64
FEEDING VALUE OF CEREALS.
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lillllllliil
Issued January 25, 1901).
U. S. DEPARTMENT OF AGRICULTURE,
BUREAU OF CHEMISTRY— BULLETIN No. 121:
H. W. WILEY, Chief of Bureau.
FOOD LEGISLATION DURING THE YEAR
KNDED JUNE 30, 1908.
BY
\V. 1). BIGELOW.
TH THE COLLABORATION OF
X. A. PARKINSON.
WASHINGTON:
GOVERNMENT PRINTING OFFICE.
1909.
ORGANIZATION OF BUREAU OF CHEMISTRY.
II. W. WILEY, Chemist and Chief of Bureau.
|. • i j i.<t. W. D. BIGELOW, Aftxixtant Chief of Bureau.
, A-. A. L. PIERCE, Editorial Clerk.
M. W. TAYLOR, Librarian.
-ion of Foods, W. I ». KH;ELO\V. r/t/V/.
ratory, L. M. TOLMAX. r /<*>/.
I jiboiatory. K. M. CH.ACE. C/nef O/K/ .-i«si»fanf Cftte/ n
aiul Wax Laboratory. O'ot appointed. ]
Division of Drugs, L. I-'. Iiief.
.iii Laboratory. (J. W. HOOVER. C7< it*/.
'nets I-ilx.raTory. W. O. EMERY, C/?ie/.
oils Lab.'iatnry. [Not appointed.]
I'h.-r, al Laboratory. [Not appointed.]
Chief Food and Drug Inspector, W. G. CAMPBELL.
Miscellaneous Division. J. K. HAYWOOD, Chief.
'.oratory. \V. W. SKINNER. Chief.
• ><1 :ind drain Laboratory. J. S. CHAMBERLAIN. Chief.
•••tiridf and Fun^iride Laboratory. C. C. MCDONNELL, Chief.
Laboratory. tuul< r CJiirf of Dirixion.
Contracts Laboratory. I'. II. WALKER, Chief.
Dairy Laboratory. <;. K. PATRICK. Chi-
Food Research Laboratory, M. E. PEXXINGTON. Chief.
Leather and Paper Laboratory, F. P. VEITCII. Chief.
Microchemical Laboratory. P.. J. HOWARD. Chief.
Sugar Laboratory, A. H. BRYAN, Acting.
Nitrogen Section, T. C. TRESCOT. /// Charge.
Special Investigations:
_ri«-:il Clu-inistry lAiiiinah. F. C. WEBER, in Charge.
_'iral ('])«• inistry t \'c.t:rTable t. J. A. Lr: PLEKr. in Charge.
_'i.-ai rin-niistry. (J. W. STILES, in I'Jmrrjc.
.\\ ClH-iiiistry. \\". P>. ALWor>u. in Chnr<j< .
Food and Drug Inspection Laboratories:
' II. SMITH. Chirf.
W. L. I»T-IMHS. Acting.
rhi. •:••_'... A. L. WINTOX. Chief.
'.. K. Il.vin. A. -fin;/.
H. Chief.
- II-LTZ. Act in</.
. I". ]'\}'vy..\'-ti»fi.
iiian Islands. II. A. I>rxcAX, Acting.
Mo.. A. V. II. MORY. Acting.
• ille. [Not appointed.]
' . HARKISO.X. chief.
'••Ik. ii. r:. DOOLITTLE. r/j/vf.
.Artinff.
Phila.i /,/,-/.
BKECH, Acting.
' (:--'i:.. A. L. KXISEI.V. Acting.
B. BIBBED Acting.
'. Chief.
;ing.
H. M. LOOM is, Act:
Issued January 25, 1900.
U. S. DEPARTMENT OF AGRICULTURE,
BUREAU OF CHEMISTRY— BULLETIN No. 121. •
H. W. WILEY, Chief of Bureau.
FOOD LEGISLATION DURING THE YEAR
ENDED JUNE 30, 1908.
BY
^Y. D. BIGELOW,
Chief ; Division of Foods,
WITH THE COLLABORATION OP
\. A. r.XUKIXSON.
WASHINGTON:
KUNMKNT PRINTING OFFICE,
1909.
LETTER OF TRANSMITTAL.
U. S. DEPARTMENT OF AGRICULTURE,
BUREAU OF CHEMISTRY,
\\'<r*Jihi</t(w, 1>. C., November 30, 1908.
SIK : I have i he honor to transmit for your inspection and approval
nipilat inn nf the food legislation during the year ended June 30,
1908. I i « ( oiniiu'inl it- publication as Bulletin 121 of the Bureau of
('heniMrv. supplementing Bulletin 112, Parts I and II, Food Legis-
lation during the Year ended June 30, 1907; Bulletin 104, covering
the year ended June 30, 1906, and Bulletin 69, Revised, Parts I to
1 X. covering all legislation prior to July 1, 1905. This compilation
i- nf -|M -rial \ alue at thi- t inie. when so many changes are being made
in the State lawi lending toward uniformity with the National food
law, and in view nf the close cooperation between State and Federal
food ollieiaU.
Revert fully, II. W. WlLEY,
Chief of Bureau.
Hon. .1 \MI > WILSON,
/ i,' "f . [(/riculttn > .
3
CONTENTS.
Page.
Federal laws 7
Tea s
Canada 9 i
Meat and canned goods , 9
Connecticut 13
:. ky 14
ruTul fiwul laws 14
i ry products. See General food la\\
Liquors. See General food la\v<.
19
19
37
37
M . 38
General food laws 38
a.l 38
M.-ut .. 39
Milk 40
41
Mississippi 42
43
food laws 43
i-ral food laws.
Milk 45
47
Dairy product* 47
Fruit 47
North Carolina 48
General food law - 48
Ohi.. 49
General food laws 49
Dairy products 51
Vinegar 52
Oklahoma 54
General food laws 54
Bread 60
Confectionery 61 '
Dairy products 61
Flavoring extracts 65
Flour : , 65
Honey? See General food laws.
1 66
M« at. ve General food laws.
Preservatives 67
Sea food. See Preservatives.
•< and condiments 67
Vinegar. Sett General food laws.
5 »
6 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
Page.
Porto Rico 68
General food law 68
Meat 68
Rhode Island 69
General food laws .- 69
Canned goods. See General food laws. ,
Confectionery. See General food laws.
South Carolina 73
Rice flour _' 73
Virginia 74
General food laws 74
Confectionery. See General food laws.
Dairy products 82
> I • a t.s. See General food laws.
\\ 'i-ronrin 85
FOOD LEGISLATION DURING THE YEAR ENDED
JUNE 30, 1908.
FEDERAL LAWS.
During the fisc-al year ended June 30, 1908, no Federal food laws
were passed with the exception of the amendment to the tea law,
\vhirh is printed herewith. The following orders, regulations, and
>ions issued by the Bureau of Animal Industry and the Board
<»f I Inspection of the United States Department of
cult iin- and \>\ tin- Bureau of Internal Revenue of the United
State- Trea-ury Department are enumerated as a matter of record,
hut are not reprinted :
Bureau «d' Animal Industry: B. A. I. Order No. 1 IT, Regulations
^ irard to Renovated Butter in Accordance with the
Ad MI Congn A; ; : «3 May 9, 1902 (July 11, 1907). B. A. I.
Ord 150, Regulations Governing the Meat Inspection of the
•'8 Department of Agriculture (effective April 1, 1908).
to B. A. I. Order No. 150, Amendment to Section 19 of
Kxempting Shipment- of Certain Inedible Grease,
Talluv. . or Other Fat from the Provi.-ion Requiring the Denaturing
of I' iible Products (April 24, 1908). B. A. I. Meat Inspection
—2 A, Colors (September 2, 1907). B. A. I. Meat Inspection
Rulings — 3 A, Xotice Regarding the Enforcement of that Portion of
Para- -a ph 5 of Section 19 of Regulation 25 of B. A. I. Order 150,
Relating to the Denaturing of Inedible Grease, Tallow, and Other
i-il «5, 1908).
Board of Food and Drug Inspection: Food Inspection Decision
71. Cerl for Imported Meats and Meat-Food Products of
Cattle, Sheep, Swine, and Goats. 75, The Labeling of Mixtures of
Cane and Maple Sirups. 76, Dyes, Chemicals, and Preservatives in
Is. 77. Certificate and Control of Dyes Permissible for Use in
Coloring Foods and Foodstuffs. 78, The Use of Labels after Octo-
1. 1907. 71), Collection of Samples. 80, Glazed Coffee. 81,
Labeling of Caramels. 82, Labeling of Coffee Produced in the Dutch
; Indies. 83, The Issue of a Guaranty Based upon a Former
Guaranty. 84, Amendments to Regulations 17 and 19. 85, Label-
ing of Bitters. 86, Original Packages: Interpretation of Regulation
2 of Rule- and Regulations for the Enforcement of the Food and
7
8 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
Drugs Act. 87, Labeling of Corn Sirup. 88, Private Importa-
tions. 89, Amendment to Food Inspection Decision 76, Relating to
ih<» Use in Foods of Benzoate of Soda and Sulphur Dioxid. 90,
The Labeling of Foods and Medicinal Mixtures for Stock and Poul-
try. 91, The Labeling of Mocha Coffee. 92, The Use of Copper
Salts in the Greening of Foods. 93, Amendment to Regulation 34.
94, The Labeling of Medicinal and Table Waters. 95, The Use of
itral Spirits Distilled from Beet Sugar Molasses in the Prepara-
tion of Whisky Compounds and Imitation Whiskies. 96, Serial
X umber Guaranty.
Bureau of Internal Revenue: Regulation No. 9, Revised July,
1907, Revised Regulations Concerning Oleomargarine, also Adul-
terated Butter and Process or Renovated Butter.
TEA.
SEC. 1. Importation of inferior tea prohibited; proviso. From and after May
first, eighteen hundred and ninety-seven, it shall be unlawful for any person
or persons or corporation to import or bring into the United States any merchan-
dise as tea which is inferior in purity, quality, and fitness, for consumption to
the standards provided in section three ° of this act, and the importation of all
such merchandise is hereby prohibited. Provided, That nothing herein shall
affect or prevent the importation into the United States, under such regulations
as the Secretary of the Treasury may prescribe, of any merchandise as tea
which may be inferior in purity, quality, and fitness for consumption to the
st.-uulards established by the Secretary of the Treasury, or of any tea waste,
tea sittings, or tea sweepings, for the sole purpose of manufacturing theine,
caffeine, or other chemical products whereby the identity and character of the
original material is entirely destroyed or changed; and that importers and
manufacturers who import or bring into the United States such tea, tea waste,
siftings, or tea sweepings shall give suitable bond, to be approved as to
ji mount and securities by the Secretary of the Treasury, conditioned that said
imported material shall be only used for the purposes herein provided, under
such regulations as may be prescribed by the Secretary of the Treasury. — As
•intruded May 16, 1908. Statutes of the United States of America, 1907-1908,
Part 1, ch. no, p. 163.
Approved March 2. 1897. United States Statutes at Large, 1895-1897, vol. 29,
ch. 358, pp. 604-607.
0 See Bui. 69, Revised, Part I, p. 7.
CANADA.
The statutes of Canada were not available and only those laws are
included of which copies could be procured from the enforcing officer.
MKAT AM> CANNED GOODS.
. 1. Short title. This Act may be cited as The Meat and Canned Foods
Act.
_'. ih-finiti"n*. In this Act, unless the context otherwise requires,
(a) "carcases" means the carcases of cattle, swine, sheep, goats or poultry;
shment" means ;my abattoir, packing house, or other premises
in which sis« -h animals are slaughtered, or in which any parts thereof or prod-
thereof, or fish, or fruit, or \ e-etables, are prepared for food for export or
are stored for export :
(c) "export " means export out of Canada, or^out of the province In which
the establishment is situated to another province;
(d) " food " includes every article used for food or drink by man, and every
ingredient intended for mixing with the food or drink of man for any purpose;
(e) "inspector" means an inspector appointed under this Act;
(/) '• .M :iieans the Minister of Agriculture;
(g) "regulations" means regulations made under the provisions of this Act.
• •ction of •inininl.i. All animals intended for slaughter in any
establishment shall be inspected as provided by the regulations.
L'. N" animal shall be allowed to enter the parts of an establishment where
slaughtering is carried on. unless it has undergone such inspection and been
found to tie healthy and tit for food.
3. K\ery animal affected, or suspected of being affected, with contagious or
other disease, shall be slaughtered under the supervision of the inspector and
I'-tl by the regulations.
'txi-H. All carcases and portions thereof of all ani-
: slaughter. -d. intended for export, shall be inspected as provided
'ing by fanners and retail butchers. Unless the Minister
otherwise diiveis. n|Nin the report of an inspector, animals owned by farmers
:-nd >:aiiL'hieivd by them on their own premises, and animals slaughtered by
: butchers on their own premises, shall not be subject to inspection under
the I Let
SEC. t;. //"/<• >e«; marks on. Every carcass, or portion thereof, found
to be healthy and fit for food, shall be marked by the inspector in such manner
as is provided !>y the regulations; and the carcass, or portion thereof, may then
l.e dealt with as the owner thereof sees fit, subject to the further* supervision of
the insjHvtor.
SEC. 7. ln*in-rtii,n ami marking of meat products. Every carcass or portion
or product thereof prepared for food in any establishment and packed in cans
:nilar receptacles, or in any package whatever, shall be subject to inspection
during the whole course of preparation and packing; and after all the require-
ments of this Act regarding inspection have been complied with, and not until
then, all such packages shall be marked by the inspector in such manner as is
provided by the regulations.
SEC. 8. n<in. The inspector may at any time re-inspect a carcass,
or any portion or product thereof, in order to ascertain whether, subsequently
to the first inspection thereof, it has undergone decomposition, or has other-
wise deteriorated, or has been tampered with or adulterated by the use of
preservatives or otherwise.
9
10 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
2. Every carcass, or portion or product thereof, sent out of an establishment,
and returned thereto for any purpose, shall not be again sent out therefrom
without re-inspection.
SEC. 9. Unhealthy meat, disposal of. Every carcass, or portion or product
thereof, found, upon inspection or re-inspection, to be unhealthy or unfit for
food, or which contains such ingredients or preservatives as may render it unfit
for food, shall be marked by the inspector in such.^manner as is provided by the
regulations, and shall thereupon be deemed to be condemned as unfit for food
and shall be disposed of as provided by the regulations.
SEC. 10. Sale, etc., of unhealthy meat. Any person slaughtering, or per-
mitting the slaughtering of, animals and selling, or offering for sale or transpor-
tation, for export a carcass, or any portion or product thereof, which is
Linhoalthy or unfit for food is guilty of an indictable offence and liable to one
year's imprisonment.
j. Kvery one who is convicted of this offence after a previous conviction for
the same crime shall be liable to two years' imprisonment.
a 11. Exemption from inspection. The Governor in Council may, upon
application of the owner thereof, exempt any establishment from the operation
of the provisions of sections 3 and 4, and of sections 6 to 10, both inclusive, of
this Act.— A* amended June 16, 1908. 7-8 Edward VII, eh. 47.
SEC. 12. Inspection and marking of packages. All articles prepared for food
in any establishment and packed in cans or similar receptacles, or in any pack-
age whatever, shall be subject to inspection during the whole course of prepara-
tion and packing ; and all such packages shall be marked with—
(a) the initials of the Christian names, the full surname, and the address, or,
in the case of a firm or corporation, the firm or corporate name and address, of
the packer ; or of the first dealer obtaining them direct from the packer who sells
or offers the said articles for sale; and such dealer shall, upon the request of an
inspector appointed under this Act, disclose the name of the packer of such
article.— A* amended June 16, 1908. 7-8 Edward VII, ch. 41.
(ft) a true and correct description of the contents of the package:
Provided, however, that if it be established to the satisfaction of the Governor
in Council that such marking would hinder the sale of any of said articles in
the British or foreign markets, he may exempt such articles from the provisions
of this section.
SEC. 13. Fish, fruit and vegetables. All fish, fruit, or vegetables used in any
establishment where these articles are prepared for export, shall be sound,
wholesome, and fit for food ; and any such articles or products thereof found in
the said establishment unsound or unwholesome shall be confiscated and de-
stroyed as provided by the regulations.
SEC. 14. Sanitary conditions. An inspection and close supervision of the sani-
tary conditions of any establishments shall be maintained as provided by the
regulations.
2. The inspector shall refuse to inspect or mark articles in any establishment
where the sanitary conditions are not in accordance with the regulations.
SEC. 15. Withdrawal of inspector and closing of establishment for violation
of Act, etc. In the event of the provisions of this Act, or any regulations,
or the lawful instruction of an inspector not being complied with in any
establishment, the Minister may withdraw the inspector therefrom, and may
refuse to it the inspection, marking, and certification of the articles prepared
therein, and may cause the establishment to be closed.
SEC. 15A. Sale in violation of Act. No person shall offer or expose or have
in his possession for sale any article subject to inspection under this Act unless
all the requirements thereof respecting the said article have been complied
with.— Added June 16, 1908. 8-7 Edward VII, ch. 47.
CANADA. 11
SEC. l<;. i:.ri,<>rt of uninspected articles. No person shall offer or accept for
export, or shall export, any articles subject to inspection under this Act, unless
its requirements regarding inspection and marking have been complied with in
i to such articles.
L1. No clearance shall be granted to any vessel carrying any carcases, or any
portions or products thereof, unless they are duly marked in accordance with
the provisions of this Act.
The provisions of this section shall not apply to meats intended for con-
sumption on board the vessels by which they are shipped from a Canadian port.
4. At the request of the owner of any establishment, the inspector in charge
thereof shall issue certificates of inspection for any carcases or portions or
products then-of intended for export. Such certificates shall be in such form
as is provided by the regulations.
:.. Notwithstanding anything in this section, the Governor in Council may,
whenever it is deemed necessary or advisable to do so, authorize the export of
any such articles without inspection.
'irking as to namr, irdyht, and date. No article subject to
inspection under this Act shall l»e offered or sold for export, or exported, under
any name intended or calculated to deceive as to its true nature.
_. No package containing any article subject to inspection under this Act
shall !>«• marked with .my label, brand or mark which falsely represents the
quantity or wight or contents of such pa- !
.:dni: any article subject to inspection under" this Act
shall be marked with any label, brand «>r mark which falsely represents the date
when the articles or goods contained therein were packed.— A* amended June
16, 1908. 7-8 Edward \ II. ,-h. 47.
. 18. Tampering tcith murk*. Kvery person who, not being an inspector,
wilfully alters, effaces, or obliterates, or causes to be altered, effaced or obliter-
ated, wholly or partially, any mark on .my article which has undergone inspec-
-hall incur a penalty of one hundred dollars.
Sic. 19. .\i,i>»intin< nt of officers. The Minister may appoint inspectors and
other officers for the carrying out of the provisions of this Act, but such appoint-
s shall be confirmed by the Governor In Council within thirty days of the
date thereof.
«>rson shall be appointed as a veterinary inspector until he has passed
such examination as Is deemed necessary by the Governor in Council.
Sic. 20. Regulations. The Governor in Council may make such orders and
regulations, not inconsistent with the provisions of this Act, as to him seem
necessary for the carrying out of the provisions of this Act.
L'. Such orders and regulations shall have the same force and effect as if em-
bodied in this An.
3. Every such order or regulation shall be published twice in The Canada
•/-.
4. Any such order or regulation may be proved by the production of a copy
thereof certified by the Minister; and such order or regulation shall, until the
contrary is proved, be deemed to have been duly made and issued on the date
thereof.
vector's certificate as evidence. The certificate of the inspector
or other officer appointed under the provisions of this Act shall, for the purpose
of this Act, be prirna facie evidence in all courts of justice and elsewhere of
the matter certified.
: Inspector's power of entry. Any inspector or other officer appointed
under the provisions of this Act may, at any time, for the purpose of carrying
into effect any of the provisions of this Act, enter any place or premises, or
12 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
any steamship, vessel or boat, or any carriage, car, truck, horse-box or other
vehicle used for the carriage of articles subject to the provisions of this Act,
but shall, if required, state in writing the grounds on which he has so entered.
SEC. 23. Obstructing inspector. Every person who refuses to admit, or who
obstructs or impedes, an inspector or other officer acting in execution of this
Act, or of any order or regulation made by the Governor in Council or the
Minister thereunder, and every person who aids-.tind assists him therein, shall,
for every such offence, incur a penalty not exceeding five hundred dollars;
and the inspector or other officer may apprehend the offender and take him
forthwith before a justice of the peace to be dealt with according to law;
but no person so apprehended shall be detained in custody, without the order
of the justice, longer than twenty-four hours.
SEC. 24. Unlawful removal. Every person who moves, or causes or allows
to be moved, any animal, or any article hi violation of the provisions of this
Act, shall, for every such offence, incur a penalty not exceeding five hundred
dollars.
SEC. 25. Bribery of inspector. The provisions of The Criminal Code respect-
ing the bribery and corruption of officials or employees of the Government
extend to all Inspectors and other persons appointed to carry out the provisions
of this Act.
SEC. !!<;. Violations of Act. Every person who violates any provision of this
Act, or of any regulation made by the Governor in Council or by the Minister
under the. authority of this Act, in respect to which no penalty is hereinbefore
provided, shall for every such offence, incur a penalty not exceeding five hun-
dred dollars.
SEC. 27. Apprehension of offenders. Any inspector or constable may, without
warrant, apprehend any person found committing an offense against the provi-
sions of this Act, and shall take any person so apprehended forthwith before a
justice of the peace to be examined and dealt with according to law ; but a per-
son so apprehended shall not be detained in custody, without the order of a
justice, longer than twenty-four hours ; and any inspector or constable may re-
quire that any animal or any article moved hi violation of the provisions of
this Act be forthwith taken back within the limits of the place whence it was
moved, and may enforce and execute such requisition at the expense of the
owner of such animal or article.
SEC. 28. Place of committing of offence. Every offence against this Act, or
against any order or regulation of the Governor in Council or of the Minister,
shall for the purpose of proceedings under this Act, or of any such order or
regulation, be deemed to have been committed, and every cause of complaint
under this Act, or any such order or regulation, shall be deemed to have arisen,
either in the place in which it actually was committed or arose, or in any place
in which the person charged or complained against happens to be.
SEC. 29. Rcc-overj/ of penalties. Every penalty imposed by this Act shall be
recoverable, with costs, before any two justices of the peace, or any magistrate
having the powers of two justices of the peace, under Part XV. of The Crim-
inal Code.— A* amended June 16, 1908. 7-8 Edward VII, ch. 47.
SEC. 30. Administration of Act. The administration of any part of this Act
may be assigned by the Governor in Council to any Minister other than the
Minister of Agriculture, and in such case the Minister to whom such assignment
is made shall have the same powers with respect to the part of this Act to him
assigned as the Minister of Agriculture now has.
>tsion of operation. The Governor in Council may suspend the
operation of any of the sections of this Act until the first day of January next.
Assented to April 27, 1907. 6-7 Edward VII, ch. 27.
CONNECTICUT.
See Appendix, Bulletin 112, Part I, page 152, for general food
law-, passed July :U. 1007, and included in that publication for con-
venience, though the compilation covered only laws passed in the
I year ended June 30, 1907.
13
KENTUCKY.
-\
GENERAL FOOD LAWS.
SEC. 1. Adulterated or misbranded food unlawful; penalty; proviso. That it
shall be unlawful for any person, persons, firm or corporation within this
State to manufacture for sale, produce for sale, expose for sale, have in his
or their possession for sale or to sell any article of food or drug which is adul-
terated or misbranded within the meaning of this act ; and any person or per-
sons, firm or corporation who shall manufacture for sale, expose for sale, have
in his or their possession for sale or sell any article of food or drug which is
adulterated or misbranded within the meaning of this act shall be fined not less
than ten dollars nor more than one hundred dollars, or be imprisoned not to
exceed fifty days or both such fine and imprisonment. Provided, That no
article of food or drug shall be deemed misbranded or adulterated within the
provisions of this act when intended for shipment to any other State or coun-
try, when such article is not adulterated or misbranded in conflict with the
laws of the United States; but if said article shall be in fact sold or offered
for sale for domestic use or consumption within this State, then this proviso
shall not exempt said article from the operations of any of the other pro-
visions of this act.
2. Food defined. That the term food, as used in this act, shall include
every article used for or entering into the composition of food or drink for
man or domestic animals, including all liquors.
SEC. 3. Uisbranding defined. For the purpose of this act, an article of food
shall be deemed misbranded :
First. If the package or label shall bear any statement purporting to name
any ingredient or substance as not being contained in such article, which state-
ment shall not be true in any part; or any statement purporting to name the
substances of which such article is made, which statement shall not give fully
the name or names of all substances contained in any measurable quantity.
Second. If it is labeled or branded in imitation of or sold under the name
of another article, or is an imitation either in package or label of another sub-
stance of a previously established name; or if it be labeled or branded so as
to deceive or mislead the purchaser or consumer with respect to where the
article was made or as to its true nature and substance, or as to any identify-
ing term whatsoever whereby the purchaser or consumer might suppose the
article to possess any property or degree of purity or quality which the article
does not possess.
Third. If in the case of certified milk, it be sold as or labeled "certified
milk," and it has not been so certified under rules and regulations by any
county medical society, or if when so certified it is not up to that degree of
purity and quality necessary for infant feeding.
Fourth. If it be misrepresented as to weight or measure or, if where the
length of time the product has been ripened, aged or stored, or if where the
length of time it has been kept in tin or other receptacle, tends to render the
article unwholesome, the facts of such excessive storage, ripening, aging or
packing are not plainly made known to the purchaser and to the consumer.
14
KENTUCKY. 15
Fifth. If the package containing it or its label shall bear any statement, de-
sign, or device regarding the ingredients or the substances contained therein,
which statement, design <>r device shall be false or misleading in any particular.
Provided, That articles of liquor which do not contain any added poisonous or
deleterious ingredients shall not be deemed to be adulterated or misbranded
within the provisions of this act, in the case of articles labeled, branded or
tagged so as to plainly indicate that they are compounds, imitations, or blends,
and tlu- word "compound," "imitation," or "blend," as the case may be, is
plainly stated on the package in which it is offered for sale. Provided, That
the term blend as used herein shall be construed to mean a mixture of like
i net's, not excluding harmless coloring and flavoring ingredients used for
the purpose of coloring and flavoring only.
4. 1 '///«'/• ration defined. For the purpose of this act, an article of food
shall !>«• .1. -fined to be adulterated:
?' any substance or substances be mixed or packed with it so as to
reduce, lower or injuriously affect its quality or strength.
ond. If any substance be substituted in whole or in part for the article.
Third. If any valuable constituent of the article has been wholly or in part
ractod; or if the product is below that standard of quality represented to
tin- purchaser or consumer.
:rth. If it Is mixed, colored, coated, polished, powdered, or stained
whereby damage Is concealed, or If it Is made to appear better or of greater
value than iMs, or if it is colored or flavored in imitation of the genuine color
or t!avnr of another substance of a previously established name.
th. If it contains added poisonous ingredient which may render such
article injurious to health, or if it contains any antiseptic or preservative which
may render rocb article injurious to health, or any other antiseptic or pre-
servathe 001 evident .•:• n. .t plainly v.-n.-d on the main label of the package.
ih. If It consists of or is manufactured from in whole or in part of a
diseased, contaminated, filthy or decomposed substainv. either animal or vege-
unflt for food, or an animal or vegetable substance produced, stored,
t in a condition that would render the article diseased, con-
Kited or unwholesome. ,,r }f jt js ;1MV j,.,rt the product of a diseased animal,
or I ! t of an animal that has died otherwise than by slaughter, or that
l upon the offal from a slaughterhouse, or if*lt is the milk from an
animal fed upon a substance unfit for food for dairy animals or from an animal
i a filthy or a contaminated stable or in surroundings that
:he milk contaminated. Provided, That any article of food which
may be adulterated and not misbranded within the meaning of this act, and
•h does not contain any added poisonous or deleterious ingredient and
which Is not otherwise adulterated within the meaning of paragraphs four,
the and Bll of wvtion four of this act, or which does not contain any filler or
Ingredient which debases without adding food value, can be manufactured or
sold, if the same be labeled, branded or tagged so as to show the exact charac-
ter then*.. f. And all such labels and all labeling of packages provided for in
any provisions of this act shall be on the main label of each package and in
such position and character of type and terms as will be plainly seen, read and
understood by the purchaser or consumer. Provided further, That nothing in
this act shall be construed as requiring or compelling the proprietors, manu-
'irers or sellers of proprietary foods which contain no unwholesome sub-
es or ingredients to disclose their trade formulas except in so far as the
provisions of this (act) require to secure freedom from adulteration, imita-
°So in Statutes.
16 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
tlon or misbranding. But in the case of baking powders, every can or other
package shall be labeled so as to show clerely * the name of the acid salt which
shall be plainly stated in the face of the label to show whether such salt is
cream of tartar, phosphate or alum. Provided further, That nothing in this
act shall be construed to prohibit the manufacture or sale of oleomargarine,
butterine or kindred compounds in a separate and distinct form, and in such
manner as^ill advise the consumer of the real Character, free from coloration
or ingredient that causes it to look like butter.
[Sections 5 to 7 relate to drugs.]
SEC. 8. Director of experiment station to make analysis, fix methods and
,//,/*; board for establishing r> julations. It shall be the duty of the
>-tor of the Kentucky Agricultural Experiment Station, or under his
direction, the head of the division of food inspection of the said station, to
make or 'cause to be made examinations of samples of food and drugs manu-
factured or on sale in Kentucky at such time and place and to such extent as
he may determine. He shall also make, or cause to be made, analysis of any
sample of food or drug which the State Board of Health or the State Board
of Pharmacy may suspect of. being adulterated or rnisbranded, and of any
sample of food or drug furnished by any Commonwealth's, county or city
attorney of this State. And the said director may appoint such agent or
agents as he may deem necessary, who shall have free access at all reasonable
hours for the purpose of examining into places wherein any food or drug prod-
uct is being produced, manufactured, prepared, kept or offered, for sale, for
the purpose of determining as to whether or not any of the provisions of this
act are being violated, and such agent or agents upon tendering the market
price of any article may take from any person, firm or other corporation, a
sample of any article desired for examination.
The director of said Experiment Station is hereby empowered to adopt and
fix the methods by which the samples taken under the provisions of this act
shall be analyzed or examined, and to adopt and fix standards of purity,
quality or strength, when such standards are necessary or are not specified or
fixed herein or by statute. Provided, That such standards shall be published
for the information and guidance of the trade. Provided further, That for
the purpose of uniformity, when such standards so fixed differ from the
legally adopted standards of the United States Department of Agriculture, the
director of said station shall arrange for a conference between the proper
food control representatives of the United States Department of Agriculture
and the director of said station and the representatives of the trade to be
affected, for the purpose of arriving, if possible, at a uniform state and national
standard. Provided further, That in the case of final dispute the validity of
such standards adopted by the director of said station shall be determined by
the Courts under the rules of evidence. And Provided further, That when the
standard or nomenclature for any food or food product has been determined
by the Supreme Court of the United States such standard or nomenclature
shall govern in the enforcement of the provisions of this act. Provided further,
That all rulings pertaining to sanitation under this act shall be collaborated in
connection with the State Board of Health. And provided further, That at
the regular annual meetings of the Kentucky Pharmaceutical association and
the Kentucky State Medical association each of said associations shall elect
one representative, which representatives, together with the director of said
station shall make and establish all rules and regulations for the governing
and carrying out of the provisions of this act relating to drugs.
a So in Statutes.
KENTUCKY. 17
SEC. 9. Prosecution. Whenever any article shall have been examined and
found to be adulterated or misbranded in violation of this act, the Director
shall certify the facts to the Commonwealth's attorney of the district, or to
the county attorney of the county, or the city attorney of any city or town,
in which the said adult era ted or misbranded food or drug product was found,
together with a statement of the results of the examination of said article of
fund or drug, duly authenticated by the analyst under oath and taken before
some officer of this Commonwealth authorized to administer an oath having
::1. And it shall be the duty of every Commonwealth's attorney, county
attorney and city attorney to whom the Director of said station shall report
any violation of this act or to whom the State Board of .Health, or the State
P.oard nf Pharmacy. ..r to whom the chief health officer of any county, city or
town shall report any such violations, to cause proceedings to be commenced
against the party so violating the act, and the same prosecuted in manner as
required by law. Provided, however, That in case of the first charge or finding
the man or dealer shall be notified of the findings and be given a
hearing within fifteen days before a report is made to the Commonwealth's,
j as herein provided. Provided further, That where
more than one sample of the same brand of product has been taken and
examined, the :irst tindini: or charge shall be construed to apply to all samples
so taken, and notice and hearing shall apply to all such samples.
rovisos. Said station shall make an annual report
to the Covernor upon adulterated food or drug products in addition to the
rep"i!- required by law which shall not exceed one hundred and fifty pages,
and su.b annual reports shall be submitted to the General Assembly at its
• 1 said station may issue from time to time a bulletin giving
the i :he inspections and of all analyses of samples taken or submitted
ination under this act, together with the names of the parties from
i the samples were taken, or where the inspections were made, and as far
the manufacturers, the number of samples found to be
,e number found not adulterated, and other information which
may ! nufact urers or dealers in food of a drug products or
idnl, however. That before such publication is made the
manufacturer ->f the irttclc and the dealer shall be furnished a true copy of the
warding the article at least thirty days before the publi-
•i and hearini: L'i\en the dealer and manufacturer, and any statements or
explanations made by such manufacturer shall be included in the same place and
I with the publication : irding the article. And provided further,
That if at the bearing of the manufacturer or dealer, as provided by section 9
hereof, said manufacturer shall produce the affidavit of a competent analytical
chemist controverting the finding of said station or its director or chemist, as
tin* case may be, and affirmatively showing that there is neither adulteration or
misbrandini: of such article under the provisions of this act, then there shall be
no publication of either the name of the manufacturer or dealer, or of the name
of the brand of the article until after a trial and a verdict of guilty as herein
pro\ ided. And provided further, That where prosecution is made for violation of
any of the provisions of this act, no official publication shall be made of the
result of the inspection and analysis until the matter has been finally adjudi-
cated, and in case of appeal, by the court of last resort.
. 1 1. Cost of analysis; «;>/>/-r>/>nu/io/i; expenditures. Said Experiment Sta-
tion shall receive seven dollars and fifty cents ($7.50) for the analysis or exam-
ination of any sample of food or drug taken or submitted in accordance with
a So in Statutes.
j>9— Bull. 121—09 2
18 FOOD LEGISLATION, YEAH ENDED JUNE 30, 1908.
this act, ami expenses for procuring samples of food and drugs and in making
inspections into the condition of and wholesorneness and purity of the food pro-
,l:i« -,..!. manufactured or sold in food factories, grocery stores, bakeries, slaugh-
tering houses, dairies, milk depots or creameries, and all other places where
foods are produced, prepared, stored, kept or offered for sale ; for studying the
problems connected with the production, preparation and sale of foods ; for ex-
pt-rt witnesses attending grand juries and courts; clerk hire and all other
.-uses necessary for carrying out the provisions of this act. Provided, The
total ivMHHiFe from all sources shall not exceed in any one year thirty thousand
dollars ($30,000.00.)
Tin- Board of Control of said Experiment Station shall furnish to the Auditor
nf Public Accounts an itemized statement of the expenditures of money under
this act. The expenditures reported to the Auditor shall be paid by the Com-
monwealth to the treasurer of the Experiment Station upon the written request
of the Board of Control of the said Experiment Station, and the Auditor for
the payment of the same is directed to draw his warrant upon the Treasurer
as in all other claims against the Commonwealth.
!± riling of label, brand, etc. When any manufacturer shall offer any
article of food or drug for sale in the State he shall file with the director of the
said station, when requested by him, the name of the brand, the name of the
product, the place of its manufacture or preparation, and a true copy of all
labeling used thereupon. Failure* to so file within thirty days shall be punished
as provided in section 1 of this act.
13. Guaranty as evidence. In all prosecutions under this act, the courts
.-hall admit as evidence a guaranty which has been made to the holder of the
guaranty by any manufacturer or wholesaler residing in this State, to the effect
that the product complained of is not adulterated or misbranded within the
provisions of this act. And said guaranty, properly signed by the wholesaler,
jobber or manufacturer or other party residing within this State from whom
the holder of the guaranty may have purchased the article or articles complained
of, and containing the full name and address of the party or parties making the
sale of such article to the holder of the guaranty, and in the absence of any
proof that the article or articles complained of were adulterated or misbranded
after they had been received by the holder of the guaranty, shall be a bar to
prosecution of the holder of such guaranty under the provisions of this act.
14. Repeal. All acts or parts of acts inconsistent herewith are hereby
repealed, but this said act shall not be construed to repeal Chapter 48 of the
Acts of the General Assembly of 1906, entitled, "An Act to regulate the sale of
concentrated commercial feeding stuffs, defining same and fixing penalties for
violations thereof."
So much of this act as relates to drugs and liquors shall not take effect until
on and after January 1, 1909.
Approved March 13, 1908. Acts of 1908, ch. 4, pp. 10-22.
DAIRY PRODUCTS.
See General Food Laws.
LIQUORS.
See General Food Laws.
LOUISIANA.
The food and drug regulations of the Louisiana board of health
have the force of law and are therefore quoted in full except when
they are the same a< the Federal law, regulation, or standard on a
given point, in which case the appropriate section is referred to.
KKGULATIONS.
i: > and Regulations. The Louisiana State Board of
.•mil establishes the following Rules and Regulations
Mire, sale, and insert iou of foods, liquors, waters, and
drills within tin- State.
Tin- Rules and lieu-illations of the Louisiana State Board of Health govern-
ing tin- manufacture, sale and Inspection of foods, drugs, liquors or waters,
shall l»e known and referred to as " The Food and Drug Regulations of the
Loni tOftld at Health."
I'l-'Jiifnthiff ailulti-rntiini or niixbramlinfl of food and drug*. It shall
l»e unlawful f«»r any person or Arsons to manufacture within this State any
article of food, drugs, liquors or waters which is adulterated or misbranded
within the meaning of these Regulations; and any person who shall violate
ions of these Regulations shall be punished as provided for
REG. 3. rrnhitiitiii'j importation or exportation of advltcr<tt< d or misbranded
f<»»l, ilrnij.'i, li'iimrs or waters. That the introduction into this State from
any other State or Territory, or from the District of Columbia, or from any
'imtry, of any article of food, drugs, liquors or waters, which is
adu: -branded within the meaning of these Regulations is hereby
prohibited. H.it any person who shall receive from any State or Terri-
; Columbia or foreign country, and having so received,
shall deliver in unbroken or broken packages, for pay or otherwise, or offer to
delher to any other person any such article so adulterated or misbranded within
the meaning of these Regulations, or any person who shall sell or offer for
in his possession for sale in this State any such adulterated or
misbranded foods, drugs, liquors or waters, shall be punished as provided for
•t9S of 1
Pro\ided: That no article shall be deemed misbranded or adulterated within
the provisions of these Regulations, when intended for export to any foreign
country and prepared and packed according to the specifications or directions
of the foreign purchaser when no substance is used in the preparation or pack-
ing thereof in conflict with the laws of the foreign country to which said article
o be shipped: but if said article shall be in fact sold or offered
for >a e [( r .!• IP. s Tie use or consumption, then this provision shall not exempt
said article from the operation of any of the other provisions of these Regula-
19
20 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
Broken or unbroken packages defined. The term "Broken or unbroken
package" as used in these Regulations, is the original package or part thereof,
carton, case, box, barrel, bottle, phial, or other receptacle put up by the manu-
facturer to which the label is attached, or which may be suitable for the at-
tachment of a label, making one complete package of the food, drug, liquor or
water article.
The original package contemplated includes bpth the wholesale and the retail
packages.
REG. 4. State Food Commissioner, Dairy Commissioner, Analyst. The Presi-
dent of the Louisiana State Board of Health shall be ex officio State Food
Commissioner. The State Food Commissioner may, with the advice and consent
of the Louisiana State Board of Health, appoint two or more Assistant Com-
missioners, each one of acknowledged standing, ability, and integrity, one of
whom shall be an expert in the matter of dairy products, and one of them shall
be a practical and Analytical Chemist, who shall be known as the State Analyst.
The salaries of each assistant shall be fixed by the State Food Commissioner,
by and with the consent of the Louisiana State Board of Health. In case of the
absence or inability of the State Analyst to perform all the duties of his office
or for the purpose of expediting the work of the Department, the State Food
Commissioner may appoint some competent person to assist in the same tem-
porarily.
REG. 5. Inspectors. The State Food Commissioner shall have authority, by
and with the consent of the Louisiana State Board of Health, to appoint neces-
sary inspectors, to assist in the work of the State Food Commissioner at such
times and for such periods of time as may be required in the enforcement of
the dairy, drug and food laws of the State. Such Inspectors shall have the
same right of access to places to be inspected as the State Food Commissioner.
The compensation of such Inspectors shall be fixed by the State Food Commis-
sioner, by and with the consent of the Louisiana State Board of Health.
REG. 6. Duty of State Food Commissioner. It shall be the duty of the State
Food Commissioner to enforce all the rules and regulations herein provided
for or that may hereafter be enacted by this Board regarding the production,
manufacture or sale of dairy products or the adulteration of any article of
food or drugs, liquors or waters, and personally or through his assistants, to
inspect any article of food, drugs, liquors or waters, made or offered for sale
or held in possession for sale, which he may, through himself or his assistants,
expect or have reason to believe to be impure, unhealthful, adulterated or mis-
branded, and to prosecute or cause to be prosecuted any person or persons, firm
or firms, corporation or corporations, engaged in the manufacture or sale of any
adulterated or misbranded article or articles of food, drugs, liquors or waters,
contrary to these Regulations.
REG. 7. Examination of foods, drugs, liquors or waters, collection of samples.
Methods of analysis. The examination of foods, drugs, liquors or waters shall
be made by the State Analyst or his Assistants under the direction of the State
Food Commissioner for the purpose of determining from such examinations
whether such articles are adulterated or misbranded within the meaning of
these regulations, and if it shall appear from any such examination that any
of such specimens are adulterated or misbranded within the meaning of these
Regulations, the State Food Commissioner shall cause notice thereof to be given
to the party from whom such sample was obtained ; any party so notified shall
be given an opportunity to be heard under such other rules and regulations as
may be prescribed by this Board, and if it appears that any of their rules and
regulations have been violated by such party, then the State Food Commis-
sioner shall at once certify the facts to the District Attorney of the District
LOUISIANA. 21
wherein the offense was committed with a copy of the results of the analysis
or the examination of such article, duly authenticated by the Analyst or officer
making such examination under the oath of such officer: after judgment of
the Court, nut ire shall be given by publication in such manner as may be
prescribed by this Board.
. s. Cttllvction of samples. Samples of broken or unbroken packages
shall be collected only by Inspectors appointed by the State Food Commis-
sioner, or by tli" Health. Food, or Drug Officer of the cities and towns of
Louisiana. Samples may be purchased in the open market, and if in bulk, the
marks, brands or tags upon the package, carton, container, wrapper or accom-
panying printed or written matter shall be noted. The Inspector shall also note
the nanios of the vendor and agent through whom the sale was actually made,
ther with the date of purchase. The Inspector shall purchase representa-
tivi- samples. A sample taken from bulk goods shall be divided into three (3)
parts and ••aeh part shall be labeled with the identifying marks-. All samples
shall be sealed by the Inspector with a seal provided for the purpose. If the
package be less than four (4) pounds, or in volume less than two (2) quarts,
tlnvc (3) packaged of approximately the same size shall be purchased when
practicable, and the marks ;md tags upon each noted as above. One sample
shall be delivered to the party from whom purchased, one sample shall be sent
to Hi.- Food Laboratory of the State Analyst, and the third sample shall be
held under seal by the State Food Commissioner.
Rio. 9. Methods 0 I nless otherwise directed by the State Board
of 1!« i ih the methods of analysis employed shall be those prescribed by the
Association of Official Agricultural Chemists and the United States Pharma-
cop.eia.
REG. 1". u.ni-iny*. 'Ai Wlu-n the examination or analysis shows that the
provisions of the '* Food and 1 >i M_- I filiations of the Louisiana State Board of
•h" have been violated, notice of the fact together with a copy of the
findings shall be furnished to the party or parties from whom the sample was
a date shall be fixed at which such party or parties may be heard
re the state Food Commissioner, or such other official connected with the
Food and Drug Iusi>ection service as may be commissioned by the State Food
Commission, -r for that punx>se; the hearings shall be held at a place to be
. -iated by the <>od Commissioner most convenient for all parties
•rned. These hearings shall be private and confined to questions of fact.
The parties interested therein may appear in person, or by Attorney, and may
propound interrogatories, and submit oral or written evidence to show any
fault or error In the findings of the Analyst or Examiner. The State Food
Comnii» order a re-exa initiation of the samples or have new samples
drawn for further examination.
When an article examined by the State Analyst is found to come in conflict
with the regulations of the Louisiana State Board of Health, a written notice
shall be served at once on the person or persons, or dealer or dealers, offering
anie for sale, warning him or them not to sell or expose for sale such con-
demned article or arti'
(B) Whenever it would appear to the best interest of the public health and
re. the Food Commissioner of the Louisiana State Board of Health is re-
quired to render such condemned articles of food, drugs, liquors or waters,
unlit for consumption by man or animals.
(C) In the event that such person or persons, shall continue to violate these
Regulations by selling, offering for sale, or hold in possession for sale or barter,
such condemned article or articles, the State Food Commissioner shall lay
22 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
before the District Attorney of the District in which the violation occurred, the
,nce of such violation, together with a. copy of the analysis of the State
\nalvst.
(D*) In the event the District Attorney should fail to promptly institute pro-
ceedings in a court of competent jurisdiction, the State Food Commissioner
shall place the whole matter in the hands of the Attorney General of the State.
11. Definition of the words foods' and drugs as used herein. (A) The
term dn« as used In these Regulations shall include all substances, compounds,
and preparations recognized in the United States Pharmacopoeia or National
Formulary, for internal or external use, and any other substance or mixture of
sul.stam-e's intended to be used for the cure, mitigation or prevention of disease
of either man or other animals.
(B) The term "food" as used herein, shall include all articles intended for
fo.,.l. drink, confectionery, condiment, or used in the preparation thereof,
whether simple, mixed, or compound.
;•_'. Food adulterations defined. For the purposes of these Regulations,
an article shall be deemed to be adulterated in case of foods: See Standards
for Foods, Reg. No. 45; [also the Federal Food and Drugs Act, " Sec. 7. In the
case of food," 1 to 6, inclusive, with the addition of the following clause after
•• Fifth "] : Not excluded under this provision are substances properly used in
the preparation of food products for clarification or refining, and elimination in
the further process of manufacture.
Powdering, eoating, and staining. [See Federal Reg. 12.]
13. Misbranding. [See Federal Food and Drugs Act, sec. 8, also.]
In ease of drugs: * * *
Fourth — If the package containing it or its label shall bear jiny statement,
design or device which shall be false or misleading in any particular.
Provided : That an article of food which does not contain any added poison-
ous or deleterious ingredients shall not be deemed to be adulterated or mis-
br.-mded in the following cases:
First — In the case of mixture or compounds which may be now or from time
to time hereafter known as articles of food, under their own distinctive names,
and not an imitation of or offered for sale under the distinctive name of another
jirticle, if the name be accompanied on the same label or brand with a statement
of the place where said article has been manufactured or produced.
ond — In the case of articles labeled, branded or tagged so as to plainly
indicate that they are compounds, imitations, or blends, and the word " com-
pound," " imitation," or " blend " as the case may be, is plainly stated on the
package in which it is offered for sale. Provided: That the term blend, as
nsed herein, shall be construed to mean a mixture of like substances.
REG. 14. Label, (a) The term "label" applies to any printed, written, pic-
torial, or other matter upon or attached to any package of a food or drug prod-
uct, or any container thereof, including ink written, typewritten, or stencilled
labels of druggists.
(b) The principal label shall consist, first — the name of the substance or
product; the name of place of manufacture in the case of food compounds or
mixtures; words which show that the articles are compounds, mixtures or
blends; the words "compound," "mixture" or "blend," or the words desig-
nating the substances or their derivatives, and proportions required to be named
in the case of drugs; and in the case of foods, the constituents are to be named
in the order of their relative proportion.
All these required words shall appear upon the principal label with no inter-
vening description or explanatory reading matter.
LOUISIANA. 28
MM.!— if the name of the manufacturer and place of manufacture are given,
they shall a!>o appear upon the principal label.
Third— Klsewhere upon tin- principal label other matter may appear in the
description of the manufacturer.
(c) The principal label on food or drugs for domestic commerce shall be
printed in Knglish (except as hereinafter provided for), with or without the
foreign label iu the language of the country where the food or drug product is
produced or manufactured.
The size of type shall not IK» smaller than 8-point (brevier) caps: Provided,
that in case the size of the package will not permit the use of 8-point (brevier)
cap type, the si/.e of tin- type may In- reduced proi>ortionately.
id i The form, character and appearance of the labels, except as provided
••. ar» left to the judgment of the manufacturer.
it- 1 i lescriptive matter upon the label shall he free from any statement,
! or device regarding the article or the ingredients or substances contained
therein, or quality thereof or place of origin, which is false or misleading in any
particular.
(f) An article containing more than one food product or active medicinal
agent inded if nam* .stiturnt.
(g) The term " design " or •• de\ ire" applies to pictorial matters of every
description, and to abbreviations. rs. or signs for weights, measures or
names of substance*.
( h i The use of any false or misleading statement, design or device shall not
he just id. . - the opinion of an expert or other person,
art of the lalx»l. nor by any descriptive matter explaining the
.»• false or misleading stat-Mm-ni. design or device.
. [See Federal Reg. 18-20 and sees, (b)
and -1.)
. [See Federal Reg. 20.]
HII A color or flavor cannot be employed to Imitate any natural product or
ame and quality, except as especially provided
for in Regulations 38 and 45 — sections covering Root Beer, Candy and Con-
fectloi
I in it nt inn. [See Federal Regs. 21-22.1
Ki ••* or compounds, with distinctive names. [See Federal
-T.|
RK. branding not a complete guarantee. [See Federal Reg. 23.]
s* of branding. [See Federal Reg. 24.]
•ntutinn. [See Federal Reg. 25.]
REG. 19. MI/. [See Federal Reg. 26.]
20. [Rein' ngs.]
"•n <>f rnir tnatt-ri'ilt. The State Food Commissioner, when
he devms it necessary, shall examine or cause to be examined, the raw mate-
rials used in the manufacture of food and drug products, and determine whether
tilthy. decomi>osed, or putrid substance is used in their preparation.
_'. Wnrkiny fnnnuln r«]inr«l. The State Food Commissioner shall
have furnished him on demand a certified copy of the working formula used
in the manufacture of any compound of drugs, foods, liquors or waters, when
in his judgment the safety of the public health and the enforcement of these
lations demand it. It being well understood that said certified copy be
and remain the property of the manufacturer furnishing the same; and shall
• led strictly as a confident ial communication.
Rt-lnti- to <lru<j*.\
24 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
REG. 26. Substances named in drugs or foods. [See Federal Reg. 28, a, b, c,
and f.]
The following articles shall be included in the above list and become subject
to the rules and regulations governing it on and after October 1, 1908 :
Nux vomica, its active principles and preparations.
Gelsemlum, its active principles and preparations.
Physostigma, its active principles and preparations.
Belladonna, its active principles and preparations.
Scopola, its active principles and preparations.
Hyoscyamus, its active principles ard preparations.
Stramonium, its active principles and preparations.
Veratrum viride, its active principles and preparations.
Staphisagria, its active principles and preparations.
Aconite, its active principles and preparations.
Colchicum, its active principles and preparations.
Pilocarpus, its active principles and preparations.
Pelletierine, its active principles and preparations.
Conium, its active principles and preparations.
Scoparius, its active principles and preparations.
Digitalis, its active principles and preparations.
Convallaria, its active principles and preparations.
Strophanthus, its active principles and preparations.
Male fern, its active principles and preparations.
Santonin, its active principles and preparations.
Ergot, its active principles and preparations.
Gossypii cortex, its active principles and preparations.
Elaterium, its active principles and preparations.
Croton oil, its active principles and preparations.
Cantharides, its active principles and preparations.
Antimony, its compounds and preparations.
Mercury, its compounds and preparations, except calomel and mercury in
metallic state.
Arsenic, its compounds and preparations.
Potassium cyanide and hydrocyanic acid.
Carbolic acid.
Any synthetical compound having the property of relieving pain, producing
Bleep, or reducing temperature.
REG. 27. [Relates to drugs.]
REG. 28. Statement of weight or measure. [See Federal Reg. 29, also the fol-
lowing] :
(c) In the case of alcohol the expression "quantity" or "proportion" shall
mean the average percentage by volume in the finished product.
(d) In the case of the other ingredients required to be named upon the label,
the expression " quantity " or " proportion " shall mean grains or minims per
ounce or fluid ounce, per unit, per tablet, pill, etc., and also, if desired, the
metric equivalents therefor, or milligrams per gram or per cubic centimeter, or
grams or cubic centimeters per kilogram or per litre.
REG. 29. Imported food and drug products. Food products intended for ex-
port containing added substances not permitted in foods intended for consump-
tion in this State, but in accordance with the directions of the foreign purchaser,
must be kept separate and labeled to indicate that they are for export.
If these products are not exported, they shall not be allowed to be sold, bar-
tered or given away for consumption in this State.
LOUISIANA. 25
Meat and meat food products as well as all other food and drug products of a
kind forbidden entry into or forbidden to be sold, or restricted in sale in the
country in which made or from which exported, must not be sold, bartered or
given away in this State.
REG. 30. Denaturing. [See Federal Reg. 34.]
'ruction t<> //(x/.r, tors. In sending in samples for analysis to this
Department of any manufactured product, the following information must
accompany each sample, to-wit :
(a) Name and location of manufacturer or dealer. If bought of jobbers, the
firm name and location plainly written in ink.
Brand or name of article, any representation by seller as to quality or char-
.
To enable correct analysis to be made, not less than the following quantities
•h article should be sent :
I'.read, not less than 16 ounces.
r.utter, not less than 8 ounces.
Baking powder, not less than 1 small can.
Beer, not less than 1 pint.
Buckwheat Hour, not less than 8 ounces.
Cheese, not less than 6 ounces.
Candy, not less than 8 ounces.
Cocoa and
< ho. ..LI t*. in small original package.
Cream of tartar, not less than 1 ounce.
Cream, not less than 4 ounces.
Extracts, not less than 2 ounces.
>. not less than 8 ounces.
Jellies, not less than » Ik. or small original package,
.lams, not less tban * Ik. or small original package.
in..!-, not less than 1 pint.
I. a id. not less than 4 ounces.
Map!.- suL-ar. not less than 1 pound.
syrups, not less than 1 pint.
Milk, not less than 4 ounces.
Olive oil, not less than 4 ounces.
Pres. • less than J lb., or small original package,
es, not less than 4 ounces,
ss tban 8 ounces.
Vinegar, not less than 1 pint.
Wine, not less than 1 pint.
Goods should be procured in original package when put up in packages con-
taining not more than two pounds solid or one-half gallon liquid measure.
«;. 32. Baking > No person in this State shall make or manufacture
baking powder or any other mixture or compound intended for use as baking
ler, or sell, exchange, deliver, or offer for sale or exchange, such baking
powder, or any mixture or comi>ound intended for use as baking powder, unless
its composition be distinctly shown by a label on the outside and face of which
is print.d with black ink in a legible tyne, with roman letters not less than
:>t — brevier — cap on a white or light black background, the manufacturer's
name and the place of manufacture and in a conspicuous place on the face
of the label of such package of baking powder and with letters similar in size,
the name of the acid ingredient together with a list of all the ingredients enter-
ing into its composition.
26 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
Provided, the use of any substance deemed poisonous or injurious is hereby
prohibited and the use thereof in the manufacture of baking powder is hereby
declared unlawful. Baking powders must yield at least 8 per cent available
carbon dioxide. The use of argolite, terra alba and all other mineral fillers is
prohibited.
linking powders must have specific name of the powder on the label and no
tagmltoQt can be named as a component of the powder not found in the article.
.;. 33. To regulate tlir manufacture and sale of substitutes of butter.
(a) That for the purpose of these regulations every article, substitute or com-
pound of any other than that which is produced from pure milk or cream, there-
from made in a semblance of butter -and designated to be used as a substitute
fur butter made from pure milk or its cream, is hereby declared to be imita-
tion butter.
Provided : That the use of salt and harmless coloring matter for coloring the
product of pure milk or cream shall not be construed to render such product
an imitation.
(b) No person shall coat, powder or color with annato or any injurious color-
ing matter whatever, any substance designed as a substitute for butter whereby
such substitute or product so colored or compounded shall be made to resemble
butter, the product of the dairy and sold as such. No person shall combine any
animal fat with butter and sell the same for consumption.
Provided: nothing in these regulations shall be construed to prohibit the
use of salt, rennet and harmless coloring matter for coloring the product of
pure milk or cream from the same.
(c) No person shall produce or manufacture any substance or semblance in
imitation of natural butter, nor sell or keep for sale, barter or give away, nor
offer for sale any imitation butter made, manufactured, compounded or pro-
duced in violation of this Regulation whether such imitation butter shall be
made or produced in this State or elsewhere; this Regulation shall not be con-
strued to prohibit the manufacture and sale under the Regulations hereinafter
provided of substances designed to be used as a substitute for butter, and not
manufactured or colored as herein provided.
(d) Every person who lawfully manufactures any substance designed to be
used as a substitute for butter, shall mark by branding, stamping or stenciling
upon the top side of each box, tub, firkin, or other package in which such
article shall be kept, and in which it shall be removed from the place where it
is produced, in a clear and durable manner in the English language the word
" Oleomargarine " or the word " Butterine " or the words " Substitute for But-
ter " or the words " Imitation Butter " in printed letters, in plain roman type ;
each of which shall not be less than three-fourths of an inch in length.
(e) It shall be unlawful to sell or offer for sale, barter or give away, any
imitation butter without informing the purchaser thereof, or the person or per-
sons to whom the same is offered for sale, that the substance sold or offered
for sale is imitation butter.
< f i No person by himself or with others shall ship, consign or forward, by
any common carrier whether public or private, any substance designed to be
used as a substitute for butter, unless it shall be marked or -branded on each
tub, box, firkin, jar or other package containing the same, as provided in this
Regulation, and unless it be consigned by the carriers and receipted for by its
true name.
(g) No person shall have in his possession or under his control, any substance
designed to be used as a substitute for butter unless the tub, firkin, jar, box or
other p;i< mining the same be clearly and durably marked as provided
in this Regulation.
LOUISIANA. 27
Every IM.TSOU who shall have possession or control of any imitation butter
for th*« purpose of selling, bartering, or giving away the same, which is not
marked ns required by the provisions of this Regulation, shall be presumed to
have known during the time of such possession or control, the true character
and name as fixed by this Regulation of such product.
(h> Whoever shall have possession or control of any imitation butter or
-ubstance designed to be used us a substitute for butter contrary to the
provisions of this Regulation, fur the puri>ose of selling the same or offering
the sam«- i'or sale, barter or give away, shall be held to have possession of such
property with intent to use it in violation of this Regulation.
(i) Whoever shall d. : >e or remove any mark provided by this Regu-
lation, with intent to mislead, deceive or violate any of the provisions of this
lation, shall be held liable to the penalties herein provided for a violation
of any of these Regulati. '
(j) That no person, firm, corporation, agent, or employe shall manufacture,
sell, a sal*' in this state, any butter that is produced by taking
•••riu'inal jui-kin:: it r. «r other butter, or both, and melting the same,
go that the butter fat OM I-.- drawn off or extracted, then mixing the said
butter tat with skimmed milk, or milk, or cream, or other milk product and re-
rhurning <T p-woruini: the said n- :\ture. or that produced by any process that
Minionly known as boiled, process, or reno\ated butter unless the same is
led in this Regulation.
ik --n, firm, corporation, agent or employe shall sell, offer or expose
liver to pun-baser any boiled, process, or
renovated butter unless the words: ••Renovated Butter" shall be plainly
branded with troth | at least three-fourths of an inch in
lemrih on i he • • li tub. or box. or pail, or other kind of a case
or pack., ;.er of prints or rolls in which it is put. If such
but i' le uncovered or not in a case or package, a placard con-
taining' the label so printed, shall be attached to them in such a manner as to
.1 l-y the purehasei. The branding or marking of all
ages shall be in tl e, in a conspicuous place so 'as to be
1 read by the purchaser.
(!i Kvry hotel, restaurant or boanlinir house, using any imitation, pro-
cessed, CM d butter, must state the true nature of the imitation or
• ssed butter used on the bill of fare or on a placard conspicuously placed,
and printed in bold tyj>e ami in the English language.
inn The siate Food < •.'tiunissioner and his assistants, -experts, chemists or
;s shall have access and ingress to all places of business, factories, stores,
and buildings used for the manufacture or sale of butter. They shall have
power ami authority to open any tub, box, pail or other kind of case or pack-
ontaining any butter that may be manufactured, sold or exposed for sale.
;. < 'i ml ii. confectionery, cocoa, chocolate, (a) In the case of con-
fectio;
It shall be considered adulterated if it contains terra alba, barytes talc,
chrome yellow, or other mineral substance or poisonous color or flavor or
othe: at deleterious or detrimental to health, or any vinous, malt or
spirit oiis liquor or compound or narcotic drug.
.dy must not be wrapped in tin foil in direct contact with the candy.
REG. 35. f'nnm-il goods. No packer or dealer in preserved or canned fruits
and vegetables or other articles of food shall sell or offer for sale such canned
rred fruits and vegetables or other articles unless they shall be en-
tirely fr. mces or ingredients deleterious to health, or use dyes
28 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
or coloring matter whereby their true character would be disguised or infe-
riority concealed.
The addition of sugar to a substance not naturally sweet, converting it into
a substance which might seem naturally sweet is permitted, if the label plainly
indicates that sweetening material has been added.
All soaked or bleached goods or goods put up from products dried before
canning shall be plainly marked, branded, stamped or labeled as such with
tin- words "Soaked" or "Bleached goods" in letters of equal size to that of
the name of the product and bearing the name of the article and name and
ad.lress of the packer or dealer who sells same.
36. Cold storage. The sale of milk or cream that has been kept over 24
hours in cold storage, the sale of fish that has been kept over 24 hours in cold
storage, the sale of meat that has been kept over three weeks in cold storage is
prohibited unless the facts in regard to the same are certified to the purchaser.
37. Coffee. Coffee must be true to name.
It must not be coated, colored or polished when such coating, coloring or
polishing injures the coffee, or conceals some damage or inferiority. .
Imitations containing no coffee cannot be sold as coffee compounds, but must
be sold as imitation coffee, with the statement that they contain no coffee.
Compounds of coffee and chicory, or of coffee and any other harmless sub-
stitute allied to it, either in flavor or strength and not used simply as an adul-
terant may be sold when labeled Coffee Compound and such compound must
state on face of label the names of the ingredients used in making the com-
pound in the order of their relative proportions, in type of equal size and promi-
nence.
REG. 38. Fruit syrup, soda water syrup, pop, soft drinks, etc. Drinks con-
taining less than two per cent of alcohol, fruit syrups, soda water syrups, pops,
soft drinks, etc., shall not contain any saccharin, salicylic, or boric acid, their
derivatives, or any harmful coloring matter or preservative. All drinks con-
taining less than two per cent of alcohol, fruit syrups, soda water syrups, pops,
soft drinks, etc., made from any substance except the natural extract of fruit,
or flavored or colored with synthetical products, must have the word " artifi-
cial " printed on the label of the package in the same size, style and color of
letter and background as the name of the article, and in such a manner as to
show that they have no relation whatsoever to the fruit which they imitate.
All soda fountains or places where the above mentioned "artificial"' articles
are sold or served, shall have printed on a placard the words, "artificial
drinks " and hung in front of the fountain or in a conspicuous place.
See Reg. 45 for list of permitted " Coal Tar Dyes."
The use of 1-10 of one per cent of benzoate of soda, is permitted in natural or
artificial fruit syrups.
The use of saccharin in any food product is prohibited.
The terms " Artificial " and " Imitation " may be used synonymously.
REX;. 39. Honey. No person, firm or corporation shall offer for sale, or pos-
sess with intent to sell, barter or give away, honey manufactured from or mixed
with glucose, sugar, or syrup of any kind, or any substance not the legitimate
product of the honey bee, unless the package containing same is so marked
and represented as such and bearing a label upon the package printed in heavy
Gothic capitals, 18 point, with the name of the person manufacturing or mixing
the same, and the name of the substance or material from which it is •com-
pounded.
REG. 40.- Ice. No person, firm or corporation shall manufacture, sell or
deliver for food or drink purposes, any ice natural or manufactured, containing
decomposed, putrid, infected, tainted, or rotten animal or vegetable substances,
LOUISIANA. 29
or any Ingredient injurious to health. Nor ice made from water of a lower
standard of purity than that required for potable water by the State Board of
Health, as indicated in its Standards and definitions of Food Products.
Ri;<;. 41. LiinL <a) No person, firm or corporation shall manufacture or
sell lard to which has been added beef or mutton fat, stearine, cotton seed oil,
or other substitute for swino fat, unless the container is plainly marked "adul-
terated " or " Lard < '.impound" in bold letters and the quantity and name of
the adulterant is made part of the label.
(b) Lard, lard compounds, or lard substitutes, containing more than one (1)
per rent of water, shall be considered adulterated.
RK<;. 4L\ Ailulti-rati'ni of irhn *. (a) All wine containing alcohol, except such
as have been produced by natural fermentation of pure undried fruit juices, or
combined with distilled spirits, whether denominated wines or by any other
name, which may l>e used as a beverage or combined with other liquors intended
for use, and all compounds of the same with pure wine, and all preserved fruit
juices compounded with substances not produced from undried fruit intended
,se as a beverage or for use in the fermentation or preparation of liquors
intended for su.-h 006, and all wines, imitations of wines, or other beverages
produced from fruit which shall contain alum, baryta, lime, carbonate of soda,
ii«- a.id. or any other antiseptic or coloring matter not pro-
ducrd from undri-'d fruit, or which contains artificial flavoring, essence of ether
or any other 'a nee injurious to health, shall be known as, or
•d to be adulterated wine, and shall not be sold, offered for sale, barter
ive away or manufactured with intent to sell, barter or give away, within
Mate.
• ;. 43. Sugars, syrups and molasses muxt mnfnnn to the standards laid
\ » It >ha!l l>e unlawful for any person or persons, firm or corporation
or ap>nt ertlse, or offer for sale, barter or d\e away within
the limits of this - J compound or mixed syrup, unless at the time of
the names of th,. ingredients in the order of their relative proportion of
mixture or compound are rh-arly stamped or labeled on the bottle, can,
case, barrel or ofh- .'-le containing: such syrup.
Tin- let in •• \li\i ;:i|x>und " as used in this Regulation is understood
to apply to all mixtures or c«>mi>ounds of two or more ingredients differing in
their nature or quality such as sugar cane syrup, sorghum cane syrup, maple
syrup, molasses or glucose (corn syrup.)
ilshed syrups or molasses, containing zinc or tin compounds, will be con-
uxl as food products.
All packages ! or compound syrups in barrels, cans, bottles or other
;iners shall be labeled with the name of the manufacturer and the place of
manufacture.
(B) In the manufacture of syrups and molasses the use of sulphur as a
clarifying agent is permissible, Provided: the residual sulphur does not exceed
l-lo of one per cent.
REG. 44. /Viwri/j/- «'/' tlic *tamlanl* are based. [See Cir. 19, Office of
the Secretary. Federal Standards. These were adopted in toto and only the
standards adopted in addition to those promulgated by the Secretary of Agri-
culture i Cir. !'.» are here given. 1
. Food standards. [See also Cir. 19, Office of the Secretary, Federal
idards.]
c. Mcnt extracts, mmt peptones, gelatine, etc. 1. Meat extract is the product
ned by extracting fresh meat with boiling water and concentrating the
liquid portion by evaporation after the removal of fat, and contains not less
than seventy-live »7.r.) per cent of total solids, of which not over twenty-seven
30 FOOD LEGISLATION, YEAK ENDED JUNE 30, 1908.
(27) per mit is ash, and not over twelve (12) per cent is sodium chlorid (cal-
culated from the total chlorin present), not over six-tenths (0.6) per cent is fat,
and not less than eight (8) per cent is nitrogen. The nitrogenous compounds
contain not less than forty (40) per cent of meat bases and not less than ten
(10) per cent of kreatin and kreatinin.
2. Fluid meat extract is identical with meat extract except that it is concen-
trated to a~lower degree and contains not more than seventy-five (75) and not
less than (50) per cent of total solids.
3. Bone extract is the product obtained by extracting fresh trimmed bones
with boiling water and concentrating the liquid portion by evaporation after
removal of fat, and contains not less than seventy-five (75) per cent of total
solids.
I. riuid bone extract is identical with bone extract except that it is concen-
trated to a lower degree and contains not more than seventy-five (75) and not
less than fifty (50) per cent of total solids.
.". Meat juice is the fluid portion of muscle fibre, obtained by pressure or
otherwise, and may be concentrated by evaporation at a temperature below the
coagulating point of the soluble proteids. The solids contain not more than
fifteen (15) per cent of ash not more than two and five-tenths (2.5) per cent of
sodium chlorid (calculated from the total chlorin present) not more than four
(4) nor less than two (2) per cent of phosphoric acid (P2O5), and not less
than twelve (12) per cent of nitrogen. The nitrogenous bodies contain not less
than thirty-five (35) per cent of coagulable proteids and not more than forty
(40) per cent of meat bases.
c,. reptones are products prepared by the digestion of proteid material by
means of enzymes or otherwise, and contain not less than ninety (90) per cent
of proteoses and peptones.
7. Gelatin (edible gelatine} is the purified, dried, inodorous product of the
hydrolysis, by treatment with boiling water, of certain tissues, as skin, liga-
ments, and bones, from sound animals, and contains not more than fifteen (15)
per cent and not less than two (2) per cent of nitrogen.
Sauces. Must be made from sound and wholesome materials. The use of a
filler is prohibited. Must contain no sweetening material other than pure sugar.
Must not contain added salicylic acid, benzoic acid, saccharin, boric acid, for-
maldehyde, chemical preservatives or their derivatives or coloring matter. If
distilled vinegar is used, it shall be so stated on the label.
I'icklcs. Must be made from sound and wholesome materials. Must contain
no sweetening agent other than pure sugar. Must not contain added salicylic
acid, benzoic acid, saccharin, boric acid, formaldehyde, chemical preservative
or their derivatives, copper salts, alum, iron salts or coloring matter. If dis-
tilled vinegar is used it must be so stated on the label.
Red pepper sauce. Must be made from sound, ripe, wholesome Red pepper,
and must contain no added filling; must not contain added salicylic acid, ben-
zoic acid, saccharin, boric acid, formaldehyde, chemical preservatives or their
derivatives or coloring matter. If distilled vinegar is used it must be so stated
on the label.
Catsup. Must be made from ripe, wholesome and sound vegetable materials.
The use of a filler of starch or other matter is prohibited. Must not contain
added salicylic acid, benzoic acid, saccharin, boric acid, formaldehyde, or their
derivatives, nor any added chemical preservative or coloring matter. If dis-
tilled vinegar is used it shall be so stated on the label.
F. Beverages, a. Fruil juice* — frexh, xiccct, and fermented. Fresh fruit
juices. 1. Fresh fruit juices are the clean, unfermented liquid products ob-
LOUISIANA. 31
tained by the pressing of fresh, ripe fruits, and correspond in name to the fruits
from which they are obtained.
± .!/>/>/r juirr, ,//,,,/, ,„,/*/. street cider, is the fresh fruit juice obtained from
apples, the fruit of PJ/HM main*, has a specific gravity (20° C.) not less than
1 onr. nor greater than 1.0090; and contains in one hundred (100) cubic centi-
metres iL'o0 c.) not less than six (0) grains, and not more than twenty (20)
grams of total sugars, in terms of reducing sugars, not less than twenty-four
r_M . centigrams nor more than sixty (60) centigrams of apple ash, which con-
tains nut loss than fifty (."»()) per cent of potassium carbonate.
<;ni i>< must, is the fresh fruit juice obtained, from grapes
i r//i* species), has a specific gravity (20° C.) not less than 1.0400 and not
eding U L'ln; and contains In one hundred (100) cubic centimetres (20°
•iot less than seven (7) grains n«>r more than twenty-eight (28) grams of
suirars. in terms of reducing sugars, not less than twenty (20) centigrams
and n<>t more than fifty-live (55) centigrams of grape ash. and not less than
iitt.cn M.V) milliirrjims nor more than seventy (70) milligrams of phosphoric
I. /.- mnn jn fresh fruit Juice obtained from lemon, the fruit of Cit-
rus Ihnnnum Uisso, has a specific gravity (20° C.) not less than 1.030 and not
i than 1 .«>!'>: and contains not less than ten (10) per cent of solids, and
nut less than ** .-id.
*wect perry, is the fresh fruit juice obtained from
pears, t lie fruit of r>/m< .-•.nnnunla or P. sincnsis.
1. xti-rili:i d fruit juices are the products obtained by
heat in- fresh fruit juices sufficiently to kill all the organisms present, and
• •spund in name to the fruits from which they are obtained.
/ fruit juices. 1. Conwntrntrtl fruit juices are clean, sound fruit
juices from which a considerable portion of the water has been evaporated, and
correspond in name to the fruits from which they are obtained.
8v- iuicea, sweetened fruit jni<-< \. fruit sirup*. 1. Sweet fruit juices,
Meec/niff/ fruit juiwM. fruit sirups, are the products obtained by adding sugar
(sucrose) to fresh fruit juices, and correspond in name to the fruit from which
they an* obtai:
sterilized fruit simps are the products obtained by the addition of sugar
rose) to fresh fruit juices and heating them sufficiently to kill all organ-
Isms present, and correspond in name to the fruits from which they are
obtained.
9. Cider, hard cider, is the product made by the normal alcoholic fermentation
of apple juice, and the usual cellar treatment, and contains not more than
seven (7) per cent by volume of alcohol, and, in one hundred (100) cubic centi-
mes of the elder, not less than two (2) grams nor more than twelve (12)
grams of solids, not more than eight (8) grams of sugars, in terms of reducing
sugars, and not less than twenty (20) centigrams nor more than forty (40)
centigrams of cider ash.
10. Sparkling cider, champagne cider, is cider in which the after-part of the
fermentation is completed in closed containers, with or without the addition of
elder or sugar liquor, and contains in one hundred (100) cubic centimetres, not
less than twenty (20) centigrams of cider ash.
b. Mead, root beer, etc. Mead. The materials used shall be pure and whole-
some according to the standards set forth in these regulations. The water used
shall be potable; shall not contain added salicylic acid, benzoic acid, saccharin,
boric acid, formaldehyde, or their derivatives, nor any added chemical preserva-
•r coloring matter.
32 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
Root -beer shall be manufactured from roots, bark, leaves, berries, herbs, or
the oils extracted therefrom, caramel, or other harmless ingredients ; shall not
contain added salicylic acid, saccharin, boric acid, formaldehyde, or their deriva-
tives, or added chemical preservatives or coloring matter.
c. Malt liquors. 1. Malt liquor is a beverage made by the alcoholic fermenta-
tion of an infusion in potable water, of barley-malt and hops, with or without
malted cereals.
Itecr is a malt liquor produced by bottom fermentation, and contains in
one hundred (100) cubic centimetres, at (20° C.) hot less than five (5) grams of
extractive matter, and sixteen one-hundredths (.16) gram of ash, chiefly
potassium phosphate, and not less tnan two and twenty-five one hundredths
(2.25) grams of alcohol.
3. Lager 'beer, stored leer, is beer which has been stored in casks for a
period of at least three months, and contains in one hundred (100) cubic cen-
timetres (at 20° C.) not less than five (5) grams of extractive matter, and
sixteen one-hundredths (.16) gram of ash, chiefly potassium phosphate, and
not less than two and fifty one-hundredths (2.50) grams of alcohol.
Malt beer is beer made of an infusion in potable water, of barley malt,
ami hops, and containing in one hundred (100) cubic centimetres (at 20° C.)
not less than five (5) grams of extractive matter, nor less than two-tenths
(.2) gram of ash, chiefly potassium phosphate, nor less than two and twenty-
five one-hundredths (2.25) grams of alcohol, nor less than four-tenths (.4)
gram of crude protein (nitrogen X 6.25).
5. Ale is a malt liquor produced by top fermentation and contains in one
hundred (100) cubic centimetres (at 20° C.) not less than two and seventy-
five one hundredths (2.75) grams of alcohol, nor less than five (5) grams of
extract.
6. Porter and stout are varieties of ale colored by the addition of highly
roasted malt to the infusion.
d. Spirituous liquors. 1. Distilled spirits is the distillate obtained from a
fermented mash of cereals, molasses, sugars, fruits, or other starch- or sugar
bearing substances, and contains all, the condensed products of the fermenta-
tion volatile at the usual temperature of distillation.
2. Rectified spirits is distilled spirit which at the time of, or subsequent to
distillation is subjected to a rectifying process by means of which a part of
the volatile products of the distillation is separated from the ethyl alcohol
therein.
3. Alcohol, cologne spirit, neutral spirit, velvet spirit, or silent spirit is dis-
tilled spirit from which all, or nearly all, its constituents are separated, except
ethyl alcohol and water, and contains not less than ninety-four and nine-tenths
(94.9) per cent (189.8 proof) by volume of ethyl alcohol.
}. \ no whiskey is the distilled sprits from the properly fermented mash of
malt cereals, or cereals the starch of which has been hydrolized by inalt, is of
an alcoholic strength corresponding to the excise laws of the various countries
in which it is made, and contains not less than one hundred and twenty-five
(125) nor more than three hundred and fifty (350) grams of the secondary
products of distillation congeneric with ethyl alcohol, not less than ninety (90)
nor more than two hundred and twenty-five (225) grams of fusel oil (higher
alcohols as amylic), not more than twenty (20) grams of aldehydes, not less
than fifteen (15) nor more than one hundred (100) grams of ethers (as acetic
ether), not less than two (2) nor more than twenty-five (25) grams of volatile
acids (as acetic) to one hundred (100) litres of proof ethyl alcohol (50 per
cent ethyl alcohol by volume).
- LOUISIANA. ^T 33
.". H'//ixAv// i iHitablc irhiski // 1 is now whiskey which has been stored in wood
for not less than four (4) yours and mixed only with pure water at the time
of its preparation for consumption, and contains unless otherwise prescribed
by law, not less than forty-five (45) i>er cent of ethyl alcohol by volume, and
the relative quantities of secondary products to ethyl alcohol corresponding to
the varieties of whiskey under six «i) to fifteen (15), inclusive.
»;. /,*//»• ir/i/N/i-f // is whiskey in the manufacture of which rye is the principal
cereal used, and contains not less than two hundred (200) nor more than five
hundred ( ~»oo ) grains of the secondary products of distillation congeneric with
ethyl alcohol, n<»t less than one hundred (100) nor more than two hundred
and lifly 'ins of fusel oil (higher alcohols as amylic), not more than
twenty-live grams of aldehydes, no't less than forty (40) nor more than one
hundred and fifty » l.'ni grams of ethers (as acetic ether), not less than thirty
(30) nor nmre than eighty-five (85) grams of volatile acids (as acetic) te one
hundred (100) litres of proof ethyl alcohol (50 per cent ethyl alcohol by
volm
7. //«'/ T//O/J I/-///*/.-' .'/ is whiskey in which Indian corn (maize) is the princi-
pal cereal used, and contai; - than two hundred (200) nor more than
live hundred (500) grams of the secondary products of distillation congeneric
with ethyl alcohol, not less than one hundred (100) nor more than two hun-
dred and fifty i -•"<» grams of fusel oil (higher alcohols and amylic), not more
than twenty five (25) grams of aldehydes, not less than forty (40) nor more
than one hundred and fifty < 1 .".«•» grams of ethers (as acetic ether), not less
than thirty i.'KM nor more than eighty live (S5) grams of volatile acids (as
ncet io to ..ne hundred litres of proof ethyl alcohol (50 per cent ethyl alcohol
by \olui:
8. Corn jr/i».sAr// is whiskey made from mai/e (Indian corn), the starch of
which has b.-vn hydroli/ed by malting or by the action of barley malt, and con-
tains the prop. if the various ingredients si>ecified for bourbon whiskey.
distilled spirit made from rice.
10. HI' n<li <l ll a mixture of two or more whiskeys, and contains the
relative quantities of secondary products to ethyl alcohol of the varieties of
whiskey forming the Mend.
11. is new whiskey deprived of a part of its secondary
volatile i ..mains not less than sixty (60) grams of the secondary
: distillation congeneric with ethyl alcohol, not less than forty
i in, t fusel oil (higher alcohol as amylic) not more than eight (8)
.grams of aldehydes, not less than five (5) grams of ethers (as acetic ether), not
less than one i 1 » gram of volatile acids (as acetic) to one hundred (100) litres
of proof eth\ 1 Alcohol ttl "*' «'thyl alcohol by volume).
!•_•. ir/M.s-A-' // is rectified new whiskey stored in wood not less than
three (3) yean, -'\.vpt where otherwise prescribed by law, and contains not less
than one hundred . imi grama of the secondary products of distillation con-
rlc with ethyl alcohol, not less than fifty (50) grams of fusel oil (higher
alcohols as a my lie), not more than ten (10) grams of aldehydes, not less than
twenty (20) grams of ethers (as acetic ether), not less than fifteen (15) grams
Is (as acetic) to one hundred (100) litres of proof ethyl alcohol
i,"(t per cent ethyl alcohol by volume).
13. Nco/c// nrir /r/,/.s /.-<// is whiskey made in Scotland solely from barley malt
in the drying of which over burning peat a smoky or peaty flavor is imparted to
the product, and contains not less than one hundred and twenty-five (125)
nor m.. re than three hundred and fifty (350) grams of the secondary product
of distillation .- with ethyl alcohol, not less than ninety (90) nor more
<;r_'M>— Hull. 121—09 3
34 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
than two hundred and twenty-five (225) grams of fusel oil (higher alcohols as
amylic) not more than twenty (20) grams of aldehydes, not less than fifteen
(15) nor more than one hundred (100) grams of ethers (as acetic ether), not
less than two (2) nor more than twenty-five (25) grams of volatile acids (as
acetic) to one hundred (100) litres of proof ethyl alcohol (50 per cent ethyl
alcohol by volume).
1 1. scotch whiskey is Scotch new whiskey which has been stored in wood for
not less than four years and mixed only with pure water at the time of its
preparation for consumption, and contains not less than one hundred and fifty
(150) nor more than four hundred anr1 fifty (450) grams of the secondary prod-
nets of distillation congeneric with ethyl alcohol, not less than one hundred
(100) nor more than two hundred and fifty (250) grams of fusel oil (higher
alcohols as amylic) not more than twenty-five (25) grams of aldehyde, not less
than twenty-five (25) nor more than one hundred and twenty-five (125) grams
of ethers (as acetic ether), not less than ten (10) nor more than forty (40)
grams of volatile acids (as acetic) to one hundred (100) litres of proof ethyl
alcohol (50 per cent ethyl alcohol by volume).
15. Irish ncic irhiskcy is whiskey made in Ireland either from barley malt, or
malt and unmalted barley, or other cereals, and contains not less than one hun-
dred and twenty-five (125) nor more than three hundred and fifty (350) grams
of the secondary products of distillation congeneric with ethyl alcohol, not less
than ninety (90) nor more than two hundred and twenty-five (225) grams of
fusel oil (higher alcohols as amylic), not more than twenty (20) grams of alde-
hydes, not less than fifteen nor more than one hundred (100) grams of ethers
(as acetic ether), not less than two (2) nor more than twenty-five (25) grams
of volatile acids (as acetic) to one hundred (100) litres of proof ethyl alcohol
(50 per cent ethyl alcohol by volume).
16. Irish ichiakey is Irish new whiskey which has been stored in wood for not
less than four years and mixed only with pure water at the time of its prep-
aration for consumption, and contains not less than one hundred and fifty (150)
nor more than four hundred and fifty (450) grams of the secondary products
of distillation congeneric with ethyl alcohol not less than one hundred (100) nor
more than two hundred and fifty (250) grams of fusel oil (higher alcohols as
amylic), not more than twenty-five grams of aldehydes, not less than twenty-
five (25) nor more than one hundred and twenty-five (125) grams of ethers (as
acetic ether), not less than ten (10) nor more than forty (40) grams of volatile
acids (as acetic) to one hundred (100) litres of proof ethyl alcohol (50 per cent
ethyl alcohol by volume.)
IT. \nc rum is distilled spirits made from the fermented juice of the sugar
cane, the massecuite made therefrom, molasses from the massecuite or any inter-
mediate product save sugar, and contains not less than one hundred and twenty-
five (125) nor more than three hundred and fifty (350) grams of the secondary
products of distillation congeneric with ethyl alcohol, not less than sixty (60)
nor more than one hundred and fifty (150) grams of fusel oil (higher alcohols
as amylic) not more than thirty (30) grams of aldehydes, not less than thirty
(30) nor more than one hundred (100) grams of ethers (as acetic ether), not
less than twenty (20) nor more than (50) grams of volatile acids (as acetic) "to
one hundred (100) litres of proof ethyl alcohol (50 per cert ethyl alcohol by
volume).
18. Rum is new rum stored not less than four (4) years in wood, and con-
tains not less than one hundred and seventy-five (175) nor more than five hun-
dred (500) grams of the secondary products of distillation congeneric with ethyl
alcohol, not less than eighty (80) nor more than two hundred (200) grams of
LOUISIANA. 35
fusel oil (higher alcohols as amylic), not more than forty (40) grains of alde-
hydes, not less than fifty (50) nor more than one hundred and fifty (150)
Drains <>f ethers las acetic ether) not less than thirty-five (35) nor more than
one hundred i KM)) Drains of volatile acids (as acetic) to one hundred (100)
lit iv* of proof ethyl alcohol (50 per cent ethyl alcohol by volume).
T.I. \i-ir brnndij is a distilled spirit made from sound potable wine, and con-
tains not less than one hundred and twenty-five (125) nor more than three hun-
dred and fifty i •"••~>0) grams of the secondary products of distillation congeneric
with ethyl alrohol. not less than seventy (70) nor more than one hundred and
fifty i !•"<» irrams of fusel oil (higher alcohols as amylic), nor more than twenty
i I'n i Brants of aldehydes, not less than thirty (30) nor more than one hundred
(100) mams of ethers (as acetic ether), not less than five (5) nor more than
twenty <L'<>) irrams of volatile acids (as acetic) to one hundred (100) litres of
proof ethyl alcohol (50 per cent ethyl alcohol by volume).
L'o. linnulii is new brandy stored in wood for not less than four (4) years,
and contains not less than one hundred and fifty (150) nor more than five
hundred I.',IH»I -rains of the secondary products of distillation congeneric with
ethyl alcohol, not less than eighty (80) nor more than two hundred (200) grams
<el oil (higher alcohols as amylic), not more than thirty (30) grams of
aldehydes, not less than thirty-five i .*>5) nor more than one hundred and fifty
i i.-.n i -rams of ethers (as acetic ether), not less than thirty (30) nor more than
• 100) grams of volatile acids (as acetic) to one hundred (100)
f proof ethyl alcohol (50 per cent ethyl alcohol by volume).
L'l. I'lujntH" is brandy prepared In the departments of the Charente, France,
from pure, sound wine produced In those departments.
• r»,tntili' -Water to be potable must be suit-
able to all forms of domestic use; must possess no objectionable smell or taste;
must l>e five from animal, especially human refuse material; must be free from
material In a state of active decompositon ; must be free from path-
i ; must be free from such an amount of suspended material of
whatever character as would make it unsightly in appearance and unsuited to
the ordinary industrial uses of a community.
CterftOM rg are waters charged with carbonic acid gas, and may be
naturally carbonated or artificially carbonated. Label must state how car-
bonated, and if the source of the water Is given thereon, the water must be true
to its label. All carbonated waters must be wholesome and potable.
Spring and ir> II imtrrs are waters derived from springs or wells; they must
be potable and wholesome; they may or may not be medicinal; and must come
from the well or spring indicated on the label and no other. The standard
_- or well water will be the water itself, sample being taken at its
source by a representative of this Board.
// mim-rnl initcrs must be so labeled, and the water used in their manu-
facture must be wholesome and potable. All waters must be true to label, and
if an analysis is published as an advertisement, or is placed on the label, the
water must conform thereto.
G. Vinegar. * * *
6. N;m-if vinegar, distilled vinegar, grain vinegar, is the product made by the
acetous fermentations of dilute distilled alcohol, and contains, in one hundred
flOO) cubic centimetres (20° C.), not less than four (4) grams of acetic acid,
and shall be free from coloring matter, added during or after distillation, and
from color other than that imparted to it by distillation.
Bread n ml i/fn*t. Bread must be made of pure and wholesome materials as
provided for in these regulations, must not contain adulterants, alums, or cop-
36 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
per salts, should not contain more than forty (40) per cent of water- nor have an
acidity in ten (10) grams of fresh bread requiring more than 10 c. c. of 1-10
normal sodium hydroxide solution to neutralize it.
Compressed Yeast should be used when fresh. Such yeast should have a
creamy white color, uniform throughout, should possess a fine even texture,
should be moist without being slimy, should not have a " cheesy " odor, such
odor indicating decomposition as does a dark streaked color.
IV. PRESERVATIVES AND COLORING MATTERS.
Standard i>rc8crratii'es are salt, sugar, vinegar, spices, and their essential oils,
wood smoke, edible oils and fats, and alcohol.
The use in food products, of any other preservatives or antiseptics, or of any
substance which preserves or enhances the natural color of a food product, or of
a coloring matter is prohibited except as provided for in these Regulations.
* * *
lie;:. 14, Section (u) [and F. I. D. 76 as to permitted coal tar dyes.]
RMB. 4(\. Taking orders deemed a sale. Taking orders for same. The taking
of orders or the making of agreements or contracts by any person, firm or cor-
poration, or by any agent or representative thereof, for the future delivery of
any of the articles, products, goods, wares, or merchandise embraced within
the provisions of these Regulations, shall be deemed a sale within the meaning
of these Regulations.
REG. 47. Person defined. The word " person," as used in these regulations
shall be construed to import both the plural and the singular, as the case de-
mands, and shall include corporations, companies, societies, and associations,
when construing and enforcing the provisions of these regulations the act, oinis-
sion or failure of any officer, agent or other person acting for or employed by
any corporation within the scope of his employment or office, shall in every
case be also deemed to be the act, omission, or failure of such corporation, com-
pany, society, or association, as well as that of the person.
REG. 48. Penalty. Any person convicted of violating any of the provisions of
the foregoing Regulations wherein penalty is not provided, shall be punished
pursuant to the provisions of Section 3, Act 98 of 1906.
These Regulations shall be in force and effect from and after their adoption
and promulgation by the State Board of Health.
The State Board of Health reserves the right conferred on it by Section 2,
Act 98 of 1906, " to further revise and amend " whenever the interests of the
public health, the advancement of scientific knowledge, or the rulings of the
National Food Department make it advisable so to do.
All laws and regulations in conflict with these Regulations are hereby re-
pealed.
Adopted April 25, 1908.
MARYLAND.
i -i :r ITS, ETC.
