on Wednesday
morning, a resolution was unanimously adopted requiring
authors to submit short abstracts of their communications be-
fore these can be included in the program.
The chairman reported progress for the committee appointed
to organize the preparation of cooperative pamphlets on synthetic
organic preparations, and announced that the manuscript of
the first of these bulletins was now complete and would shortly
be in the hands of the publishers.
A somewhat extended discussion took place on the policy of
the Division, with especial reference to members associated with
the universities, regarding the purchase of research chemicals
from abroad. The general sentiment prevailed that no such
supplies should be purchased abroad when it was known that
they were obtainable in this country. Every effort should be
made to ascertain before ordering whether they are available in
the United States. It was urged by several members that
there should be compiled and issued a periodical bulletin enumer-
ating every organic chemical useful for research purposes which
can be supplied from domestic sources. It was also suggested
that a list should be drawn up of materials required, but not
obtainable here. It was resolved that the secretary be instructed
to take up the question with representatives of the National
Research Council and appropriate governmental departments.
At the meeting on Wednesday afternoon the secretary was able
to report that a committee had been appointed by the chairman
of the Chemical Division of the National Research Council to
consider this work, Dr. W. D. Collins to act as chairman.
An appeal was made to organic chemists to assist the study
of the chemistry of petroleum by accurate determination of the
physical properties of hydrocarbons prepared during the prog-
ress of other researches. Information so obtained would be
greatly welcomed by Dr. A. C. Fieldner of the Bureau of Mines
in Pittsburgh.
DIVISION OF INDUSTRIAL AND ENGINEERING CHEMISTRY
In many respects this meeting of the Division was the most
successful in its history. The second of the symposiums on
chemical engineering subjects was held, and it was devoted to the
subject of drying. Both a large attendance and an interesting
discussion were attracted. The general papers covered a wide
range of topics which brought out an unusual number of ques-
tions and long discussion.
In the business session the resolution adopted by the Council
relative to the submission of papers in advance was approved,
and it was decided that beginning with the next meeting of the
Society all papers referred to this Division should be submitted
sufficiently in advance to allow them to be reviewed by a com-
mittee. This review will be made with reference to the suit-
ability of the paper for a general meeting and whether it shall
be given in abstract or in full. The Division held meetings on
Wednesday afternoon and Thursday.
DIVISION OF RUBBER CHEMISTRY
Two sessions were held by the Division of Rubber Chemistry
under the chairmanship of W. W. Evans. Almost the entire
first day was devoted to a discussion of methods for the analysis
of rubber goods. It is the desire of the Division to have ready,
in the near future, tentative methods for standard analytical
procedure. Various methods dealing with different determi-
nations were discussed, and the following committee was ap-
pointed to formulate the first outline of analytical methods:
S. Collier, chairman, F. J. Dugan, A. H. Smith, W. Wiegand,
and H. E. Simmons.
It was the desire of many members of the Division that ab-
stracts of information on technical, manufacturing, and patent
articles, which cannot be printed in Chemical Abstracts, be sup-
plied in some form. A committee, consisting of W. W. Evans,
chairman, R. E. Hall, and C. W. Bedford, was instructed to
cooperate with the rubber trade journals so that abstract infor-
mation not published by Chemical Abstracts, because of limited
space or the nature of the articles, be published in the trade
journals.
The present accelerator committee was instructed to tabulate
all available information on accelerators and forward copies to
all members of the Division. A new committee on Physical
Testing was appointed, including the following members: C. O.
North, chairman, W. Wiegand, S. Collier, H. E. Simmons, and
E. H. Grafton. This committee was instructed to consider
primarily the standardization of test compounds for the testing
of rubber, the standardization of the manner of plotting stress,
strain, and curing curves for rubber, and the advancement of
other physical and mechanical tests by which rubber chemists
measure the degree of vulcanization.
The outstanding feature of the meeting was the increased
freedom with which the supposed secrets of the rubber trade
were discussed. It has been very noticeable during the last
400
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
two years that chemists have been cooperating to a greater
extent, and at this meeting in particular the spirit of cooperation
was manifest.
One of the striking developments at this meeting was the
increased use of the high-power microscope in the study of
rubber compounds. For high-grade rubber compounds, mag-
nifications of over one thousand diameters are necessary, the
rubber sections being cut 0.5 /j. thick to permit the use of trans-
mitted light.
It was the general feeling of the members of the Division
that thts meeting was the most successful held in the two
years of its existence, and that the future looks very promising.
DIVISION OF DYE CHEMISTRY
Two meetings of this Division were held on Wednesday and
Thursday, and besides the eleven papers presented there was a
very interesting discussion on the subject of cooperation with
government and other laboratories interested in color problems.
The meetings were presided over by A. B. Davis, chairman.
Dr. A. W. Joyce of the Chemical Foundation, New York, gave
some valuable information on "Dyes Derived from (3-Oxynaph-
thoic Acid and from J-Acid with Reference to the Chemical
Foundation Patents." The head of the chemical department of
the Tariff Commission of Washington, D. C, communicated
some interesting statistics on the imports of dyes from foreign
countries into the United States during 1920.
There was some feeling on the part of members of the Division
that insufficient attention was being given to the relation of the
dye industry to the textile industry. A suggestion was made to
change the name of the Division to the Division of Dye and Tex-
tile Chemistry, but no action was taken on this question.
A motion to appoint a committee of three, of which Dr. Derick
was to be one, for the purpose of bringing about cooperation of
the Dye Division with government laboratories and other insti-
tutions interested in color and textile problems was carried after
considerable discussion by Dr. C. L. Alsberg, chief of the Bureau
of Chemistry of the U. S. Department of Agriculture, Dr. C. G.
Derick, Dr. L. A. Olney, Dr. R. B. Moore, chief chemist of the
Bureau of Mines, and others. Dr. Alsberg stated that the Color
Laboratory of the Bureau of Chemistry would welcome any
cooperation on the part of the Dye Division in solving color
problems which confront the industries. The general tone of
the discussion indicated a desire on the part of all to bring those
working on these matters more closely together.
DIVISION OF BIOLOGICAL CHEMISTRY
Two sessions of this Division were held on Wednesday and
Thursday under the chairmanship of A. W. Dox. The program
was very interesting and contained a notable group of papers
dealing with the vitamines, which occasioned much interesting
and valuable discussion. The interest in vitamines is so great at
the present time and so much scientific work is being done upon
them that it was decided by the executive committee of the Di-
vision to run a symposium on vitamines at the New York meeting
of the American Chemical Society in September, under the
auspices of the Biological Division. Professor W. T. Bovie's
paper entitled "The Intensity of Light Necessary to Initiate a
Photochemical Change in the Retina," presented in collaboration
with E. L. Chaffee, also brought forth considerable discussion.
DIVISION OF CHEMISTRY OF MEDICINAL PRODUCTS
This Division held one meeting on Wednesday morning, at
which ten papers were read and one was presented by title. Dr.
Charles E. Caspari, chairman of the Division, presided. Inter-
esting discussions developed on the subject of derivatives of
arsphenamine presented by George W. Raiziss and J. L. Gavron.
New benzyl compounds used as substitutes for opium alkaloids
were also discussed. The question of securing proper clinical
evidence of results of the administration of various remedies
received some attention, and the discussion on the subject
resulted in the appointment of a committee of five to study the
subject of obtaining proper clinical evidence of the value of new
medicinal compounds. This committee is to report at the next
meeting of the Division. The committee consists of the follow-
ing: R. P. Fischelis, chairman, A. D. Hirschfelder, H. C. Fuller,
F. R. Eldred, and F. C. Taylor.
DIVISION OF WATER. SEWAGE AND SANITATION
A well-attended meeting of the Division of Water, Sewage
and Sanitation was held under the chairmanship of W. P. Mason
on Wednesday morning. An especially interesting paper entitled
"Reaction in the Dorr-Peck Tank" was presented by A. M.
Buswell. This paper was supplemented in the afternoon by a
trip to the Filtros plant near Rochester, where the manufacture
of filtros cells, etc., was fully demonstrated. The analysis of
mine and drain water was considered in a paper by J. A. Shaw
and N. A. Bailey.
The radioactivity of miscellaneous waters was discussed in a
paper by W. W Skinner and J . W. Sale. In this paper it was stated
that there are no markedly radioactive springs in the United
States and that it would be necessary to drink several thousand
gallons of water daily of even the most active of these waters in
order to obtain an approximate minimum dose of radium emana-
tion prescribed for therapeutic purposes.
DIVISION OF AGRICULTURAL AND FOOD CHEMISTRY
The Division of Agricultural and Food Chemistry held one
meeting on Thursday morning with C. E. Coates, chairman,
presiding. In the absence of the secretary, T. J. Bryan, Mr. F.
C. Cook was elected to act as temporary secretary. Of the
sixteen papers on the program, fourteen were read. The dis-
cussion of these papers was interesting and instructive. The
following resolution was adopted by the Division:
// is hereby resolved, That the action of the Sugar Section in
appointing a committee to revise the refractometer scale for the
determination of total solids in sirups be heartily approved,
That Dr. Coates, our chairman, is requested to confer with
Dr. Browne, the chairman of the Sugar Section, relative to the
membership of the committee.
SUGAR SECTION
The growth of interest in the work of the recently organized
Section of Sugar Chemistry is illustrated by the increasing
number of papers presented at the successive meetings. At the
first meeting in St. Louis twelve papers were presented, at the
second meeting in Chicago eighteen papers, and at the Rochester
meeting thirty-three. The growth in interest and members has
been such that the Section voted to petition the Council of
the Society that it be made a Division of the American Chemi-
cal Society at its next meeting.
The program of the Rochester Meeting contained papers
along several distinct lines. On the analytical side new forms
of sugar testing apparatus were illustrated by display material,
and new methods for estimating sugars, color, ash, etc., were
described. On the technical side, factory experiments in de-
saccharifying beet molasses, results obtained by decolorizing
carbons and infusorial earth in removing coloring matter and
colloidal impurities from sugar juices, methods of sampling
sugar liquors, causes of caking of sugars, filtration devices, and
other topics were discussed. The growing interest in the manu-
facture and standardization of rare sugars gave rise to five
papers. That the interest in the work of the Section is a widen-
ing one is shown by the fact that two contributions came from
France and one from St. Croix.
Four sessions were necessary to complete the work of the
Section. Owing to complications that may arise from the
increasing number of papers, a special committee was appointed
to arrange immediately for the program of the September
meeting.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
401
Owing to the common use of the refractometer in food and
sugar analysis, a joint committee was appointed by the Division
of Agricultural and Food Chemistry and by the Section of Sugar
Chemistry to study the technical uses of this instrument, in
cooperation with the U. S. Bureau of Standards, in the commercial
grading of sirups and other saccharine products, and to make a re-
port with recommendations at the September meeting of the
Society.
It was voted to request the president and secretary of the
Society to continue the present officers of the Sugar Section in
office until the organization of the Section as a Division, at which
time by-laws will be presented by the executive committee for
adoption.
PETROLEUM SECTION
The first meeting of the Petroleum Section proved very
successful, and confirmed the belief which had existed in
the minds of its originators as to the need of such a section and
the purpose it would fulfil. The cramped quarters first assigned
for its sessions proved inadequate, and a first and a second moving
were found to be necessary. Some seventy -five persons were
enrolled as members; the turn-out of men interested in the
technical side of the industry was excellent, and the universities
and research institutions were also adequately represented.
The officers appointed for the meeting by the Council of the
Society were: Dr. T. G. Delbridge, chairman, and Dr. W. A.
Gruse, secretary. Subject to the approval of the Council, a vice
chairman and an executive committee of five members were
nominated. The outstanding features of the tentative by-laws
adopted were the establishment of committees on papers,
on membership, and on nomenclature, and the adoption of an
arrangement for the circulation of preprints, in abstracted form,
of all papers to be presented at a meeting. It was believed that
this feature would stimulate discussion of papers and facilitate
to some extent the release of much valuable scientific information
now in the files of many private research laboratories.
The brevity of the program may be accounted for by the fact
that the existence of the Section had been a definite fact for only
six weeks before the Rochester Meeting. This handicap was
compensated for by the high quality of the papers presented,
which were twelve in number. Dr. C. F. Mabery, dean of petro-
leum research chemists in this country, in a paper on "Petroleum
Hydrocarbons Which Cannot Be Distilled," presented a method
for studying the composition of the higher fractions of petroleum
oils, a subject which, until this time, has been wrapped in mys-
tery. Dr. C. E. Waters reported on the catalytic influence of
metals on the oxidation of lubricating oils; E. W. Dean and F.
W. Lane, on the change with temperature of the viscosity of
typical crude oil fractions; R. E. Wilson and D. P. Barnard, on
a new and accurate method for determining condensation tem-
peratures and total heats of kerosene-gasoline-air mixtures; R.
E. Wilson and L. W. Parsons, on a method for measuring the color
of oils; W. F. Faragher and F. H. Garner, on the elimination of
hydrogen chloride from chlorohydrocarbons of low molecular
weight; W. F. Faragher, F. H. Garner and W. A. Gruse, on the
changes with time and quantity of the iodine numbers of un-
saturated hydrocarbons and cracked gasolines; C. J. Rodman,
on the accurate determination of very small amounts of moisture
in transformer oils; and B. T. Brooks read a general paper on
some chemical considerations of refining. Several papers were
read by title, and the meeting closed with an open discussion of
some scientific problems of the petroleum industry.
cellulose section
The first regular meeting of the Cellulose Section was by all
odds the most enthusiastic and successful of the three meetings
of cellulose chemists in conjunction with recent meetings of the
Society. Over one hundred members were present and took
part in the discussions. Twenty-one interesting papers were
presented. The outstanding feature was a series of four papers
dealing with the possibility of obtaining motor fuel from cellu-
losic materials. These were followed by an extended discussion
in which many took part.
In a paper on "Nitrocellulose and Its Solutions as Applied to
the Manufacture of Artificial Leather," Mr. W. K. Tucker called
attention to the desirability of having standards to which all
viscosity measurements might be referred. The chairman ap-
pointed G. J. Esselen chairman of a committee to consider the
matter, with power to appoint others to serve with him.
Dr. B. Johnsenmade the suggestion that the Section supervise
the preparation of a lot of pure cellulose to be available to
workers in this branch of chemistry, so that all results of the differ-
ent experimenters might be obtained with the same lot of cellu-
lose and thus be strictly comparable. The Section voted that
the chairman appoint a committee, of which he shall be a member,
to consider the preparation of such a lot of cellulose and report
at the New York Meeting. The Section was advised that the
Atlas Powder Company had kindly agreed to prepare this cellu-
lose if the Section cared to have them do so, and this offer was
accepted with thanks.
After listening to a paper by Mr. Philip Drinker in which he
summarized some of the voluminous data gathered by the
Army during the war on "European Practice in Cellulose Acetate
and Dopes," it was voted "that it is the opinion of the Cellulose
Section of the American Chemical Society that it would be of
great assistance not only to the advance of cellulose chemistry
in this country, but also to the more effective application of
cellulose and its compounds for both peace and war purposes,
if the large report entitled 'Aviation Chemistry, 1914-1915,'
properly expurgated, and from which we have just heard ex-
tracts, could be made accessible to the public in the Congres-
sional Library, the Library of the Chemists' Club in New York,
or otherwise."
The Section also put itself on record as congratulating the
Forest Products Laboratory on its increased government grants;
the Section looks forward to further activity in the acquisition
of necessary fundamental data and its publication in technical
monographs.
It was further voted that the president and secretary be
requested to authorize another meeting of the Cellulose Section
to be held in conjunction with the meeting of the Society in
New York next fall, and with the same officers as at the present
session.
Committee Reports
REPORT OP METRIC SYSTEM COMMITTEE
During the movement to secure the Postal Savings Banks in
America it was noticed that many bankers opposed the project,
thinking that it would be an injury to their business. Events
have shown that Postal Savings Banks have assisted the regular
banks of the country, particularly in floating the enormous war
loans. So in connection with the proposed adoption of the
Metric System, there are certain mechanical engineers who are
loud in their opposition, whereas we as chemists use the Metric
System and sympathize with those who are obliged to use the
cumbersome traditional units. The Council of the American
Chemical Society has passed various resolutions in favor of
the adoption of the simpler system. There are two questions
of importance to us as chemists: Will the adoption of the
Metric System work a great and permanent hardship to the
country and, if not, what can we properly do to bring about the
change?
There are many arguments advanced against the adoption
of the Metric System, that it is "academic and impractical,"
that the millimeter is an unsuitable unit, whereas the hundredth
part of the inch is an ideal unit. Such arguments make no im-
pression on the scientist. The only serious argument against
the change is one of cost. It is urged that the change cannot be
made gradually and, if made quickly, it would seriously menace
our national life because it would involve a complete change of a
very large part of our machinery. Friends of the system state
402
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
that it does not have to be made suddenly, and that the change
is now being made slowly and should be greatly accelerated.
The two systems can exist side by side to a considerable extent,
and thus the screws, pipes, bolts, etc., as well as much scientific
apparatus, may be made exactly as at present for an indefinite
period, and the change would mean listing them in the catalogs
with their sizes expressed in millimeters, etc. Many of our
machines would remain exactly as at present. This idea is
already being carried out by the Wholesale Grocers' Association,
who put the metric equivalent on their containers, thus gaining
an advantage in foreign trade and with our foreign population.
At first sight, this would lead to awkward numbers, since the
English sizes are supposedly based on even units, but it is com-
mon knowledge that a barrel of flour is determined by weight
and is not an even 200 lbs., but 196 lbs., i. e., 14 English stone.
An inch pipe is not an inch in diameter, but 1.31 in. outside
diameter and 1.05 inside diameter, etc. The change to metric
units will naturally avoid the use of names which are deceptive
and give the opportunity for greatly needed improvement as
new sizes are introduced. It will eliminate fractions. It will
do away with two or more units having the same name as, for
example, the long ton, the short ton, the gross ton, the dead
weight ton, the U. S. gallon, the imperial gallon, the liquid
quart and the dry quart, which cause inconvenience, encourage
fraud, and produce friction. We shall continue to use a hybrid
system for a long time. No one seriously proposes to apply the
Metric System to the division of time or the divisions of the
circle, and probably we would continue to use the units which
are now used in the textile and printing industries, as in France
and Germany.
Changes in styles of automobile parts, and accessories are
made from year to year in spite of standardization; and repair
shops carry spare parts for the old models. Of course, it is a
nuisance, but progress demands improvement and the manu-
facturer can better afford to supply the additional parts than to
go out of business. So, as a country we will make the change
to the Metric System if we are forced to do so by seeing our
trade go to our competitors who have a more up-to-date system.
There is no doubt but that the nations using the Metric System
prefer to use the simpler metric units and that we should meet
their needs instead of trying to force them to use our complex
and awkward system. Opponents of the Metric System have
tried to show that in the metric countries the Metric System is
not actually used. But the British Consuls in South America
have made an investigation as to the truth of this argument
and they find that in every country the Metric System is rapidly
making progress.1
The great advantage of the Metric System is that it is decimal
and, therefore, there is a great saving of time in computations;
and as our tables of weights and measures become obsolete,
there will be an enormous saving in education, calculated by
Dr. Wolf to amount to a million of years of time for one individual
in a single generation. That the Metric System can be easily
learned and used by American workmen with ordinary tools is
proved by the experience of the American Locomotive Company
in manufacturing locomotives for Russia. Having the blue
prints in metric units, they tried converting to English units but
found it a useless effort. The workmen were given copies of the
original drawings and made the locomotives on the basis of the
metric specifications and with less mistakes than when making
locomotives on the basis of English units. Mr. Fred J. Miller,
past president of the American Society of Mechanical Engi-
neers, says of the DeLaval Separator Company that the DeLaval
separator was first made in Sweden on metric specifications.
It is also made in this country on those same specifications by
American workmen and without any difficulty whatever. The
purchaser of the machines does not know what the basis of the
measures is and suffers no inconvenience whatever.
Admitting the correctness of our conclusion that America
would be benefited by the adoption of the Metric System, the
question remains, what can we do to help forward the move-
ment? Considerable correspondence between members of this
Committee, dealers, manufacturers, and others leads to the fol-
lowing conclusions. Chemists are at present purchasing and
selling the greater part of their supplies on the basis of the
English units, while a few manufacturers such as the Eastman
Kodak Company and Bausch & Lomb print their catalogs on
the metric basis exclusively. Other firms, such as Baker &
Adamson (General Chemical Co.) and J. T. Baker Chemical
Company, quote freely in metric units, and the great majority
1 Since this report went to press, the news has come that Japan has
adopted the Metric System, the law to go into force in April 1922. A Metric
Standards Bill (H. R. 10) has been introduced into Congress by Hon. Fred
A. Britten, of Illinois. — E. C. B.
of others would like to see the change made to a metric basis
throughout. In our journals English units and hybrid units are
being used. For example one reads of the use of "a platinum
electrode 1 in. in diameter to which is fastened a platinum wire
5 cm. in length," and "one ton of dry coal yields in by-products
Dry tar 34 gal.
Gas 8457 cu. ft.
Ammonium sulfate 21 pounds
Pitch 43 per cent
Light oil from gas 1 .87 gal.
Other tar oils 19 . 3 gal."
The calculation of yield to a percentage basis makes a very
pretty problem.
We, therefore, recommend:
1 — That all chemists who purchase chemicals either for
university or for laboratory use, and as far as possible those who
purchase chemicals for other purposes, should place their orders
hereafter in units of the metric system.
2 — That all manufacturers of chemicals be requested to
fill such orders with chemicals labeled in units of the metric
system, and as soon as practicable furnish price lists of chemicals
on the same basis.
3 — That the Committee on the Metric System be requested to
send a copy of these resolutions to the Director of the Chemical
Laboratory in every college and university in the United States,
and also to every chemical firm dealing either with the manu-
facture or purchase of chemicals of this type.
4 — Authors shall be requested to use the metric system
wherever possible; and the editors shall have authority to make
or require changes from English to metric units when in their
opinion it is desirable.
Other activities have been suggested to this Committee, but in
good faith we can do but little until we have "cleaned our own
house." We ask for the voluntary cooperation of a large num-
ber of our members and discussion of the advantages of the
Metric System in meetings of our local sections and elsewhere.
Eugene C. Bingham, Chairman
REPORT OF COMMITTEE ON GUARANTEED REAGENTS
AND STANDARD APPARATUS
The Committee on Guaranteed Reagents and Standard Ap-
paratus has made recommendations in regard to a large number
of reagents and forms of apparatus. Specifications have been
adopted for some items, and selections of standard sizes and
shapes of apparatus have been made. A number of tentative
recommendations have been published as noted below, while
others have been submitted for publication or are discussed in
detail in following sections of this report. The recommendations
are published for the consideration of the whole membership of
the Society, so that after inclusion of any changes made necessary
by general demand of the members they may be taken as repre-
senting the action of the Society as a whole.
REAGENTS
Tentative specifications for sulfuric, nitric, and hydrochloric
acids and for ammonium hydroxide have been submitted for
publication. These are intended to provide for regular careful
analytical work without requiring such a degree of purity as to
render unnecessary blank tests in the determination of very
small quantities of different elements.
guaranteed reagents — Although the Committee has urged
members of the Society to report complaints of the quality of
reagents, very few responses have been received. When these
have been brought to the attention of manufacturers they have
been glad to take steps to correct the errors. A considerable
proportion of the unsatisfactory deliveries have been due to
failure in inspection, but conditions in this regard seem to be
improving.
unit weights — Lists of suggested unit weights for the pur-
chase of reagents have been published in the Journal of Industrial
and Engineering Chemistry.1 In all instances metric units are
suggested in accordance with resolutions which have been adopted
by the Council favoring this usage.
APPARATUS
elimination of sizes — The greater part of the work on ap-
paratus has been in conjunction with the Committee on Stan-
dardization of the Association of Scientific Apparatus Makers
of the United States of America.
The multiplicity of shapes and sizes of apparatus on the market
has troubled dealers and manufacturers and those buyers who
realized that in the long run the purchasers are standing the
expense involved in carrying in stock an excessive number of
sizes and styles of apparatus.
•This Journal. 12 (1920), 1206; IS (1921), 473.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
403
The Committee of the Association of Scientific Apparatus
Makers has furnished information as to sales of different items.
These data obtained from representative large dealers show
what the chemists as a whole have been buying. Your Com-
mittee has studied these figures, and the recommendation of
the dealers and manufacturers, and in the light of the experience
of the committee members has made recommendations for
elimination of unnecessary sizes. Later the question of specifi-
cations will be taken up.
The detailed report on this subject, which will be published
separately for comment by members of the Society, gives about
1025 items, of which 470 were considered unnecessary. Many
of these pieces of apparatus listed in catalogs had never been
seen by some members of the committee. It is not intended
or expected that the items eliminated will no longer be available
for those who want them. Some dealers claim to have on hand
now a supply of certain items which will last for 5 or 10 years.
Other articles can be made to order if desired, but by concentra-
tion of the business on fewer items the cost will be less and the
service better, and improvement in quality can be more
easily brought about.
The topics considered included burners, calcium chloride
tubes, condensers, desiccators, flasks of various kinds, beakers,
porcelain ware, and wooden supports.
If the Council approves this project and authorizes its continu-
ance another year, the committee designated to do the work
will be helped and guided by comments of members of the
Society on the recommendations which will be published.
gas analysis apparatus — Apparatus for gas analysis is one
of the troublesome items for manufacturers, dealers, and users.
Two conferences were held with experts in gas analysis, and
some steps were taken towards drawing up specifications. It
seemed desirable, however, to change the plan of handling the
subject and therefore no recommendations for this kind of
apparatus are offered in this report.
glass tubing — The question of glass tubing has been con-
sidered for some time, and improvement in quality has been
found ever since the manufacture was first started on a large
scale in the United States. At the present time glass tubing
can be obtained for making lamp-blown apparatus which is
giving satisfaction in a number of large shops. A special quality
is also on the market which, although higher in price, is said to
be a little more satisfactory for certain difficult work.
thermometers — The Committee suggested a set of ther-
mometers for chemical laboratory work based on specifications
prepared by E. F. Mueller of the Bureau of Standards. These
specifications were published in The Journal of Industrial and
Engineering Chemistry, 13 (1921), 240.
W. D. Collins, Chairman
REPORT OF DELEGATE TO CONFERENCE CALLED BY THE
AMERICAN PETROLEUM INSTITUTE,
NEW YORK, APRIL 11, 1921
So far as I can judge there was no action taken in which the
American Chemical Society would be interested directly. The
action of the meeting was along the following lines:
1 — The American Petroleum Institute will create an advisory
committee of experts to act under Dr. Manning in cooperating
with the American Society for Testing Materials in preparing,
revising, publishing, and putting into use standard methods of
testing petroleum products.
2 — The American Petroleum Institute through its Division of
Research will investigate existing commercial laboratories and
issue revocable certificates of approval to such laboratories as
prove to have the proper personnel and equipment for individual
tests on petroleum products. The Institute will later publish
lists of such approved laboratories.
3 — The Institute will be asked to establish a laboratory or
some other agency whereby disputes arising over tests on pe-
troleum products shall be authoritatively decided.
4 — The present methods of the American Society for Testing
Materials are approved.
5 — You will note that the plan of certifying commercial lab-
oratories as to fitness for making tests on petroleum products
is a somewhat radical move, but it is the firm belief of those of us
familiar with the situation that this is a necessary step, not only
to eliminate "quacks" but also to keep the really good labora-
tories up to a high standard. The advisory committee of ex-
perts has not yet been appointed by Dr. Manning and for this
reason I cannot give you any further information at the present
time.
T. G. Delbridge
REPORT OF THE COMMITTEE TO COOPERATE WITH
CHEMICAL WARFARE SERVICE
At the time of filing this report, no formal meeting of the
entire Committee has been held, but some of the individual
members of the Committee have from time to time visited the
plant at Edgewood, Maryland, and conferred with the officers
and research workers at that plant. The work of the Committee
has not been pushed for the reason that the Chemical Warfare
Service has had such a hard struggle for existence in the light
of the unfriendly attitude of high officials of the War Depart-
ment and of the tendency to restrict severely appropriations
for the maintenance of the Service. In this situation it has been
felt that these were matters that had to be worked out by the
officers of the Service rather than by this Committee.
At the request of General Fries, chief of the Service, a general
meeting of the Committee has been called for Saturday, April
23, at which time it is hoped effective plans for cooperation with
the Service will be developed.
Supplementary Report
The Committee to Cooperate with the Chemical Warfare
Service held a general meeting at Edgewood Arsenal on Saturday,
April 23.
During the morning a thorough inspection of the laboratories
and plants was made, under the guidance of Brigadier General
Fries, chief of the Chemical Warfare Service, and Major E. J.
Atkisson, in charge of Edgewood Arsenal. The Committee
reports that the grounds, buildings, plants, and equipment are
in admirable condition. Invaluable work has been done in
restoring to a high state of efficiency this valuable property of
the Government which was so badly neglected for a few months
following the armistice, when the future of the Chemical War
fare Service seemed so doubtful.
Those plants which are not now being operated are being
maintained in such condition that they can be put into full
production at a moment's notice.
A number of processes were found to be in operation in single
small units.
The manufacture of gas masks is being carried out on a thor-
oughly organized production basis. The labor in this plant, at
first totally inexperienced, is gaining each day in proficiency,
with consequent daily increase in output of completed masks.
It gives us pleasure to report that the present governmental
policy is to concentrate at Edgewood Arsenal all divisions of
work bearing on chemical warfare.
We found the Navy heartily cooperating with the Army in
this work.
Saturday afternoon was devoted to a joint conference of the
Committee with General Fries and military and civilian members
of the Arsenal staff. Various problems were discussed, and the
Committee offered numerous suggestions to the members of
the staff.
The Committee feels that the Arsenal is effectively organized,
and that the work has now reached a stage of development
where important results will be quickly obtained.
The Committee appreciates most heartily the fine sprrit
shown towards its members by the personnel of the Chemical
Warfare Service.
In conclusion, your Committee feels that the activities of the
Chemical Warfare Service merit the hearty approval and gen-
erous support of the American Chemical Society and of the
American people.
Chas. H. Herty, Chairman
REPORT OF THE COMMITTEE ON AN INSTITUTE FOB
CHEMO-MEDICAL RESEARCH
The Committee on an Institute for Chemo-Medical Research
begs to report that on October 11, 1920, at the request of the
president of the Chemical Foundation, Inc., a joint meeting of
your Committee and the officers of the Chemical Foundation,
Inc.was held in the rooms of the University Club, New York City.
At this meeting the officers of the Foundation expressed
their deep and sympathetic interest in the work of the Committee
and the president of the Foundation expressed his strong desire
to aid the Committee in raising funds for the purpose of carry-
ing out the foundation of the proposed Institute. As a result of
the discussions at this meeting, the Foundation felt that to aid in
its effort to raise funds for the work there should be placed in its
hands a carefully drawn, complete statement of the needs and
purposes of such an Institute. The Foundation expressed its
willingness to meet any expenses connected with the preparation
of such a report and to recompense the members of a Subcom-
mittee for their work on the report. The suggestion and offer of
404
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
the Foundation were accepted and the Chairman was authorized
to appoint a Subcommittee. At the request of the full Com-
mittee, the Chairman has acted as Chairman of the Subcom-
mittee and appointed on this Subcommittee Professors Julius
Stieglitz, Reid Hunt, Treat B. Johnson, and Dr. F. R. Eldred.
The Subcommittee has held three meetings in New York City
and has just completed a final draft of the tentative report
which has now been submitted to the full Committee for its
criticism. The final meeting of the Committee will be held dur-
ing the meeting in Rochester, at which time it is hoped to com-
plete the report which will then be turned over to the Chemical
Foundation, Inc.
Chas. H. Herty, Chairman
Convention Side Lights
Those who landed at the Lehigh Valley depot upon arriving
at Rochester found the following words staring them in the
face from a huge sign on the side of a large building: "National
Casket Co." Since spending a week in the Flower City we have
caught the real significance of this. Only the live ones seem
to remain above ground in Rochester.
Hans T. Claske, Vicb Chairman op Executive Committee
There was a most comforting lack of haste in all of the pro-
ceedings of the meeting and yet things were accomplished with
dispatch. It takes a set of past masters at the art of entertain-
ing conventions to run things off on schedule time and yet make
you feel at home and not in the least hurried. The Rochester
Convention Committee belongs to this class.
One of the real treats of the meeting was the address of E. G.
Miner at the first general session. He referred to pure research
as insurance for the chemical industry7. Coming from one who
includes himself in the business group rather than the purely
scientific class, this statement is highly encouraging and should
be shouted from the housetops, particularly to those concerns
which are cutting down their research activities because of tem-
porary business depression.
It was pleasing to note the presence of quite a number of
officers of the Chemical Warfare Service. General Fries, the
head of this organization, attended some of the meetings himself,
and with his co-workers took an active interest in the proceed-
ings. Meetings of the Society are incomplete now without the
presence of these active workers in the Government's newest
branch of war activities.
To anyone who suffered from chemical blues, either colloidal
or temperamental, the Rochester Convention was a sure anti-
dote. Congressman Longworth made the industrialists happy
and Dr. Bancroft dispersed the blues for the other fellows.
The Advisory Council of the Society has placed an order for
a complete file of all available almanacs and weather reports
dating back over a period of ten years. Not a scientific in-
vestigation, but just following out the instructions of the Council
Meeting that the 1922 Spring Meeting of the Society be held at
Birmingham, Ala., during a week of clear weather in April.
Bernard Haggarty, who represented the Mayor of Rochester
at the opening meeting, remarked that the Mayor was somewhat
of a chemist himself. He had succeeded in mixing men of many
different nationalities and temperaments in one great melting
pot in the city of Rochester and had developed a concoction
known as Rochester Spirit. We are ready to testify to the ex-
istence of a real live Rochester Spirit.
It was an unusual experience for many of the members of the
Society to be starred in the movies. Through the courtesy
of the Eastman Kodak Co., a film was shown at the entertain-
ment on Thursday evening which embodied convention pictures
that had been in the making bj' the movie camera men on the
previous three days. Some people who had never been "shot"
before were greatly surprised to watch themselves "act" and with
this surprise came the shock of realization that they were in the
film records of the A. C. S. for good. It is planned to send these
films around to the various sections of the Society.
It was a sorry lot of chemists that wended their way to the
New York Central depot on Thursday evening to make the
11:03 P. M. train for New York. They had to leave the grand
entertainment at the Bausch and Lomb auditorium at 10:30
p. M., thus missing some of the best numbers. We are not cer-
tain, but according to the schedule of events, 10: 30 came just
in the middle of that oriental dance number. If they had only
not had their reservations, but — alas! chemists must heed when
duty calls.
Through the courtesy of Mr. George Eastman, the members
of the Society saw the initial exhibition of "Filmland," which
will soon be shown in the moving picture theaters of the country.
This film tells the story of the production of moving picture
films from the technical standpoint. Yet it is as little technical
as a subject of this kind can remain. The various processes
entering into the manufacture of film from the raw cotton to the
completed picture are wonderfully illustrated. Throughout the
picture there are little corner cartoons which artists might de-
scribe as thumbnail sketches illustrating the point that is being
made by the film itself, making it understood by the youngest
movie enthusiast. Spontaneous applause and cheers greeted
various portions of the film, showing such especially intricate
camera performances as the depicting of the actual formation
of crystals of silver nitrate.
A total registration of 1234 was reported by the convention
committee on the final day of the meeting. Of this number
806 were members of the Society. By Monday night 592 had
signed registration cards. On Tuesday this number was swelled
to 842. Wednesday added 250 more and by Thursday the total
was raised to 1229, with five more coming in on the last day.
The registration of members of the Society by states follows :
California 3
Colorado 1
Connecticut 8
Delaware 7
Illinois 22
Indiana 12
Iowa 4
Kansas 1
Louisiana 1
Maine 1
33
■419
Maryland 20
Massachusetts 50
Michigan 16
Minnesota 4
Missouri 8
Nebraska 2
New Hampshii
New Jersey
New York
North Carolina 1
Ohio 58
Oklahoma 1
Pennsylvania 57
Rhode Island 4
Tennessee 3
Vermont 3
Virginia 2
Washington 1
Washington, D. C 37
Wisconsin 8
Canada
China
Sweden
U
Total A. C. S. Members.
Guests
428
Total registration 1234
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
405
The concentration of divisional meetings in one building as
arranged by the convention committee gave an excellent oppor-
tunity to hear papers read before several sections. It was easy
to circulate from one meeting room to another, and the system
of recording papers that were being read before the various
divisions on tie blackboard at the entrance to the Mechanics
Institute worked out very well.
Photographers seemed to be everywhere, and undoubtedly
the story of a meeting of the Society has never been so well and
profusely illustrated in the daily papers with photographs of
leading members, group pictures, etc., as was this Rochester
meeting.
Speaking of publicity, there is one young man in Rochester
who is the best deliverer of newspaper stories we have yet run
across. For weeks before the convention and especially during
the convention he had the Rochester newspaper men eating
out of his hand. He not only did a fine piece of work for his
city but a splendid piece of work for the Society. Always on
the job and always doing the job well — that's Benjamin V.
Bush, chairman of the Publicity Committee, Rochester Section.
The reduced fare offered by the railroads was taken advantage
of by nearly 500 of those attending the convention, and to the
credit of the railroad officials in charge of adjusting the details
connected with issuing this reduced transportation be it said
that they were most patient and accommodating.
"Good fellowship" meeting was the right name for that jolly
good time provided by the hosts of the Society' on Thursday
evening at the Bausch and Lomb plant. The arrangements
for handling the 1500 or more people who attended must have
been well thought out in advance, for everything went off with
clock-like precision. Xobody had to worry about anything
and good fellowship reigned supreme.
Benjamin V. Bcsh. Chaibman of Pxtblicity Committee
EDITORIAL NOTES
This issue appears late, owing to strike conditions
in the printer's plant. We have assurances that the
day of delays is about ended. Resolutions in connec-
tion with this subject, adopted by the Council at the
Rochester Meeting, will be found on page 379.
In this issue, the first time we believe in the his-
tory of chemical literature, we present a signed tech-
nical contribution from a United States Senator, a
book review by Senator E. F. Ladd of North Dakota.
In the midst of the many duties incident to assuming
his new duties, the Senator has found time to continue
his work with his fellow-chemists. The sterling activi-
ties of Dr. Ladd in the earlier days in making chemis-
try so helpful to the people of his state is an earnest
of the broader influence he will be able to wield in
behalf of the nation through his incumbency of the
high position he now occupies. The very best wishes
of his former colleagues attend him.
In every line of modern effort more and more thought
is being given to social industrial relations. Perhaps
This JorRXAL may be of some help in this direction.
In this hope part of our space for an indefinite period
will be devoted to this subject under the leadership
of Dr. H. W. Jordan, who has given much thought
to these questions. Dr. Jordan alone is responsible
for the views he puts forward. Discussion, criti-
cism and suggestions are freely invited. Frankly this
is an experiment. As in all experiments, the result can't
be foretold. We reserve the right to ring the bell for
the curtain drop whene%-er conditions demand it.
The third annual dinner of the Chemical Warfare
Service held in Washington April 16, 1921, was an
inspiration to all who attended. The presence of
high officers of the Army and the Xavy, of prominent
senators and congressmen, of distinguished repre-
sentatives of the press, in addition to the large number
of members, past and present, of the Chemical War-
fare Service, was indicative of the steadily growing
appreciation of the importance of this unit of the War
Department. The speeches were all enthusiastically
received, and the toastmaster informed us that he had
a fine old time.
Another link in the chain of economic independence
is forged. Xo longer do we have to look abroad for
supplies of highest grade filter paper. Dr. Little has
made good his promises and is "in the game" to stay.
Who next?
The Reports of the Committee on the Metric
System and the Committee on Guaranteed Reagents
and Standard Apparatus, pp. 401 and 402, show clearly
that the psychological moment has arrived to establish a
uniform practice of purchasing supplies in metric units.
For many years there has been a vicious circle, the
purchasers blaming the manufacturers, while the manu->
facturers insisted that lack of uniform practice among
purchasers made necessary the maintenance of an
undesirable basis of dealing in chemical supplies
and laboratory apparatus. At last the ball is well
started and your aid is needed to put it squarely across
the line. Then only can it be said that we practice what
we preach.
406
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
ORIGINAL PAPERS
The Role of Acidity in the Dehydration of Sewage Sludge1
By John Arthur Wilson and Henry Mills Heisig2
Sewerage Testing Station, Milwaukee, Wisconsin
One of the problems which has arisen in the applica-
tion of the activated sludge process to the treatment
of the sewage of the City of Milwaukee is the efficient
dehydration of the sewage sludge. The raw sewage
is passed through open tanks with bottoms fitted with
Filtros plates through which air is forced so as to
produce continuous streams of tiny bubbles. A frac-
tion of thickened sewage sludge is shunted back and
enters the aeration tanks along with the raw sewage.
The combined effect of this sludge and the aeration
process is to produce the precipitation of from 90
to 95 per cent of the organic matter present in the
sewage. The precipitated sewage is then run into a
Dorr thickener which separates the heavy sludge,
containing about 2 per cent of solid matter, from the
clear effluent above, which is run away. Part of the
sludge is returned for mixing with the raw sewage to
assist the activation process, and the remainder is
passed through a filter press or centrifuge in order to
reduce its moisture content as much as possible.
In using the filter press it was found that the time
required to press a given amount of sludge varied
greatly from time to time, but that adding sufficient
sulfuric acid to make the sludge slightly acid to methyl
orange usually facilitated the pressing. Sludges were
encountered occasionally, however, which could not
be pressed satisfactorily even after this acid treatment,
owing to some unknown and disturbing influences.
The present investigation was begun with the object
of discovering the nature of these disturbing factors
and devising means for their control.
PRELIMINARY DISCUSSION
An examination of a typical sample of sludge showed
it to consist largely of protein and cellulose fibers,
tissues, hair, and colloidal organic matter. Materials
of this sort may conveniently be divided into two
general classes:
(1) Coagulated matter which is peptized or redissolved by
certain solutions.
(2) Organized jellies which do not dissolve, but increase in
volume by imbibition or absorption of water.
When substances of the first class are peptized, they
become electrically charged, and the greater the value
of this charge the more difficult it becomes to separate
them from the solution, other things remaining constant.
It has been pointed out by one of us3 that the stability
. of such dispersions is a function of the electrical differ-
ence of potential existing between the bulk of solution
and the thin layer of solution immediately in contact
with the surfaces of the colloidal particles. The col-
loid may be separated most easily from the solution
1 Received February 2, 1921.
2 With the cooperation of Wm. R. Copeland, chief chemist of the Mil-
waukee Sewerage Testing Station.
• J. A. Wilson, J. Am. Chem. Soc, 38 (1916), 1982.
when this potential difference is a minimum. It may
be lowered:
(1) By increasing the electrolyte content of the solution, as
in "salting out," provided the value of the electrical charge itself
is not materially increased.
(2) By decreasing the value of the electrical charge, which
can be done by adding to the solution an equivalent amount
of a colloid or polyvalent ion of opposite electrical charge, or
by suitably altering the acidity or alkalinity of the solution.
Many colloids are strongly negative in alkaline solu-
tions, but as the solution is made more acid, the value
of the electrical charge decreases to zero, the isoelectric
point of the colloid, which .is also the point at which it
coagulates most readily; but with still further addition
of acid the electrical charge on the colloid changes
sign and becomes more and more strongly positive
and the dispersion more stable.
The behavior of the jellies can be described by refer-
ence to gelatin, a typical substance of this class. If
a sheet of. purified gelatin is placed in water at 18°
it will swell to about eight times its original volume by
absorbing water, but in 0.005 N hydrochloric acid it
swells to about fifty times its original volume and in
0.005 N sodium hydroxide to about thirty volumes.
A comparison of the action of acids of different strengths
upon gelatin shows that the swelling is a function of
the H+-ion concentration rather than of total acid
concentration. If the volume of the gelatin plate is
plotted against the pH value1 of the solution, it will
be found that the volume increases to a maximum
at 2.4, then decreases to a minimum at 4.6, increases
again to another maximum at about 11.5, and then
decreases again. The molecular mechanism of this
phenomenon is explained quantitatively by the Procter-
Wilson theory of imbibition, which should be consulted
in the literature,2 which also describes the action of
other acids and of neutral salts upon gelatin and dis-
cusses the properties of organized jellies in general.
Other jellies swell like gelatin in various solutions,
but not to the same extent, nor do their points of
maxima and minima occur at the same pH values.
In dealing with the wet sewage sludge, it is essential
to recognize that the water exists in more than one
phase. A closely packed mass of fibers readily ab-
sorbs water, which is drawn up into the capillary
spaces between the fibers. The bulk of such water
may easily be squeezed out again by mechanical
pressure. But the fibers themselves are capable of
1 pH is a term now widely used to indicate — logH -ion concentration.
2 H. R. Procter, "Action of Dilute Acids and Salt Solutions upon
Gelatin," Kolloidchem. Beihefle, 243 (1911); H. R. Procter and J. A. Wilson,
"Acid-Gelatin Equilibrium," J. Chem. Soc, 109 (1916), 307; J. A. and W.
H. Wilson, "Colloidal Phenomena and the Adsorption Formula," J.
Am. Chem. Soc, 40 (1918), 886; D. J. Lloyd, "Swelling of Gelatin in HC1
and NaOH," Biochem. J., 14 (1920), 147; J. A. Wilson, "Imbibition of
Gels," Colloid Chemistry and Its Industrial Applications; Third British
Assn. Report, 61 (1920).
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
407
pH Value of Filtrate
Fig. 1— Sludge of December 29, 1920
Lower curve: Set filtered 15 min. after mix
ing with acid. Upper curv
24 hrs. later
:: Set filtered
pH V»lue of Filtrate
Fig. 2 — Sludge of December 30, 1!
Lower curve: Set filtered 15 min. after
ing with acid. Upper curve: Set filte
24 hrs. later
pH Value of Filtrate
Fig. 3 — Sludge of January 4, 1921
Lower curve: Set filtered 15 rain, after
mixing with acid. Upper curve: Set
filtered 24 hrs. later
absorbing water by increasing in volume, as was de-
scribed for gelatin, and such water cannot be removed
mechanically except by the application of enormous
forces. This was shown very strikingly in the case
of a strip of raw calf skin taken from a lime liquor.
Although it contained 80 per cent of water, it was
almost impossible to remove any by trying to wring
it by hand. But when the same strip was brought into
equilibrium with a solution whose pH was 8.0 and then
removed, it again contained 80 per cent of water, but
the bulk of this water could easily be squeezed out by
hand. The fibers had contracted, giving up their
imbibed water to the capillary spaces between the
fibers. It is necessary, to get the best results in de-
hydrating sludge, that the per cent of imbibed water
be a minimum.
Two practical methods of treating the sludge were
planned, one dealing with changing the acidity of the
solution and the other with adding salts yielding polyva-
lent ions. The work described in this paper deals only
with the first method, but the other will be studied
later.
If the sludge consisted merely of a single substance,
the problem would be simply that of finding the acidity
corresponding to the isoelectric point of that substance
and then of maintaining that acidity. But the sludge
contains numerous substances in variable proportions.
For any particular sample of sludge the acidity giving
the best results can, of course, be easily determined.
As to how this optimum acidity might vary from time
to time, one could tell only from experience.
EXPERIMENTAL
The general procedure adopted for this investigation
was to set up a series of cylinders into each of which
were measured 90 cc. of sludge and 10 cc. of standard
acid or alkali. After mixing thoroughly, the sludges
were allowed to stand a definite length of time and
were then thrown on to Buchner funnels and filtered
by suction. The number of minutes required to re-
move the bulk of water was noted, and the pH value
of the filtrate was determined colorimetrically by
means of the Clark and Lubs series of indicators. The
electrically driven pump furnished a high and prac-
tically constant vacuum, but to offset any slight varia-
tions all members of one series were, whenever possible,
connected to the pump at the same time. It was
thought that a record of the volumes occupied by the
sludges in the cylinders just before filtering might be
of value, but owing to fermentation and gas formation
this reading was never found to be sensitive enough
to have any significance.
Table I
(Sludge of Novemb
er8, 1920:
Solid matter 1
57 per cent; pH of solut
To 90 Cc.
Minutes
pH
Appearance
Sludge Added
to
of
of
10 Cc. of
Filter
Filtrate
Filtrate
l.OOiV NaOH
Over 60
Brown, turbid
0.20 N NaOH
Over 60
Brown, turbid
0.10 AT NaOH
29
8^3
Brown, turbid
0.05 W NaOH
27
8.2
Gray, turbid
0.01 A7 NaOH
22
8.2
Gray, turbid
Water
20
8.1
Gray, turbid
0.01 N HC1
20
8.1
Gray, turbid
0.05 N HC1
16
8.1
Gray, turbid
0.10 N HC1
18
7.6
Milkv
0.20 A7 HC1
6
3.3
Colorless, clear
1.00 AT HC1
Over 60
1.5
Brown, turbid
At first, short series of experiments were run daily
in order to get some idea as to where the points of op-
timum acidity might lie. A typical example of one
of these is given in Table I. This particular series
was allowed to stand over night after mixing and was
then filtered. It was noteworthy that the sludges
which filtered most rapidly always gave the clearest
filtrates, and that the pH values of these filtrates always
lay between 2.8 and 3.8.
THE TIME FACTOR
After a sample of sludge and acid have been mixed,
the acidity of the solution slowly falls over a period of
hours, on account of the slow absorption of acid by the
substance of the fibers and other organized jellies in
the sludge. Since it takes a filter press several hours
to handle its capacity of sludge, it is apparent that the
drifting of the acidity out of the optimum range may
cause considerable practical difficulties. The effect
of the swelling of the jellies also will become more
pronounced with time. In planning how best to treat
sludge to be pressed, it is necessary to know not only
the immediate effect of change of acidity, but also
how the character of the sludge will vary during the
time of pressing.
Experiments made to show both the effects of change
of acidity and of time are being carried out regularly
in order to cover every type of sludge likely to be en-
408
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
TablB II
(Sludge of December 29, 1920:
Solid matter 1.67 per cent; pH of solution 8.2)
To 90 Cc. 15 Minutes after Mixing
24 Hours after Mixing
Sludge Added Minutes
pH of
Minutes
pH of
10 Cc
of to Filter
Filtrate
to Filter
Filtrate
Water 30
8.1
32
7.9
0.05
29
7.6
38
7.6
0.10
27
7.1
50
7.3
0.15
24
5.7
Over 60
6.7
0.20
23
4.9
Over 60
5.3
0.22
19
4.5
Over 60
5.2
0.24
16
4.2
Over 60
5.1
0.26
15
3.9
Over 60
4.9
■0.27
13
3.7
Over 60
4.9
0.28
12
3.6
Over 60
4.9
0.29
8
3.6
Over 60
4.9
0.30
10
3.6
Over 60
4.9
0.31
10.5
3.4
Over 60
4.8
0.32
11
3.3
Over 60
4.5
0.33
N H2SO4 J2
3.3
Over 60
4.4
0.34
3.2
Over 60
4.3
0.36
12
3.0
60
4.1
0.38
16
2.8
21
3.8
0.40
15
2.7
15
3.6
0.42
14
2.6
16
3.4
0.44
15
2.6
18
3.3
0.46
20
2.4
45
3.1
0.50
22
2.2
60
3.0
0.60
23
2.1
Over 60
2.3
0.80
30
1.7
Over 60
1.9
1.00
38
1.5
Over 60
1.7
1.50
40
1.3
Over 60
1.3
2.00
45
1.1
Over 60
1.2
3.00
55
Over 60
4.00
60
Table III
Over 60
(Sludge
of December 30, 1920:
Solid matter 1.94
per cent; pH of solution 7.4)
To 90
Cc. 15 Minutes
after Mixing
24 Hours after
Mixing
Sludge
Vdded Minutes
pH of
Filtrate
Minutes
pH of
10 Cc
of to Filter
to Filter
Filtrate
Wate
r 40
7.3
47
7.5
0.051
35
7.1
45
7.2
0.10
33
6.5
42
7.0
0.15
32
5.5
40
6.1
0.20
27
5.1
38
5.4
0.22
25
4.9
37
5.2
0.24
18
4.8
35
5.1
0.26
17
4.3
33
5.0
0.27
16
4.2
27
4.9
0.28
14
3.9
25
4.6
0.29
12
3.9
32
4.8
O.30
14
3.9
31
4.7
0.31
15
3.9
33
4.6
0.32
14.5
3.S
30
4.6
0.33
15.5
3.7
29
4.5
0.34
N HjSCU 16
3.7
27
4.4
0.36
16.5
3.5
25
4.4
0.38
17
3.3
19
4.1
0.40
17.5
3.2
18
3.9
0.42
18.5
3.1
17
3.7
0.44
19
3.1
17
3.7
0.46
22
3.0
20
3.4
0.50
26
2.8
25
3.1
0.60
33
2.1
60
2.3
O.80
44
1.7
Over 60
1.9
1.00
60
1.5
Over 60
1.7
1.50
Over 60
1.3
Over 60
1.3
2.00
Over 60
1.2
Over 60
1.2
3.00
Over 60
Over 60
4.00
Over 60
Table IV
Over 60
(Sludge
of January 4, 1921: Solid matter 1.70 per cent; pH of solution 7-5)
0.1 t?:i. 1
To 90
Cc. 15 Minute.
after Mixing
24 Hours aftel
Mixing
Sludge
\dded Minutes
pH of
Filtrate
Minutes
pHof
10 Cc
of to Filter
to Filter
Filtrate
Wate
r Over 60
7.7
Over 60
8.1
0.05
Over 60
7.1
Over 60
7.9
O.10
Over 60
6.5
Over 60
7.7
0.15
Over 60
5.9
Over 60
7.3
O.20
60
5.1
Over 60
5.7
0.22
50
5.0
Over 60
5.4
0.24
45
4.7
Over 60
5.3
0.26
26
4.1
Over 60
5.2
0.27
33
3.9
Over 60
5.1
0.28
20
3.9
Over 60
5.0
0.29
18
3.9
Over 60
5.0
0.30
18.5
3.9
Over 60
5.0
0.31
20
3.9
Over 60
4.9
0.32
21
3.8
Over 60
4.9
0.33
20
3.7
60
4.5
0.34
N H2SO, 19
3.7
45
4.5
0.36
18.5
3.5
50
4.5
0.38
IS
3.3
45
3.9
0.40
17.5
3.1
24
3.7
0.42
17
2.8
32
3.5
0.44
20
2.6
21
3.3
0.46
22
2.4
28
3.0
0.50
24
2.2
35
2.9
0.60
26
2.0
60
2.2
0.80
33
1.7
Over 60
1.8
1.00
37
1.5
Over 60
1.7
1.50
45
1.3
Over 60
1.2
2.00
53
1.0
Over 60
1.1
3.00
60
Over 60
4.00
Over 60
Over 60
countered. There are seasonal changes in the general
character of sewage, as well as sudden changes due to
the occasional dumping of unusually large amounts
of certain industrial wastes. Thus far all samples of
sludge examined can be divided into three distinct
types. Examples of each of these types are given in
Tables II, III, and IV, and Figs. 1, 2, and 3. Each
cylinder of treated sludge was set up in duplicate,
but one was filtered 15 min. after the mixing and the
other 24 hrs. later.
The sludge of December 30 is apparently the common
type which never caused any serious difficulties in
pressing. According to the old rule of adding acid
according to a titration, the acidity would probably
have been increased to the equivalent of a pH value
of about 3.5. The time of filtering is shortened and,
although the sludge filters with increasing difficulty
as time goes on, its condition is always better than if
no acid had been added.
The sludge of December 29 differs from the pre-
ceding in having a very pronounced point of maximum
in its 24-hr. curve at a pH value between 5 and 6.
If the pH value of this sludge had been brought to
3.5, its condition for pressing would immediately have
been greatly improved, but it would then rapidly be-
come worse until it would cease to filter in any reason-
able time, and the press would be tied up. The sludge
actually would have been better without any acid.
The experiment reveals what was probably a dis-
turbing influence in, many poor pressings in the past,
and points out the remedy. By bringing the pH
value of the sludge to 3.1 its condition for pressing is
improved and remains so, even though the pH value
drifts to 3.7.
The sludge of January 4 differs from the others in
requiring acid to bring it into condition to be filtered
at all. In this case the time effect on the condition
of the sludge can be eliminated by bringing the pH
value to 2.6.
THE DILUTION FACTOR
It is evident that the drift in pH value with time
can be lessened by diluting the sludge with water
before bringing it to the desired pH value, because
the sludge then has a greater reservoir of acid from
which to draw. A sludge like that of January 4 can
be filtered satisfactorily only when its pH value is
confined within definite limits. If such a sludge were
so concentrated that the drift in pH value exceeded
these limits, it would seem that the sludge never could
be pressed satisfactorily immediately after a single
acid treatment, regardless of the amount added. If
the pH value were brought within the optimum range
just before pressing, it would drift out of it during the
pressing, whereas, if the pressing were started on the
acid side of the optimum range, the filter cloths would
immediately become clogged.
A good example of such a sludge was encountered
on January 20. Only three members of the series of
fourteen could be filtered in less than an hour, and
none in any time that could be considered really satis-
factory. In order to test out the theory regarding the
effect of dilution upon the drift in pH value, and, there-
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
409
fore, upon the speed of filtration, we diluted some of
the original sludge with an equal volume of water and
then treated the diluted material exactly as we had
the original sludge, excepting that 200 cc. were thrown
on to each filter in order to give the same yield of dry
sludge as in the case of the undiluted samples, and that
more dilute acid was used because of the lesser drift
in pH value expected. The result was very striking.
(Sludge of January 20, 1921:
10 Cc.
Water
0.06)
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0 24
0.26 ftfH:SO« Qv
0.28
0.30 Over 60
0.32 Over 60
0.34 Over 60
0.36 Over 60
0.38
0.40
0.42
0.44
0.46
Table
v
Solid matter 1 .79 per cent ; pH of solution 7.S
Sludge Diluted
with Equal
Vol. Water before 1
pHof
Minutes to
pHof
Filtrate
Filter 200 Cc.
Filtrate
7.6
Over 60
7.6
Over 60
6.5
Over 60
6.1
Over 60
Over 60
5.1
Over 60
4.8
Over 60
4.4
60
3.9
40
3.3
5.0
4.8
4.6
4.3
3.0
2.8
2.7
Although more than twice as much water was being
passed through the filters, seven members out of the
fourteen filtered within 1 hr., and one in 35 min.,
as compared with 55 min. for the best of the undiluted
samples. The results are shown in Table V and Fig. 4.
£ 60
w
\ Tl /
V * /
9 /
ft. 50
\ /
o\ /
** W
V /
•o
^_ /
•J 3 40
\r
uta
y
II 30
*
x a
■» U
» e ao
a
a 10
pH Value of Filtrata
Fig. 4— Sludge of January 20, 1921
Lower curve: Time required to filter 200 cc. sludge diluted with an equal
volume of water before treating. Upper curve: Time required to filter
only 100 cc. of undiluted sludge
The extent to which it is desirable to concentrate
sludge in the Dorr thickeners is evidently a question
of prime importance where the sludge is to be de-
hydrated by means of filter presses.
PROBLEMS CONNECTED WITH CENTRIFUGING
The filter press and centrifuge present problems of
quite different types. Which will ultimately prove
the more efficient for dehydrating sewage sludge prob-
ably will depend in a large measure upon the method
adopted for treating the sludge. The centrifuge acts
so quickly as to avoid the time factor, so serious in
pressing, and possibly also the dilution factor. At
present, however, the centrifuge removes considerably
less than half of the organic matter from the wet sludge,
making it necessary to return the effluent to the aeration
tanks for mixing with the raw sewage. The press,
while acting more slowly, yields a clear effluent which
adds no further burden to the plant when returned to
the aeration tanks.
The efficiency of the centrifuge is dependent upon
two factors: the magnitude of the electrical charge on
the colloidal matter, and the ratio of the specific
gravity of this colloidal matter to that of the effluent.
The latter as well as the former can be altered by change
of acidity, which will probably prove to have as great
an effect upon the efficiency of the centrifuge as upon
the speed of filtration in the laboratory tests.
When an organized jelly swells by imbibition of
water, its specific gravity tends to approach that of
the water, and since the jellies in the sewage have an
average specific gravity greater than unity when dry,
the effect of imbibition is to lower their gravities and
make them more difficult to remove by centrifuging.
It is now a well-known fact1 that jellies in swelling ab-
sorb a solution of lesser concentration than that in
which they are immersed. It is therefore possible
for a jelly actually to assume a gravity less than that
of the solution surrounding it, and the effect of such
a condition upon the centrifuging of sludge will readily
be appreciated.
CONTROL OF ACIDITY
If control of acidity alone should prove sufficient for
practical purposes, it is believed that this can be done
automatically by means of a hydrogen electrode and a
recorder equipped to control a solenoid arrangement
for regulating the flow of acid into the sludge line so
as to deliver the sludge to the press or centrifuge at any
desired pH value. Such an arrangement is being
installed and will soon be put to the test. While
the optimum pH value varies somewhat from time to
time, it is possible that maintaining an average of
these optimum values may prove satisfactory, es-
pecially if the concentration of the sludge itself is
properly regulated.
SUPPLEMENTARY CONTROLS
In every one of our experiments an acidity has been
found that will make the sludge filter much more
rapidly than if left untreated. It, therefore, seems
that control of acidity will increase the efficiency of the
plant. But even if each sample of sludge is brought
to its optimum acidity, there will still be considerable
differences in the time required to filter equal quanti-
ties of different sludges on account of differences in
composition. This is shown clearly in the tables. It
is reasonable to believe that the effect of these differ-
ences can be largely overcome by simple supplementary
control systems, with a corresponding further increase
in the efficiency of the plant.
If a given sample of sludge contained a relatively
small amount of a jelly whose point of maximum im-
bibition lay close to the optimum acidity of the sludge
as a whole, the effect would be to make the sample
more difficult to filter. But, by adding common salt,
imbibition of this jelly could be diminished and the
1 Procter and Wilson, Loc. cit.
410
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
rate of filtration of the sludge correspondingly in-
creased. In practice it might prove feasible to have
salt added whenever the rate of filtration falls below
some determined value.
Another scheme for overcoming irregularities in
the sludge scheduled for investigation is to maintain the
pH at a value slightly higher or lower than the opti-
mum in order to give the sludge a small electrical
charge, and then to add a small amount of a suitable
salt yielding a polyvalent ion, such as a phosphate, if
it is decided to keep the sludge positively charged, or
alum for negatively charged sludge.
SUMMARY
Change of acidity has a very marked effect upon the
speed of filtration of sewage sludge. The greatest
rate of filtration of sludge from the city of Milwaukee
occurs at a pH value of about 3.
After a sample of sludge has been acidified, its
acidity falls during a period of hours, owing to the
slow absorption of acid by the substance of fibers and
other organized jellies present. The character of the
sludge changes upon standing because of this drift
in acidity, as well as because of the gradual swelling
of the jellies. It is shown how to regulate the acidity
to overcome these effects.
It is pointed out that proper dilution of sludge to be
dehydrated by means of filter presses is a matter of
prime importance. Under certain conditions a dilute
sludge can be dehydrated more quickly and efficiently
than a more concentrated one containing the same
amount of solid matter.
The effect of change of acidity upon the specific
gravity and value of the electrical charge of the col-
loidal matter in the sludge is of great importance in-
dehydrating sludge by means of a centrifuge.
It is believed that the automatic control of the acidity
of the sludge will increase the efficiency of the plant,
and that this efficiency can be still further increased
by simple supplementary systems of control.
Applications of Maleic and Fumaric Acids and Their Salts in the
Textile Industry1
By J. H. Carpenter
Technical Service Department, The Barrett Company, 17 Battery Place, New York, N. Y.
The article by Weiss and Downs entitled "Catalytic
Oxidation"2 outlines the method by means of which
maleic and fumaric acids can be manufactured by
the direct oxidation of benzene with air in the presence
of a catalyst.3 Since these acids have never before
been available in commercial quantities, the literature
contains very little information concerning their ap-
plications in the manufacture of textiles. It was
therefore deemed advisable to undertake the follow-
ing investigations in the dyeing and finishing of wool-
ens, silks, and cottons.
GENERAL PROPERTIES
The properties of maleic and fumaric acid which
are probably of greatest interest to textile manufac-
turers are the per cent of their ionic dissociation and
the extent to which they corrode copper.
In 0.1 N solutions maleic acid is dissociated 30
per cent and fumaric acid 10.2 per cent.4 These
figures are of special interest as compared with the
other most highly ionized organic acids of importance
to the textile industry, namely, oxalic acid, which is
45 per cent dissociated in 0.1 N solutions, and tar-
taric acid, which is 9.4 per cent dissociated in solu-
tions of the same strength. As free hydrogen ions
are generally considered as the cause of tendering
fabric5 the degree of ionization of maleic acid is a great
disadvantage with vegetable fibers which have no
basic qualities,6 and hence do not combine with an acid
and neutralize it. On the other hand, free hydrogen
1 Presented before the Division of Dye Chemistry at the 60th Meeting
of the American Chemical Society, Chicago, 111 , September 6 to 10, 1920.
' This Journal, 12 (1920), 228.
> U. S. Patents 1,318,631; 1,31S,632; 1,318,633, Oct. 14, 1919.
< Landolt-B6rnstein, "Tabellen," 4th ed., 1912, 1142, 1144.
» Chemical Age (N. Y.), 28 (1920), 162.
4 J. Merritt Matthews, "Applications of Dyestuffs," 1920, 36.
ions play a very important part in assisting the
dye to combine with the fibers; therefore, with animal
fibers which, on account of their basic qualities, com-
bine chemically with the acid, maleic acid is not ex-
cessively injurious.
For the copper corrosion determinations, investiga-
tions were made with pieces of copper of approxi-
mately equal weight, having a surface area of 10 sq.
cm., completely surrounded by acid. It was found
that in a 0.2 per cent solution of these acids kept at a
boiling temperature continually for 7 days, there was.
a 3 . 2 per cent loss of copper due to the action of maleic
acid, whereas for fumaric acid there was only an 0.4
per cent loss. Other acids of importance which were
tested under the same conditions were lactic, formic,
and tartaric, these acids causing a loss of copper of
0.6, 1.6, and 1.5 percent, respectively.
APPLICATIONS FOR WOOLENS
In the consideration of the subject of the dyeing
of woolens, the applications for which these organic
acids and their salts have actually been tried may be
enumerated under the following divisions:
1 — Mordanting "assistant" for bottom-chroming of wool.
2 — For the top-chroming and meta-chroming processes.
3 — For the dyeing of wool with the indocyanines, fast wool
cyanones, etc.
4 — Wool printing.
MORDANTING "ASSISTANT" FOR THE BOTTOM-CHROM-
ING of wool — This application seems to be by far
the most important, and the results obtained look
very encouraging. White worsted wool in skeins was
used throughout the investigation. It was first treated
with a solution of olive oil soap and soda ash in the
ordinary manner, and was then mordanted in baths
containing 2.5 per cent of potassium dichromate (on
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
411
the weight of the wool) dissolved in a quantity of water
equivalent to 25 times the weight of the wool treated.
The reducing agents used in the two series of runs
were as follows, the percentage being the quantity by
weight, considering the weight of the wool as unity:
No. First Series
1 2.5% Acetic acid
2 2.5% Sulfuric acid
3 2.5% Cream of tartar
4 2.5% Tartaric acid
5 2.5% Lactic acid
6 2.5% Oxalic acid
7 2.5% Fumaric acid
8 2.5% Maleic acid
9 1.0% Maleic acid
10 2.0% Maleic acid
11 3.0% Maleic acid
12 1.5% Fumaric acid
13 2.0% Fumaric acid
14 3.0% Fumaric acid
Second Series
f.5% Acetic acid
1.5% Tartaric acid
!.5% Lactic acid
!.5% Fumaric acid
1.5% Maleic acid
!.5% Cream of tartar
1.5% Sodium acid fumarate
!.5% Sodium acid maleate
1.5% Cream of tartar with 2%
acetic acid
! 5% Sodium acid fumarate
with 2% acetic acid
!.5% Sodium acid maleate
with 2% acetic acid
>.0% Cream of tartar
i.0% Sodium acid maleate
The wool was allowed to remain in these mordant
baths 1 . 5 hrs. at a boiling temperature. The rate of
deposition of the chromium compounds on the fabric
was carefully noted. In all cases the mordant liquor
was a golden yellow in the beginning, but where the
"assistant" used actually reduced the acid chromium
of the K2Cr207 to the green basic chromium com-
pound Cr203l the mordant liquor gradually changed
to a greenish tint and the wool itself acquired a green-
ish color. The color changes of the mordant baths
therefore gave an excellent basis of comparison for
maleic and fumaric acids and their salts as compared
with the other reducing agents used. The ideal re-
ducing agent is generally considered as the one which
most completely converts the yellow compounds —
— chromic hydroxide, chromic acid, and the higher
oxide, Cr03 — to the green lower oxide, Cr203. It
was found in this investigation that maleic acid and
the sodium acid maleate both with and without acetic
acid gave a green color in the mordant liquor and a
greenish tint to the mordanted wool. This coloration
was very similar to that obtained with the lactic acid,
tartaric acid, and cream of tartar, whereas fumaric
acid and sodium acid fumarate acted like sulfuric and
acetic acids, and gave a yellow color in the mordant
liquor and a yellowish color to the mordanted wool.
The change of color of the mordant liquor from yellow
to green was about the same for the two reducers,
sodium acid maleate and cream of tartar, and for the
three acids, maleic, tartaric, and lactic. The cream
of tartar with acetic acid and sodium acid maleate
with acetic acid also gave a slow change to a greenish
color.
After mordanting, the wool was dyed in baths
containing Glauber's salt, acetic acid, and a quantity
of the dye equivalent to 2 per cent of the weight of
the wool treated. For the first series Anthracene
Blue S. W. G. G. (Badische), Alizarin Red, W. B. N.
(Badische), Alizarin Orange R (Sandoz), and Alizarin
Blue 5 R (Bayer) were used, and for the second series
Anthracene Blue S. W. G. G. (Badische) and Alizarin
Red W (Badische) were used. The dye baths were
brought to a boil in 0.5 hr. and boiled for 1 hr., after
which the woolen skein so obtained was used for fulling,
rubbing, washing, and light fastness tests.
1 Matthews, Loc. cit., p. 349.
In Run 1, the dyes Alizarin Orange and Alizarin
Red gave uniformly good results with all of the various
"assistants" used. Alizarin Blue 5 R showed up well
in all of the fulling and washing tests, but the light
fastness tests showed bad fading in 228 hrs. of ex-
posure. All the rubbing tests were poor with this
dye, and a considerable difference in the depth of
color of the dyed wool was noted. The deepest color
was obtained with cream of tartar and tartaric acid,
and a slightly lighter color was obtained with maleic,
acetic, oxalic, lactic, and sulfuric acids. The four
different percentages of fumaric acid gave the lightest
color. Anthracene Blue furnished an excellent basis
of comparison and showed that for the washing test
the best results were obtained with the mordant
baths containing 3 per cent fumaric acid, 2 per cent
fumaric acid, 1 . 5 per cent maleic acid, sulfuric acid,
acetic acid, and cream of tartar. The fulling test
showed that there was some staining in almost every
instance, but that the least was produced by the 3 per
cent fumaric, 2 per cent fumaric, oxalic, acetic, lactic,
and sulfuric acids. The rubbing test showed a pro-
nounced discoloration in every instance, but oxalic,
lactic, and 3 per cent maleic acids were probably slightly
the best. There was no variation in the color of the
dyed wool, nor was there any fading after 490 hrs. of
exposure to light.
In Run 2 all of the tests with Alizarin Red showed
up excellently, and no variations were observable. The
washing tests with Anthracene Blue showed that the
least staining was obtained with maleic, fumaric, acetic,
and lactic acids, sodium acid fumarate with and with-
out acetic acid, and sodium acid maleate with and
without acetic acid. The fulling test also showed the
least staining with these reducers. The rubbing
test with this dye showed that 2 . 5 per cent cream of
tartar gave the best results. All light fastness tests
showed up excellently after 490 hrs. exposure.
In consideration of the subject of selecting an "as-
sistant" for the bottom-chroming of wool, the dye to
be used must be carefully considered. In dyeing
dark blues and blacks with alizarins, lactic acid is
very satisfactory, while for light shades and light
tones the proper effect is more likely to be obtained
with cream of tartar,1 which, it is generally considered,
gives the best all-round results.2 It is claimed that a
deeper shade is obtained with lactic acid than with
tartaric acid; hence, for the same shade, it is possi-
ble to effect a saving of from 10 to 12 per cent of the
coloring matter.3 For some colors, such as Alizarin
Brown M, tartar does not give colors fast to fulling,2
and for certain dyes, such as Alizarin Blue N, lactic
acid cannot be used successfully because it affects
the colors unfavorably.4 It has been found that
Brilliant Alizarin Blue R will give best results with
chrome and oxalic acid, and that Gallocyanine gives
colors much faster to rubbing with a mordant of
chrome and tartar than with a mordant of chrome and
sulfuric or oxalic acids.1 Sulfuric acid furnishes an
» Matthews, Loc. cit., p. 347.
•■ Ibid., pp. 346-350.
> Farben-Zlg., April 15, 1896.
' J. Sac. Dyers Colourisls, 13 (1897), 112.
412
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
oxidizing mordant which is very valuable in dyeing with
logwood.1 It therefore seems very probable that de-
tailed investigations may reveal the fact that maleic
acid and its salts can be used successfully in certain
places where tartar and lactic acids do not work well,
and that fumaric acid may be used successfully to
replace sulfuric acid if an oxidizing effect is desired,
or if sulfuric acid is apt to exert an injurious effect on
the fabric, such as is the case in using it for dyeing
shoddy. Another place where lactic acid does not
work well is for the chroming of milled material such
as that used for hat bodies.2
FOR THE TOP-CHROMING AND META-CHROMING PRO-
CESSES— Other investigations which we have made in
this connection are in the processes of top-chroming
and meta-chroming of wool. For the top-chroming
process the dye used was Superchrome Blue B Double,
3 per cent of it having been used with 20 per cent of
Glauber's salts. The acids used were fumaric, maleic,
and acetic, 3 per cent of the two former and 5 per cent
of the latter. After the addition of the acids each
dye bath was brought to a boil in 20 min. and kept
there for 0.5 hr., after which 2 per cent sulfuric acid
was added to each, and the boiling continued for an-
other 0.5 hr. Finally 1.5 per cent potassium dichro-
mate was added to each bath and the boiling continued
for a third 0.5 hr. It was found that 3 per cent
fumaric acid and 3 per cent maleic acid gave results
practically as good as those obtained with 5 per cent
acetic acid.
In the meta-chroming process, the dye Super-
chrome Blue B Double was also used, and the meta-
chrome mordant was composed of a mixture of potas-
sium dichromate, Glauber's salt, and ammonium
sulfate. Each bath contained 3 per cent of the dye,
20 per cent Glauber's salt, and 6 per cent of the above-
mentioned meta-chroming mordant. The baths were
exhausted with 2 per cent acetic acid, 1 per cent
maleic acid, and 1 per cent fumaric acid, respectively,
but these acids were not added until each bath had
been boiled for 0.5 hr. After the addition of the
acids, the baths w7ere allowed to boil half an hour
longer before the woolen skeins were removed. It
was found that acetic acid gave better results than
either maleic or fumaric acids when twice as much
was used.
FOR THE DYEING OF WOOL WITH THE INDOC YANINES,
fast wool cvanones, etc. — Certain dyes, such as
Fast Wool Cyanone 3 R, are apt to be very unevenly
deposited upon the woolen fiber, and for this reason
ammonium acetate or other ammonium compounds
are used. As the dye bath is gradually heated the
acetate liberates the ammonia, and the acetic acid
set free is thus enabled to dissolve the dye and make
the color absorption possible. It was thought that
possibly maleic or fumaric acids might give a slow
deposition, and therefore dye baths were prepared
containing 2 per cent of the dye, 20 per cent Glauber's
salt, and the following quantities of the dyeing
assistants:
1 Matthews, hoc. cil., p. 347.
» Dcut. Hutmanhrr Z., 31, 30.
ll) 5 per cent ammonium acetate
(2) 5 per cent sodium acid maleate
(3) 2 per cent maleic acid
(4) 2 per cent fumaric acid
These solutions were boiled for about one hour.
The results obtained prove that neither of the above-
mentioned acids nor the sodium acid maleate will
work successfully for this purpose, as the dyeing with
ammonium acetate was much the best. We have
found that both ammonium fumarate and ammonium
maleate liberate ammonia when heated, and, since
neither of the liberated acids are volatile, as is acetic
acid, these salts should prove to be very good substi-
tutes for ammonium acetate.
wool printing — For printing wool, maleic acid
was substituted for tartaric acid with an acid color,
such as Azo Rubin. The pastes were made with
5 per cent maleic acid and 5 per cent tartaric acid,
respectively, the other constituents being 1 per cent
of the dye, British gum. Senegal, water, and alum.
It was found that maleic acid gave results equally
as good as did tartaric acid, and apparently gave a
slightly brighter color with this particular dye.
applications for silks
In considering the subject of the dyeing of silks,
the only important application of these acids investi-
gated was for the dyeing of silk with acid colors, al-
though organic acids are of importance for scrooping
and finishing for luster, and for dyeing with chrome
colors.
Maleic and fumaric acids were tried for replacing
such acids as sulfuric, acetic, and formic, which are
necessary in dyeing silk with acid colors. The dye
used was Wool Orange A Concentrated, 1 per cent of
it having been present in the dye bath together with
5 per cent of a neutral soap solution. The dye baths
were brought up to a temperature of about 190° F.
in from 10 to 15 min., and boiling was continued for
10 min. The following percentages of acids were
used in these baths.
(1) o per cent acetic acid
(2) 2.5 per cent fumaric acid
(3) 2.5 per cent maleic acid
(4) 2.5 per cent formic acid
(5) 2.5 per cent sulfuric acid
It was found that maleic and acetic acids gave
colors most intense, that sulfuric acid was next, and
that formic and fumaric acids gave colors which were
not quite so bright. Another run was made with
the same percentages of dye and soap, but with 5
per cent of acetic, fumaric, maleic, and formic acids.
10 per cent acetic acid, and 2 per cent sulfuric acid.
It was found here that the 10 per cent acetic acid
gave the brightest color, and that the maleic acid was
next and almost as bright, with the remaining four
dyeings somewhat less intense and each having about
the same intensity. This run was duplicated with
exactly the same percentages of acid and dye, but
with no soap solution, and it was found in this instance
that maleic acid gave a more intense color than even
the 10 per cent acetic acid, and that the fumaric,
formic, and sulfuric acids were almost as intense.
It may therefore be said that maleic acid w-orks
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
413
better than any of the other acids in baths of the
same acid concentration, which is in accordance with
expectations when an acid having such a high per-
centage of free hydrogen ions is used with an acid
dye, because high hydrogen-ion concentration causes
better penetration, more even dyeing, better exhaus-
tion, and brighter colors.1
APPLICATIONS FOR COTTONS
In the consideration of the subject of the dyeing of
cottons, laboratory investigations were made where
organic acids are necessary in cotton printing, and
the following results obtained.
For this particular work the insolubility of fumaric
acid is a great disadvantage and renders its use al-
most impossible, but some very interesting laboratory
results were obtained with maleic acid when used for
"discharges." Maleic acid was first tried instead of
tartaric acid for "discharging" Alizarin Red. Pastes
containing 10, 20, and 30 per cent maleic acid, respec-
tively, and one containing 30 per cent tartaric acid
were made with wheat starch and water. It was
found that the paste containing 20 per cent maleic
acid "discharged" as well as that containing 30 per
cent tartaric acid, and that the 30 per cent maleic acid
paste "discharged" equally well. Another place
where maleic acid works successfully is in the di-
chromate "discharging" for indigo. For this purpose
a paste was made with water, starch, dextrin, sodium
dichromate, and ammonium hydroxide, and the mix-
ture printed on pieces of cloth dyed with indigo. A
cutting bath was used which contained, in one in-
stance, oxalic and sulfuric acids and, in the other in-
stance, maleic and sulfuric acids, the concentration
being the same for each. Both acids "discharged"
the color successfully, but maleic acid did not do so
as thoroughly as did the oxalic acid. Investigations
were also made with maleic acid as a "discharge"
for basic colors in comparison with tartaric acid for
this purpose, and it apparently worked just as well
for cloth dyed with Methyl Violet 2 B. It was also
tried against tartaric acid in a tin discharge for direct
colors, and here it did not work nearly as well when
the dye Niagara Blue 2 B was used. When tried
against tartaric acid for a chlorate "discharge" for
sulfur colors, maleic acid was not as satisfactory as
tartaric acid with the dye Sulfur Blue L. It was
also found that the maleic acid can be used success-
fully to replace tartaric acid in printing with basic
colors when the dye Safranine A is used. In printing
with basic colors, such as Gallo-Navy Blue N. P. R.,
maleic acid works as well as acetic acid.
It must be remembered, however, that, in using maleic
acid for printing with pastes containing high per-
centages of acid, there is likely to be some tendering
of the fabric and also an injurious effect upon the
copper rolls, and hence it does not seem very proba-
ble that maleic acid can be used very advantageously
for a purpose of this nature, although both oxalic
and tartaric acids are likely to cause some tender-
ing.
i Chemical Age (N. Y.), 28 (1920), 162.
SUMMARY
For the bottom-chroming of wool both maleic and
fumaric acids and their sodium acid salts gave uni-
formly good fulling, rubbing, washing, and light fast-
ness tests, as compared with the results obtained with
the important lactic and tartaric acid compounds so
extensively used for this purpose. The action of
maleic acid most closely resembled that of lactic and
tartaric acids; the action of sodium acid maleate
closely resembled that of cream of tartar; and the ac-
tion of fumaric acid most closely resembled that of sul.
furic and acetic acids. The best comparative results
were obtained with the dye Anthracene Blue S. W. G. G.
For the top-chroming process, both maleic and fu-
maric acids successfully replace larger percentages of
acetic acid. For the meta-chroming process neither
of these acids can be substituted successfully for twice
as much acetic acid, although their ammonium salts
might be more valuable than ammonium sulfate for
meta-chroming shoddy. Neither of the acids works
satisfactorily as a substitute for ammonium acetate,
but their ammonium salts liberate ammonia when
heated, and the acids, not being volatile, remain in
the dye bath. For wool printing, maleic acid works as
well as tartaric acid.
For the dyeing of silks with acid colors, maleic acid
gives brighter colors than the same percentage of any
other acid tried, and fumaric acid gives colors as in-
tense as formic acid, thus proving that either can be
used successfully. For "discharging" in cotton print-
ing, maleic acid is a good substitute for tartaric acid
when used for certain colors, and for oxalic acid when
used for "discharging" indigo.
The above-outlined investigations give some very
definite ideas as to where these acids and their salts
are likely to be of greatest commercial importance. It
can be readily understood that their application to
the textile industry is a problem still in its infancy
and that there is much work to be done before any
comprehensive report can be submitted.
ACKNOWLEDGMENT
In conclusion, it is desired to acknowledge especial
indebtedness to Mr. A. E. Sampson, chief chemist
of the Dye Application Laboratory of the National
Aniline & Chemical Co., from whom many of these
suggestions originated.
The Summerland Kelp-Potash Plant
The United States Congress during its last session decided to
terminate its kelp-potash work at Summerland, California, and
to turn over the plant there in operation to private enterprise
to operate for the manufacture of bleaching or decolorizing car-
bon, potash salts, and iodine — the three products so far com-
mercialized. The manufacture of these three commodities
from the large and inexhaustible source of raw material — the
giant kelps of the Pacific — now seems to offer an advantageous
commercial opportunity. The plant is now being operated
under the direction of the Bureau of Soils of the U. S. Depart-
ment of Agriculture. It has a drying capacity of 100 tons of
wet kelp per day, fro mwhich there are being produced 1500 lbs.
of bleaching carbon of standard grade and 2 tons of potash
salts. The plant will be offered for sale.
414
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
A New Lead Number Determination in Vanilla Extracts1
By H. J. Wichmann
Denver Station, Bureau of Chemistry, Department op Agriculture, Denver, Colorado
Winton3 and his co-workers devised a lead num-
ber, now the official A. O. A. C. method, for analyzing
vanilla extracts. It has been found useful in detecting
diluted extracts, because it is a measure of the flavor-
ing principles, exclusive of vanillin, extracted from
the vanilla bean. Winton, Lott and Berry4 have de-
termined the lead numbers of many authentic ex-
tracts and found the minimum to be 0.40.
According to Winton, the number is determined sub-
stantially as follows:
After the de-alcoholization of 50 cc. of the extract at a tem-
perature below 70° C, the residue is transferred to a 100-cc. flask,
2.5 cc. of 8 per cent neutral lead acetate are added, and the volume
is made up to the mark with carbon-dioxide-free water. The
flask is kept at a temperature of 37° to 40° for at least 18 hrs.
After cooling, the solution is filtered and the lead in 10 cc. of the
filtrate is precipitated with sulfuric acid The lead sulfate is
collected on a Gooch crucible, dried, ignited, and weighed. The
difference between the lead sulfate weighed and that found in
a blank, calculated to lead and multiplied by 20, gives the lead
number. It is the quantity of lead precipitated by 100 cc. of
the extract.
There are two objections to the method. It is
time-consuming and represents, not a complete
precipitation, but only that which occurs under an
arbitrary set of conditions. Its slowness hinders
the development or use of speedy methods for a com-
plete analysis of vanilla extracts. Winton5 found
that the value was influenced by time and tempera-
ture, since the reaction does -not come immediately to
an equilibrium, and the equilibrium varies with the
temperature. The temperature of the bacteriological
incubator was selected by him as convenient. Winton
combined his lead number determination with that
for vanillin. To obtain a maximum precipitation
and save time, the temperature has been increased to
the boiling point, and the lead number and alcohol
determinations combined. For this purpose the fol-
lowing method was devised.
NEW LEAD NUMBER
To 175 cc. of boiled water in a liter flask add 25 cc.
of 8 per cent neutral lead acetate solution and 50 cc.
of extract. Place the flask over an asbestos board
provided with a circular hole and of sufficient width
to prevent heating the sides of the flask. Distil 200
cc. with a medium flame. Calculate the approximate
alcohol content from the specific gravity of the dis-
tillate. (Accurate work will require redistillation
from alkaline solutions.) Transfer the residue to a
100-cc. flask with carbon-dioxide-free water and a
bent policeman. When cool, fill to the mark and fil-
ter. To a 10-cc. aliquot part add 25 cc. of water, 10
cc. of dilute sulfuric acid, and, with stirring, 100 cc.
of 95 per cent alcohol. When settled clear, filter on
1 Received September 10, 1920.
1 Published by permission of the Secretary of Agriculture.
"» Proceedings A. O. A. C, Bureau of Chemistry, Bulletin 132, 109.
' Ibid., 152, 155.
' Proceedings A. O. A. C, Bureau of Chemistry, Bulletin 137, 120.
a Gooch crucible, wash with alcohol, dry, ignite at
low redness, avoiding the reducing flame, and weigh.
Considerable time may be saved by precipitating as
above in a nursing bottle, then centrifuging at high
speed for 10 min., or until the supernatant liquid is
clear. Conduct a blank experiment, employing water
containing 5 drops of glacial acetic acid in place of the
extract. Calculate the number of grams of metallic
lead precipitated by 100 cc. of the sample.
In the above method no de-alcoholization or long
standing is required. When the precipitation is made
at boiling temperature an equilibrium is quickly estab-
lished. Consistent Winton lead numbers cannot be
obtained unless the extract is first de-alcoholized. In
the new method the alcohol is distilled off and its in-
fluence on the lead number removed. Practically
the same lead numbers were obtained before and after
evaporation of the alcohol.
In the enforcement of the Food and Drugs Act,
different analysts, often stationed far apart, must ob-
tain check results on the same sample. The lead
numbers of three extracts determined at Denver
(boiling point of water about 95° C.) and San Francisco
checked so closely that it would appear that differ-
ences in boiling point due to altitude have no appreci-
able effect.
LEAD NUMBERS OF AUTHENTIC AND UNADULTERATED
COMMERCIAL VANILLA EXTRACTS
Lead numbers were determined on authentic vanilla
extracts, prepared from the beans by the U. S. P.
method, in the Denver and Chicago Station Labora-
tories, and on available commercial extracts which
analysis indicated to be free from adulteration. The
results are given in Table I.
Table I — Lead Numbers op Unadulterated Vanilla Extracts
Tahiti
Cook Island
Mexican
Madagascar
Comores
Tahiti
Cook Island
M
IS
Tahiti and Bourbo
Bourbon
Tahiti"
Tahiti and Bourbo
Tahiti
Unknown
Unknown*
Unknown
Unknown2
Unknown
Source
Authentic
Authentic
Authentic
Authentic
Authentic
Authentic
Authentic
Commercial
Commercial
Commercial
Commercial
Commercial
.1
Commercial
Commercial
Commercial
Commercial
Commercial
Ethyl
Alcohol
Per
cent
51.0
51 5
48.8
52.2
50.2
52.0
52.2
43.0
31.2
41.0
42.8
31.2
53.4
35.8
37.6
35.8
33.0
31.0
Lead
No.
A.O.A.C.
Method
0.53
0.69
0.59
0.47
0.60
0.42
0.74
0.63
0.42
0.66
0.43
0.42
0.52
0.62
0.48
0.76
0.53
0.60
Method
over
Lead Official
No. Method
New Per
Method cent
34.0
0.90
0.82
0.66
0.84
0.57
0.96
0.82
0.55
0.88
0.71
0.55
0.68
0.S4
0.67
0.97
0.76
0.77
30.4
39.0
40.4
40.0
35.7
30.0
30.1
30.9
33.3
65. 1»
30.9
30.7
35.4
40.0
27.6
42.9
28.5
Average 0.56 0.76 34.1
1 An extremely colloidal extract. Almost impossible to filter when de-
termined by official method. No difficulty experienced in the new method.
■ Colloidal, but not excessively so.
1 Excluded from average.
An inspection of the table shows that the lead
numbers, as determined by the new method, are about
one-third higher than by the official method. If the
minimum Winton lead number of undiluted, pure ex-
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGIN EERI NG CHEMISTRY
4 15-.
tracts is 0.40, that by the new method should be
approximately 0.53. The lowest value found was
0.55.
Included in the table are data on Tahiti Extract 11,
which appears to be abnormal. This was one of the
extracts occasionally met which are almost impossi-
ble to filter when precipitated according to the Winton
method. The difficulty appears to be due to unusual
colloidal properties which these extracts possess. No
trouble in filtering was experienced with the new
method. The increase in the lead number was 65
per cent; about twice the usual figure. It seems,
therefore, that colloidal phenomena are connected with
the Winton lead number which may prevent com-
plete precipitation and thus give low results. In
the' writer's opinion, the results obtained by the new
method are more reliable, especially in the case of the col-
loidal extracts already mentioned. For example, Ex-
tracts 6, 9, 11, and 12 show low lead numbers by the
official method, and might be considered poor extracts
or better ones diluted to near the danger line. The
new method reveals the difference, however. The
Wichmann lead number of Extract 11 is close to the
average, while the others have nearly minimum values
by both methods.
When neutral lead acetate is added to a vanilla ex-
tract, water-insoluble lead salts and free acetic acid
are produced. This reaction may be reversed by add-
ing excess acetic acid, and even 0.1 cc. of glacial acetic
acid added to 50 cc. of de-alcoholized extract was
found to have a surprising lowering effect on the lead
numbers. The complete precipitation of organic
lead salts from vanilla extracts may be partially pre-
vented by the free acetic acid and by hitherto not
well-understood colloidal forces. The Winton lead
number is therefore only the average of various op-
posing factors. Heat appears to hasten and increase
precipitation by destroying or minimizing the col-
loidal factor. Theoretically, basic lead acetate should
be the best lead number reagent, because the solvent
action of the liberated acetic acid would be prevented
by its irtimediate neutralization. Unfortunately, how-
ever, vanillin produces an insoluble compound with
basic lead acetate. Its use, therefore, defeats the
purpose for which lead numbers were devised. Un-
less a method can be found for completely extracting
the vanillin without at the same time removing some
of the other extractive matter of the vanilla bean, we
shall be compelled to continue to use the somewhat
defective neutral lead acetate. We possess at this
time comprehensive data on lead numbers of authentic
extracts, all determined by the Winton method.
These data have been extremely useful in interpreting
analyses. However, results can in most cases be in-
terpolated, with a fair degree of accuracy, from one
method to the other by multiplying by four-thirds or
three-fourths. When this cannot be done, as for ex-
ample in the case of those peculiar colloidal extracts,
the lead numbers by the new method are the most
trustworthy.
Of course the new method will eliminate all color
values on the filtrate. These are now tentatively
official. However, they have not been as useful in
detecting caramel' coloring as was originally expected.
The modified Marsh test is much simpler and just as
reliable. To offset this disadvantage, the new method,
is believed to have the advantages of speed, repre-
senting as complete a reaction as it is possible to ob-
tain with neutral lead acetate, and reliability, especially
in the case of colloidal extracts.
LEAD NUMBERS OF ADULTERATED EXTRACTS
In Table II are given analyses of adulterated ex-
tracts:
Table II — Results of Analyses of Adulterated E
Lead No. Lead No. Official
Alcohol A.O.A.C. New Method
No. Composition Per cent Method Method Per cent
1 Mexican Tahiti extract adul- 37.4 0.36 0.50 38.8
terated with prune juice
2 1.0 g. vanillin. 0.2 g. cou- 14.6 0.13 0.26 100.0
marin, solids including
glycerol 5.5 g., ash 0.07 g.
per 100 cc.
3 1.2 g. vanillin, 0.14 g. cou- 7.6 0.065 0.13 100.0
marin, 0.03 g. ash, 13 g.
solids per 100 cc; colored
with caramel
4 0.3 g. vanillin, 0.1 g. cou- 10.2 0.060 0.095 60.0
marin, 0.07 g. ash, 23 g.
sugar per 100 cc; colored
with caramel '
5 Second extraction of Cook Is- 50.6 0.05 0.08 60.0
land beans, according to
U. S. P. method
The increase in the new lead number in four exam-
ples seemed to be abnormally large. Experiments
were undertaken to determine the cause.
EFFECT OF VANILLA EXTRACT INGREDIENTS ON LEAD
NUMBER
sugar and glycerol — Two extracts were prepared
from the beans with an alcoholic, non-sugar menstruum.
Various quantities of sugar were added to these ex-
tracts, and the sweetened and original solutions were
analyzed. It was found that sugar up to 20 per cent
(U. S. P. strength) had no effect on the lead number,
determined by either method. This statement ap-
plies to both U. S. P. extracts and those highly di-
luted. Glycerol was added to extracts in increasing
quantity up to 20 per cent by volume. The slight
lowering effect of glycerol, especially in the case of
dilute extracts, was hardly more than the limit of
error of the methods, and might have been due to the
presence of a little acid in the glycerol.
coumarin — Coumarin is rarely found in adulterated
extracts in excess of 0.5 g. per 100 cc. When this
quantity of coumarin was added to extracts, no ap-
preciable effect on the lead number could be observed.
These experiments served to indicate that sugar,
glycerol, or coumarin in the quantities usually found
in extracts were not responsible for the abnormali-
ties appearing in Table II.
vanillin — The addition of vanillin to an extract
does have an effect on the lead number, the degree
varying with the quantity added and the dilution of
the extract. Equal volumes of extract were placed in
graduated flasks, and increasing weights of vanillin
added. After making up to volume with dilute alco-
hol, the resulting solutions contained equal quantities
of extractive matter, but different amounts of vanillin.
416
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No 5
The first experiments were made with solutions con-
taining 80 per cent of the original extracts. The Win-
ton lead numbers of these solutions were 0.43 and
0.58, and the vanillin varied from 0.18 to 1.84 g.
per 100 cc. The addition of vanillin seemed to have
no. appreciable effect on the lead number, by either
method. It was therefore surprising to note the de-
cided effect when greater dilutions of the same extract
were used. Table III shows some of the results ob-
tained.
Ill— Ef
CT OF ADDITH
[LLIK
ad Number
Increase New
Approximate Lead No. Lead No. Method i
Vanillin Content A O AC. New A.O.A C. Method
G. per 100 Cc. Method Method Per cent
Tahiti: 25 Per cent Original Extract
0.055 0.105 0.176 67.6
1.055 0 109 0 194 78.0
1.66 0 166 0.277 66 2
50 Per cent Original Extract
0.11 0.251 0.366 45 8
1.11 0 246 0.370 50 4
1.73 0.266 0.380 42 8
75 Per cent Original Extract
0.16 0.392 0.519 32.4
1.16 0.400 0.515 28.7
1.80 0.407 0.530 30.2
Cook Island: 25 Per cent Original Extract
0.07 0.179 0.242 35.2
1.07 0 172 0 246 43.0
1.77 0 213 0.314 47.4
40 Per cent Original Extract
0.12 0.253 0 369 45.8
1.82 0.270 0 410 51.8
Commercial Extract: 25 Per cent Original Extract
0.035 0.094 0.127 35.1
1.03 0 110 0.160 45 4
1.78 0 162 0 296 82.7
50 Per cent Original Extract
0 07 0.183 0.244 33 3
1.07 0.188 0.272 44 6
1.82 0.225 0 363 61 3
75 Per cent Original Extract
0 10 0.293 0.370 26.3
1.80 0.292 0.426 45.8
Hitherto food analysts have considered that the
vanillin took no part in the Winton reaction. The
data in Table III show that under certain circum-
stances this may not be true. When an extract has
been diluted and at the same time sufficiently rein-
forced with vanillin, the lead number, by either method,
is apt to be too high and not proportional to the de-
gree of dilution. There are numerous examples of
such extracts on the market. In interpreting analyses,
the writer has frequently observed that in adulterated
extracts greater percentages of extractive matter ap-
peared to be present on the basis of lead number than
on the percentage of ash. The data in Table III
seem to offer a clue to the reason. Unwarrantedly high
lead numbers are obtained only when there has been
a decrease in vanilla and, at the same time, an increase
in vanillin. The explanation of these curious results
appears to be as follows: Vanillin has an acid hydro-
gen atom replaceable by bases, lead among them.
Lead subacetate produces a water-insoluble lead-
vanillin compound, soluble in slight excess of acetic
acid. This salt is precipitated from even very dilute
solutions. Eight per cent neutral lead acetate will
not produce a precipitate with a vanillin solution un-
less the concentration of the vanillin is over 0.15 g.
per 100 cc. at room temperature. At boiling tempera-
ture the critical concentration is about half that at
room temperature. The precipitate found at greater
concentration is also soluble in acetic acid. When
neutral lead acetate is added to a vanilla extract, in-
soluble lead salts are precipitated and an equivalent
quantity of the acetic acid necessarily liberated. If
this is sufficient it will prevent the precipitation of
the lead-vanillin salt, and no undue increase in the
lead number results. The data in Table III show
that if enough extractive matter from the bean is
present to make a Winton lead number of about 0.3,
almost 2 g. of vanillin per 100 cc. can be added with-
out a very appreciable effect on the lead number.
With dilutions greater than that corresponding to this
critical value of 0.3, less and less vanillin can be added
without raising the lead number unduly. With no
vanilla extract present, the lower limit of vanillin is
0. 15 g. per 100 cc. by the Winton and less by the new
method. This difference in the lower limit probably
accounts for the greater sensitiveness to the addition
of vanillin exhibited by the new method in the data of
Table III.
LEAD NUMBER METHODS MODIFIED TO FIT VANILLIN
REINFORCED EXTRACTS
In food analysis it is often necessary to estimate
the quantity of extractive matter or degree of dilu-
tion in adulterated extracts. Since the addition of
vanillin to an extract may or may not have an effect
on the lead number, some modification that will give
proportional results on reinforced or compound ex-
tracts is very desirable. Alcoholic vanillin solutions
cannot be extracted with ethyl ether without extract-
ing some vanilla, as indicated by the brown coloring
matter. This can be prevented by adding petroleum
ether to the ethyl ether. The solubility of vanillin
in ethyl ether is lessened thereby, but not enough to
prevent the extraction of excess vanillin. Upon these
facts is based the modified method for vanillin rein-
forced extracts.
Table IV — Efficiency of Mixture of Ethyl and Petroleum Ethbr3
in Extracting Vanillin from Water-Alcohol Solutions
Vanillin
Extracted
by 25 Cc
Ethyl Ether
and 25 Cc. Vanillin Vanillin
Vanillin Petroleum Extracted Extracted Total
in 50 Cc. Strength Ether in 3 Fourth Fifth Vanillin
Solutions Alcohol Extractions Extraction Extraction Extracted
Grams Per cent Per cent Per cent Per cent Per cent
1.0 50 70 1 13 1 7.0 90.2
0.5 50 75 3 12.7 7.0 95.0
1.0 25 87.0 7.3 3 1 97 4
0.5 25 88.4 6.4 3 0 97.8
Vanillin
Extracted
by 25 Cc.
Ethyl Ether and
50 Cc. Petroleum
Ether in 3
Extractions
1 0 50 57.1 13.8 10.0 80.9
0 5 50 62.8 14.4 10.6 87.8
1 0 25 81.9 8.7 4.9 95.5
0.5 25 83.2 8.2 3.8 95.2
modified method — Shake gently 50 cc. of the ex-
tract with 25 cc. of ethyl ether in a separatory funnel.
If the alcohol content of the extract is high no separa-
tion into layers may occur. Add 25 cc. of petroleum
ether and shake again. If no clear-cut separation
into brown aqueous and colorless ether layers has
been effected, add more petroleum ether in small por-
tions, shaking after each addition until the ether layer
is colorless. A greater amount than 25 cc. is rarely
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
.41.7
required. If an emulsion forms, break it with a few
cc. of alcohol. Draw off the aqueous layer into a
beaker, add 2 cc. of water to the ether, and shake again.
Draw off the water and discard the ether. Repeat
this two or more times, as indicated later. The water
solution after the last extraction is used for lead num-
ber determinations according to either method, as
desired. The efficiency of the above method of ex-
traction is well illustrated in Table IV.
These efficiency data show that three extractions
with equal quantities of mixed ethers are sufficient
to remove the vanillin from low alcohol extracts to
such a degree that a correct lead mtmber can subse-
quently be obtained. More than 25 cc. of petroleum
ether may have to be used as an extracting medium
if the extract contains more than 25 per cent alcohol.
In such cases, and also when alcohol has been used to
break emulsions, an additional extraction should be
made. In general, the alcoholic strength of the ex-
tract, as indicated by the effectiveness of the first 25
cc. of ethyl ether in separating the extract into clean-
cut layers, governs the number of extractions.
In Table V are given the results of some experi-
ments intended to demonstrate the erroneous lead
numbers which excess vanillin may produce and the
corrective effect of previous extraction of the vanillin.
Two 50-cc. portions of vanilla extract were made up
to 200 cc. with dilute alcohol, one having also an ad-
dition of vanillin. The vanilla content was the same
in both.
Table V — Lead Numbers of Diluted and Reinforced Extracts by the
WlNTON AND WlCHMANN METHODS, AND A MODIFICATION OF THE SAME
Increase
New
Method
does. This was tested by determining lead numbers
on three extracts diluted as indicated in Table VI.
Alcohol Lead No. Lead No.
Vanillin Content Content by Winton by New
G.perlOOCc Percent Method Method
Winton
Method
Per cent
0.05
1.75
40
40
0.098 0.142
0.165 0.305
44.9
84.8
Excess vanillin of No. 2 extracted
3 times with 25 cc. ethyl and
25 cc. petroleum ether
40
0.095 0.138
45 2
0.05
1.75
Excess vanillin of No. 5 extracted
as in No. 3
25
25
25
0.101 0.145
0.155 0.285
0.097 0.142
43.5
83.8
46.4
0.035
1.637'
Excess vanillin of No. 8 extracted
4 times with 25 cc. ethyl and
35 cc. petroleum ether; vanil-
lin extracted equivalent to
1.49 g. per 100 cc.
25
25
25
0.067 0.113
0.136' 0.276
0.063 0.109
68.6
102.9
73 0
The amount of vanillin determined ii
i the filtrate was found to be
equivalent to 1.534 g. per 100 cc. Since 1.637 g. were originally present,
the difference, or 0.103 g.. was made insoluble by the lead and caused an
increase in the lead number of 0 069. In certain kinds of extracts, therefore,
the Winton method not only gives erroneous lead numbers but incorrect
vanillin percentages as well.
When the greater part of the vanillin is extracted
before precipitation the lead numbers are correct
and proportional to the amount of extractive matter
actually present. This is necessary only in the case
of diluted extracts reinforced with vanillin.
EFFECT OF DILUTION ON LEAD NUMBER
A scrutiny of some of the previous tables will show
that the percentage increase of the lead number by
the new over the official method was generally higher
in diluted than in the stronger extracts. This might
be due to the fact that on dilution the Winton does
not give proportional results, while the new method
ABLE VI-
-Lead Numbers of Vanilla Extracts and of
Dilutions of
the Same
Increase New
Method over
Original
Lead No.
Lead No.
Winton
Extract
Winton
Calculated New
Calculated
Method
Per cent
Method
Lead No. Method
Extract 1
Lead No.
Per cent
100
0.640
0.920
43.7
50
0.330
0.320 0.460
o!460
39.4
30
0.208
0.192 0.287
0.276
38.0
20
0.125
0.128 0.173
0.184
38.4
10
0.055
0.064 0.094
0 092
70.9
5
0.027
0.032 . 0.049
Extract 2
0 046
81.5
100
0.565
0.800
41.5
50
0.293
0.282 0.414
o!46o
41.3
30
0.173
0.169 0.238
0.240
37.5
20
0.109
0.113 0.162
0.160
48.6
10
0.052
0.056 0.078
0.080
50.0
5
0.020
0.028 0.034
Extract 3
0.040
70.0
100
0.480
0.648
35.0
20
0.057
0.096 0 121
0T29
112.0
10
0.028
0.048 0.057
0.065
103.5
The extracts employed for dilution in two of these
experiments appear to have been somewhat abnormal,
because the percentage increase of the lead number
was rather high to begin with. The table indicates,
especially in the case of the third extract, that the new
method produces results more nearly proportional to
the degree of the dilution than does the Winton method.
Addition of vanillin and dilution seem to work in the
same direction, and the high percentage increase in
lead number observed in the adulterated extracts in
Table II is fully explained.
It seems to the writer that the new method is worthy
of consideration by food analysts. It produces ac-
curate and quite trustworthy results on pure or di-
luted extracts in a comparatively short time. This
cannot be said of the Winton method. On vanillin
reinforced extracts, especially those which have been
diluted, both methods must be modified. The effects
of excess vanillin, in such special cases, can be neu-
tralized by first extracting it. The time required is
certainly less than that needed for a de-alcoholization.
The new has the further advantage over the Winton
method in that it represents as complete a reaction as it
is possible to obtain with neutral lead acetate, and thus
obviates all uncertain or variable colloidal phenomena.
If the vanillin were completely extracted previous to
precipitation, it is probable that subacetate of lead
would prove to be the better lead number reagent,
because of the neutralization of the liberated acetic
acid. A lead number would not then be a compromise
as at present. The writer has in mind a scheme for
extracting the vanillin and estimating it by a volu-
metric method, and then determining the lead num-
ber by making a hot precipitation with lead subace-
tate. Such a method should be both speedy and re-
liable. The details, however, remain for future
work.
SUMMARY
1 — A new method for determining lead numbers of
vanilla extracts has been developed.
2 — Lead numbers of authentic and commercial
extracts have been determined by both new and old
methods.
418
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
3 — Certain abnormalities found in adulterated ex-
tracts are shown not to be due to the addition of reason-
able amounts of sugar, glycerol, or coumarin.
4 — High lead numbers by both methods are shown
to result from reinforcing extracts with excess vanillin,
especially in the case of diluted extracts.
5 — A modified method for removing excess vanillin
before precipitation with lead acetate has been de-
vised, which nullifies the effect of the excess vanillin
on the lead number.
6 — The new method produces results in the case of
diluted extracts more nearly proportional than the
official method.
7 — It is demonstrated that the new method has the
advantages of speed and reliability over the Winton
official method.
The Mineral Constituents of Potatoes and Potato Flour: Effect of Process of
Manufacture on Composition of the Ash of Potato Flour1
Commercial Dg
ratory, Bureau
By C. E. Mangels
5K Chemistry, U. S. Department of Agriculture, Washington, D. C.
The potato flour industry became established in the
United States during the war, and the question of
whether loss of mineral constituents occurred during
manufacture has frequently been raised. It has also
been claimed that if potatoes were not peeled a greater
portion of the mineral constituents would be conserved.
The purpose of this investigation was, therefore, to
obtain analytical data which would settle such ques-
tions.
PROCESSES OF MANUFACTURE OF POTATO FLOUR
The "hot drum" process is now commonly used
by the different companies engaged in the manufac-
ture of potato flour and in detail is as follows: The
potatoes are washed and unsound potatoes sorted out
and discarded. The peel is partially removed by fric-
tion paring machines, and the potatoes placed in a
steam retort cooker where they are subjected to cook-
ing by steam at 15 lbs. pressure for 15 to 20 min.
The soft cooked potatoes then pass to hot steam-heated
revolving drums over the surface of which they are
spread in a very thin layer, and are thus quickly dried.
The dried potato film is removed from the drum as it
revolves by stripper knives, and the dry flakes are
reduced to flour, after which the flour is bolted and the
tailings discarded.
This process differs in detail from that previously
used, in which potatoes were not peeled and the
flour was not bolted. Peeling and bolting gave a
flour of much lighter and better color, but claims
that the darker and less attractive flour from unpeeled
potatoes was more nutritious were made on the ground
that a greater portion of mineral constituents was
retained.
EXPERIMENTAL PROCEDURE
Samples of both the fresh potatoes and potato
flour were obtained from different mills. The fresh
potatoes were secured from the individual mills in
order to avoid errors due to difference in composition
of the individual potatoes, and the flour samples (from
peeled potatoes) were from the same lots of potatoes.
Samples of flour from unpeeled potatoes were se-
cured, but it was impossible to obtain fresh potatoes,
since only samples from the previous year's operations
were available.
The usual food analysis was made on each sample of
1 Received December 10, 1920.
potatoes and flour, and in addition the following min-
eral constituents were determined: CaO, MgO, K»0,
P205, S, and CI. Table I shows the composition of
the fresh potatoes and of the flour as received. Table II
gives the composition of potatoes and flour on a mois-
ture-free basis for comparative purposes. Table III
shows the relative per cent of the different mineral
constituents in the ash of the potato and flour.
DISCUSSION OF RESULTS
Table I indicates that some variation exists in the
composition of the fresh potatoes; and this difference
in composition of the fresh material is reflected to
some extent in the composition of the flour. The
total ash content of both potatoes and flour from Mill C
is appreciably higher than in the remainder of the
samples. The calcium content is higher in samples
from Mills C and D.
Table II gives the composition on a moisture-free
basis for comparative purposes. Comparing the po-
tatoes with the flour (from unpeeled potatoes) from
each mill, it will be noted that the percentage of total
ash is lower in the flour in each case, and the average
percentage of this constituent is also appreciably
lower. The percentage of potash is also appreciably
smaller in the flour, while the percentage of phos-
phorus is very slightly smaller in the flour. The pro-
portion of other ingredients is practically the same in
the flour (peeled potatoes) as in the fresh potatoes.
An examination of the flour from unpeeled potatoes
shows that the percentage of total ash and of potash
is higher than in the flour from peeled potatoes. This
indicates a slight loss of mineral constituents due to
peeling. The loss of potash, however, is almost negli-
gible, while the loss of total ash is somewhat larger.
Since the proportion of other ingredients is unchanged,
this would indicate that the loss of total ash was due
to loss of some undetermined element, probably silicon,
which would be found on the outer surface of the fresh
potato, even when well washed.
The loss in potash may be accounted for by the fact
that the steam condensation would dissolve some of the
potash salts, and this solvent action would take place
more readily if the potatoes were peeled. The loss
of potash, however, is small, and for practical purposes
can be considered negligible.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
419
Table I — Composition of Fresh Potatoes and Potato Flour
Fat
(Ether Protein Crude Total Starch
Mill Water Extract) N (NX 6.25) Fiber Ash (Diastase) N. F. E. CaO MgO KiO PjO« S Cli
Potatoes — Fresh Basis
A 78.07 0.078 0.38 2.38 0.62 0.99 14.37 17.86 Trace 0.052 0.4:. 0.146 0.030 0.017
B 77.03 0.123 0.41 2.56 0.55 0.99 15.70 18.75 Trace 0.056 0.52 0.134 0 038 0 020
C 75.02 0.160 0.27 1.69 0.54 1.42 18.26 21.17 0.040 0.064 0.65 0.140 0.031 0.061
D 76.11 ' 0.080 0.33 2.01 0.56 1.03 16.25 20.21 0.017 0.069 0.57 0.174 0.026 0.062
Natural Potato Flour — Bolted and Made from Peeled Potatoes
A 6.41 0.312 1.67 10.44 2.36 3.29 63.73 77.19 Trace 0.205 1.70 0.557 0.136 0.062
B 8.50 0.425 1.57 9.81 1.59 3.49 63.71 76.19 Trace 0.181 1.84 0.525 0.142 0.063
C 8.57 0.551 1.28 8.00 1.55 4.90 63.38 76.43 0.132 0.225 2.27 0.473 0.126 0.180
D 6.85 0.19 1.19 7.44 1.53 3.93 57.89 80.06 0.100 0.240 2.07 0.610 0.186 0.067
Natural Potato Flour — Unbolted and Made from Unpeeled Potatoes
C 6.40 0.16 1.26 7.98 1.66 4.53 62.62 79.27 0.125 0.242 2.32 0.410 0.132 0.160
C 7.11 0.16 1.27 8.04 1.54 4.55 62.80 78.60 0.135 0.240 2.33 0.440 0.128 0.170
D 6.55 0.17 1.27 8.04 1.66 4.34 63.02 79.24 0.100 0.260 2.34 0.415 0.098 0.130
Table II — Composition of Fresh Potatoes and Potato Flour (Moisture-Free Basis)
Fat
(Ether Protein Crude Total Starch
Mtll Water Extract) N (N X 6.25) Fiber Ash (Diastase) N. F. E. CaO MgO KiO PsOi S Cb
Fresh Potatoes
A 0.354 1.75 10.94 2.81 4.50 65.53 81.40 Trace 0.236 2.12 0.667 0.136 0 076
B 0.537 1.80 11.25 2.40 4.33 68.35 81.48 Trace 0.243 2.27 0.584 0.164 0 086
C 0.639 1.10 6.88 2.17 5.70 73.10 84.61 0.161 0.256 2.60 0.570 0.126 0 243
D 0.320 1.39 8.69 2.35 4.31 68.00 84.33 0.070 0.290 2.39 0.730 0.108 0.260
Average 0.463 1.51 9.44 2.43 4.71 68.75 82.96 0.058 0.256 2.35 0.638 0.134 0.166
Natural Potato Flour — Bolted and Made from Peeled Potatoes
A 0.333 1.78 11.12 2.52 3.51 68.10 81.52 Trace 0.219 1.82 0.595 0.145 0.066
B 0.464 1.72 10.75 1.74 3.82 69.63 83.23 Trace 0.198 2.01 0.574 0.155 0.069
C 0.603 1.39 8.69 1.70 5.36 69.32 83.65 0.144 0.246 2.48 0.517 0.138 0.197
D 0.200 1.28 8.00 1.64 4.22 62.15 85.94 0.107 0.279 2.22 0.655 0.109 0.072
Average 0.400 1.54 9.64 1.90 4.23 67.30 83.83 0.063 0.236 2.13 0.585 0.137 0.101
Natural Potato Flour — Unbolted and Made from Unpeeled Potatoes
C 0.170 1.34 8.38 1.77 4.84 66.90 84.84 0.134 0.259 2.48 0.438 0.141 0.171
C 0.170 1.37 8.56 1.66 4.90 67.61 84.71 0.145 0.258 2.51 0.474 0.138 0.183
D 0.180 1.36 8.50 1.78 4.64 67.44 84.90 0.107 0.278 2.50 0.444 0.105 0.139
Average 0.173 1.36 8.48 1.74 4.79 67.32 84.81 0.129 0.265 2.50 0.452 0.128 0.164
Table III shows the relative percentage of the differ- of total' ash, and a very slightly smaller percentage of
ent mineral constituents in the ash. Some variation, potash than the corresponding fresh potato.
due probably to difference in composition of the fresh 3 — The relative distribution of different mineral
potato, exists. The amount of phosphorus in samples constituents in the ash is not appreciably changed
from Mill C is appreciably lower than in the others, during the process of manufacture of the flour,
with the exception of a sample of flour from unpeeled 4 — In so far as mineral constituents are concerned,
potatoes from Mill D. the nutritive value of potato flour is practically the
Table III— Mineral Constituents op Potatoes and Potato Flour Same as that of the fresh potato.
Mill CaO 'mso' 'D K,0 P.O. S CI, ACKNOWLEDGMENT
Fresh Potatoes The analyses given in this paper were made by
A \\l\P, %ltt fit «i' ill! 3?9 J'99 Miss C. J. Prior, of the Plant Chemical Laboratory,
SiillG'.i:::::: lie i.n UaI IS.w ill! 6:0! Bureau of Chemistry. The samples of potatoes and
Average 1.11 5.52 50.19 13.81 2.88 3.49 flour were secured through the courtesy of the Falk
Potato Flour— Peeled Potatoes American Flour Corporation, Pittsburgh, Pa., and the
A (1919) Trace 6.24 51.85 16.95 4.13 1.88 National Potato Machinery Co., Chicago, 111.
B (1919) Trace 5.18 52.62 15.03 4.06 1.81
C (1919) 2.69 4.59 46.27 9.65 2.57 3.68
D (1919) 2.54 6.61 52.61 15.52 2.58 1.71
average 1.31 5.66 50.84 14.79 3.34 2.27 Government Needs Chemists and Other
Potato Flour— Unpeeled Potatoes Laboratory Workers
C (1918) 2.77 5.35 51.03 9.05 2.91 3.53
C (1918) 2.96 5.27 51.22 9.67 2.82 3.73 The United States Civil Service Commission states that there
D (1918) 2.31 5.99 53.88 9.57 2.26 3.00 ., , . . , _.
. „ „ . ,„ ., „. „ ., ., ,, , ., are openings in the government service for associate chemists
Average 2.68 5.54 52.04 9.43 2.66 3.42 ^ ° ° .
at $2500 to $3600 a year, assistant chemists at $1800 to $2o00
When the average percentages are examined it will a year, and junior chemists at $1200 to $1800 a year. Ap-
be noted that the different groups vary but little pomtees at an annual compensation of $2500 or less will also
in MgO or K20 content. The CaO content in case be alIowed the increase of $20 a month granted by Congress.
, a ,c i j i j. \ • t.- l „.,;j„„+i„ It is stated that the openings offer opportunities for those who
of flour (from unpeeled potatoes) is higher, evidently "• ° . . . ... , ,
,, , . f, . , , , ,,.„ „ JT> are qualified in the various specializations of chemistry,
owing to the fact that only samples from Mills (_ and D „, . , . , , . ... ,
° j r- n j • There is also need in a number of government establishments
are included in the average. This is also reflected m fof laboratory assistants> iaboratory aids, and laboratory ap-
the lower percentage of phosphorus in the same prentices 0f various kinds, requiring training in chemistry,
group. physics, ceramics, textile technology, paper technology, civil,
CONCLUSIONS mechanical, and electrical engineering, etc.
„ , . ,._ Full information and application blanks may be obtained by
1— Samples of fresh potatoes from different sources communicatmg with the United States civil Servilx Commission.
show differences in the amounts of mineral constituents Washmgtorjj D. C., or by calling upon the secretary of the United
present. States Civil Service Board at the post office or customhouse in,
2 — Potato flour contains a smaller relative amount any city.
420
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
Notes on the Volumetric Determination of Aluminium in Its Salts1
By Alfred Tingle
E. B. Eddy Co., Ltd., Hull, P. Q., Ca
In valuing aluminium sulfate for use in paper making,
the ordinary gravimetric estimation of "total alumina"
is useless, since "combined alumina," i. e., alumina
which goes to the formation of neutral A1i(S04)j is
alone of importance in sizing, while the salt as sold
commonly contains 1 per cent or more of uncombined
alumina, which dissolves in the aluminium sulfate
solution but takes no part in the reactions involved.
Several volumetric methods for the determination of
"combined alumina" have been proposed, most of
which can be set aside at once as unsuitable for tech-
nical control purposes.
There remain a few which are all, in reality, variants
of one another. They turn on the fact that phenol-
phthalein remains colorless in the presence of normal
aluminium sulfate, but turns pink when so much alkali
has been added that sodium aluminate begins to form.
The object of all the variations is to bring about a
quantitative precipitation of alumina, without the
formation of basic salts. The comparisons which fol-
low have been carefully made, and it seems desirable
to publish them for the information of those who need
to select a reliable method but have no opportunity
to go into the matter in detail for themselves.
DESCRIPTION OF METHODS
method A — This is proposed by Scott.2 The
aluminium sulfate solution is boiled, phenolphthalein
solution added, and the still boiling solution titrated
with sodium hydroxide solution (not stronger than
0.5 N). The end-point is reached when the pink
color persists after boiling for 1 min. For details,
the original paper should be consulted. In the present
work the method was modified in that smaller quanti-
ties were taken for titrations, while in most cases more
dilute alkali was used. In one or two instances the
strength of alkali was increased to give some idea of
how far Scott's limits might be overstepped.
method b — This is one with which the writer has been
familiar for many years without knowing the origina-
tor's name or where it was first described. It does not
seem to be well known in America, but is stated to
have been adopted by the German Pharmacopeia.
The solution of aluminium sulfate should be of such
strength that one liter contains approximately 10 g.
of the salt. To 100 cc, while boiling, 5 cc. of a satu-
rated barium chloride solution are added in drops,
followed by 4 to 5 drops of phenolphthalein solution
(0.1 per cent). While still almost boiling it is titrated
with sodium hydroxide solution of a convenient
strength. The mixed precipitate settles rapidly and
the end-point is very delicately shown by the pink
color of the supernatant liquid, best viewed hori-
zontally. If the maximum accuracy is not demanded,
a very slight excess of alkali may be used, producing
a coloration which can easily be seen without waiting
the short time necessary for the precipitate to settle.
1 Received December 20, 1920.
! This Journal, 7 (1915), 1059.
In the present work it was always the most delicate
indication which was taken as the end. Barium chlo-
ride is used to convert the soluble sulfates to chlorides,
because the basic chlorides of aluminium are less
stable and more soluble than the basic sulfates, so
that titrations need not be made (as in Method A)
while the liquid is actually boiling.1
method c — This is described by Gyzander.2 The
essential point is that the aluminium sulfate solution
is titrated while cold with sodium hydroxide solution
not stronger than 0.33 N, the claim being made that
at such dilution no insoluble basic salts are formed. It
is also stated that near the end a pink lake is formed
by the phenolphthalein and alumina, and that this
obscures the true end-point. This alleged difficulty
is overcome by using methyl orange in addition to the
phenolphthalein. As the present writer never suc-
ceeded in observing the formation of such a lake he
omitted to use any methyl orange. Gyzander's
claim that no basic salt is formed is not substantiated
by some of those who use his method. One such
worker, while remaining an ardent advocate of the
method, has kindly supplied me with a curious table
of the necessary corrections. These vary for every
0.1 per cent of "AI2O3 found" and also for every de-
gree of temperature at which the titration is made.
The magnitudes run from +0.74 per cent on an ap-
parent 18 per cent A1203 at 20° C. to — 0.41 per cent
on an apparent 16 per cent A1203 at 30° C. If these
"corrections" are correct this is obviously not a method
which should be taken seriously when quick and ac-
curate ones are available. A few determinations were
made in this way, but it was seen at once that the re-
sults were far from reliable.
method d — This is merely a minor variation on
Method B, the titration being made on a cold solution
after precipitation with barium chloride. If the solu-
tion is largely diluted, practically the same degree of ac-
curacy is obtainable as with a hot titration. Even
if not diluted at all, the variations from the truth are
relatively small, but the end-point is often obscured
because the precipitate does not settle so readily. It
is greatly superior to C but has at its best no advantage
over A or B.
method e — Some titrations were made, on both hot
and cold solutions, with and without the previous addi-
tion of barium chloride, using barium hydroxide
(approx. 0.33 N) instead of sodium hydroxide. It was
thought possible that the former alkali would not show
an end-point with phenolphthalein if any basic sul-
fate remained unconverted to hydroxide. The re-
sults do not fully bear out this expectation. Barium
hydroxide is certainly not so convenient to handle as
1 Here and elsewhere the writer has used the terms "basic sulfate"
and "basic chloride," but does not wish to commit himself to the opinion
that such basic salts necessarily exist. It seems at least as likely that they
are solutions, e. g., of hydroxide and sulfate in water, sulfate in hydroxide,
2 Chem. News, 84 (1901),
Methods of Chemical Analysis,
296, 306. See also Lunge's "Technical
' English translation, 1908, I, 613.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
421
the caustic alkalies, and unless it showed marked su-
periority over the latter for the present purpose it
was not intended to pursue this development.
EXPERIMENTAL DATA
STANDARD SOLUTIONS OF ALUMINIUM SALTS Two
such solutions were made, one from potash alum, the
other from aluminium sulfate, both of "T. P." quality.
Table I — "Com:
BINED
AI2O3" in Alum:
:nium
SULFATE
Each determination t
solution = 0.2713 A'
lade c
in 100-cc. solution
(= 1
g. of salt); I
Method of
Determination
NaOH Used
Ce.
AIjOi Found
Per cent
B
D'
34.9
34.7
16.13
16.03
16.12
1 Solution not diluted before titration.
Table II — Combined AI2O3 in Potash Alum
Each determination made on 100-cc. solution (= 1 g. of salt); NaOH
solution = 0.27 N
AI2O3 Found
( Corrected for
Method of NaOH Used Apparent AI2O3 Acidity of Alum)
Determination Cc. Per cent Per cent
A 22.7 10.74 10.70
B 22.5 10.64 10.60
C> 21.5 10.17 10.13
D* 22.4 10.60 10.56
Gravimetric3 ... 10.78
1 Titration temperature 20°.
- Solution not diluted before titration.
3 Mean of two determinations.
Table III — Titration
Each determinat
solution = 0.3671 N
Conditions of Ba(OH)i I
Titration Cc.
While boiling 25.90
While boiling 25. 85
At laboratory temperature 25.35
Hot, after addition BaCh 25 . 45
Hot, after addition BaCh 25 . 40
Gravimetric
of Aluminium Sulfate by Ba(OH): Solution
(Method E)
made on 100-cc. solution ( = 1 g. salt); Ba(OH);
AI2O3 Found
Per cent
16.19
16.16
15.85
15.91
15.88
16.12
Table IV — Titration of Potash Alum by Ba(OHI; Solution (Method E)
Each determination made on 100-cc. solution I = 1 g. salt). Ba(OH).
solution = 0.3671 AT
Conditions of Ba(OH), Used AI2O3 Found
Titration Cc. Per cent
While boiling 17.30 10.82
While boiling 17.35 10.85
At laboratory temperature 16.70 10.44
At laboratory temperature 16.70 10.44
Hot, after addition BaCh 17.10 10.69
Gravimetric1 10.78
1 Mean of two determinations.
Table V — Titration of Commercial Aluminium Sulfate ("Paper
Makers' Alum") Containing about 0.3 Per cent Fe
Each determination made on 100 cc. solution ( = 1 g. salt); NaOH
o-ution = 0.2861 N
Combined AhOi
Found (Not Corrected
Method of NaOH Used for Fe)
Determination Cc. Per cent
A 32.1 19.69
B 32.3 19.81
D' 31.5 19.32
D- 31.8 19.51
D3 32.3 19.81
1 Not diluted before titration.
2 Added 300 cc. water before titration.
3 Added 700 cc. water before titration.
Table VI — Titration of Aluminium Sulfate as 1
NaOH solution = 0.9861 N
I Table I
Method of
Determination
Na( )H Used
Cc.
AI2O3 Four
Per cent
id
A
B
Dl
9.4
9.4
9.4
15.79
15.79
15.79
16.12
Not diluted before titration.
In each case 20 g. of the salt were weighed, dissolved
in water, and diluted to 2 liters. The solutions were
clear. A colorimetric test showed that the iron con-
tent was well below 0.01 per cent, and therefore negli-
gible for the required purpose. Examination for free
acid or basic sulfate by the Craig-Scott method1
showed free acid in the potash alum equivalent to
1 Scott, hoc. cit.
0.13 per cent H2SO4 (100 cc. alum solution = 0.1 cc.
0.27 .V NaOH). Corresponding corrections were
made in calculating the results of titration. The
aluminium sulfate used was free from either acid or
basic contamination. The solutions were standardized
by the determination of AI2O3 in 100 cc. of each by
the method of W. Blum.1 The titration results are
given in Tables I to VI.
Considering together Tables I and II, we see that
Methods A and B are both sufficiently accurate for
almost any technical purpose and for many purposes
of purely scientific investigation. Table II shows
the great inferiority of C to all the others, while Tables
III and IV show that while it can be improved by
substituting Ba(OH)2 for NaOH it cannot even so be
placed in a position of substantial reliability. In
general, Ba(OH)2 does not give such good results as
NaOH. Table V shows that Method D gives as good
results as any, if the solution used is largely diluted,
but such dilution has drawbacks in practice. Table
VI shows how the results of Methods A, B, and D are
equalized when a strong solution of NaOH is used,
but also shows the loss of accuracy that accompanies
this equalization.
So far there seems little choice between Methods
A and B. What does not show in these tables, how-
ever, is the superior convenience of B when iron ac-
companies the aluminium. Iron makes the end-point
more difficult to see in A, but in B the color of the iron
is completely masked by barium sulfate. Scott sur-
mounts the difficulty by adding a larger amount of
phenolphthalein, but at the same time he notes that
any considerable quantity of indicator changes the
end-point.
Table VII — Comparative Results in Titration of Various Commercial
Materials for "Combined Alumina"
NaOH
Method of Normality Used
Titration of NaOH Cc.
A 0.2713 23.3
A 0.2713 23.2
A 0.2713 23.3
A 0.2713 23.4
B 0.2713 23.6
B 0.2713 23.6
B 0.2713 23.6
C 0.2713 22.3
W- 0.2713 23.5
D= 0.2713 23.4
II AIHSOOj, crude A 0.27 34.2
B 0.27 34.0
C 0.27 32.7
D* 0.27 33.7
III Al;(SO.)3. crude A 0.27 35.1
B 0.27 35.3
IV Al=(SO<K C P. A 0.27 19.3
B 0.27 19.5
V AL-(SO.)3, C. P. A 0.27 19.2
B 0.27 19.5
VI Al:(SO<)i. very basic A 0.27 17.5
B 0.27 K 7
VII Al:(SOib, very basic A 0.3246 20.0
B 0.3246 26.2
(Identical results were obtained by A and B in the analysis of 5 samples
of commercial AUOO^a.)
1 Titration temperature 27°.
- Not diluted.
3 Titration temperature 21°.
The slight superiority of A over B to be observed
in Table II is balanced in Table I. A consider-
able number of comparisons have been made in the
course of routine work in this laboratory. Those
which do not give an equality between A and B have
always shown (with the exception of Sample II in
Table VII) B as indicating the higher percentage of
' J. Am. Chem. Sac, 38 (1916), 1282.
Nature of Material
Titrated
I Potash alum
No
422
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
A1203 and, therefore, in such cases, the more prob-
able result. These results are included in Table VII.
SUMMARY1
1 — The methods here compared all turn on the
titration of the aluminium 'salt with an alkali, using
phenolphthalein as indicator.
2 — The manipulation details to be observed in
carrying out this principle are all-important and consti-
tute the differences between the methods.
3 — Methods A and B alone are both trustworthy
and convenient.
4 — Method B has some slight advantage over A,
especially in the presence of iron.
5 — It is quite essential to use an alkali of titer not
more than 0.5 N.
The Detection of Phenols in Water2
By R. D. Scott
State Department of Health, Columbus, Ohio
The presence of very small quantities of phenols in
certain public water supplies has been found to cause
quite offensive tastes and odors, which are greatly
intensified if the raw water is chlorinated, owing proba-
bly to the formation of chlorophenols.
The detection of traces of phenols in such waters
by chemical tests has been impossible until recently.
While numerous tests for phenols are known, none
sensitive enough to detect these minute quantities
was available until Folin and Denis3 presented their
colorimetric test, widely used in the estimation of
phenols in urine.
The reagent is prepared as follows: To 750 cc. of
water add 100 g. of sodium tungstate, 20 g. of phos-
phomolybdic acid, and 50 cc. of 85 per cent phosphoric
acid. Boil for 2 hrs. under a reflux condenser, cool,
and dilute to one liter. (Owing to the fact that several
formulas may be found for phosphomolybdic acid, it
would seem desirable to substitute for it 18 g. of 85
per cent molybdenum trioxide. This change has been
found to give satisfactory results in practice.) One
to two cc. of this reagent are mixed with an equal vol-
ume of the solution to be tested, 3 to 10 cc. of saturated
sodium carbonate solution are added, and, in the pres-
ence of phenols, a blue color is produced. In addition
to phenols, the authors mention tyrosine, protein,
and uric acid as producing the same color. Folin and
Wu4 mention cuprous oxide. Tisdall5 mentions indol
and ferrous iron. Thus the original test is by no
means specific.