'•'< nn>l r<-i/i tnt,l< .v /o /«• mnrk«l. All shippers and sellers of all
fruits Mini vegetables in Wicomico county shall be compelled to stamp or mark
all baskets, barrels, boxes, packages, crates, parcels or other receptacles used
by them fur the shipment or sale of any fruit, fruits or vegetables with his,
her or their name ..r names, initials, or with some distinguishing device or
mark which may !»•• readily and easily read and seen on the same before such
fruit, fruits . -hall be offered for shipment or sale; and if any
shipper • :' any fruit, fruits or vegetables, shall neglect or fail to com-
ply with the pn>\ his section, he or she, or they, shall pay a fine of
ti\.- dollars; said tine to be applied to the public school fund for Wieomico
county, but nothii:. Act shall apply to hucksters selling in quantities
less than full packages, or to anything delivered to canneries.
. This Act Shall take effect from May 1, 1908.
Approved April <;, 1908. Laws of 1908, art. 23, ch. 712, p. 1125.
37
MASSACHUSETTS.
GENERAL FOOD LAWS.0
SEC. 70. General inspection authority. Boards of health of cities and towns,
by themselves, their officers or agents, may inspect the carcasses of all slaugh-
tered animals and all meat, fish, vegetables, produce, fruit or provisions of any
kind found in their cities or towns, and for such purpose may enter any build-
ing, enclosure or other place in whicf such carcasses or articles are stored,
kept or exposed for sale. If, on such inspection, it is found that such car-
casses or articles are tainted, diseased, corrupted, decayed, unwholesome or,
from any cause, unfit for food, the board of health shall seize the same and
cause it or them to be destroyed forthwith or disposed of otherwise than for
food. All money received by the board of health for property disposed of as
aforesaid shall, after deducting the expenses of said seizure, be paid to the
owner of such property. If the board of health seizes or condemns any such
carcass or meat for the reason that it is infected with a contagious disease,
it shall immediately give notice to the board of cattle commissioners of the
name of the owner or person in whose possession it was found, the nature of
the disease and the disposition made of said meat or carcass. — As amended
April 17, 1908, Acts and Resolves of 1908, ch. 411, p. 276. See Bui. 69, Rev., pt.
3, p. 266.
SKC. 72. Penalty for hindering inspectors. Whoever prevents, obstructs or
interferes with the board of health, its officers or agents, in the performance
of its duties as provided herein, or hinders, obstructs or interferes with any
inspection or examination by it or them, or whoever secretes or removes any
carcass, meat, fish, vegetables, fruit or provisions of any kind, for the purpose
of preventing the same from being inspected or examined under the provisions
of sections seventy to seventy-six, inclusive, shall be punished by a fine of not
more than one hundred dollars or by imprisonment for not more than sixty
days, or by both such fine and imprisonment. — As amended April 17, 1908;
Acts and Resolves of 1908, ch. 411, p. 276. See Bui. 69, Rev., pt. 3, .p. 266.
Revised Laws, 1902, vol. 1, ch. 56, p. 555.
SEC. 1. Repeal. Sections twenty-five and twenty-six of chapter seventy-five
of the Revised Laws (Bui. 69, Rev., pt. 3, p. 248), relating to the sale of adul-
terated food and drugs, are hereby repealed.
SEC. 2. Effect. This act shall take effect upon its passage.
Approved March 18, 1908. Acts and Resolves of 1908, ch. 238, p. 153.
BREAD.
SEC. 6. Penalty. Whoever violates any provision of the preceding three sec-
tions shall be punished by a fine of not more than ten dollars for each offence.
The sealer of weights and measures in the respective cities and towns, or the
commissioner of weights and measures of the commonwealth, shall cause the
provisions of the said three sections to be enforced.— As amended March 10,
1908; Acts and Resolves of 1908, ch. 197, p. 114. See Bui. 69, Rev., pt. 3, p. 252.
Revised Laws 1902, vol. 1, ch. 57, pp. 557-8.
°See also Meat, page 39.
MASSACHUSETTS. 39
MEAT.?
SEC. 1. Prohibition; penalty. The sale, offer or exposure for sale, or delivery
for use as food, of the carcass, or any part or product thereof, of any animal
which has come to its death in any manner or by any means otherwise than by
slaughter or killing while in a healthy condition, or which at the time of its
death is unfit by reason of disease, exhaustion, abuse, neglect or otherwise for
use as food, or of any calf weighing less than forty pounds when dressed, with
head, feet, hide and entrails removed, is hereby declared to be unlawful and
prohibited. Whoever sells or offers or exposes for sale or delivers or causes or
autliorix.es to be sold, offered or exposed for sale or delivered for use as food
any such can-ass or any part or product thereof, shall be punished by fine of not
more than two hundred dollars or by imprisonment for not more than six
months.
Sir. L«. Inspectors of state and municipal boards of health; seizure and de-
tttnn-tion »f unlan-ful products. The state board of health and its inspectors,
and the state inspectors of health and all boards of health of cities and towns
and their insi>ector8, officers, agents and assistants in their respective districts,
shall have and exercise the same powers and duties in and for the enforcement
of this act as are at any time conferred or imposed by law upon any board of
health, inspector, officer, agent or assistant in respect of any other article or
substance the sale or use of which for food is unlawful or prohibited ; and it
shall l>e their duty to seize any such carcass or part or product thereof as
ribed In section one hereof, and cause the same to be destroyed forthwith
or disposed of otherwise than for food ; and all moneys received by any board
of health for any property so disposed of shall, after deducting the expenses
:«-h sei/.ure and disposal, be paid to the owner of such property if known.
' a to be inspected. Such Inspectors, officers, agents and assistants
shall visit and keep under observation all places within their respective districts
at which neat cattle, sheep, swine or other animals intended for slaughter or
for sale or use as food are delivered from transportation, and shall have at all
times free access to all such places and to all railroad trains or cars or other
vehicles in which such animals may be transported, for the purpose of pre-
vent i: >ns of this act and of detecting and punishing the same.
•i. Pouters of inspection. The state Inspectors of health in their re-
spective districts, and the inspectors appointed by the state board of health for
duties relative to the sale of food and drugs, shall have the same rights, powers
and authority for and in respect of the inspection, seizure and disposition of all
carcasses, meats and provisions which are tainted, diseased, corrupted, decayed,
unwholesome. «.r from any cause unfit for food, or the sale of which for food
is unlawful, as are conferred by sections seventy and seventy-one of chapter
tifty six ami by section one hundred and two of chapter seventy-five of the
Revised Laws, or by other laws, upon boards of health of cities and towns or
their insi>ector8 in respect of the articles therein specified; with power to prose-
cute all offences relating thereto.
« -effort of slaughter houses. In addition to the supervision now
provided for by law, all slaughter houses shall be under the supervision of the
state board of health and subject to inspection by the state inspectors of health
in their respective districts.
SEC. 6. Amendment. Section one hundred and five of chapter seventy-five of
the Revised Laws, as amended by section two of chapter three hundred and
twelve of the acts of the year nineteen hundred and two, and by section two of
0 See also General Food Law, page 38.
40 FOOD LEGISLATION, YEAK ENDED JUNE 30, 1908.
chapter two hundred and twenty of the acts of the year nineteen hundred and
three, is hereby further amended by striking out all after the word " old," in
the seventh line, so as to read as follows: Sec. 105. Exemption. The provi-
sions of the six preceding sections shall not apply to a person not engaged in
such business, who, upon his own premises and not in a slaughter house, slaugh-
ters his own neat cattle, sheep or swine, but the carcass of any such animals
shall be inspected by an inspector at the time of slaughter, unless said animal
is less than six months old.
7. Authority of other officers unimpaired. Nothing in this act shall
affect or impair the rights, powers or authority of any board or officer not
herein mentioned.
Approved March 31, 1908. Acts and Resolves of 1908, ch. 329, pp. 218-20.
SEC. 71. Inspection of veal. The board of health, by themselves, their officers
or agents, may inspect all veal found, offered or exposed for sale or kept with
the intent to sell in its city or town, and if, in its opinion, said veal is that of a
calf less than four weeks old when killed, the board shall seize and destroy or
dispose of it as provided in the preceding section, subject, however, to the pro-
visions thereof relative to the disposal of money.— As amended April 17, 1908;
Acts and Resolves of 1908, ch. 411, p. 276. See Bui. 69, Rev., pt. 3, p. 266.
Revised Laws, 1902, vol. 1, ch. 56, p. 555.
MILK.
SEC. 3. Unclean vessels without name of owner; penalty. Every licensed
milk dealer who sells, or has in his possession with intent to sell, milk not
contained in clean vessels bearing his own name, or the name under which his
business is conducted, and bearing no other name, shall be punished by a fine
of ten dollars for each offence; but the provisions of this section shall not
apply to persons using clean vessels bearing the name of another person whose
written permission for such use shall have been obtained previously and regis-
tered in the office of the milk inspector, in municipalities having such officer, and
in other municipalities registered in the office of the city or town clerk. — As
amended April 22, 1908; Acts and Resolves of 1908, ch. 435, p. 292. See Bui. 104,
p. S3.
Approved March 1, 1906. Acts and Resolves 1906, ch. 116, p. 62.
SEC. 2. Repeal. Section four (Bui. 104, p. 33) of said chapter one hundred
and sixteen is hereby repealed.
Approved April 22, 1908. Acts and Resolves of 1908, ch. 435, p. 292.
SEC. 12. Expenditures; report. The bureau may expend not more than eight
thousand dollars annually in its work, and it may co-operate with the state
board of health and with inspectors of milk, but it shall not interfere with the
duties of such board or officers. It shall annually, before the fifteenth day of
January, report to the general court in detail the number of agents, assist-
ants, experts and chemists employed by it, with their expenses and disburse-
ments, of all investigations made by it, of all cases prosecuted with the results
thereof, and other information advantageous to the dairy industry.— As amended
April 17, 1908; Acts and Resolves of 1908, ch. 416, p. 278. See Bui. 69, Rev.,
pt. S, p. 253.
Revised Laws 1902, vol. 1, ch. 89, pp. 778-9.
MASSACHUSETTS. 41
SEC. 56. Standard for mi/A:. In prosecutions under the provisions of sections
fifty-one to sixty-four, inclusive, milk which, upon analysis, is shown to con-
tain less than twelve and fifteen huiulredths per cent of milk solids or less than
three and thirty-five hundredths per cent of fat, shall not be considered of good
standard quality.— .-I* umemlnl -June 13, 1908; Acts and Resolves of 1908, ch.
6'M. y. •>'>•'•'. 's'"' /*"'• '>'•'• /"''•'••. l>t. 3, p. 258.
Revised Laws V.M>L>. v.il. 1, ch. 56, pp. 547-54.
. 1. Ih-ntfil milk; fine if not Inlteli-rt. Whoever, himself or by his servant
or agent, or as the servant or agent of any person, firm or corporation, sells,
e.\« -hanges or delivers «>r has in his custody or possession with intent to sell,
exchange or deliver any milk which has been subjected to artificial heat
greater than one hundred and sixty-seven degrees Fahrenheit, not having the
words "heated milk" distinctly marked upon a light ground in plain black
imcondensed got hie letters at least one inch in length in a conspicuous place
ujHtn every vessel. can or package from or in which such milk is, or is intended
to 1..-. sold, exchanged or delivered shall for a tirst offence be punished by a fine
ot" not less than titty nor more than two hundred dollars, for a second offence
by a tine of not less than one hundred nor more than three hundred dollars,
and for a subsequent offence by a fine of fifty dollars and by imprisonment for
not less than sixty nor more than ninety days. If such vessel, can or package
is of the capacity "f "«'t more than two quarts, said words may be placed upon
a detachable label or tag attached thereto and said letters may be less than one
inch in length, but not smaller than brevier gothic capital letters.
SEI. tiiitinn*. Nothing In this act shall be construed as applying to
condensed milk or to milk which has been concentrated to one-half its volume
or less.
Approved June 1, 1008. Acts and Resolves of Massachusetts, 1908, ch. 570,
P. l"l.
WATER.
Sir. 1. Defiling water supply. Any police officer or constable of a city or
town in which any jioiid. stream or reservoir used for the purpose of domestic
water supply is wholly or partly situated, acting within the limits of his city
or town, and any executive officer of a water board, board of water commis-
sioners. public institution or water company, furnishing water for domestic
purposes, or agent of such water board, board of water commissioners, public
institution or water company, duly authorized in writing therefor by such
hoards, institution or company, acting upon the premises of such board, insti-
tution or company and not more than five rods from the water, for such supply
may. without a warrant, arrest any person found in the act of bathing in a
pond, stream or reservoir, the water of which is used for the purpose aforesaid,
and detain him in some convenient place until a complaint can be made against
him therefor.
_'. l-.'ffect. This act shall take effect upon its passage.
Approved May 26, 1908. Acts and Resolves of 1908, ch. 539, pp. 377-78.
MISSISSIPPI.
SEC. 2. Repeal. That sections * * 1766 * * * of the Mississippi
Code of 1906 be, and the same are hereby, repealed. — Repealed February 19,
1908; Laws of 1908, ch. 115, p. 118. See Bui. 69, Rev., pt. 4, p. 326.
Annotated Code, 1892, ch. 37, p. 430, or Code of 1906, sec. 1766.
4L'
NEW JERSEY.
GENERAL FOOD LAWS.
SEC. 3. Adulteration defined. For the purposes of this act an article shall be
deemed to be adulterated * * *
In the case of confectionery:
It it contains terra alba, barytes, talc, chrome yellow or other mineral sub-
stance, or poisonous color or flavor, or other ingredient deleterious or detri-
mental ti» health, in- any vinous, malt or spirituous liquor or compound or
nan-otic drug.
In the case of food:
First. If any substance has been mixed or packed with it so as to reduce or
lower or injuriously afl'ect its quality or strength.
• •ml. If any substance has been substituted wholly or in part for the
article.
Third. If any \aluable eonstituent of the article has been wholly or in part
abstracted.
Fourth. If it be mixed, colored, powdered, coated or stained in a manner
whereby damage or inferiority is concealed.
Fifth. If it contain any added poisonous or other added deleterious ingredient
which may n-nder such article injurious to health; i>r<>ridcd, that when in the
preparation of food products for shipment they are preserved by any external
application applied in such manner that t be preservative is necessarily removed
HUM •hanically. or by maceration In water, or otherwise, and directions for the
ivnio\;il of said preservative shall be printed on the covering or the package,
the provisions of this act shall be construed as applying only when said products
are ready for consumption.
Sixth. If it consists in whole or in part of a filthy, decomposed or putrid
animal or vegetable substance, or any portion of an animal unfit for food,
whether manufactured or not, or if it is the product of a diseased animal, or
one that has died otherwise than by slaughter. — As amended April 16, 1908,
. .fox. i>i>. ii.".> -630. Kcc Hul. 112, pt. 2, pp. 7-8.
Sn . I. Misbranding d»fin»d. The term " misbranded," as used herein, shall
apply to all drugs, or articles of food, or articles which enter into the composi-
tion of food, the package or label of which shall bear any statement, design or
de\ ice regarding such article, or the ingredients or substances contained therein,
which shall be false or misleading in any particular, and to any food or drug
product which is falsely branded as to the State, Territory or country in which
it is manufactured or produced.
r the purposes of this act an article shall also be deemed to be mis-
bra ruled * * *
In the case of food :
First. If it be an imitation of or offered for sale under the distinctive name
of another article.
Second. If it be labeled or branded so as to deceive or mislead the purchaser,
or purport to be a foreign product when not so, or if the contents of the package
as originally put up shall have been removed, in whole or in part, and other con-
43
44 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
tents shall have been placed in such package, or if it fail to bear a statement on
the label of the quantity or proportion of any morphine, opium, cocaine, heroin,
alpha or beta eucaine, chloroform, cannabis indica, chloral,' hydrate, acetanilide,
acetphenetidine, or phenacetin or antipyrin, or any derivative or preparation of
any such substances contained therein.
Third. If in package form, and the contents are stated in terms of weight or
measure, they are not plainly and correctly stated on the outside of the package.
Fourth. If the package containing it, or its label shall bear any statement,
design or device regarding the ingredients or substances contained therein,
which statement, design or device shall be false or misleading in any particu-
lar.-As amended April 16, 1908; Acts of 1908, ch. 308, pp. 630-632. See Bui.
112, pt. 2, p. 8.
SEC. 46. Guarantee for protection of dealer. No dealer shall be prosecuted
under the provisions of this act for distributing or selling, or having in his pos-
session with intent to distribute or sell, any article of food or drug which under
any of said provisions shall be deemed to be adulterated or misbranded ; pro-
vided, that said article of food or drug is distributed or sold or had in posses-
sion with intent to distribute or sell in the original unbroken package in which
it was received by said dealer, and that, in case said article was purchased by
said dealer from a wholesaler, jobber, manufacturer, or other person residing
in this State, and said dealer can establish a guarantee signed by such whole-
saler, jobber, manufacturer or other person from whom he purchased such arti-
cle, to the effect that the same is not adulterated or misbranded within the
meaning of this act, designating it; or in case said article was purchased by
said dealer from a wholesaler, jobber, manufacturer or other person residing in
the United States of America, but outside of this State, and said dealer can
establish a guarantee, signed by such wholesaler, jobber, manufacturer or other
person from whom he purchased such article, to the effect that the same is not
adulterated or misbranded within the meaning of an act of the Congress of the
United States of America, entitled "An act for preventing the manufacture, sale
or transportation of adulterated or misbranded, or poisonous or deleterious
foods, drugs, medicines and liquors, and for regulating traffic therein, and for
other purposes," approved June thirtieth, one thousand nine hundred and six,
and the supplements and amendments thereof. Such guaranty, to afford pro-
tection, shall contain the name and address of the person making the sale of
such article to such dealer, and in such case said person, if he is a resident of
this State, shall be amenable to the prosecution, fines and other penalties which
would attach in due course to the dealer under the provisions of this act. If
the guaranty is signed by a person who resides outside of this State, then the
Board of Health of this State shall report the facts in the case to the Secretary
of Agriculture of the United States, or the proper officer appointed for the
enforcement of the above-mentioned act of Congress ; and provided further,
that no guarantee that any article is not adulterated or misbranded within the
meaning of the above-mentioned act of Congress, shall be effective to exempt
any dealer from prosecution under this act, unless the provisions of the above-
mentioned act of Congress and of this act covering the adulteration and mis-
branding of such guaranteed article are identical.
The provisions of this act relating to misbranding shall not apply to the dis-
tribution or sale or to the possession with intent to distribute or sell by any
dealer of such proprietary foods and medicines as were in such dealer's stock
in this State on October first, nineteen hundred and eight; provided, that the
package or other container in which such foods or medicines shall be contained
a So in Statutes.
NEW JERSEY. 45
shall be plainly and conspicuously marked with the words and figures "On
hand Oct. 1st, 190S."— A* amended April 16, 1908; Acts of 1908, ch. 308, pp.
If ul. 11!, lit. ~J. i>i>. l.!-13.
Approved May 20, 1907. Acts of 1907, ch. 217, pp. 485-502.
mptions for exports; preservatives. No article shall be deemed
to be adulterated or misbranded within the meaning of this act when specially
prepared for export to any foreign country, if such article shall be prepared
and packed according to the directions of the foreign purchaser, and if no sub-
stance is used in the preparation or packing of such article which is prohibited
by the laws of the foreign country for export to which said article was pre-
pared; i>n,ri<i> 'I, that if such article shall be sold or offered for sale for use or
consumption within the I'nited States of America, then all the provisions of this
net. with regard to adulteration and misbranding, shall apply thereto; and pro-
rith-il furtln-r. that all food products manufactured in this State during the
- ..n»' thousand nine hundred and seven and one thousand nine hundred and
fight, in which preservatives are used, which preservatives are not now spe-
cifically prohibited by the Department of Agriculture of the United States, shall
be exempt from the provisions of this act; provided, the use of such preserva-
tives is stated UJKHI the label or in branding such products, and also the date
of their mauuf.i. -ture .— As amended April 13, 1908; Acts of 1908, ch. 242, pp.
447-478. tfrc Hul. 112, pt. 2, sec. 6 (5), p. 8.
Appro\ed May 20, 1907. Laws of 1907, ch. 217, p. 488.
OONFBOTIONIIRY.
See General Food Laws, page :
.MILK.
Sic. 6. Btamlnn! : ! mill:. No person shall distribute or sell, or have
in bis possession with intent to distribute or sell, any milk which contains less
than twelve JKT centum of milk solids, or more than eighty-eight per cent, of
watery tin ills, or less than three per centum of milk fats; provided, however,
that it shall not be unlawful for any i>erson to distribute or sell, or have in his
possession with intent to distribute or sell, in a container having a capacity of
not m«. re than twelve fluid ounces, milk especially prepared for infant or in-
valid feeding by adding thereto pure water, lime water, milk sugar, cereal
stan-bes, or other suhM.-mees which shall not differ in purity, quality or strength
from the standard tixed by this act, or by removing therefrom the sugar or
any part thereof, if e\ ery su.-h container have blown or moulded in it the words
"modified milk" in letters which shall not be less than one-quarter inch in
height and the several lines of which shall not be less than one-sixteenth of an
inch in width: nn*l, /,/•', r///r,/ also, that the milk in such container, before modi-
fication, shall have been milk of the standard fixed by this act. — As amended
Al.ril I ',, 1908; Laws of 1908, ch. 260, p. 551. See Bui 112, pt. 2, p. 15.
SEC. s. A'lultrmted or uncban milk prohibited. No person shall distribute or
sell or have In his possession with intent to distribute or sell any milk or cream
which contains any water, drug, chemical, preservative, coloring matter, con-
densed milk, or any substance of any kind or character which has been added
thereto or mixed therewith; provided, however, it shall not be unlawful for any
person to distribute or sell or have in his possession with intent to distribute or
sell, any milk or cream modified especially for infant or invalid feeding, by adding
thereto or mixing therewith pure water, lime water, milk sugar, cereal starches
46 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
or other substances, as provided for in section six of this act, if such modified
milk shall be in a container having a capacity of not more than twelve fluid
ounces, which container shall be marked as provided for in section six of this
act No person shall distribute or sell, or have in his possession with intent to
distribute or sell any milk or cream which is the product in whole or in any
part of any animal kept in a crowded, uncleanly or unhealthy place or condition,
or which is the product in whole or in part of* any animal fed on swill, or any
substance in a state of rottenness or putrefaction, or on any substance of an
unwholesome nature, or on any food or substance which may produce diseased
or unwholesome milk. No person shall distribute or sell, or have in his posses-
sion with intent to distribute or sell, any milk or cream which is produced in
whole or in part from any animal within fifteen days before or five days after
parturition. — As amended April 14, 1908; Laics of 1908, ch. 260, p. 552. See
Bui. 112t pt. 2, p. 15.
Approved May 20, 1907. Acts of 1907, ch. 217, pp. 488-499.
NEW YORK.
DAIRY PRODUCTS.
See Appendix, Bulletin 112, Part II, page 148, for law regulating
dairy product-, approved July 18, 1907, and included in the compila-
tion for the year ending June 30, 1907, for convenience.
FRUIT.
.185. Other thnn standard apples prohibited. No person shall buy for
• •, sell, or expose or offer for sale as and for evaporated apples any evapo-
rated apples intended to be used for food, or for consumption by any person
other than standard evaporated apples. — As amended May 23, 1908; Laws of
. }»;. />. miL Nrr Kul. //J. y,f. J. /,. ._>/.
. is*',, standard evaporated apples defined. Evaporated apples containing
nut more than twenty-seven per centum of water or fluids as determined by
dryinir for four hours at the temperature of boiling water shall be considered
standard evaporated apples for the purposes of this act. — As amended May 23,
1908; Laws of . 2, ch. 486, p. 1704. See Bui. 69, Rev., pt. 5, p. 428.
. 1^7. nn <,rk fruit to be so labeled. No person or persons shall
sell, offer or exjwse for sale apples, pears or peaches as and for New York
stat«- :m«wn apples, pears <>r peaches if they were not grown or produced within
the state "I New York; nor shall they brand or label the package or barrel
(•MiitaiiiiiiL- sueh apples, pears or peaches as New York state apples, pears or
pea • -I if* if they were not grown or produced within the state of New York.
Any person or persons packing or repacking or causing apples or pears to be
packed ..r repacked to be sold upon the markets, shall pack or repack or
cause them to be packed or repacked in such a manner that each separate
.!i;e or barrel shall be packed substantially uniform without intent to
•.••the purchaser. Any person, persons or corporation buying from a grower
apples or liich are packed in packages or barrels, marked or labeled
with the name "f the grower who causes such apples or pears to be repacked
In the same packages or barrels or who uses the same packages or barrels for
the pa. king of other fruit or apples or pears shall erase from such package or
barrel the name of the grower or packer first or originally placed thereon.
P. ut the facing of such package or barrel is not prohibited by this act. — As
am. n,l. / !/'/// 25, 1908; Laws of 1908, vol. 2, ch. 486, pp. 1704-1705. See Bui.
ll.'. pt .'. p, 21.
.188. Karrel" defined. The term "barrel" when used in transactions
of purchase or sale of apples, pears or quinces shall represent a quantity equal
ne hundred quarts of grain or dry measure and shall be of the following
dimensions: head ilia meter, seventeen and one-eighth inches; length of stave,
twent\ -eiirht and one-half inches; bulge, not less than sixty-four inches outside
measurement, if the barrel shall be made straight, or without a bulge, it shall
contain the same number of cubic inches as the barrel above described. Any
sons making, manufacturing or causing to be made or manufac-
tured barrels for use in the purchase or sale of apples, pears or quinces, or any
person or persons packing apples, pears or quinces in barrels for sale or selling
apples, pears or quinces in barrels containing a less quantity than the barrel
herein specified shall brand said barrels upon each end and upon the outside,
conspicuously, in letters one and one-half inches in length with the words,
"short barrel."— As added May 23, 1908; Laws of 1908, vol. 2, ch. 486, p. 1705.
Uiil. 69. /?€-r., pt. 5, p. -i
Laws of 1803, ch. 338 ; Gumming and Gilbert's General Laws and other Gen-
eral Statutes, Supplement 1904, vol. 4, art. 13, p. 45.
47
NORTH CAROLINA.
GENERAL FOOD LAW.
SEC. 6. Colors and preservatives prohibited; benzoic a.id sulphurous acids
excepted. For the purpose of this ac* an article of food shall be deemed adul-
terated * * *
Sixth. * * *
If it contain any of the following substances, which are hereby declared
deleterious and dangerous to health when added to human food, to-wit : Colors
which contain antimony, arsenic, barium, lead, cadmium, chromium, copper,
mercury, uranium or zinc; or the following colors: gamboge, corallin, picric
acid, aniline, or any of the coal-tar dyes ; dulcin, glucin or any other artificially
or synthetically prepared substitute for sugar except saccharine; paraffine,
formaldehyde, beta-napthol, abrastol, benzole acid or benzoates, salicylic acid or
salicylates, boric acid or borates, sulphurous acid or sulphites, hydrofluoric or
any fluorine compounds, sulphuric acid or potassium sulphate or wood alcohol ;
Provided, that catsups and condimental sauces may, when the fact is plainly
and legibly stated in the English language on the wrapper and label of the
package in which if; is retailed, contain not to exceed two-tenths of one per
cent, of benzoic acid or its equivalent in sodium benzoate. Fermented liquors
may contain not to exceed two-tenths of one per cent, of combined sulphuric
acid, and not to exceed eight-thousandths of one per cent, of sulphurous
acid.— A* amended February 1, 1908; Public Laws Extra Session 1908, ch. 117,
pp. 1SO-1S1. See Bui. 69, Rev., pt. 5, p. 487.
Approved April 13, 1899. Public Laws 1899, ch. 86, p. 216.
48
OHIO.
<;KNERAL FOOD LAWS.
SFC. 1. Adulteration and misbranding prohibited. That no person shall,
within this state, manufacture for sale, offer for sale, sell, deliver or have in
his possession with intent to sell or deliver any drug or article of food which
is adulterated, within the meaning of this act; that no person shall, within
this state, offer for sale, sell, deliver or have in his possession with intent to
sell or deliver any drug or article of food which is misbranded, within the
meaning of this act. — As amended Hay 1, 1908; Laws of 1908 (Senate Bill No.
414), p. .2.77. svr Itui. tin. AV,.. }>t. r>. it. 459.
CUB. .\dnlt<rntion defined. An article shall be deemed to be adulterated
within th*» meaning of this act:
(a) In the case of drugs: * * *
rin In the case of food, drink, flavoring extract, confectionery or condi-
ment : ill if any substance or substances have been mixed with it, so as to
lower or depn* -into or injuriously affect its quality, strength or purity; (2) if
any inferior ,,r cheaper sub stance or substances have been substituted wholly,
or in part. f»r it : (8) it' any valuable or necessary constituent or ingredient has
been wholly, or in part. abMracted from it; (4) if it is an imitation of, or is
sold under the name of another article; (5) if it consists wholly, or in part,
of a diseased, decomposed, putrid, infected, tainted or rotten animal or vege-
table lubstance or article, whether manufactured or not or, in the case of milk,
if it is the produce of a diseased animal; (6) if it is colored, coated, polished
•\vdered. \\ hereby damage or inferiority is concealed, or if by any means it
is made to apjiear better or of greater value than it really is; (7) if it contains
any added substance or Ingredient which is poisonous or injurious to health;
(8) if. when sold under or by a name recognized in the eight decennial revision
of the lulled States pharmacopoeia, or the third edition of the National
Formulary, ir .litT.-r- from the standard of strength, quality or purity laid down
therein; ('.» if. when sold under or by a name not recognized in the eighth
-ion nf the 1'nited States pharmacopoeia, or the third edition
of the National Formulary, but is found in some other pharmacopoeia, or other
stan. lard work on materia medica, it differs materially from the standard of
strength, quality or purity laid down in such work: (10) if the strength, quality
or purity falls below the professed standard under which it is sold; (11) if it
.•I ins any methyl or wood alcohol. — As amended Hay 1, 1908; Laws of 1908
•fr Hill \». 41',). pp. 257-8. See Bui. 69, Rev., pt. 6, pp. 459-60.
. 3a. J/iVt6r«M«/»X'/ d< fund. An article shall be deemed to be misbranded
within the meaning of this act:
(a) In the case of drugs: * * *
(b) In the case of food, drink, flavoring extracts, confectionery or condi-
ment : ( 1) If the package fails to bear a statement on the label of the quantity
or proportion of any morphine, opium, cocaine, heroine, alpha or beta eucaine,
chloroform, cannabis indica, chloral hydrate or acetanilide, or any derivative or
preparation of any such substances contained therein; (2) if it be labeled or
branded so as to deceive or mislead the purchaser, or purport to be a foreign
product when not so; (3) if in package form, and the contents are stated in
terms of weight or measure, they are not plainly and correctly stated on the
js^— Bull. 121— 09 4 49
50 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
ontside of the package; (4) in case of any flavoring extract, for which no
standard exists, if the same is not labeled " artificial " or " imitation " and the
formula printed in the same manner hereinafter provided for the labeling of
"compounds" or "mixtures" and their formulae; (5) if the package contain-
ing it or any label thereon shall bear any statement, design or device regarding
it or the ingredients or substances contained therein, which shall be false or
misleading in any particular ; Provided, that the provision of this act shall
not apply to mixtures or compounds recognized as ordinary articles or ingre-
dients of articles of food or drink, if each and every package sold or offered for
sale be distinctly labeled in words of the English language as mixtures or com-
pounds, with the name and percentage in terms of 100 per cent., of each in-
gredient therein. The word " compound " or " mixture " shall be printed in
letters and figures not smaller in either height or width than one-half the
largest letter upon any label on the package and the formula shall be printed
in letters and not smaller in either height or width than one-fourth the largest
upon any label on the package and such compound or mixture must not con-
tain any ingredient that is poisonous or injurious to health.— Added Hay 1,
1908; Laws of 1908 (Senate Bill No. 414), PP- 258-9. See Bui. 69, Rev., pt. 6,
p. 460.
SEC. 5. Penalties. Whoever refuses to comply, upon demand, with the re-
quirements of section 4, and whoever violates any of the provisions of this act,
shall be fined not exceeding one hundred nor less than twenty-five dollars, for
the first offense, and for each subsequent offense shall be fined not exceeding
two hundred dollars nor less than one hundred dollars, or imprisoned in the
county jail not exceeding one hundred, nor less than thirty days, or both. And
any person found guilty of manufacturing, offering for sale or selling an
adulterated article of food or drug under the provisions of this act, shall be
adjudged to pay in addition to the penalties hereinbefore provided for, all
necessary costs and expenses incurred in inspecting and analyzing such adul-
terated articles of which said person may have been found guilty of manu-
facturing, selling or offering for sale. — As amended May 1, 1908. Laics of
1908 (Senate BUI No. 414), p. 259. See Bui. 69, Rev., pt. 6, p. 460.
Passed March 20, 1884. 81 O. L., 67 ; Laning's Revised Statutes and Recodi-
fied Laws, 1905, title 5, ch. 8, pp. 1477-78.
SEC. 3a. Hindering inspector; penalty. Any person or persons who refuse to.
allow said commissioner, or any assistant commissioner or any inspector, or
any of his agents entrance to any creamery, factory, store, salesroom, drug store,
laboratory, booth, vehicle, steam or electric cars, or place which he desires to
enter in the discharge of his oflicial duty ; or in any manner interfere with said
commissioner, or any assistant commissioner, or any inspector, or agent in the
discharge of his official duty ; or refuse to deliver to him a sample of any article
of food, drug, or linseed oil made, sold, offered or exposed for sale by such
person or persons, when the same is requested and when the value thereof is
tendered, shall be fined not exceeding two hundred nor less than fifty dollars,
for the first offense, and for each subsequent offense shall be fined not exceed-
ing three hundred nor less than one hundred dollars, or imprisoned in the county
Jail not exceeding one hundred, nor less than thirty days, or both.— Added May
9, 1908; Laics of 1908 (Senate Bill Xo. 542), p. 386. See Bui. 69, Rev., pt. 6, p.
461. _
Laning's Revised Statutes and Recodified Laws, 1905, vol. 1, title 3, ch. 22,
pp. 193-94.
OHIO. 51
DAIRY PRODUCTS.
SEC. 1. Renovated buttrr must foe so marked. No person, firm or corporation
shall niaiiufiu-tuiv for sale, offer or expose for sale, sell, exchange or deliver, or
have in his possession with the intent to sell, exchange or deliver, any butter
that is produced by taking original packing stock butter or other butter, or
both, inciting tin* same so that the butter fat can be drawn off or extracted,
mixing tin- said butter fat with skimmed milk, or milk or cream, or other milk
product, and ivehurning or reworking the said mixture; nor shall any person,
firm or rorporation manufacture for sale, offer or expose for sale, sell, exchange
or deliver, or have in his possession for any such purpose any butter which has
been subjected to .-my process by which it is melted, clarified or refined, and
made to resemble butter, and is commonly known as boiled, or cold extracted
process or renovated butter, and which for the purpose of this act is hereby
designated :,s "renovated" or " process butter." unless the same shall be
branded or marked as provided in section two of this act.
Whoever, himself or by his agent, or as
the sen ant <>r :iLrcnt of another person shall sell, expose for sale or have in his
: possession with intent to sell any " renovated " or "process butter,"
lined in • •• of this act, shall have the words "renovated butter"
or ••pp-cess butter" conspicuously stamped, labeled or marked in one or two
lines anil in plain <Jothic letters, ;it least three-eidiths of an inch square, so that
the vrordfl cannot 1 nitty defaced, upon two sides of each and every tub, firkin,
ho\ or ; -renovated" or "process butter." or, if such
bun- uncovered or not in a case or package, a placard
containing >ni 1 \\.>n!> in the same form as above described in this section shall
>'ich a manner as to be easily seen and read by the
purc|ia>er. When process butter" is sold from such package
iieruise at retail, in print, roll or other form, before being delivered to the
purchaser, 11 Bhall be u:.ipped in wrappers plainly stamped on the outside
thereof \\ith the words •• iviioxatttl butter," or "process butter" printed or
stan 'ii in one or two lines, ami in plain Gothic letters at least three-
eidnl;- of an inci. and such wrap|>er shall contain no other words or
printinu' tl;er,-..n ami said words •• renovated butter" or "process butter" so
stamped or printed on the said wrapper shall not be in any manner concealed,
l>ut shall be in plai-. : he purchaser at the time of the purchase.
Any one violating any of the provisions of thn act shall for
a tirst offense be punished by a tine of not less than fifty nor more than two
hundred dollar-: for a sevond offense by a tine of not less than one hundred
nor more than three hundred dollars or by imprisonment in the county jail or
workhouse f..r not less than thirty days nor more than sixty days, or both.
t I'.ffvvt. This act shall take effect sixty days after its passage.
Approved April :'.". 1'.»U8. Laws of 1908 [Senate Bill No. 478], pp. 243-4.
. i. \<lult< rated or watered milk; i>rnaltic*. That whoever by himself or
by his servant or agent, or as the servant or agent of any other person, sells,
exchanges or delivers, or has in his custody or possession with intent to sell or
exchange or exix>ses or offers for sale or exchange adulterated milk, or milk
to which water or any foreign substance has been added, or milk from cows
fed on wet distillery waste, or starch waste, or from cows kept in a dairy or
place which has been declared to be in an unclean or unsanitary condition by
eertiticate of any duly constituted board of health or duly qualified health oflS-
rer. within the county in which said dairy is located, or from diseased or sick
cows, shall for a first offense, be punished by a fine of not less than fifty nor
52 FOOD LEGISLATION, YEAB ENDED JUNE 30, 1908.
more than two hundred dollars; for a second offense, by a fine of not less than
one hundred dollars nor more than three hundred dollars, or by imprisonment in
the jail or workhouse for not less than thirty nor more than sixty days: and
for a subsequent offense, by fine of fifty dollars, and by imprisonment in the
jail or workhouse for not less than sixty nor more than ninety days.— As
amended April SO, 1908; Laws of 1908 [Senate Bill No. 3o9~\, pp. 239-40. See
Bui. 69, Ren, pt. 6, p. 472.
Passed April 10, 1889, 86 O. L., 229; Laning's Revised Statutes and Recodified
Laws, 1905, vol. 1, title 5, ch. 8, p. 1482.
SEC. 1. Refilling of milk containers. It shall be unlawful to fill or refill, with
milk, cream or other milk product, any glass jar or bottle having the name of
any i>ersoii, firm or corporation blown therein, with intent to sell or vend such
milk, cream or other milk product, provided, that the provisions of this section
shall not extend to the person, firm or corporation whose name is blown in such
glass jar or bottle, or a duly authorized agent or employe thereof.
SEC. 2. Sterilization of milk containers. It shall be unlawful to fill or refill,
with milk, cream or other milk product, any glass jar or bottle with intent to
sell or vend such milk, cream or other milk product, unless such glass jar or
bottle be first thoroughly cleansed and sterilized.
SEC. 3. Penalty. Any person or persons guilty of violating the provisions of
the preceding section of this act shall be fined not more than one hundred
dollars.
Approved May 9, 1908. Laws of 1908 (House Bill Xo. 901), p. 454.
VINEGAR.
. 1. Cider or apple vinegar defined. That no person shall manufacture for
sale, offer, or expose for sale; sell or deliver, or have in his possession with in-
tent to sell or deliver, any vinegar not in compliance with the provisions of this
act. Any vinegar manufactured for sale, offered for sale, exposed for sale, sold
or delivered, or in the possession of any person with intent to sell or deliver,
under the name of cider vinegar, or apple vinegar, or any compounding of the
word " cider " or " apple " as the name or part of the name of any vinegar, shall
be the product made by the alcoholic and subsequent acetous fermentations of
the juice of apples, shall contain no foreign substance, drugs or acids, is Irevo-
rotatory, and shall contain not less than four (4) grams of acetic acid, not less
than 1.0 grams of apple solids, of which not more than fifty (50) per cent, are
reducing sugars, and not less than twenty-five hundredths (0.25) grams of apple
ash in one hundred cubic centimeters (at a temperature of twenty [20] degrees
centigrade) ; and the water-soluble ash from one hundred (100) cubic centi-
meters (at a temperature of [20] degrees centigrade) of the vinegar shall con-
tain not less than ten (10) milligrams of phosphoric acid (P-O5), and which
shall require not less than thirty (30) cubic centimeters of decinormal acid to
neutralize its alkalinity.
(2) Wine or grape vinegar defined. Any vinegar manufactured for sale.
offered for sale, exposed for sale, sold or delivered or in the possession of any
person with intent to sell or deliver, under the name of wine vinegar, or grape
vinegar, shall be the product made by the alcoholic and subsequent acetous fer-
mentations of the juice of grapes, and shall contain, in one hundred (100) cubic
centimeters (at a temperature of twenty [20] degrees centigrade), not less than
four (4) grams of acetic acid, not less than one (1.0) gram of grape solids, and
not less than thirteen hundredths (0.13) grams of grape ash.
OHIO. 53
(3) Mult rincynr defined. Any vinegar manufactured for sale, offered for
Siil<>. exposed for sale, sold or delivered or in the possession of any person with
intent to sell m- deliver, under the name of malt vinegar shall be the product
mud.' by tlu» alcoholic and subsequent acetous fermentations, without distilla-
tion, of .-in infusion <«f barley malt or cereals whose starch has been converted
by malt, is dextrorotatory, and shall contain In one hundred (100) cubic centi-
meters (at a temperature of twenty [20] degrees centigrade), not less than four
(4) grams of acetic acid, not less than two (2) grams of solids, and not less
rlian two tent: .-rams of ash; and the water-soluble ash from one hun-
dred (KM)) eiibie centimeters (at a temperature of twenty [20] degrees centi-
grade i, of the vim-gar shall contain not less than nine (9) milligrams of phos-
phoric a. -id t I'.o, » and which shall require not less than four (4) cubic centi-
meters of deeinormal acid to neutralize its alkalinity.
Dixtili'til rini-i/nr d< final. Any vinegar manufactured for sale, offered
for sal--. ,o. sold or delivered or in the possession of any person
with intent to sell or deliver, under the name of distilled vinegar, shall be the
product made wholly or in part by the acetous fermentation of dilute distilled
alcohol, and shall contain in one hundred (100) cubic centimeters (at a tem-
perature of twenty [ it) | degrees centigrade), not less than four (4) grams of
acetic acid, and shall be free from coloring matter, added during, or after
distillation, and from coloring other than that imparted to it by distillation. —
mended / J8, 1908; Laws of 1908 [Amni<l«l House Bill No. 931],
/*/. '-, />. 488.
>it>'t niKf ilixtillrii rinriinrx: other fermented rine-
0Bl* \ : .••_;!• made by fermentation and oxidation without
the interventi' 'illation shall be branded "fermented vinegar," with the
name «.f tin- t: i.-m which the same is made. And all vinegar
made wholly or in VD distilled liquor shall be branded "distilled vine-
and all lied vinegar shall be free from coloring matter added
duri: ; ion and from color other than that imparted to it by
distillation. And all fermented vinegar not otherwise provided for in said
section 1. and not :!led \inegar as defined in said section 1, shall con-
tain not less than two i •_• i p.-r cent, by weight, upon full evaporation (at the
temperature of boiling water) of solids, contained in the fruit or grain or sub-
stance from which said \ ine-ar i- fermented, and said vinegar shall contain not
than two and a half-tenths of one per cent, ash or mineral matter, the same
beinir the product of ihe material from which said vinegar is manufactured.
And all rlnegar shall be made wholly from the fruit or grain from which it
pur i ...us to 1 • is represented to be made, and shall contain no foreign sub-
stance, and shall contain not less than four per cent., by weight of absolute
J, 1908; Laws of 1908 [Amended House Bill
J9.
Laninc'i Kevised Statutes and Kecodified Laws, 1905, vol. 1, title 5, ch. 8,
P. i ;
OKLAHOMA.
GENERAL FOOD LAWS.
SEC. 1. Personnel of food commission. A pure food, dairy and drug commis-
sion for the State of Oklahoma is hereby created, which shall be composed of
the president of the State Board of Agriculture, the secretary of the State Board
of Agriculture, the treasurer of the State Board of Agriculture, the State Com-
missioner of Health and the secretary of the State Board of Pharmacy.
SEC. 2. Officers of the commission. The president of said commission shall
be the president of the State Board of Agriculture ; the secretary of said com-
mission shall be the State Commissioner of Health, and the treasurer of said
commission shall be the treasurer of the State Board of Agriculture.
SEC. 3. Powers and duties of commission; report. It shall be the duty of
said commission to carry into effect the provisions of this Act, and all other
Acts in force or which may be hereafter enacted relating to foods, drugs and
dairy products, and said commission is hereby authorized and empowered to
promulgate and enforce such rules and regulations as they may deem proper
and necessary to amend, alter and abolish the same from time to time not incon-
sistent with the provisions of this Act. They shall also have the power to
appoint one dairy inspector, one food inspector, and one drug inspector, to pre-
scribe their duties and powers, and to fix their compensation as hereinafter
provided. Said commission shall make an annual report to the Governor on or
about the first day of November of each year, giving in a concise manner, in
said report, a full statement of the work of said commission, and accounting for
all receipts and disbursements of the commission. Said commission shall be
authorized and empowered to print their rules, regulations and announcements
from time to time as they may deem necessary. The annual report of said com-
mission shall be printed, published and distributed the same as reports of other
State commissions. Said commission shall have authority to lease, rent and
contract for such office or offices as they may deem necessary for the convenient
transaction of the business of said commission at the seat of the State
government.
Six . 4. Dutirx of officers. The president of the commission shall preside at
all meetings of the commission and perform such other duties as the commis-
sion by their rules may prescribe.
The secretary of the commission shall keep a record of all proceedings of the
commission and perform such other duties as are prescribed in this Act, or
which may be prescribed by said commission. He shall keep an accurate ac-
count of the expenses of said commission and file monthly itemized statements
of such expenses with the State Auditor. He shall receive all moneys collected
by said commission, and promptly pay the same to the treasurer of said corn-
in ission, taking a duplicate receipt therefor, one of which shall be filed with
the State Auditor, and the other retained by said secretary. He shall make,
on the first day of each month, a report to the Governor, covering the entire
work of said commission for the preceding month and show, among other
things, the number of manufactures ° and other places inspected, and by
whom ; the number of specimens of food articles analyzed, and a list of cases
°So in Statutes.
OKLAHOMA. 55
in which adulteration was found, the number of complaints entered against
persons for the violation of the law relative to the adulteration of articles
named in this Act : the number of convictions had and the amount of fines
imposed and collected and sentences passed; and it shall be his duty to cause
tn l>e made against parties violating the provisions of this Act.
i he adjournment of the commission the secretary shall be authorized
and empowered to carry on the work of the commission.
It shall be the duty of the treasurer to receive, receipt for, and safely keep
all funds comim; into his hands, and to deposit the same with the State Treas-
urer at least once each month, taking his receipt therefor, and make to the
president of the commission on the first day of each month a full statement of
the receipts and disbursements of his office for the month next preceding.
The members of said commission shall make and subscribe to the same oath
of oilier as that prescribed in the Constitution of the State of Oklahoma for
other olIieiMls. and the secretary and treasurer shall each give bond in the sum
of live thousand dollars «-,n h for the faithful performance of the duties of their
ectlve "Hiccs, which bond shall be approved by the Governor and filed with
the Secretary of State.
•Hun. The said hoard of commissioners shall receive their
actual expense! \\ :• •••«! in the performance of their duties in connection
with this A.M. authorized to employ a stenographer or clerk
at a salary DOl y-tivo dollars per month, also to fix the com-
not to exceed three dollars per day and actual
•
fin- iinn ///.s/x n f santiih'tt. For the purpose of this
there is 1 ihlished two state laboratories /or the analysis of food,
which shall he under the supervision of
said commission. One of said laboratories shall be established and located at
the g ;ul the director of said laboratory shall be the professor
of the department ' niversity. The other laboratory
i he State Agricultural and Mechanical College at Still-
d the di, 'aboratory shall be the chemist of the experi-
ment station in the said Airri.-iiltural and Mechanical College. To the said
laboratory at :y all samples of drugs and medicines shall be
filiation. And to the said laboratory at the said
:i It lira I ; vp' shall be sent for analysis and examination
nuples of foods and feeding stufts. and all samples of dairy products. The
v ami the sai.l Agricultural and Mechanical College shall employ
such additional chemists and assistants as are necessary properly and expedi-
aiine and analy/e such dniirs. medicines, food and dairy products
,. sent tl :• said commission for the purpose of determining whether
such art • --I, misbranded and mislabeled within the meaning
,,f thlfl Act, and 11 11 <h:il! app.-ar that any of such specimens are adulterated,
mislabeled or mNbranded within the meaning of this Act, the secretary of the
commission shall at once certify the facts to the county attorney of the county
in which rod) sample was taken, with a copy of the results of the analysis of
the examination of such samples, duly authenticated by the analyst or officer
making such examination or analysis, under oath of such analyst or such officer;
Provided, that said commission may submit to the department of chemistry at
the I University or at the said experiment station of Agricultural and
.lle-e, any sample or samples of any article of food, drugs, medi-
« or dairy product for analysis, and the directors of such departments
shall make and furnish the commission such analysis or analyses.
56 FOOD LEGISLATION, YE\B ENDED JUNE 30, 1908.
The said commission, out of the appropriation hereinafter provided, may
employ and fix the compensation of other and additional clerical and profes-
sional assistants.
SEC. 7. Inspection and prosecution. Said pure food commission is hereby
given full jurisdiction over the regulation and control of the manufacture and
sale of all foods, drugs and medicines and dairy products, and shall be author-
ized and empowered to make inspections concerning the purity of the same and
to bring prosecutions for violations as provided herein in the case of foods,
drugs ami dairy products, and shall exercise the necessary police authority in
the enforcement of this Act for the preservation of the public health.
SEC. S. .\<Ui11cration and misbrandr-ig prohibited. The manufacture, produc-
tion, preparation, compounding, packing, selling, offering or keeping for sale
within the State of Oklahoma, or the introduction into the State from any other
State or Territory, or the District of Columbia, or from any foreign country of
any article of food or dairy product which is adulterated, mislabeled or mis-
branded within the meaning of this Act is hereby prohibited.
Any person, firm, company or corporation who shall import or receive from
any other State, Territory, or the District of Columbia, or from any foreign
country, or who having so received, shall deliver, for pay or otherwise, or offer
to deliver to any other person any article of food or dairy product mislabeled
or misbranded within the meaning of this Act, or any person, firm or corporation
who shall manufacture or produce, prepare, compound, pack or sell or offer or
keep for sale in the State of Oklahoma any such adulterated, mislabeled or mis-
branded food or dairy product shall be guilty of a misdemeanor : Provided, that
no article of food or dairy product shall be deemed adulterated, mislabeled or
misbrauded within the provisions of this Act, where prepared for export beyond
the jurisdiction of the United States and prepared or packed according to the
specifications or directions of the foreign purchaser, when no substance is used
in the preparation or packing thereof in conflict with the laws of the foreign
country to which said article is intended to be shipped.
SEC. 9. Term " person " defined. The word person, as used in this Act, shall
be construed to impart the singular and the plural, as the case may demand,
and shall include corporations, companies, societies and associations. When
construing and enforcing the provisions of this Act, the act, omission or failure
of any officer, agent or other person acting for or employed by any corporation,
company, society or association, within the scope of employment of his office,
shall in every case be also deemed to be the act, omission or failure of such cor-
poration, company, society or association, as well as that of the person.
SEC. 10. " Food " and " dairy products " defined. The term " food," as used
in this Act, shall include all articles of food, drink, liquor, beverage, confec-
tionery or condiment used by man or other animal, whether simple, mixed or
compound. The term " dairy product," as used in this Act, shall include milk,
cream, butter, cheese, skimmed milk, buttermilk or any modification of the fore-
going materials or compounds containing one or more of same and all products
derived from milk.
11. Food standards. The standard of purity of foods shall be that
proclaimed by the Secretary of the Department of Agriculture of the United
States.
28. Food adulteration defined. Food shall be deemed to be adulter-
ated within the meaning of this Act in any of the following cases :
First: If any substance has been mixed or packed with the food so as to
reduce or lower or injuriously affect its quality, purity, strength or food value.
Second: If any substance has been substitued wholly or in part for the
article of food.
OKLAHOMA. 57
Third: If any essential or valuable constituent or ingredient of the article
of food has been wholly or partly abstracted.
Fourth: If it be mixed, colored, powdered, coated or stained in any manner
whereby damage or inferiority is enneealed.
Fifth: If it contain any added poisonous or other added deleterious ingredi-
ent in the food.
Sixth: If it consists in whole or in part of a filthy, decomposed or putrid
animal or vegetable substance, or any portion of an animal or vegetable unfit
for food, whether manufactured or not, or if it is the product of a diseased
animal, or one that has died otherwise than by slaughter.
Si<\ i".». Mixhriimlhin nf f»<t>l <l< n»<'<l. Food shall be deemed mislabeled or
misbranded within the meaning of this Act in any of the following cases:
First : If if In- in imitation of or offered for sale under the distinctive name
other article of food.
•>nd : If it be labeled, or branded, or colored so as to mislead or deceive
the purchaser, or if it be falsely labeled in any respect, or if it purport to be
a foreign product when not so, or if the contents of the package as originally
put up shall have been removed in whole or in part and other contents shall
have been plac.-d in such package.
Third: If in \. :<>rm and the contents stated in terms of weight or
measure, they .n-e not plainly and correctly stated on the outside of the package.
:rth: If tin- ; ••ntaining it or its label shall bear any statement,
• ganling the ingredients or the substance contained therein,
which statement, design or device shall be false or misleading in any par-
ticular.
Fifth: When the package bears the name of the manufacturer, jobber or
seller, or ili.- grade of the product, it must bear the name of the real manu-
facturer, jobber or •eller, a:nl the true grade or class of the product, the same
to be expressed in . lish words in legible type; Provided, that
an article be deemed misbranded if it be a well known food
product of a nature, qua lily and a pi >ea ranee, and so exposed to public inspec-
tion as not to "!• deceive or tend to mislead or deceive a purchaser,
and not misbranded and not of the cljaracter included within the definitions of
one to four of this s«-diou; 1'rovided, that all packages of imitation butter and
cheese shall be so labeled.
8«c. 30. <ig proprietary preparations. * * * Before any
manufacturer or propi ny food, proprietary or secret preparation, or
product of ;iny food or article used in the preparation of food, drug or liquor,
or medicine, shall sell, expose or offer for sale or exchange within said State,
he shall first pp. cure from the said commission a license or permit to sell the
same, and shall pay a tiling fee. and for each license or permit so filed in any
sum not to exeeed $30.00, as required by said commission, said filing fee to be
paid annually.
[Sees. :;i :\\ relate to drugs.]
Mititrnmlinu //»•//*/»»/. That the term "misbranded," as used herein,
shall apply to all articles which enter into the composition of foods and drugs,
the packa-e ,.r label of which shall bear any statement, design or device regard-
ing such article or the ingredients or substances contained therein, which shall
be false or misleading in any particular.
•• riiricni/c " d< fhn <!. The term "package," as used in this Act, shall
1 oust rued to include the original unbroken package, phial, bottle, jar, demi-
john, carton, i <-an, box, barrel, or any receptacle, vessel or container
of whatsoever material or nature which may be used by a manufacturer, pro-
58 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
ducer, jobber, packer or dealer for enclosing any article of food or any drug
or medicine when exposed or offered for sale.
SEC. 37. Possession evidence of violation of act. The possession of any adul-
terated, mislabeled or misbranded article of food, dairy product or drug, or
the offering for sale or the sale of any adulterated, mislabeled or misbranded
food, dairy product or drug, by any manufacturer, producer, jobber, packer or
dealer in £ood or drugs, or broker or commission merchant, agent, employee or
servant of any such manufacturer, producer, jobber, packer or dealer, shall be
prima facie evidence of the violation of this Act.
SEC. 38. Hotel signs for imitation butter and cheese, adulterated milk and
lard. Whenever any hotel, tavern, restaurant, or boarding house shall know-
ingly serve for the use of their patrons such food as is defined in this Act as
compounds, imitations, blends, renovated butter, imitation cheese, adulterated
milk or adulterated lard [they] shall keep conspicuously posted or printed in
a bill of fare a list of the articles of food so served in plain and legible words,
the brands or labels upon the original package or the constituent parts of such
food articles.
SEC. 44. Imitation honey must be so labeled. It shall be unlawful for any
person to sell, offer, or expose for sale or exchange, any honey which has not
been wholly made by bees, unless the same is labelled " imitation " and con-
tains nothing that is injurious to health.
SEC. 47. Protection of meat and game. Every dealer or peddler in slaughtered
fresh meats, fish, fowl or game for human food, at wholesale or retail in the
transportation of such food from place to place, to customers, shall protect the
same from dust, flies and other vermin, or substances which may injuriously
affect it by securely covering it while being so transported.
SEC. 48. "Sale " defined. The taking of orders or the making of agreements
or contracts by any person, firm or corporation, or by an agent or representa-
tive thereof, for the future delivery of any of the articles, products, goods,
wares or merchandise embraced within the provisions of this Act, shall be
deemed a sale within the meaning of this Act.
SEC. 49. Penalty for misbranding or defacing label. Whoever shall falsely
brand, mark, stencil or label any article or product required by this Act to be
branded, marked, stenciled or labeled, or shall remove, alter or deface, mutilate,
obliterate, imitate, or counterfeit any brand, mark, stencil, or label so required,
shall be deemed guilty of a misdemeanor, and upon conviction thereof shall be
punished by a fine of not less than fifty dollars nor more than five hundred
dollars, or by imprisonment in the county jail for not less than six months nor
more than one year, or by both such fine and imprisonment, for each and every
offense.
SEC. 51. Penalty. Whoever shall do any of the acts or things prohibited or
willfully neglect or refuse to do any of the acts or things enjoined by this Act,
or in any way violate any of its provisions, shall be deemed guilty of a misde-
meanor, and where no specific penalty is prescribed by this Act, shall be pun-
ished by a fine of not less than twenty-five nor more than five hundred dollars
or by imprisonment in the county jail for a period of not less than thirty days
nor more than ninety days, or by both such fine and imprisonment.
SEC. 55. Colored distilled vinegar illegal. It shall be unlawful for any person,
firm, or corporation to sell or offer for sale in this State, any colored, distilled
vinegar.
SEC. 58. Possession shows intent to commit offense. If any person shall have
in his possession or control any article or articles of adulterated or misbranded
or mislabeled food, drugs, or medicines, contrary to the provisions of this Act, he
shall be held to have possession of property with intent to use it as a means of
OKLAHOMA. 59
committing a public offense, and all the provisions of the chapter in the statutes
of the State of Oklahoma relating to search warrants and proceedings thereby
shall apply.
SEC. .7.). Apprftprintiitn. There is hereby appropriated out of the funds in the
state treasury not otherwise appropriated, the sum of five thousand dollars, or
so much thereof as may be necessary for the purpose of paying the salaries and
expenses of the officers created under this Act, and for the maintenance of the
state Laboratories created under this Act, and the necessary expenses incurred
in the enforcement of this Act.
. 60. Dutit* nml powers of food inspectors; sheriffs appointed agents;
snmpaiii/. It shall be the duty of the pure food inspectors to make, or cause to
he made, by one of the directors of the state laboratories examinations and
analyses of foods or drugs on sale in Oklahoma, suspected of being adulterated,
mislaheled, misbranded. impure or unwholesome, in contravention of the law.
And if upon examination or analysis, it is found that said food or drug is adul-
terated, mislalteled. misbranded. impure or unwholesome, it shall be the duty of
the pur*- food inspector to make complaint against the manufacturer or vendor
1 hen-ot' in tin- proper county and to furnish the evidence thereon, and thereof to
obtain a c.mvietion of the offense charged. And the sheriffs of the respective
counties of tli-- - hereby appointed and constituted agents for the enforce-
ment of this Aet, and the pure food inspector or any sheriff shall have free access
at all reasonable hours for (he purpose of examining any place where it is sus-
IH-cieii i bat any article of adulterated, mislaheled, misbranded, impure or
unwholesome !'«•• d. medicine «>r drui: exists, and such food inspector or sheriff,
upon tendering the ma: of such article, if a sale be refused, may take
from any person, tinn , tion, samples of any article suspected of being
adulterated, t ;ded, impure or unwholesome, for the purpose
of examination or anal\ si>. and divide the said article into three parts, and each
part shall be sealed by the pure food inspector or sheriff seizing the said article,
with a seal pn>\ ided for that purpose. If the package be less than four pounds
or in volume less than two quarts, tlmv packages of approximately the same size
shall be pun based and the marks and tags upon each package noted as above.
one shall he delivered to the party from whom purchased, or the party guaran-
teeing such merchandise, one sample shall be sent or delivered to one of the
di ret tors of the ^tate laboratories for examination and analysis, and the third
shall lie held by the sheriff of the county in which said article was seized, under
seal, for futui. -• should the case come to trial.
. ''.I. SI * and es IK- matures. For his services hereunder, the
sheriff shall he allowed the same fee for travel allowed by law to sheriffs on
servi.-e ,,f erimina! process, together with such compensation as by the board
of county commissioners of his county, may be deemed reasonable, and all
amounts expended by him in procuring and transmitting the said samples,
which f.vsand amount expended shall be audited and allowed by said board of
county commissioners and paid by said county as other bills of said sheriff.
..'iow. It shall be the duty of all prosecuting officers of the
State to prosecute to completion all suits brought under the provisions of this
Act. upon the complaint of any member of the pure food, dairy and drug com-
mission or any other citixen of the State of Oklahoma. It shall be the duty of
all city and county health officers to take cognizance of and to report all prose-
cutions or violations of this Act, which may be brought to their notice or they
have cognizance of within their jurisdiction.
IH*pt,xitii,n <>f tin**. One half of all fines collected by any court or
judge for the violation of the provisions of this Act, shall be paid to the state
60 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
treasurer, one half shall be paid into the treasury of the county where such
cases are prosecuted.
SEC 64. hindering inspectors a misdemeanor; penalty. It shall be a misde-
meanor for any person, firm or corporation to refuse to sell to the pure food in-
spector, sheriff or agent of the pure food, dairy and drug commission any sample
of food' or drug suspected of being adulterated, uiisbranded, mislabeled, impure
<T unwholesome, UJMHI the tender of the market price thereof, or to conceal
such f«>i>d. liquor, dmi: or medicine from such officer, or to with-hold from him
Information where such food or drug is kept or stored. Any such person so
refusing to sell, or concealing such food, medicine, or drug or with-holding such
information from said officer upon c< aviction, shall be punished by a fine of not
It-ss than twenty-five dollars, nor more than one hundred dollars, or by impris-
onment in the county jail for not less than thirty days nor more than ninety
days.
SKC. »'.."). <! iinruntrc for protection of dealer. No dealer shall be prosecuted
under the provisions of this Act, when he can establish a guarantee signed by
the wholesaler, jobber, manufacturer, or other party residing in the United
States from whom he purchased such article to the effect that the same is not
adulterated, mislabeled, or misbranded within the meaning of this Act. Said
guarantee to afford protection must contain the name and addresses of the
party of0 parties making the sales of such articles to said dealer, and an
itemized statement showing the article purchased, or a general guarantee may
be filed with the secretary of the United States department of Agriculture,
by the manufacturer, wholesaler, jobber, or other party in the United States
and given a serial number, which number shall appear on each and every
package of goods, sold under such guarantee with the words "guaranteed un-
der the food and drugs Act, June thirtieth, nineteen hundred six." In case the
wholesaler, jobber, manufacturer, or other party making such guarantee to
such dealer resides without this State, and it appears from the certificate of the
director of the state laboratory that such article or articles were adulterated,
mislabeled or misbranded, within the meaning of this Act or the " National
Pure Food Act " approved June thirtieth, nineteen hundred six, the attorney
general of this State must forthwith notify the attorney general of the United
States of such violation.
SEC. 66. Repeal. All acts and parts of acts in conflict with this Act are hereby
repealed.
SEC. 67. Goods bought prior to passage of law exempt. That in any prose-
cution for any violation of any provisions of this Act, relative to the manufac-
ture, possession or sale of any alleged food product or drug, it shall be a valid
defense for the defendant to prove that the articles described in the complaint
were in his possession as a part of his stock in trade in this State prior to the
time of the passage and approval of this Act.
SEC. 68. Date of effect. An emergency is hereby declared by reason whereof
it is necessary for the immediate preservation of the public health, peace and
safety, that this Act take effect from and after its passage and approval.
Approved May 26th, 1908. Session Laws 1907-1908, ch. 37, pp. 403-426.
BREAD.
SEC. 55. * * * Labeling of bread as to time of baking. It shall be
unlawful for any person in this State to sell, or offer to sell any loaf bread,
manufactured outside of the State of Oklahoma without having pasted on
0 So in Statutes.
OKLAHOMA. gl
each loaf of such bread, a label having written or printed thereon the date
and hour of the day the same was baked, and it shall be unlawful to sell any
bread over >eventy-two hours after the same was baked, without informing
each person purchasing or offering to purchase the same that it is "stale
bread."
Session Laws 1907-1908, ch. 37, p. 422.
CONFECTIONERY.
SKC. .TT. Atlultcrati'ni of confectionery; iirnalti/. Any person manufacturing
for sale, <>r selling or offering to sell or exchange any candies, or confection-
eries, adulterated by admixture of terra alba, barytes, talc, or other earthly0
or mineral substances. or any poisonous colors, flavors or extracts, or other
deleterious ingredients detrimental to health, shall upon conviction thereof
before a court of competent jurisdiction be punished by a fine of not less than
ten nor more than one hundred dollars <>r by imprisonment in the county jail
not less than ten days nor more than thirty days, or by both such fine and
Imprisonment
Session Laws P.M.: i:*>s. ,-b. :;:. p. 423.
I'AIKY PRODUCTS.6
stanil'iniM ]<>,- mill.* an>l <T«IIH. The following minimum standards
;rit y for milk and civain are hereby established: Milk shall contain not less
than three per centum of butter fat. and cream contain not less than eighteen
• •lit inn of butter fat. and it is hereby made unlawful for any person or per-
il or offer for Bale in this State, except under test, any milk or cream
falling below said minimum standard therefor. In no event shall milk or cream
be sold or offered for sale when produced within thirty days before or fifteen
days after rah in;:.
In testing milk or en-am for commercial purjioses under the provisions of this
the same shall be done in accordance with the rules and regulations there-
for prescribed by said commission.
All cream sold in the State of Oklahoma shall be tested for butter fat by the
following prescribed method
The I'.abco.-i. .ill be employed, using u weighed sample of eighteen
gran.- d on a delicate balance and tested in a nine inch bottle, gradu-
ated t-.u least •:•-•••••• - • cut of the column of fat read above a tempera-
ture of one hundred thirty <: hrenheit. It is hereby made unlawful for
any person to test milk or cream at any milk or cream receiving station or at
any place where mi!k op .ream is tested for commercial purposes, without first
securing a permit issued by said commission. Said commission is hereby
authori/.ed to js>ue to any IKTSOII making application therefor, a permit to test
milk or cream, if. on examination such person be found competent to test milk
or cream ; said examination shall be given under the direction of said commis-
sion at convenient places therefor throughout the State. All permits so issued
shall expire on the thirtieth day of June next succeeding the date of issuance.
It is hereby made the duty of said commission to supply to each inspector, a
r under this Act, at the time of issuing to him a license or permit and copy
of all rules and regulations formulated by said commission relating to the dairy
industry then in force. It shall be unlawful for any owner or employe of any
0 So in Statutes. & See also General Food Laws, page 54.
62 FOOD LEGISLATION, YEAK ENDED JUNE 30, 1908.
creamery or cheese factory, or for any person, to improperly manipulate or
under-read the Babcock test.
It shall be unlawful for any person, agent or employe of any creamery,
cheese factory or person to so manipulate the sampling that the sample taken
does not fairly represent the uniform mixture of the cream or milk from which
It was taken.
If milk sold or offered for sale under the provisions of this Act as pure milk,
is shown upon analysis by weight, to contain more than eighty-seven and five
one-hundredths per centum of watery fluid, or to contain less than twelve and
fifty one-hundredths per centum of milk solids, or less than three per centum of
butter fnt, <>r if the gravity at sixty degrees Fahrenheit is not between one hun-
ilivd twenty-nine one-thousandths to one hundred thirty-three one-thousandths,
it shall be deemed adulterated. If milks sold or offered for sale under the pro-
visions of this Act as skimmed milk has a gravity at sixty degrees Fahrenheit
less than one and thirty-two one-thousandths, and greater than one and thirty-
seven one-thousandths, it shall be deemed to be adulterated.
SEC. IS. Aimliixis of suspected mill's. Whenever the pure food inspector has
reason to believe that any milk found by him is adulterated, he shall take speci-
mens thereof and test the same with such instruments as are used for such pur-
pose, and he shall make an analysis thereof, showing total solids, the percent-
age of butter, the percentage of water and the percentage of ash, and if the
result of such test and analysis indicated that the milk has been adulterated
or deprived of its fat below the requirements of section twelve ot this Act, the
same shall be prima facie evidence of such adulteration in a prosecution under
this Act.
SEC. 14. atti milk inspectors. Authority is hereby given the city council of
any city, or the board of trustees of any town or village, to appoint an inspector
of milk in any such city or town and to fix his compensation, and when ap-
pointed the said inspector of milk shall have all the powers given him by sec-
tion twenty of this Act, and shall perform all the duties required of inspectors
of milk as provided herein, and such other powers and duties as may be con-
ferred or imposed by the ordinances of said cities or towns.
SEC. 15. Adulteration of milk prohibited ; milk defined. No person shall offer
for sale, sell, exchange or deliver or have in his possession with the intent to
sell, exchange or deliver, any milk, to which water, chemicals or preservatives,
or any other foreign substance has been added. The term " milk," as used in
this Act, shall include all milk, cream or milk, in its natural state as drawn
from the cow.
SEC. 16. Adulteration of milk a misdemeanor. Whoever shall adulterate, by
himself, or by his servant or agent, or sell, exchange or deliver, or have in his
custody or possession, with intent to sell or exchange the same, or expose or
offer for sale, adulterated milk, or milk to which water or any foreign sub-
stance or substances in any state of fermentation or purification or from any
sick or diseased cows shall be guilty of a misdemeanor.
SEC. 17. Skimmed milk regulations. Whoever shall adulterate, or cause to be
adulterated, sell, exchange or deliver, or have in his custody or possession, with
intent to sell or exchange the same or expose or offer for sale or deliver as pure
milk, any skimmed milk, from which the cream or any part thereof has been
removed, shall be guilty of a misdemeanor.
SEC. 18. Labeling of skimmed milk. Any dealer in milk who shall, by him-
self, servant or agent, sell, exchange or deliver, or have in his custody or pos-
session, with intent to sell, exchange or deliver the same, milk from which the
fat has been removed, so as to reduce the same below the requirements of sec-
OKLAHOMA. 63
tion thirteen of this Act, unless in a conspicuous place above the center upon
tin- outside of every vessel, can or package from which any such milk is sold,
the words " skimmed milk " are distinctly painted or printed, shall be guilty of
u misdemeanor.
. r.». Mn mi fnrt ii n-r and dealers in imitation cheese and butter defined;
" rrnimi ru" <in<l " cheese factorji " defined. Every person who in any manner
product's imitation butter or imitation cheese shall be considered a manufac-
turer thereof.
Any person who sells imitation butter or imitation cheese in packages or
quantities containing more than ten pounds, shall be deemed a wholesale dealer
thereof.
Any person who deals in imitation butter or imitation cheese in packages con-
taining less than ten pounds each, shall be deemed a retail dealer thereof.
The word "creamery," as used in this Act, is hereby defined as a factory
where cream or milk from two or more dairy herds, with or without the addi-
tion of salt and coloring matter, is churned into butter. The term "cheese fac-
tor,}." as used in this Act. is hereby defined to be a factory where milk from
two i,r more dairy herds, with or without the addition of salt and coloring mat-
- manufactured into cheese. The term *' to test milk or cream," as used in
this Act. defined as the process or method by which the percentage of
butter fa I in said milk or en-am is determined.
. •_'". /•• rmitt ;'"/• /*////• /•. ••//. , >. . <///./ i,-> n-rum factories, etc. It is hereby
made unlawful for any manufacturer, wholesale dealer or retail dealer in imi-
tation butter or imitation cheese, or both, to enter upon or engage in the busi-
:iianufacturing. handling or selling imitation butter or imita-
tion ciieese without lirst procuri'i:: fmni said commission a permit describing
the o, , i; atiOD and place of business of the person cngaircd in the same, which
it shall . i he thirtieth day of June following its issuance unless
. made unlawful to operate any creamery or cheese
•h. without firM securim: from said commission }l permit, in which
jn'rniit shall he described the place of business of tho applicant and the business
to in- c,.:iducted under said permit, h is hereby made unlawful for any person
igagr in the business of buying cream for any butter, cheese or ice cream
ry without tirst securing from said commission a permit, in which permit
shall be .lex, ribed the place of "business of the applicant and the business to be
conducted ut!' permit. It is hereby made unlawful for any person
i the business of buying cream in this State for the purpose of manu-
: shipment out of the State to make discriminations in the price paid
'ich cream when purchased upon the same day at different places in said
Cost of permits. For permit issued in connection with this Act,
there shall be charged and collected annually as follows: From each manu-
facturer of imitation butter or imitation cheese, the sum of fifty dollars; for
wholesale dealer in imitation butter or imitation cheese, twenty-five dol-
: from each retail dealer in imitation butter or imitation cheese, ten dollars;
from each creamery or cheese factory, five dollars; from each person engaged in
esting of cream or milk for commercial purposes, one dollar; said fees shall
aid as pro\ ided by law, in advance of the issuance of any permit. All
permits so issued shall expire on the thirtieth day of June next succeeding the
date of issuance. When a permit is issued to such manufacturer, dealer, cream-
ery or factory after the beginning of any license year, the fee charged and col-
••d therefor shall be proportioned to the unexpired portions of such year,
counting from the first day of the month in which such license is issued.
64 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
SEC. 22. Unsanitary implements unlawful. It is hereby made unlawful to use
or employ, in and about the keeping or handling of any milk, cream or dairy
products to be used as food, any pail, can, vessel, churn, separator or other
implement which is in an unclean or unsanitary condition, or to operate any
creamery or factory in the manufacture of any dairy products which is in an
unclean condition.
SEC. 23. Diseased cows. It shall be unlawful knowingly to sell or offer for
sale any milk or cream from diseased or unhealthy cows, or from cows kept in
a filthy or unsanitary condition, and the pure food, dairy and drug commission
is hereby empowered to adopt and promulgate such rules and regulations gov-
erning the use of diseased milch cov s, and products derived from such cows,
and to employ such scientific assistance in the enforcement of said rules and
regulations.
SBC. 24. Duties of chief dairy inspector. The said chief dairy inspector shall
act on all reports and complaints he may receive from the secretary of the com-
mission and from owners or managers of creameries, cheese factories, farmers
and others who are interested in dairy products, wherein are reported to him
any violations of this Act, or conditions which result in making or rendering
dairy products used or to be used for dairy, food or commercial purposes,
unclean or unwholesome, and take such action thereon as may be directed by
said commission or the secretary thereof and as may be permitted by this Act,
or he may deem necessary and proper for improving and advancing the best
interests of the dairy industry in this State and public health. He shall also,
each month make to the commission a concise report of his transactions as said
chief dairy inspector, and make such recommendations in the premises as he
shall deem proper and for the better perfection and encouragement of said
industry. It shall be the duty of said chief dairy inspector, and such other
dairy inspectors as may be appointed by the commission from time to time, to
inspect farm dairies, milk and cream receiving stations, creameries, factories
and places where dairy products are produced, handled, tested, manufactured,
sold or offered for sale and the products thereof, and all utensils, machinery,
appliances, implements and methods used or employed in connection therewith.
SEC. 25. Authority of inspector; sampling. The said dairy inspector shall
have full access, ingress and egress to and from all places where dairy products
intended for sale are produced, manufactured, stored, transported, kept or
offered for sale. They shall also have the power and authority to open any
package, can or vessel containing such products, and may inspect the same and
take true samples therefrom for analysis upon paying therefor the full value
thereof to the party entitled thereto. Each sample so taken shall be divided into
three parts, each equal to the other in amount and quality, two of said parts
to be delivered to the chemist of said commission at the Agricultural and
Mechanical College at Stillwater, the other sample so taken to be preserved
in the office of the commission, and upon application delivered to the person
or persons from whom taken when applied for by him, his agent or attorney,
provided that said samples shall each be carefully sealed and labeled when and
where taken. It shall be unlawful for any person or persons to obstruct, hinder
or delay any of said inspectors in the discharge of their official duties.
SEC. 26. Prosecution. If it shall appear from the report of the chemist, report
of said dairy inspectors, or any of them, that any of the provisions o* this Act
have been violated, the secretary shall certify the facts to the proper county
attorney with a copy of the result of the analysis, if any has been made, duly
authenticated to by the chemist under oath. It shall be the duty of every county
attorney to whom the secretary shall report any violation of this Act, or any
OKLAHOMA. 65
other Acts relating to dairy products, to cause proceedings to be commenced in
the name of tin- State of Oklahoma and prosecute the same without delay for
the recovery of any tines and penalties in such cases provided.
. I'T. "('r' <iin dn'rk;" {H-nnlty. It shall be the duty of every person engaged
in the buying of cream for manufacture into butter, cheese, ice cream or other
products, to give a receipt or "cream check" therefor, clearly and thoroughly
stating the name and principal place of business of the person, firm, corpora-
tion or association f»\- whom such cream is purchased, and any person, firm,
corporation or association who shall violate any of the provisions of this Act
shall IM- deemed guilty of a misdemeanor, and in addition thereto, shall forfeit
his license or permit to engage in such business.
BEC, • // ///»»/«// *«/•• "/ w'/A- n xrimratr nffcnxc ; hindering inspector.
Kach and e\ cry quantity of milk sold or exposed for sale or exchange con-
trary to the provisions of this Act, shall constitute a separate offense.
Any person who shall refuse to permit the pure food inspector, or his
•ant, to perform his duty under this Act, either by refusing him entrance
to his premises, or by concealing any milk or refusing to permit any animal or
milk on premises wherein the animals are kept to be viewed and inspected as
herein provided, or t.y in0 any manner hindering or resisting any said inspector
:or in the performance of his duty, shall be guilty of a mis-
demeanor.
Session Laws 1907-1908, eh. .TT, pp. 4os -i •_•:;.
FLAVORING EXTRACTS,
SEC -I."., linit-- mu*t bf m t IntH'h'il. It shall be unlawful
:iy person t<« manufacture, sell or offer for sale or exchange as extracts,
••TOring which was i from the natural fruit unless the same are
that the word " Imitation" must immediately
be name of the flavoring. in the same type and style. Such flavoring
shall I ;• deleterious to health.
It shall be unlawful for any person to manufac-
ture. -\ tract of vanilla, essence of
• >t wholly made from the extracted matter of
vanil
Session Laws P.M.; p. M.S. ch. .",7. p. 420.
FLOUR.
/ nf fl,,ur ri,,,ti><,nml-:. Within this State no person shall
i MI- sale. keep in his possession with intent to sell
lour made from wheat containing any products of corn, rice
or other foreign I I, unless each and every package thereof be dis-
tinctly and legibly branded or labeled "Hour compound" in letters not less
thai.. i,h 1, j:i length and be followed with the name of the maker and
mill ami t: such tlouring mill.
- fli.ur rtiminiiimlx rridence of intent to sell. The hav-
ing possession of any "tlour compound" or "meal compound" which is not
branded .,,- labelled as hereinbefore required and directed upon the part of any
on en-aged in the public or private sale of such article shall, for the pur-
\ct. be deemed prima facie evidence of intent to sell the same.
°So in Statutes.
64289— Bull, ll'l— O9 - 5
66 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
SEC. 54. " Sale " defined. The taking of orders or the making of agreements
or contracts by any person, firm or corporation, or by an agent or representa-
tive thereof, for the future delivery of any " flour compound " or " meal com-
pound " shall deemed a a sale within the meaning of this Act.
Session Laws 1907-1908, ch. 37, p. 422.
HONEY.
«•
See General Food Laws, sec. 44, page 58.
LARD.
SEC. 39. Exemptions; lard compoun < and substitute defined. The provisions
of this Act shall not apply to substances for sale in this state, made in the
semblance of lard, if the ingredients or component parts shall consist of pure
lard, beef fat or pure steariue and cottonseed oil that is one per cent of the
legitimate and exclusive fat of the hog, .or pure lard, pure stearine or beef fat,
and ninety-nine per cent of cottonseed oil, and the tierce, tub, pail or package con-
taining the same is distinctly and legibly branded, marked or labeled, " lard com-
pound " or " compound lard " or " lard substitute " in letters proportional to
the size of the package, and if such mixture contain any other substance than
pure lard, pure stearine or beef fat, or pure cottonseed oil, then the person or
corporation so manufacturing shall cause the tierce, barrel, tub, pail or package
containing the same to be distinctly and legibly branded, marked or labeled
" adulterated lard " ° the term " lard compound " or " compound lard," as
used herein, shall include all articles of food used as lard, or made in the
semblance of lard, which shall be composed of two or more ingredients or com-
ponent parts, consisting of either cottonseed oil, pure lard or hog lard, beef fat
or pure stearine, the percentage of either of the two or more ingredients used
to be in the discretion of the manufacturer. The term " lard substitute," as
used herein, shall apply to any compound which may consist of two or more
of the aforesaid ingredients or of cottonseed oil alone. Neither shall the pro-
visions of this Act apply to mixtures or compounds consisting of mixtures
of beef suet, beef fat or pure stearine, and cottonseed oil, or of cottonseed oil
alone, when said mixtures or compounds used as ordinary articles of food, or
cooking "compounds" are manufactured and sold under their proper trade-
mark, and when the tierce, barrel, tub, pail or package containing the same
shall be distinctly and legibly branded or labeled with the name of the mixture
or compound, in letters proportioned to the size of the package, and the name
and location of the person, firm or corporation manufacturing the same.
SEC. 40. Labeling of lard compounds, etc. Every manufacturer, trader or
dealer who, by himself or agent, or as the servant or agent of another person,
offers or exposes for sale, or sells or exchanges any form of lard substitute
or adulterated lard as hereinbefore defined, shall securely fix or cause to be
affixed to the package wherein the name0 is contained, offered for sale or
sold, a label upon the outside and face of which is distinctly and legibly printed
in letters not less than one-half inch in length, the words " lard substitute,"
" adulterated lard " or " lard compound " or other appropriate words which
shall correctly express its nature and use.
SEC. 41. Possession of lard substitute cridcnce of intent to sell. The having
hi possession of any lard substitute or adulterated lard compound, as herein-
before defined, which is not branded or labeled as hereinbefore required or
0 So in Statutes.
OKLAHOMA. 67
directed upon the part of any manufacturer, trader or dealer, or any person
eu-a-'cil in the sal.- of such articles, shall, for the purpose of this Act, be
:«•<! prima t'acic evidence of intent to sell or exchange the same.
;on Laws 1! 107-1908, ch. 37, pp. 418-419.
MEAT.
See General Food Laws, sec-. 47. paw 58.
PRESERVATIVES.
• !-'• '"'•• H '""' ;•-• -hibited; exemptions. It snail be unlawful for any
:i to manufacture, sell or expose for sale or exchange any article of food
t<» which has been added forma Idc-hyde, borax, boracic acid, benzole acid, sul-
phurous arid, salicilic" arid. al.rastol0 beta-napthal,° flourine compounds0 sac-
charine, alcohol : provided that in the case of molasses and syrups and bleached
dri«-d fruits, tlwit in thr tiuishrd products sulphurous acid, flourine compound0
and chi<>riiir are entirely removed subject to the rulings of the National Pure
: Commission. pp.vidrd. that the spreading of dry borax over the surface
of iur.it cannot be construed to be a violation of this Act.
•v added to oyst< / •*, etc. Any corporation, firm or person,
rithrr in prrson or hy an a^rmt who shall sell or e.\iK>se for sale within the state
vlahoina ..r other sea food products, to which salicilic °
arid. I'--: •iiiaMelmle or any drug, or othrr preservative has been added or hi
pr. si-r\ inu' \vhirh any iMrfsonous or deleterious substance has been used, shall be
• I iruilty of a
Session Laws 1907-1908, ch. .TT, pp.
SEA FOOD.
See Preservatives, sec. 50, abo\
SPICES AND CONDIMENTS.
SBC. 46. Compound apkr* mu*t be so labeled; terms defined* It shall be
unlawful for any person to manufacture, sell, offer or expose for sale or ex-
c-liaii^r to tln» residents of this state, any spices and condiments,0 either ground
or uuurouiid. which are adulterated with any foreign substance or substances
within thr niraninu' of this article, which are Injurious to health and provided
th;ir wlu-n foreign substances are used, the package containing said article
>r sale shall contain the word "compound." The term spices and
nu-iits as used herein chall ° embrace all substances known and recognized
in r.iininerce as spices, and used as condiments, whether the same be in natural
"t- in the form which would result from grinding, milling or mixing, or
the compounding of the natural product.
Session Laws 1907-1908, ch. 37, p. 420.
VINEGAR.
See General Food Laws, sec. 55, page 58.
0 So in Statutes.
PORTO RICO.
GENERAL FOOD LAW.
SEC. 1. Repeal. Section 336 of the Penal Code is hereby repealed. [See
U. S. Dept. Agr., Bureau of Chemistry, Bui. 69, Rev., pt. 7, p. 549.)
Approved March 12, 1908. Laws of 1908, p. 93.
474. False statements of agents, etc.; false weight or measurement; penalties.
Every commission merchant, broker, agent, factor or consignee, who shall wil-
fully and fraudulently make, or cause to be made, to the principal or consignor
of such commission merchant, agent, broker, factor or consignee, a false state-
ment concerning the price obtained for or the quality or quantity of any prop-
erty consigned or intrusted to such commission merchant, agent, broker, factor
or consignee, for sale, shall be deemed guilty of a misdemeanor and on con-
viction thereof shall be punished by fine not exceeding five hundred dollars, or
imprisonment in jail not exceeding six months, or by both such fine and im-
prisonment. Every person who is putting up in any bale, bag, box, barrel or
other package any sugar, tobacco, coffee, rice or other goods usually sold in
bales, bags, boxes, barrels or other packages, by weight or otherwise, puts in or
conceals therein any extraneous substance whatever for the purposes of fraudu-
lently increasing the weight or measurement of such bale, bag, box, barrel or
other package with intent thereby to sell the goods therein, or to enable another
to sell the same, for more than the actual weight or measurement of such goods,
is punishable by fine not less than twenty-five dollars for such offense, or con-
fined in jail for not less than thirty days, or by both fine and imprisonment in
the discretion of the court. — As amended March 12, 1908; Laws of 1908, p. 93.
Revised Statutes and Codes of 1902, Penal Code, ch. 8, p. 588.
MEAT.
SEC. 7. Use of refrigerated meat in public institutions. The Director of
Health, Charities and Correction, is hereby authorized to determine whether
refrigerated meat may or may not be supplied to institutions under his direction.
Approved March 12, 1908. Laws of 1908, p. 74.
RHODE ISLAND.
GENHKAL FOOD LAWS.
rrnnJtji for ntluUrrntinfj or mi*l>ran<Ung ; exemption of articles for
' t. It shall be unlawful for any person, firm, or corporation to manufac-
ture, sell, or offer for sale within this state, any drug or article of food which
iuli.-rated . T misbranded within the meaning of this act, and any person,
linn, ni- corporation violating any of the provisions of this act shall be guilty
of a misdemeanor, and shall, upon conviction, he punished for the first offense
by a line ii"t exceeding fifty dollars, for the second offense by a fine not exceed-
in- on,- hundred dollars, and for the third and each subsequent offense by a
lin«- of two hundred dollars .,r imprisonment for one year: l>rori<Ic<l, that no
article shall he deemed misl.randed or adulterated within the provisions of
this act when intend. -d for export to any foreign country and prepared or
• ••iiica tions or directions of the foreign purchaser,
when no suhstance IB us4«d in the preparation or packing thereof in conflict with
:-eign country to which said article is intended to be shipped;
hut if >.i l»e in fa «-t sold or offered for sale for domestic use or
mption. then this proviso shall not exempt said article from the operation
of au\ of tin- other pn.\ Moiis of this act.
[Sees. 2 and D to drugs.]
SEC. 4. A<lult> i-ntinn iii fiif <i. Food shall be deemed to be adulterated:
l-'ii>'. if ;,• ice has heen mixed and packed with it so as to reduce
or lower ot- injuriously affect its quality, strength, or purity. Second. — If any
substance hai i.een si il ist i t ii ted wholly or in part for the article. Third. — If any
valuable constituent of the article has been wholly or in part abstracted.
Fourth. If it is mixed, colored, jM.wdered. coated, stained, or put up in a man-
ner whereby damage or inferiority is concealed. Fifth.— If it contains any
add'-d poisonous or i.th.-r added ingredient which may render such article in-
jurious to health: Provided, that when in the preparation of food products for
shipment the\ --rved by any external application applied in such man-
ner that the preservati -Airily removed mechanically or by maceration,
in water, or otherwise, and directions for the removal of said preservative shall
be printed on the eoverini: of the package, the provisions of this act shall be con-
strue! as applying only when said products are ready for consumption. Sixth. —
If it consists in whole nr in part of a filthy, decomposed, or putrid animal or
able substance, or any portion of an animal unfit for food, whether manu-
factured or not, or if it is the product of a diseased animal, or one that has died
otherwise than by slaughter.
\<litlt<niti<,n «j <•<,„!> <-tlnn<'nj ilr/inrfl. Confectionery shall be deemed
to be adulterated if it contains terra alba, barytes, talc, chrome yellow, or other
mineral substances <»r poisonous colors or flavors, or other ingredients deleteri-
r detrimental to health, or any vinous, malt, or spirituous liquor or com-
l>ound or narcotic drug.
70 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
SEC. 6. Misbrandinff defined. A drug or an article of food, or an article which
enters into the composition of food, shall be deemed to be misbranded :
First.— If the package containing it, or the label on such package, shall bear
any statement, design, or device regarding such article, or the ingredients or
substances contained therein, which shall be false or misleading in any particu-
lar, or if the same is falsely branded as to the state, territory, or country in
which it isTnanufactured or produced. Second.*-If it be offered for sale as an
Imitation of, or under the name of, another article. Third. — If it is in the pack-
age form, and the contents are stated in the terms of weight or measure, the
same is not plainly and correctly stated on the outside of the package.
Fourth. — If the package contains a proprietary or patent medicine, or a proprie-
tary or patent food, and the label fails to bear a statement of the quantity or
the proportion of any alcohol, morphine, opium, cocaine, heroin, alpha or beta
eucaine, chloroform, cannabis indica, chloral hydrate, or acetanilid or any deriv-
ative or preparation of any such substances contained therein: Provided, that
the provisions of this section shall not apply to the sale and distribution of such
proprietary or patent medicines or proprietary or patent foods as were in the
possession of any dealer within this state at the time of the taking effect of
this law.
SEC. 7. Guaranty for protection of dealer. No dealer shall be convicted tinder
the provisions of this act, when he can establish a guaranty, signed by the
wholesaler, jobber, manufacturer, or other party residing in the United States,
from whom he purchases such articles, to the effect that the same is not adul-
terated or misbranded within the meaning of the food and drugs act of the
United States, approved June 30, 1906, or of this act. Said guaranty, to afford
protection, shall contain the name and address of the party or parties making
the sale of such articles to such dealer, and in such case said party or parties
shall be amenable to the prosecutions, fines, and other penalties which would
attach, in due course, to the dealer under the provisions of this act.
SEC. 8. Sampling; penalty for hindering execution of law. Every person
offering for or exposing for sale or delivering to a purchaser any drug or article
of food included in the provisions of this act shall furnish to any commissioner,
or other officer or agent appointed hereunder, who shall apply to him for the
purpose and shall tender to him the value of the same, a sample or samples,
of any drug or article of food which is in his possession, sufficient, after divi-
sion into two equal or nearly equal parts, for the purpose of analysis. The
official or agent thus taking said sample or samples shall then and there, in the
presence of the person from whom he obtained it, unless said person refuse to
witness the operation, divide said sample or samples into two equal or nearly
equal parts or specimens, and seal and label the same, said label to state the
kind of food or drugs, the date of such taking, and, if obtainable, the name of
the person from whom they were taken ; also, if obtainable, the name or names
of the parties, if there be any, whom said person represents. Said official or
agent shall then and there deliver one of said specimens to the person from whom
the same were taken. If any such sample or samples so taken shall appear to
be adulterated within the meaning of this act, notice in writing of the fact of
such adulteration, containing a description of such sample or samples, shall
forthwith be given by mail or otherwise, directed to the person from whom the
same were obtained, to the address given by him at the time such sample or
samples were taken, before any prosecution shall be instituted thereon: Pro-
•I, however, that if the person from whom such sample or samples are taken
shall omit or refuse to give his name or address, such notice shall not be re-
quired. Whoever hinders, obstructs, or in any way interferes with any com-
missioner or other officer or agent appointed hereunder, in the performance of
I UNIVERSITY j
V OF /
KHODE ISLAND. 71
his duty, shall, upon conviction, be fined a sum not exceeding one hundred
dollars.
SEC. 9. 6 Any article of food or any drug that is adulterated or mis-
branded within the meaning of this act shall be liable to be proceeded against in
the courts of this state within the county where found, and seized for forfeiture
by tln> same process of law under which liquors illegally sold or for sale may be
i I'm- forfeiture; and if such article or drug is condemned as being adulter-
ated «.r misbranded or of a poisonous or deleterious character within the mean-
ing of this act, it shall be disposed of by destruction or sale, as the court may
din* -i. anil the proceeds thereof, if sold, less the legal costs and charges, shall
be paid into the treasury of the state: Provided, however, that upon the pay-
ment of the costs of such proceedings and the execution and delivery of a good
and siiflirient bond t«> the effect that such articles or drugs shall not be sold or
otherwise disused of contrary to the provisions of this act, the court may, by
order, direct that such articles or drugs be delivered to the owner thereof.
Either party may demand trial by jury of any issue of fact in any such case,
and all such proceedings shall be at the suit of and in the name of the state.
.10, Soaked • ••imn-d goods. All canned articles of food which have been
prepared from dried pn>du< -t> and have been soaked before canning shall be
plainly marked by a brand or label having on its face the word "Soaked," in
:>e not smaller than eight-point (Brevier) caps.
SE« . 11. /•*. There shall be a board of food and drug
commissioners, consist inu' of three members, who shall hold office for the term
of their appointment, and until their successors, respectively, shall be elected
ami qnaliii
At the January session of the general assembly in the year A. D. 1908, the
nor. with the ad\ ice and consent of the senate, shall appoint three persons
members of >aid board, one for a term ending January 31, 1»10, one for a
r.M'J. and one for a term ending January 31, 1914.
At the .Fa nuary session of the general assembly in the year A. D. 1910, and
in every second year thereafter, the governor, with the advice and consent of
tin- >ei!.it«», shall appoint a person to be a member of0 said board, and the per-
son so upimlntetl shall hold hi* othVo until the first day of February in the fifth
of his appointment. Any vacancy which may occur in said board when
i session shall be tilled by the governor until the next session
thereof, when he shall, with the advice and consent of the senate, appoint some
r the remainder of the term.
a ml xtniulnnlx; organization. It shall be the
duty of said b..ard to enforce the provisions of this act. They shall adopt such
nt with the provisions of this act, as may be necessary for its
<Miforeem'-nt, ;lnd shall adopt rules regulating minimum standards of strength,
purity, and quality for food and drugs, defining specific adulterations when
su.h itied or tixed under this act or by the laws of this
to the provisions of this act, declaring the proper methods of
•Minim: dniu's and articles of food; but such rules and stand-
more stringent than, nor conflict with, the rules and stand-
adopt MI. or which may hereafter be adopted, for the enforcement of the
and dm- act of the Tinted States, approved June 30, 1906, or of any food
and drug ad of the I'nited States hereafter in force, regulating the misbrand-
ini: «»r adulteration of food and drug products for interstate commerce: Pro-
/-. that in prosecutions under this act when the strength, quality,
irity of a drug or an article of food is in issue and the standard of strength,
o So in Statutes.
72 FOOD LEGISLATION, YEAK ENDED JUNE 30, 1908.
quality, or purity of such drug or article of food is fixed by said board, proof
that such drug or article of food is below the standard of strength, quality, or
purity fixed by said board shall be evidence that such drug or article of food
is adulterated within the meaning of this act.
The said commissioners shall have an office in the state house. They shall
be allowed such office, traveling, and personal expenses as may be approved by
the governor, to be paid, upon the order of the state auditor, out of any money
in the treasury not otherwise appropriated.
They shall meet at least once in three months and as much oftener as may
be necessary. They shall proceed to organize by the election of a chairman
and an executive secretary, who shall oe a practical chemist. Said board shall
have authority to appoint such other agents as may be necessary to assist in
the enforcement of this act. Said executive secretary and agents shall work
under the direction of the said board of commissioners and shall perform such
duties as the said board shall prescribe for them .to perform.
. 13. Appropriation. The sum of thirty-five hundred dollars is hereby ap-
propriated annually, commencing January 1, 1909, from the treasury of the
state, to be expended by the board of food and drugs commissioners, for the
imriHjse of meeting the expenses incurred in the enforcement of this act, in-
cluding fifteen hundred dollars the salary of an executive secretary, the cost
of collection of samples, purchase of laboratory supplies, and aid in prosecuting
offenders against this act.
SEC. 14. The sum of fifteen hundred dollars or as much thereof as may be
necessary, including seven hundred and fifty dollars as recompense for the
services of an executive secretary, is hereby appropriated out of the treasury of
the state for the purpose of meeting the necessary expense of preparation and
notification ; and the state auditor is hereby directed to draw his order upon the
general treasurer for the payment of the same upon the receipt of vouchers ap-
proved by the chairman and secretary of said board.
- ' . l.j. Milk, meat, feeding stuffs, and contagious disease laics not repeal (.-<!.
This act shall not be construed to repeal Chapter 147 of the General Laws, enti-
tled "Of milk," or any acts in amendment thereof or in addition thereto, or
Chapter 131 of the General Laws, entitled " Of the inspection of beef and pork,"
or any acts in amendment thereof or in addition thereto, or an act entitled "An
act authorizing the city of Providence to elect an inspector of beef and pork for
ity." passed June 29, 1833, or sections 1 and 2 of Chapter 281 of the Public
Laws, entitled "An act in amendment of and in addition to Title XIV, Chapter
74, of the Revised Statutes, ' Of regulations for the prevention of infectious and
contagious diseases,' " passed March 5, 1858, or Chapter 631 of the Public Laws,
entitled " An act regulating the sale of concentrated commercial feeding stuffs,"
passed at the January session, 1899.
SEC. 16. Effect. Sections 11, 12, and 14 of this act shall take effect immedi-
ately, and all other parts of this act shall take effect January 1, 1909.
Approved May 20, 1908. Public Laws passed at the January Session, 1908,
ch. 1597, pp. 295-303.
< AXXED GOODS.
See General Food Laws, page 71.
CONFECTIONERY.
See General Food I.aws, page 69.
SOUTH CAROLINA.
RICE FLOUR.
. 1. /v> N in •• of chaff, etc., must be stated on label. From and after the
approval of this Act it shall be unlawful for any person to sell, or expose for
salt'. ri« ••• il«»ur which contains chaff or any other adulteration, without giving
notice l»y label or otherwise the nature and extent of such adulteration.
. 2. A'lidtt rntcd rice flour liable to seizure. Any rice flour so adulterated,
which is sold or exposed to sale without being labeled or advertised as such,
shall !>e liable to seizure and sale by any Magistrate having jurisdiction, on the
pn.set -in ion i,f any person, tin- proceeds of such sale to be paid into the Treas-
ur\ of Hi- Oountj in which such rice flour may be seized.
Appi :-uary 17, 1008. Acts of 1908, No. 476, p. 1053.
73
VIRGINIA,
GENERAL FOOD LAWS.
SEC. 1. Appointment of dairy and food commissioner. Within thirty days
after this act shall take effect, the governor, by and with the consent of the
general assembly in joint session, shall appoint a suitable person to be dairy
and food commissioner, which office is hereby created within the department of
agriculture and immigration, and which commissioner so appointed shall hold
his office until January thirty-one, nineteen hundred and twelve, and until his
successor is appointed and qualified. At the regular session of the legislature
in nineteen hundred and twelve, and every four years thereafter, the governor,
by and with the advice and consent of the general assembly in joint session,
shall appoint a dairy and food commissioner, who shall hold his office for the
term of four years from the thirty-first day of January, in the year of his
appointment, and until his successor is appointed and qualified.
SEC. 2. Governor may remove commissioner. The governor shall have the
power to remove such commissioner any time, in his discretion, but the reasons
for such removal shall be laid before the general assembly in joint session at
the next regular or special session of the legislature thereafter ; and in case of
a vacancy in the office of commissioner from any cause, the governor shall
appoint his successor to fill the unexpired term.
SEC. 3. Oath and bond of commissioner. Before entering upon the duties of
his office, the person so appointed shall make, subscribe and file in the office of
the secretary of the Commonwealth, the usual oath of office as provided for in
the Constitution of this State, and shall enter into bond, payable to the Com-
monwealth, in the sum of five thousand dollars, with securities approved by the
governor, conditioned for the faithful performance of his duties.
SEC. 4. Salaries and assistants. Said dairy and food commissioner shall re-
ceive an annual salary of two thousand five hundred dollars. There shall be
a deputy dairy and food commissioner, who shall be appointed by the commis-
sioner of agriculture and immigration and the dairy and food commissioner,
acting jointly, subject to the confirmation of the State board of agriculture
and immigration. The salary of the deputy commissioner shall be fifteen hun-
dred dollars per annum. The said commissioners may also appoint by and
with the advice of the board of agriculture and immigration such other special
assistants as the proper performance of the duties of the office may require,
which special assistants shall be paid for the time actually employed, as said
commissioners and board may direct. The persons so appointed shall have
power to administer oaths in all matters relative to the dairy and food laws,
and shall take and subscribe to the constitutional oath of office, and file the
same in the office of the secretary of the Commonwealth ; and they shall hold
office during the pleasure of the commissioners. The assistants shall have the
same right of access to the places to be inspected as the said commissioner.
The salaries and expenses authorized by this section shall be for the unex-
pired part of the fiscal year ending nineteen hundred and eight, and each fiscal
year thereafter. Said salaries are to be paid monthly. The salaries and actual
and necessary expenses of the said commissioner, deputy commissioner and
74
FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908. 75
iants, in the performance of their official duties, shall be audited by the
State hoard of agriculture and immigration, and paid upon warrants issued by
the daily and food commissioner upon the State auditor. The board of agri-
culture and immigration shall provide office room and the necessary furniture
and tix tu ITS. and the necessary stationery, supplies and printing for the con-
duct of the business of said dairy and food commissioner, on his application
I" Bald hoard therefor. Said office shall be, and remain in the city of Rich-
. .". f 'limi it-ill fro/7,-. The chemical work incident to the execution of the
dairy and pure food laws shall be done in the chemical laboratory of the de-
partment <>f agriculture and immigration.
lntii< x of roj/im/xx //,//( /-,- <tn<ili/xcs; inspection; penalty. It shall be the
duly of the dairy and food commissioner to carefully inquire into the dairy
ami food and drink products, and the several articles which are food or drinks,
or the necessary constituents of the food or drinks, which are manufactured or
sold, or c-x posed or offered for sale in this State, and he may, in a lawful man-
ner, procure samples of the same, which shall be duly and carefully examined
or analy/ed by the State chemist, who shall report to the said commissioner the
result-- of such examination or analyses: and it shall be the duty of the saidcom-
oiier to make a complaint against the manufacturer or vendor of any such
or drink TO dairy products M> are adulterated, impure or unwholesome, in
contravention of the laws of this Slate, and furnish all evidence thereof to ob-
tain a conviction of the oft. _ed. The dairy and food commissioner or
his deputy, or ;my person ap{x.inted by him for that purpose, may make com-
plaint and cause proceedings to be commenced against any i>erson for enforce-
ment of the laws re'; . 1 ii 1 1 era t ion. impure or unwholesome food or
drink, and in such cases he shall not be obliged to furnish security for costs,
ami shall ha \ in the performance of his duties, to enter into any
cre.i torn, dm'.' si ore-, or laboratory, or place where
lie has reason to believe food and drinl: is made, stored, sold, or offered for sale,
ami open ai y c:i>k. tub. jar. Lottie or package containing, or supposed to con-
tain, any art: ••! or drink, and examine or cause to be examined the
• f. and take therefrom samples for analysis. The person making
su.-h Lnq ill take such samples of such article or product in the pres-
;uess, and he shall, in the presence of said witness, mark
1 shall tender at the time of taking to the manufacturer
or \< «iich product. ..r to j he person having the custody of the same, the
value thereof, and the statement in writing for the taking of such sample.
YVhene', er ii li determined by the dairy ami food commissioner, his deputy or
•ants, that tilthy or unsanitary conditions exist or are permited to exist
in the o(HM-ation of any bakery, confectionery, or ice cream plant, or at any
place where anv food or drink products are manufactured, stored or deposited,
d for at:. whatever, the proprietor or proprietors, owner or owners
onfectionery or ice cream plant, or any person or persons
owning or operating any plant where any food or drink products are manu-
factured. st< -ited or sold, shall be first notified and warned by the
said commissioner, his deputy or assistants, to place such bakery, confection-
ery, or : - ,-ivam plant, or any place where any food or drink products are
manufactured, stored, deposited or sold, in a sanitary condition within a reason-
;!i of time: and any person or persons owning or operating any bakery,
confectionery ,.r ice cream plant, or any place where any food or drink products
arc manufactured, stored, deposited or sold, failing to obey such notice and
warning, shall be guilty of a misdemeanor, and, upon conviction thereof, shall
line of not less than twenty-five dollars nor more than three
76 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
hundred dollars and costs of prosecution, or imprisonment in the county or
city jail not to exceed ninety days, or until such fine or costs are paid, or both
fine and imprisonment, at the discretion of the court.
SEC. 7. Seizures, sampling, and analysis; prosecution. The dairy and food
commissioner, his deputy, or any person by said commissioner duly appointed
for that purpose, is authorized at all times to seize and take possession of any
and all food and dairy products, substitutes therefor, or imitation thereof kept
for sale, exposed for sale, or held in possession or under the control of any
person which in the opinion of said commissioner, or his deputy, or such per-
son by him duly appointed, shall be contrary to the provisions of this act or
other laws which now exist or which may be hereafter enacted.
First. The person so making such seizure, as aforesaid, shall take from such"
goods as seized a sample for the purpose of analysis and shall cause the re-
mainder to be boxed and sealed and shall leave the same in the possession of
the person from whom they were seized, subject to such disposition as shall
hereafter be made thereof according to the provisions of this act.
Second. The person so making such seizure shall forward the sample so taken
to the dairy and food commissioner who shall turn over the same to the State
chemist and the said chemist shall certify the results of such analysis, which
certificate shall be prinia facie evidence of the fact or facts therein certified
to, in any court where the same may be offered in evidence.
Third. If upon such analysis it shall appear rhat said food or dairy products
are adulterated, substituted, mis-branded, or imitated within the meaning of
this act, said commissioner, or his deputy, or any person by him duly author-
ized may make complaint before any justice of the peace or police justice having
jurisdiction in the city, village or magisterial district, where such goods were
seized, and thereupon said justice of the peace shall issue his summons to the
person from whom said goods were seized, directing him to appear not less
than six or more than twelve days from the date of issuing of said summons
and show cause why said goods should not be condemned and disposed of.
If the said person from whom said goods were seized cannot be found, the
said summons shall be served upon the person then in possession of the goods.
The said summons shall be served at least six days before the time of appear-
ance mentioned therein. If the person from whom said goods were seized can-
not be found, and no one can be found in possession of said goods, and the
defendants shall not appear on the return day, then said justice of the peace shall
proceed in said cause in the same manner provided by law where a writ of
attachment is returned not personally served upon any of the defendants and
none of the defendants shall appear upon the return day.
Fourth. Unless cause to the contrary thereof is shown, or if said goods shall
be found upon trial to be in violation of any of the provisions of this act or
other laws which now exist or which may be hereafter enacted, it shall be the
duty of said justice of the peace or police justice to render judgment that said
seized property be forfeited to the State of Virginia, and that the said goods
be destroyed or sold by the said commissioner for any purpose other than to be
used for food. The mode of procedure before said justice shall be the same
as near as may be hi civil proceedings before justices of the peace. Either party
may appeal to the circuit or corporation courts as appeals are taken from the
justices' courts, but it shall not be necessary for the Commonwealth to give
any appeal bond.
Fifth. The proceeds arising from any such sale shall be paid into the State
treasury and credited to the general fund; provided, that if the owner or
party claiming the property or goods so declared forfeited can produce and
VIRGINIA. 77
prove a written guaranty of purity, signed by the wholesaler, jobber, manu-
facturer, or other party residing within this State from whom said articles
were purchased, tluMi tin* proceeds of the sale of such articles, over and above
the rusts .if seizure, forfeit mv and sale, shall be paid over to such owner or
claimant t<> reimburse him. to the extent of such surplus, for his actual loss
resulting from such seizure and forfeiture as shown by the invoice.
Sixth. 1 1 shall he the duty of the prosecuting attorney when called upon by
• .mmissioner, or by any person by him authorized as aforesaid, to render
any legal assistance in his power in proceeding under the provisions of this
r any subsequent act relative to the adulteration of food, for the sale of
impure or unwholesome food or food products.
. Bn Annual n i><>rt ; <i u n rt < rly bulletin. The dairy and food commissioner
make an annual report to the commissioner of agriculture and immigra-
tion to be. by -a ill cOBBtfaplMMV of agriculture and immigration transmitted
to the governor on or before the first day of January in each year, and which
shall be printed and published on or before the first day of January next
thereafter, which report shall cover the doings of his office for the preceding
r. which shall show, among other things, the number of manufac-
1 other places inserted and by whom, the number of speciments0
•od articles analyzed and the State chemist's report upon each one; the
number of compl.i • rsons for the violating of the laws
iltcrati« 'ii <>f I'.M.,I. the number of convictions had, and the
amount -of fines imposed therefor, together with such recommendations rela-
:»• statutes In force as his experience may justify. The dairy and
-hall prepare, print and distribute to all papers of the State,
h persons as may be Interested or may apply therefor, a quarterly
bulletin in suit ab'. taininu' results of inspections, the results
with the popular explanation of the
!ier information as may come to him in his official capacity
relaiin:: to the adulteration of food and drink products and of dairy products,
t he same of, benefit and advantage to the public ; also a
summary "f .ill th.- work d^ne during the quarter by the commissioner and.
in the enforcement of the laws of the State, but not more than
ten copies of such quarterly bulletin shall be printed.
••'/// for fiiml'iini/ uncr. Any person who shall wilfully
hinder or the dairy and food commissioner, or his deputy or other per-
or assistants by him duly authori/ed, in the exercise of the powers con-
d upon him by this act, shall be deemed guilty of a misdemeanor and on
:i shall be punished by a fine of not less than ten dollars nor more
than one hundred dollars, or by imprisonment in the county or city jail for not
ihan ten da\s n..r more than ninety days, or both such fine and imprison-
:. in the discretion of the court.
iiitinn. For the purpose of carrying out the provisions of
this ,-iet the sum of seven thousand five hundred dollars isjiereby appropriated
he tiscal year endin- February twenty-eighth, nineteen hundred and nine,
la like manner for each fiscal year thereafter, there is hereby appropriated
;m of seven thousand live hundred dollars.
Approved March 11, 1908. Acts of 1908, ch. 188, p. 266.
An act entitled an act to prevent the sale of adulterated and mis-
branded foods in the State of Virginia, approved February twenty-seventh,
°So in Statutes.
78 FOOD LEGISLATION, YEAH ENDED JTJXE 30, 1908.
nineteen hundred [Bui. 69 Rev., pt. 8, pp. 639-642], be and the same is, hereby
repealed and be it further enacted by the general assembly of Virginia :
1. Sampling and analyses; appointments. For the purpose of protecting
the people of the State from imposition by the adultering ° and misbranding of
food, the dairy and food commissioner shall cause to be procured from time to
time, and under the rules and regulations to be prescribed by him, with the
approval of the board of agriculture and immigration in accordance with the
provisions 'of this act, samples of food offered for sale in this State, and shall
cause the same to be analyzed and examined microscopically or otherwise by
the chemists or other experts of the department of agriculture and immigration ;
and he is hereby authorized to make such publication of the results of the
examination, analyses, and so forth, as he may deem proper ; and for the proper
execution of the provisions of this act, the dairy and food commissioner shall
with the approval of the board make such appointments as may be necessary
and the board shall fix the compensation of such appointees.
SEC. 2. Adulteration a misdemeanor; penalty. No person, firm or corporation,
either directly or through any agent, shall manufacture, sell, expose for sale or
have in his possession with intent to sell, any article of food, which is adul-
terated or misbranded within the meaning of this act, and any person who shall
violate any of the provisions of this act shall be guilty of a misdemeanor, and
for such offense, shall be fined not exceeding two hundred dollars for the first
offense, and for each subsequent offense not exceeding three hundred dollars,
or be imprisoned not exceeding one year, or both, in the discretion of the court ;
and such fines less legal costs and charges, shall be paid into the treasury of
the State.
SEC. 3. Results of analysis as evidence; hearings. The chemists or other
experts of the department of agriculture and immigration shall make, by the
methods hi use at the time by the association of official agricultural chemists
of the United States, examinations of specimens of food offered for sale in
Virginia, which may be collected from time to time as prescribed by this act
in various parts of the State ; and if it shall appear from any such examinations
that any such specimen is adulterated or misbranded within the meaning of this
act, that notice thereof shall be given to the manufacturer, guarantor, or person
from whom the sample was obtained. Any person so notified shall be given
an opportunity to be heard under such rules and regulations as may be pre-
scribed by the dairy and food commissioner and the commissioner and board of
agriculture and immigration, and if it appears that any of the provisions of
this act have been violated, the dairy and food commissioner shall certify the
facts to the Commonwealth's attorney of the city or county in which the sample
was obtained, and furnish the officer with a copy of the results of the analysis or
other examinations of such article, duly authenticated by the analyst or other
officer making such examination under the oath of such officer. In all prose-
cutions arising under this act the certificates of the analyst or other officer
making the analysis or examination, when duly sworn to by such officer, shall
be prima facie evidence of the fact or facts therein certified.
SEC. 4. Prosecution. It shall be the duty of every Commonwealth's attorney
to whom the dairy and food commissioner shall report any violation of this act
to cause the proceedings to be commenced and prosecuted without delay for the
fines and penalties in such cases prescribed.
SEC. 5. " Food " defined. The term " food " as used in this act shall include
all articles used for food, drink, confectionery, or condiment by man or other
animals, whether simple, mixed, or compound.
°So in Statutes.
VIRGINIA. 79
. 0. AiluUrratinn tli-fincij ,• mnfivtiimrnj ; food. For the purpose of this
net .-in article shall be deemed to he adulterated:
In the case of confectionery :
I-'irst. If it contains terra alba, barytes, talc, chrome yellow, or other mineral
substance or poisonous color or flavor, or other ingredient deleterious or detri-
mental to health, or any vinous, malt, or spirituous liquor or compound or
nan-otic drug.
In case of other food:
First. If any substance has been mixed or packed with it, so as to reduce or
lower or injuriously atTect its quality or strength.
Second. If any substance has been substituted wholly or in part for the
•le.
Third. If nny valuable constituent of the article has been wholly or in part
abstracted.
Fourth. If it be mixed, colored, powdered, coated, polished or stained in a
manner whereby damage or inferiority is concealed.
Fifth. If it contains any added poisonous or other added deleterious ingre-
dient which may render such article injurious to health. Provided, that when in
the preparation of food products for shipments they are preserved by any ex-
ternal application in such manner that the preservative is necessarily removed
me< •hanicjiiiy. or by maceration in water, or otherwise, and directions for the
removal of said preservative shall be printed on the covering of the package
: mi shed with the article, the provisions of this act shall be construed as
applying "iily when said products are ready for consumption.
Sixth. If it consists in whole o/ in part of diseased, filthy, decomposed, or
putrid animal or \e-»-table matter, or any portion of an animal unfit for food
whether manufactured or not, or If it is the product of a diseased animal, or
one that had died otherwise than by slaughter.
Seventh. If the containing vessel or any part of it be of such composition as
will be acted ui»on, in the ordinary course of use, by the contents thereof in
wieh a way as to produce an injurious, deleterious, or poisonous compound.
. 7. Mixhrnn-i The term "misbranded" as used herein shall
apply to all articles of food, or articles which enter into the composition of
the package or label of which shall bear any statement, design or device
regarding such article, or the Ingredients or substance contained therein, which
shall be false or misleading in any particular, and to any food product which
is f.iS. \ branded as to the State, territory, or country in which it is manufac-
tured or produ
the pun>ose of this act an article shall also be deemed misbranded:
i f it be an imitation of, or offered for sale under the distinctive name
• ther an
••lid. If it be labeled or banded0 so as to deceive or mislead the purchaser,
or purport to be a foreign product when not so, or if the contents of the pack-
age as originally put up shall have been removed in whole or part, and other
contents shall have been placed in such package, or if it fail to bear a statement
;l>el of the quantity or proportion of any morphine, opium, cocaine,
In, alpha or beta eucaine, chloroform, canna"bis indica, chloral hydrate, or
acetanilide or any deriviative or preparation of any such substance contained
therein.
Third. If in package form, and the contents are stated in terms of weight or
measure, they are not plainly and correctly stated on the outside of the package.
Fourth. If the package or its label shall bear any statement, design, or device
ding the ingredients or substance contained therein, which statement,
0 So in Statutes.
80 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
design, or device shall be false or misleading in any particular: Provided,
that an article of food which does not contain any added poisonous or dele-
terious ingredients shall not be deemed to be adulterated or misbranded in the
following cases :
First. In the case of mixtures or compounds which may be now or from
time to time hereafter known as articles of food under their own distinctive
names, and not an imitation of, or offered for sale under the distinctive name
of, another article of food, if the name be accompanied on the same label or
brand with a statement of the place where said article has been manufactured
or produced.
Second. In the case of articles labeled, branded, or tagged so as to plainly
indicate that they are compounds, imitations or blends, and having the word
"compound," "imitation," or "blend" as the case mny be, plainly stated on
the package in which such article is offered for sale: provided, the labeling
is according to the rules prescribed by the dairy and food commissioner with
the approval of the commissioner and board of agriculture and immigration :
Provided, that the term " blend " as used herein shall be construed to mean
a mixture of like substances, not excluding harmless coloring or flavoring in-
gredients used for the purpose of coloring and flavoring only : and provided
further that nothing in this act shall be construed as requiring or compelling
proprietors or manufacturers of proprietary foods which contain no unwhole-
some added ingredient to disclose their trade formulas, except in so far as
the provisions of this act may require to secure freedom from adulteration
and misbranding.
SEC. 8. Sanitary conditions for handling of human food, especially meats.
It shall be unlawful for any person or persons, firm or corporation, to sell, or
to have in his possession with intent to sell for human food, meat or meat
food products which has been slaughtered, prepared, or kept where the sani-
tary conditions, are such that the meat or meat food products are rendered
unhealthy, unwholesome, or otherwise unfit for human food.
All peace and health officers shall have the power and are required to seize
any animal carcass or parts of carcasses which are intended for sale or offered
for sale for human food, which have been slaughtered and prepared, handled
or kept under unsanitary conditions, and shall deliver the same forthwith to
and before the nearest police judge or justice of the peace, together with all
information obtained, and said police judge or said justice of the peace shall,
upon sworn complaint being filed, issue warrant for the arrest of all persons
who have violated the provisions of this section, and proceed to try the case.
Any person, persons, firm or corporation found guilty of violating the provisions
of this Section shall be fined not less than ten nor more than one hundred
dollars, and the meat in question shall be destroyed.
SEC. 9. Guaranty. No dealer shall be prosecuted under the provisions of this
act when he can establish a guaranty signed by a wholesale dealer, manufac-
turer or other party, residing in Virginia, from whom he purchased such articles,
to the effect that the same is not adulterated or misbranded within the mean-
ing of this act, designating it. Provided, however, that if the article in ques-
tion is in a broken or open package, said guaranty shall not afford immunity
from prosecution, unless such dealer shall furnish satisfactory proof that the
article has not been changed in quality. The affidavit of such person shall be
accepted as such proof, and the person making such affidavit falsely shall be
guilty of perjury, and punished accordingly : Said guaranty, to afford pro-
tection, shall contain the name and address of the party or parties making the
VIRGINIA. 81
sale of such articles to such dealer, and in such cases said party or parties
shall he amenable to to0 the prosecutions, fines, and other penalties which
would attach in due course, to the dealer under the provisions of this act:
provided, that the above guaranty shall not afford protection to any dealer after
the first offense in connection with a product from a particular wholesale
dealer or manufacturer.
. 10. Simula nix. The dairy and food commissioner with the approval of
the commissioner and board of agriculture and immigration shall from time to
time, tix and publish standards or limits of variability permissible in any article
of food and these standards when so published shall be the standards before
all courts: provided, that when standards have been or may be fixed by the
secretary of agriculture of the United States, they shall be accepted by the
department of agriculture and immigration and published as standards for
Virginia, but said standards shall not go into effect until a reasonable time
after publication. The dairy and food commissioner, with the approval of the
commissioner and board of agriculture and immigration shall have authority
to make uniform rules and regulations for carrying out the provisions of
this act.
SEC. 11. Sampling. 1 son who exposes or offers for sale or delivers
to a purchaser any food, shall furnish within business hours and upon tender
and full p.iyiuoni of the selling price, a sample of such food, to any person duly
authorixrd to secure the same, and who shall apply to such manufacturer or
vendor or person delivering such food to a purchaser for such sample in suffi-
cient quantity f..r the analysis of such article or articles in his possession.
Samples may he purchased on the open market and shall be representative
samples; the collector shall also note the name of the vendor and agent through
whom the sale was actually made, together with date of purchase, and all
samples not taken in unbroken and sealed original packages shall be sealed by
the u the presence of the vendor with a seal provided for the purpose,
iien possible, samples shall be unbroken and sealed original packages, or
taken ..ut ,,f unto -ealed original packages. Three like samples shall
Alined when- •• is in the original package, or, if not in the original
package, the sample obtained shall he divided into three equal parts and each
^hall be labeled with the marks, brands or tags upon the package, carton,
mpanying printed or written matter. One sample
shall i»e delivered to the party from whom purchased, or to the party guarantee-
Ing V !»les shall be sent to the dairy and food com-
0 l»e analyzed, as provided in this act and the other
shall l»e held under seal by the dairy and food commissioner.
for Inndirinij mf »/•<•< nnnt. Any manufacturer, dealer or
person who refuses to comply UJMHI demand with the requirements of this act or
who shall iiui>ede, obstruct, hinder or otherwise prevent or attempt to prevent
any .-heinisi inspector or other person in the performance of his duty in con-
nection with this act, shall be guilty of a misdemeanor, and upon conviction be
lined not less than ten dollars nor more than one hundred dollars, or be im-
;ied not more than one hundred days, or both, in the discretion of the court;
and said fines, less the legal costs, shall be paid into the treasury of the State.
SK '. The word " person " as used in this act shall be
construed to import both the plural and the singular, as the case demands, and
shall include partnership, corporations, companies, societies and associations.
When construing and enforcing the provisions of this act, the act, omission or
a So in Statutes.
64289— Bull. 121—09 6
82 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
failure of any officer, agent or other individual acting for or employed by any
partnership, corporation, company, society, or association within the scope ot
his employment or office, shall in every case be, also deemed the act, omission,
or failure of such partnership, corporation, company, society, or association, as
well as that of the individual.
SEC. 14. Seizure and condemnation. Any person, firm, or corporation who
shall manufacture, sell or offer for sale any article of food that is adulterated
within the meaning of this act, shall be guilty of a misdemeanor, and in addi-
tion to being subject to the penalties already provided in this act, the article of
food shall be subject to seizure and condemnation, followed by sale or de-
struction.
Approved March 14, 1908. Acts of 1908, ch. 372, pp. 654-659.
CONFECTIONERY.
See General Food Laws, sec. 6, page 79.
DAIRY PRODUCTS.
SEC. 11. Investigation of creameries, cheese and milk factories, etc.; assist-
ants. It shall be the duty of the dairy and food commissioner to foster and
encourage the dairy industry of the State, and, for that purpose he shall investi-
gate the general conditions of the creameries, cheese factories, condensed milk
factories, skimming stations, milk stations and farm dairies in this State, with
full power to enter upon any premises for such investigation, with the object in
view of improving the quality and creating and maintaining uniformity of the
dairy products of the State; and should it become necessary in the judgment of
the dairy and food commissioner, he may cause instruction to be given in any
creamery, cheese factory, condensed milk factory, skimming station, milk sta-
tion or farm dairy, or in any locality of this State, and in order to secure the
proper feeding and care of cows, or the practical operation of any plant pro-
ducing dairy products, and in order to procure such a uniform and standard
quality of dairy products in this State, he shall furnish a sufficient number of
competent assistants, the appointment of whom is provided for in section four
of this act, and they shall be duly qualified to act as such assistants.
SEC. 12. Penalty for furnishing unclean milk to factories. Whenever it is
determined by the dairy and food commissioner, his deputy or assistants, that
any person is using, selling or furnishing to any skimming station, creamery,
cheese factory, condensed milk factory, milk depot, farm dairy, milk dealer,
the retail trade or to any consumer of milk, any impure or unwholesome milk
or cream, which impurity or unwholesomeness is caused by the unsanitary or
filthy conditions of the premises where cows are kept or by the unsanitary or
filthy care or handling of the cows, or from the use of unclean utensils or from
unwholesome food, or from any other cause, the person so using, selling or
furnishing to any skimming station, creamery, cheese factory, condensed milk
factory, milk depot, farm dairy, milk dealer, the retail trade or to any con-
sumer of milk, any such milk or cream, shall first be notified and warned by the
said commissioner, his deputy or assistants not to use, sell or furnish such milk
or cream to such skimming station, creamery, cheese factory, condensed milk
factory, milk depot, farm dairy, milk dealers, the retail trade or to any con-
sumer of milk, and any person failing to obey such notice and warning and
continuing to use, sell or furnish to any skimming station, creamery, cheese
VIRGINIA. 83
factory. condensed milk factory, farnrdairy. milk dealer or to the retail trade
such impure or unwholesome milk or cream, shall be guilty of a misdemeanor,
anl, upon conviction thereof shall be punished by a fine not less than ten dol-
lars nor more than til'ty dollars and costs of prosecution or imprisonment in
tlu- county or city jail not to exceed ninety days or until such fine and costs are
paid nr 1'oth tine and imprisonment at the discretion of the court.
•iltij fur unxnnitaru conditions of creameries, etc. Whenever it
is determined by tin- dairy and food commissioner, his deputy or assistants, that
unsanitary conditions exist, or are i>ermitted to exist, in the operation of any
skimming station, creamery, cheese factory, condensed milk factory, milk depot,
or farm dairy, tin- proprietor or proprietors or manager of said skimming station,
creamery, cheese factory, condensed milk factorj\milk depot, or farm dairy, shall
be first notified and warned by the said commissioner, his deputy or assistants,
to place such skimming station in a sanitary condition within a reasonable
length of time: and any person or persons owning or operating such skimming
station, creamery, cheese factory, condensed milk factory, milk depot, or farm
dairy, failing to obey such notices and warnings, shall be guilty of a misde-
meanor, and upon conviction thereof, shall be punished by a fine of not less
than twenty ti\e dollars nor more than three hundred dollars, and cost of prose-
cution, or imprisonment in the county jail not to exceed ninety days, or until
such fine and costs are paid, or both fine and imprisonment, at the discretion of
the court.
SEC. 14. Rcyixtrntinn of creaitu xe factories, etc. It shall be the duty
of tin- proprietor or proprietors of every skimming station, creamery, cheese
factory, condensed milk station, or milk depot, in the State where milk or cream
• •i\rd. b\ piM-clia*..' ..r otherwise, from three or more persons, to register
with tin- dair\ anil food commissioner, on or before April first of each year,
upon blanks furnished by said oilieinl. the location of such skimming station,
tnerj, cheese factory, condensed milk factory, or milk depot, and the name
- owner or 0WHen and manager. And it shall be the duty of the proprietor
••••prletors of every skimming station, creamery, cheese factory, condensed
milk fa.-ii.n ..r milk depot, in this State, where milk or cream is received, by
pu re base or othenv ise. from three or more j arsons, to file a report with the dairy
and food commissioner, said rei>ort to be made on or before April first of each
tijM.ii blanks furnished by said official, and to show the amount of milk or
I by said skimming station, creamery, cheese factory, condensed
milk factory, or milk dei>ot during the year ending December thirty-first pre-
ceding; and said report shall show the amount of butter, cheese, or condensed
milk, manufactured during tin- year. t.. -ether with a list of the names and
• tlice addresses of the patrons of said skimming station, creamery, cheese
ry. condensed milk factory, or milk depot. Every skimming station,
creamery, cheese factory, condensed milk factory, or milk depot, so registering
and so reporting, shall pay to the office of the State dairy and food commis-
sioner an annual registration fee of five dollars, to be paid at the time of such
registration. The money so collected by the dairy and food commissioner shall
u paid into the State treasury, and be" used to help defray the expenses of the
• •ffi.-«. of the dairy and food commissioner in addition to the annual appropria-
tion therefor. _
1.",. [Relates to commercial feeding stuffs.]
SEC. Hi. An mini report of commissioner. The published annual report of the
dairy and food commissioner, which shall be made to the commissioner of agri-
culture and immigration, shall include a complete accounting of all moneys
received and expended by the said commissioner for the period covered by
said rei>ort.
84 FOOD LEGISLATION, YEAR ENDED JUNE 30, 1908.
SEC. 17. Enforcement of food laws by dairy and food commissioner. The
enforcement of all existing laws to prevent the manufacture and sale of adulter-
ated and misbranded articles of food heretofore placed under the direction of
the commissioner and the board of agriculture and immigration, shall hereafter
be placed under the dairy and food commissioner, and shall be enforced by him
and under his direction; and all books, papers, and matters referring to the
enforcement of such laws shall be transferred to the office of the dairy and food
commissioner.
SEC. 18. Effect. An emergency existing, because of the large and unlawful
sale of adulterated and misbranded food products, this act shall take effect
from its passage.
Approved March 11, 1908; Acts of 1908, ch. 188, pp. 266-274.
MEATS.
See General Food Laws, sec. 8, page 80.
WISCONSIN.
food ami dairy la\v> and laws regulating the sale of bread,
incut, and Mrup. a- ainendt-d July 0, 1907, are given in Bulletin 112,
Part II. pair*' I-"'-, having boon included for convenience in tha,t com-
pilation, win. -li mvnvd only laws for the year ending June 30, 1907.
Issued June 7, 1900.
U. S. DFPARTMFXT OF AGRICULTURE.
BUREAU OF CHEMISTRY— BULLETIN No. 122.
II. W. \\ILKV, Chi,-t «.t Bureau.
PROCEEDINGS
r\v i:\Ty-riFTii ANNTAL CONVENTION
OF TllK
ASSOCIATION OF HFFICIAL AIIRICULTURAL CHEMISTS,
WASHINGTON, h. ('., NnVKMlil-K 1^-16,1908.
IDIIKI) HY
1IAKVKY W. \VILKY,
.I.IAKV OF TIIK ASSOCIATION.
GOVEKNMK NT PRINTING OFFICE
1909.
Issued June 7, 1001*.
U. S. DEPARTMENT OF AGRICULTURE.
BUREAU OF CHEMISTRY— BULLETIN No. 122.
H. W. WILEY, Chief of Bureau.
PROCEEDINGS
OF THE
TWKXTY-FIFTH
OF THK
.\Nsnri.\TiiiN OF OFFICIAL AGRICULTURAL CHEMISTS,
WASHINGTON. H. I ., XOVKMKKR I'M 6, 1908.
I MITKU BY
1IAKVKV W. WILEY,
>1 ( KETAKY OF THE ASSOCIATION.
WASHINGTON:
GOVERNMENT PRINTING OFFICE
1909.
LETTER OF TRANSMITTAL
U. S. DEPARTMENT OF AGRICULTURE,
BUREAU OF CHEMISTRY,
Washington, D. C., January 15, 1909.
SIR : I have the honor to submit for your approval the Proceedings
of the Twenty-fifth Annual Convention of the Association of Official
Agricultural Chemists. The reports have been prepared in the most
concise form practicable in consideration of the detailed and tech-
nical character of the work, all general discussion being practically
eliminated. I recommend that these proceedings be published as
Bulletin 122 of the Bureau of Chemistry.
Respectfully, H. W. WILEY,
Chief of Bureau.
Hon. JAMES WILSON,
Secretary of Agriculture.
(2)
CONTENTS.
THURSDAY — MORNING SESSION.
Page.
Mi -Fill "•!•- ami visitors pi. -nit 7
KepMrt on f 1 adulteratiMn. My II K. Barnard 11
RepMrt on wine. My Julius Hurt vet 12
! u- port mi Keer I> • II 1- Marnard 25
Rrp<>rt MM di-til Ifil liquors, My I.. M. Tolman 25
t ..ii vim-jar. My Charles H. Hickey 27
rt on flavoring extracts. My K M rhace 29
•r MII spices. By A. I.. \Vint MH 35
rs. By H. M. Loom is 38
Tin KSDAY — AFTERNOON SESSION.
;-t MM meat and fi.-h. M\ I < \\et.er 42
Report on the adulteration of dairy products. By Hermann ('. Lythgoe 51
M "ii cereal product-. My K !•'. I.add 53
Report mi ve.jetaUe- .canned peas). By W. L. Dubois 58
• •paraii"ii "i" meat proteids. By P. F. Truwlirid^1 61
rt on preservatives. M\ \\ . 1>. Mi^-low 64
< offee, and cocoa. By A. G. Woodman 78
i:>i iiii.ii i-n ..i rai'fj-iaiiiiir arid and caffein in coffee. By A. G. Woodman and
\V. ( . Ta\ 1, .r 82
FRIDAY MORNING SESSION.
•t «.n th»- determination <>i nitrogen. By Charles L. Penny 85
• i <>n iii'irirani" plant cnn.-t it uents. By H. D. 11 ask ins 92
•i MII nu-.lirinal plant- and dru--. My I.. I''. Kebler 94
A preliminary study of th»- micriK-hemical analysis and identification of
alkal..id-. My M..F. Howard and C.H. Stephenson 97
( 'oMprrat iv<> work on headache mixtun-s. My \\'. (). Emery 100
The Decant} iW animal experimentation in determining the purity and
.-trenu'tli «i medicinal preparations. M\ William Salant 103
;t MII instH-ticides. My ('. C. McDonnell 105
dent Snyder'* address: The training of the agricultural chemist 110
FRIDAY — AFTERNOON SESSION.
Uepm-t MII soils. My S. D. Averitt 114
rt on the determination of calcium carbonate in soils. By Jacob G. Lip-
man 120
potash. By B. B. Ross 121
rMinniittee < , food adulteration). By L. M. Tolman 126
Report of committee on the testing of chemical reagents. By L. F. Kebler 127
Report i if committee on food standards 128
Report of committee on nominations • 128
The assaying of alkaloidal drugs. By C. E. Parker ...
The macroscopy and microscopy of drugs. By H. H. Rusby 136
(3)
SATURDAY — MORNING SESSION.
Page.
Report on phosphoric acid. By J. M. McCandless 140
Thomas slag. By J. B. Lindsey 148
Valuation of phosphoric acid in basic slag. By H. D. Haskins 151
Report on dairy products. By J. M. Bartlett 152
Report on foods and feeding stuffs. By Fred W. Morse 159
The determiftation of acidity in cattle feeds. By John Phillips Street 160
The manufacture of gluten feed. By T. B. Wagner 164
Report on the separation of nitrogenous bodies: Milk and cheese proteids. By
L. L. Van Slyke 167
Report on sugar. By A. H. Bryan and Fritz Zerban 168
Detection of small percentages of commercial glucose in sirups and honey. By
A. II. Bryan 180
Report of Committee A on recommendations of referees. By R. J. Davidson.. 183
Conversion tables 184
Report of committee on fertilizer legislation 185
Report of committee on the revision of methods. ^y J. K. Haywood 187
Report of Committee B on recommendations of referees. By B. B. Ross 187
Report of committee on resolutions. By L. L. Van Slyke 189
Appointment of committee on the revision of methods and recommendations
of referees 190
MONDAY — MORNING SESSION.
Methods relating to the rate of decomposition of organic matter in the soil. By
Jacob G. Lipman 191
The possibilities of muscovado sugar as an adulterant for maple products. By
R. E. Doolittle and A. F. Seeker 196
Notes on the Winton lead number of mixtures of cane and maple sirup. By
R. E. Doolittle and A. F. Seeker 198
The determination of fusel oil by alkaline permanganate. By A. S. Mitchell
and C. R. Smith 199
M ft hods of analysis of distilled spirits. By L. M. Tolman and W. E. Hillyer.. 206
Determination of the iodin number of the nonvolatile ether extract of paprika.
By W.Denis 213
Determination of starch in cocoa products. By W. L. Dubois 214
MONDAY — AFTERNOON SESSION.
Examination of oysters. By W. D. Bigelow 215
Simple tests for detecting bleaching in flour. By A. L. Winton and E. J.
Shanley 216
A modification of the Bamihl test for detecting wheat flour in rye flour. By
A. L. Winton 217
Moisture determinations without the aid qf heat. By P. F. Trowbridge 219
The unification of saccharimetric observations. By C. A. Browne 221
< 'itral and its analysis in terpeneless extract of lemon. By Samuel H. Baer. . . 229
An outline to assist in the identification of certain water-soluble coal-tar colors
By C. B. Cochran 230
Officers, referees, and committees for the year 1908-9 234
< ^institution 237
Index ---"- 239
ILLUSTRATIONS.
Page.
Apparatus f.»r <!••!. Tnunin.: volatile and fixed acids in \viiii' 21
aphic of colhn :.-ult- »n amyl alcohol by the Allen-Mar-
<piardt method and ih»- propo-rd modification 26
• lal nitro^'ii and ammonia and changes in
th<- r « ..ri-iitucni- -.nluhlr in i,-. \van-r. ni t'n-sh, cold-stored,
and prctHTvi-d rhirkrn int-ai, during srvcn days 4G
hangos takiiiL: pla. ••• during' M-VI-II days in 'he nitrogenous constituents
•in t.-mp«-ratiir«" «.f fn-h, cold-stored, and pre-
. d chii-ki-n in* -at 47
mi'iluMls f.ir th«- drtcrmination of amyl alcohol 212
Kamihl -'hit.-n i.-i.. 218
I'lioi KKDIXGS OF THE TWENTY-FIFTH ANNUAL CONVENTION
OF THE ASSOCIATION OF OFFICIAL AGRI-
CULTURAL CHEMISTS.
DAY.
THURSDAY— MORNING SESSION.
Tin- t went y-tiftli annual convention of the Association of Official
Agricultural CheniM- was called to order by the president, Mr.
Harry Snyd. i. .»(' St. Anthony Park, Minnesota, on the morning of
N-. vemher I'J. in the Annex Hall of the Normandie Hotel, Washing-
tun. I). C.
T\vn hundred and sixteen members and visitors registered during
the rnnvrntinn, <-. .n-t it 1 1 1 iiiLr the largest attendance ever recorded.
The li-t i- afl f"ll"\\-
MEMBERS AND VISITORS PRESENT.
A. lain-. Arthur I'. . I'.un-an of Internal Revenue. Washington, D. C.
Albreeh. Maximilian C., I 8. Food and Drug Inspection Laboratory, Pittsburg, Pa.
Allen. Rolx-rt M uliural Experiment Station, Lexington, Ky.
Alwood, William Bradford, ' ' Stonehenge " Laboratories, Charlottesville, Va.
Am«..-<. Harold I... Bureau <>f Chemistry, Washington, I). C.
Averiti s l> \-n« ultural Experiment Station, Lexington, Ky.
Hail«-v, H.-rl..-n S , I'.un-uu ,if ( hemistry. U'ashington, D. C.
Mak.-r. I! I ..... .. in N Y.
I Jab •••in. R. Wilfred, Food and Drug Inspection Laboratory, New York, N. Y.
I'arber, Kat.- (, , Uun-au <>f I'hemisiry, Washington, D. C.
Hainan I. Harry E., State Food and Dairy Commission, Indianapolis, Ind.
Kanleti. James M.. Agricultural Experiment Station, Orono, Me.
. •!•>!(. n. Hun-ail m" < 'ht-misiry, Washington, D. C.
P.eal. W. H.. office of Experiment Stations, Washington, D. C.
Bell, James Munsie, Bureau of Soils, Washington, I). C.
Bithvell, (i.oru'e I... Bureau of Chemistry, Washington, D. C.
l>k'i-ln\v, Willard D., Bureau of Chemistry, Washington, D. C.
Billing. <ieor->- A . Department of Agriculture, \Vashington, D. C.
Rmvker, W. II., Bowker Fertilizer Company, Boston, Mass.
Boyle, Martin, Bureau <>f Ch«-iuistry. Washington, D. C.
Boyle.--. Frank M.. Bureau of Chemistry. Washington, D. C.
Brea/.eale. James Frank, Bureau of Chemistry, Washington, D.' C.
Brt-ckenridge, John E., American Agricultural Chemical Company, New York, N. Y,
(7)
8
Bridges, Benjamin H., Food and Drug Analyst to State of Florida, Tallahassee, Fla.
Brinton, Clement S., U. S. Food and Drug Inspection Laboratory, Philadelphia, Pa.
Broughton, Levin B., Agricultural Experiment Station, College Park, Md.
Browne, Charles A., New York Sugar Trade Laboratory, New York, X. Y.
Bryan, A. Hugh, Bureau of Chemistry, Washington, D. C.
Bryan, Thomas J., State Analyst, Chicago, 111.
Burnet, Wallace C., U. S. Food and Drug Inspection Laboratory, Savannah, Ga.
Burnett, Lyle B., Bureau of Chemistry, Washington, D. C.
Campbell, Walter Gilbert, Bureau of Chemistry, Washington, D. C.
Carpenter, Frank B., Virginia-Carolina Chemical Company, Richmond, Va.
Carroll, John S., German Kali Works, Atlanta, Ga.
( usileman, Philip, Department of Agriculture, Washington, D. C.
Cathcart, Charles S., Agricultural Experiment Station, New Brunswick, X. J.
Cavauaugh, George W., State College of Agriculture, Cornell University, Ithaca, X. Y.
Chace, E. M., Bureau of Chemistry, Washington, D. C.
Chapin, Robert M., Bureau of Animal Industry, Washington, D. C.
Chesnut, Victor King, Bureau of Chemistry, Washington, D. C.
Church, C. G., Bureau of Chemistry, Washington, D. C.
Cochran, C. B., Department of Agriculture, West Chester, Pa.
Cole, Frank, College Park, Md.
Collins, Arthur T., Philadelphia, Pa.
Collins, Paul, Agricultural College, College Park, Md.
Collins, William Dennis, Bureau of Chemistry. Washington, D. C.
Cook, Frank C., Bureau of Chemistry. Washington, D. C.
Davidson, Robert James, Polytechnic Institute, Washington, D. C.
Deemer, Ralph B., College Park, Md.
Denis, Willey, Bureau of Chemistry, Washington, D. C.
Dietrich, Harry W., Xoblesville, Ind.
Dodge, C. O., Bureau of Chemistry, Washington, D. C.
Donk, M. G., Bureau of Chemistry, Washington, D. C.
Doolittle, Roscoe E., U. S. Food and Drug Inspection Laboratory, Xew York, X. Y.
Doran, James M., Bureau of Internal Revenue, Washington, D. C.
Dorset, Marion, Bureau of Animal Industry, Washington, D. ( .
Doyle, Aida M., Bureau of Chemistry, Washington, D. C.
Dubois, Wilbur Latimer, U. S. Food and Drug Inspection Laboratory, Buffalo, X. Y.
Dunbar, Paul B., Bureau of Chemistry, Washington, D. P.
Dunlap, F. L., Bureau of Chemistry. Washington, D. C.
Eat«»n, Edgar O., Bureau of Chemistry, Washington, D. C.
Edmond, Herman D., Agricultural Experiment Station, Storrs, Conn.
Ellett, Walter B., Agricultural Experiment Station, Blacksburg, Va.
Emery, James Armitage, Department of Agriculture, Washington, D. C.
Emslie, Benjamin Leslie, Toronto, Canada.
Feldstein, Leonard, Department of Agriculture, Washington, D. C.
Fetzer, Lewis William, College Park, Md.
Fi><-her, Louis A., Bureau of Standards, Washington, D. C.
Forst, Leo B., Bureau of Internal Revenue, Washington, D. C.
Fox, Paul J., Bureau of Chemistry, Washington, D. C.
Frear, Julia Reno, State College, Pa.
Frear, William, Agricultural Experiment Station, State College, Pa.
Fuller, Aubrey V., Bureau of Animal Industry, Washington, D. C.
Fuller. F. D., Department of Agriculture, Harrisburg, Pa.
Fuller, Henry C., Bureau of Chemistry. Washington! D. C.
(iei-ler, Joseph F., State Department of Agriculture, New York, N. Y.
Given, Arthur. Bureau of Chemistry , Washington, D. C.
Good now, Kdw. II., Bureau of Chemistry, Washington, D. C.
irirh. Charlr.- K., Bureau of Chemistry, Washington, D. C.
(Ion-. II. C., Bureau <>f < 'hemi-try, Washington, D. C.
C.udeman, Edward, Chicago, 111.
urt, Robert, Ontario Agricultural College, Guelph, Canada.
Hart, U. II.. I". S. Food.and Drug Inspection Laboratory, Cincinnati, Ohio.
Harthran, Will II., Bureau of Chemistry, Washington, D. C.
Hart man, .Jo-eph Vance, Washington, D. C.
Hart \\cll. Hurt L., Agricultural Experiment Station, Kingston, R. I.
Hay wood, John K., Bureau of Chemistry, Washington, D. C.
Hayw'MMl. W. (irimes, Department of Agriculture, Raleigh, N. C.
Hillyer, William Kldridure, Bureau of Chemistry, Washington, D. C.
Holland. Kdu . B., Agricultural Experiment Station, Amherst, Mass.
Hiif. U'Tt Holmes, Agricultural Experiment Station, Morgantown, W. Va.
r, George W., Bureau of Chemi-trv, Washington, D. C.
Ho|.kin . < 'yril G., Agricultural Experiment Station, Urbana, 111.
, i i. .Julia -. State Dairy and Food Department, St. Paul, Minn.
II ;,'hton, Harry W , Uun-aii of Chemistry, Washington, D. C.
Howard. U. J., Bureau of Chemi-trv, Washington, D. C.
llud-on. < laude S., Hureau of Chemistry, Washington, I). C.
Humphn-y. 11 . ' . < orn Products Refining Company, New York, N. Y.
Ingereoll, Edwin Henry, Bureau of Animal Industry, W'ashington, D. C.
Jiu-"h-. r.enjamin Richard, Bureau of Chemistry, \\ a>hington, D. C.
Jaffa. Myer Kdward, State Food and Drug Laboratory, Berkeley, Cal.
Ji-nkin-. l.awn-in ••• J.. Hureati of ( 'hemi>tr\ , \\"a.-hington, D. C.
>r\<-- II., Agricultural Experiment Station, Burlington, Vt.
Kel,l,-r. l.vman F.. I'.ureau ..f < 'hemi-try, Washington, D. C.
ter, JohnT., Uur. -an -i '« liemistry. Washington, D. C.
K. llo--. Jam.-- W.. Tenn-ylvanitt Department of Agriculture, Harrisburg, Pa.
Kerr. K l.ert II., Uureau of Animal Industry, Washington, D. C.
Kniu'lit. (ieorge W., Hureau of Ch«-mi.-try, Washington, D. C.
it. Henry G., Agricultural Experiment Station, Laramie, Wyo.
Kniirht. Howard L., OflSce of Experiment Stations, Washington, D. C.
I.aUa. h, .! Vgricultural Experiment Station, Lexington, Ky.
I.add. K.lwin 1 .. Agricultural College, Fargo, N. D.
l.ane, ( larence I',., Dairy Division, Department of Agriculture, WTashington, D. C.
Cieorge D., Agricultural Experts' Association, New York, N. Y.
ft, Sherman, Bureau of Chemistry, Washington, D. C.
LeClerc, .1. A . Uureau of Chemistry, Washington, D. C.
Liep-ner, F. \\ .. Bureau of Chemistry, Washington, D. C.
hinder, \\ illiam Vanarsdale, Bureau of Internal Revenue, Washington, D. C.
I.ipman, Jacob G., Agricultural Experiment Station, New Brunswick, N. J.
Loomis, Henry M., U. S. Food and Drug Inspection Laboratory, Seattle, Wash.
Loweu.^ein. Arthur, Morris & Company, Chicago, 111.
LyiK-h, William D., Bureau of Chemistry, Washington, D. C.
Lythijoe, Hermann C., State Board of Health, Boston, Mass.
10
McCaughey, William John, Bureau of Soils, Washington, D. C.
McCormick, R. A., McCormick & Co., Baltimore, Md.
McCormick, W. M., McCormick & Co., Baltimore, Md.
McDonnell, Henry B., State Chemist, College Park, Md.
McGill, A., Inland Revenue, Ottawa, Canada.
McKeefe, Edward P., State Department of Agriculture, Albany, N. Y.
M< Neil, H. C., Bureau of Chemistry, Washington, D. C.
Magruder, Egbert Walton, Department of Agriculture* Richmond, Va.
Martin, Charles W., Bureau of Chemistry, Washington, D. C.
Mason, G. F., H. J. Heinz Company, Pittsburgh, Pa.
Michael, Louis G., Agricultural Experiment Station, Ames, Iowa.
Miller, Charles C., Philadelphia, Pa.
Mitchell, Andrew S., U. S. Food and Drug Inspection Laboratory, St. Paul, Minn
Moore, C. C., Bureau of Chemistry, Washington, D. C.
Moore, C. S., Bureau of Chemistry, Washington, D. C.
Morgan, Francis Patterson, Bureau of Chemistry, Washington, D. C.
Morgan, Will John, Bureau of Chemistry, Washington, D. C.
Morse, Fred W., Agricultural Experiment Station, Durham, N. H.
Morton, Grant J., Agricultural College, N. D.
Osborne, N. S., Bureau of Standards, Washington, D. C.
Palmore, Julian I., Bureau of Chemistry, Washington, D. C.
Paradis, El wood M., Maryland Agricultural College, College Park, Md.
Parker, Charles E., Bureau of Chemistry, Washington, D. C.
Parkinson, N. A., Bureau of Chemistry, Washington, D. C.
Patten, Andrew J., Agricultural Experiment Station, East Lansing, Mich.
Payne, Robert L., Baugh & Sons Company, Baltimore, Md.
Pennington, Mary E., Food Research Laboratory, Philadelphia, Pa.
Pierce, Anne L., Bureau of Chemistry, Washington, D. C.
Pinkerton, Thomas C., Baugh & Sons Company, Baltimore, Md.
Price, Thomas Malcolm, Bureau of Animal Industry, Washington, D. C.
Proctor, M. Fergus, Bureau of-Chemistry, Washington, D. C.
Read, Erne Alberta, Bureau of Chemistry, Washington, D. C.
Reed, Edward O., Bureau of Chemistry, Washington, O. C.
Richardson, William D., Chicago, 111.
Rieger, John B., Bureau of Chemistry, Washington, D. C.
Roark, Ruric Creegan, Bureau of Chemistry, Washington, D. C.
Robertson, B. F., Clemson College, S. C.
Robb, John Bernard, Department of Agriculture, Richmond, Va.
Ross, B. B., State Chemist, Auburn, Ala.
Rudnick, Paul, Armour & Co., Chicago, 111.
Rupp, Dr. Philip, Bureau of Chemistry, Washington, D. C.
Rusby, Henry H., Newark, N. J.
Salant, William, Bureau of Chemistry, Washington, D. C.
Schorger, Arlie William, Bureau of Internal Revenue, Washington, D. C.
Schulz, Henry L., U. S. Food and Drug Inspection Laboratory, Detroit, Mich.
Scovell, Melvill A., Agricultural Experiment Station, Lexington, Ky.
Seidell, Atherton, Hygienic Laboratory, WTashington, D. C.
Seil, Harvey A., U. S. Food and Drug Inspection Laboratory, New York, N. Y.
Sheib, S. H., Tennessee Chemical Company, Nashville, Tenn.
Shepard, James K., Agricultural Experiment Station, Brookings, S. Dak.
Shurly, R. Rex, Bureau of Chemistry, Washington, D. C.
11
Sindall, Harry E., Weikel & Smith Spice Company, Philadelphia, Pa.
Skinner, \Y. \V., Bureau of Chemistry, Washington, D. C.
Spencer, George Carl, Bureau of Chemistry, Washington, D. C.
Spra^ue, L. P., Board of Health Laboratory, Burlington, Vt.
Smith, Bernard H., Food and Drug Inspection Laboratory, Boston, Mass.
Smith, F. G., Department of Agriculture, New Orleans, La.
Smither, F. II., Bureau of Chemistry, Washington, D. C.
Snyder, Harry, Agricultural Experiment Station, St. Anthony Park, Minn.
Speare, Howell Davis, Agricultural Experiment Station, Lexington, Ky.
Stephenson, C. H., Bureau of Chemistry, Washington, D. C.
Stewart, Guy Robertson, U. S. Food and Drug Inspection Laboratory, New York, N. Y.
Stiles, George W., jr., Bureau of Chemistry, Washington, D. C.
Stone, I. Victor, Maryland Agricultural College, College Park, Md.
Straughn, M. N., Bureau of Chemistry, Washington, D. C. ,
Stn-.-t, John Phillips, Agricultural Experiment Station, New Haven, Conn.
Sullivan, Arthur L., Bureau of Chemistry, Washington, I). C.
Tul>er, Walter 0., Bureau of Chemistry, Washington, D. C.
Taylor, .him.- Norman, Bureau of Animal Industry, Washington, D. C.
Taylor, S. F., 108 Hudson Street, New York, N. Y.
That* her, Arthur S., Bureau of Chemistry, Washington, D. C.
Thatcher, R. W., Agricultural Experiment Station, Pullman, Washington.
Tolman, L. M., Bureau of Chemistry, Washington, D. C.
Trescot, Thomas Cuthbert, Bureau of Chemistry, Washington, D. C.
bridge, P. F., Agricultural Experiment Station, Columbia, Mo.
Valaer, Peter, jr., Bureau of Internal lie venue, Washington, D. C.
Van Slyke, Lucius Lincoln, Agricultural Experiment Station, Geneva, N. Y.
V.-iti-h, I . P., Bureau of Chemistry, Washington, D. C.
Wadr. Harold Rollins, Bureau of Chemistry, Washington. D. C.
Waggaman, William 11., Bureau of Soils, Washington, D. C.
I: » hicago, 111.
Walker. Perry 11 , Bureau of < h.-mi.Mry. Washington, I>. C.
M. I ewifl K.. Bureau of Chemistry, Washington, I). C.
Wat kins, Howard II., Army Medical Museum, Washington, D. C.
C., Bureau of Chemistry, Washington, I). < .
Wheeler, H. J., Agricultural Experiment Station, Kingston, R. I.
\\hittield, James M., City Board of Health, Richmond, Va.
Wiley. 11. \\ . Bur.-aii of t 'In'inistry, Washington, D. C.
Wiley. S, W.. Wiley A Hoffman. Baltimore, Md.
Wilhird, Julius T., Agricultural Experiment Station, Manhattan, Kans.
Wilson. C. P., Bureau of Chemistry, Washington, I). C.
Winton, A 1... Food and Drug Inspection Laboratory, Chicago, 111.
Wither*. \\ . A . Agricultural Experiment Station, Raleigh, N. C.
Ynunir, William J.. Bureau of Chemistry, Washington, D. C.
REPORT ON FOOD ADULTERATION.
By H. F. BARNARD, Referee.
The demand for analytical data bearing on the composition of normal and abnormal
food products that has arisen in the past three years because of the enactment of food
le-islation has shown most clearly the absolute necessity for accurate, precise, and
at the same time rapid methods for food analysis. It did not at first appear that the
12
problems of the food analyst were greatly different from those of the analytical chem-
ist, but as the work has developed, a new literature and a new chemistry have by
rapid evolution been added to the broad field of chemical science. The boast of the
manufacturing chemist that he is always a year in advance of the official chemist who
is hunting down iniquities is a constant stimulus and makes necessary the continual
development of new methods of analysis and the refinement of old practices.
No radical departure from established methods is advocated by those who have
studied the different phases of food adulteration this past year, but the reports of the
associate referees show the necessity for continued research.
On fruit products, baking powder and baking chemicals, fats and oils, condiments
other than spices, and the determination o* water in foods no reports were made.
These subjects are all worthy of careful study, and it is to be hoped that this coming
year they may be taken up.
I take occasion to call the attention of all food chemists to the imperative ner-es.-it y
for the adoption of uniform methods of analysis which have been proved accurate and
reliable. The work of this association is most valuable in providing official methods,
but no association can compel chemists to employ standard methods or insist upon
more careful analytical work. The food analyst is to-day working constantly in the
limelight and his results very frequently are carried to the courts and are subject to
the scrutiny of expert chemists and the counsel for the defendant. In too many cases
it has appeared that the results of analyses have been published and even used in court
which later were found to be inaccurate, thus compelling those responsible for
the publication and use of such reports to make public retraction. The value of our
work is greatly impaired by the constant recurrence of such mistakes. The necessity
for more careful work is well shown by data published in the Proceedings for last year,
where chemists analyzing similar condensed milks report an ash content varying
from 1.34 to 2.17 per cent and a fat content varying from 7.50 to 9.24 per cent. If
the fat in the original milk is determined in these samples on the ash basis, in one case
the original milk content is 4.2 per cent fat, in the other case 2.56 per cent, figures
which indicate that the same sample of evaporated milk was in one instance made
from whole milk and in the other from skimmed milk.
Attention is again called to the fact that we have no satisfactory alcohol table which
i> accepted by all chemists as a standard. The several alcohol tables now in use,
namely, those published in the Official and Provisional Methods of Analysis, the
tables given in the United States Pharmacopoeia, and those in use by the Internal
Revenue Bureau, are not alike. More than that, they are all calculated at 60° F.,
instead of at the generally accepted standard temperature of 20° C. Can not this
association be of assistance to the puzzled chemist who is constantly compelled to
recalculate and correct his results and who is confronted in court by alcohol per-
centages so different from his as to discredit his testimony, but which when calculated
to the same basis on the same table are found to be identical?
The Bureau of Standards may well cooperate with the committee from this associa-
tion for the purpose of revising the alcoholometric tables, and it is recommended that
a committee be appointed for this pin-pose.
REPORT ON WINE.
By JULIUS HORTVET, Associate Referee.
OUTLINE OF THE WORK.
On February 28, after some preliminary correspondence, the referee on wine sent
out the following letter, accompanied by methods of analysis for alcohol, extract,
glycerol, ash, fluorids, and total sulphurous acid, substantially as given in Bulletin
107 and in Windisch's Untersuchung des Weines. On June 11 these instructions
13
were supplemented hy a further letter submitting a modified method for the deter-
mination <>f volatile and fixed acids. The subjects reported upon included the deter-
mination of u'lycerol in wines, the examination of natural coloring matter in wines,
and the determination of total, fixed, and volatile acids; besides which there was
submitted a special report on the determination of reducing sugars, by R. M. West.
Th.-.- pa pi-rs, together with the letter of instructions and a statement of the modified
methods which were studied, constitute the report of referee.
INSTRUCTIONS.
FEBRUARY 28, 1908.
Di.\i:Sii;: I wnd you herewith an outline of methods for analysis of wine. It is my
desire that you subject these methods t • careful investigation, using for the purpose
samples of your o\vn mlliTtion. In general the plan of work for this year will be to
allow each collaborator Considerable latitude as to how he is to conduct his work. ' In
..flier word.-, you are requested to make an independent investigation of all or as many
of ihe-e methods as possible and prepare a paper giving your results and criticisms.
i.il attention i, directed to the following points:
(\) The change to 20° C. as the standard temperature for specific gravity and alco-
hol determinations.
(2) t'niformity of terms in which to express results, considering especially (a) the
i e\pn->.-in-.' all results when possible in grams per 100 cc of sample, (6)*the idea
Lpremng total, volatile, and li\«-d acids as cubic centimeters of normal acid in
>le.
1 tnpr»\ emeu?.- iii the method for detenniniiig glycerol.
A thorough trial <-f the new method of determining volatile and fixed acids
(see below). A drawing and a description of the apparatus used are given in this
conne
:n of the uranium method for determining phosphoric acid * *.
:h'- -cheme f, -r ••\amination of the natural coloring matter
of \\in.-s, n-ini: i'..r the purpose samples of the red-wine class.
(7) A .Tiiici.-m ..f the method for detecting lluorids ami the method for determin-
.Iphun.us .
- An inxe.-iiuMiion and . -niicism ..f any of the other provisional methods for wines.
perially the \olumetric metho<l for determining reducing sugars.
It is desired that the i .ur in\ est i-jat ions be reported in full, showing all
important numerical data. ConcluriODB, and reo.mmendat ions. * * *
PKOI'OSKI> MKTIK i - fOB MM W I I I: M 1 \ A I H > \ ol TOTAL, VOLATILE, AND FIXED ACIDS.
Total acids."
.inure 10 cc of the sample into a 300 cc flask, add 100 to 200 cc of recently boiled
distilled water, according t<> the color of the wine, and boil three minutes under a
retlnv condenser. Alter «-.... liny add '1 «>r :i drops of phenolphthalein and titrate with
tenth-normal sodium hydmxid. Kx press the result for total acids as cubic centi-
mei.-r- '.i n.irmal K*ld in l"(l CC of the wine.
\'<>la'ii> amlji.rfil acids.
The apparan: 1 con<i-i< of a cvlindrical flat bottomed flask of about 300 cc
capa«it\. provided with an elongated wide neck. Into the neck of this flask is fitted
by mean- of a -hort .-«•« -tion of thick rubber tubing a cylindrical shaped flask in the
but torn of which is a small opening leading inward through a siphon-shaped tube
bent back upon it-elf ami terminating at a point close to the bottom. The inner flask
IB O mnected to a condenser by means of a bent tube and safety bulb. In the stopper
i- al-o tilted a small funnel provided with a glass stop-cock. The distillate from the
condenser i- received in a cylindrical graduate.
Pour 100 cc of recently boiled distilled water into the larger flask, tightly fit the
smaller tlask into the wide neck, run in 10 cc of wine through the funnel, rinse out the
funnel with a little water, close the stop-cock and heat the water to boiling. The steam
nir through the siphon tube and through the wine carries out the volatile acids.
When 50 cc of distillate have passed over, empty the graduate and continue the
Pierre Breteau, Guide pratique des falsifications et alterations des substances
alimentaires, p. 318.
14
distillation Titrate the 50 cc distillate with one-tenth normal sodium hydroxid,
u.-ing phenolphthalein as an indicator
Stop the distillation when an additional 10 cc of distillate requires only one drop
of the standard alkali solution to neutralize. Usually 80 cc of distillate will include
practically all of the volatile acids. . .
On cooling the apparatus the liquid remaining in the inner flask is siphoned into
the outer flask Rinse out the remaining small amount of sample by running several
portions of hot -water through the funnel tube and Disconnect the two flasks. In
case of a light colored wine or a white wine, add 100 to 200 cc of recently boiled dis-
tilled water and titrate with one-tenth normal sodium hydroxid, using phenol-
phthalein as an indicator. In the case of a highly colored wine, after cooling the liquid
make up to 100 cc, measure out 25 cc, dilute with recently boiled distilled water and
titrate as before. Express the results for ,-olatile and fixed acids as cubic centi-
meters of normal acid in 100 cc of the wine.
THE DETERMINATION OF GLYCEROL IN WINES.
The method submitted to collaborators has been subjected to trial on a dozen
samples of genuine California wines. After the residues obtained by the method
had been weighed, they were analyzed for glycerol by the acid-dichromate oxidation
method, as follows:
The residue was dissolved in a little distilled water, filtered and washed through
a previously dried and weighed small filter, and the solution made up with water
to 50 or 100 cc, the volume depending on the amount of the dissolved residue. An
aliquot portion of the solution (equivalent to from 0.3 to 0.5 gram of residue) was
run into a 200 cc beaker, 20 cc of sulphuric acid (1:1) and 50 cc of standard potassium
dichromate solution (1 cc equivalent to 0.01 gram of glycerol) run in and the beaker
placed in boiling water. During the heating the strength of a prepared solution of
ferrous-ammonium sulphate (240 grams in 1,000 cc) was determined by titration with
the dichromate. At trie end of two hours the beaker was removed from the boiling
water, 100 cc of water added, and the excess of dichromate titrated with the ferrous-
ammonium sulphate. From the result of the titration the weight of the oxidized
glycerol was calculated.
A sample of chemically pure glycerol, which by specific gravity determination and
refractometer reading was shown to be 99.3 per cent pure, gave by this method 97.7
per cent pure glycerol by weight. The filter containing the residue insoluble in
water was again dried at 100° C., cooled in a desiccator and weighed. Tannin was
determined in another aliquot portion of the solution by the official provisional
method given for tannin in wine. The results of these determinations are shown in
the accompanying table. In three instances, owing to insufficient material, no results
for tannin were obtained.
There seem to be no means of estimating the loss of glycerol which takes place
during the determination. It appears, however, that the material which is extracted
and weighed as glycerol is never pure glycerol, as is generally assumed. The pro-
portion of glycerol obtained by the method of oxidation ranges from 84.7 to 88.5 per
cent of the weighed residues. Also it appears that in some cases a considerable
amount of the residue consists of matter insoluble in water, and also tannin.
Mr. C. S. Ash, chemist of the California Wine Association, recognizes the need of
an improved method for the determination of glycerol, and describes the following,
which has been employed in his laboratory:
Measure put 100 cc of wine in a porcelain dish, evaporate to a thick sirup, then
make alkaline with milk of lime and evaporate almost to dryness. Dissolve out the
flycerol with successive portions of boiling hot alcohol, evaporate the alcohol to about
cc, transfer to a stoppered flask or cylinder of 100 cc capacity, make up to 100 cc with
acetic ether, and allow to stand over night. Filter the liquid from the precipitate,
evaporate off, and dry the glycerol to constant weight at a temperature not above 55°
or 60 C.
The method is said to give fairly uniform results, and the most unsatisfactory part
of the procedure is the evaporation of the solvent. A small percentage of glycerol is
undoubtedly lost, especially toward the end of the process, but this and other diffi-
culties, it is hoped, may be overcome in great measure.
15
niparison of two methods for the determination of glycerol.
<;i\i.'rol(lnlOOec).
Water-
insoluble
Tannin
in
Percentage composition of extract
weighed as glycerol m provisional method.
Kind of win*-.
in • x-
extract
By pro-
visiuii.il
method.
Hv oxi-
dation
method.
tr;u-t
from 100
ccof wine.
from 100
ccof
wine.
Glycerol
by oxi-
dation.
Insoluble
residue.
Tannin.
Unde-
termined
residue.
Zinf.uid.-l
Grams.
0. t.974
Grams.
•
Grams.
0.0066
Grams.
0 0115
Per cent.
87 86
Percent.
0 95
Per cent.
1 65
Per cent.
9 54
; • 1 v
.2226
.0016
0083
85 88
62
3 20
* 10 ''O
Bharry '
MM
. 8-194
0059
88 48
61
Port • " '
1 ,*. i
.0046
0440
86 79
<0
3 79
9 02
MllM- I?
1.0424
BQQQ
.0019
0325
85 38
18
3 12
11 32
Hock
'.'•;:
.6014
0037
0010
86 57
53
14
J9 yg
.vine
.64<0
.5458
.0010
84 75
16
15 09
Whit.- wine
,| IIS
.5498
.0000
85.79
.00
14.21
Port
.OH
.cm
.0012
.0135
88.01
.18
2.02
9.79
8QQO
.0015
.0210
89. (3
.19
2.70
7.48
.0033
.0053
85.00
.-:5
.72
13.83
.aio6
.0014
.0273
85.24
.20
3.97
10.59
THE DETERMINATION OF REDUCING SUOAXS is WINE.
The foil. .win-.; criticism,! the provisional volumetric method of the association was
.n-.l l,\ 11 M Paul, Minn.:
Tin- chin' ..l.jection to the present pn»\ i.-i..ual methods for the determination of
reducing sugar* in win*- . liul. 107, p. 87) is the length of time necessary for the opera-
ti"ii tempi- have been made to remedy this defect by the introduction of
Volumetric method-, \\hich as a rule have been unsatisfactory either through the
necessity i.f preliminar\ mm I.>H- or through the excessive errors caused by the
•>l«- 1-. >n<lit i"!i-> under \\ hich the copper i.- precipitated. It was decided after care-
ful ( on -i.it -ration that th*- actual precipitation of the copper by the provisional method
o>uld not l.e modified to a.l\ antaire. 1'iit that the ordinary methods of preparing the
sample, in addition to bi-ini; Imii: ami tedious in operation, are the sources of several
• rore. A strong solution of alcohol fails to reduce Fehling solution, and,
such being the case, it is apparent that the addition of 25 cc of a 15 per cent solution
of ah c.hnl to l_'<) <•«• . .f boiling diluted Kehlini: solution, from which it would be almost
immediately boiled off, could have little or no influence on the precipitation of the
copper. Since ihe pro\iM..nal nielli."! calls for the dealcoholization of the wine
previous to clarification, its omission would save at least a half hour without decreasing
the accuracy of the result. Furthermore, it has long been realized that the use of
lead subacetate as a clarifying ai^-nt has been attended with several errors. In the
tir.-t place, the precipitated soli.L- carry with them small amounts of sugar, and, in the
i taking an aliquot portion of the filtrate the volume of the precipitate
is not considered. This second error is repeated when the excess of lead is removed
with sodium sulphate, and all these errors together, when multiplied by the number
of times that the sample has been diluted during the preparation of the solution in
which the sugar is determined, may amount to a considerable proportion of the total
reducing sugar content of the wine.
It is proposed, then, that the preliminary treatment of the wine consist of only the
dilution necessary to obtain a solution containing not more than 1 per cent of reducing
su-ar, that the copper be precipitated in the usual way, filtered as quickly as possible,
n -dissolved, and determined volumetrically or by electrolytic deposition. Analyses
were made on fourteen samples of wine by both the provisional and the proposed new
methods, with the results shown in the accompanying table. To make these results
more easily comparable, the sample was diluted with the same amount of water
for both determinations.
16
Comparison of methods for the determination of reducing sugars in wines.
Kind of wine.
Total
solids in
100 cc.
Reducing sugar in 25
cc of diluted solution
(containing not more
than 1 per cent of re-
ducing sugar).
Times
diluted.
Reducing sugar in
100 cc of wine.
By pro-
visional
method.
By pro-
posed
method.
By pro-
visional
method.
By pro-
posed
method.
Red wine
Grams.
2.40
2.17
2.18
4.37
4.77
12.00
16.22
1.72
1.79
1.61
13.08
5.47
2.34
12.83
Mg.
32.6
27.0
66.9
145.9
164.6
201.9
169.5
25.8
21.0
22.5
132.2
87.2
51.8
126.5
Mg.
31.6
28.1
62.1
146.5
162.5
201.5
169.7
26.4
19.4
18.9
130.3
85.7
59.1
127.9
4 '
4
4
16
16
40
80
4
4
4
80
40
4
80
Grams.
0.1304
.1080
.2736
2.3344
2.6336
8.o:eo
13.5600
.1032
.0840
.0900
10. 57CO
3.4880
.2072
10. 1200
Grams.
0.1264
.1124
.2484
2.3440
2.COOO
8.0600
13. 57CO
.1056
.0776
.0756
10. 4240
3.4280
- .2364
10. 2320
Red wine
Red wine - -
Sherry
Sherry
Port
Muscat
White wine
White wine -
White wine
Port
Sherry
Claret
Angelica
EXAMINATION OF THE NATURAL COLORING MATTER IN WINE.
The following statement was contributed by Genevieve Imus, St. Paul. Minn. A
complete tabulation of results of tests made on wine colors is given in the Twelfth
Biennial Report of the Minnesota State Dairy and Food Department, pages 250 to 253.
During the past two years a considerable amount of time has been given to the
examination of the natural coloring matter of wine. The work has not included the
detection of coal-tar dyes or other added colors but was intended primarily for the
purpose of obtaining on samples of known purity data that would be of value as criteria
in future routine analyses. The plan of making all color comparisons and descriptions
with reference to reliable standards has been adopted, and to this purpose the color
standards employed by Mulliken in his book entitled "A Method for the Identifica-
tion of Pure Organic Compounds," have been found to be admirably suited. These
standards consist of 18 pure colors, and of derived tones, 36 tints, 36 shades, and 12
medium broken colors. They are mounted on cardboard in compact form to facilitate
their use in the laboratory. A description of the standards and a discussion of the
application of color reactions to the examination of unknown substances are given by
Mulliken on pages 230 to 234. In matching colors the best results are obtained if
the operator stands with his back to a window and not in direct sunlight: The mate-
rial to be examined should be held about an inch away from the white cardboard
accompanying the color charts and alongside the square opening. The cardboard is
moved about until the exposed color matches as nearly as possible the color of the
material. A clear day is necessary for satisfactory results.
The tests which are described below were made upon the undiluted wine unless
otherwise stated. In tests with the various reagents the resulting colors of the solu-
tion have been noted as well as the color of any precipitate which may have been
formed. In the solubility tests with amyl alcohol the colors of both the alcohol and
resulting wine have been matched on the color chart. and recorded.
(a) About 5 ccof the sample are poured into each of six test tubes and the folio wing
solubility tests are applied: To each of two portions, one acidified with a few drops
of hydrochloric acid and one made alkaline with ammonia, 5 cc of ether are added.
To each of two portions, made, respectively, acid and alkaline in the same manner,
17
.", cc "i am\l alcohol are added. The tubes are thoroughly shaken and the liquids
allowed tn ,-eparate. If in any case an emulsion is formed, afew drops of ethyl alcohol
UK- added. Similar tests are made on the remaining portions of the sample without
tin- addition of acid or alkali.
(6) Ten cubic centimeters of the sample are made alkaline with baryta water,
shaken with an equal volume of amyl alcohol and, after observing the colors of the
two layers as directed, acetic acid is added to a filtered portion of the amyl alcohol
(c) To 50 cc of the wine in a beaker an equal amount of water and a few cubic centi-
meters of dilute hydrochloric acid are added. In this is placed a piece of white,
fat-free WIM.I (loth, about 10 cm square, and the solution is boiled from five to ten
minutes. The < loth is removed, washed in a stream of water, and after noting the
color the wo<>l is tr«-at i-d with a 2 per cent ammonia solution.
(d) l"\\ e nibic cent i meters of concentrated nitric acid are added to an equal amount
of the wine in a test tube.
(e) To 10 cc of the Cample in a test tube 5 cc of a neutral or slightly alkaline mix-
>f a 10 per cent potas.-ium alum solution and a 10 per cent sodium carbonate
.-olution are added, the mixture is shaken and the precipitate formed is separated
by filteriii'.;. In like manner the -uine is te-ted witli 5 cc of a mixture of lOpercent
aluminum acetate solution made alkaline with 10 per cent sodium carbonate solution.
A port ion of the .-ample i- al-o treated \\ithalOperceiitsoliitionofmercuricchlorid.
• f the sample in a te-t tube are added 3 cc of a 10 per cent solution of
I- i i hakeii and filtered. It has been found difficult at
time- to match the color of the precipitate closely with the color chart and in such
cases the coli.r ha.- 1 ,ate.l in general terms such as blue-gray or brown-gray.
About <)(>"> u'ram of pulverized yellow oxid of mercury is added to 20 cc of
the -ample and the mixture heated to boiling and poured through -a double filter.
After lir-i noting the color of the filtrate a few drops of hydrochloric acid are added.
(h) To each of two 10 re portions of the sample in test tubes a few drops of 10 per
t ferric chlorid and of ferrous sulphate are added, respectively.
Application of the solubility tests described above has shown the natural color in
\\ine- t,, be insoluble in ether under all conditions and in amyl alcohol when the wine
i- previously made alkaline with ammonia. A second dye was obtained with one
wine, but its dull appearance and its reaction with ammonia afforded a ready means
of di-tin-uishinu' the dye from those of coal-tar origin and from vegetable dyes of the
lichen group. Hydrochloric, .sulphuric, and acetic acids brighten or intensify the
color of the original wine, ammonium and sodium hydroxids darken the solution, and
ammonia alum produces no change. Tests with chalk steeped in albumen a gave
u n. -a ti.- factory results.
In general the follo\\in_' com lusions may be drawn from the results obtained by
the.-e te-t.-:
1. Nitric acid darken- the original solution of red wines, but produces practically
no change in white u
The lead precipitates vary from a pale yellow in white wines to a
deep blue-gray in red wines, but a violet or red color is never found in the precipitate
from a genuine wine.
3. Some highly colored red wines give a slight coloration upon the addition of
hydrochloric acid to the filtrate from the yellow oxid of mercury.
1 Ferric salts give a precipitate, ferrous salts do not.
The following results were obtained by II. V. Frost on a sample of red wine labeled
"Vino \ ecchio del ( hianti, Toscano, Italia." No evidence as to the authenticity of
the \\ine was secured, although it was known that the sample was imported from
Italy. The designations as to color correspond to those in Mulliken's chart.
"I". S. Dept. Agr., Bureau of Chemistry, Cir. 25, p. 17.
73t>73— r.ull. 11'2— 01) 2
18
Color reactions using different solvents under varying conditions (Frost).
GROUP A.
See wine shaken with —
5 cc solvent.
Hydrochloric acid +
5 cc solvent.
Ammonium hydroxid
+ 5 cc solvent.
Upper
layer.
Lower
layer.
Upper
layef.
Lower
layer.
Upper
layer.
Lower
layer.
Ether
Colorless..
NR-T2....
R-NT
R-NT
Colorless . .
R-T1...
R-T1... .
R-NT... .
Colorless..
Colorless . .
Black
Colorless..
Blackish..
Black.
Black.
Colorless.
Blackish.
Colorless.
Amyl alcohol
R-S1
Colorless.. R-NT
R-S1 ! Colorless..
Colorless.. R-NT
Colorless .
R-NT... .
Colorless .
Petroleum ether "
Colorless . .
R-S1..
GROUP B.
10 cc wine shaken
Determination.
15 cc wine shaken
with 3 cc of 10
percent solution
of lead acetate.
with 5 cc slightly
alkaline mixture
of 10 per cent
potassium alum
solution and 10
20 cc wine
boiled with 0.5
gram pulverized
yellow ox id of
per cent sodium
mercury.
carbonate.
Color of wet precipitate. . .
B-BTM...
BG-S2...
Color of filtrate...
GROUP C.
A piece of fat-free white wool cloth, 10 cm square, was boiled five to ten minutes
in 50 cc of wine to which were added 50 cc water and a few cubic centimeters of
dilute hydrochloric acid. The cloth was removed and washed in a stream of water.
The dyed cloth matched OR-T2; treated with strong ammonium hydroxid, it became
yellow-green, matching Y-BTM.
•
THE DETERMINATION OF TOTAL, FIXED, AND VOLATILE ACIDS IN WINES.
The first methods of determining the volatile acids in wines consisted in distilling
a measured quantity of the sample to about one-third of its original volume and
titrating the distillate; the results must obviously have been too low. The next step
appears to have been in favor of an indirect course of procedure whereby the total
acids were first titrated, then another portion of the wine evaporated off and the fixed
acids titrated in the residue. From the difference between these titrations was
calculated the amount of volatile acids. Various modifications of this method came
into use,« in all of which the aim appears, to have been to liberate the total volatile
acids by a prolonged heating of the extract. That an appreciable change might
occur in the extract constituents as a result of such treatment was not at first conceived.
At a later date, however, there developed grounds for the belief that certain of the
fixed acids disappeared, in consequence of which on titrating the residue there was
obtained too small a result; hence the result for volatile acids would be too high.
These considerations finally resulted in the abandonment of the so-called indirect
methods, and it was again proposed to separate the volatile from the fixed acids by
means of distillation and to titrate the volatile acids in the distillate.^ But because
the volatile acids pass over only slowly and with difficulty, a simple distillation, as in
the determination of alcohol, could obviously not be employed. Following a number
of attempts which had been made to devise a successful method, Lindemann,& in
a Methods proposed by Kissel, Weigert, Nessler and Barth, and Wolff: Zts. anal.
Chem., 1869, 8: 416; 1879, 18: 208; 1883, 22: 166; Repert. anal. Chem., 1883, 1: 213.
b Zts. anal. Chem., 1883, 22: 516.
19
1883, 1 - ribed u method of driving out the volatile acids with steam, and this forms
tin- ba.-i.- "i the utlicial methods which for some years have been prescribed in Europe
and in Anu-rica. In essential details the present official methods0 appear to comply
with the following procedure:
Fifty cubic centimeters of wine are distilled in a current of steam, in the meantime
heating the flask containing the sample until the liquid boils, and regulating the
flame so that the volume remains constant. Two hundred cubic centimeters of
distillate UP- collected and titrated with tenth-normal sodium hydroxid, using phenol-
phthalcin as indicator.
< 'heini.-i s who have had considerable experience with this method must have noticed
that it often happens that distillates collected beyond 200 cc show a more or less
acid reaction. This is the case especially with certain red wines, notably
buivundys. p«»rts, and clarets, and wines of the sauterne type. In fact, as the accom-
panying table .-how-, it .-eld "in if ever occurs that the first 200 cc distillate contains
even a fair approximation of the total volatile acids. In some instances it is seen that
by canying the distillation beyond L'OO cc the error is very considerable. Forexam-
ple. Pillowing closely the pp.vi.-ional method and carrying the distillation to 400 cc,
there are .-hown the following rates of increase in total volatile acids: In a burgundy,
approximately 1 1 per cent; in two samples of port, respectively, 13 and 14 per cent;
in a • laret, 1:5 percent; and in a white wine, <) percent. There occur, indeed, wines
in which the volatil ;»ear never to become completely exhausted, in which,
in fact, i he di.-tillalr fails to appear permanently neutral even after very prolonged
di.-tillinu'. This phenomenon may be attributed not so much to acids of difficult
volatility as to a possible , i :: ion of the extract constituents under the influence
longed heating by the direct action "f the flame which the official directions
."iilil be maintained below the flask containing the sample. It would
t at ni"-t KM) cc, of distillate should contain practically
all "f the volatile acid-, and that it may not be necessary or practical to prolong the
dUill.uion until the la.-t portion- of the distillate are neutral.