It is believed that the method was first applied to
water examination by C. E. Trowbridge, chemist at
the Newcastle (Pennsylvania) Filtration Plant, his
adaptation being: To 100 cc. of the sample add 1 cc.
of phenol reagent, then 5 cc. of sodium carbonate
solution. Trowbridge states that amounts as low as
1 part in 20,000,000 give a positive test.
Numerous tests made by the writer on natural
waters to which phenol was added indicated that
amounts at least as low as 0.5 p. p. m. could be de-
tected. However, it was found that tannin in dilute
solution also gives the test. This was not surprising,
1 Since writing the above, the author has met with the recent paper of
I. M. Kolthoff in Z. anorg. Chcm., 112 (1920), 172. He describes a titra-
tion of aluminium salts essentially similar to Method B, but with variations
which would destroy its accuracy in certain circumstances.
• Received January 24, 1920.
• J. Biol. Chcm.. 12, 239.
« Ibid., 38, 106.
• Ibid., 44, 409.
in view of its composition, but presented a complica-
tion in the practical use of the method. Later this
test for tannin was used in connection with an investi-
gation of stream pollution by waste from a leather
products factory, and effort was made to distinguish
between tannins and phenols by other colorimetric
methods. It was found that the ferric chloride test,
using 1 cc. of 1 per cent FeCl3.6H20 to 100 cc. of sam-
ple, produced a blue color with as little as 2 p. p. m. of
tannin, but not with less than 500 p. p. m. of phenol.
This, however, would not distinguish between them if
less than 2 p. p. m. of either were present.
Distillation proved an effective means of separation.
It was found, on acidifying and distilling tannin solu-
tions of various strengths, that the distillates gave no
test with the Folin phenol reagent. With phenol
solutions the distillates all gave positive tests. Dis-
tillation has certain other advantages.
1 — A slight degree of concentration takes place in the first
portions of distillate, thus making possible the detection of ap-
preciably smaller amounts than when the test is made on the
original sample.
2 — The precipitate of calcium carbonate, which is formed in
many waters on the addition of sodium carbonate, is eliminated.
3 — As applied to water examination, the test becomes prac-
tically specific for phenols.
A 500-cc. sample is acidified with 10 cc. of 1 : 1 sul-
furic acid, 100 cc. of distillate are collected in a Ness-
ler jar, and the phenol reagent and sodium carbonate
are added as previously described. The distillate
from a solution containing as little as 0.1 p. p. m. of
phenol gives a distinct blue tint.
In the examination of samples of unknown phenol
content, a quantitative estimation may be made by
comparing with standards prepared at the same time,
containing known amounts of phenol. Ten minutes
should be allowed for the color to develop before ob-
serving the tubes.
CONCLUSION
The detection of phenols in water may be effected
by distilling with acid and testing the distillate with
the Folin and Denis phenol reagent.
Chandler Medal Award
On Monday evening, April 18, 1921, the Charles Frederick
Chandler Medal was awarded to Frederick Gowland Hopkins,
D.Sc, F.C.S., F.I.C., F.R.C.P., F.R.S., professor of biological
chemistry in the University of Cambridge. The subject of Dr.
Hopkins' medal lecture was "Newer Aspects of the Nutrition
Problem."
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
423
The Setting and Melting Points of Gelatins1,
By S. E. Sheppard and S. Sweet
Research Laboratory, Eastman Kodak Company, Rochester, N. Y,
In the course of an extensive investigation of gelatins
it was felt desirable to compare the so-called "melting-
point" test with the jelly strength. This was ex-
tended to include the "setting point." Since the transi-
tion from the hydrosol to the hydrogel condition with
gelatin jellies is practically continuous, the same being
true for the reverse change, both the "melting point"
and the "setting point" are more or less arbitrary con-
ceptions, and their determination depends mainly upon
standardized experimental conventions.3 According to
Clerk Maxwell's elasticity theory, which in several
respects is of particular interest for gelatinous systems,
the elastic modulus
T
where tj = coefficient of viscosity and T = time of
relaxation, i. e., time for a deformation to fall to 1/e
of its initial value.
Now, the "melting point" is the temperature at
which the elastic modulus becomes very small. Since
77 remains of considerable magnitude, this can only
be by T becoming very large. Hence, both "melting
point" and "solidification point" (setting point)
might be defined as the convergence temperature at
which the "time of relaxation" becomes infinite. 4
It is apparently in this sense that Bogue has used the
term "melting point" in a recent paper on the properties
and constitution of glues and gelatins.5 We have,
however, felt it desirable to have a direct method of
determining "melting" and "setting" points. If the
same apparatus can be used for observations at both
rising and falling temperatures, and if rates of heating
and cooling, respectively, be made as nearly equal as
possible, then definite differences between observed
"setting points" and "melting points" can be referred
to differences in the gelatins. These "differences"
may well include past thermal histories, but will not
be the immediate result of unsymmetrical heat con-
duction in the two cases. The principal apparatus used
in our investigation was modeled, with some altera-
tions, on that used by Flemming6 for the study of the
rate of coagulation of colloidal silicic acids.
DESCRIPTION OF APPARATUS
The principle used is as follows: An intermittent
stream of air bells, under constant pressure, is passed
through the test solution, the latter being cooled with
ice water. A thermometer is immersed with its bulb
next to the air passage, and the temperature at which
1 Received January 11, 1921.
* Published as Contribution No. 110, Research Laboratory, Eastman
Kodak Company.
3 A fuller bibliography will be given in a forthcoming monograph on
gelatin. The present references are to more recent articles only: C. F.
Sammet, "Determining the Comparative Melting Points of Glues as a
Measure of the Jelly Strength," This Journal, 10 (1918), 595; A. W. Clarke
and L. DuBois, "Jelly Value of Gelatin and Glue." Ibid., 10 (1918), 707;
A. Coblenzl, "Setting Points of Gelatins," Phot. Ind., 1919, 317.
* In a plastic state a small deformation is permanent.
' Chem. Mel. Eng., 23 (1920), 5, 61, 105, 154, 197.
« Z. physik. Chem., 41 (1902), 427.
the bubbles cease to pass is taken as the "setting
point." Inversely, after sufficient undercooling, the
set jelly is surrounded with water at a definite higher
temperature, and the "melting point" taken as the
temperature at which bubbles again pass through.
The operation of the apparatus will be evident from
the diagrams. In Fig. 1 is a diagram of the general
assembly. Compressed air passes manometer A
and the manostat bottle B to the first U-tube E,
containing mercury. This tube is used as a valve to
produce intermittence in the delivery of air. A sole-
noid, D (Fig. 2), the current through which is made and
broken by the timer C (see Fig. 3) every 15 sec,
effects this interruption by operating an iron plunger.
From this U-tube E the air passes the compensating
U-tube F to the setting or melting tube K. The out-
let in K is shown in detail at G. To obtain satis-
factory and reproducible results with this apparatus
the following precautions are necessary:
(1) Fifteen-second intervals between passage of air bells.
(2) Slow flow (i. e., slight overpressure).
(3) Exit at definite depth below surface.
(4) Water in compensation tube at same level throughout
the test.
A further arrangement, by switching the air when
stopped to operate a pneumatic release on the clock,
permits the use of the apparatus, as in Flemming's
experiments, to record the total time of setting. We
have under consideration the adaptation of the in-
strument to automatic viscosity recording, and hope to
deal with this later.
In use, solutions of gelatin in water at various con-
centrations (1, 3, 5, 10, 15, and 20 per cent, air-dry
424
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
basis, converted to dry weight at 105° C. as required)
were prepared^under standard conditions, i. c,
(1) Definite period of swelling in cold water.
(2) Definite period of heating and stirring at 70° C.
(3) Definite short period of heating at 100° C.
20 cc. of solution thus prepared were placed in a
1.25-in. test tube, this fixed in a wider test tube (2 in.),
serving as an air-jacket, and the whole immersed in
the cooling vessel.
RATES OF COOLING AND HEATING
Figs. 4 and 5 give illustrations of the determinations,
with the checks made as to rates of cooling and heat-
ing. Under these conditions the curves connecting
setting point and concentration, and melting point
and concentration, respectively, do not coincide, but
Fig. 2 — Diagram of Solenoid and Plunger
remain nearly parallel. Examples of several such curves
for different commercial gelatins and glues are given
in Figs. 6 and 7. In Fig. 6, the setting-point curves
1, 2, and 3 are for American glues; 4 for a hard American
gelatin; 5 for a hard German gelatin, and 6 for a soft
American gelatin. The setting-point curves in Fig.
7 are a different series from those in Fig. 6, while the
melting-point curves are for American gelatins.
RELATION TO CONCENTRATION
The general or characteristic relation of the setting
point to concentration of dry gelatin (at 105° C.) is
shown in the curves of Fig. 8. Since "100 per cent
dry gelatin" decomposes instead of melting, the parts
of the curve approaching this value have no experi-
mental basis. They are curves of double flexure, the
region in the neighborhood of the point of inflexion,
where
d'S
dc2
gives a period in which an approximately linear re-
lation obtains between setting (or melting) point and
concentration, of the forms
S. P. = a + Br, and
M. P. = A + Be.
B, the slope, is nearly the same for both curves, corre-
sponding to the parallelism between them, while
0
SIDE VIEW
MERCURy\;^
A>a, corresponding to the approximately constant
difference of temperature between M. P. and S. P.
This linear region agrees with statements as to the
proportionality between M. P. and concentration,1 but
the present results show that the relation is only ap-
proximate, and its extent and locus, on the complete
curve, is liable to vary very considerably from one gela-
tin to another.
RELATION TO JELLY STRENGTH
We have shown elsewhere2 that jelly strength is
not dependent on concentration according to any
simple and universal relation, i. e., by a function in-
dependent of the kind of gelatin. Hence, it is not a
matter of indifference at what concentration different
gelatins are compared in regard to jelly strength.
From the present work it is evident that a similar
restriction is true for melting points and setting points.
The concentration curves for these variables, plotted
for different gelatins, frequently cut each other.
Hence, any "grading" of gelatins by melting points
1 1 1
'
•s '
nnnnr
i »
\
j
v
'.
\
,
. f _
"f
^
u^
s
a
jlst- -
■f
.....
K
- ,»W
a
-
•jl
s
a.
I
K
£
/
, '-*
.
**" *i
S
|\
'
^
It's
s
i
"
S
*
T
7\,-^
mm ls-
ii 1. 1. n
,.s
— J
,
at one and the same gelatin concentration involves
an entirely arbitrary selection. Further, the order
thus obtained will not necessarily coincide with the
grading by jelly strength. This will be evident from
the two sets of curves, for the same gelatins, in Fig. 9.
1 See J. Herold, Chem.-Ztg., 36 (1911), 93.
« This Journal. IS (1920), 1007.
May, 1921 THE JOURNAL_OF INDUSTRIAL AND ENGINEERING CHEMISTRY
425
X
i
GELATINE
SETTING POlN
TuTl
S
4-
fl
2„
1 V
■
3„
4.
I;
7 .
!^j
I
•
26
■'
-7
{IPC
Y
"
-
/
1
■
'
/
/.
". ! /
//'
//
/
'
y^
i
[l
'
2
-
/
/
/
//
-
R
nr
mi
r,F
NT
RA
11
:-
If
nil
■^-i
i
i
?
7
1
K
COMPARISON OF
■ i MELTING
SETTING ^
POINTS /
200
150
100
50
40
30
20
10
0
1
•
GELATINE
SETTING
>01NT!
/;
/i
/i
//
/
/
/
-1 //
IS / /
1 s
■■
4 1
/ /
'/
i J •
/
/
-/-
1
u
/
LJ
/
/
3
lj
'
1 i PER CENT
!r-^> „ .
-
CONCENTRATION
a.
y
a.
Hi
ljcem:
AT ION
M
T!
IE
50
75
TOO
JELLY-CAPACITY VALUES
It is obvious that the most direct way of adjusting
these difficulties would consist in comparing the inte-
gral values of jelly strength-concentration, or setting
point-concentration, respectively, over the complete
range of 0 to 100 per cent concentration.
This is not practicable over the entire range, owing
to the indetermination of the parameters as 100 per
cent concentration is approached, but the comparison
can be made for a lower range, e. g., up to 25 or 50
per cent concentration. The areas enclosed by the
corresponding curves may be determined either by
a planimeter or by weighing.
Grading of certain gelatins by comparison of the
jelly-value areas, from the jelly-strength curves and
the setting-point curves, is given in the following
tables. The curves used are shown in Figs. 9, 10, and
11, respectively.
The comparisons are for concentrations up to 20
per cent, hence the grading is valid only for that range.
The values are arranged in order of decreasing magni-
tudes in each figure.
JEU.V
No.
Strength Value
Relative Area
Setting-Point Value
No. Relative Ar«
From Fig
9
3....
697
1 1345
2
1
615
321
3 1320
2 1297
4....
146
4 922
96
Frotr
Fit.
10
2....
760
9 1387
9....
672
12 1364
8 , ,,
10
11....
380
380
318
7 1283
8 1261
10 1237
7....
210
11 1181
Frorr
Fit
II
17....
878
14 1550
4....
610
17 1515
3....
537
13 1478
6....
356
15 1461
.8....
306
18 1437
:5....
294
16 1422
Two things will be seen from these tables. First,
there is much less difference between the individual
setting-point values (or melting-point values), within
the range of concentration tested, than between the
jelly-strength values for the same sets of gelatins.
Second, the order in any set is not the same for
both values. Since both jelly strengths and setting-
point curves spread out with increasing concentra-
tions, though tending to converge again as 100 per
cent dry gelatin is approached, a comparison of the
mechanical solidus area with the thermal solidus area
up to 20 per cent is necessarily only valid for that
range. It does appear, however, that the mechanical
grading and the thermal grading of gelatins according
to their jelly capacities do not coincide, and that each
type of test is desirable for adequate characterization.
The great variety of results with different commercial
brands of gelatins indicates the necessity of study of
conditions for grading gelatins, so that they may be
compared under specific corresponding conditions.
In a paper1 on "The Elastic Properties of Gelatin
Jellies" certain of the factors in regard to jelly strength
are discussed, and this intensive investigation is being
extended to the case of setting, melting, and viscosity
phenomena.
ALTERNATIVE MELTING-POINT APPARATUS
For certain work we have found useful a "melting-
point" tester as follows: The jelly is set in a test tube
with a thermometer centrally imbedded, the bulb
being just below the surface. Round this thermometer
slips a small test piece, resting on the jelly by three
equidistant wedge-shaped feet, as shown in Fig. 12.
The test tube is air-jacketed and heated at a constant
rate, and the temperature read. The point at which
the tester just begins to penetrate the jelly surface
is taken as the softening or yield point (Y. P.), and the
temperature at which the tester has sunk just above
the feet as melting point (M. P.). The values ob-
tained in this way are not quite as satisfactory as
those obtained by the method already described, but
are about equal to those by the similar method of
Bechhold2 in which the surface is loaded with a definite
weight of mercury. The use of an annular solid tester
i S. E. Sheppard and S. S. Sweet, J. Am. Chcm. Soc, 43 (1921), 539.
5 "Die Kolloide in Biologic und Medizin."
426
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
avoids the dosage on the recovery of the mercury,
•and hence saves much time where a large number of
tests have to be made.
annular pra^s
wc/qht
Fig. 12 — Mblting-Point Apparatus
It is obvious that the criticisms in regard to jelly-
strength tests by superposed loads1 apply in some de-
gree to this test. That is, the skin formation involves
a certain displacement. Error from this cause is less
here, however, than for jelly-strength tests at constant
temperature, because the skin does not remain un-
altered. It is possible that part of the difference
between "melting" and "setting" points is due to the
surface skin formation. In Fig. 13 melting point-
concentration curves obtained by this method for
different gelatins are shown compared with "setting
points" by the air-bell method.
» This Journal, 1* (1920), 1007.
SUMMARY
1 — The definitions of "melting point" and "setting
point" of jellies are discussed.
2 — It is considered that, while theoretically "setting
point" and "melting point" should be an identical
temperature at which the "time of relaxation" of
mechanical strain is infinite, practically they can
be arbitrarily defined by standardized experimental
conditions.
3 — An apparatus for determining both setting and
melting points is described.
4 — Characteristic curves with concentration of
gelatin as abscissae are given, in comparison with
jelly-strength curves.
1 [J
III l_l ! 1 | i 1 --'
COMPA
1S0H OF SFTTING ! . -f . -"
a ! »'l
HLTIIC POINTS .-" L:--
, «- .*W
■ ^i'"l '
a t
L<fr,l L'
#7 \m - ..\-
>-\ \ .)£&■■* J
.-/ 1 ..jT
'' k;/1
.- 0 i J
•
n ' -7
' /
' A) i ■-''
1 ;
•'! ' y''
^J '} .
V 1 ' M*'
* i I i
t ! 1 / *?
-J?X- J?^
s-H-t
7±^ " ±
A >x
-, lZ2
- 7
/
//
^ru
V- ^"-X~" 4-
0^2r -t
' ■ -A-
u . . ,
il
K> 1' t j/7
FIR CEKT CONCENTRATION
PITTJ, i "ulrtl:
5 — The arbitrary character in grading gelatins by
values at a single concentration is discussed.
6 — An alternative "melting-point" tester is de-
scribed.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
427
THE SYMPOSIUM ON DRYING
presented before the Div
i of Industrial and Engin
ing Chemistry at the 61st Me
April 26 to 29, 1921
Chemical Society, Rochester, N. Y.
The Rate of Drying of Solid Materials
By W. K. Lewis
Department op Chemical Engineering, Massachusetts Institute op Technology, Cambridge, Mass.
In the design of drying equipment and processes the
engineer must provide
1 — An adequate supply of heat for the evaporation of moisture.
2 — Sufficient air to sweep away the moisture under the con-
ditions in question.
3 — Such control of temperature and humidity as will protect
the product against injury.
4 — Sufficient time for the escape of the moisture from the
material being dried.
The factors governing the first three of these are well
understood and are covered in present designing prac-
tice; regarding the fourth, there is little in the literature,
and mistakes in design are not infrequent. It is the
purpose of this article to present the conditions gov-
erning the rate of drying of solids.
FUNDAMENTAL FACTORS AFFECTING DRYING RATE
Because it has such an important relation to drying
rate it will first be necessary to call attention to one
factor, the character of which is already well under-
stood. This factor is the moisture retained on solids
under ordinary conditions of temperature and hu-
midity. Most solids hold a certain amount of moisture,
The moisture content of a material which corresponds
to equilibrium with the air with which the material is
in contact will be spoken of as "equilibrium moisture."
The total moisture content less this equilibrium mois-
ture represents the moisture which can be evaporated
by drying in the air in question. This difference will
be called "free moisture." Moisture will be reported
as pounds per 100 lbs. of dry material (or, in some
cases, per pound of dry material).
While the equilibrium moisture content of a material
varies with both temperature and humidity, it changes
but slightly with the temperature of air, the relative
humidity of which is held constant. It is therefore
more convenient to plot the equilibrium moisture con-
tent against the relative humidity rather than against
the absolute humidity. If the temperature in question
does not vary widely it is allowable to draw a single
such curve; where the temperature variation is large v
a series of curves, one for each specific temperature,
should be drawn, and results interpolated between them.
The equilibrium water content of wood, leather,
soap, and textiles is shown in Figs. 1 to 4. Such
1
|
1
rn-t
1 1
—
1 1 1
s
1
—
1
Equilibrium Water-Wood
from Bulletin forest Praifacrs lateral
US Pept of Agriculture
Equilibrium
fromM
Walrr -Leather
1 T Thesis 1919 C n
meli
Equilibrium Water-Soap
from MIT thesis I92P
Coiamellt Spiehter
Equilibrium Water- Teiti/es
from Sehloesinq -Teihle Herldfero'd-
, 1 Sli\
1
1
t
k\
/
1
(J.J
/
1
f!
i
' /
\ JC%-
,1
i
&
/
/
ste^
ij&s
■/<
>>4
/
yJ$k
'
'■' '■
s'
JL
/ /
/V
/
y
rfi^
J^
^
'.'
0
'/
_/£.
<■■ r
(,
g
ef'
'"'
r'
/O 20 30 40 JO GO 7V SO 90 lOQ /0 20 JO 40 SO go TO SO 90 ,
fer Cert Relative Humidity fer Cent Relative ttum,d,tij
Fig. 1 Fig. 2
even when in contact with unsaturated air. This
moisture is probably adsorbed on the surface of the
solid; at any rate, the amount retained under equilib-
rium conditions is a definite function of temperature
and humidity. Thus, at ordinary temperatures cot-
ton in contact with air of 50 per cent humidity retains
6 per cent of moisture. Cotton holding less moisture
than this will pick up moisture from air of 50 per cent
humidity; cotton damper than this will lose moisture
in such air. It is obvious, therefore, that air of 50
per cent humidity cannot dry cotton below 6 per cent
moisture, because this moisture content of cotton rep-
resents a true equilibrium with the air.
i Received April 5. 1921.
to 7O3O4OJO6U7OSO9O0O
Per Cent Relative Humidify
Fig. 3 Fig. 4
curves must be determined experimentally in each in-
dividual case.
The rate of drying of any material is obviously de-
termined by the temperature and humidity of the air -
with which it is in contact, by the velocity of that air
past its surface, and by the heat supply to which it is..
exposed. These controlling factors, characteristic of
the external surroundings of the material being dried
rather than of the material itself, will be referred to as .
the "drying conditions" of the problem in hand.
Fig. 5 represents a typical drying curve for a solid
material, the moisture of which is evaporating under -
constant drying conditions. This particular material
has an equilibrium moisture content of 9.5 per cent. .
428
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
It will be noted that the rate of drying is at first rapid,
and then decreases, the moisture content falling off in
a characteristic "fade-away" curve. This curve be-
comes asymptotic to the equilibrium moisture, but
theoretically never really reaches this limiting Value.
Even in the case of very thin films the curve has this
(i
0 &
Time m Minutes
Fig 5 — Rate of Twine Drying
shape, so it seems reasonable to assume that the rate
of surface evaporation falls off as the moisture content
of the surface decreases. The simplest assumption is
that the evaporative rate is proportional to the free
moisture content of the surface. Probably the actual
surface exposure of moisture itself is proportional to
the moisture content of the surface, and it is obvious
that the rate of evaporation would be proportional to
the water surface actually exposed.
The drying of a solid of necessity involves two inde-
pendent processes, first, the evaporation of the moisture
from the surface of the solid, and, second, the diffusion
of the moisture from the interior of the solid out to the
surface. The evaporation of an extremely small
amount of moisture from the surface will leave the
surface practically dry unless and until fresh moisture
diffuses from the interior of the solid out to the surface
to restore its moisture content. Since the surface can
be conceived as extremely thin, no appreciable evapo-
ration can take place without sufficient diffusion to
compensate quantitatively for surface evaporation.
The two must, therefore, be equal.
DERIVATION OF DRYING FORMULAS
For purposes of derivation, assume a sheet material,
the thickness of which is L. Assume that the
equilibrium moisture of the material in question is neg-
ligibly small. Let Fig. 6 represent a cross-section of
the sheet, the line CM representing the surface and
DX the center line of the sheet. From DC as a base,
plot the concentration of moisture in parts by weight
per unit volume vertically upward. Call the initial
concentration equal to CM, so that the area under line
X M represents the initial moisture content of the sheet.
When surface evaporation starts the moisture content
of the surface will drop to some point such as B. Dif-
fusion will immediately start and at the time in ques-
tion the moisture content will have fallen to some such
condition as AB. This line AB will not be straight,
but its equation will be determined by the integral of
the diffusion equation.
S*y/L = —Sy/se.
The exact integration of this equation is, however, so
involved that we have chosen to integrate it by ap-
proximation by assuming the line AB straight. Tall
EF the average concentration of moisture in the
'sheet y. Call the surface concentration of moisture Vj.
Call the total weight of moisture in the sheet for
each unit of surface w. Obviously, w = —v. The
- ' 2
rate of diffusion of moisture from the interior of the
sheet will be proportional to the difference in con-
centration (y — ys), and inversely proportional to the
distance to be traveled, L/4; the proportionality con-
stant we shall call A. The rate of surface evaporation
will be equal to a coefficient, R, times the surface
concentration. These two must be equal to each other
and equal to the rate of loss of moisture by the sheet, i. e.,
dw 4A(y — ys) dtv 8ARw
= Rys = — , whence = .
de h de L(4A + RL)
This may be looked upon as the basic differential
equation governing the drying of solid materials in sheet
form. Since the water content appears as dw w, this
expression is independent of the units in which wrater
is measured. One may therefore call W the free
water content of any desired quantity of the material
and write dW/W in place of dw/w.
The quantity R is obviously a function of the drying
conditions. Furthermore, when the water content W
becomes very high (100 to 200 per cent on the dry ma-
terial, depending on the substance) the drying rate no
longer increases with increasing moisture, but remains
constant, i. e., the surface is water-saturated. This
condition is not often met, and this discussion assumes
the water content less than this critical amount.
This equation was derived on the assumption that
the equilibrium moisture was negligible. Where this
is not true the moisture content to be used in the equa-
tion is the free moisture; or the total moisture W less
the equilibrium moisture E, *'. e.,
—d(W — E)/(W — E)<# = 8AR/L(4A + RL).
— ^
F /f
F
1
\
<1
\
ir
\
^S
\
*
\
>
\
f
3
^
1
C
l>
—L '
Fig. 6 Fig. 7
Assuming constant drying conditions, and a given ma-
terial that does not shrink greatly during drying, the
right-hand side of this equation is a constant, which
may be called the drying coefficient K. Integration
gives log (W — E) = — K0 + constant, or. calling the
initial content at time zero W„,
log (W0 — E)/(W — E) = K0.
Figs. S to 11 represent experimental data on the
drying of twine passing around steam-heated drums.
May, 1921
THE TQURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
429
-+--
ct{W-E
\
d&/
\
V
tfci+e of eraporaf/on
TWtne rfrtfthq
1
1
\
w
N
^
\<t/
0
V
\
\
A
''afe of Twine Ore,
inn
\
^
OS ^ /o
^ It
—
'°S>r,
l^n
01 |<W
\
Time in Minutes
Fig. 8
Time in Minutes
Fig. 9
Time in Minutes
Fig. 10
In Fig. 8 the free moisture is plotted against the time
the twine is in the dryer. From this curve the slope
was read off graphically at each point, and also plotted
against the time. Finally, the slope divided by the
free moisture was plotted, giving, with exception of the
last point, substantially constant values. The graph-
ical determination of slopes is always inaccurate, and
it is far more satisfactory to use the integrated expres-
50
40
30
•"5
X
/.0
V 0.8
\o.s
•kO.3
0.1
*\
\
i. -^
"^' -
"6
^
P<y
,^
"^y
"^
k^"
N*%1
X,
\
sion and plot the logarithm of the free moisture
against the time, as is done in Figs. 9 and 10. It is
more convenient to use semi-logarithmic paper, as in
Fig. 11.
SPECIAL CASES SURFACE EVAPORATION THE LIMITING
FACTOR
The drying coefficient, K = SAR/L(4A + RL),
varies with rate of diffusion and of surface evaporation,
and with thickness. Two special cases are of impor-
tance. First, if diffusion is very rapid in comparison
with surface evaporation, RL may be neglected in
comparison with 4A, and K = 2R/L. Second, if
diffusion is very slow compared with surface evapora-
tion, 4A is negligible compared with RL, and K =
8A/L2.
For sheet materials with rapid diffusion we have no
data available except for such as shrink greatly in
drying. Results are given for one of these, heelboard,
made of a pulp of ground leather and paper, the thick-
ness of a given sheet of which is found experimentally
to increase linearly, with the moisture content, ;'. e.,
L = L0(l + »W), where L0 is the thickness of the
dry sheet, and a is a constant coefficient. Therefore,
the drying coefficient, K = 2R/(1 + aW)L„. Sub-
1.0 2.0
Time in Minutes
3.0
v
II 1 1 1 1
\
■■
s
Hee/ Soard
..
\
\
\,
>
V
\
i \-s.
\
k
^•M^
<s
s
5
'
^
'
K
!
1 1 1 1 II 1
\
^
*
\
\
'
-
$.
\fe, |-
m*
-
^
k
\
s,
t
K
430
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
con
1 1 1. 1 1 1. 1 1
Showing propor f Zona// fy of
Pate of 'drying to vapor prersure diffi
- Ad<at>otic Air Drying of Heel Board
[?3i0Q(KB)r*W0]
-[Z3 /ogf#-£) raJY]* *&■
/?ttns af rary/ng Ap
M?/oc,fy /SO. 7
c
urn:
eat
0M2
/
-$ O.OiZ
0.010
^ OOOi
^ aoot
^ aooz
~ 8 10 12 14 1G 18 20
Water vapor parr/a/ pressure difference
in mm
Fig. 14
' 1 1 1 I 1 1 < '
_ Show/ng mverse proport/ona/fty of S.
Rate of drying to thickness /
Adiaeatic Air Drying
A./
/°
/
s
/
<,y
1 1 1 1 1 1 | 1 1
_ yarialion of rate of drying _
tvith air ye foe fry
Adiobafic AirQry/nqofHeel Board
emi:
MM
una
C MM
o
*!..-£.
*P ./6IO0 '
u.
Thickness of board in cm.
100 200 300 400 500
fiir yelocifu in cm. per sec.
stitution of this value into the differential equation and
integration gives
oW + 2.3 log10 (W — E) = K8 + const.
If the left-hand side of this equation be plotted against
the time a straight line should result. Figs. 12 and 13
show the data of two drying runs on this material. The
logarithmic plots are also included to show the magni-
tude of the correction for variation in thickness of
sheet.
As long as the free moisture content of a material
being dried is reasonably high, in the absence of direct
exposure to a heating element the material will remain
at the wet bulb temperature of the drying air. When
the free moisture becomes very low, the material is
heated up to the temperature of the air. The transition
is gradual, and unless the drying is carried, say, close to
equilibrium it is a safe approximation to assume the
stock at wet bulb temperature throughout the drying
operation. The rate of surface evaporation is deter-
mined by the rate of diffusion of water vapor through
the stationary film of air surrounding the sheet. This
diffusion is proportional to the difference between the
partial pressure of the water on the surface of the
sheet (wet bulb temperature) and that in the drying air.
This difference can be read off directly from the usual
psychrometric tables or charts, and will be called p.
The rate of diffusion will increase with increasing air
velocity, due to decreasing thickness of the air film.
At constant velocity, therefore,
2R bAp
K = — = — -
L L
where b is a proportionality constant, and K is the slope
of the logarithmic plots of Figs. 9 to 11, and of the
corrected logarithmic plots of Figs. 12 and 13. Fig.
14 shows K for five separate runs on heelboard at con-
stant sheet thickness and air velocity, but at variable
Ap (due to wide variation in both temperature and
humidity of the drying air), plotted against Ap. K is
proportional to Ap within the experimental error.
Fig. 15 shows K plotted against 1/L for two series of
runs in which air velocity and Ap were kept constant.
Table I shows the constancy of b = KL/'A p at a fixed
air velocity for runs in which L and Ap each vary five-
fold. Fig. 16 indicates the variation of 6 = KL/A^
with air velocity.
ABLE I —
Showing Coi-
SIANCY OF K — A
(Velocity 180.7)
t Constant Air
Velocitt
Run No
K
I
*
Kh
1
0.0031
0.985
3.9
0 . 000795
2
0.0051
0.666
3.9
0.000870
3
0.0107
0.313
3.9
0.000859
4
0.0151
0.204
3.9
0.000790
5
0.0059
0.985
8.0
0.000723
9
0.0103
0.985
12.1
0 . 000838
13
0.0134
0.985
15.1
0.000874
17
0.0188
0.985
19.7
0.000940
DIFFUSION THE LIMITING FACTOR
Where the ratio of the diffusion of moisture inside
the material itself to the rate of surface evaporation is
low, i. e., where K = 8A/L2, the concentration of free
moisture in the outside surface layer is negligible, air
velocity has no marked effect except as it increases
heat transfer, and the temperature of the stock is much
nearer that of the drying air. A case in point is the
drying of closely twisted cord traveling over rotating,
steam-heated drums. The process may be looked upon
as a diffusion of heat into the cord as much as of mois-
ture out. Experimental results are given in Fig. 17 to
demonstrate the proportionality of drying rate to the
inverse square of the diameter (the thickness of th&
o
Van a Hon of rate of druinq
A
6
/
>
40 60 80
[Diameter of Twine)'
Fig. 17 — Twine Drying
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
431
sheet of cords traveling over the drum) rather than
to the inverse thickness as in the preceding case.
SKIN EFFECT
In the drying of a thick layer of a material in which
internal diffusion is very slow {e. g., soap, glue, jellies, or
1.4
%
I1-2
\ as
0
^ az
>*
Rat
e ofdryinq with time
*7s
<w
0
■ if
*/,
-if
[b
g
f
&
O y
'/
V
a
0.
z a
s 0
i
4 0.
5 0
6 (2
7 a
8 a
9 I.
7 >«
f /Z
Fig. 18 — Adiabatic Air Drying of Soap
wood), the diffusion gradient is not quickly set up into
the center of the mass so the basic differential equation
given above must be modified. Let GD (Fig. 7) be
a cross section of the sheet. Plot water concentrations
up from CD, GE being the initial concentration, y0,
and B the surface concentration, ys. y$ will be substan-
tially equilibrium concentration with the drying air.
Diffusion will start, the gradient being the line AB,
the point A moving back as drying proceeds. Call the
thickness, AE, through which diffusion is actually tak-
ing place, 1. This is a variable in the equation
— dw/de = A(y0 — ys)/l.
Thislayer AE is the "skin effect" of the drying operation.
By comparison of areas in this diagram one sees that
1 = L(y0 — y)/(y0 — Vs).
Furthermore, w0 — w = L(y0 — y)/2, and w0 — E =
L(?o — ys)/2;
whence — (w0 — w)dw = 2\{w0 — E)<20/L2, or (W, — W)»/-
(W„ — E)2 = 4A0/IA
Since the water content appears as a ratio, it may be
taken for any desired amount of material, e. g., if
W = water per 100 lbs. of dry material,
(W0 — W)V(W0 — E)2 = 4A0/L2.
According to this equation, the drying time is propor-
tional to the square of the loss in moisture since the
start of drying over the initial free water, and to the
square of the sheet thickness. Because of the simpli-
fying approximations used in its derivation it is better
to interpret it as indicating that the drying time is a
power function of these quantities, the power being
nearly 2. An analogy is found in the case of liquid
friction, which is usually assumed proportional to the
square of the liquid velocity, but is actually a power
function with an exponent of about 1.8. When the
point A has receded to the center of the sheet, F, the
character of the drying curve will change and trans-
form itself into the case originally considered.
Illustration is found in the drying of bar soap, data for
which are plotted in Fig. 18. Because the exact exponent
is unknown, the equation has been thrown into the form
n log (Wo — W) = log 0 + log K,
where
K = 4A(W0 — E)"/L2,
and log (Wo — W) plotted against log 6. The curves
are straight within the experimental error, and for this
case the value of n is seen to be about 1.93.
GENERAL SIGNIFICANCE OF THE FORMULAS
While these equations have been derived for sheet
materials, they apply satisfactorily to lumpy, granular
solids, except that the correction for lump or grain size
must be modified. Furthermore, these equations as-
sume constant drying conditions throughout the drying
operation, a state of affairs never met in equipment of
the heat design. We have integrated and tested out
these equations for the most important cases arising
in industrial practice, but it would require too long to
present them here. Usually, however, in calculating
the drying time it is sufficiently exact to employ for A/>
its average value during the drying period, using the
arithmetic mean of the initial and final values if these
differ by less than two- or three-fold, but using the
logarithmic mean of the terminal values if differing
more than this. For E use its value at the end of the
drying period or operation, because at this point W • — E
will be small and must be accurately determined. The
use of this value of E will introduce no serious error
in the earlier stages of drying, where W is large.
«%•
-/ 0 +/ 2 3 4 5 6 7
200
\ /80
\ 160
\ 140
>
\ 100
I
* 40
^ 0 15 30 45 HO 75 90 705 170
Time in Minutes
Fig. 19 — Adiabatic Air Drying
With regard to the two basic drying coefficients, A
and R, the variation of R with temperature, humidity,
and air velocity has already been shown. A varies for
each specific solvent and material, but always in-
creases rapidly with temperature. This is made use
of in drying materials which shrink and harden upon
evaporation of the solvent, but which must not be
allowed to crack, as will happen if the surface dries and
contracts around a still swollen and incompressible
Rate oi
r Drh
inq
/
\
/
\
f
/
\
&
>
^
/
A
■■/,
/
'^
^
/
£ £^8.5
i i
432
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
<
K
'06
10
N, I
\
Time in Minutes
Fig. 20 — Adiabatic Air Drying
interior. Such substances, e. g., wood, varnish, films,
artificial leather coatings, etc., are dried at high hu-
midity so that even the outer surface is not too dry be-
cause of the high equilibrium moisture, and at high
temperature, so diffusion will be rapid. There is a
certain concentration gradient which may be main-
tained through the surface layer without straining it
to rupture. The humidity is adjusted to get this
gradient, and the temperature raised to get the most
rapid diffusion possible with this limited concentration
difference. As drying proceeds the surface layer gets
thicker so that a greater total concentration difference
is allowable without increasing the concentration
gradient, i. e., the humidity can with safety be pro-
gressively reduced.
The values of the drying coefficients should where
possible be determined from the measured performance
of full-scale equipment. The result of plant tests can
even be used to determine the equilibrium moisture.
Thus Fig. 19 shows the rate of loss of water of a porous,
spongy, lumpy material, exposed at a point in a com-
mercial dryer where the drying conditions are sub-
stantially constant. By reading the slopes off this
curve and plotting against the total water, the inter-
cept of the line obtained gives the equilibrium moisture,
E = 8.5, at which evaporation ceases. One can now
draw the logarithmic drying curve for this material
(Fig. 20) from which the time required to reduce the
moisture content to
any required point
can be determined.
The slope of this last
line is the drying co-
efficient K. From
runs under other dry-
ing conditions the
variations of K de-
termine A and R.
Fig. 21 shows the
application of these
general equations to
the drying of an or-
ganic solvent from a
fibrous material.
It is believed these
facts demonstrate
that the drying of a
solid material repre-
sents a balance be-
tween a process of
diffusion of moisture
through the sub-
stance and of evap-
oration from its sur-
face; and that these
processes can be
quantitatively repre-
sented by the differ-
ential equation, — dw/dd = 8ARw/L(4A 4. R)) which
can, after modifications dependent on the material
being dried, be integrated into simple and usable formu-
las which answer the question as to drying rate.
7.0
6.0
We* 0
, L~-L0(i+aM
1 a =.030 -
5.0
Vs
^
4.0
ft
3.0
\\
\
20
)
\
\
/.0
\
0 10 20 30 40 SO 60
Time in Minutes
Fig. 21 — Drying op Organic Solvent from
Fibrous Material at Constant Drying
Conditions
The Theory of Atmospheric Evaporation— With Special Reference to
Compartment Dryers
By W. H. 1
Carrier Engineering Corporation, 39
In this paper an attempt is made to state as concisely
as possible the fundamental theory involved in air
dryers with particular reference to compartment dry-
ing, although the greater part of the theory developed
applies equally well to the tunnel type, the continuous
type, and the spray type of dryers.
We have endeavored to make the theory general to
apply to the evaporation of any volatile liquid in any
kind of atmosphere. In this respect, we believe the
theory is somewhat new.
Moisture exists in material in two distinct forms — as
free moisture, and as hygroscopic or absorbed mois-
ture.
Cortlandt St., New York, N. Y.
Evaporation is the term usually applied to the con-
verting of a liquid into a vapor in an atmosphere whose
pressure is above that of the vapor pressure of the
evaporating liquid, *. e., causing vaporization below
the boiling point. The heat of vaporization is usually
taken entirely from the air itself, and this will be chiefly
the basis of the theory considered. The theory will be
considered (1) with reference to the evaporation of free
moisture, and (2) with reference to hygroscopic mois-
ture.
The rate of evaporation depends upon:
1- — The vapor tension of the moisture in the material cor-
responding to its temperature.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
433
2 — The vapor tension of the moisture in the air corresponding
to its absolute humidity or dew point temperature.
3 — The effective velocity of air over the surface.
4 — The physical and chemical properties of the material being
dried.
The rate of evaporation at any instant per unit of sur-
face is proportional to the difference in vapor pressure
between the liquid and the vapor of that liquid in the
immediate vicinity, that is,
dw
— = x(e — e).
at
(a) This law holds only for free liquid surfaces or for vapor
pressures of the liquid at the surfaces of a wet material.
(A) It holds only when the total pressure is greater than the
vapor pressure of the liquid.
(c) It holds only for like conditions of relative atmospheric
movement with respect to velocity and direction.
(d) It probably holds true for any gases or any superheated
vapor of a nonmiscible liquid or even for the pure superheated
vapor of the liquid itself, regardless of the specific heat, specific
weight, or partial pressure of the gases or superheated vapor.
(e) It holds true where the liquid is above or below the temper-
ature of the surrounding atmosphere.
(/) The coefficient x in the equation is probably independent
of the latent heat of evaporation, but varies directly as the molec-
ular weight of the evaporating liquid.
It has been found that the rate of evaporation, other
conditions being constant, increases in direct proportion
to the velocity. Therefore, the rate of evaporation
may be expressed by the following equation:
dw
— = (a + bv)(e' — e)
dt
where a = the rate of evaporation in still air.
b = rate of increase with velocity.
«' = the vapor pressure of the liquid.
e = the vapor pressure in the atmosphere.
For example, with water evaporating in still atmos-
phere R = 0.093(e' — e), where R is the pounds of
water evaporated per sq. ft. per hr. If we express this
in terms of heat units, we shall have H = 97(e' — e)
B. t. u. per sq. ft. per hr. The effect of velocity de-
pends upon whether the flow of air is parallel to the
surface or transverse, that is, perpendicular to the
surface. For flow of air parallel to a horizontal surface
H
■(' + 4)
093 (1 + — ]
^ T 230)
{e' — e) B. t. u. per sq. ft. per hr.
(e' — e) (approximate).
ixi = lbs. evaporated per sq. ft. per hr.
v = velocity of atmosphere over surfaces in ft. per min.
e' = vapor pressure of the water corresponding to its tem-
perature.
e = vapor pressure in the surrounding atmosphere.
That is, at 230 ft. per min. velocity, the evaporation
is twice that in still air; at 400 ft. per min. velocity it is
three times, etc.
This law was determined by extensive experiments
in the rate of cooling of a body of water by evaporation
in still air and at definite measurable velocity up to
2000 ft. per min. Corrections for the radiation and
convection effects were made by the usual calorimeter
methods, and the water stirred to secure uniform cool-
ing.1 The same law was indicated by the evaporation
experiments of Thomas Box.2 With transverse flow
or impact and vertical surfaces, the rate is nearly twice
as great at corresponding velocities. With the same
frictional losses, however, the rate is substantially the
same, regardless of the type of air flow, as is the case in
heat transmission. In Fig. 1 are given the curves of
evaporation determined experimentally by Coffey and
Home,3 and independently by the writer.1
J
HC*
r ,-~* im
met 3* .' tvKwio/
I
/
■1-
•I
*
1 •' ^pteerroM w o
' £-<v>«.
,Ab~m
, #
i«
...
OnLr.rv*-*^*
<--
V
X 1 <-fi
y\ jit
:
fl
/
*M
A\
r«""
£
1 ' j-'Z-
a
4-
f
V
/
/*■- tft*K.fy ft ■ Sf/"
fe»
i
i
\
i
1
i ■
n
~\ J
n 1
. ,
l
Inasmuch as — is always directly proportional to
dt
(e' — e) for all experimental ranges, it would seem that
the evaporation is practically dependent on the surface
tension of the liquid.
The effect of velocity is apparently to increase the
rate of diffusion of the vapor at the wetted surface.
There is undoubtedly a surface film of vapor saturated
at the liquid temperature, and admixed with air (or gas) .
and this is broken up and removed in direct proportion
to the velocity or to the square root of the surface
frictional head effects caused by atmospheric move-
ment.
A free wetted surface unaffected by internal or ex-
ternal heat (apart from the air itself) tends to assume
a definite minimum temperature of evaporation with a
corresponding vapor pressure (e').* This temperature
is definitely calculable for any vapor and atmosphere,
and is dependent upon the latent heat and specific
weight of the saturated vapor, the specific heat and
density of the atmosphere and degree of initial satura-
tion with the vapor {i. e., the vapor pressure in the at-
mosphere). In psychrometry, this temperature is
known as the "wet bulb" and the difference between
the atmospheric temperature and the wet bulb
temperature, or temperature of evaporation, is termed
the wet bulb depression. It has been shown that in
becoming saturated with vapor, the atmosphere cools
to the wet bulb or temperature of evaporation, and
the latent heat of the water or liquid evaporated is
I W. H. Carrier, Proc Am. Soc. Heal. Vent. Eng., 24 (1918), 25.
■ "A Treatise on Heat," 1870
3 Am. Soc. Refrigerating Eng., 2 (1916), 5.
< W. H. Carrier, Trans. Am. Soc. Much. Eng., 33 (1911), 1005.
434
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
exactly equal to the loss in sensible heat of the atmos-
phere.
For any liquid evaporating in any atmosphere, let Wi =
initial weight of vapor content per lb. of vapor free air.
0 = temperature of the air.
Cpa = specific heat of air.
Cps = specific heat of vapor.
w = the lbs. of moisture in a lb. of air at an unknown tem-
perature.
r' = the latent heat of evaporation.
From the relation, change in latent heat = change
in sensible heat, we have
rrfw = (Cpa + wiCps)de. (1)
Integrating between the limits W\ and w«, di and 02,
r'(wi — w,) = (Cpa + wiCps)(e1 — e,), (2)
which is the fundamental equation for evaporation and
for the temperature of evaporation 6' if we substitute
6' and «>' for 02 and w2, or
r'(iv' — iv,) = (Cpa + w1CPs)(6 — 8') (3)
and if w = 0, then
nwt = Cpa(6i — 82) (4)
or if the superheated vapor alone is present and u>\ —
1 lb. then
r\(w2 — 1) = Cps(8l — 0,). (5)
It will now be shown that the rate of evaporation is
substantially proportional to the wet bulb depression
6 - — 8' as well as to e' — e, the difference of vapor
pressure.
Let B = barometric or total pressure.
t\ = initial vapor pressure.
e' = vapor pressure in the saturated air at wet bulb
temperature 8'.
S = the specific weight of the vapor with reference to the
molecular wt. of vapor
atmosphere =
molecular wt. of atmosphere
Then by Dalton's law,
Sei . . Se'
(approximate).
and w' =
B — ei B — er
Substituting these values in (3) and assuming S ap-
proximately constant, we have by rearrangement
Cpa)]
(6)
[xote: — (SC^j — CPa) is practically negligible], which
is one form of the psychrometric equation, applying
to any vapor and any atmosphere.
Assuming B = 29.92 in., Cj„ = 0.2411 -f 0.000009* (for air).
Cps = 0.4423 + 0.00018*' (approximate).
S = 0.6620 + 0.00003* (approx).
0' = 100°, e' = 1.92, e = 0.92, r' = 1036.
Then 0 — 0' — 96° depression = 1 in. difference.
Or letting e' = 0.92, 0' = 76.6°, r' = 1048.7, e = 0.
Then
= 93° depression per 1 in. difference.
From the above it will be seen that the wet bulb de-
pression is proportional to the vapor pressure difference
for any given wet bulb temperature, and approximately
proportional for different wet bulb temperatures, when
e' is small with reference to B; therefore
The rate of evaporation of free "water is substantially
proportional to the wet bulb depression when the material
is not heated, and 95° depression is approximately
equivalent to 1 in. difference in vapor pressures in the
evaporation formula.
Also the drop in temperature of the air in a dryer
is proportional to the rise in vapor pressure of the air.
If we apply the wet bulb depression formula to the
rate of evaporation H = 97(e' — c) ( r + — I B. t. u
F V 230/
I 1 + — 1 ( ~g ) Cpa(0 — 0'
\ 230 J \ SV / P
per hr. Then
H = 9
Let R = lbs. per sq. ft. per min
1.63 B —
- e' / v \
— Cpal 1 + )(0 — 0')
r' \ 230 J
= 0.0000165 ( 1 — J (0 — 0') at 8' = 100°, B = 29.92,
^ 230/
and
R = 0.0000166 | 1 — J (0 — 0') at 8' = 60°, B = 29.92,
y 230/
or the weight of evaporation is substantially the same at any tem-
perature per degree depression.
d*
J
j
>>
A
M
war
/erWeioea
his
CqPf.CITY
1
OF
flie /\nd Co/teesPoHOiHG mmimu*
/
1
1
De
V O.
IB Tt
IK
"\1V
?c
/
1
*
1)
/
1
n
V
/
5"
^
y
/
\
V
V
/
«
f
fc
4
V
f
A
Kt
1?
-•;/
0
A
i/
i,
X
A
t;/
*i
V
Cj
/
_>-
V
<u
V
9
■
.■
c-
,<LT
dUL
! TCI
PCK.
\TUS
r
Q
7
6
c
*
0
/«
v
1
0
o -
Air passing over a moist surface (as in a drying
compartment) drops in temperature toward the wet
bulb or evaporative temperature, and its vapor pres-
sure and "dew point'' rise correspondingly toward that
of the "evaporative" or wet bulb temperature. It
follows that the wet bulb temperature remains con-
stant although the dry bulb temperature drops, and
also that temperature of the material is substantially
constant at the wet bulb temperature, if evaporating
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
435
m
I
0.1
»
t\
jIUjM
nm
,'
H
rl
5
£
tl 1
?l
■'1
e
■v.i
1 A
1
^
--
v.
«1
III,
? ,i
>.;
•■/ /
\
y
-
TH
?.<'>
•
s
1i<
1
ii
><
£
1;
\
^>
j^-i
700
f .,1
?* \i
£m
■g.M
rb
N^
\.
(SjJ
^
"~
I
V
i
•:
1
M.
wf
:,w.
t$£.
fit"!
tl?.9
} : 1
g.J
if-
m
g
1&Sb
^7
16,
ora
•<:.v.t
- '.I
rj
i^
:
M
400
<'l
D?l
?. .-
u
^
<
><//
■9
too
'■\
tin
m
15
, ."
,
•'
'■
^
'A
o
if
P^i
*»
.,'■ :
> V
$$7 '''
.,-> ' v
<m
H
<i,'4
..*'
5^
-~
1J
^■•4 """*"" I • - i i" ^ ■
A
<
/
i
S
7
,'
*
0
>t
0
14
7
«
3
£
0
<B
i
St
i
.
0
n
0
,:
i
•
0
I
»
w
KO
«
0/> &//0 'enperdturr
Fio. 3 — Drying Chart
freely. These facts are easily deducible from the pre-
ceding paragraph and they are substantiated in practice.
It also follows that the capacity of air for producing
evaporation is directly proportional to its wet bulb de-
pression (and the actual evaporation procured is mea-
sured by the decrease in wet bulb depression), *. e., the
drop in dry bulb temperature. See Fig. 2 for capacity
of air for evaporating moisture.
The rate of evaporation at any instant has been shown
to be proportional to difference in vapor pressure be-
tween that of the liquid or material, and that in the air
adjacent to the material. Therefore, the rate of drying
is proportional to the difference between the average
vapor pressure of the air and vapor pressure correspond-
ing to the wet bulb temperature (or temperature of
•evaporation).
MEAN RATE OF EVAPORATION OF FREE MOISTURE
As the air passes over a wetted surface progressively,
the dry bulb temperature drops in proportion to the
moisture evaporated per lb. of air, and approaches the
wet bulb temperature which remains constant throughout.
The rate of evaporation constantly decreases in pro-
portion as the wet bulb depression decreases.
If we let It = B. t. u. absorbed per sq. ft. per min.,
(9)
G = 0.071 Av at 100° + 29.92 in. barometer.
Then from (9)
\8t-eJ \v 230/
/at 100° and 29.92 in.
barometer. (10)
This evidently holds approximately for any baro-
metric pressure and any temperature, since the change in
air density affects the numerator and the denominator
in nearly the same proportion. (See Equation 6.)
If we let Q = cu. ft. of air per min., Q = A„ and
/el — e'\ i v \F
log, ( , \ = | 1 H J— (11
The mean depression may easily be determined equal
log.
\«2 — 0l/_
= (0m - 6').
(12)
K
0.0000164
\ 230/
at B = 29.92 in., G = lbs.
230y
air per min., and F = sq. ft. of surface, then
GCPad(e — 0') = dh = K(e — 6')dF
which by integration between the limits 0\,
to F gives
(8)
and 0
This enables us to calculate (02 — 8'), the final de-
pression, if the initial depression (0i — 0') is known;
also the maximum temperature drop (0i — 02) of the air
through the material being dried.
The weight of water in lbs. evaporated per min. is
GC»« G
w = (0i — 02) = ■ ■ (0i — 02) =
r 4300
Q(0i — 02)
I ill,-,! HI
(approx. at 0' = 100°J.
(13)
436
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
That is, approximately 1 grain is evaporated per
cu. ft. for each 85/s° F. drop, or 1.62 grains per lb. of air
per degree drop at 100°.
The above values of coefficient
V 230/
apply only
to wet material freely exposed; as the drying progresses
the area of effective wet surface is reduced and the
coefficient is correspondingly changed. Also many
surfaces are complicated and impossible of determina-
tion. Therefore, it is usual to determine the factor /
in Equation 9 experimentally, and to use this experi-
mental value in the design of a compartment dryer.
In other cases, however, as in the drying of films or
sheets, the calculations are sufficiently accurate.
A useful relation to know is also shown by Equation
9, *". e.,for any given exposed surface (S) and air quantity
(G) the ratio of the final depression (<?2 — di) to the
initial depression (0i — 6') is constant regardless of
changes in dry bulb temperature or moisture content of
the air.
DRYING CHART
While all the engineering problems may be solved by
the physical formulas, previously given, the results may
be read directly from the drying chart (Fig. 3) here
presented. The principal curves are the saturation
curve, giving the lbs. weight of water vapor per lb. of
dry air at saturation (B = 29.92 in.) and the cor-
responding vapor-pressure curve. The slanting lines
represent definite wet bulb temperatures with cor-
responding dry bulb temperatures and weights of water
vapor per lb. of air. In using the chart, one merely has
to keep in mind that the temperature drop and cor-
responding increase in weight of water vapor always
occur along a constant wet bulb line, and that, in heat-
ing air, the weight of water vapor remains constant.
s
.
1
■■
t
k
s
:•
■
^
'•■;
i
i
i
t
«
t.
I
■
',
\«,.,
~
:n.
'■'
O'
c
6
t
* •
' •
b t
For example, if air has a vapor pressure of 0.52 in., it
has, according to the chart, a dew point of 60° and
contains 84 grains of moisture per lb. of dry air. If
heated to 172°, at the same moisture content, it has a
wet bulb temperature of 90. If the efficiency of mois-
ture absorption were 100 per cent, the air would become
saturated at this wet bulb temperature, the tem-
perature-moisture content relation passing to the left
and upward along the slanting line denoting the con-
stant wet bulb temperature condition of 90° to the
saturation curve where 211
contained per lb. of air.
grains of moisture will be
ov
*. '
iso'
ao
too'
|
*ij-
-22--
■v
10
6
3^
iWU-
%r^
6y^
B^"'
60
la
^
\p/^
|
iij!
*$^
KAXhWM
THCoecriCM
>r
7
E
^ncirncy oroeytei
I
IC
IHITIH. vJfT OULB
dzs zees
DCPErS
61011 '^
-&'
The weight of moisture absorbed is the difference, or
133 grains per lb. of air. The maximum possible
thermal efficiency is
E' =
However, 100 per cent drying effect is both impossible
and undesirable. The per cent drying effect (M) is
M = 1 —
= 1
0+i)
)/• (14)
Fig. 4 gives the drying effect M for various values of
I/, also 1— M.
\v 230/'
Fig. 5 gives the maximum thermal efficiencies E and
dry bulb temperature By, various saturation tem-
peratures do from 40 to 120° corresponding to wet bulb
temperatures 6'. The actual efficiency E = ME'.
The above is based on the assumption of all fresh air
being used. That, however, is not the usual or best
practice. Instead,, it is customary to use only from
50 to 5 per cent fresh air, depending upon the wet bulb
temperature and depression desired. The per cent of
fresh air with a saturation 0O may be represented by
the factor n and its initial temperature as 8„ assuming
that it contains all the heat applied to the kiln. Then
the maximum possible efficiency becomes
E' = B^=4. (15)
The per cent drying effect of the fresh air admitted may
be calculated from the relations.
fl, — 02 = «(»« — fl2) (16)
0i-
1 — M
(17)
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
437
M„ = 1
ft,
(18)
from Fig. 3
All values are known except di, 02, and M (or 6„).
For example:
Let the wet bulb temperature 6' = 100°
The max. dry bulb temp, in kiln ft = 120°
The saturation temperature of entering fresh air ft =60°
Ratio of depression drop in kiln
determined from assumed kiln factors M = 0.30
Then,
Temp, of fresh air ft, = 232°, from Fig. 3
Temp, at back of kiln ft — 114°, from Equation 17
Drying ratio M„ = 0.894, from Equation IS
Per cent fresh air n = 0.05, from Equation 16
ft, — ft 132°
Max. possible eff. E = = = 0.77
• e„ — e0 172°
Actual efficiency E = M„E' = 0.894 X 0.77 = 0.69
Note the extremely small percentage of fresh air
required and the high efficiency of evaporation. The
efficiencies calculated are of course exclusive of radia-
tion losses and heat required to warm up the material,
which are independent and must be calculated sep-
arately. In practice it is found that the average value
of M is about two-thirds the maximum depression drop.
That is, M maximum would equal 0.45 if the average
was 0.30.
Now assume that all fresh air were used to obtain
the same rate of drying, that is, the same wet bulb de-
pression.
Assume, as before, ft = 60°, ft — ft = 20°, and M = 0.30
Then ft =90°
ft = 70°
Then ft = 84°
20
E' = — = 0.67
30
E = 0.30 X 0.67 = 0.20
Note the great decrease in possible and actual effi-
ciency using all fresh air. In general, it may be stated
that the higher the temperature and greater the per
cent of air recirculated, the greater the efficiency.
EVAPORATION OF HYGROSCOPIC OR ABSORBED MOISTURE
In the foregoing we have considered the theory of
evaporation purely from a physical and thermodynamic
standpoint and without reference to the chemical or
physical behavior of material being dried.
The moisture content of a hygroscopic material de-
pends upon the relative humidity and temperature of
the surrounding air. This is a perfectly definite re-
lationship for any given material, but varies widely
for different materials. This content of hygroscopic
moisture is termed regain, and is expressed in parts of
water per hundred parts of dry material. In Fig. 6
are given the regain curves of cotton and wool for dif-
ferent humidities.
In calculating the rate of evaporation of the hygro-
scopic moisture in a material, account must be taken
of the fact that the physical (or chemical) effect of
absorption is to reduce the effective vapor pressure of
the contained moisture in relation to its temperature
by a definite ratio. This ratio of effective to normal
vapor pressure at a given temperature depends upon
the regain, or per cent moisture content of the material,
and corresponds to the same ratio (or per cent) of rel-
ative humidity. This ratio increases slightly with the
temperature. The same thermal laws hold as in the
evaporation of free water in unsaturated air, providing
we consider the air to reach its maximum possible
saturation (from the material) not on the normal
saturation curve but on a per cent saturation curve
corresponding to the regain. (See Fig. 6.) For ex-
ample, in cotton, a regain of 6.0 parts water per hundred
corresponds to 60 per cent relative humidity at 77° F.
Then the 60 per cent relative humidity curve on the
drying chart corresponds to the maximum air satura-
tion in contact with cotton having 6 per cent regain.
1
/
'
/
J
:
t
a
■^c
it*"
/
e
M7
TH.iMtonr,
°c,
•«
, 7?'Pe
3,.
>
Fig. 6 — Relation of Regain and Relative Humidity
Thus, air at 110° and 70° wet bulb (or 50° dew point)
would continue to evaporate moisture from the cotton
and cool along the constant wet bulb temperature line
until it reached the 60 per cent saturation line at 80.5°
F., which temperature is the temperature of evapora-
tion of the material in air of 70° wet bulb temperature.
The rate of evaporation with air at 110° and 70° wet
bulb would be proportional to the difference of 60 per
cent of the vapor pressure corresponding to 80.5°, and
the vapor pressure (corresponding to 50° dew point) in
the air. This rate approaches 60 per cent of that with
free water.
The process of absorption is the reverse of that of
evaporation and may be calculated in the same manner
from Fig. 3. For example, saturated air at 70°, when
brought in contact with cotton at 6 per cent regain,
would approach 80.5° at 60 per cent saturation, and
therefore the absorption temperature of the material
would be 80.5°. In short, the temperature of material
having a definite regain is always fixed with reference to
the wet bulb and independent of the. dry bulb temperature.
DIFFUSION
It has already been pointed out under the "Theory
of Evaporation" of free moisture that the laws hold
exactly only for free moisture at the surface, that is,
for relatively thin materials or porous materials, in
which the moisture flows rapidly to the surface.
In thicker and denser materials, the rate of evapora-
tion is limited by the rate of diffusion, that is, by the
rate at which moisture will flow from the interior to the
exterior. As will be appreciated, this rate varies
greatly for different materials, and can only be de-
438
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
termined by experiment. For low rates of evaporation,
that is, low wet bulb depressions, the theory of evapora-
tion for free moisture and hygroscopic moisture holds
very exactly. For high rates of evaporation of heavier
materials, such as ceramics, for example, there is a
maximum rate for any temperature at which an in-
crease of velocity will have no appreciable effect in in-
creasing the rate of drying. Under these conditions,
s
5
\
\
\
\
\
\
f>
|
\
\
^
\
"
\
\
i
\
A
i
\
i
\
\
*
%
' -.
iter
,t..
* -..'--
••
■
,
*
i
■
^
Fig. 7 — Variation op Rate of Evaporation with Moisture Content
the dry bulb temperature plays an important part for
the reason that the temperature of the material is not
at the wet bulb temperature, but at an intermediate
temperature between the wet and dry bulbs, depending
upon the evaporation determined by diffusion. The
higher the temperature the more rapid is the diffusion,
for the reason that the vapor pressure of internal
moisture increases rapidly with the temperature.
In such materials, the rate of evaporation per degree
depression decreases as the surface of the material dries.
This variation of rate of evaporation with moisture con-
tent is well illustrated by the curves in Fig. 7. These
results are from actual tests of ceramic materials in
commercial dryers, and serve very well to illustrate this
practical point. The 100 per cent line indicates the
rate of evaporation with free moisture. It will be seen
that this holds up fairly well until about one-half of
the moisture is removed, and then falls off rapidly as
the material is dried out. The average rate of evapora-
tion is almost exactly 67 per cent or two-thirds of the
theoretical free evaporation from a moist surface. In
Material 1 it is about 30 per cent of the free evaporation
from a moist surface.
In applying the foregoing theory these practical
considerations must always be borne in mind, and for
certain classes of materials experiments must be made
on a small scale to obtain accurate data as to the rate
of drying as affected by diffusion. The general theory,
however, has its practical value, since it indicates very
well the effects of arrangement of material and of ve-
locities, temperatures, and wet bulb depressions, so that
from any known operating condition comparative re-
sults may be calculated for some other desired condi-
tion. In this a knowledge of the fundamental theory
is of great assistance and value.
The Compartment Dryer
By W. H. Carrier and A. E. Stacey, Jr.
Carrier Engineering Corporation, 39 Cortlandt St., New Yo
The art of successful air drying, or, more properly,
air processing, is coming to be appreciated more and
more as a process of chemical and physical treatment
apart from the mere removal of moisture. There are
numerous classes of materials which require special
treatment with respect to (1) temperature, (2) rela-
tive humidity, and (3) rate of moisture removal.
Most such materials are of animal or vegetable origin,
and usually possess exceptional hygroscopic or ab-
sorption properties. Frequently they are of a col-
loidal nature. Among such materials to which air
processing is being successfully applied, the following
may be mentioned:
Green lumber
Textiles (natural ai
Cured tobacco
Green tobacco (in i
Tea
Photographic films
Gelatin capsules
Certain industrial <
Macaroni
Developed films
Coated paper
Milk
Washed rubber
Writing paper (after siz
Certain chemicals
Chicle (lor chewing gur
Painted and varnished surfaces, etc.
The optimum temperatures and humidities for
the above vary over a wide range — from 75° to 180°
F. in temperatures, and from 90 per cent to 15 per
cent in relative humidities. The temperature and
humidity requirements usually vary considerably in
accordance with a definite established schedule. A
vigorous air circulation is usually important to secure
uniformity and maximum allowable effect. The time
element is best regulated by controlling the wet bulb
depression and temperature.
In some processes there are certain chemical or
biochemical changes that must be accurately timed
with respect to the percentage of moisture removed.
In these, it must be kept in mind that the velocity
of chemical reaction at a given moisture content of the
material depends upon the temperature of the material
(which corresponds to the wet bulb temperature of
the air). As chemists will appreciate, this velocity
of reaction doubles approximately for every 18° F.
increase in temperature. Since the vapor pressure
also approximately doubles with each 18° F. increase
in temperature, the velocity of chemical reaction is
practically in proportion to the variation in vapor
pressure, as produced by variation in wet bulb tem-
perature. On this account, there are certain critical
temperatures, as well as humidities, in the processing
of such products as green tobacco, macaroni, etc.,
where certain definite chemical changes are necessary,
but where further chemical action must be prevented.
In drying many hygroscopic substances, there are
two critical points with respect to relative humidity.
The first is where the free or nonhygroscopic moisture
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
439
is being removed. In this stage, the high relative
humidity must be carried to prevent hardening and
shrinkage of the exterior, which would injure or spoil
the product. A relative humidity of 80 per cent or
more is usually necessary for this purpose, this being
approximately the critical point at which all hygro-
scopic substances retain their maximum elasticity
or plasticity. In this stage of drying, the free moisture
alone is being removed. Again, in the final removal
of hygroscopic moisture, a certain required amount
of residual moisture must be retained, the removal
of which would injure the product physically or reduce
its value. This is especially true of materials con-
taining colloids. The regulation of the final or re-
tained moisture is accomplished by maintaining in
the dry room at the end of the process, a definite
relative humidity, depending upon the final moisture
content desired. It is also often found necessary,
between the initial and final moisture removal, to
graduate the relative humidity in stages, as the product
dries, to prevent ..an excessive rate of drying at any
stage, which, in some cases, is found to injure the
product.
This accurate processing of the material in dehydra-
tion is made possible and practicable by recent im-
provements in drying equipment and in the design
and application of automatic temperature and humid-
ity control. Especial attention will be devoted to
these later developments, both on account of their
novelty and of their great practical importance in
many industries. Process drying, in which air drying,
as distinguished from vacuum drying, is essential,
can be accomplished equally well in either the con-
tinuous or the compartment dryer, with which latter
type this paper deals.
The compartment dryer, however, frequently per-
mits of manipulation and control of conditions which
are difficult, if not impossible, with the progressive
type of dryer, and entirely out of the question with
the tunnel type of dryer.
When the continuous dryer is used for such pro-
cessing, it is really divided up into a series of consec-
utive compartments, which are handled indepen-
dently; so, in fact, it is treated exactly as several
compartment dryers in series, and should be classed
as such, except for the matter of handling of material.
FIELD OF THE COMPARTMENT DRYER ADVANTAGES
AND LIMITATIONS
Solid or plastic materials are usually best handled
either by the vacuum system or the atmospheric
system of air drying. The vacuum dryer, of course,
recommends itself from the standpoint of speed, but
it cannot readily be used for processing, the require-
ments for which have already been pointed out, nor
can it be used successfully where the physical or
chemical properties of the material are affected unde-
sirably. Systems of atmospheric drying usually have
the advantage in first cost and frequently, where
properly designed, may also have a slight advantage
in cost of operation. As a rule, however, the efficiency
of the atmospheric type of dryer is considerably
lower than that of the vacuum dryer. If the mechan-
ical and physical problems in the drying and handling
of a material indicate an atmospheric drying system,
then the choice lies between three types:
1 — The continuous automatic type, in which the material
is conveyed mechanically through the dryer, or from compart-
ment to compartment of the dryer, and a transverse circulation
of air is usually maintained.
2 — The tunnel type of dryer, in which the material is passed
through on trucks and heated air is blown in at one end and
exhausted from the other, usually in opposite direction to the
movement of the material. Material is usually handled on
trucks, one truck being put in at one end while another truck
is removed at the opposite end.
3 — The compartment dryer, which may be entirely self-
contained, as a unit dry kiln, all parts being furnished and
set up in the building independent of the building construction,
or it may be simply a room or compartment in the building,
this fitted with coils, fans, or other apparatus used in the drying
process.
The continuous automatic type of dryer is usually
indicated wherever the drying period is less than 6
hrs., or wherever the process is continuous for 24 hrs.,
even though the time of drying may be considerably
longer. In other words, with a continuous dryer
material must be fed continuously at one end and
unloaded continuously at the other end. If the
material requires more than 5 or 6 hrs. to dry, it will
not be practicable to operate the apparatus continu-
ously at full capacity. This will reduce the overall
efficiency of the installation and will render it ex-
tremely difficult to control uniformly the conditions
within the dryer. In other words, the continuous
dryer is inefficient and expensive whenever it is not
operated to full capacity. The compartment dryer,
on the other hand, can be loaded during the produc-
tion period, and the drying can be carried on at night,
the dryer being unloaded the following morning,
ready for a fresh charge. In certain cases, the drying
process may require several days or even weeks. In
these cases, of course, the continuous dryer is not
applicable.
The compartment dryer, on the other hand, is not
applicable where a continuous process of handling
material is desired. The efficiency, also, tends to-
be lower than that of the continuous dryer. Uni-
form drying is more difficult to obtain than with the
continuous dryer, but the compartment dryer usually
has the advantage of first cost over the continuous
mechanically operated dryer. However, under certain
conditions of production, more labor is required in
handling the material with the compartment dryer
than with the continuous mechanical dryer, which
will more than offset the saving in first cost. On
the other hand, where the material has to be carried
to and from continuous dryers, on trucks, there may
be actual saving in labor with the compartment
dryer, in addition to a saving in first cost, since the
material can remain on the trucks until dry. The
use of the compartment dryer in preference to the
continuous mechanically operated dryer is usually
advantageous whenever the period of drying exceeds
5 or 6 hrs., and where production is not continuous
during the 24 hrs.
440
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
The compartment dryer also has a great advantage
in intermittent or interrupted production as contrasted
with the requirements of a continuous dryer for uni-
form and steady production. It also has the advantage
of being adaptable to the drying of different articles
in small quantities at the same time. While it is
true that there is more difficulty in obtaining uniform
drying in the room dryer than in the continuous dryer,
this is true only on account of faulty design of the
compartment dryer, and various means have been
proposed and tried to increase the uniformity and
efficiency of the compartment dryer. It is these
features that are of chief interest in the study of the
compartment dryer. Considerable effort has been
spent in perfecting the compartment dryer in work
requiring accurate processing, and it has been found
easier to maintain a constant condition of temperature
and humidity in the compartment dryer than in the
progressive dryer, because the control is unified.
Control of drying is becoming an important con-
sideration in many industries, and its value is just
beginning to be appreciated. For many types of
controlled drying, the compartment dryer has been
found superior to the continuous dryer, especially
where constant control for definite periods is desired.
CLASSIFICATION OF COMPARTMENT DRYERS
Compartment dryers may be classified under three
general headings:
1 — As to the methods of loading and handling.
2 — As to the methods of supplying heat.
3 — As to the methods of moisture removal.
The various classifications may best be shown by
the following tabulation, important examples of which
are illustrated by accompanying figures and diagrams.
Types op Compartment Dryer
A — Classification as to Methods op Loading and Handling
(1) Method of Support of Material
(a) Trays (fixed or movable)
(6) Movable pallets
(c) Sticks
(d) Hooks or clasps
(2) Method of Loading
(a) Cabinet dryi
(b) Rack dryers
(c) Truck dryers
B — Methods op Heating
(1) Heating Medium
Hot water
Steam
Superheated steam
Electricity
Heated oil
Heated air
Products of combustion
(a) Direct application
(6) Heated flues
Latent heat of absorption
(2) Method of Heat Application
(a) Direct heat (radiation or convection)
Wall coils
Floor coils
Distributed coils
(o) Indirect heat
Gravity circulation
Mechanical circulation
Direct fans (disk fans)
Housed fans with distributing duets
Induced circulation
Water sprays
Steam jets
Air jets
th drawers or sliding trays
C — Methods op Moisture Removal
(1) By Ventilation
(a) Gravity of air supply and exhaust
(6) Mechanical (fans or blowers)
Exhaust
Plenum
Combination
(2) By Condensation
(a) Direct surfaces (water or brine)
(W Spray
Fresh water supply and recirculated water artificially
cooled (refrigeration)
(3) By Absorption
(a) Chemical (calcium chloride or sulfuric acid)
(b) Physical (silica gel)
(4) Transpiration (through cloth walls)
Dryers may also be classified as low temperature
dryers, or high temperature dryers. Low tempera-
ture dryers are heated either by steam, hot water,
or indirect steam, using hot air, and the temperatures
in the dryer are usually below the boiling point. In
high temperature dryers, the temperatures are usually
carried above the boiling point, and the heat is sup-
plied directly or indirectly by electric resistance, by
heated oil having a maximum temperature of about
600° F., by direct introduction of the combustion
gases into the dryer, or by flue air heaters, where the
air is conducted through tubes exposed to the com-
bustion gases. In these high temperature dryers,
the object is to secure an extremely rapid rate of
drying, or to procure certain chemical and physical
changes in the material, which may or may not be
associated with the true drying process. However,
it is the method of applying the heat required for
evaporation that is of chief interest, and in which
the various types of dryers vary most widely one from
another.
HEATING
The earliest types of dryers depended upon radia-
tion and convection from internal heat sources for
their heating effect. Little or no attention was paid
to the arrangement of the material so that uniform
heat distribution could be effected, the air moving,
—Dikcc T Raoia r/o/y Kicn —
Fio. 1 — Direct Radiation Kiln
first, over the heating surfaces, and, second, through
the material itself. Evaporation ceases, of course,
at any temperature below the boiling point, whenever
the air has become saturated. The air immediately
surrounding the material is cooled, by evaporation,
to a temperature lower than that of the other air
in the kiln, and this air is therefore heavier, having a
tendencv to fall to the floor. Because of these facts,
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
441
it is essential that positive air circulation be effected,
if rapid and uniform drying is expected.
Although it is possible so to arrange the heating
surfaces within the kiln, and the material, that fairly
good circulation can be obtained by convection, as
:
Fig. 2 — Kiln with Internal Condenser Coils
will be described later, the demand for more rapid
and controlled drying has led to the development of
kilns in which the circulation is made mechanically
positive by the use of fans or blowers. In some kilns,
also, circulation is induced by means of water sprays
and steam or air jets. The arrangement of the
material within the dryer and the method of air
circulation are of utmost importance in the design
of a dryer, and the various methods now in use will
be discussed in detail in a later section of this paper.
MOISTURE REMOVAL
Not only must heat be supplied to the dryer to
produce evaporation, and circulation of air secured
through the material to remove the moisture as it
evaporates from the material, but means must also
be provided to remove the moisture thus evaporated
from the compartment itself, otherwise it is quite
evident that the entire content of the dryer will become
saturated and evaporation cease at any temperature
below the boiling point, below which atmospheric-
drying is usually conducted. An obvious method
is to introduce a certain amount of fresh air with
relatively low moisture content, and to remove a
corresponding amount of more highly saturated air.
This is often accomplished through ventilating stacks
by a natural gravity system, depending on the lesser
density of the moist heated air within the dry kiln.
The moist air can be removed either at the ceiling or
at the floor line, the only condition being that the
stack is of sufficient height to give the necessary
gravity pull just as a chimney would do. In the fan
systems of drying a difference of pressure is produced
by the fan, and advantage is usually taken of this
fact to admit air on the inlet side of the fan, allowing
it to escape, at fan pressure, from some part of the
dryer. This will tend to put the dryer under slight
pressure, unless a relief stack of sufficient size is supplied.
The pressure on the kiln may be exactly balanced by
means of dampers, if this is essential. In some cases,
it is found desirable to remove the moist air in accurate
amounts and positively by means of an exhaust fan.
This is found desirable where the rate of evaporation
is rapid, and large quantities of air have to be removed.
Advantages of an exhaust fan are that it will handle
the fixed quantity of air at high velocities through the
ducts, enabling relatively small ducts to be used,
and that it is relatively unaffected by variations in
wind pressure outside. Exhaust fans are usually
found desirable where the drying compartments are
located on the lower floors, while gravity removal
is often desirable on account of simplicity, whenever
the dryers are near the roof. An approved type of
roof ventilator should always be used in connection
with gravity exhaust systems to prevent back draughts
and the entrance of rain or snow.
A second form of moisture removal is by direct
condensation of the moisture in contact with the water-
circulating condensing coils, or in direct contact with a
spray of cold water, Advantages of such a system
are that it is entirely self-contained, and the moisture
can be removed at a definite and controllable rate.
This system is found of particular advantage where
definite temperatures and humidities are required
in the drying process. The older types usually em-
ploy water-circulating coils, but the modern types
Fig. 3— Wenborne-Karpen Kiln
are using sprays, in which the contact is much more
efficient and the moisture removal equally effective,
as in any case the air is practically saturated. En-
trained moisture with the spray system is removed
by a series of baffles, or eliminators, and the apparatus
closely resembles the air-conditioning equipment used
442
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
in various industries for maintaining definite atmos-
pheric conditions. Another advantage of the spray
type is that definite conditions are more easily con-
trollable. There is also a lower depreciation than
mm*
s w\ ^
a ovo
Fig. 4 — Hunter Dry Kiln
in the case of condensing coils, which tend to rust
rapidly on account of being continuously covered
with condensation. This type of dryer is also used
for drying at very low humidities, particularly at
temperatures and humidities below normal atmos-
pheric conditions. Gelatin capsules are dried in
this manner in summer, when otherwise successful
drying would be impossible. In such cases, the
cooling for condensation is procured by means of
refrigeration applied directly to the spray water.
The application of dehumidifiers, using refrigeration,
for sueh purposes is becoming increasingly more
important, and is coming into use in many industries.
There are two other methods of moisture removal,
which are little known, but are perhaps worth men-
tioning on account of their novelty. These are chem-
ical or physical adsorption and transpiration through
cloth or canvas walls. Calcium chloride or sulfuric
acid may be used for absorption, but are found prac-
ticable only on a small scale. Calcium chloride brine
of a high concentration will absorb moisture actively,
but it is objectionable on account of the entrain-
ment of the calcium chloride itself, which it is
practically impossible to eliminate. For this
reason, it has not been developed commercially.
Another absorbent, however, promises greater success
and is of special interest to chemists. This is known
commercially as "silica gel," and consists of pure
silica precipitated in a colloidal state, then aggregated
at temperatures which do not destroy its colloidal
and absorption properties. The material is then
crushed to a granulated state or ground to a fine
powder. This material is entirely inert, except with
respect to moisture and soluble gases, and, in saturated
air, will absorb a large per cent of its volume. The
amount of moisture absorbed, or the regain, depends
upon relative humidity of the air with which it is in
contact. The silica gel is dehydrated at temperatures
slightly above the boiling point, either with or without a
current of air. It is then capable of reducing the
moisture content of the air to a very low point and
is comparable, in its effect, to sulfuric acid. In this
process, the air in the dryer may be used over and
over, its moisture being removed by absorption.
One feature, however, must be taken into considera-
tion, and that is that the heat of moisture absorption
is exactly equal to the latent heat of evaporation,
so that no additional heat need be supplied. Where
the moisture is absorbed chemically or physically,
sufficient heat will be added to the air to compensate
for the latent heat of evaporation, inasmuch as the
total heat of the air does not change anywhere through-
out the cycle. In the dryer there is a change from
sensible heat into latent heat, while in the absorption
process there is a corresponding change of latent
heat into sensible heat, and the two changes, theoreti-
cally, exactly counterbalance each other. On this
account, however, if low temperatures are required,
some cooling means must be provided to maintain
the desired temperature level and to counterbalance
external radiation. Otherwise, the temperature in the
dryer would tend to be at or above the outside tem-
perature. It might seem at first that such an absorp-
tion system would have a great many advantages
over condensation by refrigeration, for low temperature
drying. Possibly this may be true, in the case of
very small plants or in cases of very large plants.
However, in the present state of the art, the cost of
an elaborate system for dehydrating, by means of
silica gel, would seem to offset its other advantages in
economy of operation. In very large plants, this
probably will not hold true, and the system in the
future may be so perfected that the construction and
space requirements may be reduced to make it prac-
ticable in moderate sized units.
■.'''■■i> ..''. \ i i, . .'■ ;*:,,-'" ' V.'v , - :- ■'• ■■' ■" ■ .. '- ..".
Moisture removal by transpiration is a unique
feature of the Cutler kiln. The moisture is absorbed
or partially condenses upon the relatively cool cloth
or canvas walls, and is evaporated from the cloth
by the relatively drier outside air. There is not
necessarily, and probably is not in fact, any appre-
May, 1921
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
443
ciable removal of moisture by diffusion of the air
itself through the cloth. This is indicated by the
fact that the amount of moisture removed is con-
siderably greater than would occur by any calculated
diffusion.
TYPES OF COMPARTMENT DRYERS
The accompanying illustrations show, chronolog-
ically, the development of compartment kilns in use
to-day.
CONVECTION CIRCULATION NO HUMIDITY CONTROL- —
In the earliest types of kilns, which are still very
common to-day, no attention was paid either to the
means of obtaining a consistent air circulation, or
the means of processing by moisture control. The
direct radiation kiln, Fig. 1, illustrates a very com-
mon type, which is simply a heated room in which
the general temperature is maintained by means,
usually, of coils or radiators around the sides of the
room near the floor. A vent for the moist air is some-
times provided, near the floor, though often very
wastefully at the ceiling, where the hot air escapes
without exerting any drying effect. The material
at the center of the room and at the floor, of course,
dries very much more slowly than the material at the
sides and in the upper part of the room, since the
heated air all tends to concentrate near the ceiling
and the material nearest the radiating surfaces is
overheated by radiation. Very frequently no pro-
vision is made for exhaust air, and the moisture re-
moval is effected largely by infiltration due to loose-
ness in kiln construction. If the kiln is built too
tightly, the material will not dry well. If it is built
too loosely, it is subject to injury by extremely rapid
drying in certain parts of the room. The conditions
in such a kiln are always very uncertain in respect
to temperature, moisture and radiant evaporation.
Fio. 6 — Tiemann's Dry Kiln
Another type of direct radiation kiln, not illus-
trated, is one in which the heater coils are placed in
trenches or a pit under the floor of the kiln.
CONVECTION CIRCULATION HUMIDITY CONTROL
Figs. 2 to 5, inclusive, exhibit various improvements
in the direct radiation type of kiln, in which a con-
trolled circulation and distribution of heat is sought
in various ways, and also certain provisions are made
with a view to controlling in some degree the condition
of atmospheric moisture to which the products are
ipr^
iRr"""
Fig. 7 — Dryer with Floor Diffisers
subjected in the drying process. This control of
moisture, as has been pointed out, is very essential
in numerous processes. Fig. 2 shows a common
type of kiln, having condenser coils along the wall
and direct radiation coils beneath the racks or trucks
supporting the material. The condenser coils in
such a kiln serve two purposes:
1 — To remove the moisture to a certain desired degree by-
means of condensation, which is carried away from the room.
2 — To induce a circulation by cooling effect which assists
the general circulation throughout the room.
Such a type of kiln is usually made as an independent
unit, and made as tight as possible, so that the amount
of infiltration is minimized. Under such conditions,
very fair moisture control can be secured, although
there still exist serious difficulties in the distribution
of heat, and consequently the rate of evaporation
varies greatly in different parts of the room. Very
good results have also been obtained by the reversal
of this arrangement, placing the condensing coils
at the floor and indirect heater coils along the side
walls. The air circulation is then downward through
the material, which is a natural scheme of circulation,
and thence upward through the indirect radiators
along the walls.
In the Wenborne-Karpen kiln, Fig. 3, the condenser
coils are arranged overhead and indirect coils are placed
along the side. Although this arrangement seems con-
trary to physical laws, very good results are said to be
produced, and this arrangement of the condensers
seems to have an advantage in producing circulation.
Fig. 4 illustrates the Hunter kiln, which is installed
as a self-contained unit, and has been very successfully
used in processing washed rubber, as well as in drying
other materials, such as lumber, etc. This is a kiln
in which the moisture content of the air is controlled
444
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
not by condensation, but by evaporation of water in
troughs, the water being held at a fixed temperature,
depending upon the humidity required in the kiln.
Raising the temperature of the water increases the
humidity. The drier the air, of course, the more
rapid the evaporation from the water troughs. A
certain amount of fresh air is drawn in through openings
in the side walls, near the floor line, and, mixed with
the moistened air, passes upward through the indirect
coils and thence downward through the material.
This arrangement gives a fairly positive gravity circu-
lation.
Fig. 5 shows the Cutler kiln as used in drying lumber,
varnish, etc., in which the moisture is removed by the
novel method of transpiration through cloth walls.
The side walls, of light canvas construction, act as
condensers to remove the moisture, and in turn the
moisture is removed from the cloth by means of the
external ventilation. The rate of moisture removal
is thus controlled by the rate of transpiration, which
in turn can be controlled by the amount of ventila-
tion on the outside surface of the canvas. This
provides a novel means of moisture control, as well
as of moisture removal. In the foregoing types of
kilns, air circulation and moisture removal are accom-
Fig. 8 — Greepf Dryer
plished by natural gravitational effects. The absence
of mechanical parts and operating machinery lends
to these types a certain advantage, and for this reason
they require, when properly installed, less attention
and operating skill than the types embodying positive
mechanical circulation.
INDUCED CIRCULATION HUMIDITY CONTROL An
intermediate form, between the gravity type of dryer
and the mechanical type, is the Tiemann lumber
dry kiln, Fig. 6. In this kiln, necessary moisture is
provided and controlled, and positive circulation
is also produced, by means of water sprayed through
nozzles so as to produce an ejector effect. The excess
water is eliminated by baffle plates, as shown, and the
moisture content of the air is regulated by controlling
the temperature of saturation or the dew point, as
in the Carrier dew-point control. This is said to be a
Fig. 10 — Lattice Floor and Ceiling Kiln
very successful form of lumber dryer for green lumber,
where high relative humidities are required to prevent
checking. By means of the ejector effect, a rapid
circulation and, consequently, uniform drying, are
secured, even at high humidities. By using cold
water, the sprays may also act as condensers to remove
the excess water, while if recirculated or warm water
is used, the moisture content of the kiln may be raised
to offset infiltration losses at high humidities.
mechanical circulation — We now come to the
large class of dryers in which the air is handled me-
chanically by means of fans, either of the propeller
type or of the centrifugal housed type. The objects
of mechanical air circulation are:
1 — To secure a more positively uniform distribution of air
in the various parts of the kiln.
2 — To produce a positive and rapid circulation of air over the
material to be dried, which, as has been shown, greatly increases
the rate of drying.
3 — To secure a positive removal of moisture, either by intro-
duction of fresh air and the removal of moist air, or by con-
densation with cold water sprays or coils.
A later development of this type of dryer is used
in connection with air conditioning equipment, em-
bodying humidity and temperature control, to secure
accurate processing of materials being dried.
The early types of fan dryers were operated as
drying tunnels in which the material passed pro-
gressively from one end to the other, usually upon
trucks. The air was blown into the dry end and
Fig. 11 — Perforated Side Walls" Dryer
exhausted, with a high degree of saturation, at the
wet end of the tunnel. By this method a high velocity
was maintained over the material, as the cross-section
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
445
Fig. 13 — Gordon Dryer
of the tunnel was small compared with its length.
Several difficulties, however, are found with this type
of fan dryer.
1 — The resistance through the material is higher and con-
siderable air is lost by leakage.
2 — The air tends to stratify, the warm air passing along the
top and overdrying the material at this point, and the satu-
rated air falling to the floor, causing a very low rate of drying
at this point.
Improvements have been made in this type of
dryer by circulating the air transversely back and
forth across the tunnel, a series of fans being placed
at intervals along the length of the tunnel with re-
heaters at each fan. This type overcomes most of
the difficulties mentioned, and affords a high rate of
evaporation. However, it is more costly and has
the disadvantage of having a large number of operating
parts.
With room or compartment dryers, the great diffi-
culty has always been to secure uniform and adequate
circulation. A great many applications of fan-system
dryers have failed for want of a means to produce
rapid and uniform circulation, which is the chief
object in substituting fan-operated dryers for gravity-
operated dryers. Many of the earlier types of fan-
operated compartment or room dryers were little
more than fan heating systems with an elaborate
system of galvanized piping for the distribution of the
air. The circulation over the material in such types
is negligible, and the rate of drying is practically that
of still air. The only advantage to be obtained by
the use of the fan is a fairly uniform distribution of
temperature and moisture throughout the room.
Even this, however, is not perfect. An illustration
of this type of dryer is shown in Fig. 7, in which there
is a main supply pipe with branch drop pipes blowing
downward on the floor, using the floor as a diffuser.
The air spreads in all directions underneath the ma-
terial, and rises through it, being exhausted, usually,
at the ceiling.
Fig. 8 shows the arrangement of air distribution in
the Greeff dryer, in which the air is blown to the floor
on one side of the compartment, and exhausted at the
floor on the other side of the compartment, the air
passing through the material in a generally horizontal
direction.
Fig. 9 shows the use of a perforated floor in which
the heated air is blown upward through the material,
the perforated or slotted floor acting as a diffuser,
and the space underneath providing a plenum chamber
for distribution. The air is exhausted at the ceiling
and may be returned to the apparatus or released
to the atmosphere. To make this type efficient, a
large proportion of the air should be recirculated, and
a large fan used so as to circulate large volumes of
air with respect to the amount of fresh air used.
Fig. 10 shows a reverse arrangement in which the
heated air is supplied through a perforated ceiling
and exhausted by a separate exhauster through a
floor grating. In this type of dryer, a small quantity
of air may be employed, and the efficiency is higher.
However, in this type the upper part of the material
will dry very rapidly, while the material nearer the
floor will dry very slowly, owing to the low velocity
of circulation.
Somewhat better results, with regard to distribution,
have been secured by perforated side walls, the air
being blown across the material as in Fig. 11.
n
'["*
—
-
-
"7 " —
-
\\h
1
ft-
•—
-
-F
j
■ —
■ H
LI
1 r**> |
1 " 1
-
-
n
in
fa
—
Plh
Fig. 14 — Disk Wheel Cross Circulation Type of Dryer
Fig. 12 shows a system in which distribution is
secured by means of mechanically operated deflectors,
which alternately rise and fall, directing the air across
446
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
the trays. The great difficulty with this system is
that large volumes of air have to be handled to secure
uniformity and rapid rates of drying. The efficiency
verv low unless the air is larpelv recirculated.
is very low unless the air is largely recirculated.
Fig. 15' — Carrier Ejector Dryer
In the Gordon dryer, Fig. 13, the air is forced back
and forth over successive trays of material, being
reheated between each pass. This results in a uni-
form rate of drying throughout, and permits of a
high efficiency of evaporation, as well as a maximum
quantity of moisture removal per unit of air circulated.
The use of disk wheels or propeller fans for agitating
the air and producing a high velocity over the material
is shown in Fig. 14. The disk fans draw the air first
through the material, then over heater coils, thence
across through a false ceiling, and back through the
material, as indicated. By this means, higher rates
of evaporation may be secured, and the efficiency is
fairly high, as the air is used over and over again, the
moisture-laden air being exhausted either by gravity
through a ventilating stack, or by a separate fan of
relatively small capacity. The only objection to
this type of dryer is its expense of construction, as it
requires a vertical partition for the fan setting and a
horizontal partition or false ceiling over the entire
kiln. There is also considerable waste space both
overhead and at each end of the dryer. The mechanical
efficiency of the disk wheel is very much lower than
that of other types of fans, which makes the installa-
tion inefficient from the power standpoint, except for
the fact that very low pressures are usually required.
Fig. 16 — Central Station Ejector System
One of the most recent improvements in the method
of air circulation and distribution is the ejector system,
which is illustrated in Fig. 15. This system employs
the high efficiency, housed, centrifugal fan, discharging
the air through nozzles at a high velocity. The
nozzles are located along one side of the kiln, near the
ceiling. These high-velocity jets of air induce a
secondary current of three or four times the original
volume, which thoroughly mixes with the air from
the nozzles, and passes with it overhead to the farther
side of the room. Here the air is deflected downward
along the opposite wall, and backward horizontally
through the material in a return circuit. All of the
air passing through the material moves in a direction
opposite to that of the discharge from the nozzles.
A slight static pressure is built up on the farther side
of the room, and a slight vacuum on the return side.
This results in a strong and uniformly distributed
return current through the material. The material
may be either arranged in trays or suspended verti-
cally from racks or trucks.
r\ooooo ,\ o|5
...:. : .1.
\ '
y
1°
1
I
5ectiohal £l£ 'sat/oh
Fig. 17 — Closed Ejector System with Dehumidipier
The ejector system is a development of great im-
portance because it makes possible the circulation.
within the kiln, of much larger volumes of air than
are practicable otherwise. This is so because an
apparatus which will condition and propel a given
volume of air can, by means of this system, circulate
within the kiln from three to five times as much air.
Prior to the development of the ejector system it was
often necessary to design a drying equipment with
regard to the maximum allowable cost of apparatus,
whereas we are now enabled to design the system with
regard only to the maximum possible efficiency, the
size of the apparatus being such, even for extremely
large air volumes, that the cost is entirely commen-
surate with the results.
With this system, the arrangement of material is of
great importance. Provision must be made for
unobstructed passage of air between the successive
tiers of material, and, if material is arranged verti-
cally, the air passages must be in the direction of the
air flow. A certain amount of space must be left
in the front and back of the room, as well as between
the top of the material and the ceiling, for ejector
circulation. The humidity conditions are either con-
trolled by a dew-point control and a humidifier, in
which all of the air is brought to a definite point of
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
447
saturation, and then reheated to maintain a definite
room temperature, or the control may be regulated
by admixture of fresh and return air, controlled by a
hygrostat located in the room. By either system, a
very accurate humidity control may be secured. The
temperature may be controlled independently.
Fig. IS — Dehiimidifier with Interchanger
Fig. 16 shows a central station, where one apparatus
supplies a group of dry rooms. For accurate humidity
control with this system, a dew-point control is neces-
sary, and various relative humidities may be obtained
in each room, by regulation of the separate heater in
the branch duct in each room. The unit system of
apparatus, however, is usually preferable.
For low temperature work, it is necessary to use
refrigeration for the removal of moisture, and this is
accomplished by dehumidification, the air being
brought into contact with a spray of refrigerated
water at low temperatures, removing the excess
moisture by condensation, as indicated in Fig. 17.
The air is then reheated by means of heater coils,
which supply the necessary heat for drying.
Fig. 18 shows a humidifier with interchanger, by
means of which most of the heat of the warm return
air is transferred to the cool dehumidified air, before
it is supplied to the room. This permits a reduction
of about one-third in the refrigerating capacity required
for a given duty in low temperature drying.
EFFICIENCY OF DRYEKS
The general theory of the efficiency of dryers has
been discussed in the preceding paper on the "Theory
of Drying." It is generally found that about 2 lbs.
of steam are required to evaporate 1 lb. of water, under
the most favorable conditions, while the more usual
figure for steam consumption is 2.5 lbs. of steam to
1 lb. of water evaporated. The principal losses in
air drying are radiation and escape of unsaturated
air, either through the usual vent ducts or by leakage
through the kiln walls.
The Spray Process of Drying-
By R. S
Merrell-Soule Co.,
The spray process of drying has been developed in
connection with the manufacture of dried milk. In
1901 a patent was granted to Robert Stauf of Posen.
Germany, relating to the drying of blood, milk, and
other highly complex organic liquids. One of the chief
claims was described as follows:
The process of obtaining the solid constituents of milk, in the
form of powder, said process consisting in converting the liquid
into a fine spray, bringing such spray or atomized liquid into a
regulated current of heated air so that the liquid constituents are
completely vaporized, conveying the dry powder into a suitable
collecting space away from the air current and discharging the
air, a vapor, separately from the dry powder.
This patent was purchased by an American com-
pany which had independently developed a spray pro-
cess, but was antedated by Stauf.
It soon became apparent that a better product could
be obtained and the process materially cheapened if
the material to be dried could be condensed to a con-
siderable degree by the vacuum method before it was
dried by the spraying process. One of the chief claims
of the patent covering this point1 is as follows:
The process of obtaining the solid constituents of liquids and
semiliquids in the form of powder, which process consists in con-
centrating the substance by removing a large percentage of water
therefrom, converting the concentrated mass into a spray, bring-
' L. C. Men-ell, I. S. Merrell. and W. B. Gere, U. S. Patent 860,929
(1907).
Fleming
Syracuse, New York
ing such spray into a current of dry heated air or gas, having
an avidity for the moisture of the substances treated, retaining
the atoms momentarily in said current so that substantially all
the remaining moisture is converted into vapor and the product
is prevented by the cooling effect of such evaporation from un-
dergoing chemical change, conveying the dry powder into a suit-
able collecting space away from the vaporizing current, and
discharging the air or gas separately from the dry powder.
APPARATUS REQUIRED
The apparattis for successful spray drying necessarily
requires the following eqtiipment:
an air filter — This is necessary in order to have
clean air which will not contaminate the product un-
dergoing desiccation. Various forms may be used,
such as washing the air with water. But the cheapest,
and in general a very satisfactory, method is to filter
through cotton.
blower— This is necessary to propel the air through
the desiccating apparatus.
heater — The air is usually heated by passing over
steam heated radiators. A direct heat by gas has been
used, and even a coal burner, the air passing over the
burning coal. The latter, however, is unsatisfactory.
drying chamber — The heated air is passed into a
drying chamber where the hot air mingles with the
sprayed liquid. There are various styles of drying
chambers, the usual form being a rectangular room,
448
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
the hot air entering one end and passing out the other.
The liquid is generally sprayed in with the ingoing air,
sometimes one spray being used and sometimes several.
Another form of drying chamber is vertical. In this
form the air frequently enters at the bottom and passes
out at the top. The liquid enters at the top.
atomizers — The liquid may be turned into a spray
by several different forms of apparatus. One is the
so-called air spray by which the liquid is atomized by
the action of compressed air which, passing through
an orifice, draws the liquid through, much on the
principle of an ejector. On emerging from the ejector
the liquid breaks into fine droplets and is thus atomized.
A better method is that disclosed in the Bevenot and
DeNeveu patent1 by which the liquid to be dried is
atomized under high pressure, a hydraulic pump being
used for this purpose. Sometimes as much as several
thousand pounds per inch is required.
dust collector — A dust collector is necessary, for
the reason that the product is frequently very fine and
light, and there would be serious loss if the outgoing
air were not filtered or some other means taken for
collecting the fine particles which are carried in sus-
pension by the outgoing moisture-laden air.
mixing devices — It will be seen that in order to use
efficiently the heat of the heated air which enters the
desiccating chamber, it is necessary to mix the heated
air and sprayed particles so that all of the heated air
shall come in contact with some of the sprayed liquid
particles. Different devices have been used for this
purpose.2
nature of spray evaporation
When the atomized liquid is mixed with the air
drying takes place practically instantaneously. We
can think of each atom of liquid as a spherical droplet,
on the surface of which an intensive evaporation is
going on. It is to be noted that the moisture passes
away from the surface to which heat is applied. This
is the reverse of what occurs in most systems of drying.
In the latter the heat is applied to one surface and the
moisture passes away at another. In such a system
the whole body of the liquid must become heated. In the
former case, however, with the evaporation taking place
on the surface to which the heat is applied, the whole
body of the liquid in the droplet does not become
heated while the evaporation is going on. We believe
that the evaporation is so rapid that the droplet is
actually kept cool until the dry state is reached; this is
due of course to the absorption of heat in vaporizing
the liquid. After the evaporation has ceased, the
temperature of the particle rises to the general temper-
ature of the drying chamber. In the dry state there
is much less likelihood of injury from heat. In fact, it
is well known that chemical changes produced by heat
are usually much more effective in the presence of
moisture.
If we are correct in our argument that the rapid evap-
oration keeps the droplet cool during the drying process,
it appears that the spray process is especially useful
■ U. S. Patent 1,020,632.
5 One of these is covered by thetl. S. Patent 1.1S3.09S granted to I. S.
Merrell and O. E. Merrell. This does the mixing very effectively.
in the desiccation of materials which are easily injured
by heat. In the ordinary concentration of liquids by
boiling, the greatest injury usually occurs just before
the dry state is reached. The greatest injury of all
probably occurs between the sirupy stage and absolute
dryness. In spray drying this stage is passed almost
instantaneously and, if our theory is correct, in a fairly
cool state. The results of many careful tests seem to
prove that the above conclusions are correct. For
instance, albumin which is coagulated at 65° C. can
be dried by the spray process without irijury at 75° C.
or higher. Bacterial cultures can be dried at tem-
peratures far above their thermal death points.
COST OF OPERATION"
It is very difficult to give the cost of operating a
spray dryer either in dollars or in heat units, for the
reason that this will depend to a very great extent on
the character of the material to be handled, and the
properties desired in the dried product. It can be said,
however, that spray drying is comparatively expensive,
mainly because it is impossible to utilize all the heat
going through the drying chamber. There is a limit
to the temperature to which the ingoing air may be
heated, while the outgoing air is necessarily fairly warm.
In other words, there is a serious loss of heat units in
the outgoing air. For instance, if we commence with
air at 15° C, heat it to, say, 135° C, dry a material
with it, and then let it pass away at, say, 75° C, we
shall have put in 135 — 15 = 120°, used 135 — 75 =60°,
and lost 75 — 15 = 60°. In other words, we have lost
half our heat. With some materials which are very
easily injured this would represent actual operating
conditions; with others not so sensitive, the loss of heat
would be less.
preconcentration
As indicated above, the cost of drying is considerably
reduced if the article to be dried is first concentrated
in vacuum. Usually the limit of concentration is
reached just before the substance becomes so viscous
that it will not readily pass through a pump.
Preconcentration not only reduces the cost of drying
but improves the quality of the product. On spraying
a very dilute liquid the solids are obtained in a very
finely powdered condition. The product is bulky,
requires large packing space, is hard to dissolve, and
usually does not have as good keeping qualities as the
product obtained by drying the more concentrated ma-
terial. The reason appears to be that the more con-
centrated liquid gives larger and heavier dry particles,
with less surface per unit of weight. When such a
powder is mixed with water or other solvent, it tends
to sink and pass into solution, the spaces between the
particles being sufficient to allow the liquid to penetrate.
With the finer powder the particles tend to hang to-
gether and form an impervious layer which the solvent
does not so readily penetrate. The finer particles
offering greater surface are more readily oxidized, or
subject to change from outside influences. Precon-
centration leads to a higher recovery. There is always
a slight loss of solids in the form of fine particles
which get by the dust collector. As precondensing
May, 1021
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
449
makes larger, heavier particles, this tendency is min-
imized.
SIZE OF UNIT
Drying units may vary a great deal in size, although
there seems to be a certain minimum below which it is
not satisfactory to operate. The unit with which the
writer is most familiar requires a floor space of about
54 ft. X 15 ft. X 14 ft. This allows for working space.
With two units there would be some saving on this.
Such a unit would evaporate 200 lbs. of water per hour
from a material which is fairly sensitive to heat, and
give a product containing less than 3 per cent moisture.
The dryness, however, will depend on the character
of the material, especially on whether it has a tendency
to retain water of crystallization.
RECOVERY OF PRODUCT
The recovery of product will depend on various
factors, but mainly the concentration before drying
and the efficiency of the dust collector. When oper-
ating under favorable conditions in these respects, it
is quite possible to recover from 95 to 98 per cent of
the total solids.
TEMPERATURE OF DRYING
The temperature of drying is affected by three things:
steam pressure in the heater, amount of air passed
through the drying chamber, and the amount of liquid
sprayed. In practice, the amount of air is constant
and the steam pressure is usually also constant. When
such is the case, a sufficient amount of the liquid is
sprayed in to reduce the temperature to the desired
degree. There seems to be a limit to the temperature
which it is permissible to use, both in the entering flue
and in the drying chamber.
APPLICATIONS OF THE SPRAY PROCESS
The spray process may be used for the desiccation
of a wide variety of substances. Whether it is the best
method to use in any particular case will depend on
the value of the material and on the properties required
in the dried product. It is sometimes difficult to pre-
dict with certainty whether a material will dry satis-
factorily by the spray process. Some materials have
a tendency to form a gummy mass on the floors and
walls of the drying chamber. It is not always a ques-
tion of hygroscopicity. Consider two substances like
refined cane sugar and commercial glucose. The glu-
cose will dry quite readily to a fine white powder, but
the cane sugar has a marked tendency to give a gummy
product. Normally, dried glucose is hygroscopic; cane
sugar is not. It appears to be a question of the rate
at which the material solidifies. Substances which
solidify slowly are likely to give trouble.
In general, it may be said that substances dried by
the spray process are likely to retain their natural
properties. In the case of milk, for instance, when
the dried product is restored by the addition of water,
it again becomes normal milk. It has the milk flavor.
There is no sediment. The albumin is not coagulated.
The casein has its colloidal character. The butter fat
is in natural emulsion. The enzymes and vitamines
are active.
Commercially, this process gives the greatest ad-
vantages in drying substances which are injured by
temperatures and methods ordinarily used in desic-
cation. On these substances the slightly greater cost
of drying will be much more than made up for by the
quality of the resulting product.
Direct Heat Rotary Drying Apparatus
By Robert G. Merz
American Process Company, New York, N. Y.
The removal of moisture by vaporization from the
various materials employed in the different industrial
processes is a subject of great commercial and technical
importance, especially for chemical engineers, and
hence a more or less intimate knowledge of the types
and characteristics of mechanical drying apparatus,
available for such work, is very desirable. In many
cases the utilization of waste products is made possible
only by the cheap and rapid elimination of the large
quantities of water which such materials usually con-
tain, and hence the mechanical dryer is a major factor
in most by-product recovery processes.
For those not thoroughly acquainted with the ne-
cessity for drying many of the materials employed in
manufacture, it may be well to review briefly the rea-
sons for such treatment. Thus drying may be
required:
1 — To permit pulverizing or fine grinding.
2 — To permit screening or grading.
3 — To permit uniform mixing.
4 — To permit magnetic and electrostatic separation or dry
table concentration.
5 — To increase capacity in later operations.
6 — To reduce weight in shipment.
7 — To prevent decomposition of organic material due to high
moisture content.
8 — To permit improved conditions of combustion when burned
in a furnace, etc.
THE DIRECT HEAT ROTARY DRYER
Although there are many kinds of mechanical dryers
in use, the present paper will be confined largely to the
discussion of a type which has a wider field of appli-
cation than any other single type, and which at the
same time possesses certain advantages which make its
use practically universal in many industries.
The direct heat rotary dryer is undoubtedly one of
the oldest forms of mechanical drying apparatus and
probably originated in satisfying a demand for a rapid
and economical method of eliminating the natural
moisture which occurs in minerals when taken from the
earth or when exposed to the elements. For many
years the use of the direct heat rotary dryer was limited
to the drying of such natural inorganic materials.
With the advent, however, of the more complex in-
450
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
dustrial processes in manufacture, the increasing cost
of fuel, and a better understanding of the principles
involved, the employment of this type of dryer has been
rapidly extended to the handling of many other in-
organic, as well as numerous organic, substances, par-
ticularly by-products, which were formerly not con-
sidered capable of treatment by direct heat because of
injury to the material.
As might be expected, different substances require
different methods of treatment on account of their
form, size, composition, physical and chemical char-
acteristics, initial and final moisture content, etc.
Hence it has been found desirable to develop several
classes of the direct heat rotary dryer the better to suit
the various materials to be handled. In many cases,
however, the same form of dryer, with slight modifi-
cations, can be satisfactorily employed to dry sub-
stances which possess entirely different physical and
chemical characteristics.
In general, the direct heat rotary dryer consists es-
sentially of three more or less distinct parts:
1 — A furnace in which the required heat energy is liberated
from the fuel by its thorough combustion.
2 — A suitably mounted cylindrical steel shell, revolving on a
horizontal axis or one slightly inclined to that axis.
3 — A chamber into which the spent furnace gases and water
vapor (and sometimes the dried product itself) are discharged
for eventual escape into the atmosphere.
The arrangement of these three parts is such that
the hot gases from the furnace are forced to pass
through the rotating steel drum, giving up a major part
of their heat content to the wet material, which likewise
passes through this drum.
TYPES OF DRYER
When the drying material and the hot furnace gases
move in the same direction through the revolving
drum, we obtain what is technically termed a "parallel
current" dryer, and when they move in opposite di-
rections, a "countercurrent" dryer.
Again, the dryer may consist of one simple cylinder,
in which case it is designated as a "single shell type."
If the interior of such a single shell drum is divided
longitudinally by partitions, it is known as a "com-
partment type," and when the cross section is
broken up into cells or pockets, it is called a "cellular
type."
If the main cylinder is fitted with a large concentric
internal cylinder, we obtain the "double shell type,"
and when the interior is fitted with a multitude of
smaller longitudinal flues or pipes, we have the "tubular
type." Sometimes the concentric internal cylinder
is employed in connection with several smaller lon-
gitudinal flues, located between the outer and inner
shells, in which case a combination or "tubular, double
shell type" is secured.
Whenever the hot furnace gases, i. e., the products
of combustion, during their movement through the
dryer, mingle immediately and directly with the ma-
terial to be dried and remain with the same during
the entire drying operation, the dryer is designated as
.a "direct heat, direct contact type;" but when the
furnace gases mingle with the material only after their
temperature has been partially reduced by the trans-
ference of some of their heat to the drying substance
by conduction through and radiation from a surround-
ing shell plate, then a "semidirect heat, direct contact
type" results.
Again, the hot gases may pass through numerous
longitudinal flues in the rotating cylinder itself and
never come in contact with the drying material at all.
Properly speaking, this is an "indirect heat type,"
although it is often included with the direct heat
dryers.
When the drying drum itself rotates within an en-
closing chamber or housing in which the hot furnace
gases circulate and surround the drum, we obtain what
is commonly known as an "indirect heat dryer." Here
the products of combustion and the material to be
dried do not mingle. On the other hand, it is some-
times desirable to draw the combustion gases from the
enclosing chamber, after their temperature has been
materially reduced, through the dryer drum in direct
contact with the drying material. In this case a so-
called "direct, indirect heat" type of dryer is se-
cured.
GENERAL MECHANISM OF THESE DRYERS
It is beyond the scope of the present paper to enter
into details as to the interior construction of the drying
cylinders themselves. Suffice it to say that provision
is made for thoroughly agitating the wet material in
intimate contact with the furnace gases so as to ex-
tract their heat rapidly and to advance the material
through the revolving drum at the same time. A
system of internal lifters and shelves usually accom-
plishes the former, while the inclination of the axis of
the drying cylinder or a series of internal spiral-formed
plates serve to move the drying material through the
drum.
Obviously the countercurrent principle cannot be
employed in a direct heat, direct contact type of dryer,
except for inorganic materials which are not affected
by very high temperatures or by the products of com-
bustion. Moreover, unless it is necessary to eliminate
practically all traces of moisture or to discharge the
dry product at a high temperature, there is little to
justify the use of the countercurrent type of dryer,
and in many cases it is a positive disadvantage to dry
material by this method.
Under certain conditions, even with organic sub-
stances, however, it is possible to use the countercur-
rent principle in connection with the semidirect heat,
direct contact type, because of the fact that the tem-
perature of the gases has been greatly reduced before
coming in actual contact with the drying product.
In the majority of cases, where wet organic products
are to be dried, the direct heat, direct contact type of
dryer, using the parallel-current principle, is by far
the most satisfactory and, in fact, the only logical
method of drying such products. Even the inorganic
materials are most successfully dried in this same
parallel-current type of rotary dryer.
The selection of the type of direct heat dryer, most
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
451
suitable for the material to be handled and the work
to be accomplished, should be left to those with ex-
tensive experience in direct heat drying processes, since
an improper type may be the cause of serious difficulties
and often considerable financial loss.
APPLICATIONS OF DIRECT HEAT ROTARY DRYERS
Only a brief survey of the numerous fields of applica-
tion of the direct heat rotary dryer is permissible here.
Each year, in fact, sees this type of drying apparatus
introduced into new industries for the handling of new
and varied products.
For many years the clay, cement, sand, and plaster
industries have employed the direct heat rotary dryer.,
and its use is practically universal for this work.
The mining and metallurgical industries very fre-
quently find it necessary to dry ores, either to reduce their
weight for shipment, to increase the capacity of furnace
processes, to permit of pulverizing for separation or
concentration, or to eliminate the moisture from flotation
concentrates, etc., and the same type of rotary dryer
is used for the purpose.
The fertilizer, by-product, and allied industries in-
variably have occasion to dry the materials which they
handle. The removal of water from animal tankage,
fish and fish offal, after cooking and grease extraction,
from manure, guano, garbage, peat and other fillers,
as well as from digested leather scrap, steamed bone,
sewage sludge, natural phosphates, potash salts, etc..
all of which eventually enter into the manufacture of
complete fertilizers, is generally carried out by direct
heat rotary processes because of the economy possible
with this class of dryer.
The chemical industries have for many years found
this type of dryer a most essential part of their me-
chanical equipment, not only for the raw material and
the by-products, but in many cases for the finished
product itself. The chemical industry is undoubtedly
one of the largest and most extensive fields for the
application of the direct heat rotary dryer, and with the
growing importance of chemical manufacture in this
country, this economic type of mechanical drying ap-
paratus is certain to become a very essential factor in
the manufacturing process and the treatment of the
by-products of the industry.
Aside from those mentioned above, many industries
find it necessary to dry the materials which enter into
the manufacture of their various products or to elim-
inate the water from waste or refuse resulting from
such manufacture. Sugar refineries, paper mills, paint
and pigment mills, petroleum works, tanning extract
plants, alcohol recovery mills, briquetting plants, etc.,
often employ the direct heat dryer. It must be under-
stood, of course, that the direct heat rotary cannot
be employed successfully for all materials because of
the possible injury caused by excessive temperature,
discoloration or contamination by the products of
combustion, physical or chemical peculiarities, etc.
ADVANTAGES OF THIS TYPE OF DRYER
As might be expected from the fact that the heat is
applied in the most direct manner to the material from
which the water is to be vaporized, the direct heat
rotary dryer, when properly designed and operated, is
capable of large capacity and great economy. Because
of the high temperatures employed, and the constant
exposure of new surfaces of the drying material to the
hot furnace gases with which they are intimately
mingled, the removal of the contained moisture is very
rapid.
The comparative simplicity of the apparatus, the
absence of high pressure joints, the ease of inspection
of all parts while in operation, the small number of
wearing surfaces and their ready replacement, also the
freedom from frequent and extended shutdowns, en-
tirely aside from the high efficiency and great capacity
obtainable, together with the possible application to
such a large number of materials, give the direct heat
rotary dryer a most important and prominent place
among the mechanical devices employed in modern
industry.
Chemical engineers and all those concerned with the
drying of materials will do well, therefore, to investigate
very carefully the application of the direct heat rotary
to any problems involving the vaporization of water
from solid or semisolid substances.
It should be remembered that, in all cases, a uniform
feed of wet material, as well as a steady and constant
supply of hot furnace gases, are absolutely essential for
satisfactory results.
DISADVANTAGES
The disadvantages of the direct heat rotary dryer
are comparatively few, and encountered mainly in the
drying of organic materials:
1 — Dust losses.
2 — Overheating or burning of the material.
3 — Production of unpleasant odors.
4 — Explosions due to gas or dust.
The three latter occur, as a rule, only in the handling
of organic materials or a combination of organic and
inorganic products.
By intelligent selection of the type of dryer, care in
its design, and proper operation of the machine, all of
the above difficulties can be overcome, or at least re-
duced to such an extent that they are no longer an
important factor.
EFFICIENCY
In a general way, the efficiency of a direct heat rotary
dryer corresponds to the efficiency of a steam boiler,
*. e., it represents the ratio of the heat usefully employed
in vaporizing the moisture in the material to the avail-
able heat in the fuel employed in the drying process.
And, as in the case of the boiler, the efficiency is a
variable quantity, but depending upon a much larger
number of factors.
As a general rule, the higher the initial and final
moisture contents of the material, the greater the
efficiency. When the final moisture must be reduced
to a very low point, the efficiency decreases very rapidly,
and when the specific heat of such material is also high,
the efficiency may fall to a comparatively low value.
452
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
Hence the same dryer may have various efficiencies
when handling different materials, owing to the char-
acteristics of the material when fed to the machine and
the requirements of the discharged product. Varia-
tions in the size of the pieces may likewise cause a re-
duction in the efficiency compared to that of uniform-
sized material, because of the necessity of overheating
the smaller pieces in order to dry the larger lumps
properly. This is particularly true of porous substances
■where the moisture permeates the entire mass, as dis-
tinguished from hard dense materials where the mois-
ture exists on the surface only.
Naturally, the kind of fuel employed for the drying
process has a considerable influence on the efficiency,
just as in the case of the boiler. This is due to the fact
that the heat losses, caused by excess air required for
the combustion of the fuel, become greater in propor-
tion to the increase in the weight of air used per pound
of fuel consumed and per unit of heat liberated. More-
over, fuels which contain considerable quantities of
water when burned, such as is usually the case with
wood, lignite, and similar materials, or where the con-
stituents of the fuel itself burn to form superheated
water vapor, as with certain gases of high hydrogen
content, likewise result in reduced efficiency.
Again, the necessity of reducing the extremely high
temperatures produced by the combustion of fuels of
high calorific intensity, in order to prevent injury when
handling certain materials, by the introduction of ad-
ditional cool air, also materially affects the efficiency
obtainable.
Although there are other factors which have a direct
or indirect influence upon the efficiency of the direct
heat rotary dryer, enough has been said to show that
such efficiency may be a very changeable quantity,
entirely aside from that due to carelessness or improper
operation.
UTILIZATION OF WASTE HEAT FROM OTHER PROCESSES
The question frequently arises as to the advisability
of employing the waste heat from other processes, such
as from steam boilers, reverberatory or smelting fur-
naces, roasting or calcining operations, etc., as a drying
medium. A satisfactory answer to this cannot be
given without a thorough knowledge of all the local
conditions involved in the problem. Although the
proposition of the utilization of such waste heat is a
very attractive one. there are a great many factors to
be considered.
For instance, when only low temperature gases are
available, such as from steam boilers, a very large
volume of such gas must be handled and passed through
the drying drum to recover a comparatively small
quantity of heat. The moving of this large volume of
gas against considerable resistance requires much power,
which, together with the probable reduction of tem-
perature, before entering the drying drum itself, es-
pecially if located at some distance from the boiler
plant, and the relatively large size of the apparatus re-
quired for a small evaporation, is usually not an eco-
nomic proposition. In other words, the installation is
very likely to become quite extensive and costly in
order to save a small amount of heat. As a general
rule, it is more profitable to recover as much heat as
possible by means of a suitable economizer and to em-
ploy a separately fired dryer to vaporize the water in
the material to be dried.
When gases of high temperature are available from
other furnace processes, especially where the drying
outfit can be located close to the source of these hot
gases, there is better chance of success. It must be
remembered that, for all such cases, these very hot
gases must flow under the influence of gravity, since
they cannot be handled by means of a fan except after
cooling.
Another important point to be considered is the
effect of the drying unit upon the installation which
serves as the source of the hot gas supply. And in
many cases the regulation of the initial outfit so seri-
ously affects the drying process as to make its use un-
profitable, unsuccessful, and at times entirely im-
possible.
APPLICATIONS OF THE MODIFIED ROTARY DRYERS
For some materials, particularly when injury results
by direct contact with the products of combustion, the
indirect heat type of dryer, previously described, is
frequently employed. Its efficiency, however, is quite
low, the capacity is small for the space occupied and
the capital invested, and the cost of repairs is generally
a very considerable item. There are certain cases,
nevertheless, where its use is advisable because of the
nature or peculiarities of the material to be dried.
There are also a large number of substances, both
organic and inorganic, which cannot be subjected to
high temperatures or to the products of combustion
without injury or complete destruction of their form,
composition, purity, or commercial requirements. For
such materials the "steam-heated air, rotary dryer" is
particularly well adapted. The essential difference
between the direct heat and the steam-heated air type
is in the source of the drying medium. Instead of the
high temperaUire furnace gases, a volume of heated air
from a pipe coil heater, using either exhaust or live
steam, is forced or drawn through some form of a ro-
tating drying cylinder, very similar to those described
under direct heat dryers, where the material to be dried
is constantly showered in direct contact with the
heated air.
Naturally the efficiency of such a form of dryer is
comparatively low, based on the heat units in the fuel
from which the steam itself is derived, except where
use is made of exhaust steam from other processes
and for which there is no special use.
CONCLUSION
In conclusion it may be said that the subject of
mechanical drying involves an intimate knowledge of
thermodynamics, including the laws of combustion,
heat generation and heat transmission, heat capacities
of various gases, effect of partial pressures upon rate of
evaporation, etc. In addition a proper knowledge of
the physical and chemical properties of the various
materials handled, as well as of the principles of mechan-
ical construction, is essential for a satisfactory and
economic installation.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
453
Tunnel Dryers
By Grahame B. Ridley
uan-Pearson Co., Rialto Building, San Francisco, California
There are many types of dryer that may be con-
sidered as forms, or variations, of tunnels, but for
the purpose of this discussion the term will be limited
to those dryers in which the material on trays is
moved progressively in one direction through a tunnel
supplied with a current of heated air which is intro-
duced at one end and removed at the other end. In
this type all the heat used in drying is assumed to be
supplied by the moving air which also removes all
the moisture evaporated. The movement of the
air is dependent on the • difference of pressure at the
two ends of the tunnel, and its direction is always
from the hot end to the cold end.
This form of dryer is typical of those used in many
of the larger fruit dehydrating plants, and, owing
to low labor costs with large capacities, it seems to be
rapidly superseding other types for this work.
THE AIR SUPPLY
The air is usually heated in one of three ways: by
steam coils, hot air furnaces, or direct heat.
steam heat — Steam is the most expensive from
the standpoint of both initial cost and thermal effi-
ciency, but is subject to very exact regulation and
thermostatic control. In some cases it is possible
to utilize steam that would otherwise be wasted in
some kindred process, as, for instance, where a dehy-
drating plant is operated in connection with a cannery.
hot air furnace — Hot air furnaces usually consist
of a furnace from which the products of combustion
are carried through a multiplicity of tubes over which
the air to be heated is drawn or blown. Sometimes
the process is reversed, and the products of com-
bustion surround the tubes through which the air
to be heated is drawn. Both of these types may be
likened to a steam boiler without any water in it, and
are adapted only to fairly low temperatures, unless
constructed of material especially selected to meet
the requirements, as the danger of destruction from
high temperatures and the accompanying high rate
of oxidation is very great.
direct heat — The use of direct heat is the most
economical method of heating the air, but is dependent
on a furnace in which complete combustion may be
secured. Some very interesting work has recently
been done in this line, and some of the largest com-
mercial plants are now using this principle in the
drying of fruit. Furnace thermal efficiencies of over
90 per cent are obtained, and repairs and replacements
are negligible.
fans — The heated air is forced through the tunnel
by a fan, or fans, which take the form of a suction
fan at the cold end, or a pressure fan at the hot end;
or a fan at each end may be used. In the case of a
suction fan any leakage into the tunnel, such as that
caused by opening the tunnel to take out a car, allows
cold air to rush in and reduces the temperature in the
tunnel. This makes it advisable in commercial
installations, where a suction fan is used, to provide
air locks large enough for an operator and car. Where
a pressure fan is used, if the door at the hot end of the
tunnel is opened hot air rushes out and there is a
reduction of the air velocity through the tunnel, but
no lowering of the temperature. Where this type
of fan is used it is not customary to provide air locks,
and the labor cost of handling the cars in and out of
the tunnel is reduced.
operation of tunnel dryers
trays and cars — The material to be dried is usually
spread on trays, which are stacked on cars with suffi-
cient space between the trays to allow of the passage
of the requisite amount of air. Sometimes the trays
are moved through the tunnel on slides or rollers and
transferred to and from cars at the ends. The cars
are guided in the tunnel by tracks, and in some cases a
track system is laid throughout the plant. In other
plants the cars have caster wheels and may be moved
anywhere on a concrete floor. This, allows of greater
flexibility and a saving of space, especially where
drying occupies a period of 24 hrs. and loading and
unloading is completed in a shorter period. In plants
having a small capacity the cars are rushed through
the tunnels by hand, but in larger plants they are
often moved by a chain conveyor, which is motof-
driven through a clutch.
In the design of large plants the handling of th'e
material during the processes preliminary and sub-
sequent to drying must be carefully considered, as
frequently these processes cost more to carry out
than the actual drying.
time interval between removal of cars ,
.In a tunnel dryer handling a uniform material
under ideal conditions the operation becomes purely
mechanical, and the tunnel should be loaded at all
times, with the same amount of material, which will
vary -from a condition of maximum moisture content
at one end to the condition of desired final moisture
content at the other. It is evident that, under these
conditions, whenever a car of dried material is taken
out a car of wet material should be put in at the other
end, and all the cars in the tunnel advanced one posi-
tion. The time interval separating the taking of the
cars out of the tunnel will be dependent on the number
of cars in the tunnel and the length of the drying' time.
Fig. t. has' been prepared to show this relation. If a
specific example is taken, such as a tunnel containing
eight cars and a drying time of 12 hrs., it will be seen,
by following up the line for 24 hrs. to its intersection
with the sloping line marked "12 hrs. drying time,"
that sixteen cars should come out in 24 hrs. and the
time interval between cars will be 1.5 hrs., as is shown
above the figure 12 denoting the drying time. Simi-
larly, if the tunnel should be operated for only 12
hrs. it will be seen that eight cars will be taken out
and the time interval between cars will remain the
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
14- 16
Hours
Figures on sloping //nes are dryinq f)rnes /h hours
ff/'afam tasec/ond'cor Funne I capacity
Fig. 1 — Tunnel Loading Diagram for Determination of Time
Interval (Headway) between Entering Cars, Output of
Tunnel per 24 Hrb., Drying Times, Etc.
same. This chart may also be useful in showing the
number of cars needed to keep up a continuous opera-
tion. If it is assumed that the trays are loaded during
an 8-hr. period, it is evident that enough loaded cars
must be provided to supply the tunnel during the
16 hrs. when no loading takes place. It will be seen
from the chart that during 10 hrs. eleven cars will be
put into the tunnel, so that a minimum of nineteen
cars must be provided. Fig. 2 shows, in slightly
different form, a condition of irregular loading as
compared to the ideal condition. This chart also
shows the number of cars in the tunnel at any one
time and the proportion of overload and underload
as compared to the normal load. A chart of some
such form as this, made up from day to day on the
job, is of great assistance in determining the effects
of variations in the operating conditions, as it gives
a graphic record of each individual car.
CAPACITY OF TUNNEL
The holding capacity of a tunnel is usually based
on the number of square feet of tray area multiplied
by the load per square foot, and the output per 24
hrs. depends on the drying time and is usually stated
in tons of wet material. The nomographs in Figs.
3, 4, and 5 may be used for the rapid determination
of these quantities. A straight line through selected
points on any two scales will intersect the third scale
at a point indicating the third factor.
WET-DRY RATIO
Before making any determinations of the amount
of air and heat needed under any contemplated con-
ditions of drying, it is necessary to know the amount
of water that must be evaporated in some given
length of time. This is probably best expressed in
pounds per hour, and is dependent on the amount
of material dried in a given time and the amount of
moisture taken out. In the fruit industry it is a
trade custom to express this in terms of the ratio
between the weight of the wet fruit and the weight
of the dry fruit. This is called the wet-dry ratio,
and the weight of the dry fruit is taken in all cases
as 1. The nomograph in Fig. 6 has been prepared
to show the relation between these factors. Expressing
the moisture removed in terms of a percentage of the
original weight of the material is probably a more
convenient mode of specifying the conditions taking
place during drying
CALCULATION OF AMOUNT OF AIR REQUIRED
Since all the heat used for evaporation is obtained
from the air, the use of this in doing the work of
evaporation will result in a drop in the temperature
of the air which is an exact function of the amount
of water evaporated and may be calculated. Taking
the weight of 1 cu. ft. of air at 60° F. as 0.0761 lb.
and the specific heat of air at constant pressure as
0.2375, the amount of heat needed to raise 1 cu. ft.
of air 1° F. is equal to 0.0761 X 0.2375, or 0.01807
B.t. u., and conversely 1 cu. ft. of air dropping 1° F.
will release 0.01807 B. t. u.
lotAL Loading Conditions
•'-'Pay infOan
Assume a condition where the atmospheric air
has a temperature of 60° F. and is to be heated to
160° F., at which temperature it enters the tunnel
from which it is exhausted at a temperature of 120°
F. If the material enters the tunnel at the cold end,
the temperature at which the evaporation of the
moisture takes place will vary from the entering
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
455
- C
Mo
- -7
^.02
»>
- a
rOIJ
i-30
^OJS
■ 10
j
b«
!
s
f
a
E? 1
I
I
i.,5 ?
i
- 2.S
I
-.2 *
- 3
,
- 30
- *
" '
,,
s
7
4.0
«
sg™.
— —
50
eoo*L5 po
•no Tint in -ouas
••
[
i
.» 1
- .3
- .35
- 3
- 8
3
- 30 a
--SS
temperature of the material at 00° F. to a temperature
which may approach 160° F. in the case of material
dried to a point beyond which no further evaporation
is possible. The heat needed to evaporate 1 lb. of
water at 60° is 1058 B. t. u., and the heat needed to
raise 1 lb. of water from 60° to 160° and evaporate
it at that temperature is 1102 B. t. u. Assuming the
mean value of 1080 B. t. u. as the average amount of
heat needed to evaporate 1 lb. of water, the number
of cu. ft. of air needed will be „ or 60,000 cu. ft.,
0.01807
in round numbers, dropping 1° F.
While this is the actual amount of air needed to
evaporate the water, an additional amount of air
must be supplied to furnish the heat required to raise
the temperature of the material and the trays and
cars to the temperature at which they are discharged
from the tunnel. Continuing the above example,
if it is desired to evaporate 900 lbs. of water an hour,
or 15 lbs. per min., with a drop in temperature of
40°, the air required for evaporation alone will equal
15 X 60,000
350 B. t. u. will be supplied by
350
X 22,500,
40
or 22,500 cu. ft. per min., and with
a wet-dry ratio of 4:1, 14.4 tons of wet material, or
3.6 tons of dry material, will be handled in 24 hrs.,
or 300 lbs. per hr. Assuming a weight for the cars
and trays needed to carry this quantity of material
of 400 lbs., and an average specific heat of the material,
cars, and trays of 0.3, the amount of heat needed
to'raise this mass to the hot end temperature of 160°
will be 700 X 100 X 0.3, or 21,000 B. t. u. per hr.
If the material is discharged at the cold end, the
amount of heat needed will be 700 X 60 X 0.3 or
12,600 B. t. u. per hour. This is equivalent in the
first case to 350 B. t. u. per min., and in the second
case to 210 B. t. u. per min. Since 15 X 1080, or
16,200 B. t. u., are supplied by 22,500 cu. ft. per min.,
16,200
or 486 cu. ft. per min. However, the full temperature
drop of 40° is not available in this case, and the mean
temperature drop of 20° may be taken instead, thus
requiring twice the amount of air, or 972 cu. ft. per
min., and the amount of air required per pound of
water evaporated with 1 ° drop in temperature will
972 X 60,000
be 60,000 +
or 62,592 cu. ft. In
22,500
the second case the full drop of 40° is available,
since, if the material, trays, and car are heated above
the outlet temperature of 120°, they will return the
heat in cooling to that temperature, and the addi-
tional air needed will be 292 cu. ft. per min.
The nomograph in Fig. 7 has been prepared to
show the relation of the temperature drop to the
volume of air used, but it must be borne in mind
that the volume of air used is based on its weight
at 60° F., and that this volume must be corrected
for the temperature at which evaporation actually
takes place. In the above example this will become
27,500 cu. ft. per min. at 160° and 26,700 cu. ft. per
min. at 120°, or in other words, 75,000 cu. ft. of air
should be allowed in order to evaporate 1 lb. of water
at 160° F. with a drop of 1° F. under the particular
conditions assumed. It is often more convenient
in making calculations of air requirements at varying
temperatures to work with pounds of air until the
final results are reached, and then transpose to cubic
feet.
RATE OF EVAPORATION
Evaporation is due to a difference in pressure
between the moisture in the material and the sur-
rounding atmosphere, and the rate of evaporation
is a function of this difference. The rate of evapora-
tion is affected by temperature, humidity, velocity
456
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
of air flow, or barometric pressure only in so far as
they determine the difference in pressure. In order
to cause evaporation the pressure of the moisture in
the material must be greater than that of the sur-
rounding atmosphere. When they are equal evapora-
tion ceases, and if the pressure of the surrounding
atmosphere is greater than that of the moisture in
the material, the material will acquire moisture instead
of losing it.