IV ;.// th,
1
1
6
10
<«11
b\-2
It
i:,
Id
' --lit i meters tenth-noniiul sodium hydroxid required to
neutralize).
Acid
in first
300 cc.
;<•> ..
BjOM :
Third
Fourth
Fifth
100 cc.
First
200 cc.
First
300 cc.
First
400 cc.
Total
500 cc.
.-, Ml
10.70
5.45
i r,
in
2. 15
5.90
4.10
2.10
1.70
2.00
1.00
.90
.80
1.65
Oklfl
.50
.50
1.10
.70
.40
.50
..80
.50
.35
.85
.95
.60
.75
a 10
.25
.55
.70
.35
.25
.25
.45
.35
.90
. r.
.40
.30
.35
a 15
.15
.20
.10
.30
.25
.15
.10
.10
.15
.20
.00
.15
.15
.10
.15
8.40
7.50
12.90
»,. •_'<>
7.80
14.15
7. 4f>
3.75
a 75
5.90
9.15
2.95
8. JO
10.30
6.05
9.00
8.00
14.15
0.70
8.90
15.40
8.15
4.15
4.25
6.70
9. 65
3.30
9.15
11.25
6.95
6.80
9.30
8.25
14.70
6.95
9.60
16. 05
8.50
4.40
4.50
7.15
10.00
3.50
9.60
11.65
7.25
7.15
9.45
8.40
14.90
7.05
9.90
16.30
8.65
4.50
4.60
7.30
10.20
3.50
9.75
11.80
7.35
7.30
Per ct.
95.2
95.2
95.0
93.6
90.0
94.7
94.2
92.2
92.4
91.7
94.6
94.3
93.8
95.7
94.5
93.1
/mfun
HurpiMdv
.MM,-....
Bbwri
i
a First 11 samples furnished by California Wine Association, 1906.
b Last 5 samples from miscellaneous sources.
The results obtained on these 16 samples of wine show that in only four cases did
the fifth 100 cc distillate require as much as 0.2 cc of tenth-normal alkali to neutralize;
hence, f -r practical purposes, it may be assumed that the vanishing point of the
« U. S. Dept. Agr., Bureau of Chemistry, Bui. 107, p. 86.
20
volatile acids ex-cure when 500 cc of distillate have passed over. On this basis the
results show that the proportion of volatile acids collected in the first 300 cc of distil-
late ranges from 90 to 95.7 per cent, only four samples showing a proportion slightly
greater than 95 per cent. Thus, even in the present provisional method of the asso-
ciation, if the entire apparatus be of fixed dimensions and relations in addition to
the other conditions stipulated, a large part of the fundamental error is still retained
even by carrying the distillation to 300 cc. If the distillation be conducted slowly
and the.volume of the wine permitted to become too large, an insufiicient amount of
volatile acids will pass over; if the distillation be too rapid and the volume of wine
be permitted to diminish too much, there may occur an overheating and the amount
of volatile acids will be too great. Finally , in order to obtain the greatest possible
concordance in results, the distillation must be watched from beginning to end with
the greatest care.
It has also been recognized that the agreement in results obtained by several dis-
t illations on a given sample fails to reach as high a degree as ought to be expected,
even in approximately exact determinations. When the distillations are carried
to 400 cc, or even until the vanishing point of acidity is fairly reached, the results
often fail to agree within reasonable limits. A difference in the results of the titra-
ti'-n< amounting to from 0.3 to 0.5 cc of tenth-normal alkali has often been noted;
.UK! the differences are commonly far greater at the close of the 200 cc period, amount-
ing to from 0.6 to 0.8 cc in several instances.
Briefly, then, the objections to the present provisional method are:
(1) The method is complicated, requiring rather elaborate apparatus and tiresome
supervision.
(2) The prolonged heating of the wine by the direct action of the flame doubtless
affects in some manner the constitution of the acid ingredients.
(3) The results do not to a sufficient extent represent the total volatile acids.
(4) The results are not reasonably concordant in the hands of different persons or
even in the hands of a single individual.
Owing to these considerations, various chemists have proposed the abandonment
of the direct method of determining volatile acids in favor of an indirect course of
procedure. After a prolonged examination of the relative merits of these two general
methods, Windisch" proposes the following:
Twenty-five cubic centimeters of wine are titrated in the usual manner for total
acids, using litmus or litmus paper as indicator. Another 25 cc portion is then evap-
orated on a water-bath in a porcelain dish to 3 to 5 cc, the residue dissolved in about
25 cc of hot water, the liquor again evaporated to 3 to 5 cc, the residue again dissolved
in about 25 cc of hot water, and the liquor evaporated a third time to 3 to 5 cc. Finally,
the residue is dissolved in hot water and the fixed acids titrated, using litmus as an
indicator. From the difference between these titrations the volatile acids are calcu-
lated:
The advantages of this over the present provisional direct method are obvious,
and have been adequately demonstrated by Windisch and others. The wine is
never heated above the temperature of the wrater-bath and the volatile acids are
undoubtedly all driven out, leaving the fixed acids probably unchanged. Further-
more, the results appear to be reasonably concordant and satisfactory. Various
modifications of the indirect method of obtaining the volatile acids have appeared. &
Sellier c has described a simple apparatus which consists of a small wide-neck flask
into which is fitted a cylindrical-shaped flask. In the bottom of the latter flask is a
« Zts. Xahr. Genussm., 1905, 9: 70.
f> Methods proposed by Roos and Mestrezat, Guerin, Curtel, and Robin: Bui. assoc.
chim. sucr., 1907,25: 41-49; J. pharm. chim., 1907, 25: 491^92; Ann. chim. anal.,
1901, 6: 361; J. pharm. chim., 1904, 19: 531-533.
'Ann. chim. anal., 1901, 6: 414.
21
small openiru; leading inward through a siphon-shaped tube bent back upon itself
an. I teniiinatini: at a point close fo the bottom. In making the determination, 50 to
60 cc of distilled water an- placed in the larger flask, the smaller flask fitted into the
wide neck by means i.f a section «»f rubber tubing, 10 cc of wine run in and the water
heated in boiling. The steam passing through the siphon-tube and through the
wine carries out the volatile acids. No appreciable change in the volume of the
wine takes place. When the water is reduced to about 5 cc, the flame is removed.
On cooling the apparatus the remaining wine liquor is drawn down into the larger
llask. The small flask is rinsed .tin with a little hot water and the two flasks discon-
nected. The liquor is cooled and the fixed acids are titrated.
This method has been employed in the laboratory of the Minnesota Dairy and Food
Department in the analysis of a number of samples of wine and in the investigation of
.11 or more of the common varieties of fruit juices, and has proven satisfactory not
only from the standpoint of conventem •»• in manipulation but on account of the fact
that results appear to !>•• relia-
ble and concordant. It has
hem noted, however, that in
I hi.- method as in others the
volatile acid.- an- n<>t roll-
hut are allowed to dissipate
into the air, and it lia-^ seem* -d
desirable to . ..nden-e th-
pore and titrate the volatile
in the distillate. l',\
joining a condenser to the
flank containing tho Rumple
there i- pn.\ ided an apparatus
\\lnTfb\ may be
det.-rniined in on.- operation
l)oth tin- \ohitile and fixed
itiM- portion of
wine.
The-tatement ,,f tin-method
proposed for total, volatile, and
fixed acid- i- '_'i\.-n «m page
13,
In the laboratory of the < ali-
fornia Wine. \ssociat ion tl
lowin- method ,,f titnition i-
empl.
i wine are measured into a 500 cc beaker without the addition
of water. The nine i- well -haken to remove carbon dioxid and titrated directly
with tilth normal sodium hydroxid. In the case of heavy-colored wines, no indicator
I; the coloring matter of the wine indicates the end point of the titration. In
the case ni white wine-, the same method of procedure is followed excepting that
a little neutral litmus is added. In titrating light-colored red wines, it may be advis-
able to add litmus, but the indicator is never used unless absolutely required.
A comparison of the results obtained by the various methods of determining total,
fixed, and volatile acids is shown in the accompanying table. Total acids were deter-
mined by the California Wine Association method, by the method of Windisch and
by the proposed new method based on that given by Breteau. Removal of carbonic
acid was assured before any of the methods were attempted. Fixed acids were deter-
mined by the method of Windisch, by the method of Sellier, and by the proposed new
Fio. 1.— Apparatus for determining volatile and fixed acids in
wine.
According to letter received from C. S. Ash, chemist, California Wine Association.
22
method of titration after driving off the volatile acids by steam distillation. Volatile
acids were determined by the indirect method of Windisch and by the proposed new
direct method of distilling by steam. In the Windisch methods the titrations were
made using litmus paper as an indicator and in the method of Sellier, as in the pro-
posed new methods, phenol phthalein was used.
Comparison ofjrtiethodsfor the determination of total, fixed, and volatile acids in wines.
[Results expressed as cc tenth-normal acid in 100 cc of sample.]
Kind of wine.
Total acids.
Method
of Cali-
fornia
Wine
Associa-
tion.
Meth-
od of
Win-
disch.
Pro-
posed
new
meth-
od.
Calcu-
lated
from
fixed
and vola-
tile acids.
Fixed acids.
Meth-
od of
Win-
disch.
Meth-
od of
Sellier.
Proposed new
method.
Using
litmus.
j Using
phenol-
phthal-
ein.
Calcu-
lated from
total and
volatile
acids.
Angelica.
Claret....
Port
Riesling..
Sherry...
Zinfandel
Sauterne.
Bordeaux
Sauterne.
Port
Sherrv...
Claret....
Port
Sherry...
Claret..^
4.30
7.70
5.20
6.00
4.00
a 70
C.70
7.10
7.70
8.90
5.50
5.60
6.80
5.90
8.50
4.16
7.52
5.60
6.36
4.50
7.92
7.58
8.16
8.20
8.44
5.80
10.60
6.30
6.40
8.40
5.80
9.60
7.20
7.45
5.35
9.70
8.55
9.15
8.90
9.55
6.60
11.90
7.10
7.20
9.50
5.80
9.55
7.15
7.50
5.35
9.75
8.60
9.20
11.90
7.10
7.25
9.60
3.32
6.80
4.36
4.80
2.96
5.64
5.48
6.00
6.00
3.60
7.40
4.40
3.60
6.20
0.14
4.90
8.00
5.90
6.15
3.95
6.75
6.40
7.30
7.75
4.80
9.60
5.50
5.70
7.90
8.20
3.40
7.00
5.00
5.20
3.00
5.50
5.00
6.00
6.50
3.70
8.20
4.50
4.00
6.40
6.55
5.00
8.00
6.00
6.10
3.90
6.75
6.50
6.95
7.30
4.40
9.20
5.20
4.80
7.70
8.10
5.00
8.05
6.05
6.05
3.90
6.70
6.45
6.90
7.25
4.40
9.20
5.20
4.75
7.60
8.05
No.
Kind of wine.
Volatile acids.
Ratio of volatile to
fixed acids.
Method of
Windisch.
Proposed new method.
Using
litmus.
Using
phenol-
phthalein.
Calculated
from total
and fixed
acids.
According According
to method to proposed
of new
Windisch. method.
1 Angelica..
2 Claret
3 Port
4 Riesling. .
5 Sherry....
a 6 Zinfandel.
67 Sauterne..
68 Bordeaux.
9 Sauterne..
10 Port
11 Sherry....
«12 Claret...
<*13 Port
14 Sherrv
15 Claret...
0.84
.72
.24
.56
.54
.94
2.68
2.20
2.44
2.20
3.20
1.90
2.80
2.20
1.78
0.70
1.40
.95
1.15
1.20
1.30
2.10
1.70
2.00
1.90
2.40
1.60
2.00
1.60
1.40
0.85
.55
.15
.40
.45
.85
2.70
2.00
2.30
2.20
2.70
1.90
2.45
1.90
1.65
0.80
1.60
1.20
1.35
1.45
1.80
2.65
1.95
2.25
2.20
2.70
1.90
2.40
1.80
1.60
:3.95
:3.95
: 3. 51
:3.07
:1.92
: 2.90
:2.04
:2.73
:2.46
:1.64
:2.31
:2.32
: 1.28
:2.82
3.44
6.25
5.16
5.21
4.35
•2. CM
3.69
2.40
3. 47
3.17
2.00
3.41
2.74
1.96
4.05
5.06
o First six wines furnished by the California Wine Association, 1908.
6 7 and 8 obtained from local dealers, 1908, St. Paul, Minn.
c 9 to 12, inclusive, from a Rochester, X. V., wine company, 1908.
<* 13 to 15, inclusive, from a Norfolk, Va., wine company, 1908.
The results obtained by the California Wine Association method were not satis-
factory, the end-point of the titrations being, in most instances, very uncertain.
In the angelicas, ports, and sherrys especially, much difficulty was experienced
23
in carrying "ut the titrations, and the results were scarcely better when litmus tine-
tun- was ued. In titrating according to the Windisch methods the point of neu-
trality was judired to be attained when a small drop of the liquor placed on delicate
bin.- litmus paper just ceased to produce a perceptible red. There appeared to
In- decided disadvantages in using litmus paper, and the use of litmus tincture even
in a dear distillate t~ open to serious objections, which will be stated presently.
In colored wines e-pe< -ially the difficulties were very great, and it was found well-
ni«;h impossible at times to devise a means whereby to judge with reasonable cer-
tainty the true end-point of the titration. It was found, however, after considerable
practice, that fairly « -onconlant results were obtainable by this method in the ma-
jority Hi instances Phenolphthalein, on the other hand, while not entirely unob-
jectionable, was found to give far greater satisfaction. While it was not always
convenient to titrate on the undiluted sample, especially in the case of wines con-
taining more ,,r Ian natural coloring matter, it was found to be entirely permissible,
'he titration .,f rider \ in. -ar-. to dilute with boiled distilled water in order to
carry out a .-ucce-.-fiil titration with phcnolphthalein. It has been shown that the
• Mid-point of a titration can he very accurately judged, even in a deeply-colored
win.-, ami that the addition of water to the extent of 100 or 200 cc does not introduce
tana error in the result. A- in a cider vinegar, the change in the color of a wine
occurs at a much earlier stage than the change in the indicator and there is never a
H difficulty in -af.-ly judging the end point.
As already pointed out. the results shown in the first column of figures are at best
only rough approximation-. In the majority of instances it was observed that when
litmus paper wa- u-.-d the til rat ions were carried somewhat beyond the point of
neutrality which -cemed to he indicated by the change in the natural coloring matter
of the wine. It i^ al-o noted that the results obtained by the titmtions employing
litmus were uniformly much lower than the result* obtained with phenolphthalein.
Thi- is inii- n-.i only in the titration- of total and fixed acids, but also in the direct
titration- of the volatile acid-. **n the basis of the results obtained with phenolph-
thal.-in. litinii- indicates approximately fn.m 77 to 92 per cent of the total acids and
from 58 to 85 per cent of the fixed acid-. Doubtless there are theoretical reasons
underlyinu' the-e ,!• and the question may well be raised as to whether
cheii:: -iviMi due attention to these considerations in choosing indicators for
titrating the arid- in wines.
In the tir-t place, there appears to be little justification for the practice adopted
by some chemi-t- of employing the natural coloring matter as a correct indicator in
titratinu' either the total or fixed acid-. Little of value is known regarding the action
of the oenocyanin or other coloring -ub-tances in the presence of acids or alkalies,
and it is certain that -u< -h .-ub.-tam -e- have not been recommended in the titration
of any of the common acids. In the rase of litmus also there are some important
considerations which should bar it as an indicator for wines as well as fruit products
in general. Litmus i- not recommended for titrating such acids as tartaric, acetic,
tannic, succinic, or malic. In titrating tartaric acid with this indicator, the change
is gradual and the end-point indistinct, while in titrating acetic acid, the acetate
of sodium formed i- alkaline to litmus and tends strongly to hasten the end-point.
On titrating solutions of tannic acid, a change takes place almost immediately on
beginning the titration, and only a small proportion of the actual acid is indicated.
Phenolphthalein, on the other hand, is a very satisfactory indicator with all these
acids, and, with the exception of tannic acid, the theoretical amount of acid is obtained.
About 80 per cent of tannic acid is indicated, but the total acid is obtained after
boiling with a measured small amount of tenth-normal hydrochloric acid.
24
As a means of shedding some light on the differences occurring in titrating winss
with the two indicators, the determinations shown in the following table have been
carried out:
Comparison of litmus and phenol phthalein as indicators in titrating some of the organic
acids existing in ivines.
„
Normal acid in 100 cc.
Per cent acid in-
dicated.
Grams
Acid.
Description.
in 100
cc.
Calcu-
lated.
Using
phenol-
phthalein.
Using
litmus.
Using
phenol-
phthalein.
Using
litmus.
cc
cc
cc
Tartaric P.lmnpr and Amend
0.4000
5.33
5.35
5.10
100.3
95.6
Acetic
Mallinckrodt's 99 per cent. . .
.4040
6.67
6.70
6.35
100.4
95.2
Fimer and \mend
.4000
2.12
2.10
1.90
99.0
89.6
trate.
Twnif
J. T. Baker Chemical Co
.5000
2.79
2.20
.40
78.8
14.3
Tannic
After boiling with dilute
2.80
.40
100.3
14.3
hydrochloric acid.
94.4
73.6
ting last item).
The results shown for volatile acids by the Windisch method (p. 22) are somewhat
higher than those obtained by the proposed new method, using phenolphthalein.
Such discrepancies, however, lose their significance when it is considered that in
the determination of volatile acids by the indirect method not only are the results
of the titrations employing litmus as indicator incorrect, but the titrations of total
and fixed acids are not made under comparable conditions. While it is unques-
tionably true that the volatile acids may be completely driven off by repeated evapo-
ration in an open dish, it does not follow that the results obtained by means of the
two titrations are correct. It is conceivable that important changes may occur during
the prolonged heating of the wine in order to reduce the material a third time to a
pasty consistency. At any rate, we have no positive knowledge that the so-called
fixed acids occurring in the final residue represent the actual fixed acids in the original
wine. A titration of the residue may suffice as an indication of the acids remaining
after driving off the volatile constituents by prolonged heating, but to employ the
result of such a titration as a factor in the calculation of the actual volatile acids
appears to be an unwarranted proceeding.
In expressing results of analysis the orthodox custom appears to be to calculate
the fixed and total acids as tartaric and the volatile acids as acetic. It is impossible
to concede any advantages in favor of this custom. It may be safe to assume that in
wines the fixed acids are in the main tartaric and the volatile acids acetic; but, even
on such assumptions, the results are strictly erroneous and not readily comprehended.
Such a method applied to the various fruit juices and ciders would fail to give sig-
nificant results in practically all cases, and the case is still worse when one adopts
the method of calculating the acids as sulphuric. Instead of these conventional
methods it has been found better to adopt the plan of expressing all results for total,
volatile, and fixed acids in terms of the number of cubic centimeters of normal acid
in a definite measure, say 100 cc, of wine. There will then be afforded results which
can be readily compared and comprehended. Furthermore, in case it be required
to calculate results in terms of any particular acid, such an operation can easily be
carried out.
RECOMMENDATIONS .
(1) The standard temperature for the determination of specific gravity should be
changed to 20° C. A statement of reasons for this change seems to be unnecessary, as
the matter has been fully discussed by others, and many chemists have for some time
25
adopted tin- custom of making determinations at a temperature not far from that of the
average lal >oratory. I f t he alcohol tables can be revised in accordance with a standard
temperature ..f jo ( '. for specific gravity determinations, a very useful service will be
performed, especially in the interest of industrial and food chemists.
Tin- method f..r glycerol should be made a subject for special study. Expe-
rience has shown that it is possible not only to increase the accuracy of the method but
to -horten the time of the operation. As the provisional method now stands, it appears
to !)»• rather tedious, and there are too many opportunities for error. A large error
undoubtedly occur- during the evaporations as well as during the repeated extractions.
AJeo, i' appear- that the residue weighed as glycerol is far from being pure.
(3) The present methods for determining total, fixed, and volatile acids are exceed-
ingly faulty. The method for volatile acids, especially, fails to give results anywhere
near the truth. The difficult y lies not only in the collection of 200 cc distillate but
in tin* operation, which is cumbersome and unreliable. The use of litmus in the titra-
tions of total and fixed acids is open to criticism, as that indicator fails to show all of
the arid-. A -tudy of the proposed new methods is recommended.
(4) A more comprehensive scheme for the examination of the natural coloring mat-
ter of wines is required. Attention is railed to the use of standard color charts as a
mean- »\ obtaining comparable results in the hands of different persons. It is rec-
ommended that the a--ocjaiioM make a special .-t inly of the character and properties
of the coloring matter- e\i -i MIL: in genuine wine<.
REPORT ON BEER.
! I ! l> \ u \ \it i » , „•! mtociate Referee.
Mr. Barnard. tvlVree mi l>r<>r. reported that no cooperative work
on the suhjrrt had hrrn duiu-. and made the following statement in
to the condition of the methods:
Two yean ago I presented beer methods which have since been adopted as provi-
sional. I ha\e been working with those methods since that time and find no special
necessity for rhamrim: them. For that reason I have not made a special report on
Murli work, ho\\e\ cr, seems to be ne< e-sary if we must determine the different
kinds of beer, and 1 would only suw>t t«. you the necessity for a careful study of
method- oi l.,-,-r an.iK -i- \\ n h -pi-cjal reference to the adoption of some method which
will enable IH to tell more accurately than is at pn-ent po-sible whether or not beer
is brewed from all malt, or part mall, or from malt substitutes.
REPORT ON DISTILLED LIQUORS: COOPERATIVE TEST OF
METHODS FOR THE DETERMINATION OF FUSEL OIL.
I'.y L. M. TOLMAN, Associate Referee.
The cooperative work undertaken this year was a comparison of the present Allen-
Marquardt method, aa given in Bulletin 107, revised, page 98, and a proposed modi-
fication worked out by the associate referee and his assistants. The modification was
based on the determination of the amount of bichromate reduced in the oxidation of
the higher alcohol-. This method eliminates the distillation of the acids, which the
experiments made have shown are not completely distilled off. In order to test this
modified method (for details see paper, p. 206) a series of samples was prepared con-
taining varying amounts of pure amyl alcohol (boiling point 131° C.) in approximately
50 per cent by volume ethyl alcohol, and the samples sent to eighteen different labo-
ratories, asking for a comparison of the modified method with the present method as
given in Bulletin 107. Eleven reports were received, and the following table gives
26
the results, the percentage yields being calculated from the grams of amyl alcohol per
100,000 of 100-proof alcohol, as determined by each method.
Comparison of the Allen- Marquardt meihodand the proposed modification for the determina-
tion of fusel oil, using varying amounts of amyl alcohol.
1 1
0.050 gram.
0.100 gram.
0.150 gram.
0.200 gram. 0.250 gram.
0.350 gram.
Collaborator.
1
|
f .
1
Marquardt
ethod.
' o
Marquardt
ethod.
|
Marquardt
ethod.
cation.
Marquardt
ethod.
^3
B
• c
<£S
S ~ =
—
C.
,1 ~
J_
[P
&
"o
1
_5>
0
i
£
•g
•o
<
%
<
a
<
<
<
*
<
X
P.ct.
P.ct.
P.ct.
P.ct.
P.ct.
P.ct.
P.ct.
P.ct.
P.ct.
P.ct.
P.ct.
P ct
99.8
100.0
102.0
122.0
78.03
74.1
111.9
78.34
77.74
62.7
97.69
85.69
100.0
62 3
85.14
88 3
\c\v York laboratory
78.7
105.0
110.0
130.4
Philadelphia laboratory. ..
Portland laboratory
82.0
56.0
113.0
106.4
72.11
99.70
86.0
105.1
73.8
80.4
85.4
96.6
78.5
83.4
88.06
95.02
74.5
79.4
87.7
104.0
79.7
76.7
87.24
87.7
Sunnybrook Distilling Co.. ,120.0
125.9
108.8
104.5
100.0
114.9
87.06
108.6
87.86
85.64
80.6
81.68
St Paul laboratory IftVO
82.64
78.0
83 22
69 06
Washington laboratory.. ..
67.3
134.2
72.1
97.1
62.2
91.5
65.2
86.2
68.3
88.5
68.8
84.6
< lah eston laboratory*. . . .
87.20
87.24
79.28
82.14
80.0
79.90
81.36
78.60
72.06
75.52
San Francisco laboratory a
42.8
63.1
50 44
74 2
53 74
80 0
50 9
73 2°
Scar tic laboratory o
75.6
70.4
61.62
66.60
70.16
62 14
61 86
68 19
Boston laboratory a.
84.40
145.7
119.1
76.04
124.5
76.36
131 4
I*7! 0
110 3
89.7
117.2
85.7
99.5
85.3
103.7
77.7
94.7
76.2
91.5
76.7
85.8
AMYL ALCOHOL (PARTS PER IOQ.,000)
ZOO ISO JOC
\
a Excluded from average.
Some of the results obtained at laboratories which had not had experience in operat-
ing the method varied markedly from the other figures and are omitted from the aver-
age. The averaged results on the various amounts by both methods are plotted, using
as the abscissa of the curves the amount of amyl alcohol used in grams per 100,000 of
proof spirit and as ordi-
nates the average percentage
yield.
This curve (fig. 2) shows
that the new modification
gives uniformly higher re-
sults, indicating a regular
loss in the old method. This
loss is undoubtedly largely
due, as is shown by the ex-
periments, to the failure to
drive over all of the volatile
acids in the distilling method
unless a much larger amount
of water is distilled than that
prescribed in the present pro-
visional method. A very
much higher yield of acids
IETHOD
FIG. 2.— Graphic of collaborators' results on amyl alcohol by the
Allen-Marquardt method and the proposed modification.
is obtained by carrying the distillation much further, as is pointed out in the sup-
plementary paper submitted on this subject (p. 206) . There is also shown a uniformly
increasing loss by both methods as the per cents of amyl alcohol increase. This is
doubtless due to the method of extraction, as a 100 per cent yield can be obtained in
the oxidation part of the method, as was demonstrated in the experimental work on the
'termination of the factor 0.001773 (see p. 2 10) . From these results it is evident that a
higher yield is due to the more correct estimation of the higher alcohols present in the
27
carl... n tetrarhlorid extract. Tlu- curve also shows that the collaborators obtained
Hint.- uniform results from the new modification than from the method as originally
state. 1. It may be concluded, therefore, that—
(1) The modified method gives higher and more uniform results.
(2) It eliminates a tedious and inaccurate distillation.
(3) It is quicker and «:i\es an opportunity to make check titrations on the same
sample.
RECOMMENDATIONS.
As a result of this year's work, including that reported on page 206, it is recom-
ntended
(1) That this modification of the Allen-Marquardt method be adopted as a pro-
vi.-ional method i see j>. L'lu .
(2) That in the present method a second washing with sodium sulphate be pre-
scribed.
(3) That the method for determining the water-insoluble color be adopted as a
provisional method -.,••• p. 20
(4) That the method for the determination of amyl insoluble color be adopted as
provisional quant itat ive Mar-h r«-i method, p. L'"
That the Koese method '.riven in Bulletin 107, page 97, be dropped as a pro-
visinnal method on account of tlie entirely unsatisfactory results obtained with it in
the jmst two or thn •
Mr. Tolman e.-illed mi Mr. Ki>eher, of the Bureau of Standards, who
spokr iii re'_ranl t«» the neees>ity of unifyiiii: the alcohol tables. He
called attention t.i tin' fact that two tables are now in use by the
Treasui] Department and a third by the Association of Official
Airricnlttiral ChemM-. Th<> disadvantages to chemists and practical
\\orkers frnin such a condition of affairs bciny; obvious, it was strongly
1 1 mended tliat the association take some action in the matter.
A table based mi t he calculations of Mendeleeff was recommended by
Mr. KiM-lier. The (jue^timi <>f temporatiiro was also discussed, and
the whole matter \\ u temporarily referre<l to Committee C on recom-
mendati..nv «,f referees, the chairman naminjj: the following members
t.. >ervr on ibis committee: Me--r-. Tolmaji, Winton, Hortvet, Bart-
let t. and .lall'a.
REPORT ON VINEGAR.
By CHAKI M II. HICKKY, Asxnn'tite Referee.
The work which has been don. by or reported to the referee deals largely with the
lead number i'«-r pure rider vinegar and other pure vinegars. The cider vinegars used
by the referee wen- made by the old-fashioned, slow process. The method employed
lilar to the one by which Winton and Kreider« analyzed maple products, with
modifications to make it applicable to vinegar. The number of grams of lead
pre< f pi t at e« i I >y 100 cc of vinegar is taken as the lead number. Other data are included
to make the results more complete. The method as modified by the referee is as
follows:
Pipette 25 cc of vinegar into a 100 cc flask; add 5 cc of a standard lead subacetate
solution and dilute to KX) cc. Let stand at least one hour, then filter and pipette out
a- filtrate. To this add 10 cc of dilute sulphuric acid and 100 cc of 95
percent alcohol; let stand over night; filter through a porcelain gooch crucible; wash
aj. Amer. Chem. Soc., 1906, 28 : 1204.
28
with 95 per cent alcohol; dry at a moderate heat for a few minutes, cool and weigh.
Calculate the amount of lead in the precipitate (factor 0.6829) and subtract this from
the amount in 2.5 cc of the standard solution as determined on a blank test, and divide
the remainder by 0.125, thus obtaining the lead number.
The standard lead eubacetate used in this work is prepared as follows: Dilute a
U S. P. lead subacetate solution until the specific gravity is 1.25; to one part of this
add four parts of water and filter. If the solution becomes cloudy, filter before using,
and determine its strength frequently. The referee found that the strength changed
but little.
Mr. E. M. Bailey of the agricultural experiment station at New Haven, Conn., has
reported work which he did independently on different kinds of samples of vinegar
of known purity. He includes other data in his results, especially those on testing a
recent method for the determination of malic acid which was formerly applied to maple
products." He found that by using this method more malic acid can be recovered
than by the old calcium chlorid method. The method for determining the load
number is as follows:
Measure 50 cc of vinegar into a 100 cc flask, add 25 cc of lead subacetate (dilute
solution used by Winton and Kreider) make up to the mark and filter. To 10 cc of
the filtrate add 1 cc of concentrated sulphuric acid, 40 cc of water and 100 cc of 95 per
cent alcohol. Filter after 12 hours, ignite, and weigh.
The amount of lead in the blank test is determined by diluting 25 cc of the lead sub-
acetate solution to 100 cc; 10 cc are taken out and the lead number determined as in the
method just given.
The modified method for malic acid as applied to vinegar is as follows:
To 10 cc of vinegar add an equal volume of water, 3 cc of a 10 per cent solution of
calcium acetate, and 180 cc of 95 per cent alcohol. Heat on the steam bath for from
20 to 30 minutes, stirring vigorously at intervals to insure a clear supernatant liquid.
Filter on 589 S and S paper, wash with 85 per cent alcohol, and ignite. Dissolve in
excess of tenth-normal hydrochloric acid (10 cc) by gentle boiling, and continue to
boil for about 10 minutes. Cool and titrate with tenth-normal sodium hydroxid,
using methyl orange as indicator.
The results of the work of the referee and those of Mr. Bailey appear in the accom-
panying table. This shows the variation in the amount of lead precipitated by the
different vinegars. In the case of malt vinegar, the results tend to run high; while
those of the sirup and distilled vinegar are very low.
It should be noted that in the case of malic acid determinations, which are, of
course, not properly such on malt and sirup vinegar, misleading results may be ob-
tained and, in the case of a suspected sample, the malic acid determination would
have to be confirmed by the procedure recommended by Leach and Lythgoe.&
In comparing the figures for malic acid, phosphates, and the lead number as worked
out by Mr. Bailey, it is his opinion that a closer relation exists between the phosphate
content and the lead number than between the malic acid value and the lead number.
The three highest lead numbers are associated with the three highest total phosphate
values; the same is true of the three lowest figures in each case. That this does not
follow, however, in the case of lead numbers and malic acid values would seem to
indicate that the precipitate produced on adding lead acetate to vinegar is due rather
to the phosphates than to the malates. This is in accordance with the statement of
Leach and Lythgoe c that the precipitate produced by lead acetate is not entirely due
to malic acid. Tolman and Le Clerc d are also of this opinion.
The other data for pure cider vinegar, included in the table, are fairly typical, and
in addition to the old figures the new ones for the lead number are of interest.
<* J. Amer. Chem. Soc., 1908, 30 : 1285.
b J. Amer. Chem. Soc., 1904, 26 : 379.
<• J. Amer. Chem. Soc., 1904, 26 : 380.
<*U. S. Dept. Agr., Bureau of Chemistry, Bui. 99, p. 89.
29
of sample* of vinegar of 'known purity.
C. H. HICKEY.
NIIIII-
HB
1
I
9
10
I!
U
15
16
20
l'hanu-t«T.
( iil« r vm> _Mr
Sol-
ids.
Acid.
Ash.
Reducing
sugars
(dextrose).
Re-
due-
ing
sug-
ars
in
sol-
ids.
Polar-
ization
(200
mm
Vent-
zke
tube).
Ma-
lic
acid.
Phosphoric
acid
(per 100 cc).
Lead
num-
ber
for
100
cc.
Di-
rect.
In-
vert.
To-
tal.
Sol-
uble.
P. a.
P.ct.
P. tt.
P.ct.
P ct
P.ct.
°V
P.ct.
mg.
mg.
0.166
.134
.087
.145
.106
.106
.112
.095
.114
.103
.114
.103
.109
a. 098
.129
.106
.087
.163
.076
.109
i it
.50
.70
.98
.04
.86
.50
.94
8.70
5.06
i . :,:
:, >
.. M
7.84
6.24
3.00
1 x,
4.60
4.72
!
" |
0. 1'J
.38
.35
.38
.37
.48
.40
.34
.46
do
0.13
.24
.12
.21
.22
.11
.11
.14
.09
.14
.16
.10
.19
.13
0.13
.24
.10
.19
.91
.11
.12
.13
.09
.18
.Hi
.10
.11
.11
7.6
11.4
6.3
10.1
10. '2
5.2
6.5
7.7
6.0
8.3
9.3
7.2
8.7
- .10
- .87
- .54
-0.88
- .43
- .21
-0.88
-1.10
-0.77
-0.88
-0.88
-.1 vs
-1.10
-1.08
So ....'....
K. M. IIAII.KY.
M
1.50
0.073
0.075
1.04
40.0
.129
is i
10 2
116
'I
l|(l
ll'l
2.34
.95
.50
.99
.53
41.4
21.3
.121
.411
15.9
16.6
9.0
6.7
.088
.148
•'-,
.86
.93
32.5
.296
26.9
13 8
174
•t,
87
89
198
46 1
39 9
290
n
.64
.221
18.4
10.8
.122
X
1 12
1 1 1
32 3
.399
30.0
16 9
220
' 1
'
.434
2.79
.90
.97
33.3
.230
106.2
17.8
.548
1 60
08
09
5 3
120
31.5
14.6
158
.01
.02
8.0
.016
5.9
3.3
.018
1 m
44*
.19
.20
17.0
.069
12.8
1.8
.021
015
Incompl.-t
* Not analyzed by E. M. Bailey.
REPORT ON FLAVORING EXTRACTS.
M. » HA. i. Associate Referee.
••••port on flavoring extract was submitted by the referee last year, owing to the
tuct i hat onl\ a \ery limited amount of work was done, and the report this year includes
also the work submitted by collaborators in 1907.
WORK OF 1907.
In 1!M)7 the follow in-.;. -um pies were sent to collaborators, with the usual instructions. <*
I. Blank containing no lemon oil or citral.
Alcohol 1,900 prams, lemon oil 100 grams.
mon oil used in preparing No. 2.
No. 4. Alcohol 2,000 grams, vanillin 2 grams, coumarin 2 grams, acetanilid 1 gram.
No. 5. Extract prepared from Mexican vanilla beans by the U. S. P. method.
"The methods f.-r citral were the same as those reported for 1908, see page 32; for
vanilla methods see Bui. 107, p. 156.
30
Reports were received in all from seven collaborators, and the results are tabulated
Citral determinations in lemon extracts and oil, 1901 .
Collaborator.
Sample 1.
Sample 2.
Sample 3.
AP «?v Washington D C
Per cent.
v None
Percent.
0.16
Per cent.
5.23
Trace
.300
6.12
£°g Brintoii Philadelphia
Not reported
.322
Not reported
j^ Y S<M'krr *NYw York
0.01
.226
4.61
.209-
4.50
k j^ grown North Dakota
.00
.229
5.41
.027
.126
3.50
a Using ice water bath.
COMMENTS OF THE ANALYSTS.
Shook
.1. 7'. Sy: Sample No. 2 — oil globules had separated in original sample,
well before making determination.
B. H. Smith: These were the first samples personally examined by this method and
I have not found time to repeat the work as was intended before reporting results.
C. S. Brinton, and T. F. Pappe: We desire to state several points which will probably
have a bearing on the value of these results: First, the metaphenylene diamin hydro-
chlorid at our disposal showed signs of being somewhat decomposed and the aldehyde-free
alcohol, as a result, gave a quite marked coloration with the reagent. Second, although
we allowed several days to elapse before making up to volume our fuchsin sulphur
dioxid reagent, it did not become colorless but showed a deep lemon yellow tint.
.1. F. Seeker: In laboratories where constant temperature baths are not at hand
and when only occasional citral determinations are required, it will be found much
more convenient to use ice water for immersion of reagents and colorimeter tubes.
Provided the standard and the unknown solutions were subjected to the same condi-
tions it was thought that the results might be as accurate. To test this, the constant
temperature bath was used in one set of determinations and in the other an ordinary
ether can filled with water in which a piece of ice was constantly kept. The latter
requires no watching and the color develops less rapidly, making it possible to read a
solution containing three milligrams of citral without difficulty . At 15° the color devel-
oped by three milligrams is a little too intense. Results at 15° are slightly higher.
In preparation of aldehyde-free alcohol, it was found that three grams of meta-
phenylene diamin hydrochlorate per liter * * was sufficient provided the alcohol
was boiled for eight hours and allowed to stand over night. * * *
To ascertain to what extent the aldehyde in commercial spirits used for making up
extracts might affect the citral determinations, a sample of ordinary 95 per cent
alcohol was run in the same manner as an extract. It showed aldehyde equivalent to
0.031 gram citral. Results obtained with extracts may thus be a little higher than
the truth for this reason.
LinwoodA. Brown: In the determination of citral by the fuchsin method, the greatest
objection to it is in obtaining alcohol perfectly free from aldehydes. The Dunlap
method failed to give a perfectly aldehyde-free alcohol even after three times on the
same samples of alcohol, i. e., the alcohol was subjected to the method three successive
times. %
The metaphenylene diamin hydrochlorid method gives the best results for this
determination.
W. A. Syme: Commenting on the method for lemon extracts, I would say that the
method for purifying the alcohol (with metaphenylene diamin) did not yield an
alcohol that would not produce a color with fuchsin solution on two trials. This
lessens the accuracy of the work. I would suggest that other methods of preparing
alcohol be studied and that other solvents be tried.
A glance at the table is sufficient to show that the results obtained in 1907 were prac-
tically of no value. The discordant figures on sample No. 2 are in part explained by
the fact that this extract was made up in 85 per cent alcohol and it was found later
that globules of oil had separated and were floating on the surface. This fact is noted
in the comments of Mr. Sy, who analyzed the sample some time after it had been
made up.
The only other explanation offered, is that the analysts were not familiar with the
method. So far as is known Mr. Seeker is the only collaborator who had had any such
31
experience and his results on samples New. 2 and 3 are very close to the theoretical
The following re.-ults were obtained on samples Nos. 4 and 5:
Analyses of vanilla extract, 1907.
Collaborator.
Sample No. 4.
Sample
No. 5.
Vanillin.
Coumarin.
Acetani-
lid.
Vanillin.
J. M Bartlctt. Maine
Per cent.
0. 122
6 244
oa
on
112
106
0007
104
on
Per cent.
0.079
.075
.076
.080
.066
.082
.0997
.076
Per cent.
0.056
.045
.022
.031
.016
.021
.0498
.032
006
Per cent.
oQ.133
.130
A. L. Nchls, Illinois
tiiiiK'ton. I>. (
1 ! I'.lplw I'hiU'lrlph; .
.103
.145
.112
J ( ' ( )Urn NV\v York
Greatest dlffereiicr
.125
l.rlmv :mioutif |.rvM-iit
. Mium ari' I iniriiiiiuiii
014
.039
.034
.014
.004
.040
.022
& Omitted from averages.
e
that
• Also reported 0.0 14 iH-rn-nt rnum:irin in this samph-.
• "MM! \ H "I TMK ANALYSTS.
.1 /.. A. /'/.,-.- it \v<>uid in- much more accurate to detennine the specific gravity of th
-olution. and pipette oif a known volume for ana!y.-i-. Ii \va- found in this work tha
solun -landing in the lM-aki-n.ii the balance pan for five minutes lost 10 mg.
Thi- mean- th.it under ordinary condition-^ the third decimal place in the result is
meaningleM.
In thi- lal»"!-- use a new te-t for coumarin which was originated by Doctor
Q. It depend- mi the fact that a drop of alcoholic potash solution containing
mi- of poia--iiini h)dr".\id to a liter will, when placed on crystals of coumarin,
.i lemon yellou color. Thi- color i< very intense, but disappears rapidly.
Neither vanillin nor acetanilid i- ai'feeted by the rea-jent. The test is applied
direi il\ on thecry-tal- by ii-in^ a glass rod for a dropper, and the results have always
much more -ati-i'a<tory than those obtained by any other test, because of its
•h vanilUo and coumarin give a yellow solution on standing for
time, but the cry-tul- of \aiiillin remain uncofored until dissolved, while the
coumarin • • • inten.-elv colored.
The color te-1 iiiilhl are n i a- -at i-factory as they might be. In this work
un. I the polari/inu' inuro-rope of the greatest use. There is little danger of
niiifu.-ini: cither of the thr. e cry-tal- which are likely to occur in a vanilla extract.
The di-«Tepancie- in th • i.--ults for vanillin are mute usual where the crystals are
\\eLrhed directly fi"in an ether .-olutioii. They seldom come out well, usually being
colored, often Dearly black. This can he remedied by another extraction, not with
ether.
.!. /'. NV. On te-tiiiij this residue for acetanilid, (RHsert's tests) no reaction for same
could be obtained A- only 25 grams extract are taken, the residues actually obtained
in and 0.0026 irrain for the duplicates. Using 4 mg of pure acetanilid,
no r- ,!d be obtained by llitsi-rt's tests as given in Bui. 107. Using chlorin
\\ater d'.S. I' i in -lead of a solution of chlorinated lime (I : 200) a good reaction was
obtained with I mu' acetanilid; 2 mg gave fair test. The chlorin water is mixed with the
a« etanilid; a pink color form- in a few ,-econds, changing gradually to a purple and
finally (•» a blue.
./. r. oiwn: Vanillin: The residue of the ether extraction for vanillin almost inva-
riably contain- a lar_re amount of resin and other impurities. It has always been
our cu-tom to extract the vanillin with petroleum ether and deduct the residue from
the weight of impure vanillin, it will be noted that the difference in results is consid-
erable. In 18 determinations the impurity with the vanillin has varied from 2 to 30
mg. the average beinir In. 4 mg.
We have al-o found that an easier drying residue of vanillin has been obtained by
extraction from the "2 per cent ammonia solution with chloroform.
/e For the separation of coumarin and acetanilid we have been unable to
obtain petroleum ether with a boiling point 30^40° 0. We have used gasoline, 86° B.
On fractionating this naphtha, fractions boiling at 35-40, 40-45, 45-50, 50-60, etc.,
32
have been obtained. It has been our experience that the higher boiling fractions
extract coumarin as well as vanillin fully as well as the lower boiling fractions.
Acetanilid: According to the official method this substance is to be looked for with
the vanillin only when it has been found with the coumarin. In one of these three
analyses of No. 4 reported all of the acetanilid was found with the vanillin.
The figures given by Mr. Olsen on vanillin by extraction with petroleum were as
follows: No. 4, 0.080; No. 5, 0.054, from which it would appear that the extraction
wa< not prolonged sufficiently.
Linwood A. Brown: Sample No. 5: The vanillin in this sample was somewhat
impure owing to coloring matter from which I was unable to purify it. .
The results would seem to show that as far as vanillin is concerned the method is
>uti.< factory. The average on both vanillin and coumarin, however, indicates that
some of the latter is weighed as vanillin. The coumarin figures are uniformly low, as
are those for acetanilid, with one exception. One collaborator reports entire failure
of the Ritsert's test for acetanilid as given in the provisional methods, and suggests a
modification.
WORK OP 1908.
The work for 1908 was confined to the colorimetric method for the determination of
citral in lemon extracts. Fifteen sets of samples were sent out to collaborators who had
previously worked with the method, and reports have been received from twelve.
A< the method had been rather severely criticised by some of the members of the
American Extract Manufacturers' Association, they were invited to name two col-
laborators, and selected Mr. Edward Kremers, of the Wisconsin State College, and
Mr. Baer, of St. Louis. Samples were sent to both, and Mr. Kremero forwarded
his set to I. W. Brandel, of the University of Washington. The following description
of the method to be used was sent to each collaborator:
DETERMINATION OF CITRAL IN LEMON EXTRACT.
Reagents.
Aldehyde-free alcohol. — Allow alcohol (95 per cent by volume) containing 5 grams of
metaphenylene diamin hydrochlorid per liter to stand for twenty-four hours with
frequent shaking. (Note, nothing is gained by previous treatment with potassium
hydroxid.) Heat under a reflux cooler for at least eight hours, longer if possible
(often twenty-four hours are necessary), allow to stand over night and distil, rejecting
the first 10 and last 5 per cent which come over. Store in a dark, cool place in well-
filled bottles.
Fucbsin solution. — Dissolve one-half gram of fuchsin in 250 cc of water, add an
aqueous solution of SO2 containing 16 grams of the gas and allow to stand until colorless,
make up to one liter with distilled water. This solution should stand twelve hours
before using and should be discarded after three days.
Standard citral solution. — One milligram of c. p. citral per cubic centimeter in 50 per
cent by volume aldehyde-free alcohol.
Apparatus.
A cooling bath.— To be kept at from 14° C. to 16° C. The aldehyde-free alcohol,
fuchsin solutioiij and comparison tubes are to be kept in this bath.
* '"lorimeter. — Any form of colorimeter using a large volume of solution and adapted
to rapid manipulation may be used.
The comparison may also be made in Nessler or Hehner tubes.
Manipulation.
Preliminary determination.— Weigh in a stoppered weighing flask approximately 25
grams of extract, transfer to a 50 cc flask and make up to the mark at room temperature
with aldehyde-free alcohol. Measure at room temperature and transfer to a compari-
son tube 2 cc of this solution, add 25 cc of the aldehyde-free alcohol (previously cooled
the bath) then 20 ccof the fuchsin solution (also cooled) and finally make up to the
50 cc mark with more aldehyde-free alcohol. Mix thoroughly, stopper, and place in
'ling bath for fifteen minutes. Prepare a standard for comparison at the same
:ime and in the same manner using 2 cc of the standard citral solution. Remove and
compare the colors developed. Calculate the amount of citral present and repeat
33
the deiermiiiuiion u>ini; a quantity sullicient to give the sample approximately the
sin-iiu'ili "i the standard, From this result calculate the amount of citral in the sample.
If tin- comparisons are made in .\ osier tubes, standards containing 1, 1.5, 2, 2.5, 3, 3.5,
and t mi; should be prepared and the trial comparison made against these, the final
. •ompari-on brim; made with standards between 1.5 and 2.5 mg varying but one-fourth
iif a milligram.
The I'nlin \viii-_' point- are to be especially noted :
Tin- aldehyde-free alcohol (26 cc) on standing for 20 minutes in the cooling bath with
the fuchsin solution Mild develop only a faint pink coloration. If a stronger
color i< developed, treat a-jain with metaphenylene-diaihin hydrochlorid.
Jt i- absolutely essential \<> keep the reagents and comparison tubes at the required
temperaiiir.-. » 'omparisons should l»c made within one minute after removing the
lulu-* from the hath. \Vh«-n- the comparisons are made in the bath (this is possible
only when- the bath i> '_da— )th«- standards should be discarded within twenty-five
mimi .Hiding tin- fuchsin solution. Give samples and standards identical
treatment.
Not.- on samples colored with turmeric whether or not the color interferes with the
come ' Mi samples '_' and .">, after making determinations on the samples sent,
• them, removing the colors as follows: After weighing the sample to be used for
anal;- .ppen-d wei^hint; bottle, add a drop of concentrated hydrochloric
acid and a -mall piece of fat-free \\oolen doth, stopper and allow to stand over night.
ve the (loth wii>hinir wilh aldehyde-free alcohol and determine the citral in the
colorle>s solution as u-ual. Repeat the above comparison heating the acidified
I woolen doth under a reflux cooler for a lew minutes, cool, remove the
cloth and d'-TeMuine the ciiral a- usual.
-ample* sent were as foil.
1. A 1« ii, • oniainii .uns of !)f> per cent alcohol and 192 grams
lemon oil, the whole colored with turmeric.
, terpen.'li-.- exiM- i of lemon <t reiiu't lictied withcitral; 300 grams lemon oil
dcohol; L',070 grams of water were-added and
iiL'ht the precipitated oil was removed and 3.76 grams of citral
1. The \\hole colored with Niiphihol Yellow S.
:al in dilute alcohol ("iO per cent volume) containing 3,000
. p. ciiral making the actual percentage of. citral 0.12 per
cent The whole . ,,|.,red with Naphthol Yellow S.
• ion of citral in dilute alcohol (~>i) per cent \>y volume) containing 3,500
hoi and .' c. |>. ciiral making the actual percentage of the latter
The whole colored with turmeric.
Th. ; in the following table:
H-itrk <>n A t, nniii I ny ntrnl in lemon extracts, 1908.
Orifetaatar.
Without removal of color.
After removal of color.
15 y heating.
At ordinary
temperature.
No. 1.
No. 2.
No. 3.
No. 4.
No. 2.
No. 3.
No. 2.
No. 3.
lilts I'hil I'lrlptii i I'-i
Per ct.
0.&W
.328
.286
.288
.354
. 3LTi
.308
0.380
.360
o. 143
.038
.040
Perct.
0.330
a.407
.329
.317
.315
o.370
.324
.316
.312
a.387
.340
o.385
.323
.017
.011
Per ct.
0.125
.136
.107
.116
.118
a.190
.133
.137
.133
a. 165
.125
.109
.124
.013
.017
.12
Perct.
0.060
.067
.056
.056
.054
o.lOO
.064
.084
.060
0.140
.070
.050
.062
.022
.017
.061
Per ct.
Perct.
Per ct.
0.28
.386
.233
.278
.188
Per ct.
0.108
.136
.100
.102
.079
Vork
0.110
.089
.090
.085
0.140
.110
.228
r.mclsco, Cal
I.. \. Bron . IgrkmH a .1 t',,ii(^c.
!i,-h
.202
.215
.031
.137
.333
.311
.294
.080
.138
.116
U. S Hiliii.-r Pniv.T Colo
• Savannah (Ja
.290
.110
.290
.110
I. W. i .MI,.. Wash
mi alxiv*' -.ivcracf
Thwrctical amount
o Excluded from averages.
. -Bull. I'.'
34
COMMENTS OF ANALYSTS.
R. W. Hilts: The methods submitted for this work were adhered to with the excep-
tion that in the removal of color from samples 2 and 3 the portions were weighed out
into the 50 cc graduated, glass-stoppered flask, acidified as directed, and the piece of
fat-free woolen cloth added (about 1.5 inches square). After standing over night the
volume was completed with aldehyde-free alcohol, without removing the cloth.
Preliminary tests of the samples were made against a series of standards, but all
final determinations were made by matching in tne colorimeter. Final comparisons
were always arranged so that the depths of tints compared were within 10 per cent,
generally less, of equal strength.
Results reported are calculated from averages of four to five readings made in rapid
succession with columns of 40 mm and 30 mm, i. e., 8 to 10 readings. Comparisons on
the different depths of liquid gave concordant results.
Color in samples 1 (turmeric) and 2 (Naphthol Yellow S) gave no trouble whatever in
comparisons. The samples are so highly diluted in the final determination that the
color does not interfere. On sample 3 (Naphthol Yellow S) considerably more of the
original liquid is present in the comparison tube, due to its lower citral content, and a
very slight modification of tint in depths of 40 mm was noticed. With depths of 30
mm there was no apparent difference and tints were matched with ease. Sample 4
(turmeric) behaved similarly to No. 3. In depths of 40 mm there was a slight differ-
ence of tint, because nearly 3.5 cc of the original liquid was present in the tube. This
slight difficulty disappeared in depths of 30 mm. Samples 2 and 3 were very satisfac-
torily decolorized by the treatment with the cloth. However, in so far as ease of
comparison is concerned this treatment seems superfluous if comparisons are made
with comparatively short columns of liquid, as above noted.
A. W. Hansen: The operator could not see that the color interfered with the com-
parisons.
W. L. Dubois: The comparisons were made in wide Nessler tubes graduated to 100
cc which were cooled to 15° in a large bath and for comparison placed in a tall beaker
containing water at 15° and around which was wrapped a piece of white paper, the
beaker being set on a white surface and lifted therefrom a few inches at the time of
reading. The color in samples 2 and 4 did not seem to interfere with the determina-
tions. The fuchsin sulphite solution when made as directed retained a slightly brown-
ish tint. The fuchsin, however, which we had available for the preparation of this
solution was not labeled c. p. and this possibly may have accounted for our failure to
get a perfectly colorless solution.
C. L. Cook: None of the readings of any of the samples was interfered with by the
presence of the coloring matter used. It was found necessary to allow the fuchsin
solution to stand at least forty hours before a blank could be obtained with the aldehyde-
free alcohol we were able to distil.
F. D. Merrill: Samples 1 and 4 colored with turmeric gave a color differing some-
what from the standard used in the determination of citral. In Nos. 2 and 3 colored
with Naphthol Yellow S less difficulty was experienced in matching colors with the
standards in the determination of citral when the original extract was used, but when
the sample was decolorized by either^method suggested it had a very different color
as compared with the standard used in citral determination, and great difficulty was
experienced in matching colors.
R. S. Hiltner: The small amount of turmeric in samples No. 1 and No. 4 did not
interfere perceptibly with the color comparisons.
Sample No. 2, when heated with hydrochloric acid and woolen cloth under reflux
condenser as directed, turned brown, apparently due to decomposition of citral. A
somewhat similar change took place with No. 3, but to a less degree.
The same result was obtained on these two samples by simply acidifying with
hydrochloric acid and treating at once with fuchsin reagent as by allowing the acidified
solution to stand over night in contact with wool.
I was unable to secure alcohol that would not respond to the fuchsin test for alde-
hyde, even after prolonged standing and heating with m-phenylene diamin
hydrochlorid.
Besides the figures obtained by the trial method, Mr. Hiltner, of the Denver Food
Inspection Laboratory, submitted a set obtained by a method devised by himself
using metaphenylene diamin as a substitute for the fuchsin sulphite reagent. The
writer makes the following claims for the method:
First. Since there is no color reaction with acetaldehyde, more correct results may
be secured in the analysis of commercial extracts.
35
In the preparation of these extract.-, ordinary rectified alcohol is, of course, used.
Such alcohol always contains more or less acetaldehyde. Any general reagent for
aldehyde-, like furh.-in, therefore tends to give too high results for citral because of
ill.- reaction on the acetaldehyde present.
Second. 1' is unnecessary, as stated, to use especially purified alcohol free from
aldehydes.
Third. All the operations may be carried on at room temperature.
Tin- following fk'' ubmitted on the official samples: No. 1, 0.251; No. 2,
- 117: No. 1. o.o.il.
1 and '2 an- somewhat below the average figures submitted by the collaborators.
Nos. 3 and \ an- much do.-er to the actual amount present than those obtained by Mr.
ililtncr with the method under trial. As the method was called to the referee's
aiirntii.n "nly a few day.- l>cf.>re the meet inn. no opportunity was offered to test it
this year.
GENKKAI. Disrrssiox OK RESULTS.
The rr-nli- obtained <m the official -a in pies as a whole exceed greatly the expecta-
tion- of the
When twelve dnteivni aiialv-i- an- working even with a well-established method
under vary in:: condition-, experience has shown that some discordant results are apt
to 1 b tained. When like di -en- pane ie- have been obtained with the official methods
for nitrogen and pota-h. it \\ould.-een-. that the results, in the present case, are highly
.-at i Mac lory.
It appears to be of no advantage to remove the color before making the determina-
tions in fact, .-everal of the collaborator- are of the opinion that it renders the solutions
harder to n-ad. The \\oik done ai \Va.-hinurt«»n also indicated that there was little
advantage to be obtained, certainly not .-nilicimt to offset the loss of citral. The results
-IL'hily l.eiii-i on the alcoholic -..Intions of citral than upon the extracts. They
brttrr on the terpenel.-s extract than on the extract containing lemon oil.
Thi- i-. in all probability, due to the effect o! the non-aldehydic constituents upon the
of the inch-in .-olntion. Where the colors are not of like tint, considerable
i'lirrd in order to correctly match them.
On the tmal comparison- the standard ami sample must contain approximately equal
amoun r lo percent i- not allowable.
The method i- not dilhrnlt of manipulation, but does require pure reagents, espe-
cially in the case of aldehyde-free alcohol. It is highly probable that the greater part
of the discordant result.- are due to the latter, (liven a cologne spirit of good quality,
there Been er, to be m> reason why good results should not be obtained. It is
miended that the method as submitted for the determination of citral in lemon
• ••adopted provi-ionally by the association.
REPORT ON SPICES.
I'.y A. I.. WIVION. A.x.xiH-liitt' Referee.
The atlention of the associate referee was directed to the adulteration of paprika
with olive oil, and the methods «>f detecting this form of adulteration, by papers pre-
d by Doolittle and Ogden and by Loewenstein at the New Haven meeting of the
American Chemical Society. Although the time was short for giving this matter suit-
able attention, a circular letter was sent out on September 5 to such chemists as had
previously expressed a willingness to cooperate, and later, samples of two kinds of
paprika were distributed, one purporting to be pure, the other adulterated with olive
oil.
36
The methods submitted for study are as follows:
METHODS.
NON-VOLATILE ETHER EXTRACT.
-Dry in a desiccator over night or until the moisture is largely removed a sufficient
amount of the material to yield an extract of from 0.2 to 0.25 grams. Extract according
to the officiaF method for the determination of crud* fat (Bui. 107, Rev., p. 39, 5 (b)
(1)), collecting the ether solution in a tared flask. Dry the extract at 100° C. for
l.Viniiiute periods until constant weight is secured.
IODIN NUMBER.
hetcrmine by the Hanus method (Bui. 107, Rev., pp. 136-7), using the extract
obtained as described in the preceding section.
Great care should be exercised in weighing the flask, both before and after extraction,'
as an error of 1 milligram is equivalent to an error of over 0.5 in the iodin number. A
-stoppered 200 cc Erlenmeyer flask may be used for the extraction and also, with-
out transfer, for the determination of the iodin number, although in our experience
more accurate results may be secured by using a vial-mouth unstoppered flask of about
rapacity, thus reducing the exposed surface to a minimum. In the latter case
the flask, after dissolving the extract in chloroform and adding the Hanus solution, is
introduced into a saltmouth, glass-stoppered bottle, broken with a glass rod and the
titration carried out in this bottle in the usual manner.
1 1 was suggested that in extracting the fat 3 grams of the pure paprika and 2 grams of
the paprika adulterated with oil be used, thus securing amounts of extract suitable
for determination of iodin number.
ALCOHOL EXTRACT.
Follow the official method (Bui. 107, Rev., p. 163).
DISCUSSION OF RESULTS.
The results obtained by the five analysts who took part in the cooperative work are
given in the following table:
Analysis of pure paprika and samples mixed with olirc oil.
Collaborator.
Pure paprika.
Paprika with olive oil.
Alcoholic
extract.
Non-
volatile
ether
extract.
Iodin
num-
ber.
Alcoholic
extract.
Non-
volatile
ether
extract.
Iodin
num-
ber.
(;«'ii<'vi<'v«> Imus, Minnesota
Per cent.
13.36
13.33
10.44
12.8
12.7
A 10.62
B 10.50
C 10. 75
Percent.
76.5
76.2
82.0
77.4
105.9
105.8
105.2
114.6
112.3
116.7
117.2
112.9
117.7
115.2
113.1
115.1
Per cent.
14.96
14.97
Per cent.
97.4
96.7
76.1
80.7
106.4
0115.05
115.2
108.0
112.0
116.1
107.2
115.6
111.4
105.1
105.8
116.1
117.6
C. D. Woods, Maine
5.43
5.81
6.10
5.27
5.36
5.52
5.54
5.37
5.45
5.47
5.32
5.47
5.46
5.40
15.30
13.18
13.76
12.01
12.10
12.58
12.64
12. 72
12.71
12.52
12.42
12.51
12.80
12.75
11'. 70
12.60
C. I'. Wilson, Washington, D. ('....
13.43
13.4
13.35
12.92
12.76
12.96
C. S. Brinton, Philadelphia
C.I. Lott, Chicago....
o Average.
37
w: This collaborator states that through a misunderstanding the po--
tiona taken f,,r analysis were weighed out after drying the materials in a desiccator
For this reason the pen-entases of alcohol extract and nonvolatile ether extract are not
comparable with thus.- -riven l»y the other analysts and are not given in the table
/>. Wood* The ether extract in the determinations made by the method
ribed not being complete, <>tlu>r trials were made, using different quantities of the
material and extracting for longer periods. The results are given in the following
table:
fjnare
tammies adulterated with olive oil, varying weight of sample
and time of extraction
PURE PAPRIKA.
Weight
Time of
tion.
Non-
vohitiln
ethor
extract.
Todin
miinlxr
of non-
volatile
ether
extract.
',>:••
3
3
3
1
Hours.
24
100
Per cent.
:.. i 1
Lfl
.Y lx
5.74
5,91
1:5. i:»
82.0
77.4
87.3
79.3
77.9
1
100
42. »i
PAPKIK \ ADULTERATED WITH ol.lVKOIL
2
16
15.30
76.1
2
16
U18
80.7
24
12.23
••;.:,
UL«8
84.0.
i ; U
84.1
100
u »
100
Ix. 71,
•unn-nis on the above result.- as full,
I ii ' >«>little au<l < >_rden rej><>rt a much higher iodin number than any of my
re.-ult.- would Indicate and alaothaJ toeirreaulta are very concordant. \\ithdirections
'•u 1 tail to see how one could place any reliance on the results of this determi-
Q. ltma\ • that by niMninu'theetherextractinuforanexactdefinite time
re>ul; 'dtained agreeing reasonably close with each other, but I doubt this
A hat, t->r it ha- been OUT experience that some detenu hint ions extract much faster
than oth.-r-. .l.-|M'iuli»tr on the rate of flow of the ether and the type of extractor used,
and that until the extraction is complete there is no surety that two determinations
will a-jree at any -jiveii time durini; the process.
The-e i'e\\ « Jet (-rn i i nat ions -eein to indicate that if the iodin number is made on the
complete ethei 'her material besides fat ^resins, etc.) will so increase the
wei-lit that the value of the iodin number will be reduced, while, if the determination
i> made before the extra tion is complete, the result scan not be depended on to agree.
r»rinton comments on hi.- results as follows:
The iodin number- 0:1 (tie nonvolatile ether of the samples prepared with oil did not
and lam reporting only the average of results obtained. I was very much sur-
i to lind the iodin number of the nonvolatile ether extract in the pure sample so
much lower by the m.-thod you suggest than that obtained by the method used by
l»oolittle, but i lii- i- easily accounted for, because a long extraction with ether carries
other material which i- not readily soluble in ether and would not be found in the
ether extract when u shorter extraction time is used. From theresults obtained bythis
method 1 do not think that it would be advisable to use an official ether extract for the
.iiination of the iodin number, as by so doing we are liable to overlook samples
prepared with olive oil, the presence of which would be revealed by using Doolittle's
method.
38
C. P. Wilson stated that he was not entirely satisfied with the results because with
the apparatus he used he found it necessary to dissolve the fat before removing it from
the flask in which it was recovered by the extraction.
C. I. Lott: In order to secure evidence with regard to the accuracy of the sampling,
analyses were made of three bottles (A, B, and C) of each paprika. The discrepancies
in the determination of the iodin number were attributed partly to differences in the
amount of extract obtained occasioned by the removal of different amounts of the
difficultly soluble resins and partly to errors in the process of determining the iodin
number. It was suggested that possibly in the earlier determinations the extract was
not completely dissolved in the chloroform preliminary to the Hanus solution. In
the later determinations special effort was made to secure a complete solution. With
this precaution the following results were obtained: Pure paprika, 116.7, 117.7, 115.1;
paprika with olive oil, 116.1, 116.1, 117.6. Further experiments are needed to ascer-
tain whether or not a better agreement of results can be secured by observing special
precautions in dissolving the extract.
CONCLUSIONS.
The radical difference in the results reported by the different analysts in the deter-
mination of nonvolatile ether extract and the iodin number of the extract may be in
part explained by differences in the extraction apparatus employed and in the rate
of extraction, some of the analysts securing an extract which contained a much greater
amount of resins than that obtained by the others, which resins have a much lower
iodin number than the fatty oil. This explanation, however, does not account for
many of the differences. For example, Messrs. Woods and Lott obtained practically
the same percentages of nonvolatile ether extract in the pure paprika, but one reports
an average iodin number of about 80 and the other of about 115. On the other hand,
Mr. Wilson obtained the highest percentage of nonvolatile ether extract, and Mr.
Brinton the lowest, yet both secured practically the same results on the iodin number.
The results reported indicate either that the method of securing the nonvolatile
ether extract for the determination of iodin number is seriously at fault, or else spe-
cial precautions, yet to be determined, are necessary to the success of the process.
The results are not only widely discrepant, but they fail to throw any light whatever
on the question of adulteration.
RECOMMENDATIONS.
It is suggested that during the ensuing year the following methods be studied:
First, extraction on filter paper, with ether, as followed by Doolittle and Ogden,a
and, second, shaking for a definite time with a definite volume of ether and evapora-
tion of a portion of the filtered extract. It is believed that satisfactory results can be
obtained only by a purely conventional method, using the same weight of material,
the same volume of ether, and the same time of extraction. It may be found impor-
tant, however, to use such portions of the ether solutions as will yield in all cases
approximately the same amount of nonvolatile ether extract. The results obtained
in the determination of alcohol extract throw no light on the question of added oil.
REPORT ON COLORS.
By H. M. LOOMIS, Associate Referee.
The work of the past year has been chiefly on the identification of colors. For this
purpose twelve samples of colored food products were prepared in the laboratory,
using the purest colors available, and samples of each were sent to six cooperating
chemists. It is only just to state that many of the colors used were not furnished as
food colors -by the manufacturers. In this work the endeavor has been to prove that
the colors used were simple commercial colors, and not mixtures, without special
regard to the presence of mineral salts, etc.
^ J. Amer. Chem. Soc. 1908. 30: 1481.
39
Since i he promulgation of F. I. D. 7G of the Board of Food and Drug Inspection,
allowing the u-e ..f . •••rtain coal-tar colors in food products and prohibiting all others,
it ha.< become quite necessary for food chemists to make a study of the methods of
identifying color- \<> find out with what degree of accuracy these methods serve their
purpose. In making this study it is of course very essential to work with pure colors,
and a.- the time available for this work would not allow of preparing these colors in
the laboratory, there were used colors furnished by manufacturers, who in most cases
gave both the commercial and the scientific name of these samples, and upon them
such tests were made as seemed necessary to establish fully the fact that they corre-
sponded \\-ith the names giv»Mi and were' simple unmixed colors.
\o originality in the methods of testing is claimed, the standard works of reference
on the subject having been freely consulted. In every case the well-known tests by
color reactions in aqueous solution, on the dyed fiber, and with concentrated sulphuric
acid on the dry color were u.-ed. This includes a test for mixed colors made by
sprinkling dry color on a surface wet with water or concentrated sulphuric acid. In
addition the following tests were made on the separate colors:
I'ri-fifiitaiinn by alcohol: Concentrated aqueous solution + 95 per cent alcohol=
Iline yellow precipitate.
o.i i» r f nt <i<{ii' <>n -\-stannou8 c/»Zor»W= yellow precipitate, soluble in
oxalic acid .-olutiou (10 per cent .
O.I pt-r cent aqueous solution + harimn chl<>ri<l .so/<//MM=yellow precipitate.
a. i JMT cent aqueous solut < >n chlnrid solution -;no precipitate.
3, c<c .1. !M.
ICON:
for coal-tar color- ; n :ni nation.
1 ;re c..l,,r.
NAPHTHOJ
r reaction with -Minions chlorid and ammonia. Test for organic sulphur.
>//•////••// ' I on platinum foil. Takes fire explosively.
lv iiiMilublc in neutral or acid solution.
i- barium chlorid solution (10 per mi<)=orange precipi-
Insoluble
" ./ j»r cent aqueous solution^- calcium cktorid solution (to j><r rr/t/)=no precipitate.
n.i mimon* solution + It-ad «r<7<i/<' = onini:r pre<-ipitate, soluble in acetic acid.
'/./ /neon* sola ' ••'/ <•/ lonil 11 ml caustic soda= olive-green precipitate.
ll.iourl:*: (»\»r nearly pure. Contains small amount of unsulphonated naphthol
yellow.
TKMI-U .)UN O O:
Kediirtion of c..lor by stannous chlorid in acid solution; separation of para amino-
diphenylamin fr-m alkalin.- - -lution by ether. Melting point, 61° to 62° C.
/'/•• hij salt: 0.1 j>er cent solution of color -f few drops 10 per cent sodium
chlorid -olmion -precipitate ..f color.
0.1 i>tr 'on + barium chlorid (10 per eett<)= colored precipitate,
like F- "11
0.1 per cent aqueous solution + calcium chlorid (10 j>crcent)=co\ored precipitate, like
'!!
Com ' ire color, S. & J. 88.
KKYTHKOSIX: (Color used in sample :J ('.)
Aq ueous s. >lu t ion , | )ink tlm )rescent (shows presence of other colors besides erythrosin.)
<'olor .-xtracte.l ir,,m acidified aqueous solution by ether. Ether solution washed
several times, evaporated and color dried.
//.//.«/, //.s: < hlorin, bromin, and iodin found in color qualitatively. (Mulliken
" Identification of ( )nranir < ompounds," p. 13). Determination of bromin and iodin
uasch and Aschotf meth«Kl gave 17 per cent bromin and 9.7 per cent iodin.
Volor a mixture of eoein colors containing chlorin, bromin, and iodin.
RHODAMIV:
Contains no bromin or iodin; 0.4 per cent ash; insoluble, even on boiling in caustic
potash solution; -p. gr. 1.3.
Aqueous solution pink; yellow fluorescence, which disappears on warming and
reappear.- uii cooling.
40
0.01 per cent aqueous solution + stannous chlorid solution=l)right crimson precipitate,
purplish by transmitted light.
0.01 per cent aqueous solution + tannin reagent; test for basic color= precipitate.
Benedikt's test with zinc and ammonia: (Allen, "Commercial Organic Analysis,"
vol. 3, part 1, page 322.)
Conclusion: Pure color, S. & J. 504.
ROSE BENGAL:
Qualitative analysis shows halogens, iodin, and chlorin — no bromin.
Benedict's test with zinc dust and ammonia. (See^ Allen, loc. cit.)
Benedikt's test: Boiling with caustic potash solution. (Sp. gr. 1.3.) (See Allen.)
Color separated from acidified aqueous solution as in the case of erythrosin.
Quantitative determination of iodin and chlorin.
Chlorin determined by silver nitrate after removal of iodin by nitrous acid and
carbon bisulphid.
Iodin determined from total halogens by difference.
Chlorin, 8.89 per cent; iodin, 49.5 per cent; ratio=l to 5.56.
Ratio of halogens in tetraiodo-dichlor-fluorescein=l to 7.2.
Ratio of halogens in tetraiodo-tetrachlor-fluorescein=l to 3.6.
iion: Color a mixture of the two Rose Bengals, S. & J.
520 and 523.
PHLOXIN:
Qualitative analysis shows presence of halogens, bromin, and chlorin; no iodin.
Determination of bromin by Mohr's method gave 39.8 per cent in color, purified by
extraction with ether.
Chlorin, from total halogens by difference =11. 9 per cent.
Ratio — chlorin: bromin=l:3.34.
Benedikt's test with zinc dust and ammonia. (See Allen.)
Benedikt's test with boiling potassium hydroxid solution. (See Allen.)
Conclusion: This color is a mixture of the two phloxins, S. & J. 518 and 521.
COCHINEAL RED A, S. & J. 106:
Tested for mixed color by precipitating part of color from solution with salt, filtering
and dyeing wool to same depth with filtrate and solution of precipitated color. Both
dyeings were nearly the same shade, indicating fairly pure color.
Dry color sprinkled on concentrated sulphuric acid shows small amount of foreign
color.
Reduction with stannous chlorid and hydrochloric acid, making alkaline with
sodium hydroxid and extracting, gave very little ether-soluble matter. This shows
absence of colors yielding ether-soluble bases on reduction.
Conclusion: Color is fairly pure, but contains a small amount of foreign color.
FAST RED C, S. & J. 103:
Tested for mixed color, as in the case of cochineal red A, by fractional precipitation
with salt and by sprinkling on concentrated sulphuric acid. Small amount of foreign
color shown.
Color is fairly pure, but contains a small amount of foreign color.
PONCEAU 2R or 3R:
0.1 per cent aqueous solution + barium chlorid solution (10 per mi£)=crimson precipi-
tate, insoluble in acetic acid.
0.1 per cent aqueous solution + calcium chlorid solution (10 per cent) =no precipitate.
0.1 per cent aqueous solution + lead acetate solution (10 per cen£)= crimson precipitate.
Color reduced with stannous chlorid and hydrochloric acid. Solution made alkaline
with caustic soda and distilled with steam. Liquid amido compound distils over,
which could not be solidified in ice water. Boiling point about 215° C. This shows
the amido compound to be xylidin.
Conclusion: Color is ponceau 2R or xylidin red, S. & J. 55.
ACID GREEN:
Solubility in absolute and 95 per cent alcohol; no sign of mixed color by sprinkling
on wet filter; no chlorin in the ash.
Conclusion: Pure color, S. &. J. 435.
PERSIAN BERRY EXTRACT:
Reactions correspond very closely to those of a buckthorn berry extract prepared in
the laboratory.
The accompanying table shows the results obtained in the identification of the
colors. Considering the fact that three of the collaborators had never undertaken
work on the identification of colors before, the results appear to be quite satisfactory
with regard to ih<j mal-iar colors.
41
I
i:-i
42
NOTES AND COMMENTS BY THE COLLABORATORS.
C. S. Brinton used the tables of Rota and others given by Allen, a Schultz and Julius,
"Organic coloring matters," and Circulars 25 and 35, Bureau of Chemistry. Consid-
erable difficulty was encountered in some cases in isolating color from fruit pulp and
sirup. Double-dyeing method was used for extracting color from material, and color
was obtained in aqueous solution by extracting wool with ammonia. Sample VI
gave considerable trouble, and definite report was not made.
F. O. Woodruff used chiefly tables of Green, Y«eman, and Jones, b also tables in
Allen and in Schultz and Julius, and Circular 35, Bureau of Chemistry. He says:
"Three difficulties attending identification are: (1) A commercial dye from different
manufacturers varies in purity and therefore in properties, though bearing the same
or a synonymous trade name; (2) amount of color on dyed fiber or in color solutions
affects the nature of the reactions therewith; (3) ordinary description of color reac-
tions varies with the observer and does not allow of fine distinctions."
Hare, Mitchell, and Pringle used Rota's table and those in Circular 35, Bureau of
Chemistry. They comment as follows: "We find Rota's scheme quite valuable
in assisting us in the general classification of the dye. An accurate and complete
color chart would be a great aid, especially to those not used to making sharp color
distinctions."
E. J. Shanley used the tables in Allen and Circular 35, Bureau of Chemistry.
RECOMMENDATIONS.
It is recommended —
(1) That an effort be made to obtain authentic samples of vegetable or natural
coloring matters, such as are used in food products. This work should be assigned
to such men as are in a position to obtain authentic samples, for it is well-nigh impos-
sible for one person to obtain any considerable number of such samples and to ascer-
tain their source and method of preparation;
(2) That characteristics of vegetable coloring matters and methods for identification
be studied ;
(3) That synthetic preparations of pure colors for standards be made;
(4) That the separation and identification of mixed colors be studied.
The president announced the following appointments as members
of Committee A on recommendations of referees: R. J. Davidson,
J. P. Street, J. G. Lipman, B. L. Hartwell, and W. A. Withers.
The association adjourned until 2 o'clock.
THURSDAY— AFTERNOON SESSION.
REPORT ON MEAT AND FISH.
By F. C. WEBER, Associate Referee.
In view of the fact that no work has ever been reported to the association on this sub-
ject , it seemed to the referee that some results showing the degree of accuracy of some
of the chemical methods ordinarily employed in separating protein nitrogen, and at
what point they show deterioration of meats, might be of interest . Owing to the nature
of the work and the difficulty of keeping samples uniform, no attempt was made to
secure collaborative work.
SAMPLES.
The determinations here reported were made on three samples of chicken meat.
Six young market chickens were obtained, killed, dressed, and allowed to stand in
the ice box over night. The next morning the flesh was separated from the bones
"Commercial Organic Analysis, vol. 3, part 1.
*>Soc. Dyers and Colorists, 1905, 21: 236.
43
and skin and thoroughly ground ami mixed by passing six times through a meat
chopper. It was i hen divided into two equal portions, one marked "fresh" and the
other, after the addition of 0.1 per cent of boric acid, was marked ''preserved."
Tin- third .-ample represents the meat from three cold-storage drawn chickens, in
:e twenty-.-ix immihs, treaied in the same manner as above, but without the ad-
dition of boric acid, and marked "stored." Each sample was placed in a screw-cap
i jar and allowed to stand for one week, at laboratory temperature during the day,
and in an ice box at nielli. During this time samples were taken for analysis on the
tirsi, .-econd, third, sixth, and seventh days of standing. Every precaution was ob-
1 toward against loss of moisture during the removal of the sample, as a result
of whieh the moisture content remained very constant.
M KTHODS.
The following deierminat ions were made at each of the periods cited: Moisture,
loud niiro-en, ammonia nitrogen, ami. in the aqueous extract afroorn temperature
and with i«-«- water, nitn :• termined as total, coagulable, amido, and ammo-
nia. The difference between the <nm of the coagulable and amido nitrogen and the
toi.il soluble niiro-rn i- . -..n id- n d as proteoeesand peptones. The fat was determined
: of the experiment.
.I/.I/A/// /•- w.i- determined on a 2-gram sample, dried in a water oven for ten hours.
Tin- !• \e < alculated as moisture.
The dried <amulr from the moisture determination was ground with dry sand
and • •xtr.ici.-d wiih anhydrous ether in a Knorr extractor for twenty-four hours for
'ermination oJ
'ininaiion- w. re made in the Nitrogen Section of the Bureau of Chem-
by Mr. 11 \\ . llon-hton, u<iii'4 the (InnniiiL,' modification of the Kjeldahl method.
The nim >gcn was determined on from 5 to 10 grams of sample distilled
from i he addition of iT><)-300 cc water and 10 grams magnesium
dlate was colic, ted in standard acid and the ammonia nitrogen de-
termined afi.-r .1 on, --half hour distilling. r><> cr being distilled off. The distillation
"titinned for thn-,- half-hour period-, i">0 cc of water being returned to the flesh
M h distillation. The results reported represent the sum of the three half-
hour pen
l ti-mfHriitur? (^>°-^5° C.) and with ice water (8° C.)]:
imple of meat were weighed into a 450 cc Erlen-
ided, and shaken for three hours in a shaking machine.
Iniheca-. chopped ice was added from time to time, the volume
in the ila-k l>eni'_r k. , nf by decanting the excess of water into a second flask.
ken ihe n-quired length of time, the Ilasks were placed in the refrigera-
toi -over niu'lu. a -mall ijuaniiiy of thymol and phenol having been added as a preserva-
tive. The IM-\I day they were poured through linen bags and extracted with room
temperan; ;ively, by vigorous manipulation with the hands
and BUCCenive porti ter, till th«« final extract gave a negative biuret reaction.
The extraction u-dioiis and re(jiiired, at first, an entire day for completion,
usiiiu'iron. -of r«M)m-temj)eratnro water, and from 1,800 to 2, 000 cc of ice
m-temperatnre exuact was made up to avolumeof 2,500 cc, while the
Ice- water < made upt«)L'.o<H)cc throughout theexperiment, though the latter
iticularly on the last two dayn, were completed with from 1,400 to 1,800
After making to volume and thoroughly mixing, the solutions were filtered
through Ji-im-h funnels containing a 38.5 cm S. & S. 588 folded filter paper. The first
which ran through was discarded (in the case of the room-temperature extract
this was used fnr the ammonia determination); the second quantity, 600 cc to 800 cc,
• d for the water-soluble nitrogen determinations.
The nitration of the .-..Intions of the first three extractions was very simple, the
solutions running through the paper readily, though the second portion was still
somewhat cloudy. As the samples spoiled, the extraction became more easy and
the nitration more difficult, until on the last two days it was quite difficult to
obtain sntiicient s .lution to make the determinations. This filtered extract was
entirely clear. The total nitrogen in the aqueous extract was made on 100 cc of
-"lution
nonia nltrn,,,,, was determined on 500 cc of the room temperature extract, by
distillation with magnesium oxid.
44
The coaqulable protein nitrogen was determined in a sample of 200 cc of the water
extract This was placed in a 300 cc evaporating dish and evaporated on the steam
bath to a volume of 40 cc. The solution was neutralized with tenth-normal sodium
hydroxid, using phenol phthalein as indicator, then replaced on the steam bath and
allowed to evaporate for ten minutes, filtered on a plain filter, and washed with hot
wat or. The filter and precipitate were transferred to a Kjeldahl flask and the nitrogen
determined.
\nrido nitrogen: The coagulable protein filtrate was made up to 100 cc volume and
5<f cc employed for the amido nitrogen determination. The 50 cc were placed in a
cc graduated flask, 15 grams of sodium chlorid added, and the flask well shaken
•laced in an ice box. A 24 per cent solution of tannin was prepared, filtered, and
placed in the ice box. After one hour 30 cc of the 24 per cent tannin solution were
added to each flask and the two flasks filled to the mark with ice cold water. The
flasks were thoroughly shaken and stood in the ice box over night. A blank must be
carried out simultaneously, as the best tannin contains some nitrogen. The solutions
an- filtered into 50 cc flasks and the nitrogen determined in the 50 cc. The nitrogen
liirure thus obtained multiplied by two, minus the nitrogen of the blank, gives the
amido nitrogen in 50 cc of the coagulable filtrate.
The sum of the amido and coagulable nitrogen subtracted from the total soluble
nitrogen is considered as proteoses and peptones. No effort was made to separate the
albumoses, proteoses, and peptones. All the results are calculated to a moisture and
fat-free basis and are also expressed in per cent of the total nitrogen of each day's
analysis.
The ice water extractions were made by Mr. H. L. Amoss and the coagulable and
amido nitrogen separations by Mr. F. C. Cook, both of the Bureau of Chemistry.
The methods as selected, while not representing all that might have been employed,
were those that have been generally used in the Bureau of Chemistry, and it is hoped
that the work may be used as a starting point in this subject and serve to show the
accuracy of the methods when.applied to meats in a progressive state of deterioration.
DISCUSSION OF RESULTS.
The moisture results show very little change throughout the period, the average
in the case of the fresh and preserved samples being 73.00 and 71.70 per cent for
the storage sample. There was 4.12 per cent of fat in the fresh chicken and 4.09 per
cent in the storage. The results on total nitrogen (see table, page 48) are as uniform
throughout as the nature of the material and the accuracy of sampling would permit,
and serve to show that there is no gaseous loss of nitrogen, while the ammonia nitrogen
(that determined directly on the sample, as well as that determined in the extract)
is markedly increased throughout and very uniform, particularly in the case of the
stored and preserved samples. The amount is quite small at the time of the first
analysis and remains so till the third analysis (made after standing two days), when the
storage sample contains a little more than the other samples. From this point the
increase is rapid. The variations in percentage amounts are from practically 1 per
cent in all cases on the first analysis, to 11, 15, and 13 per cent for the fresh stored and
preserved samples, respectively, on the last analysis, after seven days standing. The
ammonia results on the water extract were unfortunately not made on the first
day. They show practically the same results as those determined directly, but are
not quite so uniform and not so high in amount. In the case of the formation of
ammonia, the increased amount seems to begin to be formed after two days standing.
In connection with these changes it may be well to state here the changes in the
samples which could be observed macroscopically. At the time of first analysis the
samples were fresh, the storage sample showing a characteristic dried appearance.
After standing one day they were practically the same, though what may be termed a
slight fermenting action seemed to be taking place. On standing two days the samples
had begun to deteriorate, especially the fresh and stored sample, while the preserved
sample appeared fairly fresh. After three days standing, the deterioration was more
45
marked. A slight od«>r <>f spoiled meat was noticeable, more markedly in the fresh
ainl -tored meat than in thr preserved. After standing si\ days the odor was quite
|>ad; thr samples had lost their texture and there was no doubt that they had spoiled.
NO .Inference in their physical condition could be detected after standing seven days
thai ua.- M"t noticeable after six days standing.
The nitrogen determined in the water-soluble material at room temperature shows
the total nitrogen extra-ted to be largely increased during the experiment, the first
decided :ncrea.-e shouin- in the <amples after standing two days. The coagulable
nitrogen sho\\s l>ut a slight tendency to increase, the most marked and uniform change
• red -ample. The amido nitrogen is not very uniform and shows a
tendency to d- •••'•ially where the samples are in an advanced stage of putre-
M. The nitrogen liere termed proteoses and peptones is markedly increased
during the final days of the experiment, the storage sample again showing a more uni-
form chaiiL'e. Tin- increase of ammonia nitrogen in the water extract conforms to that
determined directly, but is not quite .-<> lar-e in amount.
The nitrogen in the ice \\at«T extract in the various forms separated shows the same
.il trend as does that of the room temperat'ure extract, though the amounts
.-ually not so large.
The graphic char' nd -t, -how these changes more plainly. It is quite
noticeable throughout that the re-ults on the storage sample are very uniform and
i. in all but two instance.-, in all the determinations, the
results on the fin( anal\-i- -ho\\ the .-lora-'1 .-ample to be lower in the various con-
iii.- than I he fresh sample-. The same -oneral tendency seems to run through-
nut tli" experiment though one would expect the storage meat to deteriorate more
rapidly.
Taking into « ,.>n the variations in the determinations and the limitations
of tin- ineiliud- ih.'in-. 1\« .-. there does not appear to he a very clearly denned point
M h deterioration .an be -aid to be-in, unless it is shown by the ammonia and
ible total nitrogen determinations. The increase in these constituents coin-
witli thei, ..itionand physical appearance of the sample. The
• in the extraction is unnecessiry, as the methods employed are not of
:ent accuracy !•• detect the -n-ater rhanges from day to day in the early stages,
much lees any change which may be due to enzymic action during the process of
Lion.
It seems probable from the results that the determination of ammonia may be a
i-.-et in shouii. t indication* of changes, as these results are the
uniform and progressive. A large amount of work has recently been done on
the methods for the determination of ammonia in animal and vegetable materials,
irdson « a: perimenting on the ammonia nitrogen determina-
tion, and in which he extracted the meat with GO per cent alcohol and distilled with
,-piratinu' air through the flask, and distilling under reduced pres-
sure, finally adopted the method as outlined above as best suited to the purpose.
Hi- re-ult- on pure ammonium chlorid distilled in a vacuum with magnesium oxid
and »io per .cut alcohol are nearly theoretical. This is in substance the method as
: in the determination of ammonia in urine and might be adapted to
thi.- u..rk
J. Amer. Them. Soc., 1908, 30: 1515.
46
-/fcs«7 TFf?)
ok;
FIG. 3.— Direct determinations of total nitrogen and ammonia and changes in the nitrogenous consti-
uents (soluble in ice water) of fresh, cold-stored, and preserved chicken meat, during seven days.
nif?*s taking j»h«t> durin. ::i th«> nitro^onous constituents (water-soluble at room
• frvsh, (ol«l-stnn-l, and pr.-s-TVr.l chicken incut.
fe£
48
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s
o
« tf tf €
o o o o
73673 -Bull. 1±2— 09 4
50
e
1
t
1
51
REPORT ON THE ADULTERATION OF DAIRY PRODUCTS.
By HERMANN (\ LYTHOOE, Associate Referee.
The referee, with the help of Messrs. Nurenberg and Marsh, assistant analysts of
tin- Ma.-.-a< •hu.-eii.- State board of health, has made a study of the different methods for
tin- preparation <>f milk serum and for the detection of calcium sucrate in cream. As
u result of thi> work it is apparent that the provisional method for the preparation of
milk serum need.- n<> modification, but the method of Baier and Neumann for the
detection of sucrone in milk or cream should be made provisional. The work done is
embodied in the two following articles.
A COMPARISON OF METHODS FOR THE PREPARATION OP MILK SERUM.
The samples of milk used in this investigation were all milked in the presence of an
inspector <>r an analy.-t «»i the Massachusetts State board of health and represented
nearly all breeds of dairy cattle, particularly the Holstein, Ayrshire, Dutch Belted,
and -rade Holstein cows. The methods employed were the provisional (acetic acid)
method, natural souring," calcium chlorid method, & and asaprol methods The
detail.- «•!' th«- nit i h<>d- "t h»-r than the provisional methods are as follows:
Natural souring method.— Allow the samples to sour spontaneously and filter off the
serum.
( 'nlrni in chloral nn (fun/. —Place 90 cc of milk in a flask, add 0.75 cc of calcium chlorid
solution -|> -r I I '.. > when diluted 1:10 this solution reads 26 on the immersion
reirartnmeter at I, ' ike thoroughly, close the flask with a cork carrying a
as a retlux condenser, place i'n a boiling water bath for twenty minutes,
o>.. I t<> _'()J, mix tin- o.nden-ed water and serum without shaking, and filter.
Aw\>rnl tntthod. — The precipitating solution is made by dissolving 30 grams of
illi/.t d • itric acid in 1 liter of water. If the refraction
of this .-.lution i- i i the scale of the immersion refractometer at 20°, add
water or < itri< a.id to make it so. Mix equal volumes of the above solution and the
milk, .-hake \\cll. ami til1-
In the accompan\ in- table are the results of the refraction of the milk serum pre-
1 from milk samples of known purity when two or more methods were applied
to the Mime sample of milk. The asaprol method is by far the easiest of manipulation.
It -ives the clearest serum in the least time and shows the lowest refraction with the
least variation. I nfortunately pure asaprol is very difficult to obtain, and, owing to
the fa«t that it decomposes readily, it is not an easy matter to prepare different solu-
tions that will give identical sera with the same sample of milk. The calcium chlorid
method is the most difficult of manipulation and is liable to give a cloudy serum rather
troublesome to read, but the results are lower than those obtained by the acetic acid
method and not so variable. The natural souring method is too slow for ordinary use,
but is valuable in the hot weather if the milk is nearly sour when it reaches the analyst.