In tunnel dryers of the type under consideration,
evaporation is caused by bringing a current of heated
air into contact with the material to be dried. This
air has a certain capacity for absorbing moisture
due to its not being saturated, and is effective in pro-
portion to this capacity.
The pressure causing evaporation of water is vapor
pressure, and saturated vapor has known pressures
for each temperature which may be found published
in steam tables and expressed in inches of mercury.
The vapor pressure of partially saturated air may be
found from various formulas, of which the following
by Professor Ferrel is probably the best known:
/ I' — 32\
f = f — 0.000367PC/ — t')fl + — — - j
where ( = the temperature of the dry bulb in ° F.
/' = the temperature of wet bulb in ° F.
/ = the actual vapor pressure in the air in inches of mer-
cury.
/' = the maximum vapor pressure present at the wet
bulb temperature I' .
P = the barometric pressure in inches of mercury.
If F be the maximum vapor pressure at the dry bulb
temperature /, then the relative humidity is — .
If no air were present, the condition of the moisture
could be likened to that of steam saturated at a tem-
perature and pressure corresponding to the dew point
and superheated to the temperature of the dry bulb
and to a pressure corresponding to F. However,
owing to the presence of the air, the temperature of
the wet bulb rises above the dew point, and the effec-
tive head is reduced b,y an amount equal to the differ-
ence between the vapor pressure, /', and the vapor
pressure of the moisture at dew point, /. i
This may be expressed as an effective head equal to:
F— /—(/'-/) or F-/'
In many material:, the moisture is held partly as
free water on the surface or between the cells of the
material, and partly as water more intimately com-
bined with the cell structure. Under certain con-
ditions of operation, a curve of the drying rate of
some materials will show a distinct break when the
free water is evaporated and the water in me<
combination alone is left. This break is accompanied
by a rise in the temperature shown by a thermometer
having the bulb immersed in the material. Until
this point is reached, the thermometer in the material
will show a temperature very close to the temperature
of the wet bulb thermometer in the air, and it is
reasonable to suppose that, as long as evaporation
is not forced to a point beyond the ability of the
material to part with its free water, the temperature
of the material will be that of the wet bulb thermometer,
and its vapor pressure will be that of saturated vapor
at that temperature, and that evaporation will take
place at that temperature.
When the attempted rate of evaporation is greater
than that at which the material can give up its mois-
ture, the temperature of the material will rise above
that of the wet bulb thermometer, and the condition
may be likened to that obtaining in a closed tank from
which the rate of flow is controlled by a vent. The
reduced head due to this condition is shown by the
increased temperature, and finally becomes zero when
the temperature of the material equals the tem-
perature of the dry bulb thermometer and drying
ceases.
Vapor pressures are directly dependent on tempera-
tures and absolute pressures for any given substance,
and since, in a
tunnel dryer, all
drying may be con-
sidered as being
carried on at at-
mospheric pressure,
the variations in
vapor pressure are
due to changes of
temperature. Since
a definite amount
of heat is neces-
sary for the evap-
oration of water, it
follows that many
calculations of dry-
ing conditions may
be worked out in
two ways: one
from the point
of vapor pressures,
and one from the
nt of the heat
utilized. While these two methods are interrelated,
still it is often possible to use one to check the other.
AIR VELOCITY
In the above, the question of the velocity of the
air has been neglected, it being assumed that the
moisture evaporated was removed as soon as the vapor
was formed. This would be the case with an infinite
velocity; but on the other hand, if there were no
movement of the air, it would become satura'
the temperature of the material would rise until
equilibrium was established.
Unless the velocity of the air is consi'i
probable that there is a condi o rying satura-
tion from the surface of the material to the main air
stream and a correspond ise in the effective
vapor-pressure head between the moisture in the
material and the atmosphere immediately in ■
with it. This is similar to the skin effect surrounding
boiler tubes, and the action of increased velocity in
securing greater heat transference is similar in both
cases. In order for full advantagi to be f.-iken of
B
" 9
- 300
5
- 400
i
- 5O0
I
"* i
I
a
-2 '•
<
i
-1000
I
■* l
i
"
t
■> f
-isoo
i
M
.$ i
-tow
*
- 5
-7500
s
i"
.30OO
-.3500
t-OHMUL*
-4500
- 5O00
M
'■■'
1 V-i"
«
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
457
i
s
- Itooo *
5
i
r ' ° i
: '"° : ei8esl»
- 3500
35
- 55
«r" !;["
i
:«o«
.re
I ° li
- 50
•
;"
-40
-
:
- 20
Ljo
:'°
|
laol
lio
|
i
:
s
i
$
\
- 5
I
-. 1
':*
:
-*
't"
- 3
- 2
- 3
. ao
too
:'s
- 10
.,.00
:>°
- 70
-i 500
!
- is
i
7 "
- 30
- 35
*
- 30
- 35
1
- *0
-45 1
- 50 «
:«
I
L to
>°
-60 j
- 70
- 8oo
7 45
-80
1-70.
I
- SO
^wHHEas:
-«0
'
" «
1u^.Sim"K»"»;T»™ »i ioogimciun
-500
SO
150 > GALS >U£L
4-
I M
t-ioo
- 300
r "°
M»
-,So
.,„
high velocities, it is necessary that the air be brought
into close contact with the surface of the material
being dried, and the trays should not be spaced farther
apart than is necessary to secure the passage of the
requisite amount of air at the desired velocity. When
determining drying rates under varying conditions,
the air velocity should be kept constant until the other
variables are investigated.
In the ordinary tunnel dryer, the velocity is sub-
stantially constant at any position, but decreases
from the hot to the cold end as the volume of air is
reduced by cooling. The usual velocities employed
are from 300 to 1000 ft. per min., and it appears that
above the latter figure the effect of increased velocity
becomes less marked, and in most cases is not worth
the cost of the power required to produce it.
In order to obtain uniform temperatures over the
cross-section area of the tunnel, a certain velocity
is needed, because, if the velocity is too low, con-
vection currents and other disturbances will cause
wide variations in temperature, resulting in uneven
drying. It is also important that the full area of the
tunnel be occupied by the trays and trucks. The
air shows a wonderful facility for taking the easiest
route and will by-pass around the trays instead of
going between them if it is given any chance.
Some heat is expended in raising the temperature
of the water vapor from the temperature at which
it is evaporated to the temperature of the surrounding
air.
THE DRYING TEMPERATURE
The advisable temperature for drying is generally
determined by some characteristic of the material.
Most materials in their finally dried condition have a
limiting temperature which cannot be exceeded without
deterioration taking place. Some materials have a
definite rate of evaporation which may not be ex-
ceeded without injury, and others show distinct
variations of condition when dried at different rates.
This is particularly noticeable with some fruits which,
when dried slowly, tend to darken and acquire the
leathery skin characteristic of sun-dried fruit, but
when dried rapidly preserve the original color and
texture of the fresh fruit to a marked degree. The
commercial tendency is naturally to hasten the drying
in order to increase the output of the plant and reduce
the equipment needed, and in many cases this also
tends to produce the best product.
Some materials must be started at a fairly low
temperature and high relative humidity and brought
up slowly to the temperature of evaporation. These
materials are characterized by poor heat and moisture
transference qualities, and, if they are put into a hot,
dry atmosphere, the surface dries rapidly, while the
center of the material remains cool and moist. A
high vapor pressure is produced at the surface, which
tends to drive the moisture both to the surrounding
atmosphere and also toward the center of the material
where the moisture is under lower vapor pressure
owing to its lower temperature. This still further
aggravates the condition and may cause a hard shell,
or coating, of dry material to form around the still
moist interior. This is similar to the action of searing
a steak and is known as "case hardening." It effec-
tually prevents further drying, unless the material
is subjected to an atmosphere of high relative humidity
for a considerable time. Hardwood lumber is typical
of this class of material.
Where the material is finished at the hot end of the
tunnel it is not safe to have the temperature of the
air higher than the temperature that the material
can stand without injury, unless evaporation is not
nearly completed.
If the material is finished at the cold end, somewhat
different conditions result. Many materials will stand
a higher temperature when moist than when dry.
458
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
Also, in most materials the rate of evaporation is
greatest when they contain the most moisture, and
their temperature will not rise above that of the wet
bulb until drying is partially completed, so the differ-
ence between the temperature of the material and
that of the air will be greater at the hot end of the
tunnel if drying is started at that end. It is evident
from this that, for a limiting maximum temperature
of the material, the allowable temperature at the hot
end of the tunnel may be greater if the material is
entered at that end and finished at the cold end.
This, of course, means more rapid drying, and if the
temperature drop through the tunnel is made suitable
to the material it is often possible to keep the tem-
perature of the material practically constant through-
out the drying operation. When the material may
be heated to a higher temperature in its moist condi-
tion than in its dry condition, a still greater saving
in the time of drying may be made by a higher entering
air temperature. When the material is entered at
the hot end, the temperature drop through the tunnel
must be regulated to suit the requirements of the
material and where a small temperature drop is used,
it is probable that the air will not be brought to an
economical point of saturation, and it then becomes
necessary to recirculate a portion of it. Recircula-
tion is also used for the purpose of regulating the
humidity with regard to the requirements of the
material. For materials which stand a higher tem-
perature in a moist atmosphere than in a dry one,
the added humidity at the cold end is an advantage.
It must be remembered that with high humidities
the temperature of the dew point is raised, and a
condition often occurs where the material put into the
tunnel has a temperature lower than the dew point.
In this case no drying takes place until the temperature
of the material is raised above the dew point tem-
perature, and during the warming-up process moisture
may condense on the material, in which case the
temperature of the air will rise owing to the releasing
of the latent heat in the vapor. This addition of
moisture is less marked when the material is entered
at the hot end, as the warming-up process is hastened
by the higher temperature, but in any case may be
serious with some materials. This is especially so
with fruit which often condenses enough moisture
to form serious dripping, which washes off the juice
and the sugar contained in it, and deposits a thick
sirup on the floor of the tunnel and on the trucks and
trays. This is a loss of the most valuable part of the
fruit, and is best avoided by preheating in an atmos-
phere of sufficiently low dew point.
THERMAL EFFICIENCY
The following observations were made at a plant
successfully using direct heat. In this plant the fuel
used had a Baumc gravity of 31.8, weighing 7.22
lbs. per gal. Its heat value was 19,875 B. t. u. per
lb. The quantity of fuel used during the 2.5 hrs.
of the test was 28 gal., equal to 1.35 lbs. per min.
The air was heated 87° from a temperature of 64° F.
to a temperature of 151° F., at which temperature
the weight would be 0.065 lb. per cu. ft. The actual
air flow, as estimated by Pitot tube readings, checked
by anemometer readings, was 18,400 cu. ft. per min..
at the higher temperature. The total number of
cubic feet of air per minute possible to heat with this
1.35 X 19,875
weight of fuel is
or 20,000
0.2375 X 0.065 X 87
cu. ft. per min., and the thermal efficiency of the
18,400
furnace was — — — — - or 92 per cent. Other tests on this
20,000 F
and similar installations have shown efficiencies
ranging from 92 to 98.5 per cent. It is very diffi-
cult to arrive at the determination of the actual
air flow, and, where efficiencies are as high as
those shown, a difference of 2 per cent of the air
flow means 1 per cent of the efficiency, but there can
be no question but that direct heat is a most efficient
way of heating the air, when it is correctly applied.
In some systems of using direct heat it is necessary
to use a high gravity and therefore expensive fuel,
but other systems operate satisfactorily with Diesel
fuel oil, and it seems probable that even straight
crude oil may be used eventually. Where the cost
is not prohibitive, electricity is the ideal method of
providing direct heat. The nomograph in Fig. S
shows the relation between various furnace efficiencies
and fuel costs.
While the furnace efficiency is of interest, it is often
desirable to know the overall thermal efficiency of the
dryer. During operation this is most easily arrived
at by taking a period of 24 hrs., or longer, and sub-
tracting the weight of the dried material from the
weight of the wet material to get the weight of the
water evaporated, and then comparing this with the
number of gallons of fuel used. This relation is
shown by the nomograph in Fig. 9, which must be
corrected to conform to the actual fuel used.
OPERATION OF A FRUIT DEHYDRATING PLANT
The method of operation of a fruit dehydrating
plant, on prunes for instance, is subject to local con-
ditions, but in general the fruit is brought to the
plant in what are known as "lug boxes," which hold
from 40 to 50 lbs. The gross weight is taken when
coming in, and the net weight is determined by weigh-
ing the outgoing boxes, or using the average of a
number of them, to secure the tare weight.
The boxes are unloaded on to a platform, or directly
on to a roller conveyor. The fruit is emptied into the
dipper from the lug boxes, and the empty boxes are
returned to the unloading platform where they are
picked up by the teams and returned to the orchards.
In the dipper the prunes are plunged into a tank of
boiling lye which removes the waxy bloom and checks
the skin with a number of small cracks, without which
drying is almost out of the question. In the larger
plants this dipping is done in a machine having an
endless draper belt conveyor which carries the prunes
through a tank of lye heated with steam coils and
then through a tank of cold running water. After
coming out of this tank the prunes are passed under
cold water sprays, which further cleanse them. This
machine handles from 4 to 5 tons of fruit an hour.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
459
and discharges on to a combined grader and shaker
feeder which sorts the prunes into two grades according
to size, and discards the small, immature fruit as culls.
The fruit is discharged from the shaker feeder directly
on to the trays where a slight additional spreading is
done by hand, and the trays are loaded by hand on to
the tunnel trucks.
The trucks are placed in the tunnels by hand and
are moved through the tunnels by a chain conveyor.
Whenever a truck of dried fruit is taken out of the
tunnel, the whole string of trucks is moved forward
one position and a truck of wet fruit put in at the other
end, thus keeping the tunnel always loaded to capacity.
The trucks holding the loaded trays of dried fruit
are moved by hand to a hopper discharging into the
boot of an elevator which carries the fruit to the
second story, whence it is distributed by belt con-
veyors, or wheelbarrows, to the storage bins.
The trays, after being emptied into the hopper, are
put on a roller conveyor which carries them direct
to the discharge end of the shaker feeder where they
are reloaded. The empty trucks are returned to the
loading point by hand.
It will be seen that, by this method, the equipment
of trays and trucks makes a continuous circuit, but
that the wet fruit and dry fruit are handled at different
points on the circuit and are kept separated. Also,
the fruit in the lug boxes and the dried fruit storage
bins is kept away from the part of the plant where
active operations are in force.
It is essential that in any plant of this kind, storage
space be provided to take care of interference in the
normal cycle of operation. Storage room must be
provided for the incoming fruit which may arrive
faster than it can be handled, and for the outgoing
lug boxes which may accumulate. Trucks may be
loaded faster than they can be put into the tunnels
and may come out of the tunnels faster than they can
be unloaded. Trays may be emptied faster than
they can be loaded, and for all these conditions space
must be provided. This question of space becomes
still more important when part of the operation, such
as dipping, takes place during only a portion of the
day, while drying is continued throughout the 24 hrs.
COST OF OPERATION
In calculating the cost of drying any given material,
it is best to bring all labor costs to a basis of hours of
labor per ton of dry material, and all other costs, such
as the cost of fuel, power, and material, to a similar
basis per unit of cost. The following example may
be considered typical of this method:
Here it is assumed that a fruit product, such as
prunes, is to be dried in a dehydrating plant having
the following characteristics:
4 tunnels, each having a tray area of .... 6400 sq. ft.
Total tray area 25,600 sq. ft.
Tray load per sq. ft 3 lbs.
Drying time 18 hrs.
Wet-dry ratio 2.25 : 1
Maximum temperature at hot end 160° F.
Allowable temperature drop 50°
Temperature at cold end 1 10° F.
Overall thermal efficiency 60 per cent
Wet capacity in lbs. per hr. per sq. ft 0.17 (Figr 3)
Wet fruit capacity of plant in tons per 24
hrs 52 (Fig. 4)
Dry fruit capacity of plant in tons per 24
hrs 23 1
Holding capacity of each tunnel in tons . 9.6 (Fig. o)
Tons of wet fruit dried in each tunnel in 24
hrs 13
Tons of dry fruit output from each tunnel
in 24 hrs 5.77
Pounds of water evaporated per hour, per
tunnel 600 (Fig. 6)
Air required per tunnel on basis of 1 lb. of
water evaporated by 70,000 en. ft.
dropping 1° 14,000 cu Ft. per mir, (Fig 7)
Tons of water evaporated per 24 hrs.,
52— 23. 1 2s 0
Gallons of fuel per 24 hrs. with overall
efficiency of 60 per cent and fuel ca-
pable of evaporating 135 lbs. of water
per gal 714 (Fig. 9)
The fruit will all be brought to the plant during 12
hrs. Taking the capacity of the dipper as 4.5 tons
of wet fruit per hour, it is evident that it can handle
the total requirements of the plant in 21 hrs.
Drying will be continuous for 24 hrs.
Unloading the trays may be continuous, or inter-
mittent.
The distribution of the labor on the job will vary
widely under different managements and different
types of labor. As an instance of this latter point,
it has been found that, owing to the small stature of
Japanese laborers, four men are required to stack
trays at a height of 7 feet, while the same work can be
done easily by two tall white men.
For purposes of illustration the labor may be dis-
tributed as follows:
N'umber Period Total
Class of Men Worked Hours
Weigher 1 12 12
Helping unload teams 1 12 12
Trucking fruit to dipper 2 12 24
Feeding fruit to dipper 1 12 12
Superintending dipping 1 12 12
Spreading fruit on travs 4 12 48
Loading trucks 2 12 2-1
Trucks in and out of tunnels 2 24 48
Scraping trays 2 24 48
Feeding tray conveyor 1 12 12
Distributing to bins 18 8
Furnaces and boiler 1 24 24
Cleaning up 1 24 24
Superintendent 1 24 24
Total Hours 332
On a daily capacity of 52 wet tons and 23.1 dry tons,
this is equal to 6.38 hrs. per wet ton and 14.37 hrs.
per dry ton.
The fuel used in the furnaces has been estimated
as 714 gal., to which must be added that used by the
boiler furnishing steam to heat the dipper, say, 100
gal., or a total of 814 gal., equal to 15.65 gal. per wet
ton and 35.2 gal. per dry ton.
The power used will be that needed to drive the
four fans and the furnace blowers for 24 hrs., the
dipper for 12 hrs., and the tunnel conveyors and
elevator for short periods. In addition, lights will
be needed for some 12 hrs. This may total some
1000 kw. hrs. per 24 hrs., equal to 19.2 kw. hrs. per
wet ton, or 43.27 kw. hrs. per dry ton.
Lye for dipping will run about 10 lbs. per wet ton,
or 22.5 lbs. per dry ton.
In addition to the above, there will be some expense
for water and other incidentals and for repairs.
To the above costs of productive operation, must be
added the overhead and fixed charges. On plants
460
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
that are operated on a single, seasonal product where
the drying of the year's crop may have to be com-
pleted in a month or six weeks, these charges become
very heavy when prorated on a tonnage basis, and
every effort should be made to extend the drying
period as far as possible throughout the year on other
products.
SUMMARY
Tunnel dryers may be built suitable for drying
any material that can be handled economically on
trays. They are particularly suitable for handling
large quantities of fairly uniform material under
conditions of progressive, continuous operation. They
are cheap to construct and economical to operate.
A successful tunnel dryer must have means for
varying the temperature of the air through any range
that may be required. It must be arranged to allow
of regulating the humidity of the air with exactness.
The velocity of the air should be under complete
control and recirculation of any desired portion of it
should be provided for. The dryer should be con-
sidered only in its relation to the rest of the plant,
and the handling of the material before and after
drying should receive close attention.
The tendency of commercial practice is to hasten
drying as much as possible, and this can often be done
without injury to the material, and in some cases
with distinct benefit, when all the conditions of the
problem are known. Materials that will stand a
higher temperature when wet than when dry can
generally be dried most rapidly when they enter the
tunnel at the hot end, as the temperature of the cold
end then becomes the limiting temperature, and a
higher average temperature may be maintained.
The highest thermal efficiencies are obtained when
the air is discharged at the highest relative humidity
that the condition of the product will permit. It is
usually more economical to use a large quantity of
air at high velocity with recirculation, than to use a
small quantity of air with low velocity and no recircu-
lation.
In closing, it may be stated that there is need of
more exact information as to the behavior of variou s
materials under different conditions occurring in
drying. Little seems to be known, even by established
manufacturers, in regard to the characteristics of the
products that they turn out, and in almost every
problem of design considerable leeway must be allowed
to take care of contingencies that cannot be foretold.
This adds to the expense of the installation, which,
to a great extent, could be avoided by more accurate
knowledge of the premises on which the solution of the
problem must be based.
Note — The paper on "Vacuum Drying" by Charles
O. Lavett and D. J. Van Marie was not received in
time for inclusion in this report, and will be printed in
a later number of This Journal.
ADDRESSES AND CONTRIBUTED ARTICLES
The Immediate Needs of Chemistry in America1
By William J. Hale
Dow Chemical Company, Midland, Michigan
Both university men and industrial men have depicted many
essentials necessary for the success of young chemists. A good
rigorous training is always to be encouraged for those who seek
a chemical future. Further, if we start this training in early
childhood, all the better; simple thinking with clear deductions
makes for better faculties in later days. Our elementary schools
and high schools may stimulate the scientific spirit when once
aroused, but more than likely they will not, amidst the deluge of
diversified devotion to things utterly foreign to mental advance-
ment. Thus, a mathematical course easily surpasses in value
the sum total of all other subjects taught in our schools; no matter
whether scientific or unscientific be the student's interests, his
mental makeup is incomplete until he has had this training.
During my experience in teaching, I found the greatest number
of freshmen more deficient in this field than in any other. Of
course their use of English is pathetic, but this slowly improves
through influence of educational environment. As a result, I
have become thoroughly convinced that mathematics makes for
the greatest good to students of our primary and secondary
schools. How far they should pursue this subject in college
and university naturally will depend on their future aims in life.
Let us grant, then, without argument that a rigorous early training
constitutes a firm foundation for the best chemical training at
the university.
1 Address delivered before the Society of the Sigma Xi at Purdue
University, LaFayette, Ind., February 17, 1921; also presented before the
Division of Dye Chemistry at the 61st Meeting of the American Chemical
Society, Rochester, K. Y., April 26 to 29, 1921.
The young men of the universities pursuing courses in chem-
istry or chemical engineering have commanded, next in order,
the chief attention of our many lecturers on this general subject.
Some have told us of the advantages accruing from a purely scien-
tific course of study; others have told us of the immense ad-
vantages which fall to those pursuing a more utilitarian course,
such as chemical engineering. I shall hesitate here no longer
than to remark that little difference does it make what course a
young man takes so long as he knows well the fundamental
principles of his science, and cognate sciences, and can readily
apply this knowledge when occasion demands.
The great majority of young chemists graduating from our
universities select some position with an industry where chemists
are essential or nearly so. In those instances where the "nearly
so" variety obtains, you may consider the young chemist as acting
in all capacities at once. In general, however, the young men
are placed directly in the research divisions or in the analytical
laboratories. The varied training of these chemical neophytes
forbids any serious discussion as to just what they are best fitted
for. They occupy, so to speak, the same relative position as
freshmen entering college. Though the proverbial rough edges
and apron strings of the verdant freshmen are long since removed,
there have appeared anew certain oddities in our graduate which
now must be corrected; such, for example, as the experimental
niceties, the more or less sanctified professorial customs of
procedure, and the textbook overdrapes. The first condition
is soon remedied when he finds himself working in vessels too
large for the fine balances; the second is removed more slowly,
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
461
but decidedly so, when he comes to realize that complexities
now enter into analytical studies which never were dreamed of
by his instructor. The third, like some heavy fog, vanishes be-
fore his eyes as he comes to learn how utterly unfamiliar with
actual conditions the average textbook writers appear to be.
After all, the great majority of young chemist graduates have
made good impressions, and many have succeeded even where
least expected. During the past few years, or since the discharge
of a large body of near-chemists who had been assembled at
Washington for the purpose of research, the industries have
become flooded with this second-grade material. True, many
real chemists were in the employ of the Government, but by far
the greater number were decidedly of inferior grade, and this
is the lot which was recently foisted on the industries, looking for
positions as chemists for no other reason, apparently, than that
they had been given that particular nom de plume in Washington.
Though their researches seemed childish in the eyes of actual
chemical manufacturers, nevertheless employment was given
without undue criticism. Months have now elasped and you
will find these same young men almost completely transplanted
into various forms of non-chemical enterprise. They soon came
to realize that nature had never intended them as chemists
The need for chemists was never so keenly felt by our chemical
industries as in the past few years. Though the poorly trained
chemists and near-chemists just mentioned have slowly been
eliminated, those who remain have shown far too clearly a lack
of that broader training so highly desirable. I do not wish to be
overly critical of our young chemists, but I do not exaggerate
when I say that the large proportion of chemical graduates have
proved ineffective in the prosecution of research. As analysts,
however, these young men have qualified admirably. Possibly
the industry expected too great a storehouse of knowledge on
the part of the young graduates, but would not you suppose that
these young graduates could at least delve into a subject and
search the literature for themselves? This does not seem to be
beyond the realms of possibility, but do we find this type of
student? The answer is decidedly in the negative. There re-
mains, therefore, but a narrow field for his employment; more
likely he is given the repetition of work outlined by others,
usually from the patent literature, and left to drift. How many
laboratories this past year or two have done anything beyond
working over a series of German patents? Results they all
obtain, of course, but of what intrinsic value are they? The
enterprising industry really wishes far more than this, and must
needs know the basic conditions of each and every problem
which primarily adapts itself to that particular industry and
which will permit of this industry expanding with confidence
of future security. In the fabric of our chemist graduate im-
agination and scientific correlation of ideas appear all too fre-
quently as mere embryonic factors. These semi-developed young
men cannot accomplish much of worth, and yet they work to the
best of their ability. One may criticize their superiors in not
lending more constant assistance, but here, if I may be frank,
let me say that their superiors have many other duties and can-
not devote their time and energy to show each beginner how to
read and think. Naturally you will suggest that these industries
need young men graduating with doctors' degrees. Very true —
but I do not believe that doctors of philosophy need be the only
type of chemists for chemical enterprises.
Just what types of chemist we do need and just what previous
training the industries hope to find in their chemists will consti-
tute the underlying current in this discussion. The needs of
chemistry to-day have grown out of deficiencies here discoverable.
A CLASSIFICATION OP CHEMISTS
In order to indicate more distinctly the points for consideration,
I cannot do better than attempt to classify the entire working
organization of chemistry in this or any country. Convention-
ally speaking, one may describe the science and art of chemistry
as enjoying the services of three classes of men: the professor of
chemistry; the consulting chemist; and the industrial chemist,
each comprehending a distinct profession.
The fallacy of such classification is apparent to anyone who
surveys the matter for a single serious moment. Thus, we have
teachers in the industrial world; those who devote time to the
education of younger chemists; professors of chemistry, they are
in almost every sense of the word, but the question of granting
degrees is not concerned. This is of little consequence, as most
of the young men already have their degrees. These professors
offer certain courses more or less dependent upon the demands
of possible students. Organic chemistry, for instance, is more
often given with us simply because of the poorer training in this
branch of the science of those young men who come into our
employment. Again, just what is a consulting chemist? Where-
fore an industrial chemist of any distinct type! His world is
limitless; he teaches; he consults; he develops processes.
Thus, such lines of demarcation among the three classes of
chemists I have specified break down completely. We must
seek new lines; lines which shall describe as accurately as possible
all categories of chemists, whether they be employed by a college,
a university, an industry, or by themselves. Such a classification
is given herewith.
ts engaged
ily in the
:ement of
1. Advisory Chemist )
2. Research Chemist >
3. Educational Chemist ]
4. Development Chemist
5. Operating Chemist
6. Control Chemist (Analyst)
Chemists engaged
primarily in the
development of
My plan comprehends six distinct types of chemists. Practi-
cally each may function in the industrial world, the world of chemi-
cal art, though the first three types are also concerned with mat-
ters outside of the industrial world. In the development of the
science proper, the first three types alone enter: the third only
indirectly, but the first and second directly and outranking all
others
the educational chemist — Professors of chemistry to a large
extent are merely chemical historians. They present a digest
of what has been accomplished and do nothing much in a con-
structive way for the furtherance of the science other than to
lend an inspiration to students wherever possible. An inspiring
teacher of chemistry is a wonderful asset, not only to a univer-
sity but to the science and art of chemistry. Those who are
content to function merely as teachers occupy, however, the
lesser positions in our active world. Not a long time back, these
men commanded the respect and prestige that grace learning
and authority, but to-day these same attributes are not out-
standing Our world is moving forward with such leaps and
bounds that the educational chemist cannot predicate a single
conclusion, for the very hypotheses he once formulated have
long since passed into oblivion. New hypotheses spring up over
night, and these he has no means of learning save through in-
timate contact with those who conduct researches in both the
science and the art. As an historian of chemistry, and that alone,
can we justify the position of one who teaches the science out of
personal touch with those who devote the labor of mind and body
in its service. The hope we entertain that the educational
chemist will ever exert an inspiration upon the student of chem-
istry is a hope strongly supported by all.
The educational chemist may function further in any of the
other capacities. As a professor in the small colleges, little
opportunity is afforded to these ends. When time actually is
found for active chemical pursuits, these professors attain highest
rank among colleagues and students. As a representative pro-
fessor in a large university, the educational chemist must func-
tion in a research or advisory capacity. Where he fails so to
qualify, his position assumes a decided mediocrity; even students
belittle his influence, an influence that brooks no favorable com-
parison with anything living.
402
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 13, No. 5
the research chemist — The research chemist, of course, is
the direct power behind the entire organization. His is the
mind that directs attention, that directs endeavors, and turns
defeat into victory. Every type of chemist functions as a re-
search chemist to a greater or less extent, depending upon his
ability and enterprise. When the educational chemist engages
in research, we have the highest type of professor to-day. His
mind, kept alert by constant application and endeavor, exerts
the greatest good upon all who study with him. These profes-
sors, our Research Professors, occupy the highest position in the
power of the university to grant. The research chemist, however,
at a university is for the mosi part concerned with pure science,
and happily thus, for little opportunity is afforded other research
chemists to delve into fields little trodden and scarcely indicative
of practical value. Out of these researches much of great import
results, and by them the science itself is advanced by sure and
measured tread.
the advisory chemist — The advisory chemist in the capacity
of an educational chemist is that type of professor who keeps
closely in touch with actual practice. The art of chemistry is
as well known to him as the science, considering, of course, his
own special interests. He makes an excellent teacher, especially
in a course of practical bent. Industrial organizations choose
in many instances to pay these men retaining fees in order that
their active chemists may be kept closely in contact with mature
and ready minds. More often are these advisory chemists in-
dependent of universities and industries. They comprise, of
course, the "consulting chemist" of our earlier remarks, and far
more besides. The advisory chemist is more often a man past
middle age and does not engage laboriously in all forms of ex-
perimentation. His position in the science and art of chemistry
is rather to correlate the work of the research chemists. After
all, the true advisory chemist is a research chemist, but he does
not confine himself to any one problem or interest. His training
and experience lead him into broader domains and, in so far as
he is able thus to progress, he can accomplish marvels for the
science and art of chemistry. The actual research chemist,
however, must give the final word on matters in the making.
Both research and advisory chemists best thrive in an environ-
ment of learning, where their energies are devoted entirely to
research in the pure science, and herein the university atmos-
phere is particularly propitious for their advancement; whereas,
in the studies upon the practical application of the science our
private laboratories and industrial laboratories, on the other
hand, offer the best incentive for progress.
the development chemist— As previously stated, the three
types of chemists just described may function both in industry
and university. The second group in our classification comprises
yet three other types of chemists, and these latter three function
only in the industrial world. Here the development chemist
is the greatest asset to a chemical plant. His services make the
other positions of operating chemist and control chemist possible.
When a process has been developed in the research laboratories
by research and advisory chemists, it is given to the development
chemist for plant installation. Naturally, a semiplant process
must first be installed where the research chemists may still
exercise a guiding eye. These installations are best studied in
larger laboratories abundantly equipped with all forms of me-
chanical devices; technical laboratories they are termed abroad,
and hence their technical chemist becomes synonymous with the
development chemist of my classification. No matter how care-
fully our research chemist may penetrate the seeming intricacies
of chemical reactions, the development chemist is sure to run
across sources of trouble little dreamed of. The training of the
development chemist is highly varied. These men should be
primarily engineers, but they should have a comprehensive
knowledge of chemistry also. I doubt, though, if you can name
a dozen men in this country who have a thorough knowledge of
chemistry in all aspects, and engineering as well. To my mind
a man can be but one thing perfectly, Thus, he is a chemist or
an engineer. From whatever viewpoint he was trained, that
view we must expect as background for every vision. He may
d'splay a positive chemotaxis or, on the other hand, the counter-
part, which we may call engineerotaxis. In the development of
processes in the manufacture of chemical products, the develop-
ment chemist cannot be other than an engineer. His co-workers
should be good chemists, but the man who directs the work is
always an engineer. So wide a knowledge of engineering is
sometimes requisite that one may easily wonder where the chem-
istry comes in; the development chemist never loses sight of this.
the operating chemist — When once a plant is placed in
operation, and the various steps in the processes are well se-
cured by satisfactory procedure, there must be placed in authority
someone who shall be able to keep the entire organization and
each distinct process in the best of condition ; a man who can get
results, and these economically. For this business the operating
chemist, or plant chemist as he is often termed, is particularly
adapted. He must be quick to sense trouble, and when sensed
he must be able to divert its ill effects. His training is usually
that of a chemical engineer, or one who has received a fair amount
of elementary chemical training and yet is versed in those points
where engineering is concerned. Considerable practical ex-
perience would be required, of course, of any young chemist
graduate before he could fill this type of position.
the control chemist — To the control chemist, or analyst,
fall the duties of checking up the various steps in plant processes.
Their labors are more or less uniform, and their tasks continue
without much interruption. The development chemist would
fear for the final cataclysm of the world were his work to proceed
without interruption. The training of the control chemist need
scarcely be more than that of the average college graduate if
he is content to remain in this capacity. Where analytical
processes are to be developed, the higher class of control chemist
is required; this falls to those who have conducted some re-
searches and are able to undertake the work with confidence.
the line of advancement of the young chemist — In lieu of
these six types of chemists, one may inquire just what is the line
of advancement to the young chemist entering the profession.
It has been the custom for graduates in chemical engineering to
enter the analytical or control laboratories and work upwards to
positions of operating and development chemists, or, if their taste
for research develops, to enter the research laboratories. Even-
tually, the more successful may become plant superintendents, or
managers, but at these stages the chemical activities are no longer
paramount, the engineering and administrative features have
gained full sway. Where the chemical outlook still remains,
we naturally have the advisory chemist, and this may be con-
strued as the chemist's goal. It had been the custom for gradu-
ates in chemistry to follow almost the same line of advancement.
but with this class a greater number have preferred to enter the
research laboratories directly, and during this period they have
made themselves so familiar with engineering that an advance
into development work soon followed.
It is quite evident to all that advancement in the chemical
industries rests largely upon the advancement our young chemists
make in engineering ability. Even those who are content to
remain in the capacity of research chemists with added responsi-
bilities, even to that of a directorate, must acquaint themselves
with every possible engineering aspect presented at that par-
ticular industrial establishment.
BRITISH REPORT ON THE GERMAN SYSTEM
After this general survey of chemists at work in the industry
and university I may now outline the needs which I believe
chemistry faces in America. Possibly I shall do well to preface
these remarks by quoting some of the conclusions reached by the
Mav. 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
463
Association of British Chemical Manufacturers in "The Report
of the British Chemical Mission on Chemical Factories in the
Occupied Area of Germany."
The qualification for the post of a chemist has been at least
three years of university training followed by two or three years
of post graduate study. The gate of entry to the factory almost
invariably has been the research laboratory; it is here that the
men have been tested and the character of their ability deter-
minined.
The half-prepared material (without any training in the art
of inquiry) too often accepted by our English works, owing to
the inability of their commercial directors to assess the value of
technical qualifications, has therefore been unknown in Germany.
If our industries are to succeed in the future, it is in this direction
probably more than in any other that improvements must be
effected. The danger is peculiarly great at the moment on ac-
count of the rush of students to our colleges and the difficulty
they will have in becoming qualified workers within the time at
their disposal.
The progress of chemical industry, moreover, has involved not
only the development of the chemist but also that of the engineer,
as well as that of the electrician and of other specialists, each in
his sphere as fully trained as the chemist ; while the chemist has
known how to select his materials, the engineer has known how
to make use of them; there has not only been the closest possible
cooperation between the two branches but full sympathy in aims
and mutual understanding of the object to be gained but
the fact should not be overlooked that, in German works, it is
usual for the chemist rather than the engineer to have the de-
termining voice.
In close collaboration with the director of research and the
chemists in the research laboratories are the workers in the
university, many of the theses presented by students
taking their doctor's degree have a connection with the work
carried out for these firms.
Much has been said of our individual achievement and inven-
tive power and in disparagement of German originality. The
fact remains that the Germans have known how to use and have
used such ability as they have had at their disposal in a highly
successful manner, while we, through lack of willingness — not
of ability — to coordinate our efforts, have too often failed to
avail ourselves of our opportunities.
I cannot overemphasize these points which the British
Mission presents. Each is pregnant with rich suggestions for
American institutions, and in so far as possible we must adjust
and readjust our practices to equal and to better foreign con-
ditions. They should be preached from every housetop of our
chemical laboratories, and to those who will not heed may the
exothermal chemical reactions of another world await your early
arrival.
FACTORS INVOLVED IN THE DEVELOPMENT OF AMERICAN CHEMICAL
INDUSTRIES
In order that I may properly allocate the lessons from the
British report, I shall state what I believe to be the fundamental
factors upon which the development of chemical industries in
America now depends; a development that alone presages the
advancement of the science itself, and hence the promotion of
each constitutes an immediate need of chemistry in our country.
Briefly stated, they are as follows:
1 — -Highest efficiency in plant operation.
2 — Scientific control of process and output.
3 — Marked ability on part of chemists and engineers.
4 — Close collaboration of university and industrial researches
upon problems growing out of the industries.
plant efficiency — Efficiency is possibly the most impressive
feature that characterizes the German plant. Somewhat broad
in implication, the term is intended primarily to connote the
saving of unnecessary labor and the arrangement of all apparatus
so that each of the operations can be carried out in regular
sequence and with highest yields of product. Without the ser-
vices of an engineer of ability no such results ever can be at-
tained. To the development and operating chemists falls the
responsibility for such efficiency. So great is this responsibility
that I doubt if you can cite a chemical plant in the country
which, during these past few months of depression, has not
strained every effort to retain this able type of chemist in its
employ — no matter whether the plant were operating or not.
Thus, the depression has come to be regarded as a godsend to
chemical industry. Through it the nonengineering type of
chemist has been eliminated and eliminated most efficiently.
scientific control — The scientific control of processes is
naturally the sine qua non of highest yields and uniformity of
product The research laboratories are working overtime to
discover every single factor which bears on this phase of the
industry. That they are accomplishing much goes without
saying; I can cite an instance where the actual cost of manufac-
turing a compound has been reduced one-half. But bear in mind
that the research chemist in the research laboratory away from
the plant operation could not have effected this saving. The
tendency that has ever prevailed in this country to leave
plant operations to be checked at distant intervals of time by
chemists is happily past. The control chemists must take on
more and more responsibilities and keep more closely in touch
with daily and hourly conditions of operation. Unlooked-for
variations then take on some semblance of significance more
than likely interpretable to mortal man in the category of a
chemist.
ABILITY ON THE PART OF CHEMISTS AND ENGINEERS — Able
chemists and engineers are now seen to be a prerequisite for the
two first-named factors of success. Those research chemists
who never familiarize themselves with technical manipulation
awake one day to find that they are of little assistance when the
industry most needs their services. Whereas, those research
men who display an aptitude for study of large-scale reactions,
and delve into the principles of mechanics and all that pertains
thereto, find ever and again that they can accomplish the results
so eagerly desired. Upon this latter class of research men
our future hope of success now depends. Competition has in-
creased and is increasing with prodigious strides. If we keep
running, we must keep producing, and if we keep producing, we
must keep cost values below that of sales.
Does it not then stand to reason that we must have the best re-
search chemists if we wish to accomplish the best results? In
those industries where greatest advancement is made you will
find their research chemists more and more familiarized with the
requirements of their development chemists. These latter cut
and slash with such apparent zeal that only those things de-
monstrable to the eye ever can hope to get by. Theories from no
matter how great an authority avail but little, and rightly so,
for theories are usually propounded from results obtainable only
upon a small scale. The development chemists command the
highest respect of the production managers, for the duty of these
latter is not to prove theory but to produce products. Young
men entering upon research problems in an industrial laboratory
will meet with many reverses and positive misfortunes before
they can help materially in the development work. They soon
learn how to correlate their findings with possible practice and,
working under constant guidance, the problems which eventually
leave their division may be attended with a reasonable degree
of probability of success.
You will discern without much ado that I am only trying to
show how very important it is that our industrial research labora-
tories employ only the highest grade of chemist, as well as carry
the finest material equipment. Heretofore, an insignificant
number of laboratories were so favored. Countless sums of
money are constantly expended in this direction; as a conse-
quence, progress is a much more measurable quantity to-day.
When you consider that recent expenditures of money for
such purposes by our chemical industries mount into the millions
and millions of dollars, you may begin to grasp my meaning when
I maintain that researches bearing directly upon plant operations
can be conducted only with success at the plant where the opera-
tions are planned, and nowhere else. I can hardly conceive of a
university laboratory undertaking, for instance, the experiments
464
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
connected with the manufacture of a certain compound when only
a few thousand dollars seemed necessary as initial outlay, yet
where fifty thousand dollars actually proved to be necessary.
These figures happen to coincide with one of our recent ventures.
Though I mention only this one instance with us, I ought at
least to call attention to a somewhat more striking example of
where a certain dye manufacturing plant expended something
over eight hundred thousand dollars before a particularly prized
dye was actually placed upon the market. So many of our uni-
versity men are wont to say that their laboratories, with a brilliant
personnel, could have accomplished these ends in so much clearer
fashion and without such expenditures. They are only dreaming
and know not whereof they speak. I can dream out a process
and so can you, but when we awake, where is it? The me-
chanical problems alone would baffle our best university men,
and I do not wish stock in any company where they are given
much influence untethered. The example I cited as pertaining
to our company was simply one of an "organic prep," as college
students usually dub it. University research chemists easily
prepare it, as they will tell you — but as a matter of fact they
never prepare it — it just happens, and when it comes to manu-
facturing it, not ten men in America know the least thing about
it. We feel reasonably certain that one of our development
chemists should be classified among the possible ten, but little
thought of regret have I ever heard expressed when our president
and production manager decided for the present not to place the
project upon an operating basis and entail a two hundred thou-
sand dollar expenditure for equipment. I hope, then, you will not
be too critical over my statement: the researches primarily and
directly connected with an industrial chemical process must be
done within the doors of the industrial establishment. Is it any
wonder that I come again and again to say that our industrial
research laboratories must and will have the best research men in
America?
COLLABORATION OF THE UNIVERSITIES WITH THE INDUSTRIES —
Upon the collaboration of universities with the industries in a
study of the problems presented by the latter, we see the dawn
of a greater and greater chemical era in America. In Germany
no better examples of this collaboration need be cited than those
which led in 1903 to the constitution of that remarkable and all
too valuable class of dyes, the indanthrenes, by a series of brilliant
researches by Roland Scholl, of the Karlsruhe Technical School,
in conjunction with the discoveries of Rene Bohn, of the Badische
Aniliu und Soda Fabrik. We may cite also the interesting re-
searches of P. Friedlander, of the Vienna Chemical Institute, upon
thio-indigo, beginning in 1905 and cooperating closely over a
period of years with Kalle & Co. in the technical development.
Again, the discovery in 1909 of dehydroindigo by L. Kalbe, of
the Munich Scientific Academy, together with its study at the
Badische Works, led to much of greatest value in the indigo field.
Industrial organizations will gladly favor any true cooperation.
University chemists should take an interest in all things chemical
and not hold themselves aloof as they have been wont to do in
the past. Through such actions they have nothing whatsoever
to gain and much, far too much, to lose.
I firmly believe that one great step to the fore was accom-
plished when many of the young instructors from our universities
entered the industrial field. They were hopelessly deficient in
practical matters, but did have a firmer grasp of chemical prin-
ciples. The practical side was certain to develop in an atmos-
phere of practicability, and many good results have come about.
One industry to my knowledge has actually come to the point
of engaging certain professors of chemistry to spend a portion of
their time at the chemical plant and thus lend valuable assistance
in matters wherein they are particularly well qualified. This,
after all, patterns after the German plan and has given those
marvelous results we have noted abroad. I cannot advocate any
such system unless the university men actually work to a con-
siderable extent at the plant itself where operating conditions
become practically second nature to them. To be highly effec-
tive, these advisory chemists must follow through each little step*
in its every aspect, else their best efforts will go for naught.
They cannot expect to solve the troubles in a distant laboratory.
During the past few years the greatest number of mistakes and
misfortunes resulted from no other reason than that industrial
men were willing to accept university or private laboratory ex-
perience as a basis for their plant operation. So vital is this
"point of attack" for research that I believe a number of these
sad adventures should be brought to the attention of every
student and professor. Let us hope that our university research
chemists will seize with vigor every possible question that may
throw light upon chemical phenomena, but let these researches
be conducted from the standpoint of the pure science — do not
let the technical side divert your steady endeavors, for therein
you work under positive disadvantage and little foresight.
Above all, let us have cooperation.
THE NEED OF PHYSICS AND ENGINEERING IN THE TRAINING OF THE
CHEMIST
When we have taken to heart the important factors which
make for progress in chemistry, and when we duly comprehend
that at the basis lies the development of high-class chemists and
these alone, then a few words concerning their training should
not be amiss. Fruitless in the extreme is the research in chemical
art as prosecuted in universities or elsewhere outside the range
of industrial plants. Wonderful, indeed, is the value of research
in pure science to the young chemist. I well recollect what some
of my friends have thought about researches on the constitution
of some complex organic molecule. Their smile with, "What's
the use of it all," amuses me still. I now affirm that this class of
research is of highest importance, and I would that every re-
search man in our company had to his experience at least a piece
of investigation on the constitution of some simple salt under
varying conditions of combined solvent, we shall say, or that of
some organic molecule, if blessed only with but one simple sub-
stituent. Herein the principles of physics and chemistry come
fully into play, and the value of such researches so far outweighs
all others that the latter seem as mere commonplace. The re-
sults in our industrial research laboratories fully bear out my
contentions, and we have come to realize that we must have men
who have engaged in research in chemical science and not in a
hodgepodge of childish delectation, which so many of our inactive
professors would pass off as research.
The possibility of a four-year trained chemist or chemical
engineer, immediately after entering the chemical industries,
being able to function in any other capacity than as a simple
analyst is veritably an absurdity. Industrial research labora-
tories are now manned with a higher personnel, thanks to the
period of depression which served to weed out near-chemists
everywhere. When further assistance is desired we shall seek
the best-trained men we can get. What is a thousand dollars
more or less in salary to a man who has his doctor's degree or
several additional years of study and research to his credit?
Thus, of greatest benefit to the young chemist are courses in
mechanical drawing, machine shop, testing materials; courses
in calculus, in advanced physics, with emphasis upon thermo-
dynamics and electrical theory; and finally, courses where prac-
tical studies are made of distillation, evaporation, and filtration.
In fact, it is not too cruel to state that those young men who
plan to enter the chemical profession without thorough training
in the principles of physics and engineering, such as are gained by
a study of subjects outlined above, are building for themselves
hazards innumerable, and it were far better for them and for the
cause itself to keep off the course.
During war operations, time and money were more or less dis-
regarded so long as production increased. To-day it is different;
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
465
a young man who requires the time of others for his assistance
costs the company twice his salary, and thus it is easy to see how
any industry would prefer to employ those who have already
had experience, many of whom are now without positions.
The chemical courses at a university are of course the mainstay
of the chemist's training, but they are not more necessary than
the engineering. Only the narrow-minded man could conceive
of a chemist as able to practice without practical learning. A
philosopher, in other words, has no place in the chemical world
of industry save as an ornament.
True, we can always make use of the newly fledged graduate
as an analyst with the hope that he will develop, but what
chances has he among those who have advanced training, and
others coming in with more and more advanced training to their
credit? And under such adverse conditions I must not pass
without acclaiming marked superiority on the part of the chem-
ists with a broad engineering training. The graduate in chem-
istry without engineering is almost hopeless. Of course he is
helpless, for he has no idea of what engineering means, and in
the research laboratories he is worse than helpless now that these
laboratories have come into an abundant supply of more ex-
perienced men. About all that is left is an apprenticeship for
washing apparatus.
Those young men who contemplate chemistry as their life work
should strain every effort to remain at the university for one to
two years after graduation. This time should be devoted, pri-
marily, to real investigation. The young chemist will thus de-
velop as nowhere else is possible. Every phase of engineering
that bears upon chemical industries should be studied with zeal.
The principles of physics should be incorporated into the student's
very being as a basic subject, not held aloof as something un-
necessary. When these young men finally enter the world of
chemistry, they will stand easily to the fore, and I assure you
they will be given preference henceforth.
We rejoice that we command the best personnel obtainable,
and we fear not to undertake the most complex of investigations.
But let us not lose sight of that deluge of half-baked material
which is likely to be cast upon us again, as the British surmise,
owing to the postbellum rush of young men into chemical studies.
Is it not fitting that our university men grasp the situation and
divert what material seems below standard into other courses
where requirements will be less stringent? Only the highest
grade of student should attempt to enter the chemical industries
this year, and even these will scarcely find favorable situations.
No better opportunity ever presented itself to the graduates in
chemistry and chemical engineering to render a service to chem-
istry and at the same time to improve their own faculties. Fol-
low some problem of research for yet another year, and you will
contribute your good share to that progress in the science in
America which we zealously covet.
The School of Chemical Engineering Practice of the Massachusetts Institute
of Technology1
By R. T. Haslam
School of Chemical Engineering Practice, Massachusetts Institute of Technology, Cambridge, Massachusetts
The need of a broader training for graduate engineers in the
composite field of Chemical Engineering has been well recognized,
but the manner of obtaining it was not so obvious. The training
given in this field ten or twenty years ago consisted of less
chemistry than that given to chemists, combined with less
engineering than that given to mechanical engineers. With
such inadequate training the chemical engineer had to meet the
serious problems arising in his new field, and the growth of this
branch of engineering is a proof of its necessity rather than
a tribute to the training. That such training survived the years
it did is due partly to the urgent need for men familiar with
both chemistry and engineering, and due partly to the new-
ness of the profession. The crystallization of ideas as to what
constitutes the science of chemical engineering is comparatively
recent, and the development of suitable educational courses and
methods is of still more recent origin.
Among the troubles encountered in giving a sound training
in chemical engineering was the difficulty of providing suitable
laboratory work. The field being new, new apparatus and
methods were rapidly being developed, and the financial outlay
for large-scale equipment, that quickly became obsolete, was out
of the question. Furthermore, the raw material cost of operating
such equipment presented a new problem not previously met in
the operation of large-scale mechanical and electrical laboratories.
Again, many of the most vital lessons to be learned from practice
with such apparatus come only wjien this equipment is in a
■cycle with other operations, and in a technical laboratory this
is out of the question.
To overcome these difficulties, Dr. A. D. Little proposed a
cooperative course in Chemical Engineering in which the Massa-
chusetts Institute of Technology would unite with progressive
chemical industries in the training of student engineers. The
cooperating companies permitted the use of their plants as a
laboratory, and the faculty of the Department of Chemical
i Received April 4. 1921.
Engineering at the Institute supplied the instructional staff.
This plan, incorporated in the School of Chemical Engineering
Practice, was first tried out under the direction of Dr. William
H. Walker in 1917,1 and although in successful operation when
the war broke out, it was discontinued, since practically the en-
tire staff and student body followed Col. Walker's lead in en-
tering war activities. In 1920 the work was re-started and the
following is a brief outline of the plan, methods, and lessons
learned to date.
STRUCTURE OF THE SCHOOL
The School of Chemical Engineering Practice is composed
of three field stations, each established in an industrial center, and
each having access to the plants of two or three chemical indus-
tries Each of these three stations is in charge of a member of
the Institute Faculty, with suitable instructional assistance,
and the entire time of these men is devoted to the educational
work of the stations. The students, entering this school after
graduation from the university or technical school, are divided
into three groups for assignment to the three stations. After
spending eight weeks at the assigned station, each group proceeds
to the next station, and by this division and rotation the work of
the entire school is covered and completed in twenty-four weeks.
The three stations are located at Bangor, Maine, Boston, Massa-
chusetts, and Buffalo, New York. The companies cooperating
in the establishment of these stations are: Bangor Station—
The Eastern Manufacturing Company and The Penobscot
Chemical Fibre Company; Boston Station — The Merrimac
Chemical Co., The Revere Sugar Refinery and The Boston
Rubber Shoe Company; Buffalo Station — The Lackawanna
Steel Company and The Larkin Company. These industries
include the manufacture of sulfite and soda pulp, writing paper,
electrolytic caustic soda and chlorine, the production of heavy
acids and chemicals, the refining of sugar, the manufacture of
rubber products, the manufacture of iron and steel, gas and
i This Journal, 9 (1917), 1087.
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
coke (including by-product recovery), and soap and glycerol.
After the completion of work at the practice stations, the student
returns to the Institute for two terms of work which is wholly
elective, and this enables him to specialize in that branch of chem-
istry and engineering in which he is most interested.
There are three points of diversion between the School of
Chemical Engineering Practice and other cooperative courses of
instruction:
1 — The men in the school devote their time wholly to intensive
educational work and therefore they receive no pay from the
industries, since they do no direct productive work.
2 — Owing to the methods used and the type of instruction,
it is first necessary that the students receive their fundamental
theoretical training before going into the Practice School, and to
insure such a thorough foundation only the best graduates of the
Institute of Technology or other university of recognized stand-
ing are admitted.
3 — In order that the instruction may be truly intensive and
individual only ten or twelve students are taken into a single
group, and this group is always under the direct and immediate
supervision of an assistant professor with an instructor as an
assistant.
We believe these points to be vital in the development of high-
grade graduate engineers.
DIVISION OF THE FIELD OF CHEMICAL ENGINEERING
It is impractical to study chemical engineering in such widely
different plants in a haphazard manner. The work must be
well organized and the time at each factory spent most advan-
tageously on those phases of chemical engineering which are best
adapted for study at that particular plant. To facilitate this,
the field of chemical engineering has been subdivided into
"unit studies." As Dr. Little pointed out in his report to the
president of the Massachusetts Institute of Technology:
Any chemical process, on whatever scale conducted, may be
resolved into a coordinate series of what may be termed "Unit
Operations," as pulverizing, drying, roasting, crystallizing,
filtering, evaporation, electrolyzing, and so on. The number of
these basic unit operations is not large and relatively few of them
are involved in any particular process. The complexity of
chemical engineering results from the variety of conditions as to
temperature, pressure, etc., under which the unit operations
must be carried out in different processes, and from the limita-
tions as to materials of construction and design of apparatus
imposed by the physical and chemical character of the reacting
substances.
We believe, moreover, that the principles underlying each
unit operation may be made clear to the student by a searching
study of the operation under one or two sets of conditions.
After careful consideration, the field of Chemical Engineering
has been divided into "unit studies," of which the following are
most important:
Unit Studies in Chemical Engineering
I — Transfer op Energy
(a) Heat transmission
I — Mechanism of heat flow
2 — Equipment
(a) Regenerators
(6) Recuperators
(c) Preheaters
(d) Coolers
II — Transfer of Materials
(a) Gases
1— Laws of flow
2 — Equipment
(o) Pipes, ducts, flues, etc.
(6) Pumps, blowers, injectors, etc.
3 — Measurement
(6) Liquids
1 — Laws of flow
2 — Equipment
(a) Pipes
(6) Pumps, injectors, etc.
3 — Measurement
(c) Solids
1 — Conveyors, elevators, trucks, etc.
2 — Measurement
lectrostatic separation
III — Preliminary Treatment of Substances
(a) Crushing and grinding
(6) Mixing
(c) Dissolving
(d) Precipitation
IV — Separation
(a) Solids from solids
1— Mechanical
(a) Screening
(6) Magnetic an
2— Hydraulic
(a) Classification
(A) Separation
3 — Air separation
4 — Flotation
5 — Leaching
(6) Solids from liquids
1 — Sedimentation and decantation
2 — Filtration
3 — Crystallization
4 — Air drying
5 — Extraction
6 — Adsorption
(c) Liquids from liquids
1 — Distillation
(a) Simple
(b) Fractional
U) Steam
2 — -Evaporation
3 — Centrifugal separation
(d) Gases from gases
1 — Absorption
2 — Adsorption
3 — Fractional distillation after liquefaction
(e) Solids from gases
1 — Deflection
2 — Electrostatic
3 — Washing
4 — Filtration
5 — Settling
CO Gases from liquids
V — Reaction Processes and Methods
(a) Combustion
1 — Fuels
2 — Furnaces (including electric)
(a) Refractories
3— Heat measurements and control
(6) Roasting and calcining
(r) Destructive distillation
(d) Electrolysis
(e) Catalysis
(/) Other reaction processes, such as
1 — Nitration
2 — Sulfonation
3 — Fermentation
4 — Digestion
5 — Saponification
VI — Plant Design and Construction
(a) Materials
■hi Layout
ifi Economic balance in design and construction
Owing to lack of time and facilities all of the above operations
are not emphasized. However, as the chemical engineer con-
trols chemical forces largely by controlling the flow of energy
(heat) and the flow of material into or away from the reacting
zone, these operations and their basic effect on the others are
examined in detail. In addition, important operations, such as
combustion, evaporation, distillation, drying, filtration, plant
layout, etc. are studied in a most thorough manner.
METHOD OF TEACHING
The method of teaching the principles back of the unit opera-
tions has been given much attention. Allowing men to operate
machines gives them only a rough qualitative idea of the process,
and we have not found work on "labor shifts" to have much
technical educational value. The method which gave the best
results and which we found to be the most advantageous is the
use of quantitative te^ts on the operation by the students them-
selves. The students are usually asked a question as to the
quantitative effect of some change in operation, and thev there-
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
vE. SiMrurANKotj
\nd Labcibatuky Equipmbnt, Filter Press Room, Revere Sugar Ref
upon design a test, carry it out, and work up the results on the
operation in question. This work of designing the test is done
by the student, and he plans and carries out the work in its en-
tirety. He decides as to the data needed, how they should be ob-
tained, the methods used in calculating his results, and what
results are needed to form a sound engineering judgment on
which a recommendation may be made that will improve the
method of operation. Thus the most difficult part of plant
testing is done by the student, properly guided by men of ex-
perience.
Furthermore, throughout the entire plant work the student
is obliged to apply the knowledge obtained in his undergraduate
work to the practical problems about him. Three of the most
important uses of theory in practical work are: To enable one
to obtain the data required with the minimum trouble and ex-
pense, to get the maximum of information from the data ob-
tained, and from the present performance to predict the results
of possible modifications of industrial conditions. It is obvious
that tests of the sort outlined above afford unrivaled opportuni-
ties for such training in the correlation of theory to practice.
process tests — Some of the tests carried out this last year
were what might be termed "process tests," while others were
related to studies of unit operations. For instance, the determi-
nation of the losses in the soda-recovery process of a soda-pulp
mill is an example of a process test. Again, a sugar balance was
carried out on char filters to determine the input of sugar, ash
and organic nonsugars and the distribution of these materials in
the effluent sirups and wash waters. Another similar investiga-
tion was a determination of the glycerol losses during the evapora-
tion of soap lye. Investigations of this type give the student a
knowledge of chemical processes and their difficulties, as well as
training in methods of detection and elimination of losses, and,
furthermore, they give the student practice both in engineering
and in applied analytical chemistry, since streams of materials
(gases, liquids, or solids) must be both measured and an-
alyzed.
unit operations — When studying chemical engineering unit
operations, the tests were usually carried out in such a manner as
to enable the student to forecast what would happen under
changed operating conditions. For example, in investigating
the manufacture of bisulfite liquor by absorption of S02 in milk
of lime, not only were the actual existing conditions determined,
but the results were worked up and expressed in such a way
that, by means of "tower coefficients," information was obtained
showing the effect of various types of tower packing, and the
results that would be produced by different operating conditions:
such, for example, as a change in the concentration of the SO2
gas, or the change in the temperature of the gas or milk of lime.
The absorption of hydrochloric acid gas was studied in a similar
manner. In studying the drying of granulated sugar, not only
was the moisture which was picked up by the air stream checked
against the moisture lost by the sugar, but in addition various
coefficients of heat transfer were determined which would be of
value in design work. Many other examples might be given
but these are illustrative of the type of work.
methods of carrying out TESTS — It should be emphasized
again that these tests are designed, carried out, and worked up
entirely by the students under suitable guidance. In this con-
nection it may be of interest to note the methods used in carrying
out such tests. First, the problem is outlined to the students
at a conference held in a room provided for this purpose at each
plant. The object of the test is usually given to the students
in the form of a question, as, "The Blank Manufacturing Corpo-
ration wishes to increase its output of chlorine and desires to
know if this can be done economically by increasing the current
density of its electrolytic cells." The problem is discussed in
a general way, and the men are then sent into the plant to get
acquainted, in detail, with the equipment, and to decide what
data are needed and how they shall be obtained. In addition,
each student lays out the work that the various men in the
group shall perform during the test. Another conference is then
held, and the methods and layout proposed by the various
students are discussed and criticized. As a result of this con-
ference, the final method of attack is outlined and each man
assigned to his part. The group is put in charge of one of the
students who is responsible to the director of the Station for
seeing that the test is carried out properly. This leader's duties
consist of seeing that sufficient analytical solutions are on hand
and that the men are skilled in their particular analysis before
the test proper is started. As many of the tests last from eight
to twenty-four hours, the leader of the test arranges proper relief
for the men during meal hours, etc. One man is assigned to the
position of "log man," and he collects and tabulates the data
which are being obtained by the other men. It is the duty of
the leader to watch the log sheet and check up the reasonableness
and accuracy of the data as they are being obtained. When the
test is completed, each man makes the necessary computations
and writes up a suitable technical report which shows not only
468
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. '.5-
the conditions existing, but, where possible, gives recommenda-
tions for improvement.
The tests have to be carried out under such conditions that the
output of the factory cooperating with the Institute is interfered
with in no way, either as to quantity or quality of production.
This often necessitates the use of considerable ingenuity in ob-
taining representative samples and in measuring the various
quantities. For example, to determine the amount of chlorine
being delivered from an electrolytic chlorine cell, the gas was
uniformly diluted with a small, known amount of air, and the
stream analyzed before and after such dilution, and from such
data the volume of the chlorine being given off was computed.
The volume of blast-furnace gas being used in a blast-furnace
stove was determined in the same way. In this last case it is in-
teresting to note that to dilute the blast-furnace gas with air to
the extent of 5 per cent required the erection of a 10-h. p. motor,
driving a 21-in. fan delivering air through a 3-in. sharp-edge
plate orifice
In cases where the factory unit to be tested can be duplicated
on a small laboratory scale, as, for example, a filter press, it has
been found very advantageous to run tests simultaneously on
both the plant and laboratory units. This illustrates to the
students the use of small-size apparatus for deriving certain
constants and characteristics of various types of equipment,
which can be applied to the design and operation of large-scale
units.
Oftentimes it is desirable to use certain equipment that is
unattainable, and makeshifts have to be made. For example,
in order to reduce the current density of an electrolytic cell, it
was necessary to shunt around it 500 amperes, but no shunt was
available. The students overcame this difficulty by making a
carbon resistance pile out of carbon anodes used in the cell
(30 in. long, 6 in. wide, and 1 in. thick) with the aid of two iron
plates from the blacksmith's shop, four tie rods with thumb
screws from the machine shop, and some oak strips from the
carpenter's shop. Again, three of the students doing a research
problem on the same cells doubted the correctness of a portable
ammeter. There was no chance of calibrating it, for neither the
laboratory nor the local power company had the meters and
direct current available (2000 amps.) . The delay of sending it to
the Institute's laboratories would make it impossible for them to
complete their work. However, the plant was equipped with
two motor-generator sets, only one of which was in use. By
making the proper connections, and assuming that the switch-
board ammeter was correct, they inserted their portable ammeter
in the line and gradually cut out one set, throwing the load on to
the other in order not to interfere with the cell room. In this
manner they were able to check the ammeter very satisfactorily.
Another unusual condition occurred during a test on the wash-
ing of soda pulp. Two tanks, one using hot, the other cold
water, were under observation. It was desired to obtain com-
parative data on the amount of color (from the black liquon
in the tanks at various stages. The plant laboratory had a
series of "color standards," but on account of variations in size
of test tubes used, thickness of glass, wide differences between
consecutive standards, etc., the reliability of such results was
much in doubt. One of the men assigned to laboratory work
devised a method of securing comparative color data by titration
with distilled water. By carefully making up a standard, he
found it practicable to titrate his sample with distilled water,
the end-point being the color which exactly matched his standard.
Throughout a thirty-six hour test this method was used with
very good results.
CONCLUSION
In conclusion, we believe the work of the School of Chemical
Engineering Practice may be summed up by stating that seven
industrial concerns permit the use, under suitable regulations,
of their plants as laboratories of chemical engineering, and that
instruction in these laboratories is given to small selected groups
of trained men, by resident faculty members of the Department
of Chemical Engineering of the Massachusetts Institute of
Technology. We believe it to be a great tribute to the broad-
mindedness of American industries, and to these seven concerns
in particular, that they are willing to cooperate in such a whole-
hearted manner in the training of the young engineers of to-
morrow.
The Reception of Madame Curie
The following chemical societies have appointed committees
to make arrangements for the reception of Madame Curie:
I n
ican Chemical Society:
Edgar F Smith. Chairma
L. H. Baekeland
W. D. Bancroft
M. T. Bogert
B. B. Boltwood
Chas. F. Chandler
Chas. H. Herty
S. C. Lind
R. B. Moore
W. H. Nichols
W. A Noyes
Chas. L. Parsons
Ira Remsen
T. W. Richards
J. E. Zanetti
.merican Electrochemical
ciety:
Dr. W. S. Landis. Chairman
Dr. H. B. Coho
Dr. Colin G. Fink
Dr. E. P. Mathewson
Dr. J. W. Richards
Societe de Chimie Industrielle
American Section:
Dr. George F. Kunz, Chairman
Dr. L. H. Baekeland
Dr. M. T. Bogert
Dr. C. A. Doreraus
Dr. J. E Zanetti
Society of Chemical Industry.
American Section:
Mr. S R. Church, Chairman
Dr. H. G. Carrell
Dr. Chas. H. Herty
Dr. Ralph H. McKee
Dr. Allen Rogers
Chemists' Club op New York
City:
Dr. J. E. Zanetti, Chairman
Dr. M. T. Bogert
Dr. Hllvrood Hendrick
Dr. Reston Stevenson
Dr. J. E. Teeple
Dr. S. A. Tucker
As Madame Curie is expected to be but a very short time in
New York City, and as it would be impossible for her to attend
functions given by any of the individual societies, the above-
named committees have appointed an Executive Committee,
consisting of
Dr. Edga
Dr. W. S
F. Smith, Chairman Mr. S. R. Church
Landis, Vice Chairman Dr. George F. Kunz
Dr J. E. Zanetti, Secretary-Treasurer
to arrange for an entertainment to be given by all of the above-
named societies.
The Committee has decided to give a luncheon in honor of
Madame Curie at the Hotel Waldorf-Astoria on Tuesday, May
17, and invitations have been sent to all the members of these
societies living in and around New York. The headquarters
of the Committee are at The Chemists' Club, 52 East 41st St.,
New York City.
Chemists Needed in Chemical Warfare Service
The establishment of the Chemical Warfare Service at Edge-
wood Arsenal, Edgewood, Maryland, will appoint fifty chemists
as soon as suitable men can be secured.
The United States Civil Service Commission has announced
that until further notice it will receive applications for these
positions in the following grades: Chemist at $3000 to $5000
a year, associate chemist at $2000 to $3000 a year, and junior
chemist at $1400 to $2000 a year. Promotion from the lower to
the higher grades will depend upon demonstrated ability and the
needs of the Service.
The examination announcement states that there are oppor-
tunities for employment in fifteen specialties of chemical science.
Full information and application blanks may be obtained by
communicating with the United States Civil Service Commis-
sion, Washington, D. C.
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
469
Our Anomalous Patent Office1
By K. P. McElroy
711 G Street, Washington, D. C.
"What's the matter with Kansas?" is an old question which
never did receive a satisfactory answer until Kansas became
prosperous and contented. Afterwards, it needed none because
it wasn't asked. Answering, or ducking an answer to, the same
question about the Patent Office is becoming monotonous. The
Office is prosperous enough, in the sense that it takes in more
money than it spends; but it is far from contented. That it is
in a bad way is shown sufficiently well by the number of em-
ployees leaving or about to leave. The Patent Office has always
been, more or less, a sort of brooder or incubator for patent
solicitors; and just now it is more so; much more so. It is full of
cocoons awaiting butterflyhood. To use army slang, its morale
is shot full of holes.
It is a serious and perplexing situation to American inventors
and manufacturers to whom a strong and virile Patent Office,
playing the game according to the rules, is a business necessity.
What we are going to do about it is not evident. The Nolan
Bill, so far as it related to the inside of the Patent Office, was
treating symptoms and not a disease. Rehabilitation cannot be
accomplished by the simple expedient of raising salaries, although
it would help. It is unquestionable that the good men in the
Office, of whom there are many, should receive salaries com-
mensurate with their merit. But men of education and standing
need something more than salary to keep them on the job; they
require a certain amount of pride of place and dignity of position.
Obviously, if a man is merely paid what he is worth and what he
can command elsewhere and there are no other inducements,
inertia is all that holds him. The cold fact is that, quite apart
from salary, to the man in the Patent Office the outside looks more
attractive than the inside. The Nolan Bill in no way cures this.
As I see it, it is to the work of the Smoot-Reavis joint com-
mittee, charged with revision and coordination of all government
activities, that we must look for relief. That that committee
will do something to the Patent Office is certain; that it will do
much for it, is to be hoped. Also, it ought to be urged; and it
is up to those interested in patent matters to do the urging. The
committee is free to do what it considers right, since there is
here no question of economy, elimination, or reduction. The
Patent Office pays its own way; it costs the taxpayer, ordinarily,
not one solitary nickel. And it must be big enough and equipped
to handle whatever business comes before it.
Intrinsically, the Patent Office is a highly dignified institution,
going back to the Constitution for its warrant for existence. It
has been the birthplace of many of our great industries, and there
is none that does not owe it something. Its records are the
records of our national industry. A fire in the old near-white
building would be more terrible to industry than an army with
Zeppelins. Its personnel is charged with duties requiring not
only a knowledge of every branch of human endeavor, but of the
principles of law as laid down in the statutes and countless de-
cisions.
Actually, it is a mere bureau in the Interior Department
bracketed with a miscellaneous lot of other bureaus, not to men-
tion St. Elizabeth's Asylum and Howard University. What
it is doing in that galley, or in any executive department, I do
not know, since it is in no sense an executive branch of the Gov-
ernment. It executes no orders of the President or of Congress —
least of all, any by the Secretary of the Interior. Its employees
are "Examiners;" but Washington is full of Examiners. I re-
member one time when I was in the Patent Office and we were
short-handed, the powers that were, to whom all "Examiners"
looked alike, detailed some from the Pension Office to help out — ■
1 Received January 20, 1921.
with results which were chaotic. There is but little dignity in
the title; and less official recognition than there ought to be.
The head of the Patent Office is a Commissioner; but Washington
is also full of "Commissioners" of all sorts — of pensions, of lands,
of fishing, of Indians, of education, and what not.
THE FUNCTIONS OF THE PATENT OFFICE
Under the Constitution, the Patent Office is there to promote
the progress of science and the useful arts; but it is to do it within
the limits of certain statutes for that purpose made and provided.
Therefore, its work is a blend or mayonnaise of law with science
and technology. In the case of a patent, as with a contract,
the wording is quite as important as the matter; what it covers
depends upon what it says and how it says it, and not at all upon
what it ought to say or ought to mean. A patent, to quote good
old Dr. Squibb's statement, is a "law of the land;" and it is not
to be granted without due consideration of all the legalities.
When an application is filed, whether the invention be in de-
termining the parallax of the fixed stars, in curing meat, or in
sewing shoes, it is first referred to Examiners who are supposed
to be expert in the particular art, familiar with everything that
has ever been done in it, and prepared to understand the new
thing; and to be able to apply their knowledge to it in view of
the numerous controlling decisions in patent cases. Which is a
quite considerable requirement; but normally the Patent Office
gets away with it. The examining branches, of which there are
some forty odd, are presumed to be manned by scientific and
technical men of high standing, acquainted, among them all.
with every branch of knowledge. The Examiners are the judges
(jury maybe would be a better term) of the fact. From them
an appeal lies to a Board of Examiners-in-Chief, members of
which are appointed by the President with the consent of the
Senate. Under the law, they must be persons of "competent
legal knowledge and scientific ability." From the Board, a
further appeal lies to the Commissioner in person, who, therefore,
in this capacity acts as a court of appeals. General Dyrenforth,
himself at that time an Assistant Commissioner of Patents, sum-
marized the procedure neatly, albeit somewhat scurrilously, per-
haps, in saying: "A case first goes to an Examiner who knows
the facts but not the law, then to the Examiners-in-Chief, who
know the law but not the facts, and then to the Commissioner
who knows neither."
In all its functions, the Patent Office acts as a tribunal to try
and ascertain fact and law. It settles the question of ownership
as regards certain alleged treasure trove between the inventor
and the public, or between rival inventors, as the case may be.
The Examiners are triers of fact, the Commissioner settles the
law, and the Board tries both fact and law. In each and every
activity, the Patent Office acts as an adjudicating body; not as
an executive body. It is really a court and should rank as such;
not as a bureau of an executive department.
The importance of all this is that very much depends indus-
trially on the kind and quality of patents we are to grant; on the
accurate working of our patent system. Bad patents, of which
there are many, are as much of a public nuisance as good patents
are of public benefit. All applications for patent should be as
carefully scrutinized and examined as human ability will permit,
and the interlocking team work on fact and law provided for by
statute in the Patent Office should be at least as good as that on
a baseball nine. Any patent may furnish the basis for litigation,
often bitter and prolonged, and the more there is of this, the
worse. Well-drawn, proper patents, like well-drawn contracts,
seldom get into court; they are respected. A good patent on a
good invention seldom needs litigation; the respective rights of
470
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
the inventor and of the public have been settled in the Patent
Office, once for all. On the other hand, a weak patent on some-
thing of importance usually does go to court and proves expensive
for the owner, the industry, and the public at large. Frequently
in such a case, where the patentee is lucky, the courts by judicial
interpretation give the patent the form and meaning in which
it should have emerged from the Patent Office in the first place.
It is better for everybody that a patent, if granted, should be well
granted. And to do this, it is necessary that the Office be
manned and headed by competent men taking pride in their
work and working together.
SUGGESTIONS FOR IMPROVEMENT
What the Smoot-Reavis committee on reorganization should
do, in my opinion, is to lift the Patent Office from its lowly place
in the Interior Department and make it independent, affiliating
it with the judicial branches and not with the executive. I
think it should be renamed the "Court of Patents," and headed
by a judge taken from the federal bench; preferably a good crisp
one. The Examiners should be high-class men, looking forward
to a career in the Office, and with office conditions made attractive
to them — much more attractive than they are now. All this
will of course cost more money; but why not? It is not the
Government's cash or the taxpayer's cash — it is the money of
those doing business with the Patent Office. And those who pay
the fees are entitled to get service for their money; service of a
grade that they do not receive to-day.
The increase of filing fees provided for by the Nolan Bill is all
right in and of itself, if it helps better the Patent Office. The
present fees are not burdensome, nor would the increase hurt
anybody. But what's the use of providing more income to an
institution that is already charging more than the value of the
services it renders! Put the Patent Office on a better footing
and then charge more.
It is simply absurd to take the money of the inventors and
use it to run a postgraduate kindergarten for patent attorneys.
The Chemical Industry from a Tariff' Viewpoint'
By C. R. DeLong
Chief Chemist of the U. S Tariff Co:
FUNCTIONS AND DUTIES OF THE UNITED STATES TARIFF
COMMISSION
As many of you probably know, the Tariff Commission was
created for the express purpose of compiling facts and informa-
tion for the use of Congress in its revision of the tariff laws.
The Commission makes no recommendations in regard to rates
of duty or as to tariff policy. One of the principal ways in which
the Commission has furnished its information to Congress has
been in the form of the so-called Tariff Information Surveys.
These surveys, following a more or less standard outline, attempt
to give, in language which the layman can understand, the facts
essential to a comprehension of the tariff problems involved by
each chemical commodity mentioned in the tariff act. The sur-
vey gives a description of the article under discussion, pointing
out its various grades and uses. It then takes up the domestic
production of the article, pointing out the raw materials required
and, if not available from domestic sources, to what extent the
industry must rely on imports for these materials. A brief de-
scription of the process of manufacture is given in order to indi-
cate whether or not it is complicated and whether it requires a
high degree of skill and chemical control. The relation of do-
mestic production to total consumption is pointed out in order
to show to what extent the domestic consumer is dependent
upon imports for his supply of any given chemical and from what
countries these imports must come. If a commodity is one in
which the United States' production exceeds the consumption
and an exportable surplus exists, the principal countries of des-
tination are shown and the export trade is discussed. The sur-
vey also shows the rate of duty on any given article under the
various tariff acts since 1883 and gives decisions by the Treasury
Department and the Court of Customs Appeals regarding classi-
fication of chemicals under these laws. The decisions are more
important than the average layman would think, as in many-
cases they change the apparent intent of the law.
The question naturally arises as to the use Congress has
made of the surveys in connection with the coming tariff re-
vision. A brief summary setting out the salient features of the
competitive situation in each industry affected by the tariff
was published for use of the Committee on Ways and Means,
and was constantly referred to during the recent tariff hearings.
Recently, all of the surveys were published in detail for use of
this committee. In the chemical schedule a total of 175 surveys,
1 Presented before the Washington Section oF the American Chemical
Sjeiety, Washington. D. C, March 25. 1921.
•ashinoton, D. C.
covering from 400 to 500 chemical commodities, were published
in 28 pamphlets which totaled nearly 3000 pages. I think I may
safely say that this is the first time in the history of tariff revision
that committees of Congress have had such comprehensive and
detailed information at hand on all articles in the tariff law.
INDIRECT COMPETITION
Next I should like to take up some of the more important
questions which arise in tariff consideration of chemical commodi-
ties. In addition to direct competition offered by imports of the
same chemical, we very often have to consider indirect compe-
tition by similar commodities which are of a competitive nature.
One of the most striking examples of indirect competition is
afforded by the vegetable oils. As you all know, practically any
vegetable oil may be used in the manufacture of soap and also,
if properly refined, in the manufacture of food products, such as
butter and lard substitutes. Taking the case of cottonseed oil:
no direct tariff problem is presented by cottonseed oil itself,
since it is produced in large quantities and a considerable surplus
is exported. However, the indirect competition offered by soy-
bean and peanut oils is an important factor in the tariff con-
sideration of cottonseed oil. The competition which vegetable
oils — in the form of oleomargarine and butter substitutes — offer
to the dairy interests is another important consideration.
Another case similar to vegetable oil is that of the starches.
There are practically no imports of corn starch itself,
but the competition of the other starches, such as potato
starch and the so-called sago and tapioca flours, greatly com-
plicates the tariff problems of the domestic cornstarch industry.
The Tariff Commission has made a careful inquiry as to the
competition between these various starches, particularly in the
textile industry, and has estimated the percentages of the various
starches used in the different industries. This inquiry has re-
vealed that certain starches have preferential uses and therefore
command higher prices for these uses than do other starches.
COMPENSATORY DUTIES
The problem of compensatory duty, or the adjustment of duties
on raw materials and finished products, offers varied tariff prob-
lems. These duties are based on the theory that any duty placed
on a raw material should be compensated for by a corresponding
increase in duty on the finished product. Let us take, for ex-
ample, the case of barytes and lithopone. Here we have a case
in which the raw material for the manufacture of lithopone was
almost exclusively imported before the war. During the war
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
471
the manufacturers of lithopone were forced to develop domestic
supplies of barytes in order to have an adequate supply of raw
material. The Commission has made a detailed investigation
of the cost of manufacturing lithopone and of mining barytes
in order to ascertain the extent to which barytes enters into the
total cost of lithopone.
Along this same line, a study of the relation between the duties
on oil seeds and oils shows that under the present tariff law there
is no definite policy or uniform treatment of this important group
of commodities. In some cases both the oil seeds and the oils
are free of duty. In other cases, the duties on the seeds and the
oils are so adjusted that there is a differential in favor of im-
porting and crushing the seeds in this country; and in still other
cases there is a differential in duties which favors crushing the
seeds in foreign countries and importing the oils. In order to
have adequate information for considering compensating duties
on vegetable oils, the Tariff Commission has made a detailed
study of the yields obtained in crushing the various oil seeds.
Another case is that of compensating duties placed on certain
manufactured articles in order to offset the internal revenue tax
on alcohol which the domestic manufacturers of these articles
must pay. For example, perfumery must be made from prac-
tically absolute grain alcohol, and therefore the domestic manu-
facturers must pay a high internal revenue tax on all alcohol used.
In certain of the foreign countries, however, no internal revenue
taxes are levied on grain alcohol. In order to offset this differ-
ence in the cost of raw materials, such additional duty is levied
on alcoholic perfumery as will compensate for the internal revenue
tax.
• COST OF PRODUCTION
I will not attempt to discuss the somewhat controversial theory
that tariff duties should be based on the difference of cost of
production at home and abroad, on the assumption that thus a
competitive market is created. In addition to this function,
costs often serve as an aid in arriving at compensatory duties,
which have been previously discussed. With changing industrial
conditions — such as decreases in wages and cost of raw mate-
rials^— it is a matter of doubt as to whether or not the cost of
production at the present time will accurately reflect the condi-
tions which may be expected to exist when a normal com-
petitive basis has been reached again. The Commission, how-
ever, has made several investigations as to cost of production in
the domestic chemical industry. These include, principally, the
cost of producing certain intermediates and dyes, barytes, barium
chemicals, lithopone, the cost of refining sugar, and the cost of
production of ferroalloys.
In many of the cost investigations the Commission found that
costs varied widely in the same industry and there was very
little uniformity in cost-finding methods. In the industries
developed as a result of war conditions this situation may be
attributed to stress in output without regard to costs, or to proper
methods of determining costs. These conditions were found
particularly in the dye industry and in the manufacture of barium
chemicals. It is to be regretted that a large number of chemical
firms do not keep adequate cost records and that many of them
simply balance their books once a year. About all they really
know is whether they made or lost money. I think it is safe to
say that the chemical industries as compared with other industries
have been somewhat backward in the exchange of cost ideas and
the discussion of problems which are common to all manufac-
turers. It is to be hoped that if the Commission's investigations
have accomplished nothing else they have started manufacturers
to thinking more about costs and exchanging ideas in regard to
cost methods. I know that this is true in the case of the dye
industry, which has had a committee studying uniform costs and
has issued a comprehensive report on this subject Also
many firms have established adequate cost-finding methods
as a result of the Tariff Commission's investigations.
I wish to point out the service which the Tariff Commission
can be to domestic manufacturers in presenting their costs to
Congress. Very few manufacturers are willing to disclose their
individual costs in a public hearing before committees of Con-
gress. The Commission has, however, found domestic manu-
facturers always willing to submit their costs to the Commission
in confidence, so that the Commission can tabulate and com-
pare individual costs and thus arrive at an average cost or at a
method of presenting individual costs which would not reveal
confidential information of the individual manufacturer.
TARIFF CLASSIFICATION OF CHEMICALS
An attempt to classify chemical commodities for tariff purposes
presents many technical and difficult problems. I believe a brief
discussion of the different methods of classifying not only chemi-
cal, but other commodities, will bring out some important prob-
lems along this line. First, let us consider the classification of
chemicals in the tariff law by specific mention, t. e., by enumera-
tion by name. In this connection it must be remembered that
trade and commercial designations prevail over scientific no-
menclature. The average person would assume that if a
chemical is mentioned by name in the tariff act there would be
no difficulty in properly classifying and properly assessing a duty
on this commodity when imported. This method, however,
sometimes presents difficulties: for example, the present tariff
law contains a provision which reads: "Antimony oxide, salts
and compounds of, 25 per centum ad valorem." I believe that
any chemist passing on an importation of antimony oxide and
antimony sulfide — the two most important compounds of an-
timony— would classify them for duty under this provision at
25 per cent ad valorem. It has, however, been held by the
courts that these two compounds are not dutiable under this
provision but are dutiable as "chemical compoimds, not specially
provided for, at 15 per centum ad valorem." In this case the
difficulty is simply one of punctuation. The courts held that
the phrase means "salts, and compounds of antimony oxide."
As antimony oxide and antimony sulfide are not salts or com-
pounds of antimony oxide, they are therefore not dutiable under
this provision. If the comma had followed the word "antimony,"
such an interpretation would not have been possible. Another
interesting case occurred under the act of 1894 when Epsom salts
was mentioned by name both on the dutiable list and on the free
list. The courts in this case held that the provision on the free
list was a later expression of the intent of Congress, and, as in other
cases of doubt arising from ambiguity, this case had to be settled
in favor of the importer who contended that Epsom salts should
be free of duty.
You may say that this occurred back in 1894 and would not
occur at the present time. In the last session of Congress, how-
ever, a bill was introduced on a certain class of chemical com-
modities, and in this bill the same chemical compound was pro-
vided for under two different names, in one place at a rate of 2
cents per pound and in the other, at a rate of 8 cents per pound.
In the past, specific mention of chemical commodities was
necessary in order to obtain import statistics and, therefore, the
more chemical commodities which were mentioned by name the
more detailed were the import statistics of chemicals.
One method of classifying chemicals is by the law of
similitude. This method is probably more unfamiliar than any
other. If an article is not mentioned by name in the tariff law,
the question to be decided is whether or not it is like some other
article which is mentioned. The law of similitude requires that
an article must be like another article in one of four particulars,
namely, material, quality, texture, or use. This law is further
restricted in that it can be applied only to dutiable goods, that is,
a chemical commodity cannot be exempted from duty because
it is similar to an article specifically mentioned on the free list.
Some of the decisions under the law of similitude may be of
interest. Butvl alcohol has been classified bv similitude as fusel
■I 7 'J
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
oil, as both are used for the same purpose, namely, as a solvent
in the manufacture of pyroxylin plastics; spruce gum has been
classified as dutiable as chicle, both articles entering into the
manufacture of chewing gum.
If an article is not free or dutiable, either by specific mention
or by similitude, it must be classed under some general provision.
The tariff laws contain provisions known as "basket clauses,"
for example, "all other aluminium compounds" and "all chemical
and medicinal compounds, preparations, mixtures and salts, not
specially provided for." If an article is not dutiable or free
under some such provision, as a last resort to obtain revenue,
customs officials may classify it as a "non-enumerated un-
manufactured article" or as a "non-enumerated manufactured
article." In many provisions in the tariff act the classification
depends upon use. Such classification is one of the most diffi-
cult to administer, since it is impossible for the customs authori-
ties to follow an importation into commerce and ascertain its
ultimate use. In some cases use is restricted to chief use. One
of the outstanding conflicts of classification occurs in the case
of dyeing and tanning extracts of natural origin. At the present
time tanning extracts are free of duty, while all dyeing extracts
are dutiable. As you all know, many tanning and dyeing ex-
tracts are similar in origin and method of manufacture and in
many cases overlap in use. It is quite obvious that where the
same commodity is used for two purposes it is to the interest of
the importer to show that the use is as a tanning material rather
than as a dyeing material, since there would be a considerable
saving in the duty to be paid.
Another example occurs in the case of ceramic enamels. At
the present time the tariff law contains three separate and dis-
tinct provisions for ceramic enamels. White glass enamel "for
clock and watch dials" is provided for in the free list; "fusible
glass enamel" is provided for at 20 per cent ad valorem, and there
is still another provision for "glass and ceramic enamels" at 15
per cent. As a result of the provision on the free list for white
glass enamels for clock and watch dials, it was not long before
the bulk of the imports of white enamels were being imported
"for clock and watch dials." White enamel, whether used for
clock dials, window signs, or bath tubs, is of very similar composi-
tion and can be used interchangeably; also all enamels to be used
must be fusible.
Another general provision and specification is provided, classi-
fying articles according to component of chief value. For ex-
ample, salts of bismuth, tin, platinum, rhodium, gold, and silver,
are dutiable at 10 per cent if any of these constitutes the element
of chief value, whereas all other chemical compounds, not spe-
cially provided for, are dutiable at 15 per cent ad valorem.
SPECIFIC VERSUS AD VALOREM DUTIES
The question as to what kind of duties should be levied on any
given commodity, that is, whether specific or ad valorem (based
on value), is a controversial one and I shall not attempt to dis-
cuss it in detail. However, it should be pointed out that, in
particular cases, either a specific or an ad valorem rate has certain
advantages. Ad valorem duties are sometimes objected to on
the theory that they offer a chance for undervaluation of
imports. Also, at the present time they would be assessed on
depreciated currency, for under the present law all ad valorem
duties are assessed on the foreign market value. On the other
hand, it is evident that, in the case of goods varying widely in
value, an ad valorem duty would bear more evenly on the differ-
ent articles or different grades of a chemical commodity than
would a single specific duty. For example, at the present time
there is a specific duty of 1.5 cents per pound on lactic acid.
This article sells in grades ranging from a low of 22 per cent to a
high of about 85 per cent in the case of U. S. P. lactic acid. It is
very evident that if a duty of 1.5 cents per pound is adequate
on the 22 per cent lactic acid it is certainly inadequate on the
85 per cent grade. Theoretically, such cases where the grades
of the same chemicals vary widely in content this difficulty might
be overcome by assessing a specific duty on each per cent of
actual content. This method, however, presents great adminis-
trative difficulties and would be of little practical application for
the reason that every importation would offer opportunities for
litigation. Under such a method there would be constant dis-
pute between the importers' laboratory and the customhouse's
laboratory. Such difficulties may be overcome by dividing the
chemical into various strengths according to percentage content,
and so adjusted that the usual grades will come about midway
between the limits suggested. For example, in lactic acid the
division could be made 30 per cent of lactic acid. Thus, the low
grade of 22 per cent would fall below this division and there
would be few importations coming near the dividing line.
Another division could be made between 30 and 55 per cent,
the ordinary 44 per cent lactic acid falling in this grade, and still
another grade could be made of 55 per cent or more. Thus, the
66 per cent to 85 per cent lactic acid would fall in this higher
grade. Many problems of a nature similar to that of lactic
acid occur in the chemical schedule.
RECLASSIFICATION OF CHEMICALS
Some of the difficulties of classifying chemicals from a tariff
standpoint have been cited, and the question arises as to how the
difficulties may be overcome. As a result of the Commission's
study in the chemical industries, it has collected much informa-
tion which would be of service in solving many of these difficulties
of classification. At the present time, the Chemical Division of
the Commission is engaged in a reclassification of all of the chemi-
cals covered by the tariff law. An attempt is being made to
avoid conflicts in language which have caused frequent litigation
in the past; to eliminate old and obsolete names for chemical
commodities, and in addition, to insert the names of chemicals
which have become of commercial importance since the passage
of the act of 1913. I would not have you think that it is possible,
even with technical knowledge and the experience which has been
gained in the past three or four years, to prepare a tariff classifi-
cation and description of chemical commodities which would
entirely eliminate possible litigation. I do believe, however,
that certain changes in language can be made which will reduce
litigation to a minimum. Such a report on reclassification of
chemicals has been nearly completed by the Tariff Commission
and is to be presented to the Committee on Ways and Means
as an aid in the present tariff revision.1
ACKNOWLEDGMENT
The Chemical Division of the Tariff Commission has called
on and consulted freely with the chemists in other Bureaus of
the Government, as it is quite evident that a limited organization
cannot know all the highly technical details of the many branches
of the chemical industry. I wish to take this opportunity of
expressing appreciation of the hearty cooperation received by the
Chemical Division from the various experts of other Departments
of the Government service. I also wish to make acknowledg-
ment of the hearty cooperation of Dr. Grinnell Jones of Harvard
University, former chief of the chemical division, and of Sidney D.
Kirkpatrick, A. R. Willis, and W. N. Watson, chemists, on the
Tariff Commission's staff.
Shipment of Phosphate Rock from Florida
More than 1,274,000 tons of phosphate rock were shipped
from Tampa, Fla., during 1920, as compared with 289,746
tons shipped during 1919. A much larger percentage than
formerly was intended for foreign shipments, the amount being
not far behind the coastwise movement.
1 Since the presentation of this paper this report has been published by
the Tariff Commission and transmitted to the Committee on Ways and
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
473
Unit Weights for the Purchase of Reagents— II1
By W. D. Collins
Chairman, Committee on Guaranteed Reagents and Standard Apparatus, American Chemical Society
At the time of publication of a previous note2 on this subject Suggested Unit Weights {Concluded)
it spptnpH nnnpppssarv to irivp a Inn? list of rpatrpnts with sup-- Potassium Aluminium Sulfate Sodium Hydrogen Sulfite
it seemea unnecessary to give a long list 01 reagents witn sug- potassium Bromide Sodium Tetraborate
gested unit weights, since such a large proportion of the ordinary Potassium Carbonate Sodium Aluminium Sulfate
, , , , . . . . .„„ ,„„ , Potassium Chlorate Sodium Carbonate
reagents should be purchased in Units of 500 or 100 g. In Potassium Chloride Sodium Chloride
order, however, that specific recommendations from the com- £*£££ Wchromate lodlum SUSE""
mittee may be on record for a larger number of reagents, addi- Potassium Ferricyanide Sodium Nitrite
, . , , ~. „ . Potassium Ferrocyanide Sodium Phosphate
tional lists are given belOW. 1 he first Contains reagents which Potassium Hydrogen Carbonate Sodium Sulfate
should be purchased in units of 500 or 100 g„ and the second &{™ g^oxfdV'11"^ |oa|um ?&«.
gives others for which different weights are recommended. Potassium iodide (also 25 g.) Sulfur, Powdered
Potassium Nitrate Tin, Metallic
Potassium Permanganate Zinc, Metallic
Suggested Unit Weights for Reagents — II' Potassium Sulfate Zinc Oxide
(500 g. and 100 g. except as noted) Sodium Hydrogen Carbonate Zinc Sulfate
Ac'd: £a'c!um Nitrate Suggested Unit Weights for Reagents— III (In Grams)
Formic Calcium Oxide .
Hydrofluoric Calcium Phosphate Ac'dJ
Metaphosphoric Calcium Sulfate i-h,r.om.IC; '■,'., 229 2?
Oxalic Carbon Disulfide (500 g. only) Iodic Anhydride 25 5
Phosphoric Carbon Tetrachloride (500 g. Monochloroacetic . 200 2o
Tartaric only) Phosphoric Anhydride 200 25
Alcohol, Isoamvl (500 g. only) Chloroform (also 3000 g.) Pyrogallic 25
Alcohol. Methyl (500 g. only) Chromium Potassium Sulfate gosol.lc ■■■ 25
Ammonium Acetate Copper. Metallic 3,a.n?!c : 2S2 r.5
Ammonium Aluminium Sulfate Cuprous Chloride Trichloroacetic 200 25
Ammonium Nitrate Copper Nitrate Aluminium Powder 200 25
Ammonium Persulfate Cupric Oxide Aluminium Chloride 200 25
Ammonium Phosphate Copper Sulfate Ammonium eliminate 200 25
Ammonium Sodium Hydrogen Phos- Kthcr (500 g. only) Ammonium Molybdate 200 25
phate Ferric Chloride Ammonium Persulfate 200 2d
Ammonium Sulfate Ferric Ammonium Sulfate Antimony Trichloride 100 25
Aniline Ferrous Ammonium Sulfate Arsenic, Metallic 25
Antimony. Metallic Ferrous Sulfate Azolitmin lo 5
Arsenic frioxide Glycerol (500 g. only) Bismuth, Metallic. 200 25
Barium Carbonate Hydrogen Peroxide Cadmium Potassium Iodide 25
Barium Hydroxide Iron, Metallic ^arm,ln*;- ™£ o-
Bismuth Nitrate Magnesium Chloride Cobalt Nitrate 200 2o
Benzaldehyde Magnesium Oxide Cobaltic Sodium Nitrate 100 25
Cadmium, Metallic Magnesium Sulfate Diphenylamine 200 25
Cadmium Chloride Manganese Dioxide EVrfur^J--; ,S« o?
Cadmium Nitrate Manganese Sulfate Glass Wool 100 lo
Cadmium Sulfate Mercuric Chloride Iron Sulfide. 2500 oOO
Calcium Carbonate Mercuric Nitrate Lead Oxide, Yellow 200 25
Calcium Chloride Nickel Nitrate Mercuric Oxide, Yellow 200 25
Calcium Hydroxide Nickel Sulfate Mercurous Nitrate 200 25
1 Mercury. Metallic 2500 oOO
1 RpppIvmI Anril 7 1Q'51 a-Naphthol 100 25
Received April ,19 Sodium. Metallic 100 25
•This Journal, 12 (1920), 1206. Sodium Nitrite, Potassium-free 200 25
» List I published, Loc. cit. Stannous Chloride 100
SOCIAL INDUSTRIAL RELATIONS
Social Industrial Relations1
By H. W. Jordan
Syracuse, N. Y.
Until recently, making money, as much and as fast as possible,
was considered the chief end of industry. Natural resources,
labor, all else, were wasted or sacrificed as secondary. But re-
alization that modern industry is a trusteeship, that social prog-
ress and civilization stand or fall with industry; that the social
structure embodied in modern cities is coordinate with or superior
to industry; that the one is as necessary to the other as the head
is to the hands, brings us face to face with the fact that industry
cannot pay dividends of money unless the social organism pays
dividends of health and contentment, of happy marriage and
children, of artistic and intellectual achievement, of growth in
this life and preparation for the next. Industry is a means to
this end, and not the end itself. In proportion as industry not
only adapts itself to, but takes constructive leadership in social
growth, so far will industry expand and prosper.
industry is business, not charity — Action and reaction are
equal in business as they are in the material world. Business is a
river which discharges at its mouth only so much as it receives
from its sources and watershed, minus evaporation and seepage
loss along its course. If the water supply diminishes, the river
becomes smaller. It dries up if the water fails. It furnishes
i Received March 26, 1921.
power, refreshment, and fertility to the inhabitants of its valley,
only so long as the water continues steady and abundant. That
is the first principle of Social Industrial Relations, that industry
must pay or it dies.
As Roosevelt said, "There is one quality worse than hardness
of heart, and that is softness of head." The social level cannot
be raised by murky sentimentality, designed to make life arti-
ficially easy, either for labor, capital, or the public. Each has its
duties. Success depends upon their complete fulfilment, directed
to the issue that life shall pay and grow, because we steadily put
into it more than we draw out.
INDUSTRY IS DEPENDENT UPON THE SOCIAL STANDARDS of the
community, state, and nation. The highest attainments of
finance, commerce, and manufacture spring from the collective
character force of the individual, of each and every individual.
Oliver Wendell Holmes urged as an addition to the church
litany, "From mediocrity, good Lord, deliver us." Continuance
and increase of the intrinsic value of our engineering plants and
of our individual investments in homes, life insurance, savings,
and all else, depend upon protecting them from the deteriorating
influences of mediocrity, and the confiscatory public spirit arising
from it. Our children and successors must be guarded against
474
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
state confiscation, or so-called nationalization of industry, by
raising individuality and intellectual standards of life to the
utmost, rather than flattening down high achievement in order
to reward the commonplace and the undeserving.
OUR WORK MUST BE FOUNDED ON THE LAWS OF EVOLUTION,
the struggle for existence, the survival of the fittest, and those
fundamentals which Darwin and his successors demonstrated be-
yond shadow of doubt. As Darwin said,
Battle within battle must be continually recurring with varying
success; and yet in the long run the forces are so nicely balanced
that the face of nature remains for long periods of time uniform,
though assuredly the merest trifle would give the victory to one
organic being over another. Nevertheless, so profound is our
ignorance, and so high our presumption, that we marvel when
we hear of the extinction of an organic being; and as we do not
see the cause, we invoke cataclysms to desolate the world, or
invent laws on the duration of the forms of life!
IT IS EVIDENT BEYOND QUESTION THAT THE LAW OF EVO-
LUTION, by which extreme specialization results in reversion to
original type or in extinction, is at work, rapidly and con-
spicuously. And that the swift decline in individual and
public mental tone and in the versatility, resourcefulness, and
efficiency of workers, manual and mental, is due to the destructive
effect of the extreme specialization which modern industry has
instituted in the conduct of its manufacturing and commercial
operations.
Automatic machine efficiency, which reduces the worker to
an automaton, will destroy us through its reflex of social medi-
ocrity, unless industry devises a new social order which adds far
more than sufficient versatility to life to offset the benumbing
industrial routine of the vast majority of the workers. "Just
as the soil requires rotation of crops to produce the best results,
so the soil of our inner being requires variety of treatment in
order to remain vigorous, elastic, and fertile and to enable us to
produce the best of which we are capable," says Otto H.
Kami.
WE NEED TO RECOGNIZE THE PROBABILITY, THE CERTAINTY,
that the twentieth century is to be one of extreme mental
growth and applied mental science, as the nineteenth century
was of material growth and applied material science. Those
industries that first grasp this idea, utilize it, and apply it
scientifically and conscientiously, not only to themselves, but to
the public and the social structure, will be the most successful
and profitable. Of all things, the mind is the only one that is
unlimited in its possibilities, and as we truly develop and expand
the mind, not of the few, but of the many, we advance civili-
zation, with its demands for more and better things. In the
aggregate, the possible achievements of mankind, through culti-
vation of mind and intellectuality, are beyond measure of con-
ception. If but a tiny percentage of the attainable results be
reached in our generation, the world of business and industry
will be expanded enormously.
WE MUST ASSURE CONTINUANCE OF OUR INDUSTRIES TO OUR
children, grandchildren, and successors. When we consider
that the ways by which most people earned their living forty
years ago have ceased or have utterly changed, it requires no
keen foresight to realize that swiftly accumulating detrimental
influences, if unrestrained, may wholly deprive our successors
of management and possession of our present industries
within our own possible lifetime of forty more years. As Roose-
velt said, "The greatest good to the greatest number, applies
to the number in the womb of time, compared to which those
now alive form but an insignificant fraction." Destruction of
our eastern and middle west lumber resources, since 1870, is a
case in point. "If unchecked popular rule means unlimited
waste and destruction of national resources, which by right be-
long as much to subsequent generations as to the present genera-
tion, then it is sure proof that the present generation is not really
fit for self-control," Roosevelt adds. This applies quite as much
to the conservation of commonsense, of individualistic, versatile,
pioneer, American character and of intellectual standards of life,
as it does to coal, forests, or water powers.
SO LET US STUDY THE SOCIAL FACTORS IN INDUSTRY. Let
us assemble the opinions of social students and begin to evolve
the sciences of social industrial engineering, through which to
apply those sciences to our national industrial program.
"the events of The coming year will not be shaped by
the deliberate acts of statesmen, but by the hidden currents
flowing continually beneath the surface of political history, of
which no one can predict the outcome. In one way only can we
influence these hidden currents — by setting in motion those
forces of instruction and imagination which change opinion.
The assertion of truth, the unveiling of illusion, the dissipation
of hate, the enlargement and instruction of men's hearts and
minds, must be the means." J. M. Keynes, author of "Eco-
nomic Consequences of the Peace."
an extensive literature is presenting the views of
thinkers of all nations upon constructive social action through
science. "Democracy and the Human Equation," by Alleyne
Ireland, is one such book. Every student of American govern-
ment should read it. He says,
"The American people have been led to adopt a rhapsodical,
an exaggeratedly ecstatic, spread-eagle position toward their
Government, and have thus lost all sense of the proper functions
of Government, as well as of the proper administration of Gov-
ernment. There has never been undertaken, either in the United
States or in any other country, a comprehensive, scientific study
of comparative government. In consequence, there is no science
of Government.
"What is now needed is that special knowledge of the biologist,
the psychologist, the sociologist, and of the political scientist
should be coordinated in an exhaustive enquiry into the form and
function of Government. The value of such an enquiry would
be inestimable. As things are now, we afford the peculiar
spectacle of a people who apply twentieth century methods to
twentieth century problems in engineering, chemistry, medicine,
surgery, and industry, and who in Government approach the
problems of the twentieth century with the theories and imple-
ments of the eighteenth century.
"Investigation of the evils which inevitably flow from bad legis-
lation is offered the people as a substitute for that good legislation
which would have averted the evils. Many such investigations
are notoriously insincere and inefficient."
They merely provide a scapegoat.
it is characteristic of man that he clings to most of his
habits long after their purpose has ceased and their origin been
forgotten. Although we have evolved a tremendously in-
tricate and effective technique in commerce and industry, by
research and applied science, yet we continue to fool ourselves
with the habit opinion that city, state, and national government
is still in the cast iron, hand-stirred kettle stage. Like a pro-
testing, hour-old baby, hanging his whole weight by one hand
grasped around a lead pencil, we cling to our habit notions of
town-meeting government.
The remedy is study of comparative government, by the
scientific research method used in chemistry, engineering, biology,
and surgery-
Spare Time — A Criticism
Editor of the Journal of Industrial and Engineering Chemistry:
In This Journal, 13 (1921), 253, there appeared a contribution
entitled "Spare Time" by H. W. Jordan. I can find in the
article no reference to chemistry, engineering, or any other science,
unless it be philosophy, and I am still wondering what place it
has in our Journal. It would probably be more appropriate
coming from the pulpit, but as it has been published in the Jour-
nal, I hope you will allow me space for a brief note on it. My
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
475
chief reason for taking your time and my own for these remarks
is that I am afraid that some of our young chemists may get un-
scientific ideas, such as, for instance, that they should not special-
ize in their profession, if no notice is taken of this unscientific
article. In addition, it is hardly necessary to state that I disa-
gree with nearly every idea expressed, and it therefore requires
little effort to comment on it. I should not want my son to read
it and retain the thought that we should not advance in civiliza-
tion, but should try to go backward and live as our grandparents
did. It is possible that other chemists' sons may also benefit
by this criticism.
The title of the article in question is "Spare Time," and the
first paragraph is given up to the question of what are we doing
with the spare time given us by reason of the use of machinery
instead of our hands. In looking the article through carefully
I cannot find the answer to the question. It is possible that the
answer which the writer wishes to convey, but which is ob-
scured by disconnected expression, is that we should bowl, play
in the band, play checkers, whist, study the play, or knit, any one
of these things. This is the only idea in the article in which the
present writer can concur. But even in this Mr. Jordan is in-
consistent. In fact the whole thing is full of inconsistencies.
If we do any of the things mentioned we are instructed to do
them well. Very good. But are we instructed to do them all
well, or just one of them well, and some of the others passably?
If the latter, what is that but specializing? If the former, then
we are going backward to our forefathers' time and doing a little
bit of everything, and nothing very well. What is it about the
Jack-of-all-trades? Does he very often succeed in any one of
them? No. He is a brother to the rolling stone. But these things
are amusements, and while it may be possible for a man, who has
nothing else to do, to be a good bridge player and also a good
bowler, when it comes to science and making a living with it, it is
entirely different. Can you visualize a chemist who is an ex-
pert, an international authority, on leather and steel, at one and
the same time? Can a surgeon be a throat specialist and an ex-
pert on women's diseases at one and the same time? Mr. Jordan
should know that a specialized leather chemist can analyze a
tannery product, almost while the unspecialized chemist is going
to the library to look for a book on the subject. He has the ex-
perience and the equipment. The goiter surgeon can remove a
serious goiter in forty minutes, before the general practitioner
can word a telegram to him for advice. In fact, I think there
is at least one surgeon who does nothing else but operate for
goiter, and yet I doubt if he is narrow and can converse on
nothing else, as the article claims. The expert diagnostician of
to-day can tell Mr. Jordan what is the matter with him, with the
aid of machines, almost before the country doctor can crank up
his Ford preparatory to a long trip over muddy roads. I gather
that Mr. Jordan would rather die of old-fashioned belly ache as
the pioneers had to do, than have his appendix removed and live
happily ever after.
Now, why should it be necessary for these specialists to "track
game for miles through the New England woods" before they
could get their dinner, and if they did, would they also know how
to prolong our lives and tell us what is wrong or right in our
factories? Are not these specialists worth more to the world
than the old timer living forty miles from a railroad who is able
to live without the assistance of any "furriners?"
I was once told that everybody should be obliged to raise their
own food. This is along the same lines as Mr. Jordan writes.
Let us follow that idea up a minute. If the farmer maintains
that I should raise my own food, then I can say that he should
make his own leather and shoes. Shoes are usually necessary,
although not as necessary as food, I admit. But, at any rate,
the end of this idea is living like the early settlers, as Mr. Jordan
seems to advocate. Our ancestors made their own leather and
shoes, I grant you, but did they make them well and econom-
ically? Did they know how to do what they had to do? I am
sure they did not. I have no quarrel with them, of course.
They had to do everything for themselves and they did it. They
were fortunate if they got their routine work done and had a little
time left to sleep each day. But gradually, owing to their energy
and progressiveness, times got easier. Some man decided to make
shoes for his neighbor, and let his neighbor raise his food in
return. He specialized, and neither he nor his neighbor had to
work so long or so hard. They deserve all the credit possible,
but I have no patience for anyone who would discard all the
advantages we have to-day, and return to those conditions. I
gather that Mr. Jordan would do away with our machines and
use nothing but our muscles. Perhaps he belongs to a Jt.bor
union.
Let me cite an example of the present time showing what I
mean by saying that the pioneers did not know how to do any
one thing well. I once had to live in a small country town, where
the old timers, among other things, repaired their own shoes.
After a while it was suggested to some of them that they could
make an easy living by setting up a shop and repairing shoes for
some of us who didn't care to learn how to do it for ourselves.
A few trials of the shop, however, were enough to convince us
that it would be cheaper and save doctor's bills to throw the
shoes away rather than wear them after the local cobbler had1
returned them. None of them knew their business. They had!
never learned it but had repaired their own shoes in a way that
they thought was right. Water would get under the sole and
wet the feet about as quickly as with the worn-out sole. Then
the sole would part from the welt in a few days. These men
were not specialists. Our city cobblers are not highly specialized
or educated men, but I never had such trouble with repaired
shoes when dealing with them. They at least know their business
as a rule. If the country cobblers knew how to make hens lay,
that did not make my soles stay on, and that is what I wanted
of the cobbler. I wanted a specialist, and I did not care if he
knew nothing else.
One idea which I think Mr. Jordan would like to give us is that
if one were to be cast away on a desert island like Robinson
Crusoe, the specialized city man would die while the man-of-all-
trades would survive. I think this is true. It is probably also
true, as the writer states, that "many other keen faculties of ear,
eye or hand that we were forced to use before we got our easy
jobs on automatic machines are fading away." But we have
acquired the automobile eye and ear, and these might be of more
use to us on Broadway then the "hunter's sense of trailing."
After considering the percentage probability I have decided that
I shall not stop specializing and prepare for the desert island, nor
stay away from New York because a good many people are killed
by automobiles and gunmen.
Why does Mr. Jordan permit us to enjoy amateur music,
amateur drama, gardening, etc., and condemn what he terms
the "talking machine" and moving pictures, which he says
"cannot be endured yesterday, to-day, and forever?" Is it
because they go by machinery? Why did he not include what
he would probably have called the "mechanical piano?" There
are different kinds of phonograph records, player rolls and mov-
ing picture films, but, considering the good ones, what has done
more for education than these three modern inventions? Mov-
ing pictures are now being used for the advancement of scientific
education. (See the January issue of the "Technology Review,"
published by the Alumni Association of Massachusetts Institute
of Technology.) Many a farmer's family is now familiar with
all the best music, and can converse about the old and new mas-
ters because of the phonograph. It is true that the phonograph
does not involve the personal eduation as amateur music does,
but nevertheless it is, or can be, an education, and the player
piano requires a more delicate touch and musical ear than most
people realize. Far from having to endure the moving pictures
470
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
forever, we want them forever, they are here forever, and the
reformers are not strong enough to take them away from us.
Mr. Jordan need not worry about our spare time; whether we go
to the movies to see a story by Dickens, Fenimore Cooper, or
Mark Twain, or listen to Caruso singing a Verdi opera while
Elman plays it, on the phonograph, as long as we don't waste
it in trying to make our own clothing or raise a steer, when we
know nothing about it.
Our best advice to the young chemist to-day is to specialize,
specialize, and then specialize more. There is no danger of get-
ting narrow.
Laboratory of F- °- SpRAGUE
Transylvania Tanning Co.,
Toxaway Tanning Co.,
Rosman Tanning Extract Co.,
Brevard, N. C.
March 27, 1921
A SELECTED BIBLIOGRAPHY OF BOOKS, IN THE ENGLISH
LANGUAGE, DEALING WITH CERAMIC CHEMISTRY
AND THE CERAMIC INDUSTRIES1
Prepared under the Auspices of the American Ceramic Society's Committee on Cooperation
Supplementary to the Section on "Industrial Inorganic Chemistry" in "Chemical Reading Courses," This Journal, 12 (1920), 701, SOG
Chemistry and the Ceramic Industries
By E. W. Washburn
SCOPE OF THE FIELD
A detailed discussion of this topic may be found in the report
of the American Ceramic Society's Committee on "Definition
of the term 'Ceramics' " (Journal of the American Ceramic
Society, 3 (1920), 526). Briefly, the ceramic industries may be
defined as those industries which manufacture products by the
action of heat on raw materials, most of which are of an earthy
nature, such as clay, sand, etc. The products of these indus-
tries include all kinds of "burned" clay products; cements, such
as portland cement, lime, plaster, etc.; all varieties of glass and
glassware, including quartz glass, glazes, and enamels; artificial
precious stones; enameled metals; refractory materials; and
abrasives.
SILICON AND ITS COMPOUNDS
Owing to the importance and widespread use of silica and the
silicates in the manufacture of the above classes of ceramic
products, the term silicate industries is sometimes employed
to designate the ceramic industries. Indeed, it would not be
inappropriate to employ the term ceramic chemistry to cover
the chemistry of the compounds of silicon in much the same
way as the term organic chemistry is employed to designate the
chemistry of the compounds of carbon.
THE WAR AND THE CERAMIC INDUSTRIES
Although the origin of many of the ceramic industries ante-
dates history itself, many of them have only recently begun to
make any extensive use of applied science.. This condition is,
however, gradually changing, and the ceramic industries are
to-day demanding the services of the chemist and engineer in
rapidly increasing numbers. The war acted as a powerful
stimulus to research in many fields of ceramics, notably in
optical glass, porcelain, refractory materials, and methods of
utilizing American clays and other raw materials in place of
foreign materials previously employed.
CERAMIC LITERATURE
Unfortunately for the general reader desirous of familiarizing
himself with recent developments in chemistry as applied to
the ceramic industries, most of the information is not available
in book form, but must be sought in the pages of scientific and
technical journals. Those devoted especially to this field are
the Journal (formerly the Transactions) of the American Ceramic
Society, the Transactions of the (English) Ceramic Society, and
the Journal of the (English) Society of Glass Technology. Many
papers of interest to the general reader will be found in the
pages of these journals.
Many of the books in this field are now largely out of date,
and in some branches of the subject they are nonexistent.
' Received December 15,1920.
Thus, there is no book in the English language which deals with
the chemistry of the compounds of silica and the other refrac-
tory earths at high temperatures, a branch of science of funda-
mental importance to all of the ceramic industries. It is en-
couraging to note, however, that a monograph on this subject
is promised in the American Chemical Society's forthcoming
series of scientific and technical monographs.
Of books which can be said to give a survey of the entire
field of ceramics with chapters on each branch of the subject,
Martin's "Industrial Chemistry, Inorganic," Vol. II (Appleton,
New York, 1918) seems to be the only representative. How-
ever, certain annuals, such as "The Mineral Industry" (McGraw-
Hill Book Co., New York) and "Mineral Resources" (U. S.
Geological Survey), should perhaps be placed under this head-
ing also, although of course the ceramic industries are only a
part of the field covered by them. Such other literature as is
available in the English language in book form at the present
time is given in the classified list which follows.
Clays and Clay Products
By C. W. Parmelee
"Clays and Clay Products," by A. B. Searle (Sir Isaac Pit-
man S: Sons, Ltd., New York), is designed to give the practical
man or beginner an insight into the nature of the various ma-
terials and products, as well as the processes used in the clay-
working industry. It is a good elementary treatment of the
subject according to English practice. *
The "Clay Worker's Handbook," by Alfred B. Searle (C.
Griffin & Co., Ltd., London, 1911), is intended for the reader
who has some knowledge of the subject or who wishes more de-
tailed information regarding the materials and their properties.
"Notes on the Manufacture of Earthenware," by E. A. Sande-
man (Crosby, Lockwood and Son, London, 1917), describes in
much detail the processes of manufacture employed by the
potter. It is a nontechnical book in which English methods
are fully described.
"A Treatise on the Ceramic Industry," by E. Bourry, trans-
lated by A. B. Searle (Scott, Greenwood and Son, London, 1911),
is a comprehensive treatment of the whole subject of the produc-
tion of clay wares according to European practice.
"The Potter's Craft," by Prof. Chas. F. Binns (D.VanNos-
trand Co., New York, 1910), is an excellent book for the amateur
potter and manual training teacher. Methods of manufacture
suited to the needs of such readers are described.
"The Manufacture of Roofing Tile," by Orton and Worcester
(Ohio Geological Survey, 1910), is an excellent presentation of
the technology of such products. The general principles and
processes described are applicable to a wider range of wares
than is indicated bv the title.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
477
"Clays, Their Occurrence, Properties and Uses," by Dr. H.
Ries (John Wiley and Sons, New York, 1914), is an excellent
book which touches only lightly on the technology of clay wares.
It is best adapted for the advanced student who has had suffi-
cient preparation in the sciences to secure the largest benefit
from its pages.
"The Pottery Industry" (U. S. Department of Commerce,
Miscellaneous Series 21, 1915) contains a wealth of material on
the technology, economics, and other phases of the pottery
industry in this country, England, Germany, and Austria. It is
largely statistical.
"Burning of Clay Wares," by Ellis Lovejoy (T. A. Randall
and Co., Indianapolis, Indiana, 1920). The treatment of the
subject is very thorough. A large amount of space is given to
the discussion of kilns, their construction and operation. It is
a very useful book.
"The Collected Writings of Herman Seger," translated by
the American Ceramic Society (Chemical Publishing Co.,
Easton, Pa., 1902), is a collection of papers on the technology
of clay wares which are of value to one who has had an adequate
preparation in the sciences.
The U. S. Bureau of Standards, the U. S. Bureau of Mines,
the U. S. Geological Survey and many state Geological Surveys
publish frequent papers dealing with clays and clay products.
Glass and Glass Manufacture
By E. W. Washburn
During the war much publicity was given to the subject of
optical glass. Important as such special glasses are, however,
they form an almost insignificant portion of the whole glass
industry, which in 1920 numbered 369 factories in the United
States.
As an introduction to the subject of glass technology, Mars-
ton's excellent little book, "Glass and Glass Manufacture" (Sir
Isaac Pitman and Sons, Ltd., New York), may be recommended.
This work, after a short historical introduction, discusses in
simple nontechnical language the main facts concerning the
physics and chemistry of glass and glass making, together with
a description of the manufacturing processes as carried out in
England and on the Continent. American methods are, how-
ever, not touched upon by Marston, and unfortunately there is
not as yet any book on the subject which can be recommended
as giving an adequate discussion of American methods. The
nearest approach to such a book may perhaps be found in the
material included in Fettke's "Glass Manufacture and the
Glass Sand Industry" (Topographic and Geological Survey of
Pennsylvania, Report 12, 1919), and Palmer's "The Glass In-
dustry" (U. S. Bureau of Foreign and Domestic Commerce,
Report 60, 1917). The latter publication contains an excellent
bibliography of 460 selected titles dealing with glass.
The most up-to-date and scientific treatise in the English
language on glass technology is probably Rosenhaiu's "Glass
Manufacture" (Constable and Co., Ltd., London, 1919).
The physical properties of glass and their application to the
manufacture of glass apparatus and instruments are discussed
by Hovestadt in his "Jena Glass," translated by J. D. and A.
Everatt (Macmillan and Co., New York, 1902).
Vitreous Enamels
By C. W. Parmelee
"Materials and Methods Used in the Manufacture of Enam-
elled Cast Iron Wares," by H. F. Staley (Technologic Paper
142), and "Enamels for Sheet Iron and Steel," by J. B. Shaw
{Technologic Paper 165), both published by the U. S. Bureau of
Standards, are the most useful discussions of the subjects which
we have.
"Raw Materials of the Enamel Industry," by Julius Grtin-
wald, translated by H. H. Hodge (Chas. Griffin and Co., Ltd.,
London, 1914), and "The Theory and Practice of Enamelling on
Iron and Steel," by the same author and translator (Griffin and
Co.), should also be mentioned.
"Enamels and Enamelling," by Paul Randau, translated by
Chas. Salter (Scott Greenwood and Son, London, 2nd Ed.,
1912), contains some material relating to special enamels for
watch dials, jewelry, etc., which are not discussed in the books
previously mentioned.
Refractories
By E. W. Washburn
It has been said that the "future industrial success of any
country will largely depend upon the extent to which it devel-
ops high-temperature processes." Refractory articles, crucibles,
retorts, fire brick, furnace parts, etc., are a prime necessity to
all high-temperature manufacturing processes. The metallur-
gical industries, the gas and coke industry, and all of the ceramic
industries are large consumers of refractory products.
Searle's "Refractory Materials, Their Manufacture and Uses"
(Lippincott and Co., Philadelphia, 1917) is the most recent
book in this field, but deals more particularly with British
practice. Havard's "Refractories and Furnaces" (McGraw-
Hill Book Co., New York, 1912) is especially valuable for its
treatment of metallurgical refractories. Ross's "Silica Refrac-
tories" (U. S. Bureau of Standards, Technologic Paper 116)
gives a good description of the chemistry and manufacturing
methods of this important group of refractories. A survey of
the field with reference to the scientific problems which it pre-
sents is given in National Research Council Circular 3 (National
Research Council, Washington, 1919).
Cements, Limes and Plasters
By R. K. Hursh
"Constitution of the Hydraulic Mortars," H. LeChatelier,
translated by J. F. March (McGraw-Hill Book Co., New York,
1905). The researches of this author, published first in 1877,
represent some of the most significant work in the studies of the
constitution of Portland cement. He introduced microscopic
methods which have since become of great importance in the
investigation of this field. The work is now largely of historical
interest.
"Manufacture of Hydraulic Cements," by A. V. Bleininger
(Geological Survey of Ohio, Bulletin 3, 4th Series, 1904). The
nature of the raw materials and the properties of natural and
pozzolana cements are taken up in the first chapters of the
report. A resume of the previous investigations into the nature
of portland cement, the methods of compounding cement mix-
tures, and experimental studies on the limits of composition by
the author are followed by a discussion of manufacturing and
burning processes and equipment and methods of testing the
finished cement.
"The Chemistry and Testing of Cement," by C. H. Desch
(Longmans, Green and Co., New York, 1911). This book in-
cludes a brief history of the development of calcareous cements,
a discussion of the materials used, the chemical components
and the mineral constitution, the processes of setting and hard-
ening of lime, plaster, and calcareous silicate cements, the phys-
ical properties of portland cement, and of concretes and arti-
ficial stones. Reference is made to the earlier work of the
Geophysical Laboratory of the Carnegie Institution, but con-
478
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
siderable development has been made in our knowledge of the
constitution and setting reactions of portland cement since the
book was written.
"Portland Cement," by R. K. Meade (The Chemical Pub-
lishing Co., Easton, Pa., 2nd edition, 1911), is a brief resume
of the development of the portland cement industry in the
United States, followed by a discussion of the nature and com-
position of cement in which reference is made to the more
significant researches up to the time of writing. It includes
the more important conclusions with reference to the constitu-
tion of portland cement developed by the work of Shepherd
and Rankin at the Geophysical Laboratory on the ternary sys-
tem CaO-AhOs-SiOj. The limits of composition, the propor-
tioning of mixtures and the characteristics of typical raw ma-
terials are discussed at length. The main part of the book is
devoted to manufacturing processes, descriptions of machinery
and equipment, and the operation of rotary kilns. There is
also an extensive discussion of the analysis and testing of raw
materia's and finished cement.
"The Portland Cement Industry," by W. A. Brown (D. Van
Nostrand Co., 1917), deals with the design and equipment of
modern portland cement plants from the standpoint of the
engineer, beginning with quarry practice. The types of crush-
ing, grinding, screening, and conveying machinery, their construc-
tion, operation, and capacities are discussed in a clear but con-
cise manner.
The rotary kiln and fuel for cement burning are briefly dis-
cussed. The selection of power-plant equipment for cement
plants is given considerable attention. A chapter on costs and
cost keeping is included. The equipment of several commercial
plants is described and finally the standard tests are discussed
somewhat briefly.
"Portland Cement Resources of Illinois," by A. V. Bleininger,
E. F. Lewis and F. E. Layman (Illinois Geological Survey.
Bulletin 17, 1912). The report first takes up the raw materials
for portland cement and the function of various constituents,
the composition of the mixture and methods of correcting de-
fects of clinker and cement. The mechanical equipment of
cement plants and manufacturing processes are briefly con-
sidered. The results of a survey of the limestone and clay
resources of the state complete the report.
"Hydration of Portland Cement," by A. A. Klein and A. J.
Phillips (U. S. Bureau of Standards, Technologic Paper 43, 1914).
The various silicates and aluminates found to exist in portland
cement have been carefully prepared, and their behavior during
hydration has been studied under various conditions both sep-
arately and in mixtures. The results on the single compounds
and on cements show the processes of hydration and setting
clearly. It is a valuable contribution to our knowledge of port-
land cement.
"The Constituents of Portland Cement Clinker" (1915), and
"Portland Cement" (1916), both by G. A. Rankin, constitute
Publications 218 and 244, respectively, of the Geophysical Lab-
oratory of the Carnegie Institution of Washington. They deal
especially with the physical chemistry of the subject and present
fully the present state of our knowledge of this field.
NOTES AND CORRESPONDENCE
The Industrial Fellowships of the Mellon
Institute
The eighth annual report of the Director of the Mellon Institute,
Dr. Raymond F. Bacon, covers the activities and progress of the
industrial fellowship system during the year ending February
28, 1921.
In discussing the growth of the system. Dr. Bacon says :
The Mellon Institute has never aspired to largeness in size.
The policy is to devote its funds to improving the quality of its
work rather than to increasing the quantity thereof. Indeed,
since the number of Industrial Fellowships in operation is limited
by the number of men on the Institute's Administrative Staff
and by the Institute's housing space, it has been required during
the past year to decline temporarily several technologic investiga-
tions of importance, offered by some of the strongest corpora-
tions in the country, owing to the fact that the Institute is at
present filled to capacity. There are now 48 Industrial Fellow-
ships, and several additional Fellowships will begin operation
just as soon as the necessary facilities can be provided. It may
be noted here that there has been in the last few years a real
scarcity of men of demonstrated research ability, and the Mellon
Institute adheres to the policy of starting a new work only as
qualified scientific investigators are available.
The following table presents the number of Industrial Fellow-
ships which have been founded in the Institute from March to
March of each year, 1911 to 1921; the number of Industrial
Fellows (research chemists and engineers) who have been em-
ployed thereon; and the total amounts of money contributed
for their maintenance by the Industrial Fellowship donors
(industrialists and associations of manufacturers).
imber of Total
Tellows Foundation Sums
24 $ 39,700
30 54,300
37 78,400
32 61,200
63 126,800
65 149,100
64 172,000
77 238,245
83 293.6*0
S3 320,848
March to
Number of
March
Fellowships
1911-1912
11
1912-1913
16
1913-1914
21
1914-1915
21
1915-1916
36
1916-1917
42
1917-1918
42
1918-1919
47
1919-1920
47
1920-1921
48
PUBLICATION OF RESEARCHES
In the long run, an industrial research establishment must be
known by the successful commercial processes which it has
inaugurated and by the published accounts of the inquiries con-
ducted under its auspices. It is of prime importance to the
progress of science and technology to transmit as soon as possible
after their completion trustworthy records of methods, theories,
achievements, and even of errors and failures. In illustration
of this function of the Institute it seems fitting to present here a
list of the contributions from the Institute during the past nine
years.
Reports of Other Scientific United States
Books Researches Papers Patents
Published Published Published Issued
Year during Year during Year during Year1 during Year
1912 1 13 3
1913 20 10
1914 17 3 7
1915 10 11 22
1916 3 18 4 20
1917 14 5 35
1918 34 S 27
1919 23 ' 17 37
1920 2 36 48 17
1 The papers enumerated related principally to the scope, value, and
administration of industrial research, and to the general consideration of
techno-chemical problems.
The research findings of the Institute's Industrial Fellowships
are released for publication in accordance with the agreements
governing their operation. It is now realized by industrialists
that the methods of science are the most effective procedures
thus far developed for the advancement of technology and that
accordingly scientific investigation is an essential economic ad-
junct to manufacturing enterprises. This understanding of the
meaning and value of research, of the importance of utilizing
available and advancing knowledge, has emphasized to a degree
not hitherto attained in the history of industry the perils of ig-
norance and destructive competition. It has indicated clearly
the necessity for sympathetic cooperation in the exchange of
information. The encouragement of research and the recogni-
tion of the desirability of disseminating the knowledge gained
are indeed among the most noteworthy signs of the times.
The evolution from an era of industrial secrecy has been remark-
ably rapid, but all evolutionary processes are secular and proceed
with a leisurely disregard of individuals.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
479
No.
Names of
Industrial Feu.'
181
Synthetic Resius
190
Bread
206
210
211
214
227
Illuminating Glass
Zirconium
Fish Products
Fuel
Plastics
228
233
234
237
Soap
Enameling
Food Container
Synthetic Acids
23S
Protected Metals
239
240
Stove
Sulfur
241
243
245
Oil-shale
Nickel
Flotation
246
247
248
Duplicator
Glass
Oil
249
250
Quartz
Gas
251
Tar Products
2S2
253
254
255
256
257
Emulsion Flavors
Inks
Cements
Perfumes
Fiber
Yeast
258 Pratt M
259 Silicate
260 Magnesia I
267 Fertilize
268 Dental Products
269 Cleaning
270 Metal Ware
271 Laundry
273 Asbestos
274 Fruit Beverages
275 Magnesia Products
Industrial Fellowships in Operation at the Mellon Institute on March 1, 1921
ps Industrial Fellows, Names and Degrees ai*
C. B. Carter (Ph.D., University of North Carolina), senior fellow $5,00C
A. E. Coxe (B.S., University of Chicago)
H. A. Kohman (Ph.D., University of Kansas), senior fellow
Roy Irvin (M.S., University of Kansas)
E S. Stateler (B.S., University of Kansas)
A. H. Stewart (B.A., Washington & Jefferson College)
Mark Sheppard (B.S., Alfred University)
D. K. Tressler (Ph.D., Cornell University)
J. G. Davidson (Ph.D., Columbia University)
G. H. Brother (Ph.D., University of Toronto), senior fellow
W. E. Vawter (B.S., University of Kansas)
(Industrial Fellow to be appointed)
R. D. Cooke (M.S., University of Wisconsin)
W. F. Henderson (B.A., James Millikin University)
G. E. Seil (Chemist, Columbia University)
Foundation Sums
• Dates of Expiration
i year. December 23, 1921
• fellow
J. H. Young (Ph.D., Ohio State University), si
A. F. Shupp (Ph.D.. University of Pittsburgh)
P. D. Gephart (B.Ch.E., Ohio State University)
J. E. Hansen (B.S., University of Illinois)
H. S. Davis (Ph.D., Harvard University)
Mary D. Davis (B.A., Dalhousie University), assistant
C. L. Jones (M.S., University of Pittsburgh)
R. J. McKay (B.S., University of California)
L. E. Jackson (B.S.. University of Kansas)
G. A. Bragg (B.S., University of Kansas)
C. L. Perkins (B.S., New Hampshire CoUege)
R. E. Sayre (M.S., University of Wisconsin)
T. E. Williams fB.S., University of Michigan)
J. L. Sherrick (Ph.D., Rice Institute)
R. R. Shively (Ph.D., University of Pittsburgh)
W. F. Faragher (Ph.D., University of Kansas), senior fellow
W. A. Gruse (Ph.D., University of Wisconsin)
F. H. Garner (M.S., Birmingham University)
William Stericker (B.S., University of Wisconsin)
J. B. Garner (Ph.D., University of Chicago), senior fellow
R. W. Miller (Ph.D., University of Pittsburgh)
E. O. Rhodes (M.S., Universitv of Kansas), senior fellow
R. B. Truster (B.S., Syracuse University)
Paul Wible (B. Chem.. University of Pittsburgh)
Melvin De Groote (B.S. in Ch.E., Ohio State University)
F. F. Rupert (Ph.D., Massachusetts Institute of Technology)
E. R. Edson (B.A., Clark College)
T. K. Senior (Ph.D., University of Chicago)
J. D. Malcolmson (B.S., University of Kansas)
F. M. Hildebrandl (Ph.D., Johns Hopkins Universitv), senior fellow
G. S. Bratton (B.A., University of Tennessee)
H. C. Hoover (B.A., Ursinus College)
C. N. Frey (Ph.D., University of Wisconsin)
Madalyne S. Schairer (B.A., Vassar College)
Ruth Glasgow (MS, University of Illinois), advisory fellow
Grace Glasgow (M.S.. University of Illinois), advisory fellow
C. K. M. Ritchie (B.A., Oberlin CoUege)
J. L. Crawford (B.S., University of Illinois)
R. H. Heilman (B.S. in E.E., University of Pittsburgh)
P. Nichols and W. L. Steffens, advisors representing the donors
F. W. Sperr, Jr. (B.A., Ohio State University), advisory senior fellon
J. W. Hepplewhite, Jr. (B.Cer. E., Ohio State University)
R. E. Hall (Ph.D., University of Chicago)
W. J. Huff (Ph.D., Yale University)
H. J. Rose (B.A., Yankton College)
J. A. Shaw (B.S., Pennsylvania State College)
C. J. Herrly (B.S., Pennsylvania State College)
H. R. Curme (Ph.D.. University of Pittsburgh)
F. W. Hightower (B.A.. University of Texas)
O. F. Hedenburg (Ph.D., University of Chicago)
Walther Riddle (Ph.D., Universitv of Heidelberg)
H. E. Gill (M.S., University of Pittsburgh), assistant
R. H. Bogue (Ph.D., University of Pittsburgh)
David Drogin (M.S., University of Pittsburgh)
Isaac Drogin (Ph.D., University of Pittsburgh)
H. H. Meyers (B.S., University of Pennsylvania), senior fellow
O. H. Schunk (B.S., University of Wisconsin)
G. E. Cohen (B.S., Pennsylvania State College), assistant
C. C. Vogt (Ph.D., Ohio State University)
(Industrial Fellow to be appointed)
W. G. ImhofT (B.A., University of Wisconsin)
H. G. Elledge (M S.. University of Pittsburgh), senior fellow
Alice L Wakefield (B.S., Carnegie Institute of Technology)
M. J. Pooley (B.S., Dakota Wesleyan University), assistant
R. M. Howe (M.A., University of Pittsburgh), senior fellow
S. M. Phelps (University of Toronto)
R. F. Ferguson (B.S.. University of Pittsburgh)
W. R. Kerr (University of Pittsburgh), assistant
G. H Katz (B.S. in Ch.E., Ohio State University)
H. A. Noves (M.S., Massachusetts Agricultural College)
H. W. Greider (M.S., University of Kansas)
S12.000 a year. June 1, 1921
Bonus: $10,000
$3,000 a year.