Four years' experience with the provisional method has shown it to be reliable, easy
of manipulation, and to give concordant results.
« Matthew and Muller, Zts. offentl. Chem., 1903, 10: 173.
kerman. Zt- I'nii-rsurh. Xahr. Genussm., 1907, 13: 180.
I'.aier and Neumann. Zts. Untersuch. Nahr. Genussm., 1907, 18: 369.
52
Refraction of milk sera from known purity milk of individual cows.
Mixed milk of known purity.
Method.
Method.
Acetic
acid.
Natural
souring.
Calcium
chlorid.
Asaprol.
Acetic
acid.
Natural
souring.
Calcium
chlorid.
Asaprol.
46.2
45.9
45.8
45.7
45.6
45.5
45.1
44.9
44.8
44.8
44.7
44.6
44.5
44.8
44.4
44.3
44.3
44.3
44.2
44.2
44.1
44.1
44.0
43.9
43.9
43 8
43.8
43.8
43.8
43.7
43.7
43.7
43.7
43.6
43.6
43.6
43.5
43.5
43.5
43.4
43.2
43.2
43.2
43.2
43.0
47.7
44.6
44.0
43.4
43.5
41.5
41.5
41.5
43.8
43.7
43.5
43. 6V
43.0
43.0
43.0
43.0
43.0
43.0
43.0
43.0
42.9
42.9
42.9
42.8
42.7
42.7
42.6
42.5
42.5
42.5
42.4
42.3
42.3
42.3
42.3
42.2
42.2
42.1
42.1
42.0
42.0
42.0
41.8
41.7
41.7
41.7
41.6
41.5
41.4
41.3
41.2
40.6
40.5
40.4
40.0
43.2
42.8
42.3
42.0
41.7
41.5
41.4
41.1
40.9
43.6
43.0
41.4
38.4
40.1
37.0
38.7
39.0
39.8
37.1
36.8
36.1
39.1
38.4
36.4
36.6
39.2
36.0
36.6
36.6
36.5
38.5
39.0
36.7
37.4
45.0
42.8
43.8
43.0
42.8
42.3
41.2
41.0
43.0
40.7
42.2
44.5
42.6
44.0
44.0
43.0
41.6
44.2
42.6
42.4
41.5
43.0
43.0
42.0
43.5
42.8
41.0
43.1
43.3
42.2
41.8
40.9
43.7
35.7
36.7
38.8
38.0
41.3
42.2
41.5
38.1
39.3
36.1
36.3
39.0
38.6
37.0
37.0
38.2
~39.'6'
36.6
36.4
37.0
36.8
36.6
36.7
37.0
43.3
43.7
41.9
41.6
40.8
42.0
41.0
44.0
43.7
41.0
40.3
40.2
40.5
40.9
39.1
38.2
38.9
36.7
36.8
39.8
38.8
36.8
36.6
36.7
37.5
37.5
37.1
36.8
36.2
35.8
36.9
38.2
38.0
36.8
36.1
40.0
38.6
36.3
36.3
40.0
43.9
40.4
40.3
40.3
40.0
40.7
39.3
38.3
40.1
36.2
36.0
35.7
35.6
36.4
38.4
38.4
36.3
36.6
35.8
38.9
36.6
37.4
43.6
43 5
42.9
42 0
39.0
38 7
37.5
42.5
42.1
41.0
39.3
39.4
36.3
43.4
40.8
38.2
36.7
THE DETECTION OF CALCIUM SUCRATE IN MILK OR CREAM.
The calcium sucrate used in this investigation was prepared by adding 2.5 parts, by
weight, of sugar to 1 part of quick lime slaked in 8 parts of water, allowing to settle,
and decanting the supernatant liquid. The sample polarized at 17.3° V. in the 200 mm
tube and its alkalinity was 1.86 normal.
Leffmann's method0 for the detection of calcium sucrate in cream, using sesame oil
and hydrochloric acid as the reagents, was found to be satisfactory only in the presence
of larger quantities than are necessary to thicken cream, therefore it was abandoned.
The method of Baier and Neumann^ was found to be entirely satisfactory for the
detection of sugar, and is as follows:
« Chem. Ztg., 1906, 30: 638.
6 Zte. Nahr. Gemissm., 1908, 16: 51.
53
To 25 cc of milk or cream add 10 cc of a 5 per cent solution of uranium acetate,
shake, allow to stand for five minutes and filter. If the filtrate is not clear pour it
through the filter aurain. To 10 cc of the clear filtrate (in the case of cream use the
total tilt rate it le.-s than 10 cc) add 2 cc of a cold saturated solution of ammonium
molyl'date ami s cc of dilute hydrochloric acid (1 part of 25 per cent hydrochloric acid
and 7 parts of water > .-hake well and place in a water bath at 80° C. for five minutes.
If tin- .-ample is pure the solution will resemble a nickel sulphate solution, but if sugar
is pre.-ent it will l.o of a Prussian blue color. These different colors can be readily
distinguished but it is advisable to compare with a standard blue solution made by
adding a few dr-'p.- <>f p«>ta.-.-ium ferrocyanid and 5 drops of 10 per cent hydrochloric
ae id to a solution of 1 cc of 0.1 per cent ferric chlorid in 20 cc of water.
.\ I kul i n i in i if ash.— Evaporate 25 cc of cream to dryness, and burn to an ash in a
inutile lM.-.-olv«' the a.-h in an excess of tenth-normal sulphuric acid, boil to expel
the carhnii dioxid and titrate back with tenth-normal sodium hydroxid, using phe-
nolphthalein as the indicator. Express results as cubic centimeters of tenth-normal
aeid required to neutralize the ash of 100 grams of cream.
Determination of nifdnm. — Add acetic acid to the final solution from the above
determination, heat to l.<>ilin<_r. add 1 gram of sodium acetate and an excess of ammo-
nium oxalate. Filter and wash the piwipitated calcium oxalate with water, dissolve
in In>t dilute sulphuric acid, and titrate hot with tenth-normal potassium perman-
Ihe number of cubic centimeters of tenth-normal potassium permanganate
multiplied l.y o.ol 12 (4 X 0.0028) gives the percentage of calcium oxid in the sample.
The table appended shows the composition and reactions of pure and adulterated
cream, usimMhe liaierand Neumann methcxl for calcium sucrate. It is recommended
that this metliM.l l,e di-tributed for rritiei-m
Results on pure and adulterated creams using th> />«//• /• and Neumann -method for calcium
sucrate.
1 Viff iTf.i:!!.
Cream containing calcium sucrate.
Calci-
T..I ll
•M ,
Fat.
Ash.
Alka-
of
Cald-
iiiu
odd.
In n i
um su-
crate
added
&.
Fat.
Ash.
Alka-
linity
of"
ash.
Culri-
iiiii
oxid.
Sucrose.
Per*.
Pact.
I.'. I
cc.
7 |
Per a.
i. on
None.
cc.
5
Perct.
K g
Perct.
i ).:,u
cc.
19.2
Perct.
0.147
Present.
i, n
.35
None.
2
37.9
.4(1
13.2
.130
Do.
47 -.
4j ^
•
ft. 4
5
41.4
. M
11.6
.095
Do.
.37
.009
None. 4
42. n
.4:{
10.0
.101
Do.
40.4
.43
. i r *
"••_
None.
None,
MARKET SAMPLES.
,i'i •
Kit (CM Noun.
30.4
. I'.t 16. 0 . 123
Do.
;••
36
065 None.
39.8
l«i.() .143
Do.
.;•• ..
'41
.083 None
_'X N
14. 0 . 135
Do.
\\ n^
•u, x
33
7 0
094 Vnn«.
H s
10. 8 . 130
Do.
4 ' xji
37 2
'41
7 2
BBI
12.0
.141
Do.
4j n
:u, s
\m
7.6
.MVi
None. |
REPORT ON CEREAL PRODUCTS.
By E. F. LADD, Associate Referee.
During the past year considerable work was undertaken in our own laboratory upon
1 products, very little of which has as yet been completed. Therefore only a
report <>f progress can be made. As the result of examinations made by A. S. Mitchell,
< -hi.-f ..f the Si Paul Finn! and Drug Inspection Laboratory, the following methods are
suggest ed:
METHODS FOR ANALYSIS OF CEREAL PRODUCTS.
MOISTURE.
I >ry a convenient quantity of the flour (approximately 5 grams) at the temperature
of 1,.,'ilin.r \\at.-r iii a current'..! dry hydrogen or in vacuo until it ceases to lose weight.
54
ASH.
Char a convenient weight of the original sample (from 2 to 5 grams) in a platinum
dish, in a muffle, at the lowest possible temperature until free from carbon. If carbon
free aish can not be obtained owing to its fusibility, exhaust charred mass with water
and proceed as under ash, Bulletin 107, page 38.
CRUDE FAT (ETHER EXTRACT).
Extract a convenient quantity of the product (from 4 to 5 grams) as dried in the
determination of moisture with anhydrous, alcohol-free ether, for 24 hours (with fine
flour the addition of an equal weight of clean dry sand is frequently necessary). Dry
the extract at the temperature of boiling water until it ceases to lose weight.
NOTE. — lodin numbers should only be obtained upon the ether extract after purifi-
cation by solution in petrolic ether, but are best made upon the petroleum ether
extract.
SOLUBLE CARBOHYDRATES (AS DEXTROSE).
Weigh 16 grams of flour into a 500 cc flask. Add 200 cc of water. Shake occasion-
ally during one-half hour. Filter through a dry folded filter. To 50 cc of the filtrate
ado! 5 cc of concentrated hydrochloric acid. Place the flask in water and invert at
70° C. for ten minutes. Cool, neutralize, and bring to 100 cc. Filter. Determine the
reducing sugars with Fehling solution, by the official method, as described in Bulletin
107, calculating the reducing sugars as dextrose.
CRUDE FIBER.
Determine the crude fiber in 2 grams of flour by the official method (Bui. 107),
filtering through linen in a Biichner funnel.
DETERMINATION OF MOIST GLUTEN.
Dough lip 30 grams of flour with 18 cc of water conveniently in an 8-ounce mortar.
Weigh off 16 grams of dough equivalent to 10 grams of flour. Place in water at room
temperature for one hour and carefully wash out the starch over bolting cloth or a fine
horsehair sieve. After expressing all globules of water, weigh the moist gluten upon
a watch glass. Dry in a desiccator for 24 hours and complete drying in water oven.
ACIDITY IN FLOUR.
Weigh 18 grams of flour into a 500 cc Erlenmeyer flask and add 200 cc of distilled
water, previously freed from carbon dioxid by boiling in tin. Place the loosely stop-
pered flask in a water bath kept at 40° C. for 10 minutes, shaking repeatedly. Remove
the flask and allow it to stand, with occasional shaking, at room temperature for one
hour. Filter upon a dry folded filter, rejecting the first 10 cc and receiving the suc-
ceeding 100 cc in a graduated flask. Titrate the filtrate with twentieth-normal sodium
hydroxid, using carefully neutralized phenolphthalein in alcohol as an indicator.
Each cubic centimeter of twentieth-normal sodium hydroxid represents 0.05 per cent
of acidity as lactic acid.
NOTE.— Results obtained with flour at temperatures of 15°, 20°, and 25°, respectively,
indicate that the acidity in the solution increases with the temperature. The method
outlined seems to give the maximum acidity.
TOTAL NITROGEN IN FLOUR.
Determine the total nitrogen in 2 grams of flour according to the official method,
preferably the Gunning method, Bulletin 107, page 7. The nitrogen times 6.25 gives
total proteids.
GLOBULIN AND ALBUMEN (EDESTIN AND LEUCOSIN) AND AMID NITROGEN.
Weigh 5 grams of flour into a 500 cc Erlenmeyer flask. Add 250 cc of sodium chlorid
solution 1 per cent. Stopper and shake thoroughly. Let stand, with occasional shak-
ing, for three hours. Filter on dry paper. Evaporate 100 cc of the filtrate to small vol-
ume in a Kjeldahl digestion flask with 5 cc of sulphuric acid. Add remainder of the
55
sulphuric acid and determine the nitrogen by the Gunning method. To a second 100
cc of the filtrate add f> ce of phosphotungstic acid, 20 per cent solution; shake thor-
oughly, allow to settle, and filter by decantation. Wash slightly with water. Con-
centrate the filtrate with 5 cc of sulphuric acid in Kjeldahl flask and determine the
nitrogen as amid.
1 ).Miurt the amid nitrogen from the nitrogen found in the first fraction to obtain the
nitrogen as globulin and albumen. This figure times 6. 25 gives globulin anrl albumen.
ALCOHOL SOLUBLE PROTEINS (GLIADIN).
\Veigh 4 grams of flour into a 500 cc Erlenmeyer flask, add 200 cc of alcohol 0.90 sp. gr.
Shak •ra.-ionally during three hours. Let stand 12 hours. Filter through a dried
filter. Kvaporate th»> alcohol from 100 cc of the filtrate. after the addition of 5 cc of
sulphuri'- arid and determine the nitrogen as alcohol soluble nitrogen. This figure,
!»•.-.- tin* amid nitrogen, gives the alcohol soluble proteid nitrogen or gliadin.
'.11 TIMS DETERMINATION BY DIFFERENCE).
heduct from the total nitrogen the salt soluble nitrogen plus the gliadin. This
time- i ;_'."> gives theglutenin.
i.l.IAUIN H\ roLAKIZATION (METHOD OF SNYDER).
Weigh r>.!»7 irrams of flour into a 300 cc flask. Add 100 cc of 0.90 sp. gr. alcohol.
Shak'- at interval- during three hours and let stand overnight. Filter through a dry
folded filter. I'olan/e in a 220 mm tube. Precipitate the proteids in 50 cc of the
filtrate with ."> cc of Millon's reagent. Shake, tilter,and polarize the filtrate in a 220 mm
ml). Ail«l •"><> per , •. 'lit to i he reading and deduct the sum from the first reading. This
dii't'eivner times. 0.2 gives the percent of nitrogen as gliadin.
FAT DETERMINATION (BASSETT).
An H'fort was made to discover a method whereby the time for determining fat
and mi «i-t iin- in cereal samples, especially flour, could be much shortened and without
a sacrifice of accura<\ IIP. Bassett, of the North Dakota laboratory, was assigned
some work along thi< line, the results of which are embodied in the following:
Fat in flour has be«-n determined usually by the method given by Leach, which is
outlined so as to be applicable to all food and feeding stuffs. However, in making fat
on tlour l'\ l.e.i. h'- method considerable time is required, and unless
are taken the analyst could never check himself. This, in any
method, in. li< -at.- inaccuracy. In examining the difficulties which might arise to
i hi.- ni. -i hod, it was especially noted that oxidation might take place in drying
th»- tlour in a hot -water o\en, as is generally practiced, since the fat in the flour is in a
tine state- of di\ i-ion, \\ liich gives the most favorable conditions for oxidation. Again,
tin- .-pi-«-ial j>r. < aution <,f removing the last trace of moisture from the flour seemed
-sary point \vh.-n the ether, as generally employed, contained probably
ten times more water than was found in the dried flour.
The extra- t ion l>y the I.eaeh extractor is also slow, requiring sixteen hours, and in
apparatus arranged in su« h a manner that it cannot always be run with safety over-
night. This mean*, then, three full workingdays before a determination can be made—
on,- for the inoi-ture determination and two for the fat determination.
In order to avoid these difficulties, the following method was developed:
Ten grams of flour were weighed into a tared gooch crucible, then placed in the
ordinary u'ooeh funnel, which was inserted into a rubber stopper in the top of a low
bell jar! whieh rested upon a ground -glass plate. Under the bell-jar and directly under
the gooch funnel was placed a second glass plate to avoid the possibility of getting
vaseline on the bulb, which was to catch the filtrate, vaseline being used to make an
air-tight joint between the bell-jar and ground-glass plate. The gooch was now filled
with ether six times, each time drawing off with the filter pump. The ether extract
was collected in a bulb similar to those with a Soxhlet apparatus. This bulb was then
removed and connected with a Liebig's condenser, and the ether distilled off with a
mdle-power incandescent bulb, this being used as it avoided the possibility of the
vapors of ether catching fire, and also has the additional advantage of not being so hot
56
as to easily burn the fat. The residue in the gooch crucible is now dried in an air
oven and weighed, the loss in weight being equal to the fat and moisture. The fat
having been determined, the moisture is easily obtained by difference.
The results by this method, however, are considerably higher than by the Leach
method often twice as much— but there is no difficulty in the analyst duplicating
his results. Following are some of the figures obtained by this method:
Comparison of methods for fat determinations.
Number
New method. Leach method.
of
experi-
ment.
1.
2.
1.
2.
Per cent.
Per cent.
Per cent.
Pir cent.
1
1.26
1.24
0. 47 0. 45
2.'. '.'. 1.70 1.71
1.21 1.23
O
2.29
2.30
1.83 1.87
4!!
1.16
1.22
.68 .70
0..
1.08
1.12
.65 .53
7..
2.66
2.66
1.17
1.27
8..
1.07
1.07
.60
.62
9..
1.32
1.36
1.30
1.28
10..
2.14
2.18
2.37
2.28
11..
.97
.99
.70
.65
12..
1.05
1.02
.65
.65
13
3.05
3.00
2.43
2.52
DISCUSSION OF RESULTS.
Comparing the results by the two methods, it is noticed at once that none of those
by the new method checks those made by the old method, and it was thought at first, that
there might possibly be an error on account of the moisture present in the flour while
extracting, the tests by the old method being carried out on dry flour. A large amount
of moisture would probably cause some of the sugar-like substances to be extracted . In
order to test this point, the following experiments were performed : Ten grams of flour
were weighed out in a gooch crucible as before and placed in a large-mouthed bottle,
which was closed with a two-hole rubber stopper. Carbon dioxid which had been
dried over concentrated sulphuric acid was conducted through the bottle, the same
being arranged in a water bath and heated for four days under these conditions. This
was then extracted with ether, according to the new method. The results obtained
checked exactly those extracted without drying.
Results obtained by new method on dried and fresh flours.
No.
Fat in Fat in
dried flour, fresh flour.
Per cent.
Per cent.
1
1.21
1.24
2
1.22
1.26
3
1.24
1.23
4
1.24
1.22
The next point considered was to determine if flour dried in carbon dioxid, under
these conditions, would give the same per cent of fat as by the new method or would
check the old method. Therefore, 2 grams of flour were weighed out in a small test
tube with a hole in the bottom, which was closed by an asbestos plug. This was then
placed in the bottle described and dried for four days, after which it was extracted by
the Leach method, the following results being obtained:
57
Fnt (It ttrntinationx, drying with carbon dioxid.
New
method.
COrdried
(lour by old
method.
1.26
1.24
1.23
1.22
1.21
1. 22
1.21
1.19
It is evident that when dried in carbon dioxid the flour does not undergo any
oxidation, while t>..m these results the point seems almost, if not completely, proven
that it does undergo oxidation when dried in the open air, and for this reason it is
hard to obtain results that check.
Numerous determinations have been made by this method and it has given perfect
sati-t'action as well as being extremely rapid. Time may be saved, as the gooch
crueihle d<M« not need a new pad every time, the same one being used for at least
liti. -n determination- by .-imply knocking out the extracted flour when through.
Further, the lla.-k r.mtainiui; the fat may he used six or eight times without cleaning,
where a number of determinati"ti- are b.-in^ made.
This work was carried out with ether as the solvent, but chloroform, acetone, or
ben/m may a ho be u-ed, .-imilar r.-uh- heinu; obtained. The following results were
obtained:
'imt by the new method, using different solvents.
No,
Ether.
Chloro-
form.
Acetone.
Benzin.
1
1.21
1.26
1.29
1.20
2
1 •
1.27
1.2i.
1.21
3
i H
1.25
1.27
1.23
4
i B
1.29
1.28
1.22
These results become of value on aeeount of the cost, chloroform and ben/in being
much cheaper than ether or aeet.-n.-
In some cases feed and foodstuffs are not well ground, nor capable of being ground
as fine as flour. These of course would not extract by the above method readily, but
may be extracted by means of the Soxhlet apparatus instead of the gooch crucible.
Th«- So\hlei apparatus was used on flours and the results check those made with the
Ur h enicible very closely.
I'.ither one ,,f th,- -oU.-nte named may be used instead of ether, as a larger amount
• nt i- required under such conditions, and unless special precautions are taken
I.KSS may take place.
( omparison of results on fat, using a gooch and the Soxhlet apparatus.
Gooch cru-
Soxhlet
cible.
apparatus.
1.24
1.24
1.2»i 1-2(1
1.23 1-27
1.22
1.28
58
MOISTURE DETERMINATION.
The moisture, as stated in the preceding method, may also be determined by
drying the residue in a hot-water oven and then weighing the crucible and residue,
the loss being equal to the weight of the fat and moisture from which the moisture
may be determined. The following results were obtained and will be compared with
the old method by Leach:
Comparison of moisture determinations by two methods.
New
method.
Old method.
Per cent.
Per cent.
Per cent.
8.60
8.76
8.66
8.80
& 76
8.66
8.88
8.76
8.66
8.92
8.76
8.66
The results here, however, are not so close as in the fat determinations, but out of
the numerous determinations that have been carried out in this laboratory the results
have checked to within 0.2 to 0.3 per cent, and, in the majority of cases, within a
hundredth of a per cent. The following table shows a few results which will give an
idea of the accuracy of the method:
Duplicate moisture determinations by new method showing degree of accuracy.
Sample.
Per cent.
Per cent.
1
12.64
12.76
2
12.36
12.56
3
11.08
11.06
4
11.40
11.84
5
12.80
12.06
6
11.40
11.30
7
11.72
11.80
This method has been a means of saving much time, since a large number of such
determinations were made during the flour investigation of the past year.
Considerable work was also undertaken in the study of the gluten and protein
content of the flour, and a large number of methods were tested. Some results of
special interest were secured, but owing to the illness of the assistant having this
work in charge only progress in this direction can be reported.
RECOMMENDATION.
It is recommended that for the coming year special attention be given to testing
methods for the separation of the gluten constituents of flour, tests being made upon
the several grades, as patent, first and second clears, and upon flours produced from
different varieties and types of wheat.
REPORT ON VEGETABLES (CANNED PEAS).
By W. L. DUBOIS, Associate Referee.
The work on this subject during the last year has been confined to the examination
of canned peas for the purpose of distinguishing soaked peas from those canned when
fresh. Such a distinction of course is made with quite a degree of certainty by a
59
simple fxuiuiiuttii.il of the physical appearance of the goods, noting especially the
maturity and firmness of the peas and the consistency of the liquor. Soaked peas
usually appear more or less broken and mashed and the most matured show well
de\( -loped cotyledons and are packed in a liquor which is cloudy and starchy in
appc'arai;
The maturity of the peas, however, can not be taken as conclusive evidence that
t hr -aim1 hu\ e been soaked, because many well developed peas, very similar in appear-
an< ••• to those soaked before canning, are packed as numbers 4 and 5, Early June and
Telephone peas, and are not soaked. Neither can the appearance of the liquor be
iiuully relied upon. .-ince the most mature, fresh peas are sometimes found in a liquor
which i- not dear and is more or less starchy; hence it is desirable to obtain data
which would Mibstaiitiate conclusions drawn from the physical appearance of the
goods. To this end 7:i miscellaneous samples of peas have been examined by the
referee and on all these the weight of the liquor and drained substance, and the per-
centage of water in the drained substance were determined. These determinations
alone are sufficient to di-t iii'jui-h the fresh peas and some of the more succulent grades
from the soaked goods, the chief difficulty arising in differentiating between the soaked
uooil.- and the more matured peas put up in the fresh state. In the water content the
latter did not differ very widely from the soaked peas. As will be seen from the table,
the a tent of water in 24 samples of soaked peas is 71.98 per cent, and the
average of 18 samples of Early June and similar grades is 77.52 per cent. The highest
moisture content of the soaked peas, however, exceeds that of the driest of the Early
June | »ea.-, .-<> that there is an overlapping of the results which makes it impossible to
pronounce a conclusive opinion from these determinations alone.
More definite eondu-ion-, however, may be drawn by also determining the crude
starch. For thi- determination 1"> grams of the ground drained material were hydro-
ly/.ed l»y hydrochloric acid according to the official method and all copper-reducing
.nice calculated as starch. The average of 16 results on soaked peas gave 14.45
per cent, the hi-hest figure being 18.19 per cent and the lowest value 11.08 per cent,
while tin- average starch content of 1 1 samples of matured peas canned in the fresh state
was 10.87 per cent 11. re airain is an overlapping, the lowest results on the soaked
peas, 11. 0> low the highest value obtained on the fresh grade, 14.38
ni This last sample, however, was probably misbranded, as will appear later.
The average starch content on soaked peas, as far as determined, is approximately 4
• •nt hi-rher than that of Karly Junes and those of similar quality. There is some
difference, furthermore, in the specific gravity of the two grades, that of Early Junes
runnin- from 1 . 10 to l.l I, whereas the values obtained for soaked peas vary from 1.12
to 1 .!•;. Takinirall these figures into consideration, it seems possible by the determi-
nation of the water, starch, and specific gravity of the drained substance to obtain
values which will supplement the conclusions drawn from the physical appearance
of the good-
The table iriv.-s in detail the results obtained. Samples numbered 81 and 82 are
interest in- in furnishing a test of the method suggested. These samples were labeled
Karly June peas, but both had the appearance of having been soaked. These were
run at the same time as numbers To to 80, inclusive, and it will be seen how the starch
content compares with the other samples labeled in the same way. By these values
alone ami the appearance of the goods it would be quite safe to conclude that they
had been soaked. Then- is also a difference in the specific gravity, which is some-
what higher than in the other samples. This conclusion is further strengthened by
the amount of water which is less than in the other samples.
The work Mem to justify further investigation along the same line by the succeed-
ing referee.
60
Examination of canned peas to distinguish soaked goods.
FRESH PEAS.
Number.l
Grade and appearance.
Liquor.
Drained
sub-
stance.
Specific
gravity.
Crude
starch.
Pro-
tein.
Water.
Grams.
194
Grams.
3981
Perct.
Perct.
Per ct.
78 61
201
389
82.68
193
400
81.87
208
387
82.61
196
396
82 94
223
360
78 35
* $7
378
,
86 84
8
do
197
390
78.53
9
in
do
205
365
360
78.87
87.04
190
380
86.87
190
380
86 95
10
Surprise peas:
No 1 small
190
395
87 20
14
No 2
220
383
86.57
1C
No 3
238
362
86.57
ifi
No 4
202
400
82 52
17
No 5
216
382
81.91
18
Alaska peas:
No 1
255
332
86.72
19
No 2
245
344
82 37
on
No 3
245
357
78 23
21
No 4
220
387
76.34
22
No 5
240
357
74 28
23
Admiral peas:
Me. 1
215
375
86.80
24
No 2
203
387
84.59
25
No 3
227
369
84.30
26
No 4
220
369
80 83
27
No 5
219
373
78.50
28
First quality a few old
224
364
83 63
29
Good quality" a few old
209
381
79.29
30
205
380
79.59
11
Large firm about same as No. 30
197
356
86.73
32
Tom Thumb very small excellent
210
359
85.99
33
Petit Pois small
238
334
85 99
34
Sifted Little Gem small
233
353
85.91
65
Early June pood quality
215
383
1 12-1.16
13.88
70 79
66
Early June Extra No 7 fair
265
305
. 10-1. 14
12.13
74.55
67
Telephone some broken and soft
218
374
. 10-1. 14
12.15
74.62
68
Early June, a little mushy
232
372
. 10-1. 16
75.10
60
Early June appear soaked
.10-1.14
70
Early June cloudy and starchy firm
10-1 14
71
Early June cloudy and starchy, old
. 10-1. 16
72
Early June, poor quality, appear
soaked
. 12-1. 16
7?
Early June good quality
.08-1.16
74
Early June, cloudy, poor, many
broken
.10-1.16
75
Early June firm large many hard
239
351
08-1 14
10 55
Lost.
76
77
Early June, medium size, good quality.
Early June medium size fair quality
229
250
366
335
Below 1. 10
08-1 16
7.37
12.00
82.30
75.45
78
do.
Lost
Lost.
Below 1.10
6.63
84.04
79
80
Early June, large, mealy, many hard . .
do
200
189
378
386
.08-1.12
08-1 14
9.34
7 20
78.88
77.89
81
Early June, large, mealy, appear
soaked
299
277
1 08-1 14
14 38
74.84
8?
Early June, appear soaked
252
294
1.10-1.14
13.95
73. 21
61
Sftanination of canned peas to distinguish soaked goods— Continued.
SOAKED PEAS.
Number.
Grade and appearance.
Liquor.
Drained
sub-
stance.
Specific
gravity.
Crude
starch.
Pro-
tein.
Water.
Soaked, some mushy
Grams.
235
Grams.
359
1 12-1 18
Perct.
Perct.
Perct.
70 71
.1..
255
335
12 i ig
243
394
1 12 1 16
38
294
274
74 ^fi
231
344
10-1 16
10 7Q
40
do
215
353
.10-1 16
74 qo
41
...do....
187
405
12-1 16
70 co
42
. .do
ni
380
u
Liquor V»TV rloii'lv. sii.iki-1
274
306
U os
6 87
71 84
52
So;ikril, VtTV |KK)r, IllllsllV.
. 222
280
18 19
6 69
70 OA
53
Soaked, li(iuor vcrv clomlv
177
401
14 23
6 56
79 4g
M
Soaked, sample poor
l.vj
418
12 83
6 13
74 fifi
55
Soaked, clouilv, IHMS f;ur
211
368
13 54
6 69
fiQ fi7
56
Soaked! cloudy, broken, and soft
175
Ms
14 47
6 44
71 97
:.7
187
HI
1 12-1 16
13 96
6 06
74 10
•
Soaked, rnanv brok-
07
300
1 12 1 16
14 79
7 31
n! ^
7»
245
; ;n
1 12 1 16
14 31
6 CO
•
Soaked, fairly firm
ft
341
1 12 1 16
14 77
6 19
70 nc
|
197
385
1.12-1 16
15 25
71 oo
H'
Soaked, many poor
M
1 12-1 16
16 04
71 70
•
Soaked, good, some black
214
323
1.12-1.16
15.77
71 06
64
Soaked, somewhat in usii \
;ni
t.lLM.16
14.34
73 62
REPORT ON THE SEPARATION OF MEAT PROTEIDS.
w i : i ; 1 1 M i : , Associate Referee.
lMirin-4 the past year no ON. jMT.it iv«- work has been asked for on the separation of
but considerable work has been dune at the Missouri experiment sta-
tion, in conni'ctioii with tin- u'eneral meat investigations, in the examination of cold
\vaN-r i-\traei> of meat from composite samples of various wholesale cuts of steers of
different ages and of different d-^rees of fatness.
In tin- preparation ••! cold water extracts the general plan as proposed by Grindley
and Kmmett " was followed with slight modifications.
With lean samples exactly 100 grams and with fat samples 150 grams were taken;
in each case being distributed through eighteen beakers in about equal portions.
Thi-.-anijili- in <M' h h.-.ik.T was thoroughly mixed with 3 to 5 cc of cold neutral nitrogen-
ii-iilltil \\.iifi and thru with 50 cc of the flame water. The mixture was allowed
nd about thirty ininut'-s, with fn-qiu-nt agitation, and then poured through pre-
viously \\.-it.-d tiltrrs. Each time the residue which was poured on the filter was
returned to the beaker. TO th.- n-~idue in the beaker 25 cc of water were added and
the i te thoroughly stirred and again filtered. This washing was continued
till •_'_' iter were u-rd; then the whole residue was transferred to the filter and
washed tui< e \\ith 10 to 15 cc of water each time.
The filtrates were eombined, the lla.-ks ringed, and the total volume made up to
5,000 cc. This cold water extract was carefully mixed without undue agitation and
filtered through a dry tiller just before the aliquot portions were taken for analysis.
1 n all tiltrations the" funnel was made to touch the sides of the flask or beaker, so as to
limit the amount of spontaneous coagulation.)
Triplicate samples were taken for analysis as follows:
a, 6, c. — 100 cc for total soluble nitrogen representing 2 grams of lean and 3 grams
of fat sample.
rf, e, /.— 100 cc for total solids and ash representing 2 grams of lean and 3 grams of
fat sample. * * *
m, n, o. — 200 cc for coagulable nitrogen representing 4 grams of lean and 6 grams of
fat sample.
« J. Amer. ('hem. Soc., 1905, 27: 661.
62
p> ?> r.— 200 cc for total albumoee nitrogen; filtrate from TO, n, o, representing 4
grams 'lean and 6 grams of fat sample.
s, t, u.— 200 cc for total amido acid nitrogen representing 4 grams of lean and 6 grams
Samples a, 6, c were transferred to 500 cc nitrogen flasks for the direct determination
of nitrogen by the Kjeldahl-Gunning method.
Samples d, e,fwere evaporated to dryness on the water bath, then dned to constant
weight in air bath at 103°, and finally ashed at a dull red heat.
Samples TKL, n, o were treated with a slight exces^ of moist magnesium carbonate, a
evaporated to about 30 cc, filtered and washed with hot water to which a little moist
magnesium carbonate had been added. The precipitate and filter were transferred
to 600 cc nitrogen flasks and the coagulum adhering to the sides of the beakers was
removed with hot sulphuric acid and transferred to the corresponding flask. The
nitrogen was determined in the usual manner.
The filtrates from TO, n, o, (p, q, r) were concentrated to about 10 cc in small beakers
and acidified with 1 cc of 50 per cent sulphuric acid, diluted to 30 cc and to each 50
grams of pure crystallized zinc sulphate were added. The mixture was then heated
upon the water bath until the complete solution of the zinc sulphate took place. If too
much zinc sulphate crystallized out upon cooling a little water was added, care being
taken to have only a slight excess above saturation. The contents of the beakers were
filtered through filters previously wet with a saturated solution of zinc sulphate
slightly acidified with sulphuric acid. After the filtrate had completely drained
through, the beaker and filter were washed three times with the saturated zinc sulphate
solution, allowing the washing to drain completely before adding the next washing.
The filter and precipitate were transferred to nitrogen flasks and each beaker washed
with water and sulphuric acid, the washings being rinsed into the corresponding flask.
If care has been used in avoiding an excess of zinc sulphate crystals there will be no
trouble with bumping during the digestion for the determination of the albumose
nitrogen.
Samples «, t, u were treated as for coagulable nitrogen. The filtrates from the coag-
ulum, not to exceed 30 cc, were rinsed into 100 cc graduated flasks, 15 grams of sodium
chlorid were added and dissolved by warming gently. The flasks were placed in the
ice box until cooled to 15° C. A, 24 per cent solution of tannic acid was made up, fil-
tered, and cooled in the ice box. When both solutions were cooled, 30 cc of the tannic
acid solution were added to each 100 cc flask, which was then filled to the mark with
cold water; the contents of the flask were thoroughly mixed and allowed to remain
in the ice box over night. The following morning they were filtered rapidly and 50 cc
of the filtrate transferred to nitrogen flasks for the determination of the amido acid
nitrogen. With all of the determinations blanks were made to correct for the nitrogen
in the reagents. From these data the nitrogen present as peptone nitrogen was cal-
culated.
The main purpose in the examination of the water extracts of the fresh meats has
been to see if age of animal or condition of fatness has any influence upon the amount
of water-soluble material, or upon its composition, also to what extent there is a varia-
tion in different parts of the animal. To this end the samples have been handled as
nearly as possible in the same manner and with the same treatment after slaughtering.
So far eight animals have been slaughtered and analyzed, but the data are still insuffi-
cient to admit of any general conclusions, and the present paper is to be regarded only
as a report of progress. A tabulation of a few of the results is appended, selecting those
for the round and rump, the rib and loin cuts of the first four animals slaughtered.
a Prepared by precipitating magnesium chlorid with sodium carbonate, heating,
filtering, and washing until no chlorids remained in the filtrate.
63
// nf nitnujt n In cold-water extracts of wholesale cuts, free from bone, from four
different steers.
Simple.
Total
solids.
Total
nitrogen.
Coagu-
lable
nitrogen.
Albu-
mose
nitrogen.
Peptone
nitrogen.
Amido-
acid
nitrogen.
Steer No. lv
Round and rump
Percent.
4.979
Per cent.
0.574
Per cent.
0 287
Per cent.
0 037
Per cent.
0 040
Per cent.
4.627
540
271
039
053
177
Loin
4.778
.550
.263
052
064
171
121:*
Round and rump
4.583
528
253
e 142
202
3.490
.413
.192
010
053
158
Loin
3.631
.409
195
042
010
162
505:«
Kuiiii'i and rump .
5.116
.587
.273
035
007
272
Kit-
4.117
.470
199
0°9
021
221
4.593
534
235
041
029
229
Steer No. 503:<*
Round and rump
5.389
.627
294
071
036
226
Rib.
Loin.
4..,JM
4.348
.530
.501
.254
.234
.033
.071
.034
.015
.209
.181
Shorthorn steer, 3 years old and extremely thin.
shorthorn steer, 3 years old and moderately fat.
'-Cni.lf llrrrfonl M.-.-r. 1 y«-.ir «.M un! IMO.|. -r.it. -ly fit.
<* < }rade Hereford steer. 1 year old and in fair condition as a stocker, much better condition than No. 18.
• pnvipitatr w.i^ w.i>h.-!
The albumose
only once; results too high.
'•1-n-nter extracts of tht- lean of wholesale cuts (bone and fat
hnnd separated) from three steers.^
, 1 I I tt .ll
Httdto,
Total
nitrogen.
Cnairu-
lablo
nitrogen.
Albu-
mose
nitrogen.
Peptone
nitrogen.
Amido-
acid
nitrogen.
Per cent.
Koiind and rump 5.736
Percent.
a 671
Percent.
0.320
Per cent.
b 0. 173
Per cent.
None.
Per cent.
0.258
» :^
.550
.251
.013
0.073
.213
:, M
.647
.306
.040
.041
.260
Bt*er No. 505:
Konii'l and rump. 6. 153
4.999
0,109
St«-«-r No. :*u
Round ;ind mini'. ... •> '••«'
4.930
.710
.565
.719
.01
.567
.332
.240
.315
.330
.276
.039
.032
.054
.074
.028
.009
.025
.038
.040
.037
.330
.268
.312
.255
.226
5.510
.643
.301
.083
.023
.236
a Steer No. 18 excluded as it was the first one slaughtered, and the hand-separated fat was weighed
separately but was ground with the lean for analysis.
'• Albumose precipitate washed but once.
Distn n itrogen in cold-water extracts of wholesale cuts, free from bone and fat, a of
four different steers.
Sample.
Total
solids.
Total
nitrogen.
Qstffr
labie
nitrogen.
Albu-
mose
nitrogen .
Peptone
nitrogen.
Amido-
acid
nitrogen.
Steer No. 18:
Round and rump
Percent.
5.740
Percent.
0.662
Percent.
0.331
Per cent.
0.043
Per cent.
0.046
Per cent.
0.242
Rfb
5.645
.659
.331
.048
.064
.216
Loin
6.103
.703
.336
.066
.083
.218
Steer No. ui:
Round and rump
6.072
.700
.335
b.188
None.
.268
5.612
.664
.309
.016
.085
.254
Loin
5.913
.685
.327
.070
.017
.271
Steer No. 505:
Round and rump
6.631
.761
.354
.045
.009
.353
Rib
6.030
.688
.291
.042
.032
.323
Loin..
6.705
.779
.343
.059
.043
.334
Steer No. 503:
Round and rump
6.167
.717
.336
.081
.041
.259
KU>
5.453
.624
.299
.039
.040
.246
Loin
5.903
.680
.318
.096
.020
.246
a The weight of the actual amount of fat (ether-soluble) is deducted from the weight of the cut.
reduces all cuts to a fat-free basis.
& Albumose precipitate washed but once.
This
64
In the first table it will be noticed that if the data concerning the albumoses and
peptones are omitted, the round and rump cuts in every case give higher figures than
the other two cuts. When the hand-separated fat is eliminated we find less variation;
the round and rump cut gives higher results than the rib but is equaled or slightly
surpassed in a few cases by the loin. When the fat is entirely eliminated, as shown
in the third table, the difference is still less. However, in only one case does the rib
cut (steer 18, coagulable nitrogen) give as high results as the round and rump cut;
and in anotKer case (steer 503, amido-acid nitrogen.) as high as the loin. In six cases
the loin cut gives higher results than the round and rump cut. In general, steer
No. 505 gives the highest results, especially in the case of the amido-acid nitrogen,
there being only one exception, namely, the coagulable nitrogen in the rib cut on the
fat-free basis. A further discussion of these results will not be attempted at this
time.
For the purpose of making an extended study of the composition of beef extract
there was prepared at the Missouri station (at the time of slaughtering) a cold-water
extract «* from a 5-kilo sample of the round of each animal. The filtered extract was
coagulated upon the water bath, filtered, and concentrated with one or two filtrations
as the concentration proceeded. The extracts -have been finally concentrated to a
semisolid mass, in which condition they appear to remain in a state of perfect preser-
vation. The life history of the animals from which these extracts have been pre-
pared is known and during the next year cooperation in the examination of these
extracts will be requested, to determine the composition of pure beef extract and to
learn to what extent variation may be expected.
The president announced the following membership for Committee
B on recommendation of referees: Messrs. B. B. Koss, R. W. Thatcher,
A. S. Mitchell, Paul Collins, and W. D. Bigelow.
The following committee was appointed to wait upon the Secretary
of Agriculture and the Assistant Secretary and invite them to address
the convention : Messrs. M. E. Jaffa, J. M. Bartlett, and W. A. Withers.
On motion by Doctor Wiley, the vote on the amendments to the
constitution was made special order for 12 o'clock, or following the
presidential address, on Friday.
REPORT ON PRESERVATIVES.
By W. D. BIGELOW, Referee,
SALICYLIC ACID.
RAPID DETERMINATION OP SALICYLIC ACID.
The methods of the association for the quantitative determination of salicylic acid
are long and tedious because of repeated extraction with immiscible solvents. An
attempt was made to simplify these methods by extracting a certain volume of the
food, or an aqueous extract thereof, by means of a definite volume of solvent, evapo-
rating to dryness an aliquot portion of the solvent used, and determining the salicylic
acid in the residue. The total amount can then be calculated by a factor to be deter-
mined by experimental work.
It is, of course, necessary that the solvent, under certain conditions to be adopted,
should extract a uniform amount of salicylic acid uncontaminated by substances that
« Trowbridge and Grindley, J. Amer. Chem. Soc., 1906, 28: 472.
65
would interfere with the reaction by which the salicylic acid should finally be esti-
mated in the iv.-idiir. Owing to its rapidity and convenience, the ferric chlorid
reaction has usually been employed for determining the amount of salicylic acid
:it. It is, therefore, important . that the solvent employed should not extract
tannin from the food.
lu order to determine what solvents should be most advantageously employed as
far a- delicacy "f reaction and freedom from tannin or other interfering bodies is con-
cerned, Mr. i 'harle- S. A-h extracted 50 cc portions of claret containing salicylic acid
in amount.- varying from 0. <)•_>:> mg to 0.5 mg and treated the residue obtained by
evaporation of tin- solvent with ferric chlorid in the usual manner. The results are
given in the following table:
Comparative efficiency of solvents on salicylic acid dissolved in 50 cc of claret (Ash}.
Ether, residue
Milli-
extracted with—
|,r,. .
Chlo-
Ktn.-r.
form.
Kth.-r Di-
aii'l IH- i-hlor-
trolruni
l-tlltT. It-Mr.
Tri-
i-hlor-
leiie.
Kther
:ili'l
hydro-
"o'ur
Petro-
leum
ether.
Car-
bon
bisul-
phid.
Carbon
tetra-
chlorid.
Tolu-
ene.
bat
ti-tni-
Petro-
leum
cut.
chlo-
ether.
rid.
F:iiMt
Good..
Ooad
Good..
Good.
Good....
Faint
Good.
Good..
Good.
trace.
.250
Fair. . .
Faint . Good.
Faint....
None..
Good.
Good..
Good.
.100
ma
mm
Trace. Fair
Nothing.
Trace
Good..
Good.
O.TO
i
None. .
.
None.
(?)
Good..
Good.
Trace ?
Good
trace.
Mr. A-h found that the tir-t live .-olvrnts u'iven in the table extract tannin in the
in which they are im>nti'»ne<l -that i-, ether extracts the greatest amount and
tn. hl..r acetylene the least. The last three solvents— carbon bisulphid, carbon
•hloriil. and toluene— do not extract tannin, and the ferric chlorid reaction in the
re-iduo obtained by them from wine is clear and characteristic of ferric salicylatc.
It will be Q0ted that the residue from the ether extraction gave no reaction whatever
witli ferric chlorid. This was due to the presence of tannin, which entirely obscured
the reaction. With chloroform much better results were obtained, but even here the
reaction was partially ol>scured by tannin, which was also true of the residue from
dichlor-acetylene.
The data given in the column headed " Kther and hydrogen peroxid" were deter-
mined by oxidi/.in- with ammoniaand hydrogen peroxid the residue obtained by evap-
orating the eth- troys the tannin and also partially converts ben/o-
nd -accharin when present into salic\ lie acid. The salicylic acid was then again
te«l with ether, the ether extra- t evaporated, and the residue tested with ferric
id. As previoii.-ly -tated, the greatest freedom from interfering substances
attended the use of carbon tetruchlorid and toluene, the latter appearing to extract
slightly !n«re -alicylic acid than the former, and thus affording a better test in the
l-r.-ence of a small amount of that substance. Chloroform was also very satisfactory,
being inferior to carbon tetrachlorid and toluene in respect of dissolving interfering
•Ubfltancee, though apparently slightly superior in the amount of salicylic acid
extracted.
T::»;T:J— r.uii. I-JL-
66
Extraction of salicylic acid from different viine?.
[Salicylic acid found.]
BY MEANS OF CARBON TETRACHLORID.
Salicylic
acid
added.
Angelica. Sherry.
Port.
Claret.
Dry white wine.
Colorimet-
rlcally.
B
fi
Colorlmet-
rlcally.
PQ
4.
Colorimet-
rlcally.
B
^1
B
ji
B
h _
B
'Colorfmet-
rically.
f
B
E .
t*33
B
Mgs.
100
50
25
10
5
2.5
0
63.2
30.6
14.6
6.0
3.0
1.6
Mgs.
63.4
30.6
14.6
Mgs.
60.8
30.6
15.2
6.2
Mgs.
60.6
30.6
14.8
6.2
3.2
1 6
Mgs.
61.6
31.6
15.2
Mgs.
60.2
32.4
15.8
6.0
J//7S.
60.0
29.8
14.8
6.0
3.0
1.6
60.2
30.4
14.6
Mgs.
60.0
30.8
14.8
6.0
49.4'
24.4
13.4
5.2
2.6
49.6
24.8
11.8
Mgs.
50.4
24.2
12.0
5.G
Mgs.
51.0
24.6
13.6
5.2
2.4
Mgs.
49.6
25.4
12.4
49.2
24.6
12.4
5.6
4.4
1.4
4.8
1.4
5.0
1.4
3.8
0.8
3.8
1.2
BY MEANS OF TOLUENE.
100
80.0
80.4
79.4
78.0
83.0
80.4
82.0
79.8
79.0
69.4
68.0
71.2
70.0
69.4
70.2
50
40.0
37.6
39.2
39.2
41.0
41.8
40.2
40.4
39.0
34.0
35.8
35.4
35.4
35.4
35.0
25
19.6
19.4
19.4
20.0
20.0
19.8
19.6
18.6
18.4
18.4
16.8
18.0
18.2
18.8
19.2
10
7 8
7.8
8.0
7.8
8.0
8.0
7.4
7.6
7.5
7.4
5
4 0
3 8
4.0
3.6
3.6
2 5
2 0
2 0
2.0
O
6 0
1 4
7 8
2 4
6 4
1.4
5.6
0.8
4.8
1.4
SHORT METHOD FOR THE QUANTITATIVE DETERMINATION OF SALICYLIC ACID.
From the results of the qualitative test made by Mr. Ash it appeared that it would
be advantageous to confine the work with the quantitative method to carbon tetra-
chlorid and toluene. Accordingly, Mr. Ash applied the method to various types of
wine containing known amounts of salicylic acid varying from 2.5 to 100 mg per
100 cc. One hundred cubic centimeters of the wine were acidified with 5 cc of sul-
phuric acid (1 to 3) and 50 cc of the solvent were added, gently but thoroughly mixed,
and the solvent separated after centrifuging; 25 cc of the solvent were transferred
to a weighed watch glass by means of a pipette. With toluene the best results were
obtained using a watch glass 4.5 inches in diameter and with carbon tetrachlorid
one 4 inches in diameter.
The solvent was allowed to evaporate spontaneously and the amount of residue
determined by weighing. The residue was then dissolved in 5 cc of neutral alcohol
and transferred into a small casserole, the watch glass being washed thoroughly with
neutral boiling water and the salicylic acid titrated with one-hundredth normal barium
hydroxid, 1 cc of the reagent being equal to 1.38 mg of salicylic acid.
An aliquot part of the solvent was allowed to evaporate spontaneously, the residue
dissolved in 2 or 3 cc of alcohol and diluted with water sufficiently for the colorimetric
determination with ferric chlorid. When the amount of salicylic acid present in the
original sample was not less than 25 mg per 100 cc, the results obtained by weighing and
titration were far superior to those obtained by the colorimetric method, but with
smaller amounts the last method was the only one applicable. No tannin was found
in any of the residues and the ferric chlorid reactions were clear and entirely charac-
teristic of pure salicylic acid.
In the gravimetric and volumetric determination small amounts of soluble sub-
stances were extracted by the solvent. The weight of the residue from 25 cc of the
solvent used in extracting normal wine varied from 2 to 3 mg and its acidity was equal
to about 0.5 cc of one-hundredth normal barium hydroxid. The results obtained
by Mr. Ash on different types of wine are given in the table. In each case these
results are the average of three closely agreeing determinations.
67
It will he noted that the results obtained by Mr. Ash with each solvent and with
each t \ pe of wine are entirely consistent, and the results obtained by weighing and
by titrating the residue agree closely with each other. For instance, by means of
.-ail). .11 tetrachlorid approximately 50 per cent of the salicylic acid present is extracted
fnuii dry, red, and white wines. The same reagent, however, extracted slightly
more than »;<> }>er cent of the salicylic acid present in the sherry, port, and angelica.
Toluene, mi the other hand, was found to extract about 70 per cent of the salicylic
arid pn-eiit in dry, white, and red wine and about 80 per cent of that present in sherry,
p.»it, and angelica. It would appear that this method might be used advantageously
at lea.-t f..r a preliminary determination of the amount of salicylic acid present.
The method was further examined by the referee and by P. B. Dunbar with a
view to determining the reason for the varying results obtained with the different
type- of wine and s«> modifying the method that uniform results with all substances
mi'-rht he obtained. This investigation was confined entirely to carbon tetrachlorid
berau.-e of the iiniiintlammability of that substance. Known amounts of salicylic
arid were dissolved in dilute alcohol, varying in concentration from 5 to 50 per cent
1 >ne hundred rubir centimeters of these dilute solutions of alcohol,
rnntainini: 1 m«; of salirylir acid i>er cubic centimeter, were shaken in a separatory
funnel with 50 cc of carbon tetrachlorid and the amount of salicylic acid determined
in L'"> cc "i the >ol \ein. The figure so obtained was multiplied by two for the purpose
nl determining the j>en ent.i-e «\ the salicylic acid extracted in the total amount
of solvent em|>lo\ed. The following results were obtained:
\ . :
taUrylir
Alcohol
Salicylic
I H
by
•old
volume.
r.-t 1 1\ . ;>• ;
volume.
recovered.
I'treent.
/'•rcrtf.
Pcrctnt.
r,rctnt.
44.0
2.r).
«,i it
-,,i M
30
MI o
40
61 8
50
ii. ii
It will he nuted that the percentage of 8alicylic acid recovered under these condi-
tion- increases with the alcoholic content of the solution up to 25 per cent and then
MNB, ihe maximum re.-ult.- bring obtained with from 25 to 30 per cent of alcohol.
California wd \\ine-. dry and sweet, were then treated in the same manner. Their
alcoholic content wa.- increased to 25 per cent and salicylic acid was dissolved in
them to ii i 1 in- per cubic centimeter. Several determinations of salicylic
acid \\ejv then made by the method described and in each instance 61.2 per cent
of the amount of salicylic arid added was recovered. The method was also applied
to 100 cc of a solution containing 10 grams of sugar and 25 per cent of alcohol by vol-
ume. The amount of >alicylic acid recovered from this solution was practically
identical with that reco\,.red from a 25 per cent solution of alcohol. Blanks were
al-o run l.\ . •xtninini; with carbon tetrachlorid 20, 30, 40, and 50 per cent alcohol
acidiiied \\ith 5 cc «i -ulphuric acid (1 to 3). It was found that no sulphuric acid
led and it iru therefore unnecessary to wash the carbon tetrachlorid solu-
tion with water after extraction.
N OF SALICYLIC ACID IX DARK BEER AND OTHER CARAMELIZED
SUBSTANCES.
Attention has frequently been called to the possibility of error in the determina-
tion of -alicylic acid in malt extract and beer prepared from highly colored malt and
in highly < -arameli/.ed substances, such as certain varieties of breakfast food.a This
a J. Brand. V.\<. u'csam. Brauw., 1893, 16: 303; H. Kiliani and M. Bazlen, Berichte,
1894, >7 (3 '. Amer. Brewer's Rev., 1907, 21 (5): 222; Western Brewer 1907,
68
matter was independently studied by A. M. Doyle and P. B. Dimbar, of the Bureau
of Chemistry. Both reported that the color given by ferric chlorid with the material
extracted from highly colored malt by ether was quite different from the salicylic
acid and one should not be mistaken for the other, although the presence of a small
amount of salicylic acid may readily be masked by the material extracted from highly
colored malt and similar material.
Experiments on malt-nutrine alone and on malifc-nutrine containing salicylic acid
(100 mg per liter) indicate that there is some possibility of being deceived by the
color when ferric chlorid is added directly to the dish containing the dried residue
obtained by evaporating the ether solution. In this case a color is sometimes devel-
oped which slightly resembles the salicylic acid reaction. If this color is examined
in a good light and compared with the color developed by salicylic acid and ferric
chlorid there is little danger of being deceived. It is better, however, to carry the
evaporation of the extract to about 5 cc on the steam bath and then to complete the
evaporation by means of a blast of air, since heating to dryness may darken the residue.
The dry residue should be dissolved in a little hot water and ferric chlorid added to
this solution. Under these conditions it seems impossible to mistake the salicylic
acid reaction. Millon's reagent, freshly prepared, which has been suggested for the
detection of salicylic acid in such substances, was not found by either Miss Doyle
or Mr. Dunbar to be as satisfactory as ferric chlorid. In the absence of salicylic acid
this reagent gives a light pink color, whereas in its presence a deep red is given. The
intensity of the color seems to vary so much with the time of boiling, however, as to
render the reaction uncertain and unsatisfactory. Both methods were also applied to
highly caramelized breakfast foods, to which these observations also apply.
DETERMINATION OF BENZOIC ACID.
Several methods for the quantitative determination of benzoic acid have been sug-
gested recently. Among these the following have been studied by the referee and his
collaborators: (1) La Wall's method; (2) La Wall's method modified by mixing a
definite weight of tomato ketchup with sufficient saturated sodium chlorid solution to
make a definite volume, filtering, and extracting an aliquot portion of the filtrate with
chloroform; (3) precipitation as copper benzoate; (4) precipitation as silver benzoate;
(5) distillation with steam after decomposing organic matter with sulphuric acid and
extracting with ether. It will be noted that the first four methods depend on extract-
ing the benzoic acid from the food or an aliquot extract of the food by means of an im-
miscible solvent, whereas the fifth depends on separating the preservative from the
food by distilling with steam.
Before applying the first four methods a preliminary study was made of the relative
advantages of several solvents. This question has been greatly altered by the intro-
duction of the principle of "salting out" the benzoic acid by means of a saturated
solution of sodium chlorid . The benzoic acid is thus rendered much less soluble in the
solution from which it is extracted and consequently much more readily extracted by
the immiscible solvent. The relation of the immiscible solvent to the preservative
thus more nearly coincides with the direct solubility of the former in the latter. An
approximate determination was therefore made of benzoic acid in several solvents.
It was found that the solvents more commonly employed dissolved benzoic acid as
follows, 100 cc of the solvent being used in each case: Ether, 25.70 grams; chloroform,
17.34 grams; carbon tetrachlorid, 7.65 grams; toluene, 7.58 grams; benzol, 6.40 grams.
The chief desiderata in the extraction of a substance of this kind are, first, com-
pleteness of extraction; second, freedom of the extract from interfering substances;
and third, noninnammability. Of the four solvents mentioned, it would appear from
the solubility that by far the most complete extraction can be obtained by means of
ether, and this is known to be true. Ether is objectionable, however, because of its
property of dissolving water and its consequent tendency to extract tannin, salts, min-
69
mil acids, and other interfering substances. The use of ether is also a source of danger
because of its great inflammability.
Chloroform has always been found inapplicable to the extraction of benzoic acid
becuii-e of tin- incompleteness of the extraction so effected. Of the solvents studied,
however, it ,-tand- -econd to ether in its power of dissolving benzoic acid. A study
wa- therefore made of the efficiency of chloroform in extracting benzoic acid in a sat-
urated sodium chlorid .-nlution, and the extraction was found to be practically com-
plete.
In onlrr to determine the efficiency of chloroform with respact to the extraction of
interfering -instances, 500 cc of saturated sodium chlorid solution were acidified with
5 cc of sulphuric acid (1 to 5), and extracted with four portions of chloroform con-
taining 100, 50, 50, and 25 cc, respectively. Each portion of chloroform was removed
as completely as possible from the solution, the four portions mixed and distilled on a
h»t plate toa low volume, the last being removed at ordinary temperature inacurrent
of dry air. The residue left by evaporating the chloroform was not weighable. It
wa- di.— olved in water and titrated with tenth-normal alkali. Duplicate determina-
tion- re<|iiire<l 0.03 and 0.04 cc of tenth-normal alkali for neutralization, thus indi-
cating that the error, owing to the extraction of mineral acids under the conditions
noted, is not greater than iu; mi: "f -odium ben/oate.
One-half gram of tannin \va- then dissolved in 500 cc of saturated salt solution and
ted with chloroform as just described. The residue left by evaporating the
chloroform was not wei-hable, but required in the duplicate determinations 0.02 and
0.04 cc of tenth-normal alkali for neutrali/.ation, which is equivalent to 0.5 mg of
so«lium ben/oate. < Hie-half gram of tannin and 5 cc of sulphuric acid (1 to 5) were
then added to 500 cc of saturated -odium chlorid solution and extracted with chloro-
form as described. The re-idue obtained 'by extracting with chloroform was not
weighable. duplicate determinations requiring 0.05 and 0.07 cc of alkali, respectively,
for their neutrali/ation, equivalent to 0.9 mg of sodium benzoate.
Tin- presence of acetic arid in the ketchups did not appear to cause any inaccuracy.
In order to determine whether a large amount of acetic acid would lead to erroneous
re-uli-. I cc of 99.5 per cent acetic acid was dissolved in 200 cc of chloroform and
variou- portion-dried, as in the case of the chloroform extract from the samples of ketch-
up, and the re-idu. 1. Ten cubic centimeters of the chloroform solution
without evaporation require 9 cc of tenth-normal alkali to neutralize it, equiva-
lent in <> <>",_> -ram <>t acetic acid, or to o.l 11 gram of sodium benzoate. Ten cubic
rentim.-t.-r portion- of the -olution were evaporated before an air blast until no liquid
was vi-ible. and HI CC oi \\at.-r were added to the dish and titrated. An alkaline
reaction was secured on the addition of O.'J cc of one-hundredth-normal alkali.
When Mice jM.rtion- were evaporate* I in the same way and 10 cc of neutral water added
to the di-h i) .-_' cc of one-hundredth-normal alkali were required to give an alkaline
reaction to phenolphthalein. When 10 cc portions were evaporated until the chloro-
form had apparently di-appear -d but a few drops of liquid remained. The odor of
ic acid was very apparent and the residue required 0.2 cc of tenth-normal alkali
for neutrali/ation. Ten cubic centimeter portions were evaporated until the chloro-
form had apparently disappeared, but still contained a slight amount of liquid with a
strong odor of acetic acid. The residue was placed overnight in a sulphuric acid
desiccator, 10 cc of water were added to the dish and titrated as above, requiring 0.1
cc of one-hundredth-normal alkali to give an alkaline reaction. It is apparent that
while acetic acid will be extracted by the chloroform, no error is occasioned if care
be taken to dry the residue either in a current of air or in a desiccator. It was also
found that no appreciable error was caused by the presence of tartaric or citric acid.
Lactic acid, when present, was extracted to a considerable extent by chloroform, but
after bein- evaporated to dry ness before an air-blast the error amounted to only 0.02
per cent.
70
If the volume of salt solution taken in this work is equivalent to 100 grams of food
extracted as in the case of the subsequent studies, the error caused by the extraction
of interfering bodies by means of chloroform is less than 0.001 per cent, and is negligi-
ble. It would appear, therefore, that chloroform possesses the following advantages:
First, after saturating a solution with sodium chlorid a practically complete extraction
of benzoic acid may be made; second, the benzoic acid extracted is not accompanied
by other bodies that interfere with its determination by means of titration; third,
the solvent i§ not combustible; fourth, it is inexpensive. In connection with subse-
quent work on the determination of benzoic acid, therefore, no study was made of
any other solvent than chloroform except as described under Method IV. The detail
of the methods studied is as follows:
LA WALL AND BRADSHAW METHOD (METHOD l).
This method was described in full by the authors in the American Journal of Phar-
macy (volume 80, pages 171-172). The principle depends upon the method outlined
by F. X. Moerk in an article published in the Proceedings of the Pennsylvania Phar-
maceutical Association for 1905, page 181. The details of the method are as follows:
To 20 grams of the substance under examination add 2 grams of sodium chlorid, 5 cc
of hydrochloric acid, and 25 cc of a saturated solution of sodium chlorid. Shake
thoroughly for five minutes, transfer to a moistened filter, and wash with a saturated solu-
tion of sodium chlorid until 100 cc of the filtrate are collected. Transfer the filtrate
to a separatory funnel and shake with three portions of chloroform, using 25, 15, and
10 cc respectively. Evaporate the chloroform at room temperature. If the residue
is white and crystalline, dry over sulphuric acid in a desiccator and weigh. If yel-
lowish and oily, dissolve in 10 or 15 cc of weak ammonia acidified with dilute sul-
phuric acid and again extract with chloroform. The residue is dissolved in 3 to 5 cc
of neutral alkali and titrated with twentieth-normal alkali solution, using phenol-
phthaleiii as indicator. The titration should agree closely with the gravimetric deter-
mination, the difference being rarely more than 1 or 2 mg.
As will be seen by a comparison of the figures obtained by various methods given
in the table on page 71, the results by weighing the benzoic acid, given under Method I,
are much higher than those obtained by titration. All collaborators report difficulty
in securing an adequate filtration. F. W. Heyl obtains very satisfactory results by
titration, whereas the figures of all other analysts were low. In the Division of Foods
the method was applied to the examination of a considerable number of commercial
ketchups. With the low-grade product, made from skin and core pulp, filtration was
possible though somewhat slow. With many of the high-grade ketchups the material
was so finely divided that filtration was almost impossible. In this connection should
be considered the limited solubility of benzoic acid in a saturated solution of sodium
chlorid to be mentioned subsequently.
MODIFICATION OF LA WALL AND BRADSHAW METHOD (METHOD II).
This method is identical with the one just described, except that no attempt is
made to obtain a complete filtration.
To 200 grams of ketchup are added 20 grams of finely powdered sodium chlorid in
a liter flask, and enough of a saturated solution of sodium chlorid is added to make a
liter. The contents of the flask are thoroughly mixed and allowed to stand overnight,
when they are filtered, and 500 cc of the filtrate are transferred to a separatory funnel,
treated with 5 cc of sulphuric acid (1 to 5) and extracted repeatedly with chloroform,
using 100, 50, 50, and 25 cc of chloroform, respectively.
In this extraction a troublesome emulsion was formed which it was found could be
broken up to a considerable extent by centrifuging and by stirring with a glass rod.
Where a centrifuge is not available much may be accomplished by swinging the sep-
aratory funnel with the hand. It is important that after each extraction the chloro-
form be removed as completely as possible, and at the same time the utmost care
must be exercised to prevent any emulsion passing through with the chloroform.
71
()winur t" the mineral acid present in the aqueous liquid, the presence of a slight
amount of thi> emulsion in the chloroform layer causes serious error in a titration of
llli- IVMillle.
Th.- refills obtained by this method, both by weighing and by titrating the chloro-
form n-idue, are given in the table below, under Method II. It will be observed
i luii in all caaea the results obtained by weighing are obviously too high, while the
results obtained by titration with this method are on the whole very satisfactory. It
would appear therefore that the method is fairly satisfactory for the determination
of ben/.oii- a«id in tomato ketchup, which presumably offers as great difficulties for
thi< determination a.- any food to which this preservative is commonly added.
Detenu ii'.itin,, o/.sW/,/m benzoate in ketchup by three methods.
Analyst.
Sodium
i«-M/.>.lU-
•dded.
Sodium benzoate found.
Method I.
Method II.
Precipi-
tation
by
silver
nitrate.o
By
weight.
Titrated.
By
weight.
Titrated.
\v . i . D
Percent.
H.JI7
.146
.168
. 1US
. |..s
.!«
.168
.L.s
Percent.
0.171
.130
.185
.IV.
.190
.183
.169
.178
Percent.
0.166
.261
.170
.170
.170
.162
.154
.162
Per cent.
0.232
.223
.109
.163
Per cent.
0.179
.172
.157
.155
Per cent.
0.166
.143
.029
.056
.056
.056
.059
.238
.241
.242
.250
.204
.168
.172
.180
.060
MO
Do
.000
Do .
,(MO
1' K \>
.247
.270
.258
.1'1,'J
.277
.171
.183
.196
.195
.244
.245
.245
.250
.170
.170
.169
.171
.247
.247
.247
. I-*
HW
i
I'.S
. H.N
M ( Ml.nih
.033
.033
164
.035
.036
.024
.030
Di
.183
.199
.177
.162
.062
.133
.149
b.150
ft. 150
.164
164
164
.060
.060
.062
.063
.063
.055
.055
.056
Do
060
Do
.060
- iiul/
.168
.168
.247
.247
.168
.168
.137
.147
.257
.253
.176
.206
.142
.140
.230
.142
.236
.222
.139
.148
& 100 grains ketchup diluted with water to 200 cc, mixed, and filtered, 50 cc portions of filtrate, diluted to
100 cc, saturated with sodium chlorid. acidified, and extracted with four portions of 100 cc each of ether.
e Same as f oxrept extraction is made with chloroform instead of ether, three portions being
used of 100, 50, and 50 cc, respectively
In some cases where the mixture of tomato ketchup and a saturated salt solution
was tillered soon after it was prepared, the amount of benzoic acid determined by
t h is met IKK! was too low. This suggests the possibility that the solution of the benzoic
arid in the saturated salt solution may not have been complete. More satisfactory
results were obtained in all cases where the mixture was allowed to stand overnight
before filtering.
72
An approximate determination of the solubility of benzoic acid in a saturated solu-
tion of sodium chlorid was made by P. B. Dunbar. In duplicate tests 0.260 and
0.259 gram of benzoic acid were dissolved in 500 cc of saturated solution of sodium
chlorid. In another duplicate determination 0.274 and 0.277 gram of benzoic acid
were found to be soluble in 500 grams of saturated solution of sodium chlorid to which
5 grams of sulphuric acid (1 to 5) had been added. No special precautions were taken
with respect to the temperature of solutions or the purity of the sodium chlorid
employed.
It is apparent therefore that a larger amount of benzoate of soda than 0.27 gram
can probably not be determined by this method. The fact that a slightly higher
amount is reported in some determinations may probably be explained by slightly
higher temperature, or slightly lower concentration of the sodium chlorid solution
employed.
It is obviously important that the method be so modified as to permit the deter-
mination of a larger amount of benzoate of soda. Attempts were made to extract
the benzoic acid from the ketchup by means of water, filtering, and saturating an
aliquot part of the filtrate with sodium chlorid. The results obtained were not alto-
gether satisfactory, although the amount of work done was not sufficient to permit of
definite conclusions. It is probable that by extracting in this manner or with a satu-
rated sodium chlorid solution, previously made slightly alkaline with sodium hy-
droxid, the method can be so modified as to permit of its application to samples
carrying a much higher percentage of benzoate of soda, and at the same time it will
be possible to extract a smaller volume of the salt solution.
PRECIPITATION WITH COPPER BENZOATE (METHOD III).
Mr. C. S. Ash, of the California Wine Association, and Mr. F. W. Liepsner, of the
Division of Foods of the Bureau of Chemistry, studied the determination of benzoic
acid by means of precipitation as copper benzoate from the residue left by the evapo-
ration of the solvent. It was hoped that this method might afford a means for deter-
mining benzoic acid either alone or in the presence of salicylic acid, but preliminary
work showed that while copper acetate is a satisfactory precipitant for benzoic acid
when present alone, no precipitate is formed in the presence of salicylic acid in con-
siderable quantity, owing probably to the formation of a soluble double salt.
A series of precipitations of benzoic acid were made in alcoholic solutions of various
strengths from 0 to 100 per cent and the curve established, giving the per cent of
benzoic acid present that may be precipitated as copper benzoate in various strengths
of alcohol. The results are as follows:
Precipitation of benzoic acid with varying strengths of alcohol.
Per cent
Per cent
Per cent
of benzoic
Per cent
of benzoic
of alcohol.
acid pre-
cipitated.
of alcohol.
acid pre-
cipitated.
0
83
50
70
10
84
60
65
20
88
70
58
30
86
80
48
40
75
100
(i
It appears that the amount of benzoic acid precipitated is somewhat increased by
the presence of alcohol up to 20 per cent of the latter. The increase in strength of
the alcohol beyond this point decreases the amount of benzoic acid precipitated, at
first slowly and then rapidly, the copper benzoate being completely soluble in strong
alcohol. All precipitations were therefore made in a solution containing 20 per cent
of alcohol by volume.
73
To further guard against error due to the solubility of the precipitate, the alcoholic
solution from which the precipitation was made was saturated with freshly precipi-
tated ki.-ir copper I.en/oate. A stock solution of the alcohol so saturated was made
up and u>ed throughout the work. It was found that the results obtained by precipi-
tatioii in neutral solution were too high and that a slight acidity in the solution was
necenarj . Thi- was accomplished by adding a little acetic acid to the copper reagent.
Tin- .-oluiion- employed and the method of determination were as follows:
•l»r acetate reagent. — A mixture of 250 cc of 95 per cent alcohol and 750 cc of
water is .-at urated with copper benzoate and 2 cc of glacial acetic acid added, fol-
lowed \>y a concentrated solution of sodium benzoate in 20 per cent alcohol to form a
.-mall amount of permanent precipitate. This solution is filtered just before using.
Alcohol anfiiti'iiii.— \ mixture of 1 part of 95 per cent alcohol and 3 parts of water is
saturated with basic copper benzoate, prepared by precipitating copper acetate solu-
tion with sodium I.en/oate. filtering, and washing. An excess of the basic copper
l>en/.oat e is added to the alcohol in order that additional alcohol may be added from
time to time.
/>> tn-ii> 'million. — The residue obtained by the evaporation of the chloroform extract
is dissolved in a small amount of the alcohol saturated with copper acetate mentioned
above and ua-hed into a .-mall beaker with the same solution, 25 cc of the copper
acetate solution is added, the mixture stirred, allowed to stand for one hour, filtered
on a g(xx-h, and the precipitate wa.-hed with the alcohol solution saturated with basic
copper l.en/.'iaie The .-«liiti<,n i.- then dried and weighed as usual. If preferred,
the re.-idiie ma\ l»e washed into a 100 cc flask with the alcohol solution described,
the copper a< ei.iie reagent added, and the mixture brought up to mark with the
alcohol -at united ropt.er benzoate. The whole is then mixed and, after standing one
hour, tilier.d, and the copper determined volumetrically by any of the standard
methods.
The following table shows the result* obtained, working on a known amount of ben-
/oic arid in aqueous solution. As before stated above, this precipitate consists of
copper !•• . pre-ented l.y the formula <\}lI-< '<)() — < 'u— Oil.
Benzoic acid w»r«r»-»//n*//i an aqueous solution by Method III.
Henzoic a
ered
cUl rocov-
I'.v-
. pro-
mt.
Gravimet-
ric I..rlll()<l
<:iSC-<>pp.T
benzoate).
Titrating
xS Of
copper.
Qnm*. .
0.04
.04
.'•'.
.05
MX
Percrnt.
83.5
84.5
97.9
100.0
101 5
Per cent.
M. 1
7:.. 4
97.9
97.9
01
100.5
.10
.10
.14
.14
.20
.20
101.0
M&a
102.0
102.5
101.5
101.8
99.1
104.2
100.5
100.5
103.6
105.1
An attempt was made to apply this method to the determination of benzoic acid
in ketchup. A number of samples were treated as follows:
Three hundred grams were made up to 1,500 cc with saturated salt solution, allowed
to stand overnight, and filtered; 500 cc of the filtrate were acidified with sulphuric
arid and extracted with 3 portions of chloroform of 100, 50, and 50 cc. The extract
. \aporated in a current of air, dried over sulphuric acid, the residue weighed,
taken up in neutral alcohol, and titrated with tenth-normal sodium hydrate. Ihe
solution was then evaporated to dryness and benzoic acid determined gravimetnc-
ally. as desrril>ed above, by use of the copper precipitation method.
74
The results obtained by this method are as follows:
Determination of known amounts of benzoic acid in ketchups by Method III.
Sodium
benzoate
present.
Sodium
benzoate
found by
titration.
Sodium benzoate
found by copper
precipitation.
• •*
Gram.
Gram.
Gram.
0.258
0.229
0.116
.359
.322
.167
.127
.101
No precipitate.
.431
.392
.183
.198
. 14-.<
No precipitate.
.387
.328
.174
.107
.079
No precipitate.
.352
.314
.222
.332
.288
.167
.251
.230
.138
.210
.193
.126
.103
.082
No precipitate.
.355
.303
.150
.307
.286
.152
.324
.277
.142
.146
.119
No precipitate.
An examination of this table shows that when there was present less than 0.15
gram of sodium benzoate no precipitate was formed, and in such cases as did give
a precipitate all results were from 0.1 to 0.15 gram low. This seemed to indicate
that there was something in the ketchup extract which held back the precipitation
and showed conclusively that the method could not be used for such materials in
combination with present extraction methods.
It appeared probable that since the completeness of precipitation varied with
the alcoholic strength it might be interfered with by sugars, higher alcohols, oils
from spices, etc., and the following experiments were performed. The alcoholic
extract from 1 gram of spice was added to solutions containing 0.1 gram of sodium
benzoate and to blanks. Also 0.1 gram of sugar, glycerin, and dextrin were added
to similar solutions with the following results:
Determination of sodium benzoate in the presence of spices, sugars, etc., by Method III.
Substance added.
Sodium
benzoate
present.
Sodium
benzoate
found.
Substance added.
Sodium
benzoate
present.
Sodium
benzoate
found.
Allspice
Gram.
1 0.1
Gram.
0.0741
Sugar
Gram.
0.1
Gram.
0.0941
Cinnamon . .
:!
.0576
.055
Glycerin
.0
.1
None.
.0955
Cloves
:?
.0511
.1621
Dextrin
.0
.1
None.
.0854
t .u
1 .1
.0634
Check
.1
.(!'.)77
Red pepper
I .0
1 .1
.0477
.1293
( .0
.1478
These figures show that it is the presence of the spices which causes the failure
of this method for the determination of benzoic acid in such products. It is pos-
sible that it may be applicable to other materials.
PRECIPITATION AS SILVER BENZOATE (METHOD IV).
This method was suggested and elaborated by Mr. W. E. Hillyer.
The sample is extracted by means of ether as directed in Bulletin 107, page 179,
or by the method given by Dubois for the extraction of ketchups." The amount
J. Amer. Them. Soc., 1906, 28: 1616.
of -ubstance u-ed should be such that the portion subsequently extracted with ether
will contain approximately 0.1 gram of sodium benzoate. The ether extract, after
washing \vith water, is allowed to evaporate to dryness spontaneously, or the first
portion of the ether may be distilled and recovered. After drying completely the
re.-idue is taken up with a small amount of absolute alcohol, for the purpose of sep-
arating interfering substances as far as possible, and filtered into a small beaker.
The alcohol is neutralized with sodium hydroxid, evaporated to dryness, and redis-
solved in a few cubic centimeters of alcohol saturated with silver benzoate. The
solution i- tillered if not clear, washed with a few drops of aldehyde-free alcohol,
saturated with silver ben/.oate, and treated with from 10 to 15 cc of a saturated solu-
tion of -ilver nitrate in aldehyde-free alcohol. The precipitate is collected in a
gooch, care beiiiLT taken that the asbestos filter be so constructed as to afford as rapid
filtration a- p<—ible. The precipitate is then heated in a water-jacketed oven until
the ether is driven off, cooled, ami weighed.
t are must be taken to perform all operations as quickly as possible in order to
prevent the separation of silver oxid. The aldehyde-free alcohol mentioned above
i- about 95 P-T <-cnt by volume, and is prepared according to the directions given
in Bulletin 107, page '.Mi, with the additional precaution of distilling over soda after
treatment with meta-phenylene-diamin hydrochlorid. This method involves the
u.-e of a « on.-iderablr quantity of ether, which is objectionable because of its inflam-
mability and the tendency to di-.-olve sodium chlorid and other interfering substances.
Notwithstanding il> "iry results are rej>orted by Messrs. Hillyer and
Flander- in the following table. No other results obtained by this method, using
ether as solvent, w. • 1, though the precipitation of benzoic acid as silver ace-
•i>inu' chloroform as a pnlvrnt. was included in the work of several other eol-
d tu silver benzntitt in tnnnttn kttctni i> (Hillyer and Flanders).
Sodium
So.lilUll
Sodium
bm
ban
U'll/
fullMil.
i.MfHl.
found.
PITCH*.
PITCH*.
r<rcrnt.
Per cent.
n <M)
0. Oo»i
.004
.050
.001
.()-«
n.,<i
0
. 14«i
.101
.003
. t-k;
.127
.003
. 1UO
.100
.01)1
a. -_M7
m
". '_M7
a. 222
.(WO
o. US
«. l.Y.t
o I>ast three results »•>• K. T. FLmd.-r,; ..ttu-rs l,y \V. K. Hillyer.
Tln->.' n -ulis were obtained by extra* tin- and pn-cipitating as silver benzoate in
the ether residue f..llowm- Method II as -iv.-n ..n page 70. The figures seem to be
in every way comparable with tho>e obtained by Method II (see p. 71). Extraction
withetherappear- to b«- much less satisfactory than <-xtraction with chloroform, owing
to the removal of interfenn- .-ubstances by the solvent. These bodies are partially
removed by means of absolute alcohol, but this introduces an additional operation
ami the n-.-uli.- obtained are not as satisfactory as by extracting with chloroform from
a >olution saturated with sodium chlorid. In the table comparing Methods I and II
(p. 71 . i.- given the percentage of sodium benzoate precipitated as silver benzoate
from i he ,a Method II; that is, the liquid titrated under Method II was
evaporated to dryness and us«-«l as a starting point for the silver benzoate method.
In the following table are iim-n t he results obtained by the examination of a number
of samples of commercial ken-hups using this method. In all cases the benzoic acid
xtra. -ted by chloroform from a saturated sodium chlorid solution. Here, again,
it will be aeen that the r.-sults obtained by weighing the residue are in all cases slightly
76
higher than those given by titration, whereas the amounts determined by precipita-
tion as silver benzoate are almost identical with the amount obtained by titrating
the chloroform residue. This method is evidently worthy of further study. It is
much more tedious than Method II, but is of value for the purpose of checking the
results obtained by that method when a further confirmation seems desirable.
Determination of betizoic acid in commercial samples of tomato hichup by precipitation
as silver salt from chloroform extract.
Analyst.
Chloro-
form
residue
weighed.
Chloro-
form
residue
titrated.
Silver
precipi-
tate.
Analyst
Chloro-
form
residue
weighed.
Chloro-
form
residue
titrated.
Silver
precipi-
tate.
C P Wilson
Percent.
0.30
Per cent.
0.28
Per cent.
0.28
P. B. Dunbar
Per cent.
0.20
Per cent.
0 17
Per cent.
0.18
Do
11
10
.09
Do
.28
26
.26
Do
.19
.16
.15
Do
.09
.08
.07
Do
16
.14
.14
Do
.21
.19
.18
Do
20
17
16
Do
20
17
18
Do
.33
.32
.31
Do
.17
.15
.15
These samples were treated according to Method II, given on page 70. The residue
obtained by the evaporation of the chloroform extract was first weighed, then dissolved
in about 5 cc of neutral alcohol, the solution so obtained diluted with water and
titrated with saturated alkali solution. This solution when exactly neutralized is
evaporated to dryness, after which the benzoic acid was determined by precipitation
as silver benzoate.
THE DISTILLATION OF BENZOIC ACID FROM SULPHURIC ACID SOLUTION (METHOD V).
This method was suggested and elaborated by Mr. R. M. West," and depends on
the distillation of benzoic acid with steam after the addition of sufficient concentrated
sulphuric acid to insure the complete charring of vegetable tissue and prevent vola-
tilization of coloring matter and oil. The distillation is conducted by means of a flask
shown on page 21, the procedure being as follows:
About 10 grams of the sample are weighed into the inner flask of the apparatus,
1.5 to 2 grams of paraffin added, and the flask connected with the condenser. Ten
cubic centimeters of strong sulphuric acid are added through a drop funnel at a rate
sufficient to complete the addition at from two to three minutes, the flask is gently
agitated, to mix the contents thoroughly, and allowed to stand from five to ten minutes
after all apparent action of the sulphuric acid has ceased. About 150 cc of distilled
water are placed in the outer flask of the apparatus and the water slowly brought to a
boil and the boiling continued until 100 cc of the distillate have been collected.
The stopcock in the outer flask is left open until the water has heated sufficiently to
prevent the contents of the inner flask being drawn into the outer flask.
The distillate is filtered into a separatory funnel and the original receiver and filter
are washed with two portions of water of about 10 cc each. The distillate is then
extracted with three portions of ether of 50, 30, and 20 cc, respectively. The com-
bined ether extracts are washed repeatedly with water until a 25 cc portion requires
not more than 0.10 cc of decinormal alkali for neutralization. The ether extract is
then distilled to small volume, after which it is evaporated before a blast of air, dried
in a desiccator to constant weight and weighed. The residue is also dissolved in
neutral alkali, using phenolphthalein as indicator.
The results obtained by titration agree closely with those obtained by weighing.
Excessive foaming is likely to occur when the steam begins to pass into the inner
flask. This may be caused by distilling too soon after the addition of the acid, by an
insufficient amount of paraffin, or by an unusual amount of sugar in the ketchup.
Care must be exercised to prevent the foam passing into the condenser.
J. Ind. and Eng. Chem., 1909, 1: 190.
I i
The distillation should be conducted at such a rate that 100 cc of the distillate may
be obtained in from twenty-five to thirty-five minutes. Occasionally some paraffin
is carried over mechanically, and this may usually be removed from the surface of
the distillate by means of a wire or glass rod.
The following results were obtained on ketchups containing a known amount of
sodium benzoate:
Determination of sodium benzoate in ketchup by Method V (West).
Sodium
benzoate
added.
Sodium benzoate
found.
weight.
titration.
Mr CM*
0.00
.10
.25
.50
Per cent.
0.01
.09
.25
.47
Per cent.
0.01
.10
.24
.47
THE DETECTION OF TINNAMIC ACID.
The statement ha.- ir« (|ucntly Keen made that cinnamic acid is being used for the
• \ai i»n "f foods, es|>ecially in the case of tomato ketchup. The claim has often
been made by those interested in the preservation of ketchup with benzole acid that
tin- i'ft-i-in-e of cinnamic acid could not be detected and that firms claiming to use
no preservative were preserving with that substance. Two qualitative methods for
the deteeii..n of eiiuiamic acid, differing slightly from each other, were elaborated by
P. 1'.. iMmbar. I loth of these methods depend u|x>n the well-known fact that cin-
namic acid is oxidized to benzaldehyde by dilute chromic acid mixture.
Method !.—( >ne hundred grams of ketchup were treated with 100 cc of water and 5 cc
of -iilplniii' a' i'! I to > and the mixture extracted directly with three portions of
chloroform, u-inu' "><>. 25, an<i :>eetively. The chloroform extract was made
alkaline \\ith ammonia ami evaporated to dryness on the water bath. The residue
\\a.- di--ol\ed in a -mall amount of hot water, filtered, again evaporated to dryness,
and heated to boiling uiih :> cc "f dilute chromic acid mixture (1 part of dilute sul-
phuric acid -aturat.d with potassium bichromate and 7 parts water). The odor of
ddehyle i> -tron<_:e-t when the mixture is cooled until the fumes of sulphuric
acid arc n.", longer apparent .
Method 2.— Two hundred grams of the ketchup are diluted to 500 cc with water,
allou !,-, and filtered. An aliquot portion of the filtrate, 250 cc or more, is
acidified with •"> cc of -ulphuric acid (1 to 5), extracted with chlorofprm, and the
remainder of the operation conducted as under Method 1.
The second method appears to be slightly more delicate than the first, although
\vii !i either it was possible to detect cinnamic acid in tomato ketchup when present to
an extent of 25 ing per kilogram.
This reaction is also «;iven by cinnamic aldehyde. The method, therefore, does
not distinguish of itself between cinnamic aldehyde, resulting from the use of cinna-
mon as a flavor and cinnamic acid used as a preservative, except that the amount of
cinnamic aldehyde present in the commercial ketchups examined was not sufficient
to give a reaction. If cinnamic acid were present in the ketchup, it would be de-
tected by the methods used for the detection of benzoic acid. Cinnamic aldehyde,
on the other hand, would not be detected by the methods suggested for benzoic acid.
The benzoic-acid residue obtained by the evaporation of the chloroform extract may
be examined by the cinnamic-acid methods described.
The iM-rmicidal and antiseptic properties of cinnamic acid were investigated by
( i . \V . St iles, who found them to be very much lower than those of benzoic acid. The
preservation of a food, therefore, would require a much larger percentage of cinnamic
78
acid than benzole acid. In fact, the antiseptic properties of a saturated solution of
cinnamic acid are so slight that this substance would probably not serve as a preserv-
ative for foods.
A method for the separation of benzoic acid and cinnamic acid by precipitation of
the latter with manganous salts a was tried unsuccessfully by Mr. Dunbar, who was
unable to secure a precipitation of either benzoate or cinnamate of manganese in
dilute solution. As is to be expected, Mohler's and Peter's reaction also give the
same end reaction in the presence of cinnamic acid."
REPORT ON TEA, COFFEE, AND COCOA.
By A. G. WOODMAN, Associate Referee.
The work of the referee for the past year has been limited to a study of methods for
the determination of caffein and caffetannic acid in coffee, extract in tea, crude fiber
and starch in chocolate, and sugars in milk chocolate. Twenty-two samples were
prepared and sent out to those who had expressed a willingness to collaborate, ten on
tea and coffee and twelve on cocoa products. These were accompanied by the
following directions and a letter of transmittal :
CAFFETANNIC ACID.
(a) Krug's method. — Proceed as directed in Bui. 107,- p. 155. (Note that the formula
for lead caffetannate should be Pb3(Ci5H15O8)2 as in Bui. 107, Rev.) Save the filtrate
for the determination of caffein. After weighing the lead caffetannate determine its
lead content as follows: Digest with aqua regia, add sulphuric acid, heat to fumes,
cool, dilute, add alcohol, settle, filter, ignite, and weigh as lead sulphate. Calculate
as per cent of lead .
(6) Method of Trillich and Gockel.b— Boil 3 grams of coffee one-half hour with water,
filter, and repeat this treatment on the residue three times. The united filtrates are
made up to 1,000 cc. To 400 cc add 1 cc of basic lead acetate solution and allow to
stand overnight. Filter, wash, decompose the precipitate with sulphuretted hydro-
gen, filter from lead sulphid, evaporate to dryness, and weigh.
CAFFEIN.
In the filtrate from the lead caffetannate precipitate the lead with hydrogen sulphid,
filter, and remove the excess of hydrogen sulphid by boiling, concentrating the solu-
tion, if necessary, to about 100 to 150 cc. Add tenth-normal potassium iodid solution
of iodin in excess, filter through a little glass wool and determine the excess of iodin
with tenth-normal sodium thiosulphate.
1 cc tenth-normal iodin equals 0.00485 gram caffein. c
EXTRACT IN TEA.
(a) Follow the provisional method as described in Bui. 107, p. 149.
(6) Follow the method proposed by Doolittle and Woodruff (Bui. 105, p. 48).
CRUDE FIBER (SAMPLE A).
Proceed as directed in Bui. 107 under "VI. General Methods," 11, page 56, except
that the fiber is filtered and weighed on a paper. The sample should be pulverized by
grinding with ether as described in the succeeding paragraph.
CRUDE STARCH (COPPER-REDUCING MATTERS BY DIRECT ACID HYDROLYSIS), SAMPLE A.
Weigh 4 grams of the material if unsweetened, or 10 grams if sweetened, into a small
wedgewood mortar, add 25 cc of ether and grind with a pestle. After the coarser
material has settled decant off the ether together with the fine suspended matter on
«Scoville, Amer. J. Pharm., 1907, 79 [12]: 549-551.
&Zts. Nahr. Genussm., 1898, 101.
cGomberg: J. Amer. Chem. Soc., 1896, 18: 331.
79
a I L cm, blue ribbon, S. and S. paper. Repeat this treatment until no more coarse
material remains. After the ether has evaporated from the filter, transfer the fat-free
iv- id in- t<> th»> mortar by means of a jet of cold water and rub to an even paste, filtering
on the paper previously employed. Repeat this process until all sugar is removed.
1 ii i lie case « >f sweetened products the filtrate should measure at least 500 cc. Conduct
tin- hydn>ly-is of the residue as directed for "Starch" under "VI. General Methods,"
8 (a), page 53, Bui. 107, Rev., except that after neutralizing with sodium hydroxid,
add •"> cc of basic lead acetate solution (prepared as directed under "VI. General
Methods, " 6 (6), (1), page 40) before completing the volume to 250 cc. To 100 cc of
the filtrate add 1 cc of 60 per cent sulphuric acid, filter off the lead sulphate and deter-
in iii'- n -d iic • in<4 matters in 25 cc of the filtrate as directed under "VI. General Methods, "
i • !• Reducing Sugars, 7, (6), (2), page 49. Determine copper by the direct weighing of
cuprous oxid, 7, (c), (6), page 53.
SUGARS (SAMPLE B).
cmine tlie lactose and sucrose as described 'by Dubois.o
Tin- amount of work requested was purposely made small in order that it should
not prove burdensome, but in spite of this results were received from only four chem-
i - 1 . two on cocoa products and two on tea and coffee.
TEA AND COFFEE.
The results on tea and coffee are shown in the following table:
Cooperative work on coffee and tea.
Analyst
* 'atlr tan tiir acid.
Caflein.
Extract in tea.