$4,000 a year.
*.".,(i00 a year.
$5,000 a year.
$7,000 a year.
October 1, 1921
July 15, 1921
April 1, 1921
April 1, 1921
February 1, 1922
$2,800 a year.
$4,000 a year. April 1, 1922
$2,600 a year. July 12. 1922
$4,500 a year. May 1, 1921
Bonus: Royalty on sales
$12,000 a year. June 1, 1921
$5,000 a year.
$10,000 a year.
$4,000 a year.
$15,000 a year.
June 1, 1921
August 1, 1921
March 12, 1921
July 1, 1921
$4,500 a year. December 1, 1921
$4,700 a year. September 1, 1921
$12,000 a year. September 1, 1921
Bonus: $10,000
$3,300 a year.
$8,600 a year.
September 8, 1921
September 15, 1921
$15,000 a year. September 1, 1921
$6,000 a year.
$4,400 a year.
$4,100 a year.
$4,200 a year.
$3,500 a vear.
$21,000 a year.
$1,500 a year.
$4,000 a year.
$5,400 a year.
November 15, 1921
November 1, 1921
November 1, 1921
November 1, 1921
November 15, 1921
November 1, 1921
December 1, 1921
December 1, 1921
January 1, 1922
$16,800 a year. January 1, 1922
$16,000 a year. January 1, 1922
$6,048 a year. January 1, 1922
$3,500 a year. January 1, 1922
$4,000 a year. January 5, 1922
$5,500 a year. January 18, 1922
$S,000 a year. January 5, 1922
Bonus: $5,000
$2,500 a year. February 1, 1922
Bonus: Royalty on sales
$5,000 a year. March 1. 1922
$5,000 a year. February 16, 1922
$10,700 a year. February 15, 1922
$2,500 a year. February 1, 1922
$5,000 a year. March 1, 1922
$3,000 a year. March 1, 1922
Food Research Institute
The Carnegie Corporation has announced the election of the
two directors who will serve with Dr. C. L. Alsberg at the head
of the Food Research Institute which is to begin work at Stan-
ford University on July first. Dr. Alsberg will direct the divi-
sion dealing with food manufacture and agriculture; Dr. Alonzo
E. Taylor, Rush Professor of Physiological Chemistry at the
University of Pennsylvania, will be in charge of the division
covering the physiology and chemistry of nutrition; and Dr.
Joseph S. Davis, assistant professor of economics at Harvard
University, will head the division of economics and food dis-
tribution.
The university has just appointed as members of the Ad-
visory Committee: Herbert Hoover; Julius Barnes, former
president of the U. S. Food Administration Grain Corporation;
Dr. J. C. Merriam, president of the Carnegie Institution of
Washington; J. R. Howard, president of the American Federa-
tion of Farm Bureaus; Dr. William M. Jardine, president of
Kansas State Agricultural College; and George Roeding, chair-
man of the Horticultural Committee of the State of California.
480
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
The Bloede and the Hoffmann Scholarships
of the Chemists' Club
Applications for the Bloede and the Hoffmann Scholarships
of the Chemists' Club of New York should be submitted by the
middle of June.
The object of these scholarships is to assist deserving young
men to obtain an education in the field of industrial chemistry
or chemical engineering. The scholarships are open without
restriction as to residence, and may be effective at any institu-
tion in the United States, which may be designated or approved
by the Scholarships Committee.
Applicants must have completed a satisfactory high school
training, involving substantial work in elementary chemistry,
physics, and mathematics, and present a certificate showing
that they have passed the examination requirements of the Col-
lege Entrance Examination Board or its equivalent. Prefer-
ence will be given to candidates who have had additional aca-
demic work, especially in subjects which will form a suitable
groundwork for the more advanced study of applied chemistry
and chemical engineering.
Applications should be sent to Mr. F. G. Zinsser, Hastings-on-
Hudson, New York.
Centrifugal Method for Determining Potash
Editor of the Journal of Industrial and Engineering Chemistry:
Since submitting my article on a "Centrifugal Method for
Determining Potash" [This journal, 13 (1921), 227] I have
learned that others have worked along this same line, among
them being Mr. H. P. Bassett, of Meigs, Bassett & Slaughter.
Inc. To him and all others to whom credit is due, due credit is
here given.
Holly Sugar Corporation ELMER ShERRILL
Huntington Beach, California
Annual Tables of Constants — Correction
In the announcement of the publication of the "Annual
Tables of Constants" in This Journal, 13 (1921), 313, the ad-
dress to which orders should be sent was inadvertently omitted.
Such orders should go to the Chicago University Press, Chicago,
111.
SCIENTIFIC SOCIETIES
Sixty-first Meeting American Chemical
Society, Rochester, N. Y., April 26
to 29, 1921
Program of Papers
GENERAL SESSIONS
Hiram Edgerton, Mayor of Rochester. Address of Welcome.
E. G. Miner, Director of Chamber of Commerce, U. S. A., and President,
Pfaudler Company. Address of Welcome.
Edgar F. Smith, President, American Chemical Society. Response.
Senator James W. Wadsworth, Jr. Some Problems of National Defense.
Congressman Nicholas Longworth. The American Chemical Industry
and Its Need for Encouragement and Protection.
E. C. Franklin. Ammono Carbonic Acids.
C. E. K. Mees. The Measurement of Color. (Illustrated.)
W. D. Bancroft. Blue Eyes and Blue Feathers. (Illustrated.)
R. E. Wilson. Surface Films as Plastic Solids.
Irving Langmutr. The Relation between the Stability and the Structure
of Molecules.
G. N. Lewis. Ionization of Electrolytes.
Charles F. Chandler, Past President, American Chemical Society.
Chemistry in the United States.
AGRICULTURAL AND FOOD CHEMISTRY DIVISION
T. J. Bryan, Secretary
Rapid and Exact Methods of
E. Coates, Chairman
. S. K. Robinson. Suggestions for Mo
Analyses for the Cheese Factory.
. H. A. Noyes. Some Problems of the Pure Food Manufacturer.
. H. A. Noyes, H. T. King and J. H. Martsolf. Variations in the
Concord Grape during Ripening.
. F. C. Cook. The Absorption of Copper from the Soil by Potato Plants.
. F. C. Cook. Pickering Bordeaux Sprays.
. Alfred T. Shohl. Analysis of the Jerusalem Artichoke.
. R. H. Carr. Measuring Soil Toxicity, Acidity and Basicity.
. R. H. Carr. What Puts the "Pop" in Pop Corn? (Lantern.)
. C. A. Peters and A. L. Prince. The Rate of Oxidation of Lime Sulfur
Solution.
'. Oscar L. Evenson. A Color Test for "Remade" Milk.
. R. C. Hummell. The Effect of Aging on the Lecithin Phosphoric
Acid Deterioration in Egg Noodles.
. J. B. Rsed. Peanut By-products.
. Owen E. Williams and Harper F. Zoller. Some Factors In-
fluencing the Crystallization of Lactose in Ice Cream.
. Harper F. Zoller. A Rotating Thermocouple and Cold Junction
Designed for Temperature Studies in the Horizontal Power Ice
Cream Machine.
i. Harper F. Zoller. Cases of Supercooling during the Freezing of
Ice Cream Mixes.
i. Edward F. Kohman. Discoloration in Canned Sweet Potatoes.
(By Title.)
BIOLOGICAL CHEMISTRY DIVISION
A. W. Dox, Chairman H. B. Lewis, Secretary
1. G. D. Beal and J. B. Brown. A Study of the Highly Unsaturated
Fatty Acids Occurring in Fish Oils.
2. S. L. Jodidi. Further Studies on the Mosaic Disease of Spinach.
3. F. C. Cook and N. E. McIndoo. Chemical, Physical, and Insecticidal
Studies of Arsenicals.
4. H. B. Lewis and Lucie E. Root. Cysteine as a Product of the Inter-
mediary Metabolism of Cystine.
5. W. D. Richardson. Avian versus Mammalian Dietary Requirements.
6. H. A. Mattill. The Influence of Fasting and of Vitamine B Depriva-
tion on Nonprotein Nitrogen of Rat's Blood. (Lantern.)
7. H. C. Sherman, V. K. LaMer and H. L. Campbell. The Effect of
Temperature and the Concentration of Hydrogen Ions upon the
Rate of Destruction of the Antiscorbutic Vitamine. (Lantern.)
8. H. C. Sherman, V. K. LaMer and H. L. Campbell. The Quantitative
Measurement of the Antiscorbutic Vitamine. (Lantern.)
9. Max S. Dunn and H. B. Lewis. The Action of Nitrous Acid on
Casein. (Lantern.)
10. A. A. Christman and H. B. Lewis. Lipase Studies. The Hydrolysis
of the Esters of Some Dicarboxylic Acids by the Lipase of the Liver.
(Lantern.)
11. H. Steenbock, Mariana T. Sell and E. M. Nelson. Vitamines in
Milk.
12. Atherton Seidell. Further Experiments on the Isolation of the
Antineuritic Vitamine.
13. V. E. Levine and F. J. McDonodgh,
of Lipases in the Animal Organism.
14. V. E. Levine and S. A. Gianelli.
Activity in the Kidney.
15. M. X. Sullivan and P. R. Dawson.
Saliva.
16. O. S. Rask and I. K. Phelps. The Extraction and Estimation of
Lipoids in Cereal Products.
17. O. S. Rask and I. K. Phelps. Estimation of Phospholipins in Cereal
Products.
18. W. D. Bigelow. Resemblance of the Thermal Death Point of Bac-
teria to Chemical Reaction.
19. E. L. Chaffee and W. T. Bovie. The Intensity of Light Necessary
to Initiate a Photochemical Change in the Retina.
20. W. T. Bovie. An "Antidote" for a "Poisoned Electrode."
21. W. T, Bovie. An Abiotic Action of Rays Due to Ozone and the Heat
Sensitization of Protoplasm by Ultraviolet Light.
CELLULOSE CHEMISTRY SECTION
Harold Hibbert, Chairman G. J. Esselen, Jr., Secretary
1. L. F. Hawley. Effect of Adding Various Chemicals to Wood, Previous
to Distillation.
2. S. E. Sheppard. The Removal of Free Acid from Nitrated Cellulose
with Special Reference to the Use of Saline Leaches.
3. T. A. Boyd. Motor Fuel from Vegetation. (Lantern.)
4. H. N. Whitford. Possibilities of the Moist Tropics to Furnish
Materials for Cellulose and Carbohydrates. (Lantern.)
The Existence of Two Types
The Distribution of Lipolytic
Uric Acid and Phenols in the
Maw 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
481
5. R. C. Hawlky. The Possibilities of a Future Fuel Supply from Our
Forests.
6. Harold Hibbert. The Role of the Chemist in Relation to Our Future
Supply of Liquid Fuel.
Papers 3 to 6, inclusive, will be discussed together under the general
subject "Our Future Supplies of Liquid Fuel." It is expected that repre-
sentatives of the Standard Oil Co., U. S. Industrial Alcohol Co., Forest
Products Laboratory and others will take part.
7. Allen Abrams. The Microstructure of Wood. (Lantern.)
S. W. J. Waite. Influence of Mixed Acids on the Character of Nitro-
cellulose. (Lantern.)
9. F. B. LaForge. Some Commercial Possibilities of Corncob Cellulose.
10. W. K. Tucker. Nitrocellulose and its Solutions as Applied to the
Manufacture of Artificial Leather.
11. E. C. Crocker. Significance of the So-called Lignin Tests.
12. B. Johnsen. A Proposal for a Standard Cellulose to Be Available for
Research.
13. Jessie E. Minor. A Discussion of Some Beater Furnish Reactions
from the Standpoint of Colloidal Chemistry.
14. Gustavus J. Esselen, Jr. The Solubility of Cellulose Acetate in
Chlorinated Hydrocarbons.
15. Harold Hibbert and Harold S. Hill. The Action of Dry Hydro-
bromic Acid on Cellulose and Related Derivatives.
16. W. S. Holzberger. The Oxidation of Cellulose.
17. Philip Drinker. European Practice in Cellulose Acetate and Dopes
during the War.
IS. W. E. Tottingham. The Influence of Temperature on Hemicellulose
Production.
19. Mark W. Bray and Joseph A. Staidl. The Chemical Changes In-
volved during Infection and Decay of Wood and Wood Pulp.
20. Sidney D. Wells. The Chemical Constitution of Soda and Sulfate
Pulps from Coniferous Woods and Their Bleaching Qualities.
DYE CHEMISTRY DIVISION
A. B. Dams, Chairman R. Norris Shreve, Secretary
1. Henry R. Lee. Contribution to the Estimation of H-acid.
2. Chas. W. Schaffer. A New Process for Alizarin.
3. J. Merkitt Matthews. Bleaching of Dyed Cotton Fabrics.
4. William J. Hale. The Immediate Needs of Chemistry in America.
5. J. R. MinEvitch. Contributions to the Chemistry of Malachite Green.
6. C. R. DeLong. New Developments in American Dyes and Coal-Tar
Chemicals in 1920.
7. A. Willard Joyce. Dyes Derived from /S-Oxynaphthoic Acid
and from J-acid with Reference to the Chemical Foundation Patents.
8. Arthur D. Williams. Quantitative Determination of Phenanthrene.
9. Max Phillips. Alkali Fusions. Ill — Fusions of Phenylglycine-o-
carboxylic Acid with Potassium Hydroxide and with Sodium Hy-
droxide for the Production of Indigo.
10. O. A. Nelson and C. E. Senseman. Vapor Pressure Determinations on
Naphthalene, Anthracene, Phenanthrene, and Anthraquinone be-
tween their Melting and Boiling Points.
11. J. Warren Kinsman. Nomenclature of Dyestuff Intermediates.
INDUSTRIAL AND ENGINEERING CHEMISTRY DIVISION
H. D. Batchelor, Chairman H. E. Howe, Secretary
I — Symposium on Drying. Charles O. Lavett, Chairman
1. W. K. Lewis. The Rate of Drying of Solid Materials. (Lantern.)
2. W. H. Carrier. The Theory of Atmospheric Evaporation. (Lantern.)
3. W. H. Carrier and A. E. Stacey. The Compartment Dryer. (Lan-
tern.)
4. R. G. Merz. Direct Heat Rotary Drying Apparatus.
5. G. B. Ridley. Tunnel Dryer. (Lantern.)
6. R. S. Fleming. The Spray Process.
7. Charles O. Lavett and D. J. VanMarle. Vacuum Drying. (Lan-
tern.)
H — Papers
8. G. C.Spencer and E. B. Smith. Tests of Countercurrent Kelp Driers.
9. Louis Schneider. The Preparation, Properties and Constitution
of Liquid and Solid Water Glasses.
•10. Charles Baskerville. Method for Treating Filter Cake Obtained
in Refining Vegetable and Animal Oils.
11. L. F. Hawley and H. M. Pier. The Application of the Cottrell Pre-
cipitator to^he Wood Distillation Process.
12. J. M. Doran. Alcohol and Chemical Industries.
13. G. A. Bole and J. B. Shaw. The Caustic Calcination of Dolomite and
Its Use in Sorrel Cements.
14. Lehman Johnson. Valuation of Oilbearing Seeds by Free Fatty
Acid of the Oil.
15. C. R. Hoover. The Detection of Carbon Monoxide. (Lantern.)
16. A. Silverman. Microscope Illumination with Reference to Brownian
Movement and Combination Lighting. (Lantern.)
17. William Stericker. The Relation of Structure to Free Alkali in
Sodium Silicate Solutions. (Lantern.)
18. Gustav Carlsson. Compression Evaporation, a New Method of
Concentrating Liquids, Developed in Europe Recently. (Lantern.)
19. R. Norris Shreve. Action of Lime on Greensand.
20. F. P. Veitch and H. P. Holman. A Modification of the Acetate
Method for Estimating Iron and Aluminium in Phosphates.
21. F. P. Veitch and T. D. Jarrell. The Water Resistance of Treated
Canvas during Continuous Exposure to Weather.
22. V. E. Grotlisch and W. C. Smith. The Detection and Estimation of
Coal-Tar Oils in Turpentine.
MEDICINAL PRODUCTS CHEMISTRY DIVISION
Charles E. Caspari, Chairman Edgar B. Carter, Secretary
1. GeorgS W. Raiziss and Joseph L. Gavron. AT-Derivatives of Ars-
phenamine. I — Introduction of Fatty Acids.
2. George W. Raiziss and Abraham C. Blatt. A/-Derivatives of
Arsphenamine. II — Aldehyde Addition Products.
3. George H. A. Clowes. Some Recent Observations on Protoplasmic
Stimulus.
4. H. V. Farr. Significance of Residue Determination as a Test for
Purity in Drugs and Chemicals.
5. Charles Baskerville. A New Use for Edible Oils in Surgery.
6. Arthur D. Hirschfelder. Further Study upon Saligenin and Allied
Compounds.
7. Oliver Kamm. Molecular Magnitude and Physiological Action.
8. E. H. VolwilER. The Preparation and Hydrolysis of Benzyl Esters.
9. A. E. Sherndal. Arsphenamine: Some Factors Which Influence Its
Colloidal Properties.
10. Robert P. Fischelis. Laboratory Test versus Clinical Results.
11. F. D. Dodge. Vanillin Glyceride. (By title.)
ORGANIC CHEMISTRY DIVISION
Roger Adams, Chairman H. T. Clarke, Secretary
1. W. Lee Lewis and H. C. Cheetham. Arsenated Benzophenone and
Derivatives.
2. W. Lee Lewis and C. S. Hamilton. Chlorophenyl-«-naphthyl
Arsazine and Its Derivatives.
3. Fred W. Upson and T. J. Thompson. Condensation Reactions with
Benzyl Cyanide.
4. T. B. Aldrich. Derivatives of Trihalogen-/t-»-/-Butyl Alcohols. IV—
The Benzoic Acid Ester of Tribromo-/fr/-Butyl Alcohol.
5. H. W. Doughty and B. Freeman. Trihalogenmethyl Reactions.
IV — Tetrachlorosuccinic Acid.
6. A. W. Dox and L. Yoder. Spiro-pyrimidines. II — Cyclohexane-
1,5-spiro-pyrimidines,
7. A. W. Dox and L. Yoder. Spiro-pyrimidines. Ill — Cyclopropane-
1,5-spiro pyrimidines.
8. A. W. Dox and L. Yoder. Pyrimidines from Dialkylmalonic Esters
and Qenzamidine.
9. J. B. Conant and H. M. Kahn. An Electrochemical Study of Certain
Reversible Reductions.
10. J. B. Conant and S. S. Negus. The Reactivity of the Chlorine Atom
in the Nitrobenzyl Chlorides.
11. J. B. Conant and S. M. Pollack. The 1,4-Addition of Phosphenyl
Chloride.
12. Nao Uyei and Oliver Kamm. A Comparative Study of Ring Stability.
13. J. H. Waldo, C. S. Palmer and Oliver Kamm. Investigation of
Isomerism in the Diphenyl Series.
14. F. J. Moore and E. H. Huntress. The Action of Hydrogen Sulfide
upon Trinitrotoluene.
15. F. J. Moore and Ruth M. Thomas. The Constitution of the Secondary
Product in the Sulfonation of Cinnamic Acid.
16. I. N. Hultman and H. T. Clarke. Separation of Aromatic Primary
and Secondary Amines.
17. Edward C. Franklin. Potassium Derivatives of the Alkyl Amines.
18. Ben H. Nicolet. The Existence and Reactions of Positive Halogens
Attached to Carbon in Aromatic Compounds. Preliminary Paper.
19. M. Gomberg and F. W. Sullivan, Jr. Diphenyl-0-naphthylmethyl.
20. Roger Adams and W. C. Wilson. Contribution to the Structure of
Benzidine: Formation of Rings through the m- and ^-Positions of
Benzene.
21. E. C. Kendall and A. E. Osterberg. The Preparation of Dihydro-
benzene and Some of Its Derivatives.
22. Edmund B. Middleton and F. C. Whitmore. Stability of the C-Hg
Linkage in Mercury Derivatives of Anisole and Phenetole.
23. L. Frances Howe and F. C. Whitmore. Preparation of Mercury
Ditolyl from Tolylmercuric Chloride.
24. Ruth Walker and F. C. Whitmore. Mercury Compounds of n-Butyl.
25. F. C. Whitmore and V. E. Meharg. Mercury Derivatives of m-
Nitrobenzoic Acid.
26. F. C. Whitmore and Edmund B. Middleton. Organic Mercury
Compounds Prepared from o-Chloromercuribenzoyl Chloride.
27. W. G. Horsch. The Quantitative Determination of Paraformaldehyde.
28. Lauder W. Jones and Charles D. Hurd. Rearrangements of Some
New Hydroxamic Acids Related to Heterocyclic Acids and to Di-
phenyl- and Triphenylacetic Acids.
482
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
29. Lauder W. Jones and Alfred W. Scott. The Hydroxamic Acid of
Cyclopropanecarboxylic Acid, and Its Derivatives.
30. John C. Hessler. Preparations of Phenylacetylene.
31. H. Gilman, P. D. Wilkinson and W. P. Fishel. On a Quantitative
Study of the Grignard Reagent.
32. R. R. Read. A Simple Type of Glass Pressure Bottle.
33. Morris S. Kharasch. An Indirect Method of Mercurization of
Organic Compounds and a Method of Carbon-Carbon Linking.
34. Robert F. Chambers. Symmetrical Tribromophenylpropiolic Acid
and Its Reaction with Acetic Anhydride.
35. E. Emmet Reid, Colin M. Mackall and G. E. Miller. The Re-
actions of a-Anthraquinonesulfonic Acids with Mercaptans.
36. G. B. and C. J. Frankforter and E. R. Kryger. The Polymers of
Pinene.
37. G. B. Frankforter and A. E. Stoppel. Contribution to Our Knowl-
edge of the Chemistry of Calcium Carbide.
38. F. D. Dodge. A New Lactone from Oil of Orange. (By title.)
39. Alvin S. Wheeler and T. M. Andrews. New Derivatives of 2,3,8-
Tribromo-5-hydroxy-l,4-naphthoquinone. (By title.)
40. Alvtn S. Wheeler and I. W. Smithey. The Bromination of 2-Amino-
f>-cymene. (By title.)
41. F. B. LaForge. The Production of Furfural by the Action of Super-
heated Water on Aqueous Corncob Extract. (By title.)
PETEOLEUM CHEMISTRY SECTION
T. G. Delbridge, Cha
W. A. Gruse, Secretary
Petroleum Hydrocarbons That Cannot Be Distilled.
Petroleum: A Raw Material for Our Chemical
Organization.
C. F. Mabery.
Sidney Born,
Industries.
B. T. Brooks. Some Chemical Considerations of Petroleum Refining.
R. F. Bacon. OU Shale.
Charles Skeele Palmer. Determination of Gasoline in Natural
and Casinghead Gas.
W. F. Faragher and F. H. Garner. Dechlorination of Chlorohydro-
carbons.
C. J. Rodman. Determination of Moisture in Transformer Oils.
E. W. Dean and F. W. Lane. Viscosity-Temperature Curves of
Fractions of Typical American Crude Oils. (Lantern.)
W. F. Faragher, F. H. Garner and W. A. Gruse. Iodine Numbers
of Unsaturated Hydrocarbons and Cracked Gasolines. (Lantern.)
W. F. Parish. Reclamation of Used Motor Oils. (Lantern.)
Robert E. Wilson and D. P. Barnard. Total Heats and Condensa-
tion Points of Kerosene-Air Mixtures.
Leon W. Parsons and Robert E. Wilson. A New Method of Color
Measurement for Oils.
C. E. Waters Catalytic Oxidation of Petroleum Oils.
L- B. Lockhart. Viscosities of Motor Oils at High Temperatures.
(By title.)
PHYSICAL AND INORGANIC CHEMISTRY
H. N. Holmes, Cha
S. E. Sheppard, Secreta
I — Symposium on Contact Catalysis
1. F. H. Pollard. Platinum Black and Carbon Monoxide.
2. C. H. Milligan and E. Emmet Reid. Esterification by Silica Gel.
3. A. F. Benton. Adsorption by Oxide Catalysts and the Mechanism
of Oxidation Processes.
4. J. C. Frazer. Dissociation of Some Mixed Oxides.
5. R. M. Burns and H. S. Taylor. Adsorption by Metallic Catalysts.
6. F. L. Simons. The Action of Nickel on Diethyl Ether: A Study in
Contact Catalysis. Preliminary Report.
7. C. H. Milligan and E. Emmet Reid. R. P. M.'s as a Catalyst.
8. R. N. Pease and H. S. Taylor. Catalysis in the Reduction of Oxides
and the Catalytic Combination of Hydrogen and Oxygen.
9. J. C. Frazer. A Case of Autoxidation: MnO; >■ HMnOt.
10. H. A. Neville and H. S. Taylor. Catalysis in the Interaction of
Carbon with Steam and Carbon Dioxide.
11. C. H. Milligan and E. Emmet Reid. Oxidation and Reduction by
Organic Compounds.
12. Homer Adkins and A. C. Krause. The Action of Alumina, Titania,
and Thoria on Ethyl and Isopropyl Acetate.
13. C. G. Fink. Catalytic Electrolytic Oxidation of Sulfur Dioxide.
14. Homer Adkins and P. W. Simmonds. The Decomposition of Ethyl
Acetate Induced by Catalytic Nickel.
15. James Kendall and F. J. Fuche. The Catalytic Influence of Foreign
Oxides on the Decomposition of Silver Oxide, Mercuric Oxide, and
Barium Peroxide.
H — Papers
16. G. S. Forbes. H. W. Estill and O. J. Walker. A New Clock
Reaction.
17. H. H. Willard, and W. E. Cake. The Volumetric Oxidation of
Sulfide to Sulfate.
18. Edward Ellery. Research for the Undergraduate.
A W. Laubengayer. The Apparent Irreversibility of the Calomel
Electrode.
D. A. MacInnes and W. R. Hainsworth. The Theory of Hydrogen
Over-Voltage.
W, R. Hainsworth. The Hydrogen Electrode under High Pressures.
Francis W. Bergstrom. Potassium Ammonoaluminate and Ammono-
manganite.
G. L. Clark and W. M. Mann. A Quantitative Study of Adsorption
in Solution and at Interfaces of Sugars, Dextrin, Starch, Gum Arabic,
and Egg Albumin, and the Mechanism of Their Action as Emulsifying
Agents.
G. L. Clark and H. K. Buckner. The Preparation, Properties, and
Molecular Volume Relationships of the Ammines and Hydrates of
Cobalt Fluoride, Bromide, Nitrate, Carbonate, and Citrate.
G. L. Clark and H. K. Buckner. Emulsification with Soaps of
Linoleic and Ricinoleic Acids.
Edward Wichers. Notes on the Preparation of Pure Platinum.
G. E. F. Lundell and H. B. Knowles. Modified Method for the
Determination of Iron and Vanadium after Reduction by Hydrogen
Sulfide.
Miller Spencer and Albert G. Loomis. The Free Energy of Dilu-
tion of Hydrobromic Acid; the Activities of Its Ions in Very Dilute
and Concentrated Solutions.
L. F. Yntema and B. S. Hopkins. Ultraviolet Arc Spectrum of
Yttrium.
R. H. Bogue. On the Viscosity of Gelatin Sols.
Irving Langmuir. The Structure of the Molecule of Water.
L. Finkelstein. The Purification of Helium by Means of Char
coal.
Robert E. Wilson and Merrill A. Youtz. The Importance of
Diffusion in Organic Electrochemistry.
S. E. Sheppard and F. A. Elliott. Observations on the Drying and
Swelling of Gelatin Gels.
S. E. Sheppard and A. Ballard. Note on the Influenoe of Silver
Salts in Catalyzing the Decomposition of Ammonium Persulfate
Solutions.
F. A. Elliott. Further Developments of the Hydrogen Electrode.
G. Stafford Whitby. Note on Silver Soap Gels.
F. O. Rice. Catalytic Effect in the Reaction between Ketones and
Halogens in Aqueous Solutions.
Alfred L. Ferguson and W. G. France. The Transference Num-
bers of Sulfuric Acid by the Concentration Cell Method.
Alfred L. Ferguson and W. G. France. The Influence of Gelatin
on the Transference Number of Sulfuric Acid.
, Gilbert N. Lewis. The Entropy of Monatomic Gases.
. D. T. Ewing and E. F. Eldridge. The Electrometric Titration of
Uranium with Potassium Dichromate and Potassium Permanganate.
. Frederick L. Brown and J. H. Mathews. The Heat of Coagulation
of Ferric Oxide Hydrosol by Electrolytes.
. Ray V. Murphy and J. H. Mathews. Some Quantitative Experiments
on Coagulation of Colloids.
. Roger C. Wells. The Alkalinity of Searles Lake Brine.
. A. F. O. Germann and Vernon Jersey. The Vapor Density of
Technical Phosgene.
. A. F. O. Germann and Marion Cleaveland. The Cryoscopy of
Boron Trifluoride Solutions. V — Systems with Methyl Ether and
with Methyl Chloride.
. A. F. O. Germann and Vernon Jersey. The Cryoscopy of Phosgene
Solutions. I — System with Chlorine.
. A. F. O. Germann and Gtlberta Torrey. Studies in Fluoride
Equilibrium. I — Calcium Boronuoride.
. Harry N. Holmes and Don H. Cameron. Chromatic Emulsions.
. Harry N. Holmes and Don H. Cameron. Cellulose Nitrate as an
Emulsifying Agent.
. Harris D. Hineune. A Theory of the Photographic Latent Image.
. S. A. Braly and O. V. Schaefer. The Interaction of Platinum Hydro-
chloric Acid and Hydrogen Peroxide.
. Eugene C. Bingham. Is There a Sharp Transition Point between the
Gel and Sol?
. Eugene C. Bingham and Delbert F. Brown. The Validity of the
Additive Fluidity Formula.
. Eugene C. Bingham and William L. Hyden. The Emulsion Colloids
as Plastic Substances.
. Eugene C. Bingham. The Properties of Cutting Fluids.
. John B. Ferguson. The Diffusion of Hydrogen through Silica Glass.
. Harold S. Booth. The Atomic Weight of Nitrogen by the Thermal
Decomposition of Silver Trinitride.
. Walter A. Patrick and D. C. Jones. Studies in Adsorption from
Solution.
. Walter A. Patrick and B. S. Neuhausen. Solubility of NHj in H-O.
. Walter A. Patrick and R. C. Grimm. Heat of Wetting of Silica Gel.
. Harry B. Weiser. Adsorption by Precipitates. IV — Acclimatization.
. Harry B. Weiser and Allen Garrison. The Oxidation and Lumi-
nescence of Phosphorus. HI — The Catalytic Action of Vapors.
i. D. C. Jones. Critical Solution Temperatures as Criteria of Liquid
Purity. (By Title.)
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
483
RUBBER CHEMISTRY DIVISION
. W. Evans, Chairman Arnold H. Smith, Secretary
Discussion of the Tentative Procedure for the Analysis of Rubber
Goods.
Reports from Executive Committee, Abstract Committee, Accelerator
Committee, and Physical Testing Committee.
A. A. Somerville. Thermal Conductivity of Some Rubber Compounds.
G. Stafford Whitby and J. Doud. Contribution to the Knowledge
of the Resins of Hevea Rubber. (Lantern.)
C. S. Venable and Tyler Fuwa. The Solubility of Gases in Rubber
as Affecting Their Permeability.
S. Collier and M. Levin. The Analysis of Rubber Goods Containing
Antimony Sulfide.
C. W. Bedford and L. B. Sebrell. Reactions of Accelerators during
Vulcanization. Ill — Carbosulfhydryl Accelerators and the Action
of Zinc Oxide.
G. Stafford Whitby and O. J. Walker. The Influence of Piperidine-
piperidyl-dithiocarbamate on Vulcanization. (Lantern.)
W. W. Evans and Ruth E. Merling. A Rapid Bomb Method for the
Determination of Sulfur in Rubber Compounds.
S. Collier and M. Levin. The Direct Determination of Sulfur of
Vulcanization.
Henry Green. Volume Increase of Compounded Rubber under
Strain. (Lantern.) (With comments on the work of H. F. Schippel.)
General Round Table Discussion. Topics are: Factory Control of
Vulcanization. Testing of Crude Rubber as Received at the Factory.
Reactions between Sulfur and Various Softeners, and Others.
SUGAR CHEMISTRY AND TECHNOLOGY SECTION
irman Frederick Bates, Secretary
A Rotary Digester for Use in Bagasse Analyses.
Determination of Reducing Sugars in Lead-Preserved
Molas
Sirups, and Juices by
A. Browne, Ch
G. L. Spencer
J. B. Harris.
Cane Juices.
G. P. Meade. Dry Substance
the Spencer Electric Oven.
M. J. Froffitt. Two Simple Tests for the Control of the Crystallizer
and Centrifugal Machine Work.
M. Potvliet. A Comparison of the Results in the Process of De-
sugarization with the Steffen Lime Process, the Barium Process,
and the Strontium Process.
J. F. Brewster and W. G. Raines. The Effect of Varying Hydrogen-
Ion Concentration upon the Decolorization of Cane Juice with Carbon.
J. F. Brewster and W. G. Raines. The Effect of Some Decolorizing
Carbons on the Color and Colloids of Cane Juice.
H. H. Peters and F. P. Phelps. The Determination of Color and
Decolorization in Sugar Products.
F. C. Atkinson. A Discussion of the Refractometer Scale for the
Evaluation of Sirups.
P. M. Horton. Preparation of Mannose from Ivory Nut Shavings.
G. L. Spencer. Flask Calibrating and Marking Device.
C. E. Coates. The Preparation of a Decolorizing Char from Sugar-cane
Bagasse.
C. A. Browne and C. A. Gamble. A Revision of the Optical Method
for Analyzing Mixtures of Sucrose and Raffinose.
M. J. Proffitt. Preliminary Note on the Causes of Caking in Sugar.
F. A. Quisumbing and A. W. Thomas. Investigation of Conditions
Affecting the Quantitative Determination of Reducing Sugars by
Fehling Solution. Elimination of Certain Errors Involved in Current
Methods.
H. T. Graber. The Standardization of Rare Sugars.
U. S. Jamison and J. R. Withrow. The Determination of Ash in
Cuban Raw Sugar.
C. A. Browne and M. H. Wiley. On the Quantities and Properties
of Lead Precipitates from Different Raw Cane Sugars.
A. Jobin. Graduation Saccharimetrique des Polarimetres a Cercle
Divise Servant en Lumiere Jaune de Sodium.
A. Jobin. Graduation des Saccharimetres a Compensateur de Quartz.
G. P. Meade. Examination of Sugar Crystals by Projection.
R. B. Black. The Rare Sugars, Their Purity and Tests.
H. S. Paine and C. F. Walton. A Study of Beet Gum. I— Separa-
tion from Final Molasses.
R. F. Jackson and C. L. Gillis. Solubility of Dextrose in Water.
H. E. Zitkowski. Some Observations from the Beet-Sugar Industry.
H. J. Runyon, Jr. Sugar Filtration in Factories and Refineries.
H. S. Paine, C. G. Church and F. W. Reynolds. Colloids in Beet-
Sugar House Liquors and Products.
Longfield Smith. Experiments with Sugar-cane Seedlings in St. Croix.
V. Birckner. A Precipitate Obtained from Cane Juice after Clari-
fication with Kieselguhr and Decolorizing Carbon.
C. A. Browne and G. H. Harden. Experiments with Schoorl's
Volumetric Method for Determining Reducing Sugars.
W. L. Jordan. The Continuous Sampling of Sugar Liquors.
E. P. Clark. Preparation of Galactose.
C. E. G. Porst. The Manufacturing of High-Purity Crystalline
Anhydrous Dextrose.
WATER, SEWAGE AND SANITATION DIVISION
W. P. Mason, Chairman w. W. Skinner, Secretary
1. A. M. Buswell. Reactions in the Dorr-Peck Tank.
2. A. M. Buswell. Definition of Alkalinity and Temporary Hardness.
3. Joseph A. Shaw and N. A. BAn.EY. Notes on the Analysis of Mine
Drainage Water.
4. Joseph A. Shaw. Method for the Determination of Free and Com-
bined Carbon Dioxide.
5. W. W. Skinner and J. W. Sale. Radioactivity of Miscellaneous
Waters Examined in the Bureau of Chemistry, U. S. Dept. of Agr.
6. W. W. Skinner and W. E. Shaefer. A Comparison of Some Mis-
cellaneous Samples of Ocean, Bay and Lake Waters.
7. S. T. Powell. The Present Status of Chlorination of Public Water
Supply.
Atlantic City Meeting of the American
Electrochemical Society
For the third time the American Electrochemical Society
has met at Atlantic City and records a highly successful meeting.
The date was April 21 to 2.3; headquarters, the Hotel Chalfonte.
Thirty-one papers were on the program, all printed in advance
and distributed to members by mail before the meeting, thus
giving abundant opportunity for intelligent discussion. The
afternoons of the 21st and 22nd were given up entirely to sports
and recreations. Several electrochemical firms offered prizes
for the sports, which added interest to these events. Thursday
evening was occupied by a fine lecture by Dr. R. B. Moore,
of the Bureau of Mines, Washington, D. C, on "Helium and
Other Rare Gases." Friday night was partly occupied by moving
picture exhibitions of the Cherry Electrochemical Gasoline
process, the Muscle Shoals Nitrate Plant of the American
Cyanamid Co., and the Chuquicamata Copper Mine of the Chile
Exploration Co.
At the annual business meeting on Friday morning, April 22,
the report of the Directors showed that the cost of printing had
absorbed 75 per cent of the Society's income during 1920 — an
unusually high factor of Society efficiency. Amendments to
the Constitution were adopted, intended particularly to lighten
the routine work of the secretary by placing increased responsi-
bility upon the assistant secretary. The annual election showed
that Mr. Acheson Smith, of the Acheson Graphite Co., Niagara
Falls, had been elected president for one year; C. F. Burgess,
of Madison, Wis., C. G. Schluederberg, of Pittsburgh, and E. L.
Crosby, of Detroit, vice presidents for two years; Carl Hering,
of Philadelphia, J. V. N. Dorr, of New York, and F. A. J. Fitz-
Gerald, of Niagara Falls, managers for three years; P. G. Salom,
of Philadelphia, treasurer; J. W. Richards, of Bethlehem, Pa.,
secretary. Retiring President Laudis delivered the presidential
address on "Our Inventory," a summation of the present con-
dition and importance of the electrochemical industries in the
United States and Canada. Mr. Landis estimates the capital
invested in North America in electrochemical plants between
six hundred million and one billion dollars. Dr. Blum, Mr.
Hogaboom, and Dr. Lukens were appointed a committee on
formation of an Electrodeposition Division of the Society.
The Board of Directors chose as the time and place of the
next meeting September 29 to October 1, 1921, at the Lake
Placid Club in the Adirondacks.
The technical sessions of the meeting were notable. There
were no less than sixteen papers upon the subject of "Corrosion,"
occupying nearly two sessions for their presentation and dis-
cussion; such notabilities as Wm. H. Walker, W. D. Richardson,
A. S. Cushman and G. W. Coggeshall, D. M. Buck, J. M.
Aupperle and D. M. Strickland, and F. N. Speller discussed
theory and facts regarding the corrosion of iron and steel, par-
ticularly the function of copper as an agent against corrosion.
The discussion was active on this latter point, almost to the
point of being heated. The summation of the evidence pre-
sented would seem to show that copper-bearing iron and steel
are less subject to atmospheric corrosion, while when subjected
-is I
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
to corrosion immersed in liquids the evidence is conflicting.
Dr. Cushman showed a ferro-hydroxyl test which excited con-
siderable discussion, being apparently a demonstration of local
circuits formed between positive and negative nodes on the
corroding substances, the phenomenon being indicated by the
setting of a colloidal gel. Mr. Speller gave statistics upon the
avoidance of corrosion of iron in closed systems by removing
oxygen from the water brought into the system — an idea which
has proved itself particularly valuable. Mr. II. A. Gardner
discussed the subject of metal protective paints; O. P. Watts,
the principles of alloying to find the least corrosive combina-
tions; H. S. Rawdon, types of nonferrous corrosion; and E. R
Shepard, electrolytic corrosion of lead.
Mr. O. H. Eschholz contributed a fine paper on the phenomena
of arc welding, which he had studied by means of cinematograph
pictures taken at a speed fifty times that used for motion pic-
tures; he further discussed the proportion of the applied electric
energy consumed in melting the metal, in vaporization of the
iron, and loss of radiation, etc. The paper was discussed at
length, and considerable detailed information about the phe-
nomena was brought out.
H. W. Gillett gave a detailed catalog of the 323 electric fur-
naces now in use in the United States for melting nonferrous
metals. He discussed the construction, advantages, and dis-
advantages of each type. This very complete information showed
that electric furnaces, having in fact revolutionized the melting
of nonferrous metals, have brought this whole industry into the
electrometallurgical field.
Dr. Carl Hering discussed the electrodynamic forces in electric
furnaces, naming the "pinch effect," "stretch effect," and "corner
effect." He claimed that many of the principles used in recently
developed furnaces were applications of the principles which
he had discovered. In the discussion, this position was con-
tradicted by representatives of the Ajax-Wyatt furnace, and
the assertion was made that this was a distinct improvement
upon the principles discovered by Dr. Hering. Dr. E. F. Xorth-
rup described in a 20-page paper the present status of his high-
frequency furnace for experimental, laboratory, and commercial
work. Seven types of furnaces were described in detail and
their actual performances given. W. G. Mylius described a
new form of electrode regulator for electric arc furnaces, intended
to work with greater precision and overcome the difficulty of
"hanging."
L. Kahlenberg and W. J. Trautmann presented a 40-page
paper on electrothermic reduction by means of silicon. Their
method of starting the reaction by an arc between two silicon
electrodes was more efficient and successful than the means
usually employed. The paper is a mine of new information upon
the reaction of silicon upon metallic oxides.
A. W. Laubengayer discussed the apparent irreversibility of
the calomel electrode, which he finds due to the formation of a
film of mercurous oxide on the anode. A current of 0 2 milli-
ampere can pass before the film forms. Above that current,
the phenomena of irreversibility appear.
T. W. Case showed exceedingly interesting light-sensitive
cells, which were nothing other than audion bulbs of the oxide-
coated filament type. These were found sensitive to light to
such an extent as to produce for average sunlight from 100 to
150 micro-amperes, which is sufficient to run recording ammeters,
and thus furnish a curve of daylight intensity. In presenting
the paper, Mr. Cushman showed photographs of daylight
intensity taken with these cells.
Two papers from the research laboratory of the Eastman
Kodak Companj' discussed organic electrochemistry; S. E.
Sheppard discussing the electrochemical aspects of photographic
development, particularly in the production of photographic
developers, while A. S. McDaniel, L. Schneider and A. Ballord
gave the details of the electrolytic manufacture of £-aminophenol.
\Y. A. Xoyes, Jr., discussed some of the properties of electro-
lytic iron; Dr. Blum, of the Bureau of Standards, the advantages
of using fluorides in nickel plating baths and the better deposits
obtained therefrom; C. P. Madsen described the obtaining of
ductile electrolytic nickel by periodically, at short intervals,
removing the cathode from the bath, thus exposing it to the air,
and re-immersing. By doing this at intervals of 0.5 to 5 min.,
extremely malleable and ductile nickel is obtained. In the dis-
cussion of Madsen's paper, it was pointed out that the advanta-
geous result was probably obtained by the oxidation of the film
of the electrolyte upon the cathode when exposed to the air,
thus displacing the hydrogen otherwise set free upon the cathode
when the current was reestablished.
C. W. Hazelett described a new high-capacity storage battery,
very light for its output, which is 50 to 200 per cent above the
standard types. This statement was contradicted in the dis-
cussion.
C. W. Marsh described electrolytic cells for chlorine, caustic
soda, and hydrogen, such as were used at the Edgewood Arsenal.
Single cells are made to take up to 5000 amperes, and work
at an ampere efficiency of 90 per cent over long periods.
One of the most valuable points brought out at the meeting
was the description by Dr. Northrup of a coating which could be
applied to graphite crucibles and which would effectually resist
the action of air or oxygen at temperatures up to 1800° C.
This statement brought forth animated discussion and general
commendation of the great usefulness of such a coating upon
graphite in various electrometallurgical processes.
More than 150 prominent and active members of the Society
were present, and the meeting was a marked success on both the
professional and social sides.
J. W. Richards
Lehigh University
South Bethlehem. Pa.
April 25, 1921
Paper Trade and Technical Association
Conventions
The American Paper and Pulp Association, the National Paper
Trade Association, and the Technical Association of the Pulp
and Paper Industry held their annual conventions during the
week of April 11, at the Waldorf-Astoria, New York, N. Y.
The two first named associations devote their meetings largely
to a consideration of business and management problems, whereas
the third named body devotes its meetings to the scientific and
technical problems connected with paper making.
The American Paper and Pulp Association, following recom-
mendations of its retiring president, Geo. W. Sisson, Jr., went
on record in favor of the creation of an information service for
the collecting and distributing of informative matter which is
of general interest to the industry and the public. This as-
sociation also passed the following resolutions as an endorsement
of the campaign for chemical preparedness:
Whereas this country, desiring peace, cannot escape the ne-
cessity of adequate preparation for war, and
Whereas, the world war has demonstrated that in modern
warfare chemistry will be as dominant as it is in modern industry,
and
Whereas, the synthetic dye industry is the backbone of the
Chemical Warfare Service, which so conclusively demonstrated
its possibilities and efficiency, now, therefore, be it
Resolved that we urge upon the Congress, and individually
upon our own respective representatives, the favorable considera-
tion of such legislation as will assure the continued growth, op-
eration and control of a dominant synthetic dye industry, and
be it further
Resolved that we also urge adequate financial support of the
Chemical Warfare Service both to protect the large investment
of the Government in that division, particularly in the Edgewood
Arsenal, and to keep our army and navy abreast of modern de-
velopments in this branch of the service.
May, 192]
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
485
The newly elected officers of the Association are: President,
W. J. Raybold, of Housatonic, Mass.; Vice Presidents, Henry
W. Stokes, of Philadelphia, and Arthur L. Pratt, of Kalamazoo,
Mich.; Secretary, Hugh P. Baker, New York (reelected).
The Technical Association of the Pulp and Paper Industry
was addressed by its president, Raymond S. Hatch, at the open-
ing meeting. He reviewed the scientific progress of the paper
industry during the past year and called particular attention
to the fact that several textbooks on paper making by American
authors had appeared after a lapse of several years. He also
called attention to the work of the Committee on Vocational
Education which is now formulating plans for carrying on its
educational work in various paper-making communities. One
of a series of three volumes on the principles underlying the manu-
facture of paper and the various operations connected with paper
making has been completed by a cooperative committee repre-
senting the various paper associations, and the other two vol-
umes are scheduled to appear in the near future. These books
are intended for the education of workers in the paper industry
with a view of increasing their efficiency and preparing them for
better positions.
A series of committee reports and papers were presented at
the various sessions under the following headings:
Economy of Steam in Drying on and Driving of Paper Machines. H. S.
Taylor.
Pulverized Fuel for Paper Mill Power Plants. L. L. Hebbard.
The New Hall Process of Grinding Wood. W. A. Munro.
Effect of Variables on Bleaching Efficiency. G. K. Spence.
Use of Waste Heat for Ventilation of Machine Rooms. W. H. Howell.
Evaluation of Lime by Causticizing Tests. Carl Moe.
How to Increase the Operating Efficiency of Existing Water Power Plants.
C. M. Allen.
Shortening Cooking Time by Preliminary Impregnation in the Production
of Sulfite Pulp. V. P. Edwards.
Economics of Electrification in the Paper Industry. S. A. Staege.
A New Weightometer for Soft Stock, Chips and Acid. E. G. Trimbey.
A Moisture Content Indicator for Paper. C. B. Twing.
Measuring Moisture of Chips in Cooking. F. M. Williams.
Method of Drying Paper on Paper Machines. W. D. Fulton.
A Classification, Filing and Indexing System for a Pulp and Paper Li-
brary. C. E. Curran.
Rinman's Pulping and Recovery Methods. B. N. Segerfelt.
The annual banquet of the Association held on the final day
of the meeting was addressed, among others, by Prof. Marston
T. Bogert of Columbia University, past president of the Society
of Chemical Industry, and Ellwood Hendrick, president of The
Chemists' Club of New York. The new officers of the Associa-
tion are: President, George E. Williamson; Vice President, F.
C. Clark; Secretary-Treasurer, T. J. Keenan (reelected).
Calendar of Meetings
American Leather Chemists Association — Eighteenth Annual
Meeting, The Ambassador Hotel, Atlantic City, N. J., June 9
to 11, 1921.
American Institute of Chemical Engineers — Spring Meeting,
Detroit, Mich., June 20 to 21, 1921.
Society for the Promotion of Engineering Education — Twenty-
ninth Annual Meeting, Yale University, New Haven, Conn.,
June 28 to July 1, 1921.*
Society of Chemical Industry — Annual Meeting, Montreal, Can-
ada, August 26 to 31, 1921.
American Chemical Society and Society of Chemical Industry —
New York City, September 6 to 10, 1921.
Seventh National Exposition of Chemical Industries — Eighth
Coast Artillery' Armory, New York, N. Y., September 12 to
17, 1921.
American Drug Manufacturers Hold Tenth
Annual Meeting
The American Drug Manufacturers' Association, together
with its Scientific and Biological Sections, met at the Biltmore
Hotel, New York, from April 11 to 14, inclusive. The first day
of the meeting was given over entirely to deliberations of the
Scientific and Biological Sections, the former holding its meeting
under the chairmanship of Dr. J. M. Francis, and the latter under
the chairmanship of Dr. E. M. Houghton.
The Biological Section, which consists of representatives of
those firms engaged in the manufacture of serums, vaccines, and
other biological products, gave considerable time to the con-
sideration of government regulations covering the production
of their products, as well as the matter of bringing about greater
uniformity in the packaging of biological remedies. Dr. George
W. McCoy, director of the Hygienic Laboratory of the U. S.
Public Health Service, addressed the Section on Tuesday, April
12, and called attention to the necessity for care in making the
various tests required for sterility, etc., in biological laboratories.
Dr. McCoy stated that the Government had succeeded in se-
curing the assistance of several able bacteriologists to work on
the problem of standardizing smallpox vaccine.
The Scientific Section devoted its sessions largely to the pre-
sentation and discussion of reports of subcommittees. These re-
ports covered acetylsalicylic acid, aconite, cannabis, chloroform
and ether, control assays, crude and milled drugs, excipients and
extracts, drug extracts, essential oils, laboratory management,,
malefern, miscellaneous alkaloid and drug standards, miscel-
laneous chemical tests and standards, nitroglycerin, pepsin,
pituitary extract, surgical dressings and plasters, and weights
and measures. As a result of the discussion of these reports, a
number of recommendations were made to the Revision Com-
mittee of the United States Pharmacopeia for changes in the
standards of certain drugs and the addition of new products
which are not recognized in the present Pharmacopeia. One
of the features of the meeting of the Scientific Section was a
lecture by Dr. Edwin E. Slosson, editor of Science Service, on
"The Opportunity of Chemistry in America." He dwelt on the
fact that medicine was becoming more and more the science and
art of prevention, rather than the practice of curing diseases, and
that the drug manufacturer has ample opportunity for research
along this line.
The business sessions of the Society began Tuesday afternoon,
April 12, with the address of President W. A. Sailer, who out-
lined the condition and prospects of the drug business in detail,
taking a very optimistic view of the future. This address was
followed by the reports of other officers and committees.
At the second session, Wednesday, April 13, Dr. C. E. Young,
of the office of the Federal Prohibition Commissioner, addressed
the membership on the alcohol situation. The third session,
held Wednesday afternoon, was devoted largely to a debate on
the sales tax, in which the principal speakers were Hugh Satterlee
for the affirmative and Fayette R. Plumb for the negative. At
the conclusion of the debate the Association went on record by
an overwhelming vote in favor of the imposition of a tax on
gross sales not exceeding 1 per cent, and the repeal of the excess
profits tax. A discussion of tariff matters, the credit situation,
and patent and trade-mark legislation concluded this session.
The fourth session, held Thursday, April 14, was devoted to a
consideration of foreign trade problems, including the possibility
of having the Pharmacopeia of the United States translated into
Chinese so as to aid commerce in American drug products in
China.
At the final session the Association adopted a resolution urging
Congress to confer immediately upon the War Trade Board,
pending the enactment of new tariff laws, authority to regulate
imports, from all countries, of chemicals now manufactured in
the United States and available at reasonable prices and in suffi-
cient quantities to supply all requirements, as is now done with
dyestuffs and chemicals of German origin, to prevent the dump-
ing of such chemicals in the United States.
The Association also went on record on the following topics:
against compulsory health insurance; in favor of simplifying the
486
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
record keeping under the Harrison Narcotic Law; in favor of the
material reduction of surtaxes; in favor of the Nolan Bill for
reorganizing the Patent Office, but opposing that portion which
permits assigning of patents to government employees; against
the prohibition of the use of saccharin in food products; in favor
of the work of the Research Committee of the American Pharma-
ceutical Association, and in favor of continuing the present tax
on nonbeverage alcohol.
The following officers were elected to serve for the ensuing year:
President, William A. Sailer, of Sharp and Dohme, Baltimore;
Vice Presidents, James E. Bartlett, of Parke, Davis & Co., De-
troit; Willard Ohliger, of Frederick Stearns & Co, Detroit; and
Charles G. Merrell, of the William S. Merrell Co., Cincinnati;
Secretary, W. J. Woodruff, Washington, D. C; Treasurer, Frank-
lin Black, of Charles Pfizer & Co., New York; Members of the
Executive Committee, James F. Pardee, of the Dow Chemical Co.,
Midland, Mich.; and S. B. Penik, of S. B. Penik & Co., New
York.
WASHINGTON LETTER
By Watson Da
1418 Rhode Island Ave., Washington, D. C.
The keynote of current Congressional activity was sounded by
President Harding in his initial address to Congress when he
"urged instant tariff enactment, "emergency in character and un-
derstood by our people that it is for the emergency only," and
declared: "I believe in the protection of American industry, and
it is our purpose to prosper America first. The privileges of the
American market to the foreign producer are offered too cheaply
to-day. Moreover, imports should pay their fair share of our
cost of government."
PROSPECTIVE TARIFF LEGISLATION
An emergency tariff bill introduced by Representative Young
has already passed the House. This measure includes the whole
of the Fordney Bill that failed last session, and has two additional
provisions that will act as "stop-gaps" between the time that
peace is declared and the regular tariff bill is enacted. The first
of these additions is an anti-dumping provision which will pre-
vent the selling of articles by foreigners in the United States at
prices lower than they ask in their own countries. This is ac-
complished by levying a duty equal to the difference in price in
this country and abroad. The second portion aims at conditions
produced by deflation of foreign money and provides that the
value of such money as a basis for the collection of duties shall
in no case be less than one-third of the par value of the money.
This provision will increase the duties from Italy, Germany,
Austria, and some of the Balkan States, whose currency has de-
preciated in some cases to only one-twentieth par. It is said
that these provisions will revive certain chemical industries that
have been drowned in the flood of foreign importations.
The regular tariff bill may not be introduced until June.
There will be no "pop-gun" bills, as Senator Penrose has called
them. Those measures of the 66th Congress whose object was
the effective safeguarding of the dye, chemical glassware and
porcelain, scientific instrument, potash, magnesite, tungsten,
and other industries have bequeathed their provisions to the
new regular tariff bill. The Bacharach Bill for the protection
of scientific instruments, chemical apparatus, and porcelain will
be among those included. It is understood that no hearings
supplemental to those of the last session will be held by the Ways
and Means Committee, but that there will be hearings when the
bill reaches the Senate.
The United States Tariff Commission has just finished com-
piling "Suggested Reclassification of Chemicals, Oils, and Paints,"
which will be the basis of Schedule A of the new tariff.
American chemistry students will not return to the use of
German apparatus and glassware, as it is planned to eliminate
the tariff clause that provides the exemption of scientific glass-
ware used in schools and colleges.
CONFERENCES WITH SECRETARY OF COMMERCE HOOVER
To learn the state of the industries and to determine how the
Department of Commerce can aid them, Secretary Hoover has
met groups of prominent chemical manufacturers and has talked
to them about their problems. Representatives of the dye, zinc,
coke products, paint, varnish, and oil industries have told him
of their export needs, domestic conditions, and the tariff pro-
tection they desire. Mr. Hoover has also called an informal
conference of trade paper editors and discussed with them how
the technical and trade information of his department may be
most satisfactorily furnished the manufacturers and industries.
According to officials, the department is very much interested in
aiding the defense of the nation's war-born dye industry against
competition of the German dye and chemical trade, and these
meetings have been held to determine what is needed to make
the industry secure and assure the independence of this country'
rom foreign sources of supply.
CHEMICAL WARFARE SERVICE
The Army Appropriation Bill that will carry with it the funds
for the Chemical Warfare Service during the coming fiscal year
has not yet been introduced. It is expected, however, that it
will soon be offered, and in practically the form in which
it failed last session. This will mean that it will carry $1,500,000
for chemical warfare work, and according to Brig. Gen. Amos
A. Fries, who has received his permanent appointment as chief of
the Chemical Warfare Service, they are planning to operate on
this amount. Although it is declared that 2 per cent of the
army's appropriations, or $7,000,000, is the amount needed to
supply all branches of the army amply and sufficiently with
poison gas and other material and to keep investigative work
going at the proper speed, it is said that the smaller amount will
provide for all activities fairly well, except the making of a proper
reserve of gas masks for the army.
Last Saturday, officers of the Chemical Warfare Service held
an annual dinner attended by about 180 officers and guests.
Various phases of chemistry and chemical warfare were discussed.
Gen. Fries told of the development of the toxic smoke candle,
which is an easily transported solid, safe against shock or bullet
puncture. He said that, owing to the use of this material and
the new "dew of death" gas, war in the future will never be free
from gas. Brig. Gen. William Mitchell, assistant chief of the air
service, told how, by sprinkling two tons of crying gas on New
York City from airplanes once every eight days, the whole city,
which is an excellent air target and without sufficient exits for
a general exodus, could be subdued. Brig. Gen. Charles E.
Sawyer, personal physician to President Harding, prophesied
that the work of the physiological chemist who is determining
the effect of gas on body cells and tissues will aid the doctors in
getting at the true nature of disease. Rear Admiral W. F. Smith
of the navy declared that measures were being taken to protect
our battleships from attack both by gas and airplane bombs.
"The Chemical Warfare Service will be just as important as any
other branch of the army," declared Assistant Secretary of War
E. J. Wainwright. Representative Kahn, chairman of the
Military Affairs Committee, said that it was his belief that the
Service should be given ample funds to prepare the army for
use of gas in warfare. Representative Mondell also spoke in
favor of chemical preparedness. Dr. H. C. Parmelee, editor of
Chemical and Metallurgical Engineering, emphasized the need
of popular understanding of the work of the Chemical Warfare
Service, and Dr. W. D. Bancroft, of Cornell, spoke on research
as the true basis of all developments in chemical warfare. Dr.
Chas. H. Herty was toastmaster.
The advisory committee of the Chemical Warfare Service is
to meet at Edgewood on April 23, and General Fries and his
staff will show them the condition of the plant, and get their ad-
vice on the further conduct of the work. A new session of the
Chemical Warfare School at Edgewood has begun with 25 officer
students of the Service, and three officers detailed from both the
navy and marine corps.
PATENT LEGISLATION
No patent legislation has been introduced in Congress during
the present session up to the present time, although it is expected
that the bill providing financial relief for the Patent Office will
be introduced jointly in a short time. The provision that
authorized the Federal Trade Commission to administer inven-
tions developed in the government service will have separate
introduction. Thomas E. Robertson, a Washington patent
lawyer, has been nominated Commissioner of Patents by Presi-
dent Harding.
OTHER BILLS
Senator Smoot has just introduced his bill for the reclassifica-
May. 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
487
tion of government salaries, and there is a Senate scrap in prog-
ress between him and Senator Sterling, a firm believer in the
importance of scientific research, as to whose committee will
have jurisdiction. There has been little opportunity for analysis
of the proposed Smoot measure, and how the government chemist
is treated cannot be said.
The use of the metric system of weights and measures in all
commercial transactions in the United States where weights and
measures are involved, beginning ten years hence, is provided
in a bill introduced by Representative Britten of Illinois. De-
claring that the United States and Great Britain are the only
two major countries that have not made the metric system their
single standard of weights and measures, Representative Britten
has announced that he intends to press his bill for an early hear-
ing.
HOUSE COMMITTEES
As yet members of the Senate Committees have not been an-
nounced, but House Committees have been selected. The chair-
men of the House Committees that are of interest to chemists
and engineers are: J. W. Fordney, Ways and Means; J. W. Good,
Appropriations; S. E. Winslow, Interstate and Foreign Com-
merce; S. W. Dempsey, Rivers and Harbors; G. N. Haugen,
Agriculture; J. Kahn, Military Affairs; T. S. Butler, Naval Af-
fairs; H. Steenerson, Post Office and Post Roads; N. J. Sinnott,
Public Lands; M. E. Rhodes, Mines and Mining; J. I. Nolan,
Labor; F. Lampert, Patents; M. P. Kinkaid, Irrigation; P. P.
Campbell, Rules; T. B. Dunn, Roads; W. A. Rodenberg, Flood
Control.
BUREAU OF MINES
Dr. H. Foster Bain, who was made director of the Bureau of
Mines in the closing months of the past administration when
Dr. F. G. Cottrell resigned, has been nominated by President
Harding to that position.
Lignite research work, which has heretofore been carried on
by the United States and the Canadian government by their
own mining bureaus without cooperation, will be conducted
jointly in the future. Dr. Bain has announced. Information and
data that have been obtained in the past will be exchanged, and
American and Canadian engineers will work together.
PERSONNEL RESEARCH FEDERATION
The formation of the Personnel Research Federation, a national
clearing house, linking two hundred and fifty scientific, engineer-
ing, labor, management, and educational bodies, has been ac-
complished at the National Research Council here. The organi-
zation aims to study the efficiency of all the personnel elements
of industry, that involve employer, manager and worker, and
make for improved safety, health, comfort, and relationships.
Its immediate purpose will be to learn what organizations are
studying one or more problems relating to personnel and the
scope of their endeavors, and to determine whether these endeav-
ors can be harmonized, duplication minimized, neglected phases
of the problems considered, and advanced work undertaken.
Robert M. Yerkes, representing the National Research Council, has
been elected chairman of the Federation, and Samuel Gompers,
representing the American Federation of Labor, vice chairman.
Robert W. Bruere, who represents the Bureau of Industrial Re-
search, was chosen treasurer, and Alfred D. Flinn, representing
the EngineeringlFoundation, secretary. Beardsley Ruml, assistant
to the president of the Carnegie Corporation of New York, was
selected as acting director.
The Secretary of War has announced after investigation that
if responsible persons can be found to take over the operation of
the Muscle Shoals Nitrate and Water Power Plant, he will recom-
mend to Congress that the $30,000,000 needed to complete the
project be appropriated.
Dr. Augustus Trowbridge, chairman of the division of physical
sciences of the National Research Council, has been appointed
the American representative on the International Research
Council.
April 19, 1921
INDUSTRIAL NOTES
The Burnham Chemical Company has been incorporated to
further the commercial development of the solar concentration
processes which have been used in experiments on the potash
brines of Searles Lake for the past year. The features of the
patented process are chilling over shallow areas during winter-
night periods and storing in deep vats between chilling periods
to avoid warming up excessively, thus removing sodium sul-
fate, as well as influencing further brine treatment in the re-
covery of potash and borax. It is hoped by this method to
produce potash more cheaply than by methods now in opera-
tion on brines.
The escape of phosgene from a defective valve in an 1800-
gal. tank at the Hemingway Chemical Plant at Bound Brook,
N. J., on April 22, 1921, caused the death of one man and threat-
ened the whole community. Workmen in gas masks who were
rilling small containers from the large tank had difficulty in
breathing and found the defective valve, but were unable to
repair it. Harold Saunders, chief chemist at the plant, was
notified, and finally succeeded in checking the flow of the gas.
Plans are under way for a laboratory building for chemical,
bacteriological, and other research work of the Netherlands
Institute of Animal Nutrition which will be completed in about
two years. An annex known as the vitamine laboratory is
already under construction for immediate occupancy.
Dyes valued at $1,343,531 were exported during the month
of January 1921. These included aniline dyes valued at $943,-
595, of which $262,954 went to China, $148,699 went to Eng-
land, and $108,026 to British India. Imports of dyes and dye-
stuffs during January totaled 399,214 lbs., valued at $324,677.
There were no imports of synthetic indigo. Alizarin and alizarin
dyes were imported as follows:
Pounds Value
France 176 $515
Germany 1500 1574
England 25 SS
Mr. Hervey J. Skinner, Mr. Herbert L. Sherman, and Mr.
Gustavus J. Esselen, Jr., have formed an association under the
name of Skinner, Sherman & Esselen, Inc., Boston, Mass., to
furnish counsel on matters relating to the application of chem-
istry and biology to industrial relations, and have acquired the
business of the Boston Bio-Chemical Laboratory.
In order to utilize to its full capacity its plant at San Antonio,
Paraguay, an American meat packing corporation has plans
under way to manufacture citrous fruit products, and has asked
the Paraguayan Congress to amplify its concession to include
this field. The company also plans to bring in seeds for the cul-
tivation of cotton, castor beans, and sunflowers. It is esti-
mated that the plant will be able to handle yearly 500 tons of
tangerines, 500 tons of bitter oranges, 1000 tons of sweet oranges,
250 tons of lemons, 500 tons of limes, 100 tons of mangoes, and
100 tons of guavas.
During the month of March 1921 thirty-two companies were
formed to engage in the manufacture or distribution of chem-
icals, drugs, and dyes. The total authorized capitalization was
$11,765,000, as compared with $6,450,000 in February, when
twenty-three companies were organized, and $22,295,000 in
January. The total capitalization for the first three months of
1921 amounted to $40,520,000, which is a considerable decline
from the total of $60,188,000 for the corresponding period of 1920.
The Societa Anonima Cooperativa, representing the fruit in-
dustries of Sicily and Calabria, has been organized under the
auspices of the Chamber of Agriculture to supervise the fruit
industries in general and arrange for the manufacture of deriv-
ative products of the lemon industry. The company is expected
to continue for ten years, and includes, in addition to producers of
essences, exporters and brokers of the essences and producers
of acid fruits and derivatives.
In spite of the attention which has been given during the
past ten years to the recovery of coal by-products in South
Africa, it is estimated that a million tons a year is now wasted.
Much experimental work has been done recently on the testing
of coal for the production of coke and tar and the distillation
of oils and creosote, as there are large accumulations of waste
and low-grade coal at the various collieries which can be treated
for by-products, although not suitable for sale purposes.
German residents in Japan are reported as steadily increasing
in number, now almost double that of pre-war days. Most
of them are employed in firms and factories as engineers, and
it is stated that nearly a hundred applications for positions in
Japan have been received from German engineers and experts.
The imports of toys, chemicals, and dyestuffs from Germany
during the first ten months of 1920 amounted to $1,000,000.
488
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 5
PERSONAL NOTES
Mr. Charles S. Hawes, in charge of the Bureau of Researc h
and Statistics of the War Trade Board Section of the Depart-
ment of State, died suddenly on Friday, April 22, 1921, in
Chicago, 111., where he was on a special investigation for the
Department. Mr. Hawes joined the War Trade Board in 1918
and remained with the new Section when the old Board was
dissolved. As head of its Bureau of Statistics, which has been
chiefly concerned of late with the inportation of dyes and chem-
icals and coal-tar products, Mr. Hawes recently compiled the
report on "Coal-Tar Dyes for Which Licenses Were Granted
during the Fiscal Year 1920." Mr. Hawes was fifty-one years
of age.
Dr. Albert C. Hale, died at his home in Brooklyn, N. Y., on
Sunday, April 24, at the age of seventy-five years. Dr. Hale
was head of the department of physical science in the Brooklyn
High School from 18S3 until his retirement in 1912. Dr. Hale was
one of the early members of the American Chemical Society,
and served as a director from 1887 to 1902, as vice president in
1889, and as general secretary from 1889 to 1902.
The executive office of the National Exposition of Chemical
Industries has been moved from 480 Lexington Ave., to 342
Madison Ave., New York, N. Y.
Dr. Ernest Fox Nichols, former president of Dartmouth Col-
lege, has been elected president of the Massachusetts Institute of
Technology, Cambridge, Mass., which vacancy was occasioned
about a year ago by the death of Dr. R. C. Maclaurin. Dr.
Nichols has been director of research at the Nela Park Labora-
tories, Cleveland, Ohio, since leaving Dartmouth. He will
be inaugurated on June 8.
Maj. Gen. Leonard Wood has been elected head of the Uni-
versity of Pennsylvania. The title of the position has not yet
been announced, inasmuch as the usual presidential duties will
be divided between General Wood and the acting provost. Dr.
J. H. Penniman.
Dr. C. L. Alsberg has resigned as chief of the Bureau of
Chemistry of the U. S. Department of Agriculture to become
a director of the Food Research Institute at Stanford Univer-
sity, California. Dr. Alsberg will assume his new duties about
July 1.
Mr. Harper F. Zoller, formerly chemist with the Dairy Divi-
sion Research Laboratory of the U. S. Department of Agriculture,
Washington, D. C, is at present bacteriological chemist for the
Nizer Laboratories Co., Detroit, Mich.
Mr. Robert S. Scull has left the post of technical manager for
Curd'& Blakemore Co., Louisville, Ky., to take the position of
chemical engineer for the Paul DeLaney Co., Inc., food manu-
facturers, Brocton, N. Y.
Dr. C. G. Storm has been transferred from the position of
professor of chemical engineering at the Ordnance School of
Application, Aberdeen Proving Ground, Md., to the office of the
Manufacturing Service, Ordnance Department, Washington,
D. C, for technical duty in the ammunition division.
Mr. Dwight Tenney, chief engineer of the Franklin Baker
Co., New York, and formerly connected with the engineer-
ing staff of the National Biscuit Co., has become associated with
the Pease Laboratories, Inc., New York City, as head of their
newly organized department of engineering. Mr. Tenney will
continue his connection with the former company as consulting
engineer, having charge of all technical development work.
Mr. R. K. Durham, who was connected with the Lexington
Roller Mills Co., Lexington, Ky., as chief chemist, has become
director of laboratory control and research with the Rodney
Milling Co., of Kansas City, Mo.
Mr. Reeves W. Hart recently joined the research staff of the
New York Quebracho Extract Co. Mr. Hart was formerly
research chemist with Kullman, Salz & Co., of San Francisco,
Cal.
Miss Ruth E. Merling, who received her Ph.D. at the Uni-
versity of Illinois last June, has left the B. F. Goodrich Co.,
where she was employed as a research chemist, and has accepted
a position as instructor in chemistry at Illinois Woman's College,
Jacksonville, 111.
Mr. Albert G. Loomis has resigned as assistant professor of
chemistry at the University of Missouri, to become physical
chemist for the new Cryogenic Laboratory, Washington, D. C.
Mr. Enoch Karrer has severed his connection with the Bureau
of Standards as physicist and now holds a similar position in the
Nela Research Laboratory, Nela Park, Cleveland, Ohio.
Mr. Silas I. Royal has resigned from the Semet-Solvay Process
Co., in order to take up his new business relations with the firm
of Royal Bros., in Atlantic City, N. J.
Dr. Colin G. Fink, of South Yonkers, who organized and for
the past four years directed the research laboratories of the
Chile Exploration Co., has resigned his post. Dr. Fink
was formerly in charge of research at the Edison Lamp Works,
and has been editor of the "Electrochemistry" section of Chem-
ical Abstracts since 1907.
Mr. Montford Morrison is now consulting engineer of the
International X-ray Corporation, New York City, having
formerly been chief engineer of the Victor X-ray Corporation of
Chicago, 111.
Mr. F. C. Fair, formerly resident representative of the American
Standardizing Bureaus, Washington, D. C, having supervision
of the manufacturing of their pharmaceutical products, has
become chief chemist for the Central Railway Signal Co., at
their Hammond, Ind., plant.
Prof. J. H. Mathews recently made a lecture tour among six
of the Michigan and Ohio Sections of the American Chemical
Society, lecturing on "Color Photography" and "Photochem-
istry."
Mr. Philip A. Patterson has resigned as chief chemist of the
Lincoln Motor Car Co., Detroit, Mich., and has accepted a
position with the chemical department of the United States
Rubber Co., at Detroit.
Dr. Warren C. Vosburgh, formerly a national research fellow
at Columbia University, is now in charge of research in the
laboratory of Marion Eppley, Newport, R. I.
Dr. Reid Hunt, professor of pharmacology in the Harvard
Medical School, has been appointed by the Surgeon-General of
the United States Public Health Service, a member of the ad-
visory board of the Hygienic Laboratory to succeed the late
Dr. W. T. Sedgwick.
Mr. C. H. Campbell has severed his connections with Garrett
& Co., Brooklyn, N. Y., and has accepted a position with Wm.
McMurray & Co., manufacturers of pure food products and
household necessities, St. Paul, Minn.
Prof. William Moore has obtained a leave of absence for a
period of six months from the University of Minnesota, where
he is associate professor of entomology, to work on the de-
velopment of arsenical substitutes for use in the control of the
Japanese beetle. His work is with the State of New Jersey and
the U. S. Bureau of Entomology.
Mr. Edgar S. Ross, who for the past eighteen months has been
doing private research work with Prof. C. James of New Hamp-
shire College, Durham, N. H., recently went to Philadelphia
and will continue research investigations at the Greenwich
Point Laboratories of the Pennsylvania Salt Manufacturing
Company.
Mr. G. L. Erikson, chemist in charge of the manufacture of
azo dyes, etc., at the Cable, Wis., factory of the Sunbeam
Chemical Co., has accepted a position in the printing ink de-
partment of the Manz Engraving Co., Chicago, 111.
Mr. Alfred A. Chambers resigned as assistant to the metal-
lurgist at the Youngstown Sheet & Tube Co., Youngstown,
O., in order to become chief chemist with the Chicago, Mil-
waukee & St. Paul Railway Co., Milwaukee, Wis., a vacancy
occasioned by the appointment of Mr. George N. Prentiss to
the position of engineer of tests.
Mr. Herbert Philipp has given up his consulting practice at
New York and New Brunswick, N. J., and has taken over the
plant management of the Dicks David Co., in Chicago, 111.
Mr. Carl Moe, previously employed at Stevens Point Pulp &
Paper Co., Stevens Point, Wis., where he had charge of the
technical work concerning their sulfate pulp mill, has accepted
a position as chief chemist with the Minnesota & Ontario Paper
Co., International Falls, Minn.
Dr. E. W. Washburn, for some years head of the ceramic
department of the University of Illinois, has become editor
of the Journal of the American Ceramic Society, succeeding Mr.
Homer F. Staley.
Mr. M. L. Berryman resigned as general superintendent of
refineries of the North American Oil & Refining Corp., Oklahoma
City, Okla., last November in order to accept a position as
superintendent of the Inter-Ocean Refining Co., Riverside, 111.
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
489
Miss Emily Grewe, chief chemist for the Seaboard Milling
Co., at Kansas City, Mo., now has charge of the laboratory
•of the Federal Milling Co., at Lockport, N. Y.
Upon the recommendation of the Mellon Institute of In-
dustrial Research, Mr. W. B. Thompson, copper industrialist
of New York City, recently received the honorary degree of
Doctor of Laws, and Mr. C. H. MacDowell, president of the
Armour Fertilizer Co., received the honorary degree of Doctor
•of Science.
Mr. J. Roy Haag, formerly assistant in soil investigaticns at
Maryland Experiment Station, College Park, Md., has been
appointed instructor in agricultural chemistry at Penn State
College, State College, Pa.
Mr. Arthur J. L. Hutchinson has resigned as chief chemist
with the Wallace Refineries at Taft, Cal., to accept a similar
position with Wallace & Brooks, Breckenridge, Texas.
Mr. R. R. Lewis, research chemist at the Experimental Station
of E. I. du Pont de Nemours & Co., in Wilmington, Del., is
now chief chemist for J. C. Haartz, Inc., of New Haven, Conn.
Miss Leone Oyster, who has been doing graduate work at
the University of Wisconsin, has taken a position as instructor
in chemistry at Albion College, Albion, Mich.
Mr. H. T. Buchanan has resigned his position with the Mauser
Mill Co., Treichlers, Pa., to become chief chemist of the Texas
Star Flour Mills, Galveston, Texas.
OBITUARIES
John Downer Pennock
John Downer Pennock, a director and general manager of
The Solvay Process Company and a member and councilor of
the American Chemical Society, died at his home at Syracuse,
New York, Friday, March 11, 1921, following a brief illness.
His death removes from the chemical profession one of its
most competent and well-known members. Mr. Pennock was
truly a leader of his profession, having been many times honored
because of his great ability. He was appointed by Secretary of
State John Hay as United States delegate to the International
Congress of Applied Chemistry at Berlin in 1903, and was the
Belgian representative on the Jury of Awards at the St. Louis
Exposition in 1904. He was a member of the Chemicals Com-
mittee of the Council of
National Defense during
the world war, and was a
member of the Executive
Board of the American
Chemical Alliance.
His activities in the
chemical field covered
practically his entire life,
from his graduation from
Harvard University in
1883, until the time of
his death. For a year
after his graduation he
acted as an instructor at
Harvard, but in 1884 be-
came affiliated with The
Solvay Process Company
as a chemist. During the
thirty-seven years which
followed, he rose to the
position of general man-
ager of that corporation.
A member of many
clubs and societies. Mr.
Pennock leaves a vacancy
in the chemical world difficult to fill. He was president
■of the Central New York Section of the American Chem-
ical Society for several years; a member of the Society of Chem-
ical Industry, the American Institute of Mining Engineers, and
the Archaeological Institute of America. He was a member
of the executive committee of the Manufacturing Chemists' As-
sociation; a member of the Electrochemical Society; a director
•of Associated Industries of New York State, and a member of
numerous technical and social organizations in his home city
and in New York.
To a number of these societies he contributed valuable scien-
tific papers.
Mr. Pennock was born August 16, 1860, at Morristown.
Vermont, being a son of Samuel McMaster Pennock and Alma
Tinker Pennock. When he was seven years old the family removed
to Somerville, Mass., where he obtained his early education and
fitted himself to enter Harvard University. His interest in his
alma mater was great. He was one of the men most instrumental
in securing the new chemical laboratories for that institution;
was a member of its Endowment Fund Committee for Central
New York, and created a scholarship there in memory of his
son, the late Stanley Bagg Pennock.
Of a lovable character, Mr. Pennock made and held a host of
friends in both the business and social world. The love and
esteem in which he was held by his associates is perhaps best
illustrated in the following tribute, incorporated in the records
Downer Peis
of the Board of Directors of The Solvay Process Company at a
meeting held shortly following his death:
"His high character commanded the respect of all, and the
spirit of unselfish devotion and cheerful loyalty with which he
served the Company was a constant inspiration to all his associates.
"His broad, human sympathy and lovable character endeared
him to all with whom he came in contact, both in business and
social life. His qualities as a good citizen were recognized by
all, and he was constantly drawn upon for service to the com-
munity to an even greater extent that he was able to undertake."
E. L. Pierce
Thomas Lynton Briggs
Thomas Lynton Briggs, born in London, December 27, 1858,
died at his home in Flushing, N. Y., April 3, 1921. His grand-
father was the first maker of aniline oil and colors in England,
a business to which his father succeeded; and he himself had
his secondary education at Wiesbaden (under Fresenius) and
at Zurich; after this he was in the employ of Read Holliday's
Sons, makers of aniline colors, at Huddersfield, Eng., and came
to New York, January 1, 1888, as chemist for their works in
Brooklyn. The day before his death he finished twenty years'
service with the General Chemical Company as research and
works chemist, for whom he was the leading expert in the use
of platinum as a contact agent, or catalyst, in making sulfuric
acid. He undoubtedly
knew more about this
than anyone else in the
world, as the practice of
this company is believed
to be in advance of that
of any foreign manufac-
turers. Impurities in the
materials used, or ab-
normal chemical condi-
tions, are liable to stop
or retard the action of
the catalyst, in regard to
which they are said to be
"poisons;" and in devising
prevention and remedies
for this his wide knowl-
edge and his inventive-
ness were of great service.
He was never satisfied be-
cause a process gave
good results; he sought
patiently to understand
it fully; then to perfect
its use, and perfection
is a high and difficult
ideal; but his mind was of that sort, persistent, resourceful,
ingenious, thorough.
He was one of the best amateur botanists about New York;
since the death of Dr. Arthur Elliott he was probably the best-
informed man in the city in regard to early photographic pro-
cesses. Socially, he was a delightful companion; a singularly
modest and retiring man, he was still accessible to everyone;
his unvarying kindness and consideration of the welfare of
others united with his unfailing humor and interesting talk to
make him attractive, and his circle of friends included everyone
who knew him.
Besides his son, Dr. T. R. Briggs, physical chemist and pro-
fessor at Cornell, his family consisted of his wife and daughter.
A. H. Sabin
Thomas Lynton Briggs
490
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
GOVERNMENT PUBLICATIONS
By Nellie A. Parkinson, Bureau of Chemistry, Washington, D. C.
NOTICE — Publications for which price is indicated can be Gems and Precious Stones in 1919. B.H.Stoddard. Sepa-
purchased from the Superintendent of Documents, Government rate from Mineral Resources of the United States, 1919. Part
Printing Office, Washington, D. C. Other publications can II. 16 pp. Published February 2, 1921. The value of gems
usually be supplied from the Bureau or Department from which and precious stones produced in the United States in 1919 was
they originate. Commerce Reports are received by all large $111,763, as against $106,523 in 1918 — an increase of about 5
libraries and may be consulted there, or single numbers can be per cent.
secured by application to the Bureau of Foreign and Domestic Foreign Graphite in 1919. A. H. Redfield. Separate from
Commerce, Department of Commerce, Washington. The regu- Mineral Resources of the United States, 1919. Part II. 30
lar subscription rate for these Commerce Reports mailed daily is pp Published February 5, 1921. The following table shows
$2.50 per year, payable in advance, to the Superintendent of tne world's production of natural graphite for the calendar
Documents. years 1913 to 1919, inclusive, so far as figures are available:
CONGRESSIONAL COMMITTEES World's Production of Natural Graphite, 1913-1919, in Metric Tons
Boron. Disposition of boron deposits, report to accompany United States ., 1913 19U 1915 1916 1917 19ls 1919
S 4749. Submitted by Mr. Smoot, January 31, 1921. Senate Amorphous 2,035 1,565 1,071 2,378 7.530 5.951 3.629'
Ronnrt 7^7 1 n Crystalline 2.297 2.368 3,209 4,959 4.801 5,834 3.372'
.Kepori idi. i [J. Canada'.... 1,961 1.495 2,391 3.588 3,369 2,826 1,199
Gold. Protection of gold reserve, hearings before subcom- Mexico'.... 4,023 3.865 1.525 4,836 6,869 5,080 4,995
mittee on H. R. 13,201, for protection of monetary gold reserve B"z"°r|a and 2-5 .... 2 l 15 45 2
by maintenance of normal gold production of United States styria*. a.° 17.282 11.062 14,815 21,000' 18,000' 17,415 17,000'
to satisfy requirements of arts and trades, by imposing excise Bohemia and
upon all gold used for other than monetary purposes, and pay- Fra^%avia- • 3\'l^\ 26'|^ 20'231 26,313 29^o "'ill 31,gn
ment of premium to producers of newly mined gold, and provid- Germany l2'o57 13 619 17 292 30 574 42 '825 64'080 «
ine penalties thereof . February 1 and 8, 1921. Part 4. 156 pp. Italy 11.145 8,567 6,176 8.182 12,117 10,966' 3,250'
i, _u.- o-i. t i *• i 4. _ * Spain 30 1,240 1,980 710 1,958
Fertilizer Situation. In response to resolution, statement Sweden 88 56 87 194 4 102 •
on fertilizer situation in the United States. February 14, Ceylon'.'.'.!! 2S.996 14.463 22.173 33.956 27,572 15,701 6.504
calendar day February 21, 1921. Senate Document 410. 27 pp. Fr^nhcma3Ind°- 8 000 15 000
CENSUS BUEEAU JgS.^ ^ sVs 6<£ I'l l.Ul l^ll ™.
Anirnaland Vegetable Tats and Oils, Production Consumption, c^™a)... UM3 9,149 7,044 16.963 16,183 13,659 12i000,
Imports, Exports and Stocks by Quarters, Calendar Years 1919 Madagascar. 7,997 n,232 15,940 26,524 35.000 16.000 2,000
and 1920. Prepared under the supervision of W. L. Austin, Union of So .
chief statistician, assisted by H. J. Zimmerman, expert special aJJJSj;"" 35 317 71 72 89 208 102
agent. 16 pp. 19-1. Total. ..136, 497. 5 105,325 112,831 183,509 216,591 205,104
FEDERAL TRADE COMMISSION ' Shipments and sales. • Exports.
Report of Federal Trade Commission on Petroleum Industry " s lma e '
of Wyoming, January 3, 1921. 54 pp. Paper, 10 cents. 1921. Water Supply of St. Mary and Milk Rivers, 1898-1917. B. E.
tt ,n -a -~m., Jones and R. J. BurlEY. Prepared under the direction of the
PUBLIC HEALTH service United States Geological Survey, United States Reclamation
Sanitary Disposal of Sewage through Septic Tank System Service, and Reclamation Service of Canada. Water Supply
of Simple Construction and Inexpensive Operation for Isolated Paper 491. 590 pp. Reprinted by permission of the Inter-
Dwellings. H. R. Crohurst. Reprint 625 from Public Health national Joint Commission.
Reports. 8 pp^ Paper 5 cent* 1921 ^^ Resources of ^ United g m7 parf T
Studies on Treatment and Disposal of Industrial Wastes. Metals H D McCasKey, Geologist in Charge. 980 pp.
Made under the supervision of E.B.Phelps. ^.Purification cloth 1921 The separate chapters which go to make up this
of Creamery Wastes. H. B. Hommon. Public Health Bulletin fa previously been reviewed.
109. 87 pp. Paper, 10 cents. 1921. * *
Ditching with Dynamite. Public Health Reports, 36, 559. Surface Water Supply of the United States, 1917. Part VI.
A demonstration of cheap and rapid ditching with dynamite Missouri River Basm. N. C Grover, W. A. Lamb and
is reported, whereby a 20-acre mosquito-breeding swamp was Robert Follansbee. Prepared in cooperation with the states
converted into valuable pasture land, near Millen, Ga. °f Colorado, Montana, Wyoming, and Kansas. Water Supply
^ x_. ^ t rM. 1 /->•! a t t-,_ ti Paper 456. 242 pp. 1921. This volume is one of a series of
Fractionation of Chaulmoogra Oil A J,. Dean and Richard ^ rts presenting results of measurement of flow made on
WrEnshall. Public Health Reports, 36, b41-60. streams in the United States during the year ending September
Preliminary Note on a Stable Silver Vitamine Compound 30 1917
Obtained from Brewer's Yeast. Atherton Seidell. Public Geology of the Igneous Rocks of Essex County, Massachu-
Health Reports, 36, 665-70. setts c H Clapp Bulletin 704. 132 pp. Paper, 30 cents.
GEOLOGICAL SURVEY 1921. The igneous rocks of Essex County have been separated
™. t_ j. t. i - imr. t> tit o_ „ o 4 , „ ,r into two great groups — the alkaline and the subalkaline. A
Phosphate Rock in 1919 R.W.Stone -Separate from Mm- ^^ st8ateme»t accompanies the report which gives the
^iv^TcT ° ^ ^oof ™ \ u ♦ i n'w • ?■?' chemical composition of rocks from Essex County.
Published February 2o, 1921. The phosphate rock sold in the *
United States in 1919 amounted to 2,271,983 long tons, valued Tungsten in 1918. F. L. Hess. Separate from Mineral Re-
at $11,591,268. As compared with the production in 1918, sources of the United States, 1918, Part I. 54 pp. Published
this was a decrease in quantity of 9 per cent and an increase in March 21, 1921. The tungsten ore produced in the United
value of approximately 41 per cent. States in 1918 was equivalent to 5061 short tons of concentrates
Magnesite in 1919. C. G. Yale and R. W. Stone. Sepa- carrying 60 per cent of tungsten trioxide, valued at $7 049,300
rate from Mineral Resources of the United States, 1919. Part au average of $23.22 a unit, of which 188 tons, arbitrarily valued
II. 9 pp. Published March 7, 1921. The total sales of crude at $225,750, were on hand at the end of the year Although large,
domestic magnesite in 1919 appear to have been 156.226 short the output was less than that of either of the two preceding
tons, valued at $1,248,415, or a decrease of about 32 per cent years- The conclusion is reached that the United States is to-
from 1918 °-av in a Position to keep control of the greater part of the world s
Sand-LhneBrickinl919 Jeeeerson Middleton. Serrate «g£- S^t^^^ffli
^"vS&ST^S^^SA oftandl "*** "telligent commercial dealing, and wise legislation,
lime brick in 1919, after the large decrease in 1918, rallied and Salt, Bromine, and Calcium Chloride in 1919. Herbert
increased considerably in quantity and nearly doubled in value. InslEY. Separate from Mineral Resources of the United States,
The increase in quantity was 48,548,000 brick, or more than 1919, Part II. 18 pp. Published March 26, 1921. The salt
49 per cent. The value increased $821,234, or 93 per cent. produced and sold in the United States in 1919 amounted to
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
491
6,882,902 short tons, valued at $27,074,694, a decrease of 4.9
per cent in quantity as compared with 1918, but an increase of
0.5 per cent in value.
The bromine produced in the United States in 1919 amounted
to 1,854,971 lbs., valued at $1,234,969. This is an increase of
7.4 per cent in quantity and 27.3 per cent in value over the
production in 1918. The quantity produced in 1918 was an
increase of 92.9 per cent over that for 1917.
The production of calcium magnesium chloride in 1919 showed
a decrease of 1.9 per cent in quantity and of 36.1 per cent in
value, compared with that of 1918. The average selling price
declined from the abnormally high mark of $18.91 a ton in 1918
to $12.31 a ton in 1919.
Fuller's Earth in 1919. Jefferson Middleton. Separate
from Mineral Resources of the United States, 1919, Part II.
8 pp. Published March 9, 1921. The activity in the fuller's
earth industry continued during 1919 with increased vigor, and is
reflected in the large output for the year. The prospects for
increased output seem good. The output in 1919 was 106,145
short tons, valued at $1,998,829, an increase of 21,677 tons, or
26 per cent in quantity, and of $852,475, or nearly 75 per cent in
value.
Mica in 1919. Herbert InslEy. Separate from Mineral
Resources of the United States, 1919, Part II. 9 pp. Published
March 28, 1921. The mica produced and sold in the United
States in 1919 amounted to 4031 short tons, valued at $541,651.
Of this quantity, 1,545,709 lbs., valued at $483,567, were sheet
mica; the rest was scrap mica. The quantity of sheet mica
produced was a decrease of 6 per cent, and the value a decrease
of 34 per cent in 1919, compared with 1918. The quantity of
scrap mica produced in 1919 was an increase of 42 per cent over
that in 1918, but was less than in most recent years.
BUREAU OF MINES
Procedure for Establishing a List of Permissible Miners'
Flame Safety Lamps. Character of Tests, Conditions under
Which Lamps Will Be Tested, and Fees. 13 pp. Paper, 5
cents.
Procedure for Establishing a List of Permissible Methane
Indicators for Mines. Fees, Character of Tests, and Condi-
tions under which Indicators Will Be Tested. Schedule 8A.
9 pp. Paper, 5 cents.
Bibliography of Petroleum and Allied Substances in 1918.
E. H. Burroughs. Bulletin 189. Petroleum Technology 58.
180 pp. Paper, 25 cents. This bulletin is the fourth in the
series of petroleum bibliographies being published by the Bureau
of Mines.
Boiler Water Treatment. Reprint of Engineering Bulletin 3.
Prepared by the United States Fuel Administration in Collabora-
tion with the Bureau of Mines. Technical Paper 218. 8 pp.
Paper, 5 cents.
Ventilation in Metal Mines — A Preliminary Report. Daniel
Harrington. Technical Paper 251. 44 pp. Paper, 10 cents.
This paper deals with the second of a series of related investiga-
tions in metal mines primarily regarding the health of miners.
Quarry Accidents in the United States during the Calendar
Year 1919. W. W. Adams. Technical Paper 275. 66 pp.
Paper, 10 cents. 1921.
Accidents at Metallurgical Works in the United States dur-
ing the Calendar Year 1919. W. W. Adams. Technical Paper
280. 31 pp. Paper, 5 cents. The calendar year 1919 shows
a considerable decrease in the number of men employed and
the number of fatal and nonfatal injuries, as compared with
1918.
Permissible Schedules Issued by the Bureau of Mines. L.
C. IlslEy. Reports of Investigations. Serial No. 2211. 3
pp. Issued February 1921.
Investigation of Dust in the Air of Granite-Working Plants.
S. H. Katz. Reports of Investigations. Serial No. 2213. 3
pp. Issued February 1921.
Some Items of Investment, Expense, and Profit in Commercial
Shale-Oil Production. L.H.Sharp. Reports of Investigations.
Serial No. 2214. 3 pp. Issued February 1921.
The Saybolt Furol Viscosimeter. E. W. Dean. Reports
of Investigations. Serial No. 2215. 4 pp. Issued February
1921. The Saybolt furol viscosimeter has a wide range of ap-
plicability in commercial transactions in fuel oil, and its use is
recommended to buyers and sellers of the more viscous types
of residuum products.
The Fluorspar Industry in 1919-1920. H. U. Davis and
R. B. Ladoo. Reports of Investigations. Serial No. 2216. 7
pp. Issued February 1921.
Explosion in High-Pressure Compressed-Air Line. E. D.
Gardner. Reports of Investigations. Serial No. 2218. 3 pp.
Issued February 1921.
The Gasoline Explosion at Memphis, Tennessee, January 24,
1921. D. B. Dow. Reports of Investigations. Serial No.
2219. 4 pp. Issued February 1921.
Third Semiannual Motor Gasoline Survey. N. A. C.
Smith. Reports of Investigations. Serial No. 2220. S pp.
Issued February 1921.
Cannel Coal in Southern Utah. C. A. Allen. Reports of
Investigations. Serial No. 2221. 3 pp. Issued February 1921.
Recent Articles on Petroleum and Allied Substances. Com-
piled by E. H. Burroughs. Reports of Investigations. Serial
No. 2222. 36 pp. Issued February 1921.
Pennsylvania Mining Statutes Annotated. J. W. Thompson.
Bulletin 185. Law Serial No. 21. 1221pp. Paper, $1.00. This
bulletin is intended to include every legislative enactment of the
Commonwealth of Pennsylvania relating to the mining and
mineral industries.
Underground Conditions in Oil Fields. A. W. Ambrose.
Bulletin 195. Petroleum Technology 62. 238 pp. Paper,
65 cents. 1921. The purpose of this bulletin is to point out
the general method of procedure in studying underground
conditions in oil fields, and to place before the petroleum industry
the results of proper cooperation between the so-called technical
men and the practical men who have applied engineering methods
to the development of oil fields. Much of the paper is devoted
to a solution of water problems.
Regulation of Explosives in the United States with Especial
Reference to the Administration of the Explosives Act of October
6, 1917, by the Bureau of Mines. C. E. Munroe. Bulletin
198. 45 pp. Paper, 10 cents. Issued February 1921. The
facts developed in the administration of the act of October 6,
1917, emphasize the need for close supervision over the control
of the manufacture, storage, transportation, and use of explosives
in order properly to protect the people of this country from acci-
dents occurring from them or outrages committed with them.
This may be accomplished by the enactment of a uniform law
by each of the States and by the United States to cover its
territories, the District of Columbia, and all other possessions,
if such laws are uniformly administered, or by a single federal
law operating throughout the land. A proposed form of peace-
time legislation is suggested which, it is believed, if efficiently
administered would go far toward securing the protection needed.
Flotation Tests of Idaho Ores. C. A. Wright, J. G. Par-
melee and J. T. Norton. Bulletin 205. 70 pp. Paper, 25
cents. 1921. This report was prepared in cooperation with the
School of Mines, University of Idaho, and the Idaho State
Bureau of Mines and Geology. The object of this paper is to
give to mining companies and to all others who are interested
some idea of the possibilities in the treatment, by differential
flotation, of lead-zinc ores of the Coeur d'Alene region and other
districts. Although the results are not to be considered final,
they indicate possibilities and may suggest others leading to a
solution of the problem of separating lead and zinc sulfides by
differential flotation in the treatment of certain ores.
Analyses of Iowa Coals. G. S. Rice, A. C. Fieldner and
F. D. Osgood. Technical Paper 269. 28 pp. Paper, 5 cents.
1921. The bulletin contains a description of the geology of
coal beds, coal resources, character of the coal, development,
transportation, uses, fusibility of ash, coking properties, markets,
future development, chemical analyses, and a list of publications
on the composition of coal.
The Detection and Estimation of Platinum in Ores. C. W.
Davis. Technical Paper 270. Mineral Technology 31. 27 pp.
Paper, 5 cents. 1921. This paper was prepared to furnish a
ready reference to those assayers who have had difficulty in
detecting or determining platinum ; it summarizes methods for the
detection of the metal, and gives a selected method for the com-
mercial estimation of platinum in ores.
Working for the Miner's Safety. D. A. Lyon. Reports of
Investigations. Serial No. 2223. 3 pp. Issued March 1921.
Dangers in Using Low-Grade Foreign Detonators. C. E.
Munroe. Reports of Investigations. Serial No. 2226. 2 pp.
Issued March 1921.
Method of Controlling Gas Well, Alkali Butte, Wyoming.
F. B. Tough. Reports of Investigations. Serial No. 2227.
2 pp. Issued March 1921.
The Estimation of Small Quantities of Gold, Silver, and the
Platinum Metals in Material High in Copper. C. W. Davis.
Reports of Investigations. Serial No. 2228. 5 pp. Issued
March 1921.
492
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. Xo. 5
A Convenient and Reliable Retort for Assaying Oil Shales for
Oil Yield. L. C. Karrick. Reports of Investigations. Serial
No. 2229. 6 pp. Issued March 1921.
Work of the Alaska Mining Experiment Station of the U. S.
Bureau of Mines. J. A. Davis. Reports of Investigations.
Serial No. 2231. 3 pp. Issued March 1921.
Recent Articles on Petroleum and Allied Substances. Com-
piled bv E. H. Burroughs. Reports of Investigations. Serial
No. 2232. 36 pp. Issued March 1921.
BUREAU OF STANDARDS
Weights and Measures. Thirteenth Annual Conference of
Representatives from Various States Held at the Bureau of
Standards, Washington, D. C, May 24, 25, 26, and 27, 1920.
Miscellaneous Publication 43. 200 pp. Paper, 20 cents. 1921.
Standards for Gas Service. Circular 32, 4th ed. 140 pp.
Paper, 20 cents.
Specifications and Tolerances for Weights and Measures and
Weighing and Measuring Devices. As Adopted by the Eleventh
Annual Conference on the Weights and Measures of the United
States Held at the Bureau of Standards, Washington, D. C,
May 23-26, 1916, and Recommended by the Bureau of Standards
for Adoption by the Several States. Circular 61, 2nd ed. 44
pp. Paper, 10 cents.
Gypsum — Properties, Definitions and Uses. Circular 108.
21 pp. Paper, 5 cents. 1921. This paper contains brief de-
scriptions of the method of manufacture, properties, and uses
of the various products made from gypsum. The Gypsum
Industries Association has established a fellowship at the Bureau
of Standards to assist in developing information about the prop-
erties and uses of the various gypsum products. Specifications
for calcined gypsum, neat gypsum plaster, gypsum plaster
board, and gypsum wall board are included in this paper.
Sand-Lime Brick — Description and Specification. Circular
109. 9 pp. Paper, 5 cents. 1921. This circular contains
a very brief history of the sand-lime brick industry, and a very
general description of the process of manufacture and the prop-
erties of the brick. The Bureau of Standards, in cooperation
with the Sand-Lime Brick Association, is conducting research
work on the subject. Recommended specifications for building
brick (including both sand-lime and clay) are given in full.
Colored Wall Plaster. W. E. Emley and C. F. Faxon.
Technologic Paper 181. 8 pp. Paper, 5 cents. A method has
been developed for producing a colored wall plaster of any de-
sired color or texture. Effects can be produced with this plaster
which are not attainable with either paint or wall paper. A
w all finished in this plaster can be washed when the colors be-
come dull or soiled, or it can be redecorated in the same way as
any other plastered wall.
National Safety Code for the Protection of the Heads and Eyes
of Industrial Workers. Handbook Series No. 2. 64 pp. Paper,
10 cents.
DEPARTMENT OF AGRICULTURE
The Flow of Water in Concrete Pipe. F. C. Scobey. With
discussion by Kenneth Allen, A. S. Bent, F. C. Finkle,
Allen Hazen, J. B. Lippincott, and H. D. Newell. Depart-
ment Bulletin 852. 100 pp. Paper, 25 cents.
The Use of Concrete Pipe in Irrigation. F. W. Stanley.
With introductory paragraphs by Samuel Fortler. Depart-
ment Bulletin 906. 54 pp. Paper, 20 cents. Issued March
23, 1921.
Articles from Journal of Agricultural Research
Relation of the Calcium Content of Some Kansas Soils to the
Soil Reaction as Determined by the Electrometric Titration.
C. O. Swanson, W. L. Latshaw and E. L. Tague. 20 (March
1, 1921), 855-68.
Comparative Utilization of the Mineral Constituents in the
Cotyledons of Bean Seedlings Grown in Soil and in Distilled
Water. G. D. Buckner. 20 (March 1, 1921), 875-80.
COMMERCE REPORTS— MARCH 1931
An order in council recently passed by the Dominion govern-
ment will result, it is expected, in the construction in the near
future of a large pulp and paper mill in western Canada. (P.
1192)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Norway during the years
1917, 1918, and 1919. (P. 1200)
The necessary intensive preparation of the soil in Italy requires
the use of fertilizers, which must be imported for the most part
(P. 1212)
Attention is called to the importance of Italy in the world's
production of mercury. (P. 1213)
The disorganized condition of the Italian sulfur industry is
described, and the rise of the United States as a tremendously
important source of sulfur is cited as the principal unfavorable
factor working to upset Italy's supremacy. (Pp. 121 1
The production of talc, zinc, and lead ore is diminishing in
Italy. (Pp. 1215-7)
There is a growing demand for aluminium in Italy, and home
production has had to be supplemented by imports to meet the
continuously growing demand. (Pp. 1217-8)
An Australian exporting company that is much interested in the
export of sandalwood oil from West Australia and is in a position
to deal in very large quantities, desires to get in touch with Amer-
ican importers or firms who could take over the agency for sandal-
wood oil. (P. 1219)
The petroleum department of the British government re-
ports that in the oil-drilling operations in the United Kingdom
during 1920 progress has been satisfactory, considering the great
depths which most of the wells have reached, the total number of
feet drilled being 7670. (P. 1237)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Denmark during the
years 1917, 1918, and 1919. (P. 1241j
The British dye and chemical trade is reviewed, and it is stated
that despite greater competition, British fine chemicals are
finding an increasing market. For British dyes it is claimed
that the markets in the Far East are especially favorable, par-
ticularly Japan. (Pp. 1258-63)
A list of manufacturers of zinc and zinc products in Poland is
available at the Bureau of Foreign and Domestic Commerce,
Washington, D. C, or its district and cooperative offices. [P.
1264)
The change in the British embargo on cocaine, opium, and their
preparations, salts, and alkaloids, is quoted. (P. 1265)
New petroleum legislation is proposed in Peru. (P. 1275)
Statistics are given showing the French petroleum production
in 1919. (P. 1279)
A market for American coke dust is reported in Czechosl' ivakiu .
(P. 1287)
The peanut and peanut-oil market in Tsingtau is reviewed.
(Pp. 1288-9)
The output of seed oils, such as linseed, mustard and rape,
in India, is reviewed. (Pp. 1301-2)
Belgium has placed an embargo on the exportation of gold,
silver, etc., from Belgium. It may be effected only under
certain prescribed conditions. (Pp. 1307-8)
Mexican export duties on silver are cited. (Pp. 1308-9)
Modifications in the export duties of Panama for minerals,
manganese, copra, rubber, and resins, are cited. (P. 1309)
The total production of alcohol in France during 1920 amounted
to 1,294,956 hectoliters as compared with 821,216 hectoliters in
1919. Exports for the year 1920 amounted to 354,682 hectoliters,
as compared with 198,234 hectoliters during the previous year.
(P. 1319)
Spain has on hand from last year 13,400 tons of olive oil,
the total quantity now on hand being 2,100,000 tons. (P. 1335)
A new oil well in Comodoro Rivadavia, Argentina, is now pro-
ducing 1,200 barrels per hour. (P. 1343)
It is reported that the bill calling for increased government
assistance in the nitrate industry will receive consideration in the
Chilean Congress. The principal shippers of nitrate to Europe
state that the stocks there have been pooled. Nearly all ship-
ments of nitrate since January 1, 1921, have gone to the United
States. (Pp. 1344 5
Japanese activities in Shensi have not resulted in securing
oil concessions, but a Chinese-English petroleum company has
been formed. (P. 1370)
A scheme is on foot to organize a British jute industry research
association. The constitution of the association has already
been approved by the scientific and industrial research depart-
ment of the government. (P. 1373)
The manufacture of palm oil at Hull, England, is described.
(P. 1374)
The Nitrate Association of Chile has fixed the prices of nitrate
for May and June at 17s., the figure now ruling for April. It has
also guaranteed that the prices from July 1, 1921, to March 31,
1922, will not be less than 14s. per Spanish quintal. (P. 1378)
A need for fertilizers is reported in India. (P. 1380)
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
493
The South African drug and chemical trade is reviewed.
(Pp. 1429-32)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Aden for the fiscal years
ending March 31, 1916, 1917, and 1918. (Pp. 1438-9)
The petroleum industry in pre-war Russia is reviewed. (Pp.
1446-54)
Statistics are given showing Italy's estimated mineral produc-
tion during 1920 as compared with production in 1919. For
1919 only the production within the old boundaries is included,
whereas in 1920 there has been added the production of the new
provinces acquired as a result of the war. (Pp. 1455-6)
The Italian sulfur industry, which has been steadily declining
for some years past, appears to have been more active in 1920,
the production during the year having increased about 15 per
cent over 1919. (P. 1455)
Restrictions on domestic sales of mineral oils in Czechoslovakia
have been removed, but a special tax of 1 crown a kilo has been
imposed on all imports. (P. 1455)
The manufacturers of dextrin in Japan are not making a profit
at present, and unless living costs and wages are reduced, it is
possible that the industry will not survive the depression.
(P. 1462)
Because of the high cost of gasoline in Pernambuco, Brazil,
the possibility of the substitution of alcohol is being seriously
considered. Alcohol is very plentiful in Pernambuco, where it is
a by-product of the sugar-cane industry and is made by prac-
tically all of the several hundred sugar mills. (Pp. 1468-9)
The Latvian paper industry is beginning to revive. (P.
1469)
The French import restriction has been removed on paper
pulp for the manufacture of newsprint paper. (P. 1473)
The paper and pulp situation in Sweden is reviewed. (P.
1475)
A depressed condition exists in the rubber market in the
Netherlands. (P. 1476)
The chicle industry in Campeche, Mexico, is reviewed. (P.
1496)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Persia during the fiscal
years ending March 20, 1917, 1918, and 1919. (P. 1503)
A recent Australian invention of an artificial composition
similar to veneer is said to be made entirely from waste fibrous
products and other vegetable matter. Sawdust can be utilized
in considerable quantities in the manufacture of the cheaper
grades of the product. (P. 1522)
The use of fertilizers in South Africa is described. (Pp.
1546-7)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Rumania during the
years 1912, 1913, and 1919. (Pp. 1548-9)
A process has been discovered in Nova Scotia of extracting
calcium malate from waste and otherwise useless apples. (P.
1563)
Statistics are given showing the metal output of Mexico for the
year 1920. (P. 1592)
The German production of nitrogen fertilizers is reviewed.
(P. 1593)
The extraction of vegetable-seed oil in Argentina is described.
(P. 1603)
British salt works have had to close down because of Spanish
and German competition in salt. German salt is said to be
selling at less than one-third the cost of the British product.
(P. 1618)
The production of petroleum in Japan during 1919 amounted
to 76,714,000 gallons. (P. 1628)
The dye industry of Japan is said to be in a most unfavorable
condition, owing to the continued arrivals of German dyestuffs.
(P. 1628)
Statistics are given showing the production of Peruvian copper
for the past four years. (P. 1637)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Belgium during the
years 1913, 1919, and 1920. (Pp. 1676-7)
Overstocking of mineral oils in Czechoslovakia is bringing
great financial loss. (P. 1701)
There was a great decrease, both in production and issues,
of salt in the Sind Province, India, for the fiscal year ended
March 31, 1920. (P. 1708)
All copper produced by Mexican mines is to be held in reserve
until the congestion of the market is relieved. (P. 1739)
The Chinese Cabinet has sanctioned the exploitation of the
oil reserves of Chinese Turkestan. (P. 1754)
The salt industry of Curacao and the Island of Bonaire is
reviewed. (P. 1755)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by the Netherlands during
1918, 1919, and 1920. (Pp. 1758-9)
An important American investment in manganese mines in
Brazil has recently been made. (P. 1792)
The Danzig gas works has recently installed a briquet factory
and benzene plant. The briquet factory has a capacity of about
100 tons of briquets per day, and the benzene plant, utilizing
by-products of the gas works, is said to be able to meet Danzig's
entire requirements for benzene. (P. 1793)
Terms are quoted under which Canadian pulp wood rights are
offered. (Pp. 1794-7)
A Chinese manufacturer of soy-bean oil is anxious to get in
touch with American oil importers, hoping to bring the leading
Chinese oil crushers into an export association, with the object
of shipping direct to the United States. (P. 1818)
A new Italian enterprise, with headquarters at Milan, has been
formed for the production of nitrogen and its products. The
latest process is to be employed for the production of ammonia
from atmospheric nitrogen. (P. 1822)
Statistics
Ceiba— (P. 1226)
Rubber, crude
Tela— (P. 1227)
Copper and brass,
scrap
Rubber
Bonacca — (P. 1227)
Mangrove dye
Rangoon (P. 1239)
Cutch
Wax, mineral
India rubber
Kingston, Jamaica —
(P. 1255)
Annatto
Bitterwood
Kola nuts
or Exports to the United States
Leathe
ufac-
-(P.
tured
Orange oil
Grapefruit oil
Tanning and
material
Port Anto>
maica— (P. 1255)
Leather, unmanufac
Logwood
Woods, fustic
dyeing
Ja-
1267)
P.
Drugs
Gums:
Asafetida
Kadaya
Karaya
Katira
Olibauum
Persian
Tragacanth
Oil, rosa
Ore. manganese
Seeds:
Castor
Poppy
Tsingtau— (P. 128S)
Peanut oil
Alaska— (P. 1347)
Copper ore
Tin ore
Tungsten ore
Palladium
Platinum
Silver ore
Gold ore
Great Britain-
IP. 1351)
Lead
Ammonium sulfate
Bleaching powder
Leather
Shanghai — (P. 1348)
Albumin
Camphor
Cottonseed oil
Peanut oil
Wood oil
Palermo— (P. 1375)
Citric acid
Tartaric acid
Sulfur oil
Lemon oil
Aden— (P 1325)
Gum myrrh
Asafetida
Cocalina bark
Quinine
Copper ores
Hides and skins
Rubber
Silver
Netherlands
1435)
Beeswax, bleached
Chemical preparations
for perfumery
Drugs and medicines
Quinine and cinchona
bark
Oxalic acid
Potash
Fertilizers
Jamaica — (P. 150S)
Chemicals, drugs
Orange oil
Tanning material
Peru— (P. 1524)
Copper
Hides and skins
Ores:
Copper
Gold, silver, and lead
Lead, copper, and
Molybdenum
Silver
Silver and copper
Silver and lead
Tungsten
Vanadium
Tungsten concentrates
Sulfide of silver
Rubber
Wolfram
Naphtha, crude, Pe-
-(P.
New Zealand -
1531)
Kauri gum
Tallow
Calcutta— (P. 1572)
Bone dust
Hides
Manganese
Saltpeter
Shellac
Liverpool — (P. 1591)
Ferromanganese
Leather
Glue stock
Bone meal
Copper
Saigon— (P. 1757)
Plumbago
Sheffield — (P. 1595)
Articles in a crude
state used in dyeing
Coal-tar products
Composition metal
Sheep dip
Fertilizers
Paints, pigments, col-
Platinum bars, sheets,
and sponge
Tungsten
Norway— (Pp. 1598-
9)
Aluminium
Chemicals
Hides and skins
Codliver oil
Platinum
Oxalic acid
Nitrite of soda
Fertilizers
Wood pulp:
Bleached, sulfite
Unbleached:
Sulfite
Sulfate
Moist, mechanical
Rio de Janeiro — (P
1684)
Manganese ore
Hides
Mex-ico — (Pp. 1658-
63)
Lead silver
Tungsten
Chicle
Hides
Jalap root
Rubber, crude
Castor beans
Saffron
Linaloa oil
Castor oil
Quicksilver
Czechoslovak i a —
(P. 1703)
Cyanide of sodium
Permanganate <•! pot-
ash
Goteborg, Sweden —
(P. 1721)
Morphine
Potash and caustic
soda
Chlorate of potash
Wood pulp
Smyrna— (P 1725)
Chrome ore
Licorice root
Licorice paste
Opium
Paris— (P. 1779)
Aluminium
Chemicals
India rubber, scrap
Potash
Saffron
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
BOOK REVIEWS
Chemistry and Civilization. By Allerton S. Cushman.
21 X 14 cm. 151 pp. Richard G. Badger, Boston, 1920.
Price, $2.50.
In the course of the first chapter the author brings the earth
from a gaseous mass to its present form, develops life, and carries
chemistry from the alchemists through the phlogistonists to
Lavoisier, Dalton, and Mendeleeff. The second chapter deals
with chemistry in the service of man. Historically it starts
from the French Revolution. A sketch of the life of Rumford
includes the foundation of the Royal Institution and leads up
to the work of Davy and Faraday. The title of chemistry in
the service of man is justified by the discussion of the work of
Liebig and of Pasteur.
The third chapter deals with chemistry and industry, the special
topics being the alkali industry, sulfuric acid, iron and steel,
including the Bessemer process, ceramics, portland cement, the
coal-tar dyes and medieinals, catalysis, and the synthesis of
indigo, camphor, and rubber. After covering all this ground in
21 pages, it is a simple matter to discuss chemistry and the war
in 25 pages. The important points as the author sees them are
the food problem and nitrogen fixation, poison gases and active
charcoal, and the use of dichloramine-T, etc., in surgery. The
fifth chapter is entitled chemistry and the future. It is rather
an interpolated one designed to permit the author to discuss
the Einstein theory, though he also takes up radium. The
last chapter is on some modern aspects of chemistry and
the sub-heads are: colloids and dispersoids; chemistry and
its by-products; the future of alcohol; chemistry at high and
low temperatures and pressures; the liquefaction of gases;
the story of helium; the electric arc furnace and its products;
the cracking of petroleum and the motor fuel problem; the
promise of the future as compared with the past. There is also
an appendix on nitrogen supplies prepared under the direction of
the author by Carleton H. Wright.
The title of the book is misleading. The author has written a
sketch of the progress of chemistry; but the bearing of chem-
istry on civilization is not discussed directly, and it is not at
all certain that there is any parallelism between the develop-
ment of chemistry and the development of art or ethics, for
instance.
A number of the proper names are spelled wrong, such as
Myer for Meyer and Thomsen for Thomson. The reviewer
does not like the way in which some of the illustrations are put
at the top of the page instead of being centered. It may be the
latest thing in book-making, but it distresses one at first. In
spite of the general excellence of the book, there are a few errors
which are rather unexpected on the part of a chemist of Dr.
Cushman's standing. The poisoning of catalytic agents is not
a profound mystery any longer. The adsorption of poison
gases by charcoal and the passage of air though the mask (p.
94) is not analogous to a "poultry brooding coop in which the
little chicks are free to run in and out and away, while the
nervous and excited mother birds are forced to confine their mo-
tions within the meshes which hold them imprisoned." The
author has evidently forgotten that toxic smokes are not stopped
appreciably by charcoal. The reviewer was surprised to find
it implied (p. 98) that the occurrence of potassium bromate in
potassium chlorate was the chief cause of primer troubles. There
is a confusion on p. 116 between dialyzing membranes and semi-
permeable membranes. The object of dialysis is not to remove
or add water, and dissolved substances do pass through the
dialysis membrane. Arrhenius was the man who put forward
the theory of electrolytic dissociation and not van't Hoff.
Wilder D. Bancroft
Fuel Production and Utilization. By Hugh S. Taylor, D.Sc.
(Liverpool), Assistant Professor of Physical Chemistry, Prince-
ton University. [One of a series of volumes on "Industrial
Chemistry," edited by Samuel Rideal, D.Sc., London, F. I. C]
xiv + 289 pp. D. Van Nostrand Co., New York, 1920.
Price, $4.00 net.
According to the preface "This volume is addressed more es-
pecially to the young college graduate, as an effort to supple-
ment his academic training with the broad facts of fuel production
and utilization. It attempts to present a survey of the whole
field of fuel as the author has learned it to be in the last few years,
when the stress of circumstances has turned men's activities
from the more specialized problems of pure science."
Naturally, one would not expect a modern physical chemist to
write the usual textbook of methods for analyzing and testing
fuels, temperature measurements, combustion data, and tables
of composition, and in this respect the reader will not be
disappointed. Indeed, there are plenty of good textbooks for
teaching the elements of fuel chemistry to undergraduate chem-
ists and engineers.
The present volume is most timely in bringing together a
record of the tremendous progress that has been made in the last
few years in the more complete utilization of the world's fuel
resources. The attention given to present-day tendencies and
possible future developments in fuel economics is of particular
interest to those engaged in fuel research The concise presenta-
tion of the physicochemical principles involved in the produc-
tion and utilization of fuels, as given in the introduction and in
subsequent sections on combustion, carbonization, and gasifica-
tion, is one of the most valuable features of the book. In such
matters the author writes from actual experience. The engineer-
ing and economic aspects of the various processes described in
the book are drawn from recent articles appearing in English
and American technical periodicals and the publications of the
United States Bureau of Mines and the Canadian Department
of Mines. The author has selected this material with proper
discrimination, for the most part, and always cites his authori-
ties. However, the inexperienced reader is occasionally left in
doubt as to which processes are current practice and which are
merely experiments where "the operation was a success but the
patient died."
Apparently there is a clerical error in the paragraph on drying
in the chapter devoted to powdered coal, since an example
is cited of drying coal from 1.25 per cent to 0.5 per cent
moisture. Were coal with 1.25 per cent moisture, available it
would be unnecessary to dry it. It is unnecessary for most
purposes to dry coal to 0.75 per cent moisture, as stated in this
article. It is rather unfortunate, too, that Fig. 5 shows an un-
usual type of feeder. Most modern low-pressure feeders are of
the screw set type. Also in Fig. 8 is shown an open-hearth fur-
nace with no means of preheating the air. Lack of preheating
rendered this particular installation useless and it was scrapped.
Much of the latter part of the article dealing with powdered coal
for steamships is purely speculative and these pages might have
been filled with more valuable material.
Following are a few typographical errors noted by the reviewer:
Page 18, the heat of combustion of methane is given as 212,500
in one place and 213,500 in two other places; on page 26 the sub-
scriptG)is omitted from T in the equation for the heat of reaction
Qs page 150, 5th line from top, the words "carbon monoxide
should evidently read "carbon dioxide."
The selected bibliography at the end of each section provides
a most useful guide to recent literature on the subject.
A. C. FlELDNER
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
495
A Text Book of Chemical Engineering. By Edward Hart,
Ph.D. viii -4- 211 pp. The Chemical Publishing Co., Eas-
ton, Pa., 1920. Price, $4.00.
This book takes up in a descriptive manner the various in-
dustrial chemical operations and is well illustrated. The chap-
ters deal successively with materials, location of works, boilers,
prime movers, plumbing, crushing, dissolving, filtration, tanks,
evaporators, crystallization, drying, distillation, absorption of
gases, mixing, and containers.
Dr. Hart, in his preface, touches one of the reasons for the
lack of adequate books, particularly textbooks, on chemical
engineering, when he states that "the writer whose own ex-
perience shall fully qualify him to cover this whole subject is
still to be discovered." In view of this lack of literature, criti-
cism from any point of view other than that of improving the
present situation is out of place.
In reading over the book, one is impressed with the necessity,
in writing a textbook, of being ever watchful of the relative weight
given various topics. The young engineer, in reading the chapter
on materials, is apt to overestimate the industrial importance of
iron-silicon alloys, and phenolic condensation products, in view
of the fact that one-half the chapter is devoted to these two
materials. Many important materials, such as monel metal,
acid-resistant bronzes, and hard rubber are not mentioned.
In the chapter on distillation, the distilling of solvents and
other volatile materials and the principles of dephlegmation are
touched only slightly, while the greater part of the chapter is
devoted to the distillation of inorganic acids, and here no
mention is made of the vacuum process for distilling nitric
acid.
The book contains too many quotations from catalogs and
letters from men directly interested in the products they de-
scribe. This is likely to contribute to a lack of balance in the
subject matter, and those practicing in the field are apt to dis-
count the quotations of one who may be over-enthusiastic. In
the chapter on drying there is inserted a 4-page quotation and
a page illustration describing the Lowden dryer. This de-
scription deals wholly with the mechanical construction and
operation of the dryer, and no mention is made of its field or use.
Another quotation in this same chapter gives the data required
for making the proper selection of a dryer.but nothing is said about
the significance of each point. Many fundamentals, such as the
use of the wet and dry bulb thermometer and the significance
of these readings, have been omitted.
There is always a difference in point of view relative to the
subject matter that might be included in a book dealing
with a field as broad as chemical engineering. From the re-
viewer's standpoint, it would be better to replace the chapter
on boilers by one on combustion, for surely combustion is an
essential chemical engineering operation. Also, it would seem
that the details of building construction in Chapter 2 might
better be replaced by a chapter giving some of the princi-
ples of factory lay-out from the standpoint of types of buildings,
future expansion, accessibility, and the ease of transportation
within, as well as to and from, the plant.
The reviewer feels that this book really describes the mechan-
ical operations of industrial chemistry and not the art or science
of chemical engineering. As the electrical engineer controls
electrical forces, so must the chemical engineer control chemical
forces, and this is done largely by the addition or withdrawal
of materials and energy (usually heat) from a given point.
Therefore, a real textbook of chemical engineering must cover
these phenomena in general and their application to the field
of chemistry in particular.
Dr. Hart's book will be found valuable to universities and
others desiring to give a course in industrial chemistry with
more emphasis on the mechanical operations than is given
in the usual textbook on this subject. R. T. Haslam
Gas Warfare. By Edward S. Farrow, xi + 253 pp. 1st
Ed. E. P. Dutton & Co., New York City, 1920. Price,
$3.00 net.
This book is a very complete compilation of data on the
use of chemicals in the world war. A student of military
science would find it of unquestionable value, but there is not
enough action to hold the attention of the average reader.
The author sketches the development of the Chemical War-
fare Service, as well as the gradual growth in importance of
chemical weapons. He discusses in considerable detail the
specific chemicals which were employed, including their properties
and methods of use, and the construction of projectiles and fuses.
It is stated in the preface that the casualties from gas equaled
2.5 per cent of the total, while those from bullets and high
explosives were 25 per cent. Presumably, this 2.5 per cent
refers to battle deaths caused by gas, since the percentage of
total casualties due to gas was approximately 30 per cent.
Some chemical statements must not be taken too literally.
The author says on page 3 that "Absorbent substances like char-
coal, soda lime, sodium phenate * * * * absorb or neu-
tralize such gases as chlorine, phosgene, * * * *, and
when used in gas masks, protect against finely divided toxic
solids such as diphenylchlorarsine." Of course, the action of
charcoal and of the chemicals mentioned is fundamentally differ-
ent, and neither protects against finely divided solids or smokes.
There was a period of several weeks during the early summer
of 1918 when this fact caused the loss of much sleep on the part
of gas officers in France, since various sources of information
had indicated that the Germans were planning to use smoke
generators for producing clouds of diphenylcyanarsine and
other similar chemicals, against which our mask would not give
protection. Great numbers of cellulose filter jackets were made
in England and sent to all the advance gas depots where they
would be available for immediate use if needed.
In stating that 45,000 gas shell were shipped over-seas, the
author gives the impression that these shell were of some
actual assistance in winning the war. It must be confessed
that none were ever fired. This is not said as a criticism of
the Chemical Warfare Service in this country, but because it
illustrates so well the necessity for preparedness. Prepared-
ness in chemical warfare means, first of all, production capacity
either for the actual chemical to be used in war, or for a
chemical sufficiently closely related so that the plant producing it
could quickly be converted into one for producing the war chem-
ical. In addition to this, there must be an extremely active nu-
cleus of the Chemical Warfare Service, which is keeping up to date
and developing new offensive weapons and defensive materials.
No mention is made of the importance of Chemical Warfare
Service "Intelligence." The intelligence service which was in
direct contact with the front line and that which consisted in the
exchange of information between the allies were both extremely
important. The former consisted of information obtained by
questioning prisoners, aeroplane observation, from listening
posts, and other means of following the movements of enemy gas
troops, and of detecting, in advance, the location of enemy gas
mines. Such intelligence was made the basis for immediate ac-
tion, offensive or defensive, by the gas officers on the spot.
Under the heading "tactics," considerable repetition occurs,
as the author goes into the question of tactics for the chemicals
themselves, and later covers the same field for these chemicals
as used by both artillery and special gas troops. If the tactical
situation requires that a certain concentration of some chemical
be placed on a definite spot, every available means should be
used for producing the desired concentration. Moreover, the
rules given under the heading of tactics should be regarded only
as general hints. The only guide to the successful use of any
gas is an exact knowledge of the properties of the chemical and
of the tactical situation
496
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
The reviewer feels that the book suffers from too little contact
with the front, which, after all, is the final and only real test of
the importance of gas warfare. The description of an incident
occurring at Hulluch in December 1917 is equal in value to a
complete lecture on the tactics of gas warfare. The English
wished to make a raid on an opposite sector of German trench to
get prisoners and information. On several nights closely pre-
ceding that of the raid, gas projectors containing phosgene and
chloropierin were discharged upon this sector of trench. On the
night of the raid, a few minutes before the men were to go over
the top, three English projector emplacements were discharged.
Two of them, on points adjacent to the objective of the attack,
contained poison gas. The third, fired upon the direct objec-
tive, threw a foul smelling mixture of bone oil which was per-
fectly harmless, and to which the Englishmen making the raid
had been exposed in advance to make them familiar with the
odor, and to teach them that it was not dangerous. The raid-
ing party found the Germans cowering in their dugouts, wearing
their gas masks.
An accurate description of several offensive or defensive ac-
tions in which chemicals played an important part, accompanied
by suitable maps and diagrams, would not only add to the in-
terest, but would suggest to the reader the value of imagination
and initiative in directing the use of gas.
B. C. Goss
Official and Tentative Methods of Analysis of the Association
of Official Agricultural Chemists. Compiled by the Com-
mittee on Revision of Methods (R. E. Doolittle, Chairman,
B. L. Hartwell, G. W. Hoover, A. J. Patten, A. F. Seeker
.and W. A. Withers) with an introduction by Harvey W. Wiley,
Honorary President of the Association. Revised to No-
vember 1, 1919. Cloth, 6x9 in., xii + 418 pp. Published by
the Association of Official Agricultural Chemists, Washington,
D. C, September 1920. Price, $5.00.
The long-awaited revision of the Methods of Analysis of the
Association of Official Agricultural Chemists has at last been
received in the form of a compact.well-arranged and well- printed,
strongly bound volume of more than 400 pages. The Com-
mittee and its Chairman are to be congratulated on the consum-
mation of an immense amount of painstaking, time-consuming,
and self-sacrificing labor done in the interests of the chemical
profession generally and without hope of personal reward. The
work has been in general very well done. Naturally, and because
of the fact that the different divisions of the work have been
delegated to committees of different personnel, the methods are
to some extent of varying value, but this fault is in part over-
come and in the main eliminated by the method of cooperative
work, conservatism in adopting or changing methods, and care-
ful revision and editing by the final committee. It would be
presumptuous for an individual, even one who uses them con-
tinuously, to criticize any special methods in a review. Many of
them are still imperfect and this fact would be readily admitted
by the officials of the A. O. A. C. All are in a state of evolution,
undergoing slow and continuous modification year by year as
improvements are accumulated or new means of attack dis-
covered. Suggestions by individuals outside the organization
of the A. O. A. C. are always welcomed by the referees, and vol-
untary collaborators in the actual work of developing and apply-
ing the methods are constantly being added by the different
committees. The proper point of appeal lies in the individual
committees of the association.
One may doubt that all the methods published are used either
by the members of the Association or by works chemists for
routine work. It is a fault of all compilations of methods of
analysis that, from fear of introducing methods which may be
criticized on the score that they are more or less unscientific
or have too large a personal factor, many simple and direct
methods in daily use in the average works laboratory are omit-
ted. Some such methods actually yield more concordant and
accurate results than so-called official methods, and are much
easier and quicker. It would seem a wise plan to incorporate such
methods so far as possible in footnotes or in a special appendix.
This is a de luxe edition, as shown not only by the price but
by the fact that the individual copies are numbered. Most of us
remember when the "Official Methods" were published in paper
covers as Bulletin 107 by the Bureau of Chemistry, and could
be had for the asking from the Department of Agriculture or by
sending 20 cents to the Superintendent of Documents, or as a
last resort by an appeal to one's congressman. The methods are
so generally useful to students, and the present price so high from
the student's standpoint, that it may be worth the attention of
the Association to consider issuing a cheaper paper edition for
the use of students. Every aid to the chemical student is in-
surance for the chemical future of the country.
That the Revised Methods have been eagerly received is indi-
cated by the fact that the first printing is exhausted and a second
is in process. W. D. Richardson
American Lubricants. By L. B. Lockhart. 2nd Edition, re-
vised and enlarged. 8vo. 341 pp. 15 illustrations. Chem-
ical Publishing Co., Easton, Pa., 1920. Price, $4.00.
The purpose of this book, as stated in the preface, is:
To aid the user and buyer of lubricants in a more intelligent
selection of oils and greases. The point of view throughout is
that of the user rather than that of the refiner. An effort has
been made to include such facts and figures in regard to lubri-
cants as will best serve to bridge the gap between the refiner
******* and the consumer. * * *
In a book of this character it is of the utmost importance that
the refiner, the seller, the buyer, and the user of lubricating oils
speak the same language.
The first two chapters deal with petroleum and refining.
Petroleum is found as a colorless to black liquid, but the author
makes the broad statement that it is a dark brown liquid. A
somewhat misleading description is given of a vertical tower
condenser: "In this condenser the heavy oils condense first
near the bottom, and the light oils condense last near the
top."
The author must have not known that nearly 40 per cent of
the lubricating oil made in the United States is from refineries lo-
cated in the western half of the country, for he states that "very
little lubricating oil is made west of the Mississippi River."
Recommendations covering the character of oils to be used
when lubricating internal combustion engines, automobiles,
electrical machinery, cylinders and steam engines, steam rail-
ways, textile mills, and miscellaneous machines are contained in
Chapters V to XI. Physical methods for testing lubricating oils
are described in Chapters XII and XIII. The methods are
mainly those which have been published by the American So-
ciety for Testing Materials. A few chemical methods are briefly
outlined in Chapter XIV. Greases and animal and vegetable
oils are similarly treated in the next four chapters.
Nearly half of the book (134 pages) is devoted to specifica-
tions which cannot do much more than confuse the "user and
buyer," and the "same language" is not always in evidence
throughout a heterogeneous collection of specifications.
On page 49, under cylinder oil, the author remarks, "The flash
point should be approximately 400° F. or higher," but on page
201 specifications are quoted ranging from 450° to 540° F. A
specification for a Saybolt viscosity at 70° F. is mentioned on page
227. This is not among the standard temperatures mentioned
(page 106) when describing the Saybolt viscosimeter.
Without doubt, buyers and consumers who have no informa-
tion on lubricating oils will find this volume interesting. Any-
one desiring specifications should welcome the collection brought
together in a convenient form.
C. K. Francis
May, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
497
Unification des Noms des Colorants les Plus Usuels. P.
SiSLEY. 196 pages. Union des Producteurs et des Consom-
mateurs pour le Developpement de l'lndustrie des Matieres
Colorantes en France, 53 Rue de Chateaudun, Paris, 1920.
A commission, of which the author is chairman, was appointed
by Professor Behal, director of the Bureau of Chemical and
Pharmaceutical Products, for the purpose of unification of the
nomenclature of dyes. Although the work did not receive
official approval, the author was urged to publish the same.
The commission early recognized the impossibility of a com-
plete work, for very few dye firms are willing to identify the
name of their products with constitution, and fewer still will
betray the nature of their mixtures. Adopting the sensible
course, the different names applied to 260 of the more common
and older dyes are classified undei espective constitution and
dye application purposes.
Other difficulties than those mentioned above may be seen
from the fact that for the 1200 to 1500 definite chemical type
dyes there are 14,000 different names or marks. The author
suggests the need of an international commission to compile a
complete volume. It is doubtful if this would solve the problem
for the reasons stated above.
In conclusion it should be pointed out that the work resembles
the Schultz "Farbstoff-Tabellen," but is less complete and omits
all literature and patent references. His classification follows
the method of dye application, viz., acid, direct, basic, chrome,
mordant, lakes, sulfur, etc. C. G. Derick
Papers on Paint and Varnish. By Henry A. Gardner. 500
pages. Sold by P. H. Butler, 1845 B St., N. W., Washington,
D. C, 1920. Price, $10.00 net, postpaid.
This volume, published by the author, is a distinct contribu-
tion to the paint and varnish industry of America by one who for
the past ten years has been making extensive studies in a field
where fifteen years ago, there was but little real scientific informa-
tion available and very little of that available was being utilized
by the leading paint manufacturers of this country. At that
time the "rule of thumb" largely prevailed, the paint fore-
man carried in his head all the practical experience and some-
times failed to deliver the goods, and misleading criticisms took
the place of sound advertising.
Since North Dakota enacted its paint labeling law and the
right to enforce the same was affirmed by the highest courts,
much progress has been made in the science of paint making as
well as of paint using. Mr. Gardner has done his full share in
the field of research, and in the present volume there have been
collected data valuable alike to the paint and varnish manu-
facturer; also to the master painter and decorator, and to the home
users of all paints and varnishes as protective and decorative
coatings.
The studies of drying and semidrying oils include soy-bean,
marine, and animal oils, fish oils, tung oil, linseed oil, and many
new foreign oils, as well as the various methods for treating oils
as practiced in the industries, and certain chemical and physical
constants for oils. Some new data for exposure tests for paints
and varnishes are presented; also an interesting study pertaining
to the resistance of various protective coatings or films against
the absorption of water. One of the most interesting and com-
plete chapters deals with' 'Tunga Resins," or, more properly,
"Ester Gums," for manufacture and use. Oil absorption by
pigments and fineness of pigments are well considered. A chap-
ter on the preservative function of paints and varnishes contains
well-illustrated photographic material. The author well says:
"The serviceability of any paint should be judged by the surface
which it leaves for repainting after a period of some four to five
years, as well as by the durability of the repainting job." Well-
painted buildings, the author maintain?, are an indication of
thrift and a big asset when one has to go to the banks for loans.
It further indicates education and refinement therein, al-
though not necessarily wholly acquired from books. Some good
suggestions are presented in the chapter on paints for the home.
One of the highly interesting and specialized sections has to do
with the development in the paint industry that came as the re-
sult of the great war and its many lessons forced upon the Ameri-
can people, including the development of the standard paint
specifications of the War Department.
My criticism would be lack of definite conclusions and lessons
to be drawn from the incomplete data, and necessary brevity in
treating in a suggestive manner so many subjects in a limited
space. E. F. Ladd
Rapid Methods for the Chemical Analysis of Special Steels,
Steel Making Alloys, Their Ores, and Graphites. By Charles
Morris Johnson, Ph.M. 3rd edition, xi + 552 pp. John
Wiley & Sons, Inc., New York, 1920.
The first edition of this work was issued in 1908, and the
third edition shows not only an increase in size but a large range
in the subjects treated. Mr. Johnson, in his preface, calls atten-
tion to thirty-two changes and additions, including methods for
the determination of elements recently added by metallurgists
to modify or improve alloy steels.
The introduction of alloy steels presented a double problem
to the chemist. He had to devise methods for the determina-
tion of the elements newly alloyed with the iron and to study
and solve the question of the interference of some of these
elements with the methods used for the determination of the
ordinary elements found in plain steels. For instance, it was
found that the presence of even very small amounts of vanadium
prevented the precipitation of small amounts of phosphorus by
the ordinary molybdate method. This was overcome by Brearly
and Ibbotson by reducing the vanadium to the vanadyl state,
and by Johnson by precipitating the phosphorus from a very
strong nitric add solution with a slightly ammoniacal solution
of molybdic acid at the boiling temperature. Johnson applies
this method to the determination of phosphorus in ferrovana-
dium, first getting rid of the greater part of the vanadium by
repeated crystallizations of the vanadic acid from the concen-
trated nitric acid solution.
The determination of sulfur by the evolution method in most
alloy steels and ferro-alloys is impracticable, but Johnson de-
vised the method of heating the material to 950° C. in a stream
of hydrogen saturated with hydrochloric acid gas, which lib-
erates the sulfur as hydrogen sulfide. The test analyses cited
are very satisfactory.
It is impossible in a review of this kind to discuss all the
methods, but it might be well to call attention to certain details
which may be of assistance to the student.
In the author's method for precipitating phosphorus as phos-
phomolybdate in boiling solutions all the arsenic is precipitated
with the phosphorus, while if the temperature of the solution
is about 40° C. all the arsenic remains in solution. Usually the
amount of arsenic in steel is negligible, but occasionally the nor-
mal phosphorus may be materially overstated by this method.
In almost all cases where the material is fused with sodium
peroxide, a platinum crucible lined with sodium carbonate is
to be preferred to an iron or porcelain crucible.
The method for the determination of arsenic in steel is not
satisfactory. The distillation method is accurate and preferable
in every way.
Many of the methods described are original with the author
or modified by him, and his descriptions bear evidence of his use
of them, but if he has tried the method given for the determina-
ation of boron in steel his courage should be highly commended.
It is a pity that a book such as this, containing so much that
is excellent, should be marred by an unfortunate style, by un-
grammatical expressions, and by colloquial phrases out of place-
in a scientific treatise. Andrew A. Blair
-1 '.IS
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
NEW PUBLICATIONS
Ammonia and the Nitrides, with Special Reference to Their Synthesis.
Edward B. Maxted. 116 pp. 16 illustrations. Price, $2.00. P.
Blakiston's Son & Co., Philadelphia.
Analysis: Technical Methods of Analysis as Employed in the Laboratories
of Arthur D. Little, Inc., Cambridge, Mass. Roger Castle Grifpin,
Editor. 666 pp. McGraw-Hill Book Co., Inc., New York.
Beet Sugar: Condensed Description of the Manufacture of Beet Sugar.
Franz Murkb. 175 pp. Price, $2.50. John Wiley & Sons, Inc.,
New York.
Benzol: Its Recovery, Rectification and Uses. S. E. Whitehead. 209
pp. Price, $5.00. D. Van Nostrand Co., New York.
Bibliotlieca Chemico-Mathematica. Catalog of Works in Many Tongues
on Exact and Applied Science. Compiled and Annotated by H. Z. and
H. C. S. 2 volumes. 964 pp. Price, 63s. net. Henry Sotheran &
Co., London.
Chemistry: A Textbook of Inorganic Chemistry for University Students.
J. R. Partington. 1062 pp. 439 figures. Price, $8.00. The Mac-
tnillan Co., New York.
Fuel Oil: Elements of Fuel Oil and Steam Engineering. Robert Siblev
and C. H. Delany. 2d edition, revised and enlarged. 466 pp. 248
illustrations. Price, $5.00. McGraw-Hill Book Co., Inc., New York.
Gasoline and Other Motor Fuels. Carleton Ellis and Joseph V.
Meigs. 709 pp. 206 illustrations. Price, $10.00 net. D. Van Nos-
trand Co., New York.
Metallography. Part II. The Metals and- Common Alloys. Samuel L.
Hoyt. 462 pp. Price, $5.00. McGraw-Hill Book Co., Inc., New York.
Organic Chemistry for Medical, Intermediate Science and Pharmaceutical
Students. A Killen Macbeth. 226 pp. Price, 6s. 6d. net. Long-
mans, Green & Co., New York.
Pharmacology: An Introduction to Chemical Pharmacology. Pharmacody-
namics in Relation to Chemistry. Hugh McGuigan. 418 pp. Price,
$4.00. P. Blakiston's Son & Co., Philadelphia.
Red-Lead and How to Use It in Paint. Alvah Horton Sabin. 3d edi-
tion, rewritten and enlarged. 139 pp. Illustrated. Price, $2.00. John
Wiley & Sons, Inc., New York.
Rubber Manufacture: The Cultivation, Chemistry, Testing and Manufac-
ture of Rubber, with Sections on Reclamation of Rubber and the Manu-
facture of Rubber Substitutes. H. E. Simmons. 149 pp. Illustrated.
Price, $4.50. D. Van Nostrand Co., New York.
Thermodynamics and Chemistry. Frank H. MacDougall. 391 pp.
52 figures. Price, $5.50 net. John Wiley & Sons, Inc., New York.
NEW JOURNAL
The American Journal of Tropical Medicine. Official Organ of the Amer-
ican Society of Tropical Medicine. Editor, H. J. Nichols, Army Med-
ical School, Washington, D. C. Price, $5.00 per volume. Published
bimonthly by Williams & Wilkins Co., Baltimore, Md.
RECENT JOURNAL ARTICLES
Alcohols: Sur la Deshydrogenation des Alcools par Oxydation catalytique.
Charles Moureu and Georges Mignonac. Bulletin de la Societe
Chimique de France, Vol. 29 (1921), No. 2, pp. 88-101.
Blast Furnace Flue Dust Recovery. George B. Cramp. The Iron Age,
Vol. 107 (1921), No. 12, pp. 775-778.
Catalysis in Industrial Chemistry. E. K. Rideal. The Chemical Age
(London), Vol. 4 (1921), No. 89, pp. 245-246.
Coal: Assay of Coal for Carbonization Purposes. T. Gray. The Chemical
Trade Journal and Chemical Engineer, Vol. 68 (1921), No. 1766, pp.
409-410.
Coal as a Future Source of Oil Fuel Supply. Sir Arthur Duckham.
Journal of the Institution of Petroleum Technologists, Vol. 7 (1921), No.
25, pp. 3-12.
Combustion: Controlling Combustion on COi Basis Alone Proves Un-
satisfactory. Roland Moeller. The Coal Industry, Vol. 4 (1921),
No. 3, pp. 161-165.
Combustion: L'Evaluation des Pertes par la Cheminee dans le Cas des
Chaudieies. Ch. de la Condamine. L'Induslrie Chimique, Vol. 8
(1921), No. 86, pp. 89-92.
Combustion: Positive Circulation of Furnace Gases. S. Trood and D.
E. Saylor. Forging and Heal Treating, Vol. 7 (1921), No. 3, pp. 183-185.
Cyanic Acid: Syntheses de 1'Acide Cyanique par Oxydation des Substances
Organiques. R. Fosse. Bulletin de la Societe Chimique de France, Vol.
29 (1921), No. 3, pp. 15S-203.
Degumming of Silk. Emile Cagliostro. Color Trade Journal, Vol. 8
(1921), No. 4, pp. 138-141.
Drugs: The Chemistry of Neoarsphenamine and Its Relation to Toxicity.
George W. Raiziss and M. Falkov. Journal of Biological Chemistry,
Vol. 46 (1921), No. 1, pp. 209-221.
Dyes: The Bearing of a Synthetic Dye Industry upon Our National Wel-
fare. Marston Taylor Bogert. Journal of the Franklin Institute,
Vol 191 (1921), No. 4, pp. 445-472.
Dyes: The Constitution of Indigotin. R. Robinson. Journal of the Society
of Dyers and Colourists, Vol. 37 (1921), No. 3, pp. 77-79.
Erosion of Bronze Propellers. O. Silberrad. Journal of the Society of
Chemical Industry, Vol. 40 (1921), No. 4, pp. 38<-45/.
Filter Paper: The Manufacture of Hand-Made Filter Paper. J. Barcham
Green. Journal of the Society of Chemical Industry. Vol. 40 (1921),
No. 6, pp. lOOr-lOlr.
Fire-Brick: Tests of Fire-Brick Made from Ganister, Flint Clay, and Plas-
tic Clay Mixtures, with Special Reference to Spalling. Raymond M.
Howe and Mark Sheppard. Journal of the American Ceramic Society,
Vol. 4 (1921), No. 3, pp. 206-212.
Flour Milling and the Cereal Chemist. R. Wallace Mitchell. Chemical
Age, Vol. 29 (1921), No. 3, pp. 85-89.
Fuel: Industrial Application of Powdered Fuel. Joseph F. Shadgen.
The Iron Age, Vol. 107 (1921). No. 13, pp. 839-842.
Gas: Condensation and Compression. J. W. Lansley. The Cas Age,
Vol. 47 (1921), No. 5, pp. 191-192.
Glass: The Composition of Opaque Glasses. J. B. Krak. The Glass
Industry, Vol 2 (1921), No. 4, pp. 81-84.
Glass: Devitrification and Revitrification of Glass. J. B. Krak. The
Class Industry, Vol. 2 (1921), No. 2, pp. 29-31.
Glass: L'Industrie du Verre de Silice. Georges Flusin. Chimie et
Industrie, Vol. 5 (1921), No. 2, pp. 119-135.
Hypochlorites: The Effect of Alkalinity on the Use of Hypochlorites. E.
K. Rideal and U. R. Evans. Journal of the Society of Chemical In-
dustry, Vol. 40 (1921), No. 4. pp. 64r-66r.
Investigations of the Chemical Literature. Frank E. Barrows. Chem-
ical and Metallurgical Engineering, Vol. 24 (1921), No. 10, pp. 423-428;
No. 11, pp. 477-479.
Leather: La Semelle: Contribution a l'Etude des Semelles et des Em-
peignes pour Chaussures Militaires. Cesar Schiaparelli. Journal of
the Society of Leather Trades' Chemists, Vol. 5 (1921), No. 2, pp. 44-56.
Liquid Chlorine for Bleaching. L. N. Goebel. Paper, Vol. 27 (1921),
No. 27, pp. 17-19.
Mercerization: Some Experimental Investigations Concerning the Effi-
ciency of Mercerization. A. J. Hall. Textile Colorist, Vol. 43 (1921).
No. 508, pp. 240-242.
Ozone and "Hyzone" and Their Technical Applications. The Chemical
Age (London), Vol. 4 (1921), No. S9, pp. 240-241.
Petroleum: America's Petroleum Problem. J. O. Lewis. Journal of the
Franklin Institute, Vol. 191 (1921), No. 3, pp. 357-380.
Photography: A Sensitometric Study of the Reduction of Developing-Out
Papers. Loyd A. Jones and C. E. Fawkes. Journal of the Franklin
Institute, Vol. 191 (1921), No. 4, pp. 503-516.
Photography: The Size Frequency Distribution of Particles of Silver Halide
in Photographic Emulsions and Its Relation to Sensitometric Character-
istics. E. P. Wightman and S. E. Sheppard. Journal of Physical
Chemistry, Vol. 25 (1921), No. 3, pp. 181-195.
Porcelain: The Effect of the Replacement of Free Silica by Alumina and
Zirconia in Electrical Porcelain. Robert Twells, Jr., and C. C. Lin.
Journal of the American Ceramic Society, Vol. 4 (1921), No. 3, pp. 195-206.
Resins: Contribution a la Caracterisation des Gommes a Vernis. P.
Nicolardot and Ch. Coffignier. Chimie et Industrie, Vol. 5 (1921),
No. 2, pp. 150-156.
Rubber: Recent Progress in Rubber Chemistry and Technology. Philip
Schidrowitz. The Chemical Age (London), Vol. 4 (1921), No. 90,
pp. 272-274; No. 91, pp. 298-300; No. 92, pp. 326-328.
Rubber: Solvents and Thinners Used in the Rubber Industry. Frederic
Dannerth. The India Rubber World. Vol. 64 (1921), No. 1, pp. 487-489.
Rubber: Sulla Solubilita delle Sostanze Cristalline nel Caucciu. G.
Bruni. Giornale di Chimica Industriale ed Applicata, Vol. 3 (1921),
No. 2, pp. 51-54.
Soap: The Hydrolytic Alkalinity of Pure and Commercial Soaps. F. C.
Beedle and T. R. Bolam. Journal of the Society of Chemical Industry,
Vol. 40 (1921), No. 4, pp. 27/-29(.
Steel: A New Process for the Estimation of Small Quantities of Chromium
in Steels. B. S. Evans. The Analyst, Vol. 46 (1921), No. 539, pp.
38-42.
Steel: Present Status of Molybdenum Steels. John A. Mathews. Forg-
ing and Heal Treating, Vol. 7 (1921), No. 3, pp. 169-170.
Tin Plating from Alkaline Tin Baths by the Use of Addition Reagents.
Frank C. Mathers and William H. Bell. Brass World, Vol. 17
(1921), No. 3, pp. 61-62.
Sugar: A Few Observations upon the Clerget Modification of Neutral
Polarization. C. A. Browne. The' Louisiana Planter and Sugar Manu-
facturer, Vol. 46 (1921), No. 11, pp. 171-172.
Testing Water in Tar Emulsions. W. W. Odell and E. W. Thtele. The
Gas Age, Vol. 47 (1921), No. 6, pp. 234-236.
Vitamines: The Physiological Value of the Vitamines. A. D. Emmett.
Journal of the American Pharmaceutical Association, Vol. 10 (1921), No.
3, pp. 176-182.
May, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
499
MARKET
FIRST-HAND PRICES FOR GOODS IN
INORGANIC CHEMICALS
April 1
Acid, Boric, cryst., bbls lb. . 14'/:
Hydrochloric, com'l, 20° lb. .01»/j
Hydriodic oz. .19
Nitric, 42° lb. .07"/:
Phosphoric, 50% tech lb. .IS
Sulfuric, C. P lb. .07
Chamber, 66° ton 20.00
Oleum 20% ton 23.00
Alum, ammonia, lump lb. .04'/,
Aluminium Sulfate (iron-free) lb. .03
Ammonium Carbonate, pwd lb., .OS
Ammonium Chloride, gran lb. . 06'A
Ammonia Water, carboys, 26°. . . .lb. .093/*
Arsenic, white lb. .08
Barium Chloride ton 65.00
Nitrate lb. .14
Barytes, white ton 30.00
Bleaching Powd., 35%, Works, 100 lbs. 2.75
Borax, cryst., bbls lb. .07
Bromine, tech lb. .27
Calcium Chloride, fused ton 28 . 75
Chalk, precipitated, light . t lb. .04
China Clay, imported ton 18 . 00
Copper Sulfate 100 lbs. 5.25
Feldspar ton 8 . 00
Fuller's Earth 100 lbs. 1.00
Iodine, resublimed lb. 3.75
Lead Acetate, white crystals lb. . 133/4
Nitrate lb. .15
Red American 100 lbs. .11 'A
White American 100 lbs. . 09 '/■■
Lime Acetate 100 lbs. 1.50
Lithium Carbonate lb. 1.40
Magnesium Carbonate, tech lb. .lO1/*
Magnesite ton 72.00
' Mercury flask, American 75 lbs. 45.00
Phosphorus, yellow lb. .35
Plaster of Paris 100 lbs. 1.50
Potassium Bichromate lb. . 121/2
Bromide, cryst lb. .IS
Carbonate, calc, 80-85% lb. .OS'A
Chlorate, cryst lb. .08
Hydroxide, 88-92% lb. .09'/a
Iodide, bulk lb. 2.50
Nitrate lb. .10
Permanganate, U. S. P lb. .40
Salt Cake, bulk ton 35.00
Silver Nitrate oz. .39
Soapstone, in bags ton 12.00
Soda Ash, 58%, bags 100 lbs. 1.90
Caustic, 76% 100 lbs. 3.75
Sodium Acetate lb. .07
Bicarbonate 100 lbs. 2 . 75
Bichromate lb. . .07»/l
Chlorate lb. OS'A
Cyanide lb. .IS
Fluoride, technical lb. .12
Hyposulfite, bbls 100 lbs. 4.00
Nitrate, 95% 100 lbs. 2.60
Silicate, 40° lb. .01 'A
Sulfide lb. .07
Bisulfite, powdered lb. .06
Strontium Nitrate lb. .13
Sulfur, flowers 100 lbs. 3.00
Crude long ton 20.00
Talc, American, white ton IS. 00
Tin Bichloride lb. .19'A
Oxide lb. .40
Zinc Chloride, U. S. P lb. .40
Oxide, bbls lb. .09
OBGANIC CHEMICALS
Acetanilide lb. .27
Acid, Acetic, 28 p. c 100 lbs. 2.50
Glacial lb. .09'A
Acetylsalicylic lb. .60
Benzoic, U. S. P., ex-toluene, lb. .70
Carbolic, cryst., U.S. P.,drs..lb. .11
50- to 110-lb. tins lb. .21
Citric, crystals, bbls lb. .47
REPORT-APRIL, 1921
ORIGINAL PACKAGES PREVAILING IN THE NEW YORK MARKET
April 1
April 15 Ac'd (.Concluded)
. 14'/2 Oxalic, cryst. bbls lb. .17
.OIVs Pyrogallic, resublimed lb. 2.00
.19 Salicylic, bulk, U. S. P lb. .23
.07'A Tartaric, crystals, U. S. P lb. .35
.18 Trichloroacetic, U. S. P lb. 4.40
.07 Acetone, drums lb. . 13'A
20.00 Alcohol, denatured, complete. .. .gal. .45
23.00 Ethyl, 190 proof gal. 4.90
,04'A Amyl Acetate gal. 3.05
.03 Camphor, Jap, refined lb. .70
.08 Carbon Bisulfide lb. .08
.06'A Tetrachloride lb. .12
.09*A Chloroform, U. S. P lb. .43
.08 Creosote, U. S. P lb. .50
65.00 Cresol, U. S. P lb. .18
.14 Dextrin, corn 100 lbs. 3.25
30.00 Imported Potato lb. .07'A
2.75 Ether, U. S. P., cone, 100 lbs.... lb. .18
.07 Formaldehyde lb. . 15'A
.27 Glycerol, dynamite, drums lb. .15
28.75 Methanol, pure, bbls gal. 1.25
.04 Pyridine gal. 2.75
18.00 Starch, corn 100 lbs. 2.58
5.25 Potato, Jap lb. .05
8.00 Rice lb. .25
1.00 Sago lb. .05
3.75
. 133/, OILS, WAXES, ETC.
'!* Beeswax, pure, white lb. .55
OQi/ Black Mineral Oil, 29 gravity gal. .22
,'[,0 Castor Oil, No. 3 lb. .087<
"' Ceresin, yellow lb. .13
101/ Corn Oil, crude lb. 07'/2
72 00 Cottonseed Oil, crude, f. o. b. mill. .lb. .04
Linseed Oil, raw (car lots) gal. .60
" Menhaden Oil, crude (southern). gal. .30
J" Neat's-foot Oil, 20° gal. 1.00
I-°T Paraffin, 128-130 m. p., ref lb. .07
' Paraffin Oil, high viscosity gal. .45
"I®. Rosin, "F" Grade, 280 lbs bbl. 5.15
'tout Rosin Oil, first run gal. .40
J|°/! Shellac, T.N lb. .50
0' Spermaceti, cake lb. .30
Sperm Oil, bleached winter, 38°. .gal. 1.73
' Stearic Acid, double-pressed lb. .10'A
' Tallow Oil, acidless gal. .75
39 Tar OU, distilled gal. .60
jo'no Turpentine, spirits of gal. .56
1 9° METALS
07 Aluminium, No. 1, ingots lb. .23
2 25 Antimony, ordinary 100 lbs. 5. 12'/!
071/, Bismuth lb. 1.65
08'A Copper, electrolytic lb. . 12'/a
'18 Lake lb. . 12'A
'12 Lead, N. Y lb. .04>/«
4 00 Nickel, electrolytic lb. .45
250 Platinum, refined, soft oz. 65.00
01 'A Quicksilver, flask 75 lbs. ea. 45.00
!07 Silver oz- -56'A
06 Tin lb. .29
13 Tungsten Wolframite per unit. 3.25
3^00 Zinc, N. Y 100 lbs. 5.10
"'" "J! FERTILIZER MATERIALS
.18 Ammonium Sulfate export. ..100 lbs. 3.00
.40 Blood, dried, f. o. b. N. Y unit 3.50
.40 Bone, 3 and 50, ground, raw ton 45.00
.09 Calcium Cyanamide, unit of Am-
monia 4 . 50
Fish Scrap, domestic, dried, f. o. b.
.23 works unit 3.50&.10
2.75 Phosphate Rock, f. o. b. mine:
.11 Florida Pebble, 68% ton 11.00
.55 Tennessee, 78-80% ton 15.00
.70 Potassium Muriate, 80% unit 1.15
.11 Pyrites, furnace size, imported, .unit .18
.21 Tankage, high-grade, f. o. b.
.4S Chicago unit 2.7S&.10
1.85
.23
.35
4.40
.13V2
.42
4.75
3.05
.65
.08
.12
.43
.50
.18
3.25
.07'A
.18
.15
• 13'A
1.25
2.75
2.58
.05
.25
.30
1.00
1.73
.10
.23
5.25
1.65
.12V.
.13
.04 'A
.45
65.00
45.00
.57
.29 'A
3.25
5.10
3.00
3.50
45.00
4.50
3.50 & .10
11.00
15.00
1.00
.18
500
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 5
COAL-TAR CHEMICALS
April 1
Crudes
Anthracene, 80-85% lb .75
Benzene, pure gal. . 27
Cresol, U. S. P lb. .18
Cresylic Acid, 97-99% gal. .90
Naphthalene, flake lb. .08
Phenol, drums lb. .10
Toluene, pure. . t gal. .28
Xylene, 2 deg. dist. range gal. .60
Intermediates
Acids:
Anthranilic lb. 1 . SO
B lb. 2.25
Benzoic lb. .60
Broenner's lb. 1 .75
Cleve's lb. 1.50
Gamma lb. 3.50
H lb. 1.25
Metanilic lb. 1 .60
Monosulfonic F lb. 2.75
Naphthionic, crude lb. .75
Nevile & Winther's lb. 1.50
Phthalic lb. .40
Picric lb. .30
Sulfanilic lb. .33
Tobias' lb. 2.25
Aminoazobenzene lb. 1.25
Aniline Oil lb. .22
For Red lb. .42
Aniline Salt lb. .28
Anthraquinone lb. 2.00
Benzaldehyde, tech lb. .45
U. S. P lb. 1.00
Benzidine (Base) lb. 1.10
Benzidine Sulfate lb. .75
Diaminophenol lb. 5.50
Dianisidine lb. 6.00
/>-Dichlorobenzene lb. .15
Diethylaniline lb. 1.40
Dimethylaniline lb. .50
Dinitrobenzene lb. .30
Dinitrotoluene lb. .25
Diphenylamine lb. .60
G Salt lb. .80
Hydroquinol lb. 1 .70
Metol (Rhodol) lb. 6.75
Monochlorobenzene lb. .14
Monoethylaniline lb. 2.15
a-Naphthylamine lb. .38
6-Naphthylamine (Sublimed) lb. 2 . 25
Z'-Naphthol, dist lb .34
"i-Nitroaniline lb. .90
P-Nitroaniline lb. .85
Nitrobenzene, crude lb. . 12l/a
Rectified (Oil Mirbane) lb. . 13V»
P-Nitrophenol lb. .75
p-Nitrosodimethylaniline lb. 2 . 90
o-Nitrotoluene lb. .15
P-Nitrotoluene lb. .90
m-Phenylenediamine lb. 1 . 15
P-Phenylenediamine lb. 1.75
Phthalic Anhydride lb. .55
Primuline (Base) lb. 3.00
R Salt lb. .75
Resorcinol, tech lb. 2.00
U. S. P lb 2.25
Schaeffer Salt lb. .70
Sodium Naphth'.onate lb. 1 . 10
Thiocarbanilide lb. .60
Tolidine (Base) lb. 1.40
Toluidine, mixed lb. .44
o-Toluidine lb. .27
_ 0-Toluidine lb. 1 . 25
w-Toluylenediamine lb. 1 . 15
Xylidine, crude lb. .45
COAL-TAR COLORS
Acid Colors
Black lb. 1.00
Blue lb. 1.50
1.80
'-' . 2.',
.60
1.75
1.30
3.50
1.25
1.60
2.75
.75
1.50
1.50
1.10
5.50
6.00
1.65
6.75
. 12>/«
. 13>/«
1.15
1.75
1.10
.60
1.40
1.25
1.15
.45
1.00
1.50
April 1
Acid Colors (Concluded)
Fuchsin lb. 2 . 50
Orange III lb. .60
Red lb. 1.30
Violet 10B lb. 6.50
Alkali Blue, domestic lb. 6.00
Imported lb. 8.00
Azo Carmine lb. 4.00
Azo Yellow lb. 2.00
Erythrosin lb. 7.50
Indigotin, cone lb. 2.50
Paste lb. 1.50
Naphthol Green lb. 1.95
Ponceau lb. . 1.00
Scarlet 2R lb. .85
Direct Colors
Black lb. .90
Blue 2B lb. .70
Brown R lb. 1.65
Fast Red 11). 2.35
Yellow lb. 2.00
Violet, cone lb. 1.10
Chrysophenine, domestic lb. 2.00.
Congo Red, 4B Type lb. .90
Primuline. domestic lb. 3.00
Oil Colors
Black lb. .70
Blue lb. .80
Orange lb. 1.40
Red III lb. 1.65
Scarlet lb. 1.00
Yellow lb. 1 . 25
Nigrosine Oil, soluble lb. .90
Sulfur Colors
Black lb. .20
Blue, domestic lb. .70
Brown lb. .35
Green lb. 1.00
Yellow lb. .90
Chrome Colors
.Alizarin Blue, bright lb. 5.00
Alizarin Red, 20% paste lb. 1.10
Alizarin Yellow G lb. 1.00
Chrome Black, domestic lb. 1.25
Imported lb. 2.20
Chrome Blue lb. 1.00
Chrome Green, domestic lb. 1.50
Chrome Red lb. 2.00
Gallocyanin lb. 2 . 80
Basic Colors
Auramine, O, domestic lb. 2.50
Auramine, OO lb. 4.15
Bismarck Brown R lb. .SO
Bismarck Brown G lb. 1 . 00
Chrysoidine R lb .75
Chrysoidine Y lb. .75
Green Crystals, Brilliant lb. 3 . 50
Indigo, 20% paste lb. .85
Fuchsin Crystals, domestic lb. 4 . 50
Imported lb. 12.00
Magenta Acid, domestic lb. 4.25
Malachite Green, crystals lb. 2 . 75
Methylene Blue, tech lb. 2.75
Methyl Violet 3 B lb. 2.75
Nigrosine, spts. sol lb. .70
Water sol., blue lb. .60
Jet lb .90
Phosphine G., domestic lb. 7.00
Rhodamine B, extra cone lb. 16.00
Victoria Blue, base, domestic lb. 6 . 00
Victoria Green lb. 2.50
Victoria Red lb. 7 . 00
Victoria Yellow lb. 7.00
2.50
.60
1.30
6.50
6.00
8.00
4.00
2.00
7.50
2.50
1.50
1.95
1.00
.85
2.35
2.00
1.40
1.65
1.00
.20
.70
1.00
.90
5.00
1.10
1.00
1.25
2.20
1.00
1.50
2.00
2.80
2.50
4.15
1.00
.75
.75
3.50
.85
4.50
12.00
4.25
2.75
2.75
2.75
.70
.60
.90
7.00
16.00
6.00
2.50
7.00
7.00
TAe Journal o£
Published 'Monthly by The American Chemical Society
Advisory Board: H. E. Barnard
Chas. L. Reese
Editorial Offices:
One Madison Avenue, Room 343
New York City
Telephone: Gramercy 0613-0614
Editor: CHAS. H. HERTY
Assistant Editor: Lois W. Woodford
J. W. Beckman A. D. Little
Geo. D. Rosengarten T.
Cable Address: JIECHEM
A. V. H. MORY
B. Wagner
Advertising Department:
170 Metropolitan Tower
New York City
Telephone: Gramercy 2145
Volume 13
JUNE1, 1921
No. 6
CONTENTS
Editorials:
Welcome to Madame Curie 502
A Tragedy Averted 502
A Call to Service 503
Less Legislation — More Cooperation 503
Original Papers :
The Alkylation of Aromatic Amines by Heating with
Aliphatic Alcohols. Arthur J. Hill and John J.
Donleavy 504
Precipitation of Grain-Curd Casein from Pasteurized
Milk, Including Sweet Cream Buttermilk. Harper
P. Zoller 510
The Relations of Hydrogen-Ion Concentration to the
Heat Coagulation of Proteins in Swiss Cheese Whey.
Yuzuru Okuda and Harper F. Zoller 515
The Variability of Crude Rubber. John B. Tuttle 519
The Relation of Moisture Content to the Deterioration
of Raw-Dried Vegetables upon Common Storage.
H. C. Gore and C. E. Mangels 523
Manganese in Commonly Grown Legumes. J. S.
Jones and D. E. Bullis 524
Effect of Heat on Different Dehydrated Vegetables.
C. E. Mangels and H. C. Gore 525
Methods for Determining the Amount of Colloidal
Material in Soils. Charles J. Moore, William H.
Fry and Howard E. Middleton 527
A Dry Method of Preparing Lead Arsenate. O. W.
Brown, C. R. Vorisand C. O. Henke 531
The Determination of Dicyanodiamide and of Urea in
Fertilizers. Erling Johnson 533
Yield and Composition of Wormwood Oil from Plants
at Various Stages of Growth during Successive
Seasons. Frank Rabak 536
Studies in Synthetic Drug Analysis. VIII — Estima-
tion of Salicylates and Phenol. W.O.Emery 538
The Determination of Cobalt and Nickel in Cobalt
Steels. G. E. F. Lundelland J. I. Hoffman 540
Improved Deniges Test for the Detection and Deter-
mination of Methanol in the Presence of Ethyl
Alcohol. Robert M. Chapin 543
Determination of Refractive Indices of Oils. Henry
S. Simms 546
Microanalytical Methods in Oil Analysis. Augustus
H. Gill and Henry S. Simms 547
The Determination of Small Amounts of Lead in Brass.
Francis W. Glaze 553
Laboratory and Plant:
The Manufacture of Citric Acid from Lemons. C. P.
Wilson 554
Apparatus for the Rapid Determination of the Avail-
able Chlorine in Bleach Liquor. Morris Schrero. . . . 559
Notes on Laboratory Apparatus. A. B. Andrews
Electric Muffle Furnaces for Laboratory Use. H. C.
Kremers
A New Type of Electrolytic Cell. Hiram S. Lukens . . .
Water Heater for Analytical Work. S. L. Meyers
Addresses and Contributed Articles:
Alcohol and the Chemical Industries. J. M. Doran. . . .
Social Industrial Relations:
Crowds and Their Manners. H. W. Jordan
Scientific Societies:
Nichols Medal Awarded to Gilbert N. Lewis; Chemical
Societies Honor Madame Curie; A. C. S. Committee
Reports; Division of Industrial and Engineering
Chemistry — Submittal of Papers; Hotel Accommo-
dations, American Chemical Society Meeting, New
York City, September 6 to 10, 1921; Division of
Chemistry and Chemical Technology of the National
Research Council; The Exposition of Chemical In-
dustries; The National Lime Association; Calen-
dar of Meetings
Notes and Correspondence:
Madame Curie Receives Gram of Radium and Many
Honors; Presentation of Medal to Dr. Frederick B.
Power; The Direct Identification of Soy-Bean Oil;
New Chemical Laboratories; Exchange Professors
in Engineering and Applied Science between French
and American Universities; The Detection of
Phenols in Water — Correction
Miscellaneous:
Annual Tables of Constants
Dr. Chandler Receives National Institute of Social
Sciences Medal
The National Fertilizer Association
The Belgian Bureau of Chemical Standards
Centennial of Philadelphia College of Pharmacy
Cryogenic Laboratory, Bureau of Mines
Bureau of Employment of the New York Chemists'
Club
American Institute of Chemical Engineers
Washington Letter
London Letter
Paris Letter
Industrial Notes
Personal Notes
Government Publications
Book Reviews
New Publications
Market Report
561
562
563
564
566
509
530
535
539
539
560
563
563
575
576
576
577
578
580
583
586
587
Subscription to n
Subscript i<
-members, $7.50; single copy, 75 cents, to members, 60 cents. Foreign postage, 75 cents, Canada, Cuba and Mexico excepted,
i and claims for lost copies should be referred to Charles L. Parsons, Secretary, 1709 G Street, N. W , Washington, D. C.
502
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
EDITORIALS
Welcome To Madame Curie!
Welcome, thrice welcome, to our distinguished hon-
orary member, Madame Curie!
Since the day of her arrival she has been over-
whelmed with honors and with entertainment, almost
to the detriment of her physical health. She has in-
spected the plants where radium and other rare mineral
salts are produced, and carries home increased
facilities for continuing her research. She has come
into touch with our bustling American life, and perhaps
when she gets back to the quiet of her laboratory she
will tell us what she thinks of it all. Her presence
has emphasized without the necessity of words the great
value of fundamental chemical research and the possi-
bilities for thoroughly equipped women in chemistry.
Her visit has proved a fitting and delightful means of
emphasizing again the strength of the tie that binds
France and America.
A Tragedy Averted
A new chapter in the fight for the protection of the
American coal-tar chemical industry opened on April
26, 1921, when Senator Knox introduced in the Senate
Finance Committee an amendment to the Emergency
Tariff Bill continuing for six months the regulations
controlling the importation of coal-tar chemicals,
which were in danger of immediate abrogation should
the Knox peace resolution become law. This law
would automatically terminate the Trading-with-the-
Enemy Act, under which the War Trade Board Section
of the State Department had been functioning. Senator
Knox was simply acting in good faith, to preserve for
the sole industry affected by his peace resolution the
protection which he recognized was necessary for its
very existence. The amendment made no change ex-
cept to transfer the administrative machinery from the
State Department to the Treasury Department.
The Finance Committee accepted the amendment and
the bill was reported favorably to the Senate. Then
what a howl was raised! Senator Moses was naturally
the high soprano in the very limited but noisy chorus
of opposition. Senator Knox disposed of the Moses
objections promptly and effectually when he refused to
view the matter from the "standpoint of a profit and loss
account of a Dolly Varden calico mill in New England."
The word "monopoly," used by Senator Moses in
referring to the American dye industry, fell like honey — ■
no, rather something highly stimulative — into the wait-
ing mouths of Senators King and Hitchcock. The result
was a flood of oratory. All of the familiar stock
phrases which characterized the "trust-busters" of old
were resurrected.
Both Senators were deeply impressed by the large
exports of American dyes during the past few years,
not caring to trouble themselves about looking into
the character and conditions of this export business.
They could have learned that it represented the natural
American genius for mass production where methods
have been thoroughly standardized, and that the prod-
ucts were marketed at a time when there were no other
available sources of dyes. They could easily have
learned of the tremendous drop in dye exports during
the past six months, as shown in the following table
from figures issued by the Department of Commerce.
Exports op Aniline Dyes
November 1920 $2,006,534
December 1920 1.788,170
January 1921 943,595
February 1921 397,123
March 1921 574,969
April 1921 305,760
A few days later Senator King exclaimed "this vora-
cious trust is determined to perpetuate in peace times
war policies and fasten upon the people an obnoxious
and vicious system under which it may conceal its
acts of spoliation and robbery." But what evidence
is there of a trust? No interlocking directorates were
mentioned, no operating agreements were exposed, no
uniform fixed prices were quoted by the Senator, nor
was any tendency of large concerns to swallow up small
ones reported.
There is no American dye trust, and the fact is well
known. The small manufacturers are on record be-
fore the Senate (Congressional Record, June 3, 1920,
pages 8306-8) in a petition urging favorable protective
legislation, without which they maintain that they
will be the first to go down in the struggle with the real
dye trust in Germany.
There is no tendency to hold up the American people
with exorbitant prices, as shown by the following
schedule of prices of typical articles, obtained on the
street a few days ago:
Dyes Price a Year Ago Price To-day
OranselT SO. 85 $0.50
DirectBlack 1.20 0.75
Gallocvanine 4.25 2.50
Fuchsin Crystals 5.50 2.75
Malachite Green Crystals 4.50 2.00
Methylene Blue Technical 3.75 2.40
Intermediates Used for Dyes
AnilineOil 0.37 Ills
Beta-Naphthol 0.88 0.32
Para-Nitroaniline 1.75 0.S0
Other Intermediates
Gamma Acid 6.00 3.25
Benzidine. Base 1.50 1.00
Dimethylaniline 2.20 0.42
Para-Phenylenediamine 2.50 1.75
It was Senator King who, in the last Congress, rushed
in a bill to restore alien property and holdings seized
during the war. This may be a mere coincidence, of
course. The bill was not reported out of committee,
but the Senator, nothing daunted, reintroduced the
the bill soon after the present Congress convened.
At the conclusion of Senator Hitchcock's address,
Senator Knox commented (Congressional Record, May
11, 1921, page 1285):
I only wanted to observe that there is something entirely
familiar in these lamentations of the Senator from Nebraska
about the probability of the German monopoly in the most dan-
gerous munitions that have ever been manufactured being inter-
fered with by this bill. We remember that during the war, when
the Germans had a monopoly of munitions and the Allies could
not obtain munitions to fight the Huns the Senator from Nebraska
advocated a bill to prevent the people of the United States from
June, 1921
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
503
shipping munitions to the French and to the English and to the
Italians, who were engaged in a death struggle with Germany
for the preservation of civilization.
When the time came for voting, the amendment was
overwhelmingly adopted by the Senate. In conference
the duration of the protection afforded by this "Dye
and Chemical Control Act, of 1921," was limited to
three months. The bill continues the licensing of
importations as hitherto carried out, except that the
power is vested in the Customs Division of the Treasury
Department, where it logically belongs.
The act was signed by President Harding on May
27, 1921. A near tragedy has been averted, but the
end is not yet.
A Call to Service
Our organic chemical industry has been spared a mor-
tal blow. The flood gates have not been opened for
the inrush of the accumulated German stocks of dyes
and other synthetic organic chemicals.
But the fight is not yet over. Those who desire
opportunity for unrestricted importation are working
bitterly. Witness the following letter sent to a con-
sumer of dyes by a firm of importers whose record shows
all too clearly their Teutonic connections:
KUTTROFF, PICKHARDT & CO., Inc.
We r.-b jijrloed th;,t the
la proponing to inclvle tr.e Dye Li
nar.ent Tariff,
In jour pm lntnro^t It
"end l-s-.edr.itcly io ycur repre-e-.t
Vaye and t/*nm
LI
rr.bargo restricting the irrport.-ulon of d.eit uf f a.
■lit!.cr License or K-cborgo -iocjie monopoly, whereFa n atrnlght
tariff would oftfec-i-ird Wth d.eituff oanuf>\ctur*ra and con-
Youra roapectfully,
EUTTnoyr, j»LraL\£j>r & ro.. i'.r.
&7P52 ■--■■■>c
What is the best method of overcoming this oppo-
sition and insuring permanent legislation which will
preserve to this nation the invaluable asset of a com-
plete coal-tar chemical industry? It is only neces-
sary to tell the whole straightforward story in lan-
guage which the man on the street can understand.
Show the organic chemical industry as it existed (or
didn't exist) before the war, conditions during the war,
and happenings (legislative and otherwise) since that
time. The story of chemistry always effects a dy-
namic conviction which expresses itself in definite
action. Continued education is needed as to its signifi-
cance for economic independence and national defense.
The daily press is doing splendid work, both in its
editorial and news columns. The Chemical Founda-
tion is playing an important part through its distribu-
tion of Dr. Slosson's book "Creative Chemistry."
65,000 copies of this fascinating, illuminative story
of chemistry have already been distributed to leaders of
thought in every state. The Commissioner of Educa-
tion has distributed the pamphlet "Treasure Hunting of
To-day" to every high school in the land. Under the
auspices of the National Research Council there has
been prepared by the Chemical Warfare Service an
exhibit, including a topographic model in relief,
charts, and specimens, showing the close relations of
the various lines of chemical industry. This exhibit
was shown not long ago in the Capitol in Washington,
where it was closely studied by members of Congress,
and has now been permanently established in the
National Museum.
In this work of furthering public understanding you,
fellow chemist, have your responsibility. Are your
neighbors, your business associates, your community
thinkers, familiar with the facts? Talk to a group —
speak before your Rotary Club — address the local
Chamber of Commerce. Arrange for an exhibit some-
where in your city. This is not the business of any
small group of men, but a task for each individual
chemist to share.
Less Legislation — More Cooperation
To meet the great difficulties being experienced in
enforcing the prohibition feature of the National Pro-
hibition Act a new enforcement bill has been introduced
into Congress. Popularly it is known as an anti-beer
bill, but it has been skilfully drawn, and restricts the
use of alcohol to an extent which will seriously handi-
cap a great number of the chemical industries and
practically prevent the development of others. The
zeal of the prohibitionist has led him to ignore com-
pletely that section of the basic law, Title III, which
seeks to encourage the development of the manufacture
of industrial alcohol and to facilitate its distribution.
It took many years to educate our legislators to the
necessity of alcohol as a sine qua non in many lines of
industry, but the good work was finally accomplished.
Manufacture began on a large scale and the needed
industries sprang up. Now the whole structure, built
in good faith, seems threatened, just at a time when
President Harding is urging that a closer and more
sympathetic relationship between government and
business should exist. Now when Congress is showing
the most friendly attitude towards chemicals in general
there comes a side swipe against the most important of
all chemical reagents, alcohol.
New laws are not needed here. The wording of the
Act is plain. Let the newly appointed Commissioner of
Internal Revenue call to his aid representatives of the
industries to advise with him about their needs and
difficulties. He can secure their wholehearted cooper-
ation. There is opportunity here for the creation of
that sympathetic relationship between government
and business for which the President pleads.
504
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
ORIGINAL PAPERS
The Alkylation of Aromatic Amines by Heating with Aliphatic Alcohols1
By Arthur J. Hill and John J. Donleavy
Department op Chemistry, Yale University, New Haven, Connecticut
It was shown in a recent publication4 that the forma-
tion of diethylaniline, C6H5N(C:>Hs)2, by the interaction
of aniline hydrochloride and ethyl alcohol could be
promoted to a considerable degree by certain catalysts,
among which the two following combinations were
found to be the most active:
Sodium bromide Sodium bromide
Calcium chloride Copper powder
Cupric chloride
The present investigation is an extension of this
problem to the toluidine series, and comprises two dis-
tinct phases, namely,
1 — The action of ethyl alcohol upon the hydrochlorides of
o-, m-, and p-toluidine.
2 — The action of w-butyl alcohol upon the hydrochlorides of
aniline, and o-, m-, and p-toluidine.
The catalysts which were- found efficient in the alkyl-
ation of aniline hydrochloride with ethyl alcohol have
likewise promoted alkylation in this new series of ex-
periments. Furthermore, the experimental results
have an important bearing, on the one hand, as regards
the comparative activity of ethyl and butyl alcohol,
and on the other, respecting the spatial influence of
nuclear substituents on the ease of alkylating aromatic
amines.
As pointed out in the previous publication,5 the na-
ture of the product resulting from the alkylation of an
aromatic amine with alcohol is conditioned, in par-
ticular, by two factors, namely, the temperature of
the reaction, and the presence of certain catalysts.
Influenced by these factors, the reaction may proceed
in one of two directions, as represented by Equations
1 and 2.
NH2HC1 NHCHj N(C,HS)2
C2HsOH
NH2HC1
C2H5
(1)
C2H5)
(2
0 — 0 - 0
C,H5 C2HS
With regard to the effect of temperature, it appears
that there is a favorable one at, or below which, nitrogen
alkylation predominates, and above which nucleus
substitution is facilitated. This temperature is highest
with methyl alcohol and is apparently lowered in pro-
portion to the complexity of the alcohol molecule.
The action of butyl alcohol upon aniline hydrochloride
1 Received February 26, 1921.
i "Researches on Amines, IX.'* The previous papers of this series, with
the exception of VII, This Journal, 11 (1920), 636, have been published
in the Journal of the American Chemical Society.
1 This paper is constructed from a dissertation presented by John J.
Donleavy to the Faculty of the Graduate School of Yale University, 1920,
in candidacy for the Degree of Doctor of Philosophy. (A. J. H.)
•"Researches on Amines, VII."
• hoc . at.
has recently been investigated by Reilly and Hickin-
bottom,1 with particular regard to the factors affecting
nucleus substitution. They have shown that the
product obtained by heating this salt with butyl al-
cohol at 200° is,2 quantitatively speaking, a mixture
of the secondary and tertiary bases, whereas at 240° to
260° the product3 is chiefly />-«-butylaminobenzene (I).
NH,.HC1
CHsOH
NH.C4H,.HC1
NH,.HC1
C4H9
(I)
Somewhat similar results were also obtained with
^-toluidine hydrochloride4 and butyl alcohol.
Reilly and Hickinbottom5 have subjected the factors
underlying the intramolecular rearrangement of p-n-
butylaminobenzene to a very thorough investigation,
and conclude that this rearrangement of alkylaryl-
amines is conditioned .by the presence of substances
which are capable of uniting with amino groups. For
example, HC1, ZnCl2, CoCl2, and CdCl2 greatly facili-
tate this reaction, while compounds such as CaSOi,
NaCl, CaCU, and Si02 are substantially inactive.
Cupric chloride is stated to be slightly active. iV-butyl-
aniline may be heated for several hours at 240° to
260° without suffering rearrangement, whereas the
introduction of the above-mentioned catalysts will
promote intramolecular rearrangement to the extent of
50 per cent or more, in 7 to 8 hrs. In the light of
these observations it is important to note that our
most efficient catalytic mixture for tertiary amine
formation is composed of CaCl2, NaBr, and CuCl2, the
first two of which are inactive with respect to pro-
ducing nucleus substitution, and the last named, active
to a small degree only. Further, in the interaction of
aniline hydrochloride and ethyl alcohol we observed6
that ZnCl2 functioned much less favorably as a catalyst
of nitrogen alkylation than CaCl2. Our results are
therefore decidedly in accord with those of Reilly and
Hickinbottom.
The latter have further contributed data bearing on
the comparative tendency for rearrangement of
methyl- and n-butylaniline, in which it seems evident
that the latter is far more prone to undergo this reac-
tion than the former, in the presence of the catalysts
previously referred to.
The object of our investigation has been primarily
to study the factors productive of the maximum yield
of the tertiary bases in the action of ethyl and n-butyl
' J. Chem. Soc. 117 (1920), 103.
1 Ibid., 113 (1918). 102.
'Ibid., 113 (191S), 976.
*Ibid., 113 (1918), 976.
Ubid., 117 (1920), 103; Chem. News, 119 (1919), 161.
e hoc. cit.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
505
alcohols upon the hydrochlorides of aniline and the
isomeric toluidines. This problem has therefore in-
volved an investigation of the conditions promoting
a maximum transformation of A to C, with a minimum
production of B on the one hand, and D on the other.
NH2 NHR NRj NHR
(A)
(B)
(C)
R
(D)
We have observed that three factors have a predomi-
nant influence on the formation of the tertiary base,
C, namely, the concentration of the alcohol, the
nature of the catalyst, and the temperature of the
reaction. It has hitherto been common practice1 to
utilize two or three moles of alcohol in the interaction
of amine hydrochlorides with alcohols for the produc-
tion of tertiary bases. The utilization of a large ex-
cess of alcohol, ten molecular proportions, greatly de-
creases secondary amine formation, B. With regard
to the use of catalysts, we have found that the com-
bined influence of calcium chloride, sodium bromide,
and cupric chloride, together with the hydrogen chlo-
ride of the salt, facilitates the transformation of A to C.
However, these same catalysts, particularly the last
named, above a temperature which is apparently
definite for each alcohol-amine mixture, initiate also
the above-described nitrogen to carbon rearrangements.
This critical temperature we have found to be 175°
to 180° in all of the alkylations herein described, the
extent of tertiary amine formation, however, being
considerably less in every case where butyl alcohol
was used, as compared with ethyl alcohol. This is
shown in the following table:
Aniline
Per cent
#>-Toluidine
Per cent
m-Toluidine
Per cent
o-Toluidine
Per cent
Ethyl alcohol
95
75
91.6
77.4
90.25
79.8
76
48.5
In other words, the temperature at which nitrogen to
carbon rearrangement sets in with butyl alcohol is
apparently lower than that of ethyl alcohol, and al-
though tertiary amine formation might hypothetically
be increased at temperatures higher than 180°, the
possible result is nullified by the initiation of the re-
action typified by the transformation of C to D.
The interaction of alcohols and the derivatives of
aniline presents a more complicated problem than is
involved with the prototype of the series. In the lat-
ter case, the entering group need only be considered,
whereas, when derivatives of aniline, such as the iso-
meric toluidines, are employed, the orientation of the
methyl groups in the benzene nucleus markedly affects
the reactivity of the amine in question. That ortho
substituents inhibit the reactivity of adjacent nucleus
groups has long been recognized. We should there-
fore expect the alkylation of o-toluidine hydrochloride
to present certain anomalies, as compared with the
reactivity of the meta and para derivatives. This has
been found to be remarkably the case in the present
investigation. While the p- and w-toluidines could
be ethylated or butylated to substantially the same
> This Journal, 12 (1920), 636.
degree, the extent of tertiary amine formation was
14 to 16 per cent less in the case of o-toluidine and
ethyl alcohol, and as much as 29 to 31 per cent less
when butyl alcohol was used as the alkylating agent.
This is by no means the first observation concerning
the steric influence1 of ortho substituents upon the
alkylation of amines. However, so far as the writers
have been able to ascertain, the present observation
on the steric influence of ortho substituents upon the
reaction between aliphatic alcohols and the salts of
aryl amines is the first of this nature to be recorded.
Quite recently, Reilly2 investigated the action of
M-butylchloride upon o-toluidine, and was able to ob-
tain only mono-butyl-o-toluidine. In an effort to pre-
pare the tertiary amine he digested mono-w-butyl-
o-toluidine with an excess of M-butylchloride for 10
days. Even under these conditions he was unable to
obtain the tertiary base.
EXPERIMENTAL
The alkylations described below were all carried out
in an iron autoclave of 1.7 liters' capacity. The latter
was equipped with the usual pressure gage and ther-
mometer well, and protected from corrosion by means
of a glass inset. The location of the thermometer well
was such that the temperatures recorded were those of
the vapor phase. The autoclave was heated in a bath
of cottonseed oil.
The method of isolating the alkylation products in
each experiment was as follows: The unchanged al-
cohol was first removed by distillation under dimin-
ished pressure. By this means very economical re-
covery could be made of the large excess of alcohol re-
quired to effect complete alkylation. The residue was
then made strongly alkaline with sodium hydroxide,
and the liberated bases distilled with steam. The
amines were separated from the aqueous distillate by
ether extraction and dried over anhydrous sodium sul-
fate. In the case of the butyltoluidines, however, the
amines were not steam-distilled but extracted directly
from the alkaline solution with ether, by reason of the
fact that the aromatic butyl amines steam-distil at a
much slower rate than the corresponding ethyl deriva-
tives. After removal of the ether, the oils were fraction-
ally distilled at atmospheric pressure, the distillates
being collected at 2° intervals.
The extent of tertiary amine formation in each ex-
periment was determined by an estimation of the
acetylizable material in the reaction product (see
previous paper for details), and the result calculated
in terms of the mono-alkylated amine.
SYNTHESIS OF THE ISOMERIC DIETHYLTOLUIDINES
Romburgh3 prepared diethyl-o- and -/>-toluidine by
the interaction of ethyl alcohol and the corresponding
primary bases in the presence of hydrochloric acid.
In order to effect alkylation he heated his reaction
mixtures at 200° to 220° for 48 hrs. Since the primary
purpose of his investigation was the study of the ni-
i Ber , 6 (1872), 707; 8 (1875), 61; 18 (1885), 1824; 32 (1899), 1401;
33 (1900), 345; 33 (1900), 1967; J. prakt. Chem., 66 (1902), 252; Ann., 346
(1906), 128.
2 J. Chem. Soc, 113 (1918), 974.
' Rec. Irav. (him.. 3 (18S4). 392.
506
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
tration of these bases, he apparently devoted but little
attention to their synthesis. This brief reference is
the only record in the literature concerning the action
of ethyl alcohol upon the hydrochlorides of o- and
/>-toluidine. However, the preparation of diethyl-o-
and -/>-toluidine from the primary amine hydrobro-
mides or hydriodides and ethyl alcohol is recorded by
Stadel,1 who states that yields of 90 per cent or better
are obtained at 150° and 125°, respectively. Mono-
as well as diethyl-o- and -/>-toluidines have also been
prepared by alkylation of the primary bases with alkyl
halides.2
So far as the writers are aware, there is no available
information concerning the action of ethyl alcohol
upon w-toluidine hydrochloride. Beilstein3 refers to
the work of Stadel4 for the preparation of diethyl-
w-toluidine, but the latter appears to have prepared
only the ortho and para derivatives. Further, the
patent which covers Stadel's alkylation procedure
does not designate the preparation of diethyl-m-tolu-
idine, although the ortho and para derivatives are
specifically mentioned. Weinburg5 accurately deter-
mined the boiling point of the mono- and diethylated
toluidines, including diethyl- »z-toluidine, but did not
state how the bases were prepared. In fact, the only
direct information respecting the preparation of this
tertiarv base is to be found in a paper by Goldschmidt
and Keller,6 who, giving no details, merely mention
the fact that they prepared this compound by Stadel's
general method.
The writers have now carefully studied the factors
affecting tertiary amine formation in the interaction of
ethyl alcohol and the isomeric toluidines. The results
of these experiments are embodied in Tables I, II,
and III.
DIETHYL-p-TOLUIDINE
The results which were obtained by heating />-tolu-
idine hydrochloride with ten molecules of ethyl alcohol
are recorded in Expt. 1, Table I. The product of this
reaction distilled for the most part within a range of
4° and contained but 9.45 per cent secondary amine.
The addition of copper powder and sodium bromide
(Expt. 2) to the reaction mixture increased the forma-
tion of the tertiary base, while the second set of cata-
lysts (Expt. 3) produced no positive effect. The best
conditions for the formation of diethyl-/>-toluidine are
therefore represented in Expt. 2.
In order to isolate pure diethyl-/>-toluidine, the crude
oil was heated for 3 hrs. with an equal weight of acetic
anhydride. The resulting product was then fraction-
ally distilled at atmospheric pressure. The tertiary
base was obtained as a pale yellow oil which boiled
at 230° at 755 mm. This result is in accord with the
previous observations of Weinberg,7 who reported a
boiling point of 229° for this amine.
> Ber., 16 (1883). 29; D. R. P. 21,243 (1883).
! Ann., 93 (1855). 313; Am. Chem. J., 7 (1885), 119.
I Vol. II, 477.
• Loc. cit.
• Ber.. 26 (1892), 1613.
• Ibid.. SS (1902), 3540.
» Loc. cit.
Table I — Diethyl-/>-Toi.uidine
(100 g. p-toluidine hydrochloride; 320 g. ethyl alcohol; time, 8 hrs.;
temperature, 175°-180*)
Expt. 1 Expt. 2 Expt. 3
Catalysts:
Sodium bromide, grams .. 10 10
Calcium chloride, grams .. .. 10
Cupric chloride, grams . . 5
Copper powder, grams . . 5
Total oil, grams 106 107 103
Acetylizable portion of oil, per cent 0 4 7.9 9.4
Calculated tertiary base, per cent 90.6 92.1 90.6
Distillation. Temperature
224°-226°, cc 2 .. 1
226°-228°, cc 68 28 42
228°-230°, cc 38 69 51
230°-232°, cc 13 7
DIETHYL- W-TOLUIDINE
A product containing 11.8 per cent acetylizable ma-
terial was formed by heating w-toluidine hydrochloride
with ten molecules of ethyl alcohol (Expt. 1, Table II).
The degree of alkylation was slightly lower in this case
than that obtained when the para salt was treated
under similar conditions. The proportion of tertiary
base in the reaction product was raised by the use of
catalysts (Expt. 3). On the other hand, it is of interest
to note that copper powder (Expt. 2) exerted an in-
hibitive action. It is difficult to explain this apparent
anomaly, since in all previous alkylations its use has
proved beneficial.
The best experimental conditions (Expt. 3) for the
preparation of diethyl- jn-toluidine were therefore pro-
ductive of oils which contained about 90 per cent of
the tertiary base. This figure is about 2 per cent lower
than the results obtained with the para base, and 5 per
cent lower than those obtained with aniline.
A procedure similar to that applied in the case of the
para derivatives was used for the isolation of diethyl-
m-toluidine. The latter was thereby obtained as a
light yellow oil which boiled at 232° under 755 mm.
pressure. Weinberg1 reported a boiling point of 231.5°
for this compound.
Table II — DiETHYt-m-ToLuiDlNE
(50 g. Wl-toluidine hydrochloride; 160 g. ethyl alcohol; time, S hrs.;
temperature, 175°-180°)
Expt. 1 Expt. 2 Expt. 3
Catalysts:
Sodium bromide, grams . . 5 5
Calcium chloride, grams .. 5
Cupric chloride, grams . . . . 2.5
Copper powder, grams 2.5
Total oil, grams 55 47 48
Acetylizable portion of oil, percent 11 8 13.7 9.75
Calculated tertiary base, per cent 88.2 86.3 90.25
Distillation. Temperature
226"-228°, cc 2 7 13
228°-230°, cc 16 19 17
230°-232°, cc 20 9 8
232°-234°, cc 4 4 4
234°-236°, cc 4 4 4
236°-238°, cc 4 4 2
DIETHYL-0-TOLUIDINE
The steric influence of o-substituents upon the
alkylation of amines is interestingly demonstrated in
the interaction of o-toluidine and ethyl alcohol. When
ten moles of the latter were heated with o-toluidine
hydrochloride (Expt. 1, Table III), the product con-
tained 32 per cent of the secondary base. It has already
been shown that the alkylation of the meta and para
isomers by this method yields a preponderance of the
tertiary amine. In fact, in neither case did the acetyl-
izable portion of the oil exceed 12 per cent. The re-
sult with o-toluidine therefore offers a striking contrast.
The effect of the catalysts (Expts. 2 and 3), however,
was more apparent with this base than with the meta
1 Loc. cit.
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
507
and para derivatives. The best results were obtained
by the use of cupric chloride, sodium bromide, and
calcium chloride (Expt. 3). The oil contained 24 per
cent of the mono-alkylated base. Even this, however,
is quite inferior to the degree of alkylation obtained
when the isomers were similarly treated.
Table III — DiETHVi.-o-Toi.iriDiNS
(100 g. o-toluidine hydrochloride; 320 g. alcohol; time, 8 hrs.)
Expt. 1 Expt. 2 Expt. 3 Expt.41
Catalysts;
175
87
32
67
5
65
15
7
rge us
3
7
ed
175
Acetylizable portion of oil, per cent.. .
Calculated tertiary base, per cent. . . .
Distillation. Temperature
28.6
71.4
230°-234°, cc
234°-238°, cc
1 One-half the usual autoclave chf
n this e
2.5
200
In order to ascertain the effect of higher tempera-
tures, an experiment was carried out at 200° C. with
most efficient catalysts. This modification of condi-
tions (Expt. 4) greatly increased the proportion of
acetylizable bases. It is quite evident from this ob-
servation that intramolecular rearrangement will take
place to some extent at temperatures of 200° C.
Owing, therefore, to the inhibitive effect of the ortho
substituent, the best experimental conditions failed to
produce a product containing more than 76 per cent
diethyl-o-toluidine.
The pure tertiary base was isolated from the reac-
tion mixtures by the use of the method previously de-
scribed for the preparation of the meta and para isomers.
It was obtained as a practically colorless oil which
boiled at 206° to 208° C. at 755 mm. Stadel,1 who has
previously prepared this base, states that it boils at
208° to 209°.
DI-W-BUTYLANILINE
As stated above, the action of w-butyl alcohol upon
aniline has recently been investigated by Reilly and
his co-workers. Their investigations, however, are of
particular value in their information respecting the
intramolecular rearrangement of «-butylaniline, while
their observations with regard to the degree of nitrogen
alkylation by this method are wholly qualitative.
The writers have therefore sought to establish the ex-
perimental conditions productive of the maximum
yield of di-ra-butylaniline. The results of these in-
vestigations are given in Table IV.
When aniline hydrochloride was heated at 175°
with ten moles of w-butyl alcohol (Expt. 1, Table IV),
the alkylated product contained but 51 per cent di-
butylaniline. It is interesting to note that under
similar conditions ethyl alcohol yielded an oil con-
taining 88 per cent diethylaniline. The difference in
the reactivity of these two alcohols is plainly evident
from these observations.
The effect of introducing the catalytic mixture
(Expt. 2) was quite marked. The yield of dibutyl-
aniline was raised from 51 to 75 per cent. The range
1 Lac. cit.
of distillation of this oil, compared with that obtained
in Expt. 1, indicates the considerable increase in the
amount of tertiary base produced by this change of
procedure.
In order to ascertain whether or not 175° was the
optimum temperature, an experiment was carried out
under the favorable conditions of Expt. 2, the tem-
perature, however, being raised to 200°. As a result,
the amount of dibutylaniline was decreased about
5 per cent. This was due, no doubt, to an intra-
molecular rearrangement, in which nuclear alkylated
amines were produced in accordance with the following
equation:
CeHi.NH.dH,
^-NH2.C6H1.C,H9
Reilly utilized temperatures of 240° to 260° in order
to obtain />-w-butylaniline, but the results of Expt. 3
suggest that alkylation of the nucleus, although not
predominant, may take place at 200° C, or even lower.
We did not operate at temperatures lower than 175°,
since the autoclave pressure, which is an important
factor, decreases materially below this temperature.
The most favorable conditions for the formation of
dibutylaniline are therefore shown in Expt. 2. Even
these, however, produce a tertiary amine formation
which is 20 per cent below that obtained with ethyl
alcohol. The wide difference in the reactivity of the
two alcohols may be seen from inspection of the follow-
ing table:
Their Reaction
Alcohol (ten moles) 88 51
Alcohol (ten moles and catalysts) 95 75.5
The above percentages refer to the amount of tertiary amine in the re-
action products.
Pure di-w-butylaniline was prepared by the following
procedure: Fifty grams of the crude amine, containing
about 25 per cent of the secondary base, were heated
for 3 hrs. with an equal weight of acetic anhydride.
The resulting product was repeatedly distilled in order
to separate the tertiary base from the acetobutylaniline.
After careful fractionation, di-M-butylaniline was ob-
tained as a light yellow oil, which boiled at 262° to
264° under 755 mm. pressure. Reilly1 reported the
boiling point of this compound as 260° to 263° under
767 mm. pressure.
Analysis (Kjeldahl) Per cent
Calculated for C.iHaN: N 6.86
Found ; N 7 . 00
(50 g. anilil
Table IV — Di-k-Butylaniline
hydrochloride; 285 g. K-but)
Catalysts:
Sodium bromide, grams
Calcium chloride, grams
Cupric chloride, grams
Temperature, ° C
Total oil, grams
Acetylizable portion of oil, per cent.
Calculated tertiary base, per cent. . .
Distillation. Temperature
244°-248°, cc
248°-252°, cc
252°-2S6°, cc
256°-260°, cc
260°-264°, cc
264 "-268°, cc
268°-272°, cc
272°-276°, cc
276°-2S0°, cc
280°-284°, cc
d1; time.
8 hrs.)
;xpt. 2
Expt.
5
5
5
5
2.5
2.5
75-180
200
53
51
24
30.3
75
69.7
/. Chem. Soc, 113 (1918), 99.
50S
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13 No. 6
SYNTHESIS OF THE ISOMERIC DI-W-BUTYLT0LUIDINES
The action of w-butyl alcohol upon the hydrochlorides
of the isomeric toluidines has not been investigated
until recently, and then only in connection with the
para derivative. Reilly heated the hydrochloride of
^-toluidine with 1.3 molecules of w-butyl alcohol at
220° to 260° for 7 to 8 hrs., and states1 that the product
of the reaction is essentially a primary amine, pre-
sumably an aminobutyltoluene. Nitrogen-alkylated
derivatives were apparently produced in such small
quantities in this reaction that the extent of their
formation was not determined. The secondary amine
is formed at 140°, but the yield of this base rapidly
diminishes with increasing temperature. Reilly, how-
ever, has prepared the mono-w-butyl-o- and -/>-to!u-
idines and the di-w-butyl-£-toluidine2 by the action of
w-butylchloride upon the corresponding amines. So
far as the writers are aware, the di-w-butyl derivatives
of m- and o-toluidine have not hitherto been prepared.
In Tables V, VI, and VII are recorded the results of
the experiments designed to determine the factors lead-
ing to the maximum degree of tertiary amine formation
in the reaction between the toluidine hydrochlorides
and w-butyl alcohol.
DI-W-BUTYL-/>-TOLUIDINE
A product containing 28 per cent of the secondary
base was obtained by the action of ten moles of w-butyl
alcohol upon />-toluidine hydrochloride (Expt. 1, Table
V). This result is considerably better than the cor-
responding one with aniline, which gave 49 per cent
of the secondary base. The utilization of the catalysts
(Expt. 2) produced an increase of about 5 per cent in
the degree of alkylation. In order to ascertain the
effect of longer heating, the time period was extended
to 12 hrs. (Expt. 3). The results were substantially
the same as those resulting from the usual time factor.
An increase in temperature to 200° (Expt. 4) not only
failed to aid in the formation of the tertiary base, but
even facilitated the formation of nuclear alkylated
amines. The best conditions, represented by Expt. 2,
gave results somewhat better than those obtained with
aniline under similar conditions.
We were unable satisfactorily to isolate and purify
di-w-butyl-£-toluidine by the use of acetic anhydride.
Hinsberg's method3 was therefore used. The pro-
cedure employed was as follows: The crude amine,
previously analyzed, was shaken with twice the cal-
culated quantity of benzenesulfonyl chloride in the
presence of four molecular proportions of alkali, as
recommended by Hinsberg. After the initial reaction,
which was strongly exothermic, had subsided, the
mixture was heated until all odor of the acid chloride
had disappeared. It was then extracted with ether
and the ether extract dried with anhydrous sodium
sulfate. After removal of the ether an attempt was
made to separate the tertiary amine from the benzene-
sulfon derivative of the secondary base by distillation.
This proved but a partial success. The distillate was
accordingly subjected to steam distillation in order to
■ J. Chim. Soc, US (191S), 983.
'Ibid., 113 (1918), 974.
* Bcr., 23 (1S90),3962.
separate the tertiary base. This proved successful,
and the tertiary base was obtained in a fair state of
purity. Fractional distillation of this product yielded
pure di-w-butyl-£-toluidine as a yellow oil boiling at
283° to 285° under 755 mm. pressure. Reilly states'
that the boiling point of di-n-butyl-^-toluidine is 282°
to 284° at 764 mm.
Table V — Di-h-Butyi,-/>-Toluidine
(50 g. i>-toluidine hydrochloride; 255 g. n-butyl alcohol)
„ , Expt. 1 Expt. 2 Expt. 3 Expt. 4
Catalysts:
Sodium bromide, grams 5 5 5
Calcium chloride, grams 5 5 5
Cupric chloride, grams 2.5 2.5 2.5
Time, hours 8 8 12 8
Temperature, ° C 175-180 175-180 175-180 200
Total oil, grams 65 65 66 64
Acetylizable portion of oil. per cent. 28 22.6 22.5 29.1
Calculated tertiary base, per cent. . 72 77.4 77.5 70.9
Distillation. Temperature
256°-260°, cc 3
260°-264°, cc 4
264°-268°, cc 4 2 2
268°-272°, cc 14 6 2 4
272°-276°, cc 20 18 14 6
276°-2S0<>, cc 16 29 24 15
280°-284°, cc 10 14 16 18
284°-288°, cc 3 3 7 12
288°-292°, cc .. 3 12
DI-H-BUTYL-W -TOLUIDINE
The results obtained with w-toluidine were slightly
better than the corresponding ones with the para
derivative. The hydrochloride, when heated with ten
molecules of w-butyl alcohol, gave a product containing
73 per cent of di-w-butyl-»z-toluidine (Expt. 1, Table
VI), while the introduction of the catalysts (Expt. 2)
reduced the acetylizable material about 7 per cent.
Our best conditions for the preparation of di-w-butyl-
w-toluidine are therefore represented by Expt. 2.
Under the conditions of the latter, the yields of tertiary
base were slightly better than those obtained with either
aniline or p-toluidine. Yet these are far inferior to
the results obtained with ethyl alcohol under similar
conditions. Hinsberg's method was used for the
isolation of di-w-butyl-w-toluidine, which has not hith-
erto been described in the literature. By this pro-
cedure the amine was obtained as a pale yellow oil
which boiled at 278° to 280° at 755 mm.
Analysis (Kjeldahl) Per cent
Calculated for CuH2SN: N 6.39
Found: N 6.54
Table VI — Di-n-BuTYi.-m-TonnDiNE
(50 g. m-toluidine; 255 g. d-butyl alcohol; time, 8 hrs.; temp., 175°-180°)
Expt. 1 Expt. 2
Catalysts:
Sodium bromide, grams o
Calcium chloride, grams 5
Cupric chloride, grams 2.5
Total oil, grams 63 50
Acetylizable portion of oil, per cent 27.4 ?°"?
Calculated tertiary base, per cent 72 13 79.8
Distillation. Temperature
266°-270°, cc 13
270°-274°, cc 17 1
274°-278°, cc 13 6
278°-2S2°, cc 9 8
282°-2S6°, cc 5 5
286°-290°, cc 4 4
DI-H-BUTYL-G-TOLUIDINE
The steric influence of the ortho-substituted methyl
group was even more apparent in the alkylation with
butyl alcohol than when ethyl alcohol was used. The
interaction of o-toluidine hydrochloride with ten moles
of w-butyl alcohol (Expt. 1, Table VII) gave a product
which contained 66 per cent acetylizable oil, and was
thus largely mono-w-butyl-o-toluidine.
1Loc. cit
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
509
The use of the catalysts (Expt. 2) materially increased
the degree of alkylation and reduced the proportion
of acetylizable material to about 51 per cent, an im-
provement of 15 per cent. Even the latter result
is distinctly inferior to those obtained with either
aniline or m- and ^-toluidine under similar conditions.
It is evident that considerable experimentation would
be required in order to secure better yields of di-»-
butyl-o-toluidine.
Di-M-butyl-o-toluidine was isolated by the same pro-
cedure which was employed in connection with the
purification of the ortho and para bases. Consider-
able difficulty was experienced in obtaining the ter-
tiary base in a high degree of purity, a comparatively
pure product being finally prepared by two successive
treatments of the crude di-«-butyl-o-toluidine with
benzenesulfonyl chloride. After this purification the re-
action product boiled at 245° to 260°. This material
was carefully redistilled, and the oil boiling between
255° and 260° was taken as the representative fraction.
The latter cut boiled largely at 256° to 258° at 755 mm.
and appeared to be a definite product. The analysis
of this base confirmed the fact that we were dealing
with di-rc-butyl-o-toluidine.
Analysis (Kjeldahl) Per cent
Calculated for CuHaN: N 6.39
Found: N 6.58,6.56
Table VII — Di-k-Butyl-o-Toluidine
(50 g. o-toluidine hydrochloride; 255 g. «-butyl alcohol; time, S hrs.;
temp., 175°-1S0°)
Expt. 1 Expt. 2
Catalysts;
Sodium bromide, grams 5
Calcium chloride, grams 5
Cupric chloride, grams 2.5
Total oil, grams 55 53
Acetylizable portion of oil, per cent 66 . 1 51 . 5
Calculated tertiary base, per cent 33.9 48.5
Distillation. Temperature
246°-250°, cc 4
250°-254°, cc 13 3
254 "-258°, cc 21 10
258°-262°, cc 9 13
262°-266°, cc • 4 7
266°-274°, cc 8
274°-278°, cc 5
SUMMARY
1 — The action of ethyl alcohol upon the hydrochlo-
rides of the isomeric toluidines has been investigated.
The formation of the tertiary bases has been promoted
by certain catalysts, namely, cupric chloride, sodium
bromide, and calcium chloride, and the utilization of
a large excess (ten moles) of the alcohol. The ac-
companying figure graphically illustrates the results of
these experiments. For purposes of comparison, the
results of the previous investigation on the action of
ethyl alcohol upon aniline hydrochloride have also been
included. Graph I represents the degree of tertiary
amine formation which results from heating the hy-
drochlorides of the bases with ten moles of ethyl alcohol,
while Graph II indicates the beneficial effect of the
catalysts. The inactivity of o-toluidine, as compared
with the other bases in either series, is very striking.
2 — The interaction of «-butyl alcohol with the hy-
drochlorides of aniline and the isomeric toluidines has
also been investigated. In this series, catalysts have
also increased tertiary amine formation. This is il-
lustrated by Graph IV, which represents the results
when the catalysts were employed, and Graph III,
when the latter were omitted. As with ethyl alcohol,
100
n
90
i
fin
ho
I
_LY
\
A
\
is
i\
v SO
\'
in
\
\
^
\
v
40
\
,\
30
w1
Aniline
Para
Toluidine
Meta Ortho
Toluidine Toluidine
I — Ethyl Alcohol (ten moles)
II— Ethyl Alcohol and Catalysts (NaBr-CaCl:-CuC10
III — Butyl Alcohol (ten moles)
IV — Butyl Alcohol and Catalysts (^aBr-CaCh-CuCl»)
the poorest yields of tertiary base were obtained in the
alkylation of o-toluidine. These results are presumably
due to the spatial influence of the o-substituted methyl
group.
3 — Two new amines have been prepared by the above-
described methods, namely, di-H-butyl-o-toluidine (I),
and di-ra-butyl-;«-toluidine (II).
N(C4H,)2 N(C4H,)2
CH* Cu
(I) (II)
4 — The comparative activity of »-butyl alcohol and
ethyl alcohol with regard to alkylation is illustrated in
the figure. It will be noted that the butyl alcohol
curve is appreciably below that of ethyl alcohol. On
the other hand, the effects produced by the catalysts
were far more pronounced in the butyl alcohol series.
Annual Tables of Constants
Owing to delays incident to the printers' strike, it has been
found necessary to advance the date at which subscriptions
at the special reduced rates will be received for the forthcoming
Volume IV of Annual Tables of Constants and Numerical Data
of Physics, Chemistry and Technology. Details concerning
this volume, the subscription rates, and a subscription blank will
be found on pages 967 and 968 of the April number of the Jour-
nal of the American Chemical Society.
The size of the edition is determined by the number of advance
subscriptions received, and promptness in subscribing is the only
guarantee of delivery.
510
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
Temp, of
Heating
° C.
Time
Min.
Per cent
Ash
gressioi
of
H* Io:
Nature of
a Curd
50
63
80
98
ruheated cc
fiO
60
60
30
■ntrol
3.80
4.28
4.84
5.21
2.02
Yes
Yes
Yes
Yes
No
Soft
Soft, feathery
Very soft, fine and dark
Very soft, fine and dark
Firm and normal
Precipitation of Grain-Curd Casein from Pasteurized Milk, Including Sweet
Cream Buttermilk12
By Harper F. Zoller
Dairy Division, Bureau of Animal Industry, U. S. Department of Agriculture, Washington, D. C.
The application of the normal grain-curd method to Table i r^o
the manufacture of casein from milk, which has some-
time during its history been heated to pasteurizing
temperatures or higher, cannot be made without certain
modifications.
It was found throughout the experimental study of
the separation of casein from pasteurized milks that
when the identical conditions of the grain-curd pre-
cipitation were observed the resulting casein was of a
decidedly different texture from the normal type of
curd from unheated milk. The curd was softer, and
the grains were less definitely formed and much smaller
in size. Changing the velocity of stirring during the
precipitation had no appreciable effect upon this
peculiar physical texture. It was found that this
curd could not be economically handled upon the
drain rack. Clogging of the pores of the cloth re-
sulted, rendering rapid draining of the whey impossible.
Working of the curd upon the cloth caused many fine
particles to pass through the pores, while that which
remained upon the cloth became soggy and puddled.
Furthermore, an additional phenomenon was ex-
perienced during the washing of the curd. When the
curd was leached with water adjusted with hydro-
chloric acid to the isoelectric condition of casein, i. e.,
pH 4.6, there was a marked retrogression of the hy-
drogen ion. This phenomenon throws some light on
the influence of heat upon the protein and salt equi-
librium in milk. The discussion of this question is
reserved for a later paper.
Some of the experimental procedures aimed towards
the restoration of the normal texture to the curd will
npw be reviewed.
INFLUENCE OF DIFFERENT PASTEURIZING TEMPERATURES
UPON NATURE OF CURD
Twenty-five-pound portions of fresh skimmed milk
were separately heated to the temperatures indicated
in Table I. After cooling to 34° C, the casein was
precipitated with normal hydrochloric acid, using
methyl red as indicator of the end-point as in the regu-
lar grain-curd method.3 The curd was then thrown
upon a cloth in a drain rack and allowed to drain free
from whey. Tap water adjusted to pH 4.6 was put
into a vat large enough to accommodate the drained
curd. The edges of the drain cloth were gathered
together, and the curd was lifted from the tray and
immersed in the wash water for a period of 10 min.
When possible, the curd was agitated in the water so
that the washing would be as thorough as possible.
The washing process was repeated in three changes
of adjusted water.
The retrogression of the hydrogen ion was marked
in these experiments, especially in B, C, and D. Within
1 Received January 26, 1921.
- Published with the permission of the Secretary of Agriculture.
3 This Journal, 12 (1920), 1163.
a few minutes from the time the curd was suspended
in the wash water (at pH 4.6) the pH of the supernatant
water had increased to 5.6. The change in pH
could be followed quite accurately with methyl
red. It must be remembered that the curd had just
been taken from its whey which registered a pH of
4.6 to methyl red. From hydrogen-electrode measure-
ments1 it is found that when methyl red registers a
pH of 4.6 in skim milk the actual concentration of
hydrogen ion is greater (pH 4.1 to 4.20) than that de-
manded by the isoelectric point of casein. Hence this
retrogression of the hydrogen ion in the wash water
is even more astonishing. This was further magni-
fied when it was found that the retrogression occurred
even after as many as ten changes of wash water,
although in these instances with protracted washings
the curd began to disperse rapidly in the medium.
This dispersion of the curd in the wash water is, again,
contrary to the experiences with normal grain curd.
INFLUENCE OF TIME, AT CONSTANT TEMPERATURE,
UPON PHYSICAL NATURE OF CURD
Like quantities of fresh skim milk were placed in
shotgun milk cans, and these were set in a large vat
of water heated to 63° to §4° C. and maintained at
this temperature throughout the experiment. The
milk was thoroughly stirred in each can during the
heating. When the period of heating was over each
can, in turn, was plunged immediately into running
water at 18° C.
The casein was precipitated under exactly the same
conditions as in the above experiments. The results
are given in Table II.
Table II
Retro-
Milk Temp of Time of gression
Portion Heating Heating
Min. H+ Ion
Yes
Yres
Yes
Yes
Nature of Curd
Softer than control
Too soft to wash
Feathery
Very soft, and disperses in w hey
Firm and normal
E Unheated
It is evident that the duration of heating has nearly
as much effect upon the nature of the resulting curd
as the degree of heating. It has been shown, however,
that it does not have quite the same effect upon the
equilibrium of milk salts.2
RESTORATION OF FIRMNESS TO THE CURD BY USE OF
DIFFERENT ACIDS FOR PRECIPITATION
Before proceeding with the influence of the various
anions of acids upon the firming of the casein curd
i W. M. Clark, H. F. Zoller, A. O. Dahlberg and A. W. Weimar, This
Journal. 12 1 19201, 1163.
a Unpublished results.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
511
from heated milks, attention should be called to another
possible factor in the acid precipitation of the casein.
This idea is not original, since Lacquer and Sackur1
found that casein which had been dried at high tem-
peratures suffered "cleavage," and the alkali-soluble
portion, which they designated as "isocasein," possessed
an increased base-binding capacity over normal casein.
From their conductivity measurements they arrived
at the conclusion that this body was a much stronger
acid than ordinary casein and consequently possessed
a greater dissociation constant.
With a set of buffer mixtures covering the probable
range of H+-ion concentration in which the isoelectric
point would be found, and a 0.1 per cent solution of
sodium caseinate at pH 7.2 made from the curd from
milk heated to 80° C. for 1 hr., the writer was unable
to note any marked displacement in the probable iso-
electric point. The idea was to note the pH zone in
which the casein precipitated. Of course, this method
is very rough, and a more elaborate study should be
made of this question.
In the manufacture of casein by the grain-curd
process in the factory the writer frequently noticed
that when the skim milk was slightly sour from lactic
acid fermentation the resulting casein curd was ex-
tremely firm and excellent to handle. Repeated
trials in the laboratory confirmed this experience.
Solutions of the following acids were prepared in normal
concentration with respect to the hydrogen ion:
lactic, citric, oxalic, tartaric, acetic, phosphoric,
sulfuric, nitric, and hydrochloric. Two volumes of the
normal acid were mixed with one volume of normal
hydrochloric acid, and the mixtures were used as the
precipitants in fresh skim milk pasteurized at
63° C. for 1 hr. The casein was precipitated at 34° C.
under the control of methyl red. The physical nature
of the curd was carefully noted. The results appear
in Table III.
Temp, of Retrogres
Acid + HC1 Precipitation of H +
2 Vols.: 1 Vol. ° C. Ion
Citric
Oxalic
Tartaric
Acetic
Phosphoi
Sulfuric
Nitric
Hydroch
Slight
No
Very slight Curd
Yes Soft ;
Yes Soft ;
Yes Firm.
Yes Soft :
Character of Curd
Quite firm and washable but
short (brittle)
Quite firm and washable but
short (brittle)
Not as firm as lactic
Quite firm and washable (brittle)
' ashable but brittle
d disperses
d disperses
but not washable
d disperses
There is a marked influence upon the physical
structure of the casein curd which suggests, aside from
any practical application, a relation to Pauli's2
and Hatschek's3 work on the production of a stiffer
gel with gelatin or agar by the addition of citrate or
tartrate. This effect is undoubtedly a manifestation
of a change in the distribution of water between the
two phases. Whether we consider this change to be
wrought by the resulting concentration of hydrogen
ion or by the distribution of electrical charges, or what
not, such considerations have no place in this paper.
1 Beilr. chem. Physiol. Pathol. , 3 (1902), 210.
» Arch. ges. Physiol.. 78 (1S99), 315.
> "Introduction to the Physics and Chemistry of Colloids," 1916, p. 49.
USE OF COPRECIPITANTS WITH HYDROCHLORIC ACID IN
PRECIPITATING CASEIN
The coprecipitants which would be suggested by
the work of Freundlich,1 Linder and Picton,2 Hardy,3
and others would be those possessing polyvalent
cations. This is because it has repeatedly been demon-
strated that casein exists in ordinary milk in the form
of a caseinate anion possessing a charge equivalent to
a tetra-, hexa-, or octabasic acid (or multiple thereof).
Hence as this charge becomes neutralized by positive
hydrogen ion, as it does in acid precipitation, the casein
finally reaches a point where its electrical charges are
equivalent, or zero in external effect (the isoelectric
point), and in this state is extremely sensitive, as a
neutral colloid, to physical stimuli. Thus we should
expect those electrolytes which affect pure suspensoids
to affect similarly this neutrally suspended casein.
Investigations by the above-mentioned workers hava
shown that polyvalent cations produce maximum
effects upon such colloids and form firm coagula or
precipitates. Further it has been shown that these
electrolytes, or "coprecipitants," as they are termed
in this paper, usually contaminate the precipitate,
which leads to the speculation that the mechanism of
this phenomenon is one of adsorption.
The polyvalent cation salts available (readily) at
this time were those of aluminium and the alums.
Solutions of 0.2 M aluminium sulfate, ammonium
alum, and potassium alum were prepared. These
solutions were strongly acid in themselves (pH 2.1
to 2.4) and served to precipitate the casein alone without
the addition of further acid, but the addition of so
much extraneous salt was inadvisable. Ash analysis
of some of the caseins prepared with aluminium sulfate
as the sole precipitant showed as much as 8.5 per cent
ash.
The precipitation mixture which yielded an average
curd from heated milks consisted of one volume of
M alum solution with two volumes of N HC1. Whgn
the regular grain-curd process was followed with this
precipitant on milk heated to 80° C. for 1 hr., the re-
sulting curd was fairly firm, could be washed quite well,
but was very brittle. The caseins resulting from this
treatment ashed from 4.5 to 5.5 per cent of mineral
matter.
EFFECT OF HIGHER PRECIPITATION TEMPERATURES
UPON TEXTURE OF CASEIN CURD
It was evident during the early studies that the tem-
peratures of precipitation had a marked influence
upon the cohesion of the curd particles. In following
the effect of temperature upon the precipitation of
grain-curd casein from fresh, unheated skim milk, the
extreme sensitiveness of the coagula to slight changes
in the temperature of the medium which bathed them
was duly appreciated. Accurate control of the precipi-
tation temperature is one of the main factors in the success
of the grain-curd method.
Now when the milk has been subjected to abnormally
high temperatures for varying lengths of time, the pro-
i Z. fihysik. Chem., 44 (1903), 129; Z. Chem. Ind. Kolloide, 1 (1907), 321.
2 J. Chem. Soc, 61 (1892), 137.
« Proc. Roy. Soc. London, 66 (1900), 110; J. Physiol., 33 (1905), 251.
512
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
teins are believed to become denatured. That is,
during the heating the physical properties of the pro-
teins are changed in such a manner that the molecules
have an abnormal absorption affinity for water. This
is a progressive process, as a glance at Table IV will
show.
Table IV>
Temp, of Time of Temp, of Moisture
Heating Heating Precipitation in Curd
Milk ° C. Min. ° C. Per cent
A 50 60 34 44.6
B 63 60 34 62.2
C 75 60 34 68.5
D 100 30 34 79.4
E 120 15 34 88.2
F Control .. 34 40.3
1 The data in this table were determined by treating the above milks
as in the grain-curd method, draining as free from whey as possible, and
washing once by decantation with equivalent amounts of water. The
curd was then thrown upon a drain cloth and allowed to drain for 30 min.
The moisture content of these curds was then determined by drying about
5-g. portions in an oven at 98° to 99° C. to constant weight. The moisture
content is expressed in per cent.
The higher the temperature the greater amount of
water will the curd hold, until at excessive temperatures
the phase approaches a reversal and the curd simulates
a gel in appearance.1 This water-holding power of
the curd must be in some degree a reversible process,
because when it is precipitated in a medium heated to
temperatures in the neighborhood of those used in
pasteurizing, the curd becomes firm again, although
its internal structure is still abnormal.
Some of the following observations will serve to
emphasize the importance of higher precipitation
temperatures with heated milk.
EXPERIMENT A
Fresh skim milk was pasteurized at 63° C. for 1
hr. It was then cooled down to the temperatures
indicated in Table V and the casein precipitated there-
from with normal HC1, using methyl red to indicate
the approach to the isoelectric point. The curd was
then drained from the whey and suspended in adjusted
water (pH 4.8).
Table V
Temp, of Retro- Ash
• Precipi- gression in
tation of Casein
Milk ° C. H + Ion Texture of Curd Washable Per cent
A 30 Yes Feathery No 2.88
B 35 Yes Soft No 3.14
C 40 Slight Firmer and grained Not readily 3.92
D 50 No Chunks Yes, but imper- 4.20
fectly
E 60 No Large clumps, Yes. but imper- 4.16
leathery fectly
F 42.5 No Very firm and Yes ' 3.85
grained
It was noticed during the washing of the curd,
precipitated at 40° C, with cold water that brittle-
ness was increased, whereas if the wash water was
warmed to about 30° to 35° the brittleness was not
so noticeable. The toughness of the curd, which is
a result of the higher temperature of precipitation,
remains unchanged in the warm wash water. All of
the curds, such as C and D, which approximated normal
grain curd in appearance were found to be very "short"
in texture. This is a characteristic property of all
pasteurized milk caseins.
The essential faet divulged in Table V is that differ-
ent precipitating temperatures influence the physical
nature of the curd from milk pasteurized under the
1 It should be mentioned that since the writing of this paper Mr.
Letghton of these laboratories has actually obtained a curd gel by heating
milk at high temperature (about 140° C.) in a sealed bomb.
above conditions of the experiment. The temperature
of 42.5° yielded by far the best curd in this series.
EXPERIMENT B
A series of experiments were designed to determine
the effect of the duration of heating upon the optimum
precipitating temperature, when the pasteurizing
temperature was held constant. The pasteurizing
temperature was 63°, probably representing the one
most commonly used. Time periods of 20, 30, 40,
60, 80, and 100 min. were studied. The results of
these studies are shown graphically in Fig. 1. The
grain-curd principle of precipitation was observed in
all save the temperature. The optimum precipitating
temperature was defined as that temperature which
produced a curd that most nearly simulated grain curd
in its uniformity of size and condition for washing.
Another series of tests were performed upon milks
pasteurized at different temperatures, in order to de-
>i
i. 50
E
E
E x
o
Time of Pasteurization Min. Temp, of Pasteurization 'C
Fig. 1 — Constant Temperature, Fig. 2 — Constant Time of Pas-
63° C TEURIZATION, 60 MlN.
termine the optimum temperature for obtaining a
workable curd from each milk in question. With
the exception of the temperature, the grain-curd method
of precipitation was followed throughout. The time
of pasteurization of the milks was held constant
(1 hr.). The results of these tests are reproduced in
the optimum temperature curve in Fig. 2.
This effect of precipitation temperature is obviously
of immense importance, and its practical application
is at once evident. Further discussion of it is reserved
till later in this paper.
EMPLOYMENT OF RENNIN IN PRECIPITATION OF CASEIN
FROM PASTEURIZED MILK
Without permitting himself to become bewildered
with the diverse considerations upon the mechanism
of rennin action in normal and heated milk, the writer
decided to determine the practicability of this method
for the separation of casein from pasteurized milk,
including buttermilk.
Fresh skim milk, which had been pasteurized at
65° C. for 1 hr.,was carefully adjusted to the zone of
the optimum activity of rennin in heated milk (about
pH6.2)J with hydrochloric acid, using bromocresol
purple to determine the pH. The milk was then cooled
to 37° C. and the usual amount of rennin added. The
clotted curd, after cutting, was digested in the whey
for half an hour at 60° C. to expel moisture and salts.
It was then drained upon a cloth in a drain rack and
washed several times with water. After pressing, it
i Biochem. J., 9 (1915), 215.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
513
was ground and dried like ordinary casein, and finally
analyzed. It was found to contain 9.5 per cent mois-
ture and 5.8 per cent of ash.
An explanation of the high digestion temperature
used above is necessary at this point. It was found
after cutting the curd that it was very soft and mushy,
and remained in this condition until the temperature
was raised above that ordinarily used in firming rennin
curd from unheated milk. It was uniformly found
that pasteurized milk required a higher temperature
for the firming of the curd, at the same time-interval
and acidity, than is necessary for unpasteurized milk.
This corroborates the temperature effect upon the
casein curd discovered in connection with acid pre-
cipitation. Members of the dairy manufacturing
section inform the writer that in their work with pas-
teurized cheese greater heat has always been found
necessary to firm the curd from pasteurized milk.
Obviously, the time required for this method and the
vat space necessary would alone mitigate against its
practical use. The character of the final casein is
not greatly different from the acid-precipitated casein
from heated milk, except that it contains higher ash.
This high ash content naturally results from the fact
that it enmeshes large quantities of insoluble calcium
and magnesium phosphates which remain insoluble
at the reaction in the pH zone in which rennin coagula-
tion takes place. The writer finds that both calcium
and magnesium phosphates (CaHP04 and MgHPOi)
are practically insoluble at this reaction, namely,
pH 6.2.
Another disadvantage of this rennin casein is its
slow rate of dissolving in alkalies. In this respect it
is not unlike cooked curd casein which it also resembles
in ash content. If the engulfed salts could be removed
from both of these caseins it would increase their rate
of solubility. This was actually found to be the case.
The caseins were redissolved in dilute ammonia, the
undissolved residue separated by centrifuging at great
speed, and the resulting solution precipitated with
dilute acetic acid, and thoroughly washed. The
resulting casein curd was still characteristic of high
temperature caseins in "shortness," but the dried
product dissolved more readily. The nonvolatile
ash amounted to less than 1.5 per cent in both cases.
DISCUSSION OF EXPERIMENTAL RESULTS
It is evident from the temperature and time studies
that the condition of the casein in pasteurized milks
varies with the conditions of pasteurization and, there-
fore, it is necessary to take these factors into considera-
tion when attempting to prepare casein from such
milks.
While the organic acids are found to yield a good
working curd, they would be impracticable industrially
because of the cost. It would be possible to consider
lactic fermentation (natural-sour process), but this is
a very unsanitary method to apply in factory practice.
In respect to the use of coprecipitants with hydro-
chloric acid it may be said that, while the alums were
found to increase the firmness of the curd precipitated
at grain-curd temperatures (34° C), thus facilitating
the draining and washing, they are not advocated
because of the effect of the absorbed precipitant upon
the ash content of the resulting casein. The high and
insoluble ash reduces its solubility in alkalies.
Certainly the simplest way to render the casein
from pasteurized milk obtainable under factory working
conditions is to increase the temperature of precipita-
tion, as the results of the studies on this factor
indicate. It is the easiest factor to control in factory
practice. In the time-worn commercial methods of
precipitating casein, high temperatures were universally
employed, viz., 45° C. and up. It is immediately
evident why little trouble was met in precipitating casein
from healed milks in the past. With the grain-curd
method this question is of the utmost importance. As
previously mentioned, the curd at the isoelectric
point is in an extremely sensitive condition and re-
sponds in a maximum degree to physical stimuli. The
temperature of 34° to 35° C. is the narrow zone for opti-
mum working condition for grain curd from normal
milk. This temperature is much too low for the opti-
mum working curd from pasteurized milk.
The modified scheme of the grain-curd process to
be applied to heated milks in factory practice is as
follows.
OUTLINE OF METHOD FOR MANUFACTURE OF CASEIN
FROM PASTEURIZED MILK
Essentially this is a modification of the grain-curd
method described by Clark, Zoller, Dahlberg and
Weimar.1
(1) The milk should be heated to a temperature in-
dicated upon the published curves that correspond to
the pasteurizing conditions to which the milk was sub-
jected. If the history of' the milk is not known the
optimum temperature may best be determined by
trial.
(2) Dilute hydrochloric acid (100 lbs. of 20° Be.
to 800 lbs. of water) should be added slowly to the
heated milk, bringing it into contact with all portions
of the milk as quickly as possible. A hardwood vat
and spigot (hardwood) prove to be the best containers
for the dilute acid in factory practice. When the milk
"breaks," i. e., when the curd first separates from the
whey, the flow of acid should be checked and the pH
of the whey determined with methyl red indicator
(5 drops of a 0.04 per cent solution of methyl red in
10 cc. of milk or whey). It is frequently noticed that
in pasteurized milks the "break" is considerably de-
layed. This makes it very easy to overstep the end-
point. The addition of acid should be ceased when the
indicator first shows a bright red.
(3) The whey is then drained from the curd. Be-
cause of the delayed "break" it is frequently impossible
to draw off a portion of the whey before adding the
remainder of the acid necessary to reach the end-
point. Wherever this is possible the reader is referred
to the regular method cited above for full details.
(4) The curd is then washed with water at a tem-
perature of about 30° to 35° C. and adjusted with
hydrochloric acid to pH 4.8. The washing may be done
in the vat by decantation before placing in the drain
rack, or afterwards, as desired, although the former
1 hoc. cil.
514
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
method is somewhat more effective. Drain racks and
screw presses are probably best adapted for very small
casein plants. Where large quantities of milk are
handled, the factory would be repaid by installing a
centrifugal which handles both operations in one. The
application of the centrifugal is discussed below.
(5) For the drying of the casein and other details
the reader is referred to the publication on grain-curd
casein mentioned above.
SEPARATION OF CASEIN FROM PASTEURIZED SWEET
CREAM BUTTERMILK
The method just elaborated has been found to work
well with this type of buttermilk. Small-scale factory
trials with buttermilk from cream that has been
pasteurized at 63° C. for 30 min. seemed to show that
40° C. was the desirable precipitating temperature
for satisfactorily handling the resulting curd.1 Cream
pasteurized at the same temperature for 1 hr. demanded
45° for precipitation of the casein from the butter-
milk. It is remarked that the fat content of the butter-
milk alters the "feel" of the curd, as well as its working
conditions. But the amount of fat which should con-
taminate sweet cream buttermilk is so small as not
to handicap seriously the use of this method.
USE OF CENTRIFUGAL IN MANUFACTURE OF CASEIN
The use of centrifugals for washing casein has been
practiced for many years in those countries where the
price of commercial casein is considerably less than it
is in normal times in the United States.2
During the war the casein campaign permitted
the writer to try out in practice centrifugals of fairly
large capacity. It was at once clearly demonstrated
that there was available in grain curd a type of product
especially suited to the centrifuging process. The
commercial casein curds in the past were either so
bulky and tough or else so soft that even loading of
the bowl of the centrifugal was impossible. But
with grain curd the particles are so uniform in size
that a case of an overbalanced bowl was never ex-
perienced in the number of trials conducted.
Large sugar centrifugals in three different milk
product factories were placed at the author's use for
study. Through the courteous cooperation of the
employees in the factories mentioned, test runs
were made with grain-curd casein. In one test with
a machine possessing a 54-in. bowl and bottom dis-
charge, the total curd from 5500 lbs. of milk was
accommodated in one load. The time required for
the precipitation of the curd, loading it mechanically
from the vat into the revolving bowl, whizzing free
from excess whey, washing with 2000 lbs. of water,
and pressing free from water for grinding within the
bowl by increased speed of revolution, was only 40
min. In another half hour it was ground and placed
upon trays in the tunnel dryer.
The advantage of the centrifugal over the drain-
rack, cloth, and press method may be enumerated as
follows:
1 The writer desires to thank Mr. A. O. Dahlberg of this Division for
trying this method on sweet cream buttermilk at the experimental creamery
located at Grove City, Pa.
' "Casein," 1911.
(1) The operation is entirely mechanical from the
precipitating vat through to the final washing in the
centrifugal bowl with adjusted water.
(2) The draining, washing, and pressing of the curd
are done in one operation. The curd may be pressed
to any degree desired by merely varying the speed
of the rotating bowl. It is ready to be ground when
taken from the bowl without further pressing, and is
ready for the dryer.
(3) The saving of considerable time by completing
in one day an operation which now generally demands
two by the rack, cloth, and press method.
(4) The improvement of the sanitary conditions
around the factory by doing away with wooden trays,
press divider-boards, drain cloths, and press cloths,
which now become the eyesore and olfactory press-
agent of every casein plant using these accoutrements.
(5) The main equipment necessary in a large factory
would be the precipitating vat, or vats, centrifugal,
curd mill, casein drying tunnel, and grinder for the
dried casein.
(6) The centrifugal would be especially well suited
to the washing and pressing of the casein prepared
from pasteurized milk by the modified grain-curd
method, because of the short character and brittle-
ness of the curd. It would receive less handling in
the centrifugal and the loss therefore would be less.
SUMMARY
I — The grain-curd method can be successfully ap-
plied to the separation of casein from pasteurized
milks only when higher precipitating temperatures
are used. The optimum temperatures are exhibited
in the form of curves for the different observed con-
ditions of pasteurization.
II — The marked differences in the physical nature
of the curd from pasteurized and unpasteurized milks
are strikingly revealed by the grain-curd method of
precipitation. Attempts to overcome some of these
physical effects by the use of organic acids as pre-
cipitants and with coprecipitants are described.
Ill — The advisability of using rennin to precipitate
casein from pasteurized milk is dismissed because of
the time required and the large quantity of mineral
matter entrained in the curd.
IV — Large centrifugals are recommended for wash-
ing and pressing the casein precipitated by the grain-
curd method from pasteurized and normal milk.
V — The phenomenon of the retrogression of the
hydrogen ion was discovered in the whey and wash
water from the curd precipitated from pasteurized
milk by the grain-curd process at 34° C. This rapid
decrease in acidity is attributed to the excessive pre-
cipitation of alkaline earth phosphates during pas-
teurization, and their subsequent re-solution at the
expense of the hydrogen ion as they are brought into
ready contact by the soft dispersing curd.
VI — The great check in the rate of this retrogression
wrought by using higher temperatures for precipita-
tion is believed to be due to the engulfing of these
precipitated phosphates by the firming of the curd,
thus reducing the intimate contact between the solution
and the phosphates.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
515
The Relations of Hydrogen-Ion Concentration to the Heat Coagulation of
Proteins in Swiss Cheese Whey1
Research Laboratorie
By Yuzuru Okuda2 and Harper F. Zoller
Dairy Division, U. S. Department or Agriculture; Washington, D. C.
Some time ago, during an emergent examination of
Swiss cheese whey, to gage roughly the zone of reaction
that would furnish the best working curd for Ricotta
cheese manufacture, one of us (Zoller) observed that
the indicator methyl red showed this zone to lie be-
tween pH,5.2 and 5.4. It was at that time believed
that this zone was not the true pH zone of the interior
of the solution, because the quantity of acid used to
reach this zone was great enough to produce a much
lower pH, according to electrometric titration curves
of skim milk. It was desirable, therefore, to study
this zone carefully with the hydrogen electrode, since
the coagulation of whey proteins is of such tremendous
importance to many of the dairy industries.
Whey produced in the case of cheese making is
chiefly a waste product, or has been in the past, but
it contains appreciable quantities of salts, proteins, fats,
lactose, and vitamines. Therefore, its utilization is
an interesting problem from the economic and nutritive
point of view.
The determination of the optimum reaction3 for
the heat coagulation of the proteins in the whey links
itself vitally with practically any method proposed for
its utilization. At present it has its greatest appli-
cation in the manufacture of lactose (to be discussed
later in the text). It is also pertinent to the manu-
facture of whey cheese, to the determination and isola-
tion of lactalbumin, to the preparation of "protein-free
milk," and to the milk condensing industry.
In this paper Swiss cheese whey only is reported on,
but the same principle should hold good in the case of
whey from other types of cheese or from casein.
TITRATION CURVES
As far as the authors know, no titration curves of
Swiss cheese whey have been published. These are
important, inasmuch as direct reference to them will
permit one to adjust any quantity of Swiss cheese
whey to any definite H+-ion concentration. This is
because the whey resulting from Swiss cheese manu-
facture, the country over, is very uniform in reaction.
The maximum variation observed by us in the wheys
examined was ±0.10 pH. This is not sufficient to
cause an appreciable overstepping of the optimum re-
action if the identical data furnished in these curves
be used in the adjustment of the reaction.
Of the methods in use at present for determining the
proper reaction point, the titration to phenolphthalein
is most widely used. It is needless to say that this is
both inconvenient and inaccurate for the average
factory man. In some milk-sugar factories litmus
1 Received January 31, 1921.
a Not a regular member of the staff of the Department of Agriculture.
The Dairy Division granted Dr. Okuda the privilege of working, while a
visitor, on the above problem in Mr. Zoller's laboratories.
3 The optimum reaction for the heat coagulation of proteins in whey
is defined as that reaction which will remove the largest quantity of protein
nitrogen from the whey in a workable form by heating to 98° C.
paper is used, but those who use this as an end-point
usually make up for the misgaged reaction by pro-
cessing their product further.
Care was exercised in determining these curves, in
view of their ultimate application in the factory. To
definite portions of whey definite quantities of the
various acids were added, and the influence of dilution
_r
1
LEGEND
1
1
M/, Ch.
-| <Mt, CH,
coop
CHOH-C0C
H
1
1
, M/j HCl
'MANaO
1
1
1
1
1
1
1
l
1
1
'/
')
'I
1
-•?
—
'
_.
-■
-""'
/
5 Z
3 Z
1
r
> 1.
l
i
b
J
•
CC. OF ABOVE ACIDS PER 100 CC WHEy
was taken into account. In factory practice it is
unnecessary to consider the dilution factor. Complete
data are furnished in Table I for the hydrochloric acid
curve. The data for the other acids are given, in the
form of their curves only, in Fig. 1.
Whey
Cc.
100
100
100
100
100
100
100
1 The concentrations in this and the following tables were: hydro-
chloric acid, 1.02 M; acetic, 1.02 M; lactic, 0.472 M; calcium chloride solu-
tion, 0.9 M; and sodium hydroxide, 1.002 M.
The H+-ion concentration was determined elec-
trometrically with Clark rocking electrodes and the
saturated calomel electrode recommended by Mich-
aelis, using a Leeds and Northrup type K potentiometer
with type R galvanometer and a Weston standard cell.
Table
I
H:0
Color
Cc.
E. M. F.
pH
PH
25
0.6257
6.42
6.5
24
0.5579
5.26
5.5
22.5
0.4809
3.98
5.1
20
0.3931
2.51
4.9
17.5
0.3493
1.77
3.3
12.5
0.3254
1.38
1.7
0.0
0.2935
0.84
516
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
The resulting potentials were expressed in the pH
scale and were calculated according to the formula:
E.M.F. (obs.) — E. M. F. (calomel)
0.0001983 T
pH
Since calcium chloride is sometimes added in the
processing of whey in lactose manufacture, a titration
curve of whey with a mixture of the chloride and
hydrochloric acid was made in order to determine its
effect upon the optimum reaction for removing pro-
teins, etc. Data for this determination are presented
in Table II.
Cc.
Cc.
Cc.
Cc.
E. M. F.
pH
100
14.5
0.6319
6.48
100
1.0
11.5
2.0
0.5365
4.88
100
2.5
10.0
2.0
0.4810
3.98
5.0
7.5
2.0
0.3960
2.56
100
7.5
5.0
2.0
ii :uvi
1.77
100
12.5
2.0
0.3153
1.22
The relative strengths of the three acids are rather
strikingly brought out in Fig. 1. One curve of an
alkali titration upon the whey is included in this figure.
OPTIMUM REACTION FOR COAGULATION OF WHEY
PROTEINS
Some preliminary tests were conducted to select a
suitable method for removing the coagulated curd from
the whey after heat treatment. Whichever method is
adopted, it should be comparable to factory results.
At present the filter-press, centrifugal, and drain-cloth
methods are used in factory practice, with slightly
different objectives in view, but with the ultimate de-
sire to remove as nvuch of the protein material as pos-
sible. Accordingly, a centrifugal machine, medium
filter paper, and a tuft of absorbent cotton placed in a
funnel were examined.
expt. 1 — One thousand cc. of fresh whey were
mixed with the correct quantities of M HC1 and water.
One-tenth of each sample was directly applied in
the determination of total nitrogen and electrometric
pH, and the remainder was heated in a steam oven for
45 min. at about 98° C. It was then cooled rapidly
and put into a centrifugal machine running at about
2000 r. p. m. Nitrogen and pH determinations were
again made upon the resulting curd-free liquid.
Nitrogen was determined according to Gunning's
modification of Kjeldahl's method, taking the results
of blank analyses into account, and using methyl red
as indicator in the titrations. The results are tabulated
as follows:
Table III — Separation
Whey HC1
Cc. Cc. E. M. F.
1000 ... 0.6266
1000 3.0 0.6047
1000 7.0 0.5720
1000 12.5 0.5353
expt. 2 — The above experiment was repeated with
the cotton filter and the filter paper, except that the
heated whey was poured hot through the filters.
Cooling caused the whey to filter slowly.
Table IV — Separation bv Means of Cotton or Filter Paper
^Before Heating— . . After Heating ; — - — ;
Whev HC1 N N in Filtrate N in Curd
Cc Cc E.M.F. pH Grams E. M. F. pH Cot- Cot-
ton Paper ton Paper
1000 0 6274 6.50 1.547 0.6026 6.08 1.328 0.895 0.219 0.652
1000 3 06077 6.15 1.547 0.5913 5.90 0.814 0.755 0.733 0.792
1000 7 0.5707 5.52 1.547 0.5S15 5.71 0.762 0.739 0.785 0.808
1000 12 5 0.5345 4.93 1.547 0.5460 5.08 0.7517.13 0.796 0.834
3N by Means o
f Centrifugal Machin
, After Heating-
B
N in
N in
N
Filtrate
Curd
pH Grams
E. M. F. pH Grams
Gram
6.48 1.492
0.6075 6.15 1.049
0.443
6.09 1.492
0.5975 5.97 0.776
0.716
5.54 1.492
0.5789 5.66 0.749
0.743
4.93 1.492
0.5405 5.02 0.725
0.767
The quantity of hydrochloric acid added to each
portion of whey to reach the desired pH was determined
by reference to the curve in Fig. 1.
It is apparent that any one of the three methods of
removing the curd would be suitable, since the nitrogen
curves are parallel and of the same order of magnitude.
The cotton filters, however, are more advantageous.
The data presented in Tables III and IV are sum-
marized in Fig. 2.
-LEGEND-
.
''lie
i
i
i
i
i
i
-::
N C
RVE.C0TT0
RVE.CENTR
RVE, FILTER
H
FUGAL
PAPER
r
Jy^(
Si
S^ i
^^T
i
i
i
1
/ /
I i ,
/
^jjy ._
_,
1"-
----
V
CC. M/i MCI. PER I00OCC WHEY
Fig. 2
expt. 3 — With absorbent cotton as filter, a some-
what wider range of H+-ion concentration was studied,
using M HC1 and M NaOH.
The results are shown in Table V and in Fig. 3.
Table V
* — Before Heating — .
HC1 NaOH E. M. F. N
Cc. Cc. pH Grams
0.6278 6.50 1.694
12 5 .. 0.5390 5.00 1.694
19 0 .. 0.5093 4.50 1.694
25 0 .. 0.4879 4.14 1.694
8 0.6763 7.35 1.694
!.. 12 0.7104 7.92 1.694
After Heating-
N in
pH Filtrate
6.14 1.451
5.09 0.791
4.58 0.709
4.23 0.770
6.80 1.528
7.12 1.571
Whey
Cc.
1000
1000
1000
1000
1000
1000
E. M. F.
0 . 6058
0.5472
0.5135
0.4927
0.6455
0.6644
N in
Curd
0.243
0.903
0.985
0.924
0.166
0.123
From these experiments we can assume the optimum
H+-ion concentration for the heat coagulation of pro-
teins in the whey to be about pH 4.5, at which point
the filtrate was clearest in appearance and contained
the least amount of nitrogen, and the curd was firmest
for handling.
The titration curves, obtained before and after
heating of the whey, intersected each other at a point
near to pH 5.7; at that point there was no change in
the H+-ion concentration of the whey as a result of
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
517
heating. This fact has an important bearing upon the
precipitation of phosphates from the milk serum by
-
1 LEGEND '
/
/
/
~"
--
>
y
s
\
"■*•
^
-"
■"
\
heat. The first four samples of Table V gave their
usual whey color reaction after heating (the opalescence
changing to a clear green color), whereas the last two
showed intense caramelization. This is in keeping
with the well-known fact that alkalinity favors car-
amelization and oxidation of lactose.
There is no apparent coagulation or increase in the
turbidity of the whey upon the addition of acid in the
cold. This proves that there is no casein as such in
the whey, and that the majority of the proteins re-
maining are of the heat-coagulable type.
expt. 4 — As a further check upon the optimum re-
action with hydrochloric acid, another series was run,
using a different sample of whey from another day's
cheese make, with the results given in Table VI.
Table
VI
> Before Heating *
.
After Heating—
Whey
Cc.
HC1
Cc.
N
E. M. F. pH Grams
E. M. F.
Nin
pH Filtrate
N in
Curd
1000
1000
1000
1000
is
19
23
0.6294 6.49 1.538
0.5262 4.76 1.538
0.5098 4.48 1.538
0.4941 4.22 1.538
0.6067
0.5312
0.5142
0.4994
6.01 1.430
4.84 0.702
4.54 0.658
4.30 0.694
0.108
0.836
0.880
0.844
The results were in keeping with all others bearing
upon the optimum reaction. We are safe in considering
that this reaction in the whey lies near to 4.5, which is
also very close to the isoelectric point of casein.
INFLUENCE OF DIFFERENT ACIDS UPON OPTIMUM RE-
ACTION
To ascertain whether different acids would exert
their anion activity to deflect this optimum as de-
termined for hydrochloric acid, a separate set of ex-
periments was planned, using the data in Fig. 1 and
Table II. The results appear in Table VII.
Thus, nearly the same amount of protein in each
whey has been coagulated in nearly equal pH, reached
by the different acids. In other words, the acids
studied have practically the same effect upon the
coagulation of the proteins in the whey. While or-
ganic acids would be preferable from the standpoint
of ease in reaching the optimum point, because of their
stronger buffer action, hydrochloric acid can be used
Tablb VII
Whey, cc 1000 1000 1000 1000 1000
HC1. cc 19 19
CaCU, cc 20
Acetic acid, cc ... ... 40 ...
Lactic acid, cc ... ... ... 40
HiO, cc 40 21 1
(E. M. F 0.6256 0.507S 0.4972 0.5114 0.5075
Before heating -j pH 6.43 4.43 4.26 4.48 4.43
(N total 1.615 1.615 1.615 1.615 1.615
l E. M. F 0.6050 0.5124 0.5021 0.5139 0.5097
After heatine PH 609 4-49 4-32 4-51 4-*l
B } Nin filtrate 1.510 0.658 0.719 0.645 0.655
iNincurd 0.105 0.957 0.896 0.970 0.960
with about the same degree of safety if the titration
curve is carefully followed. In this particular experi-
ment the quantity of calcium chloride solution added
lowered the pH of the mixture somewhat below the
optimum reaction for the coagulation, and hence
caused the re-solution of a portion of the coagulated
proteins upon the acid side of the optimum. It is
evident even here that it exerts no favorable effect
upon the removal of coagulable proteins, and its use
could be discontinued in the factories.
USE OF INDICATORS TO DETERMINE OPTIMUM REACTION
In another section of this paper attention is called to
the probable conduct of methyl red in whey, and to
possible misinterpretations accompanying its use. The
conduct of methyl red in skim milk has been strikingly
revealed already.1 If we now refer to Table I we ob-
serve that the colorimeiric pH of whey-HCl is 5.5 at
pH 5.26 (electrometric), and 5.1 at pH 3.98. Upon
heating the whey as usual, however, the methyl red
indication of pH changes in the opposite direction from
the pH as indicated by the hydrogen electrode. This
is brought out in the following example:
Before Heating
After Heating
4.49
4.8
It is apparent that methyl red cannot be relied upon
to give an indication of the proper reaction in this
problem, and it is extremely doubtful if any indicator
which covers this region of pH could be employed to
this end, because of the great protein error.
One of us (Zoller) has had the opportunity to try
methyl red in the treatment of whey in milk-sugar
factories. It was there observed that when a great
bulk of whey (10,000 to 25,000 lbs.) had been adjusted
with hydrochloric acid and lime to pH 5.4 by methyl
red, using a block comparator, and the whey heated
with live steam to 95° to 100° C, the resulting clear
green liquor showed a pH of 4.9 to 5.0 with the same
indicator. Hydrogen-electrode measurements on the
same clear liquor showed a true reaction of about 4.5.
It is clear, therefore, that if we make use of methyl
red in the adjustment of whey to reactions within its
range, we must do so with a realization that it is only
approximate and that we are following color reactions
which have a value in themselves other than the ex-
pression of pH.
SIMPLE ANALYSIS OF CURD
It is imperative that the composition of the coagulum
or curd be known. This knowledge gives us an idea
of the nutritional value of the curd, and, in case of the
' W. M. Clark, H. F. Zoller, A. O. Dahlberg and A. C. Weimar, This
Journal, 12 (1920), 1163.
518
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
lactose industry, it informs us of the quantity of sub-
stances removed from the whey by simple heating pre-
vious to its concentration for lactose production.
A sample of whey having a H+-ion concentration of
about pH 6.5 was divided into two portions, one of
which was acidified with hydrochloric acid to a pH of
about 4.5. These solutions were heated in a steam
chamber for 50 min., and the curds separated from them
were strained through a piece of muslin, then suspended
in alcohol, and strained again. Such samples of curd
were dried to constant weight at 100° C, and then
extracted with carbon tetrachloride to remove fats.
The loss in weight was 60.2 per cent in the acidified
curd A and 59.2 per cent in the unacidified curd B.1
The results of analysis of the fat and moisture-free
curd are given in Table VIII.
Table VIII
Curd A, pH 4.5 Curd B. pH 6.5
Nitrogen 12.00 10.79
Protein (N X 6.381 76.7 69.0
Ash 2.17 6.67
Organic matter 97 . S3 93.33
CaO 0.68 2.2S
PjOs 0.97 2.57
Lactic acid 0.27 0.07
The above analysis reveals that at pH 4.5 there is
more protein in the whey curd and less calcium phos-
phate. The increased precipitation of calcium phos-
phate at the normal reaction of Swiss cheese whey
(higher pH) is in perfect harmony with the facts of
general chemistry.
SOME INDUSTRIAL APPLICATIONS
lactose production — In the production of lactose
it is imperative, at some time during the process of its
isolation, to free it from proteins other than casein.
The bulk of these other proteins are coagulable by
heat, as has been shown by a number of investigations.
No matter whether the whey has resulted from casein
manufacture or cheese production, these coagulable
proteins can best be removed more thoroughly by one
heating if the whey is adjusted to the reaction of pH
4.5. It is not essential, as the presented data show, to
have excess calcium present.
If the whey results from casein manufacture under
the grain-curd method,2 then we know that this whey
is too acid, i. e., it has a reaction of about pH 4.1 to 4.2,
as shown by the hydrogen electrode. Therefore, it
will be necessary, when treating this whey, to add some
alkali to bring the reaction back to pH 4.5. In case
methyl red is used to indicate this optimum it will be
necessary to add alkali (lime or soda) until methyl red
shows pH 5.4. It would be easier to make this adjust-
ment only once to the exact pH and then, having de-
termined the exact quantities of alkali to be added to
a given weight of whey to produce this reaction, it
would be practicable to use these quantities as constant
factors as long as the whey resulted from the same source,
and was treated while fresh.
If the whey results from cheese manufacture, then
in case of fresh Swiss cheese whey it is necessary only
to refer to the titration curve to find out how much
1 These figures correspond to fat contents in the ordinary sense, but
may be somewhat larger than real fat contents because such samples as
analyzed contain some water even after drying to constant weight.
2 Clark, el al., hoc. cil
acid is necessary to reach a given pH with 100 cc. of
whey. From this the quantity can be readily cal-
culated that will be necessary to adjust a given bulk
of whey (say, 10,000 lbs.) to the correct optimum re-
action.
From Table VIII it will be seen that we cannot ex-
pect to remove very much of the salts at this reaction,
but in the lactose processing these will be readily re-
moved in the vacuum pan through concentration and
subsequent filtration.
whey cheese industry — The maximum amount
of nutritive product can be removed from the whey for
cheese making provided it is first adjusted to pH 4.5
before coagulating the protein.
Thus from 1000 cc. of whey it is practicable to re-
move 0.9 g. in coagulable form (57 per cent), or about
0.5 lb. from 100 lbs. of whey. One-half lb. of protein
corresponds to the quantity of protein in about 2 lbs.
of cheese, assuming the average content of protein in
various cheeses to be 26 to 27 per cent;1 or, upon a nitro-
gen basis alone, we would be able to get more than 2
lbs. of cheese from 100 lbs. of whey.2
distribution of nitrogen in whey
The following data indicate the distribution of
nitrogen in 1000 cc. of whey:
Per cent of Total Per cent of Total
N in Whey N in Filtrate
Total N in whey 1.577 100
N in curd at pH 4.5' 0.902 57
N in filtrate 0.675 43 100
Albuminoid N in filtrate3. .. 0.109 7 16
Nonalbuminoid N 0.566 36 84
1 HC1 was used.
2 Stutzer's method.
NOTE ON PREPARATION OF PROTEIN-FREE MILK AND
ISOLATION OF LACTALBUMIN
Osborne and Mendel,3 as well as Mitchell and Nelson,4
have prepared "protein-free" milk from skim milk or
milk powder, by removing lactalbumin from the casein-
free filtrate. Van Slyke and Bosworth5 and Palmer
and Scott6 have conducted some investigations on the
coagulation of lactalbumin in milk, but it seems that
they did not actually seek the optimum pH for the
heat coagulation of the crude protein, termed "lactal-
bumin" by so many.
In such cases as the preparation of "protein-free"
milk and the determination and isolation of "lactal-
bumin" from its solutions, it is advantageous or neces-
sary to determine the optimum reaction for the heat
coagulation of these proteins, because this protein is
soluble in water at any pH. It is difficult to know
whether the addition of acid is short, overstepped, or
just enough for complete coagulation by heating, un-
1 Average protein content of various cheeses is about 26 per cent, cal-
culating from Sherman's "Food Products," 1919, 105; and that of fifteen
American Swiss cheeses is 27 per cent, according to U. S. Department of Agri-
culture, Bulletin 608.
2 According to T. R. Pirtle of the Dairy Division the total production
of whey in the United States in 1919 was about 3,780,000,000 lbs. If we
assume the average nitrogen content of the whey is similar to the whey ex-
amined above (perhaps slightly less), the quantity of available proteins in
the whey corresponds to 75,600.000 lbs. of cheese.
3 "Feeding Experiments with Isolated Food Substances," Carnegie
Institution, Washington, D. C, Publication 166 (1911), Part. 2, 80.
< J. Biol. Chem., 23 (1915), 459.
' Ibil., 20 (1915), 135.
tlbid., 37 (1919), 271.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
519
less the solution is heated, filtered, and examined very
carefully after each addition of acid.
It is believed that the above determination of the
optimum reaction will prove beneficial in the prepara-
tion of these so-called "protein-free milks." If we
compare the nitrogen-distribution data with the brief
analytical data to be found on the subject of protein-
free milk one cannot help but feel that the method of
their preparation can be improved upon.
RELATION OF OPTIMUM pH FOR HEAT COAGULATION TO
ISOELECTRIC POINT OF WHEY PROTEINS
The optimum reaction for the heat coagulation of
proteins (dehydration or denaturation) is not neces-
sarily synonymous with their isoelectric condition.
We would not say, therefore, that the reaction pH 4.5
is the isoelectric point of the mixture of those proteins.
If we could consider, in view of the fact that at pH
3.8 the heat-coagulated curd redissolves and thereby be-
comes positively charged with respect to the acid with
which it has combined, that the isoelectric zone had been
overstepped during the addition of acid, then we could
assume that at the point of maximum curd formation
by heat we had the minimum overstepping in either
direction. This being the case, it would be natural
to believe that pH 4.5 is near to the isoelectric zone for
the mixture of heat-coagulable proteins in the whey.
The isoelectric point of lactalbumin would then be
within this zone. Lactalbumin is only the major con-
stituent of the heat-coagulable proteins of whey.
SUMMARY
1 — Using methyl red as indicator, titration curves of
whey were determined for hydrochloric, acetic, and
lactic acids. Data are also presented for composing a
similar curve for a mixture of hydrochloric acid and
calcium chloride.
2 — The optimum reaction for the heat coagulation
of the proteins in whey is about pH 4.5 (electrometric).
3 — The different acids seem to have the same effect
upon the zone of optimum coagulation.
4 — The inaccuracy of methyl red in the determina-
tion of the correct reaction of whey is discussed.
5 — The composition of the curd and the distribution
of nitrogen in the whey were briefly examined.
6 — The utility of this optimum reaction is empha-
sized in (a) the determination of "lactalbumin," (b)
production of lactose, (c) manufacture of whey cheese,
and (d) preparation of "protein-free" milk.
The Variability of Crude Rubber1
By John B. Turtle
Bank Street, New York
When plantation rubber first came on the market
in appreciable quantities, the rubber manufacturers
found that there was considerable variation between
any two lots, and for some time this fact created quite
a prejudice against the use of plantation rubber.
At first, it was thought that the trouble was entirely
due to the way in which the rubber was coagulated and
dried; and, by exposing the wet coagulum to smoke
during the drying, attempts were made to duplicate,
as far as possible, the method of coagulation used in
preparing the best grade of wild rubber, viz., Fine Para.
The special efforts to produce a smoked sheet of high
quality were quite successful, and for some time such
rubber commanded a premium over the rest of the
plantation rubber. These smoked sheets were quite
uniform in quality, but from our present knowledge,
it is quite safe to say that this superiority was not
caused by the smoking, but rather by the unusual care
which was taken in coagulating, drying, and smoking,
and by the fact that only the best quality latex was
used in their preparation.
Notwithstanding the improvement in smoked sheets,
it soon developed that the problem of variability in
crude rubber had not been solved, and at the Rubber
Exposition in London in 1914 the subject received wide
attention. By this time, the volume of plantation
rubber being marketed had increased enormously,
and the importance of this problem of variability grew
correspondingly. With the increase in the number of
factories using plantation rubber, especially where it
' Presented before the Rubber Division at the 58th Meeting of the
American Chemical Society, Philadelphia, Pa., September 2 to 6, 1919.
included those factories without adequate control,
the losses became more serious than ever. Although
the conference held in connection with the 1914 ex-
hibition discussed this subject at some length, no con-
clusions were reached as to the correct explanation of
the trouble. Since that time, the results of consider-
able work have been published, largely from the labora-
tories of the Department of Agriculture, Federated
Malay States. These investigators have advanced
many explanations as to the cause of variability, and
they have adopted a method of measuring the varia-
bility in terms of "the rate of cure" and the tensile
properties.
The investigations on this subject took the form of
vulcanization experiments on compounds containing
various proportions of plantation rubber and sulfur.
Eaton and his co-workers at Kuala Lumpur, F. M. S.,
worked entirely with a compound of 90 per cent rubber
and 10 per cent sulfur. Stevens used the same formula,
while Schidrowitz used 92.5 per cent rubber and 7.5
per cent sulfur. Others used one or the other of these
two formulas, but the point to be noted in this connec-
tion is that rubber and sulfur were the only constituents
of the mixture. The rubber used was prepared in a
variety of ways, and the rate of cure and tensile prop-
erties were supposed to show the effect of changes in
the methods of preparation.
SUMMARY OF EATON'S WORK
Eaton's work has been summarized in Bulletin 27
of the Department of Agriculture, F. M. S., which
gives in detail the methods of preparing the various
520
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
grades of crude rubber, methods of curing and test-
ing, and the results of the tests. The principal studies
were with reference to the effect of the various coagu-
lating agents, washing, creping, and drying. As a
result of his work, Eaton concludes that there are two
agencies present in plantation rubber, which act as
accelerators in vulcanization. These are:
(1) The vulcanization accelerating agent formed by the bio-
logical degradation of proteins or organic nitrogenous matter
in the coagulum during the early stages of drying.
(2) A vulcanization accelerating agent, preformed in the
latex and retained by the dry rubber under certain conditions
of preparation. The second substance may possibly be identical
with the first, although there are certain indications that they
are different.
The accelerator formed by the degradation of the pro-
teins consists probably of an amine or amino acid,
probably the former, since it is known that putrescine,
which is a degradation product of animal proteins,
behaves like an accelerator.