KniK
method.
Trillion
and
Ofekel
method.
Krauch
method.
Doolittle
and
Woodruff
method.
I 0. Woodruff, New York
\ i; \V(xxlman, Boston...
Percent.
12.41
11.05
12.17
11.25
11.49
12.27
12.23
12.27
12.28
11.19
i .v_»i
Percent.
14.42
17. Id
15.20
16.26
1 4. L'S
16.09
Per cent.
0.38
.33
.29
.53
.38
Per cent.
Per cent.
52.95
51.50
51.69
50.92
51.42
45.90
45.64
(Whole)
40.74
(Ground)
vn:<
7.80
v.v,
8.22
.68
.75
.88
.74
.78
39.60
42.15
40.82
49.72
50.16
50.28
50.99
Mark Millikin Hamilton Ohio
.81
11 09
11.86
10.11
9.33
8.8
.67
1.06
44.8
42.7
COMMENT BY MR. WOODRUFF.
nirthfxtfor caffetannic acid.— (I) The water must be kept to constant volume
durin- thirty-*! \ houn' di-e-tion.
I'nlrss u'n-ai can is used, the addition of lead acetate to the hot alcohol solution
will cause violent ebullition and partial loss of contents. A safety tube helps to
oven-., me this difficulty.
(3) In deiennining the lead content of the caffetannate it is advisable to filter the
•annaf •• through a tared gooch. This will allow of digestion of contents in nitric
acid and precipitation of th.- lead with sulphuric acid without using a filter paper the
• •arbon of which does not completely oxidize and produces a blackening of the lead
sulphate. The final w.-iirhini: of the sulphate should also be made in a gooch.
a J. Amer. Chem. Soc., 1907, 29: 560.
80
Caffein method.— It is suggested that the caffein iodin precipitate does not form
immediately and that the low results are due to filtering and titrating the solution too
quickly. Other work indicates that after the iodin is added the flask should be
allowed to stand in an ice chest overnight before titrating.
Much better results can be secured by Gomberg's original method for caffein,
iven in the Journal of the American Chemical Society (1896, 18: 331), and modified
Extract 2 grams some time with four portions of water, cool, and make to 1,000 cc.
Treat 500 cc "with 15 cc of saturated lead acetate solution, let settle, filter, remove
lead with hydrogen sulphid, boil off excess of hydrogen sulphid, divide filtrate into
two parts, concentrate each to 50 cc, add 0.2 cc of concentrated hydrochloric acid to
one and 6.5 cc of acetic acid to the other, cool to 15° C., add 20 cc of tenth-normal
iodid solution, stopper flask, and let stand in ice two hours, filter on a gooch. Caffein
does not precipitate unless mineral acid is present, so the acetic acid portion shows
if any other materials are present which would precipitate with the iodin solution.
If any absorption of iodin is found in the acetic portion, it must be deducted from
the titration containing mineral acid. The difference represents the iodin used up
in the formation of the periodid of caffein: 1 cc of tenth-normal iodin equals 0.00485
gram of caffein. Using this method, 0.78 per cent of caffein was obtained from the
coffee reported.
Krauch method for extract in tea. — The bulk of sample (20 grams) makes complete
removal of water-soluble substances almost impossible. The absorption of water by
large filter paper and on surface of flask during weighing is also a serious objection to
the method. If sample is ground, filter paper is clogged and filtration prevented.
Doolittle and Woodruff method. — Care should be used to keep the entire sample in
the boiling liquid during extraction or low results will be obtained. Any loss of water
by evaporation should be replaced.
NOTES BY REFEREE.
The discrepancy in the results obtained by the two analysts with the Trillich and
Gockel method is due principally to the fact that Mr. Woodruff used 5 cc of basic lead
acetate in the precipitation instead of 1 cc, as prescribed in the method. Determina-
tions made by the referee on the same sample gave 10.08 per cent where 2 cc of basic
lead acetate was used and 12.04 per cent when 4 cc was used. The lower results
obtained by Mr. Woodruff in the caffein estimation may have been due to the greater
volume of solution in which the caffein periodid was precipitated, he using a volume
of 100 to 150 cc, while the referee employed a volume of 20 cc. Experiments made
by Mr. W. C. Taylor in the writer's laboratory have shown the necessity for concen-
trating the caffein solution to small bulk.
The determinations made of extract in tea by the referee convinced him of the
great superiority of the Doolittle and Woodruff modification over the Krauch method
as regards convenience, time, and liability to error.
COCOA PRODUCTS.
The following results were obtained from the collaborating chemists on cocoa
products:
Cooperative work on cocoa products.
Analyst
Plain chocolate
(Sample A).
Milk chocolate
(Sample B).
Crude
fiber.
Crude
starch.
Lactose.
Sucrose.
G. M. Bartlett, Boston. . .
Per cent.
2.25
2.50
2.65
2.84
2.69
Per cent.
11.61
9.69
9.97
10.37
10.03
Per cent.
5.05
4.83
5.25
5.13
Per cent.
25.72
27.83
27.32
27.02
R. W. Hilts, Philadelphia
A. G. Woodman, Boston
81
COMMENTS BY ANALYSTS.
G. ^f. Bnrtlrtt: The <•« inversion of the starch was carried out as outlined, no difficulty
occurring in tin- procedure. The aliquot for precipitation was obtained as follows:
After converting, neutralizing, and adding basic lead acetate the sample was made
u p to volume at about 35° C. To 100 cc at this temperature was added the 60 per cent
<>f sulphuric acid, cooled so that the volume of liquid contracted to 100 cc. It was
necessary to n.ol only to about 18° C. The sample for precipitation was taken when
the liquid hud contracted to the mark. Two determinations were made — one by pre-
cipitating by the \\alker-Munson method (J. Amer. Chem. Soc., June, 1906,) and the
other following the method in Bulletin 107. The latter gave 11.83 per cent of starch.
In determinm- crude liber the electric stove was used for boiling the 1.25 per cent
crude liber, even though it is not to be ignited, and would prefer filtering on a weighed
platinum <_roorh filter.
In calculating the suirar in chocolate by Dubois's method" it seems illogical to
multiply (0—6) by l.Oor (x equaling the volume obtained by dissolving sugar in
HH> cc "i her than by 105 plus the increase in volume due to the solution of
the mgar. Tin- a- tually makes but little difference in the result, but the following
ment of tin- formula -e.-ms preferable:
(a-6)(l05+ ff)
'• = per cent sucrose.
111-.,
Where , ' increase of volume ..\\in^ loth,- solution of t ho sugar in water. In calcu-
• the l.ido-.- ihe compleie formula read.-: Per cent. lactose=CX4Xl.llX1.05£
volun f solution when the sugar is dissolved in 100 cc.
A'. I! //•'' The sampli-4 on arrival were immediately placed in glass-stoppered
bottl. •- I1.. : '•• removing portions for analysis they were rubbed down to a coarse
powder in a lur_'e porcelain mortar and mixed as well as possible. This was done
quite ruptdl), both toa\oid (xtteible changes in moisture content and to avoid forma-
tion of a p.c-ty maw.
Crude liber First filtration was made on closely woven linen in a 4-inch Biichner
funnel \\iih liL-lit sueti..n. Second filtration was on a llcm U & A ashless filter paper
without .-net ion. lloth tiltratimis were rapid and satisfactory.
lite are multiplied by the far tor 1.01 to correct for the dilution of 100 cc
of the M.lution by th- lllphuric arid.
The method of Duboiswas followed exactly. It was necessary in extract-
ing \\ith uuterto break up \\ ith a u'la.-s rod the compact cake left after centrifuging the
la.-t time with 'ju.-olme. In \.-r-i--ns were made in the cold (50 cc-f-5 cc of hydro-
chloric acid, being allow. -.| to stand over night. All volumes were adjusted at 20° and
all poluri/.ution- \\ere made in jacketed tube at exact temperatures. The actual
pohiri-cop.- rea ragc»s of four t<> five close readings) illustrate the very great
influence that small ditTen-in .- in readinu's have upon the results, in these dilute
solution*, in .pit,- ,,f this fart, the method seems to be satisfactory and convenient
for judging milk chocolates. The methods are, in my opinion, in as simple a form as
possible, and can not well be improved.
KM M\I\1KM>ATI()NS.
In view of the Muall number of collaborators it is hardly possible for the referee
to make any formal recommendations based on collaborative work. It is evident,
however, that the Mudy of certain of these methods should be continued by the
aaaociatio: lly the cai'foin estimation and the determination of sugars in
chocolate. There would appear to be no reason why the determination of extract in
tea as outlined by Doolittle and Woodruff should not be substituted for the cumber-
some Kraurh method. The experience of the referee on numerous samples of cocoa
products suggests that the requirement for filtering and weighing the crude fiber on a
aj. Amer. Chem. Soc., 1907, 29: 556; see also Bui. 107, Rev., p. 256.
T.-.r,::; Hull. l£i— 0!) 0
82
paper should be omitted, as the determination can be made more conveniently on a
gooch crucible as ordinarily used.
Attention is also called to the accompanying paper involving some of Mr. \V. C.
Taylor's work on caffetannic acid and caffein.
ESTIMATION OF CAFFETANNIC ACID AND CAFFEIN IN COFFEE.
By A. G. WOODMAN and W. C. TAYLOR.
In connection with an examination of the methods for coffee analysis the writers
have made a study, in the limited time available, of the provisional methods for
determining caffetannic acid and caffein, especially the former.
CAFFETANNIC ACID.
Experience has shown that with the directions as given at present it is practically
impossible to obtain concordant results or a lead caffetannate of constant composition-
It has been the general experience of those who have worked with the Krug method
that it is tedious in the extreme, and, furthermore, that the composition of the so-called
lead caffetannate obtained varies with the conditions of precipitation. It was our
purpose to ascertain if possible the source of some of these difficulties.
It was seen early in the work that variations in the amount of lead acetate used
for precipitation gave variations in the proportion of lead caffetannate obtained, as
well as in its content of lead. This is shown in the following table, in which the
determinations were made on aliquot portions of a coffee infusion and varying amounts
of saturated lead acetate were used, all other conditions being kept constant.
Determination of caffetannic acid, using varying amounts of lead acetate.
Caffetan-
Lead
nic acid bv
Lead in
acetate.
Krug's
factor.
precipitate.
cc.
Per cent.
Per cent.
1
7.66
50.04
2
9.73
50.35
4
11.14
6
11.70
48.31
8
12.28
55.16
10
14.28
55.93
The averages of several results are stated in each case, although the results showed
very considerable variation. While too much reliance can not be placed on these
figures, owing to variations among themselves, they show the necessity of using a
definite amount of lead acetate for the precipitation.
Another source of error is the difficulty of washing the lead caffetannate free from
lead acetate. Those who have attempted it know the tediousness and the difficulty
of washing the precipitate on the filter. It is of course necessary to use alcohol of 90
per cent strength in washing, on account of the solubility of the precipitate in water
or dilute alcohol. On the other hand, the lead acetate which is to be removed is only
slightly soluble in 90 per cent alcohol. Hence it will be readily seen that it is practi-
cally impossible to wash the bulky precipitate on the filter. It is true, also, that when
the wash water no longer reacts for lead the precipitate is not necessarily free from it,
since owing to its character the wash water easily forms channels and does not wash it
thoroughly.
After numerous experiments, washing by the centrifugal machine was tried, giving
several treatments with 90 per cent alcohol in the tubes of the centrifugal before trans-
83
ferring to filter paper. This method gave results which were in much closer agree-
ment, a- .-hown by the following results on the same sample:
Per cent cat'fetannic acid 9.69 9.69 9.57 9.40
Per cent lead 48.28 48.35 48.01 48.71
Teefa made "ii a considerable quantity of the lead caffetannate washed in this
way .-howed it to be free from fat and nitrogen.
It would seem as if the long pnx-ess of digestion with water and with alcohol pre-
scribed by Krug could be materially shortened. In much of our work extracts of the
(MII...- \>. . •;• prepared by the use of a shaking machine, shaking the sample for an
hour with water and half an hour with alcohol. Results obtained in this way agree
very well with those obtained by the official method of digestion, although there is
e\ idem -c to -how that neither method extracts all of the caffetannic acid.
Regarding the vexed question of the composition of caffetannic acid, we seem not
miieh nearer a -< -tt lenient . The views previously held, which seem to lead to the
formula for a di-glucosid, have been clearly set forth in Bulletin 105 by Mr. Howard.
Lack of time prevented any extended investigation of this problem, but an endeavor
was made to confirm the work of Cazeneuve and lladdon in regard to the di-glucosid
formula f.-r < arietannic arid. \\ e were unsuccessful, however, in preparing more
than traces of the osazone prepared by them, although carrying out the experiments
1 v in the manner prescribed. In this connection the paper recently published
by (i< t, in which the correctness of the Tazeneuve and Haddon
formula i- que-t i»u<-«l < M>M. i -tales that he was unable to form more than a few small
cry-tal- ..f the o-a/.me, which he was unable to isolate and considered that it was
due t" -•me impurity in the • -aiTetannic acid. The caffetannic acid is considered
to be a mixture of chlorogenic and coffalic acids. Numerous derivatives
ami -all- of the-e arid- have been prepared and are described by the author to sup-
p..n hi- content
Tin- methyl f..r carrying out the Krug test which we found to work most satisfac-
torily may be summed up as follows:
me finely ground coffee (passing 0. 5 mm sieve), add 10 cc of water and shake
i h»ur in a mechanical -halting device. Add 25 cc of 90 per cent alcohol and
.-hake again f"r half an hour. Filter and wash with 90 per cent alcohol. Bring the
united lili rat.- and about 50 cc, to boiling and add G cc of saturated lead
- parate tin- precipitated lead caffetannate by means of a centri-
intini: the -upernatant liquid through a tared filter. Repeat the centrifu-
•carineiit tui- •«• with !M> per cent alcohol, decanting each time through the filter.
the preen he filter and wash free from lead. Wash with ether,
dry at iwj.and wciirh. The weight of precipitate multiplied by 0. 51597 gives the
lit ..f cai'fetannic acid.
CAFFEIN.
In the work on caffein a comparison was made of three methods: The official
meth.nl (Bui. H>7, p. IMi; the titmtion of caffein with iodin, according to Gom-
in the tiltrate from tin- lead caffetannate; and the method proposed by Gorter
in tin- paper previously mentioned.
Our attention ha.- been directed by Mr. C. D. Howard to a source of error in the
pp.vi-ional methyl, ari-ing from the fact that the extraction with dry chloroform
of the -aiid-ma-ne-ia mixture does not yield the whole of the caffein. Mr. Howard
says in his letter:
My practice ha- been to add to the concentrated filtrate, contained in a tin-foil dish,
about "10 Drains of sand and 1 gram of magnesium oxid, evaporate and dry in the water
The brittle ma-, easily stripped from the dish, I grind finely,
in a paper ext
oven for a short time. l lie hrime mass, easny sinppeu uum tue ui<-n, ± &uim m±mj,
place in a paper extraction cartridge, and extract for ten to twelve hours in the usual
aAnnalen, 1908, 359: 217.
84
Now my recent experience has been that if the extracted residue be shaken with
water and the latter further extracted, an additional quantity of caffein, sometimes
equivalent to 10 per cent of the whole, is thus obtained.
Our experience has been a similar one. To illustrate by a specific instance, the
residue from twenty hours' extraction with chloroform was shaken with water, filtered,
and the aqueous solution extracted four times with chloroform, One-half the chloro-
form extract was tested for caffein, and gave positive tests with Wagner's reagent and by
the "murexid" test. The other portion showed by a Kjeldahl determination 0.0035
gram of caffein, corresponding on the whole sample to about 10 per cent of the amount
present.
Gorter finds that a considerable proportion of the caffein in coffee is present as a
double salt, the potassium caffein chlorogenate, from which the caffein is extracted
by dry chloroform only with great difficulty. Whether or not this be the cause of the
incomplete extraction, it is evident that the official method needs revision.
Preliminary experiments with the Gomberg method showed it to be practicable for
the small amount of caffein (approximately 20 mg) that would be present in the
filtrate from the lead caffetannate, providing the volume of solution were not over 25
cc. On account of the slight solubility of the caffein periodid in the wash water it
was found best in working with this small amount to suck the precipitate as dry as
possible on the gooch filter and not to wash it. Determinations made on 20 mg of
caffein in 25 cc of water in this way gave from 98 to 99 per cent of the caffein present
Numerous experiments made on the filtrate from the lead caffetannate precipitate by
precipitating the lead with hydrogen sulphid and evaporating the filtrate gave fairly
concordant results, which were uniformly lower than those given on the same coffee
by the other methods for caffein. It was observed that the variations in amount of
caffein as determined in this way corresponded roughly with the variations in amount
of caffetannic acid as found by the Krug method. Whether these variations and low
results are due to incomplete extraction of caffein by the process of digestion employed
in the Krug method is a matter which we expect to investigate further.
Gb'rter's method was not given a thorough trial. As far as the work goes it has been
-uti-factory, and the method is worthy of further trial by the association. It reads
briefly as follows:
Eleven grams of the finely powdered coffee are moistened with 3 cc of water and
after standing a half hour extracted for three hours in a Soxhlet extractor with chloro-
form. The extract is evaporated, the residue of fat and caffein treated with hot water,
filtered through a cotton plug, and washed with hot water. The filtrate and washings
are made up to 55 cc, 50 cc pipetted off and extracted four times with chloroform.
This chloroform extract is evaporated in a tared flask and the caffein dried at 100°
and weighed.
In the determinations made it has never been possible to weigh the caffein directly
on account of impurities, the caffein having been calculated from a determination of
nitrogen in each case. From the work done there seems to be a strong probability that
a combination of the Gomberg and Gorter methods will prove to be the best and most
convenient process for determining caffein in coffee .
FRIDAY— MORNING SESSION.
REPORT ON THE DETERMINATION OF NITROGEN.
I'.y I'IIAKI.KS L. PENNY, Referee.
An a poll .-y i* due the association for failure to carry out the instructions of 1906 con-
<•( -n i i i ig t he permanganate im -t In >« Is . A in >ther phase of the nitrogen question considered
Li-i year ami di-cu<sed in correspondence with the National Fertilizer Association
• ••1 to i>uiwci-h in importance and urgency all others, namely, the determination
of total nitrogen in mixed fertilizers to which nitrate of soda is added. With a view
to making a thorough investigation of this subject, the following instructions were sent
h members of thU association as W«TC supposed to be interested in the work and
to in. .re than I maly-i- nuiifd by the secretary of the National Fertilizer
Association :
INSTRUCTIONS.
<'h<'tiii-i- <• - >peratin'_: in this work are requested to ^ive t hoir attention exclusively
to ni.-tli.-.l- applicable in the presence of nitrates. Mulletin 107, page 7 (c), page 8 (d),
I (h). I here seema to be urgent need of this investigation, especially
ih.- pn — -iii iif-hods used to determine nitrate nitrogen have been formally
call.-d in question by the repreeentatiyee of great commercial interests.
samples are sent h. -.- it is thought that each analyst, by calculating the
nitrate u-ed from a volution of nitric acid carefully compared with his own standard
alkali and acid, may _;••' more reliable results, through the balancing of possible errors,
than in -in u-inu' a common Mil.-ta--
t the .-i.urce ..f nitrate u-ed b«> a solution of pure nitric acid, about fifth normal,
nio-t ie iirately tilrat.-d airain-i the -tandard alkali used in the Kjeldahl work. In
ea« li case measure accurately into the digestion flask enough of this nitric acid to con-
tain :'.D to "><> niilligninis of nitr
Follow in linu' the water in the nitric acid and without
neiiirali/.ini;.
l-'.-lloW likewise inetho.1 (d).
(3) Follow met h< K! (g), adjust in-: the proper amount of water, distilling first with
i.i. then with caustic >oda and water added to the residue in the distillation
Ma-k. collect ini: KffMinih- di.-i illaie< and titrating each separately.
(4) Similarly follow method ih , beginning in second line "in a distillation flask,"
If the yield ,,f nitrogen is less than the calculated in (1), (2), (3), or (4), test the resi-
due in distillation Mask for nitr.
- in (I), (2), (3), (-».) with the preliminary addition of 2 grams of cane
r to the digestion lla-k.
U in U'. <-'. (:i), (4) with the preliminary addition of 1 gram, accu-
rutely u.-i-hed, ,,f -r-anic nitn^en substance, such as dried blood, fish scrap, or
tanka-e. to the di-.-ticn flask. In a separate operation treat 1 gram, accurately
weighed, Mt i hi- added .-ubstuiice similarly except that no nitrate be present; that is,
analy/e the added -ubsumce alone according to (c), (d), (g), and (h). Any nitrate-
free "mixed fertili/.er may be used for the added substance.
While the above plan "entail- much work, it is hoped that a large number of chemists
will ted 1 1 1,-ast some of the several official methods in question, if not all. Ihe figures
for each separate determination should be reported and the precise method pursued
should be fully explained. The results of any other plan of studying the nitrate ques-
tion, rarried «mt by chemists at their own suggestion, will be welcomed.
(85)
Answers were received from five chemists engaged in official work and three engaged
in commercial work, viz, Messrs. E. M. Bailey, New Haven, Conn.; F. B. Carpenter,
Richmond, Va., reporting work of Mr. W. D. Cooke; H. S. Lansdale, Buffalo, N. Y.;
C. B. Morrison, New Haven, Conn.; J. Bernard Robb, Richmond, Va.; B. F. Robert-
son, Clemson College, S. C.; Paul Rudnick, Chicago, 111., and T. C. Trescot, Wash-
ington, D. C.
It is regretted that cooperation has not been more general, but the work required
seemed burdensome, and doubtless few could find the time to engage in it. Several
of the cooperating chemists, however, have shown extraordinary industry, reporting
an amount of work seldom equaled in voluntary investigation of this sort. The ques-
tions involved in the plan of work are not less than 14; hence analytical results
are too complicated to admit of convenient tabulation. It seems better, therefore, to
deduce from the analytical figures the answers to the several questions.
Before judging the results it is well to bear in mind the reasonable expectation of
agreement or accuracy from a number of chemists working on the same subject. I ,ast
year on the simpler problem of determining nitrate-free nitrogen, the work of over
50 chemists, possibly the largest number of the association ever engaged on a single
question at one time, seems to indicate that about 98 per cent of the truth is the average
with present methods and present personnel. Then in the more difficult question of
nitrates and the separation of several forms of nitrogen, this expectation would seem
to be at least high enough. Thus methods for nitrates that give as much as 98 per cent
of theory are at least as accurate as the average results on nitrate-free substance. While
this limit may easily be exceeded by experienced and skillful individual analysts, it
is useless to deny that it is not exceeded by the average results.
The analysts used chiefly as their source of nitrate nitrogen amounts of their own
standardized nitric acid containing from 28 to 160 rugs of nitrogen. The results obtained
are reported as percentages, the basis of which is the amount of nitrogen that should
have been obtained.
The questions involved follow, with the answers deduced from the figures of the
several analysts.
Percentages of nitrogen recorded based on amount present, using different methods.
[Is nitric acid, in the absence of organic matter, reduced to ammonia without loss?]
(1) BY METHOD (C).
Analyst.
Number
of deter-
mina-
tions.
Range of
determina-
tions.
Average.
Bailey...
2
Per cent.
74.5-82 9
Per cent.
78 7
Cooke
5
94 o_96 0
95 0
Lansdale
2
97 4_98 6
98 0
Morrison . . .
2
86 6-86 7
86 7
Robb
8
87 0-96 0
91 4
Robertson...
4
99.2
Rudnick o(Thio.)..
4
61 1 76 9
67 4
(Zn)
4
80 8-86 8
83 2
(Zn+Thio.)
4
76 4-82 5
79.8
(2) BY METHOD (D).
Bailey...
2
74 8- 75 7
75 3
Cooke
3
96.0- 96.0
96.0
Lansdale
2
95 7- 97 4
96.6
Morrison
1
76 4
Robb
3
93 0- 95.0
94.0
Robertson
4
98.5
Rudnick
3
55 0-100 0
76 0
o Analytical work reported by F. W. Rudnick throughout the report was done by F. Fenger, K. J. Mon-
rad, and A. C. Johnson.
87
M/I .s <>/ n itroi/fit worded based on amount present, using different methods — Cont'd.
(3) BY METHOD (G).
[Distilled of! imiRni'sui followed by soda, the sum of both distillates being used.}
Analyst.
Number
of de-
termina-
tions.
Range of
determina-
tions.
Average.
0
Per cent.
99 8-100 0
Per cent.
1
2
2
98 1 98 9
QO C
KoM.
g
89 0 98 0
Kll.lmr;-.
3
54 q 95 o
76 8
(4) BY METHOD (II).
2
2
12
95. 6-99. 3
95.4-97.2
91.6-99.9
97.5
96.3
95.8
| /.<•• /• ' / 1" niniiionin irittmut loss in the presence of 1.4 to 2 grams of sugar?]
(5) BY METHOD (C).
H uI.".
2
2
3
4
8
4
35. 6-49. 5
39.6-63.9
61.0-63.0
42.6
51.8
61.7
100.0
79.4
98.0
71.7-89.9
(«;) BY METHOD (D).
2
40 0-42 1
41 1
2
24.8-44 2
34 5
3
61. 0-63. 0
61 7
99 5
8
70. 0-86. 2
76 7
4
99 0
(7) BY METHOD (<!).
•:-.l off maffnraia followed by soda, the sum of both distillates being used.]
|
2
95. 4- 98. 9
97.2
M..II
2
98. 0- 99. 3
98.7
liudnirk
3
103.6-111.2
6106.6
V METHOD (II).
Bailey
2
97. 0-110. 0
103.5
Morrison
2
95. 8- 98. 1
97.0
[h the sum of nitnujcn in nitric arid and nitrogenous organic matter fully recovered as
ammonia?}
(9) BY METHOD (C).
Bailey
2
79. 2-86. 5
82.9
Morrison
2
84. 0-87. 1
85.6
Rudnick ( Thio )
3
77. 4-82. 4
80.7
(Zn-f-Thio )
4
66. 6-74. 7
70.6
o In the presence of 1 pram of a nitrate-free mixed fertilizer instead of sugar.
fc In thiw d,.t,.nnin;U ions I ,y i h.- I 'Isch method, the small quantity of water undoubtedly caused spurting
Of alkali suflk-ient to drive it over into the condenser. The bumping was terrific. Rudnick.
88
Percentages of nitrogen recorded based on amount present , using different methods — font' d .
(10) BY METHOD (D).
Analyst.
Numl)er
of de-
termina-
tions.
Range of
determina-
tions.
Average.
2
Per cent.
77. 5-81. 0
Per cent.
79. 3
2
77. 3-86. 5
81.9
Riidnick
8
42. G-T3. 7
So. 0
[Is any of the nitrogen in nitrate-free and ammonia-free nitrogenous bodies obtained?]
(11) BY METHOD (G).«
Bailey 2
1.9-2.4
Morrison
2. 4-3. 5
3.0
o These figures were obtained distilling with magnesia only. Soda being added and distillation con-
tinued, the following additional percentages were obtained: Bailey, 8.3 to 9.3, average 8.8; Morrison, 8.3
to 11, average 9.7. These four determinations were made on cotton-seed meal containing 0.0739 gram of
nitrogen, on which nitrogen the percentages are based.
(12) BY METHOD (F).
Bailey and Morrison, who alone worked on this question, report that distillation was
rendered impossible by excessive frothing.
[How complete is the liberation of ammonia when distilled with magnesia?}
(13) BY METHOD (D).«
Analyst.
Number
of de-
termina-
tions.
Range of
determina-
tions.
Average.
Bailey
4
Per cent.
92 2-97 9
Per cent.
94.3
Cooke
2
19. 0-22. 3
20.7
Morrison . .
4
93. 0-97. 9
95.8
Robb
G
15 5-31.6
22.4
Rudnick
g
42 4-73 7
63 8
a These figures represent the fraction of total ammonia liberated by magnesia, the complement lacking
to make 100 per cent having been liberated by soda. Thus, Cooke's lowest result was 19 per cent distilled
from magnesia and the remaining 18 per cent was obtained by adding soda solution and continuing the
distillation. Trescot, reported below, recovered practically all of the ammonia by magnesia alone.
(14) Is the loss of nitrogen by methods (c) and (d) caused by heat generated in mixing the
acid and water f
Rudnick, using potassium nitrate instead of a solution of nitric acid, obtained the
following figures, and as compared with these results those found with the solution of
nitric acid by the same methods averaged 79.8 to 66.1 per cent. Trescot obtained
80 per cent when using nitric acid, as compared with 100 per cent with potassium
nitrate.
Rudnick' 's results, using potassium nitrate.
Method.
Number of
determina-
tions.
Range of
determina-
tions.
Average.
(e) (Zn-f-Thio.)..
(d)
4
4
Per cent.
93. 5-97. 4
88 3 94 0
Per cent.
95.4
92 i
89
Tli«- work of 'Present <.n potassium nitrate is reported separately, as follows:
(15) BY METHOD (D).
Material.
Number
of deter-
mina-
tions.
Range of
determina-
tions.
Average.
. .;i n. trail-
5
3
3
Percent.
99.8-100.1
97. 7- 99. 2
98.0- 98.8
100. 6-101. 6
Per cent.
100.0
98.8
98.5
101.1
1. luMitmlizi'd
u nit rate and d
ind evaporated
ri*-d l>lood
round bom-
(Hi) BY METHOD (C,). (ULSCII-STHEET.)
j mlraN' 3
irnl .Innl l»l<x><l
QQ 0 QQ 0
Potassium nitrate and tfruun<i IM>IH* ; 2
Impurities in n •, konc.l «>n the nitrogen as the basis of percentage, were
^ported as follows l»y two analysts only:
fjiuriti,* in rmgents based on nitrogen present.
Method.
(c)
(d)
(g)
(h)
0.9
0.7
0 4
A 4
.8
7
4
4 4
< (.M MK.vr 18 Y ANALYSTS.
Carpenter, reporting the work of <'<»<>ke, says:
Th«> Kji-ldahl im-ihod, or in fan any of the methods described in the "Official
Methods of Analysis," are very unsatisfactory for the determination of nitrates. In
our own work for tin- analysis of nitrate of soda, nitrate of potash, etc., we use an
method.
Robb says:
[•lil.l.- !..<> of nitric oxid when I added the salicylic-acid
mixture both in li the nitric-acid solutions containing a nitrate-free fer-
tili/.iT ami ih-.-e containing cane sugar.
Rudnirk says:
InasmiK li as all of the work could not be carried out in full, such features as seemed
to me of less interot from the stand |>oint of a fertilizer manufacturer's laboratory
omittcil. These had to do chiefly with the determination of nitrate nitrogen
I" i -' W* are not «o much interented'in this feature, inasmuch as there are several
good methods now in u>«- for this purpose. Of these we prefer the Schloesing- Wagner
method, as described in Bulletin 107 of the Bureau of Chemistry, page 111.
It is not the determination of nitrate nitrogen that we are so vitally interested in
but tin- determination of total nitrogen where nitrates are present.
The results with the tilth-normal nitric acid were very unsatisfactory indeed.
This was probably due to the great dilution with water, which we never meet with
in our work. Every precaution was taken to prevent undue heating on adding the
strong saiiryl-sulphonic acid.
A great many more determinations than appear in the preceding report were made
in this laboratory, but none of them was any more satisfactory than those reported
on, and there seemed to be no special significance in the results obtained. The Ulsch
met hi M I as -iven in Bulletin 107 with a number of variations has been tried in this
laboratory at various times during the past years, but has never given satisfactory
90
results. The zinc-iron method works very smoothly, and some of the results are
quite as satisfactory as those obtained by the Schloesing- Wagner method.
But, as stated above, we are mostly interested in the Gunning and Kjeldahl methods
for total nitrogen in the presence of nitrates. These methods have not given satis-
factory results in the past. There are some details in the manipulation of these
methods not described in Bulletin 107 which seem to tend materially to a closer
approximation of the true amount of nitrate nitrogen, such as quick covering of the
sample with enough salicyl-sulphonic acid to absorb all of the evolved nitrogen pxids,
sufficient time for thorough nitration of the acid, thorough cooling of the mixture
before adding the thiosulphate, and heating to a free boil before adding the mercuric
oxid or the potassium sulphate, respectively. We" find also that the tendency to
foam is very largely obviated by heating the flask containing the mixture in a boiling
water bath for an hour, or possibly less, prior to adding the thiosulphate.
In view of the poor results obtained with nitric acid it seemed that the use of a
Eure nitrate weighed directly into the digestion flask might prove much more satis-
ictory for determining the accuracy of the various methods. Our work following
this plan has given much better results than by using nitric acid as the source of the
nitrate.
In the large majority of cases we have to do with mixed fertilizers containing a
nitrate. Any inaccuracies due to the water present in nitric acid or in the solution
of a nitrate could easily be obviated by evaporating to dryness in the digestion flask,
preferably in vacuo, after neutralizing when necessary to prevent the loss of nitric
acid.
But even in the determination of an added nitrate the results leave much to be
desired. This is not only the case in this particular work, but has been a generally
recognized fact among fertilizer chemists for a long time. If the secret of success
lies in certain details of manipulation not commonly known, which make the method
reliable, these details should certainly be mentioned in the description of the method.
Trescot says:
I inclose results on neutralizing with soda and evaporating down, also on mixtures
of potassium nitrate and blood, and potassium nitrate and bone by the Gunning
modified method for nitrates and the Ulsch-Street method. These results only con-
firm my previous work on such materials with these methods. The zinc-iron method
is a failure in my hands. I never could get concordant results. If there is anything
more I can do, let me know and I will be glad to do it; only I do not wish to repeat
my work on the Ulsch-Street and Gunning modified methods, for after the most care-
ful checking for many years I am convinced that if handled properly, and on dry
materials, both methods will give all the nitrate present,
DISCUSSION OP RESULTS.
The opinions quoted and results reported show wide variations. By methods (c)
or (d) with and without organic matter, Robertson and Trescot alone get satisfactory
results; those of the other chemists are low, mostly impossible, in fact. This may
be due to heat generated by the acid and water, as many chemists think and as Rud-
nick's and Trescot's work on potassium nitrate seems to show. On the other hand,
Robertson's work shows no appreciable loss. An important question is, Must not
this possible loss from heat be reckoned with even with a comparatively dry sub-
stance? Even with potassium nitrate Rudnick falls far short of acceptable accuracy.
In view of these facts may not a too speedy application of heat in methods (c) and (d)
cause loss of nitrate vapors? It is a practice of some careful analysts to allow nitrate
samples to stand several hours after the thiosulphate or zinc dust is added. Hence,
recommendations are offered fixing a minimum time limit in methods (c) and (d).
Method (g) as carried out by Bailey, Morrison, and Trescot gives good results; as
carried out by the other analysts uncertain and varying results, mostly far too low.
It must be noted, however, that to test the completeness of the reduction of nitric
acid to ammonia the distillation is made at first off magnesia and completed off soda,
except in Trescot's work, the amount of ammonia from each distillation being esti-
mated separately and the sum taken. It appears further from this process that the
distillation from magnesia is usually far from complete, giving in several instances
less than one-fifth of the total amount of ammonia; that is, less than one-fifth of what
91
should have been obtained. As method (g) permits the use of magnesia only, no
soda, in distilling, it is evident how very inaccurately this method is practiced by
-nun- chemi.-is. It would seem that the magnesia distillation process is conducted
by many ehemi.-t.- !»•>.- .- uccessfully than any other analytical process.
Furthermore, the work of Bailey and Morrison shows that by method (g) some
ammonia is obtained from cotton-seed meal, about 2 or 3 per cent of the total nitrogen
in the Mib.-tance coming off as ammonia, when the distillation is off magnesia, and
about three time.- as much in addition, when soda is used in the distillation. This is
fortunately a compensating error and contributes something toward making up the
deficit ju>t described due to distilling ammonia off magnesia.
Afl practiced by some chemists the process of distilling off magnesia is worse than
u.-elc.— . A.- method (g) does not affect the amount of total nitrogen, errors are not
MB, however, as in methods (c) and (d).
Method . hi show.- better agreement among different chemists and also gives figures
somewhat approximating theory.
The only report on method (f) is to the effect that excessive frothing prevented
distillation.
Of the 54 answers to the 14 questions stated above, 39, or nearly three-fourths, must
• iiMdered unfavorable, either as failing to reach the 98 per cent standard of
accuracy or us showing reactions contrary to the plan and purpose of the method.
It iiiu.-i be admitted, whatever may be the inherent accuracy of the several methods
heir di.-cussed, that m<»i of them in the hands of some experienced chemists fail to
i:ive reasonably reliable and accurate results. It must also be admitted that these
method- \\ith D a variation in detail are commonly accepted by chemists as
reliable, and, a.- tin- report -how-, may be made to give exceptionally accurate results.
<)b\iou-l\ method- >o firmly established, and by some analysts so successfully em-
ployed, .ire hardly to be condemned, or even seriously questioned, without a study
of them by a large number of chemists. The data obtainable for this report are too
meager to justify any criticism or proposed radical change.
Th- -t ill of the opinion that the methods here discussed are fairly accurate
when properly followed, le-.- a« < urate perhaps in the hands of some analysts than
method- applied to -impler determinations, nuch as of nitrate-free nitrogen, but yet
urate as the difficulty of the case permits; and furthermore, that unquestionably
the.-.- methods are not always successfully followed, as evidenced by the criticisms
of chemists as well as by the reported results, and that probably some analyses made
:ding to these methods arc erroneous, giving too low results; that the complaint
of the officers of the National 1-Vrtili/er Association may possibly be based on fact in
n cases, probably due in part to erroneous analyses and in part to actual loss
of nitric acid, but that it is not within the power of this association at present to remedy
the e\ il complained of, if it exists.
KM OMMENDATIOX8.
Two recommendations of 1!M)7, referred to the referee for 1908, are recommended
ioption as ollicial. Nor-. _' and 4, Circular 38, page 1, or Bulletin 116, page 129.)
Th.-se changes relate to the use of copper sulphate in the Kjeldahl and Gunning
methods. For detailed statement of changes see page 183.
Recommendation 3: Bulletin 107 Rev., page 8, fourth line from top, after the word
''time " insert : "Allow the flask to stand without heat for not less than six hours."
K> commendation 4: Same reference, page 8, under (d) (3) "determination,"
fifth line of paragraph, after word "and" insert: "Allow the flask to stand without heat
for not !«•>.- than six hours; then". So changed the sentence beginning with "Add
i ins" would read: "Add 5 grams of sodium thiosulphate and allow the flask to
*und without heat for not less than six hours; then heat the solution for five minutes;
cool; add 10 grams," etc.
92
At the close of the reading of the nitrogen report, the president
announced the following committees:
Committee on amendments to the constitution: J. P. Street, J. T.
Willard, P. F. Trowbridge.
Committee on nominations: R-. J. Davidson, C. H. Jones, B. B.
Ross.
Committee on resolutions: L. L. Van^Slyke, A. J. Patten, V. K.
Chestnut.
REPORT ON INORGANIC PLANT CONSTITUENTS.
By H. D. HASKINS, Referee.
The work on inorganic plant constituents has been along lines recommended by
the referee of the preceding year, particularly with reference to the development
of a method for the determination of iron and aluminum in ash. The sample which
has served for the work was prepared by thoroughly mixing the ash of a species of
Lycopodium, known to contain a large proportion of aluminum, with a finely ground
and incinerated sample of wood ashes, the latter being known to contain considerable
quantities of iron.
PROPOSED METHODS.
The method proposed for study contains some of the features incorporated in the
official method of determining ferric and aluminic oxids and phosphates in .soils
(Bui. 107, p. 15). See also Bui. 56, Proceedings of the Fifteenth Annual Convention
of the association in which recommendations are made by Ilartwell in regard to a
method described in Crooke's Select Methods of Chemical Analysis. The method
as outlined for the work this year was in detail as follows, a hydrochloric acid solution
of the ash being used:
SEPARATION OF FERRIC AND ALUMINIC OXIDS IN ASH ANALYSIS.
Use a solution corresponding to 0.2 gram of ash. After removing the phosphoric
acid the filtrate from the precipitate of ammonium phosphomolybdate, consisting of
a nitric acid solution of molybdic acid, ferric oxid, alumina, lime, and magnesia, is
placed in a beaker and cautiously neutralized with ammonia, care being taken that
the temperature does not rise above 40° C. and that the alkali is added only in slight
excess; allow to stand in a warm place until the precipitate completely settles, filter
the clear supernatant fluid, wash the precipitate with hot water by decantation,
then transfer it to the filter, and finish the washing. Next, redissolve the precipitate
through the filter in weak, hot nitric acid (1 to 5), reprecipitate with ammonia, filter,-
and wash in the same careful manner. The precipitate is dried, ignited, and weighed
as ferric oxid and alumina.
METHOD (b). — The weighed precipitate of ferric oxid and alumina is dissolved,
on the hot water bath, in a covered flask by the addition of about 20 cc of dilute sul-
phuric acid (1 part sulphuric acid to 4 parts water). The iron is reduced to the ferrous
state by adding iron-free metallic zinc (about 5 decigrams at each addition) until
the solution is completely decolorized and the iron is all reduced; cool by immersing
in cold water, dilute with cold distilled water which has been recently boiled, pour
off and wash into beaker, leaving behind any residue of zinc. Titrate with standard
permanganate solution.
METHOD (c). — An aliquot part of the original solution A, corresponding to 0.2 gram
of ash, is evaporated on hot water bath with the addition of 10 cc of sulphuric acid
until all hydrochloric acid is expelled; dilute with water, reduce with zinc, and
estimate iron by standard solution of potassium permanganate. The per cent of
ferric oxid obtained is deducted from the per cent of ferric oxid and alumina, cor-
rections being made for filter ash, to obtain the per cent of alumina.
93
MAKING AND STANDARDIZING PERMANGANATE SOLUTION.
l)i.-olve 2.82 grains of pure crystallized potassium permanganate in distilled water
by MM- aid of lu-at; cool and dilute to 1 liter and preserve in stoppered flask. Stand-
ardize this solution l>y titration with metallic iron solution as directed in the second
American edition "f Kresenius's Quantitative Chemical Analysis, pages 268-269.
A copy "f the method as outlined above, together with the ash sample, was sent to
eiuhi cliemi-is \vh.. had signified their intention of cooperating in this work. The
result- received from five analysts are given in the tabulated statement which follows:
n-nrk on ash sample.
Analyst.
Method B.
Method C.
Alumina
(Alj03).
Ferric
oxid
(FesOs).
Alumina
(A1203).
Ferric
oxid
(Fe203).
I \ 1..- ' lei
6.56
7.12
o7.45
6.74
6.64
2.54
2.73
o3.35
2.66
2.63
6.43
7.17
o7.45
6.74
6.69
2.67
2.68
o3.35
2.66
2.58
I I'll!!"
•B r>in*n'""
11. 1). 1!
Average
6.77
2.64
6.76
2.65
•t im-lii(l«'<l in average.
COMMBMTI il ANALYSTS.
J. A. I.e I'lcrc found thai ii u.i- necessary to redigest tin- asli residue with hydro-
chlorie .« id in order to remove all of the iron present. In Method C some organic
mailer M-« nied to interfere with the end point of permanganate titration.
Andrew .1 Patten used an approximately hundredth-normal solution of perman-
te -"lut ion, thi.- heiirj preferred mi account of the small amount of iron present.
0 M. >hedd found objection to the determination of iron by Method B in that it
a 1'iii'j time to di--ol\ e the oxids in the sulphuric acid solution, and at this point
intended tin- fusion of the oxids with potassium hydrogen sulphate.
The referee i- of the opinion that a weaker solution of permanganate is preferable
t-i the on,- recommended.
Th- -Mined by the two method- airree very closely and indicate
b'lt little ehoi.-e in method of procedure.
The variation-* obtained between the various chemists in the results reported may
be due 1,1 the method of standardixiiig the permanganate solution. The referee has
u-ed for t hi- purpose a solution made from iron of a known composition furnished
by the I'.un-a'i of ^tandard-, \Va-hington, I>. <'. The personal equation must also
enter int., cooperative .'"rk of thi* nature to a greater or less extent.
>MMI:\I>ATI<)\S.
In view of the f.iet that the two methods gave results agreeing within 0.01 of a per
cent, the referee feels justified in rccommciH 1 i ng the one which involves the least
manipulation. The following is therefore recommended as an official method for the
separation of iron and aluminum in inorganic plant constituents:
an aliquot part of solution A corresponding to 0.2 to 0.5 gram of ash for the deter-
mination. After removing the phosphoric acid, place the filtrate from the precipitate
of phoBphomolybdate, consisting of the nitric acid solution of molybdic acid, ferric oxid,
alumina, lime.' and magnesia, in a beaker and cautiously neutralize with ammonia,
care being taken that the temperature does not rise above 40° C., and that the alkali
is added only in slight excess; allow to stand in a warm place until the precipitate
completely settles. Filter the clear supernatant fluid, wash the precipitate a couple
94
of times with hot water by decantation before transferring it to the filter, wash four or
five times on the filter with hot water. Dissolve the precipitate through filter with
weak, hot nitric acid (1 to 5), reprecipitate with ammonia, filter and wash in the
same 'careful manner. Dry, ignite, and weigh the precipitate as ferric and aluminic
Transfer an aliquot part of the original solution A, corresponding to 0.2 to 0.5 gram
of ash, to an Erlenmeyer flask and evaporate with 10 cc of sulphuric acid on a hot water
or steam bath until all of the hydrochloric acid is expelled; dilute with distilled
water to original volume and reduce the iron to the ferrous state by adding iron-free
metallic zirfc (about 5 decigrams at each additiotf) until the solution is completely
decolorized and the iron is all reduced. Cool and estimate the iron by standard solu-
tion of potassium permanganate. Deduct the per cent of ferric oxid obtained from
the per cent of ferric and aluminic oxids to obtain the per cent of alumina. Use a
fiftieth-normal solution of potassium permanganate standardized by a solution of me-
tallic iron of known composition.
It is also recommended that further work be done with the peroxid method for
the determination of total sulphur in plants and plant products, as suggested by the
committee at the last association meeting. Lack of time has prevented the referee
from taking up this important subject during the past year.
REPORT ON MEDICINAL PLANTS AND DRUGS.
By L. F. KEBLER, Referee.
Much activity has been shown during the past year by both federal and state offi-
cials charged with the enforcement of the various laws governing medicinal agents.
The drugs studied were both imported and domestic. Many interesting results have
been observed, a few of which will be noted in the referee's report. The feature
standing out most prominently is the lack of standards and recognized methods for
detecting the presence and determining the amounts of many active medicinal
agents, and from the nature of some of these agents no satisfactory methods will prob-
ably be provided in the near future. Even some of the methods available and the
standards set are found wanting. In this connection it is desirable to call atten-
tion to certain features of the Pharmacopoeia. A plant product is described, and
in some cases a standard relative to alkaloidal content is prescribed, but in many
instances no provisions are made for excluding or permitting the presence of any
foreign materials, such as stems, sticks, etc. It is a very common experience to meet
with importations of leaves containing large quantities of these impurities. The same
holds true with other commodities, such as cubeb berries, in which frequently a large
percentage of stems and twigs is found, together with unmatured or overripe berries,
and the question arises, To what extent is it permissible for these materials to be
present? It is contended by producers and importers that a standard precluding the
presence of these foreign agents would be purely theoretical, academic, if you please,
and has no standing in the business world. On the other hand, it is well known that
the medicinal value of a preparation is enhanced or depreciated in value in proportion
to the quantity of these foreign agents present. For example, the per cent of alkaloid
material present in belladonna root will be lowered in proportion, other things being
equal, to the amount of adulterant present. In other words, it is depreciated at least
in medicinal value proportionately to the foreign material present, and to what extent
these foreign bodies unfavorably influence the medicinal action of a drug in which
they are found is unknown.
Another feature is the amount of sand or incidental earthy matter present. For
example, normal senna leaves do not contain to exceed 10 per cent of sand and other
inorganic material, but it is not uncommon to meet with sif tings, sweepings, etc., of
senna containing from 20 to 35 per cent of such impurities. There is no provision in
the Pharmacopoeia setting an ash limit to a product of this character, but it is reason-
able to expect that sand does not constitute a material part of a normal product used
95
fur medicinal purposes. How many would be willing to administer to children
compound licorice jniwder prepared with senna leaves containing 25 per cent of sand?
Probably n«. other drug has caused so much annoyance and dissatisfaction during
the past year as a>af«etida. When the drug sections of the federal law were put into
eiYect ai the various ports it was found that this commodity was brought in containing
various amouii's <>i' alcohol-soluble material. No important quantity of exceedingly
inferior matt-rial was offered, and for the time being no detentions were made, even
though this druuf was somewhat below the strength prescribed by the U.S. P. for
alcohol-eoluble matt-rial. It soon developed, however, that importers were bringing
in Micce.-sivi' lower irrades of this product, for example, the alcohol-soluble material
dimini.-hed gradually from 40 to 30 to 25 and to 20 per cent, and one consignment was
offered « oiitainin-. according to the declaration on the containers, as low as 15 per
cent of this material, while one case of this consignment was found to possess only a
tritle over »; per cent of sin-h alcohol-soluble material. The Pharmacopoeia also
ribea an ash limit. of 1"> per cent. The virtue of asafoetida resides largely, if not
exdu-ively, in the al« •ohol-oluhle material, and it would therefore seem that the
a.-h limit should be liberal. If an importation were offered containing on the average
ii'o-iiila al< -ohol-soluble material, but the ash was materially
ali«.\e the limit pn-< ribed by the Pharmacopoeia, such an importation should not be
considered illegal.
Attention i- al.-o dm-< -ted to another drui:. namely, copaiba. During the past year
<|iianiiiies of this produ< -t \\ere imported and correspondingly large examinations
wen- made ai the porti parn< ularly New York. It will be recalled that the test as
originally pre.-cribed by the commit! f revision of the I ".S. P. was modified at the
liciiaiion of man\ dealers in this commodity. The result is that the new
meih -.reliable ami unsatisfactory as to permit the entry of copaiba containing
at le.i-i 25 per ci-nt "Hiurjun bal-am, the common agent used for its adulteration. A
:on ari-in- it- • •oinie. t h ,11 with this commodity is, Shall the definition given
relati\e to ei.paiba as contained in the I'. S.I', be strictly adhered to, or shall we
inder the name copaiba. qualified or otherwise, any other commodity which
• i\e,| from other -nin-m than tho>e definitely prescribed by the above authority?
;.le, then- i- c on-tantly oiirn-.l for importation a product known as African
Copaiba, which i- derived from an entirely different geographical source than the
comm..,|! ,-d by the Pharmacopu-ia. It is well known that the African
oleoresin duiers materially in coin|M.siii«ni and therapeutic action from the copaiba
; by the IS. P. African copaiba certainly is not copaiba within the mean-
ihe pharmacopu-ial detinition for this commodity.
Another problem requiring attention is the dilution of certain drugs with inert
iie 1'harmacopo'ia prescribes a lower limitof alkaloidal content forcer-
tain INIII-IH druu'- :m.i ii ha.- developed that millers are adding to alkaloidal drugs
assaying above the 1.. \\i-r limii pn •>• ribed by the Pharmacopoeia such inert material as
;. Te.l oli\e .-lone- -o a.- !•• reduce th,> alkaloidal content to the lowest limit pre-
d by the abo\e auihorii\ . There is nothing in the Pharmacopoeia that would
indicate that such a practice wa> contemplated or recognized. The committee
undoubtedly WM familiar with the fact that alkaloidal drugs frequently contain a
amount of alkaloidal material than the lower limit prescribed, but only in one
and that i> opium, is there a specilic provision made for the addition of a foreign
inert matt-rial so as to reduce the product to a strength conforming to both a lower and
an upper limit. This is an imjx>rtani question and requires adjustment in the near
future.
Attention has al>o been directed to the fact that there are many commodities on the
market which probably owe their virtues to their alcoholic content; for example,
then- an- a number of so-called (for want of better names) medicinal wines, bitters,
etc., which contain only a dash of some medicinal substance such as extract of cm-
96
chona, gentiana, etc., or very small amounts of one or more of the cinchona alkaloids.
Mixtures of quinin and whisky are cases in hand. One of the products examined was
found to contain not more than one-fortieth of a grain of total alkaloidal matter to an
ounce of the product, and even then the alkaloidal matter consisted only in part of
quinin. Without informing a prospective consumer or partaker, he, as a rule, would
not detect any abnormal odor or taste, excepting the one imparted by the so-called
whisky itself. One of the arguments frequently used to justify the existence of
products of this character is that the National Formulary, a standard quoted by the
food and drugs act, recognizes preparations of a similar type. The preparation
referred to most frequently is beef, wine, and iron. The point raised is an exceedingly
important one and requires adjustment. If it is permissible to add simply enough of
an agent to merely suggest a certain physiological action, be it ever so remote, pri-
marily for the purpose of using the name of a substance possessing recognized medici-
nal properties, in conjunction with the trade name of a commodity, one helpful feature
of the law will be largely negatived and an increased number of so-called medicinal
products of the most absurd character can be placed upon the market.
As before stated, there are many drugs for which we have no satisfactory chemical
methods for determining whether or not given samples are active or inert. In some
few cases it has been possible to employ animal experimentation. The drugs amen-
able to this form of study are digitalis, cannabis indica, strophanthus, etc. The
methods at present available appear to give fairly satisfactory results in the hands
of experienced operators, but there is much to be done before it can be definitely
stated whether or not a given consignment possesses sufficient medicinal properties.
One specific case in this connection should be noted, namely, digitalis leaves. This
product is of such great importance to the medical practitioner for the treatment of
certain heart affections that nothing relative to this drug and its preparation should
be left to chance. No less an authority than Doctor Dixon, of England, says: "For
my part I unhesitatingly express the belief that many hundreds of patients die
annually from digitalis and allies not possessing the virtues which are required of
them."
At the meeting of the association last year the referee urged the appointment of a
number of associate referees for the purpose of studying certain features which need
careful investigation; for example, it is absolutely necessary to have an intimate
acquaintance with the macroscopical and microscopical features of crude plant
products. Satisfactory methods are also wanting for analyzing the many mixtures
containing modern synthetic chemicals, used for the treatment of headache and numer-
ous other affections. We are in possession of fairly reliable methods for determining
and estimating morphin in certain combinations or if present in considerable amounts,
but it is quite another matter to detect and estimate this agent when present in very
minute quantities in mixtures containing various solvents, and much study will
be required before this single item is placed upon a footing which will be absolutely
reliable. During the past year some work has been attempted along this line with
cocain. It may at first appear to be a very simple matter to detect the presence and
estimate the amount of cocain in mixtures, but when it is remembered that there are
quite a number of products which respond to one or more of the tests laid down for
detecting cocain the difficulties can readily be appreciated. Careful, thoroughgoing
investigations on all these points are greatly needed, and until more work is done
it will be difficult to satisfactorily enforce some features of the federal and state laws
dealing with these products.
State officials are making frequent requests for information as to methods of analysis
and standards for certain products. The referee has been actively engaged on both
of these lines of work and has now in preparation standards for certain products for
which no standards of a satisfactory character exist, and in cases where the existing
standard is somewhat deficient it is the intention to add certain features which will
97
enable all u.,rk«-rs throughout the United States engaged in the investigation of these
products t.. arrive at just conclusions relative to their quality. For example, it is
intended to lix an upper limit of the amount of foreign material that may be present
in a loaf described by the United States Pharmacopoeia and to provide an ash limit
i. >r . ertain drills. < onsiderable progress has also been made relative to testing exist-
ing anah tical methods and formulating new methods for examining certain com-
In order to facilitate the investigation, and in harmony with the instructions of the
association, the referee appointed several associates to take up specific features of the
work. whose results will be given in separate papers.
A PRELIMINARY STUDY OF THE MICROCHEMICAL ANALYSIS AND
IDENTIFICATION OF ALKALOIDS.
By 15. J. HOWARD and C. H. STEPHENSON.
The large number of alkaloids used at present in drugs as well as the increasing
number of .-\ nthetir product.-* being placed on the market has made felt the want of
additional means for their identification. Microchemical methods have been sug-
gested and used to a limited extent by such workers as Wormley, Earth, and Behrens,
hut the principal application of the method has been rather for the purpose of localiz-
ing the alkaloid in the- tissues, by such investigators as Errera, Maistriau, Clautriau,
Hollinu'. and others.
the suggestion of the Chief of the Division of Drugs this investigation was taken
up by the Mien* heinical Laboratory and a study of several alkaloids begun. Only a
preliminary report of program can as yet he made, and the field has extended itself in
many directions a* the work progressed. The investigation as originally outlined
anticipated -e\eral lines of work, among which the following might be mentioned:
The normal reaction of each alkaloid with each of the various reagents which
are known to he of -er\ x e w ith one or more of them. This involves a study of dilu-
the dilution ni the alkaloid which will respond to the test and also the weight
limit of alkal'. ill \\hidi \\ill u'ive po-iti\e i,.sts with the reagent. It also involves a
.-tudy of the form- of crystals produced at the various dilutions, the conditions for
producing the reaction, or the manipulation, the determination of melting points,
photographing the crystals as a ma; -rd, and in some cases the measurement
udy ni' the inlluence u|H>n the reaction of another alkaloid present than the
one sought.
(3) A study of the influence upon these reactions of such substances as glycerin,
rch, oilfl, and t'.ir -. -_":m-. u .> v -, and other compounds likely to be found in
drui:-. and from trace- of uhich it i- often difficult to remove, for testing, small traces
of alkaloid- in .-••me medicinal preparations.
(4) The adaptation of alkaloidal purification methods for use microchemically so
as to |H-rmit minute quant it ies of the alkaloids to be separated and prepared for testing.
The developing of an analytical scheme for systematically identifying micro-
chemically the various alkaloids "present in unknown mixtures. This last can only
be accomplished after a considerable number have been studied and compared.
During the la.-t year the work has been practically confined to the first two lines,
which naturally constitute the foundation of the whole investigation. The alkaloids
studied comprise a list of about forty, besides two or three salts of two of them, most
of which were obtained through the Division of Drugs. They were commercial speci-
mens and apparently of average purity. The list also embraces several synthetic
compounds as well as the more common natural alkaloids. Among the natural alka-
l.id-.-r their -alts -tudiod might be mentioned the following: Cocain, codein, atropin,
(inchonin, morphin, papaverin, narcein, caffein, strychnin, tropacocain, hydrastin,
coniin, berberin, solanin, etc., while among the synthetic bodies studied are anaes-
73C73— Bull. 122—09 7
98
thesin, beta-eucain, holocain, gujasanol, and acoin. The dilution of the alkaloid
in the solvent in many cases has a most marked effect upon the form assumed by the
precipitate. There is always a limit beyond which the dilution of the product is
too great for crystallization to take place, while on the other hand the concentration
may be so great as to cause too sudden precipitation and an unsatisfactory product
results. In this work dilutions of 1 : 100 or 1 : 200 were most frequently tested. Other
dilutions would possibly have given crystalline products where only noncrystalline
products have, thus far been obtained or where no reaction at all has been noted.
The reagents used embraced a list of more than ninety compounds or mixtures
and included the standard reagents and as far as known, the special alkaloidal reagents
with the exception of two or three which have recently been brought to the authors'
attention. Thus far crystalline precipitates have been obtained in about 400 combina-
tions. Noncrystalline deposits resulted in nearly 600 other combinations, but their
usefulness in identification is very limited and they can usually only be employed
as corroborative tests.
Unfortunately some of the well known alkaloidal reagents, though giving reactions
with most of the alkaloids, produce only noncrystalline precipitates. As ordinary
analytical tests they may be satisfactory, but as microchemical reagents they leave
much to be desired. To the analytical chemist they serve a good purpose as indicating
alkaloidal presence, but rarely its identity. This is shown in the following examples:
Mayer's reagent, 11 crystalline, 23 noncrystalline; Kraut's reagent 10 and 33 and
Marine's reagent 11 and 25, respectively.
Picralonic acid gave 21 crystalline precipitates out of 37 positive reactions, but
the forms unfortunately are in most cases too much alike to be of much sevice for
identification. The alkaloids studied showed a great diversity in the character of
the precipitate formed, as is seen from the following examples, which serve to illus-
trate the extremes, the first four giving a high number of crystalline forms, the last
five giving a high number of noncrystalline.
Character of precipitate obtained with different alkaloids.
Alkaloid.
Crystal-
line.
Noncrys-
talline.
Alkaloid.
Crystal-
Noncrys-
talline.
Strychnin
36
3
Apomorphin
6
35
Berberin
25
.6
Papaverin
9
32
Tropacocain
22
2
Hydrastin
1
32
Anaesthesin
20
7
Solan in
1
29
Acoin powder
2
40
With piperin, sanguinarin, emetin, and apocodein noncrystalline precipitates only
have been obtained thus far, though it may be that by some change of manipulation
crystals may yet be produced.
The melting point of the products is likely to be of service at times in establishing
the identity of certain compounds though some of the precipitates apparently are
too unstable for this test. For this purpose, however, an apparatus which had been
devised in the Bureau of Chemistry for use on the stage of the microscope has been
tested with promising results. It allows of the microscopic examination and deter-
mination of the melting point of an individual crystal in a mixture of various kinds
either with plain or polarized light. In some crystals, especially some of the compact
spherical forms, this last point is an important means of telling where melting begins,
since as soon as a crystal melts it loses its polariscopic activity, and as all systems,
except those belonging to the regular system, are active this feature can be used to
advantage in determining the point where melting begins and where it ends even on
small crystals.
99
The alkaloid thus far most thoroughly examined is cocain. Crystalline deposits
have been obtained with each of the following eleven reagents, viz, palladous chlorid,
platinum chlorid, gold chlorid, picric acid, chromic acid and hydrochloric acid'
potassium dichroiiiate and hydrochloric acid, potassium permanganate, potassium
chromate, sodium carbonate, ferric chlorid, and potassium hydrate or sodium hydrate;
noncr\>tallim- deposits were obtained with chlorzinc iodid, picralonic acid, Mayer's
reagent, phosphomolybdic acid, phosphotungstic acid, Kraut's reagent, Wagner's
it, barium mercuric iodid, and potassium cyanid.
The following observations were noted concerning the various reactions with cocain
iii which crystals were produced:
full minus chlorid. — This ia one of the most characteristic tests for cocain though
in.t quite M -ensitive as u'old chlorid. The crystals vary in form greatly, according
to tin- conditions of precipitation. There is at first formed, except in very dilute
solutions ( 1 :3<M) and up), an orange-colored amorphous-like or oily precipitate from
which, on standing, crystalline forms of golden brown color are produced. One of
the most ( '0111111011 forms i> that obtained with a 1:100 dilution, when feathery crystals
are formed which have a mdencyto twin. With a solution of 1:20 a dense
precipitate i- thrown down, out of which hexagonal plates are at first formed and fre-
(juently followed later by sheaf-like clusters of fine-pointed acicular crystals. A
dilution greater than 1:500 gives crystals only with difficulty, crystallization being
induced by rubbini: the >lide with the glass stirring rod. The limit of the test is
0.2 '
/'/'" '"rid. — With a 1:20 solution a dense white precipitate is formed and
quickly followed by the production of very narrow feathery crystals — many times
twinned so as to resemble a bird with outspread wings. Clusters of more than two
umlaut. If the reagents are mixed slowly the crystals are more like those
dilution. With a 1:100 dilution the feather type is much more prominent,
the secondary i l.ein- well developed into frost-like forms. With 1:1,000
Dilutions either .-h-.rt thick crystals are formed or else plate crystals twinning in a
manner are produced. The dilution limit is about 1:4,000, and
the limit in 1 : 1 ,000 is 0.2 ^gr.
/ i-lilnr'nl. This is the most sensitive reagent for cocain so far found. At 1:100
feail • ke crystals are produced, together with some nearly smooth star-like
aggregates. At 1:1,000 the form is much the same, but the branches usually bear a
i outline. iMamond plates are also roduced. At 1:4,000 a cross-like form
predoniinaii--. i h< • n >ss-bar beiiiir short. A few rosette crystals frequently are present.
.1- can be . I Mined in dilution up to 1:20,000 and the limit of the test for dilu-
ut I::UMM) is 0.033 //gr.
tic acid.- Tin- i- a good reagent for dilutions up to 1:800, though the crystals
produced are n.,i very characteristic for this alkaloid. They are produced in spherical
<f tine lemon-yellow acictilar forms. The reaction takes place
quickly, and no dillicuh rienced in producing them nearly to the limit of
dilution. At 1 ::;m the limit i.- O.L' //i;r.
ni i»rmnnganate. — With cocain, solutions up to a dilution of 1:700 give
purple -«-o|,,red .square plates, or aggregates of this form. Vigorous rubbing of the
slide is often necenar] to -tart the crystallization, which then proceeds readily.
When they b. -in to cry.-tallize spontaneously, the plates are sometimes deposited in
spherical aggregates. The limit at 1:400 is 2 //gr.
Chromic nriil ami hydrochloric acid.— This test is made by adding a small drop of 5
per r.-nt chromic acid solution to the test drop. A precipitate is formed which on
stirring di-app. -ar- if too much has not been added). A small drop of strong hydro-
chloric a«id is added and a yellowish deposit is produced, which after rubbing of the
slide should in a few moments be transformed into loose spherical clusters of an acicular
crystal. This test appears to be one of the most uncertain because of the difficulty
with which the ery.-talli/atioiiis sometimes induced to begin in dilutions greater than
A concentration of 1:1,000 has produced positive results on standing several
minute.-,. The limit appears to be for 1:100 about 3 //gr.
/'...• hromale and hydrochloric add.— This test gives the same form of crystals
as the chromic acid and the test is conducted in a similar manner. The limit of
dilution is about 1 I. (MM) while at 1 :100 the limit is 3 Agr.
Ferric rhlnrid.- The crystals are spherical aggregates of rather coarse blade-like
Is with chisel-shaped ends. The limit of dilution is about 1:1,000 and in a
dilution ,,f l; KMI the limit is li //gr.
/'"tnsifium hydrate, or sodium hydrate. — This produces a white amorphous precipitate
which changes into crystals on standing or by rubbing the slide with a glass rod.
100
The crystals are rod-like, frequently with more or less chisel-like ends and a V-shaped
recess extending backward into the crystal. There is a strong tendency to form
coarse clusters up to about 15 branches. In open drops tree-like forms are frequent.
For each of these reagents dilutions up to 1:1,000 give the reaction and the limit at
Sodium carbonate— This gives a precipitate with cocain like that produced by
potassium hydrate, both in the amorphous and crystalline forms. Limit of dilution
is 1:1,000. In 1:100 solution the limit is 3 //gr.
In order to ^determine the usefulness of some of the above tests when other alka-
loids are present the palladous chlorid test was made*on test drops to which had been
added solutions of one of the following alkaloids, codein sulphate, atropin sulphate,
heroin, dionin, acoin powder, cinchonin sulphate, hydroxylamin hydrochlorid,
apomorphin hydrochlorate, narcotin, papaverin, brucin, narcein, morphin, thebain,
gujasanol, orthoform (new), cinchonidia sulphate, quinidia sulphate, beta-eucain,
holocain, caffein, quinin sulphate, strychnin, and tropacocain. In each case the
crystals of the cocain compound were obtained and in the case of brucin, gujasanol,
caffein, strychnin, and tropacocain, with which the palladous chlorid regularly gives
a crystalline precipitate, it was found that when cocain was also present the cocain
product was given in addition to that for the other alkaloid, though occasionally with
modified form.
The foregoing serves to give an idea of the scope of the work undertaken, which it
is hoped will be carried much further during the coming year.
COOPERATIVE WORK ON HEADACHE MIXTURES.
By W. 0. EMERY.
After making investigations of various suggested methods for determining the different
constituents present in the many headache mixtures containing acetanilid and similar
agents, a method was finally devised which proved quite satisfactory to the members
of the Division of Drugs, and it was therefore decided to place this method in the
hands of as many chemists interested in this line of work as could assist. A circular
letter requesting cooperation was sent out, and a gratifying number responded, sig-
nifying their willingness to assist, eleven of whom sent in results. All who expressed
a desire to cooperate were supplied with a sample of a mixture containing known
amounts of acetanilid, sodium bicarbonate, and caffein, with the following instruc-
tions, the U. S. Pharmacopoeia, eighth revision, as amended and corrected May 1 and
June 1, 1907, being used as a basis for all calculations and reagents unless otherwise
specified:
SEPARATION OF CAFPEIN, ACETANILID, AND SODIUM BICARBONATE.
Caffein.
\Yeigh out about 0.3 gram of headache powder on a small (5.5 cm) tared filter,0
wash with successive small portions of chloroform to the amount of about 30 cc, col-
lecting the solvent in a 100 cc Erlenmeyer. Distil off chloroform by means of a small
flame until only a few cubic centimeters remain. Add 10 cc of dilute sulphuric acid,
then continue the distillation till all the chloroform has gone over, disconnect from con-
denser, heat gently, first on wire gauze to complete solution, & finally on a steam or hot-
<»In cases of powder mixtures or tablets containing ground celery seed, much color-
ing matter, cinchona alkaloids, laxative or extractive principles other than acetanilid
or phenacetin, it is our practice to shake out the latter by means of chloroform from
dilute sulphuric acid solution.
*> In case the preparation contains ground celery seed or certain oily principles,
it sometimes happens that the acid solution does not become entirely clear at this
point.
101
water hath until thecontentsof the flask have evaporated to about 3 to 4 cc. Cool, trans-
fer by washing with water to a separatory funnel, so that the final volume does notgreatly
ex« -e'ed L'O cc. Add four times the volume, or about 80 cc of chloroform, shake for some
time vigorously, allow to stand until the chloroform clears perfectly, pass through a
small dry filter into a dry 100 cc Erlenmeyer, distil off the solvent and use distillate
for a second extra* lion, observing the same method of shaking, clearing, and filtering
as above noted. Distil off chloroform to a small volume, transfer residue to a small
tared beaker, or crystallizing dish, by means of a few cubic centimeters of chloroform.
Allow to evaporate spontaneously, or if desired on a steam or hot-water bath to dry-
n. -, in the latter case partially covering the dish toward the end of operation with a
watch glass in order to avoid possible loss from "popping." Cool in desiccator and
weigh as caffein, dry alkaloid. a
Acetanilid.
First method.— The acid solution remaining in the separator and containing anilin
sulphate is run into a 100 cc Erlenmeyer, the filter through which the chloroform
MHBed i v. ..-h'-d <>nce with a little water, allowing the latter to run into the separator.
Km -«• tin- latter thoroughly, adding the aqueous rinsings tothe acid solution. Now,
run in slowly and with constant agitation a standard solution of potassium bromid-
l.i ornate 6 to a faint but distinct yellow coloration. The number of cubic centimeters
eni ployed, multiplied by the value of 1 cc in terms of acetanilid, will give the amount
of acetanilid present.
Second method. — The acid solution aforesaid is treated with successive small por-
tion.s of sodium bicarbonate until an excess of this reagent is observed in the bottom
• •I the separator. Add 50 cc of chloroform and 15 to 20 drops of acetic anhydrid, shake
for some turn- \iirorou-ly, allow the chloroform to clear, then pass through the same
filter n-ed i'or the cam-in intou, 100 cc Erlenmeyer, and distil off most of the chloroform.
Use this distillate I >r a .-ec. >nd shake out, clear, filter, and distil down to a small vol-
ume. transferring the residue and t he subsequent chloroform washings to a tared beaker
«>r di-h precisely as m the case of caffein. Allow the solvent to evaporate spontane-
»»u>l\ or by means of a bla.-t or fan, avoiding, however, undue heat.c Dry in desic-
>ver quicklime t" con-taut weight.
nv the final wei-lit by means of titration with standard potassium bromid-
bromate solution as in t ho first method. Heat the residue with 10 cc dilute sulphuric
.i hall h'.ur on the steam or vapor bath, cool, add 5 cc of water and titrate as
• 1 above.
Sodium bicarbonate.
The residue left after the first treatment with chloroform is weighed when dry and
v nearly the amount oi sodium bicarbonate present. It may be more
accurately estimated by titrating with tenth-normal sulphuric acid, using congo red
licaior. or it may "l»- unite. I with dilute sulphuric acid arid weighed as sodium
BUlpfa
< alculate results in parts per 100.
a Should the cat'fein not be colorless or nearly so, the residue is dissolved in about
11 necessary (in case oily matters are present), through a wet
filter, the filtrate acidified with dilute hydrochloric acid, the caffein precipitated
with ream-lit, allowed to stand a half hour, filtered, and the
.pilule washed with a lew cubic centimeters of same reagent, the filter, together
with precipitate. tran-iVrred to separator, decolorized by means ot sodium sulphite,
and the cat'fein finally extracted with chloroform.
ft For this purple the solution is prepared by adding bromin in slight excess to a
concentrated aqueous >oluti»n of 50 grams caustic potash, the liquid diluted till the
separated salte redissolve, boiled, to expel any excess of bromin, and finally made
up to 1 liter. This solution is standardized with weighed amounts of acetanilid, or
it ma> be s.) adjusted by further dilution that 1 cc is exactly equivalent to 1 centi-
gram of acetanilid. Kor purposes of titration 1 to 2 decigrams are heated a half hour
on the steam or water bath with 10 cc of dilute sulphuric acid.
c Acetanilid suffers appreciable loss when heated above 40°.
102
The results reported are tabulated as follows:
Results obtained in the cooperative work on an acetanilid mixture.
Analyst.
Caffein.
Acetanilid.
Soda bicarbonate.
Total.6
Volu-
metric.
Gravi-
metric.
Volu-
metric.
Gravi-
metric.
Per cent.
12.16
10.93
11.05
10.40
11.50
10.73
11.33
11.53
11.00
11.00
510.55
10.49
10.48
10.62
9.80
10.06
9.93
10.20
f 10.90
\ 11.17
| 11.30
\ 11.37
Per cent.
65.93
66.10
65.93
66.10
63.00
61.50
63.40
63.44
63.00
62.00
65.78
Per cent.
Per cent.
23.20
Per cent.
Per cent.
101.29
100.53
100.18
L D Havenhill Kansas
23.50
23.20
25.10
25.00
24.90
25.00
24.60
24.80
25.03
25.11
25.13
25.13
25.06
24.93
25.00
24.93
25.07
24.54
25.57
25.33
25.43
24.99
24.79
24.92
24.95
25.01
99.60
97.23
99.63
99.97
98.60
97.80
101.36
100.86
101.41
103. 47
99.96
99.57
98.25
98.64
100.50
99.71
H L Schulz Michigan
H A Seil New York
T F Darling New York
65.80
65.26
E L Redfern Nebraska
65.10
64.58
63.03
63.21
64.53
64.00
67.72
63.60
63.80
C B Morrison o, Connecticut
25.93
25.67
25.93
""ioi.'is
99.82
100.12
99.94
100.09
99.70
A R Mehrtens California.
I 10.67
10.30
10.00
10.23
10.29
10.01
64.80
64.53
65.33
64.79
64.85
G E Colby California
W O Emery Washington D C
Average ...
64 68
10.71
64.38
65.01
25.18
24.89
99.98
Maximum
12.16
9.80
66.10
61.50
67.72
63.60
25.93
23.20
25.57
23.20
103. 47
97.23
Minimum
Difference
2.36
4.60
4.12
2.73
2.37
6.24
Known composition of acetanilid mixture
(acetanilid, 453 parts; caffein (anhyd.),
70 parts; soda bicarbonate, 174 parts)
10.04
64.99
24.96
99.99
o Reported by J. P. Street.
& In cases where two percentages for volumetic and gravimetic determinations of the same substance \ve; e
reported, the mean of such percentages has been taken in computing the total percentage.
Owing to an ambiguity in the expression "dilute sulphuric acid" employed in the
method under caffein, as also in the footnote a, page 100, for standard bromid-bromate
solution, some of the workers quite naturally used the pharmacopoeial strength,
with the result that the acetanilid was not completely hydrolyzed. This undoubtedly
explains the somewhat high results for caffein and the correspondingly low ones for
acetanilid. The strength of acid intended and the one actually employed ior this
purpose in the Bureau of Chemistry is that ordinarily used in laboratory work and
is made by diluting 1 part of concentrated sulphuric acid (whose specific gravity is
not less than 1.826 at 25°) with 5 parts of water. From two to three hours' heating on
the steam bath is usually required to completely hydrolyze the acetanilid.
Notwithstanding this ambiguity the results obtained are very gratifying, in view
of the fact that the method is new and the workers have entered into a comparatively
new field. The percentages of variation are so small as to almost warrant the referee
in recommending it as a provisional method to the association. He believes, how-
ever, that the method should receive additional study, and so recommends. It is
also recommended that additional mixtures be tested with this and such other methods
as may be found desirable.
103
President Snyder introduced the Secretary of Agriculture with a
few words of appreciation concerning the long-sustained attitude of
the Sccivtary in fostering agricultural chemistry, especially the
\\ork of the ollicial chemists, by making possible the close affiliation
between the Department of Agriculture and the association. The
Secretary then briefly addressed the convention, after which the read-
ing of the drug reports was resumed.
THE NECESSITY FOR ANIMAL EXPERIMENTATION IN DETER-
MINING THE PURITY AND STRENGTH OF MEDICINAL PREPA-
RATIONS.
By WILLIAM SALANT.
Experiments on animals have long been recognized in medical jurisprudence as a
valuable adjunct to chemical and microscopical methods in the detection of poisons in
animal tissues and fluid. Notwithstanding the improvements in the methods of
analytical chemistry witnessed within recent years, tests on animals, or, as Roberta
terms it, "hi.. logical testing," is still resorted to in order to corroborate the findings of
ih. analytical chemist in cases of suspected poisoning with alkaloids and other
substances of plant or animal origin. The French chemist, Boutmy,&
who made . -xiensive studies on poisoning with alkaloids, concluded that in all cases
in whirh the j.n .-• -nee of an alkaloid in the body is suspected experiments on animals
should be made for tin- j»urjM)«e of confirming the results of chemical analysis.
Tli-- -ome investigators indicates that the biological method is in certain
owes much more delicate than the chemical. Rankec reports experiments on dogs
which were given O.I of a grain of strychnin by mouth. Chemical examination of
; -an.- • if these animals failed to show the presence of strychuin, but when extracts
of the same organs wen- injected into frogs tetanus followed. Falck<* has shown long
ago that oue-twcnticih of u milligram of strychnin was sufficient to induce tetanus
in a mcdiiun -i/.c«l frog. It might be added that if smaller frogs are used the same
effect may be obtained with one-eightieth of a milligram. Atropin is another example
tru_' --I which .-.mall quantities are sufficient to produce a physiological reaction.
Only one-twentieth of a milligram is necessary to produce dilation of the pupil.
Likewise cocain, which produces characteristic effects on the mucous membranes,
and by iu« action <>n the frog's pupil, can be identified, even when very small quan-
are present in biological solutions.
Aconitin can be identified in milligram doses by its action on the tongue, eye,
heart, and central nervous system. No chemical methods have as yet been devised
by which such small quantities of this alkaloid can be detected. A striking illus-
tration of the delicacy of the biological method is afforded by the work of Hunt.«
In his investigations on the functions of the thyroid he has shown that mice fed for a
few days with the extract of this gland acquire greater resistance to poisoning with
acetonitrile. One milligram of the official dried thyroid fed to white mice daily for
a few days may enable the animals to recover from double the dose of acetonitrile
fatal to the controls. Seidell,/ working under the direction of Hunt, found that
forty to fifty times as much thyroid would be required to give the iodin test.
«Ber. deutsch. pharm. Ges., 1903, 13: 325.
ft Ann. hyg. publique med. legale, 1880, [3] 4. 193.
Virchow's Archiv, 1879, 75: 20.
d Vierteljahrschr. gericht. Med., N. F., 1874, 20: 198.
'J. Amer. Med. Assoc., 1907, 49: 240.
/Ibid.
104
Even more delicate are the methods employed in the study of immunity. As
shown by the work of Meyer a and Uhlenhuth,& by means of the precipitin test the
presence and nature of proteins may be ascertained in a dilution of 1: 100,000. As is
well known, the chemical tests for albumin are of no value in dilutions over 1: 1,000,
and it is not specific.
For the identification of some poisons and the standardization of certain drugs
of vast therapeutic application experiments on animals are practically the only
reliable method.
There are no satisfactory chemical methods for the identification of the saponins,
but owing to their powerful hemolytic action and their effect on the heart and volun-
tary muscles their identification has become possible. According to Robert, <= picro-
toxin can be identified by experiments or animals only. The detection of curarin
by chemical tests is very unsatisfactory; by its action on the motor end organs, how-
ever, its identity can be established even when mere traces are present. Thus motor
paralysis in frogs has been induced by injecting 0.005 milligram of curarin.
Adrenalin has been the subject of numerous investigations. On account of its
powerful action and its extensive therapeutic application, the strength of the various
preparations should be accurately known. A number of color tests have been pro-
posed for this purpose, some of which are of doubtful value and some may be employed
if properly controlled by tests on animals, which are very delicate. Meltzer and
Auer d have shown that a drop of a solution of 1: 120,000 dropped into the conjunctival
sac of a rabbit causes blanching of the conjunctiva and dilation of the pupil. Accord-
ing to Ehrmann, « a reaction of the pupil of the excised eye of the frog may be obtained
with 0.000025 milligram of this drug. Similar results were obtained by other inves-
tigators who worked on the pharmacology of the drug. Cameron's / experiments with
this drug on rabbits have shown that 0.0003 milligram per kilogram will cause a rise
of blood pressure.
Preparations of digitalis have been found to vary enormously in physiological
activity. Frankel Q states that the strength of the tincture varies from 200 to 400
per cent, and the infusion varies from 100 to 125 per cent. In a recent article
Lutzkaja'1 states that the infusion of digitalis he examined was only 60 per cent of
the strength represented by the firm which prepared it. Barger and Shaw,*' in
England, examined nine tinctures of this drug, and found a variation of 75 per cent
in their strength. These authors made a comparative study of Keller's method and
the physiological test on an artificial infusion of digitalis made by adding a known
quantity of the drug to a mixture of hay and chaff. This was extracted with 60 per
cent alcohol. Chemical analysis of the extract showed the presence of 0.1 per cent
of digitalis, whereas the mixture contained 0.4 per cent. The same extract was
tested on frogs, however, and found to contain approximately 0.4 per cent.
In the case of some drugs the physiological test above must be relied upon, no
chemical method having as yet been devised for their identification or quantitative
determination. Cannabis belongs to this category. Houghton and Hamilton, J in a
recent article, state that previous to the adoption of this test, preparations of the
o Lancet, 1900 (2), p. 98.
*>Deutsch. med. Wochenschr., 1900, 26: 734.
cLoc. cit.
dCentrbl. Physiol., 1904, 18: 317.
«Arch. exp. Path. Pharmak., 1905, 53: 97.
/Proc. Roy. Soc. Edinburgh, 1905, 26: 161.
^Ther. Gegenwart, N. S., 1902, 4: 112.
^Arch. intern, pharmacodynamie, 1908, 18: 77.
* Yearbook of Pharmacy, 1904, p. 541.
J'Ther. Gazette, 1908,32: 26.
105
drug were so unreliable that hospital physicians used to experiment on patients with
samples of this drug before placing an order for it. Since experiments on animals
with this driii? have been introduced, the practice of testing the preparations on human
beings was abandoned.
Ergot is another drug whose activity can at present be determined only by experi-
ments on animal-. < 'raw ford," who made a study of chemical tests, came to the conclu-
M..II that they an- ..f no value, while its action on the cock's comb after subcutaneous
injection, i.nm the isolated uterus of the cat, is characteristic and may therefore be used
' advaiita-e in its identification or in determination of the strength of the preparation.
to
REPORT ON INSECTICIDES.ft
I'.y ( . ('. MrDoNNELL, Referee.
A study of methods for the examination of insecticides and fungicides was taken up
by the association only ten years ago at the fifteenth annual convention, when the
fir-t referee on thi- -ubject was appointed.
th<- two years following this no analytical work was reported, but methods were
compiled and -uu"-:c-t.'d for the examination of this class of materials which were then
IMO-I ini|>ortani, and th.-e were ad.pt, -d provisionally. All of them have been tested
.-inn- that time and tho~«- proving of value have been officially adopted by the associa-
tion. A number however have -in<-e been replaced by more rapid and accurate
method-. AJ the ii-i i -ub-tan.es used as insecticides and fungicides increases, as it
ofltantly doing, new method- must be devised and changee in old methods intro-
duced in order that th.-y may be adapted to a particular material.
At the present time the mi, -t irnjM)rtant of these is lead arsenate, and it is to methods
for the examination of thi- -ub-tan.-e that considerable study is now being given. The
work as carried out thi- year ha.- been largely along the line of the recommendations of
the r. -ft •'•••<• tot year, which were adopted by the association. In addition a modifica-
tion pro|x»-ed by the pre-ent referee for the determination of total arsenic oxid in
London purple ha- bei-n -_'i\en a trial.
WORK .w < M-n.iN-Ki).
\ : ; .-f the pro\i-ional niethiMls for London purple given in Bureau
of ( h. mi n> < ircular l<>, ie\i-ed, the method as modified by Davidson, given in the
I' 'he twenty-e< -.Hid annual convention of the association, also in Bureau
oM'hemi-try P.ulletin L 07, revised, and the iniM!ifi(>d method as proposed by the pres-
ent n :
A further -i udy of the precipitat i'-n method for soda-lye, using fifth-normal acid
id ..f half-normal, aI-«> with and without removal of the barium carbonate pre-
cipitate before Miration.
(3) Determination of formaldehyde in strong solution by the provisional hydrogen
x:d method, and on dilute solutions by the cyanid method to determine the
amount of dilution nece-sary.
(4) Further te-t of the Avery method for the determination of sulphur in sulphur
dips.
(5) A continuation of the study of the methods for lead arsenate proposed by Hay-
wood (Pnx-eedin.:- I'.MM;, Bulletin 105, p. 165) and tried last year.
Samples were .-ent to five chemists, who had expressed a willingness to cooperate
in the work, aixl more or le-s complete reports have been received from three of these.
« Amer. J. Pharm.. 1908, 80: 326.
*> Owing to the illness of the referee, this report was not ready for presentation to the
i -on vent i«>n at the time of its meeting. Through the courtesy of the association the
referee wa- permitted to present the report at a later date for insertion in the Pro-
:i_r-.
106
LONDON PURPLE.
Owing to the considerable variation in results and the difficulties encountered in
the carrying out of the present methods for the determination of total arsenic oxid in
London 'purple, methods for this substance have been receiving considerable atten-
tion from the association for several years. The three principal objections to the
methods thus far proposed are: (1) The difficulty in reading the end point when using
up the excess of liberated iodin with sodium thiosulphate after the reduction of the
arsenic oxid To arsenious oxid. (2) The difficulty in reading the end point in the
final reaction on adding the standard iodin solution. (3) The great tendency to
foaming on adding sodium carbonate to neutralize the acid. Both the first and second
are caused entirely, and the third largely, by the great amount of organic matter (dye)
contained in London purple. Several methods have been proposed, which are more
or less successful, for overcoming these difficulties. The two which are most used,
however, have not given satisfactory results in the hands of all the analysts using
them, in many cases the results running several per cent too low. The modification
proposed by the referee and tried this year overcomes these difficulties and renders
the determination of total arsenic oxid much easier, particularly for one who has not
had considerable experience with the present methods.
In the following tables are given the results obtained by the different analysts, fol-
lowed by their comments:
TOTAL ARSENIOUS OXID.
Method I is a provisional method and may be found in Bureau of Chemistry Bulle-
tin 107, revised, page 28. Method II may be found on page 29 of the same bulletin.
The results are very satisfactory, Method II appearing to give slightly lower figures.
Total arsenious oxid (As203).
Analyst.
Method I.
Method II.
R J Davidson Blacksburg Va
Per cent.
/ 22.10
Per cent.
21.90
R W.Thatcher Pullman Wash
\ 21.91
I 22.45
21.90
21.99
C D Woods Orono Me
^ 22. 37
22.01
22.01
22.38
22.38
C C McDonnell Bureau of Chemistry
( 22.07
{ 22.23
21.74
21.74
21.74
21.90
21.83
I 22.26
21.86
Average
22.20
21.93
TOTAL ARSENIC OXID.
Method I is a provisional method and may be found in Circular 10, revised, and
also in Bulletin 107, revised, of the Bureau of Chemistry, page 28. Method II may
be found in Circular 10, revised. Method III is Davidson's modification of Hay-
wood's method for removing a part of the coloring matter and may be found in Bulle-
tin 107, revised, where it is designated as Method II, Provisional (p. 29).
Method IV is that proposed by the referee and is as follows:
Place 2 grams of the .sample in a 200 cc graduated flask, add 5 cc of concentrated
nitric acid and 20 cc of concentrated sulphuric acid. Place on a hot plate or over low
flame and heat nearly to boiling; after ten or fifteen minutes add powdered sodium
nitrate, in small quantities at a time, until all organic matter is destroyed and the
solution is colorless. Cool, add about 50 cc of water (to decompose any nitro-sul-
107
phuric acid formed), and heat to boiling till nitric acid fumes are all expelled Cool
make up to mark with distilled water, mix thoroughly, filter through a dry filter and
take .-><> «•<• "i tlu- iiltrate (0.5 gram) for the determination of arsenic oxid Transfer
this •"><> «•«• portion to a 400 cc Erlenmeyer flask, dilute to about 100 cc with water add
grame . -i p< .tassium iodid and 5 cc of concentrated sulphuric acid, heat to boiling
and evaporate to about 40 cc. Cool, dilute to 150 cc to 200 cc and add approximately
tenth-normal sodium thioeulphate just to disappearance of color caused by the free
iodin. In case the solution is slightly colored from iron or incomplete oxidation of
the oiganic matter, add the thiosulphate until nearly colorless, then add a few drops
in-h paste ami continue adding the thiosulphate slowly until the blue color just
disappears. The exact end point can easily be obtained in this way. Neutralize
immediately with sodium carbonate, make slightly acid with dilute sulphuric acid,
and u hen all Lumps of sodium carbonate are dissolved add sodium bicarbonate in con-
siderable excess. Titrate with twentieth-normal iodin solution in the usual way
iisin- -tardi solution a- indicator. Subtracting from this the number of cubic centi-
meters <>f iodin solution corresponding to arsemous oxid as determined by Method I,
the number of cubic centimeters of iodin solution corresponding to the arsenic
oxid (As..,() ram of the sample.
Totul arsenic oxid (As.20&).
Analyst.
Method I.
Method II.
Method III.
Method IV.
R. J. I-
Percent.
18.69
/ 17.53
Per cent.
18.76
Per cent.
I 18.55
\ 18.55
15.64
Per cent.
18.63
19.01
18 29
i i :.:,()
15.56
15.83
18.06
15.55
15.95
C. l».
15.15
15.50
15.75
15.79
15.15
McDiiiim-ll. HiiriMii of < h. IIM u
I 19.34
{ 19. 73
\ 19.52
18.29
18.23
18.42
17.74
18.04
17.90
19.29
19.42
19.30
COMMENTS OK AJTAIiYVH AM) KISCU88ION.
/.'. J.Danihtnn: Then- i- n-.-^n-at dilliculty in working the London purple by Method
I\ i rhaps a little more troublesome and you have to use
another in« th : ::iu' tin- ar.-enimis oxid. I believe Method III, provided it
factory re-ult-. i- the simplest method, both determinations being made
from the same weighed sample.