Under the normal temperature conditions in Malay
(about 85° F. in the shade), the maximum amount of
the first accelerator is produced during the first 6
or 7 days of drying. By hot-air drying at about 120°
to 130° F., the amount of the accelerator produced
during the first 6 days is increased, the change being
progressive up to the seventh day, after which time
little further change takes place. The amount of this
accelerator may also be increased by allowing the un-
pressed, or slightly pressed coagulum (slab .rubber)
to mature for the period mentioned above. Creping
the rubber after this time removes little or none of the
accelerator. On the contrary, in coagulum which is
machined in thin sheets on the day of, or the day follow-
ing coagulation, only a small amount of the first ac-
celerator is formed. Thicker sheets take longer in
drying and, therefore, will have an intermediate
amount of the accelerator. Smoking the fresh coagu-
lum, on account of the antiseptic nature of the smoke,
inhibits the formation of the accelerator. The products
of the smoke which are absorbed by the rubber have
in themselves a retarding effect on vulcanization.
Sterilization by heat, and refrigeration, inhibit the
formation of the accelerator. It will be noticed that
mild heating increases the amount of accelerator,
whereas strong heat retards the reaction.
The second accelerator, which exists preformed in
the latex, will be retained in the coagulum and also
in the finished rubber, by any process of preparation
which retains all or part of the serum, as, for example,
evaporating thin films of latex to dryness, etc. Slab
rubber evidently contains both accelerators because,
owing to the fact that the coagulum has been allowed
to dry for 6 days before machining, it is more difficult
to wash than the fresh coagulum.
Thus Eaton and his co-workers arrive at the con-
clusion that the variability in crude rubber is the
variability in the amounts of accelerators which may
exist before coagulation or may be formed later, and
which by the processes of washing and drying are per-
mitted to remain in the crude rubber.
In only one case in the w^ork of the authors cited
above, has any attempt been made to work on this
problem with compounds at all comparable with those
used in commercial work. It is interesting to note
in this connection that Eaton, commenting on these
tests, states that the variability in the rate of cure has
probably been obscured in the case of researches in
which such mixings have been employed. He fur-
ther maintains that although the variability has been
obscured, it still exists. Practically no attempts have
been made in these researches to use the ordinary com-
mercial accelerators in vulcanizing plantation rubbers.
In ordinary commercial practice in this country
there is a small, but certain, amount of material which
is produced by the vulcanization of crude rubber and
sulfur only. It is customary to attempt to blend the
various rubbers by the process of "massing," consist-
ing simply of working a large quantity of crude rubber
on the usual mixing mills until it is quite soft, and
when thoroughly mixed, cutting off the rubber in
the form of small rolls or sheets. In spite of this,
it is evident, from the work of Eaton, that there will
be considerable variation in the rate of cure from day
to day, owing to the different methods employed on
different estates. It is evident, therefore, that manu-
facturers must be constantly on the watch to see that
only grades of rubber of as nearly the same rate of
cure as possible are used.
EFFECT OF ADDED ACCELERATORS
However, the vast bulk of plantation rubber to-day
is used in mixings in which either organic or inorganic
accelerators are present in sufficient quantity to pro-
duce a fairly rapid cure. For this reason, it seems
as though the work which has been done has been for
the benefit of a very small amount of plantation rubber,
and does not apply to the balance. We may divide
the substances found in crude rubber, which may in-
fluence vulcanization, into two classes:
(1) The accelerators formed in the latex or in the coagulated
rubber.
(2) Retarding agents which have been added to the latex
or coagulum (such as any coagulating agent which has not been
removed by washing), or substances in the smoke which are
absorbed by the rubber, etc.
These two classes of substances will always react one
against the other, as Eaton has pointed out. The
balance between the two will determine the rate of
cure. It should be noted here, however, that these
substances are necessarily present in very small quan-
tities, and consequently variations, which in them-
selves are small, will in the absence of fillers and added
accelerators produce considerable effect on the rate
of vulcanization and the tensile properties. When
accelerators are used these differences are of little
importance, because the amount of accelerator which
is added to a compound is sufficient in itself to vul-
canize the compound correctly, and the presence of
these minute amounts of accelerators found by Eaton
will have little, if any, effect on the vulcanization and
tensilejproperties of such compounds. Not only are
these differences small, but they are not necessarily
indicative of the true quality of the rubber.
Let us consider, for example, a comparison of
latex which is coagulated immediately after collec-
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
521
tion, machined at once, and dried as quickly as possi-
ble. According to Eaton's experience, such a rubber
would have very little of either type of accelerator,
and would therefore have an unusually slow rate of
vulcanization, and the tensile properties would be
abnormally low. In spite of this, it must be obvious
that this rubber should be of superior quality, because
it has not been exposed to the fermentation processes
and to other deteriorating agents. On the other hand,
slab rubber has been exposed for some time to these
agencies, and it does not seem probable that their
effect would be beneficial. Yet this is exactly the
conclusion which we must draw if we are to accept
Eaton's explanations.
The author has at various times tested rubber which
had different rates of cure when rubber and sulfur
only were used, and found that in many cases these
differences largely disappeared with the addition of,
say, 2 to 4 per cent of litharge, or 0.50 to 1 per cent of
the common organic accelerators, such as aniline, hexa-
methylenetetramine, etc. Some of the results of
these tests are given in Tables I, II and III.
Compound Compound Compound Compound
120
150
180
210
600
850
1250
900
850
450
550
700
450
950
1100
1400
900
1450
1900
2050
Table II — Rate of Cure
2IJ50
3050
3150
3000
2(100
3100
3200
3300
2700
3150
3150
3250
2000
2800
2950
2S00
Table III — Effect of Small Amounts of Accelerators
105
120
150
180
210
1150
1250
1800
1100
500
450
500
625
600
2350
2150
1850
950
2100
2400
2950
3150
3250
2950
1550
2700
3300
3400
3250
The results given in Tables I and II are represented
graphically in Fig. 1. Curves A, B, C, and D (from
Table I) show the rate of cure on rubber from differ-
ent estates, using a compound containing 90 per cent
rubber and 10 per cent sulfur. Curves AA, BB, CC,
and DD (from Table II) represent the same estates,
mixed according to the formula: 48 per cent rubber,
48 per cent zinc oxide, 3 per cent sulfur, and 1 per
cent hexamethylenetetramine. In these compounds,
A contains the same rubber as AA; B the same as BB;
C the same as CC; and D the same as DD. We have
here a few illustrations, among many that could be
quoted, where different estates, which vary widely
when only rubber and sulfur are present, show an
excellent degree of uniformity when mixed with zinc
oxide and a sufficient amount of accelerator.
15 30 45 60 75 190 I OS 120 135 150 165 180 195 2i0
Time 'in Minutes
Fig. 1 — Rate of Cure
(Vulcanized at 287° F.)
It may be that the mere fact that Compounds AA,
BB, CC, and DD cure at the same rate does not neces-
sarily prove that the lots of rubber are of the same
quality. However, this criticism will hold for all of
the work done by Eaton, Stevens, and the others, who
compare lots of rubber by means of tensile properties,
and the rate of cure.
The results given in Table III are plotted in Fig. 2,
and show the effect of the addition of another acceler-
ator (the carbon bisulfide addition product with di-
methylamine), with and without zinc oxide. The
rubber used in these tests was blended from ten es-
tates, all of them regarded commercially as of excellent
quality. The formulas used are as follows:
G — 90 per cent rubber; 10 per cent sulfur
H — 99.9 per cent compound G; 0.10 per cent accelerator
I — 90 per cent compound H; 10 per cent zinc oxide
J — 48 per cent rubber; 4S.96 per cent zinc oxide; 3 per cent S; 0.04 per
cent accelerator
K — 48 per cent rubber; 48.9 per cent zinc oxide; 3 per cent S; 0.10 per
cent accelerator
From these curves it will be seen that the addition of
only 0.10 per cent of what, under proper conditions, is
a remarkably active accelerator is sufficient to retard
almost entirely the vulcanization of the rubber.
The addition of 10 per cent of zinc oxide is sufficient
to overcome this retarding effect, as is shown in Curve
I. The remarkable qualities of this accelerator are
shown in Curves J and K, which contain 0.04 per cent
and 0.10 per cent, respectively.
In an effort to find out whether or not the zinc oxide
was responsible for the change in the rate of cure,
portions of compound H were mixed with neutral
barium sulfate, lampblack, talc, whiting, and lime,
522
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
J400r
3200
\%
3000
\f\
2800
2600
2400
a
??00
/
\
2000
(
s
\
—
1800
\
1600
\
1400
w
\
1200
\
1000
\
3j>-|
800
V
600
hi
400
H^
200
0
IS 30 45 GO 75 90 105 120 ISO
Time in Minutes
180 210
Fie. 2 — Effects of Small Amounts c
(Vulcanized at 287° F.)
Accelerator
in the ratio of 90 per cent of compound H to 10 per
cent of the pigment. The barium sulfate and the
lampblack produced no effect, and the talc practically
none, while the whiting and lime showed a vast im-
provement in the rate of cure and tensile properties.
The results with whiting and lime do not quite reach
the values for Curve I, but this is only to be expected,
since it is well known that the coarser pigments do not
give as high tensile properties as the finer ones.
The whole point in this discussion is that it is not
sufficient to bring together rubber and sulfur, and then
assume the presence and action of an accelerator,
merely because one method of preparation produces
a somewhat more rapid cure than another. The
above results could be extended to show that with
many organic accelerators (and Eaton is dealing with
organic accelerators in the latex) it is necessary to
have the proper environment in order to develop the
maximum, or even any accelerating action. It is
not the intention of this article to doubt that certain
methods of preparation which are used on some plan-
tations are actually injurious to the rubber, and this
injury will be reflected in the short life of articles made
from such rubber; but on the other hand, it is un-
doubtedly true that certain methods of preparation
permit the formation of small amounts of accelerators
or other substances which affect the rate of cure,
without really changing the quality of the rubber.
It has been assumed that when the rate of cure is in-
creased, these substances are accelerators, whereas
it may be true that the change is only one of passing
from an acid to an alkaline environment, in which
state it is possible for the accelerators already present
to function in their normal manner.
The real object of this article is to point out the fact
that it is absolutely unfair to compare the rate of cure
under such limited conditions as obtain in the tests
where rubber and sulfur only are used. What has
really been done is to discuss the variability, not in
the grade of rubber itself, but in either the presence or
absence of what we may call foreign substances, which
may be accelerators themselves, or may produce an
environment which will permit other accelerators to
function. In this way, the real variation in the rubber
is obscured by unduly emphasizing the variation in
the rate of cure caused by minute quantities of de-
composition products. The proper procedure would
be to add to each mixture a sufficient quantity of zinc
oxide to be certain that the vulcanization will take
place in an alkaline medium. Probably 2 to 5 per
cent would be sufficient for this purpose, and the results
thus obtained would be of real value in determining
the variation in the rate of cure, because in this way
the conditions of vulcanization would be more uni-
form than is the case at present, and hence the results
would be more truly comparable.
SUMMARY
Attention is called to the fact that the usual method
of testing for variability in crude rubber really deter-
mines the variability in the amounts and character of
certain foreign substances which, in the absence of
pigments which will produce an alkaline medium for
the reaction, tend to obscure the variation which may
exist in the rubber. Tests show that as little as 0.10
per cent of a remarkably strong accelerator is sufficient,
in the absence of alkaline fillers, to retard the vul-
canization almost entirely. It is recommended that
all tests, intended to discover the variability in the
crude rubber, be performed on mixtures to which has
been added from 2 to 5 per cent zinc oxide, in order to
eliminate the retarding effect which might be caused
by small quantities of foreign substances or decomposi-
tion products.
Statistics of Benzene Production
150,000,000 gal. was the potential capacity for light oil of
the 65 plants existing in the United States during 1920. These
plants are located as follows:
Illinois
Indiana
Kentucky
Maryland
Michigan
Minnesota
M
New Jersey
New York
Ohio
Tennessee
Pennsylvanis
West Virgini;
Wisconsin
The actual production, however, was:
Light Oil
Gallons
1919 90.000.000
1920 110.000.000
Benzene
1914 . 2.000.000
1915 9.000,000
1916 27.000,000
1917 38,000,000
1918 55,000,000
1919 63.000,000
1920 77,000,000
Toluene
1914 600,000
1915 3.500,000
1916 6.500,000
1917 10.000,000
1918". . . 14,500.000
1919 1,000,000
1920 2,500,000
'Does not include Ordnance Department stiipping plants.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
523
The Relation of Moisture Content to the Deterioration of Raw- Dried
Vegetables upon Common Storage1,2
By H. C. Gore and C. E. Mangels
Bureau of Chemistry, U. S. Department of Agriculture, Washington, D. C.
The simplest and one of the best ways of drying
many kinds of vegetables is to wash, trim, and cut
them finely, and dry in a current of warm air. Carrots,
onions, turnips, tomatoes, celery, parsnips, and cabbage
yield excellent products when dried in this way. Un-
less, however, the products are dried to below certain
moisture contents they will not retain their original
color and flavor during storage at ordinary tempera-
tures. Fading of the natural colors occurs, accom-
panied by darkening of the tissues and changes in
flavor and aroma. For example, sliced carrots, dried
without taking special precautions to dry thoroughly,
lose their brilliant color and distinctive flavor. Turnips,
cabbage, and onions similarly dried slowly darken
upon keeping at room temperatures, becoming finally
as dark as tobacco, and at the same time suffer serious
losses in distinctive flavor. Spinach fades and ac-
quires a hay-like flavor unless dried very thoroughly
and kept in air-tight containers. If the products have
been cooked before drying the deterioration is less
rapid, but no less certain. Microorganisms cannot be
concerned in this deterioration, because the moisture
content is almost invariably well below that at which
yeasts, molds, and bacteria will grow. The purpose
of the work described below has been two-fold:
1 — To demonstrate that the moisture content bears a definite
relation to the rate of deterioration.
2 — To determine the critical moisture content for each of
the important dried vegetables below which the changes in
color and flavor on keeping at ordinary temperatures are very
slow.
A steam-heated commercial dryer was used. A
substantial quantity of each vegetable (about 100
lbs.) was cut finely, spread on trays, and dried in a
current of warm air until it reached a moisture con-
tent below that at which it would spoil as a result of
invasion by microorganisms. A portion of the ma-
terial, usually one-fourth to one-fifth, was then re-
moved, the remainder further dried, again sampled,
and the operation repeated until four or five samples
of different moisture content were secured. This
set of samples, called a "moisture series," was kept at
room temperatures ranging from 70° to 90° F. in the
dark in tightly sealed, glass fruit jars. The moisture
content of each jar of material was determined by
drying to constant weight in vacuum at not over 70°
C. As the products were finely divided before drying,
the samples taken for moisture were not ground before
drying. Notes made on the stored samples from time
to time are given below. The principal indication of
deterioration was change in color. Changes in aroma
and flavor also occurred, but usually were less clearly
evident.
1 Received January 21, 1921.
1 Published by permission of the Secretary of Agriculture.
Tabus I — Carrots (Dried December 31, 1917)
A dried 6 hrs. at 122° F.; B, 6 hrs.
C, 6 hrs. at 122° F. + 3 hrs. at 140° F.;
140° F. + 1 hr. at 158° F.
Days of
Stor-
11.11 Per cent
7.39 Per cent
4.99 Per cent
4.54 Per cent
age
HsO
H2O
H2O
H2O
40
No color change
Strong carrot
No change
No change
No change
68
Distinct fading
of color notice-
able
No change
No change
No change
86
Color faded.
Odor and fla-
vor still dis-
tinctive
Color slightly
235
Carrot color
Color faded.
Color faded
LikeC
faded. Sam-
No darkening.
slightly less
ple darkened
Odor and fla-
vor still dis-
tinctive
than B
690
Color faded and
Color faded and
Color faded.
Sample lost
browned. Dis-
darkened
No darkening
tinctive aroma
and flavor lost
942
Distinctive color,
flavor, and
aroma lost
Color faded.
Distinctive
flavor still
present
Sample lost
Table II-
—Turnips (Dried January 2, 1918)
A dried 6 hrs. at 122° F.; B.10 hrs. at 122° F.; C. 10 hrs
. at 122° F. +
1 hr. at 140° F.; D, 10 hrs. at 122° F. + 2 hrs. at 140° F.
Days of A
B
C
D
Stor
- 11.51 Percent
6.57 Per cent
5.00 Per cent
4.55 Per cent
age
H20
H30
H2O
H2O
33
Browned dis-
tinctly. Strong
turnip odor
No change
No change
No change
65
Darker than
above. Still
has strong
turnip odor
Darkened very
slightly. Very
little odor
No change
No change
80
No change
No change
233
Color dark
Darkened and
Slightly dark-
Same as C
brown. Strong
has strong
ened. Tur-
turnip odor
turnip odor
nip odor
588
Color dark
Color brown.
Slightly
brown. Lacks
Slight turnip
browned
distinctive
odor
940
Same as previous
Same as previous
Same as previous
1 Same as C
examination
examination
examination
Table III — Onions (Dried January 6, 1918)
A dried 10 hrs. at 113° F.; B. 20 hrs.
at 113° F.; C.24 t
irs. at 113° F.;
D.24 hrs. at 113° F. + 0.5 hr. at 113°-12
2° F.
Days of A
B
C
D
Stor-
■ 9.65 Per cent
6.64 Per cent
5.74 Per cent
5.34 Per cent
age
HjO
HsO
H2O
H2O
29
Slight darken-
ening. Onion
odor
No change
No change
No change
76
Same as previous
No change
No change
No change
227
Color light
Sample lost.
Slightly yellow.
tike C
brown. Fla-
Jar defective
Flavor good
554
Color dark
brown. Fla-
vor poor
Distinctly
browned.
Flavor and
odor good
905
Same as previous
examination
Color light
brown. Fla-
vor deterior-
ated, but still
distinctive
Table IV— Spinach (Dried May 13, 1918)
B dried 1.25 hrs. at 140
F.; E, 3 hrs. at 140° F.
Days of B
Stor- 8.90 Per cent
age HsO
103 Flavor poor,
hay-like
F.; C, 1.5 hrs. at 140° F.; D, 2.5 hrs. at 140°
1>
Color slightly
browned. Fla-
vor poor, hav-
like
5.38 Per cent 3.81 Per cent
HjO H»0
Color slightly Color unchanged.
faded. Fla- Flavor fair
vor fair
Same as pre- Color very
vious exami- slightly faded.
nation Flavor fair
!03 Per cent
H.O
Like D
524
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
Tablb V — Cabbagb (Dried January 2, 1918)
A dried 6 hrs. at 122° F.; B. 10 hrs. at 122" F.; CIO hrs. at 122° F. +
1 hr. at 140° F.; D, 10 hrs. at 122° F. + 1 hr. at 140° F. + 1 hr. at 150°-
160° F.
Days of A B C D
Stor- 11.15 Per cent 5.49 Per cent 3.54 Per cent 3.00 Per cent
age H2O HsO HjO HsO
33 Slightly browned
80 Browned. Pe- No change No change No change
culiar taste
and odor
232 Quite dark. Un- Slightly dark- Slightly dark- Same as C
pleasant aroma ened. Flavor ened. Flavor
good good
588 Same as previous Distinctly Same as previous Same as C
examination browned examination
940 Same as previous Distinctly Same as previous Same as C
examination browned. Un- examination
pleasant ;
DISCUSSION OF RESULTS
The results of the observations clearly demonstrate
the extremely important influence of low moisture
content on the retention of distinctive color and flavor
by raw dried vegetables upon keeping in air-tight con-
tainers at ordinary temperatures. Carrots of 11.11 per
cent moisture content faded distinctly during 68 days'
storage, while carrots of 7.39 per cent moisture kept
well for this period. Turnips of 11.51 per cent moisture
content browned distinctly and developed a peculiar
turnip-like odor in 33 days, while turnips dried to.
5.00 per cent moisture had not changed in 80 days.
The same general facts were noted in case of the samples
of onions, spinach, and cabbage.
The moisture content below which to dry for satis-
factory retention of color and flavor during common
storage in air-tight containers can be approximated
from the results given in the tables.
SUMMARY
The moisture content of dehydrated raw vegetables
was found to be a factor of considerable importance
for successful storage in air-tight containers at ordi-
nary temperatures.
The initial moisture contents at and below which the
distinctive color and flavor are well retained for 6
mo. or more are as follows: Carrots, 4.99 to 7.39
per cent; turnips, 5.00 per cent; onions, 5.74 to 6.64
per cent; spinach, 3.81 to 5.38 per cent; cabbage, 3.00
to 3.34 per cent.
Manganese in Commonly Grown Legumes1
By J. S. Jones and D. E. Bullis
Division op Chemistry, Oregon Experiment Station, Corvallis, Oregon
Whatever may be the function of manganese in
plant nutrition there is no doubt of its common occur-
rence in soils and of its utilization in limited amounts
by plants generally. In the course of some analytical
work on the legumes that are characteristic of various
parts of Oregon, the frequent development of a blue
or bluish green color in the ash determinations was
noted. This color we took to be indicative of man-
ganese in the legumes burned — possibly in unusually
large amounts — but this latter surmise proved to be
wrong. The color could be developed almost at will
by raising the temperature of the combustion furnace
to a point just below incipient fusion of the ash, and
exceedingly small amounts of manganese were suffi-
cient to produce it. The explanation is the formation
of an alkali salt of manganic acid. Because of other
determinations to be made on the ash it was undesir-
able to ignite at the high temperature required for the
formation of the bluish green melt, hence the ash
determinations neither proved nor disproved the pres-
ence of manganese in all samples of the several kinds
of legumes uftdej. examination.
Although the 'literature makes it plain that man-
ganese is utilized <,o ->n appreciable e- ->nc by -plants
generally, analytical data indicative of actual amounts
found in plants as a whole or in their several parts are not
of frequent occurrence. Jadin and Astruc,2 reporting on
some vegetable substances used as fodders, claim 0.36
mg. of manganese per kg. of dry material in potatoes
and varying amounts in other fodders, up to 80 mg.
per kg. in poplar leaves and meadow grasses. The
green or chlorophyll-containing parts were always
richest in manganese. McHargue3 found, in many
kinds of seeds and nuts, the largest amounts of man-
1 Received January 3. 1921.
= Compt. rend., 165 (1912), 300; 169 (1914), 268.
' J. Am. Chem. Soc, 36 (1914), 2932.
ganese in those parts of the seed coats that imme-
diately surround the cotyledons. He found, too, that
manganese is relatively high in those parts which
secrete large amounts of oxidizing enzymes. His in-
ference is that manganese serves as a catalyst to the
enzymes. Headden1 found in the grain of wheat
amounts ranging around 40 p. p. m. of dry matter. He
concluded that manganese is present in the wheat ker-
nel in practically the same amounts as iron, and that
fertilizers and irrigation waters do not affect to any
appreciable extent the amount of manganese stored
by the wheat plant in iis seeds. The meagerness of
quantitative data for this element whose function in
plant nutrition is imperfectly understood, and our
plans for using certain of the legumes in animal nutri-
tion investigations made it worth while to determine
for the commonly grown legumes the extent to which
they utilize manganese in growth. Incidentally, that
portion of the work which determined the relative
amounts of manganese in the several parts of these
legumes gives additional support to the theory that
its primary function is catalytic, inasmuch as by far
the largest amounts were found in the leaves.
METHOD OF ANALYSIS
Manganese in organic material is usually determined
colori metrically, following its leaching from the ash
and its conversion to permanganate. For the conver-
sion lead oxide is used alone, or ammonium persulfate
is used with silver nitrate as a catalyst. It is fre-
quently recommended, too, that the material to be
ashed should first be mixed with some oxidizing agent,
such as nitric acid or ammonium nitrate. Five grams
of rather finely ground material were ashed in a silica
dish without mixture with any kind of oxidizing agent.
The practically pure white ash was taken up with a
1 J. Agr. Res., 6 (1915), 349.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
525
few drops of concentrated sulfuric acid which was
then driven off over a free gas flame. One repetition
of the treatment with sulfuric acid and its elimination
by heat was necessary to insure the elimination of
chlorine, the presence of which is undesirable in the
subsequent procedure. The slightly acid residue was
washed with hot water on to a filter and leached re-
peatedly with 15 to 20 cc. of hot water. Conversion
of manganese to permanganate was then accomplished
by the addition of 2.5 to 3 g. of ammonium persulfate
and 2.5 to 3 cc. of 0.5 N silver nitrate to the flask
containing the filtrate and heating in a water bath at
90° to 95° C. for 15 min. The cooled permanganate
solution was titrated with a very dilute solution of
sodium arsenite standardized against potassium per-
manganate. The end-point was sharp, and the whole
procedure was very satisfactory.
The reaction involved is:1
2HMn04 + 5NaaAs03 + 4HN03 =
5NasAs04 + 3H20 + 2Mn(NOa)2
In Table I are shown the maximum, minimum, and
average contents of manganese for the several legumes
where the entire (aerial portion) plant is considered.
Determinations were made on air-dry samples secured
as they would be cut for hay in the various parts of
the State.
Table I — Summary op Analytical Data
(Manganese in mg. per kg. air-dried material)
Red Alsike Field Sweet White
Vetch Clover Clover Alfalfa Peas Clover Clover
Samples
analyzed... 15 13 7 15 6 4 2
Maximum.... 53 70 140 29 52 50 35
Minimum 17 19 40 16 20 15 33
Average 42 33 68 23 33 27 34
From these data we would conclude that alsike
clover utilizes manganese in larger amounts than any
other legume commonly grown in this State, and that
alfalfa makes least use of it.
In Table II are shown the relative amounts of man-
ganese accumulated by or stored in the several parts
of the plant. The leaves are unquestionably the rich-
est in manganese.
Table II — Manganese in the Several Parts op Legumes
(Mg. per kg. dry material)
Stems Bloom Leaves Seed Pods
Red Clover, 1 20.0 66.0 84.0 12.0
Red Clover, II 15.0 30.0 40.0 6.0
Alfalfa, 1 13.0 42.0 76.0 11.0
Alfalfa.II 11.0 27.0 45.0 6.0
Vetch, 1 11.0 17.0 33.0 10.0 6.0
Vetch, II 8.0 ... 27.0
Field, Pea 14.0 21.0 38.0 11.0 21.0
Effect of Heat on Different Dehydrated Vegetables2
By C. E. Mangels and H. C. Gore
Bureau op Chemistry, U. S. Department op Agriculture, Washington, D. C.
In the production of dehydrated vegetables the tem-
perature at which the drying is conducted is an im-
portant factor, since excessive heat causes scorching
and consequent injury to quality. The manufac-
turer, however, generally wishes to use the highest
temperature permissible, since the drying will proceed
more rapidly at higher temperatures. Practically
no systematic study has been made, up to this time,
to determine relative limits of tolerance, and the dry-
ing operation is generally conducted by "rule of
thumb." Different commercial plants use wide ranges
of temperature, the extremes being 110° and 180° P.
Unexplained failures at times show a need of more
knowledge on the subject of temperature.
In this investigation, studies were made at as high
a temperature as 194° F. (90° C). A short period of
heating at high temperatures is often recommended
for destroying insect eggs in dried products, and these
studies were made in order to gain some idea as to the
length of exposure and degree of temperature which
would not injure the quality of the product.
The object of the investigation was to determine, if
possible, the limits of tolerance for different vegetables
and also to determine the importance of three variables:
(1) The degree of temperature used.
(2) The time of exposure to such temperature.
(3) The relative humidity of the surrounding me-
dium (air).
PROCEDURE
In the experiments reported, the testing was limited
to finely divided vegetables which had already been
'Scott, Standard Methods of Chemical Analysis."
* Received February 5, 1921.
dried. It was impracticable to use fresh vegetables,
since the drier or outer portions of such products would
take approximately the air temperature within the
cabinet, while the inner or any wet portions would still
remain cool, owing to evaporation. The vegetables
were dried in the laboratory at low temperature in
such manner that they would not deteriorate from
overheating or other cause. The method consisted
of cutting up finely with a slicing machine, spreading
on trays, and drying before an electric fan at room
temperature until partially dry, when the drying was
finished by a short exposure in a steam-heated dryer
at a temperature not exceeding 120° F.
An experimental cabinet in which a constant and
uniform temperature could be maintained was used.
Electric heating units were provided, and the tempera-
ture was controlled by a sensitive thermostat. The
circulation of the air by a fan placed ' . the cabinet
insured a uniform temperature througnout the cabinet.
Two series of experiments were conducted. In
the first, dry air was used, while in the second the
highest relative humidity obtainable was used. This
was obtained by placing pans of water in the cabinet.
This method did not give saturation or a constant
humidity at different temperatures, and the values
obtained were as follows:
iperature
Per cent
50° C.
64
fiO°C.
49
In the first series, tests were made at 5° intervals at
temperatures ranging from 50° C. to 90° C. In the
526
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
case of the second series, 10° intervals were used over
the same range of temperatures.
The dried vegetables were spread on wire trays,
placed in the cabinet, and exposed to the desired tem-
perature for definite periods of time; then compared
with the original material. This comparison was
always made on a white background in good daylight.
For example, a series of carrot samples exposed 10,
20, 30, and 40 min., respectively, at 90° C, were com-
pared with the original sample. The 10- and 20-
min. samples did not differ in appearance from the
original, but the 30- and 40-min. samples were some-
what darkened by exposure, and the 40-min. sample
showed a greater degree of injury than the one exposed
30 min. The first point where injury was indicated
by darkening was taken as the end-point, in this case
30 min.
In general, it may be said that the injury point
as determined by this method was quite distinct and
definite at temperatures of 70° C, and higher. For
temperatures below 70° C. the injury point could not
be as readily recognized, but there appeared to be a
very gradual change in appearance of the product.
RESULTS OF EXPERIMENTS
string beans — No injury resulted from 18 hrs.'
exposure to dry heat at 55° C, and injury was doubt-
ful at 60° C. Moist heat caused no injury in 20 hrs.
at 50° C, but injured the beans in from 9 to 11 hrs.
at 60° C. At 90° C, both dry and moist heat injured
the beans within 1 to 2 hrs.
cabbage — In dry heat, cabbage was injured in 16
to 20 hrs. at 50° C, in 12 to 14 hrs. at 55° C, in 3.5
hrs. at 70° C, and in 1 hr. at 75° C. In moist heat,
injury occurred in 6 to 8 hrs. at 50° C, in 5 hrs. at
60° C, and in 3.5 hrs. at 70° C.
carrots — Carrots are not easily damaged by over-
heating, and in this respect are comparable to string
beans. Moist air at 50° C. injured the carrots in from
17 to 18 hrs., while at 60° C. injury occurred in from
8 to 9 hrs. In the dry atmosphere, no injury occurred
in 18 hrs. at 60° C. At 65° C, the product was injured
in from 10 to 12 hrs. The moist heat curve was con-
sistently below the dry heat curve and gradually
approached it at higher temperatures.
celery — Celery may be classed with the easily
injured vegetables. In a moist atmosphere at 50°
C, injury occurred between 6 and 8 hrs. In a dry
atmosphere, no injury was found at 20 hrs.' exposure.
At 60° C, injury occurred after 4 hrs.' exposure. The
moist heat line was consistently under the dry heat
line to 80° C, where they coincided, injury being found
after 30 mins.' exposure. The observations coincided
again at 90° after 10 min. Celery is especially sus-
ceptible to color changes in a moist atmosphere at low
temperatures.
onions — Onions are very susceptible to heat, both
dry and moist. In a dry atmosphere, the injury
occurred after 12 to 16 hrs.' exposure at 50° C, while
in a moist atmosphere, injury occurred after 8 to 10
hrs. at this temperature. Injury occurred in 6 hrs.
in a dry atmosphere at 55° C, and in 5 hrs. at 60° C.
In a moist atmosphere at 60° C, injury occurred
after 4 hrs. From 70° up to 90° C, dry and moist
heat had about the same effect. Injury occurred
very quickly (in 10 min.) at 90° C.
potatoes — shredded and blanched — Potatoes are
not especially susceptible to heat injury. The injury
is very easily detected on account of the light color
and translucence of the pieces. Moist and dry heat
had about the same effect, except at the lower tem-
peratures. In dry heat, injury occurred after 16 hrs.'
exposure at 50° C, in 11 hrs. at 55° C, and in 8 hrs.
at 60° C. In a moist atmosphere, injury occurred after
11 hrs. at 50° C, and in 7 hrs. at 60° C.
potatoes — riced — Riced potatoes have almost the
same resistance to heat as the blanched, shredded
potatoes. The end-point is not so easily distinguished.
sweet potatoes — Sweet potatoes are very resistant
to heat, as compared with the other vegetables. In a
moist atmosphere at 90° C, injury occurred in from
8 to 12 hrs. No injury after 10 hrs. was found in a
moist atmosphere at 80° C. In a dry atmosphere at
90° C, injury occurred after 5 hrs., and after 10 hrs. at
80° C. Temperatures lower than 80° C. did not seem
to injure sweet potatoes, at least not for many hours.
sweet corn — Sweet corn is fairly resistant to heat,
being more resistant than carrots, although not so
resistant as sweet potatoes. Moist heat in general
is more harmful than dry heat. In a moist atmosphere
at 50° C, no injury was found after 20 hrs.' exposure.
In a dry atmosphere at 60° C, no injury was found
after 20 hrs.' exposure, while in a moist atmosphere
at this temperature the product was injured by 10
hrs.' exposure.
tomatoes — Tomatoes are easily injured by heat
at 60° C, and above. The peculiarity of the tomato
results was that, at 70° C. and above, moist heat was
less injurious than dry heat. At 50° C, tomatoes
were injured by between 8 and 10 hrs.' exposure in a
moist atmosphere, while they did not show injury
until after 16 to 18 hrs.' exposure in a dry atmosphere.
The resistance to dry heat decreased rapidly, however,
as the temperature rose, and at 60° C, injury occurred
after 6 hrs.' exposure.
turnips — Turnips are easily injured by heat, and may
be classed with celery, onions, and tomatoes. At
50° C, in a moist atmosphere, injury occurred after
8 to 10 hrs.' exposure, while with a dry atmosphere
they had to be exposed 16 to 20 hrs. before injury was
noticeable. The resistance to dry heat decreased very
rapidly, however, and at 60° C. the material showed
injury after 5 hrs.' exposure.
conclusion
The dried vegetables studied can be classed as
follows in regard to sensitiveness to heat:
Very easily injured: Onions, turnips, celery, tomatoes, cabbage.
Fairly resistant: White potatoes, carrots, string beans,
sweet corn.
Very resistant: Sweet potatoes.
As the degree of temperature is increased, the ex-
posure necessary to cause injury decreases. Exposure
in an atmosphere of comparatively high relative
humidity at the lower temperatures appears more in-
jurious than the same exposure in a dry atmosphere.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
527
Methods for Determining the Amount of Colloidal Material in Soils1-2
[PRELIMINARY PAPER]
By Charles J. Moore, William H. Fry and Howard E. Middleton
Bureau op Soils, U. S. Department op Agriculture, Washington, D. C.
The study of soil solutions and the aqueous ex-
tracts of soils has engaged the attention of this Bureau
for some time past. Investigators in this field have
realized for a long while that the aqueous extracts
frequently contain considerable colloidal material
which renders them opalescent, and that it is quite im-
possible to clarify such solutions by any ordinary
means of filtration. Very recently Anderson and Fry
completed a preliminary study of the solid phases
obtained by the evaporation of certain soil extracts.
In order to obtain sufficient material they found it
necessary to work up from 500 to 2000 lbs. of soil.
The amount of colloidal material obtained from so
large a quantity of extract was, of course, considerable,
and it possessed such striking properties that some
time was devoted to the study of it.
METHOD OF PREPARATION3
A battery of barrel-type churns was used for stirring
up the soil with water. Twenty-five lbs. of soil were
placed in each churn and 125 lbs. of pure distilled
water added. The churns were rotated for several
hours and then allowed to remain at rest for 24 hrs.
before the supernatant liquid was siphoned off into
well-tinned milk cans. The next step was to pass the
turbid liquid through a Sharpies centrifuge. While
this is a continuous process, it is calculated that each
portion of the liquid was subjected to the force of
17,500 gravity for at least 5 min. The liquid issuing
from the centrifuge was usually quite opalescent with
colloidal material, which was next separated from the
dispersing medium by means of batteries of Pasteur-
Chamberlain filter tubes (Bogie F). The clear filtrate
was concentrated in steam kettles for other researches.
The colloidal material collected on the outside of the
tubes in a slimy, sticky mass which soon clogged the
filters. However, it was easily removed by blowing
air into the tubes. We have given the, name "ultra
clay" to this material.
The ultra clay was purified in many instances by
dialysis. This process proved very slow and was
finally given up, and the purification was carried out
by stirring the colloid up with distilled water and
drawing the water off by means of clean filter tubes.
This method was very satisfactory.
COMPOSITION AND PROPERTIES
The chemical composition of ultra clay varies con-
siderably. We are convinced that it is a mixture of
colloids, consisting mainly of the hydrated silicate of
aluminium, and containing varying amounts of ferric
hydroxide, silicic acid, organic matter, and possibly
aluminium hydroxide. There are always present
small but varying amounts of calcium, magnesium,
potassium, and sodium — whether chemically combined
1 Received January 31, 1921.
2 Published by permission of the Secretary of Agriculture.
> Method developed by R. O. E. Davis, L. B. Olmstead and M. S.
Anderson.
or physically adsorbed has not yet been determined.
When ultra clay is suspended in water, it gives
every evidence of being a true colloid. Under the
ultramicroscope, it appears as droplets of an amber-
yellow color and shows the Brownian movement to
a very marked degree. When very dilute solutions of
electrolytes are allowed to diffuse under the cover
glass on the slide, the Brownian movement is at once
arrested. When suspensions are concentrated, much
flocculation occurs. The addition of any electrolyte
or of alcohol will, of course, have the same effect.
When the thick mass is diluted or the coagulating
material is removed by washing, a free suspension of
the colloid is again obtained. If the colloid is very
thoroughly dried on the water bath, it resuspends in
water very slowly. The dry material is resinous
and of an amber-yellow color.
Clay soils that have been thoroughly elutriated, as
in the mechanical analysis of soils, lose much of their
plasticity. The ultra clay, on the other hand, is
very plastic when moist, and exceedingly sticky. Cer-
tain experiments have been carried out to determine
the adhesive properties of ultra clay. The results re-
corded in the following table show that, up to 10 per
cent, ultra clay is a much stronger binding agent than
Portland cement. However, this is true only when the
material is dry. Briquets cemented together with
ultra clay go to pieces very readily when thoroughly
moistened.
Crushing Strength op Briquets
(Briquets 25 mm. high and 25 mm. in diameter, made up with 18
per cent of moisture under 1800 lbs. pressure per sq. in. and dried at 100° C.)
Cementing Portland Cecil Susquehanna Commercial
Material Cement Ultra Clay Ultra Clay Kaolin
Per cent Kilos Kilos Kilos Kilos
With Standard Grade of Sand as Used in Cement Testing
0.00 0.00 0.00 0.00 0.00
0.50 0.00 3.13 5.42 0.00
1.00 0.00 7.35 6.70 0.00
2.00 0.00 1.348
5.00 3.23 61.57 54.84 0.00
10.00 19.16 122.52 96.39
With Quartz Flour
0.00 17.38 17.38 17.38 17.38
0.50 29.86 33.66 28.08 17.56
1.00 44.37 50.61 52.32 19.40
2.00 72.89 65.54 69.70 17.96
5.00 85.32 128.18 80.68
10.00 112.30 304.30 206.82
It seems evident, therefore, that ultra clay is the
principal binding material of the soil, giving it plas-
ticity, cohesiveness, or hardness, according to the
moisture content. The recognition of these important
properties shows the fundamental relation the material
bears to tillage and to certain engineering problems,
including subgrades in road construction. The possi-
bility of finding a means to control certain of these
properties offers a field of research, with the promise
of results of economic importance to agriculture and to
engineering.
ABSORPTION OF AMMONIA
That soils freely absorb gases is a very well-known
fact, generally looked upon as a surface phenomenon,
characteristic to some extent of all finely divided sub-
528
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
stances. It seems just as reasonable to assume that
the absorptive properties of soils are due to the col-
loids they contain, and it was with the view of dis-
covering some characteristic property of colloids, not
possessed by the other components of soils, which
could be made the basis of a method for determining
their amount in different soils, that the following work
was undertaken. Ultra clay was dried in an electric
oven at 110° C. for 24 hrs. It was immediately trans-
ferred,while still hot, to a Schwartz U-tube, and weighed,
and the tube placed in a train of drying apparatus.
The Schwartz tube was then immersed in boiling water
and thoroughly evacuated with an oil pump. The
U-tube was next placed in an ice bath, and dry ammonia
gas was passed over the ultra clay until it would ab-
sorb no more under a pressure of one atmosphere.
The current of gas was then shut off, and the apparatus
was allowed to stand for 1 hr. to make sure that
equilibrium had been reached, as shown by a manometer
attached to the U-tube. The next step was to draw
off the ammonia and collect it in a train of absorption
apparatus filled with a saturated boric acid solution.
When a good deal of ammonia had been drawn off,
the U-tube was again placed in boiling water and the
residual ammonia displaced with a current of air.
The ammonium borate solution was titrated with
0.1 N sulfuric acid, using methyl orange as indicator.
amount of exposed SURFACE — At the outset it
seemed desirable to investigate to some extent the
influence on the absorption of ammonia of surface
actually exposed. For this purpose ultra clay ob-
tained from Cecil clay loam was divided into two parts.
One part was carefully granulated so that all the parti-
cles would pass through a 1-mm. sieve, and the other
half was made into cylindrical masses under a pressure
of 3000 lbs. These cylinders measured 5 mm. in di-
ameter and 5 mm. in height. They were extremely
compact and presented exceedingly smooth surfaces.
Both samples were air-dried and oven-dried as above
described. The following results were obtained:
Each cc. of Cecil ultra clay, granulated, absorbed 111.1 cc. NHi
Each cc. of Cecil ultra clay, cylinders, absorbed 110.3 cc. NHa
These values are averages of several independent
and fairly closely agreeing determinations. The hard,
compact pellets apparently absorbed ammonia as
readily and to practically the same extent as the loose,
incoherent material. The absorption and evolution of
ammonia in no way disintegrated the pellets.
Susquehanna clay soil — Since the compactness
or looseness of the material made no difference, the
determinations on ultra clay obtained from Susque-
hanna clay soil1 were made on the granulated material
only, and the following result is the average of five
good determinations:
Each cc. of Susquehanna ultra clay absorbed 93.05 cc. NHi
1 For the sake of completeness the mechanical analysis of the Susque-
hanna clay soil is appended:
Diameter Conventional
Mm. Names
2 -1 Fine gravel
1 -0.5 Coarse sand
0.5 -0.25 Medium sand
0.25-0.1 Fine sand
0.1 -0.05 Very fine sand
0.05 -0.005 Silt
0.005-0 Clay
Weight Percentages
0.000
0.00
0.000
0.00
0.025
0.50
0.105
2.10
0.815
16.30
2.263
45.30
1.793
35.90
In all of the above determinations from 7 to 10 g.
of the colloid were used, and the volume was calcu-
lated from the weight and the absolute specific gravity,
which in the case of the Cecil was found to be 2.76
and the Susquehanna 2.64.
It may be worthy of note that on the whole the
Susquehanna colloid proved to be a weaker binding
material than that obtained from the Cecil soil, and
that its ability to absorb ammonia was less, to roughly
the same extent.
effect of heat — The above results show conclusively
that soil colloids possess a remarkable capacity for
absorbing ammonia. If the other components of the
soil should absorb none, it would be necessary only to
determine the capacity of the colloid and of the soil
itself in order to calculate the quantity of colloid in
a given soil. Light would be thrown upon the point
in doubt by heating the colloid to a temperature at
which its nature is entirely destroyed. The Cecil
colloid was selected for heat treatment, because it
could be readily obtained in very pure condition. Later
Susquehanna clay soil was treated in practically the
same manner, except that in some instances the inter-
mediate temperature stages were slightly different.
The heating was carried out as follows: A large quan-
tity of pellets was made up as above described and
placed in sixteen silica crucibles. The crucibles were
then put into a large, specially constructed, auto-
matically controlled electric oven. The temperature
was carefully checked by means of a good pyrometer.
At the end of 24 hrs.' heating, two of the crucibles were
removed and the temperature was stepped up to the
next higher stage and maintained for 24 hrs., when the
next two crucibles were removed. This procedure
was continued to the end. As soon as the samples
were removed from the furnace, ammonia absorption
determinations were made, and the following results
were obtained:
Cecil Ultra Clay
Temperature, ° C 110 265 374 559 754 1130
Cc. NHs absorbed per cc.
colloid 110.3 100.8 80.0 74.1 57.5 2.2
Susquehanna Clay Soil
Temperature, ° C. 110 190 265 374 522 673 844 1130
Cc. NHi absorbed
per cc. sod 27.7 25.3 24.8 19.7 14.9 13.6 7.4 1.4
The assumption that the absorption of ammonia
by soils is due to the colloids they contain seems to
be borne out by the above results. There is evidence
of progressive destruction of colloids that is not con-
nected with the process of dehydration, as will be shown
later on. A careful microscopic examination of the
material heated to 1130° C. showed no evidence of
fusion even on sharp edges. There was some change of
color and a very decided shrinkage.
calculation of results — In the light of the above
results, the following calculations seem to be justified:
Susquehanna ultra clay, heated to 110°. absorbed 93.0 cc. NHa
Susquehanna clay soil, heated to 110°, absorbed 27.7 cc. NHj
Susquehanna clay soil, heated to 1130°, absorbed 1.4 cc. NHa
Deducting 1.4 cc. NH3 absorbed by material, pre-
sumably not colloidal, from 27.7 cc. absorbed by the
unaltered soil leaves 26.3 cc. absorbed by the colloid
of the soil. Therefore, if the pure colloid absorbs
93.0 cc. NH3 and there is sufficient colloid in the soil
June, 1921
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
529
to absorb 26.3 cc. NH3, the colloidal content of the
soil must be 28.3 per cent.
ABSORPTION OF DYESTUFFS
That filtration through soil clarifies water and removes
many colored bodies from it has been known for a
great many years. It seems very probable that soil
colloids play an important part in this phenomenon.
A large number of experiments were carried out with
colored inorganic and organic substances with the view
of testing the ability of soil colloids to absorb them.
It was found that ultra clay removed from true solu-
tion none of the inorganic substances tested, such as
salts of copper, cobalt, and nickel, but that it was highly
absorbent of organic dyestuffs. Many dyes were
tested, and while the ultra clay absorbed them in
large measure, in every instance except one some factor
developed that interfered with the quantitative esti-
mation along the line we wished to pursue, viz., the
placing of a weighed sample of ultra clay in water con-
taining an excess of dye, the coagulation and removal
of the colloid after a time, and the estimation of the
quantity of dye left in solution by comparison with a
standard dye solution. Usually a change of shade made
such a comparison impossible. In our experience,
malachite green oxalate proved to be best suited to
our method, thus confirming Ashley's experience in
his work on clays. Ashley found that lime decolorized
the malachite green by combining with the oxalate
radical and forming the insoluble calcium oxalate.
This is to be expected in view of the fact that the car-
bonate radical is apparently not able to combine with
the pentavalent nitrogen atom of the quinone-like
secondary benzene residue of the dye, resulting in the
loss of the quinoid structure upon which the color of
the dye depends. The writers attempted to remedy
this difficulty by adding an excess of oxalic acid, but
any appreciable excess of the acid over and above that
required to precipitate the calcium altered the shade
and diminished the intensity of the color. It was found,
however, that a considerable excess of sodium oxalate
had no effect upon the dye. After the difficulty with
the calcium had been overcome, variations in the size
of samples used with a constant initial amount of
dye showed that a distribution effect was playing a
part in determining the amount of dye absorbed, as the
following results indicate:
Susquehanna Clay Soil,
Wt. of Dye
Wt. of Sample Absorbed
Gram Gram
0.2 0.0076
0.4 0.0150
0.6 0.0234
0.8 0.0304
Cecil Ultra Clay
Wt. of Dye
Wt. of Sample Absorbed
Gram Gram
0.1 0.0106
0.2 0.0212
Susquehanna
Clay Soil
Cecil
Ultr
a Clay
Wt. of Sample
Gram
Wt. of Dye
Absorbed
Gram
Wt
, of Sample
Gram
Wt. of Dy<
Absorbed
Gram
0.2
0.4
0.6
0.8
0.0114
0.0168
0.0212
0.0250
0.1
0.2
0.3
0.4
0.0156
0.0200
0.0264
0.0312
All of the above samples had been heated for 72 hrs.
at 265° C. A second series run with Cecil ultra clay
heated at 110° gave similar results.
In the next series the weights of the samples taken
were the same as above, but instead of adding a constant
initial amount of dye, the amount added was such as
to leave an approximately constant quantity in solu-
tion after the sample had absorbed all it would under
the conditions. The following results were obtained:
The above determinations prove conclusively that
comparable results can bo obtained only when cer-
tain conditions of dye concentration are carefully
observed.
description of method — A gram sample is shaken
up with 40 cc. of distilled water in a large test tube.
A 0.1 JV sodium oxalate solution is then added until
there is a slight excess over the amount required to
precipitate the calcium. The tube is corked and
placed in an end-over-end shaking machine for 15
min. to insure complete precipitation. The suspen-
sion is next treated with a certain small excess of
0.2 per cent malachite green solution. The mixture is
made up to definite volume (70 cc.) with distilled
water, and the tube again placed in the shaking machine
for 1 hr. Five cc. of normal sodium chloride solution
are now added to flocculate the colloidal material,
and the tube is centrifuged in a large mechanical anal-
ysis machine until the supernatant liquid is perfectly
clear. This liquid is compared in a Duboscq colorim-
eter with a standard solution of dye to which have
been added all of the reagents contained in the other.
Two complete series of Susquehanna clay soil
samples were heated as previously described under
absorption of ammonia; in fact, the samples for this
work were heated in the same furnace and at the same
time with the clay pellets in order to be sure the con-
ditions were exactly the same. The dye absorption
determinations were then made as above described,
with the following results:
Susquehanna Clay Soil
(1 g. of soil, weighed after heating, was used in all determinations)
- Weight of Dye Absorbed . Average Loss of
Temp., ^First Series — . ^Second Series — . Average Wt. of Sample
o q_ /l 2 12 on Heating
110 0.0358 0.0360 0.0352 0.0358 0.0357 0.000
190 0.0344 0.0338 0.0344 0.0342 0.0342 0.003
265 0 0200 0.0200 0.0203 0.0197 0.0200 0.005
374 0.0194 0.0202 0.0204 0.0198 0.0200 0.010
522 0 0 ... 0.0194 0.0196 0.0195 0.055
673 0.0190 0.0185 0.0197 0.0197 0.0192 0.064
844 0 0 ... 0.0105 0.0111 0.0108 0.065
1130 0.0018 0.0015 0.0019 0.0019 0.0018 0.065
Calculation of amount of colloid in Susquehanna clay soil from data
obtained by dye absorption method:
Susquehanna ultra clay, heated to 110° C, absorbs 0.1196 g. dye
Susquehanna clay soil, heated to 110° C, absorbs 0.0357 g. dye
Susquehanna clay soil, heated to 1130° C, absorbs 0.0018 g. dye
Deducting the 0.0018 g. dye absorbed by material,
presumably not colloidal, from 0.0357 g. dye absorbed
by the unaltered soil leaves 0.0339 g. dye absorbed by
the colloid of the soil. Therefore, if the pure colloid
absorbs 0.1196 g. dye and there is sufficient colloid in
the soil to absorb 0.0339 g. dye, the colloidal content
of the soil must be 28.3 per cent. This is exactly the
same result as was obtained by the ammonia absorp-
tion method.
Calling the maximum absorption of ammonia and of
dyestuff 100, and expressing the other values as per-
centages of the maximum in each instance, we obtain
the accompanying graphs, showing the diminution in
the ability of the soil to absorb these substances as
the temperature is raised.
530
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13. No. 6
It will be observed that the ammonia absorption
graph slopes very uniformly, while in the dye absorp-
tion graph there is a very decided break at 190° and
1
I »
•9-
Fiat
i
I *
■^
*J<
Temperature
100
200 300 400 SOO 600 700 $00 900 1000 l/OO
*«5
^5
§
\
\
;:"
\
Fig. 1
%
\
,:.,.
t"l' Gn3&.
%
v>
hs
1
"s
^
■£
*'"
•J:
another at 673°. The loss in weight graph (in reality
a rough dehydration curve, there being present only
0.13 per cent of organic matter) shows no apparent
relationship to the other two. This indicates that it
is not the process of dehydration alone that causes the
diminution in ability to absorb ammonia and dye,
but that the heat actually alters the nature of the
absorbing material.
composite samples — The next point investigated
was to ascertain whether composite samples made by
mixing soil in which the colloid was completely de-
stroyed and the pure colloid in definite proportions
would actually absorb the quantity of dye calculated
on the basis of data obtained for the two components.
Susquehanna
Soil
Wt.
Cecil
Colloid
Wt.
Susquehanna
Colloid
Wt.
Absorpti
Obtained
Dn of Dye
Calculated
0.6614(1130°)
0.7271 (1130°)
0.8146(110°)
0.3385(110°)
0.2729(110°)
0.1859(110°)
0.0388
0.0304
0.0496
0.0370
0.0300
0.0513
The results indicate the correctness of the assump-
tion that the colloids of the soil are the only active ab-
sorbing components of the soil.
In order to gain still further evidence on this point,
samples of Susquehanna soil heated to 844° C,
which showed considerable absorptive power, and
samples of the same material heated to 1130° C,
which showed practically none, were ground to im-
palpable powders in the dry state and then ground for
a long while under water. The size of the samples
was the same, and the two were ground to exactly the
same extent. When grinding was completed, the
samples were shaken up with a large quantity of dis-
tilled water in tall cylinders. After 3 wks. of standing
undisturbed, the supernatant liquid of the sample
heated to 844° C. was quite cloudy and an ultra-
microscopic examination and other tests proved that
the material was truly colloidal, while the other sample
gave a perfectly clear supernatant liquid after 3 days'
standing. We failed absolutely to find any evidence
of colloidal material in this sample.
Briquets were next made of Susquehanna clay soil,
which had been previously heated to 844° and to
1130°, and the crushing strength tested and compared
with tests given by the original soil. The following
results were obtained:
Kilos Required
to Crush
Susquehanna clay soil (original) 234. 10
Susquehanna clay soil (S44°) 8.23
Susquehanna clay soil (1130°) 4.23
The results indicate the correctness of the statement
that ultra clay is the principal binding material of
soils. It is not a question of minute particles sticking
together, but of the actual presence of a powerful
binder, the nature of which is destroyed by the applica-
tion of heat. Pure quartz flour, in a much finer state
of subdivision than the soil, heated to 1130° gave a
test of 8 kilos, as compared to 17 kilos given by the un-
heated material. It is difficult to conceive how the
application of 1130° could change this material in any
direction other than the destruction of the small
amount of colloidal silicic acid it contains.
SUMMARY
1 — A method has been described for separating
large quantities of soil colloids from soil.
2 — The effect of heat upon pure soil colloids and upon
Susquehanna clay soil has been studied and dis-
cussed.
3 — Two methods for determining the quantity of
colloidal material in soil have been developed, one
based upon the absorption of a dry gas by a dry colloid,
and the other upon the absorption of dye from true solu-
tion by an aqueous suspension of the material. The
fact that methods so entirely different in nature give
the same results seems to justify confidence in them.
There still remains the possibility that the pure col-
loid we are able to separate from the soil does not
possess the same absorptive ability as the whole col-
loid of the soil. If the values found for the pure col-
loids separated from the soil are higher than for the
whole colloid of the soil, our methods give low results,
and vice versa. The possibility is remote, but the
point will be further investigated.
4 — The methods have been applied to one soil only.
The investigation must be extended to a number of
other soils before anything definite can be said of their
general utility. If success is met with, they will be
used in connection with the finding of means to con-
trol soil colloids, which have been shown to be the
natural binding material of the soil — a factor which
largely determines physical properties.
Dr. Chandler Receives National Institute of Social
Sciences Medal
Another honor came to Dr. Charles Frederick Chandler on
May 19, 1921, when he received the gold medal of the National
Institute of Social Sciences, for his service in the field of sanitation.
In his presentation address. Dr. M. T. Bogert characterized
Dr. Chandler as:
Nestor of American chemical industry and its foremost ex-
ponent whether in the lecture hall or the patent court, beneficent,
public-spirited citizen, for sixty-five years he has served humanity
with tireless energy and skilfully directed zeal, ever eager to find
new ways in which to make his life of greater usefulness to his
fellows.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
531
A Dry Method of Preparing Lead Arsenate1
By O. W. Brown, C. R. Voris and C. O. Henke
Labokatoky o» Physical Chemistry, Indiana University, Bloomington, Indiana
Lead arsenate is formed when a mixture containing
lead oxide and arsenious oxide is roasted.2 The
authors have investigated this reaction by roasting a
mixture of litharge and white arsenic in a rotatory
electric furnace described by Brown and Nees in an
earlier paper.3 In these experiments the porcelain jar
which contained the charge together with a number of
flint pebbles (used to keep the charge well stirred) was
rotated at a speed of about 20 r. p. m.
EXPERIMENTAL DETAILS
materials — Picher's sublimed litharge and chemi-
cally pure white arsenic were used in the different ex-
periments. The litharge contained a small amount of
carbonate, and the loss of the carbon dioxide caused
an apparent increase in arsenic during the process of
roasting. The relative amounts of the two substances
used were calculated from the equation
3PbO + As203 = Pb3(As03)2.
according to which the mixture would contain 22.81
per cent AS2O3 and 77.19 per cent PbO. In some ex-
periments a slight deficiency of arsenic was used
(21.76 per cent AS2O3), while in others it was used in
slight excess (23.37 per cent AS2O3). The desired
amounts of each material were weighed out and the
two intimately mixed.
procedure — When a charge was to be roasted the
furnace was previously heated to the desired tem-
perature, the jar set in motion, and the current of air
started. The charge was then put into the furnace,
and the door immediately closed. Immediately after
introducing the charge a loss of arsenic could be noticed
by odor and fume for a short time. The materials in
the jar formed a brittle slag-like substance, which at
first had a yellowish gray color. The lumps were soon
ground to a fine powder by the pebbles in the rotating
jar, and very soon the substance took on a white ap-
pearance. When proper proportions of the con-
stituents were used it became pure white. During the
roasting, samples were analyzed from time to time in
order to follow the stages of the process of oxidation.
When a sample was taken out, the door of the furnace,
was open for only a short period, and as a result the
continuous roasting was only slightly disturbed. The
samples were analyzed for arsenic pentoxide, arsenious
oxide, and water-soluble arsenic.
methods of analysis
total arsenic — The total amount of arsenic was
determined as arsenic pentoxide by the modified Gooch
and Browning method.4 A charge of 2 g. was dissolved
in 80 cc. of water and 15 cc. of concentrated nitric acid,
and diluted to 250 cc. Of this solution 100 cc. were
evaporated with 6 cc. of concentrated sulfuric acid till
fumes of sulfuric acid appeared, and then diluted in a
' Received January 12, 1921.
' Sprague, U. S. Patent 1,064,023; Luther and Volck, U. S. Patent
929,962.
• This Journal, 4 (1912), 867.
* Haywood and McDonnell, Bureau of Chemistry, Bulletin 131.
flask to 100 cc. A 25-cc. portion of this solution was
diluted to about 100 cc, 4 cc. of concentrated sulfuric
acid and 1 g. of potassium iodide were added, and the
resulting solution was boiled until the volume was
reduced to about 40 cc. The solution was cooled,
washed into a 500-cc. Erlenmeyer flask, diluted to
about 300 cc, and the free iodine exactly used up with
decinormal sodium thiosulfate solution. After being
made alkaline with sodium bicarbonate it was titrated
with standard iodine solution, using starch as indicator.
arsenious oxide — To determine the arsenious oxide,
a 2-g. sample was boiled with 50 cc. of dilute sulfuric
acid (1:5) for 1 hr., after which it was cooled and di-
luted in a flask to 250 cc. After filtering through a
dry filter, an excess of sodium bicarbonate was added
to a 25-cc. portion, which was then titrated with a
standard iodine solution, using starch indicator.
water-soluble arsenic — The water-soluble arsenic
was determined as arsenic pentoxide. A 1-g. sample
was digested at room temperature in 1000 cc. water for
10 days with frequent shaking each day. A 400-cc
portion of this solution was concentrated by boiling,
and, after the addition of sodium bicarbonate, was
titrated with standard iodine solution.
effect of time and temperature of roasting
The results of five experiments are tabulated in
Table I. In the first column is given the time after
the roasting was started, at which a sample was taken
from the furnace for analysis. The analyses of the
samples are given in the succeeding columns.
Table I
Expt.
E
A
C
D
B
Temp.
^300° a—
^350° C— -
^-400° C-*
^450° C.^
,-500 ° C^
Time
AS2O3 AsaOe
AsaOs AsaOs
AS2O3 As:Os
AssOa AS2OS
AsjOj AsjOs
0
21.76 0.00
21.76 0.00
21.76 0.00
21.76 0.00
21.76 0.00
5 Min
5.84 18.20
5.16 19.27
10 Min
!l7.'oS 4^50
li!83 ii.22
2.44 22.17
2.57 22.27
3i54 20^67
211 Miu
.15.96 6.38
2.03 22.63
2.44 22.42
1 Hr.
14.13 8.51
3i67 26]59
1.08 23.74
1.64 23.37
6!S2 23^83
2 Hrs.
1.39 23.34
0.95 23.90
0.81 24.31
0.27 24.46
3 Hrs.
l6'06 li!26
0.82 24.00
0.81 24.05
0.27 24.94
0.14 24.62
4 Hrs.
8.97 14.50
0.74 24.09
0.54 24.37
0.12 24.64
5 Hrs.
0.54 24.32
0.41 24.53
6 Hrs.
0.41 24.48
7 Hrs.
0.27 24.63
The results given in Table I are shown graphically
in Figs. 1 and 2. In Fig. 1 the time of roasting is
plotted against the per cent of arsenic pentoxide. The
curves show the rate of oxidation at the different
temperatures. The curves for 400° and 450° C. are
close together and have an abrupt ascent, the greater
portion of the oxidation occurring in the first 5 min.
The slope of the other two curves is more gradual,
which means a slower rate of oxidation. The differ-
ences in the rates of oxidation are much more marked
between the temperatures of 300°, 350°, and 400° than
between 400° and 450°. This is also brought out in
Fig. 2, in which the temperature is plotted against the
per cent of arsenic pentoxide for 10 min., 1 hr., and
3 hrs. Thus, in the curves for 10 min. and 1 hr. the
percentage of the pentoxide increases rapidly up to
400°, after which the increase, if any, is slight. In the
curve for 10 min. there is actually a decrease from 450°
532
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
to 500°. In every case above 300°, the rate of change
from arsenious oxide to arsenic pentoxide becomes
quite slow after the first hour.
The last amounts of arsenious oxide were very diffi-
cult to oxidize. Thus, at 400° one hour of roasting
decreased the arsenious oxide from 0.54 to 0.41 per cent,
while at 500° the last hour of roasting decreased the
arsenious oxide only 0.02 per cent, only a small amount
of oxidation taking place in both instances. This may-
be accounted for by assuming that the arsenious oxide
is covered with the pentoxide, which keeps the oxidizing
agent from coming in contact with the lower oxide.
LOSS OF ARSENIC
As was stated above, when a charge was put in the
furnace, a loss of arsenic was detected. This loss could
be noticed for a period of 1 to 3 or 4 min., and after a
brief period there was no appreciable loss. During
this period the lead oxide and the arsenious oxide pre-
sumably unite to form lead arsenite. A certain amount
of loss by volatilization occurs at first, but owing to the
short period in which it is noticeable, it probably oc-
curs only as long as the arsenious oxide and lead oxide
are in an uncombined stage, and probably ceases as
soon as they combine. This is also borne out by the
fact that at low temperatures the loss extends over a
longer period of time than at higher temperatures,
where we would expect the union of the two substances
to take place more rapidly. This is especially notice-
able when comparing temperatures of 350° and 500°.
At 500° the loss is much more rapid but lasts for only
a short time, as compared to the slower loss over a
longer period of time at 350°.
WATER-SOLUBLE ARSENIC
The results of the determination of water-soluble
arsenic in the lead arsenate are tabulated in Table II.
The first five samples contained an excess of lead oxide
over molecular proportions, while the last three con-
tained a slight excess of arsenic.
Table II
Percentage of
Experi-
Temper-
Time Roasted,
Water-Soluble
ature
Hrs.
Arsenic as AsiO«
H
300
3
BB
350
3
0.237
MM
350
4
400
3
0.159
LL
500
2
0.159
HH
350
5
GG
400
3.5
0.556
II
450
3
0.318
The table shows that the amount of water-soluble
arsenic varies with the time and temperature of roast-
ing, and also depends upon the relative proportions of
the substances taken at the start. The samples pro-
duced at a low temperature show a higher per cent of
soluble arsenic for the same period of roasting than
those made at a higher temperature. Samples MM,
KK, and LL each show practically the same amount of
soluble arsenic, but the time of roasting decreases as
the temperature increases. The same conditions seem
to govern the water-soluble arsenic in the last three
samples, where the arsenic is in slight excess. Here,
however, the amount is greater than where an excess of
lead oxide was used, which is as would be expected.
The highest percentage of water-soluble arsenic in these
samples is only about one-third the amount which Hay-
wood and McDonnell estimate will occur in the ma-
terials when made by the ordinary wet process.1
JOO 350 400 450 SOO
Temperature, °C.
POSSIBILITY OF CATALYTIC ACTION
Brown and Nees2 found that the best temperature
for roasting litharge to produce red lead was in the
neighborhood of 450° C. That is, the oxidation of
lead monoxide to the higher oxide was most easily
effected at about 450° C. In these experiments we
have found that the best temperature for oxidizing a
mixture of lead monoxide and arsenious oxide to lead
1 hoc. cit.
* Loc. cit.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
533
arsenate is about 450° C. The fact that these two
oxidations take place best at the same temperature
lead one to think that possibly the lead oxide has played
the role of a catalyst in this formation of lead arsenate;
that is, that the litharge is first oxidized to red lead,
which in turn oxidizes the arsenious oxide to the pent-
oxide, or the lead arsenite to lead arsenate. From this
it would follow that the temperature at which a catalyst
for oxidation would work best would be that tempera-
ture at which it is most easily oxidized to the higher
oxide. Then in selecting a catalyst for any particular
oxidation, that catalyst should work best which is
oxidized most easily at that temperature at which the
desired oxidation is most easily effected.
SUMMARY
1 — Lead arsenate is produced by roasting a mixture
of litharge and white arsenic at the proper temperature.
2 — The best temperature for roasting is about 450° C.
3 — The first part of the oxidation is very rapid, while
later it becomes very slow.
4 — The possibility of catalytic action has been
pointed out.
The Determination of Dicyanodiamide and of Urea in Fertilizers1
By Erling Johnson
Laboratory of A/S Northwestern Cyanamide Co.
DICYANODIAMIDE
In the course of work upon cyanamide about four
and a half years ago, it became necessary to find a more
rapid method for the determination of dicyanodiamide
in cyanamide and mixed fertilizers. At that time the
author and Mr. Berbom obtained the same dicyanodi-
amide-silver picrate complexes as have recently been
described by Harger.2 The results of this work are
published at this time as confirmatory and supple-
mentary to those of Harger.
For the purpose of rapidity, a volumetric determina-
tion is desirable. Such a determination of dicyano-
diamide in the mono-compound is practically impossible
on account of the large excess of silver salt necessary
in its preparation. Attention was therefore directed
to the double complex, silver picrate dicyanoguanidine,
C6H2(N02)30Ag.2C4H2N4. Under certain conditions
the di-compound is so insoluble, and its conversion
into the mono-compound according to the reaction
Odda, Norway
C6H2(N02)3OAg.2C4H2N4 + C6H2(N02)3OAg
= 2C6H2(N02)3OAg.C4H2N4
is so slow that the amount of standard silver solution
used can be made the basis of a volumetric method.
The conditions necessary involve dilute solutions, low
temperature, and a large excess of picric acid.
DESCRIPTION OF METHOD
reagents. Silver Nitrate — Stock solution (0.223
N), containing 18.96 g. AgN03 in 500 cc. From this
the standard solution is made by diluting 100 cc. to
500 cc. (0.0446 N).
Sodium Picrate — Solution made by neutralizing
7.5 g. picric acid with sodium carbonate and making
up to 100 cc. This solution must be used at about
40° C, because the salt crystallizes out at lower tem-
peratures.
Ammonium Thiocyanate — About 0.00446 N, stand-
ardized against the standard silver nitrate solution.
Ferric Sulfate — Five per cent solution acidified with
nitric acid.
Glacial Acetic Acid.
Nitric Acid — Twenty per cent.
procedure — For material containing from 5 to 15
per cent of dicyanodiamide nitrogen, a 5-g. sample is
1 Received January 17. 1921.
! This Journal, 12 (1920), 1107.
necessary. With a lower content a correspondingly
larger sample must be taken.
The weighed sample is placed in a 500-cc. bottle,
which is then filled with 450 cc. of water at 10° to
25° C. If the material is nitrolime or other lime-con-
taining substance, there is next added approximately
enough glacial acetic acid to dissolve the lime. (For 5 g.
of ordinary nitrolime 5 cc. of the acid are sufficient.)
By this treatment the nitrolime is hydrolyzed, and the
nitrogen compounds are dissolved more completely
and rapidly than if no acid is used. A slight excess of
acetic acid does no harm, whereas the stronger mineral
acids cause a change in the nitrogen compounds. Fur-
thermore, the acetic acid solution can be used for a
Kjeldahl determination of total water-soluble nitrogen.
This is not the case if nitric acid is used, as has been
suggested, to shorten the shaking time.
The bottle is now shaken on a machine for 3 hrs.,
then filled to the 500-cc. mark, and the contents filtered.
To a 100-cc. sample of the filtrate in a 200-cc. graduated
bottle are added 5 cc. of 20 per cent nitric acid and
20 cc. of sodium picrate solution. (These amounts are
sufficient so that there is present a slight excess of
nitric acid, while sufficient free picric acid is formed to>
saturate the solution when made up to the mark.)
The mixture is now cooled to about 5° C. by standing
in ice water, and the standard silver nitrate solution is
added drop by drop from a buret, with constant
shaking, until a slight excess (about 2 cc.) over what
is required for the dicyanodiamide assumed to be pres-
ent has been added.
It may be added that the reaction of dicyanodiamide
with greater excesses of silver nitrate and picric acid
offers a means of demonstrating the course of a time
reaction. The thick gel of the di-compound changes
over, more or less rapidly, depending upon the excess of
silver and the concentration, into the small charac-
teristic crystals of the mono-derivative.
The double compound comes down as a gel, more or
less thick, depending upon the amount of dicyanodi-
amide present. After shaking vigorously, the mixture
is left at 5° C. for 15 min., shaken two or three times
to make the precipitation of the dicyanodiamide as
complete as possible, made up to the mark with cold
water, and filtered.
To 100 cc. of the filtrate are added 5 cc. of nitric
534
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
acid and 2 cc. ferric sulfate solution, and the excess
silver is titrated with the thiocyanate solution.
calculation of eesults — For a 5-g. sample the
silver solution is of such strength that 1 cc. = 1 per
cent of nitrogen as dicyanodiamide. This is indicated
by the following calculation:
5 g. sample.
AgNOj solution = x cc.
For formula CeHjCNOjhOAg^CuH^Nt, 8 N require 1 Ag, or 22,400 cc.
112 X 100 I
%
22,400 X
For satisfactory results certain corrections are neces-
sary. These every analyst should work out for him-
self, since the personal factor plays an important part.
In the hands of a competent analyst, however, the
method gives a rapid method of determining the ap-
proximate amount of dicyanodiamide.
The following data show the corrections found neces-
sary at 7° C. and applied by the author.
excess of silver nitrate — Inasmuch as the di-
compound goes over into the mono-compound with
excess of silver, the excess of silver nitrate solution used
may be expected to affect the results. That this is so
is indicated by the data of Table I and Fig. 1. In this
case pure dicyanodiamide is used, with 1 cc. 20 per cent
nitric acid added.
Table I — Excess Silver Nitrate
Dicyanodiamide Nitrogen Found .
Excess — . . — 6 Cc. Excess — .
Dicyanodiamide
Nitrogen
Present
G. Per cent
0.05 S
0.10 10
0.15 15
-2 Cc. Excess^
AgNOj AgNOj AgNOj
Percentage Percentage Percentage
of N of N of N
Per cent Present Per cent Present Per cent Present
4.90 98 5.15 103 5.40 108
9.95 99.5 10.00 100 10.15 101.5
14.50 97 14.65 97.5 14.80 98.7
Per Cent of Dicyanodiamide Nitrogen Present
Fie. 1 — Influence of Excess Silver Solution on Titration of
Dicyanodiamide
nitric acid — Table II and Fig. 2 show the influence
of increasing additions of nitric acid.
Table II — Nitric Acid
Dicyanodiamide ' Dicyanodiamide Nitrogen Found .
Nitrogen . 1 cc. HNOj . . 10 cc. HNOi
Present Percentage Percentage
Gram Per cent Per cent of N Present Per cent of N Present
0.05 5 4.90 98 4.5 90
0.10 10 9.95 99.5 9.5 95
0.15 15 14.50 97 14.3 95.5
nitric acid and acetic acid — Table III and Fig. 3
show the effect of varying amounts of nitric acid and
of calcium acetate, which will be present when acetic
acid has been used in the preparation of the sample.
The curves and the effect of the varying amounts upon
the precipitation of the dicyanodiamide offer many
points for discussion which must be omitted at present.
IV8
IS"
i
Ice HNOj
i
/
>
/
Sc\
UNO,
— x —
1
I2cc
AqNO, solution in excess)
/Occ.HNO. /
5
i
3
«
Per Cent Dicuanodiamide Nitrogen Present
Fio. 2 — Influence of Varying Amounts of Nitric Acid
Table III — Nitric Acid and Calcium Acetate
Dicyano-
diamide
Nitrogen
Present
-Dicyanodiamide Nitrogen Found—
1 Cc HNOi 1 Cc HNOj 1 Cc HNOj 5 Cc HNOi IOCc.HNOi
-HG.CaAc -fSG.CaAc +lG.CaAc -fSG.CaAc
Per- Per- Per- Per- Per-
centage centage centage centage centage
Per Per of N Per of N Per of N Per of N Per of N
G. cent cent Present cent Present cent Present cent Present cent Present
0.05 5 4.90 98 4.5 90 4.0 80 5.10 102 4.20 84
0.10 10 9.95 9.95 9.8 98 8.9 99 9.98 99.8 9.50 95
0.15 15 14.50 97 14.8 98.7 14.20 94.7 14.65 97.5 14.40 96
temperature — Table IV and Fig. 4 show the in-
fluence of the temperature.
Table IV — Temperature
Dicyano-
Die
diamide
— 5°C. .^
Nitrogen
Per-
Present
centage
Per
of N
Gram cent
Gra
m Present G
Dicyanodiamide Nitrogen Found-
10 0.0996 99.6 0.098
Per- Per- Per-
centage centage centage
of N of N of N
Present Gram Present Gram Present
0.0964 96.4 0.0850 85.0
It is obvious from the above results that good approxi-
mate results, without corrections, are obtained with
nitrolime when 5 cc. of 20 per cent nitric acid per 1 g.
calcium acetate and about 2 cc. excess silver nitrate
are employed.
The new method has been tested in the presence of
urea and of dicyanodiamidine, neither of which affects
the results. When chlorides or soluble sulfides are
present, a blank test must be run by titrating the silver
solution without the addition of picric acid.
The analyses in Table V show the reliability of the
new dicyanodiamide method as applied to samples of
cyanamide.
Iq. Cot
5c<
CI
HNOj
X
A
HN0%
"-X
i
.-.*-
•X
!"'
Iq.Ca
IccHN
Sq.Cah
let/
x^
I
9
"/
X
S^
/
V
£ 02
/
6
C
'a Ac*
5cc.HH
o,
(2cc.i
xcess
4a NO,
used a
lallcc
sesL
80
r
• H
'aAc* Ice. HNOj
L_
c
0
li
Per Cent of Dicyanodiamide Nitrogen Present
Fig. 3 — Influence of Addition of Different Amounts of Nitric
Acid and Calcium Acetate
June, 1921 TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
535
aiOg.Dxyano
di amide '
Npment-
5 10 15 20 2S
Temperature °C
Fig. 4 — Effect of Temperaturb
Table V
Dicvanodiamide
Nitrogen
Sample
Analyst
Per cent
la
E.J.
2.86
16
D.
2.74
2a
E.J.
2.99
2d
D.
2.82
3a
E.J.
2.70
si-
M. D.
2.50
Some samples of old
cyanamide gave the analytical
results recorded in Table VI.
Table VI — Comparison op Old and New Method
Di-
Di-
Cyana- cyanodi- Urea Water-sol-
Cyana- cyanodi- Urea
Sam- mide Ni- amide Ni- Ni-
uble Ni-
nide Ni- amide Ni- Ni-
ple trogen trogen trogen
trogen
trogen trogen trogen
Total
I.... 1.11 10.67 1.14
12.92
1.11 10.62 1.21
12.94
II... 0.86 10.16 1.96
12.98
0.86 9.94 1.89
12.69
III.. 0.86 10.31 1.27
12.44
0.86 10.22 1.29
12.37
IV... 0.77 10.49 1.59
12.85
0.77 10.51 1.62
12.90
V.... 1.12 10.44 0.96
12.52
1.12 10.46 1.00
12.58
VI... 13.25 1.76 0.45
15.46
13.25 1.8 0.4
15.45
Av. 2.995 S.97 1.23
13.20
2.995 8.93 1.24
13.16
1 A modified Caro method.
2 Sum of cyanamide. dicvanodiamide,
and urea nitrogen.
OTHER DICYANODIAMIDE-SILVER COMPLEXES
Further research showed at once that the formation
of these complexes is not limited to picric acid. The
reaction is typical for all aromatic water-soluble nitro-
phenol compounds. Further investigation will show
whether other groups than the nitro will give the hy-
droxyl groups of phenol and naphthol the property of
reacting with silver salts and dicyanodiamide. It is
to be expected that all benzene and naphthalene deriv-
atives containing phenolic hydroxyl groups, which give
definite silver salts, will give mono- and di-compounds
with dicyanodiamide. Compounds such as trinitro-
benzoic acid do not give the reaction. Nitrohydroxy-
benzoic acids, however, should give it.
The following new compounds have been prepared:
Silver dinitrophenol monocyanoguanidine
Silver dinitrophenol dicyanoguanidine
Silver trinitrodiphenol monocyanoguanidine
Silver trinitrodiphenol dicyanoguanidine
Silver trinitrocresol monocyanoguanidine
Silver trinitrocresol dicyanoguanidine
Of these, the trinitroresorcinol (styphnic acid) seems
to give a more quantitative precipitation and better
results than picric acid.
DETERMINATION OF UREA IN FERTILIZERS
A new standard method for the determination of
urea in fertilizers and fertilizer mixtures depends on
the well-known fact that urea gives a characteristic,
difficultly soluble salt with oxalic acid. By selecting
the right conditions the solubility can be made so slight
that a quantitative determination can be made.
method — From 2 to 5 g. of the urea-containing sam-
ple are dried and shaken out with 100 cc. of amyl al-
cohol. From 25 to 50 cc. of the filtrate are mixed with
the same volume of ether, and the urea is precipitated
as oxalate with 25 cc. of a 10 per cent solution of an-
hydrous oxalic acid in amyl alcohol. After completing
the precipitation by stirring and standing in cold water
for half an hour, the mixture is filtered through a
Gooch crucible, and washed by filling one time totally
and one time half with mixture of half amyl alcohol
and half ether, then in the same way with ether alone.
The precipitate is dried in a vacuum desiccator and
weighed. According to the formula (COOH)2.2CO-
(NH2)2, it contains 26.67 per cent nitrogen and 57.01
per cent urea.
<S 95
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 09
Urea Found-Grams
10 1.1 1.7 1.3
Fig. 5 — Correction Curve for Determination of Urea as Oxalate
Fig. 5 shows the necessary corrections with regard
to solubility.
In some cases when urea is present as a salt or in
complexes such as Ca(N03)34CO(NH2)2, the urea does
not go into solution without calcium with amyl alco-
hol, but must first be set free. It is of importance
that sample and reagents be as nearly anhydrous as
possible.
The National Fertilizer Association
The Twenty-eighth Annual Convention of the National
Fertilizer Association, which will be held at White Sulphur
Springs, W. Va., the week beginning June 20, 1921, will have a
program of reconstruction and cooperation.
The program will include addresses and discussions on sub-
jects of vital interest to the fertilizer manufacturer, in view of
present business conditions. These subjects will include costs
and cost accounting systems, chemical and manufacturing
problems, sales methods, labor and transportation problems,
etc.
During the same week the Southern Fertilizer Association
will hold its summer meeting; the Soil Improvement Com-
mittee of the National Fertilizer Association will hold a
subscribers' and committee meeting ; and the Soil Improvement
Committee of the Southern Fertilizer Association will hold a
committee meeting.
536 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
Yield and Composition of Wormwood Oil from Plants at Various Stages of
Growth during Successive Seasons1
By Frank Rabak
Omcs or Drug, Poisonous and On. Plant Investigations, Bureau of Plant Industry, Washington, D. C.
The plant Artemisia absinthium L., commonly tation, average mean temperature, clear, partly cloudy,
known as wormwood, which is found growing wild in and cloudy days. The figures given represent the con-
European countries and cultivated in several localities ditions during the growing months of April, May,
in the United States, principally in Wisconsin, Michi- June, and July, before harvest and distillation.
gan, and New York, yields upon distillation a volatile table "-comparison o» yields o^oil wirac™*™ cond.t.ons
oil of considerable importance. For the production of Average ,— Weather conditions— *
... , , . . a • , _, • j- Yield Precipita- Mean Partly
the Oil Of commerce the whole flowering plant IS CllS- of ou tion Temperature Clear Cloudy Cloudy
tilled in the fresh condition. The oil is described as a ^ . . . .^oT/ ifos °lfT °7s "T "S*
brownish green liquid with a strongly aromatic, un- 1908:"::"":; 0\18 12.72 67!? 42 57 23
pleasant odor and bitter taste, the principal constitu- 1910!;;;;;;;;;; (K20 1^47 67lo 59 37 26
r .... ., . , , .. ,x .v ■ 1 „i„„t,_t 1911 0.21 10.04 68.2 54 35 28
ents of which are thujone (absynthol), thujyl alcohol, 1912 0 17 i8 82 66.7 57 23 42
esters of thujyl alcohol, phellandrene, pinene, and }^;;;;;; ; ; ; l\\ \l\% f7j II 1? 33
cadinene. The oil is used principally as a medicament JQJg °15 }|-g» £7.o 35 48 39
for both internal and external application. isit::" ... 0.1s 17.31 66.0 36 sj 32
DISTILLATION OF PLANTS l^V::.\\\\\V. O.U 17^ 67^ 38 34 50
The following observations were made with worm- lt will be noted that the hiShest >'ield of oil in most
wood under cultivation at the Arlington Experi- c*ses **s during those seasons in which the precipita-
mental Farm, Arlington, Virginia, for a period of years. tion was lowest this being especially true of the years
During that time the plant was distilled both in the 1908, 1911, and 1914. It is also significant that the
fresh flowering and in the dry condition, and also at highest mean temperature prevailed during these
different stages of growth. A number of the oils ob- seasons. Some relationship also apparently exists
tained were subsequently examined in the laboratory between the clear, partly cloudy, and cloudy days and
and compared from the standpoint of their physical the yield of oil. The greater the number of clear and
and chemical properties Partly cloudy days' the greater was the tendency of the
As the volatile oil is contained in both the flowers and Plants to high yields of oil. High precipitation and
leaves, the whole plant was distilled in every instance, low temperature, together with much cloudy weather,
Distillations were made of both fresh and dry plants a* « 1915, 1916, 1917 and 1918 apparently tended
in order to ascertain the effect on yield and quality toward low content of oil. Such a combination of
of the oil. Since the oil is distilled commercially during conditions would be conducive to high moisture content
the flowering stage of the plant, this stage was selected *» the plants, thereby increasing the weight of the plant
in making the following comparisons as regards yield and lowering the yield of oil. Under the same condi-
of oil. The conditions of distillation in every instance t.ons it also appears that stimulation of the plant with
were identical, the same distilling apparatus and like reSard to the formation of the volatile oil is likewise
steam pressure being employed each year. The re- retarded. .......
suits of the experiments are embodied in Table I. In general, * maybe stated that the yield of oil from
wormwood is dependent upon the particular combma-
Table i— yield^ ™°™™°g°v°£*%™cl**l" year's""' Flowkring tion of climatic conditions existing during each grow-
(Aii yields of oil calculated on basis of fresh herb) jng season, and will vary from year to year in propor-
1907 1908 1909 1910 1911 1912 1913 1914 1915 1916 1917 1918 1919 Av. tion to the varying conditions of precipitation, tem-
o 120 is o.i3 0.20 05.1 0.17 oFrifoH24 o.io .. o.i5 o.u o.i6 0.166 Perature, and sunshine.
_ Herh effect OF drying — Discussing further the results
0.09 .. o.u .. 0.050.16 .. .. 0.08 0.098 in Table I, it is apparent that drying of the plants
r^LiTL it. i. iu ■ u c -1 c before distillation invariably results in a loss of volatile
A study of Table I shows that the yields of oil from .. ,. . , J . ., ,
. * , ,._ ., ,, r oil, causing, thereby, a decrease in the percentage of
the fresh herb differ considerably from year to year. ., „, ..,,..,. , *\ . .
. . . , . . , . . . . .. , oil. The average yield of oil from fresh flowering
This observation is of material interest since the plants . .. ,„„., . inin • , -
, , . .. , , . , , herb during the seasons 1907 to 1919, inclusive, was
were cultivated during the whole period of years on & ' '
, .. ... ... ., 0.166 per cent, while the yield of oil from dry herb was
the same heavy clay soil with approximately the same n nno ' ™ . , , , ., , ' .. .
„. J „ ,.j. .. ,, ... 0.098 per cent. The average yield of oil from the dry
fertility. Since all conditions were practically alike, ...... . . ' . . ,
* ,,,.,... ■ ., • ,j r -i herb is, therefore, approximately 41 per cent lower
it may be concluded that the variable yields of oil were , , ' . . . ' ff c . , .
' . , ,. .... than the yield from the fresh herb.
due entirely to climatic conditions.
EFFECT OF CLIMATIC CONDITIONS— For the purpose Of PHYSICAL AND CHEMICAL EXAMINATION OF OILS FROM
correlating the yields of oil from the fresh flowering FRESH AND DRY flowering herb
herb with the climatic conditions which prevailed during In order to study further the effect of seasonal
the several seasons, Table II was prepared. The par- changes and drying on the plants, determinations were
ticular conditions taken into account were the precipi- made of the physical properties of the oils and also the
i r ved February 21 1921 percentage of free acids calculated as acetic acid, esters
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
537
Table III — Physical Properties, Acid, Ester
Physical Properties,
Acid, Ester and 1906
Alcohol Content Fresh
Color Dark brown
Odor Very strongly ara
' Flowering Herb during Several
Specific gravity
Solubility in
alcohol
Bitter, pungent
0.9251
3 vols. 90 per cent
ale. with clear
Free acids as acetic
(per cent)
Esters as thujyl
acetate (per cent)
Alcohols as thujyl
alcohol (per cent)
i At 25° C. »
Dry
Nearly black
190S
Fresh
Dark brown
Strong, penetra- Fatty, strongly Strongly character-
ting, aromatic aromatic, dis- istic but not dis-
agreeable agreeable
Bitter, pungent Aromatic, slight- Bitter, pungent,
ly bitter aromatic
0.935" 0.93082
I per cent 1 vol. 90 per cent
nth clear ale. with clear
sol. Turbid with
10 vols.
0.91691
1 vol. SO per cent 1 vol.
ale. with cle
it
0
Fresh
Dark brown wi
green tint
Strong, unplea
ant, aromatic
Dry
th Dark brownish
black
Very bitter,
0.9274
1.2 vols
with
cohol
Very strong un-
pleasant, aro-
Very bitter, aro-
matic
0.92643
SO per 1.2 vols. 80 per
cent ale. Clear
al-
with
cohol
0.14
24.1
19.3
0.21
27.3
21.5
Dark brownish green
Characteristic, aro-
matic, not un-
pleasant
Bitter, aromatic,
very pungent
0'. 94202
0.5 vol. 80 per cent
ale. Clear with
more alcohol
0.25
33.2
13.8
Table IV — Yield, Physical Properties, Acid, Ester, and Alcohol Content i
Yield
Wormwood Oil from Fresh Herb at Various Stages op Growth
Year
1908
Material
Budding
Flowering
Fruiting
Budding
Flowering
Fruiting
i At 22° C.
Oil
Per cent Color, Odor, and Taste
0.17 Dark brown; strongly aromatic, disagreeable odor; pungent
0.1S
0.10
0.14
0.20
0.08
* At 24
aromatic taste
Dark brown ; strongly aromatic, not unpleasant odor; bitter
pungent aromatic taste
Dark brown ; rather pleasant characteristic odor, extremely
bitter, slightly pungent taste
Dark greenish brown; strong aromatic not unpleasant odor;
bitter aromatic and strong pungent taste
Specific
Gravity
0.92731
0.930S1
0.949'
0.9594'
0.9420'
Solubility
10 vols. 90 per cent ale. with
turbidity
1 vol. 90 per cent ale. with
clear solution. Turbid
Free Esters as
Acid as Thujyl :
Acetic Acetate
Alcohol Per cent Per cent
26.0
ith
ale.
0.5 vol. 90 per cent ale. with . .
clear solution. Turbid in
4 vols.
1 vol. 80 per cent ale. with 0.30
clear sol. Clear with more
ith 0.26
0.9410' 0.5 vol.
32.5
Alcohols
ls Thujyl
Alcohol
Per cent
14.7
11.7
12.0
16.8
13.8
13.18
of thujyl alcohol as thujyl acetate, and alcohols as
thujyl alcohol, in the oils. The results of these de-
terminations are shown in Table III.
No material differences are observed in the color,
odor, and taste of the oils distilled from the fresh herb
during the five successive seasons beginning in 1906.
The colors range from a dark brown to a dark brownish
green, and the odors differ principally in their intensity.
The specific gravity and the solubility of the oils show
appreciable differences, indicating differences in com-
position.
The percentage of free acids in the oils from the fresh
herb varies considerably. The contents of esters as
thujyl acetate are in close conformity, with the ex-
ception of the oil from the 1909 crop, which shows a
decided decrease in these constituents. The greatest
differences in the constituents appear to be in the
thujyl alcohol content, which ranges from 11.6 to 19.3
per cent. High ester content in the oils appears to be
accompanied by correspondingly low alcohol content,
and vice versa.
The oils distilled from the dry plants are uniformly
darker in color and stronger in odor than those distilled
from the fresh plants; and the thujyl acetate content
is higher than that of the fresh herb in both 1907 and
1909, while the thujyl alcohol content, on the other
hand, is higher only in the oil from the 1909 crop.
Observations on a larger number of oils from dry
plants would probably show that these oils differ no-
ticeably from the oils from the fresh plants, as shown by
the marked divergence of the 1909 oil.
During the seasons of 1908 and 1910, the whole, fresh
wormwood plants were distilled at three stages of
growth, namely, budding, flowering, and fruiting, in
order to study the resultant oils as they occurred in
the plant at these distinct stages of maturity. The
yields of oil and the physical and chemical properties
are tabulated for comparison in Table IV.
It will be observed from Table IV that the maximum
yield of oil is attained in the plant during its flowering
period. A decided decrease in oil content is noted
during both seasons in its fruiting stage, being con-
siderably lower in yield at this time of growth than in
either the budding or flowering stages.
Only minor differences are evident in the color, odor,
and taste of the oils, and no definite relationships seem
to exist in their specific gravities. A uniform increase,
however, in solubility of the oils from the plants during
both seasons is noted, especially in 1908. It will be
seen, however, that the oil from the budding stage of
plants in 1910 is much more soluble in alcohol than that
from the same stage of growth in 1908. Increase in
solubility of the oils appears to be accompanied by a
high percentage of esters, since the content of thujyl
acetate is greatest in the oils most soluble in alcohol.
It may also be pointed out that a high percentage of
thujyl acetate in any of the oils is invariably accom-
panied by high specific gravity, and vice versa. The
content of free acids (as acetic) in the oils from the 1910
crop diminishes as the plants mature.
The relationship between the alcohol content and the
solubility and specific gravity is not so marked. There
is, however, a decrease in the percentage of thujyl
alcohol during both seasons as the plants pass from the
budding to the fruiting stage.
538
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
CONCLUSIONS
1 — The yield of oil from the fresh herb during its
flowering stage varies greatly from year to year,
owing entirely to varying climatic conditions. Low
precipitation, coupled with high temperature and much
sunshine, affects the yield of oil favorably, while
converse conditions cause a lower yield.
2 — Drying of the plants before distillation invariably
causes a reduction in the yield of oil, but apparently
promotes esterification in the oils. The ester constit-
uents of the oils from the fresh herb over a period of
years appear to be in closer conformity than the al-
coholic constituents.
3 — The highest yield of oil is obtained during the
flowering period of the plants. Solubility of the oil in
alcohol apparently is a criterion of the percentage of
esters present. Likewise, specific gravity bears a close
relationship to the ester content of the oils. The
alcoholic constituents decrease as the plant approaches
maturity.
Studies in Synthetic Drug Analysis. VIII— Estimation of Salicylates
and Phenol1
By W. O. Emery
Synthetic Products Laboratory, Bureau op Chemistry, Washington, D. C.
The estimation of salicylates in general, and of salol,
phenol, salicylic acid, aspirin, etc., in particular, are
constantly recurring problems, the satisfactory solu-
tion of which depends in large measure upon the nature
of the preparations in which such medicaments occur,
whether alone or in simple admixture with inert ma-
terials susceptible of easy separation, or again in more
complicated mixtures containing, besides vehicular
matter, combinations of several therapeutic agents.
In a former paper,2 one of the two procedures outlined
involved the alkaline hydrolysis of salol preliminary
to its separation from phenacetin by the aid of im-
miscible solvents, the subsequent steps constituting in
principle, in so far as they related to salol, the well-
known Koppeschaar method. While a similar or
slightly modified procedure can undoubtedly be ap-
plied also to mixtures in which the phenacetin is re-
placed in whole or part by acetanilide, it not in-
frequently happens that knowledge of the salol con-
tent appears desirable without the necessity of first
eliminating the accompanying medicaments, particu-
larly in preparations which involve not only acet-
anilide but phenacetin and caffeine as well. With this
object in view, and in the belief also that most cases of
drug analysis are facilitated in proportion to the num-
ber and accuracy of alternative methods available for
the solution of any given problem, advantage has been
taken of the characteristic behavior of salol, or rather
its constituent elements, phenol and salicylic acid,
toward iodine. The final product of such action in
the presence of alkali or alkaline carbonates is a pur-
plish red amorphous compound3 having the composition
C6H2l20, and variously termed diiodophenylene oxide,
tetraiodophenylene oxide, and tetraiodophenylene qui-
none, the derivation of which may be represented in the
following manner:
1 Received February 11, 1921.
2 Emery, Spencer and LeFebvre, "Estimation of Phenacetin and Salol
in Admixture," This Journal, 7 (1915), 681.
" The formation of this substance, first reported by Lautemaun, Ann.,
120 (1861), 309, and later corroborated by Kekute, Ibid., 131 (1864), 221,
was observed in studying the iodine substitution products of salicylic acid.
The same compound was more fully described by Kammerer and Benzinger,
Ber., 11 (1878), 557, who operated with iodized potassium iodide on phenol
in hot aqueous soda. Bougault, J. pharm. chim., [6] 28, 147, was apparently
the first to suggest its use in a gravimetric way, employing it successfully in
estimating salicylic acid admixed with either benzoic or cinnamic acid.
2CeH6OH + 6I2 + 4Na2C03 =
2C6H2I20 + 8NaI + 4C02 4- 4H20
2C6H,(OH)C02H + 6I2 + 4Na2C03 =
2C6H2I20 + 8NaI + 6C02 + 4H20
from which it appears that every molecule of salol is
capable of yielding two molecules of the iodine deriv-
ative, expressed in its simplest form. Irrespective of
the chemical constitution — whether an oxide or quinone
in character — the physical properties are such as to
warrant its analytical application not only in cases
involving salol, but also as a check on the various
methods hitherto employed to determine salicylic acid
and phenol.
EXPERIMENTAL
The tabulated data are representative of several
hundred determinations carried out on both control
and commercial mixtures. The individual products
required for these controls were checked as to purity,
being selected from both domestic and foreign brands.
In general, the treatment consisted, in the case of pills
and compressed tablets, in triturating with or without
sand, exhausting the finely powdered sample with chlo-
roform, then, after dissipation of the solvent, hydro-
lyzing the residue (in the case of salol) with aqueous
sodium hydroxide, heating with iodine in the presence
of sodium carbonate, and finally filtering, drying, and
weighing the precipitate.
Results Obtained on Controls
Salol
Acetanilide
Phenacetii
i Caffeine
CbHjIsO
Salol
0. Gram
Gram
Gram
Gram
Gram
Per cent
0.10 "R"
0 3209
99.9
0.10 "M"
ii :-;.'iil
99.6
! 0.10 "C"
0.3211
100.0
0.10 "C"
o!io
0.3203
99.7
> 0.10 "C"
0.20
0.3204
99.7
0.10 "C"
0.50
0.3220
100.2
0.10 "C"
0.10
0
10
0 3220
100.2
! 0.10 "C"
0.10
0
30
0.3217
100.1
) 0.10"C"
0.20
0
20
0.3207
99.8
) 0.10 "C"
0.25
0
20
o!o5
0.3214
100.1
0.10"C"
0.25
0
20
0.10
0.3215
100.1
» 0.10 "C"
0
10
0.3216
100.1
i 0.10-C"
0
30
0.3219
100.2
1 0.10-C"
0
50
0.3225
100.3
Phenol cryst.
> 0.10 "K"
0.3627
99.1
i 0.10"M"
0.3648
99.8
Salicylic acid
0.10 "K"
0.2471
99.2
> 0.10"Mt"
0.2474
99.3
0.10 "Mk"
0.2464
98.9
Acetylsalicylic
acid
) 0.10 "D"
0.1897
99.3
0.10 "B"
0.1894
99.2
0.10 "H"
0.1899
99.4
0.10-E"
0.1905
99.9
Sodium salicylate
1 0.10 "Mk"
0.2115
98.4
> 0.10 "K"
0.2136
99.4
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING 6HEMISTRY
539
Results Obtained on Commercial, Samples
Tablets
Declared
Grains
Found
Grains
Salol
Salol
Salol
2.5
5.0
2.5
2.46
4.82
2.49
Salol
Acetanilide
2.5
2.5
2.49
Salol
Acetanilide
2.5
2.5
2.47
Salol
Phenacetin
2.5
2.5
2.51
Salol
Phenacetin
2.5
2.5
2.02
Salol
Acetanilide
Phenacetin
Caff. citr.
Acid tartar.
Sodium bicarb.
0.5
1.25
1.0
0.5
0.25
1.5
0.51
Salicylic acid
Sodium salicylate
Sodium salicylate
Sodium salicylate
Strontium salicylate
5.0
3.0
5.0
5.0
5.0
4.94
2.98
4.96
5.01
4.99
Acetanilide
Caffeine
iey.ate
2.5
2.5
0.5
2.49
Ammonium salicylate
Caffeine
Salicin
Phenacetin
3.0
0.5
1.5
1.0
2.97
Acetyl salicylic
Acetyl salicylic
Acetyl salicylic
Acetyl salicylic
Acetyl salicylic
acid
acid
acid
acid
acid
METHOD
5.0
5.0
5.0
5.0
5.0
4.95
4.97
3.92
4.80
4.90
On a small (5.5 cm.) tared filter, carefully fitted
while moist and subsequently dried in a suitable funnel,
weigh out an amount of the uniformly triturated ma-
terial equivalent to or containing about 100 mg. of
salol, as calculated from the alleged content. Wash
with successive small portions of chloroform, in quan-
tity from 25 to 30 cc. — sufficient at least to insure
complete extraction of all therapeutic agents present
and soluble in this medium — receiving the solution in
a 300-cc. Erlenmeyer, and evaporating the solvent at
the ordinary temperature by means of an air blast to
apparent dryness. Add 10 cc. of a 1 per cent solution
of sodium hydroxide, connect with a vertical reflux
over a wire gauze, and apply gentle heat so that the
contents of flask begin to boil in about 2 min. Now
add more water in 10-, 30- and 50-cc. portions, so ad-
justing the heat that the liquid reaches the boiling
temperature at the end of about 3-, 5- and 10-min.
intervals, respectively. Just prior to the addition of
the 50-cc. portion, introduce into the top of condenser
1 g. of dry sodium carbonate, washing it down with
the water. To the absolutely clear boiling solution add,
in the case of salol and acetanilide mixtures, 55 to
60 cc. of approximately 0.2 N iodine (iodized potassium
iodide), sufficient at least to insure an excess of this
reagent, then heat to boiling, disconnecting the flask
at this juncture, and washing off the lower end of con-
denser into the flask below. Add another gram of
dry sodium carbonate, and boil very gently for a period
of 15 to 20 min., being careful to gage the heat so that
the liquid, and with it the precipitate, does not froth
over the rim of container and thus jeopardize the de-
termination. Any undue tendency in this direction
may be largely obviated by the addition of a few drops
of water from time to time, or, better, by the timely and
vigorous rotation of the flask, thus greatly facilitating
the expulsion of carbonic acid gas liberated in the final
phase of the reaction. In the case of salol and phen-
acetin, or of salol, acetanilide, and phenacetin mixtures,
the quantity of iodine solution added should be in-
creased over that above specified by 5 cc. for every
100 mg. phenacetin known or believed to be present
in the sample taken for analysis. Allow the precipitate
to settle, then decant the supernatant liquid on to a
Gooch crucible, add hot water to the flask, mix
thoroughly, and gradually transfer the entire pre-
cipitate quantitatively to the filter, washing with not
less than 200 cc. of hot water. Dry in an air bath
at 100° to constant weight; finally, multiply the weight
of the precipitate obtained by 0.3113. This product
gives the quantity of salol in the aliquot taken.
COMMENTS AND SUGGESTIONS
With salol and acetanilide mixtures, the filtrate from
the diiodophenylene oxide should be nearly or quite
colorless, while with phenacetin present light to deep
amber-colored solutions will result, thus rendering it
not altogether easy to recognize the point which in-
dicates that an excess of iodine has been added. The
second gram of sodium carbonate is added partly to
effect the final elimination of such excess iodine, partly
also to facilitate the complete conversion of all iodine
substitution products of phenol and salicylic acid into
the completely insoluble diiodophenylene oxide. In
the absence of phenol, this method may be carried
out in an Erlenmeyer flask without a reflux condenser.
The Belgian Bureau of Chemical Standards
At the last meeting of the International Union of Pure and
Applied Chemistry, held in Rome in July 1920, the Belgian
delegates reported on a plan to establish a collection of samples of
pure chemicals at the University of Brussels. The Union there-
upon decided to establish such a Bureau, leaving the details of its
development to Belgium.
Inasmuch as a collection of pure organic liquids had already
been begun by Dr. J. Timmermans, this has been used as a
nucleus, and it is planned to devote attention to this group of
substances for the present, though eventually the collection
is to contain all types of chemical compounds.
It is hoped to make this Bureau an international center of
exchange, through which European chemists may obtain Amer-
ican standard chemicals, and vice versa. It is still further planned
to make it a center of information for everything dealing with
pure products, including publications on the subject, etc.
The Bureau is asking for financial support at home, in order to
establish research scholarships, and for the cooperation of manu-
facturers in undertaking the production of the pure materials,
after the Bureau has worked out the details of manufacture,
and of laboratory heads, in furnishing pure samples which they
have had occasion to prepare.
Centennial of Philadelphia College of Pharmacy
During the week of June 12 to 15, 1921, the Philadelphia
College of Pharmacy and Science will celebrate its centennial.
In addition to the usual Commencement festivities the program
includes a centennial banquet and reception to Rear Admiral
William C Braisted, Surgeon General (retired) U. S. Navy,
president of the College. This will occur on Tuesday, the 14th,
at the Bellevue-Stratford.
540
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
The Determination of Cobalt and Nickel in Cobalt Steels12
By G. E. F. Lundell and J. I. Hoffman
Standards. Department op Commerce, Washington, D. C.
Unfortunately there is available for the determina-
tion of cobalt in steels no such simple, rapid, and ac-
curate method as the dimethylglyoxime method for
nickel. There are some methods, such as the a-
nitroso-/5-naphthol method1, * and the sodium cobalti-
nitrite method,2 which aim at the separation of cobalt
as such. These methods all call for more or less in-
volved preliminary treatments, and the final cobalt
precipitates cannot be directly dried, ignited, and
weighed, but must be converted into other forms.
Most methods for the determination of cobalt aim at
the simultaneous determination of nickel and cobalt
with subsequent deduction of nickel as determined
separately. Such are the phosphate,3 the cyanide,4
and the electrolytic5 methods.
The method to be described is of the last-named type
and is based, for the most part, on well-known facts.
The effects of some interfering elements, notably
vanadium in the electrodeposition of cobalt, have been
discovered and overcome. The method is not a short
one and is therefore not suitable for routine works
analysis. It is, however, a well-tested, accurate method
which is suited to the primary standardization of cobalt
steels for cobalt and nickel. In addition, it possesses
the merit, from the standpoint of the analyst engaged
only occasionally in the analysis of this type of material,
of providing for the simultaneous accurate determina-
tion of chromium, vanadium, copper, and manganese
in the same sample.
The method was developed during the analysis
at the Bureau of Standards of the Ridsdale British
Standard Chrome-Tungsten-Vanadium-Cobalt Steel
"W." This steel also contains nickel, molybdenum,
and copper, in addition to the ordinary steel constitu-
ents. The method was also carefully tested in the
analysis of the Bureau of Standards Chrome-Vanadium
Standard Steel No. 30a, to which had been added
known amounts of nickel and cobalt.
PRELIMINARY REMARKS ON PROCEDURE
The following digest of the method will make
clear the purpose of the various steps. The steel is
dissolved in hydrochloric and nitric acids, and any
tungstic and silicic acids are filtered off and treated
with sodium hydroxide. Any insoluble matter is
filtered off, dissolved in hydrochloric acid, and added
to the main solution. The major part of the tungsten
and silicon is thus eliminated, and any contaminating
cobalt, nickel, or chromium recovered. The solution
is then subjected to an ether treatment, which removes
the major part of the iron, together with the most of
any molybdenum present. The acid extract is then
heated with sulfuric acid till fumes escape, after which
chromium, vanadium, and manganese are oxidized
by potassium persulfate. The hot oxidized solution
is poured into hot sodium hydroxide solution, and
i Received February 11, 1921.
* Published by permission of the Director of the Bureau of Standards.
* Numbers refer to references at end of article, p. 543.
filtered. This quantitatively separates chromium,
vanadium, and any residual tungsten and molybdenum
from cobalt, nickel, manganese, copper, and iron.
The precipitate is dissolved in sulfuric acid by the aid
of sodium bisulfite and treated with hydrogen sulfide
to remove copper quantitatively. After expulsion of
hydrogen sulfide and reoxidation, a double precipita-
tion with ammonium hydroxide serves to remove iron.
The combined filtrates are then electrolyzed for nickel
and cobalt, which are weighed, dissolved, and treated
with dimethylglyoxime to obtain nickel. Manganese,
which does not interfere in the electrolysis, may appear
as a deposit on the anode, as a sludge, or remain in
solution.
PROCEDURE
Dissolve 2 to 4 g. of the sample in 50 cc. of dilute
hydrochloric acid (1:1) and oxidize with 5 cc. of
concentrated nitric acid (sp. gr. 1.42). Digest until
the tungstic acid is bright yellow, add 150 cc. of hot
water, and boil for 1 min. Filter and wash free from
iron with dilute hydrochloric acid (1 : 9). Treat
the impure tungstic acid with a small amount of a
10 per cent solution of sodium hydroxide, and if any
dark-colored residue remains, dissolve it in hydro-
chloric acid and add the solution to the main filtrate.
Evaporate this filtrate twice with 30 cc. of hydro-
chloric acid (sp. gr. 1.2), but not to complete dryness
on account of the slight volatility of divanadyl chloride.
Take up in hydrochloric acid (sp. gr. 1.11), filter, if
tungstic or silicic acid is present, and separate by means
of ether6 the major portion of the iron, together with
molybdenum, from nickel, cobalt, copper, chromium,
vanadium, and manganese.
Boil the acid extract to expel the ether, add 4 cc.
of sulfuric acid (sp. gr. 1.84), and evaporate to the ap-
pearance of fumes. Dilute the solution to 300 cc,
add 40 cc. of a saturated solution of potassium per-
sulfate, and boil until the manganese is completely
precipitated as oxide. This requires about 10 min.
Pour the hot solution into 200 cc. of a warm 5 per
cent solution of sodium hydroxide. If the precipitate
is not black add a small amount of potassium persulfate
solution. When the precipitate has settled, filter
through asbestos and wash7 with a 2 per cent solution
of sodium hydroxide.8 Place the crucible with the
precipitate in the original beaker, add 100 cc. of water,
5 cc. of sulfuric acid, and a crystal of sodium bisulfite,
and warm until the precipitate has dissolved. Filter,
wash with hot water, and repeat the persulfate oxida-
tion, the sodium hydroxide precipitation, and the
filtration and washing, in order to remove all chromium
and vanadium. Combine the sodium hydroxide fil-
trates.9
Dissolve the precipitate containing nickel, cobalt,
copper, manganese, and iron as before, filter off the
asbestos, neutralize with ammonia, acidify with sul-
furic acid (1 cc. of acid for 100 cc. of solution), and
pass in hydrogen sulfide. Filter off any copper sulfide
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
541
and wash with a 1 per cent solution of sulfuric acid
saturated with hydrogen sulfide.10
Boil the solution to remove hydrogen sulfide, adding
persulfate toward the end to destroy sulfur. Dissolve
any manganese dioxide which has separated out by
the addition of the least possible amount of sodium
bisulfite. Make ammoniacal and filter.
As the ferric hydroxide invariably contains a little
cobalt, it should be dissolved in 20 cc. of sulfuric acid
(1 : 4), reprecipitated with ammonia, and filtered.11
Evaporate the combined filtrates to a volume of
100 cc. In case a precipitate has formed, acidify
the solution with sulfuric acid, add a crystal of sodium
bisulfite, and warm.
The solution should now contain ammonium sulfate
equivalent to 10 cc. of concentrated sulfuric acid.
Neutralize with ammonium hydroxide (sp. gr. 0.90),
and add 35 cc. in excess and 2 g. of sodium bisulfite.
Electrolyze in a volume of 150 cc. for 6 to 8 hrs.,
using gauze electrodes and a current density of 0.2
to 0.3 ampere per dm2. Wash the cathode with cold
water, dry at 100° C, and weigh.12
The electrolyte, which usually contains from 0.1
to 1.0 mg. of nickel and cobalt (mainly cobalt), should
be tested as follows: Boil with an excess of ammonium
persulfate, keeping the solution strongly ammoniacal
to precipitate manganese, filter, wash,13 and treat with
hydrogen sulfide. If a precipitate forms, filter on a
small filter, wash with water containing a little am-
monium chloride and ammonium sulfide, ignite, and
weigh as combined oxides of nickel and cobalt. Mul-
tiply by the empirical factor 0.75, and add to the
cathode weight.14
Dissolve the nickel and cobalt on the cathode and
the oxides recovered from the electrolyte in 20 cc. of
nitric acid (sp. gr. 1.42), neutralize with ammonium
hydroxide, and then make just acid with hydrochloric
acid. Add sufficient 1 per cent alcoholic solution of
dimethylglyoxime to react with both nickel and co-
balt, make faintly ammoniacal, and allow to digest
for 2 hrs.15
Filter through asbestos, dissolve back into the orig-
inal beaker by means of 20 cc. of warm nitric acid
(1 : 1), and precipitate and digest as before. Filter
through a tared Gooch crucible, wash with a little hot
water, dry at 120° C, and weigh.
Calculate nickel and subtract from the total nickel
and cobalt.
DETERMINATION OF CHROMIUM AND VANADIUM
If determinations of chromium and vanadium are
desired, the two filtrates from the sodium hydroxide
separation7 should be combined and analyzed accord-
ing to the electrometric titration method of Kelley,
Wiley, Bohn and Wright,16 Johnson's method,17 or the
Bureau of Standards procedure,18 which is as follows:
Evaporate the solution, make up to exactly 500
cc. and divide into two 250-cc. portions, A and B.
determination of chromium — Acidify Portion A
with sulfuric acid, add 5 cc. of silver nitrate solution
(2.5 g. per liter) , and boil with 5 cc. of a 10 per cent solu-
tion of ammonium persulfate until the persulfate is
entirely destroyed (about 10 min.). Cool, add ferrous
sulfate, and titrate with permanganate.
In this operation quinquivalent vanadium is reduced
to the quadrivalent condition by the excess for ferrous
sulfate added and then oxidized back to the quinquiva-
lent condition by the permanganate, thereby causing
no net change. Sexivalent chromium is permanently
reduced to the trivalent condition. The chromium
may therefore be calculated from the difference be-
tween the volume of ferrous sulfate added and the
ferrous sulfate equivalent of the permanganate con-
sumed.
determination of vanadium — Acidify Portion B
with sulfuric acid, boil, and reduce in a Jones reductor
containing ferric alum and phosphoric acid in the re-
ceiver.19 Titrate the hot solution with permanganate.
In order to obtain accurate results a blank (which
usually requires about 0.8 cc. of 0.03 N permanganate)
must be carried through the various steps of the de-
termination with the proportionate amounts of sodium
hydroxide, potassium persulfate, sodium bisulfite, and
asbestos. In this operation vanadium is reduced to
the bivalent condition and afterwards oxidized to the
quinquivalent state, while chromium is reduced to the
bivalent condition and afterwards oxidized to the tri-
valent state. The volume of permanganate consumed
by vanadium is therefore represented by the difference
between the volume of permanganate used in B and
one-third of the permanganate equivalent of the fer-
rous sulfate required by the chromate in A.
determination of manganese — Manganese may
be conveniently determined in the nitric acid solution
(References 11, 12, and 13), by the bismuthate
method.
determination of copper — Copper may be de-
termined as described in Reference 10.
TESTS OF THE PROCEDURE
The experiments listed in Table I were performed in
order to establish the accuracy of the electrolytic
method for cobalt and nickel under such varying con-
ditions as might obtain in steel analysis. Unless
otherwise specified, the electrolyses were carried out in
150-cc. solution, containing 25 g. ammonium sulfate
and 35 cc. ammonium hydroxide (sp. gr. 0.90), at
0.20 to 0.30 ampere per dm2, for 16 hrs.
The data show that:
1 — The deposition of cobalt is seldom complete and recoveries
must be carried out as specified in the method.
2 — The addition of ammonium acetate or sodium bisulfite
(particularly the latter) has a beneficial effect.
3 — Potassium, manganese, and chromium sulfates, moderate
amounts of platinum, and chlorides are without harmful effect.
4 — Vanadium does not interfere seriously in the deposition of
either nickel or cobalt alone, but does interfere most seriously
when both are electrolyzed simultaneously.
5 — Tungsten interferes in depositions involving cobalt or
cobalt and nickel, but not nickel alone.
6 — Ferrous salts, chromates, tartrates, and molybdenum
interfere markedly.
Table II summarizes the results obtained in the
analysis, by the method as described, of the British
Standard "W" and the Bureau of Standards Standard
542
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
Table I— Effect of Various Substances on the Electrodeposition
Weight of
Nickel-Cobalt
Taken
Substances Added Gram
0.0977 Co
0 . 0979 Ni
0.0979 Ni 0.0977 Co
2 g. NaHSOi 0.0979 Ni 0.0977 Co
2 g. NaHSOi 0.0979 Ni 0.0977 Co
0.0977 Co
0.0979 Ni
1 g. NH.CiHjO* 0.0979 N
2 g. NaHSOi 0.0979 N
3 g. Tartaric acid 0 . 0979 N
1 g. KiSO. 0.0979 N
0.0035 g. Mn as KMnO( 0.0979 N
0.0035 g. Mn as KMnO< 0.0979 N
0.0035 Mn as KMnOi, 1 g. NH.CjHiO; 0.0979 N
0.01 g. Mn as KMnO<, 2 g. NaHSOi 0.0979 N
0.01 g. Mn as KMnO,, 2 g. NaHSOi 0.0979 N
0.01 g. Mn as KMnOi, 2 g. NaHSOi 0.0979 N
0.005 g. V as ViOs 0.0979 N
0.001 g. V as V2O1 0.0979 N
0.001 g. V as V.Os
0.001 g. V as ViOs
0.001 g. V as "" '
0.001 g. V as
0.001 g. V as
0.005 g. V as
0.005 g!Cr a
0.001 g. Cra
0.01 g. Cras
0.001 g. Cr a
0.005 g. Wa
0.005 g. W a
0.005 g. Wa
0.005 g. Mo
0.001 g. Pt
0.001 g. Fe
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
0.0977 Co
V2O4 0.0979 Ni 0.0977 Co
ViOi 0.0979 Ni
VjO< 0.0977 Co
V1O4 0 0979 Ni 0.0977 Co
5 KiCnOi 0.0979 Ni 0.0977 Co
i KiCnO; 0.0979 Ni 0.0977 Co
Cri(SO()j, 3 g. tartaric acid 0 . 0979 Ni 0 . 0977 Co
i CnlSOili, 2 g. NaHSOi 0.0979 Ni 0.0977 Co
i NaiW04 0.0979 Ni 0.0977 Co
I NaiWOi 0.0979 Ni
I NaiWO. 0.0977 Co
!S (NH,).MoOi 0.0979 Ni 0.0977 C
i PUSCb, 2 K. NaHSOj 0.0997 Ni
Mohr's salt, 2 g. NaHSOi 0.0979 Ni
. cone. HC1 0.0979 Ni
: Electrolyzed for 4 hrs. ' Recoveries in the electrolytes of Expts. 1-
0.0977 Co
0.0977 Co
0.0977 Co
Weight of
Deposit on
Cathode
Gram
0.0965
0.0970
0.1939
0.1951
0.1954
0.0972
0.0980
0.1952
0.1952
0.0308
0.1947
0.1948
0.1953
0.1953
0.1988
0.1958
0.1957
0.0225
0.11S5
0.0983
0.0971
0.1212
0.0976
0.0984
0.0100
0.0000
0.0922
0.0284
0.1956
0.2011
0 . 0983
0.1034
0.0032
0.1954
0.1967
0.1951
Deposits
Dark gray
Platinum-like
Gray
Good gray
Good gray
Dark grav
Platinum-like
Gray
Good gray
Purplish and discolored
Good gray
Good gray
Good gray
Good gray
Good gray
Good gray
Good gray
Good gray
Good gray
Dark but good
Purplish and discolored
Good gray
Good gray
Good gray
Dark but good
Slightly copper colored
Good gray
Slightly discolored
Good gray
1 Electrolyzed for 6 hrs.
Electrolyzed for S hr;
> Solution contained only 13 g. (NH<)iSOi.
■ II mill, n II01M. 115. (I 1 1, II (1(1(1(1. II (1(106, an. I 0 0000 g
1 Solution contained 38 g. (NHiJiSO*.
Error
Gram
— 0.0012'
— 0.0009'
—0.0017'
—0.0005'
—0.0002'
—0.0005'
+ 0.0001'
—0.0004
— 0.0004
—0.1648
—0 . 0009
-II HOOf,
—0.0003
—0.0003
+ 0.0002
+ 0.0002
+ 0.0001
—0.1731
— O.0771
+ 0.0004
— 0.0006
— 0.0744
—0.0003
+ 0.0007
— 0.1856
—0.1956
—0.1034
—0.1672
0 . 0000
+ 0.0055
— 0 . 0004
+ 0.0047
— 0.1924
— 0.0002
+ 0.0011
—0.0005
respectively.
Table II — Analyses Made
Cobalt
Present Found
4.73 4.78
British Standard "W"> 4.73
Material Used
British Standard
4.73 4.
4.73 4.
: Proposed Method (Results Expressed in Per <
Nickel Chromium Vanadium
Present Found Present Fi
0.44 0.41
0.42
0.43
0.43
Bureau of Standards Cr-V Standard No 30a. . . 2 .44.
Bureau of Standards Cr-V Standard No 30a. . . 2.44
Bureau of Standards Cr-V Standard No. 30a. . . 2.44
■ Wet peroxidation used as describedin Reference 8. !
2.45
2.45
2.46
0.44
0.44
0.44
2.57
2.57
2.57
Manganese
Present Found
0.102 0.097
1.02
2.94
2.94
2.93=
1.05
1.04
0.21
0.21
0.21
0.788
0.795
0.797'
0.19
0.20
0.20
0.102
0.102
0.102
0.805
0.805
0.805
103
0.090
0.089
0.819
0.820
0.81S
0.063
0.063
0.063
0.062
0.068
0.060
■ By electrometric titration, Kelley, Wiley, Bohn and Wright's method.
No. 30a to which cobalt and nickel had been added.
Standard "W" contains 16.20 per cent tungsten,
0.05 per cent molybdenum, in addition to the per-
centages of other elements listed in Table II. The
values given in Table II are the averages of the ranges
of the values reported by British, Scotch, French,
Italian, and American chemists, which are as follows:
Cobalt, 4.53 to 5.06
Nickel, 0.41 to 0.48
Chromium, 2.91 to 3.12
Vanadium, 0.71 to 0.85
Manganese, 0.08 to 0.14
Copper, 0.047 to 0.07
Cobalt and nickel were added to Standard No.
30a to give the percentages indicated in the table.
Expts. 5, 6, and 7 demonstrate conclusively the ac-
curacy of the method as applied to the determination
of cobalt and nickel. The data also show that the
method satisfactorily provides for the determination
of manganese, chromium, vanadium, and copper, in
the presence of tungsten and molybdenum.
COMMENTS ON THE METHODS
The following comments are worthy of note:
1 — The method demonstrates that it is possible
to separate chromium and vanadium completely from
iron, manganese, nickel, and cobalt by a persulfate
oxidation in acid solution, followed by two sodium
hydroxide precipitations performed by pouring the
hot acid solution into an excess of hot alkaline solution.
2 — Phosphorus and aluminium undoubtedly also
quantitatively accompany chromium and vanadium.
3 — The determination of manganese is free from the
troublesome interference of chromium or cobalt.
4 — Elements like cerium, zirconium, and titanium
(see Note 5 below) would be quantitatively present in
the ammonium hydroxide precipitate along with iron.
5 — Titanium, if present, would be oxidized by per-
sulfate and might escape complete precipitation by
sodium hydroxide. This would affect only the de-
termination of chromium and vanadium, and the error
could be avoided by boiling the alkaline solution for
2 or 3 min.
6 — Uranium in the absence of vanadium would go
with cobalt and iron and be caught subsequently with
iron in the ammonium hydroxide precipitate. In
the presence of vanadium, uranium would divide
between the sodium hydroxide filtrate and the pre-
cipitate. In this case it would not interfere with the
cobalt and nickel determination, or with the chro-
mium and vanadium determinations if the electro-
metric or Johnson methods were employed.
SUMMARY
I — This paper presents a method for the accurate
determination of cobalt and of nickel in cobalt steels.
The method is based on the electrodeposition of cobalt
and nickel in a solution freed from iron, chromium,
and such interfering elements as tungsten, molyb-
denum, vanadium, and copper.
II — Methods for accurate determinations of chro-
mium, vanadium, copper, and manganese in the same
portion of steel are also provided.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
54.3
REFERENCES
1 — W. W. Scott, "Standard Methods of Chemical Analysis," 2nd Ed.,
D. Van Nostrand Co., 148.
2 — A. A. Blair, "The Chemical Analysis of Iron," 8th Ed., Lippincott
Co., 175.
3 — C. M. Johnson, "Chemical Analysis of Special Steels," 2nd Ed.,
John Wiley & Sons, Inc., 304.
4— Johnson, Loc. tit., 307; Blair, Loc. cil., 180.
5 — Johnson, Loc. eit., 316; Blair, Loc. cil., 177.
6— J. W. Rothe, Mitt. kgl. Tech. Versuchsanstalt zu Berlin, 1892, Part
III; Blair, Loc. tit., 177, 202.
7 — It is important that the filter be not allowed to run dry, lest the
hydroxide coagulate and retain traces of vanadium which would subse-
quently prevent a satisfactory deposition of cobalt and nickel,
8 — Sodium peroxide was employed in two preliminary experiments for
the oxidation and separation of chromium and vanadium from iron, cobalt,
etc. A. A. Noyes, W. C. Bray and E. B. Spear [Tech. Quarterly, 21 (1908),
14], and also C. M. Johnson [Chem. Met. Eng., 20 (1919), 588]. The separa-
tion was complete (Expts. 1 and 2, Table II), but the procedure was aban-
doned because it was necessary to repeat the separation twice and the pre-
cipitates were difficult to handle.
9 — For the determination of chromium and vanadium see page 541.
10 — This precipitate represents a quantitative recovery of copper, and the
percentage may, therefore, be determined by ignition to oxide or, preferably,
by electrolysis in a small volume of solution.
11 — If manganese is to be determined, the precipitate should be dissolved
in 40 cc. of nitric acid (1 : 3), and reserved.
12 — If a determination of manganese is desired dissolve any anode de-
posit in the solution described in preceding reference.
13 — If a determination of manganese is desired add the precipitate to the
solution reserved for manganese (two preceding references )
14— The factors for NiO, CoO and CoaOi are 0.786, 0.787, and 0.734,
respectively. The use of the factor 0.75 on a precipitate weighing 2 mg.
could, therefore, not occasion an error greater than 0.004 per cent on a
2-g. sample. With large precipitates, ignition to metal in hydrogen must
be carried out. Cf. Treadwell-Hall, "Analytical Chemistry," Vol. II,
4th Ed., page 139, John Wiley & Sons, Inc.
15 — There is no difficulty at all in precipitating traces of nickel in the
presence of any amount of cobalt if this method is followed. The precipi-
tate will contain cobalt, however, and must be purified as directed.
16 — This Journal, 11 (1919), 632.
17— Johnson, Loc. cil., 8.
18 — Unpublished method originating with Dr. L. F. Witmer at the
Bureau of Standards.
19— D. L. Randall, Am. J. Sci., [4] 24 , 313.
Improved Deniges Test for the Detection and Determination of Methanol in
the Presence of Ethyl Alcohol12
Biochemic Division,
By Robert M. Chapin
tu op Animal Industry, U. S. Department of Agriculture, Washington, D. C.
The examination of alcoholic products for methanol
has been a problem of interest to many chemists.
If a certain few published papers are consulted the
matter would appear to be rather simple, at least from
the qualitative side. But a thorough survey of the
voluminous literature, comprising a large number of
methods with contradictory comments and conclu-
sions, does not lead one to undertake exacting work
along this line with entire confidence.
One of the most recent investigators, Gettler,3 having
reviewed fifty-eight existing tests, recommends sub-
jecting the sample to nine qualitative tests, se-
quentially applied. In passing it may be noted that
his eighth test, a refractometric one, is essentially
quantitative in nature, being based upon a numerical
difference between physical constants, and is only
secondarily of qualitative significance. Also his first
seven tests are merely tests for formaldehyde, applied
after treating the sample with a single oxidizing agent.
If this oxidizing agent is capable of producing formalde-
hyde from any substance other than methanol, all the
seven tests must be subject to a common source of error.
Purely qualitative findings, however, seldom afford
solid ground for action in matters of commercial or
legal importance. The question "How much?" is
almost certain to arise. It is a pertinent question here,
inasmuch as several investigators4 have stated that
methanol is naturally produced in certain fermenta-
tions. If methanol, like fusel oil, is a normal con-
stituent of alcoholic products, then the legitimacy of
its presence in any case may be satisfactorily settled
only by quantitative examination. The analytical
chemist needs, first, a simple but dependable qualitative
test which shall possess semiquantitative value in that
1 Received February 16, 1921.
2 Published by permission of the Secretary of Agriculture.
3 J. Biol. Chem., 42 (1920), 311.
• von Fellenberg, Milt. Lebcnsm. Hyg., 5 (1914), 172; Biochem. Z., 86
(1918), 45; Takahashi. J. Coll. Agr. Imp. Univ. Tokyo, 5 (1915), 301;
J. Am. Chem. Soc, 39 (1917), 2721.
it is able to serve as a "limit test," and, second, a quan-
titative method which shall enable him to assert with
positiveness very nearly the exact percentage present.
The quantitative method must be subjected to intensive
study in order:
(1) To develop its highest inherent precision.
(2) To devise methods for the elimination of interfering sub-
stances.
(3) In case elimination is impossible, to determine the size
of the "blank" involved by the presence of each such sub-
stance.
The Deniges1 test seems most promising for both
qualitative and quantitative application. It consists
in treating the alcoholic solution with potassium per-
manganate and acid, whereby methanol is oxidized to
formaldehyde. The latter is detected by Schiff's
reagent in the presence of sufficient sulfuric acid to
prevent development of color from acetaldehyde.
There appears no evidence that other proposed oxidiz-
ing agents, such as bichromate and acid or persulfates,2
are inherently superior to permanganate and acid.
The latter agent is preeminently simple and con-
venient, requiring no heat for its action and finally
affording a colorless solution. No reagent effects a
quantitative yield of formaldehyde. All require strict
adherence to a standard set of conditions under which
it is assumed that a certain concentration of methanol
originally present results in a certain concentration
of formaldehyde at the end.
Likewise, for the demonstration of formaldehyde
there appears to be no reagent any more convenient
or reliable than Schiff's reagent, prepared according to
i Compl. rend., 150 (1910), 832.
a Preliminary experiments have indicated that persulfates, especially
in strongly acid solution, may produce a notable quantity of formaldehyde
from pure ethyl alcohol. The possibility of such a reaction has been noted
by previous observers in the application of several oxidizing agents. Bi-
chromate and acid, in comparison with permanganate and acid, appears
to afford a high yield of acetaldehyde from ethyl alcohol, but a low yield of
formaldehyde from methanol.
544
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
the Elvove' formula. Its chief comparative disadvan-
tage is the slowness of development of the final color.
QUANTITATIVE METHOD
The Deniges method has been used with more or less
modification by a considerable number of investiga-
tors. Since in routine analyses following the procedure
of Elvove the observed margin of precision seemed un-
necessarily large, the whole process has been subjected to
close scrutiny with a view to attaining greater pre-
cision. It was decided that 0.04 cc. of total alcohol
should be the standard quantity for each test, which,
including the necessary acid, should be made to a
volume of 5 cc. The nature and proportion of the
acid is of very great importance. The highest yield
of formaldehyde results from slow action of perman-
ganate in presence of low hydrion concentration;
but practical considerations prohibit an inordinately
long reaction time, while the total acid must be kept
up to a safely high figure. The conditions finally
chosen were the addition of 0.2 cc. of phosphoric acid
(C. P., 85 per cent), previously diluted to 1 cc. for ac-
curacy in measurement, and an oxidation period of
30 min., instead of the 0.2 cc. of concentrated sulfuric
acid and oxidation period of 3 min. employed by El-
vove. Next, after deciding that the necessary per-
manganate should be added in a volume of 2 cc, it
remained merely to find a concentration of the per-
manganate solution such that either more or less than
2 cc. of it would give a lower yield of formaldehyde than
exactly 2 cc. The desired strength was found to be 3
per cent. In a similar way the volumes of sulfuric
acid and Schiff-Elvove reagent were tested. Direc-
tions for the method may be given as follows:
Dilute the solution, previously purified as necessary,
to 1 per cent by volume of total alcohol (Sample Solu-
tion A). Of this, pipet 10 cc. into a 50-cc. volumetric
flask, add 10 cc. of a 4 volume-per cent solution of
pure ethyl alcohol, and make to the mark with water
(Sample Solution B). Of the latter, likewise, dilute
10 cc. plus 10 cc. of the 4 per cent ethyl alcohol to
50 cc. (Sample Solution C). Into 50-cc, tall-form
Nessler tubes pipet 4 cc. of the three sample solutions.
Prepare standard methanol tubes containing, respec-
tively, 1, 2, and 3 cc of a 0.04 volume-per cent aqueous
solution of pure methanol, plus 1 cc. of 4 per cent pure
ethyl alcohol, plus sufficient water to make 4 cc.
After the tubes are properly arranged in a rack the fol-
lowing operations are put through in strict parallelism,
remembering that each reagent is to be added to all
tubes before any are mixed:
1 — Add 1 cc. of a 1 in 5 volume solution of phosphoric acid
(C. P., 85 per cent), and mix.
2 — Add 2 cc. of 3 per cent potassium permanganate solution,
mix, and let stand 30 min.
3 — Add 1 cc. of 10 per cent oxalic acid solution, mix, and let
stand till a clear brown (about 2 min.).
1 This Journal, 9 (1917), 295. Fuchsin (0.2 g.) is dissolved in 120
cc. hot water. After cooling to room temperature there are added 2 g. of
anhydrous sodium sulfite dissolved in 20 cc. water, followed by 2 cc. con-
centrated hydrochloric acid. The solution is diluted to 200 cc. and is
allowed to stand 1 hr. before use. If well stoppered in an amber bottle
it may remain fit for use for several weeks. The Schiff-Elvove reagent
appears decidedly superior to the original Schiff reagent, and should super-
sede the latter.