/•'. IT 'H»ir modification (Method III) makes the end point some-
whai ietermine. The modification suggested by the referee does not seem
to mi- to off, T any advantage over the otlicial method, since the yellow color left after
oxidation with nitrate mixture ob-cun-s the end reaction as badly as does the original
an«l ha- the di-ad vantage of requiring a separately weighed sample for the deter-
mination of th«- ar-enic in arsenious form.
l>. UW/.v; I would emphasize the fact and recommend that it be included in
din-et ion- for in-e, ticide work, that this kind of work is difficult for a beginner and
that -.-v.-nil preliminary determinations should be run before a man new to this work
attem; rt results.
A - ha- been the case in previous years, the results on arsenic oxid are very unsatis-
ry, there being a difference of over 4 per cent between the highest and lowest
determinations by Methods I and III, and over 2 per cent difference by the same
method by different analysts. Methods II and III give lower results than Method I,
but there dot^ not appear to be any uniformity in the amount that these methods
fall short, the determinations made by different analysts and even those by the same
analy-t at different times sometimes agreeing with those made by Method I and at
other^ showin.i; a variation of several per cent. Why this is so has notas yet been
determined, but is under investigation. It is the referee's opinion that on precipi-
108
tating the coloring matter with sodium carbonate a varying amount of arsenic is
carried down in the precipitate.
The determinations made by Method IV, while not agreeing as closely as might be
desired, are close enough to justify a more extended trial of the method in the hands
of different analysts. The writer has found it very satisfactory and, when properly
carried out, a perfectly clear solution can almost always be obtained. Of course it is
desirable to be able to determine both forms of arsenic on the same solution, but if
it Ls found tiiat this can not be done accurately thjb objection to the method becomes
of minor importance.
LEAD ARSENATE.
The methods used for lead arsenate were proposed by Haywood at the meeting of
the association in 1906 and were tried last year. They may be found in Bureau of
Chemistry Bulletin 105, page 165; also Bulletin 107, revised, page 239.
The sample sent out for the work was made by the referee from C. P. di-sodium
arsenate and lead acetate.
Lead arsenate.
Analyst.
Moisture.
Total
arsenic
oxid
(As,06).
Total lead
oxid (PbO).
Percent.
Per cent,
f 30.07
Percent.
R J Davidson Blacksburg Va
( 0.11
1 30.07
\ .12
30.14
29.97
R. W. Thatcher, Pullman, Wash
( .09
30.39
08.38
C. D. Woods, Orono, Me
\ .09
| .14
\ -17
30.24
29. C3
29.81
29.95
30.22
08.48
a 06. 31 C5.96
05.76 05. OG
05.70 00.66
66.22 07.54
C. C. McDonnell, Bureau of Chemistry
.14
{ .15
30.22
30.22
29.47
29.80
29.83
66. 14 66. 89
65.94 67.17
65.85 66.95
66.58 67.32
( 67.55 07. S8
67.35 67.^0
I -17
29. CO
67. 57 07. 15
67.58 07.10
a Porcelain gooch used in all determinations of lead oxid.
DISCUSSION.
C. D. Woods states that in the determination of total arsenic oxid it was not found
necessary to add thiosulphate to use up free iodin because if care is used in boiling
the solution a colorless point is easily obtained.
The results on lead arsenate are not so uniform as might be desired, particularly on
total lead oxid. However, the difference between the highest and lowest determina-
tion of arsenic oxid is only 3 per cent of the total amount present and for lead oxid 5
per cent of the total amount present. The method is certainly the best that has thus
far been proposed and if carefully followed good results should be obtained.
SODA LYE.
METHOD I. — This is the precipitation method, and may be found in Circular 10,
revised, page 8, and Bulletin 107, revised, page 31.
METHOD II. — This is the same as Method I except that the titration for hydroxid
is made without removing the barium carbonate precipitate.
The acid potassium sulphate method was not submitted for trial, as satisfactory
results had not been obtained by it in previous years and the association voted that
it be dropped, as recommended by the referee in 1907.
109
As it was desired to send out samples containing considerable carbonate, and such
urn- not at hand they were prepared as follows: The sample bottle was weighed and
into this was \\ ei-hed 2 grams dry sodium carbonate C. P. then, as rapidly as possible,
18 grains of < -ommerc -ial sodium hydrate. The bottles were then stoppered and sealed.
The analyst \va.- directed to dissolve the entire content of the bottle in carbon
dioxid-free water, make up to 2,000 cc and use 50 cc portions for the titrations (0.5
gram sample). The n -suits submitted have been multiplied by two and reported in
percent in the following table:
Soda lye.
Analyst.
Method I.
Method II.
Sodium
hydroxid
(NaOII).
Sodium
carbonate
(NajCO,).
Sodium
hydroxid
(NaOH).
Sodium
carbonate
(NajCOs).
R. J. l>:ivi.U..ri. Khwksburn, V:i
K. \V. Thatrhrr, Pullman. \V:ish
•i.-ll. Hun-im of ( 'hciuLstrv
Per cent.
M. in
j 83.36
1 83.76
j 84.72
\ 84.72
Per cent.
13.25
14.92
14.40
11.80
11.80
Per cent.
84.80
83.68
83.52
84.92
84.92
Per cent.
12.72
14.50
14.74
11.54
11.54
84.19
13.23
84.37
13.07
The nvulis on sodium hydroxid arc very good. As expected, Method II gives
1\ higher re-nit- i'-»r hydroxid and lower on carbonate than. Method I. The
rence, ho\ mail. The referee determined carbon dioxid in a portion of
i In- -ample gravimetrically and found 11.62 per cent and 11.71 per cent calculated as
sodium carbon.;
I '.-ing these two indicator* in the same determination, as is done in this method, the
:icv would always be to high results on sodium carbonate. Phenolphthalein, .
more -en-it ivo to acids, becomes colorless immediately when the solution is
neutral, while with methyl-orange the acid must be in slight excess to develop the
pink color, tlu> excess required depending on the amount of indicator used and the
depih «.i « olor titrated to. A blank should be made, using the same amount of water
and indicator, and deducted in each case when methyl-orange is used. For the
determination- in tin- --cnnd report in the table the analyst used normal acid. This
may account for the results in -odium carbonate being high, as 0.1 cc normal acid is
equivalent to ..\er I per ci-nt sodium carbonate, when operating on 0.5 gram of sub-
stain-. •
1'oKMAI IH.HYHK.
x » samples were sent out for analysis, No. 1, a strong solution to be worked by the
modified hydrogen peroxid method, and No. '_', a dilute solution to be worked by the
nd method. lx>th found in Bulletin 107, revised, page 33.
Formaldehyde.
Analyst.
Sample
No. 1.
Method I.
Sample
No. 2.
Method II.
R J D-ivi'lson I Hacks burg Va.
Per cent,
i 36. 81
Per cent.
t 3.92
< 3.98
R \V Th-itrhiT I'ullmm Wish
I 36. 64
\ 3.92
3.83
CP \li>I ><>nni'll Rurpan nf Choinistrv
1 37.00
( 3.98
3.84
\ 36. 93
I 4.02
36.76
3.90
rag
110
COMMENTS AND DISCUSSION.
R. J. Davidson Bays: "I believe it would be well to state the amount of dilution
necessary in Method II and not say, as the method does, 'a weighed quantity of the
dilute formaldehyde solution.' The directions should be more specific."
The results on formaldehyde are very good. Method I is an excellent method for
strong solutions, and Method II for dilute solutions, containing preferably not over 5
per cent. Even solutions of the latter strength rmist be diluted before making the
determinations.
The referee is in favor of the recommendation made last year and referred to again
in Mr. Davidson's report, that more specific directions should be given this method.
If, instead of the words "a weighed quantity of the dilute formaldehyde solution,"
line 8, the following were inserted, "a weighed quantity of the formaldehyde solution
containing not over 2 cc of a 1 per cent solution or the equivalent," it would make the
method clearer and sufficiently explicit.
SULPHUR DIPS.
The method is that of Avery and is given in Circular 10, revised, also Bulletin 107,
revised, page 34 The sample submitted for analysis was prepared in the laboratory
by boiling together lime and sulphur according to the regular formula for the lime-
sulphur spray mixture.
Sulphur dips.
Analyst.
Date of
analysis.
Weight of
sulphur.
1Qft«
f 0. 03452
R. J. Davidson, Blacksburg, Va August 18 { . 03455
. 03452
C C McDonnell Bureau of Chemistry
1 .03096
{ . 03536
July 20 { . 03583
1 . 03575
Average
I .03568
1
The results are all very close, the greatest difference being only 0.25 per cent. This
method has also given satisfactory results in past years.
In view of the fact that this report was not presented at the meeting of the associa-
tion, no recommendations will be made at this time.
PRESIDENT SNYDER'S ADDRESS: THE TRAINING OF THE
AGRICULTURAL CHEMIST.
I have selected as the subject of the president's address for this , the twenty-fifth
annual convention of the Association of Official Agricultural Chemists, "The Training
of the Agricultural Chemist."
Any society or organization in order to be effectual and progressive must look well
to its membership. Our society has been most fortunate in this respect, and it is to
be hoped its ranks will continue to be filled with the same class of earnest, energetic
workers as are here to-day. During the past quarter of a century this organization
has accomplished most excellent results. I believe, however, that it has only entered
upon its career of usefulness. Much credit is due to the founders for the high ideals
of the association and for the cultivation of the true scientific spirit. Many of them
Ill
r.-c,-ived their training in the great European laboratories, where they were students
..i 1. it-big, Fn-enius, \'oit, Hoffman, and Pasteur, and they have planted in this
country tin- see. I of true agricultural research. Most of the older members have
relinquished their labors, and the work of the society may now be said to be in the
hands < >i the second generation, "who, it is hoped, will meet with as much success and
r tin- sain*- spirit and ideals.
( Jri.u'inally agricultural chemists were in a way self-educated. They secured what
kno\\ -led ire they could of general and analytical chemistry and then applied it to the
.- -ilutii.il i»i agricultural problems. Naturally the work was largely analytical. "What
hi- -ul.-tance contain? " was and is to-day the quest of the chemist. During the
i'.-\v years, however, the domains of agricultural chemistry have been greatly
enlarged and then- is probably now no other branch of chemistry that calls for so wide
a i raining. Organic, inorganic, industrial, physical, physiological, and sanitary
cheniM- have definite channels within which their activities are confined, while the
agricultural chemi-t mu-i necessarily include in his domain a large portion of all of
these. In dealin- with the soil an extended knowledge of both inorganic and organic
chemi-try a- well as of physical chemistry is requisite. Our knowledge of soils is
sarily much restricted because the chemistry of the silicates is so imperfectly
under-tood, arid -•in the analy-is of plant and animal substances and the interpreta-
tion of the n-.-ult- our knowledge is likewise very limited. While the data gained
from the aiialy-i- of f..od~tui'f- i- exceedingly valuable, I do not believe that it is as
much BO as it i.- de-tMted to be, and while chemistry is one of the most useful of the
es in the -nidy f agricultural problems, it is capable of being made still more
valuable and u-eful.
One of the chief fum -tii.il- of the agricultural chemist is to correctly analyze agri-
cultural prod uc t<. In order to do thin methods of analysis based upon rational prin-
ciple- mu-t l.i- devised, and Jhi- is one of the principal features of the work of this
association. It is scarcely necessary for me to dwell upon its importance. Correct
method-, of analy-i-i are essential, as without these chemistry would be entitled to no
hiu'ht rrank than alch.-my I do not believe that the importance of the development
methods for the analysis of agricultural products is as fully appreciated by
ion workers a- it -hould be. A large amount of the work that has been
don, u ,1. -tined to !>•• di- redited and discarded because of errors in methods employed.
j.erirncnt -tat ions have been too impatient to secure immediate results
and have not paid -utHcieiit attention to methods of investigation. The study of the
method- f'»ranaly-i id agricultural products can well be continued as the
promiiH-nt feature of this organization.
With the advance that i- I.eini: made in general science and the greater recognition
i agriculture, more extended provision should be made for the education and
training «>i the pn>spe. live agricultural chemist. There are many institutions that
offer « \< client four-year « ..tir-es in chemical engineering and other branches of chem-
i-try leading to degrees. I know of no American institution where such a course is
D in a-ri« ultural chemistry. lias not the time arrived for the establishment, in
some of our institutions of courses of study having for their object the training of agri-
cultural chemist-.' Certainly the importance and magnitude of the field would sug-
gest the need of such courses. I shall not discuss the subjects that could most
!y form a part of the curriculum, but there should be a correlation of the
different s. -fences Mended with general and technical chemistry. As matters now
stand, it >- Jem-rally necessary for an experiment station to secure as assistants
yoiini; • hemi.-ts who have had but little training in analytical chemistry and give
them special training in agricultural analysis. The experiment stations have to
train their own assistants and by the time they have become reasonably proficient
another institution or some industry offers a higher salary and then new assistants
must be initiated, the process in some cases being repeated several times a year. Our
112
research work suffers because of this condition. Experiments are undertaken with
one corps of assistants, a part of the work is done by another, and if the investigation
is completed at all it is after many changes have been made. If some of our larger
institutions would furnish more extended training in agricultural chemistry and better
remuneration were given assistants so as to retain their services, conditions would be
greatly improved. I do not consider that this lack of training of assistants is neces-
sarily the fault of agricultural colleges, as their courses of study have been formu-
lated with o$ier objects in view than the training of scientists for research work.
There are many interesting problems in agricultural chemistry which await investi-
gation, and their correct solution would be of great benefit to mankind. The field of
research is so large that this association can consistently encourage a larger number
of workers.
In addition to the special technical training the agricultural chemist needs broad
equipment in other lines so that he may be able to inaugurate useful lines of research
and properly interpret his results. There are many chemists who are capable of
making accurate and rapid analyses and prosecuting routine work, but are unable to
outline an investigation, plan intricate details, carry the work to a satisfactory con-
clusion, and correctly interpret the results. There need be no fear of overcrowding
in the realm of agricultural chemistry or necessity for forming a trade union to regulate
the number practicing the profession. In this connection it is pleasing to note the
greater recognition that is being given the agricultural chemist. About a decade ago
the number of positions in this line were limited and the compensation exceedingly
small. While neither the number of positions nor the compensation is now particu-
larly large there has certainly been a material increase in both. For example, in the
Department of Agriculture in 1897 the maximum salary paid was $2,500 per year and
the average to 12 chemists was $1,541, while in 1907 the maximum salary was con-
siderably greater and 47 chemists received an average of nearly $2,000. On the
whole, however, these salaries are smaller than are paid in many of the large educa-
tional institutions, although the rate of increase during the past ten years has been
greater than in educational institutions, and if this continues the agricultural chemist
bids fair in the near future to receive as large a compensation as workers in other
lines of science. Much credit is due to our present Secretary of Agriculture for recog-
nizing the importance of agricultural research and having the courage to advocate
and recommend to Congress suitable compensation for agricultural scientists.
The position of the agricultural chemist in both the educational and business world
is undergoing transition. He is being regarded as a greater factor in human and
industrial progress than heretofore and I believe that with each decade he may reason-
ably expect greater opportunity to do good work, coupled with better compensation.
Agricultural chemists have as a -rule been underpaid; neither have they been given
sufficient funds with which to prosecute their labors. In many laboratories book-
shelves are not filled as they should be and makeshift apparatus is employed where
better results could be secured if the chemist had at his command the literature
covering the work of others upon the subject which he is investigating, and suitable
apparatus and means for his work. There has been many a scientific surrender
because of lack of funds for effectually carrying on the work.
As a nation we have taken great pride in the progress made by our industries, an
advance more rapid than that of any other country. This in a large measure has
been due to the work of the American chemist. There is scarcely an important
industry but employs a well-trained chemist and has a suitably equipped testing
laboratory. The steel, sugar, cement, and other great industries are practically
applied chemistry. It has been said that the American chemist has contributed less
than his quota to the advancement of science; he has, however, contributed his full
share to the advancement of our industries. Instead of being a devotee of pure science
he has advanced the domains of applied science. The agricultural chemist should
113
concern himself not only with the economic production of foodstuffs but should
extend his work along the lines of their preparation and utilization. The production
of f. KM!, while a very large and important subject, has associated with it its proper
manufacture and utilization. The agricultural chemist should take a broader view
than that of mere critic of the industries; and there is some danger when working
alniiu' special fo<xl lines of his becoming too narrow in his consideration of the questions
that present themselves. While adulteration and sophistication in any form should
not In- tolerated by the chemist, he should first make sure that it is adulteration, and
in this connection tin-re are destined to arise questions upon which scientific men
materially arid honestly differ. I should not care to see all scientists agree on all
questions, as thi- would be detrimental to progress. There must be some attrition,
ami when differences arise they should be met in the true scientific spirit, each one
lieini; sure that the data and facts which he presents are absolutely correct in every
detail. I believe the province of the chemist is first doing accurate analytical work.
Tin- stand which has been taken by this association is a most excellent one: That
the meetings shall be open for discussion, that we invite thorough discussion of all
subjects relating to the analysis of our agricultural products and the interpretation
of their re-nit.-, but that the views expressed by any one individual are not necessarily
the otlirial \iews of the association. In controversial questions it is well for the
•v to be conservative. We all recall the attempt of the French Academy of
Science to settle the much-vexed question of atmospheric nitrogen as a source of plant
io.nl. an-! how. after examining the conflicting reports of Ville and Boussingault, the
learned committee of the s<». iety reported that M. Ville's conclusions and results
irere condatenl \\ith hi- experiment-. We well know how the conflicting work of
the-e two in\> harmonized, and while the society attempted to
decide the qiir-t i> >n the real question was not settled until years later. The best
ser\ ice this so« iety ran render the cause of agriculture is to continue along the lines
followed by the founder-. I" improve the methods of analysis so that the work done
by the otlirial methods of the Association of Official Agricultural Chemists will
command respect wherever quoted.
The food rheini-t should make a more careful and extended study of processes
employed in the manufartureof foods. A purely theoretical knowledge of manufactur-
in-.: processes may lead t... -m.neous conclusions. Some manufacturers of foods are doing
more in the\\a\ "f -<ientilir investigation than are many of our universities and experi-
ment stations. The encc.urau'ement given by the industries for the investigation of
srientitir subjivtshas been productive of fruitful results. Pasteur's classical work on
fermentation was made possible by his connection with the industries. The agri-
cultural rhemi.-t needs the help and assistance of the technical chemist.
One,. f,,ur-reat m-ed- is more funds with which to prosecute scientific inquiry. Men
MI science ha\«- the /eal and ability, but often fail for lack of funds to procure and con-
ntilic apparatus. And too often men in our universities who are specially
adapted b> nature for the prosecution of scientific investigations are overburdened
with elementary instruction that could be more eflBciently done by others. Many
scientists attempt to do too much, and the result is a dissipation of energy.
Scientific u,,rk often suffers, too, because of the natural modesty of scientists, and
sometimes those who accomplish the least but make the most noise, secure the lion's
share of the funds for carrying on work. Some pseudo-scientists resort to cheap ad-
vert isim; that can not be too severely condemned. The best advertising a scientist
• an do is the publication of high-grade scientific work. It is a slow but a sure way of
building up a permanent reputation. A scientist who maintains a press agency is not
destined to make a premanent record.
Often science lan-uishes because those immediately in authority are not sufficiently
educated or naturally liberal enough to appreciate her claims or able to give wise and
T.,;7:j_Huii. 122—09 8
114
intelligent direction to scientific investigations. Science should be completely seg-
regated from politics as it is sometimes practiced, and she should not be dependent
for her existence upon the whims of the spoilsman.
Science seeks to determine the truth. True science will not tolerate a falsehood
nor perpetrate a fraud, and there is no place for the drone in the ranks of science; there
have been a few who have made some progress by conjuring with scientific terms,
looking wise, cultivating society, and catering to the whims of those in temporary
authority and neglecting science. Others have had a brief but precarious existence
as scientific pirates, appropriating to themselves the work and results of others, some-
times of advanced students and underpaid and dependent assistants. All true teach-
ers and investigators enjoy having their assistants and students do good work and
secure noteworthy results. A true scientist can honestly rejoice at seeing his col-
league or coworker make a discovery. Petty jealousies are unworthy of science.
Agricultural chemistry is a great constructive agency and wealth producer. We
are building our science for review by future generations. Let us build it well so as
not to be ashamed of the workmanship. The true scientist bequeaths to mankind an
invaluable legacy. Let us cultivate true science and not false ideals.
The proposed changes in the constitution, which had been made
special order following the president's address, were considered.
These changes were as follows :
In article 1, first sentence, substitute for the words " the United States," the
words "North America."
In article 2, first sentence, second and third lines, insert the word "provincial"
after the word "State;" also, in the third line of this sentence insert after the word
"body" the phrase "in North America."
After discussion, the amendments were put to a vote and were
carried.
A motion was made by Mr. Wiley to the effect that a referee and
an associate referee on water analysis be appointed to study mineral,
sanitary, irrigation, and technical waters, inasmuch as, under the
food and drugs act, standard methods for potable waters were
needed as well as for foods, while the analysis of irrigation waters
was a purely agricultural question and also needed study and elabo-
ration.
The motion that such referees be appointed was carried.
FRIDAY— AFTERNOON SESSION.
REPORT ON SOILS.
By S. D. AVERITT, Referee.
The association at its last meeting made only two recommendations affecting the
referee's work this year.
(1) That the modified J. L. Smith method for total potassium be further tested.
(2) That the sodium peroxid fusion method for total phosphorus be adopted as a
provisional method of this association and be further tested.
Including this year, these methods have been before the association three years,
and it seemed very desirable to place before the association work sufficient in quan-
tity and of such a quality as to enable it to dispose of them. From his experience as
115
a ...operator in the past, the referee thought it best not. to ask for too much work, and
in accordance with this view only one other line of investigation was requested of
those who expressed a willingness to cooperate. In the opinion of the referee, the
sodium peroxid fusion method for total phosphorus had some very serious disad-
vantages, particularly as to manipulation and length of time required for the determi-
nation. It was thought desirable to ask that a method in use in this laboratory be
tested with a view to proposing it as a provisional method for total phosphorus in
soils.
This method, which may be known as the magnesium nitrate method, is easy of
manipulation and rapid, and in this laboratory has given uniformly as good results
as the sodium peroxid fusion. Accordingly, it was asked that these two methods be
compared.
Two well-known Kentucky soils were selected for this work. No. 1 is a cultivated
soil from the western coal field. A complete analysis made by this station shows it
to l.e poor in pho-phaies, organic matter, and nitrogen. No. 2 is a virgin soil from
thr I >e\onian in the eastern part of Clark County, known by analysis, as in the case of
NM. 1. i" !>«• particularly rich in phosphates, organic matter, and potash.
•uples were prepared and sent to fourteen chemists, who volunteered to aid in
t hi- work, with the following instructions:
INSTRUCTIONS.
(a) Make a determination of moisture by the official method, reporting the per-
centi
(6) \\ eiL-h lo irraiiH of sodium peroxid into an iron or porcelain crucible and thor-
euiirhl) mi \ \\ iih it 5 grains of the soil. If the soil is very low in organic matter, add
a link .-larch '" ha.-teu the action. Heat the mixture carefully by applying the
flame of a Hun-en burner directly upon the surface of the charge and the sides of the
crucible until the action start- < 'over crucible until the reaction is over, and keep
at a low red heat for fifteen minutes; do not allow fusion to take place. By means
of a large funnel and a stream of hot water transfer the charge to a 500 cc measuring
flask. Acidify with hydnx-hloric acid and boil. Let cool and make up to the mark.
If the action has taken pi. ire properly there should be no particles of undecomposed
soil in the bottom of the flask. Allow the silica to settle and draw off 200 cc of the
clear sol u i
Precipitate the iron, alumina, and phosphorus with ammonium hydroxid; filter,
wash, return the precipitate to the beaker with a stream of water, holding the funnel
the beaker, and dissolve the precipitate in hot hydrochloric acid, pouring the
acid upon the filter to dissolve any precipitate remaining. Evaporate the solution
and to complete dryness on the water bath. Take up with dilute hydro-
chloric acid, heating if necessary, and filter out the silica. Evaporate filtrate and
to about lo cc, add '2 cc of concentrated nitric acid, and just neutralize with
ammonium hydroxid. Clear up with nitric acid, avoiding an excess. Heat from 40°
to 50° on water bath, add 15 cc of molybdic solution, keeping at this temperature
f.»r from one to two hours. Let stand overnight, filter, and wash free of acid with
0.1 per cent solution of ammonium nitrate; finally, once or twice with cold water.
Iter to beaker and dissolve in standard potassium hydroxid (1 cc equal to
0/J mi; of phosphoru.- , titrate the excess of potassium hydroxid with standard nitric
acid, using phenolphthaleiu as indicator.
(c) Weigh into a 50 cc porcelain dish 5 grams of soil. Moisten with 5 to 7 cc of
magnesium nitrate solution ( (g) p. 2, Bui. 107, Bureau of Chemistry). Bring to
dryness on water bath, burn off the organic matter at low redness; when cool, moisten
slightly with water, add 10 cc of concentrated hydrochloric acid, digest two hours
on wafer l.ath, keeping the dish covered with a watch glass; stir up two or three
times during digestion.
Make up to i'50 cc, mix well and throw on a dry folded filter, pouring back on the
filter till the solution runs through clear. Take aliquots corresponding to 2 or 4
irrams <4 Drains in Xo. 1, 2 grams in No. 2), depending upon the amount of phos-
phorus pre-ent . Hrin.u' to dryness, take up with hydrochloric acid and water, filtering
over pump. Filtrate and washings should not exceed 30 or 40 cc. Make alkaline
with ammonia, and dissolve the precipitate with concentrated nitric acid, using a
slight excess. Add gradually, while shaking, 5 to 15 cc molybdate solution (p. 2,
Bui. 107). After standing a minute or two add 15 cc of ammonium nitrate (p. 2,
116
Bui. 107), shaking thoroughly. The solution should be kept at 40° or 50° C. for
an hour, then let stand overnight at the room temperature, filter, and wash well
with cold water. A Hirsch funnel with a double qualitative filter, S and S No. 597,
cut to fit, and well pressed down around the edge with the finger after wetting and
putting on pressure, is recommended. Put filter and precipitate back into the same
flask, using as little water as possible for washing back into flask. Determine phos-
phorus volumetrically, using standard potassium hydroxid and nitric acid.
(d) Fuse 1 gram of soil according to the well known J. Lawrence Smith method.
Transfer the fused mass to a porcelain dish, slake with hot water, grind finely with
an agate pestle, and transfer to a filter. After washing free of chlorids, concentrate
the filtrate and washings in a Jena beaker to about 20 cc, and filter. Slightly acidify
the filtrate and washings with hydrochloric acid, concentrate in a platinum dish,
add 1.5 cc of a platinic chlorid solution (10 cc contains 1 gram of platinum). Evapo-
rate to a sirupy consistency, as usual, and wash with 80 per cent alcohol and ammonium
chlorid solution.
(e) Determine potassium according to the regular J. Lawrence Smith method."
The referee inclosed with his instructions to those who expressed a willingness
to cooperate in the work a short personal letter, and had hoped that each one would
contribute something to this report, but unfortunately, as it often happens, manv
were not able to send in results in time for use. The referee desires to express his
thanks to the following chemists who have aided him in the work: A. W. Gregory, for
the Illinois station; W. P. Kelly, for the Hawaii station; P. E. Brown, for the New
Jersey station; G. S. Fraps, for the Texas station; W. B. Ellett, for the Virginia station;
I. O. Schaub, for the Iowa station; and P. F. Trowbridge, for the Missouri station.
It will be seen from Table 1 that the results obtained by the sodium peroxid fusion
and the magnesium nitrate method show practically no difference. One chemist
gets results in Soil II somewhat higher than the others, but the amounts of phos-
phorus obtained by the two methods on three determinations are almost identical.
In Soil I, with the exception of one determination, the maximum and minimum
results are not bad duplicates.
a Fresenius's Quantitative Chemical Analysis, p. 426.
117
T\m i \.-Comparison of sodium peroxid fusion and magnesium nitrate methods for
total phosphorus.
[Water-free basis.]
Analyst.
Soil No. I.
Soil No. II.
Sodium
peroxid.
Magnesium
nitrate.
Sodium
peroxid.
Magnesium
nitrate.
A. W. <!r«Korv. Illinois
Per cent.
0.029
.028
Per cent.
0.027
.027
Per cent.
0.211
.210
Per cent.
0.224
.226
Average
.029
.027
.211
.225
W. P. Kelley. Hawaii
.030
.240
.244
.236
Average
.030
031
.030
.240
P. K. Hrown. New Jersey
.021
.029
.025
.025
.025
.025
.029
.281
.281
.285
.281
.285
.285
Average
.025
.026
.282
.284
>r!vl... Texas
.025
.197
.201
Average
.023
.024
.199
I. O. Schauh, lowaa
.025
.213
\v. 15. Kil.-it. Virginia...
.025
.024
.027
.028
.231
.230
.232
.232
Average. .
.025
.027
.231
.232
8. D. Averitt, Kentucky.
.031
.032
.030
.030
.220
.213
.227
.229
Average
.031
.030
.217
.228
P. F. Trowhridge, Missouri • .
.030
.029
.242
.219
(JpiMT.iIuvi- rip-
.028
.028
.237
.230
• Duplicates not reported.
Tlu» n-foriM' did not ask that these methods be checked by the carbonate fusion or
standard method, a.« it is sometimes called, his work with the method having shown
that it has the disadvantage of a large amount of soluble silica, necessitating dehy-
dration, and in the cane of a soil with any considerable amount of organic matter
there exist favorable conditions for reduction and, consequently, some loss of
phosphorus.
In Table 2 will be found the results of the referee's determination of total phos-
phorus in the two soils, working as follows: Making a carbonate fusion, then proceeding
as for an accurate determination of silica, the silica evaporated with hydrofluoric acid,
the residue taken up with hot, strong hydrochloric acid and added to the filtrate
from the silica. Iron, alumina, and phosphorus precipitated with ammonium
hydroxid, washed, redissolved, and the phosphorus determined volurnetrically, as
in the magnesium nitrate method.
It will be seen from the table that in Soil I, containing very little organic matter,
the results compare very favorably with the other methods, but in Soil II, rich in
organic matter, the average is lower.
118
TABLE 2. — Duplicate determinations of phosphorus by carbonate fusion.
[Water-free basis.]
Soil I.
Soil II.
Per cent.
0.025
.033
.026
Per cent.
0.202
.220
.207
.207
.028
.209
In Table 3 will be found duplicate determinations of total phosphorus in soils by
the magnesium nitrate digestion. Of these, Nos. 1127, 1202, and 1204 are presumably
Texas soils, and the determinations were made by Mr. E. C. Carlyle, of the Texas
station. The others are low phosphate soils of western Kentucky and were made as
checks in the general work of this laboratory.
TABLE 3. — Duplicate determinations of phosphorus by magnesium nitrate method.
[Water-free basis.]
Soil No.
Determi-
nation 1.
Determi-
nation 2.
Soil No.
Determi-
nation 1.
Determi-
nation 2.
Per cent.
Per cent.
Per cent.
Per cent.
13
0.030
0.027
120
0.034
0.034
14
.051
.052
600
.035
.035
15
.046
.040
601
.043
.039
16
.052
.053
602
.028
.026
117
.046
.045
1127
.029
.027
118
.045
.045
1202
.031
.032
119
.034
.034
1204
.020
.021
Table 4 shows the modified method to compare very favorably with the regular
J. Lawrence Smith method for total potassium, the former method giving in the gen-
eral average 0.01 per cent more potassium in both soils. Taking into consideration
the fact that the work is done on 1 gram the agreement is as close as could be expected.
Referring to the work done by these methods in 1906 and 1907, it will be seen that
the results are in the main concordant.
119
TABLE 4.— Comparison of modified and Smith methods for total potassium.
[Water-free basis.]
Analyst.
Soil I.
Soil II.
Modified.
Smith.
Modified.
Smith.
A. \V. »;n-gorv, Illinois
Percent.
1.156
1.157
1..182
1.156
1.158
Per cent.
1.205
1.175
1.164
1.208
1.223
Per cent.
1.568
1.547
1.566
1.552
1.547
Per cent.
1.582
1.598
1.594
1.586
1.566
Average
1.162
1.195
1.556
1.585
W. H. Kllett, Virginia
1.068
1.081
1.183
1.121
1.495
1.487
1.564
1.536
Average
1.075
1.190
1.185
1.214
1.152
1.162
1.170
1.202
1.491
1.552
1.546
1.531
1.550
1.491
1.541
1.565
8. D. Averitt. K.-iitiicky
Average
1.196
1.178
1.543
1.532
P. F. Trowbridge, Missouri <
1.177
1.186
1.512
c 1.357
\ V \\Vlls Iowa
1.271
1.275
1.121
1.134
1.608
1.702
1.751
1.760
Avrrw
1.273
1.127
1.655
c 1.755
O. M. Sh»-.M . Km t ucky b
1.511
1.627
Average
1.569
uiub, Iowa
1 320
1.656
1 678
Average. . .
1.440
cl.380
1.667
' i''iM»ral average
1.177 1.168
|
1.571
1.556
tr.s not rrportril.
b Too late to be included in the general average.
Not included in the general average.
MMENTS OP ANALYSTS.
/'. E. Brawn: The magnesium nitrate method is undoubtedly quicker and easier of
manipulation than the |K»roxid fusion method. It has the advantage that there is
not nearly >u< h a large amount of silica to get rid of, as it was found necessary to dehy-
drate three or four times with the peroxid fusion method. Then, top, in the first oper-
ation of tin- iii-ion method there seems to be an uncertainty of reaction while avoiding
fu.-ioM, which is of course eliminated in the other method.
You will notice from the results that the agreement is fair with a tendency for the
new method to giv»» slightly higher results. However, if the first determination in
Soil I by the fusion method is eliminated, the agreement is much better. On the
whole the magnesium nitrate method seems to me to be undoubtedly superior to the
other.
\V. /'. Kdley: I find the magnesium nitrate method as outlined by you to be a very
simple and convenient scheme for determining the phosphoric acid in soils; and while
I have not had an opportunity to compare this method with others, I have no doubt
that the results are reliable.
RECOMMENDATIONS.
The work done this year, while not as extensive as the referee had wished, still
warrants in his opinion three conclusions, especially when it is remembered that work
along the same line last year and the year before is mainly concordant in the matter
of results: First, that the modified J. Lawrence Smith method for total potassium
compares very favorably with the regular method and is somewhat shorter; second,
120
that the sodium peroxid fusion method for total phosphorus gives good results, but
the manipulation presents some difficulty, and the time required for making the deter-
minations is a disadvantage; third, that the magnesium nitrate method gives uni-
formly as good results for total phosphorus as the sodium peroxid fusion, and is quick
and easy of manipulation. With these facts in view, the referee would make the
following recommendations:
(1) That the modified J. L. Smith method for total potassium be adopted as an
optional method of this association.
(2) That the sodium peroxid fusion for total phosphorus be adopted as an official
method.
(3) That the magnesium nitrate method for total phosphorus be adopted as a pro-
visional method of this association and be further tested.
REPORT ON THE DETERMINATION OF CALCIUM CARBONATE IN
SOILS.
By JACOB G. LIPMAN, Associate Referee.
Systematic determinations of calcium carbonate in cultivated soils seem highly
desirable in view of its important functions in crop production. Unfortunately, there
is no unanimity of opinion among chemists as to the methods best adapted for this
work. When the proportion of calcium and magnesium carbonates exceeds 1 per
cent, fairly accurate determinations may be made by the liberation of carbon dioxid
and its absorption and weighing in potash solutions. But when the proportion of
carbonate is small, as is true of so many of our soils, the quantity of carbon dioxid
which remains in solution in the acid is very large in proportion to its entire amount.
This source of error has frequently been commented upon and has led to several
more or less successful attempts to correct it."
The associate referee on soils thought it advisable, therefore, to outline some cooper-
ative work on one or two promising methods for the determination of carbonates in
soils. Samples of two different soils were sent to eleven members of the association
who had signified their willingness to cooperate in the testing of soil-analytical meth-
ods. It was suggested that determinations of carbonates be made in the samples by
Knorr's method as described in Wiley's Agricultural Analysis, b Where possible, the
results secured by Knorr's method were to be checked by the method described by
Amos in the Journal of Agricultural Science, c
The samples were sent out early in September, and analyses were made and reported
by W. B. Ellett of the Virginia station, by Percy E. Brown of the New Jersey station,
and Ernest Van Alstine of the Illinois station. Mr. Van Alstine's data were trans-
mitted to the associate referee by Mr. Hopkins.
Mr. Ellett and Mr. Brown used Knorr's apparatus for the determination of the car-
bon dioxid. Mr. Van Alstine employed the method regularly used at the Illinois
station and consisting of the liberation of the carbon dioxid "by boiling with hydro-
chloric acid and ascertaining the quantity of carbon dioxid evolved by measuring
before and after absorption by a caustic potash solution," The results were as follows:
a See Hall and Russel, A Method for Determining Small Quantities of Carbonates,
Transactions, J. Chem. Soc., London, 1902, 81: 81.
&Vol. 1, p. 338.
c 1905, 7:322.
121
Determination of carbon dioorid in soils.
(Percentage of dry soil.]
Analyst.
Soil No. 1.
Soil No. 2.
E. Van Alstine, Illinois
0 025
Average
.025
.027
.024
.020
.020
.020
\V. M. Kllett, Virginia
.030
.025
Average
r 1 Brown, New Jersey
031
.034
.030
.026
.021
Average
flOO
The result* submitted by Ellett and Brown agree very satisfactorily. Those sub-
mit ted by Van A \<\ ine are markedly lower, especially in the case of soil No. 2. Appar-
ently tin- amount of carbon dioxid which remained in solution in the latter work is
the cause of the |,,\v. T n-ults. Evidently Knorr's apparatus is efficient for the deter-
mination of comparatively slight amounts of carbonates; however, it is desirable that
further w.rk !>«• done aloni; this line, and the associate referee would therefore recom-
mend, that it be continued with certain modifications for at least another year.
REPORT ON POTASH.
I'.y I', H. K,,ss, Referee. *
The w..rk mi pi.ta.-h for the past year lias included cooperative tests of the regular
otlii-ial method in comparison with the phonphomolybdic volumetric method, and,
in addition, the reft-ree, associate referee, and some cooperating chemists have made
comparative tests with some special methods which will be described in the latter
portion of thi< report.
Twenty laboratories expressed a desire to take part in the cooperative work on
P >ia-h sample-, but reports were received from only eight laboratories.
Two .-ample.-, were sent out for analysis to each laboratory taking part in the work,
sample No. 1 being high-grade commercial sulphate of potash, while sample No. 2
was a mixed fertili/er, the ingredients of which were acid phosphate, cottonseed meal,
dried Mood, potassium chlorid, and a small amount of magnesium sulphate.
The following instructions with regard to the work were sent out to all cooperating
chemi>is. the details .if the volumetric method being those given by the referee for
!?«»; and 1907, Mr. A. L. Knisely, who had given much time and attention toastudy
of the phosphomolybdic method.
OUTLINE OF ASSOCIATION POTASH WORK.
Sample No. 1. Commercial sulphate of potash.
Sample No. 2. A complete mixed fertilizer, the nitrogen of which is derived from
cotton.-eed meal and dried blood.
Pota.-h in these samples should be determined both by the official method and the
pn>{>osed volumetric method involving use of phosphomolybdic acid.
122
Reagents.
Nitric add. — 50 cc of nitric acid (1.40 sp. gr.) in 1,000 cc of water.
Sodium nitrate wash. — 10 grams of sodium nitrate per 1,000 cc of water.
Phosphomolybdic acid solution. — 100 grams of phosphomolybdic acid (Kahlbaum's
preferred) in 750 cc of water and 250 cc of nitric acid (1.40 sp. gr.). 'This solution
must be freshly prepared — not over three or four days old before using. If properly
made the evaporated residue from a portion of this solution is never white and readily
redissolves in the dilute nitric acid solution in the cold.
Standard solutions. — Standard caustic potash and nitric acid prepared for volu-
metric phosphoric acid diluted to 2 volumes. One cubic centimeter of this potassium
hydroxid solution is equal to 0.812 mg of potassium oxid.
Determination.
Transfer 10 cc of solution to a platinum dish, add 0.25 cc of sulphuric acid (1 to 1).
Evaporate to dryness and ignite to whiteness. Dissolve residue in hot water plus a
few drops of hydrochloric acid and transfer to a tall 200 cc beaker, add 30 cc phos-
phomolybdic acid solution and slowly evaporate to complete dryness on top of a
steam bath.
It requires approximately 22 mg of phosphomolybdic acid, in order to have an
excess, for each milligram of potassium oxid present.
Add 30 cc of nitric acid wash to the dried residue and stir thoroughly in the cold,
with a grinding motion with a policeman, allow to settle a moment and decant super-
natant liquid at once through a gooch crucible packed with moist filter paper pulp,
approximately one-sixteenth inch in thickness. Wash twice by decantation with
sodium nitrate wash, transfer precipitate to a gooch and wash with sodium nitrate
wash until acid free. Transfer gooch to casserole, run in excess standard alkali solu-
tion and add phenolphthalein. Heat to boiling and titrate excess alkali with standard
acid.
Some samples of asbestos seem to hold or "fix" some of the excess acid, making the
gooch filter very hard to wash acid free. Hence it is suggested to use a paper pulp
filter. It is also desirable to make comparative tests, employing the usual asbestos
filter.
If excess of phosphomolybdic acid has been used, the dried residue has a reddish
hue. If excess has not been added the residue is bright yellow. Residue should not
appear white.
In each case, run blanks to ascertain corrections to be made for impurities.
It is also desired that in sample No. 1 determinations of potash be made, not only
by the official method (which provides for direct evaporation of the solution without
addition of ammonia and ammonium oxalate), but also by the method applicable to
mixed fertilizers, adding ammonia and ammonium oxalate, followed by evaporation
and subsequent ignition with sulphuric acid.
Several chemists have urged that this latter method of procedure be tried, as it is
claimed that the official method for potash salts gives too high results owing to impure
precipitates.
The reports of results of cooperating chemists are as follows:
123
Potas h results reported by cooperating chemists.
Analyst.
Sample No. 1.
Sample No. 2.
Official
method.
Volu-
metric
method.
Official
method
plus am-
monia
and
ammoni-
um
oxalate.
Official
method.
Volu-
metric
method.
K. I.. Bak»T, (ifiirvu, N. V..
Per cent.
\ 51.32
j 51.24
Per cent.
51.26
51.30
Per cent.
50.16
50.16
Per cent.
4.41
4.43
Per cent.
4.89
4.89
4.72
S. K. \>i.iirv. Colletfe Station, Tex
51.40
50.66
4.42
E. C. Carlyle, College Station, Tex
/ 4.65
\ 4.40
G. Farnham, Cincinnati, Ohio
50.60
50.56
50.80
50.75
50.71
50.82
50.84
""56." 68
50.73
oSO.29
050.43
51.02
49.81
49.77
50.64
50.62
50.22
50.46
50.55
4.44
4.40
4.44
4.47
4.31
4.35
4.34
ham, Cinri limit i, Ohio
J 11 MitrhHl CU-insuM College, 8. C
50.41
50.60
50.09
50.61
50.09
50.09
4.45
4.49
4.20
4.45
.u-rtson, CU'inson College, 8. C...
O.T. Beyer, < i
Laboratory of Armour & Co
50.16
50.08
4.38
4.43
II 1 luylor, Chicago. Ill
Laboratory of Swift A
58.19
i :,:<.<.»<)
61.60
{ 58.00
57.96
I 59.62
58 80
50.28
4.42
4.66
4.68
5.01
5.14
4.99
C. H. H rair«l«>n Chicago, Ill
4.43
4.90
4.69
/ 4.30
\ 4.60
Laboratory of -
59.11
C. L. llar*», Auburn, Ala
A. M. Kiiiisotu ami T. Bragg, Auburn, Ala
51.20
51.36
51.96
52.60
49.80
50.10
4.44
4.38
Average.. '.
M. O. Donk. Washington. D. ('. *
50.87
50.23
4.40
4.21
4.32
4.41
4.36
:.i >."-'
50.80
49.08
49.00
4.38
4.35
HI I t-r mi u-.-l
'• Ufsiilts received too late to be included in the averages.
COMMENTS BY ANALYSTS.
/ / linker, Gene xi. V ) Moist filter paper pulp was used in one of each set of
(lupin-ait-.-" ami a thick pad of asbestos in the other, with no appreciable variation in
results. In some cases the precipitate showed a tendency to run through the filter
paper pulp. It was easier, however, to wash the filter paper free from acid. Cor-
rertions were made fur a blank of 0.3 cc of potassium hydroxid. Corrections were
•to mad*- for blanks in the official method. You will notice that in the case of the
mixed fertili/er the two methods differ by about 0.4 of a per cent. During a series
of determinations I was unable to obtain any closer agreement.
E. C. Carlyle, College Station, Tex.: The use of pulped filter paper for filtering the
phosphomolybdate is found satisfactory and it reduces the bumping when the liquid
is heated for the purpose of dissolving the potash salt.
G. S. Farnham, Cincinnati, Ohio: I regret to report that I failed to get checks for
the volumetric method.
P. Rudnick, Chicago, III.: It seems from the results by the official method that
there is some truth in the claim that the method for mixed fertilizers when applied
to sulphate of potash gives somewhat lower results, The proposed volumetric method
124
was given as thorough a trial as time and opportunity permitted, and although the
results obtained were not very satisfactory, the method itself certainly looks very prom-
ising. The difficulties are, first, the very small amount of sample taken; second, the
extreme proneness of the precipitate to go through the filter; third, the great difficulty
of removing the precipitate from the sides of the beaker or casserole; fourth, the diffi-
cult v in washing all the nitric acid out of the precipitate. Asbestos is much inferior
to paper pulp for filtering.
W. D. Richardson, Chicago, III.: With the volumetric method, following your
directions, we did not have very good success.
0. M. Shedd, Lexington, Ky.: From my work, I would suggest on samples similar
to No. 1 that ammonium hydroxid and ammonium oxalate be added as in the case
of mixed fertilizers, and that an aliquot be used of 0.10 to 0.20 gram and not over
0.25 gram, instead of 0.50 gram, for the smaller potassium platinic chlorid precipitate
can be worked better; besides it is my experience that very large precipitates carry
down a greater proportion of impurities.
In addition to the above results Mr. Shedd made determinations in sample No. 1
by evaporating with sulphuric acid, igniting, and then evaporating with platinic
chlorid. The results secured were 49.75 and 49.88 per cent.
M. G. Donk, Washington, D. C.: Could get no satisfactory results on sample No. 1
by the volumetric method.
E. L. Baker, associate referee, made additional comparative determinations of
potash in several samples of potash salts, both with and without the use of ammonia
and ammonium oxalate, in making up the solution, the results being as follows:
Comparison of results obtained with and without the use of ammonia and ammonium
oxalate.
Sample.
With.
Without.
Sample.
With.
Without.
Kainit
Per cent.
12.94
Per cent.
13.13
Kainit
Per cent.
/ 13.42
Per cent.
13.48
12.95
49.68
13.18
51.20
Muriate
\ 13.30
/ 49.12
13.52
50.04
49.64
51.16
\ 49. 14
49.84
Mr. Baker also reported results of determinations of potash in a number of samples
by the sodium cobalti-nitrite method first proposed as a quantitative process by
Adie and Wood." This method involved the use of sodium cobalti-nitrite as a pre-
cipitant, and in the original process precipitation was effected in the presence of acetic
acid in a solution which should contain from 0.5 to 1 per cent of potash. Drushel *>
has modified this method as follows:
The solution of a potassium salt, containing not more than 0.2 gram of potassium
oxid and free from ammonium salt, was treated with a rather large excess of sodium
cobalti-nitrite solution, acidified with acetic acid, and evaporated to a pasty condi-
tion over the steam bath. It was then cooled and treated with from 50 to 100 cc of
cold water, and stirred until the excess of sodium cobalti-nitrite was dissolved. It
was allowed to settle and was decanted through a perforated crucible fitted with an
asbestos felt. The precipitate was washed two or three times by decantation, after
which it was transferred to the crucible and thoroughly washed with cold water. In
the meantime a measured excess of standard potassium permanganate was diluted
to ten times its volume and heated nearly to boiling. Into this the precipitate and
felt were transferred and stirred, after which the crucible was also put into the solu-
tion, since particles of the precipitate stick persistently to its sides. After the oxida-
tion had proceeded five or six minutes manganese hydroxid separated out and the
«J.Chem. Soc., 77:1076.
bAmer. J. ScL, 24: 433; Chem. News, 97: 124.
125
color of the solution darkened At this point from 5 to 25 cc of sulphuric acid (1- 2)
u«-n- added, and t he rotation, after stirring, was allowed to stand afew minutes Tnpr
a measured amount of standard oxalic acid, containing 50 cc of strong sulphuric acid
per liter, was run in from a burette taking care to add an excess. The temperature
was maintained a little below the boiling point until the solution became colorless
and t he manganese hydroxid had completely dissolved. It was then titrated to color
by permanganate in the usual manner. From the whole amount of permanganate
employed, the permanganate equivalent of the oxalic acid used was subtracted and
t!,,- remaind^ multiplied by the factor calculated for the strength of permanganate
used, 0.0008o6 being the factor for strictly tenth-normal potassium permanganate
While work was in progress in the referee's laboratory with a view to testing the
adaptability of the cobalti-nitrite methods, letters were received from several coop-
erating chemists commending this process quite strongly, as a result of some prelimi-
nary work which had been done with it. Mr. A. M. Peter, of the Kentucky station,
reported that by the cobalti-nitrite method results of 49.89 and 49.92 per cent were
obtain.'.! by Mr. Q. Edgar for sample No. 1, as against 49.82 by the official method,
while for sample No. 2, 4.50 and 4.48 per cent of potash was found, as against 4.41
by t h<- oili.-ial method. Mr. Baker obtained the following results on the official sam-
pl,- by hrur.li.-rs modification: No. 1, 50.24 and 50.85 per cent; No. 2, 4.46 and 4.31
nt. Following an- results reported by Mr. Baker, using the original Adie and
Wood method, in which precipitation is effected without evaporation:
1'tnnjnirixnn of pottuk </> '• > munition* hi/ ttu nriijiiinl Adir aiid Wood cobalti-nitrite method
mt-irir.) and the official method.
Sample.
Ofld .1
method.
Cokilli-
nitrite
method.
Sample.
Official
method.
Cobalti-
nitrite
method.
Sulphate
to MM
/ 53.54
Percent.
M.M
Kainit*
Per cent,
j 13. 13
Per cent.
10.14
Muriate ami sulphate
54.08
.^).71
Mixed fertilizer o
\ 13. 18
/ 4.95
10.28
4.21
Mixed fertilizer «.
},/! M
10.41
.»<>. 1 1
10.78
Mixed fertilizer a
I 5.06
j 1.28
4.21
.40
Kainit •» . . . .
\ 10. 41
1 13.48
10.92
10.64
10.71
\ 1.29
.40
o The kainits and mixed tertillxers evidently did not entirely precipitate owing, probably, to improper
roruvntr itm::.
CONCLUSIONS.
It apiKmre from the result of this year's work, that while some good results are
obtained by the volumetric method, there are difficulties connected with the working
of the procettt which affect the reliability and rapidity of its execution. Among these
may be mentioned the trouble experienced in washing the precipitate free of acid and
the tcmlency of the precipitate to run through, while the smallness of the aliquot
used in the determinations would, of course, tend to affect the accuracy of the results.
On this account it would seem desirable that work with this method be held in
abeyance for the present and that a trial be made of the cobalti-nitrite method with a
\iew to determining its adaptability to fertilizer work.
The results of tests of the employment of ammonia and ammonium oxalate in potash
determinations in j>otash salts indicated that lower figures are secured in this way, so
that from this partial investigation the contention of those who claim that the usual
method gives impure precipitates would seem to be sustained. However, no positive
conclusion can be reached from the limited data at hand and hence this question
should be investigated further.
126
REPORT OF COMMITTEE C (FOOD ADULTERATION).
By L. M. TOLMAN, Chairman.
WINES.
It is recommended —
(1) That a committee of five be appointed to cooperate with the Bureau of Standards
in drawing up a standard alcohol table. <%
Adopted.
(2) That the question of a standard temperature of 20° for specific gravity and
alcohol determinations be also referred to the committee of five.
Adopted.
(3) That the following subjects be given further study:
(a) Methods for determining glycerol.
(6) Methods for determining total, fixed, and volatile acids.
(c) Methods for determining coloring matter in genuine wines.
Adopted.
FLAVORING EXTRACTS.
It is recommended —
That the colorimetric method for the determination of citral in lemon extract be
adopted as provisional. (See page 32.)
Adopted.
DAIRY PRODUCTS.
It is recommended —
That the Baier and Neumann method for the detection of sucrate of lime in milk
and cream be studied. (See page 53.)
Adopted.
DISTILLED LIQUORS.
It is recommended—
(1) That the modified Allen-Marquardt method for the determination of fusel oil
be made a provisional method.
Adopted.
(2) That in the present method (Bui. 107, Rev., p. 98) a second washing with
sodium sulphate be prescribed.
Adopted.
(3) That the method for the determination of water-insoluble color in whiskies be
made provisional. (See page 207.)
Adopted.
(4) That the modified Marsh test for the quantitative determination of the color
insoluble in amyl alcohol be adopted as a provisional method. (See page 206.)
Adopted.
(5) That the provisional Roese method for determining fusel oil (Bui. 107, Rev.,
p. 97) be dropped.
Adopted.
SPICES.
It is recommended —
That methods for the detection of added oil in paprika be further studied.
Adopted.
MEAT AND FISH.
It is recommended —
(1) That the study be continued in an attempt to apply, improve, or devise methods
for the most accurate separation possible of the various protein bodies in meat.
(2) That the method for determining ammoniacal nitrogen by distillation under
reduced pressure be compared with the magnesium oxid method now generally used.
(Bui. 107, p. 9.)
127
CEREAL PRODUCTS.
It is recommended —
That methods applicable for the separation of the gluten constituents of flour be
studied, tests to be made upon the several grades, as patents, first and second clears
and on flours produced from different varieties and types of wheat.
Adopted.
CANNED VEGETABLES.
It is recommended —
That methods for the detection of soaked peas be further studied.
Adopted.
MEAT PROTEIDS.
It is recommended —
That the work on the separation of meat proteids be continued along the lines
pursued i In- past year.
Adopted.
TEA, COFFEE, AND COCOA.
IM- rtM ommended —
(1) That methods for the estimation of caffein be further studied. (Original Gom-
berg Method, J. Amer. ('hem. Soc., 1896, p. 331, and modifications.)
Adopted.
Hut th.- hulioi- in.-thod for the determination of sugars in chocolate be further
studied. (J. Amer. ( h.-rn S.K-., 1907, 29: 556; Bui. 107, p. 256.)
(3) That tin- Doolittle and Woodruff method (Bui. 105, p. 48) for extract in tea be
substituted for the Krauch method (Bui. 107, p. 149, sec. 5) as provisional.
Adopted.
COLOBS.
hi- r. < > in mended —
(1) That an effort be made to obtain authentic samples of vegetable or natural
coloring matters, such as are used in food products.
(2) That a study be made of the characteristics of vegetable coloring matters and
mnh.Hls of identification.
(3) That pure colors be synthetically prepared to serve as standards.
(4) That the separation aiut identification of mixed colors be studied.
These recommendations were adopted.
REPORT OF COMMITTEE ON THE TESTING OF CHEMICAL
REAGENTS.
By L. F. KEBLER, Chairman.
There has been a marked improvement in the chemical reagents examined by the
chairman of the committee during the past year. This, however, may be largely
due to a we<>d ing-out process that has been going on for several years. It was a com-
mon experience a few years ago to be compelled to report adversely on the quality
of many chemicals which included not only actual adulteration, but indicated gross
carelessness in manufacturing and packing. The chemicals found to be of inferior
quality during the past year were generally lacking in certain minor respects; for
example, contamination with insoluble material or some associated impurity which
would be detrimental to the analytical operations for which the reagent was to be
employed.
One of the difficult features at present is a satisfactory nomenclature. In the past
it has been common to use in connection with chemicals supposed to be of high
quality the abbreviation C. P., but this abbreviation has come to be meaningless and
should be discontinued. It still serves one good purpose and that is, if a chemical
128
is accompanied by this designation the chemist can reject it on general principles if
found to be of unsatisfactory quality. Other specifications, such as pure, purissimum,
reagent, commercial, etc., also have vague meanings which are used by manufacturers,
dealers, and brokers, simply as a means for selling certain chemicals. The past year
has seen a marked improvement along these lines, due largely to the instrumentality
of the food and drugs act. The term "commercial" has been replaced largely by
the term "technical" for the reason that the former name was vague and was used
in connection with products which might be used for^ either food, drug, or technical
purposes; for example, "sodium phosphate, commercial," did not give any informa-
tion at all as to the quality of the product, and while the name would suggest that
it was not of high grade, yet it was not uncommon for highly arsenical sodium phos-
phate to find its way into the drug trade, rather than to the boiler compound manu-
factory, and thus do harm. The terms pure, purissimum, and reagent are also grad-
ually losing their standing, and the question arises, What form of nomenclature
should be employed in order to obtain chemicals of the desired quality?
The chairman, therefore, recommends that the committee be instructed to inves-
tigate the question of nomenclature to be used in connection with chemical reagents
and report at the next meeting.
The report was accepted and the recommendation made was ap-
proved by the association.
REPORT OF COMMITTEE ON FOOD STANDARDS.
On behalf of the food standards committee of the association, the
chairman, Mr. Frear, submitted a detailed report of the work done
by the joint committee on food standards during the year. This
covers the adoption of tentative standards for manufactured meats,
malt liquors, and spirituous liquors. The report of the committee
was accepted by the association.
The president announced the following committee on the stand-
ardization of alcohol tables: L. M. Tolman, M. E. Jaffa, A. B. Adams,
R. J. Davidson, H. E. Barnard.
REPORT OF COMMITTEE ON NOMINATIONS.
Mr. Davidson, as chairman of the committee on nominations, then
presented the following report: For president, Mr. W. D. Bigelow:
for vice-president, Mr. W. A. Withers; for secretary, Mr. H. W.
Wiley; for additional members of the executive committee, Mr. E. F.
Ladd and Mr. E. B. Holland.
The chairman of the committee was instructed to cast the unani-
mous vote of the association for the officers named.
On motion by Mr. Davidson the question of the amount of wash
water to be employed in the treatment of the residue from the
ammonium citrate digestion in the determination of phosphoric acid
was referred to Committee A for recommendation.
129
THE ASSAYING OF ALKALOIDAL DRUGS.
By C. E. PARKER.
The original drug assay methods of the last revision of the United States Pharma-
copeia, (in t he whole, fairly represented the existing status of this branch of chemical
unuK ris. They were formulated under the instruction of the convention for revising
tin- I'harmai -ofxi -ia that assay processes should be "reasonably simple (both as to
nu't hods and apparatus required) and lead to fairly uniform results in different hands."
The probability being somewhat vague that they would be made the basis for gen-
eral l.-u-al regulation, a high degree of accuracy did not appear important, and similar
moderate standards of requirement have possibly influenced the evolution of drug
assay methods generally. . After the passage of the federal food and drugs act of June
30, 1906, the committee on revision made a number of corrections and modifications
in the text of the Pharmacopoeia that it might better meet the new requirements.
Judged from the point of view of the official chemist and prospective expert witness
before the courts, the cooperative work as far as it has gone has not shown that the
pharmacopu'ial methods lead to fairly uniform results in different hands. This is
probably due more to lack of detail in the instructions than to any fundamental
defects in the methods. It is evident that losses occurring at certain stages in the
processes may be prevented by suitable alterations in the methods, and that the
unfavorable results on some drug samples may, to a considerable extent, be attributed
to the i>o\vder not being of a proper fineness.
'I'll- samples sent out this year were from supplies ordered to be according to the
I'nited Mate- Phannacopieia. both as to assay and fineness of powder. The sample
oi belladonna root has been criticised as being a finer powder than specified by the
Pharmacopo-ia, and, therefore, likely to giv<» higher results and too favorable reports
on the met ho, 1 < ttliei samples of drugs have been said to be too coarse, and, there-
unt'air to tin- method-. The point is well taken, but the only way to obtain a
powder oi" exactly the pharrnacopu'ial si/.e would be to separate with suitable screens
all larger and smaller particles produced by the mill, and such a product would not be
-entati\e i.i tin- ..ri-jinal drui;. The proper solution of the difficulty would seem
to be the pro\ i.-ion of -nitable apparatus for grinding all drug samples for assay at least
as fine as the Pharmacopoeia requires and as much finer as experience shall show to be
expedient
The theoretical ..bjeetion- to the aliquot method of extraction may be justified when
the grosser imperfection- in the methods have been eliminated, but so far results fail
to demonstrate the -nperior reliability of the total extraction method, and judgment
mil.-t be Ml-pellded.
It was thought advisable to traverse again the ground covered last year when only
three anal\.-t- participated, comprising methods for the assay of aconite root, bella-
donna 1- a\er. belladonna root, cinchona bark (yellow and red), cocoa leaves, colchi-
cum conn, and colehiciim seeds. Samples of these drugs delivered as being of phar-
macopceial quality and as ground to the fineness of powder specified in the respective
pharmacopceial assay method- were supplied to all collaborators with the following
dire, tion-, and instructions that all calculations and solutions except as otherwise
specified be based on the data of the United States Pharmacopoeia, eighth revision,
with the additions and corrections dated May 1 and June 1, 1907.
The provisional methods appearing in Bulletin 107, revised, pages 258-259, were
slightly modified in accordance with the experience of last year. Only the modifica-
tions are reprinted bflon- and the changes are italicized.
73673— Bull. 122—09 9
130
DETERMINATION OF ALKALOID.
Total extraction method.
Into a 200 cc flask weigh 10 grams of the powdered drug, add about 75 cc of ether-
chloroform mixture (5 to 1 by volume), rotate and add 5 cc of 10 per cent ammonia
water, cork, shake well and often during two hours.
Aliquot method.
Into a 200 cc flask weigh 15 grams of the powdered drug, add 150 cc of ether-
chloroform mixture (5 to 1 by volume), cork and shake often for several minutes. Add
5 cc of ammonia water (10 per cent), shake frequently during two hours. Add 15 cc
of water, or sufficient to agglomerate the drug, shake, let settle a few minutes, and
then decant 100 cc of the clear solution into a graduated cylinder. * * *
NOTE. — Under both methods substitute "a few cubic centimeters" for the words "a
small portion," referring to the ether-chloroform rinsing.
CINCHONA BARK.
Method I.
•
United States Pharmacopoeia VIII, page 102. Report total and ether-soluble
alkaloids.
Method II.
Total extraction, gravimetric. In extracting the drug let stand over night.
The work on yellow and red cinchona and colchicum conn and root being quite
incomplete is not included in this report. The instructions should be followed as
strictly as possible, notes being taken during the work of any difficulties encountered,
objections to the methods, necessary or advisable modifications with the reasons
therefor, and any ambiguity or indefiniteness in the instructions should be indicated.
The value of collaborators' reports is much enhanced by this practice. (See tabula-
tion at close of report, p. 134.)
For comparing in respect to their variability the results obtained by the different
methods from the several drugs, the average result for each method is taken as a basis,
and the proportion of all the results approaching within 10 per cent above or below
this average is given, and in addition the proportion approaching within 15 per cent
of the average. Reserving the question of absolute accuracy, results commonly vary-
ing over a range of more than 20 per cent in different hands can scarcely be described
as fairly uniform, nor can methods yielding such results be considered satisfactory
for the purposes of the official chemist. Only one operator has reported any dissatis-
faction with the behavior of cochineal as an indicator, though another has substituted
hematoxylin for it throughout.
DETAILS OF MANIPULATION.
The United States Pharmacopoeia assay methods generally direct that the initial
digestion of the drug with a solvent for the purpose of extracting the active principle
be accompanied by an indefinite amount of agitation. In certain cases continuous
agitation by means of suitable mechanism is alternatively directed, or preferred. The
expression "frequent shaking" is susceptible of various interpretations, and it would
be advisable to adopt the requirement of continuous agitation in all cases.
A number of collaborators reported difficulty in decanting 100 cc of the solvent
mixture in extracting the drug by the aliquot method, and some were compelled to
use forcible expression or continue the assay with less than 100 cc, computing the
result on the basis of the aliquot part decanted. This occurred especially with bella-
donna leaves and cocoa leaves and is attributable to the coarseness of the samples.
In the Drug Division it was found practicable to obtain 100 cc by decanting the mix-
ture of drug and solvent as completely as possible into a small percolator provided
131
with a purified cotton plug in the neck, and loosely stoppering the same while the
filtrate rolleeted in a 100 cc flask. Excessive evaporation was thus avoided. With
samples of a suitable degree of fineness 100 cc could be decanted without difficulty.
One worker filters the final solution of alkaloid in volatile solvent before evaporat-
ing <>n the latter. If the funnel be kept covered during filtration, and if the filter be
properly washed, losses may be avoided and the alkaloid obtained in a cleaner con-
dition than without filtration.
DISCUSSION OF RESULTS.
ACONITE ROOT.
This sample was delivered as No. 40 powder. The following proportions passed
through the respective sieves:
Grams.
\". HO 0
.0 7
10 n
No. 20 82
Total /....loo
M'.-t ,,f the powder was therefore coarser than the Pharmacopoeia directs for assay
samples.
The throe gra\ imetrie results by Method I are too few in number to base upon them
any conclusion Only :',_' p«-r eent of the volumetric results by Method I (U. S. P.)
come within 1<> \» -r rent of the average and only 59 per cent come within 15 per cent,
and tin- results, both 'jravi metric and volumetric, by (II) are, on the whole, as bad
or worse. Tin- a\« raur<- n-snlts by the two methods are in very good agreement, but
considerably under the I'nited States Pharmacopoeia standard of .0.50 per cent. It is
quite possible that higher and more uniform results might have been obtained with
a finely pou.l. ',-d sample.
On comparison of the corresponding gravimetric and volumetric results by (II)
whirh we may assume were obtained by weighing and then titrating the same alka-
loidal r«v-iilin-. it will be observed that in about one-half the instances the volumetric
result i- hi-ln-r than th. irnivinn'tric, though it can not be assumed that these residues
absolutely pun- alkaloid. The factor for aconitine (0.064) employed in
computing tin- \olumetri< result is too high, and the residue contains alkaloidal mat-
ter of lower molecular w.-i-ht than 640, resulting from the decomposition of aconitin.
It i- probubli- that the volumetric results by (I) are affected by a similar error. These
<•< moderations tend to support the contention of Doctor Lyons and others that chem-
ical assay's of aconite should be confirmed by the so-called "physiological test."
In Method, I Mr. Fuller considers the evaporation of the alcoholic percolate to dry-
ness at a temperature not exceeding 60° as too tedious, and carried evaporation only to
the point where alcohol was all expelled, acidifying the aqueous residue with normal
acid and filtering as usual. lie also washed the acid solution with ether before mak-
ing alkaline and shaking out. A number of workers note the usual difficulty in fil-
tering the acidified residue from evaporation. Mr. Hankey added powdered pumice
to the residue to aid filtration and titrated finally with half-strength lime water. He
found the marc on repeating the extraction yielded no more alkaloid. Mr. La Wall
in a parallel experiment shook out finally with chloroform-ether mixture instead of
ether and obtained lower results, viz, gravimetric 0.35 per cent and volumetric 0.416
per cent. Doctor Lyons used paper pulp to aid filtration, and after the final shaking
out with ether further shaking out with chloroform yielded about 0.1 per cent alka-
loid, titrating 0.07.~> per cent as aconitin and producing its characteristic effect on the
tongue. He believes that aconite assays should be confirmed by the Squibb physi-
ological test. He also suggests a direct titration method for aconite, similar to the
132
United States Pharmacopoeia method for belladonna in the details of extracting' the
drug, but instead of shaking out the ethereal extract with acid, the former is to be
evaporated, ammonia expelled by repeated addition of a few cubic centimeters of
ether and evaporation, and the impure residue titrated. It might either be dis-
solved in alcohol diluted with water and titrated with acid, or dissolved in excess of
standard acid and the excess of acid titrated with standard alkali, preferably with
iodeosin indicator. This method, he thinks, could be adapted for many alkaloidal
drugs. Professor Ruddiman criticises the use of decinormal acid, especially in titrat-
ing an alkaloiol of such high molecular weight as aconitin, where a slight difference
in measurement seriously affects the result.
In Method II as well as in I, Mr. Lyons obtained a further yield of about 0.1 per
cent of alkaloid by shaking out with chloroform following the final extraction of the
alkaline liquid with ether. Mr. Pearson redissolved the alkaloidal residues from the
gravimetric determinations in (II) in acid and purified by submitting them to a shak-
ing-out process with ether, obtaining much lower results, viz, 0.312 and 0.315 per cent.
In view of the fact that both methods gave practically the same average volumetric
result and variability, the greater convenience and rapidity of Method II are in its
favor.
BELLADONNA LEAVES.
This sample was delivered as No. 60 powder. The following proportions passed
through the respective sieves:
Grams.
No. 60 40
No. 50 35
No. 40 25
Total 100
A considerable amount of coarser powder than the Pharmacopoeia permits in assay
samples of belladonna leaves was present. By Method I (U.S. P.) the few gravimetric
results reported varied exceedingly, none of them coming within 10 per cent of the
average, and only 14 per cent within 15 per cent of the average. Of the volumetric
results, 41 per cent came within 10 per cent and 65 per cent within 15 per cent of the
average. By (II) gravimetric, 86 per cent of the few results were within 10 per cent;
also 86 per cent within 15 per cent of the average. Of the volumetric results by (II)
39 per cent came within 10 per cent, and 73 per cent within 15 per cent of the average.
The average results by (I) are slightly higher than by (II), but both are somewhat under
the United States Pharmacopoeia standard of 0.30 per cent. A slight impurity in the
residues is indicated by the higher gravimetric results. In (I) Mr. Hankey used 2 cc
of ether to assist solution of the alkaloidal residue in acid, expelling it by gentle warm-
ing before titration. J. G. Francis and Parker used 50 cc more ether-chloroform mix-
ture than directed to exhaust the drug. It has been observed in the Drug Division
when assaying belladonna leaves and root and coca leaves by the pharmacopceial
method n that a large portion of the last 50 cc of solvent mixture which is intended to
complete the percolation has to be used in rinsing the drug into the percolator. The
drug should be packed after it is all transferred and percolation carried to practical
exhaustion. The combined acid solutions obtained by shaking with the percolate
should be shaken with fresh solvent in small portions until no more color is removed
before making alkaline and shaking out the alkaloid. Instead of measuring out 3 cc
of decinormal sulphuric acid to dissolve the alkaloid, a number of workers in such
« Workers in the Division of Drugs recommend cylindrical nursing bottles (8
ounces) which taper to the neck without any shoulder instead of Erlenmeyer flasks
for digesting the drug with solvent, as the former are more easily clamped on a me-
chanical shaker.
133
cases prefer to add an equivalent amount of fiftieth-normal acid as a quantity less
liable to error in measurement.
In < II i Mr. Blome suggests increasing the amount of ether-chloroform mixture for
ex. radii,- ih«- drug to 180 cc and decanting 120 cc. Mr. Fuller suggests that instead
of din-, tin- the use of neutral alcohol for dissolving the alkaloid before titration it
would be preferable to compare the result with that of a blank titration made with the
same amount of the same stock of alcohol, water, and indicator. Mr. Hankey reports
di-aiisfadion with the titration results owing to an indefinite end reaction. Though
his alcohol was redistilled over alkali, a blank titration with the amounts of acid,
ulrohol. and water direct, ,1 required only 14.3 cc of fiftieth-normal alkali, while the
-ame amount of acid by direct titration required 15 cc of the standard alkali. Mr.
Parker prepared ••neutral" alcohol by adding fiftieth-normal potassium hydroxid to
alcohol until a I. lank titration with the amounts of acid, alcohol, and water directed
agreed with a direct titration of the acid alone. This method or that suggested by
Mr. Fuller eliminates the effect of any deviation from neutrality by the alcohol or
water under the working conditions. Mr. Lyons made a parallel experiment, evap-
orating th«- eth.-r chloroform extract of the drug instead of shaking out with acid
and titrating the re.-idue directly, as outlined in the discussion under aconite root.
The re-nit wa.- !>:;•_' p.-r cent .
BELLADONNA ROOT.
This sample was delivered as No. 60 powder,«and passed through the several sieves
in the following pro|M>rli«>n-
Grams.
SO 98
No. 60 1
Total.
It was, then-!'.. re. -'inewhai liner than the Pharmacopeia requires for assay samples
"i 'I"- dru.' P.\ Method Id'. S p. . d the tew gravimetric results 29 per cent came
within 10 per .mt ..f the average and 43 per cent within 15 per cent. Of the volu-
metric result*, 46 JMT cent came within 10 per cent of the average and 80 per cent
within r> per cent, My (II) the gravimetric results varied more than the similar
detrrminatii.n- l.y I . Th«- volumetric results by (II) were decidedly better than
the cORQBponding results by (I), 73 per cent coming within 10 per cent of the average
and 80 JKT cent within 1"> per cent. The averages by the two volumetric determina-
tion- are practically identical, likewise those by the two gravimetric determinations,
Inn no explanation is apparent for the fact that by both methods the gravimetric
result.- average lower than the volumetric. This relation occurs also in four instances
i in II where the results apparently represent the same residue.
In I Mr Hank. \ d;--ol\vd the alkaloidal residue in Ice of neutral alcohol before
adding excess of standard acid and titrating back with half-strength limewater, com-
paring the same with a blank titration. C. H. La Wall made parallel assays by
both methods, evaporating the ether-chloroform extract instead of shaking out with
acid, and titrating the impure residue directly, the results obtained being (1)0.514
and (II) 0.529 per cent, duplicate results agreeing well. J. G. Francis used 25 cc, and
Mr. Parker 50 cc more ether-chloroform mixture than the amount directed to extract
the driu,'. Their results are all well above the average. The remarks made in the
discussion on belladonna leaves, Method I, regarding the percolation of the drug
also apply to belladonna root. With belladonna root Method II, by evaporation of
th. ether-chloroform extract, and direct titration of the impure residue, Mr. Lyons
obtained a value of 0.617 per cent.
134
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COCA LEAVES.
This sample, delivered as No. 60 powder, passed through the several sieves in the
following proportions:
Orams.
No. 60 29
No. 50 18
No. 40 v ' Vi 9
No. 20 ! 43
Total 99
A large portion of the powder was coarser than the pharmacopoeial requirement for
assay samples of this drug. The gravimetric results by Method I (U. S. P.) are too
few to justify any conclusions. Of the volumetric results, 36 per cent come within
10 per cent and 58 per cent within 15 per cent of the average. Of the gravimetric
results by (II), 75 per cent come within 10 per cent and 82 per cent within 15 per cent
of the average. Of the volumetric results, 33 per cent come within 10 per cent and 72
per cent within 15 per cent of the average. The gravimetric averages and likewise
the volumetric averages by the respective methods are in substantial agreement, the
gravimetric results being somewhat higher than the volumetric, owing probably to
impurities in the alkaloidal residue. In (I) Mr. Fuller accomplished the final shaking
out with three portions of 20 cc each of ether instead of 25, 20, and 15 cc. He thinks
the drug should be digested with the solvent mixture longer than one hour, as the marc
in this case still contained alkaloid. Mr. Hankey dissolved the alkaloidal residue
with 1 cc of "neutral spirits" and titrated with acid and diluted limewater as with
belladonna root. Cochineal gave an unsatisfactory end reaction. Messrs. La Wall and
Parker noted considerable emulsification in shaking out by both methods. The latter
used 50 cc more solvent than is directed for percolating the drug, and J. G. Francis
used 75 cc more, and shook the drug finally with five portions of 25 cc of ether. The
extraction was not complete.
For coca as for belladonna the amount of solvent mixture directed in the United
States Pharmacopoeia method is scarcely adequate for the proper manipulation and
extraction of the drug. In the final shaking out process further extraction with ether
is desirable. In (II) Mr. Blome suggests increasing the ether-chloroform mixture to
180 cc and decanting 120 cc. Mr. Hankey obtained a better end reaction with iodeosin
than with cochineal. Professor La Wall obtained equally low results in a duplicate
assay. J. G. Francis found that the final extraction was not complete. Mr. Pearson
could not decant 100 cc without forcible expression, and therefore objects to the
method. As in (I), further extraction with ether in the final shaking out is probably
desirable.
In both (I) and (II) considerable impurity evidently passes into the alkaloidal
residue, and a more thorough washing with solvent before making alkaline is indicated.
THE MACROSCOPY AND MICROSCOPY OF DRUGS.
By H. H. RUSBY.
The object of this brief paper is to direct the attention of the members to the
importance of chemists supplementing their chemical methods by suitable physical
methods in identifying and estimating drugs; and to the facility with which the
chemist can acquire enough knowledge of such physical methods, and of the physical
properties of drugs, to be of great assistance in his analytical work.
When the subject of the chemical standardization of vegetable drugs was being
agitated in connection with the approaching United States Pharmacopoeia Conven-
tion of 1890, the writer was astonished to hear Prof. John M. Maisch declare himself
137
opposed to the introduction of such standards into the Pharmacopoeia. This surprise
was considerably augmented when Doctor Maisch gave as his reason the statement
that if a man kiu-\v drugs as he should it would not be necessary to examine them
chemically to determine their quality. Although we can not in these days admit
the propriety of neglecting chemical standardization, for this or any other reason,
yet subsequent experience has shown that Doctor Maisch's claim to be able to judge
the quality "f drugs without recourse to chemical methods is largely justified.
The Deceafflty of such knowledge is apparent when we reflect that of the 167 crude
vegetable drugs of the Pharmacopoeia, chemical standards are prescribed for only 22, and
\ct the Pharmacopoeia does not recognize more than one-half of the nonstandardized
artieles in i -omnion use. It is true that chemists employ quantitative methods, all
iii'M.- or less satisfactory, in the case of ten or a dozen others, which are not thus
in -a i «-d in the Pharmacopoeia. Admitting these to full membership, how over-
whelming still is the majority upon the other side! Let it not be said that the non-
assayahle li.-t n- presents only unimportant drugs. It is one of the great temptations
of the « •hcmi.-t t<> underrate subjects with which he does not deal, and he is apt to
p IHIX! //o/-, tryn j>r»pter hoc. Let us not forget that it is the extreme variability
in ;u ii\it\ of surh drugs as veratrum, digitalis, ergot, and cannabis indica, coupled
with their exceeding importance in medicine, which has forced a resort to physio-
logical standardization, applicable as yet to but few drugs. It is this tendency to
vary in quality and our general inability to estimate such quality that has to a great
e\ lent destroyed the usefulness of some drugs which would otherwise be generally
relie.l n|M.n. A.- illu.-trat ions, let us note male fern, spigelia, cusso, and other anthel-
inintics, Winter'.- hark, • ..t<> bark, and chrysarobin. The importance of the drugs
named is relatively greater than that of the assayable ones, by virtue of the fact that
the latter -an be -ul..-t ituted by their proximate principles, while the former can not.
Th< lenient of weakness in the chemical assay of drugs, which
ally mil L'ate.l by attention t«> their macrosopical and microscopical characters,
••q unit ly more or less chagrined by the thought that after all he
does not know what it i* that he has in hand after he has extracted the full required
pen-enlace ,,f alkaloid by the prescribed method, since part of it may have been
extracted fnun an admixture. Impurities in drugs, either from accident or design,
may and frequent 1\ d<> fail of detection by the chemist, even in the case of freely
assayable drugs, where detection would be simple by intelligent physical examina-
tion before a«8a\
en the great array of unofficial and unimportant drugs can not be dismissed
from the eln-mi.-t'> ken because of their want of substantial therapeutic activity.
They are in common use and some one pays for them the money which is his property
and \vhieh entitle.- him to the receipt of what he pays for. He may be deprived of
the pro tret i\e aid of the Pharmacopoeia without having his legal or professional
ri.u'ht.- in an\ degree curtailed. Indeed, the chemist himself is a deeply interested
party in this class of transactions. Every commercial chemist will admit that some
of his most profitable work lies in the field of the unofficial materia medica, and
where the di.-tinctly chemical indications are usually indefinite and faint. It seems
quite unnecessary to argue further that a knowledge of the physical identification
characters of vegetable drugs is of great service to the chemist. Is it too much to
say that the field of success thus opened to him is far greater, as to crude vegetable
drugs, than that which he can control by chemical methods alone? I feel very
sure that such a statement is just and moderate.
Thi, l.eint,' so, how far can macroscopical and microscopical methods supply the
deficiency? And how great an expenditure of effort and time does it require?
may he admitted at once that to secure an expert knowledge of this subject requires
the .-am*- kind and degree of application that it does to become an expert chemist,
but it is at the same time true that a very moderate amount of effort, intelligently
138
and judiciously applied, will add more to the general efficiency of the chemist than
the same amount applied in any other direction. I believe that no chemist should
proceed with the chemical examination of a drug of this class until after he has examined
it physically, with or without the microscope, according to the requirements of the
case, to ascertain its general characters and particularly whether it is a single article
or a mixture. This requires a fair knowledge of macroscopy and microscopy, as to
both methods and drugs. The time and labor necessary to acquire such a knowl-
edge are not Excessive. As to all the official and important unofficial drugs, it should
be gained by from one hundred to one hundred and fifty hours of practical work,
say two or three hours per week during a two-year course.
The following examples will serve to illustrate the class of drugs to which refer-
ence is here made: Goto and paracoto bark are among the most reliable therapeutic
agents in the materia medica, often the only means of saving life in severe cases of
dysentery, yet the use of this medicine has almost ceased owing to the fact that the
genuine drug is now scarcely ever seen. In two years the writer has not known of
an importation of it to the United States that was not spurious. A brief macroscopic
examination will enable anyone immediately to recognize every one of these pre-
tenders. The same statement applies, in a somewhat less serious degree, to Winter's
bark, a most valuable aid in nutrition.
The belladonna invoice covers a multitude of fatal and dangerous imperfections.
A very large part of our belladonna root contains poke root, not only an exceedingly
active poison but an article that counteracts the medicinal effect of belladonna. It
is sometimes difficult to distinguish the smaller roots by macroscopical means, but
the dust in the package will always show, under the microscope, the needle-shaped
crystals t)f the poke root. The same statement applies to an admixture of poke leaves
to belladonna leaves. Scopola leaves are often mixed with and substituted for bella-
donna leaves. This is liable to destroy the life of the patient receiving the medicine.
In any case the medicinal actions of these two are antagonistic. Some indication of
the identity of these plants is almost always present with the leaves; for example,
the belladonna has black berries, while the scopola has pale yellow circumscissile
pods, and the two can be instantly distinguished.
A spurious henbane sometimes contains from ten to fifteen times as much alkaloidal
matter as the genuine and has a different action. These alkaloids are so poisonous that
they are given in doses of only one two-hundred-and-fiftieth to one one-hundredth
of a grain. Imagine the effect of giving a dose containing fifteen times as much as
it should. When powdered, the spurious can be recognized by its stellate hairs and
by certain cells with wavy thick walls. Henbane and digitalis may contain stramo-
nium leaves. Any considerable amount of such an addition to digitalis must put
the life of the patient in danger, because with heart failure life often depends upon
the full and prompt action of the latter remedy. Here the microscope is almost
necessary, as a single hair from the leaf of the stramonium, densely covered with
minute warts, will tell the story.
Strophanthus seed is another drug of great service in heart failure, and used when
promptness is necessary. There is one variety of the seed which produces no good
effect, and there has been ten times as much of this used in the United States as of
the other, because it has cost only one-tenth to one-fifth as much. During the past
year the use of the spurious kind has been largely stopped. The two seeds have such
different macroscopic characteristics that they can not be mistaken when once the
difference has been noted.
So-called saffron is frequently found which consists of marigold flowers, colored
red with anilin and heavily weighted with mineral matter. The evil result of this
fraud is peculiar. Saffron is largely used for giving an agreeable color to medicinal
preparation, so it is added to medicines in a prescription. This mineral matter is
139
apt to destroy the effect of other substances in the mixture, and may easily bring
about changes in them that will result in poisoning the patient.
Let us now turn to the distinctively microscopical class of examinations and observe
the facility "f identification. Starch grains taken from different drugs, under the
microscope are as conspicuously different as are larger objects. The same is true
when they are modified in appearance by moist heat. The presence of such grains
often -hows that the drug has been partly exhausted of its activity. Powdered
elecampane illustrates a very large class of drugs that do not contain any starch. If
we tiiul starch grains in any of these powders, we know that there must be an admix-
ture. The various forms of crystals of calcium oxalate are very distinctive, the par-
ticular form iM-iii.u' always the same in a given drug. Merely glancing at the powder
under the microscope would identify a drug by this means. Ground olive pits have
been used to the extent of hundreds of tons for adulterating such important drugs as
ijiecac, L'entiaii, belladonna, and aconite. While stone cells occur in many drugs,
similar to those of the olive pit, they are absent from most, and their characteristic
appearance in sufficient for ready detection. The very similar stone cells from cocoa
nut -hells have been largely used to adulterate chocolate, but when compared with
the jc.uder- "i chocolate under the microscope they could not fail of detection.
Plant hairs arc often so characteristic as to insure instant recognition. The stellate
hai rs oft he chestnut leaf, one « »f the favorite articles used to adulterate medicinal leaves
and herbs, are very distinct i\e; the peculiar hairs of stramonium and spurious hen bane
have already l>een mentioned. Genuine and spurious matico are easily distinguished,
the hit ter having only about one-third the medicinal activity of the former. Its hairs
are large, strong, and thi< -It-walled, the cavity being little more than a faint line.
The hair of the genuine, on the other hand, is nearly all cavity, its wall so thin that
the hair frequently collapses.
It i- earnestly hoped that this presentation of the subject may lead some here to
interest themselves, at least a little, in this matter. The attention of this association
ha- Keen chiefly directed to other things than drugs. Important as those subjects
are, your aid is equally needed in the drug field . There are only a few of us to struggle
with this great subject. Efforts to secure just action by the final authorities are met
by the most energetic and often very plausible misrepresentations by interested
parties, to the great detriment of the cause, and there is great need of your moral
sii|»|x>rt in promoting public interest in the rigid enforcement of the laws regarding
pure drugs.
"THIRD DAY.
SATURDAY— MORNING CESSION.
Mr. J. P. Street introduced a resolution approving national legis-
lation regulating the composition and sale of insecticides and fungi-
cides. The matter was referred to the committee on resolutions.
(See page 189.)
REPORT ON PHOSPHORIC ACID.
By J. M. MCCANDLESS, Referee.
On May 19, 1908, the referee sent out a letter to twenty-one chemists, quoting the
recommendations made by the association, as follows:
(1) That the referee on phosphoric acid take up for report at the next meeting of
the association methods applicable under American conditions to the official exami-
nation of basic slag phosphates.
(2) That the subject of an accurate determination of iron oxid and alumina in rock
phosphates be examined by the referee on phosphoric acid and an official method be
recommended to the association next year.
(3) That a number of chemists be requested to send to the referee on phosphoric
acid samples of the citrate ammonia solution employed by them, and that the referee
examine such samples as to neutrality and that such examination be reported to the
chemists at the next annual meeting.
In compliance with these instructions the referee requested those who desired to
cooperate in the work to send him a bottle (200 cc) of their solution of ammonium
citrate and a short statement of the method used in making the samples neutral.
In response to this letter the referee received nine samples of ammonium citrate
solution for examination and forwarded to ten chemists three samples each, one of
pulverized brown Tennessee rock, one of pulverized Florida rock, and one of a syn-
thetic solution made from microcosmic salt, recrystallized potash-alum, ferrous
ammonium sulphate, calcium carbonate, magnesium sulphate, and calcium fluorid,
so that 100 cc would represent 1 gram of substance, and on that basis the solution
should contain exactly 3 per cent of ferric oxid and 2 per cent of alumina.
A letter of instructions was forwarded with the samples requesting that the coopera-
tors test the following methods for iron and alumina, it being deemed best to restrict
the work to these phases'
METHODS FOR THE DETERMINATION OF IRON AND ALUMINA IN PHOSPHATE ROCK.
It is recommended that before beginning the work each analyst make up for him-
self a synthetic solution from C. P. chemicals, containing 10 grams of microcosmic
salt, 10.4 grams of calcium carbonate, 0.050 gram of magnesium oxid or its equivalent
in magnesium sulphate, 0.300 gram calcium fluorid. To these should be added
accurately known weights of C. P. crystallized potash, or ammonia alum, and ferrous
ammonium sulphate or iron wire. The material should be dissolved in hydrochloric
acid and water and made up to a liter. The methods should be tried upon this solu-
tion to acquire confidence and applied to the referee's samples, using the following
methods:
(140)
141
Gladding method.
I»i<s..lve \ -rams of tho rock in 30 cc dilute hydrochloric acid (1 to 1), heating just
below the boiling point for half an hour. Filter into a 200 cc flask, add a few drops
c.f nitric and, and boil to oxidize the iron; cool and dilute to mark. Take 50 cc, con-
taining 1 gram, and run into 20 cc of a solution of C. P. caustic potash, made by dis-
Bolving -">00 grams of caustic potash free from alumina, in distilled water and diluting
to i. in- liter. Digest in water bath at 70° for one hour, stirring occasionally. Let the
precipitate settle and filter on a large paper, first decanting the supernatant liquid
on th.- paper and finally washing on the precipitate. Wash two or three times with
hot water. To the filtrate add 1 gram of ammonium phosphate; acidify with hydro-
chloric acid. Add ammonia until a permanent precipitate is formed; add dilute
hydrochloric acid, drop by drop, until it is just dissolved.
Add a mixture of 15 cc neutral ammonium acetate solution and 5 cc acetic acid
(30 per cent) and digest for half an hour at 70° C., by which time the precipitation is
complete. Filter, washing five or six times with hot ammonium acetate solution
(10 per cent), stirring ui> the precipitate with the jet each time. Ignite with a low
flame till the paper is charred, increase the heat until the paper is consumed, then
bla.-i lor a minute.
The precipitate is A1PO4 and its weight multiplied by 0.418 gives the AL>O3. Glad-
din- determines the iron oxid volumetric-ally by the bichromate method in a solu-
tion of the precipitate of iron oxid and calcium phosphate thrown down by the caustic
potash, or by the same method in a separate solution of 5 grams of the rock in dilute
hloric acid (1 to 1).
Glaser method.
nuns of pho-phaio r,M.k thirty minutes in 30 cc concentrated hydrochloric
acid. Make up to :tm <-.- and filter off 100 cc. Add 25 cc concentrated sulphuric
arid: -hake ami allow to -tand a few minutes; add 100 cc strong alcohol and cool.
'i cc with alcohol and allow to stand thirty minutes; filter off 100 cc or
ram and evaporate in a larje beaker to expel alcohol.
M-fer i,, a -mall (Jriflin beaker, boil, remove from flame, and make slightly alka-
line with ammonia l'."il to neutrality, cool, filter, and wash with boiling ammonium
nitrate solution. Burn and weigh, weight divided by 2= oxids of iron and aluminum.
Proposed modification of acetate method.
Weigh 2.5 grams of phosphate rock into a 250 re flask; cover with 25 cc of concen-
t rated h\drochlorir and: keep just below the boiling point for thirty minutes; dilute
and COOl; make up to the mark: filter off 50 cc, equivalent to one-half gram of rock;
add a few drops of nitrir arid, to oxidi/e any ferrous iron, and boil.