4 — Add 1 cc. concentrated H2SO4 (C. P.), mix, and let stand a
few minutes for temperatures to become equal.
5 — Add 5 cc. Schiff-Elvove reagent, mix well, and let stand till
colors are sufficiently developed (0.5 to 2 hrs.).
Each 1 cc. of the 0.04 per cent methanol in the stand-
ard tubes is equivalent to volume percentages of meth-
anol in total alcohol contained in the sample as fol-
lows:
Sample Solution Per cent
For more precise results the determination is repeated
on the appropriate sample solution with more closely
set standards. The sharpest results are obtained with
standard tubes containing not over 1 cc. of standard
methanol. To bring the sample into this range it is
often best to use only 2 cc. of a sample solution, adding
thereto 0.5 cc of the 4 per cent ethyl alcohol and sufficient
water to make 4 cc. Approximate readings may be
made after 30 min., precise ones after 1 hr., but best
under 2 hrs., for the colors fade later. The limit of
detection is 0.2 cc. of the standard 0.04 per cent
methanol.
Tests on four "unknown" mixtures of methanol,
ethyl alcohol, and water prepared by an assistant
indicated that, including the necessary determination
of total alcohol via specific gravity, the results need not
be in error by more than 1 part in 20.
QUALITATIVE METHOD
A modification of Deniges' method is official as a
qualitative test in the U. S. Pharmacopeia IX. The
U. S. P. test has been criticized as unreliable because a
false reaction sometimes occurs. Ehman1 attributes
the fault to temperature and overcomes it by running
a blank with pure ethyl alcohol, adjusting the tem-
perature until the blank remains colorless. In the
judgment of the present writer the difficulty is pri-
marily due to an undesirably high concentration of total
alcohol. Since the substitution of phosphoric acid for
sulfuric acid considerably more than doubles the yield
of formaldehyde from a given amount of methanol,
the concentration of the sample in the test here pro-
posed need be only half that employed in the U. S. P.
test and still leave the proposed test more delicate than
the U. S. P. test at its best. The proposed test has
been run at temperatures of 15° and 35° C. without
experiencing difficulty with false reactions.2 It may
be conducted as follows:
Dilute the liquid, purified as necessary, to a content
of 5 per cent by volume of total alcohol. To 5 cc.
add 0.3 cc. of phosphoric acid (C. P., 85 per cent),
mix, add 2 cc. of a 3 per cent solution of potassium
permanganate, mix, and let stand until the perman-
ganate is entirely decomposed (about 10 min.).
Add 1 cc. of 10 per cent oxalic acid, mix, and let stand
till a clear brown (about 2 min.). Add 1 cc. concen-
trated sulfuric acid, mix, add 5 cc. Schiff-Elvove
reagent, immediately mix well, and observe the color
after exactly 10 min. The solution may then possess
i Am. J. Pharm., 91 (1919), 594.
2 It may be that in the U. S. P. test the presence of sulfuric acid pro-
motes oxidation of ethyl alcohol to formaldehyde at an elevated tempera-
ture.
June, 1921 TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
545
a pale greenish tint, but should show no distinct blue
or violet color against a white background (less than
0.2 per cent methanol in the total alcohol).
In carrying out the qualitative test it is essential
not to be misled by any colors developing in less than
10 min. Concentrated sulfuric acid often becomes
decidedly weak in the ordinary laboratory reagent
bottle, and a transitory color from acetaldehyde may
accordingly appear. This is also likely to happen if
the Schiff-Elvove reagent is not mixed with the solu-
tion immediately after addition. The color arising
from acetaldehyde will have disappeared in 10 min.
after mixing, but, needless to say, it is a safeguard
against error to run a blank along with the test. On
longer standing, the test can naturally detect smaller
proportions than 0.2 per cent.
PURIFICATION OF SAMPLES
The directions given for both quantitative and qual-
itative work specify that the original material must be
"purified as necessary." In general, the test must
never be run directly on any material unless it is posi-
tively known to contain only water, alcohol, and other
substances known to be innocuous. Alcoholic prep-
arations vary so widely that no entirely general methods
of purification may be given. The analyst can gen-
erally determine approximately the nature and amount
of the nonalcoholic constituents, and must decide
whether, in addition to purification, it will be necessary
to run a blank on a synthetic mixture.
carbohydrates and glycerol — These substances,
against which Salkowski1 has given warning, are to
be separated by distillation, a step which is also neces-
sary to permit determination of total alcohol via
specific gravity.
formic and acetic acids — These acids are stated by
Rosenthaler2 to yield color with Schiff's reagent.
They can be separated, if necessary, by distillation after
neutralization, but the present writer did not find that
10 per cent by volume of either acid added to pure
ethyl alcohol produced any color by the qualitative
test.
formaldehyde, terpenes, etc. — These impurities
are removed by von Fellenberg3 by treatment with
sodium hydroxide and silver nitrate, followed by dis-
tillation.
phenol — As noted by Scudder,4 phenol interferes
with the test to a degree dependent on its concentra-
tion. It may probably be adequately separated by
distillation after addition of a liberal excess of caustic
alkali.
fusel oil — -This has been stated5 to afford a slight
false reaction after oxidation. The present writer ob-
tained one sample of "fusel oil," and two of C. P.
amyl alcohol (rectified fusel oil), one of the latter being
an "analyzed reagent," all from different manufac-
turers. Each sample was made into a 10 volume-
per cent solution in pure ethyl alcohol, and the qualita-
i Z. Nahr.-Genussm., 28 (1914). 225.
1 "Der Nachweis organischer Verbindungen," 1914.
» Biochem. Z., 85 (1918), 45.
' J. Am. Chem. Soc, 27 (1905), 842.
>von Fellenberg, Biochem. Z., 85 (1918), 45; Salkowski, Z. Nahr.-
Cenussm.,36 (1918), 262.
tive test was applied. The heaviest color was given
by the presumably purest sample, namely, the "ana-
lyzed reagent." Upon making the qualitative test
quantitative by running it in comparison with known
mixtures of methanol and ethyl alcohol and letting
stand an hour or more, the color produced was found
markedly fainter than the color produced from ethyl
alcohol containing 0.08 per cent methanol. By the
regular quantitative test the color was indistinguish-
able, being clearly less than the equivalent of 0.1 per
cent methanol. Hence the present writer has been
unable to demonstrate interference by fusel oil, pro-
vided that it be not attempted to strain the test beyond
the limit recommended, namely, 0.2 per cent.
acetone — This ingredient, constituting up to 10
per cent of the "total alcohol," does not appear to
affect significantly qualitative or quantitative results.
summary
The Deniges test has been modified to increase sen-
sitiveness and precision, and is recommended for
practical work in the detection of, and especially in
the quantitative determination of, methanol in the
presence of ethyl alcohol, inasmuch as the possible
normal presence of methanol in alcoholic products
renders purely qualitative tests unsatisfactory. Though
capable of greater refinement, the tests are adjusted to a
minimum limit of 0.2 per cent methanol in total alcohol.
Procedures for the removal of certain interfering sub-
stances are outlined.
National Research Council Notes
The Research Information Service of the National Research
Council has recently compiled information about funds for sci-
entific research. From this compilation it appears that there
are hundreds of special funds, trusts, or foundations for the en-
couragement or support of research, in the mathematical, phys-
ical and biological sciences, and their applications in engineer-
ing, medicine, agriculture, and other useful arts. The income
from these funds, which amounts annually to at least fifty
million dollars, is used principally for prizes, medals, research
scholarships and fellowships, grants, and sustaining appropri-
ations or endowments.
So numerous have been the requests to the Research Council
for information about sources of research funds, availability of
support for specific projects, and mode of administration of par-
ticular trusts or foundations, that the Research Information
Service has created a special file which it is proposed to keep up
to date in order to answer the questions of those interested in
such funds. Furthermore, in order to give wider publicity to
the immediately available information, the Council has issued
a bulletin under the title "Funds available in IQ20 in the United
States of America for the encouragement of scientific research."
The Research Information Service is prepared also to assist
investigators by locating scientific publications which are not
generally or readily accessible. It will also, as is desired, have
manuscripts, printed matter, or illustrations copied by photo-
stat or typewriter. The cost of copying varies from tea to
twenty-five cents per page. No charge is made for this service
unless an advance estimate of cost has been submitted and ap-
proved by correspondent.
Inquiries concerning the bulletin or for information about re-
search funds or requests for assistance in securing copies of
scientific articles should be addressed. National Research Coun-
cil, Information Service, 1701 Massachusetts Avenue, Wash-
ington, D. C.
546
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
Determination of Refractive Indices of Oils1
By Henry S. Simms
Massachusetts Institute of Technology, Cambridge, Massachusetts
The usual methods for the determination of the re-
fractive index depend upon the bending of a beam of
light on passing through a portion of the substance
having flat surfaces. The angle of total reflection is
measured. This is illustrated by the Abb6 refractom-
eter and the immersion refractometer. Other meth-
ods depend upon the optical effects produced when
light passes through portions of the substance having
curved surfaces. This is the principle involved in
methods for obtaining refractive index by means of
the microscope.
The method to be described is based upon this
latter principle and may be called a "refractoscopic"
method to distinguish it from methods using the re-
fractometer, since the observed optical effect is not
measured.
It requires more oil than the Abbci refractometer,
but has two distinct advantages over the latter:
1 — It is cheaper. The Abbe refractometer costs about $300
and therefore cannot be purchased by every laboratory. The
cost of the method to be described is negligible.
2 — The oil may be totally recovered.
We are all familiar with the fact that if wTe look at
an object through a transparent medium there is no
alteration in the size of the object, provided the medium
has flat, parallel sides. If we look through a convex
lens of glass, the object is magnified if we are within
the focal length. Similarly, a concave lens makes
the image smaller than the object.
If the substance of which the lens is composed has
a smaller refractive index than the surrounding medium,
the phenomenon will be reversed. Thus, for any
given shape of lens, its ability to magnify or reduce de-
pends upon its refractive index with respect to the sur-
rounding medium. A convex lens of crown glass
immersed in carbon bisulfide would not magnify, but
would give an image smaller than the object.
The same principle may be applied to oils. If a
spherical bulb of oil is immersed in a medium of an-
other oil it will magnify or reduce, depending on
whether it has a greater or smaller refractive index
than the medium. If it has the same refractive index
there will be no effect (disregarding the small effect
of the glass in the bulb).
The formula for the focal length of a lens is:
= (»-!)
/
(*-*)
where/ = the focal length,
n = the refractive index with respect to the medium,
R and R' = the radii of curvature of the lens.
Since the two radii are equal to each other and equal
to one-half the diameter of the bulb, the formula
which applies here is:
i{n~ 1)
D
where D = the diameter of the bulb.
Hence, with a given bulb the focal length of the
1 Received January 21, 1921.
lens produced would be inversely proportional to
» — 1. The value of the refractive index is given by:
n = 1 +
y
It would be possible to obtain the focal length of
the bulb of oil immersed in another oil, but this would
be a difficult method for determining the refractive
index.
A more practicable method is to observe qualita-
tively whether the lens is magnifying or reducing, by
comparing the height of a distant building with the
image produced by looking through the bulb of oil
immersed in another oil. The effect is more pro-
nounced when the bulb is held at arm's length away
from the eye, but the size of the bulb makes it diffi-
cult to judge the size of the image, hence another more
delicate method is desirable.
In this method the bulb is raised up and down while
looking through it at a distant object. If the image rises
as the bulb is raised and sinks as the bulb is lowered, the
refractive index of the oil is less than that of the medium.
This is represented in the bottom line of Fig. 3.
The bulb is acting as a concave lens in air (shown on
the right). Likewise, if the bulb is filled with an oil
having a greater refractive index than the medium,
the effect is produced which is represented in the top
line of Fig. 3. On raising the bulb the image goes down,
and on lowering the bulb the image rises. The bulb
is acting as a convex lens in air.
F.q. 3
APPLICATION OF METHOD
The method of making the bulbs is shown in Fig. 1.
It is essential that they be as thin as possible.
The bulbs are filled with oil by sucking through
one stem. The lower stem is sealed off and the top
one bent into a hook (Fig. 2) without sealing it, thus
leaving the oil at atmospheric temperature.
At first, square receptacles, made by cutting the
tops off square bottles, were used to contain the oil
which acted as a medium. It was later found that
test tubes have many advantages over these in that
they are more convenient to handle, have no irregu-
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
547
larities in the glass, may be stoppered readily, require
less oil and, being thinner, may be more easily seen
through.
The bulb is suspended in the top of the test tube,
as shown in Fig. 2. The tube is held in the hand at
arm's length, in such a position that some distinct
horizontal line in the distance may be seen through
the bulb. This may be, for instance, the horizon or the
border line between a grass lawn and some distant
buildings. The tube is tipped forward or backward
slightly until it is vertical, as is shown by the fact
that the line as seen through the center of the bulb
appears straight. Then by slowly raising and lower-
ing the bulb about an eighth of an inch it may be readily
observed whether the oil in the bulb has a greater
or lower refractive index than the surrounding
medium, according as it shows the phenomenon
represented in the upper or the lower line in Fig. 3.
The refractive index of an unknown oil in the bulb
may be obtained by comparing it with a series of
known oils contained in test tubes. A series of such
oils was prepared and arranged in order so that with
a bulb of an unknown oil it was a simple matter to
obtain the refractive index.
These, together with a solution of glycerol (1.4545)
and a sample of toluene (1 .496), constitute a series
with which the refractive index of oils may be deter-
mined with an accuracy greater than the normal
variation between different specimens of the same oil.
This method was proved to be accurate to 0.0005.
The exact values for these oils were obtained on the
Abbe refractometer, and were as follows:
Sperm 1 . 4655
Olive 1 .4703
Olive-cottonseed mixture 1 .4713
Cottonseed 1 .4735
Corn 1 . 4758
Rape-seed 1 . 4778
Castor 1 .4796
Linseed 1 . 4830
(Corrected to 15° C.)
The Abbe refractometer is said to be accurate to
0.0002, but does not always check up as closely as
that. The lard oil and olive oil with which the author
was working were very close to each other in refractive
index. The lard oil is usually listed below olive oil,
but was shown to be higher by the above-described
method. Values obtained on the Abb£ refractometer
showed this to be correct, the difference being 0.0005.
There is one difficulty in the use of this method
which should be mentioned. The glass of which the
bulbs are made produces a slight effect similar to that
of a concave lens in air. So for a bulb filled with an
oil and immersed in a tube of the same oil there is a
slight effect, as shown in the middle line of Fig. 3.
With a little practice one can tell how much of the
effect is due to the oil and how much is due to the glass
in the bulb. This effect is reduced to a minimum by
the use of bulbs with extremely thin walls blown as
shown in Fig. 1, which is drawn a little smaller than
natural size. The bulbs should have a diameter be-
tween three-eighths and one-half inch.
Microanalytical Methods in Oil Analysis1
By Augustus H. Gill and Henry S. Simms
Massachusetts Institute op Technology, Cambridge, Massachusetts
Although much work has been done on perfecting
the methods for identifying oils, little attention has
been paid to reducing the quantity required for anal-
ysis. Occasionally, as in extracting oils from leather,
the oil chemist is called upon to identify a quantity
of oil so small in amount as to handicap him in ob-
taining accurate results. The purpose of this paper
is to show that an accurate proximate analysis may
be made upon an oil when only a few drops are avail-
able, and with an accuracy comparable to that of the
usual methods.
For the present work attention has been focused
on four oils, selected because of their widely differing
properties. These were olive, lard, cottonseed, and
raw linseed. It is safe to assume that these oils
represent in their properties all classes of saponifiable
oils. Any adaptation of the general tests which would
apply to them would apply equally well to others.
The tests to which most attention was given were
the iodine number, saponification value, and specific
gravity.
APPARATUS
The apparatus used in obtaining the iodine num-
bers and saponification values is shown in Figs. 1 to 7.
Fig. 1 represents the ordinary titration apparatus
on a small scale. The bottle was a liter bottle and
1 Received January 21, 1921.
the buret was an ordinary buret-pipet of 10-cc. capacity.
For this purpose one 30 cm. long was selected. A
ball or bead valve was used. It was of course neces-
sary that the drops falling from the nozzle tip be as
small as possible. To this end the tip was so drawn
out that the outlet was on the side of the tip about
half way down, the lower half being a fine glass rod
down which the solution would run and fall off in fine
drops. (The same effect may be produced with a
finely pointed tube smeared with a layer of grease.)
Apparatus of this description was used for the sodium
thiosulfate in the iodine number determinations
548
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
and for the standard hydrochloric acid in the saponi-
fication value determinations.
Figs. 2 and 3 show the arrangement for filling the
pipet used for the iodine solution, the potassium iodide
solution, and the alcoholic potash solution. The capaci-
ties of these pipets were 3 cc, 1.5 cc, and 2.5 cc,
respectively. They were blown for this particular
work with unusually fine stems. They were fitted
into stoppers of the respective reagent bottles, to-
gether with a fine capillary tube, as shown. On
blowing through the capillary tube the pipet was filled
with the reagent. It was raised (Fig. 3), allowed to
drain to the mark on the stem, and emptied in the
usual manner. With a very fine stemmed pipet small
q quantities of liquids may be han-
dled with negligible error. With the
arrangement described above, such
liquids as iodine solution may be
handled without danger of breath-
ing the fumes, and alcoholic potash
solution may be handled without
danger of serious contamination.
It might be advisable in this lat-
ter case to seal a bulb of lime in the
mouth tube to absorb the carbon
dioxide in the breath. This was not
done by the authors, and no trouble
resulted from this, since blanks were
run with each determination.
Fig. 4 shows the syringe pipet
devised by the authors to measure
the chloroform in the iodine num-
ber determinations. It was blown
and ground to fit the bottle, and was
calibrated to deliver 1 cc. of chloro-
form.
Fig. 5 shows the dropper used to
deliver two large drops of starch
solution in the iodine number deter-
minations. A similar dropper used
for phenolphthalein would deliver
one small drop.
Twenty-five-cc. Erlenmeyer flasks
with small funnels made from glass
tubing, as shown in Fig. 6, were
used in obtaining the saponification
Fig. 8 — Gravitometbr values
Iodine numbers were determined in 25-cc. glass-
stoppered weighing bottles, as shown in Fig. 7. A
stirrer was used to stir the solution while titrating.
This proved to be very necessary in keeping the solu-
tion mixed during the titration.
The apparatus used in determining the specific
gravities will be discussed later (Fig. 8).
The general size of the apparatus used may be seen
by comparing the hand in Fig. 3 with the apparatus
in Figs. 1 to 7.
QUANTITIES USED
The quantities of reagents were, in general, one-
tenth those usually required for the same tests. It
would be possible, without doubt, to obtain good re-
sults with still smaller quantities. This, however,
seems unnecessary. More dilute reagents would be
required, and this would involve many difficulties,
aside from the trouble of preparing the reagents. The
rate of addition of iodine to the oil would have to be
studied with the new strength of iodine solution.
Difficulty might be encountered in saponifying some
oils in more dilute alcoholic potash solution.
The reagents used by the authors were those cus-
tomarily used for saponification and iodine number
determinations (Hanus method), except that the stand-
ard hydrochloric acid was 0.1 N rather than 0.5 N.
Similarly, the thiosulfate solution might be diluted
from 0.1 N to 0.05 N, if desired. However, the
results obtained by the authors could be reproduced
more easily than could results obtained with more dilute
solutions. Furthermore, it is doubtful if it would
be desirable to obtain the saponification value with
less than an ordinary drop of oil or to find the iodine
number on less than 11 mg. (a small drop of oil).
It was found that the samples of oil could be reduced
to considerably below one-tenth the normal quantity,
while still using the same quantities of reagents. In
the case of the iodine number, the quantity was re-
duced to 11 mg., which is one-fourteenth to one-
twenty-seventh of the usual sample.
Even better results were obtained with the saponifica-
tion value, for here the weight was reduced to less than
25 mg. without preventing accurate results. This is
one-fortieth to one-eightieth of the usual amount.
It is not to be expected that the oil analyst would be
called upon to make an analysis with such small sam-
ples on any but rare occasions. On such occasions
he would find it a simple matter to make such an anal-
ysis if the size of his apparatus and the quantities of
his reagents were all reduced by the same factor —
one-tenth.
METHOD OF WEIGHING
The method of weighing used throughout this work
was the single-swing method of Paul.1 The principle
involved is that of taking a single scale reading as the
pointer makes its first swing. The pans are so ad-
justed that when the pans are released the pointer
will swing to the right. The distance to which it
swings is observed, and the pan release is thrown off.
This can be done very quickly. The balance which
was used worked so well by this method that its ac-
curacy could be relied upon without repeating the
swing, though it was always checked up by a second
reading taken in the same way. For convenience, the
scale was so numbered that the mark three spaces to
the right of the center was zero. Scale divisions to
the right of this were positive, while those to the left
were negative.
The weight on the pointer arm was so adjusted that
a swing of one scale division was equal to a difference
in weight of 1 mg. The balance was so adjusted that
when there were no weights or equal weights on both
pans the pointer would swing to the right as far as
the zero mark on releasing the pans.
Thus, in adding the weights in making a weighing,
the pans are released when each weight is added just
■ J. Am. Chtm Soc , 41 (1919), 1151.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
549
long enough to see which way the pointer starts to
swing, and, when weights have been added to the near-
est 10 mg., a reading is taken of the distance which
the pointer swings. If, for instance, it swings to
the +2 mark, one knows that the object weighs 2.0
mg. more than the weights on the pan. Accordingly,
the rider is placed on the 2.0 mg. mark and another
reading is taken, which should be exactly zero.
This method gave entire satisfaction, being not only
quick but accurate.
DATA FOR OILS BY USUAL LARGER-SCALE METHODS
Before going into the microanalysis of the oils
which had been selected it was necessary to determine
first the properties of these oils by the usual methods
and with the usual amounts. This was done with
care, a sufficient number of determinations being run
in each case to warrant reliance on the results ob-
tained.
Oil Specific Gravity Saponification Iodine
15° C. Value Number
Lard 0.932 195.1 60.9
Olive 0.918 193.9 84.2
Cottonseed 0.922 195.0 110.3
Linseed 0.934 191.4 173.8
EFFECT OF EXTRACTION ON OILS
It was highly important to know with certainty
whether or not any change is brought about in the
properties of an oil when it is extracted with an or-
ganic solvent, such as gasoline or ether, and subse-
quently freed from that solvent by evaporation. If
the solvent were able to affect the iodine number, for
instance, of an oil, the practical application of micro-
chemical methods for identifying oils would be se-
riously handicapped. If the analyst has a small sam-
ple of leather from which he can extract only a few
drops of oil, he can identify that oil by microchemical
methods only if he is certain that there is no change
in its properties as a result of the extraction.
This was tested with the four oils by the following
method: A few drops of the oils were poured into an
Erlenmeyer flask and dissolved in ether or gasoline.
The solvent was then evaporated off in a current of
air in the case of the nondrying oils, and of carbon
dioxide in the case of the drying oils. When the oil had
been dried to a constant weight, samples were removed
by means of a stirring rod, the weight of the samples
being determined by difference. Both the iodine
number and saponification value were determined on
each oil.
The results of the iodine number determinations
are given below.
From From Original
Oil Gasoline Ether Value
Lard 60.8 60.7 60.9
Olive 84.0 83.2 84.2
Cottonseed 110.6 111.0 110.3
Unseed 173.0 172.0 173.8
The saponification values agreed with the true values
within the limits of error of the determination.
From the above results it may be seen that there
need be no doubt in the mind of the analyst as to the
possibility of error as a result of chemical action dur-
ing the extraction, provided, of course, that the pre-
caution is taken in the case of drying oils to evaporate
off the solvent in an inert atmosphere, such as car-
bon dioxide or illuminating gas.
The gentle heat of a water bath may be used to aid
the drying if this seems advisable. The authors used
a water bath consisting of two tin pans of 2- or 3-qt.
capacity, 26 cm. in diameter by about 8 cm. deep.
One of these was filled a third full of water and placed
on a tripod over a burner. The other pan floated on
the water in the first. Flasks containing solutions to
be evaporated could be placed in the upper pan and
receive a constant and even heat.
DETERMINATION OF IODINE NUMBER
The apparatus has already been described. In
general, the method is the same as that commonly
used for the Hanus method. The quantities of the
reagents were reduced to one-tenth the usual amounts.
The samples were reduced to 11 mg.
A few grams of oil were poured into a small beaker.
A short stirring rod was placed in the beaker and
the weight obtained to the fourth decimal place. A
drop of oil was allowed to run from the rod into the
weighing bottle, and the beaker was weighed again.
The second sample was removed and the beaker was
weighed the third time. The difference between two
weighings gives the weight of that sample. Six samples
and two blanks were usually run at a time.
The oil was dissolved in 1 cc. of chloroform deliv-
ered from the syringe pipet.
After all (or nearly all) of the samples had been
weighed out, 3 cc. of iodine solution were delivered
from the pipet (Figs. 2 and 3) into the first sample. Five
minutes later iodine was added to the second sample,
and in like manner all the samples were treated at
5-min. intervals. After each sample had been acted
upon by the iodine solution for exactly 15 min., 1 . 5 cc.
of potassium iodide solution were added from a pipet,
and immediately titrated with 0.1 N Na2S203 solu-
tion.
The above method allows 5 min. for each titration.
It is essential that the time of reaction be exactly 15
min., as the iodine number will be high or low, accord-
ing as the action is allowed to continue more or less
than this time.
During the titration the solution cannot be mixed
by putting the cover on and shaking, as this is sure to
cause a loss. The mixing can be done very satisfac-
torily by the stirrer shown in Fig. 7. With this stirrer
the standard solution may be run in fairly rapidly
right up to the point where the starch is added with-
out danger of running past the end-point.
the bead valve — Another precaution has to do
with the use of the bead valve of the buret. It is
customary when using one of these to pinch the bead
between the fleshy surfaces of the thumb and fore-
finger, thus producing a wrinkle in the tubing through
which the solution may pass. This invariably pro-
duces an error which, while it may be negligible in ordi-
nary work, is a serious matter when an error of 0.01
cc. is not allowable. The surface of the thumb presses
not only on the tubing around the bead but also on
the tubing above and below the bead. On removing
the pressure of the thumb the tubing resumes its
normal shape and a bubble of air is drawn up into
the tip. This would be permissible if the bubble
550
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
were the same size in all cases, but its size depends
upon the manner in which the thumb is removed,
and it may be large or not form at all, according to the
amount of pressure on the tubing below the bead
after the flow had ceased.
Instead of pressing with the fleshy surfaces of the
thumb and forefinger, one should press on one side
with the end of the thumbnail and on the other side
with the end of the forefinger near the nail. In this
way no air is drawn up and the flow may be so easily
regulated that no drops of solution are allowed to re-
main on the tip.
reading the buret — In analytical laboratories
various devices are used to aid in reading burets.
Among these are the use of paper (usually black paper)
wrapped around the buret and fastened with a pin;
the telescope which is fastened to the buret and slides
up and down on it; and the use of burets having a blue
line flashed on the side opposite the scale.
The experience of the writers is that these methods
are all cumbersome, inconvenient, slow, and not so
accurate as might sometimes be desired. Accord-
ingly a different method, which has none of these
faults, was adopted. A pocket mirror was placed
against the back of the buret at the level of the meniscus
and swung around so that the observer was looking
directly into it. By raising or lowering his head until
the scale graduation nearest the meniscus was in line
with its image in the mirror he was sure that there
could be no error through parallax. . Without moving
his head, the observer then swung the mirror around
(keeping it in contact with the buret all the while)
until the image of the light from the window could be
seen in such a position as to make the meniscus very
clearly denned. The observer must be facing in a
direction neither toward nor directly away from the
window.
This can be done very quickly, and one can read
with remarkable accuracy, without taking any more
time than would be required to get an approximate
reading without any appliance.
The tip of the buret was of the type described above.
Even in this way it was difficult to get drops smaller
than one-sixtieth cc. Since the required accuracy did
not permit an error of 0.01 cc, this caused another diffi-
culty which was overcome by transferring, near the
end-point, half a drop at a time from the tip to the
solution by means of the stirring rod.
More accurate results were obtained, however, by
the use of a tip having a longer glass thread on the end
which dipped into the solution. In this way drops
were not formed at all, but the standard solution
could run out in quantities much smaller than a drop.
There was the serious difficulty, however, that it was
hard to tell how fast the solution was flowing.
The results obtained show that the method is prac-
ticable. Time did not permit the continuation of
the work after this point.
The values for linseed oil were obtained in the first
attempt to use the microchemical apparatus. The
samples in Determinations 3 and 4 were only 0.9
and 11.2 mg., respectively. While they both gave
rather high values, it is worthy of notice that the
error was no greater.
Table I — Iodine Numbers Determined by Microchemical Methods
Weight of Sample
Nc. Gram Iodine Number
Linseed Oil
1 0.0167 170
2 0.0196 175
3 0.0109 179
4 0.0112 (182)
5 0.0155 (181)
Avbraoe 177.4
Average of first three values 174 . 7
Value previously obtained 173 . 8
Lard Oil
1 0.0140 61
2 0.0112 63
Averace 62
Value previously obtained 61
Cottonseed Oil
1 0.0158 102
2 0.0171 102
3 0.0125 109
4 0.0158 113
5 0.0173 113
6 0.0175 102
Average 107
Value previously obtained 110.3
The weight of the second sample of lard oil was only
11.2 mg. Of the six values for cottonseed oil, it is
noteworthy that the one coming closest to the true
value is that obtained from the smallest sample, 12.5
mg.
DETERMINATION OF SAPONIFICATION VALUE
Samples of the oil were weighed out by the methods
already discussed. The samples were of one or two
drops. After it had been found that good results
could be obtained with a single drop, no larger samples
were used. The samples were dropped into a 25-cc.
Erlenmeyer flask, and 2.5 cc. of alcoholic potash were
added from a fine-stemmed pipet (Figs. 2 and 3).
The flasks were covered by means of small funnels
made from glass tubing.
The saponifications were carried out in the arrange-
ment of two sauce pans, previously described. This
gave a low even heat. The ebullition of the water pro-
duces a movement of the upper pan which serves to
keep the flasks agitated, thus aiding the reaction and
preventing bumping. With some oils a greater heat
may be required.
After the reaction was complete the excess of potash
was titrated against standard 0. 1 N hydrochloric acid.
It was impossible to obtain sufficient accuracy in read-
ing the buret with the 0.5 N acid ordinarily used.
However, two out of six values for lard oil with 0.5 N
acid were 196, the true value being 191.5. The other
values were all abnormal.
Table II — Saponification Values Determined By Microchemical
Methods
Weight of Sample Saponification
No. Gram Value
Cottonseed Oil*
1 0.0750 194
2 0.0833 195
3 0.0528 193
4 0.0244 195
5 0.0511 195
Average 194.4
Value previously obtained 195
Olive Oil
1 0.0486 193.7
2 0.0470 196
3 0.0244 194
4 0.0255 192
Average 193 . 5
Value previously obtained 193 9
1 The values for cottonseed oil represent the results of five simultaneous
determinations.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
551
The above values speak for themselves. Good re-
sults were obtained with as little as 15 mg. These
were usually mixed in with poor values, however.
Probably the greatest error occurred in the titra-
tions, since the end-points were not sharp. Phenol-
phthalein was used as the indicator. This normally
gives a sharp, distinct end-point; but with dilute
solutions, when an accuracy of 0.01 cc. is required, the
end-point is less satisfactory.
ATTEMPTS TO PERFORM MORE THAN ONE TEST ON THE
SAME DROP OF OIL
Considerable time was spent in an attempt to make
two or more determinations on the same sample of
oil. It was thought, for example, that it might be
possible to get the refractive index on a drop or two
of oil, absorb the oil on filter paper, obtain the saponi-
fication value, and then get the melting point of the
fatty acids and their iodine value. These attempts
were entirely unsuccessful.
In recovering the oil after having obtained the re-
fractive index by the Abbe refractometer, the method
first employed was to absorb the oil on filter paper,
extract with ether, evaporate off the latter, weigh, and
run a saponification number on the oil. The values
obtained were low in all cases. This was not due to
anything absorbed by the ether from the filter paper,
as blanks run with the filter paper showed no error.
The error may have been due to the condensation of
moisture during the evaporation of the ether. Al-
though the oil was dried carefully, the water may not
have been totally removed.
In the second method the filter paper was weighed
before and after absorbing the oil, and the saponifica-
tion was made in the presence of the filter paper. The
results were all high. Subsequent investigation showed
that the filter paper itself was hydrolyzed and used up
some of the potash. Hardened filter paper was also
acted upon by the alcoholic potash. Asbestos was
unsatisfactory as an absorbent because it absorbed the
caustic to such an extent that a distinct end-point
was impossible. Inasmuch as there seemed to be
no material which would act satisfactorily as an ab-
sorbing agent, this part of the work was abandoned.
It was next attempted to isolate the fatty acids
produced during the saponification and to use these
to obtain the iodine number and melting point. After
the saponification values had been determined the
solution was acidified with an excess of hydrochloric
acid. It was allowed to stand in contact with ether
until the water layer became clear. The ether was
separated, and the aqueous layer was washed twice with
ether. The combined ether extracts were evaporated
in a 25-cc. weighing bottle to constant weight, and the
iodine number was determined. Although extraction
with chloroform was tried, as well as other modifica-
tions, the results were in all cases low.
An attempt which was made to remove the last traces
of water from the fatty acids from an olive oil saponifi-
cation by means of a current of air resulted in their
oxidation. It is probable that if the fatty acids were
dried carefully in an inert atmosphere, after alcohol
had been added to lower the vapor pressure of the
water, satisfactory results could be obtained.
SPECIFIC GRAVITY
Specific gravity may be obtained by a variety of
methods. The Westphal balance is the most common,
but requires a large amount of oil. Small pycnometers
may be used, but require much care in handling, espe-
cially when dealing with small quantities of oils.
The gravity may be determined by weighing a definite
volume measured from a pipet, but it is hard to de-
liver a definite volume from a pipet, on account of
the viscosity of the oil.
It was accordingly deemed advisable to devise a
different method for obtaining specific gravities
when only small quantities of the oil are obtainable.
It was thought possible to obtain the gravity by smear-
ing a weighed quantity of oil on the bottom of a very
delicate hydrometer and noting the difference in the
height to which the hydrometer would rise. Hydrom-
eters were made for the purpose, but the method
proved to be impracticable, even when the bottom of
the bulb was made concave to prevent drops of oil
from rising to the surface of the water.
The sensitivity of a hydrometer depends on the size
of the stem and the difference between the densities
of the medium and air. The density of air being
negligible in comparison with that of liquids, we may
say that the sensitiveness of a hydrometer is inversely
proportional to the diameter of the stem squared.
Hence to make a hydrometer sensitive it is necessary
to make the stem as fine as is practicable.
The hydrometer1 shown in Fig. 8 was devised to
obtain the specific gravities of small quantities of
oils. After experimentation with different sized stems
and bulbs, the hydrometer shown was found to give
the best results. There are two bulbs: the lower one,
the usual hydrometer bulb, while the upper one (not
connected with the lower) is filled with the oil or other
substance whose gravity is desired. This is filled by
dipping the little side tube into some of the substance
placed on a flat watch glass and sucking through
the stem, which is open at the top. The bulb is filled
to a little above the mark on the stem with the liquid,
which is then drawn down to the mark by means of
a piece of filter paper applied to the end of the short
tube. The stopper of soft rubber with a small hole in
it is then placed on the end of the stem. This pre-
vents the entrance of water into the bulb by capillary
attraction when the bulb is immersed in water.
The bulb having been filled with oil, the hydrometer
is immersed in water in a 2-liter graduate. The height
of the hydrometer in the water is observed by reading
on the scale of the graduate the height of the bottom
of the hydrometer. In this way it is not necessary
to calibrate the stem of the hydrometer, and a smaller
stem may be used. The bulb is emptied by blowing
through the stem. It is rinsed out with alcohol and
ether.
1 With regard to this reservoir hydrometer it should be said that the
same principle has been used before by Eichhorn [Z. anal. Chem., 30 (1891),
216], but the instrument here described has advantages over other instru-
ments in the ease of filling and emptying the bulb and the method of read-
ing the height of the liquid.
552
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
The hydrometer must first be calibrated by filling
the bulb with water. After the reading has been
taken, it is filled with an oil of known specific gravity
and another reading taken.
The gravity is calculated as follows:
1 — G 1 — Gs
R — W ~ Rs — W
where G = specific gravity sought
Gs = specific gravity of the standard oil
R = reading with unknown oil
Rs = reading with standard oil
W = reading with water
The gravity sought is then:
(R_w)u=M
G = 1
(Rs — W)
was
After the hydrometer has been standardized the
.. (1 — Gs) . .
ratio is known.
(Rs — W)
Substituting for this the letter F, we have:
G = 1 — (R — W)F
where W is known when the jar is filled to a certain
height. All that is then necessary is to take a reading
with the oil and to substitute this in the last formula.
The factor F for the hydrometer used by the writers
1
2570"
The factor depends not only on the size of the stem,
but also on the capacity of the reservoir bulb. This
bulb, in the writers' instrument, has a capacity of 1 . 2
cc. Smaller bulbs were tried but found impractica-
ble, owing to the extreme fineness of the stem neces-
sary to produce the desired accuracy and sensitivity.
The diameter of the stem used was 1 mm.
It is true that this does not offer a method for obtain-
ing specific gravities when the total amount of oil
available is less than 1 cc. It offers, however, certain
advantages over the use of the pycnometer or the
weighing of a definite volume measured from a pipet:
1 — The method is much simpler, since no weighings are re-
quired.
2 — The chances for error are much smaller, since there is
always a danger of a large error in weighing a glass vessel, owing
to the adsorption of an appreciable layer of moisture, the amount
depending upon the humidity of the atmosphere. When a
pycnometer is used, three weighings must be made, unless the
instrument has been calibrated and the weight etched on it.
With the hydrometer described, one reading is sufficient after it
has once been standardized. The only source of error lies in
reading the scale, providing there is not much variation in tem-
perature and care is exercised in filling the bulb exactly to the
mark on the stem. A glance at the instrument after taking the
reading would show whether the meniscus of the oil in the stem
had crept up, because of a leak in the stopper. The error in
reading the scale would be negligible if a graduate were used
having graduations passing all the way around the cylinder.
The errors involved in weighing a measured amount of oil
are large, both in measuring the volumes and in weighing the oil.
3 — The time required is less. It is much easier to take a
reading of the height of the hydrometer in the jar than to weigh
a. pycnometer.
As in the pycnometer, the oil may be totally recov-
ered and used for other determinations.
To distinguish this instrument from an ordinary
hydrometer, it might be called a "gravitometer."
It was used to determine the specific gravities of
the four oils. The bulb was filled roughly to about
the right height, and the readings were taken rather
hastily.
The variations from the reading's obtained on the
Westphal balance were as follows:
Oil Error
Lard 0.000
Olive 0.003
Linseed 0 . 004
Cottonseed 0.001
Average 0.002
These results are remarkable when it is considered
that there was no mark on the stem of the instrument
at the time that the readings were taken. It was
found necessary to etch a mark on the stem and to be
very careful to fill exactly to the mark. This having
been done, the error was reduced to less than 0.001.
Had the marks on the graduate passed all around the
cylinder, it is probable that the results would check
to 0.0001.
This is a greater accuracy than is required for oils,
because various specimens of the same oil vary among
themselves from 0.003 to 0.01 or more. How-
ever, it is worth knowing that this accuracy may be
obtained when it is desired. An instrument to be
used exclusively for oils might have a smaller bulb
and still be sufficiently accurate.
Another possible method for determining specific
gravities is as follows: If a drop of oil is suspended
in a mixture of alcohol and water of such a concen-
tration that the drop neither rises nor sinks, the oil
and the mixture have the same density. If the density
of the alcohol-water mixture is determined, that "of
the oil will be known. This might be done by run-
ning alcohol into water until a drop of oil floating on
the surface of the water would remain suspended in
the solution without tending to rise or sink, and de-
termining the specific gravity of the solution with a
pycnometer or Westphal balance.
When this method was tried in a qualitative way
the following objection was discovered: If, after the
proper mixture had been obtained to suspend a drop
of oil, a fresh drop of the same oil is dropped in, it sinks
to the bottom and remains there for a time (possibly
half a minute, depending on the size of the drop)
before it can be made to remain suspended in the
solution. Evidently the oil absorbs a certain amount
of alcohol from the mixture and then, becoming lighter,
will remain suspended. Hence it may be seen that
the values obtained would all be low. The magnitude
of this error was not determined quantitatively. It is
furthermore difficult to mix the alcohol solution so
thoroughly that it will have the same density at the
top as at the bottom.
SUMMARY
1 — Very close analytical results on the saponification
and iodine values of oils are obtainable with 15 and
11 mg., respectively, or about one one-hundredth and
one-thirtieth the usual quantities.
2 — Good results can be obtained for specific gravity
with 1-g. samples.
3 — The apparatus is that ordinarily found in the
laboratory or easily made by a good manipulator.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
553
. HN03 (
3p. Gr.
1.42) per
1
100 Cc.
Gram PbO
0 0034|
0.0030
0.0011
0.0007
2
11 nn.,l
0.0030
0.0010
0.0005
3
0.0054
0 . 0030
0.0011
0.0004
4
0.0055
0.0029
0 . 0009
0.0004
5
0.0054
0.0028
0.0010
0.0004
6
0.0054
0.0028
0.0010
"" o"oooo
7
0.0056
0.0028
0.0008
8
0.0055
0.0028
0.0009
9
0.0058
0.0027
0.0008
10
alculated
0.0056
0.0057
0.0029
0.0029
0.0005
m PbOz C
0.0011
0.0006
The Determination of Small Amounts of Lead in Brass1
By Francis W. Glaze
Chemical Research Laboratory, Scovili Manufacturing Co., Waterbury, Connecticut
In the course of research investigations in this lab-
oratory, an accurate, as well as fairly rapid, method
was needed for the determination of small amounts of
lead in brass. In looking over the literature on the
electroanalysis of lead as lead dioxide, we could find
no reference to the determination of such small amounts
as those with which we had to deal. It was therefore
decided to make a complete study of all the variables,
with the idea of eventually developing a method to
fit our needs.
EXPERIMENTAL WORK
A current of N.D.100 of 1.5 amperes and 2.9 to 3.1
volts was used in all of this work, as the literature gave
this density as the one best suited for the deposition
of lead as the dioxide. The regular cylindrical gauze
electrodes, with the anode fitting inside of the cathode,
were used.
Ten samples were taken, each containing an amount
of lead equivalent to 0.0057 g. of lead dioxide. To each
of these samples were added 1, 2, 3, etc., cc. of nitric
acid, of specific gravity 1.42. The electrolyte was di-
luted to 100 cc, and electrolyzed, the current being
interrupted for 5 sec. at the end of 0.5 hr. It was
found that all the lead was deposited at the end of
1 hr., which was later found to be practically the mini-
mum time for the deposition of that amount of lead
dioxide. The electrolyte was then removed, the anode
being dropped into distilled water, rinsed in alcohol,
and dried at 200° to 230° C. for 0.5 hr. The time re-
quired from the moment the first of the deposit ap-
peared above the surface of the electrolyte until the
last of it disappeared below the surface of the wash
water was 2 sec. The anode with the deposit was cooled
in a desiccator, and weighed. It was then cleaned,
dried, cooled in a desiccator, and weighed again, the
difference being taken as lead dioxide. This was found
necessary, as the anode often lost as much as 0.3 mg.
during a determination.
This same procedure was repeated with one-half,
one-fifth, and one-tenth the above amount of lead in
the electrolyte. The results of these runs are contained
in the table given below. For 0.001 g. of lead, 9 cc.
of nitric acid per 100 cc. of electrolyte is the upper
limit, while, for 0.0005 g. of lead, the acid should not
be over 5 cc. Also, when the amount of lead present
is 0.005 g., at least 2 cc. of nitric acid must be present.
Consequently, for our work, where the deposits range
from 0.001 to 0.0025 g., 5 cc. of acid per 100 cc. was
taken as the best concentration to use.
With this acid concentration, 0.005 g. of lead can be
deposited in about 1 hr. The rate of deposition can
be increased by using a higher current density, but,
when the density is raised to about 4.5 amperes, de-
composition of the nitric acid begins, tending to make
the electrolyte reducing. Also, when copper is pres-
ent, a higher current density deposits more copper,
thereby increasing the acid concentration.
• Received February 8, 1921.
Although it is found necessary to interrupt the cur-
rent to obtain all the lead as dioxide when pure lead
solutions are analyzed, it is not necessary when copper
is present, as lead is far enough above copper in the
electromotive series of metals so that any lead de-
posited on the cathode would immediately redissolve.
Hence, all that is necessary to obtain an accurate de-
termination of lead without interrupting the current
is to have plenty of copper in the electrolyte at all
times during the electrolysis. Large amounts of cop-
per have no other effect at the current density used,
for the amount of copper deposited is equivalent to
1 cc. or less of nitric acid (1.42).
For the most accurate work, the electrolyte must be
siphoned off, as the deposit often loses 0.2 to 0.3 mg.
when taken down by the routine method mentioned
above.
An 8.643-g. sample of brass is weighed into a 150-cc.
electrolytic beaker, and is carefully treated with 30 cc.
of 1:1 nitric acid, after which the sample can be brought
into solution with a reasonable amount of care by
means of 10 to 15 cc. of nitric acid (1.42). It is warmed
to complete solution on a hot plate, and evaporated
until cupric nitrate begins to crystallize out, to remove
all the acid. After cooling, 5 cc. of nitric acid and a
small amount of water are added. It is then warmed
until all the crystallized salt dissolves, diluted to vol-
ume, and, electrolyzed at a current of N.D.ioo of 1.5
amperes and 2.9 to 3.1 volts. At the end of 1 hr., all
the lead will have been deposited. However, it is best
to add a little distilled water and continue the current
for about 10 min. longer, watching to see if any lead is
deposited on the clean surface. The electrolyte is
siphoned off, the anode being washed with distilled
water and alcohol, and finally dried at 200° to 230° C.
for 0.5 hr. It is then cooled in a desiccator, and weighed.
After cleaning and drying, it is weighed again, the dif-
ference being lead dioxide. The weight of the lead
dioxide in grams, multiplied by 10, gives the percentage
of lead in the brass.
This method will work for all amounts of lead less
than 0.06 per cent. No doubt, it will work for larger
amounts, but no study has been given to that phase
of the problem. It has proved very satisfactory and
has given most concordant results.
554
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
SUMMARY
The electrolytic method for the determination of
lead as lead dioxide has been investigated with the idea
of using it to determine small amounts of lead in
brass.
The methods given by Dr. E. F. Smith in his
book "Electro-analysis," and by Price and Meade in
their book "Technical Analysis of Brass," under spelter
analysis, with a few modifications, are found to apply
very well.
The current density and the acid concentration are
the most important variables.
LABORATORY AND PLANT
The Manufacture of Citric Acid from Lemons'
Research Laboratory, Cali
The first serious attempt to convert the lower grades
of California lemons into by-products was made in
1898 at National City, San Diego County.
Other factories for the production of various products
from citrus fruits have been started at various times
at Pasadena, Redlands, Santa Ana, Riverside, and
other places. An excellent account of these has been
given by Will.2
Work along similar lines in connection with Florida
oranges has been published by McDermott3 and by
Walker.4
The United States Department of Agriculture
became interested in the possibility of developing a
citrus by-products industry in this country, and in
1907 sent Mr. E. M. Chace to Italy to study similar
industries there.5
Mr. Chace made a survey of the lemon industry in
California in 1908, and as a result of his work the
Department established the Citrus By-products Lab-
oratory in 1911 at Los Angeles.
The early work of this laboratory was done by Mr. H.
S. Bailey and the author under the direction of Mr.
Chace, who has been in charge of the laboratory since
its beginning. The Citrus By-products Laboratory
secured accurate data on the methods applicable to
the manufacture of citric acid, and the yield to be ex-
pected from lemons.
It must be remembered that the average haul by
which citrus fruit raised in California reaches its market
is about 2500 miles. This precludes the shipment
of anything but sound fruit of good appearance and
keeping quality. There is necessarily left a large
quantity of fruit that is not fit to pack and ship. This
is culled out for reasons such as: irregular shape,
oversize, undersize, frost damage, heat damage, clipper
cuts caused by careless picking, thorn pricks, wind scars,
thrip marks, excessive scale, or any sort of mechanical
injury or indication of decay or infection of any kind.
The steps in the process of manufacture of citric
acid may be readily followed by means of the accom-
panying sketch.
EXTRACTION OF JUICE
All the citric acid in a lemon is contained in the
1 Read before the Southern California Section of the An
cal Society, Los Angeles. Cal., December 1920.
' This Journal, 8 (1916), 78.
• Ibid., 8 (1916), 136.
« Florida Agricultural Experiment Station, Bulletin 136.
Bureau of Plant Industry, U. S. Department of Agriculture, Bulletin
160.
By C. P. Wilson
Fruit Growers Exchange, Corona, California
juice, so that the separation of juice from the pulp
may be considered the first step in the recovery of the
acid.
The fruit is shoveled or dumped on to a broad belt
conveyer and, if other products than acid are to be
made, is graded to give the kind of fruit needed for
such a product. Any lemon can be used to make
citric acid, though, of course, the yield varies enor-
mously from as low as 15 lbs. per ton from badly frozen
lemons to 50 lbs. or more from the thin-skinned juicy
lemonettes. It is interesting to note that the effect
of frost is to decrease the amount of juice in the fruit
and also the percentage of acid in the juice which
remains.
The fruit passes from the grading belt by way of a
bucket elevator to a pair of cutting knives which tear
the lemons coarsely and drop them into a set of wood
roller crushers which thoroughly bruise the fruit and
press out some juice. The crushed fruit drops into
the hopper of a continuous screw press where most
of the juice is removed. The continuous presses
are similar to those used for pressing moisture, fat,
or oils from garbage, fish scraps, copra, vegetable
seeds, etc.
From the first press the juice runs to the measuring
tank, while the pulp is passed through a soaking box
where it is saturated with water. From this box the
wet pulp is dumped into another continuous press
and the juice goes to the same measuring tank as
did the first juice. Pulp from the second press is ele-
vated to the hopper of a third press, receiving a spray
of water as it ascends the elevator. Juice from the
third press serves as maceration water for the first
soaking, while the pulp passes out and is used as fer-
tilizer.
One ton of lemons contains on the average about
70 lbs. of total acid (calculated as crystallized citric
acid). Using the extraction process described above,
85 per cent or more of this acid is obtained in the juice.
Pure pressed lemon juice contains from 6 to 7 per
cent citric acid, but on account of the dilution by
maceration water the mixed juice obtained in factory
practice averages about 4 per cent acid and contains
about 5 to 5.5 per cent of total solids. The juice
contains about 0.5 per cent of insoluble solids and is
rather thick and pulpy. It is stored in wooden tanks
of about 57,000 liters capacity, in which it is allowed
to undergo fermentation for about 4 or 5 days in warm
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
555
weather, or about 10 days in cold weather. This
fermentation seems to liquefy some of the mucilagi-
nous, slimy constituents and to coagulate others. The
sugars are completely removed. The chemistry of
this change has not been worked out in detail, but
it has been shown that the loss of citric acid by fermen-
tation is negligible for the first few days. Factory
experience has thoroughly demonstrated that fresh
Manufacture of Citric Acid — Diagrammatic Flow Sheet
juice is very difficult to filter, while properly fermented
juice filters easily and requires a minimum of filter-eel.
After proper fermentation, the juice is thoroughly
agitated so as to reincorporate the pulp, which during
fermentation has partly sunk to the bottom and partly
risen to the top, leaving a clear layer in the middle.
In earlier practice this middle portion was drawn off
and used without nitration, and the pulp was washed by
agitation with water and subsequent settling and de-
cantation. This was a slow, wasteful process and left
in the tanks a slimy voluminous residue that was
very troublesome to handle. The present practice
is to filter the whole juice after boiling with filter-eel.
The well-mixed fermented juice is pumped into pine
tanks 2.4 meters deep and 2.4 meters in diameter,
equipped with copper heating coils and mechanical
agitators. About 7500 liters are handled at a charge,
and enough filter-eel is added to clarify the juice on
boiling. The operator adds the amount of filter-eel
he deems necessary, as indicated by experience, and
brings the juice to a boil. A sample is withdrawn, and
if it clears quickly by settling it is ready to filter. If
it does not clear readily, more filter-eel is added. The
juice is again boiled and the test repeated until the
juice is ready to filter. On the average, about 12 to
20 kilos of filter-eel are required for each 1000 liters
of juice.
Filtration is carried out by means of a copper-lined
Sweetland press. A 30-in. wood plate and frame,
open delivery, washing type press is used when greater
capacity is necessary. The cake is thoroughly washed
with hot water. The filter-eel may be recovered from
the press cake by burning out the organic matter,
or it may be used for the production of decolorizing
carbon, as mentioned later.
PRECIPITATION OF CALCIUM CITRATE
The filtered juice is a brilliant, light amber liquid,
averaging about 4 per cent acid. It is pumped into
wooden tanks 2.4 meters in diameter by 1.5 meters
high, with staves made of Oregon pine 7.6 cm. thick.
Each tank is equipped with copper heating coil and
mechanical agitator. A charge consists of about
3700 liters of juice, and from a laboratory assay the
amount of calcium required to precipitate the citric
acid is calculated. In practice, sufficient hydrated
lime of high purity is added to precipitate 90 per cent
of the total acid, calculated as citric. Sufficient calcium
carbonate is then added to neutralize the remaining
10 per cent of acid, and an excess of 7 kg. of calcium
carbonate is added.
Experience has shown that if the juice is completely
neutralized with calcium hydroxide, dark-colored
compounds are formed. These compounds are diffi-
cult, if not impossible, to wash out, and if not removed
cause the liquor produced by the decomposition of the
citrate to be very dark colored. This increases the
difficulty of securing satisfactory crystals.
It has also been shown that, however great the
excess of calcium carbonate added to the juice, there
is always a small residual acidity, varying from 0.08
to 0.20 per cent, depending on the acidity of the original
juice.
The resistance to corrosion of the copper coils placed
in these tanks is noteworthy. For 2 yrs. the tanks
containing these coils were used for decomposing the
citrate as well as precipitating it from the juice. The
coils were therefore subjected to the action of liquors
containing 10 to 20 per cent of citric acid and about
0.2 per cent of sulfuric acid for a great many days.
During the last two years the tanks were used only
for precipitating citrate. Apparently the coils were
worn thin by the swirling calcium citrate, rather than
by reaction between the copper and the acids.
The precipitated citrate is pumped into an iron
plate and frame filter press and thoroughly washed
with water at as near 100° C. as possible, and then
partly dried by blowing air through the cake. The
citrate is dumped by way of a convenient chute directly
into one of a series of pine tanks exactly like those
used for precipitating the citrate, except that it has
no heating coil.
DECOMPOSITION OF CITRATE
The citrate is suspended in dilute liquor obtained
in washing the previous batch of gypsum, and the
amount of 66° Be. sulfuric acid needed for the com-
plete decomposition is added. The accuracy of this
reaction is checked by filtering off a sample of the acid
liquor, after thorough agitation for 30 min., and adding
about 5 cc. of 45 per cent CaCU solution to an equal
556
TEE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
volume of the filtered liquor. A faint precipitate of
calcium sulfate should be noticeable after holding in
the steam bath 5 min., indicating an excess of not
more than 0.2 per cent sulfuric acid.
If too much sulfuric acid has been added it is nec-
essary to add calcium citrate, the amount of which is
ascertained as follows: Total acidity of the liquor is
determined by titration of a 10-cc. sample, using phenol-
phthalein. A solution is then made up which is
exactly 10 cc. in volume and 10 per cent acid (as citric)
in strength. As the liquor always contains over 10
per cent citric acid, this is a simple dilution. A stand-
ard solution is made containing 10 per cent citric
acid, with a drop or two of ferric chloride solution
added to give a depth of color equal to that of the
solution to be tested. This is for the purpose of over-
coming the difficulty in comparing depths of color
which are not the same shade, and in practice has been
very successful. Three drops of a 1:1000 solution of
thymolsulfonephthalein and 1.5 cc. 0.5 N sodium
hydroxide are added to each solution. The pure
citric acid solution assumes a characteristic yellow
tint, while the sample containing sulfuric acid con-
tinues to display the red color due to the more highly
ionized mineral acid. The latter is titrated with
0.5 N sodium hydroxide until the color matches that
of the standard. The number of cc. of 0.5 iV alkali
used in the last titration measures the excess of sulfuric
acid, and hence the amount of calcium citrate which
will be decomposed by it. This method has been
found very practical in factory control work.
The decomposition of the citrate is usually com-
pleted in about 3 hrs. The precipitated calcium
sulfate is allowed to settle by gravity and the acid
liquor drawn off. The precipitate is washed free from
acid by decantation by the countercurrent principle,
using a five-step cycle. The calcium sulfate residue
is sun-dried and sold as fertilizer.
The acid liquor thus obtained is a light amber solu-
tion containing about 12 to 15 per cent acid. It has a
density of about 5° to 6° Be., contains about 0.2 per
cent sulfuric acid, and has a purity of about 95 to
98 per cent.
CONCENTRATION OF LIQUORS
.ue acid liquor from the decomposition of citrate
is run into lead-lined open evaporators of about 17,000
liters capacity, equipped with lead steam coils, and
in these evaporators the liquor is concentrated to
20° to 25° Be. The liquor is kept at incipient boiling
a„,j -..„r b0iie(j hard. Agitation is maintained by
Tuc .. ^acent.ation is completed in lead-lined vacuum
pans of about 7000 liters capacity. The concentrated
liquor is delivered to the lead-lined crystallizers at
37° to 38° Be. In 3 to 5 days a good crop of crystals
is set, and the mother liquor is drawn off and reboiled
to produce another crop. The crystals are washed
with cold water in a basket centrifugal. These cen-
trifugals are standard 30-in. Weston type machines
with bronze baskets. The inner lining is perforated
sheet monel metal. The curbs are lined with lead.
The crude crystals are usually made by the granu
lation process in which the crystallizing liquor is kep
in gentle agitation. A heavy crop of small crystal
is thus produced.
The crude crystals are dissolved in warm water ii
a lead-lined tank by dumping them in a perforatei
lead basket suspended at the top of the tank, utilizin
the well-known principle of the heavy solution goin
to the bottom while the most dilute solution is alway
at the surface where the crystals are continually dis
solved.
PURIFICATION OF CRUDE ACID
The solution of crude acid is subjected to laboratory
tests and purifying treatment prescribed and carriei
out under strict laboratory control.
The impurities to be removed are mainly: (1) or
ganic color, (2) lead, (3) copper, tin, and antimony, (4
iron and nickel, (5) sulfuric acid, and (6) calciun
sulfate. All of these, except organic color, would appea
in the ash on incineration, and their elimination au
tomatically brings the ash to a negligible quantity
organic color — Organic coloring matters an
present in the raw juice, others are formed on heatinj
and remain in the filtered juice, and to some exten
are held by the citrate throughout the washing, am
appear in the liquors. Some color is added by de
composition of the citric acid and organic impuritie
on heating in the evaporators. If not removed thi
color appears in the final crystals, bringing them belo-s
standard as to color and translucency.
In our early work bone-black was used, but it hai
to be thoroughly washed with hydrochloric acid t<
remove the calcium phosphate, and then with wate
to remove the acid and soluble salts. This was ex
pensive and laborious. Experiments with a numbe
of decolorizing carbons soon showed the product knowi
as filtchar 5B to be well suited to the work, and a
compared with the bone-black to be cheaper in firs
cost, and in operating cost. Since then another carboi
has been applied very successfully.
Filtchar is added to the liquor in the proportion o
about 1 to 2 per cent of the weight of the liquor, abou
6000 to 7000 kilos of liquor being treated in a batch
The liquor is slowly warmed to about 70° C. Othe
corrective treatments are given at the same time
The completion of the decolorization is tested b;
filtering a sample of the liquor, treating a portion o
the filtered liquor with more filtchar, heating am
filtering, and comparing the color of the two filtrates
More filtchar is added or not, as indicated by thi
test. The final decolorized filtrate is a very pal
straw color in layers several inches deep, and appear
practically water-white when seen through a three
fourths-inch test tube.
lead — A part of the lead is removed as sulfate b;
the sulfuric acid, a small amount of which is normall;
present in this liquor. The remainder of the lead i
removed by precipitation as lead sulfide.
copper, tin, and antimony — Copper and tin ar
taken up from pipe lines, pumps, and valves, and an
timony from the lead pipe lines and containers, whicl
are alloyed with 2 to 4 per cent of antimony for stiffen
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
557
ing. All three metals are precipitated as sulfides
at the same time that the lead is removed.
iron and nickel — Iron enters the process as a
slight impurity in the filter-eel, calcium hydroxide,
calcium carbonate, and sulfuric acid, and is dissolved
from certain parts of the presses and other machinery
with which the liquor comes into contact.
Iron in the^ ferric state imparts a dirty brownish
color to the acid crystals. In the ferrous state iron
gives no noticeable color, but it slowly oxidizes and
causes the crystals to become distinctly yellow on
standing, even in closed containers. The color due
to iron strikes the eye immediately, and from a commer-
cial point of view is one of the most undesirable defects
the crystals can possess.
Nickel is taken up from monel metal containers and
conducting lines, etc., and, though present in small
amounts, it imparts a brownish tint to the crystals.
In some cases there seems to be deposited a very fine
precipitate of oxide of nickel which gives the crystals
a dirty grayish appearance and seriously modifies
their translucency. Both iron and nickel appear in
the ash and are also for that reason undesirable.
Both ferric iron and nickel form ferrocyanides which
are practically insoluble in acid solutions. In the
treatment with filtchar, etc., the liquor is constantly
agitated by blowing air in at the bottom of the treating
tank. This serves also to bring all or nearly all of
the iron into the ferric condition so that it can be
removed by precipitation as ferric ferrocyanide.
Calcium ferrocyanide is admirably adapted to the
removal of iron and nickel, as it is very soluble in
water, precipitates both metals from the acid solution,
and forms free citric acid and precipitates calcium
sulfate, without the introduction of a new ion into the
solution.
In using the ferrocyanide ion for the removal of
iron and nickel, the liquor to be treated is sampled, and
the sample filtered clear. To several 25-cc. portions
of the clear filtrate varying amounts of a 1 per cent
solution of Ca2Fe(CN)6.12H20 are added, together
with about 0.5 g. filtchar, and the mixture is heated
on the steam bath for 10 min., or just brought to a
boil on a hot plate, and filtered.
If difficulty is experienced in securing a clear filtrate,
a little filter-eel, which has been washed perfectly free
from iron with hydrochloric acid and freed from acid
by washing with distilled water, may be added before
heating. This is very effective in holding the finely
divided prussian blue precipitate.
To all of the filtrates a drop of the 1 per cent solution
of Ca2Fe(CN)6 is added. That sample which shows
the least blue color, but in which there is nevertheless
a visible blue color, is used as the basis of calculating
the amount of Ca2Fe(CN)6 necessary to remove the
iron and nickel from the batch of liquor in question.
Care must be taken that an excess of calcium ferro-
cyanide is not introduced into the liquor, as it passes
through the vacuum pan and into the crystallizers.
These are lined with monel metal and rapidly become
coated with a film of nickel ferrocyanide, which ap-
pears in the crystals. In practice, enough calcium
ferrocyanide solution is added to precipitate about
90 to 95 per cent of the iron and nickel present, since
the 5 or 10 per cent left never appears in the crystals.
As these metals become concentrated in the mother
liquors they are removed by subsequent treatment
with the ferrocyanide.
It is to be noted that the other metals mentioned,
notably copper, also form insoluble ferrocyanides.
As calcium ferrocyanide is the most expensive reagent
used in the treatment, the several steps naturally
take place in the order of the ascending costs of the
reagents used: sulfuric acid, filtchar, hydrogen sulfide,
and calcium ferrocyanide.
When the tests with filtchar, hydrogen sulfide and
calcium ferrocyanide show that the treatment is com-
plete, the liquor is filter pressed and sent to the vacuum
pan for final Concentration.
sulfuric A£iD — At times sulfuric acid may ac-
cumulate in excess as the liquor is concentrated in the
vacuum pan. If not removed, some of this sulfuric
acid may appear in the finished crystals, even after
thorough washing in the centrifugal. When a point
is reached in the final boiling where the liquor has
about 2 or 3 hrs. yet to remain in the pan, a test for
free sulfuric acid is made. A sample of filtered liquor
is mixed in a test tube with an equal volume of 45 per
cent calcium chloride solution and heated in the steam
bath for a minute or two. If more than a slight pre-
cipitate is obtained, an appropriate amount of calcium
hydroxide in the form of a thin milk is drawn into the
pan, throwing down the excess of sulfuric acid as cal-
cium sulfate.
As the vacuum pan is lined with lead, the liquor
always takes up more or less of this metal in the final
cooking, and an extra precaution against this is taken
by sucking into the pan about 20 liters of hydrogen
sulfide water at the same time that the milk of lime is
added. By the time the strike is withdrawn the sul-
fide has had ample time to precipitate the lead, and
any excess has been boiled off.
calcium sulfate — Calcium sulfate is always
present in greater or less amount in acid liquor, and
more of it is formed by the combined treatments with
sulfuric acid, calcium ferrocyanide, and calcium hy-
droxide. It seems a fair assumption that these lit
are always saturated with calcium sulfate, and Ja.-. a
matter of fact there is, at the end of any concentration
of the liquor, a considerable amount of calcium sulfate
suspended as a fine precipitate in the liquor. This
is true of the final boiling in the vacuum pan, which
rapidly becomes coated on the inside with »*38tst of
the precipitated calcium sulfate.
The liquor is filtered immediately upon withdrawal
from the pan to remove the calcium sulfate and all
other insoluble matter. A wood plate and frame filter
press is used, which is clothed not only with usual
filter cloth but with heavy paper as well, to insure a
brilliant filtrate.
Our experience has shown that this final filtration
of the acid liquor is probably the most important single
operation in the production of high-grade crystals.
The precipitate removed is mainly calcium sulfate,
558
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
but there are usually also some filtchar, iron and nickel
ferrocyanides, and metallic sulfides, with sometimes
small amounts of lead and calcium citrates. All of
these precipitates, if not removed, appear in the crystals
and raise the ash above the limit of 0.5 per cent.
Proper filtration removes them completely, giving a
brilliant light straw- or amber-colored liquor of about
36.6° Be\ at 50° C. This yields a good crop of clear,
colorless crystals of pure citric acid.
carbonized filter-cel — If the liquor is difficult
to filter, use is made of a carbonized filter-cel made
at our plant.1 It was noted earlier in this paper that
the raw juice is clarified by filtering after boiling
with filter-cel. The press cake from this operation
contains roughly equal amounts of filter-cel and organic
matter from lemon pulp. When heated in closed
retorts to a bright red heat the organic matter is sub-
jected to destructive distillation, and very fine parti-
cles of carbon are deposited throughout the pores of
the filter-cel. The carbonized filter-cel thus obtained
is ground to a coarse powder. It is extremely light
and porous, wets easily, and has a high decolorizing
value when applied to citric acid liquors. It is par-
ticularly useful, however, in producing a porous, easily
filterable press cake in the clarification of liquors
which are slimy or viscous and clog the filter cloth
rapidly, or which contain precipitates so fine that
they pass through the cloth and paper. The car-
bonized filter-cel is far superior to the fresh unused
filter-cel in this respect and is the best filter aid which
has ever come to our attention.
In using this carbonized filter-cel a small amount is
added to the liquor to be filtered and thoroughly
mixed with it, and the mixture is passed through the
filter press. If the liquor shows a tendency to come
through cloudy, the press cloths are precoated with
carbonized filter-cel by mixing a few pounds with water
and passing this through the filter press just before
the liquor is sent through.
CRYSTALLIZATION
The purified liquor is passed from the filter presses
directly into the crystallizers.
These are monel-lined wooden tanks, 130 cm. X 435
cm. X 20 cm., with a capacity of about 1150 liters.
Other crystallizers of varnished wood, stoneware,
porcelain, lead, and acid-proof enamel were tried. With
wood, even with a good varnish, crystals stick to the
surface, with eventual trouble from chips. Stone-
ware chips quite easily under the blows necessary to
remove the crystals, and acid-proof enamels are open
to this same objection. Porcelain is too expensive
to use in this country, though we are reliably informed
that it is used on a large scale in Germany for similar
work. Lead is objectionable because of the contamina-
tion of the crystals. Monel metal has been found
quite satisfactory, although the liquors slowly take
up both nickel and copper from it. It is hard and
tough, the crystals are easily removed from it, and
it is easy to keep clean and bright.
Where crystals are desired, the liquor is kept per-
fectly still for from 3 to 5 days, depending on the tem-
perature of the surrounding atmosphere.
1 Patent on this product has been applied for.
When granular acid (small crystals) is wanted, the
liquor is kept in constant motion by a small air jet
or mechanical agitator.
After crystallization is complete the liquor is drawn
off and recooked in the vacuum pan, and refiltered.
Further crops of crystals are removed as long as a
satisfactory product is obtained.
In ordinary weather the acid crystals are simply
washed in a basket centrifugal, and spread on a clean
mixing floor to evaporate surface moisture. They
are then graded for size by means of a monel metal
screen, and packed for shipment. In wet weather
it is necessary to use artificial means of drying, and
for this purpose a vacuum shelf dryer has been used.
TREATMENT OF OLD LIQUOR
Xo citric acid liquor is ever discarded. When white
liquors no longer yield crystals of U. S. P. quality,
these liquors are classed as brown, and the crystals
taken from them are dissolved and purified as indicated
above. When brown liquors fail to yield a sufficient
crop of crude crystals they are returned to the neu-
tralizing tanks, diluted, and treated like fresh juice,
recovering the acid as citrate of lime, which passes
again into the regular process.
QUALITY OF PRODUCT
The standard of purity for U. S. P. Citric Acid is
quite high,1 but the rigid laboratory control established
when the first acid was produced has kept this factory
free from complaints on the score of quality.
USE OF METRIC SYSTEM
It may be interesting to note that from the start
of actual production of citric acid, the metric system
has been in use throughout the -factory. Tanks are
calibrated in liters per centimeter of depth and the
various chemicals are weighed in kilograms. There
has been no difficulty at all in teaching ordinary labor-
ers to use meter sticks and metric scales, and the saving
in calculation in the laboratory has been enormous.
ACKNOWLEDGMENT
The writer wishes to acknowledge his deep indebt-
edness to all who have been his co-workers on this
problem. In addition to those already mentioned
Mr. S. A. Weirman, Miss Eloise Jameson, Mr. Oliver
Loud, and Mr. H. H. House deserve a great deal of
credit for the factory and laboratory details they have
worked out from time to time. Our thanks are due
also to Mr. H. M. May, manager of the Exchange
By-products Co., for his practical help rendered in
many ways.
Discovery of Borax Deposit
What is reported to be the largest known deposit of borax in
the world has recently been discovered in Clark County, Ne-
vada, and has been acquired by the West End Chemical Co.,
of California.
The deposit consists of a hill of pure colemanite, some 3000
ft. in length and 300 to 500 ft. in height, and it is estimated that
more than half a million tons of ore are in sight. The location
of the deposit within easy access to the railroad and the ease
with which the product can be mined will make its development
simple.
U. S. Pharmacopeia IX, No. 9.
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
559
Apparatus for the Rapid Determination of the Available Chlorine in
Bleach Liquor1
By Morris
Research Laboratory, American Writing
The usual paper-mill practice of determining avail-
able chlorine in bleach liquor by means of the hydrom-
eter is open to a serious objection, in that there is
no definite relation between the specific gravity of
the solution and the available chlorine.2
Since the customary laboratory methods of titrating
bleach liquor are not easily adaptable for use in the
mill by men with no chemical training, the apparatus
shown in the sketch was designed for the purpose.
It has been in use in the mill for over 6 mo. and
has given very satisfactory results. It can be used
not only for determining the amount of available
chlorine in bleach liquor, but for the analysis of per-
manganate, peroxides, perborates, carbonates, etc.
METHOD
The method depends upon the measurement of
the pressure exerted by the oxygen generated when
hydrogen peroxide reacts with hypochlorites in alka-
line solution according to the equation:
CaOCl, + H202 = CaCl2+H20+02
The results obtained by this method do not vary more
than 0.02 lb. of 35 per cent bleach per gal. from those
obtained by titration with sodium thiosulfate. It
is probable' that if
all necessary correc-
tions were made it
would be fully as
accurate as some of
our present labora-
tory methods.
This method was
suggested by an ar-
ticle by W. H.
Chapin,3 describing a
rapid pressure meth-
od for the determina-
tion of carbon dioxide
in carbonates.
APPARATUS
The apparatus con-
sists of two bulbs
connected by means
of a stopcock and a
by-pass. The upper
bulb has a neck which
allows the apparatus
to be clamped, and .
the flower bulb hasV£^\
an opening attached
to it at an angle of
5°. A manometer
tube is fitted into a rubber stopper, and to this tube
is attached a sliding scale, graduated to read in lbs. of
1 Received February 8, 1921.
1 Ross Campbell, Paper, 20 (1917), No. 14, 11.
> This Journal, 10 (191S), 527.
Schrero
Paper Co., Holyoke, Massachusetts
35 per cent bleach per gal. of liquor. Readings can
be made to hundredths of a pound. It is obvious
that the dimensions need not necessarily be those
given in the sketch, but they have been found to be
the most convenient for a bleach liquor containing
about 0.5 lb. of 35 per cent bleach per gal. of liquor.
CONSTRUCTION OF SCALE
The calculations and the calibration of the apparatus
are carried out as follows: The volume of the apparatus
is determined by filling with water and weighing.
The difference between this weight and the weight
of the apparatus empty gives, for all practical pur-
poses, its capacity. To determine the volume the
evolved gas occupies, the volume of the liquid put
into the apparatus must be subtracted from the ca-
pacity obtained above. From the equation given
above, it can be seen that the amount of oxygen evolved
is equivalent to the available chlorine of the bleach
liquor. Designating the volume as V, the pressure
of the oxygen as read on the manometer as P, and the
temperature as /, the following equation corrects the
volume V for temperature and pressure, and gives:
Lbs. of 35 per cent bleach per gal. =
VX273XPX0. 00317X8. 3.3
(273+i) X760X0.35Xcc.sample
where 0.00317 =g. of chlorine gas per cc. (standard)
8.33= factor to convert g. per cc. to lbs per gal.
0.35= wt. of chlorine in one unit of 35 per cent
bleach
In plant control work the size of the sample and
the volume V are constant, the temperature / is
assumed constant, and hence the bleach strength is
directly proportional to P. Therefore the equation
becomes
Lbs. of 35 per cent bleach per gal. =KP.
The number of mm. of mercury P that would cor-
respond to 0.1 lb. of 35 per cent bleach would then be
P=0.1/K.
Having determined the number of mm. that cor-
responds to 0.1 lb. of 35 per cent bleach per gal. of
liquor, the scale can be constructed by marking off
on any convenient material multiples and submultiples
of the number obtained.
PROCEDURE
In actually using the apparatus, it is first clamped,
with the stopcock closed, in a rubber-covered buret
clamp. Ten cc. of the bleach liquor are pipetted
into the lower bulb, while with another pipet 10 cc.
of hydrogen peroxide are measured out and put into
the upper bulb. The opening in the lower bulb is
then tightly stoppered, and the manometer with its
attached scale is put into the neck of the upper bulb.
The manometer should be tapped gently so that no
small particles of mercury adhere to the glass. When
the manometer is inserted, there is usually a slight
pressure developed, but, for the purposes for which
560
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
this apparatus is intended, this can be disregarded.
The stopcock is then opened, allowing the two liquids
to come together. In order to make sure of complete
reaction, it is usually necessary to shake the apparatus.
This is done by placing a finger on the rubber stopper
containing the manometer, and the thumb and a finger
on the neck of the apparatus, and shaking until the
bubbles of gas are set free. The reaction is usually
complete in 40 to 50 sec. The scale is then adjusted
so that the zero point coincides with the top of the
lower arm of mercury and the number of lbs. of 35
per cent bleach per gal. of liquor is read at the mark
that coincides with the top of the upper arm of mercury.
The whole operation does not take more than 90 to
100 sec.
It is not necessary that the temperature of the
apparatus and its contents be at exactly the tem-
perature for which the scale is graduated. It has
been calculated that if the temperature of a bleach
liquor that would give a reading of 0.5 lb. of 35 per
cent bleach per gal. at 22° C. be 8° higher or lower
than the assumed temperature, the reading would be
less than 0.015 lb. higher or lower than it should be.
In view of the fact that the error in measuring out
the liquor in the mills is much greater than this error
or those that are introduced by the solution of the oxy-
gen in the liquid, the slight pressure developed on
inserting the manometer, etc., corrections need not
be made for any of these.
RESULTS
The results given in the following table were ob-
tained in actual practice by an inexperienced man.
The apparatus was kept at the temperature for which
the scale was graduated by being placed in a bucket of
water. The titrations were made in the laboratory.
By Sodium Thiosulfate Titration By Pressure Method
Lbs. per Gal. Lbs. per Gal.
0.49
0.51
0.42
0.30
0.35
0.28
0.36
0.34
0.28
0.32
0.34
0.30
0.27
0.37
0.3S
0.46
0.47
0.51
0.41
0.29
0.36
0.30
0.36
0.33
0.28
0.32
0.34
0.31
0.25
0.39
0.36
0.44
ACKNOWLEDGMENT
The writer wishes to make acknowledgment to Dr.
R. E. Rindfusz, and to Messrs. George G. Taylor and
V. Voorhees for suggestions and assistance given during
the work on this apparatus.
Notes on Laboratory Apparatus'
By A. B. Andrews
Lewiston, Maine
LARGE-CAPACITY AUTOCLAVE
Some time ago, need arose in this laboratory for a
large-capacity autoclave capable of withstanding ex-
treme pressures and heat.
A discarded 150-mm. Russian shrapnel case was
secured at one of the local munition plants. This
case had been rejected on account of warping during
the heat treatment and not for any cause of weakness.
About 2 in. of the nose were turned off, and the end
recessed to retain the packing necessary for tightness.
A head, 1.5 in. thick, was turned from a billet of nickel
steel, and to this was attached a heavy stuffing box
through which passed the shaft of the stirring device.
Holes were tapped in the end of the shell, and special
nickel-steel cap screws were made to hold on the head.
To the head was attached a pressure regulating de-
vice from a Stanley steam automobile which was
arranged to break an electric contact when a certain
predetermined pressure was reached, and which by
means of a relay operated a by-pass on the gas main,
partly shutting off the gas and allowing the pressure
within the autoclave to fall slightly. On making the
contact, the gas was again admitted at full volume to the
burner, and the pressure slowly rose. This worked per-
fectly on less than 2 lbs. pressure variation, so well, in
fact, that often during runs at 600 to 800 lbs. pressure
per sq. in., the whole was left unattended and unwatched
for days at a time.
' Received March 10, 1921.
GOLD CATHODES FOR ELECTROLYTIC WORK
Another problem that was successfully solved was
the sudden need of several cathodes for electrolytic
copper determinations. To avoid the large investment
for platinum, if indeed it was available at the time,
cathodes of 24-carat gold were tried. They proved
to be, to all appearances, the equal of platinum, at
one-tenth the price. Since then we have had several
open cylinder cathodes, of the same dimensions as the
platinum cathodes, in constant use with perfectly
satisfactory results. Their weight is very constant,
and the deposit is apparently as smooth and desirable
as on platinum. Of course, we still have to use plati-
num as anode. One precaution in using the gold
cathode is in igniting to remove any traces of grease;
if one is not quite careful, he may slightly fuse the
edges or corners. With this exception, these cathodes
seem to be the equal of platinum.
Cryogenic Laboratory, Bureau of Mines
The new low- temperature research laboratory of the Bureau
of Mines was dedicated by Mme. Curie on May 21, 1921.
The laboratory is under the direct charge of Dr. R. B. Moore,
chief chemist of the Bureau of Mines, and the technical person-
nel consists of Mr. J. W. Davis, mechanical engineer, of Cornell
University and the University of Illinois, Mr. C. W. Seibel,
physical chemist, of the University of Kansas, Dr. A. G. Loomis,
physical chemist, of the Universities of Missouri and California,
and Dr. L. Finkelstein, physical chemist, of the Armour Insti-
tute of Technology and the University of Chicago.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
561
Electric Muffle Furnaces for Laboratory Use1
By H. C. Kremers
Chemical Laboratory, University of Illinois, Urbana, Illinois
Most research chemists have found the small elec-
trically heated muffle furnace a very valuable asset
to their laboratory equipment. Rather high costs
and limited varieties, however, have restricted their
use. Many chemists have found frequent occasion
to build their own furnaces.2 Here again the limit
has been set by the size and shape of muffle at hand.
Special sizes and shapes of muffles made to order can
usually be obtained only after considerable delay and
expense. The author has had frequent occasion to
use electric muffle furnaces of special shapes and sizes,
and by following the procedure outlined below these
furnaces were constructed with minimum delay and
expense.
CONSTRUCTION OF MUFFLE
An ordinary glass bottle of low melting glass is
selected of a size to correspond to the inner dimen-
sions of the muffle desired. This bottle is first cov-
ered with a single layer of asbestos paper (b, Fig. 1).
By moistening the asbes-
tos paper it will be found
to adhere very well. Next
in order, a 0.25-in. layer
of alundum cement, c, of
the consistency of a stiff
mortar is applied. The
built-up muffle is then
dried in an air bath at a
temperature of approxi-
mately 150° C. The heat-
ing element d is next
wound on in the regular
way. The author's fur-
naces were all wound with
a nickel-chromium alloy
wire. The data for cal-
culating the size and quan-
tity of wire required can
usually be obtained from the manufacturers of
these products. It has been found very desirable
to double the lead-in wires and also to have part
of the first coil doubled. A reference to the draw-
ing will make this point clear. It has been the
general experience that a furnace will frequently burn
out first at the point of the lead-in wire; thus, by doub-
ling this wire, the life of a furnace is much prolonged.
Considerable difficulty is frequently met with by the
novice in holding the winding in place. It was found
that the first and last coils of the winding can be held
well in place by tying them in position with asbestos
cord. This asbestos cord can simply be cemented
over, and left intact. A second coating of alundum
cement, e, is then applied over the winding. Here a
0.125-in. layer is usually sufficient. The completed
1 Received March 28, 1921.
2 An arrangement essentially similar to that herein described was used
by F. P. Venable and J. M. Bell, J. Am. Chcm. Sac. 39 (1917), 1602.
muffle is again heated to 150° C in an air bath. It will
usually be found that numerous very small cracks
will result, but a wash of thin alundum cement will
remedy this.
The completed muffle
with the glass core still in
place is mounted as shown
in Fig. 2. The upper edge
of the muffle c is usually
mounted flush with the
upper edge of the container
g. A 0.25-in. layer of alun-
dum cement, /, will effec-
tively seal the upper open-
ing of the container. Cal-
cined magnesia or sil-o-cel
will make an effective insu-
lator, j. ■ The lead-in wires - 2
can be very conveniently
attached to binding posts, h. The latter must, of
course, be well insulated from the container g.
The current can now be turned on and the furnace
allowed to come up to a red heat slowly. For the
first heating this should take at least 3 or 4 hrs. As
the furnace comes up to red heat, the glass core will
gradually begin to soften, and can in most cases be
withdrawn. If this is not possible, the glass may very
easily be shattered by a small spray of cold water and
then easily removed. Upon allowing the furnace
to cool the single layer of asbestos paper b can be
peeled off, and the muffle given a wash of alundum
cement.
A furnace thus constructed will satisfactorily main-
tain a temperature of 950° to 1000° C, and will have a
life equal to any furnace using a nickel-chromium
heating element. In place of the cement seal / a
ring of asbestos millboard is found very satisfactory.
A slight modification in construction will provid,e a
very satisfactory covering for the muffle, as follows:
The muffle c is set enough lower so that a por-
celain water-bath ring may be cemented in position
on the upper edge of the muffle, in such a manner that
the upper surface of the porcelain ring will be flush
with the cement /. When in use, the opening of
the furnace can be partly or entirely closed by nesting
in one or more rings.
COMBUSTION FURNACES
Furnaces of the combustion type with both ends
open may be constructed along the same lines. A
furnace of this latter type was recently constructed,
having a muffle with an opening 2 in. in diameter
and 18 in. long. An ordinary 2-in. soft glass tube
was used as the core, and the same general plan of
construction as outlined above was used. This furnace
has been in use for several days, and has been found
entirely satisfactory for temperatures up to 950° C
562
THE JOURS' AL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
A New Type of Electrolytic Cell1
Harrison Laboratory of Ch
By Hiram S. Lukens
;trv. University of Pen
ixvANiA, Philadelphia, Pennsylv
In attempting to study the influence of the electric
current on suspensions of insoluble or sparingly soluble
substances in various electrolytes, it was found that
the literature of the subject offered few suggestions
for maintaining uniform suspension of the insoluble
substance throughout the electrolyte. The type of
cell to be described has proved most satisfactory for
the study of the electrolysis of such suspensions as
that of nitrobenzene in dilute sulfuric acid, benzene
and toluene in dilute sulfuric acid, anthracene in dilute
sulfuric acid, etc., as well as for the electrolysis of
electrolytes in which all of the constituents were in
complete solution.
The cell is of the two compartment type, the outer
vessel, constructed of a suitable metal, forming the
outer compartment, as well as serving as one electrode.
A porous cup serves as the inner compartment, the walls
acting as a diaphragm separating the anode and cathode
liquids. The principal novelty of the cell consists in the
construction of the inner electrode within the porouscup.
This electrode, which may be either an anode or
cathode, depending on whether an oxidation or re-
duction process is to be studied, was constructed as
follows: A sheet of the metal desired, 1 to 2 mm. in
thickness, was cut to a rectangle of such size that the
longer dimension represented the circumference of a
cylinder that would fit loosely within the porous cup.
The shorter dimension represented several millimeters
less than the height of the porous cup inside. Using
a chisel of appropriate width (about 6 mm.), the
sheet of metal was then cut as indicated in Fig. 1. It
will be noticed that the sheet is thus divided into small
rectangles cut through the metal on three sides. Alter-
nate rectangles were then bent out to opposite sides
of the sheet so that they formed an angle of about
DDD3IlZlZlIlIlZlZIIlDZIZiani]IlZ|
DDnniiziiiiiiiiDDiinnnniiiin
DHUDIIIIIIDDIIDIIUIIIIHUHU:
ZIZIZIZIZ1Z1ZIZIZIZIZIZIZ1DZ1ZIZ1Z1Z1I]
nnnniininuiinnDuniiniizi:]:]
UDDUDDDUUUHIIIlIlUnilllll^
iiDniinnuiiinnnDiiniiniiiinn
dhhhhhhiiiiziziiiiiziziiiiiiii::
zinziziziziziziziziziziziziziziziiiziz)
dhi1di1z1dz1z1i1i1i1di12i1i1i3z1i]
hhhhhdi]iidzizidiizizii]ii3zi:
hidiidiihiiiihhuiiiihiiiiudud
Fig. 1
30° with the plane surface. The sheet was then bent
into the form of a cylinder that would loosely fit the
inside of the porous cup.
'Received March 12, 1921.
The electrode so constructed was made fast to a
circular plate of lead (about 4 mm. in thickness), which
served as cover-plate for the porous cell. A circular
hole, 25 mm. in diameter, was cut through the center
of the cover-plate, in which was inserted a cork which
—Stirrer
Gas Vent — -C
Mercury Seal
- Binding Post
-Hard Rubber
Collar
-Inner
Electrode
Containing ■
Vessel and
Outer
Oectrode
served as mounting for the mercury seal device through
which a stirrer passed. The stirrer was of glass, bent
as indicated in Fig. 2. The stirrer was rotated in such
a direction that the contents of the inner cell flowed
against the open end of the fins on the electrode and
flowed alternately in and out of the passages created
by the openings under the fins. At a stirrer velocity
of 500 to 700 r. p. m., the suspension was entirely
uniform from top to bottom. This was ascertained
by testing the efficiency in a glass beaker, of the same
dimensions as the porous cell.
To close the inner compartment and render it gas-
tight, a hard rubber collar, 2 mm. in thickness and
55 mm. in width, was fitted to the edge of the circu ar
lead cover-plate, as indicated in Fig. 2. When the
level of the electrolyte in the outer compartment was
brought above the lower edges of the rubber collar,
the inner compartment was rendered entirely gastight,
and any loss occasioned by the diffusion of gas through
the unimmersed portion of the porous cup was elimi-
nated. A vent was provided by means of a cork and
tube through the cover-plate, as indicated in Fig. 2.
This cell is now in use in the study of several electro-
lytic oxidation and reduction processes.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
563
ADVANTAGES OF THE CELL
The cell has the advantages of being easily assembled
and dismantled for the removal of electrolyte.
Gas loss by diffusion through the porous cell is
entirely eliminated.
The electrodes are brought close together, thereby
reducing the voltage drop through the electrolyte.
The efficiency of reaction of anodically liberated
oxygen or cathodically liberated hydrogen, as the case
may be, may be conveniently studied at varying current
densities by observing the amount of gas escaping
through the vent-tube under the conditions being
studied.
Water Heater for Analytical Work1
SOUTHWESTER
By S. L. Meyers
Portland Cement Co, Victorvil
California
The heater herein described
has the advantages over the or-
dinary hot water bottle that the
only attention needed is in re-
filling the reservoir, the force of
the washing stream is supplied
by gravity, and no blowing is
necessary.
The heater, shown in section
in the diagram, consists of a cop-
per or brass cylinder of about
1000-cc. capacity, closed at each
end except for connections. The
cylinder is insulated with sheet
mica, around which are wound 25
ft. of resistance wire, and the
whole is covered with asbestos.
The wire is a German silver wire,
0.057 in. in diameter (B & S
gage 015).
A further 5 ft. of this wire is
wound round the tube which
carries the water from the heater to the washing
spout, thus preventing the water in the tube from be-
coming cool on standing. There is no danger of over-
heating the rubber tubing if the heating element is in
series with a hot plate or lamp in an ordinary lighting
circuit. The resistance wire around the rubber tubing
is covered with a light cotton cloth in order to avoid
danger from exposed live wires.
Water enters the lower end of the heater, and the air
evolved on heating passes out through the air escape
in the top of the apparatus.
The elastic to the ceiling serves to support the weight
of the lower tube and to increase the ease of manipula-
tion of the washing spout.
The National Research Council has formed an Alloys Re-
search Association to furnish an informational service concerned
with metals and their alloys. It proposes to supply information
as to current literature, discoveries, etc., and references and ab-
stracts of all known information upon a given subject.
Bureau of Employment of the New York
Chemists' Club
The annual report of the employment bureau connected with
the-New York Chemists' Club for the year ending April 30, 1921,
clearly reflects the state of chemical industry at the present
time. To quote:
Although the year 1919-1920 was none too favorable, taken as a
whole, yet 1920-1921 makes its predecessor seem easy in compari-
son. * * During the past year we have registered 920 men who never
before have been on our lists and 606 former registrants have re-
turned to the active list. With such numbers of men to aid,
it is easy to see that many must be disappointed when it is said
that at the end of April we had only 85 positions on file and of
these many are practically withdrawn or impossible to fill.
The recompense of the chemist has not declined but is above
pre-war level, as shown by the following comparisons: In 1915
and 1916 more than 50 percent of the calls filled were at salaries
under $1000 a year; in 1917 and 1918 less than 37 per cent were
under $1000 a year; while in 1920-1921 only 4 per cent are under
$1000 a year, 43 per cent are from $1000 to $1800, 35 per cent
from $1800 to $2500, and 18 per cent at $2500 or more. We
note that out of 800 men registered a year ago, only 24 per cent
said thev would take positions paying less than $1800. 38 per
cent wished $1800 to $2500, while 38 per cent would not work for
less than $2500. One hundred and ninety-three for one reason
or another were not classified. This year, out of 1179 registered
men we find that 26 per cent will work for less than $1800,
that 38 per cent will accept $1800 to $2500, and 36 per cent
want $2500 or more. We therefore conclude that in these less
active days those who do receive appointment will not work
for materially less.
Another phase repeatedly brought to our notice is the decrease
in willingness to consider the employment of woman chemists.
This is unfortunate. Those who have employed them report
that they are uniformly satisfactory and in some ways more
desirable than men, especially for routine work. It is only
natural that the demand should fall off under present conditions,
but the Bureau wishes to call attention to the fact that women's
colleges have in the last five years greatly improved their chemi-
cal departments and much better trained chemists are now
graduated.
In cooperation with Drs. Parsons and Howe of Washington,
the Bureau is attempting to establish the status of the chemist
with the Bureau of Immigration.* ** In this Bureau we are
not classed as a "professional" group. Lawyers, clergymen and
physicians are allowed to enter the country under contract, but
chemists are not, unless they receive $25,000 or more, or can be
shown to be able to do work which no one already in the country
can do.*** The discrimination particularly affects the free
movement to and from Canada.
The Bureau filled approximately 38 per cent of the positions
received during the calendar year 1920. This is about an aver-
age record.
Received February 24, 1921.
American Institute of Chemical Engineers
Plans for the Thirteenth Semiannual Meeting of the American
Institute of Chemical Engineers, to be held in Detroit, Michigan,
June 20 to 25, 1921, promise a meeting of great interest. Head-
quarters will be at the Hotel Statler.
The opening meeting at the Hotel Statler will include papers
on the relation of the chemical engineer to the auto industry,
automobile finishes, pyroxylin artificial leather, and monel metal.
The afternoon will be devoted to a visit to the plant of the Cadil-
lac Motor Co.
Tuesday, June 21, will be spent at the University of Michigan,
at Ann Arbor, where several papers will be presented at the
afternoon session.
Wednesday will be devoted entirely to excursions, to the
Ford River Rouge plant, and to the plant of Hiram Walker &
Sons, Ltd., Walkersville, Ont.
The presentation of papers will be continued on Thursday
afternoon, and the two remaining days of the convention will
be devoted entirely to optional visits to manufacturing plants
in Detroit.
564
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
ADDRESSES AND CONTRIBUTED ARTICLES
Alcohol and the Chemical Industries'
al Alcohol
By J. M. Doran
Chemical Division, Internal Revenue Bureau. Washington, D. C.
To appear before a gathering of representative industrial
chemists engaged in practically every branch of chemical ac-
tivity and to call attention to the essential relationship of the
alcohol industry to the other chemical industries would, at first
thought, seem so elemental and unnecessary as to be almost ab-
surd. The chemist knows that alcohol as a solvent bears the
same relation to organic chemistry that water does to inorganic
chemistry. It may be regarded along with sulfuric acid, nitric
acid, and the alkalies as among the chemical compounds of
greatest value and widest use.
To enumerate to the chemist the compounds in the prepara-
tion of which ethyl alcohol is necessarily used, either as solvent or
as the reacting ethyl group, would almost amount to a reading of
Beilstein. To the layman might be mentioned a variety of use-
ful things such as anesthetic ether, quinine, paint, varnish, ink,
smokeless powder, dyes, liquid pharmaceuticals, motor fuel, and,
properly to end up with, embalming fluids.
If a chemist is asked the question: "Why can we not get along
without alcohol," he becomes bewildered. It starts a train of
thought similar to what might be started if the question were
asked: "Which element can be dispensed with most readily,
oxygen, hydrogen, or nitrogen?" Chemical industry to-day
without alcohol would be impossible. As well imagine structural
engineering without steel or cement.
The past, present, and future status of industrial alcohol under
our laws is what I wish to discuss briefly. A review of this indus-
try in its change from a beverage to a nonbeverage industry will
assist us in properly visualizing its present position.
EARLY LEGISLATION ON DENATURING OF ALCOHOL
■In 1906 Congress, realizing the necessity of relieving from the
high beverage tax the alcohol used for industrial purposes, passed
the first act permitting the withdrawal of alcohol free of tax from
distillery bonded warehouses for use in the arts and industries,
and for fuel, light, and power, provided it were so treated that its
character as a beverage was destroyed and it was rendered unfit
for use in liquid medicinal preparations. We must bear in mind
that at this time intoxicating liquors were paying a large part
of the Federal revenue and the first authorizations for the use of
denatured alcohol were very conservative. The first year showed
a denaturation of about 1,000,000 gallons. This largely went
into varnishes, shellacs, and felt hat manufactures, and for do-
mestic fuel purposes, such as spirit lamps. Each succeeding
year saw additional formulas for completely denatured alcohol
and specially denatured alcohol authorized, and the extension
of these formulas to many additional products.
It was early seen that in order to cover many specialties par-
ticular formulas must be authorized, as the general formulas for
completely denatured alcohol were of such a character as to ren-
der them of little use in many special industries. Hence, there was
inaugurated the system of authorizing specially denatured alco-
hol and handling it under the permit and bond system which en-
abled the Government to keep a record and control of it from
the time it was denatured until it was finally used in some
specific manufacturing process.
In 1913 Congress passed an act permitting the manufacture of
alcohol for denaturation only, and further provided that the alco-
hol should be treated so as to render it unfit for use as an intox-
icating beverage. It should be particularly noted that the only
1 Presented before the Division of Industrial and Engineering Chemistry
at the 61st Meeting of the American Chemical Society, Rochester, N.
Y„ April 26 to 29, 1921.
condition laid down in the 1913 Act was that the alcohol be
rendered unfit for beverage use. No limitation as to its use in
the arts and industries, or for fuel, light and power, or prohibition
against its use for liquid medicinal purposes was set out.
Since the 1913 Act, the Department has authorized the use of
specially denatured alcohol in medicinal preparations solely for
external use. Tincture of iodine and the official soap liniments
were among the earlier authorizations.
With the opening of the war in Europe in 1914 the withdrawal
of alcohol free of tax for denaturation increased rapidly. When
we became involved in 1917 it became a question of sufficient ca-
pacity to supply the demand. Alcohol, ether, and acetone,
for smokeless powder, and, at a later date, alcohol itself for the
manufacture of poisonous gases, were required in immense
quantities. The old beverage whiskey industry, which had not
heretofore produced high-proof alcohol, was called on, and by
installing re-distillation columns in many whiskey plants our
alcohol-producing capacity was further enlarged.
ODR PRESENT CONDITION
The end of the war naturally left us with a greater capacity
than we required for normal needs, but the development of many
chemical industries during the war, producing dyes, pharma-
ceuticals, and various chemical specialties heretofore supplied
principally by Germany, had so enlarged and broadened the use
of denatured alcohol that the withdrawal for denaturation was
several times greater in quantity than pre-war figures. Coin-
cidentally, the Food Control Act, the War Time Prohibition
Act, and, finally, the National Prohibition Act itself wiped out
the use of high-proof alcohol for the manufacture of intoxicating
beverages. Title III of the National Prohibition Act provides
for the denaturation of alcohol by the admixture of materials
that render the alcohol or any compound in which they are au-
thorized to be used unfit for use as an intoxicating beverage.
No authorizations have yet been made, however, for the use of a
denatured alcohol in a preparation that may be intended for
internal use.
Our present production is something like 60,000,000 gallons
per annum. We occupy a peculiarly favorable position as to
raw materials and distribution; our seaboard plants, utilizing
Louisiana, Cuban, Porto Rican, and Hawaiian molasses, are
particularly fitted to supply the industrial needs of the East and
extreme West; our Middle West plants, utilizing corn and mo-
lasses, can likewise obtain raw material close at hand and dispose
of their product in their local territory. We have the largest
molasses and grain alcohol plants in the world. During the past
year a number of breweries have installed alcohol recovery plants
incidental to the manufacture of cereal beverages.
In touching on the present alcohol industry we cannot ignore
the question of national defense. The chemist foresees the next
war as one of gases, aeroplanes, and high explosives. Much
has been said of the necessity of a self-contained dye industry
with its useful peace-time production which may be immediately
converted into offensive and defensive weapons in time of war.
We may well place the alcohol industry in the same position,
for not only is its production necessary in peace-time activities in
order to sustain these other chemical industries, but it must be in
a position to expand at once in war time. It is of great impor-
tance, therefore, that we keep these facts in mind and lose no
opportunity as chemists to educate others in the fundamental re-
lations of these industries to the national welfare.
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
565
At present not less than two-thirds of the total production
goes into denatured alcohol, largely for technical uses. These
uses, as stated before, are the development of some fifteen years
and have no relation to prohibition, nor are the consuming manu-
facturers affected in any great degree by the National Prohibition
Act. At present there are five formulas for completely denatured
alcohol and fifty-three formulas for specially denatured alcohol.
The specific products in which the use of tax-free alcohol has
been authorized number several thousands.
THE PROBLEM OF THE FUTURE AND ITS POSSIBLE SOLUTION
The balance of the production, that goes to the trade as pure
alcohol, is the crux of the present trouble. The National Pro-
hibition Act at present may be said vitally to affect and be affected
by about one-third of the total alcohol production. An industry
that may be one-third crippled; a law that may be only partially
enforced, and a consuming manufacturer who spends a substan-
tial part of his time endeavoring to protect himself from thieves
constitute what the chemist might term a system not in equi-
librium. Let us see if a little further chemical treatment cannot
assist in the restoration of equilibrium in this system. The con-
structive solution of this pure alcohol problem is, in my opinion,
the most vital question affecting the enforcement of prohibition,
the industry producing alcohol, and the trades using it to-day.
The National Prohibition Act, under Title II, defines alcohol
along with whiskey, wine, and beer as an intoxicating liquor.
Every chemist knows that 95 per cent ethyl alcohol cannot be
used as a beverage, but the comparative ease with which it may
be diluted and converted into a beverage has caused it to be
classed as an intoxicating liquor. On the other hand, Title III of
the National Prohibition Act provides for the protection and en-
couragement of high-proof alcohol for industrial purposes. In
view of the dual purpose of this law, it has become extremely
difficult to administer the handling and use of high -proof alcohol
in the pure state for industrial purposes.
To say that the handling and use of pure alcohol in the trade
during the last year and a half has been unsatisfactory to the en-
forcement of prohibition, to the legitimate user, and to the pro-
ducer of alcohol, is to put it mildly. On the assumption that
the enforcement of prohibition will be increasingly effective,
one naturally seeks to find a remedy for the common ills and
troubles.
Is it possible to treat practically all alcohol at the industrial
alcohol plant or denaturing plant with some compound or mate-
rial that will render it unfit for use as an intoxicating beverage,
protect it from the thief and bootlegger, and make it fully as
available, or practically so, to the manufacturer as pure alcohol?
In other words, while the sociologists and reformers are engaged
in the laudable work of denaturing men's thirsts and appetites,
may we not hasten the day of that accomplishment by denaturing
the alcohol itself?
If I should say that alcohol treated as above is denatured al-
cohol, the question might at once be asked by a chemist, as well
as by a layman not familiar with the legal term denatured alcohol:
"Why, I thought denatured alcohol was poisonous, contained
wood alcohol, and smelled bad. How could you use it in medicines
or articles of delicate character?" The first formula of denatured
alcohol authorized after Congress passed the original denatured
alcohol law in 1906 was ethyl alcohol to which were added approx-
imately 9 per cent wood alcohol and 0.5 per cent of kerosene.
The present conception of denatured alcohol was formed, to a
large extent, from a knowledge of this first and most widely used
denatured alcohol. It is essential to know that the term de-
natured alcohol is merely a legal term, and that the denaturant
used need not only be nonpoisonous but may simply be one or
more of the compounds which enter into the final manufactured
product. These denaturants may be medicinal compounds, if
the alcohol be subsequently used for medicinal purposes, or they
may be other chemical compounds rendering the alcohol suit-
able for technical purposes.
A barrel of pure alcohol, tax paid, costs from $250 to $300.
When converted into bootleg whiskey and sold at current quo-
tations of $10 per quart it returns approximately $4000. This
tremendous profit is a lodestone that attracts the thief or the
criminal. If this alcohol were denatured, this conversion into
bootleg whiskey would be impossible.
The present policy of the Department has resulted in the re-
cent issuance of a number of formulas for specially denatured
alcohol for external pharmaceuticals, perfumes, toilet waters, etc.
There is great room for improvement as to denaturants that may
be selected, technical as well as medicinal. The time is now ripe
for the chemists to convince the Government and the Public that
they can successfully denature alcohol for practically all non-
beverage uses, such as medicinals and flavoring extracts. This
opens up an immense field for constructive research, involving
problems both chemical and therapeutical.
It is obvious that the use as a denaturant of some specific drug
will in no wise affect the therapeutic properties of the finished
preparation of the same drug. Our present Formula 25 is a case
in point. Iodine is used as a denaturant for alcohol to be sub-
sequently used in the manufacture of tincture of iodine. The
authorization of formulas where specific denaturants are used
might, through multiplicity, become a difficult administrative
problem, to say nothing of burdening the drug and extract trade.
The ideal solution would be some solvent which, if mixed with
alcohol, would render the mixture unfit for use for beverage
purposes, to the extent that it could be controlled under the permit
and bond system, and yet would have practically no appreciable
effect on the physical character or therapeutic properties of the
finished drug, fluid extract, or tincture.
It seems to me that the chemist with the aid of the therapeutist
can here devote himself to a problem which, when successfully
worked out in detail, offers a real solution of some of our present
troubles. It is but natural that those charged with law en-
forcement will seek to correct unsatisfactory conditions by rules
and regulations. It seems inevitable that regulations will be
added to regulations. The physical presence of an agent of the
Department wherever pure alcohol is handled in order to prevent
unlawful diversion is impossible.
THE PART OF THE CHEMIST
What we, interested in chemical industries, wish is to get the
alcohol industry on an absolutely nonbeverage basis as soon as
possible. Then, and then only, can it prosper, and the legitimate
alcohol user hope to free himself from the burdensome restric-
tions surrounding the traffic in intoxicating liquors. The tech-
nique of the present regulatory control, by the Internal Revenue
Bureau, of the alcohol industry, both producer and consumer, can
be made more efficient and less burdensome if the liquor phase
can be disposed of. The Department can then bend its efforts
to cooperation along strictly economic lines.
Those of you who are associated with educational institutions
could perform a most valuable service to the country at the pres-
ent time by devoting more attention to the problems involved
in denaturation. Those of you who are engaged in industry and
who are affected by the present situation of alcohol will, of
necessity, continue to direct your attention to this problem.
It is the purpose of the Department to cooperate to the fullest
extent with you. The law must be enforced. We believe it
may be done in a way that will conserve the good while elimi-
nating the bad.
As the chemist has demonstrated to the country in the last
few years that the United States has the brains and resources to
develop and maintain a well-rounded chemical industry, let us
not confess our inability to solve the alcohol problem.
566
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
SOCIAL INDUSTRIAL RELATIONS
Crowds and Their Manners
By H. W. Jordan
Syracuse, N. Y.
THE STUDY OF CROWDS AND THE EXPRESSION OF THE
crowd mind through public opinion is a social topic to
which industry needs give serious attention. Development of
crowd instincts is a manifestation of the laws of evolution
in their action upon our city, industrial population. The in-
creasing tendency of public opinion to promote legislation that
restricts industry, by excessive taxation and burdensome regu-
lation, springs from the national crowd mind. We are swiftly
losing our Yankee, self-reliant individuality, and are blending
into a mental conglomerate of shallow thinkers who expect
the Government to solve our troubles and carry our burdens.
"Events are making it more and more clear that, pressing
as are certain economic questions, the forces that threaten
society are really psychological," says Everett D. Martin.
in his recent book. "The Behavior of Crowds," published by
Harper's. The science of crowds, of public opinion, whereby
industry and commerce can more easily and correctly forecast
public action in its relation to business, is as important as chem-
istry or electricity.
The behavior of crowds is based on the emotions, far more
than upon reason or common sense. Crowd action is mainly
selfish and short-sighted. Its mental processes are led by
precedent, by kindergarten demonstration, rather than by logic
or argument. The crowd ridiculed Langley and pronounced
him insane, as it did Morse and Bell and the Wright Brothers.
But when the Wrights actually flew — achieved and demonstrated
flying— the crowd accepted it as heartily as it had previously
condemned. In the war, aviation was the most popular branch
of service.
THE CROWD MIND, EXPRESSED IN PUBLIC OPINION, is by
nature resistant and often hostile to science. The hos-
tility springs from lack of familiarity with science. Our public
schools, below high school, teach almost nothing of science,
in this age of science. And ninety per cent of us do not enter
high school. The public clings to conventional practices.
It fears whatever it does not understand.
The crowd imagines that the industries of applied science,
of chemistry, electricity, and metallurgy, have unlimited capacity
to earn profits and pay taxes; to build and operate city railway
systems on nickel fare in dime times. It does not realize that
the New York subway is an engineering structure second only
to the Panama Canal. Nor does it realize the huge cost of
experimentation and research that must precede every suc-
cessful engineering undertaking.
THE CROWD MAKES NO ALLOWANCE FOR AMORTIZATION of
engineering equipment through new processes or changed
conditions. It gives no credit to the New York Central
or the Pennsylvania Railroad, whose expensive former New
York City and Jersey City terminals became obsolete and
were scrapped at heavy loss a decade ago, and replaced by
modern terminals. While denouncing railroads, the crowd
has no thought of the fact that the savings bank deposits and
life insurance that its thrifty individuals hold are based to a
large degree upon the bonds of the railroads it criticizes.
The crowd that wisely prescribes remedies against every
public waste, jumps to its feet on leaving 125th Street or Man-
hattan Transfer and, valises in hand, as a crowd, stands in the
aisle five to fifteen minutes every time it enters New York,
or any other city. Why? Just because some unthinking per-
son gets up and tugs his heavy suitcase to the door, miles up
the track. So all the others do the same. The crowd doesn't
think. It follows precedents
THE CROWD PROTEST AGAINST THE HIGH COST OF LIVING
is directed against effects, which are present and visible,
rather than against the causes, which are obscure. It de-
nounces the high cost of lumber, but it institutes no work
of reforesting the farm wood lots at our back doors. It balks
at paying 15 cents a wedge for apple pie, but it lets the
New York State apple crop rot on the ground and fills its
pies with apples from Oregon. In thoughtless, vicarious
retaliation against many such wasteful practices, the crowd
urges and secures legislation that is repressive and costly to the
engineering industries. It doesn't realize that if the auto
knocks and stops on hills the answer is not to get out and hit
the engine with a sledge, but to burn a thinner mixture through-
out the season.
' A GREAT STIRRING AND MOVING IS GOING ON IN THE
land. The old order changeth; giving place to new. The
people at large are astir groping, seeking for a condition
of things which shall be better and happier, which shall give
them a greater share, not only of the comforts and material
rewards, but of the joys and the recreations, the beauties and
inspirations of life. It is a movement full of promise, and a
menace only if ignored, or falsely and selfishly led. Most of
it will find expression in politics, in economic and social legis-
lation; some of it will find expression in art," says Otto H.
Kahn.
To the research chemist or engineer, the answer appears
to be that the chemical and engineering industries unite, and
direct and finance simple, typical, social industrial experiments
by which to solve the problems that truly harass our producing
population, and that unduly increase our costs of industrial
production. Let us establish social research, using our indus-
trial cities and the surrounding agricultural country as our
laboratory; and let us evolve a twentieth-century order of in-
dustrial city social economics, that pulsates in unison with
twentieth-century scientific attainments in industry.
If, by experimental, scientific research, chemists and engineers
have been able to raise a whole litter of catalytic processes
and to perfect the phonograph, the automobile, the aeroplanes,
moving pictures and wireless telegraphy — all of them created
by a man's imagination within a generation — it should be an
easy job to bring city food supply, housing, and secondary edu-
cation of harmony with these industrial achievements.
" THE DAY OF THE INDUSTRIAL PIONEER IS OVER, and
with it has gone — if it ever existed — the day of the almighty
dollar. The day of the pioneer of culture and idealism has
come, and the power of the idea is, and has always been, even
in America's most materialistic days, far mightier than that
of the dollar. After more than a century's stupendous effort
and unparalleled — almost too rapid — economic advance, we
have reached a stage where we can afford, and ought, to occupy
ourselves increasingly with questions affecting the mental,
moral, and psychical well-being and progress of the race."
Social industrial research will be recreation and pastime
to the chemists and engineers who undertake it. "Just as
the soil of agricultural land requires rotation of crops in order
to produce the best results, so does the soil of our inner being
require variety of treatment in order to remain vigorous and
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
567
elastic and fertile and to enable us to produce the best of which
we are capable."
The quotations are from "Our Economic and Other Problems,
a Financier's Point of View," by Otto H. Kahn. It is a book
recommended to anyone interested in the study of social in-
dustrial relations.
education of labor. " It is strange that so few em-
ployers are doing anything in the educational line. Nearly
all labor disturbances are due to misunderstanding or no un-
derstanding of economic principles. The remarkable feature
of this is that most employers realize the truth of this fact,
yet nothing of any importance is done. Our forecast is that
the industrial future of this country will be in the hands of that
side which takes advantage of educational opportunity and brings
its point of view to the labor element. One of the two sides
must take the initiative in formulating a constructive policy,
and the employer is better equipped for that purpose," says
Babson's "United Bulletin Service."
This idea is identical with that of Martin, expressed in "The
Behavior of Crowds," that education is the preventive and cure
of the costly crowd disturbances that harass business and prevent
steady, industrial growth.
"true democracy is not a flattening, leveling process.
True democracy must build up the most promising individuals
to their highest powers of serviceability. It must develop
them under the essentially democratic teaching that how-
ever great their powers, or their freedom, they cannot live
to themselves alone, but must devote all their powers to the
good of their fellows. "—Edward W. Parmelee.
SCIENTIFIC SOCIETIES
Nichols Medal Awarded to Gilbert N. Lewis
The May meeting of the New York Section of the American
Chemical Society was given over entirely to the presentation
of the William H. Nichols Medal for the year 1920, and the
scientific address on "Color and Molecular Structure," by Dr.
Gilbert N. Lewis, Professor of chemistry at the University of
California, the recipient of the award. A large attendance
crowded Rumford Hall, where the presentation took place, and
the lecture, which was illustrated with a series of experiments,
was very well received.
The William H. Nichols Medal is awarded annually for the
best original paper published in any of the journals of the
Society during the previous year. The New York Section
acts as the trustee of the medal fund. One of the conditions of
the award is that the recipient shall present a paper or deliver
a lecture on some subject connected with his researches. Dr.
Lewis was awarded the medal for his paper entitled "Third
Law of Thermodynamics and the Entropy of Solutions and of
Liquids," published in the Journal of the American Chemical
Society, 42 (1920), 1529.
After a short business session, Dr. John E- Teeple, chairman
of the New York Section, who presided at the meeting, in-
troduced Prof. Arthur B. Lamb of Harvard University, who
spoke in a very happy vein of Dr. Lewis' personal attributes,
and lauded his scientific accomplishments. Dr. Lamb, who had
been a graduate student under Dr. Lewis, spoke of the keen
interest in thermodynamics and related subjects which the
medalist always aroused in his students. He briefly reviewed
Dr. Lewis' career as a teacher at Phillips Exeter Academy,
Massachusetts Institute of Technology, and finally at the Uni-
versity of California, where Dr. Lewis now heads the Department
of Chemistry. Dr. Lamb also called attention to the splendid
war record which Dr. Lewis had made, having first been sent
abroad as an observer with the Fifth British Army, and sub-
sequently heading the Defense Division of the Chemical War-
fare Service.
Dr. Teeple then introduced Prof. John Johnston of Yale
University, who also paid a tribute to the medalist's scientific
achievements. "Dr. Lewis is not a cloistered type of high-
brow," said Dr. Johnston, "he mixes well with his fellowmen, and
has exhibited unusual capacity for taking a leading part in the
world's work. He has raised the school of chemistry of the
University of California to a high pinnacle and has attracted
students from all over the United States and foreign countries.
Dr. Teeple read a letter from Prof. Richards of Harvard,
who had been Dr. Lewis' teacher, in which he expressed his
regret at being unable to attend the function, and paid an elo-
quent tribute to the work of his former pupil. A letter from
Dr. Nichols, the donor of the medal, who was sojourning in
Europe, was also read.
Dr. Teeple then made the presentation. After prolonged
applause by the audience, Dr. Lewis responded briefly, voicing
his thanks and appreciation for the honor that had been con-
ferred upon him, and then proceeded with his lecture.
Dr. Lewis first outlined the early use of vegetable and animal
pigments, referred to the coming of the synthetic dyestuffs
beginning with Perkin's discovery, and then proceeded to demon-
strate by means of tinted glasses the difference in color produced
by reflected and transmitted/ light. Color depends largely
on light absorption, said Dr. Lewis. Certain atoms possess a
mechanism for absorption of light, as copper atoms, for example.
Three cupric salts dissolved in alcohol, water, and ammonia water,
respectively, were shown to yield blue solutions. It is pretty
certain, the speaker maintained, that the color is due to the cop-
per atom, but the exact quality and intensity of the color de-
pends on the environment constituted by the attached groups.
On the other hand, there is the other type of colored substance
composed of elements like C, H, and O, where the color absorp-
tion mechanism is- not in any one atom but rather in the group-
ing of the atoms.
In order to demonstrate how slight physical and chemical
changes affect color, Dr. Lewis heated a glass cylinder contain-
ing N2O4, which was light brown in color. The heat promptly
dissociated the gas, forming NO2, and a deep brown color re-
vealed its presence.
Dr. Lewis further demonstrated this phenomenon with a solu-
tion of methyl violet indicator. A series of changes from violet
to blue to green took place as the amount of acid in the solu-
tion was increased.
It is evident by analogies with resonance in sound, said the
speaker, that a body which absorbs light must be assumed to
possess charged particles held with just such firmness as to
resonate with light of visible frequency. Electrons in mos.
chemical substances are too tightly held to absorb in the visiblet
Cases in which electron constraints are loosened were cited as
follows :
An electron which is not a part of a stable pair is always loose,
and with one exception (nitrogen monoxide) all known odd
molecules are colored.
A pair of electrons acting as a bond may act as light absorbers
if the bond is weakened, as in the case of the halogens, where
the absorption of light shifts more into the visible as we pass
from the tight bond of F2 to the loose bond of I2.
Then, finally, in the double bond the electrons are never held
as tightly as in the typical single bond. All organic colored
568
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
bodies, except those few which are odd molecules, contain double
bonds. By the introduction of new radicals, the electrons of
some one double bond may be loosened to such a degree as to
absorb visible light.
Chemical Societies Honor Madame Curie
The chemists of New York City and vicinity, under the aus-
pices of the American Chemical Society, the American Electro-
chemical Society, the American Sections of the Societe de Chimie
Industrielle and the Society of Chemical Industry, and the
Chemists' Club of New York, united to pay tribute to Madame
Marie Sklodovska Curie at a complimentary luncheon given in
her honor at the Waldorf-Astoria, Tuesday, May 17, 1921.
Wyndam, Paris
Mme. Marie Curie Weighing Radium in Her Paris Laboratory
Although Madame Curie still showed the effects of her strenu-
ous voyage across the sea and appeared somewhat tired out from
the many engagements that had been crowded into her short
visit, she seemed greatly pleased with the splendid reception
accorded her by the American chemists. It was the first oppor-
tunity that members of the American Chemical Society had for
giving Madame Curie, who was elected to honorary membership
in that Society in 1909, a more or less personal welcome, and
Madame Curie's happy smile during the prolonged applause
which greeted her entrance into the dining hall indicated that
she enjoyed the occasion thoroughly and appreciated the good
will of the assemblage.
President Edgar F. Smith of the American Chemical Society
presided, and after the luncheon he formally welcomed Madame
Curie in what he termed her triple capacity of discoverer of
radium, benefactress of humanity, and splendid representative
of our sister republic, France.
Dr. George B. Pegram, dean of the School of Mines, Engineer-
ing and Chemistry of Columbia University, welcomed Madame
Curie in behalf of the physicists of America.
Dr. Richard B. Moore, chief chemist of the U. S. Bureau of
Mines, recounted the painstaking research that had led up to the
discovery of radium. He termed Madame Curie the "Mother
of Radium," and said that since the chemistry of war with its
untold destruction had given way to the chemistry of peace and
of healing, Madame Curie, in going about the various hospitals,
where her discovery was bringing relief to hundreds, would feel
very proud of the appellation "Mother of Radium." Dr. Moore
also paid a tribute to Mrs. William B. Meloney, Madame Curie's
hostess, as well as to the Marie Curie Radium Fund Committee
for having arranged the visit of the distinguished woman scien-
tist to this country, as he felt her presence here had already
quadrupled the appreciation of women in science in America.
Dr. Francis Carter Wood of the Crocker Cancer Research
Laboratory of Columbia University lauded Madame Curie as
the woman who had done more to bring comfort to human
beings than anyone who has made any important discovery
in the present generation.
At the conclusion of the addresses, Dr. Smith formally pre-
sented Madame Curie, naming her the "Queen of Scientists of
the World," and as she arose, the entire audience also stood and
applauded for several minutes. Madame Curie made no formal
response to the addresses, but those present realized that she
was greatly appreciative of all that had been said and of the
warm welcome that had been accorded her by her fellow scien-
tists.
A. C. S. Committee Reports1
REPORT OF THE COMMITTEE ON OCCUPATIONAL DISEASES
IN THE CHEMICAL TRADES
(1) The reduction of occupational diseases in the chemical
trades may be asserted, on general principles, to be due to the
let-down in chemical industries during the current year. Sta-
tistics are not yet available, but a general improvement in sani-
tary conditions in chemical works, put into effect by operators,
may be recorded. In this connection it may be noted that dur-
ing the world war many chemical factories were driven under
high pressure, offended communities, and exposed workers by
unusual escapes of objectionable gases and fumes. The people
worthily submitted to the attendant discomfort through a
spirit of loyalty. However, on the signing of the armistice,
complaints against the offenses multiplied, in some instances,
with exaggeration. Numerous installations to minimize atmos-
pheric contamination from such sources have been installed
as a result. While some of the cessation of air pollution has
been due in part to the closing down of factories on account of the
general business depression referred to, rather than improved
works conditions, it must be noted that more companies have
undertaken to safeguard workers from diseases arising in the
production and handling of chemicals.
(2) methanol — The Committee is pleased to report the
cordial cooperation of various publications and directors of
official communications in adopting the term at the head of this
paragraph. The changed nomenclature no doubt had some-
thing to do with decreasing the casualties from drinking the
liquid for ethyl alcohol, although some accidents have been re-
ported. The number of deaths due to methanol was lowered
in New York City alone from 54 in 1919 to 19 in 1920. The
withdrawal of general formula No. 1 for denaturing alcohol
and wide publicity undoubtedly were the prime reasons for this
improvement.
(3) protection oP head and eyes — A very exhaustive
National Safety Code covering this matter has been prepared
under the supervision of the Bureau of Standards, and issued as
Handbook Series No. 2. The Committee was represented in
the conferences which resulted in the Code, copies of which
may be had on application to the Bureau of Standards (price, ten
cents).
(4) gas masks in industries — The use of gas masks provided
with canisters containing special absorbents, depending upon
the objectionable material present in the air, has been much
extended in the chemical industries. Full information as to the
gas involved should be given to, and requests for information
as to specific efficiency should be made of, the several companies
supplying the masks. For example, gases in some of the Mexican
oil camps have killed men and mules. The men die with marked
cyanosis, a quick pulse, and apnoea. The ordinary army gas
masks proved to be useless. Contrivances like divers' helmets
have been employed, but were very cumbersome. The gas
causing the trouble in this instance consists principally of hy-
i Concluded from This Journal, 13 (1921), 404.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
569
drogen sulfide. It remains difficult to persuade civilian em-
ployees to use gas masks on account of the inconvenience. In
military service the strict discipline enforced their use.
(5) tuberculosis among workers in sulfur dioxide ap-
pears to be practically nonexistent, with the exception perhaps
of fibroid phthisis, according to Tweddell (Medical Record, Aug. 31,
1920, p. 310), who used the gas with good results in the treatment
of pulmonary and laryngeal tuberculosis for four years (Medical
Record, Dec. 21, 1918). Dr. Tweddell gives the results of a
survey of some thirty-eight factories producing sulfur dioxide
and sulfuric acid, twenty -nine of which employed 11,085 men.
Shufflebotham (Brit. Med. J., 1919, 478) reported for twenty
different war gas plants in different localities, "that, with the
exception of phosgene gas, workers engaged in the production
of other poison gases have enjoyed a high degree of immunity
from influenza infection." The gases manufactured where the
investigation was made were hydrogen sulfide, chloropicrin,
chlorine, mustard, and phosgene. Catton (Mil. Surgeon, 45
(1919), 65) describes the aftermath of gas warfare as varied,
but marked. The pathological changes may result from manip-
ulating these and similar substances in peace times.
(6) Therefore, the previously expressed hope may be re-
peated, namely, that some qualified institute or group of in-
vestigators will give more study to the problem of the actual
influence of very dilute gases in disease. An excellent type of
such an investigation is seen in D. C. Parmenter's paper on
"Tetrachloroethane Poisoning and Its Prevention," just pub-
lished in the current number of the Journal of Industrial Hygiene
(April 1921, 456). An adequately endowed Institute of In-
dustrial Hygiene must eventually be established, as was urged
in the Committee's last report. The work done by the U. S.
Public Health Service, at Harvard and other medical schools,
is all first class as far as it goes, but generous financial aid from
the Government and the industries will more than repay in
health, efficiency, and happiness of the workers.
Insurance companies are devoting more and more attention
to occupational hazards and diagnostic signs, as is shown in
a very important paper (Modern Medicine, January 1921) from
the statistical department of the Metropolitan Life Insurance
Company, New York, which deals primarily with dangers from
chemicals.
(7) khaki cloth from certain factories developed some
peculiar dermatic conditions, which are being investigated by
the United States Public Health Service. The possible presence
of some unchanged dinitrobenzene may have been the origin
of the trouble. An excellent treatment of the eczema arising
from such sources is washing with a 2 per cent carbolic solution.
(8) The "purples," a rare disease, "Purpura hemorrhagica,"
has been attributed to benzene fumes; these diseases decrease
the volume of white corpuscles in the blood so as to destroy the
power of coagulation. The patient then bleeds from the mucous
membrane — gums, mouth, nose, etc. — and bleeds beneath the
skin until death results. (N. Y. State Industrial Commission,
Bulletin 6 (1920), 22.)
gas for death penalty — This method of execution of con-
demned criminals, recently enacted by the State of Nevada,
is recorded as a novel hazard upon which no comments are made.
(9) emollient for skin protection of users of dope and
varnish — H. A. Gardner (Educ. Bur. Paint Mfgrs. Assn. and
National Varnish Mfgrs. Assn. in the U. S., Circular 91) has
recommended a hand salve to be rubbed in before starting to
work and after washing up at the end of a shift. It keeps the
skin in good condition and as it is not rapidly attacked by
solvents, it is suggested for use in industries where coating com-
positions containing large amounts of volatile organic solvents
or thinners are used. It is composed of lanolin (Adeps Lanae
Hydrosus), petrolatum, stearin, and glycerol in equal parts by
weight.
In this connection it may be noted that W. A. Pusey (J.
Ind. Hyg., 1 (1919), 385) has published an excellent article
on "Industrial Dermatoses," in which he states "by far the great-
est number of irritants that affect the skin are chemical irritants"
and "the control of industrial dermatoses manifestly presents a
great many special problems which vary with the numerous
irritants that are involved and with the conditions of their
use." He urges that well-directed investigations be under-
taken. Bettmann (Therap. Monatsh., 33 (1918), 117) has
directed especial attention to skin troubles from various oils
and vaselines, which contained irritating tar products.
zinc stearaTE preparations have been found to be useful
in treating skin diseases arising from certain lubricants.
(10) "acid burns and their treatment" is an important
report by Dr. G. A. Welsh, medical officer to H. M. Factory,
Gretna. During a period of thirty-seven and one-half months,
a total of 17,414 accident cases were treated at the dressing
station. Of these, 4292 were for acid burns, and of these,
only thirty-eight were serious, and 226 were severe, while the
remainder were slight. In the cotton nitrating house, which
had 1711 cases, 1642 were caused by the splashing of the acids.
Methods of distinguishing the source of burns by their ap-
pearances are given, and variations in the treatment made
necessary by the differences. A description of the Factory
Rule Book, containing first-aid rules for these cases, and given
each employee, is given with description of first-aid supplies,
and of the centrally located dressing station. The require-
ments of a suitable dressing are listed, and the satisfactory
material, picric acid, is compared with ambrine, used for ordinary
burns, showing how picric acid is superior in these cases, as there
is no chance of scalding the patient.
(11) OVERCOMING INFECTION AND DECAY of ground Wood pulp
has been demonstrated by the Wood Products Laboratory at
Madison, Wisconsin, where mono-nitrotoluene, mono-nitro-
benzene, and o-nitrophenol were used for that purpose. The
toxicity of these antiseptics towards the operators is being in-
vestigated.
(12) heavy orchard spraying in the Pacific Coast States
has resulted in some cases of poisoning alfalfa.
(13) The Dow Chemical Company operating through a period
of twenty-three years with chlorine and bromine has noted no
occupational diseases resulting from chlorine or caustic soda,
but a poison was developed on the sides of wooden cells, to
which horses seemed to be especially susceptible. This poison
made itself manifest when tearing down old cells and carting
them away. Several horses were killed. No men appeared
to be seriously injured, but sores developed on their hands in hot
weather. In cold weather there were no apparent harmful
results.
Men who have distilled bromine in that locality for forty
years are among the healthiest men in the district.
(14) increased WORK OF THE COMMITTEE — While not specifi-
cally within the province of the work of the Committee, at-
tention may be directed to improving the sanitary conditions
attending the manufacture of such a popular article of food as
candy. Sporadic efforts of individual members of the Com-
mittee are all that may be counted upon, as no funds are avail-
able for general propaganda even in its specific field.
It will be readily recognized that under the circumstances
this report makes no attempt at a complete summary of the
condition of occupational diseases in the chemical trades. The
correspondence incident to the work of the Committee has
steadily increased in volume. Many requests have come in for
advice, data, sources of information, etc. They have been
complied with in so far as possible. This has been done in part
through assistance from Mr. W. H. Pearce, librarian of the
chemistry department of the College of the City of New York.
He is now compiling abstracts of the current literature on the
subject, which matter will be available to the members of the
Society.
(15) national safety council and financial support —
The chairman of the Committee continues membership in the
National Safety Council, which is rendering a splendid service
to society. The intimate relationship of occupational hazards
and chemical production with human welfare is now well rec-
ognized. The chairman inaugurated our Society's official
recognition of this fact and consented to carry on the essential
work of the Committee up to the time of such recognition.
It has now developed to such a degree that some one better
situated, professionally and by affiliation (perhaps a member of
the U. S. Public Health Service, or an expert of one of the large
insurance companies), and one who can devote a larger portion
of his time to work of the Committee, should be selected as
chairman. The Society should recognize that the Committee
has a great welfare work, richly promising in scientific outcome,
ahead of it. Steps should be taken to provide adequate financial
support.
Chas. BaskervillE, Chairman
REPORT OF THE REPRESENTATIVE OF THE AMERICAN
CHEMICAL SOCIETY ON THE JOINT COMMITTEE SUPER-
VISING THE PUBLICATION OF THE CHEMICAL EN-
GINEERING CATALOG FOR THE YEAR 1920
The fifth edition of the Chemical Engineering Catalog was ready
for distribution during the week of the Chemical Exposition in
New York, N. Y., in September 1920. The book went forward
systematically thereafter, the entire distribution being effected by
January 1, 1921.
570
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 6
This year a slight change was made in the method of placing
the work. In order to obviate the possibility of copies of the Cat-
alog being wasted, it was decided to charge a fee of $2.00 for the use
of the volume for the year. It was found that the introduction of
this fee did not in the least diminish the demand for the Catalog,
and that it materially improved the character of the mailing list.
Eleven thousand and five hundred copies of the Catalog were
sent out, and a list has been printed giving the name, address,
and business connection of each recipient. This list is furnished
to all the firms represented in the Catalog, and its use is con-
fined strictly to them.
In the 1920 edition there were 748 firms using space, an increase
of 144 over the previous year. This represents a remarkable
development when one considers the fact that only 132 firms used
space in the first edition in 1916. The total number of catalog
pages in the 1920 edition was 1048, as compared with 850 in the
1919 edition. Several firms used amounts of space in excess of
ten pages in order to catalog completely the equipment which
they are prepared to offer to the chemical industries.
The directory pages showed a slight increase, and the direc-
tory was revised and edited carefully with a view to increasing its
convenience and usefulness.
These facts as to the growth of the Catalog prove that the chem-
ical industries and the chemical engineering profession are gradu-
ally coming to realize that the book means a great deal more to
them than a mere collection of advertisements. It is the aim of
your Committee — and we have found that the publishers' views
with regard to the improvement of the Catalog always have con-
curred with the ideas advanced by the Committee — to make the
Chemical Engineering Catalog the most complete and reliable ref-
erence work that it is possible to compile with regard to all kinds
of equipment, supplies, raw materials, chemicals, and miscella-
neous commodities required in the chemical industries.
The officers of the Chemical Catalog Company constantly re-
fer copy of proposed data and information to the Committee for
suggestions and criticisms, and in many cases we have convinced
manufacturers that this work is not merely advertising in the or-
dinary sense of the word and that they must include correct and
concise data with regard to their products in order to obtain the
best results from their copy in the Catalog, and, furthermore, some
copy has been refused because of the fact that the manufacturers
would not give this information.
The individual members of the American Chemical Society
can render the greatest possible assistance to those in charge of
the compilation of the Chemical Engineering Catalogby constantly
bringing to the attention of the manufacturers from whom they
purchase equipment and supplies the fact that the Catalog is their
official, standard reference work, and it is through this book that
they wish to be supplied with information about the equipment
and supplies which the manufacturers have to offer them.
Unfortunately, the majority of manufacturers using space in
the Catalog carry on their relations with the publishers through
their advertising departments, and the men in the advertising
departments of these concerns are prone to regard the work as
merely another advertising proposition. Nothing can so effec-
tively dissipate this erroneous idea as constant emphasis on the
value of the Catalog by the individual members of the Society
who use it.
Your representative attended a meeting of the entire Com-
mittee, together with the officers and editor of the Chemical Cat-
alog Company, in New York, N. Y., in November 1920, and at
this meeting a number of topics connected with the future devel-
opment of the Chemical Engineering Catalog were discussed
thoroughly. In addition to this formal meeting, your repre-
sentative has had a large number of informal conferences with the
officers and editor of the Chemical Catalog Company and has en-
deavored to be of assistance to them in their activities in every
possible manner. Various members of the Committee frequently
get together to discuss certain phases of the work, principally
dealing with matters of policy, as we are often called upon to
assist the officers in obtaining from manufacturers the proper
data and information.
The 1921 edition of the Chemical Engineering Catalog will in-
clude even more concise data with regard to products relating to
the chemical industries.
E. R. Weidlein
American Chemical Society when unanimously approved
by the Advisory Committee. The following resolutions have
been unanimously approved:
Whereas, the use of alcohol in many important industries
is absolutely necessary not only to the continuance of such
industries, but also for the manufacture of articles needed by
other industries and even for the production of articles necessary
to the protection of and sustenance of life itself, and
Whereas, it is the policy expressed in the National Prohibition
Act to encourage the use of industrial alcohol for nonbeverage
purposes such as the manufacture of thousands of necessary
medicinal and countless dyes, chemicals, and perfumes, and for
the production of heat, light and power,
Be it Resolved that the American Chemical Society advises
and most strongly urges for the national welfare that all legis-
lation for the enforcement of prohibition be so clearly drawn
as not to restrict the activities of legitimate industries which
must have industrial alcohol and that all such legislation be
so drawn as to provide in specific sections for the encouragement
of the proper use of alcohol in the industries.
REPORT OF COMMITTEE ON INDUSTRIAL ALCOHOL
At the Rochester meeting of the Society the Council appointed
a Committee on Industrial Alcohol, and voted that resolutions
prepared by this Committee should become resolutions of the
Division of Industrial and Engineering Chem-
istry—Submittal of Papers
The Division of Industrial and Engineering Chemistry wishes
to call the attention of the members of the Society to the action
taken at the Rochester meeting, this action being designed to
improve the quality of papers to be presented before the Di-
vision. Another object is to assist in making the program at-
tractive by according to papers of major interest sufficient time
for their proper presentation and assigning shorter periods to
those papers which appear to be of minor importance. The
Division officers also plan to suggest to authors whether their
papers be presented in their entirety or abstracted, leaving cer-
tain details for publication in the Journals. Experience has
shown that the mere reading of lists of analytical data or of
formulas is futile, and that time devoted to historical statements
is largely wasted. The brief, pointed presentation of results
with the assistance of lantern slides undoubtedly makes the best
impression.
The action of the Division is to the effect that papers them-
selves are to be submitted one month in advance of the meeting
to enable them to be reviewed by specialists or by the executive
committee of the Division, which will then suggest to ' he author
whether the paper should be presented in extended form or in
abstract or by title.
The Division officers have often been impressed by the ex-
cessive time required to presen' certain papers which the authors
evidently have never read against time. The Division has a
rule, which heretofore has not been enforced, that no more than
five minutes can be taken for the presentation of a topic unless
other arrangements have been made previously. Authors are
urged to read their papers against time in order that they may
know how long it will require them to present their subject.
It has also been noticed tha' lantern slides are sometimes em-
ployed, although they are unintelligible, and evidently have not
been tried out by the author before coming to the meeting.
The Division wishes to do all in its power to encourage the
presentation of a suitable number of hi^h-grade papers. It will
insist that only new material be offered and wishes to emphasize
the importance of discussion which, however, cannot be had if the
authors consume all the available time for the presentation of
their papers.
The action of the Division may at times seem rather drastic;
but it is believed that the proposed regulations are a proper step
in the interest of progress.
Comments are solicited from members of the Society.
H. E. Howe, Secretary,
Division of Industrial and Engineering Chemistry
Washington, D. C, May 26, 1921
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
571
Hotel Accommodations, American Chemical
Society Meeting, New York City,
September 6 to 10, 1921
Hotel headquarters for the meeting of the American Chemical
Society in New York City, September 6 to 10, 1921, will be at the
Waldorf-Astoria Hotel, Fifth Avenue and Thirty-third Street.
Through the courtesy and cooperation of the Hotel Association of
New York City, the committee has arranged to receive applica-
tions and make reservations at the various hotels throughout
the city. Applications should be made promptly, and it is
suggested that two or more persons take advantage of double
rooms and suites wherever possible. Prices at the various
hotels range from $1 .50 to $5.00 per day for single rooms, and
from S3 . 00 to $10 . 00 for double rooms.
Columbia University has offered the facilities of its dormi-
tories to aid in meeting the requirements of those desiring to at-
tend the meeting. Rooms for men, rooms for women, and rooms
for married couples have been reserved in the dormitories at the
rate of $1.50 per day per person, with a maximum per person
■of $10.00 for the period September 6 to 16, for those wishing to
stay for the Chemical Exposition.
Applications, giving the following information, should be
forwarded as soon as possible to the chairman of the Hotels
Committee, c/o United States Rubber Co., 1790 Broadway, New
York City.
Application for persons
Names of those in party
Type of reservation desired
Maximum price per day per person
Time of arrival Expected departure
Reservations will be confirmed from the designated hotels.
Charles F. Lindsay, Chairman
Division of Chemistry and Chemical Technol-
ogy of the National Research Council
The Division of Chemistry and Chemical Technology of the
National Research Council met during the American Chemical
Society meeting in Rochester, N. Y., Wednesday, April L'7,
1921.
The officers elected were:
Chairman: F. G. Cottrell
Vice Chairman: Julius Stieglitz
Executive Committee: F. G. Cottrell, chairman, Julius Stieglitz,
vice chairman, W. F. Hillebrand, C. G. Fink, R. B. Moore
Members at Large: Treat B. Johnson, R. B. Moore
The following members were appointed by the constituent
■societies for three-year terms (expiring in 1924):
American Chemical Society
E. C. Franklin, John Johnston, J. E. Teeple
American Ceramic Society
A. V. Bleininger
B. E. Livingston was appointed by the Division of Biology
and Agriculture as liaison member before the Division of Chem-
istry and Chemical Technology for a term of one year.
The following men will attend the meeting of the International
Union of Pure and Applied Chemistry at Brussels in June as
representatives of the Division: F. G. Cottrell, James B. Conant,
E. S. Chapin, Hugh S. Taylor, Frederick G. Keyes, and Collin
McCall.
The committees on the Chemistry of Colloids, Contact Ca-
talysis, Ceramic Research, Methods of Organic Analysis, Phar-
maceutical Research, Sewage Disposal, and Explosives Investi-
gations were continued for the ensuing year. The small number
of inquiries received by the Committee on Synthetic Drugs
during the past year would seem to indicate that the manufacture
of synthetic drugs in this country has returned to a normal
basis, and this committee was accordingly discontinued.
The report of the Committee on the Chemistry of Colloids,
Harry N. Holmes, chairman, appeared under the title of "Colloid
Development,'" This Journal, 13 (1921), 357.
The Committee on Ceramic Research, A. V. Bleininger,
(hair ma ii, reported the establishment of a fellowship dealing
with the relation between the viscosity and the temperature of
fused glass, maintained by the Corning Glass Works, Corning,
N. Y., and conducted at the University of Illinois under the
direction of Dr. E. W. Washburn. The attention of the Committee
has been directed especially to the following points: A study of
the elements which determine the plastic nature of clays, a
critical examination of certain methods used in silicate analysis,
a study of American pot clays and their compounding for the
production of refractories used in the glass industry, and the
relationship between crazing and the expansion coefficients of
bodies and glazes. Attempts to secure industrial cooperation
in research along these lines have been for the most part un-
successful, but it is believed that within the present year positive
cooperation may be secured. First steps have been taken in
organization for cooperative research with certain associations
of brick and refractories manufacturers.
The Committee on Explosives Investigations, Charles E.
Munroe, chairman, reported that it had been engaged in, arrang-
ing for, cooperating in, or supervising numerous investigations on
explosives manufacture, analysis, and use. The Committee has
also continued its cooperation in the industrial utilization of
surplus military explosives. The entire surplus of 21,000,000
pounds of TNT has been distributed. The surplus of 12,000,000
pounds of picric acid is also to be disposed of, as soon as field
tests by the inexpert under the supervision of experts indicate
that its distribution will be safe. Work has been continued
in bringing Munroe's "Index of the Literature of Explosives"
up to 1907, at which date the Chemical A bstrarts begins. The
Committee has prepared translations of several publications
dealing with explosives, and is continuing its card indexing of all
explosive reports passing through its office. Numerous papers
have been published this year as a result of the activity of the
Committee, and several more are approaching completion.
At the suggestion of Dr. Yerkes, chairman of the Research
Information Service, a joint committee of the Service and the
Division of Chemistry and Chemical Technology was appointed,
for the purpose of preparing a list of research chemicals available
in this country. The Committee consists of W. D. Collins,
chairman, Capt. D. B. Bradner, G. C. Spencer, H/T. Clarke,
Roger Adams, Clarence J. West, and W. F. Hillebrand.
Other subjects which came up for discussion at the meeting
included the publication of information obtained through the
development of our explosives industries during the war, possible
means of assisting the newly established Belgian Bureau of Chem-
ical Standards, and several matters dealing with the coming
meeting of the International Union of Pure and Applied Chem-
istry. A letter was read from Mr. Charles Marie, urging that
the delegate from the United States receive full powers re-
garding the affairs of the Commission on Annual Tables of Con-
stants and Numerical Data, that he be instructed to request
the Union to appoint a committee to inquire into the financial
participation of the different countries in the publication of the
Annual Tables, and that he receive from the National Research
Council instructions to ask the Union to take such action as
may be necessary to persuade the International Research Coun-
cil to bestow its effective patronage upon the work of the Com-
mission to the greatest possible extent. It was the sense of the
members that the Division should give its moral support to the
carrying out of these suggestions.
572
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. G
The Exposition of Chemical Industries
The Seventh Annual National Exposition of Chemical Indus-
tries will be held in New York in the Eighth Coast Artillery
Armory, during the week of September 12 to 17, 1921, inclusive.
The Grand Central Palace has been discontinued as a place
for weekly expositions, and all the expositions given there annu-
ally have taken new quarters in other buildings throughout the
country. The Chemical Exposition was, however, the largest
industrial exposition ever held in the Palace building — in fact,
it is now the largest industrial exposition of any kind given in
the world. This very greatness brought a problem when the
Exposition had to seek new quarters. Exhibitors advised against
going to a city other than New York for this year, and the
management made an exhaustive study of the buildings in the
city suitable for their purpose. The one most used and perhaps
best known as an exposition hall proved so small that at least
one-half of the exhibitors occupying space in the last exposition
would be excluded. The purpose in the mind of the manage-
ment is to further the expansion of the industries of the country
through the Exposition. Plainly, therefore, the exhibits require
more and not less space. It was good fortune which brought
the managers to the Eighth Coast Artillery Armory, which has
the largest covered floor space of any armory in the country,
with a parade area equivalent to five city blocks.
The center of the building rises a few hundred feet, insuring
exceptionally good ventilation, a fact which will prove a boon
to the exhibitors, who have always suffered because of poor
ventilation and dense tobacco smoke.
In this building the Exposition will have all the appearance
of a world's fair. From the spacious balcony around the build-
ing visitors may secure a general view of the exhibits and gain
the inspiration which was impossible in the former home of the
Exposition. There is a commodious dining hall in the building
where fourteen hundred diners may assemble at one time.
Transportation facilities are the best: there is a Lexington
Avenue subway express station at the door, and the Sixth and
Ninth Avenue "L" trains run to the same station.
This Exposition promises to be the largest yet. At the present
time the managers report more exhibitors than at the same
period last year. Furthermore, the interest of men who inquire
about exhibits to be shown is greater, and it would seem that
the thoughts of men are turning to this Exposition for assistance
in their plans for the future.
The dates for the Exposition were set much earlier in the
month this year in order to follow immediately the general
meeting of the American Chemical Society, which will be held
in New York the latter part of the previous week, when the
Society of Chemical Industry will also meet, partly in joint
session with the American Chemical Society. The meeting
of the Society of Chemical Industry will have an international
complexion, since it is a continuation of the big general meeting
in Canada, a large contingent coming from Great Britain and a
considerable number coming from Canada. Programs for all
these events are now in the formative stage and will be announced
in later issues of This Journal. The Societies expect the
largest registration in their history because of this arrange-
ment by which their meetings occur just prior to the Exposi-
tion.
The program of the Exposition promises to be an interesting
one. Many new motion pictures will be shown, and, it is not
inappropriate to say, this will be the first time the program will
be carried out in a suitable auditorium. The one available in
the Armory building has a seating capacity equal to many of
New York's best theaters.
Special sections of exhibits are being organized in the Ex-
position, which will commend themselves to the careful con-
sideration of technical men when they visit the Exposition.
The new standards of business procedure and revision of costs
make necessary the adaptation of every business to the new de-
mands, and much real information along this line will be gained
from careful study of these exhibits.
The executive office of the National Exposition of Chemical
Industries is now located at 342 Madison Avenue, New York.
The National Lime Association
The annual convention of the National Lime Association is to
be held at the Hotel Commodore, New York City, June 15 to 17,
1921.
The program for Wednesday, the 15th, deals with lime pro-
duction problems, and includes papers on lime kiln efficiency,
lime burning, machine methods in quarrying, and social service
work and labor efficiency as applied to the lime industry. The
discussions on Thursday will deal with the extension of the use of
lime, while Friday will be devoted largely to the hearing of
committee reports.
Among the special speakers are included Dr. S. W. Stratton,
chief of the Bureau of Standards, who will speak at luncheon on
Wednesday on "Standardization — Government Research and
Industrial Development;" Willard A. Eckman, welfare special-
ist with the United Security Life Insurance and Trust Co.,
Philadelphia, who will discuss the "Relations of Banking In-
stitutions to Social Service" at the afternoon session of the same
day; and Dr. A. D. Little, of A. D. Little, Inc., Cambridge. Mass.,
who will speak on Thursday afternoon on "The Dependence of
Modern Industry on Research."
Calendar of Meetings
American Leather Chemists Association — Eighteenth Annual
Meeting, The Ambassador Hotel, Atlantic City, N. J , June
9 to 11, 1921.
Insecticide and Disinfectant Manufacturers Association — Mid-
summer Meeting, Hotel Traymore, Atlantic City, N. J., June
13 and 14, 1921.
National Lime Association — Annual Convention, Hotel Commo-
dore, New York, N. Y., June 15 to 17, 1921.
National Fertilizer Association — Twenty-eighth Annual Meeting,
White Sulphur Springs, W. Va., week of June 20, 1921.
American Institute of Chemical Engineers — Spring Meeting,
Detroit, Mich., June 20 to 21, 1921.
American Society for Testing Materials— Twenty-fourth Annual
Meeting, New Monterey Hotel, Asbury Park, N. J., June 20
to 24, 1921.
Society for the Promotion of Engineering Education — Twenty-
ninth Annual Meeting, Yale University, New Haven, Conn.,
June 28 to July 1, 1921.
American Ceramic Society — Summer Meeting, Hotel Court-
land, Canton, Ohio, July 25 to 27, 1921.
Society of Chernical Industry — Annual Meeting, Montreal,
Canada, August 26 to 31, 1921.
American Chemical Society and Society of Chemical Industry —
New York, N. Y., September 6 to 10, 1921.
Seventh National Exposition of Chemical Industries — Eighth
Coast Artillery Armory, New York, N. Y., September 12 to 17,
1921.
American Electrochemical Society — Fall Meeting, Lake Placid
Club in the Adirondacks, N. Y., September 29 to October 1,
1921.
In 1919 there were 116 establishments in the United States
engaged in the distillation of wood, and their products for the
year were valued at $32,635,000. In 1914 there were 101 es-
tablishments, with products valued at $10,530,000.
The total production of Alsatian potash during the year 1920
reached 1,661,197 tons, of which 450,000 tons were sold in France,
372.000 tons were exported to Belgium, and 92,000 tons to the
United States.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
573
NOTES AND CORRESPONDENCE
Madame Curie Receives Gram of Radium and
Many Honors
Scientists in various sections of the United States, as well as
the general public, are paying a well-deserved tribute to Madame
Curie, the co-discoverer of radium, on her visit to the United
States. The Marie Curie Radium Fund Committee arranged
to have Madame Curie visit the United States and receive in
person the gram of radium, valued at $100,000, contributed
to her by the American people. President Harding presented
the gram of radium to Madame Curie in the White House on
May 20 in the presence of a distinguished gathering of gov-
ernment officials.
Various scientific societies and institutions took the oppor-
tunity of Madame Curie's presence in this country to confer
upon her degrees, medals, and other honors in recognition of her
researches. She arrived in New York on the Steamer Olympic
on May 11 and was given a great reception by a large throng
of people. On the following day a dinner was given in her honor
by Mrs. Andrew Carnegie. On May 13 she visited Smith Col-
lege, at Northampton, Mass., where she received an honorary
degree. From there she was taken by automobile through
the Berkshire Hills to Vassar College at Poughkeepsie, passing
Mt. Holyoke College where the student body had gathered to
give her a welcome as she passed through. May 14 and 15 were
spent at Vassar College, and from there she returned to New
York, spending Monday, May 16, quietly at the home of Mrs.
William B. Meloney, who is acting as Madame Curie's hostess
throughout her visit. On May 17 the combined chemical so-
cieties tendered Madame Curie a luncheon, which is described
elsewhere in this issue. On the following day the college women
of New York tendered a reception to Madame Curie at Car-
negie Hall under the auspices of the American Association of
University Women. On May 19 the National Institute of
Social Sciences awarded a gold medal to Madame Curie at the
annual meeting held at the Waldorf-Astoria. The following
day Madame Curie was received by the President at the White
House and given the gram of radium which had been contrib-
tuted by the people of the United States. On the evening of
the same day a meeting of scientists was held in Madame Curie's
honor at the National Museum. This meeting was addressed
by Dr. Charles Walcott and Dr. Robert A. Millikan of the
University of Chicago. On May 21 Madame Curie dedicated
the new low-temperature laboratory of the Bureau of Mines at
Washington, and later visited Mt. Vernon. On the evening of
the same day she was the guest of honor at a dinner given by
the French Embassy, and on the following day she was the
guest of honor at a dinner given by the Polish legation. On
May 23 Madame Curie journeyed to Philadelphia, where she
received degrees from the Women's Medical College of Penn-
sylvania and the University of Pennsylvania. She was also a
guest at the meeting of the College of Physicians and Surgeons
of Philadelphia on the evening of this day, and presented a piece
of the original apparatus used in her laboratory to the cancer
museum of this institution. The following day Madame Curie
visited the laboratories of the Welsbach Company at Glouces-
ter, N. J., spending two hours inspecting the manufacture of
mesothorium. At the end of her visit she was presen'ed
by the firm with 50 milligrams of mesothorium. That evening
Madame Curie took her seat as a member of the American
Philosophical Society at its regular meeting, and received the
John Scott Medal and the sum of §800 which goes with this
award. She left for Pittsburgh the same night, and on May 26
the honorary degree of Doctor of Laws was conferred upon her
by the University of Pittsburgh. Whi'.e in Pittsburgh she
visited the radium plant of the Standard Chemical Company
and other chemical plants in that district.
The balance of her traveling schedule, as tentatively ar-
ranged at the time This Journal went to press, included
returning to New York from Pittsburgh and spending several
days quietly at the home of Mrs. Meloney and visiting such
laboratories and institutions as are of especial interest. A
dinner in her honor is to be given by the Poland-American So-
ciety on May 30 at New York. On June 1 Madame Curie
is scheduled to leave New York for Dayton, Ohio, leaving there
June 2 and arriving at Chicago the following day, whence she
will immediately depart for Grand Canyon, Colorado. From
there she is to go to Los Angeles and Pasadena, returning to
Chicago by June 13, where a great welcome is being planned by the
Association of Collegiate Alumnae and the Associated Women's
Organizations of Chicago. On June 14 Madame Curie is ex-
pected to be the guest of the Chicago Section of the American
Chemical Society and will be awarded the Willard Gibbs
Medal. On June 15 she will be the guest of President Scott of
Northwestern University at a luncheon in her honor, after which
she is scheduled to leave for Buffalo, arriving there June 16.
She will be the guest of the combined women's clubs of Buffalo
and will spend the following day visiting Niagara Falls and
inspecting the power plants on the American side. On June
18, Madame Curie is to leave for Boston, and on the 20th she is to
be the guest of the American Academy of Arts and Sciences of
Boston. On June 21 it is expected that Madame Curie will at-
tend the dinner given by Yale University in honor of James
Rowland Angell, the newly elected president of the University.
While at New Haven, Madame Curie will be the guest of Prof.
Henry W. Farnum. She is scheduled to return to New York
on June 23 to be the guest of honor at a special ceremony on
June 24 which is being arranged by the Poles of New York to
wish her bon voyage on the eve of her departure for France.
According to present plans, Madame Curie will sail for France
June 25.
Presentation of Medal to
Dr. Frederick B. Power
An interesting presentation took place at the Cosmos Club,
Washington, D. C, on the evening of May 9, 1921, when Dr.
Frederick B. Power received a gold medal, conferred upon him
by Mr. Henry S. Wellcome, as a tribute to his many years of
research, and in commemoration of those years which he spent
as director of the Wellcome Chemical Research Laboratories
of London.
Dr. Power graduate*! from the Philadelphia College of Phar-
macy in 1874, in the same class with his life long friend, Mr. Well-
come. After four years of study in Strassburg, Dr. Power spent
nine years in organizing and building up the School of Pharmacy
in the University of Wisconsin, followed by four years of research
on the essential oils. In 1896, he became director of the Well-
come laboratories, where for eighteen and a half years he devoted
his time exclusively to chemical research and to the direction of
a staff of research workers. One hundred and fifty important
scientific memoirs were published from the laboratories during
this period. These covered a wide field of investigation, for
which material was obtained from all parts of the world. Among
these a very notable and complete study was made of the East
Indian chaulmoogra oil, which resulted in the discovery of some
physiologically active acids of an entirely new type. These
form the basis of the new treatment of leprosy, which gives
promise of effecting a complete cure of one of the most terrible
diseases of mankind.
574
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 6
In 1908 the University of Wisconsin, commemorating the
twenty-fifth anniversary of the formation of its Department of
Pharmacy, conferred upon Dr. Power the degree of LLD.,
and in 1913 the Chemical, Linnean and Pharmaceutical Societies
of London awarded him the Hanbury gold medal, a distinction
only once previously bestowed upon an American.
In the presentation address Dr. Charles D. Walcott, secretary
of the Smithsonian Institution and president of the National
Academy of Sciences, characterized Dr. Power as one "who,
because he possesses that peculiar faculty of exhausting each
subject which he takes up, has had the greatest influence both
in America and Great Britain in raising the standard of our
pharmacopeias; who has gained distinction by his most difficult
and life-consuming researches into the chemical composition of
plant compounds."
The Direct Identification of Soy-Bean Oil
Editor of the Journal of Industrial and Engineering Chemistry:
To be able to detect adulteration of linseed or chinawood oils
with soy-bean oil would be a great satisfaction and help to paint
and varnish chemists. Numerous methods have been tried
with only partial success. The most recent suggestion coming
to our attention was that of Charles A. Newhall, appearing in
This Journal, 12 (1920), 1174.
This test depends on the formation of a lemon-yellow emulsion
when a chloroform solution of soy-bean oil is shaken with a so-
lution of uranium nitrate and a little gum arabic.
The tests run in this laboratory show that while it is true that
soy-bean oil gives this lemon-yellow emulsion, the same color is
also given by linseed oil. Chinawood oil does not show the color-
ation, but fish oil produces a slightly yellow emulsion.
It is believed that the proposed test is neither characteristic of
soy-bean oil nor sufficiently sensitive to be of practical value.
In the work in this laboratory the test was performed exactly
as directed in the original article, the uranium nitrate solution
being used. The following table shows the results obtained:
•Color Produced by Different Oils When Emulsified with Uranium
Nitrate
Oil Color op Emulsion
Soy-bean Lemon-yellow
Linseed, as used in plant Lemon-yellow
Linseed, A.S.T.M. No. 42 Lemon-yellow
Linseed, A.S.T.M. No. 46 Lemon-yellow
Chinawood Practically white
Fish (Menhaden. W.P.) Slightly yellow
10 per cent Soy-bean j v slightly yellow
90 per cent Chinawood)
The linseed oil referred to as Nos. 42 and 46 was furnished by
the American Society for Testing Materials as commercially
pure linseed oil.
R. D. Bonney
W. F. Whitescarver
congoleum co., inc.
Marcus Hook, Pa.
March 18, 1921
Editor of the Journal of Industrial and Engineering Chemistry:
The shortcomings of the uranium emulsion test for s ■•>--
bean oil are fully recognized, and in my paper special note was
made that the test should be used with caution.
Messrs. Bonney and Whitescarver attribute the same lemon-
yellow color to the sample of soy-bean oil as to the three samples
•of linseed oil. In our work we have always found that linseed
■oil gives a distinctly browner shade of yellow than does the soy-
bean oil. However, mixtures of the two oils, as noted in our
paper, could not be differentiated by the color.
Charles A. Newhall
11303 21st Ave . X. E
Seattle, Washington
April 4, 1921
New Chemical Laboratories
The trustees of Cornell University have approved the plans
for the new chemistry building, the funds for which were given
to Cornell nearly two years ago by an anonymous donor, and
bids for its construction have been advertised. The building
will be four stories high, 300 ft. long and 200 ft. wide, and
will cost $1,500,000. The large laboratory will accommodate 780
students. Some of the features of the new laboratory building
will be heating and ventilating systems which will obviate nox-
ious gases, honeycombing, hot, cold, and distilled water mains
with outlets in each room, and mains carrying compressed air,
steam, and gas to the various rooms. The main lecture room
will be fitted with a moving picture projector and theater to
illustrate technical lectures on chemical subjects.
The legislature of West Virginia has just approved the ap-
propriation of $400,000 for a new chemistry building at West
Virginia University.
The Massachusetts Agricultural College at Amherst is having
plans prepared for the erection of a chemical laboratory which,
when completed, will cost about $125,000.
Exchange Professors in Engineering and
Applied Science between French and
American Universities
The plan for an annual exchange of professors of engineering
and applied science between French and American universities
is being put into operation with the coming academic year.
This plan, which corresponds to the exchange professorships
established in academic subjects some years ago, was suggested
by the late Dr. Richard C. Maclaurin of Massachusetts Institute
of Technology in 1919, and was elaborated by representatives
of the seven institutions entering into the undertaking.
The French have selected for their representative Professor
J. Cavalier, rector of the University of Toulouse, and a well-
known authority on metallurgical chemistry. Professor Cava-
lier will come to America this fall, and will divide his time
during the ensuing academic year among the cooperating in-
stitutions, namely, Columbia, Cornell, Harvard, Johns Hopkins,
Massachusetts Institute of Technology, Pennsylvania, and Yale.
The American Universities have selected as their representative
for the same first year Dr. A. E. Kennelly, professor of electrical
engineering at Harvard University and Massachusetts Institute
of Technology.
TheDetection of Phenols in Water — Correction
The date of receipt of this paper [This Journal, 13 (1921),
422] should read January 24, 1921.
Supreme Court Decision on Mixed Acids
The United States Supreme Court has rendered an opinion
in the customs controversy which involved the dutiable classi-
fication of nitric and sulfuric acids, mixed, imported from Canada
by the Aetna Explosives Company. The decision of the United
States Court of Customs Appeals is upheld, giving the mixed
acids free entry under paragraph 387 of the tariff law\ The
decision was as follows: "Nitric acid was imported in tank cars,
with a sufficient addition of sulfuric acid to prevent it from
corroding the tanks, in accordance with the regulations of the
Interstate Commerce Commission. It was shown that it was
commercially impracticable at that time to ship nitric acid in
any other way; that the mixture had no commercial use; that
no commercial advantage was gained by the importation of
either acid in this manner; that there was no union of the two
acids; and that, before being used by the importer in manu-
facturing explosives, it was necessary to add more sulfuric acid.
This is not a 'chemical mixture' within the meaning of that term
in paragraph 5. tariff act of 1913. What was imported was
nitric acid, admissible free of duty under paragraph 387, tariff
act of 1913. The sulfuric acid (also admissible free of duty under
paragraph 387 i should be treated as a part of the packing of
the goods for shipment."
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
WASHINGTON LETTER
By Watson Davis, 1418 Rhode Island Ave., Washington, D. C.
THE EMERGENCY TARIFF BILL
Action taken by both the House and Senate during the past
week has practically assured the inclusion in the emergency
tariff bill of the "dye and chemical control act, 1921" which
extends for six months [changed later to three months by the
Conference Committee] the control by license of dye and chemical
imports now exercised by the War Trade Board Section of the
Department of State. This legislation will prevent any influx
of foreign chemicals and dyes such as would have occurred if the
proposed Knox peace resolution, which would have ended the
power of the War Trade Section to require importation licenses,
had been passed before this extending control amendment.
The dye and chemical control amendment proposed by Senator
Knox was adopted in the Senate by a 62 to 25 vote, after Senator
Moses had made a fight against it. When it reached the House,
there was an effort on the part of Democrats, led by Representa-
tive Garrett, of Tennessee, to send the bill back to the Ways
and Means Committee. This failed, however, and after Repre-
sentatives Longworth of Ohio and Kelly of Pennsylvania had
urged the amendment, the tariff bill was sent to conference by a
vote of 132 to 98. It is expected that the bill will get to the
President in essentially the same form as it is now, so far as dyes
and chemicals are concerned.
A feature of the new legislation is that it does not absolutely
prohibit the importation of dyes and chemicals under all cir-
cumstances, but that it does allow the entry of such articles as
cannot be obtained in sufficient quantity on reasonable terms
as to quality, price, or delivery in the United States and when such
articles are required for consumption within six months after
importation. The act applies to sodium nitrite, dyes or dye-
stuffs, including crudes and intermediates, products derived from
coal tar (including crudes and intermediates, finished and partly
finished products, and mixtures and compounds of such coal-tar
products) synthetic organic drugs and synthetic organic chemicals.
The War Trade Section is transferred from the State to the
Treasury Department.
While the subcommittee on chemicals of the Ways and Means
Committee has been considering the schedules that will go into
the regular tariff bill to be reported probably within the next
two or three weeks, no information is being given out as to what
the rates will be. When the bill is once reported there will be
ample opportunity for those interested to have their say, par-
ticularly on the Senate side.
THE ARMY APPROPRIATION BILL
The army appropriation bill is now being considered by the
Senate Committee on Military Affairs, and has not yet been
reported out. In the House the appropriations for the Chemical
Warfare Service were placed at only $1,350,000, a cut of ten per
cent from the figures in the bill which was passed last session and
which did not receive President Wilson's signature. Plans had
been made to operate on $1,500,000 during the coming year, and
work of the Chemical Warfare Service will be hampered if the
Senate allows the cut to remain.
The appointment of General Pershing to be Chief of Staff of the
Army has been received with favor by those interested in chemical
warfare, and it is believed that, with the interest that the new
administration is showing in gas warfare research and develop-
ment, there are better days ahead for this branch of the service.
FIXED NITROGEN
The Secretary of War has determined that the government
nitrate plants both at Sheffield, Ala., and at Muscle Shoals shall
be placed in the most economical stand-by condition, pending the
development of the fixation of atmospheric nitrogen by private
industry to such a point that the supply will meet governmental
requirements. Legislation providing for the leasing of the
government plants has been introduced in Congress, but early
action or consideration is not probable.
Researches on the fixation and utilization of nitrogen that
.have been carried out at the Fixed Nitrogen Research Laboratory
at American Lmiversity will be completed, and the work on the
problems already begun will be continued, at least until basic
work is fully developed, according to a recent decision of Secre-
tary Weeks. It is understood that shortly there will be released
for publication many data which have been obtained during the
War Department's researches and which have up to now been
held confidential.
THE PATENT OFFICE
Salary increases for the Patent Office are provided in H. K 210,
which has not yet received consideration. Commissioner
Robertson and those who are interested in relieving the conditions
in the Patent Office had hoped that favorable action could be
obtained by the end of the present fiscal year, but this seems
improbable now. As the portion of last session's bill that pro-
vided for the administration of government-developed patents
by the Federal Trade Commission has not been included in the
new bill, which deals with financial relief alone, it is believed
the progress of the bill this session will be easier.
DEPARTMENT OF COMMERCE CONFERENCES
During the past week steps have been taken toward standard-
ization and simplification of the chemical industry, particularly
in regard to heavy chemicals. Secretary of Commerce Hoover
has asked Dr. S. W. Stratton, director of the Bureau of Standards,
to call a conference of representatives of the various industries
and chemical associations to consider in what way the Govern-
ment, and particularly his department, can aid in the standard-
ization of chemicals and apparatus. The meeting is being ar-
ranged. The chemical manufacturers have also been asked to
attend conferences that will consider how the statistical gather-
ing work of the Department of Commerce can be made more
helpful. These meetings are the outgrowth of Secretary Hoover's
policy of forming and getting the advice of committees of leaders
in the industries.
PLANS FOR DEPARTMENT OF COMMERCE IMPROVEMENT
Secretary Hoover has taken definite steps to make the De-
partment of Commerce a more vital factor in domestic and
foreign trade, and he has asked Congress for supplemental appro-
priations of over $618,000. Twelve new divisions of the Bureau
nf Foreign and Domestic Commerce would be established with
$250,000 of the appropriation. A separate division for each
group of industries, including the chemical and dyestufis industry,
would be created, and would utilize the large amount of foreign
trade information and the market investigations of the Bureau
to the advantage of the industries. Another $250,000 would be
given the Bureau of Standards. Industrial wastes and the
development of commercial utilization of by-products would be
investigated with $100,000 of this sum. A like amount would be
used for the extension of the Bureau's work in establishing manu-
facturing standards of machinery and equipment and eliminating
unnecessary forms and qualities. Standardization of building
codes, housing construction, and building materials would be
accomplished with the remaining $50,000. The remainder of the
appropriation would be used for salary increases in the
Department.
THE METRIC SYSTEM
Opponents and proponents of the metric system of weights
and measures for general use will have a chance to be heard
before the House Committee on Weights and Measures, as Repre-
sentative Vestal has announced that he sees no reason why the
changing from the present system of weights and measures
should not be considered now. The fourteenth annual meeting
of the National Conference on Weights and Measures, which will
be held at the Bureau of Standards from May 23 to 26, will dis-
cuss this question at one of its sessions. Delegates from many
states and representatives of scale manufacturers will attend the
conference, which will also discuss mine and coal scales, bread
weight legislation, liquid measuring devices, and other weights
and measures questions.
GOVERNMENT SALARIES
Reclassification of government salaries is holding the attention
of the joint Congressional Committee on Reclassification at hear-
ings this week. Nearly half a dozen bills for reclassification
have been introduced into Congress, and it is the hope of govern-
ment employees, especially the scientific workers, that some
favorable legislation, equalizing government salaries will be
passed promptly.
The joint Congressional Committee on Government Reorgani-
zation has been increased by the addition to its membership of
W. F. Brown of Toledo, as President Harding's personal repre-
sentative.
576
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
Both a Public Welfare and a Public Works Department were
discussed at meetings of the Senate Committee on Education
and Labor held during the past week.
One feature of the new Administration is the fact that there
have been practically no changes in the heads of scientific or
technical departments.
During the past month the following heads of technical corps
in the War Department have been appointed and confirmed:
Brig. Gen. Amos A. Fries, chief of Chemical Warfare; Brig. Gen.
Harry Taylor, assistant chief of Engineers; Maj. Gen. G. O.
Squier, chief Signal Officer; Brig. Gen. W. S. Peirce, assistant
chief of Ordnance; Maj. Gen. Charles T. Menoher, chief of Air
Service; Brig. Gen. William Mitchell, assistant chief of Air
Service.
In order to undertake a study of structural clay products and
other nonmetallic building materials, the Bureau of Mines has
asked Congress for an additional appropriation of $47,000. It
is proposed to study brick and tile manufacture, as well as the
cement, slate, and feldspar industries.
May, 16, 1921
LONDON LETTER
By Stephen Miaix, 28, Belsize Grove, Hampstead, N. W. 3, England
We are now experiencing another coal strike, and tomorrow we
are to have a strike of railway men, transport workers, elec-
tricians, and others. These events have so far excited little in-
terest in the minds of many of us. We have had so many
threatened strikes which did not take place and so many others
that did take place that we are becoming hardened to them.
Although we vaguely recognize the danger of them and acutely
feel the monetary loss involved, we are more annoyed and dis-
appointed than excited. The air raids we had in London during
the war had somewhat similar psychological effects; the first ones
greatly excited and alarmed us; after experiencing half a dozen
of them, many of us began to regard them merely as a nuisance
causing no doubt a few deaths of people who were not engaged in
warlike pursuits, destroying a few private houses, spoiling the
night's rest of great numbers of people, but not giving us the feel-
ing that they were occurrences of first-rate importance. Just as
we got blase with air raids, so we are now with strikes. They
disturb us hardly more than a new outbreak of war in the east
of Europe, or some other disagreeable event of common occurrence.
But whether caused by strikes, high prices, general poverty of the
world, or other conditions, we cannot dismiss from our minds the
lack of business, the increasing unemployment, the decreasing
wealth, if indeed it can still be called wealth. The chemical
factories which are at work so much as half the time are few, and
fortunate are those who can sell as fast as they are making.
THE REPARATIONS ACT
The Reparations Act, which compels the buyer to hand over
to the government half the purchase money for German goods,
has now been in operation a few weeks. Its immediate effect
was to destroy at once trade between this country and Germany.
There are faint indications that here and there the measure is
having the desired effect in causing Germany to pay us some-
thing of the money due to us. If the German need to export
is greater than our need to import, the measure may in time be
a success; we can only give it a pretty good trial and trust that
if it seems likely to be effective our allies will adopt a similar
plan. Meanwhile the experiment is being made on our vile
bodies.
THE KEY INDUSTRIES BILL
Entangled with this problem is the Key Industries Bill to
prevent the manufacture of fine chemicals and other industries,
vital to our well-being, from being crushed out of existence by
dumping from countries whose low rate of exchange gives them
so great an advantage in export. The bill is expected to pro-
vide for a tariff of 33 1/3 per cent, but so far has not yet been
printed, and the government is too busy with labor difficulties
to consider any other problem at the moment. The Federal
Council for Pure and Applied Chemistry is asking the govern-
ment to provide for the free importation of research chemicals
which are not manufactured in this country.
JOINT MEETINGS OF THE CHEMICAL SOCIETIES
If only the tax collectors would have a prolonged strike, how
many delightful prospects lie before us. The International
Union of Pure and Applied Chemistry* is holding its meeting in
Brussels at the end of June. The Societe de Chimie Industrielle
is holding its annual meeting in Paris in July and has been so
good as to invite some of their English colleagues to attend.
Sir William Pope and a few others of us look forward very much
to this visit. And then in August and September those of us
who are so fortunate as to have a bank manager of an easy-
going nature will strain his indulgence almost to the breaking
point to enable us to visit our kith and kin in Canada and the
United States. This year is going to be so serious a one for us
all in Europe that unless we get a little change of scenery and
mental atmosphere we shall not pull through. When, with
prices falling as they have been, we find firms like Brunner
Mond and Co., Lever Brothers, the Mond Nickel Co., and the
other dreadnaughts coming out for loans of a million or so
sterling, as fast as the market can supply them or even faster,
the plight of the small cruisers and gunboats may easily be real-
ized to be fairly pitiable. None of us who visit you next summer
will be able to put before you new developments, new industries,
or processes. Warehouses filled to the roof with products of
all kinds are the features of the day. It is as hard for a ton of
salt-cake to find a home to-day as it was a year ago for a new-
comer to London or Washington.
April 14, 1921
PARIS LETTER
By Charles Lormand, 4 Avenu
Despite the present state of uncertainty in France, occasioned
by Germany's bad grace, the industrial crisis seems to have
reached its limit, and signs indicative of the resumption of a
certain amount of trade activity are already visible. The
welcome given to President Viviani during his tour in the States
showed France that it could rely on American sympathy, and
we fully realize how important it is for us that our policy in
present discussions should have the approval of the American
government.
INDUSTRIAL CONDITIONS IN GERMANY
German industry has not suffered from the war; in fact,
the latter proved an incentive to very active improvements in her
industries, so much so that a great many German companies are
now distributing large dividends to their shareholders; to quote a
few examples: Hallische Maschinenfabrik of Halle, 35 per cent;
The Johann Faber A. G. Pencil Manufacturing Company, 25
per cent on a six months' operation, or, in other words, 50 per cent
on a full financial year ; Sektkellerei Kupferberg und Co. of Maienz,
24 per cent plus a 20 per cent bonus, i. e., 44 per cent altogether;
Phil. Penin Gummiwarenfabrik A.-G. of Leipzig, 20 per cent plus
a 20 per cent bonus, i. c, 40 per cent altogether.
: de 1'Observatoire. Paris. France
These figures are very significant and serve to show that
Germany's capacity to pay is by no means so feeble as she would
have us believe.
CONDITIONS IN FRANCE
As for ourselves, we have to rebuild our devastated regions.
Our mines in the "Nord" are not yet capable of working at full
capacity. Although our coal production has increased from 22,300
tons in 1919 to 25,200 tons in 1920, our import figures are still
very large. They are given as 22,000 tons for 1920, e. g., we
produce about half the quantity of coal needed for home con-
sumption.
When we are certain as to our political safety, we shall gradu-
ally regain our industrial equilibrium.
All French traders and manufacturers deplore the customs
measures which the government has had to take to protect French
industry. In his speech at the inaugural meeting of the Office
National du Commerce Exterieur (National Office for Foreign
Trade) the Minister of Trade, Mr. Dior, who is himself one of
the most important manufacturers of sulfuric acid and fertilizer,
expressed the point of view of the French government: "France,"
he said, "is not protectionist. The customs measures that it is
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
577
at present making are purely temporary and are meant to pro-
vide against labor troubles and such industrial crises as that
through which we have just passed." Unemployment is de-
creasing and the cutting of wages, which we have seen in the
United States, does not appear to have caused (at any rate,
so far) any very great difficulties.
DEVELOPMENTS IN NITROGEN FIXATION
In spite of the competition between the Haber and Claude
processes, which has not yet been settled (I will notify you
immediately when it has been), the other processes for the fix-
ation of nitrogen are in active development.
The government has just reassigned the Lannemezan gun-
powder factory and the hydroelectrical works at Borderes and
Loudenoille to the Societe des Produits Azotes (Nitrogen Prod-
ucts Company) for the manufacture of cyanamide. In two years
this company is going to produce an annual quantity of 20,000
tons of cyanamide. In six years it will produce 40,000 tons
annually. At the moment, French agriculture demands a con-
siderable quantity of cyanamide while awaiting supplies of
nitrogen compounds made by direct synthesis.
Mr. Claude has recently brought to light one of the new
important points in his process which, up to now, he had pur-
posely kept secret. It is the preparation of pure hydrogen. As
Mr. Claude hinted a year ago, and as I pointed out to you, he
thinks he can obtain hydrogen from a gas generator. By cooling,
he can easily eliminate water and heavy gases from carbonic acid.
There remains the problem of separating hydrogen from carbon
monoxide. Mr. Claude has luckily solved it by making use of
the solubility of carbon monoxide in ether under pressure. After
a certain time, he recovers the solvent which can, theoretically,
be used indefinitely. The hydrogen thus separated does not
contain more than two parts per thousand of carbon monoxide
and can be used for the synthesis of ammonia.
LIQUID OXYGEN AS AN EXPLOSIVE
Before leaving the subject of low temperatures, I must touch
upon the experiments now being carried on in the use of liquid
oxygen as an explosive.
We have followed German efforts in this direction, and liquid
air is now in everyday use in our Lorraine iron mines. We are
also cognizant of the experiments conducted at the Pittsburgh
Station of the Bureau of Mines and wish to make general the use
of liquid air in stone, plaster, and slate quarries.
The reason for the success of this explosive lies in the safety
with which it can be used and especially in the fact that with it
the large explosives stores, which in France are not only subject
to very high taxation but also to extremely strict warehousing
regulations, very difficult in their application, are no longer
necessary. Since with liquid air the chief difficulty is its trans-
portation, it is desirable to have small-sized, mobile machines,
which can manufacture liquid oxygen actually in the mine or
quarry itself. At the present time, as far as I know, we have only
German machines in France. It is possible that machines of the
Geffries Nerton type could be used to advantage.
METALLIZATION WITH THE SCHOOP PISTOL
The problem of metallization appears to have been perfected
completely in the use of the Schoop pistol. The uses to which
this apparatus can be put are numerous. With it pylons 20
meters high have been zincked, and coppering has also been
satisfactorily done.
The principle of the apparatus, which consists, for all practi-
cal purposes, in pulverizing a thin wire thread of the metal,
brought to a state of white heat, is already well known. This
principle has been applied with very satisfactory results to
enameling. Here the metal wire is replaced by glass or enamel
rods. This process will certainly prove extremely useful in the
manufacture of apparatus for industrial chemistry.
DRYING OF FOOD PRODUCTS
Mr. Sartory, a professor at the Strasbourg University, is
building a commercial apparatus for drying food products,
which is based on the following principle : Air is dried by cooling
( — 8°) so as to lower its moisture content. In this manner it
can be projected on to the product to be dried at a different
temperature. The same air can be used indefinitely.
Such an apparatus would consume 9000 frigori hour and permit
of the desiccation of food products, at a very low temperature
(about +5°), thus greatly simplifying the manufacture of all
kinds of preserves.
May 6, 1921
INDUSTRIAL NOTES
Announcement has been made of a new plan of membership
in the National Canners' Association to secure better coopera-
tion of trade activities. One of the main features of the plan
is the enlargement of the scientific work now being done at
Stanford University, the University of California, and Harvard
Medical School, and the establishment of similar research
work at two other universities, one in the Northwest and one
in the South. An organization is to be created to cooperate
with boards of health and physicians, giving them the fullest
information as to the fundamental principles of canning and
sterilization methods in use.
Dr. Eugenio Donegani of Italy, Professor Georges Flusin,
Dr. Pierre Selaudoux, and Dr. Hippolyte Copaux of France
are visiting this country for the purpose of obtaining information
concerning recent developments in the design and construction
of equipment for the manufacture of sulfuric acid and calcium
superphosphate, having their headquarters in New York City.
The $4,000,000 elevator of the Armour Grain Co., in South
Chicago, 111., the world's largest reinforced concrete grain
elevator, was wrecked and six workmen killed by an explosion
of grain dust which occurred recently. The walls of the building
were torn open and the entire structure twisted and cracked
by the explosion. The cause of the ignition of the dust has not
been determined. The present agricultural appropriation act
contains an item of $25,000 for resumption of dust explosion
investigation work, which will be available July 1, 1921.
The British Chemical Plant Manufacturers' Association has
just been formed to cooperate with the Association of British
Chemical Manufacturers in endeavoring to improve the effi-
ciency of British chemical plants and to promote the manufac-
ture of chemicals made in England. The membership already
includes 22 firms.
The chemical division of the Texas Experiment Station will
again conduct cooperative fertilizer experiments in different
parts of the state, in order to enable the farmer to decide what
fertilizer is best suited to his own conditions by actual tests
in the field. The farmers agree to follow directions, pay the
freight on the fertilizer, and report results. Fifty experiments
will be made, each covering one acre, for crops such as peanuts,
sweet potatoes, and Irish potatoes.
The value of dyes and tanning materials imported by Canada
during January 1921 was $316,579, of which $51,473 was from
Britain, $158,299 from the United States, and $106,807 from
other countries, as compared with total imports of $637,960
during January 1920, of which $73,092 was from Britain, $527,855
from the United States, and $37,013 from other countries.
Imports of aniline and coal-tar dyes included above amounted
to 63.314 lbs., valued at $81,246, as compared with 285,970
lbs. valued at $225,585 in January 1920. Imports of fertilizers,
nearly all from the United States, were valued at $136,505,
as compared with $258,302 in January 1920. Drugs, and
medicinal and pharmaceutical preparations valued at $199,206
were imported in January 1921, of which $83,418 came from
Britain, $90,69S from the United States, and $25,090 from other
countries, as compared with total imports during January 1920
valued at $362,288, of which $136,986 came from Britain,
$192,139 from the United States, and $33,163 from other coun-
tries. Imports of perfumery, cosmetics, and .toilet preparations
were valued at $54,121 as against $76,970 in January 1920.
It is expected that the British beet-sugar factory of Home-
Grown Sugar, Ltd., in which the Ministry of Agriculture holds
half the capital, will be ready for operation by next fall. Much
of the plant ordered from France has arrived, and supplies of
sugar beet for the present year have been contracted for. The
tonnage for the first year is to be limited to 20,000 in order not
to overload the factory until the staff has been accurately
trained by the French specialists, although the capacity of the
factory is 600 tons per day.
At the meeting of the American Paper and Pulp Association
in New York City it was announced that owners of paper mills
representing an investment of $SOO,000,000 are to undertake
the training of their mill employees upon a larger scale than
ever before attempted by any American industry. The work
of preparing textbooks for the technical training of the mill
workers has been going on for three years and has already cost
$30,000. A detailed survey of the industry to determine the
578
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. G
lines of promotion to be followed has been made by the assistant
director for industrial education of the Federal Board for Voca-
tional Training, and was presented at the recent meeting.
The various trade and technical chemical organizations of the
country are being brought into cooperation with the Government
in securing statistics necessary in the consideration of tariff
schedules. It is desired to continue and elaborate the "Summary
of Tariff Information" issued last year. It is planned that each
organization shall appoint a member to whom all suggestions
for amplifying, deleting, or revising the data in the "Summary"
will be sent by the individual members, and that periodically
the information thus obtained will be gathered together, revised,
and forwarded to the proper government officials with appro-
priate recommendations. Communications have been sent to
the American Institute of Chemical Engineers, the Manufac-
turing Chemists' Association of the United States, the American
Chemical Society, and the American Electrochemical Society.
Dr. Charles A. Doremus has been appointed as the representa-
tive of the American Electrochemical Society. The other
societies have not as yet taken definite action in the matter.
Fire started by sparks from a passing railroad engine par-
tially destroyed the plant of the American Potash Company
at Antioch, Neb., causing damages estimated at between
$500,000 and $700,000. '
At the recent meeting of British Dyestuffs, Ltd., the chairman
outlined plans for research. During the first two years of the
corporation's existence £289,366 were spent, this sum including
the large capital expenditure necessary to lay the foundations
of a permanent research organization, and a further fund of
£100,000 is available for research.
The Thatcher Process Company of Syracuse, N. Y., began
operation May 7, 1921, in the production of anthraquinone.
At present 1000 lbs. per day are being produced, and the plant
runs continuously seven days a week. The Thatcher process
is an electrochemical one, depending upon the use of a special
type of cell. Heretofore anthraquinone has been manufactured
from anthracene by dissolving it in acetic acid and oxidizing
the mixture with bichromate, a process which is too expensive
to encourage manufacturers of vat dyes to continue research on
a large scale. It is believed that the production of 1000 lbs. per
day will assure an ample supply of anthraquinone for the country
for the next few months, as the present consumption does not
equal that amount. It is estimated that there is a market in
this country for 4,000,000 lbs. of vat dyes annually, which
would require nearly 3,000,000 lbs. of anthraquinone for their
manufacture, and with the development of the manufacture
of vat dyes the demand for anthraquinone will increase.
During the week of May 16 the National Research Council
had on display in the Caucus Room of the House Office Building,
Washington, D. C, its exhibit illustrating the relationship be-
tween the chemical industry and the national defense. By means
of models it was shown how the crude materials are carried
through the various processes for the manufacture of products
necessary in peace and in war. There was also a display of
American-made dyes, flavoring extracts, coloring extracts, per-
fumes and coal-tar products. The exhibit has been shown since
February in the building of the National Research Council,
but this is the first time that such an exhibit has been seen in the
halls of Congress.
An important chemical industry is being established at Yonda,
Saskatchewan, where there are large beds of sodium sulfate.
The Salts and Potash Co. of Kitchener, Ontario, has a refinery
for the treatment of sodium sulfate approaching completion.
Brunner, Mond & Co., Ltd., of London, England, has just
raised £2,500,000 additional capital in the sale of 7.5 per cent
cumulative preference shares, in order to carry' out extensive
developments in the manufacture of synthetic ammonia, etc.
The company is closely allied with the Solvay Process Company
of Syracuse and with Solvay & Co. of Brussels, and has branches
in Canada, China, and Japan. It has secured all the common
stock of Synthetic Ammonia and Nitrates, Ltd., formed for the
production of ammonia products and nitric acid from atmos-
pheric nitrogen, and has obtained complete control of the Castner-
Kellner Alkali Company and the Electro Bleach & By-Products
Co. , both of which manufacture caustic soda, chlorine, and
bleaching powder. Large interests have also been acquired in
colliery companies and freeholds in the mineral rights of brine-
bearing lands in Cheshire for brine in the raw material of alkali
as manufactured by the Solvay process. The company has
obtained the license of the British government under the Peace
Treaty to work the English patents of the Badische Anilin und
Soda Fabrik, as well as the British government's inventions
worked out by the munitions inventions department during the
war. A plant is now being erected at Northwich which will
represent the highest achievement of chemical and engineering
knowledge as applied to the manufacture of soda ash, which is the
company's chief product. Brunner, Mond & Co., the Castner-
Kellner Co., and the United Alkali Company are the three most
important firms engaged in the manufacture of heavy chemicals in
Britain, the United Alkali Company being the only concern of
any importance manufacturing soda ash not associated with
Brunner, Mond & Co.
The Chemical Foundation, Inc., has opened an office in the
Munsey Building, Washington, D. C. The business there will
be in charge of William F. Keohan, formerly assistant to F. P.
Garvan in the office of the Alien Property Custodian.
A decision in the suit brought by the Bayer Co., Inc., of New
York, against the United Drug Co., of Boston, concerning the
general use of the name "aspirin" has been handed down by
Judge Learned Hand of the U. S. District Court in New York.
The court ruled that aspirin is a valid trade-mark when applied
to pharmacy and medicine, but not when used in the lay trade;
and that an injunction might be possible against the defendant
offering acetylsalicylic acid to the trade or to physicians under
the name aspirin, but no relief was given against selling the prod-
uct to the public under that name. No damages were allowed
and the charge of unfair trading was not sustained to any ex-
tent. A mandatory decree was not given, but the court inti-
mated that it would be along the lines mentioned. It was also
intimated that use of the word "genuine" in advertisements be-
fore the word "aspirin" by the defendant might be prohibited.
An appeal is expected to be taken.
PERSONAL NOTES
Dr. Henry P. Talbot has been appointed Acting Dean of Massa-
chusetts Institute of Technology to succeed Dr. A. E. Burton,
who recently resigned. Dr. Talbot is chairman of the faculty,
and will also retain the directorship of the department of chemis-
try.
Mr. Hubb Bell has left the Pittsburgh Testing Laboratory,
New York City, and is now with the United States Testing
Co., Inc., of the same city.
Mr. C. F. Bousquet, formerly chief chemist of the Westend
Chemical Co., Westend, Gal., has accepted a position in the
research department of the Standard Oil Co., Richmond, Cal.
Mr. Hugo Schlatter of Wilmington, Del., who for several
years has been manager of the Chemical Products Division of the
Hercules Powder Co., has resigned his position with the Her-
cules organization and is planning a trip to Europe in June.
While abroad, Mr. Schlatter will visit a number of manufac-
turing plants and will make special investigations and reports.
Dr. Paul H. M.-P. Brinton, professor in the chemical de-
partment of the University of Arizona, has been appointed
professor of analytical chemistry in the School of Chemistry
of the University of Minnesota, St. Paul, Minn.
Mr. Roland Woodward, Jr., has left the dye works, E. I. du
Pont de Nemours & Co., and has been appointed assistant lique-
faction engineer at U. S. Helium Plant No. 3, Petrolia, Texas.
Mr. Harry R. Tisdale has resigned his position with Brainerd
Armstrong Co., silk manufacturers, of New London, Conn.,
as superintendent and chemist of the Dye House, to accept a
similar position with the New England Spun Silk Corp., formerly
William Ryle and Co., at their Newton Mills, Newton Upper
Falls, Mass.
Mr. B. H. Sherman left Edgewood Arsenal, where he was
working on poisonous gases, to assume the position of chemist
for the Northern Paper Mills Co., Green Bay, Wis.
Mr. Chester M. Clark, formerly head of the Corporation De-
partment of Stone & Webster, Inc., has been elected treasurer
of Arthur D. Little, Inc., Cambridge, Mass.
Mr. Merton R. Sumner has been appointed chief engineer of
Arthur D. Little, Inc., Cambridge, Mass. Mr. Sumner was
formerly chief engineer of the Fuller Industrial Engineering Corp.,
a subsidiary of the George A. Fuller Company.
Dr. E. A. Bilhuber, who was manager of the color department
of C. M. Childs & Co., has become assistant sales manager of
the Imperial Color Works, Glens Falls, N. Y.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
579
Mr. A. R. Willis, who was engaged primarily in the com-
pilation of the census of dyes and other coal-tar chemicals since
he entered the employ of the Tariff Commission in January
1918, accidently met his death while he and his wife were the
guests of Mr. Warren N. Watson at his cottage on the Potomac
River, April 24. It is not known just how the accident happened,
but it is known that Mr. Willis alone in a canoe started to paddle
across the river to get Mr. Watson, while Mrs. Willis was pre-
paring lunch on the Maryland shore. Neither Mr. Watson nor
Mrs. Willis saw him fall from the canoe, and Mr. Willis' body
had gone down before anyone could get to him. The body was
recovered later and taken to Springfield, Ohio, for interment.
Mr. William B. Cogswell, founder of the Solvay process and
for years a commanding figure in mining and engineering circles,
died recently at his home in New York City. Mr. Cogswell was
born in Oswego, N. Y., September 22, 1834. He was educated at
Hamilton Academy and also at a private school. He finished his
education in Rensselaer Polytechnic Institute at Troy. Mr.
Cogswell has been a superintendent of machinery for a railroad,
superintendent of the Broadway Foundry of St. Louis, and also
organized the firm of Sweet Bros. & Company. During the Civil
War he was rated as a mechanical engineer in the army, and later
was retained by the Franklin Iron Works to superintend the
construction and operation of blast furnaces in Oneida County.
From 1874-79 he was in the mining business, and three years
later became engaged in the process of manufacturing ammonia
soda, in a firm that, through his efforts, became famous under
the name of Solvay Process Company, of which he was manag-
ing director.
Mr. C. R. DeLong has been appointed chief of the chemical
division of the U. S. Tariff Commission, succeeding Dr. Grinnell
Jones, who has returned to Harvard University but retains
connection with the Commission in an advisory capacity.
Dr. Paul E. Klopsteg, who has been connected with the sales
and advertising department of Leeds and Northrup for several
years, has recently accepted a position with the Central Scien-
tific Company of Chicago as manager of development and manu-
facturing.
Mr. Ossian G. Lye has resigned his position as technical
manager of Malt Products Company of Canada, Ltd., Guelph,
Ontario, to accept an appointment as patent examiner at Ottawa,
Ontario, Canada.
Dr. Otto Kress, who for the past four years was in charge of
the pulp and paper work of the Forest Products Laboratory of the
U. S. Forest Service, has resigned to join the staff of the Con-
solidated Water Power and Paper Co., of Wisconsin Rapids,
Wis., where he will be engaged with technical problems in con-
nection with the control and development of pulp and paper
products.
Mr. Charles H. Chandler, formerly research chemist for the
United Fruit Company at their sugar estates, Preston, Cuba, is
.at present connected as chief chemist and assistant superin-
tendent with Thomas J. Dee &Co., Chicago, 111.
Mr. C. L. Bachelder, for the last two and a half years assistant
chemist in the Pulp and Paper Section of the U.S. Forest Products
Laboratory at Madison, Wis., has severed his connections with
the government laboratory and is now with the Consolidated
Water Power and Paper Co., under Dr. Otto Kress, also formerly
of the Forest Products Laboratory. Mr. Bachelder is at the
present time in charge of a liquid chlorine bleaching plant which
has just been added to the equipment of the Stevens Point Mill.
Mr. J. Benson Darlington, formerly chief chemist with E. I.
du Pone de Nemours & Company at Carney's Point, N. J., has
resigned his position with that firm to go into other work.
Mr. D. M. Goetschius, who was engaged in March by B. F.
Drakenfeld & Company, Inc., to take charge of their plant at
Washington, Pa., has arranged to continue for the present
his research and experimental work on radium extraction for
the Standard Chemical Company of Canonsburg, Pa.
Dr. Raymond F. Bacon, director of the Mellon Institute of
Industrial Research of the University of Pittsburgh, has re-
turned from an investigation of European nitrogen-fixation
processes.
Mr. J. T. Orr, formerly lamp research engineer at the Wee-
hawken Lamp Works of the General Electric Co., is now con-
nected with the Air Reduction Co., at Elizabethport, N. J., as
research chemist.
Dr. E. E. Slosson, formerly managing editor of The In-
dependent and associate in the Columbia School of Journalism,
has been appointed director of the Science News Service, at-
tached to the Scripps Foundation, Washington, D. C.
Mr. Henry W. Easterwood recently accepted a position in the
Bureau of Soils at Washington. D. C. He was formerly with
E. I. du Pont de Nemours & Co., at their Jackson Laboratory,
Pennsgrove, N. J.
Mr. Carl D. Ulmer, a former sergeant in the C. W. S. Labora-
tory at Puteaux Seine, A. E. F., has left the University of
Minnesota to resume his pre-war position as chemist for the
Minnesota By-Product Coke Co., St. Paul, Minn.
Mr. Howard C. Arnold, formerly chief chemist and plant
manager of B. F. Drakenfeld & Co., New York City, has re-
cently joined the staff of Arthur D. Little, Inc., of Cambridge,
Mass.
Mr. E. B. Fulks recently gave up his position as vice president
of the American Tar Products Co., Chicago, 111., and has
organized the Arkansas Preservative Co., St. Louis, Mo., of
which firm he is president.
Mr. Glen S. Houghland, formerly a sales engineer for the
Walter H. Lummus Co., Boston, Mass., manufacturers of chem-
ical plant equipment, is now connected with the Redpath Lab-
oratory of E. I. du Pont de Nemours & Co., Parlin, N. J., in
connection with the manufacture of motion picture films.
Mr. Vance P. Edwardes who for the past three and a half
years has been with the Forest Products Laboratory, U. S.
Department of Agriculture, specializing on sulfite pulping, and
various research problems, now holds a position in the sulfite
department of the Interlake Pulp & Paper Co., Appleton, Wis.
Mr. G. W. York who was chief chemist for the Arkansas Zinc
and Smelting Corp., Van Buren, Ark., is now chemist with the
Agricultural Experiment Station of the University of Missouri,
Columbia, Mo.
Mr. Harry P. Taber, who during the war served in the Ord-
nance office and who later, after the armistice, was detailed to
the Bureau of Standards for research work in relation to pro-
tective coatings for ammunition and artillery material, which
work he will continue until completed, has been made laboratory
director of the new plant of the American Chemical Manufac-
turing Corp., of Cranford, N. J.
Mr. Charles R. Gerth has resigned as technical chemist for
the Union Sugar Company, Betteravia, Cal., and is at present
connected with the research department of the Chemical Lab-
oratories of the Standard Oil Company of California, Richmond,
Cal.
Mr. Thomas J. Kavanagh, who was formerly associated with
the American Sugar Refining Co., is now general manager of
the McCahan Sugar Refining & Molasses Co., of Philadelphia,
Pa.
Mr. H. H. Barker who until recently was chief chemist and
plant manager of the Ore Products Corp., of Denver, Col., has
assumed tie position of chief chemist of Corning & Co., Albanv,
N. Y.
Dr. Arthur S. Klein, paper technologist and chief of the
technical department of Billeruds Aktiebolag, Seffle, Sweden,
one of the largest producers of cellulose in Europe, was a recent
guest at the Chemists' Club. Dr. Klein was at one time editor
of Papierfabrika.nl and is one of the founders of the Association
of Cellulose and Paper Chemists. He is an active member of
the United States Technical Association of the Pulp and Paper
Industry.
Mr. Ernest H. Chapin, formerly in the chemical division of
Procter & Gamble Co., has joined the forces of the Wheeler
Condenser and Engineering Co., of Carteret, N. J., as sales
engineer.
Mr. Jack H. Waggoner has resigned as assistant to Dr. A. H.
Gill in the oil and gas laboratory of the Massachusetts Institute
of Technology, Cambridge, Mass., to accept a position as chem-
ical engineer with the Standard Oil Company at their Sugar
Creek, Mo., refinery.
Dr. H. M. Stadt, analytic chemist, has severed his relations
with the Guasti-Bissirri Chemical Co., of Los Angeles, Cal.,
and has acquired the property of the Glendale Belladonna
Products Co., of Glendale, Cal., which firm will be continued
under the name of Glendale Chemical Manufacturing Co.
Mr. Reiman G. Erwin, formerly with the Roessler and Hass-
lacher Chemical Co., of St. Albans, W. Va., has accepted a posi-
tion as chemical engineer with the Celluloid Company, of Newark,
N.J.
Mr. M. P. Keister has resigned as assistant superintendent
of Burke Tannery, Kistler, Lesh & Co., Morganton, N. C,
and has accepted a position as junior chemist and tanner with
the Leather and Paper Laboratory, Bureau of Chemistry,
Washington, D. C.
580
THE JOURS AL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, Xo. 6
GOVERNMENT PUBLICATIONS
By Nellie A. Parkinson, Bureau of Chemistry, Washington, D. C.
NOTICE — Publications for which price is indicated can be
purchased from the Superintendent of Documents, Government
Printing Office, Washington, D. C. Other publications can
usually be supplied from the Bureau or Department from which
they originate. Commerce Reports are received by all large
libraries and may be consulted there, or single numbers can be
secured by application to the Bureau of Foreign and Domestic
Commerce, Department of Commerce, Washington. The regular
subscription rate for these Commerce Reports mailed daily is
$2.50 per year, payable in advance, to the Superintendent of
Documents.
PUBLIC HEALTH SERVICE
Botulism and Spoiled Canned Food. Public Health Re-
ports, 36, 751-2.
Hypochlorite Process of Oyster Purification. Report on
Experimental Purification of Polluted Oysters, on a Commer-
cial Scale, by Floating Them in Sea Water Treated with Hypo-
chlorite of Calcium. F. A. CarmEUA. Public Health Reports,
36, S76-83. The calcium hypochlorite practically sterilizes
and clears the sea water in which the oysters are placed. The
water, for a brief period following the addition of the hypo-
chlorite, is more or less irritating to the oyster, which repeatedly
and forcibly rejects the water. This removes mechanically
gross particles from within the outer chamber between the
shells, and for this reason the oysters when opened present a
nice, clean appearance.
Distribution of Spores of B. Botulinus in Nature. K. F.
Meyer and J. C. Geiger. Reprint 635 from Public Health
Reports. 4 pp. Paper, 5 cents.
Preliminary Study of Physiological Effects of High Tem-
peratures and High Humidities in Metal Mines. R. R. Savers
and D. Harrington. Reprint 639 from Public Health Reports.
16 pp. Paper, 5 cents.
Factors Governing Selection and Protection of Sources of
Water Supply (with List of References). J. K. Hoskins.
Supplement 39 to Public Health Reports. 20 pp. Paper,
5 cents. 1921.
GEOLOGIGAL SURVEY
Helium-Bearing Natural Gas. C. S. Rogers. Professional
Paper 121. 113 pp. Paper, 30 cents. 1921. This paper is
based on the results of the investigation of the helium resources
of the country, in order to locate the richest supplies of the gas
and to form estimates of the quantity available. The paper
describes the distribution of helium-bearing natural gas and
makes brief mention of the technologic problems involved in the
extraction and purification of the helium.
Surface Water Supply of the Pacific Slope of Southern Cali-
fornia. H. D. McGlashan. Prepared in cooperation with the
State of California. Water-Supply Paper 447. 557 pp. Paper,
65 cents. 1921.
Ground Water in the Meriden Area, Connecticut. G. A.
Waring. Prepared in cooperation with the Connecticut State
Geological and Natural History Survey. Water-Supply Paper
449. 83 pp.
Surface Water Supply of the United States 1917. Part XII.
Northern Pacific Slope Drainage Basins. (A) Pacific Basins
in Washington and Upper Columbia River Basin. N. C.
GrovER, G. L. Parker and W. A. Lamb. Prepared in coopera-
tion with the States of Washington, Montana, and Idaho.
Water-Supply Paper 462. 181 pp. 1921.
Ground Water in the Southington-Granby Area, Connecticut.
H. S. Palmer. Prepared in cooperation with the Connecticut
Geological and Natural History Survey. Water-Supply Paper
466. 219 pp. 1921.
Permian Salt Deposits of the South-Central United States.
N. H. Darton. Bulletin 715-M. Separate from Contri-
butions to Economic Geologv, 1920, Part I. 19 pp. Issued
April 28, 1921.
Preliminary Report on Petroleum in Alaska. G. L. Martin.
Bulletin 719. 83 pp. Paper, 50 cents. Indications of petro-
leum have been found in five districts in Alaska, four of which
are on the Pacific seaboard, whereas the fifth is on the Arctic
Coast. The petroleum of the Pacific Coast of Alaska is a high-
grade refining oil with a paraffin base. The petroleum found
near Smith Bay, or the Arctic Coast, appears to have an as-
phaltic base.
Zinc in 1918. C. E. Siebenthal. Separate from Mineral
Resources of the United States 1918. Part I. 48 pp. 1921.
The production of primary zinc from domestic ores in 1918 was
492,405 short tons, valued at SS9.61S.000, based on the average
selling price, as compared with 584,597 short tons, valued at
$119,258,000, based on the average selling price in 1917 — a
decrease of 92,192 tons, or nearly 16 per cent, in quantity, and of
$29,640,000, or about 25 per cent, in value.
Coke in 1918. C. E. Lesher and F. G. Tryon. Separate
from Mineral Resources of the United States, 1918, Part II.
89 pp. Published April 22, 1921. This report is confined
practically to setting forth the results of the 1918 canvass of
coke production. Tables are given in a form to preserve the
continuity of the records collected by the Survey since 1880.
Manganese and Manganiferous Ores in 1919. H. A C. Jenison.
Separate from Mineral Resources of the United States, 1919,
Part I. 56 pp. Published April 6, 1921. The great industrial
reaction that followed the world war was immediately trans-
mitted through the steel industry to the dependent manganese
industry, with disastrous results. The condition of the steel
industry, the expected renewal of importation of manganese,
and the fact that large stocks of manganese were being held by
the steel producers and brokers reacted so severely upon the
domestic manganese industry that it began to disintegrate rapidly.
In the summer of 1919 nearly all the war contracts expired, and
the collapse of the domestic industry was complete.
Quicksilver in 1919. F. L. RansomE. With a supplemen-
tary bibliography by I. P. Evans. Separate from Mineral Re-
sources of the United States, 1919, Part I. 32 pp. Published
April 5, 1921. The decline in mining activity and in the pro-
duction of quicksilver, already marked in 1918, was still more
plainly evident in 1919. The prices obtainable in 1919 were
decidedly lower than in 1918.
Gold, Silver, Copper, Lead, and Zinc in California and Oregon
in 1919. C. G. Yale. Separate from Mineral Resources of
the United States, 1919, Part I. 46 pp. Published April 20,
1921. In common with other metal-producing states of the
Union, California showed a material reduction in the aggregate
value of its metals in 1919, as compared with 1918, the reduction
amounting to $S,985,909. By far the larger part of this loss
was due to the falling off in the value of copper, which was
$7,733,395 less than in 1918.
The total metal output in Oregon in 1919 was valued at
$1,514,255, or $469,687 less than in 1918. The decrease in gold
was $292,620 and in copper $193,446.
Gold, Silver, Copper, and Lead in Alaska in 1919. A. H.
Brooks and G. C. Martin. Separate from Mineral Resources
of the United States, 1919, Part I. 7 pp. Published April
25, 1921. Gold and copper mining have always been the prin-
cipal mineral industries of Alaska, and in 1919 both were subject
to great depression throughout the world. Hence the value
of Alaska's mineral production decreased from about $2S,300,000
in 191S to about $19,600,000 in 1919, of which gold, silver,
copper, and lead amounted to $27,507,392 in 1918 and $1S,987, 190
in 1919.
Talc and Soapstone in 1919. J. S. Diller. Separate from
Mineral Resources of the United States, 1919, Part II. 4 pp.
Published April 14, 1921. The depression of the talc business
during the early months of 1919 consequent upon the end of the
war was followed by its recovery a few months later. In 1919
the total sales of domestic talc amounted to 168,339 short tons,
valued at $1,882,512, a decrease as compared with 1918 of
approximately 13 per cent in both quantity and value.
The total sales of soapstone in the United States in 1919
amounted to 16,504 short tons, valued at S530.163, as compared
with 15.330 short tons, valued at S576.059, in 1918, an increase of
nearly 8 per cent in quantity but a decrease of S per cent in value.
BUREAU OF MINES
Metal-Mine Accidents in the United States during the Cal-
endar Year 1919 (with Supplemental Labor and Accident Tables
for the Years 1911 to 1919, Inclusive). W. W. Adams. Tech-
nical Paper 286. 99 pp. Paper, 10 cents. 1921.
New Talc Grinding Capacity in the United States. R. B.
Ladoo. Reports of Investigations. Serial No. 2233. 3 pp.
Issued April 1921.
Ten Years of Mine Rescue and First-Aid Training. H. F.
Bain. Reports of Investigations. Serial No. 2234. 8 pp.
Issued April 1921.
June, 1921
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
581
Monthly Statement of Coal-Mine Fatalities in the United
States, February 1921. W. W. Adams. 8 pp. Paper, 5 cents.
Issued April 1921.
Monthly Statement of Coal-Mine Fatalities in the United
States, February 1921. W. W. Adams. 8 pp. Paper, 5 cents.
1921.
Report of Committee on Standardization of Petroleum Speci-
fications. Effective December 29, 1920. Bulletin No. 5. 71
pp. Paper, 10 cents. 1921. This bulletin gives a practically
complete list of petroleum products used by the United States
Government and its agencies, together with complete speci-
fications for each product and full descriptions of the methods of
testing employed in the government laboratories. In general,
the committee has adopted the methods recommended by the
American Society for Testing Materials.
Iceland Spar. Oliver Bowles. Reports of Investigations.
Serial No. 2238. 6 pp. Issued April 1921.
Emergency Fans for Fighting Metal-Mine Fires. B. O.
Pickard. Reports of Investigations. Serial No. 2240. 3 pp.
Issued April 1921.
Recent Articles on Petroleum and Allied Substances. E. H.
Burroughs. Reports of Investigations. Serial No, 2241.
30 pp. Issued April 1921.
Coal-Dust Hazards in Industrial Plants. L. D. Tracy.
Reports of Investigations. Serial No. 2242. 5 pp. Issued
April 1921.
Picric Acid as a Blasting Agent. C. E. Munroe and S. P.
Howell. Reports of Investigations. Serial No. 2243. 15 pp.
Issued April 1921.
BUREAU OF STANDARDS
A Study of Test Methods for the Purpose of Developing Stand-
ard Specifications for Paper Bags for Cement and Lime. P. L.
Houston. Technologic Paper 1S7. Paper, 5 cents. This
paper is published in order to aid the paper-bag manufacturers
to meet the requirements of the lime and cement manufacturers
in obtaining a suitable paper bag in which to ship their product.
It contains information relative to the methods of testing and
the apparatus employed in determining the quality of paper
bags for lime and cement. In determining the characteristics
of a good quality bag special consideration is given to the follow-
ing points: Good bursting strength; high tensile strength in
both directions; high endurance or resiliency; high folding
endurance; a fiber composition of not less than 50 per cent
manila and jute with the remainder as chemical wood; ash not
over 3 per cent; and rosin sizing at least 3.5 per cent.
Some Properties cf White Metal-Bearing Alloys at Elevated
Temperatures. J. R. Freeman, Jr., and R. W. Woodward.
Technologic Paper 188. Paper, 5 cents. This paper describes
apparatus for determining the yield point and ultimate strength
of these alloys in compression at temperatures up to 150° C.
A similar apparatus is also described for determining the Brinell
hardness at these elevated temperatures.
Method for Differentiating and Estimating Unbleached Sul-
fite and Sulfate Pulps in Paper. R. E. Lofton and M. E.
Merritt. Technologic Paper 189. Paper, 5 cents. 1921.
This paper discusses briefly the two possible bases on which to
develop methods of differentiating between unbleached sulfite
and sulfate pulps, viz.: (1) The different chemical natures of the
two pulps due to different cooking treatments; and (2) the
different amounts of ligneous matter that may be retained by the
two pulps. The paper also contains tables showing the possi-
bilities of making quantitative determinations of the percentages
of these fibers in various mixtures of the two pulps.
"Black Nickel" Plating Solutions. G. B. Hogaboom, T. F.
SlaTTERy and L. B. Ham. Technologic Paper 190. Paper,
5 cents.
It was found that a sulfocyanate solution having the follow-
ing composition proved satisfactory:
oz./gal. g./l.
Nickel ammonium sulfate 8 60
Zinc sulfate 1 7.5
Sodium sulfocyanate 2 15
It is desirable to keep in suspension an excess of zinc carbon-
ate, which maintains the neutrality and the zinc content of the
solution.
The War Work of the Bureau of Standards. Miscellaneous
Publication 46. Paper, 70 cents. 1921. The report consists
of short descriptions of the various investigations which were
carried out, each description being complete in itself and having
no reference to the organization of the Bureau or the scientific
divisions which carried out the work. A very large number of
subjects are treated, among which will be found the following:
Balloon gases, including the work which the Bureau of Standards
performed in connection with the recovery of helium from natural
gas; various chemical investigations, including analyses of
ferrous and nonferrous metals, the development of platinum sub-
stitutes, the routine testing of soap, oils, and paints, experi-
ments in connection with the prevention of corrosion, etc.
DEPARTMENT OF AGRICULTURE
Commercial Utilization of Waste Seed from the Tomato Pulp-
ing Industry. J. H. Shrader and Frank Rabak. Department
Bulletin 927. 29 pp. Issued April 16, 1921. Investigation
of the practicability of utilizing this waste shows that by the
application of proper methods the seeds may be separated from
the waste and made to yield oil and press cake or meal of con-
siderable commercial value, the former as a table or culinary oil
and the latter as stock feed.
The Sporogenes Test as an Index of the Contamination of
Milk. S. H. Ayers and P. W. ClEmmER. Department Bulle-
tin 940. 20 pp. Paper, 15 cents. Issued April 25, 1921. This
bulletin contains a report of the study of this question which is of
interest to chemists and bacteriologists.
COMMERCE REPORTS— APRIL 1921
Polish industries that are dependent on copper are at a total
standstill owing to the lack of this metal in Poland. (P. 27)
The development of dehydrating processes in foreign countries
is described. (Pp. 29-31)
The month of February marked the first actual net decline in
the total value of Canada's exports of pulp and paper in a period of
almost four years, during which time the trend has been con-
sistently upward. (Pp. 42-3)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Austria-Hungary during
the years 1913, 1916, and 1917. (Pp. 44-5)
Petroleum has been discovered in the Hinsun Mountain,
Northern Manchuria. (P. 52)
The invention in India of a new process for degumming ramie
fiber is reported. (P. 52)
The annual production of gypsum in Hupeh Province, China,
amounts to about 100,000 long tons and that of salt to about
20,000 tons. (Pp. 52-3)
The manufacture of paints and varnish in Argentina is reviewed
.(Pp. 65-70)
The mineral production of Quebec Province, Canada, in 1920
had a value of $28,223,141, or nearly ten times that of 1901.
(P. 77)
Statistics are given showing the imports of vegetable oils and
vegetable-oil material by Finland during the years 1917, 1918,
and 1919. (P. 78)
Statistics are given showing the average yearly price of anti-
mony metal, crude antimony, and antimony sulfide ore for 1913-
1919, and the world's production of antimony, expressed in long
tons, during the years 1913, 1918, and 1919. (P. 93)
The mineral production of Burma in 1919 was valued at
$12,889,718, a decrease of 5.4 per cent compared with the pre-
ceding year, owing chiefly to the diminished output of tungsten
ore. (P. 94)
The production of petroleum in the oil wells of upper Burma
continues to increase. (P. 94)
During January the shipments of petroleum from the Tampico
consular district reached a total of 18,602,498 bbls., which was
an increase of more than 10,600,000 bbls. over the exports for the
corresponding month of 1920, and 1,000,000 bbls. over the ship-
ments for December 1920. (P. 106)
The development of the Malavan oil-palm industry is de-
scribed. (P. 112)
The paint and varnish trade of Canada is reviewed. (Pp.
122-5)
The bauxite mines in the Guianas have suspended operations.
(P. 125)
The first of a series of papers known as "Technical Papers of
the Fuel Research Board," deals with experimental work carried
on in the Fuel Laboratory of the Imperial College of Science and
Technology at South Kensington, England, whereby a new lab-
oratory method of coal assay has been developed. The papers
describe the purpose of the investigation, the apparatus used,
the methods employed, and the results obtained. (Pp. 138-9)
Statistics are given showing the stocks of fertilizers on hand
in the United Kingdom on January 31, 1921. (P. 139)
582
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. &
Appropriations have been made for Finland's sulfuric acid
and superphosphate factories which, it is believed, will be finished
this year. (P. 148)
A deposit of fairly pure iron pyrites has recently been dis-
covered in Eastern Finland, which, it is thought, will be of con-
siderable economic importance for the production of sulfuric
acid and the preparation of sulfite for the cellulose industry.
-(Pp. 148-9)
The completion of a new paper mill and tar factory is reported
in Finland. (P. 149)
A list of mines and mining companies in British Malaysia,
including tin, wolfram, gold, and antimony mines, is available at
the Bureau of Foreign and Domestic Commerce. (P. 194)
It appears that Hull, besides being the leading center of the
seed-crushing and oil-extracting industry of the United King-
dom, is also the largest oil-crushing center of the world. Hull's
position as an oilseed center is shown by tables giving statistics
for various years. (Pp. 227-33)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Greece during the years
1916, 1917, and 1918. (P. 249)
The asbestos mining industry of Quebec is reviewed. (Pp.
250-2)
Jugoslavia produced 150,000 kilos of opium in 1920. (P. 260)
It is reported that there is under consideration the building of a
sulfuric acid plant by Bradford, England, in connection with the
city's sewage works. (P. 266)
Sicily has on hand large quantities of citrate of lime and sulfur,
and unless governmental action is soon taken to reduce the prices
on these products to a competitive figure the industries will face
a severe crisis. (Pp. 270-1)
It is reported that the Piedmont peppermint crop for 1921
will be approximately 20 per cent larger than the 1920 crop.
(P. 271)
Petroleum production in Argentina is reviewed. (Pp. 279-81)
The pulp-wood business in Quebec is practically at a stand-
still. (P. 295)
Indications of petroleum deposits have been discovered in the
Province of Almeria, Spain. (P. 306)
Statistics are given showing the production of iron ore in the
Province of Vizcaya, Spain. (P. 306)
A Spanish chemical company is reported to be seeking an
alliance with a German firm to engage in the manufacture of
products derived from resin and fish and olive oils. (P. 306)
Two new joint-stock oil companies have recently been formed
in Poland. (P. 309)
Statistics are given showing the value of oil-producing nuts
and fruits exported from Brazil during the past five years. (P. 343)
An account is given of a meeting held at the Institute of Pe-
troleum Technologists, London, England, where M. Paul de
Chambrier described a new method of working petroleum by
shafts and galleries instead of wells. (P. 350)
The British Empire, through the transfer of the Island of
Nauru and Ocean Island in the Pacific Ocean from Germany,
has acquired one of the richest supplies of phosphates in the
world. The results of a chemical analysis of the phosphate
are given. (Pp. 351-2)
A market for paints and varnishes is reported in Mexico. (Pp.
370-3)
Statistics are given showing the final estimate of India's 1920-1
peanut crop. (P. 388)
Attention is called to the importance of the oil resources of
Mesopotamia. (P. 389)
The pulp and paper industry of Ontario is reviewed. (Pp. 390- 1 )
Statistics are given showing the production and exportation
of Madagascar graphite from the beginning of the industry in
1907 to 1920, inclusive. (Pp. 398-9)
The production of camphor in Taiwan during the year ended
March 31, 1921, it is anticipated, will exceed that of the preceding
year by 275,000 lbs,, the total production being pla ced at 6,000,-
000 lbs. (P. 400)
The rubber industry of Brazil, at one time one of the most
important of Brazilian activities, has suffered a decline. (P. 408)
A new oil well drilled on the Argentine government reserva-
tion at Comodoro Rivadavia on February 18 produced 3,600
cubic meters of oil in 24 hrs. (P. 426)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Argentina during the
years 1917, 1918, and 1919. (P. 431)
A syndicate has been formed to develop the extensive beds
of lignite located in the Bovey Basin, near Newton Abbot, Devon^
England. This deposit of lignite is estimated to consist of mil-
lions of tons. (P. 436)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Brazil during the years
1917, 1918, and 1919. (P. 443)
The mineral-oil trade of Belgium is reviewed. (Pp. 452-3)
Charcoal is replacing coke in the manufacture of iron at Vor-
dernberg, Austria. (P. 461)
The British Industries Fair of 1921 is described. The exhibits
in connection with the chemical and dye industries were of great
national interest. (Pp. 472-83)
The development of a new source of tannin in the Fiji Islands
by an Australian Company is reported. (P. 532)
Statistics are given showing the imports and exports of vege-
table oils and vegetable-oil material by Peru during the years-
1917, 1918, and 1919. (P. 536)
The British Research Association for Light Fuels for the Oil
Engines Industry has been approved by the Department of
Scientific and Industrial Research. (P. 560)
The Directors of the British Dyestuffs Corporation state that
the decreased demand for dyestuffs during the past few
months "has been very marked and rendered necessary a con-
siderable curtailment in production, in consequence of which raw
stocks have accumulated." (Pp. 561-2)
The total estimated value of the metal and mineral produc-
tion of Canada in 1920 was $217,775,080, which is greater than
the total value reached during any preceding year.
A Belgian company has been started to exploit papyrus, which
grows in great abundance in the Belgian Congo. Analyses have
shown this plant to contain 37.8 per cent of cellulose. (P. 584)<
A company is being formed in South Africa to work nickel
ore and talc deposits. (P. 584)
The Lomagundi mica fields are described. (P. 585)
Statistics are given showing the quantity and value of the
production of both crude and prepared minerals in Spain in 1919.
(P. 588)
Prices of German coal-tar products are quoted. (P. 606)
There were 33,380,205 lbs. of carbonate of potash, valued at
$1,218,851, imported into the United States during the calendar
year 1920. (P. 607)
The salt industry of Guerande, France, is reviewed. (P. 609)'
The British trade in paints and oils is described. (Pp. 621-3)
The dye industry in Japan is reviewed, and it is stated that
this industry has suffered from the present business depression
quite as seriously, if not more so, than any other business, not-
withstanding that it was among the first of the war-born in-
dustries to be protected by a high tariff. (Pp. 634-6)
Statistics of Exports to the United States
Malaga — (P. 20)
Aniseed
Essential oils
London— (P. 38)
Rubber
Leather
Hides
Tin
Gums
Drugs and chera
cats
Linseed oil
Ether, volatile oils,
perfumes
Colors and dyes
Chemicals and drugs
Fertilizers
Amsterdam — (P.
167)
„ Drugs and chen
Nottingham, Eng- cajs
land— (Pp. 60-1) Fertilizers
J?ru?s . Hides and skins
fertilizer, nitroor- Leather
,. ?anic Metals
Paints oils
Plumbago Paints
Holland— (Pp. 96, Quinine and ci
210) _ c>>°na t>ar>-
Linseed Rubber, crude
seed Vladivostok— (P
202)
Hides
Linseed
Saltpeter
Para— (P. 215)
Vegetable oils
Hides and skins
Tampico, Mexico— Jndia ™bber, crud
(P. 106)
Petroleum Belize, British Hu>
Finland — (P. 153) _ duras— i
Wood pulp
Poppy seed
Caraway seed
Mustard seed
Quinine and
chona bark
Paper stock
Rubber, crude
Brazil — (P. 303)
Rubber
Karachi District —
(P. 423)
Asafetida
Gum tragacanth
Saltpeter, refined
Hides and skins
Seeds, castor
Leeds— (P. 496)
Orchil liquor
Leather
British Columbia —
(Pp. 512-0)
Antimony ore
Blood and tankage
Ammonium sulfate
Bark, cascara
Gum, camphor
N'itrate of soda
Quinine sulfate
Sulfate of copper
Copra
Fertilizers
Gas liquor, ammoni-
Hides and skins
Magnesium sulfate
Metals
>ils
Rubber
Tin
Copper c
Maganes*
Oil seeds
Fluorspar
Lead ore
Platinum
Winnipeg District-
Hides and" skins Liverpool— (P. 2S7) (P. 547)
Minerals Palm oil Flaxseed
Oils and greases Ferromanganese Lime, hydrate 1
Chicle
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
583
BOOK REVIEWS
A Dictionary of Chemical Terms. By James F. Couch, iv +
204 pp. 43A X 63/4 in. D. Van Nostrand Co., New York,
1920. Price, $2.50 net.
In chemistry the word "dictionary" immediately suggests a
work in several volumes — in reality an encyclopedia — on the
plan of Watts or Thorpe. It may be for this reason that the
need for .a true chemical dictionary, or word book, has not been
sufficiently appreciated, although surely it must have been
obvious enough. It is perfectly true, as the author states in
his preface, that chemistry has developed a complex and scat-
tered terminology and that it is often difficult, s6metimes almost
impossible, to find the meaning of a term.
This is the need which the book is intended to meet. In
scope it is quite different from the "Condensed Chemical Dic-
tionary." It includes the elements but not chemical compounds,
except sporadically. Its definitions, approximately 3000 in
number, relate chiefly to chemical and physical phenomena
and properties, reactions, laws, class names of compounds,
and the like.
One cannot conscientiously call Mr. Couch's interesting
little work a good dictionary. The essence of dictionary mak-
ing is clear, concise, and accurate definition, and this is lacking.
A single example will show what is meant: hydroxide is defined
as "a compound of a metal derived from water by replacement
of one or more hydrogens by an equivalent quantity of element,
except that one molecule of water furnishes but one atom of
hydrogen." The result in many cases is a statement that is
too narrow or too broad, confused, or even flatly wrong. There
is no distinction between definitions and encyclopedic informa-
tion. The book represents no definite standards of nomen-
clature. There is a curious sprinkling of terms from descrip-
tive botany which are out of harmony with the rest of the vocabu-
lary. And, of course, with such a small number of terms, the
claim for completeness is not justified; even so common a word
as "reagent" is not defined.
Nevertheles , the author has gathered together information
not to be found in any other one book or, with readiness, any-
where else. The handy pocket size, clear type, and flexible
binding are sure to find favor. Austin M. Patterson
The Chemistry and Technology of the Diazo-Compounds.
By J. C. Cain. 2nd edition, xi + 199 pp. Longmans,
Green & Co., New York, 1920. Price, $4.20.
The diazo-compounds are the factotums among organic
substances. They will make you anything in reason if you will
but give them suitable material from which to fashion what you
want; indeed their energy is so abundant that if they are isolated
and thus deprived of the chance of producing something else,
they blow up.
They are a milestone to the student of organic chemistry,, who
feels that he is really mastering the subtilties of the science when
he learns of the ten major reactions of these substances, and he
feels that he is mature enough to take his place among the chosen
when he finds himself able to follow the intricacies of the great
controversy regarding the constitution of these bodies. Later
in his career, the mature organic chemist turns ever again to this
group, because of this interest; it is to him as a volume of brilliant,
beautifully fashioned sketches is to the student of literature.
Because the reactivity of these substances makes them a
fascinating study and confers on them a great technical impor-
tance, it is desirable to have brought together in a condensed
form all the essential facts about them, as in Cain's book.
The title of the new edition promises that the technology of
the diazo-compounds will receive attention in the text. This
promise is fulfilled in a measure only. It is true that references
are given to the literature of the commercial application of the
reactions of the group, but that fact hardly warrants the change
in title, more especially as the treatment is purely theoretical,
as it should be in a book of this kind, and therefore there is noth-
ing to emphasize the technically valuable from the technically
useless.
There can be no serious quarrel with the arrangement of the
subject matter of the book except, perhaps, the inclusion of the
paragraph on the explosibility of dry diazo-compounds in the
chapter on the mechanism of the diazotization process. As a
suggestion, the reviewer would like to point out that a chart
or series of charts showing the many transformations described
in the text would be a very great help in threading one's way
through the maze. Semmler has used this method to great ad-
vantage in his volumes on the chemistry of the ethereal oils, in
order to summarize the multitudinous reactions characteristic
of such a substance as pinene or camphor.
These comments are not intended to cast any doubt on the
truth that this little book is one that every student of organic
chemistry should know well enough to be able to use when neces-
sary'- It is a very real loss that Dr. Cain's death makes it im-
possible for us to have a fuller discussion of his theory of the
structure of these compounds. This theory is the most logical
one so far advanced, and the place it occupies in the book, in
consequence of Dr. Cain's modesty, does not emphasize suffi-
ciently its value, and it will be impossible for anybody to give
us what its originator could have done. R. E. Rose
Chemistry of Pulp and Paper Making. By Edwin SuTER-
meister. vii + 479 pp. John Wiley & Sons, Inc., New
York; Chapman & Hall, Ltd., London, 1920. Price, $6.00
postpaid (33s. net).
This book not only discusses the chemistry of pulp and paper,
but gives short descriptions of practically all the mechanical ap-
paratus and operations involved. In general the arrangement
follows the usual outline of a book on paper making. A chapter
on printing is an innovation which should be valuable for book
mills.
In his review of cellulose properties and paper-making fibers,
the author has done an excellent piece of work, although nothing
particularly new is presented. There is just about enough said
for the paper-mill chemist, and the matter is clearly stated and
well coordinated. Probably the most valuable material in these
chapters is the collection of data on woods. This includes a
study of woods available for paper making, their relative value
for this purpose, the lengths of fiber produced, specific weights
of wood and chips, moisture content, etc.
The chapter on rags, straw, esparto, and waste paper is probably
the least valuable in the book. The author shows only a surface
acquaintance with these subjects. For example, in the recovery
of waste paper, only printed paper is spoken of, and the data are
apparently obtained from machine manufacturers.
The outstanding feature of the work on pulp manufacture is
the description and study of the soda cook. The author shows
a very intimate knowledge of this subject and presents many
valuable data of his own. He is able, therefore, to discuss the
results of other investigators and come to a definite conclusion
as to the best methods of operation. The description of sulfate
and sulfite cooks is also good. On the several processes many
important data are lacking, for example, the mass action laws
involved in causticizing, the furnace conditions desirable in the
recovery of sulfate liquor, and the application of the gas laws in
the making and recovery of sulfite acid. These are data which
are not available in any book, but which would be a boon to the
industry.
584
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
The chapter on bleaching gives good descriptions of bleaching
processes as commercially carried out, and some data regarding
best conditions of operation, mostly obtained from other investi-
gators and showing widely varying results. Unfortunately, the
fundamental factors of the action, such as concentration, tem-
perature, and agitation, are not clearly brought out. The same
criticism may be made of the chapters on sizing, loading, and
coloring. A great many very interesting data are presented,
but insufficient information is available for either the author or
reader to come to definite conclusions. This criticism can be
made of every book published on the subject, and in many places
the author has shown distinct improvement over older books.
The chapter on coating is a distinct addition to the literature
of paper chemistry. The work on water, while not new, is a
valuable part of the book. The chapters on pulp and paper
testing bring together into a comprehensive whole the various
methods which are in common use throughout the industry.
Summing up, the book is particularly valuable for the dis-
cussions on soda cooking, the manufacture of book and coated
paper, and for the collections of tables and constants applying
to all branches of the industry. It would be much more valuable
— and this is true of practically all books on pulp and paper — if
the various applications of chemistry and engineering were dis-
cussed with regard to fundamental science as applied to com-
mercial operation. H. H. Hanson
The New Stone Age. By Harrison E. Howe, xvii + 289
pp. Century Co., New York, 1921. Price, $5.00.
In his introduction Dr. Howe states that he has attempted to
tell his story in "everyday language." This expression is vague
because every group of persons has a different everyday language.
Of course one would not expect such a book to be written in the
argot of the streets, but the language used is the language of the
scientist rather than that of more ordinary men. That is to say,
the author has assumed a larger acquaintance with scientific
terms and engineering methods than is possessed by the average
reader. Furthermore, in telling the story, numerous technical
details have been included which are unnecessarily complicated
for the general reader and not complete enough for the engineer.
The book will be read with interest, however, by both these
classes because it is readable, and because it covers the subject in
a scholarly manner. The historical chapter might have been
expanded with advantage. When a story is to be told one wishes
to learn about the beginning, and this part has been treated quite
briefly. It is to men like the present author that the world looks
for accurate information on the development of scientific pro-
cesses, and it would appear that more emphasis might be laid
upon this phase of the subject.
The author is at his best when he writes about concrete as a
structural material. He is evidently more at home here than
he is in the manufacture of cement, but even in this account the
criticism made above seems to hold. Several tables of engineer-
ing data are given, but no attempt is made to explain them; while
on the other hand, the author expressly disclaims the intention of
making every man his own concrete engineer.
A good description is given of the cement gun and its use,
with possible applications of this method of distribution, but
when the author essays to write of art in concrete he is evidently
on unfamiliar ground. It is, of course, true that fine decorative
works can be and have been produced in concrete, but to suppose
that art consists in using a colored aggregate or in inlaying tiles
is to reduce the matter to an absurdity. In fact, a fine model
would usually appear to much greater advantage in the quiet
gray of the natural cement than if it were sprinkled with marble
chips, however brilliant. Even if the inlaid tiles should be
beautiful, as many are, the art of their use is their own and does
not belong to the cement in which they are set.
The work gives the impression of having been run off hastily.
Besides several typographical errors, there is a curious lack of
uniformity in expression. Sometimes we read of "alumina"
and again of "aluminium oxide," once even of "alumina oxide."
"Iron oxide" and "ferric oxide" are used interchangeably, as also
are "silicon oxide" and "silica," on the same page. "Calcium
aluminate" and "aluminate of lime" are referred to, and the
phrase "the oxides of calcium alumina and silica" is certainly
not what the author intended to say. It is rather surprising also
to find one with the reputation of Dr. Howe stating that "ferric
oxide is believed to act similarly on alumina in promoting the
combination of silica and lime."
Without appearing to be captious it may be said that inac-
curacies such as those quoted mar the pleasure of reading an
interesting and useful book, and one is forced unwillingly to the
conclusion that the work has been prepared in a hurry.
Chas. F. Binns
Vitamines — Essential Food Factors. By Benjamin Harrow,
Ph.D. xi + 219 pp. F. P. Dutton & Co., New York, 1921.
Price, $2.50 net.
There are few recent developments in science which have
appealed so strongly to the general public as the discovery of
the class of substances now known as vitamines. Magazine
and newspaper articles on vitamines have recently appeared
with increasing frequency, and now we have a book which treats
the subject from the popular standpoint. In the present case
the author begins with the most elementary principles of nu-
trition. The analogy between the body and a furnace is first
pointed out, and from this the expression of food values in terms
of calories is developed. Then follow chapters dealing with
carbohydrates, fats and proteins, mineral matter, water and
oxygen, amino-acids, glycogen or animal starch, soap, and
glycerol. This preparation of the reader for an understanding
of the conception of vitamines occupies about one-half of the
book, and is presented in such simple language that a person of
very limited previous training should be able to obtain a clear
idea of the subject
In regard to the development of the conception of vitamines,
the author follows the historical sequence and presents first
the work of Hopkins on milk. This makes it necessary to define
the name vitamine before the work of Funk or that of any other
investigator of beri beri is mentioned. Although the experi-
ments of Hopkins and of others antedate those of Funk, it is to
the latter that special credit is due for focusing the attention of
the scientific world upon the remarkable properties of these
hitherto unrecognized food constituents and their intimate con-
nection with certain nutritional diseases. A presentation of the
subject from this standpoint would have a stronger public appeal.
This book has been written particularly for the benefit of
those who are called upon to select the dietary of families or
other groups of individuals. The last chapter contains many
well-chosen points on the practical application of the knowledge
which has been gained in regard to vitamines. In this connec-
tion, however, attention should be called to one statement
which is not in harmony with what is generally considered to
be the safer practice. On page 170 it is stated that, whenever
possible, milk should be taken in a fresh unheated condition.
This, of course, is true from the standpoint of its content of
vitamines, but the possibility of milk-borne infections, due to
failure to pasteurize, is of so much more importance than loss of
nutritional value resulting from pasteurization that this recom-
mendation should certainly not be made without proper refer-
ence to the positive source of danger in the consumption of raw
milk. Atherton Seidell
Les Ethers Cellulosiques; Premiere Partie, Les Ethers Mineraux
de la Cellulose; Tome I, La Nitrocellulose et le Celluloid.
By Andre Dubosc. 344 pp. A.-D. Cillard, 49, Rue des
Vinaigriers, Paris.
This book is Volume I of the first part of what is apparently
planned to be a complete and authoritative work on the cellulose
June, 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
585
esters. Nitrocellulose, as the most important ester of cellulose,
is naturally considered first, and the present volume takes the
discussion through the bleaching of the nitrocellulose. The
book opens with a brief historical outline of the development
of celluloid, and this is followed with a consideration of its
constitution and properties, both physical and chemical.
The raw materials are next discussed in considerable detail.
Nitric acid, sulfuric acid, and alcohol are not considered because
they are treated so well in other places. In considering cellu-
lose, 35 pages are devoted to an excellent summary and dis-
cussion of the various constitutional formulas which have been
proposed for cellulose, including that of Barthelmy published
in 1917. This is admirable as far as it goes, but the recent work
of Denham and Woodhouse, of Pictet, of Hess, and of Hibbert,
have added much to our knowledge since that time. In the
next 46 pages what is known to-day about cotton is well sum-
marized, including its formation in nature, its constitution,
composition, physical, chemical and microscopic properties, and
methods of purificati&n. The last are given in considerable
detail. Linters and special papers are also considered as
cellulosic raw materials. The section closes with a discussion
of camphor.
The rest of the present volume (210 pages) is devoted to a
general consideration of the preparation of nitrocellulose for
celluloid manufacture. Nitration is first presented in a general
way, many proposed acid mixtures and methods of calculating
theoretical mixtures being cited. Fifteen methods of nitration
which have actually been in commercial operation are discussed
in considerable detail, often with descriptions of the apparatus
giving dimensions and capacities. A valuable feature of the
book is that it is more than a mere summarized compilation of
previous publications, in that the merits and defects of each
method are pointed out. The author concludes this chapter by
presenting the two methods which in his opinion are the only
ones giving entire satisfaction. The same sort of detailed
consideration of stabilization, washing, pulping, and bleaching
completes the present volume.
One cannot help being impressed with the thoroughness with
which the subject matter is presented. On this account it is the
more regrettable that no references to the literature are given,
nor is a bibliography of any sort included. One misses also
illustrations which would add so much to the description of the
various pieces of apparatus. In spite of this lack of certain
desiderata, however, the book is a very valuable contribution
to the literature of the cellulose esters and one which should be
of interest and help, not only to the student of cellulose chem-
istry, but also to those primarily interested in the practical
manufacture of cellulose esters and their application in industry.
G. J. Esselen, Jr.
An Introduction to Chemical Pharmacology. By Hugh Mc-
Guigan. xii + 418 pp. P. Blakiston's Sons & Co., Phila-
delphia, Pa., 1921. Price, $4.00 net.
This little volume will be useful to the organic chemist who
desires to know more regarding the medical aspect of the sub-
stances with which he deals, and to the medical student who
wishes to become more familiar with the chemical aspect of
pharmacology.
The work is divided into 34 chapters, covering the various
types of organic and inorganic compounds, and the final chapter
of 28 pages is devoted to a very cursory review of chemical
toxicology. The author deals with the constitution of the various
types of substances considered, and touches upon the relation
of chemical constitution to pharmacological action in connection
with certain groups.
The field covered by the author is really so large that none
of the material is handled in detail, and a considerable part
is devoted to tests for the various substances.
On page 76 the author repeats an error which is present in
most works on the subject. It is stated that hydrocyanic acid
is toxic to all ferments. It has been repeatedly shown that
hydrocyanic acid is toxic only to the oxidizing enzymes and
catalase. It is not toxic to the digestive and hydrolyzing enzymes.
The book should prove especially useful to medical students
who desire to increase their knowledge of chemistry. The
pharmacological action of the various drugs is presented in
barest outline, the emphasis throughout being on the chemical
aspect of the subject. If the book succeeds in stimulating
medical students to attain further chemical knowledge of their
subject, it will fill a real want.
A. S. Loevenhart
Red Lead and How to Use It in Paint. By Alvah Horton
Sabin. xi + 139 pp. 3rd Edition. John Wiley & Sons,
Inc., New York, 1920. Price, $2.00 postpaid.
This little book was first written in 1916 and published by
the author for private circulation. A second edition containing
some corrections was similarly circulated in 1919. The present
book is a third edition including much of the original text, but
rewritten and amplified.
The book is true to title, giving only the briefest outline of
methods of manufacture and uses other than in paint.
The main body of the book is an excellent treatise on the
theory and practice of the use of red lead -linseed oil paints for
protecting iron and steel, written in a very attractive and read-
able style. The information necessary for calculating amount
of paint required for a variety of structures, computing amount
of raw materials required per unit volume of red lead paints
of varying composition, and calculating cost of paint in both
American and English units of volume and money is more
complete and more clearly given than in any other publication
that the reviewer has seen. This matter is given partly in
the main text and partly in charts and tables inserted between
Appendix I and Appendix II. The former deals with methods
of analysis of red lead, while the latter gives specifications for
painting bridges, ships, water tanks, gas holders, and structural
iron and steel.
The author is a firm believer in single pigment paints, as
against the proponents of the composite pigment paints. He
is also an advocate of the use of red lead free from litharge,
that is, the product containing at least 98 per cent Pb304 as
against the more common material containing 10 per cent or
more of PbO. The advantages claimed for the high purity
red lead are greater fineness, with consequent greater smoothness
and spreading capacity of the resultant paint, and less tendency
of chemical change. While an ordinary red lead paint will
turn white on exposure, one made of high purity red lead will
retain its color. A linseed oil paste made of ordinary red lead
will soon harden and become useless, while such a paste made
with high purity red lead "is so nearly inactive toward linseed
oil that it may be safely ground in oil and put up like white
lead in paste form." This statement is not entirely consistent
with the suggested specification given on page 89. "The paste
shall contain only red lead and 6 to 7 per cent of linseed oil
and shall be guaranteed for three months against hardening
if kept sealed in the original package at ordinary temperature."
Certainly any user of white lead paste can demand and secure
paste that will keep for much longer periods than three months.
The principal adverse criticism that the reviewer makes of this
book is the failure to call attention to the fact that, while high
purity red lead can be and is marketed in paste form and this
paste remains soft longer than similar paste made from, say,
85 per cent Pb304 pigment, it does harden more rapidly than
white lead.
This book should be read and used by every one interested
in protecting steel by paint, whether he be master painter,
paint manufacturer, structural engineer, or chemist.
Percy H. Walker
5S6
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 6
NEW PUBLICATIONS
American Chemistry: A Record of Achievement the Basis for Future Prog-
ress. Harrison Hals. 215 pp. 63 illus. Price, $2.00. D. Van
Nostrand Co., New York.
Cellulose Esters: Technology of Cellulose Esters. E. C. Wordsn. Vol.
I. (Five Parts.) 3087 pp. -296 illus. Price, £10. 10s. net. E. & G. N.
Spon, London.
Chemical Effects of Alpha Particles and Electrons. Samuel C. Lind.
American Chemical Society Monographs. 180 pp. Price, $3.00. The
Chemical Catalog Co., Inc., New York
Cocoa and Chocolate: Their Chemistry and Manufacture. R. Whvmpbr.
2nd edition, revised and enlarged. 568 pp. Illustrated. Price, $10.00,
net. P. Blakiston's Son & Co., Philadelphia.
Dyes: The Testing of Dyestuffs in the Laboratory. C. M. Whittakbr.
100 pp. Price, $4.50. D. Van Nostrand Co.. New York.
Electronic Conception of Valence and the Constitution of Benzene. Harry
Shipley Fry. Monographs on Inorganic and Physical Chemistry. 300
pp. Price, $5.00. Longmans, Green & Co., New York.
French- English Dictionary for Chemists. Austin M. Patterson. Price.
$3.00. John Wiley & Sons, Inc.. New York.
Phase Theory: The Principles of the Phase Theory: Heterogeneous
Equilibria between Salts and their Aqueous Solutions. Douglas A.
Clibbens. 383 pp. Illustrated. Price, 25s. net. Macmillan & Co.,
New York.
Physical Chemistry: Principles of Physical Chemistry from the Stand-
point of Modern Atomistics and Thermodynamics, Edward W. Wash-
burn. 2nd edition, revised, enlarged, and reset. 51S pp. S3 illustrations.
Price, $4.00. McGraw-Hill Book Co., Inc., New York.
Poisons: Their Effects and Detection. Alexander W. Blyth and
Meredith W. Blyth. 5th edition, revised, enlarged, and rewritten.
779 pp. Illustrated. Price, $12.00. D. Van Nostrand Co., New York.
Qualitative Chemical Analysis: Introduction to Qualitative Chemical
Analysis. H. Wilhelm Fresenius. Translated by G. Ainsworth
Mitchell. 17th edition. 954 pp. Illustrated. Price, $8 00. John
Wiley & Sons, Inc., New York.
Stoichiometry: The Calculations of Analytical Chemistry. Edmund H.
Miller. 3rd edition, revised. 201 pp. Price, $2 00. The Macmillan
Co., New York
Rubber, Resins, Paints and Varnishes. R. S. Morrell and A. de Waele.
236 pp. Price, $4.00. D. Van Nostrand Co, New York.
Wood: Traite de la Conservation et de l'Amelioration des Bois. Mau-
rice de KeghEL. 360 pp. Illustrated. Price, 15 fr. J.-B. Bailleire
et Fils, Paris.
NEW JOURNALS
Journal of Indian Industries and Labour. Published quarterly by the
Government of India, Calcutta, India. Price, Rs. 4-8-0 a year.
Scientific Agriculture. Canadian Society of Technical Agriculturists.
Editor, F. H. GrindlEy. Published by Industrial & Educational Pub-
lishing Co., Ltd., Montreal, Canada.
RECENT JOURNAL ARTICLES
Acetic Acid: Fabrication deJlAcide Acetique Synthetique au Depart du
Carbure de Calcium. Maurice Deschiens. Chimie el Industrie,
Vol. 5 (1921), No. 3, pp. 239-256.
Benzoic Acid: Synthesis of Chlorine-Free Benzoic Acid from Benzene.
Ralph H. McKee and Frank A. Strauss. Chemical and Metallurgical
Engineering, Vol. 24 (1921). No. 15, pp. 638-644.
Bleaching of Colored Cotton Goods. J. Merritt Matthews. Color
Trade Journal, Vol. 8 (1921), No. 5. pp. 157-161.
Briquets: Factors to Be Borne in Mind in Making Briquets of Fine Ma-
terials. J. E. Stevens. The Coal Age, Vol. 19 (1921). No. 15, pp. 663-
666.
Bronze: Investigation into Special Bronzes. F. Giolitti and M. Mar-
antonio. Pulp and Paper Magazine of Canada, Vol. 19 (1921), No. 15.
pp. 397-399; No. 16, pp. 423-426; No. 17, pp. 449-451. Translated
from Cazelta Chimica Italiana.
Catalysis: Les Principales Applications Industrielles de la Catalyse.
Paul Razous. VInduslrie Chimique, Vol. 8 (1921), No. 87. pp. 135-138.
Cellulose: Distillation of Cellulose and Starch under Reduced Pressure.
A. Pictbt and J. Sarasin. Paper, Vol. 28(1921). No. 6, pp. 25-28.
Translated from Helvetica Chimica Acta.
Chemical Analysis of the Soil. G. S. Fraps. The American Fertilizer,
Vol. S4 (1921), No. 9, pp. 100-104.
Chemical Engineer in Biscuit Manufacture. Julius Rohn. Chemical Age,
Vol. 29 (1921), No. 4, pp. 129-131.
Clay: Note on the Effect of Time on the Drying Shrinkage of Clays. R. F.
Geller. Journal of the American Ceramic Society, Vol. 4 (1921), No. 4,
pp. 282-287.
Coal: Low Temperature Carbonization of Coal. Stewart J. Lloyd
American Gas Journal, Vol. 114 (1921). No. 17, pp. 353-54, 303-64-
Coal: Methods for the Identification and Valuation of Coals F. S.,
Sinnatt. Journal of the Society of Dyers and Colourists, Vol. 37 (1921),
No. 4. pp. 108-112.
Coal: Sulfur Present in Coal and Coke. Alfred R. Powell. The Coal
Industry, Vol. 4 (1921), No. 4. pp. 228-232.
Combustion of Fuel in the Steel Industry. C. F. Poppleton. Combustion,
Vol. 4 (1921), No. 4, pp. 34-36. 11.
Control of Temperature in the Acid Bessemer Blow. Henry D. Hibbard.
The Blast Furnace and Steel Plant, Vol. 9 (1921), No. 5, pp. 287-290.
Decolorizing Carbons. Stuart M. Littlemorb. Chemical Engineering
and Mining Review, Vol. 13 (1921). No. 150. pp. 211-14.
Dust Control and Ventilation in Metal Mines. D. Harrington. Engineer-
ing and Mining Journal, Vol. Ill (1921), No. 18, pp. 738-43.
Dyes: After-Treatment of Sulfur-Dyed Yarn with Copper Sulfate and
Acetic Acid. Arthur S. Eichlin. Textile Colorisl, Vol. 43 (1921),
No. 509, pp. 323-24.
Dyes: Key Index for Dyestuff Intermediates. W. N. Watson, A. R.
Willis and R. N. Shreve. Color Trade Journal, Vol. 8 (1921), No. 5,
pp. 189-193.
Fire Brick: Comparing Brick for Boiler Furnace Linings. R. C. Brierly.
Combustion, Vol. 4 (1921), No. 4, pp. 20-22.
Gas: Elliott Gas, A Substitute for Natural Gas. F. J. Denk. Forging
and Heal Treating, Vol. 7 (1921), No. 4, pp. 208-212.
Gas Progress Related to B.t.u.'s. Alfred I. Phillips. The Gas Age,
Vol. 47 (1921), No. 8, pp. 327-330.
Gas: Purification of Water Gas. Erwin C. Brenner. The Gas Agt,
Vol. 47 (1921), No. 8, pp. 315-318.
Gas: Removal of Sulfur Compound. Erwin C. Brenner. American
Gas Journal, Vol. 114 (1921). No. 16, pp. 339-40, 348-49.
Glass: Electrically Heated Glass Annealing Lehrs. E. F. Collins.
The Glass Industry, Vol. 2 (1921), No. 5, pp. 107-09.
Government Fixed Nitrogen Research. R. C Tolman. Chemical and
Metallurgical Engineering, Vol. 24 (1921), No. 14, pp. 595-599.
Gypsum: The Relation between the Fineness and Other Properties of
Calcined Gypsum. W. E. Emley and F. C. Welch. Journal of tht
American Ceramic Society, Vol. 4 (1921), No. 4, pp. 301-305.
Heat Transfer in Open-Hearth Furnaces. Henry Wm. Seldon. Tht
Blast Furnace and Steel Plant, Vol. 9 (1921), No. 5, pp. 299-304.
Heat Treatment of Drop Forgings. Leslie Aitchison. Forging and
Heal Treating, Vol. 7 (1921), No. 5. pp. 255-264.
Ink: The Acidity of Ink and the Influence of Bottle Glass upon Ink. G.
Ainsworth Mitchell. The Analyst, Vol. 46 (1921), No. 541, pp. 129-35.
Leather Nomenclature. J. H. Yocum and T. A. Faust. Journal of the
American Leather Chemists' Association, Vol. 16 (1921), No. 5, pp. 259-64.
Materials of Construction Used in a Chemical Works, George B. Jonbs.
The Chemical Age (London), Vol. 4 (1921). No 94. pp. 394-5.
Metal Plating: Iron Plating. W. G. Knox. The Metal Industry, Vol.
19 (1921), No. 4, pp. 160-62.
Metals: Failure of Metals under Repeated Stress. H. F. Moore. Forg-
ing and Heat Treating, Vol. 7 (1921), No. 4. pp. 228-29.
Microscopy of Textiles. F. J. Hoxie. Textile World, Vol. 59 (1921), No.
16, pp. 59-61.
Munitions: War-Time Production of Optical Munitions. F. E. Wright.
,4rmy Ordnance, Vol. 1 (1921), No. 5, pp. 247-51.
Open-Hearth Furnace Waste Heat Utilization. G. R. McDbrmott ano
F. H. Willcox. The Iron Age. Vol. 107 (1921), No. 14, pp. 899-900.
Packing Industry: The Trail of the Chemist in the Packing Industry. Chas.
H. MacDowell. American Fertilizer. Vol. 54 (1921), No. 8, pp 43-47.
Phenol Losses in the Decomposition of Phenate Liquors. B. Hardman.
Chemical Trade Journal and Chemical Engineer, Vol. 68 (1921), No. 1771.
pp. 501-02.
Photochemistry of the Sensitivity of Animals to Light. Selig Hecht.
Science, Vol. 53 (1921), No. 1372. pp. .147 :>->
Poisons: Detecting Poisons in Food Substances. E mil Kohn-Abrbst.
Scientific American Monthly, Vol. 3 (1921), No. 4. pp. 325-28. Trans-
lated from La Science et la Vie.
Pouring Temperatures: How They Affect Casting Shrinkage and Solidity.
R. R. Clarke The Metal Industry. Vol. 19 (1921). No. 4, pp. 147-48.
Promotion of Scientific Research. William Hoskins and Russell Wilbs.
Chemical and Metallurgical Engineering, Vol. 24 (1921), No. 16, pp. 689-
91.
Sugar: The Comparative Values of Decolorizing Carbons. F. E. Thomas.
International Sugar Journal, Vol. 23 (1921). No. 267. pp 162-65.
Tanning: L'Evolution des Differentes Methodes de Tannage. W. J.
Thuau. Journal of the Society of Leather Trades' Chemists, Vol. 5 (1921).
No. 3, pp. 70-S4.
Technical Research and the Textile Industry. Benjamin T. Brooks.
Textile World. Vol. 59 (1921). No. 18, pp. 125-27.
Zirconia: The Preparation of Zirconia from Brazilian Ore and a New
Method of Determination. E. C. Rossiter and P. H. Sanders. Journal
of the Society of Chemical Industry, VoL 40 (1921), No. 7, pp. 70f-72l.
June. 1921 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
MARKET REPORT-MAY, 1921
FIRST-HAND PRICES FOR GOODS IN ORIGINAL PACKAGES PREVAILING IN THE NEW YORK MARKET
5S7
bbls
d. Boric, cryst.,
Hydrochloric, com'I, 2(
Hydriodic
Nitric, 42°
Phosphoric, 50% tech.
Sulfur
INORGANIC CHEMICALS
May 1
...lb. .14'/i
...lb. .01'/ s
C. P lb.
imber, 66° ton
urn 20% ton
Alun
Alun
Ammonii
Sulfate (iron-free) lb.
i Carbonate, pwd lb.
i Chloride, gran lb.
Ammonia Water, carboys, 26 ° lb .
Arsenic, white lb.
Barium Chloride ton
Nitrate lb.
Barytes, white ton
Bleaching Powd, 35%, Works, 100 lbs.
Borax, cryst., bbls lb.
Bromine, tech lb.
Calcium Chloride, fused ton
Chalk, precipitated, light lb.
China Clay, imported ton
Copper Sulfate 100 lbs.
Feldspar ton
Fuller's Earth 100 lbs.
Iodine, resublimed lb.
Lead Acetate, white crystals lb.
Nitrate lb.
Red American 100 lbs.
White American 100 lbs.
Lime Acetate 100 lbs.
Lithium Carbonate lb.
Magnesium Carbonate, tech lb.
Magnesite ton
Mercury flask 75 lbs.
Phosphorus, yellow lb.
Plaster of Paris 100 lbs.
Potassium Bichromate lb.
Bromide, cryst lb.
Carbonate, calc, 80-85% lb.
Chlorate, cryst lb.
Hydroxide, 88-92% lb.
Iodide, bulk lb.
Nitrate lb.
Permanganate, U. S. P lb.
Salt Cake, bulk ton
Silver Nitrate oz.
Soapstone, in bags ton
Soda Ash, 58%, bags 100 lbs.
Caustic, 76% 100 lbs.
Sodium Acetate lb.
Bicarbonate 100 lbs.
Bichromate lb.
Chlorate lb.
Cyanide lb.
Fluoride, technical lb.
Hyposulfite. bbls 100 lbs.
Nitrate, 95% 100 lbs.
Silicate, 40° lb.
Sulfide lb.
Bisulfite, powdered lb.
Strontium Nitrate lb.
Sulfur, flowers 100 lbs.
Crude long ton
Talc, American , white ton
Tin Bichloride lb.
Oxide lb.
Zinc Chloride, U. S. P lb.
Oxide, bbls lb.
18.00
23.00
18.00
5.25
8.00
1.00
3.75
.13
.15
.11'/.
.09 'A
2.00
1.40
.lOi/i
72.00
47.00
.35
ORGANIC CHEMICALS
Acetanilide lb.
Acid, Acetic. 28 p. c 100 lbs.
Glacial lb.
Acetylsalicylic lb.
Benzoic, U. S. P., ex-toluene. .lb.
Carbolic, cryst., U. S. P., drs..lb.
50- to 110-lb. tins lb.
Citric, crystals, bbls lb.
2.75
.10'/'
IS. 00
23.00
.06'/.
.06 V.
09 Vi
.093/,
08
.OS
00
60.00
14
.14
00
30.00
75
2.75
07
.06»/i
18.00
5.25
8.00
1.00
3.75
.13'/,
.15
.11'/.
.09'A
2.00
1.40
.10'/,
1.50
.!!>/■
12.00
12.00
1.90
1.90
3.75
3.75
.06
.06
2.25
2.25
.07V.
.07V.
07' /2
.07' /;
.13
.13
3.00
3.00
20.00
20.00
18.00
18.00
Acid (Concluded)
Oxalic, cryst. bbls lb. .16'A
Pyrogallic, resublimed lb. 1.85
Salicylic, bulk, U. S. P lb. .23
Tartaric, crystals. U. S. P.. . .lb. .35
Trichloroacetic, U. S. P lb. 4.40
Acetone, drums lb. . 13'A
Alcohol, denatured, complete. . . .gal. .40
Ethyl, 190 proof gal. 4.75
Amyl Acetate gal. 3.05
Camphor, Jap. refined lb. .65
Carbon Bisulfide lb. .OS
Tetrachloride lb. .12
Chloroform, U. S. P lb. .43
Creosote, U. S. P lb. .50
Cresol. U. S. P lb. .18
Dextrin, corn 100 lbs. 2.90
Imported Potato lb. . 07 'A
Ether, U. S P., cone, 100 lbs.. ..lb. .18
Formaldehyde lb. .15
Glycerol, dynamite, drums lb. .13'/?
Methanol, pure, bbls gal. 1 . 25
Pyridine gal. 2.75
Starch, corn 100 lbs. 2.08
Potato, Jap lb. .05
Rice.
Sago.
OILS, WAXES, ETC.
Beeswax, pure, white lb.
Black Mineral Oil, 29 gravity. .. .gal.
Castor Oil, No. 3 lb.
Ceresin, yellow lb.
Corn Oil, crude, tanks, mills lb.
Cottonseed Oil, crude, f. o. b. mill. .lb.
Linseed Oil, raw (car lots) gal.
Menhaden Oil. crude (southern) .gal.
Neafs-foot Oil, 20° gal.
Paraffin, 128-130 m. p.. ref lb.
Paraffin Oil, high viscosity gal.
Rosin, "F" Grade, 280 lbs bbl.
Rosin Oil. first run gal.
Shellac, T. N lb.
Spermaceti, cake lb.
Sperm Oil, bleached winter, 38°. .gal.
Stearic Acid, double-pressed lb.
Tallow Oil, acidless gal.
Tar Oil, distilled gal.
Turpentine, spirits of gal.
Aluminium, No. 1, ingots lb.
Antimony, ordinary 100 lbs.
Bismuth lb.
Copper, electrolytic lb.
Lake lb.
Lead, N. Y lb.
Nickel, electrolytic lb.
Platinum, refined, soft oz.
Quicksilver, flask 75 lbs. ea.
Silver oz.
Tin lb.
Tungsten Wolframite per unit.
Zinc, N. Y 100 lbs.
Ammonium Sulfate, export . ..100 lbs.
Blood, dried, f. o. b. N. Y unit
Bone, 3 and 50, ground, raw ton
Calcium Cyanamide, unit of Am-
Fish Scrap, domestic, dried, f. o. b.
Phosphate Rock, f. o. b. mine:
Florida Pebble, 6S% ton
Tennessee, 78-80% ton
Potassium Muriate, 80% unit
Pyrites, furnace size, imported, .unit
Tankage, high-grade, f. o. b.
Chicago unit
.05'/:
.04 'A
.16'A
1.85
4.40
.13V.
.43
45
.18
3.15
.07'A
.18
.14 'A
.15
1.25
2.75
2.33
5.12'A
1.50
.12'A
65.00
65.00
47.00
47.00
.62'A
.62>/»
.29
.29 'A
3.25
3.25
5.10
5.10
2.50
2.50
3.50
3.50
45.00
45.00
4.50
4.50
3.50 &
.10
3.50 &
10
11.00
11.00
15.00
15.00
1.00
1.00
.18
.18
2.75 &
.10
2.75 &
. 10
588
THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No.
COAL-TAB CHEMICALS
May 1
Crudes
Anthracene. 80-85% lb. .75
Benzene, pure gal. .27
Cresol, U. S. P lb. .18
Cresylic Acid, 97-99% gal. . 90
Naphthalene, flake lb. .08
Phenol, drums lb. .10
Toluene, pure gal. .28
Xylene, 2 deg. dist. range gal. .60
Intermediates
Acids:
Anthranilic lb. 1.80
B lb. 2.25
Benzoic lb. .60
Broenner's lb. 1.75
Cleve's lb. 1.30
Gamma lb. 3 . 25
H lb. 1.25
Metanilic lb. 1 .60
Monosulfonic F lb. 2 . 75
Naphthionic, crude lb. .75
Nevile & Winther's lb. 1 . 50
Phthalic lb. .40
Picric lb. .30
Sulfanilic lb. . 30
Tobias' lb. 2.25
Aminoazobenzene lb. 1 .25
Aniline Oil lb. .20
For Red lb. .42
Aniline Salt lb. .28
Anthraquinone lb. 2 . 00
Benzaldehyde, tech lb. .45
U. S. P lb. 1.50
Benzidine (Base) lb. 1.10
Benzidine Sulfate lb. .75
Diaminophenol lb. 5 . 50
Dianisidine lb. 6.00
/>-Dichlorobenzene lb. .15
Diethylaniline lb. 1.40
Dimethylaniline lb. .50
Dinitrobenzene lb. .25
Dinitrotoluene lb. .25
Diphenylamine lb. .60
G Salt lb. .80
Hydroquinol lb, 1.65
Metol (Rhodol) lb. 6.75
Monochlorobenzene lb. .14
Monoethylaniline lb. 2.15
a-Naphthylamine lb. .38
6-Naphthylamine (Sublimed) lb. 2.25
6-NaphthoI, dist lb. .34
m-Nitroaniline lb. .90
^-Nitroaniline lb. .85
Nitrobenzene, crude lb. . 121/.
Rectified (Oil Mirbane) lb. . 13V«
^-Nitrophenol lb. .75
p-Nitrosodimethylaniline lb. 2.90
o-Nitrotoluene lb. .15
£-Nitrotoluene lb. .90
m-Phenylenediamine lb. 1.15
p-Phenylenediamine lb. 1.75
Phthalic Anhydride lb. .55
Primuline (Base) lb. 3.00
R Salt lb. .70
Resorcinol, tech lb. 2 . 00
U. S. P lb. 2.25
Schaeffer Salt lb. .70
Sodium Naphthlonate lb. .70
Thiocarbaoilide lb. .60
Tolidine (Base) lb. 1.40
Toluidine, mixed lb. .44
o-Toluidine lb. .27
p Toluidine lb. 1 . 25
m-Toluylenediamine lb. 1.15
Xylidine, crude lb. .45
COAL-TAB COLOBS
Acid Colors
Black lb. 1 .00
1.80
2.25
.60
1.75
1.30
3.25
1.25
1.60
2.75
.70
1.40
.40
.30
.30
2.25
1.25
.42
.28
2.00
.45
1.50
1.10
.75
5.50
6.00
.15
1.40
.50
1.65
6.75
2.25
.34
.12>/«
.13V.
.75
2.90
.15
.90
1.15
1.75
.55
3.00
.75
2.00
2.25
.70
1.25
1.15
1.00
1.50
Acid Colors (Concluded)
Fuchsin lb.
Orange III lb.
Red lb.
Violet 10B lb.
Alkali Blue, domestic lb.
Imported lb.
Azo Carmine lb.
Azo Yellow lb.
Erythrosin lb.
Indigotin, cone lb.
Paste lb.
Naphtho! Green lb.
Ponceau lb.
Scarlet 2R lb
Direct Colors
Black lb.
Blue 2B lb.
Brown R lb.
Fast Red lb.
Yellow lb.
Violet, cone lb.
Chrysophenine, domestic lb.
Congo Red, 4B Type lb.
Primuline, domestic lb.
Oil Colors
Black lb.
Blue lb.
Orange lb.
Red III lb.
Scarlet lb.
Yellow lb.
Nigrosine Oil, soluble lb.
Sulfur Colors
Black lb.
Blue, domestic lb.
Brown lb.
Green lb.
Yellow lb.
Chrome Colors
Alizarin Blue, bright lb.
Alizarin Red, 20% paste lb.
Alizarin Yellow G lb.
Chrome Black, domestic lb.
Imported lb.
Chrome Blue lb.
Chrome Green, domestic lb.
Chrome Red lb.
Gallocyanin lb.
Basic Colors
Auramine, O, domestic lb.
Auramine, OO lb.
Bismarck Brown R lb.
Bismarck Brown G lb.
Chrysoidine R lb.
Chrysoidine Y lb.
Green Crystals, Brilliant lb.
Indigo, 20% paste lb.
Fuchsin Crystals, domestic lb.
Imported lb.
Magenta Acid, domestic lb.
Malachite Green, crystals lb.
Methylene Blue, tech lb.
Methyl Violet 3 B lb.
Nigrosine, spts. sol lb.
Water sol., blue lb.
Jet lb.
Phosphine G, domestic lb.
Rhodamine B, extra cone lb.
Victoria Blue, base, domestic lb.
Victoria Green lb.
Victoria Red lb.
Victoria Yellow lb.
2.50
2.50
.60
.60
1.30
1.30
6.50
6.50
6.00
6.00
8.00
8.00
4.00
4.00
2.00
2.00
7.50
7.50
2.50
2.50
1.50
1.50
1.95
1.95
1.00
1.00
1.65
1.05
2.35
2.35
2.00
2.00
1.10
1.10
2.00
2.00
.90
.90
3.00
3.00
.SO
.80
1.40
1.40
1.65
1.65
1.00
1.00
.70
.70
.35
.35
1.00
1.00
.90
.90
5.00
5.00
1.10
1.10
1.00
1.00
1.25
1.25
2.20
2.20
1.00
1.00
1.50
1.50
2.00
2.00
2.80
2.80
2.50
4.15
2.50
4.15
.75
.75
3.50
3.50
.85
.85
4.50
4.50
12.00
12.00
4.25
4.25
2.75
2.75
2.75
2.75
2.75
2.75
.70
.70
.60
.60
.90
.90
7.00
7.00
16.00
16.00
6.00
6.00
2.50
2.50
7.00
7.00
7.00
7.00
TP
1
113
v. 13
pt.l
I&EC. Industrial and
engineering chemistry
Engineering
PLEASE DO NOT REMOVE
CARDS OR SLIPS FROM THIS POCKET
UNIVERSITY OF TORONTO LIBRARY
'!»• •/'<}'! '-lllili iii'l1/''!' 'h?;! W/' Ifill flfc/PrftHH
■ ■ • ■■.' '
Live Music Archive
Librivox Free Audio
Metropolitan Museum
Cleveland Museum of Art
Internet Arcade
Console Living Room
Books to Borrow
Open Library
TV News
Understanding 9/11