Add ammonia until the precipitate formed dissolves slowly on agitation. Then
riMil toahout l.">° C., neutrali/e, adding dilute ammonia drop by drop until the precipi-
tation i- complete < lear up with dilute hydrochloric acid added drop by drop,
slowly ami with frequent shaking toward the* last until the solution is clear. Make
a solution of ammonium acetate by neutralizing strong ammonia with acetic acid
;. l.oi; to l", <c of this solution add 5 cc of acetic acid, sp. gr. 1.04, in a tall beaker
ha\ in- a • -apu- ity of about one liter; fill the beakerabout seven-eighths full with hot
water, so that the mixture will have a temperature of 70° to75°C.; pour the solution of
pho-phate in a thin ,-tream into the dilute hot solution of the ammonium acetate,
stilling ron-taiitlv. The precipitated phosphates of iron and aluminum are allowed
ml alter ben .in ing dear the greater part of the supernatant fluid is siphoned,
off, the beaker is filled up again with hot water at about 70°, again allowed to settle,
and the supernatant fluid is siphoned off.
The remainder in the beaker is now filtered off on a large, rapid filtering paper
(S. & S. black band ashless) washed thoroughly with hot water containing ammonium
nitrate, keeping the precipitate on the filter well stirred up with a strong jet from the
wash bottle. Ignite at a low temperature, till the paper is charred, increase heat
until the paper i> fully consumed, and finally blast for a minute. The weight of the
precipitate in centigrams gives the percentage of the mixed oxids.
It is desired that in the last two methods the percentage of the mixed oxids of iron
and alumina be given and also that the oxid of iron be determined separately by any
volumetric method preferred by the analyst, always observing the precaution of
oxidizing the organic matter to be found in solutions of phosphate rock by digesting
with potassium chlorate and boiling off the excess of chlorin previous to the reduction
and titration.
142
The referee desires to remind the analysts cooperating in this work that it has been
undertaken under the auspices of the A. O. A. C. for the purpose of establishing, if
possible, a standard method for the estimation of iron and alumina which should have
the indorsement of the association. At present all is chaos, and when two chemists
differ on iron and alumina it is impossible to say who is right and who is wrong.
The great majority of rock sales to-day are settled either by Gladding method or by
the G laser method, as outlined above.
The referee submits the above modification of the acetate method, which he believes
to be simpler and fully as accurate as the others, and will welcome the comments
and criticisms of the analysts when they have completed the work on the three samples
by the methods outlined above. In regard to the synthetic solution sent, the referee
would say that it was not practicable to send more than 300 cc to each analyst, but
that in his opinion one-half gram, or 50 cc, is sufficient for any of the tests required,
and used in this way there is sufficient of the synthetic solution for six tests.
Reports were received from six chemists cooperating in the work on iron and alu-
mina, whose results are given in the following tables:
Determination of iron and alumina in Tennessee and Florida rock.
TENNESSEE ROCK.
Analyst.
Determination.
Method of-
Gladding.
G laser.
M<£nd' Veiteh-
Von
Grueber.
Stillwell and Gladding, New
York City.
F. B. Carpenter, by R. Henry,
Richmond, Va.
G. Farnham, Jarecki Chemical
Co.
P. Rudnick, by G. F. Beyer,
Chicago, 111.6
McCandless, Burton, and At-
kinson, Atlanta, Ga.
S. H. Wilson, Georgia Depart-
ment of Agriculture".
O. M. Shedd, Kentucky sta-
tion.
Average.. .
FejO3
Per cent.
2. 79-2. 79
3.50-3.44
Per cent
Per cent. Per cent.
Per cent.
AljO3
Total
6.29-6.23
6.26
6.80
6.20
Average
6 10
3.17
3.50
|AljO3
[ Total
6.67
6. 48 7. 20
(FezOs
3.06
2.29
3.06
3.92
A12O3
[ Total
a5.35
6.98
FejOs
3.22
3.21
3.22
3.68
A12O3
Total
6.43
7.04
6.19 '
6.90
Average
Fe2O3
3.04
3.26
AljO3
Total
6.30
6.48
6.22 '.'
fFejO3
2.91
3.21
A1ZO3
Total
6.12
5.86
5.90
fFezOs. . .
^—
2. 92-2. 92
A1ZO3
Total
I
6. 39-6. 49
6.44
4.32-4.13 ..
Average..
04 22
6.35
6.60
6 19
o Omitted from average.
* Per cent calculated from average of three determinations.
143
Determination of iron and alumina in Tennessee and Florida rock — Continued.
FLORIDA ROCK.
Anal\st.
Determination.
Method qf—
Gladding.
Glaser.
McCand-
less.
Veitch.
Von
Gnieber.
StillwHI and Gladding, New
York City.
F. M.rariH-ntrr. l.y li. Henry
Richmond, Va.
rnham, Jamrki Chemical
Co.
1-. Ru.in ck. by G i B
Chit-ago, lll.o
McTandlrss, Burton, and At-
klMMMl. All. lilt I.
S. II \V«
ment of Agriculture.
0. M. Shedd, Kentucky sta-
tion.
\ \ iTl '«'
Fe«Oa
Per cent.
1.71
1.49
Per cent.
Per cent.
1.70-1.75
.92-1.00
Per cent.
Per cent.
AljOi
Total .
3.20
3.51
2.62-2.75
2.68
Average
FetOi
1.85
.94
AljO»
[ Total
2.79
2.73
2.89
IFetOj .
1.65
.66
1.65
1.33
AlsOi
Total
2.31
2.98
1.86
1.03
1.86
1.53
1\l .< i
Total
2.89
3.48
1.95-1.97
ol.96
3.43
Average
fFeiOa
1.73
.94
I M.I >
1 Total
2.67
3.90
2.72
1.68
.90
Total...
2.58
2.98
2.62
> , .1 1
1.68-1.66
1.67
\ i < >
Total
2.96-2.98
2.97
a 1. 50-1. 69
Average
2.74
3.30 2.69
• Fw cent calculated from average of three determinations.
144
Determination of iron and alumina in synthetic solution.
[Synthetic solution— made to contain 3 per cent Fe2O3 and 2 per cent A12O3, or 5 per cent combined oxids.]
Analyst.
Determination.
Method of—
Gladding. Glaser.
McCand-
less.
Vpif^h Von
tcn- Grueber.
Stillwell and Gladding, New
York City.
F. B. Carpenter, by R. Henry,
Richmond, Va.
G. Farnham, Jarecki Chemical
Co.
P. Rudnick, by G. F. Beyer,
Chicago, 111.*
McCandless, Burton, and At-
kinson, Atlanta, Ga.
S. H. Wilson, Georgia Depart-
ment of Agriculture.
O. M. Shedd, Kentucky sta-
tion.
\.verace
!Fe2O3
Per cent. Pfr cent.
2.60 ...:
Per cent.
2.50
2.73
Per cent. Per cent.
AljOa
Total
3.68
a6.28 o6.12
5.23
Cppf)
A1203 ""-'-'- '-"-
l"
[ Total
5.01
5.83
(fTp ()
3.08 3.08
1.86 1.86
\i,o,
Total
4.94 4.94
FezOs
3.11 ...
3.11
1.50
I - -
AljO3 2.15 i
Total
5.26 ! 5.62
4.61
!Fe»Oi
3.05 .
\llo3 2! OR
'
Total
5.11 5.55-5.60
(5.57)
5. 07-5. 05
(5.06)
Fe2O3
2.91 .
AhOs
2 55
Total
Fe2O3
5.46 5.40
5.18
. 3. 12-3. 12
\12O3
(3. 12)
Total
j
4 92-4 98
4 10-A 38
.
i (4.95)
a(4.24)
5.28 5.29
5.02
Omitted from average.
b Per cent calculated.
145
The determination of iron and alumina by various modifications (Shedd).a>
GLADDING METHOD.
Modification.
Florida
rock
(25198).
Tennessee
rock
(25199).
Referee's
synthetic
solution
(25200),
50 cc.
Shedd's
synthetic
solution,
50 cc.
Al ' - t.v siihtnu-tinu Fi'l'o, from weight of FePO4+
AII'< >, uii'l multiplying by 0.419:
i. 'terminal ion.
Per cent.
Per cent.
Per cent.
Per cent.
0 0108
1 .l.'t.-rminution
0111
Mean
0110
Theory
.0100
••l.Liined from tin- pnvipitate of FePO4+ A1PO4
obtained alK>vo:
Kir>t determination
niqo
Second <it't«-nnination
.0195
Mean
.0194
FetO, obtained from independent portions of 50 cc of the
solution:
l.'t.TinllMtloM
0194
Second determination
0194
Mean
0194
Theorv ...
0194
MODIFIED At KTATE METHOD.
AJjOj by subtract in.
-0.10
1.25
1.09
0.0051
.0058
-0.0020
-
- .025 1.17
.0055
F*OH-Al|Oiby halving the weight of |>h«»i
1.50
1.69
4.32
4.13
.0205
.0219
.0158
. .
Mean
1.60
4.23
.0212
FetOi from independent 50 cc portions of the solution:
First determination
Second determination:
M •
1.74
1.69
3.03
2.94
.0157
.0157
1.72 j 2.99
.0157
G LASER METHOD.
AlsOi by subtracting FePOi. as abov«>:
l-termination
1.16
3.05
0.0082
0.0047
Second determination
1.17
3.13
.0084
1.17
3.09
.0083
Fe,Oi+ AI»Oi by halving the weight of phosphates:
2.96
2.98
6.39
6.49
.0246
.0249
.•0239
Mean
2.97
6.44
.0248
Fe»O, from independent 50 cc portions of the solution:
'..•termination
1.68
1 66
2.92
2 92
Second determination
Mean
1.67
2.92
a Analyses made by O. M. Shedd. of the Kentucky station, but received too late to incorporate in the
report.
73673— Bull. !£!— 09 10
146
DISCUSSION OF RESULTS.
P. Rudnick (results by G. F. Beyer): Commenting on the results in general, I do not
believe that any of the methods proposed are preferable to the modified Von Grueber
method in point of simplicity, rapidity, accuracy, and general applicability to various
kinds of rock. Although the results obtained for ferric oxid in the synthetic solution
prepared in this laboratory are high, they agree very well with the results obtained
by the determination of iron in the precipitate from the method proposed by you,
and the results on aluminum by the modified Von "Grueber method are certainly very
close to the calculated quantity. Although I have not had time nor opportunity to
prove the point, I am inclined to believe that ammonium acetate is not sufficient to
prevent the partial hydrolysis of the aluminum phosphate, and that ammonium nitrate
is more efficient in this respect. I believe the fairly good agreement between the
results by the Glaser method and the modified Von Grueber method obtained in this
work, as well as at other times, supports this view.
S. H. Wilson: For simplicity and ease of execution the McCandless laboratory
method leaves little to be desired.
Remarks by the referee: On the whole the results seem to be encouraging and to show
that all three of the methods for which instructions were sent are capable of giving
good results. One analyst used the Von Grueber method, another the Veitch method.
A study of the results on the synthetic solution, in which the percentages of iron
and alumina are accurately known, reveals a tendency on the part of those getting
the lowest results on the phosphate rocks to get them also on the solution and vice
versa; excluding the lowest and highest results, the agreements and approximations
to the truth are about as good as would be found in the determination of other ele-
ments, as, for instance, phosphoric acid by the accepted methods.
The referee would call attention to the fact that this subject has been taken up
by the National Fertilizer Association, and would recommend cooperation between
the next referee and the committee of that association, with a view to reaching a
decision as to what method shall be adopted.
EFFECT OF DILUTE AND CONCENTRATED HYDROCHLORIC ACID ON PYRITES IN PHOS-
PHATE ROCK.
The referee also requested the analysts cooperating to test the effect of dilute
(1 to 1), and concentrated hydrochloric acid as to its solvent effect on pyrites, present
to a greater or less extent in nearly all phosphate rock.
It has been claimed on the one hand that dilute hydrochloric acid (1 to 1) fails to
dissolve all the iron and alumina, especially when the latter is present in the form
of clay; it has been claimed, on the other hand, that concentrated hydrochloric acid,
while it dissolves the alumina and iron oxids better than the dilute, also decom-
poses pyrites present in the phosphate rock and therefore yields too high a percentage
of iron. It is desired that the analysts test this latter point as follows:
Procure a sample of freshly pulverized pyrites and weigh half a gram into a 250 cc
flask, cover with 25 cc of hydrochloric acid (1 to 1), heat just below boiling for thirty
minutes, dilute with 100 cc of water, shake, allow to settle, decant the liquid, repeat
the washing by two or more treatments with 125 cc of cold water slightly acidulated
with hydrochloric acid, followed by decantation. This preliminary treatment is to
remove any oxid or sulphate of iron already existing in the pyrites. Have ready 2.5
grams of phosphate rock, add it to the flask on top of the washed pyrites, then cover
with 30 cc of concentrated hydrochloric acid, heat just below boiling for thirty minutes,
cool and make up to the mark. Determine the iron volumetrically in an aliquot
of the solution and compare the results with that obtained from a similar treatment
of phosphate rock and pyrites with dilute hydrochloric acid (1 to 1) the second time.
Only two chemists beside the referee took part in this work.
147
- «•/ nf dilute and concentrated hydrochloric acid oyfoyriter.'
Analyst.
Phosphate
«r — M«^ -
'*;.'.."• UTUIIIS
^^gKtfjJ
rock.
Concen-
trated HC1.
Dilute HC1.
<;. F licvr. ( •hi.-iuro. Ill
3 51 3 51
(i. K;irnh:im. .l;invki ( hriiik-ul Co
2 91
J. M. Mr! i:.
3 48-3 50
3 49-3 5^
While one of the results in the above table must be explained, the referee is con-
vinced from a number of tests made years since that neither dilute nor concentrated
hydrochloric acid ha- any appreciable effect on pyrites, and would therefore recom-
mend i In- u -« • of the corn-cm rutr<l acid in the solution of phosphate rock, heating for a
definite linn-.
Of cour.-e, tin- u-e .)f sulphuric acid of 50° li. (which also has no action on pyrites),
followed b\ -illation in dilute hydrochloric acid, would more nearly approximate
actual condition-, and it iniirht be well if the next referee would investigate this method
of -olution as compared with simple solution in concentrated hydrochloric acid.
RXAJONJ M (ITRATE FOR NEUTRALITY.
B \\.i- IK decide whether the solutions were neutral or not, and as no
t\\o chem n the exact |Niint of neutrality, whether from lack of sensitiveness
of the indicator.-. ..r • olor-hlindne-s on the part of the operators, he decided to make
an analysis of each sample according to the method outlined in his last report to the
association, and he guided by iho.-e re-nits in deciding upon neutrality. The follow-
ing method nf anal\ -i~ \\a- ad. -pled:
'r\\ent\-!ive cubic ccntiinci. r- of ,-ach solution was pipetted into a 250 cc flask,
made to mark, -hakeii. and •_'.*> CC i»ipette.l into a distillation flask; to the solution in
the ila-k. in ' • of fourth-normal caustic soda solution were added, and the contents of
the ila.-k distilled into -JO cc of half-normal acid, continuing the distillation until the
volume of i he di.-tillate measured from 65 to 70 cc. The ammonia in the distillate
was then titrated l»\ mean- of tenth-normal alkali. The residue in the retort was
• 1 into an Brlemneyer tla-k. excess of standard acid added, then a few drops of
phenolphthalein, and the excess estimated by means of tenth-normal alkali. From
the icMilt the weight of citric acid originally combined with the ammonia was cal-
culated. Calculating fnun the formula of the pure salt, (NH4) 3C,jH5O7, that the ratio
of ammonia (Nil i" citric acid was as 1 to 3.765, a basis of comparison was established.
The re-nli- obtain. -d are giveo in the table below. As only three official chemists
sent their solution-, the anal\ -i- are designated by number and not by name.
Dettrintnntmn »f n< utrnlitij of ammonium citrate solutions.
NuniU-r of
Ammuiu.i in
2ftocofdlhit«d
•olutkw
original.
Citricat-idin
•_>:, iv of diluted
solution— 2i cc
original.
Ratio of am-
monia to
citric acid.
Ratio in neu-
tral salt
(NH«)A
H50r.
Reaction with
corallin.
Milligrams.
113.9
109.3
104.9
113.7
Milligrams.
433.2
412.8
424.%
433.9
1:3.803
: 3. 775
:4.051
: 3. 816
1:3.765
1:3.765
1:3.765
1:3.765
Neutral.
Alkaline.
Acid.
Neutral.
110.5
430.08
: 3. 891
1:3.765
Slightly acid.
111.5
43<i 48
: 3. 915
1:3.765
Acid.
108.7
104.7
102.8
421.1
398.7
430.7
: 3. 874
:3. 808
: 4. 189
1:3.765
1:3.765
1:3.765
Slightly acid.
Neutral.
Acid.
148
In this table all the solutions which showed materially more citric acid than 3.765
parts to 1 of ammonia also showed a decidedly acid reaction to coralliu.
It appears that some chemists prepare their ammonium citrate solution by treating
the citric acid with excess of ammonia and then leave the hot solution to neutralize
itself, or finally adjust it, some by means of red and blue litmus paper, others by cor-
allin. Some state that they have never been successful in the use of corallin; others
adjust finally by means of the alcoholic solution of calcium chlorid. In the opinion
of the referee,-if a chemist has succeeded in getting his solution neutral or practically
so, he will almost certainly put it out of joint by attempting to make it exact with the
calcium chlorid solution. The referee finds that an alcoholic calcium chlorid solution
which is exactly neutral to corallin is acid to phenolphthalein, and alkaline to cochineal ;
that after the precipitation of the citric acid from 10 cc of the ammonium citrate solution
by 50 cc of the calcium chlorid solution, calcium citrate still remains in solution in the
filtrate, which may be proved by boiling some of the clear solution, when a precipitate
of calcium citrate will appear. The presence of this salt, in the opinion of the referee,
renders the use of cochineal as indicator unreliable. One of the solutions in the above
table, which is the most acid of all by analysis, was neutralized in this way. There
are materials (notably fertilizers containing bone) on which a slight difference in
neutrality of the ammonium citrate solution makes a great difference in the results. It
is a reproach to the association that it has suffered the matter to remain in its present
condition so long. While the referee has a strong personal conviction that the only
proper method of making the solution neutral is by analysis and calculation of the
exact quantity of ammonia or citric acid to be added to it, still he hesitates to urge it
officially, as no work has yet-been done by any other referee along this line, and because
the referee is himself no longer an official chemist.
The referee desires to acknowledge the valuable aid and suggestions of Mr. J. Q.
Burton in all of this work and the analytical assistance of Mr. F. C. Atkinson.
THOMAS SLAG.
By J. B. LINDSEY.
Thomas slag or basic phosphatic slag is a by-product in the modern method of steel
manufacture from ores containing noticeable quantities of phosphorus. The process
of removing the phosphorus from the ore was discovered by the English engineers
Gilchrist and Thomas and, briefly stated, consists in adding to the so-called "con-
verter " containing the molten ore a definite quantity of freshly burned lime, which
after a powerful reaction is found to be united with the phosphorus and swims upon
the surface of the molten steel in the form of a slag.
COMPOSITION.
The composition of the Thomas or Belgian slag varies according to the character of
the ore and the success of the process for removing the impurities. The following
figures show such variations: a
Per cent.
Phosphoric acid 11-23
Silicic acid 3-13
Calcium oxid (lime) 38-59
Ferrous and ferric oxids 6-25
Protoxid of manganese 1- 6
Alumina 0. 2- 3. 7
Magnesia 2- 8
Sulphur 0. 2- 1.4
a Adolf Mayer, Agricultur Chemie, 6th ed., vol. 2, pt. 2, pp. 138-139.
149
More or less metallic iron is inclosed in the coarse slag which is generally thoroughly
removed from 'he ground material by the magnet.
MANURIAL VALUE.
The manorial value of the slag was not recognized for a long time. Finally experi-
ments revealed that a considerable portion of its phosphoric acid was soluble in dilute
citric and carbonic acids, which led to successful field experiments. The only prepa-
ration of the slag for fertilizing purposes, when its value was first recognized, consisted
in having it finely irnnmd in especially prepared mills, so that 75 per cent would pass
through a sieve with perforations 0.17 mm in diameter. This requirement was sug-
gested by M. I-Mei>cher, who used the slag with much success in improving the condi-
tion of marsh and meadow lands.
\l \ ni'ii.s FOR DETERMINING AVAILABILITY AND ADULTERATION.
Previous to 1890, by means of pot experiments, as well as by laboratory investiga-
tion-. Wanner demonstrated that tin- phosphoric acid in different slags of the same
« of fineness vari.-d in its availability from 30 to 90 or more per cent, and, further,
thai many brand.- were adulterated with Belgian or other insoluble mineral phos-
phate-;. The method therefore of determining the value of a slag by the percentage
.il ph"-phoric acid present and the degree of fineness was of secondary impor-
tance.
In order to detect adulteration with mineral phosphates, Wagner originally used a
dilute Dilution of « -itrate of ammonia and free citric acid.0 The phosphoric acid in
all «.f the mineral pho-phate< \va> sparingly soluble in such a reagent, while an unadul-
terated. hL'h -ride >|;,,_, .^ve up 80 to 90 parts of its phosphoric acid. Further investi-
gations on various soils with many brands of slag made clear that the results obtained
f i ..MI p.. t experimei ponded quite well with those secured by means of the
.. id -olntion Thi- may be illustrated as follows:
Dt / ' iliihilitii of phosphoric add. *
•»>___ J _»
Phosphoric acid avail-
able.
tiruuil CM
slag.
In citric-
:iriil solu-
tion.
In pot ex-
[HTiments.
1
100
100
2
85
80
3
81
72
4
72
72
5
73
66
6
76
63
7
39
40
8
48
38
9
42
38
10
45
31
11
38
30
Etemlta similar to these were secured by Maercker,& who stated that "the results
removed all doubt that the citrate solubility and plant experiments were so nearly
proportioned that one had the same right to value the slag according to its content of
phosphoric arid soluble in citrate solution as to value the superphosphate by its con-
tent of water-soluble phosphoric acid."
flChemiker Zeitung, 1895, No. 63; also Dimgungsfragen, 1896, No. 1, p. 16.
*>Landw. Presse, 1895, No. 82.
150
As a result of these investigations the union of German experiment stations at its
meeting at Kiel, in September, 1896, adopted the method « of determining the rela-
tive value of the slag according to its phosphoric acid solubility in a 2 per cent citric
acid solution and did away with the previous standard of total phosphoric acid and
fineness.
Wagner, as well as Maercker, repeatedly called attention to the fact that experi-
ments both in the laboratory and with plants gave positive evidence that those slags
of like phosphoric acid content which were richest in silicic acid gave the best results.
G. Hoyermann, working independently, came to similar conclusions. At the present
time, according to Wagner, practically all of the iron works treat the molten slag as it
flows from the converter with hot quartz sand, with the result that the availability of
the phosphoric acid is increased from 10 to 30 per cent.&
CHEMICAL COMBINATION OF PHOSPHORIC ACID IN SLAG.
The form in which the phosphoric acid exists in the slag has never been fully
explained. It was formerly supposed that it was combined with lime as a tetracal-
cium phosphate and the latter being less stable than tricalcium phosphate became
easily available to the plants by being decomposed, under the influence of dilute
acids, into the calcium salt of the dissolving acid and dicalcium phosphate. The
tetralime phosphate, however, has never been made artificially, c although it has
been recognized by the aid of the microscope in the slag and exists as a mineral under
the name of isoklas.
M • >re recent investigations having shown, as already indicated, that those slags richest
in silicic acid of like phosphoric acid content gave the best results, the conclusion
followed that a part of the lime must be in the form of lime silicate. It is now gen-
erally held, especially by Wagner, d that the phosphoric acid is combined in the slag
as a double salt of tricalcium phosphate and calcium silicate and that in this form
the roots are able to utilize it. It is also believed probable that some of the phosphoric
acid is more or less united with iron as a basic iron phosphate.
THE USE OF PHOSPHATIC SLAG.
Basic slag has been shown to work especially well upon sour marsh and meadow
lands, upon porous, well-aired soils rich in humus, and upon sandy soils deficient
in lime.
When a rapid development of the crop is not desired, the slag may be used exclu-
sively in place of acid phosphate. On the other hand, in cases when it is feared that
the crop will not mature early enough upon heavy, cold land and in high altitudes
where the season is short, acid phosphate should be given the preference.
The phosphoric acid in slag is comparable in its quickness of action to nitrogen in
barnyard manure, tankage, and green crops; and the phosphoric acid in acid phosphate
to the action of nitrogen in nitrate of soda. A combination of slag and sulphate of
potash (500 pounds of slag and 100 pounds of potash) has been found to work especially
well upon grass land and to be very favorable to the development of clover.
a Method slightly modified from the original. Present method described in Konig's
Untersuchung landwirtschaftlich und gewerblich wichtiger Stoffe, 3d ed., pp. 173-174.
& Loc. cit.; also Wagner, Anwendung kiinstlicher Dimgemittel, pp. 74-75.
c Hilgenstock, Jahresber. chem. Technologic, 1887, p. 282, after Adolf Mayer, loc.
cit.
cit.
151
QUANTITY OP SLAG PER ACRE.
If the soil is particularly deficient in phosphoric acid, one can use as high as from
. !MM) pounds of -la- to the acre, plowed in and supplemented with 200 pounds of
a«-i<l phosphate in the hill or drill.
If, on the contrary, the soil is naturally rich in phosphoric acid or has been made so
by lar-e additions of .-lug for several consecutive years (1,000 or more pounds yearly)
then it is necessary- only to replace from year to year the amount removed by the
rn>j>. In surh ra.-es Maer.-ker >iates that one part of phosphoric acid in basic slag is
table as an equal amount in acid phosphate.
VALUATION OF PHOSPHORIC ACID IN BASIC SLAG.
By H. I). HASKINS.
Thoma.- lia.-ir .-lai: is being used in Massachusetts and some of the other New England
\ten.-ively each yi-ar, and it is therefore highly desirable that more
Mctory methods of analyzing and valuing this product be worked out by the
association.
At the la.- 1 ni'-eiin- ..i' the asso< -iatit.n the referee on phosphoric acid recommended
thai the pho-phorir acid in Thomas basic slag be valued by the degree of fineness of
the -I. i- along tin- -aim- lines as are employed in the case of ground bone, but the
recommendation did not specify the diameter of the openings in the sieve used in the
me. hani. al .-..•paraiimi. If \alued by its fineness the diameter of the openings in the
i fort hi.- pnrpo-i- i- obvioii>lv of great importance, a.- is shown by the follow-
' ,vo samples of ,-hig \\ere analy/.ed mechanically by the use of 100-, 50-,
an-! I1", n . the latter having circular oj>enings one-fiftieth of an inch in
<liam>
( 'in,. , 'ininiint ami i nhn of phosphoric arid (intilable by using sieves of different
mesh.
Total
Met-haiiit -;il in ilysis.
Valuation.
«»«**».
:-<>-llli- .
25-mesh sieve.
100-mesh
sieve.
50-mesh
sieve.
25-mesh
sieve.
Kim-
• QM |
Fin.-.
Coarse.
Fine.
Coarse.
1
.'
Percent.
17.45
17 '",
Per ct
71 s-i
Percent.
• 17
Perct.
s. ,.\
90.74
Percent.
10.36
9.26
Perct
93.72
94.97
Percent*
6.28
5.03
Dollars.
12.86
13.36
Dollars.
13.59
14.04
Dollars.
13.74
14.18
An average of the two samples shows that 94.34 per cent of the slag passes a 25-mesh
» per rent paaeee a 50-mesh sieve, and only 70.15 per cent passes a 100-mesh
I .....king at the matter from the point of valuation, we find that allowing 4 cents
f..r the phosphoric arid in the line and 3 rents for the phosphoric acid in the coarse
aluation of thr two samples of slag by use of the 25-mesh sieve
would be $l:{.!»»;. by u-e of the f,o-mesh sieve $13.81, and by use of the 100-mesh sieve
;.!!; a ditferenre of nearly $1 per ton in the extremes.
The next .|ii.-tion to be considered is whether this method of valuing the phos-
phoric arid in baM. -lag is a safe one for us to adopt. During the month of August
the writer's attention was called to a product put forth in large quantities in northern
New York. The material was a waste product said to be largely apatite and quartz,
romin- from iron ..re u.-e.l in that locality. It was finely ground, 69.44 per cent passing
a lm-m,-h sieve, and contained 16.78 per cent of total phosphoric acid; the phos-
152
phoric acid in this material, however, by the Wagner method of analysis showed
only 1.029 per cent of available phosphoric acid or 6.13 per cent of the whole, while the
basic slag by this same method showed 15.48 per cent of available phosphoric acid or
87.4 per cent of the whole. The point in making mention of this apatite is to show
that in case the phosphatic slag is adulterated with material of this nature the mechan-
ical method of valuing the slag would prove decidedly misleading, and it is because
of this that the method of valuing the phosphoric acid in basic slag has become obsolete
in European countries.
During the past year the writer has had experience with the Wagner method of
determining available phosphoric acid in basic slag and the valuations of this material
that appear in our fertilizer bulletin have been based on this method.
The Wagner method as used in foreign Countries has shown results agreeing closely
with those obtained in field trials. It is as follows:
Weigh 5 grams of the slag and transfer it to a half-liter, bottle-shaped flask containing
5 cc of alcohol to prevent the slag from adhering to the flask. Make up to the mark
with a 2 per cent citric acid solution at 17.5° C. The flask is fitted with a rubber
stopper and put at once into a rotary apparatus for thirty minutes, making thirty to
forty revolutions per minute. At the end of a half hour the solution is immediately
filtered and the phosphoric acid is determined in an aliquot part of the clear solution
by means of molybdic solution in the usual manner.
The analysis of two samples of slag by this method at the Massachusetts experiment
station shows the following close agreement. No. 1, available phosphoric acid,
15.42 and 15.38; No. 2, 15.81 and 15.75.
In case of a bona fide sample of basic slag the valuation based upon mechanical
analysis by use of a 100-mesh sieve agrees closely with the valuation based on the
availability of the phosphoric acid by the Wagner method. In case, however, of a
sample of slag adulterated with the natural mineral phosphate, the valuation based
on mechanical fineness is obviously open to severe criticism. I think this question
of sufficient importance to warrant a motion that I would herewith make, that the
referee on phosphoric acid be instructed to make a study of the Wagner method of
analysis with samples of basic slag and natural mineral phosphates, with a view to its
adoption as an official method for the determination of available phosphoric acid in
The papers by Mr. Lindsey and Mr. Raskins relating to the valua-
tion of phosporic acid in basic slag were referred to Committee A for
action on recommendations contained therein.
REPORT ON DAIRY PRODUCTS.
J. M. BARTLETT, Referee.
According to instructions given by vote of the association last year the referee has
continued the study of analytical methods for condensed milks. The results reported
at the last meeting indicated that the analysis of the sweetened product presented
much greater difficulties than the unsweetened, particularly in the determination of
fat; therefore, the referee decided to confine the work to one brand only, the sweetened
milk. Twenty-six analysts signified a desire to cooperate, but not all of them were
official chemists, many being commercial chemists more or less directly interested in
food analysis.
SAMPLES OP MILK.
On about April 1, a can of sweetened condensed milk together with a copy of instruc-
tions was sent to each chemist requesting the same. It was first intended to get a
quantity of milk in bulk, thoroughly mix it in the laboratory, and send out the samples
153
in bottles to insure uniformity, but a letter from the Borden Company, who furnished
th.- mnplee, «!••>. -ribing their process, whereby the milk is continuously agitated
until it reaches the cans, convinced the writer that all cans from the same batch
must be as uniform as it is possible to make them.
INSTRUCTIONS FOR ANALYSIS OP CONDENSED MILK.
Preparation of sample.
Mix thoroughly by transferring the contents of a can to some dish sufficiently large
to thoroughly -tir and nuik.- the whole homogeneous. Weigh 40 grams into a 100 cc
flask and make up to the mark with water.
Total solids.
M,tl,n<l A.— Dilute a measured portion of the above 40 per cent solution with an
equal amount of water. Use 5 cc of the diluted mixture and proceed as in the case
of mi Ik anal\-i~ according to the method given in Bulletin 107, page 117, Method I
drying either on aand or asbestos fiber.
Mittinil /;. I ~e l., M, h'- method which is as follows: Dilute a portion of the 40 per
cent solution with an ••«|iuil amount of water and take enough of this solution to
repre-ent I -nun of the condensed milk. Put in a tared platinum dish which will
hold at lea.-t •_'."• cc and -till further dilute with water until the dish is nearly full,
rin-iiiu' the pipette into th«- dish, then allow the dish to remain in contact with live
steam fm at |ea-i two h<-ur- after the last traces of the water have apparently been
evaporated, then transfer to the drying "\en for a few minutes, cool in the desiccator
and \\ejijh.
Ash.
Ignite the residue from total solids, cool and weigh in the usual manner.
1'rott in .
I '• termine nitrogen by Kjaldahl or Gunning method in 5 cc of the 40 per cent
solution and multiplv l.\
Lactose.
of the Hi per cent solution in a 250 cc flask to about 200 cc, add 6 cc
"t Fehlinj pper -ulphaie -olution. and make up to the mark, filter through a dry
Idler and d- t- mime lactose as follou-:
h of the copper sulphate and alkaline tartrate solution, add 50 cc
water and brim: to boiling, then add 2~> cc of the filtered milk solution and boil two
minute- by longer boiling the sucrose appears to throw down some copper), remove
from the lamp and allow to settle one or two minutes then filter on a gooch crucible
in the n-ual manner, wemhinu' the cuprous oxid after drying at 100 degrees. Give
M- of < nproii- oxid found as well as percentages of lactose so methods of calcula-
tion can be compared. Also, if possible, determine lactose by polariscope in this
solution.
Sttcrose.
Place 25 cc of the above solution, used to determine lactose, in a 100 cc flask. Add
of water and 0 'am of citric acid and heat on the steam bath for thirty
minute-, nearly neiitrali/.e with -odium hydrosid and determine total sugars in 25 cc
with I'ehlin/- solution in the usual manner, giving the weight of cuprous oxid as
well a.- the per. entases of .-ucrose. Also determine sucrose by difference, subtracting
the lactose, protein, fat and ash from total solids.
Fat.
„/ A- Determine by double extraction method. (See Bureau of Chemistry,
Circular 32. p -
M.tt.n.t H. llv the liabcoek centrifugal method using the modification given in
Bulletin 107. pu-ie I
Method ( . The ( Gottlieb method, the directions for which are as follows:
Ten cubic centimeters of milk are measured into a glass cylinder three-fourths inch
in diameter and about 14 inches long (see Landw. Vers. Sta., *>:«:» 100 cc burette
or ft eudiometer tube will do); Ice of concentrated ammonia is added and mixed well
with themilk The following chemicals are next added, in the order given: 10 cc of
!»L' per cent alcohol, 25 cc of washed ether, and 25 cc petroleum ether (boiling point
154
below 80° C.), the cylinder being closed with a moistened cork stopper and the con-
tents shaken several times after the addition of each. The cylinder is then left
standing for six hours or more. The clear fat solution is next pipetted off into a small
weighed flask by means of a siphon drawn to a fine point (fig. 6, loc. cit.), which is
lowered into the fat solution to within 0.5 cm of the turbid bottom layer. After
evaporating the ether solution in a hood, the flasks are dried in a steam oven for two
or three hours and weighed. This method is applicable to new milk, skim milk,
buttermilk, whey, cream, cheese, condensed milk, and milk powder, but has been
found of special value for determining fat in skim milk, buttermilk, cheese, and con-
densed milk.T In the case of products high in fat, a^econd treatment with 10 cc each
of ether and petroleum ether is advisable in order to recover the last trace of fat.
Chemists are requested to make at least two determinations by the methods given.
On account of the quite large variations in the results reported by the chemists last year,
the referee is very anxious to determine whether the differences are due to the inac-
curacy of the methods or to the manner ia which they are handled by different men.
Everyone who has had much experience in making sugar determinations realizes
how easy it is to get quite large variations in results by varying the method slightly.
If methods materially different from those given above are being used by anyone
taking part in the work for the determination of sugars or fat in condensed milks, the
referee will be glad to have results by such methods reported.
J. M. BARTLETT,
Referee,
L. G. MICHAELS,
Associate referee.
Eleven different chemists reported on the samples sent them and their results are
given in the following table, together with some obtained at the Maine station:
Cooperative work on samples of sweetened condensed milk (percentage results).
Analyst.
Solids.
1
Protein NX6.25.
I
Sucrose.
Fat.
Dried on
sand or
asbestos.
Leach's
method.
1
P
By differ-
ence.
Polar*
scope.
~ — E
0,*
Modified
Balicork.
Gottlieb.
W. A. Brennon, Wisconsin
station
72.44
73.14
73.06
72.08
73.19
72.90
1.81
1.82
1.66
11.47
11. 56
11 56
44.76
44.50
8.10
8.24
8.32
8.10
8.64
8.04
Average
44.01
a48. 51
8.21
8.34
72.89
72.25
72.06
72.72
73.71
73.50
1.76
7.42
11.53
44.68
8.17
E. M. Bailey, Connecticut
station
8.00
7.80
8.25
8.40
Average
72.15
70.70
70.50
73.60
7.90
8.33
8.7
8.5
J. M. Bartlett, Maine station.
Average . .
1
11.3
11. 1
8.50
8.70
70.60
1.70
7.20
6.96
11.2
43.24
8.66
8.60
8.6
Sidney Davis, department of
health, New York City
73.13
1 - —
7447
74.70
1.72
1.53
1.52
11.72
11.42
11.42
44,09
9.00
L. W. Fetzer, Maryland sta-
tion.
72.01
72.03
=
7.20
7.23
8.66
8.63
7.80
7.95
7.90
\ verage
72.02
74.53
«1.53
7.22
11.42 37.85
44.20
8.65
67.29
H. B. Holland, Massachu-
setts station:
Average of 4 tests
:
71 ?f>.
1 66
7 42
Second sample, average
of3tests 71.41
C. H. Jones, Vermont station:
Average of 2 tests 09. 75
Second sample, average i
of 2 tests . 79 90
c7.8/i
70.58
1.68
7.09
11.63
43.77
41.19
8.16
8.56
8.10
8.55
6.6
C. P. Moat, Vermont board
of health
7000
72.51
al.51
:
a Omitted from average.
b Dried on sand and extracted once.
Extracted twice.
155
Coopemlnr imrk on samples of sweetened condensed milk (percentage results)— Cont'
Analyst.
Solids.
1
ProteinNX6.25.
hi
Sucrose.
Fat.
§S|
III
Leach's
method.
«
By differ-
ence.
Polari-
scope.
Double
extrac-
tion.
Modified
Babcock.
Gottlieb.
rrison, Connecticut
>t;ltiuli N.-U 1 l;t\.
A. 1 1 it ten, Michigan station
••rigR
NYNi.n A I..UI.IIT-. I'.uiKham-
l.m.N V
A.r. U hi M i.-r, Maine station.
II II
us.-»7
70.55
70.81
1.95
2.05
7.03
7.06
8 19
8.04
7.5
7.98
6&86
72.35
7-.V .;:
70.68
7.', s7
73.88
02.00
7.06
7.06
7.06
8.12
7.35
7.20
7.20
7.96
7.80
1.80
1.82
12.05
11.90
"
==
==
7.01
:_• .<•.
:
72.45
7i) 7n
711 Ml
73.88 1.81
!-1.47
7.06
TT
11.95
10.30
11.02
44.63
44.59
43.65
7.01
7.20
8.40
8.70
8.70
7.88
43.70
8.52
8.30
73. 20 1. 73
73. 33 1. 72
8.54
8.45
7.89
7.78
11.06
™*e
\. D M.-.-I,. Minneapolis,
Minn
. •
7U75
72. C7
71 Ml
7127
:.; jn
Taoo
1 71
1.74
1.74
7.19
6.50
6.50
11.04
9.78
ft 7 1
4479
46.64
46.74
44.79
8.50
8.04
8.05
8.70
7.20
7.20
7.83
43.07
43.06
8.25
8.11
72.74
am
71 :,;
73.10
1.74
6.50
a9.76
43.07
46.68
8.05
8 57
7.20
8.18
uition..
Average
=
7J Ml
1.60
7.25
11.35
43.80
44.18
8.17
"sTie
44.12
7.87
' nitt«-.l from average.
COMMENTS OF ANALYSTS.
U .1. BlVftHOM, iriawwn station: The solids were determined in Method A by
dr\ in- "ii -ami fi\ .• and a hall hours and in \\ hy drying three hours on steam bath and
t\\«. h..iir- MI h-.t air OVen.
: Total solids were determined in Method A by
;i aliiiiiinuiii dish, flirrc hcin"; enough 8and to make a total
Kvaiiorati'.n \va.- tir-i niad<> on live steam, with frequent stirring.
Tin- di-h ua- iln-n wiped dry and put in a drying oven at 100° for thirty minutes,
and wri^lird, th'-n ai,rain hcatrd three hours, and for seven hours.
Per cent.
Av.-ni«o for thirty minute* .............................. .. .................. 72. 74
/Lvenge I-T thn-.- hours ..................................................... 72. 40
A\ t r . ,•!! Imurs ................................................... 72. 11
In MftluNl \\ th»- manipulation was the same as in A, except that no absorbent was
used. Average for heating thirty minutes was 73.58 per cent; for two hours, 73.60 per
cent.
In th»- doiiM' M method for fat the first and second extractions were made
iWriirhi hours ea« h and the third for four hours. In the centrifugal method the
pi|><-Ho \\a- rins.'d into the h"ttle.
\lnrijlaml stntinn: The methods involving dilution of a 40 per cent
formed by inverting the milk suuar evidently has a different reducing capacity from
dextrose and levuln.^-. In the .use of the Leach- Babcock test for fat one can readily
see that err-T- < an • reep in while drawing off the supernatant fluid in three instances.
/ It. Hnlhind, Massachusetts station: Solution: A 20 per cent solution was pre-
pared hy diluting KM) Drains of the milk to 500 cc. There was some separation of curd
"r far. presumably the latter, \vhichmusthavevitiatedtheresultstosomeextent.
MoiMun-: S.-\i-ral aliquotsof 5and 10 cc were evaporated on quartz sand in a flat*
l>o itemed di.-h at a low temperature until the bulk of the water was expelled, then
156
dried in an electric oven for two hours at 100° C. or in a vacuum oven below 70° C.
(gauge reading, 29 inches).
Evaporation in a flat-bottomed dish without sand yielded low results, probably due
to a retention of moisture by the nitrogenous film which formed on the surface. -Simi-
lar treatment in a vacuum oven gave higher results, but below that obtained on sand.
These figures are not reported.
Ash: Twenty-five cc were evaporated in a platinum dish with 5 cc of concentrated
nitric acid and burned to a white ash.
Protein: Ten cc were treated by the Kjeldahl-Gunning method.
Fat: Our work of last season indicated that a single extraction gave higher results
than the double and saved time and work. The dried solids on the sand were pul-
verized, washed with water, dried, and extracted with dry ethyl ether in a continuous
extractor. Long heating of the residue containing fat (at 100° C.) should be avoided,
as it appears to reduce the amount of fat that can be extracted.
C. H. Jones, Vermont station: The result reported on fat by the modified Babcock
method is the average of ten determinations on three distinct 40 percent solutions.
The individual readings were 2.60, 2.65, 2.80, and seven readings of 2.70. Lactose
determinations were made on distinct portions of the original sample. In the sucrose
determination it was necessary to dilute the solution after inversion to 200 cc in order
to have an excess of copper in the Fehling solution.
The- result reported by the Leach method is the average of two determinations,
70.70 and 70.58 per cent* respectively. The platinum dish used did not have an ab-
solutely flat bottom, but it was the nearest approach to anything of the kind available.
I am at present unable to explain the difference obtained by the two methods, unless
a too complete drying and consequent breaking down is obtained with Method A.
The result reported on the double-extraction method for fat is the average of two
determinations from distinct solutions. They were, respectively, 8. 20 and 8.12 per
cent. The only awkward feature is the size of the filter paper used. The following
modification of the Babcock method described was suggested by the use of the hard-
ened filter on other laboratory determinations:
Method: Place 15 cc of the 40 per cent solution (6 grams) in a small-lipped beaker,
diameter 1.5 inches, height 2 inches. Dilute with an equal amount of water; add
4 cc Fehling's copper solution; stir with glass rod. Filter through a 12.5 cm C. S. and
S. 575 hardened filter. Wash thoroughly with water; stir on the filter with glass rod
(100 cc is usually enough, though 160 cc had no lowering effect on the result). Return
precipitate to original beaker, removing any remaining particles by washing with hot
water through a fine-jet wash bottle. (The bulk is easily kept below 17 cc.) Stir
with a glass rod. Pour into Babcock milk bottle. Add a portion of the acid to the resi-
due in the beaker. Mix thoroughly, using stirring rod. Transfer to Babcock bottle.
Repeat with remainder of acid. Shake milk bottle thoroughly, and then rinse beaker
with a little hot water from the wash bottle and put into test bottle. Run as usual.
The individual results obtained by this procedure were 2.70 for five readings and 2.65
on the sixth, three different 40 per cent solutions used.
I find it desirable, both with this method and with Method B, to use rather more
sulphuric acid than is specified ; often 18.5 cc. While the results by this procedure are
not different from those obtained by Method B, yet when a number of samples are run
a considerable gain is made in actual working time.
DISCUSSION OF RESULTS.
The results obtained this year are quite satisfactory on all determinations except
fat. The lactose results, with three exceptions, are probably as good as one could
hope to get from a number of chemists working independently and not making a spe-
cialty of sugar determinations. There are some variations in total solids for which it
seems difficult to account. One might think it due to variations in the different cans
of milk were it not for the fact that in some cases when the solids were as much as 2
per cent low, the other determinations, such as proteids, ash, etc., were as high or
higher than the average. The referee can only account for these discrepancies in
one of two ways, faulty sampling, or that the sugars were allowed to ferment and
cause loss before the determinations were made. It is believed that all determina-
tions should be made as soon as the solutions are made up, and no solution which has
stood in a warm laboratory twenty-four hours should be used for the determinations
of solids or sugars. Leach's method appears to give high results, probably because of
the large amount of sugar present to hold the water.
157
The ash results are for the most part very good and concordant, with the exception
of three, which were probably burned down hard without leaching. It is very evi-
dent that leaching with hot water after thorough charring is necessary in the presence
of sucrose.
The sucrose results are probably as good as one could expect to obtain, but inasmuch
as this is not a normal but an added constituent of the milk it is best determined by
difference.
The results on fat, one of the most important constituents of the milk, are far from
bein- satisfactory. The referee believes that these discrepancies are due to three
Fir-t. lack of experience with this kind of material. Second, a lack of
(I. -tail in irivini: tin -do ub le extraction method in Circular 32, and, third, faulty instruc-
tions in directing a 40 per cent solution to be used for this method. This solution,
as shown by the tables below, is too concentrated to get the best results when as large
an amount as 40 per cent cane sugar is present. This degree of concentration makes
such a thick layer ..f -u<;ar on the paper coil that quite a large proportion of the fat
on the paperafterthe first extraction, and then soaking in water causes a mechan-
ical lo- ..f fat when i hi- -ii-ar js dissolved off. Such loss was proven by examination
of ih" -IL'ht .-cum ri.-iii'j »n the water, which, under the microscope, showed the pres-
i'liles. When the work is carefully done, however, and dry ether is
this 1.*.- i- only small, amounting t<> one or two tenths of 1 percent. Our results
show that OH hiirh re-ult- can be obtained with 1 gram in a 10 or 20 per cent solution
in .1 -ini:le extraction of fourteen hours as with a more concentrated 40 per cent solu-
tion .uid a «l«.uMe extraction. The highest and most concordant results, however,
btained with a 10 or 20 percent solution and double extraction.
Mr. (iei-1. r. tht- originator of the double-extraction method, stated, under date of
January, 1908, that he had no changes to suggest from those given in his original
i published in the Journal oHhe American Chemical Society in 1900 except
that the time of each extraction should be extended to seven or eight hours instead
of lour or five and that strictly dry ether probably is the best solvent on account of
n-tain boiling point. In Mr. Geisler's paper he emphasizes the fact that the
milk should be evenly distributed over the surface of the paper coil; also that the
et h« r r-hould be anhydrous to prevent the paper coil from becoming soggy. The
method <>f drying on asbestos or paper in tubes is not so desirable as on strips of paper
on account of the l,,m; heating required to dry out completely.
The modified Habcock method, in the hands of men who have had much experi-
en< ••• with it, usually gives very good results, but it is not to be considered as accurate
as the gravimetric, and as the reading is multiplied by three every error is increased
threefold. When the milk was fresh we were able to get very clear separations with
the copper sulphate in the centrifuge, and the sugar solution could be easily decanted
with. .111 lo>s of fat. the curd and fat remaining in a hard mass at the bottom of the
bottle, but in te.-ting some cans later, which had stood in the laboratory for three or
four month-, the -eparation was not so complete, and it was necessary to pass the solu-
tion through a tiller, washing the particles of curd back into the bottle to obtain all
the fat. and in several instances the results were low. This operation made the
method somewhat longer and more tedious.
The results reported by the Gottlieb method are not very satisfactory and the ref-
: .11111,1 but little time to test it. Only two tests were made and they gave by
direct weight over 9 percent fat, but it was found that some proteid or foreign matter
was clinging to the bottom of the flasks after the fat was dissolved out with hot ben-
/ine. After weighing and deducing this weight from the original the results agreed
very closely with the gravimetric. The writer believes that by observing proper
precautions this method can be made very reliable, particularly for sweetened con-
densed milk. Small separatory funnels are more desirable than the long tubes recom-
mended in the method.
158
Some figures obtained in the Maine laboratory are given in the following table, and
lead the writer to believe that good results can be obtained when the double-extrac-
tion method is carried out as follows:
Prepare strips of soft white filter paper 4 by 24 inches of the quality of the S. & S.
No. 597, by soaking two or three hours in alcohol, then after thoroughly drying in the
oven extracting several hours with ether until no residue is left from the* ether as it
comes through. Then take 10 cc of a 20 per cent solution of the condensed milk and
distribute it carefully over the whole surface of the thoroughly dried paper. This is
best done by attaching one end of the paper to some object and holding the other end
out straight so that the pipette can be emptied by passing the point back and forth
over the whole surface. To dry the paper, suspend it over a copper wire in the drying
oven, where it will thoroughly dry out in two hours or much more .rapidly than if
coiled up or put in a tube. After drying roll up in a coil, wind with thread or small
copper wire, place in the extractor, and extract not less than eight hours. If it is the
sweetened product remove the coils from the extractor, loosen the wire or thread, dry
and suspend in 500 cc of water for two hours, then return the coils to the oven and dry
as before, and extract again for not less than five hours. Five cc of milk and a coil 4
by 12 inches may be used if preferred.
Determination of fat in condensed milk by modifications of the double-extraction method.
Modifications.
Fat.
5 cc (2 grams) of 40 per cent solution extracted 8 hours with ether:
Per cent.
Exhausted with water and extracted 5 hours more (average of 4 samples)
Exhausted a second time and extracted a third time 8. 45
cc (2 grams) of a 20 per cent solution on a coil 5 by 24 inches:
10 Extracted 10 hours a 55
Exhausted with water and extracted 5 hours more 8. 78
cc (2 grams) of a 20 per cent solution on a coil 5 by 24 inches:
Extracted 14 hours 8. 42
Exhausted with water and extracted again 6 hours 8. 69
5cc (1 gram) of a 20 per cent solution on a coil 5 by 12 inches:
Extracted 5 hours a 45
Exhausted with water and extracted 5 hours more : 8. 78
5 cc (1 gram) of a 20 per cent solution on a coil 5 by 12 inches:
Extracted 10 hours with ether & 36
Exhausted with water and extracted again 8. 85
10 cc (1 gram) of a 10 per cent solution on a coil 5 by 24 inches:
Extracted with ether 14 hours 8. 42
Exhausted with water and extracted 5 hours more 8. 95
RECOMMENDATIONS.
It is recommended that —
(1) The following methods be adopted as official methods:
1. PREPARATION OF SAMPLE.
Place the can, if cold, in water at 30° to 35° C. until warm. Open and mix thor-
oughly by transferring the contents of the can to s*ome dish sufficiently large to thor-
oughly stir and make the whole mass homogeneous. Care must be taken to scrape
out all milk adhering to the interior of the can. Weigh 100 grams into a 500 cc flask
and make up to the mark with water. If the milk will not completely dissolve, each
portion must be weighed out separately for analysis.
2. TOTAL SOLIDS.
Use 10 cc of the above 20 per cent solution and proceed as in the case of milk analysis
according to the method given in Bulletin 107, page 117, Method I, drying either on
sand or asbestos fiber.
3. ASH.
Ignite the residue from 10 cc of the 20 per cent solution at low red heat, leach with
hot water if sucrose is present, ignite the residue and filter until white, add the leach-
ings, evaporate to dry ness again in usual manner and weigh.
159
4. PROTEIN.
Determine nitm-en by Kjeldahl or Gunning method in 10 cc of the 20 per cent
solution ami multiply by 6.38.
5. LACTOSE.
Dilute lOOccof the L'O pen-em solution in a 250 cc flask to about 200 cc; add 6 cc of
Fehlin</> copper Milphate solution and make up to the mark; filter through a dry
filter and determine lactose by the Walker method, boiling only two minutes with
the I-'flllillL' solution.
The method- for determining sucrose and fat be given further study.
REPORT ON FOODS AND FEEDING STUFFS.
By FitKD \\ . MOUSE, Associate Referee.
The request t" •• t'er >n cattle foods was unexpected and found me un-
familiar with the nio-i recent work of the association on this class of materials. Noting
that ii \\a- n -. •oinincndeii last year to continue the trial of the methyl pentosan deter-
mination after the method of F.llett. an attempt was made to simplify the method
before a.-kiuu- for cooperation from other members. \VTiolly satisfactory results have
not > i.tained, but it seems possible, with a little more time, to accomplish
MII h a nullification.
It was al.-> planned to compare the effects of the use of Ellett's method on some
lard cattle food alongside of a substance known to contain methyl pentosan.
For the latin- there was accessible plenty of t he sea weed, Fucus vesiculosis or rock weed,
ami a quantity was obtained, dried, and pulverized. For the standard cattle food,
wheat, bran was selected, since its content of pentosan is good, and Widtsoe reported no
evidence of methyl furfural in it by the qualitative tests.
The method of procedure was to follow the provisional method for pentosan deter-
mination throughout and, after weighing the precipitated phloroglucid, to extract
with alcohol b\ Klletfs method of diu'i'sting the crucible and contents in a small
quantity of alcohol at 6-VM'., filtering, and repeating the operation until the filtrate
finally becomes colorless. A marked solubility of the precipitate was observed in
both cases. This was unexpected in the bran, and considerable time was spent in
'in- determinations. Results on bran varied much; but the seaweed gave rea-
sonably conei.nlant figures. By this time it was too late to send out samples to
other chemiata. Another |N>int was noticed in the prosecution of the work, namely,
that the provisional method for peniosans seldom if ever yielded furfural-free dis-
tillates when the pro. ri bed limit of volume was reached. The drops would still
show traces of furfural.
Tlu-e jM.ints of di.-a-reement from published matter about the different forms of
peniosans have convinced the referee that more work is needed on this provisional
method in some of the details. There is an important field for research in our common
lenaod the concentrated by-products in working out the constituents of the
nitro-en-free extract. Most of the methods now in use are difficult of manipulation
and more or less approximate in their results. Comparatively little attention is paid
in , si nee the conventional methods of fodder analysis answer the practical feeder's
purpose.
vert Helen, progress in nutrition studies demands more attention to the less-
known carbohydrates, since their digestibility and consequent food value are unknown
quantities.
The referee has no recommendations to make; but if no instructions are received
from the association it is his intention to continue the study of these newest methods
ot determining the less-known carbohydrates.
160
ElletCs method applied to Fucus vesiculosis.
[Two grams of material.]
Loss bv ex-
Total phloro-
glucid.
traction
with
alcohol.
Gram.
a 2403
Gram*
Q.04C9
.2467
.0516
.2497
.0341
.2405
.0434
.2664
.0446
Mean .2487 .0433
BEST RESULTS BY WASHING WITH HOT ALCOHOL.
Gram.
Gram.
0.2366
OLMN
.2533 .0366
THE DETERMINATION OF ACIDITY IN CATTLE FEEDS.
By JOHN PHILLIPS STREET, Referee.
The acidity of a cattle food is due to the presence of hydrogen ions. In a solution
containing a mixture of salts of organic and inorganic acids it makes practically no
difference whether this acidity was originally produced by the addition of a small
amount of an organic or of an inorganic acid, for the final result is essentially the same;
that is, the presence of a certain proportion of free hydrogen ions and of the ions of all
the various salts which are present in the solution. The question of acidity, there-
fore, is one of degree rather than of kind and, from a physiological view point, depends
on the nature of the salts which are present in the solution under consideration. Let
us take an example. We have a solution containing sodium chlorid and sodium
acetate. In this we have sodium ions, chlorin ions, acetate ions, undissociated sodium
acetate molecules, and undissociated sodium chlorid molecules. If a small quantity
of hydrochloric acid is added to this solution it will then contain, in addition to the
substances above named, a certain quantity of hydrogen ions and a correspondingly
greater quantity of chlorin ions. If a molecularly equivalent quantity of acetic acid
is added instead of hydrochloric, the solution will contain the hydrogen ions, as in the
first case, and the number of acetate ions will be correspondingly increased.
• If we now measure the acidity of each of these two solutions with phenolphthalein
as an indicator, the result will be the same, for this indicator gives a pretty accurate
measure of free and potentially free hydrogen ions. If we measure the acidity of these
solutions by means of delicate litmus paper the degree of acidity will be found to be
less than that as determined by phenolphthalein. The reason for this is to be found
in the fact that litmus is a relatively stronger acid than phenolphthalein and reacts
with the base before all the acid hydrogen of the acetic acid has been acted on. The
effect of the presence of organic salts is to reduce the number of free hydrogen ions,
in comparison with that which would be present in a solution to which had been added
the same quantity of mineral acid in the presence simply of inorganic salts of strong
bases with strong acids, such as sodium chlorid or sodium sulphate, and it is also clear
that it is not possible to determine in a solution containing a mixture of organic and
inorganic salts, which show an acid reaction, whether this reaction was originally
caused by the action of a mineral acid or of an organic acid. The indicators that are
commonly supposed to distinguish between mineral and organic acids in mixtures
161
containing *lUoi w.-ak buefl and strong acids, or of strong bases and weak acids, give
entirely different results from those obtained in solutions free from such salts, for by
hydrolytic dissociation these salts contribute to the solution a certain quantity of
hydro-,-!! '>r hydn.xyl ions, according to the nature of the salts present and the con-
centration .•! the solution, which ions exert an effect on the indicator in one direction
or the other.
In u mixturv of weak and strong acids and their salts, phenolphthalein, which is the
\\vake.-t indicator commonly employed, gives the total amount of acids present
Htnmii.T than phenolphthalein, itself an exceedingly weak acid. If a stronger acid
indicator, e. g., litinue, is in the above mixture, it will appear to have less total acid,
because the litmus itself reacts with the base before the weaker acids are acted on.
It is thus clear that, for such a mixture, it is impossible to determine the acidity
of it> solution, and, furthermore, it is not even possible by titration to determine the
actual concentration in free hydrogen ions, which, from a physiological standpoint,
i.- tin- true question under consideration.
h has been th»- practice «>f physical chemists to determine the concentration in
hydrogen ions by inverting cane sugar, a process which closely corresponds with the
enzym reaction.- »i physiological processes.
The acidity of a . attic feed may come from a mineral acid used in its preparation,
from ..r_Miiic .Hid- natural to the product itself, or developed by fermentation during
it- preparation, and poewihly, in some cases, from phosphates having an acid reaction
and normally present in the feed.
Jordan'- .-tudie- Bulletin i.':>s, (ieneva station), however, indicate that "our com-
IIHTI i.d feed- of vegetable iiu'in do not contain appreciable quantities of phosphorus
in inorganic combination."
l-'.n-ilaL'e i- .in example of a feed containing considerable amounts of organic acids
de\. -loped in the -il. i by fermentation. A n urn her of other feeds which are by-products
of manufacturing processes contain organic acids resulting, likewise, from fermenta-
•akiiiir place diirini: manufacture.
In \ ie\\ of the net that the presence of free mineral acids in certain feeds has been
'ted or allirmed, I wish to raise the question of the methods involved and ask
the a.-s.K-iation to make it the subject of inquiry, in order that an accurate method of
te-tin- for acidity may In- found and adopted. As matters now stand, we are depend-
in- \\holly on volumetric methods and the use of indicators, and the question to be
settled first of all is. .Ju.-t what do indicators indicate?
little attention has Keen «,MVIMI to the acidity due to the proteins themselves and
their varying action with different indicators. Osborne « has pointed out that the
pfOteinc are Dot neutral hodies, like the carbohydrates, and that the general assump-
tion that u solution containinu' protein matter, and showing neither acid nor alkaline
with litmus, is chemically neutral, is erroneous. Many experiments have shown that
certain protein solutions, when neutral to litmus, are acid to phenolphthalein and
alkaline to lacmoid It ha- also been established that a notable amount of acid can
Ulded to a protein solution before an acid reaction with tropaeolin, alizarin, or
phloro^lucin and vanillin is given.
A - ( )sborne says, b it is of importance "to know whether litmus can be used to deter-
mine the point when all combined acid has been converted into neutral salts of potas-
sium or sodium and all the protein substance has been set free, or whether, as we know
i- i he case, when tropaeolin or lacmoid is used as an indicator, more acid still remains
combined '
A.pieous solutions of crystallized ovalbumin, solutions in sodium chlorid brine of
ex. -elsin. amandin, vignin, conglutin, glycinin, corylin, phaseolin, and legumin, and
solution, ,,f /, n,, -riiadin, and hordein in 75 to 90 per cent alcohol, which were either
" J. Amer. Them. So,-., 1902, 24: 39. b Loc. cit.
7. :• 173— Bull. 122—09 - 11
162
neutral or acid to sensitive neutral litmus paper, when made neutral to litmus were,
in every case, still acid toward phenolphthalein.
Osborne further says:
To render gram portions of these several protein preparations neutral to litmus
required in a few cases not any, in most cases from 0.1 to 1.5 cc of decinormal alkali;,
while to make the same gram portions neutral to phenolphthalein required the further
addition of from 0.7 to 1 cc of decinormal alkali, except for legumin, which required
2 cc. Edestin made neutral to phenolphthalein and dissolved in sodium chlorid solu-
tion reacts distinctly alkaline toward litmus. This Alkaline reaction is caused by the
edestin itself and not by organic salts of the alkali, since such preparations yield a
very small amount of ash, less than 0.05 per cent, which is neutral to both litmus and
phenolphthalein. Solutions of all the other protein bodies I have exam-
ined, when similarly made neutral to phenolphthalein, react decidedly alkaline with
litmus.
In the investigation which the referee reports at this time no attempt was made to
determine total acidity, only those acids being taken into account which were extracted
by a rather prolonged treatment with water. Sixteen samples of gluten feed, repre-
senting five brands, two of wheat bran and one each of wheat middlings, wheat feed
and cottonseed meal, were examined.
Ten grams of the feed were weighed into a beaker and stirred with 50 cc of water
for ten minutes, then transferred to a plain wet filter and washed with successive
small portions of water, until the washings amounted to 150 cc; the extract was
then made up to 200 cc with water and 20 cc portions (=1 gram feed) used in the
subsequent titrations. A blank determination was also made with 200 cc of water
run through a filter paper as before, and the washings were found to be neutral to
methyl orange, phenolphthalein, and litmus.
The following indicators were used:
Phenolphthalein: One gram dissolved in 100 cc of 50 per cent alcohol.
Litmus paper: Very sensitive neutral paper.
Methyl orange: One gram dissolved in 1,000 cc of water.
Congo red: One gram dissolved in 100 cc of 30 per cent alcohol.
Gunzburg's reagent: Two grams of phloroglucin and 1 gram of vanillin dissolved in
30 grams of alcohol.
Toepfer's reagent: One per cent solution of phenolphthalein in alcohol and 0.5 per
cent solution of dimethylamidoazobenzol.
The alkali used was approximately decinormal sodium hydroxid, 1 cc being equal
to 0.003996 gram sodium hydroxid.
Twenty cubic centimeter portions of the watery extract, equal to 1 gram of feed,
were taken for each test. Owing to the usually highly colored solutions, the aliquot
was diluted with 500 cc of water for the test with methyl orange, and with 50 cc for
the other indicators, except in the Giinzburg test, where 0.5 cc of the extract and
the same quantity of the reagent were used. Three hydrochloric acid solutions were
also prepared, N/14, N/28, and N/56, respectively.
The Giinzburg and Toepfer tests and Congo Red are recommended as reliable in
determining whether or not free mineral acid is present. These tests were applied
first to the three hydrochloric acid solutions and unmistakable positive results were
secured with all, the most dilute acid used, N/56, equivalent to about 0.065 per cent
of hydrochloric acid, responding perfectly to the reactions indicated. A mixture of
one of the aqueous feed extracts and dilute hydrochloric acid, the total mixture con-
taining 0.065 per cent of free hydrochloric acid, was likewise subjected to these tests
and positive proof was secured that nothing present in the feed extract in any way
interfered with the delicacy of the reactions. However, following the suggestions of
Osborne's work, when the salt of a weak acid, for instance, sodium acetate, was added
to these same test solutions, none of the above prescribed tests for free mineral acidity
responded, although hydrochloric acid had been added in every case. This experi-
ment shows quite conclusively the danger and inaccuracy of asserting either the
presence or absence of mineral acids from data obtained by these tests.
163
None of the feed extracts showed any acidity to methyl orange, a result quite to be
expected. Referring to methyl orange, Ostwald says « "should the acid be weak,
only slightly ionisable (the ionization being still further reduced by the presence
«.f i In- neutral salt formed in the liquid), the quantity of hydrogen ions on passing the
point ••!' neutralization is too small to allow of the formation of a visible amount of the
Donionised moleculefl of methyl orange, and the red color only appears after a con-
Mderahle excen has been added, and then only by degrees."
The conditions thus described by Ostwald seem to be identical with what we have
in these feed extracts. Five samples of Buffalo gluten feed required from 1.10 to 1.80
<•<• of dccinormal alkali to neutralize the acidity of 1 gram of feed, using litmus; from
usin- phenolphthalein, and from 2. 70 to 3.65cc, using Toepfer's reagent.
Five samples <.f <ilo[,,. -luten feed, with the same amount of feed, required from
1 .:'••"• i" I .'•«' CC with litmus; 2.95 to 3.80 cc with phenolphthalein and from 2.90 to
3.80 cc with T<>epfer's reagent.
(ream of corn gluten feed and Pekin gluten feed gave corresponding results with
the three indi< lule Douglas gluten feed showed the same relation, but a
inurh lower aridit \ . (>.:!'> cc with litmus, 0.40 cc with phenolphthalein and 0.35 with
reairenl.
The .-ample- ..f wheat bran, middling, and feed required 0.50 to 1 cc with litmus,
I .o with phenolphthalein and 1 to 1.80 with Toepfer's reagent.
( otton-eed meal required 0.65 cc, 1 cc and 1 cc, respectively, with the three
imli< .1
Th- .1 \erauc acidity »»f all the feeds was 1.18 cc with litmus, 2.37 cc with phenol-
phthalein and _'."•«» cc with T'epfer's reagent.
These retnultn c«>rres|>ond perfectly with what we should expect if the acidity came
from n of protein salts alone, or from salts of weak organic acids. I there-
he a-sociation to take up the matter of acidity of cattle feeds and consider
lio\\ the re.-ulis obtained by current methods can be applied to agricultural problems.
The appended table pre-eni> the determinations in detail.
Acidity of </ln ten feeds.
[In trrms of 1 gram of feed.]
Num-
ber.
JI1.V1
•_M »:«i
ItMB
21488
21618
•jt i.;1'
ZUM
21000
21MO
21668
jui:.
•ji I.VN
21428
Brand.
Protein.
l-h.-nol phi halt-in.
Litmus.
Toepfer test (dime-
thylamidoazoben-
zol and phenol-
phthalein).
Tenth-
normal
sodium
hydroxid.
Equal to
grains of
sodium
hydroxid.
Tenth-
normal
sodium
hydroxid.
Equal to
grams of
sodium
hydroxid.
Tenth-
normal
sodium
hydroxid.
Equal to
grams of
sodium
hydroxid.
Buffalo
Percent.
26.62
28.08
• tj
25.00
24.75
20.12
2ft B
•J», mi
•jt; •'(
•Ji.. :<7
25.06
28.78
28.19
•J-J. 76
21. (.2
15.31
14.81
18.06
15.94
45.06
cc.
3.40
2.55
3.10
3.35
2.70
2.60
.40
3.55
3.40
3.80
2.95
3.40
2.85
3.65
.50
1.05
1.00
1.00
1.70
.90
1.00
0.0136
.0102
.0124
.0134
.0108
.0104
.0016
.0142
.0136
.0152
.0118
.0136
.0114
.0146
.0020
.0042
.0040
.0040
.0068
.0036
.0040
cc.
1.80
1.20
1.60
1.65
1.10
1.20
.25
1.85
1.85
1.90
1.45
1.35
1.70
1.60
.40
.60
.50
.50
1.00
.60
.65
0.0072
.0048
.0064
.0066
.0044
.0048
.0010
.0074
.0074
.0076
.0058
.0054
.0068
.0064
.0016
.0024
.0020
.0020
.0040
.0024
.0026
cc.
3.50
3.10
3.65
3.65
2.70
3.00
.35
3.80
3.50
3.70
2.90
. 3.45
3.20
3.80
.70
1.30
1.30
1.10
1.80
1.00
1.00
0.0140
.0124
.0146
.0146
.0108
.0120
.0014
.0152
.0140
.0148
.0116
' . 0138
.0128
.0152
.0028
.0052
.0052
.0044
.0072
.0040
.0040
lo
.. .
lo
Cream of corn
Globe
do
do
io
do
IVkin
liraiiil unknown
. ..|o
lo
\V ht>at bran
lo
Wheat middlings
Wheat feed
Cottonseed meal
a Foundations of Analytical Chemistry, pp. 125, 126.
164
THE MANUFACTURE OF GLUTEN FEED.
By T. B. WAGNER.
Among the concentrated feeding stuffs found on the American market we may
concede to gluten feed the first place, not only because of the high percentage of
nutritive materials in gluten feed, but because of its palatability and its remarkable
degree of digestibility. Within the last few months various statements have appeared
in chemical journals, as well as in bulletins issued by 'agricultural experiment stations,
with reference to the chemical analysis of this product. Considering the importance
of gluten feed as an animal food, anything published on the subject will be read with
interest, not only by officials connected w:th agricultural experiment stations, but by
dealers and buyers, and, last but not least, by the manufacturers themselves. In
view of this general interest, it may not be amiss to state the details of its manufacture.
Broadly speaking, gluten feed is the ground kernel of Indian corn, from which the
germ and most of the starch have been removed. The following steps lead up to its
production:
The com bought by us is of the No. 2 and No. 3 grades. To remove impurities,
stones, dirt, dust, etc., the grain is passed through cleaning and separating machinery
and the purified corn is then delivered to the steeping tanks, wherein it is soaked in
warm water, slightly acidulated with sulphur dioxid. This treatment brings about a
softening of the grain and facilitates the subsequent separation of the germ, which
is effected after it has passed through a preliminary grinding whereby the corn is
broken up and the germ set free. The balance of the material is now ground fine
in Buhr mills, the coarser part, namely, the bran, being separated by running the
mass over silk sieves, while the starch liquor is concentrated and sent over slightly
inclined planes, the "starch tables," upon which, by a process of settlement and
washing, the starch fills up in a solid layer. The lighter ingredients, gluten, fiber,
etc., are carried off in the current of water over the end of the starch tables. We
have thus obtained, first, the* germ from which the well-known corn oil and corn-oil
cake are obtained; second, the starch which furnishes the raw material for the corn
starch of commerce and the manufacture of corn sirup and corn sugar; third, the bran,
being the hulls of the kernel; and, fourth, the gluten. The third and fourth, after
repeated washings, are united, when still in a wet state, deprived of the largest part of
the water by filter pressing, and delivered to the driers, where the water is reduced
to approximately 10 per cent. The feed is now passed through grinding mills and
reduced to a considerable degree of fineness.
The gluten feed thus obtained varies in composition in proportion to the efficiency
factor prevailing in the individual works. For instance, in a well equipped and well
regulated factory the amount of protein usually runs at 26 per cent (on a commercial
basis), whereas in factories conducted less efficiently the amount of protein may
not exceed 18 per cent. The amount of starch in the feed will vary correspondingly.
I have made the statement before that gluten feed represents the corn minus germ
and starch. You will ask, and very properly so, What becomes of the mineral con-
stitutents of the corn and the soluble organic matter, which are extremely valuable —
as, for instance, the organic phosphorus compounds? By far the largest amount of
these constituents is leached out in the steeping of the corn. Were it desired only to
recover the phosphorus salts, there would not be much difficulty involved in isolating
them, but the steep water contains a large amount of other ingredients which greatly
add to the food value of the gluten feed, such as albuminoids, sugar and other car-
bohydrates, potassium salts, etc., which, however, are hygroscopic and frustrate all
efforts to recover them in dry form. Dr. Arno Behr devised ways and means of recover-
ing these substances, which are fully described in United States patent No. 491.'_):-U.
issued February 7. 1893. Briefly explained, Behr recovers these constituents of the
165
<>rn by evaporating the steep water after careful treatment to a thick sirup, which
contains these substances partly in solution and partly in suspension. This sirup
is added to the feed, which latter forms an ideal absorbent.
An analysis of gluten feed thus prepared has the following average composition:
Per cent.
\\atcr 10 36
I'rotoin 25.95
I''"1 2.18
Starch ... 18. 09
I'ilx-r 6. 50
A-h 3.70
Nitrogen-free substance (by difference) « 33. 22
Soluble i approximate) 15. 50
From the process outlined above it is obvious that no extraneous matter is intro-
duced into the feed and that the ingredients which go to make up the feed occur there
in the same form as in the corn itself, although, of course, in a more concentrated
form. It was not without surprise, therefore, that I noticed in a number of analyses
published recently a reference to an "acidity" of the feed, which was reported as
hydrochloric acid. It is not quite plain why the acidity was expressed in such a
manner, as no hydrochloric acid, or for that matter any other mineral acid, is present,
none having been introduced at any stage of the process of manufacture. It cer-
tainly would not occur to anyone to report the acidity in fruits, vegetables, cider,
or u in. - as hydrochloric acid, no more than in the case of wheat flour — patent flour —
in which the aridity runs nearly as high as some of the acidities reported in gluten
fei-d-. I am not prepared to -tate at this moment with any degree of finality whether
thi- appnreni aridity i- due to acid salts, such as the organic phosphorus compounds,
or to the presence of a slight amount of lactic acid, or to proteid bodies, such as the
acid albumins; but, whatever causes it may be due to, if the absence of free mineral
a« i«l- has been proved, it should be reported as an organic acid, preferably lactic.
It might perhap- be -till better in state the number of cubic centimeters of normal
alkali rei|iiiri-d to neutral:
In this connection it i- of import to note the varying results obtained in acidity
determination.-, depending upon the character of the indicator employed. To cite
an instance, we have found that phenolphthalein causes the acidity to appear two to
three timi - higher than rosolic acid. Again, when methyl orange is used, an alka-
linity is indicated. The-e discrepancies and variations make it desirable — in fact,
-ary ihat the othcial methods governing the analyses of feeding stuffs provide
i u lard indicator for such acidity; means should also be provided for expressing
properly such acidity as may be found in the feed.
If, as a safeguard, it is deemed advisable to test for free mineral acid, Toepfer's
limethylamidoazobenzol), or the even more delicate Giinzburg test (phloro-
glucin), are to be recommende. 1 . These tests are generally employed in physiological
research and reveal the slightest traces of free mineral acids in the presence of organic
arid-.
A great desideratum in gluten feed is uniformity; that is, the feed made at the dif-
ferent fa< tories located in different sections of the country should be uniform in
composition as well as in appearance. So far as the first is concerned, the variation
is very slight . the processes employed in our various factories being under such control
as to insure practically uniform composition, irrespective of point of manufacture.
The appearance of the feed is of considerable moment. In former years the corn
delivered to our factories was mostly of the yellow type, the amount of white corn
delivered I- in- rather insignificant. During the past four years, however, the situa-
Contains 17.18 per cent pentosans.
166
tion has been quite the reverse. The supply of corn is not within our control. We
have accomplished uniformity in our feeds so far as protein, fat, and the other ingre-
dients are concerned, and so far as the physical condition of the feed is involved, but
we can not reach the same degree of uniformity as regards color so long as the selection
of the corn is not within -our power. Gluten feed obtained exclusively from yellow
corn has a beautiful yellow color, whereas feed made from white corn has an unin-
viting grayish color, so that, depending upon the amount of yellow and white corn
going through, the process, the color of the resultant feed may vary from a golden
yellow through all the hues down to a grayish white. You will recognize the diffi-
culties connected with the marketing of a product which to-day may run yellow and
a week from now white. Speaking from my own experience, this point was brought
home to me very forcibly in 1904, when the white variety of corn predominated in
our corn supply. The feed produced from such corn was uninviting in appearance.
In a very short time dealers, particularly in the Eastern States, began to complain,
stating that they were not receiving the old standard gluten feed which they had
been familiar with for a long period of years. Our assurance that the feed was the same,
that the amount of proteid matter was the same, that the feed value was the same,
and that the feed was up to standard in every particular, except color, did not avail,
and we were not only threatened with, but actually suffered, a considerable loss of
business. We advised the trade fully of the existing conditions, emphasis being laid
upon the fact that the color should not be the determining factor in fixing the intrinsic
or commercial value of the feed. Feeders, however, refused to accept such expla-
nations. It seemed impossible to convince them that a brand of feed, yellow one
day and white the next, could have been made by the same methods and be the
same feed in fact.
As a solution of this difficulty, it was suggested that wherever the feed ran "short,"
so far as color was concerned, that the feed be standardized by the addition of the
requisite amount of artificial color, preference being given to naphthol yellow-S.
The feeder readily accepted this changed condition. Although informed that the
feed is artificially colored, he prefers to buy it that way. It is plain from the above
that the manufacturer is not acting from choice when adding color to his feed, but
he is forced to do so by a popular demand. The practice of standardizing the color
of gluten feed is no different than that practiced by the farmer in coloring butter.
June butter is his standard, and in adding color to the butter he aims at matching the
natural color of June butter, because the consumer likes that particular color best.
Thus the feed obtained exclusively from yellow corn is the standard for color, and
when a factory receives only two-thirds or less of its supply in the form of yellow
corn, sufficient coloring matter is added to match the feed obtained exclusively from
yellow corn. It thus happens that at one of our factories, located in southern Illinois,
we do not add at this time a grain of color to the feed, whereas in another factory,
located in Iowa, color is added in approximately the same proportions as in the
case of colored confectionery. In other words, the practice of standardizing the color
of the feed is not a regular practice, but depends from day to day entirely upon the
character of the corn supply.
As a matter of chemical interest I would like to call attention to the rapidity with
which the gluten of the corn combines with azo colors, such as naphthol yellow-S,
forming an insoluble lake. This combination is effected without the use of any mor-
dant, acids, or similar agents and tends to prove the acid character of some of the pro-
teid compounds.
167
REPORT ON THE SEPARATION OF NITROGENOUS BODIES: MILK
AND CHEESE PROTEIDS.
By L. L. VAN SLYKE, Referee.
The referee selected the following subjects for investigation:
(1) The acetic-acid-precipitation method for determining casein in milk, especially
with reference t<> the following points:
(a) The use of less acid.
(6) The influence of acid on the redissolving of casein.
(r) The effect of temperature on the solution of casein by acetic acid.
(d) The effect of various preservatives on the accuracy of the acetic-acid method.
(2) The selection ,,f an official method by the association for the determination of
milk albumin.
(3) A simple. rapid, ami accurate volumetric method for determining milk casein .
F,,r the cooperative u<,rk of 1907-8 the referee selected the Matthaiopoulos volu-
metric method for the determination of casein. Results from only one of the cooper-
at.>r- WM received. The method is as follows:
SOLUTIONS REQUIRED.
I \:i .<:'M \miately i \venty-tifth-normal solution of sulphuric acid.
\ tenth-norm*] solution of sodium hydroxid.
\ 1 per cent alcoholic solution of phenolphthalein.
Ml.THOD OF PROCEDURE.
Into each of two 200 re beakers measure 20 cc of milk and 80 cc of water. Call one
A ami the niher />' Into .1 lei the i went \ -fifth-normal sulphuric acid run drop by
drop with c<>ri-iaiit -^tirrin_' of the diluted milk until the casein precipitates in large
flak«-". After three to five minutes filter through a dry filter (S and S 589, 9cm, recom-
mended an. I collect the filtrate in a graduated, dry, 100 cc flask. If the first portions
of the lilt rai.- an- turbid, |*>ur back on filter. If the filtrate continues turbid, not
enough acj«l has been used to precipitate the casein completely; in which case take
h sample and add 0.2 or 0.3 cc more acid. The amount of acid required varies
\\iih different milks, ranirinu' in the sample studied from about 23 to 27.5 cc. Any
M id must be avoided. Collect 1 00 cc of clear filtrate and transfer it to a beaker,
rinsinir ihe flask carefully, add I cc of the phenolphthalein solution and titrate to a
pal- pink color with tenth-normal sodium hydroxid. Note the number of cubic cen-
timeter- of alkali u-ed
Treat theconteiiK <>f beaker li with twenty-fifth-normal sulphuric acid, usingexactly
the -line amount as in the case of .1. Add 1 cc of phenolphthalein solution and
titrate to a pale pink \\ith tenth-normal sodium hydroxid. Note the amount of alkali
ll-ed
The values obtained in .1 and B are then used in making the following calculations:
in which /; H the amount of alkali used in titrating the mixture of water, milk, and
tweiity-fifth-nnrmal sulphuric acid; A is the amount of alkali used in titrating the fil-
trate;'// is the amount of twenty-fifth-normal sulphuric acid used in precipitating
in; <> II:'. I", i- a constant factor based on the equivalent weight of casein as shown
by Itottlte witb buee. The results are then calculated from 20 to 100 cc.
Each cooperator \\a- requested to apply this method to samples of fresh milk of his
own selection and compare the results with those obtained by the official method.
168
Determination of casein in milk.
Analyst.
Official
method.
Volumetric
method.
L. W. Fetzer, Maryland station. . . .
f 2.54
\ 2.52
2.73
2.79
A. W. Bosworth, New York station.
f 3.06
3.06
3.07
[ - 6. Oo
3.06
f 3.00
\ 3.03
2.88
2.90
3.05
From the results thus far obtained, the method appears to be a promising one. It
will probably require some modification to give uniform results.
RECOMMENDATION.
It is recommended-
That the referee for 1908-9 be requested to study the following subjects as fully as
may be practicable:
(1) The official method for determining casein as indicated under 1.
(2) The perfecting of the method for determining milk albumin.
REPORT ON SUGAR.
By A. H. BRYAN, Referee, and FRITZ ZERBAN, Associate Referee.
The work of the referee and associate referee upon sugar during the past year has
been substantially along the lines recommended by the association at its last meeting
and has comprised (1) work upon special methods of analysis in their relationship to
sugar chemistry; (2) work upon purely chemical methods; and (3) work by a number
of collaborators upon methods for the analysis of cane molasses and sugars.
In the investigations of special methods the work has been confined very largely to
the study of the application of the refractometer to the estimation of dry substance in
the liquid sugar products. This study was published in the Journal of the American
Chemical Society Q and is not here repeated, but a recommendation based on the
work is made.
The associate referee has confined his work mostly to the study of methods of esti-
mating reducing sugars, trying the Monroe-Neubauer crucible (a platinum gooch
with a filtering substance of platinum sponge), instead of the ordinary porcelain gooch.
The results are given in the Journal of the American Chemical Society. &
The collaborative work consisted of two lines of determinations: (1) Methods .of mois-
ture determinations; (2) effect of clarifying agents on the polarization. Two samples
were sent out, one of a yellow sugar and the other an open kettle cane molasses. In
the circular letter sent out with these samples, the following instructions were given:
INSTRUCTIONS.
(1) Moisture on both samples.
a) Two grams of material on sand to constant weight in vacuum oven at 70° C.
b) Two grams of material without sand to constant weight in vacuum at 70° C.
c) Two grams of sample on sand in water-jacketed oven for ten consecutive hours.
Weigh at end of ten hours. Then heat for two-hour intervals until weight is constant.
(d) Repeat (c), but do not use sand.
«1908, 30: 1443.
&1908, 30: 1456.
169
(e) Two grams of sample on sand in water-jacketed oven for six hours on one day
and four hours the following day. Weigh at end of the ten hours. Then heat for two-
hour intervals until constant weight is attained.
• ), but do not use sand.
Uy rrira. n.in.-i.-r. The procedure is the same as for any work with the refrac-
tometer. The readings an- laken at 28° C. or any other temperature. A few drops
of the solution are placed on the prism and the border line adjusted and read as per
in-t ructions I'nimd m Bulletin 107, page 132. The per cent of water is obtained from
table of Geerligs herewith. A table of temperature corrections is also given, so that
corrections can be made for any other temperature.
V«7*'* table for dry substance in sugar-house products by the Abbe refractometer, at
lll.l.-X.
|vr,,.,,t
dry sub-
:i ils to !«• ;i.Mt><l for frac-
tional n-u'linus.''
Index.
Per cent
dry sub-
stance.
Decimals to be added for frac-
tional readings. &
1.3335
1 .U',4
L»7i
I .U'U
i (>"••
LS434
i MM
1 UM
i MM
1
2
3
4
5
6
7
8
9
10
0.0001-0.05
a 0002-0.1
0.0003-0.2
0.0004-0.25
ii mn-. n .;
i, .„,,,. 0 »
0.0007-0.5
O.OOOH-0.6
0.0009-0.7
0.0010=0.75
0.0011-0.8
0.0012-0.8
0.0013-0.85
0.0014=0.9
0.0015-1.0
1.4083
1.4104
1.4124
1.4145
1.41«fi
1.4186
1.4207
1.4228
1.4249
1.4270
45
46
47
48
49
50
51
52
53
54
0.0004=0.2
0.0005=0.25
0.0006=0.3
0.0007=0.35
0.0008=0.4
0.0009=0.45
0.0010=0.5
0.0011=0.55
0.0015=0.75
0.0016=0.8
0.0017=0.85
0.0018=0 9
0.0019=0.95
0. 0020= 1. 0
0.0021=1.0
1
1 (»x4
LMOO
1.3516
i ma
i r,i..
i MO
i nn
1 .I.VH
i .{.-.I
I 1878
1 :<7IJ
11
U
13
14
U
H
17
II
20
22
23
24
25
28
a oooi-o. 05
0. 0002— 0. 1
,. ..,.; 0 -'
0.0004-0.25
0.0005-0.3
1. nil. n I
0.0007-0.45
II UNIX I. I
n ••> IB
H mill n 7
M "> 12 -0. 75
IM. H3-0.8
n ..ill n H
o ooid-o.95
1.4292
1.4314
1.4337
1.4359
1 ».{SJ
L nn:,
1. 4428
1.4451
1. 4474
.4497
.4520
.4543
IB87
. 4591
.4615
.4639
. 4<m
.4687
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
0.0001=0.05
0.0002=0.1
0.0003=0.1
0.0004=0.15
0.0005=0.2
0.0006=0.25
0.0007=0.3
0.0008=0.35
0.0009=0.4
0.0010=0.45
0.0011-0.5
0.0013=0.55
0.0014=0.6
0.0015=0.65
0.0016=0.7
0.0017=0.75
0.0018=0.8
0.0019=0.85
0.0020=0.9
0.0021=0.9
0.0022=0.95
0.0023=1.0
0.0024=1.0
0.0012=0.5
\
UJ871
1 .<VH.
i MOB
I MM
i NT
I.MM
LMM
L4MI
*
•
29
M
U
33
I
•
.i'i
•
41
0.0001-0.05
•.OOa—a.1
0.0003-0.15
0.0004-0.2
0.0005-0.25
0. 000ft- a 3
9.007— a as
n nNIK-0.4
ii r.
0.0010-0.5
1). (Mil 1-0. 55
0.0012-0.6
0.0013-0.65
o (1014-0.7
0.0015-0.75
0.0016-0.8
0.0017=0.85
0.0018-0.9
0.0019-0.95
0.0020=1.0
0.0021=1.0
1.4711
1. 4736
1.47H1
1.4786
1.4811
1.4836
.4862
.4888
.4914
.4340
.4966
.4992
.5019
.5046
.5073
.5100
.5127
.5155
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
0.0001=0.0
0.0002=0.05
0.0003=0.1
0.0004=0.15
0.0005=0.2
0.0006=0.2
0.0007=0.25
0.0008=0.3
0.0009=0.35
0.0010=0.35
0.0011=0.4
0.0012=0.45
0.0013=0.5
0.0014=0.5
0.0015=0.55
0.0016=0.6
0.0017=0.65
0.0018=0.65
0.0019=0.7
0.0020=0.75
0.0021=0.8
0.0022=0.8
0.0023=0.85
0.0024=0.9
0.0025=0.9
0.0026=0.95
0.0027=1.0
0.0028=1.0
I
1.4003
L4MI
d
43
44
0.0001-0.05
0.0002-0.1
0.0003-0.15
0.0012=0.6
0.0013=0.65
0.0014=0.7
* Find in the tabl»- th«- r-fnu-tiv index which is next lower than the reading actually made and note the
:,.n.linK whol.- iiiim»*T for th«> IMT cent of dry substance. Subtract the refractive index obtained
from to UiM.* from th.- obs.Tv.-d n-adiriK; tlw decimal corresponding to this difference, as given m the
column so marked, is added to the whole per cent of dry substance as first obtained.
170
Table of corrections for tlie temperature.
Dry substance.
Temperature of the
prisms in ° C.
0
5
10
15
20
25
30
40
50
60
70
80
90
20
0.53
0.54
0.55
0.56
0.57
0.58
0.60
0.62
0.64
0.62
0.61
0 60
0 58
21
.46
.47
.48
.49
.50
.51
.52
.54
.56
.54
.53
52
50
22
.40
.41
.42
.42
.43
.44
.45
.47
.48
.47
.46
.45
.44
23
.33
.33
.34
.35
.36
.37
.38
.39
.40
.39
.38
.38
38
24
.26
.26
.27
.28
.28
.29
.30
.31
.32
.31
.31
30
30
25
.20
.20
.21
.21
.?2
.22
.23
.23
.24
.23
.23
.23
.22
26
.12
.12
.13
.14
.14
.15
.15
.16
.16
.16
.15
.15
. 14
27
07
07
07
.07
.07
.07
.08
.08
08
08
08
08
07
Add—
29
0.07
0.07
0.07
0.07
0.07
0.07
0.08
0.08
0.08
0.08
0.08
0 08
0 07
30
.12
.12
.13
.14
.14
.14
.15
.15
.16
. 16
16
15
14
31
.20
.20
.21
.21
.22
.22
.23
.23
.24
.23
.23
.23
.22
32
.26
26
.27
.28
.28
.29
.30
.31
.32
.31
.31
.30
30
33
.33
.33
.34
.35
.36
.37
.38
.39
.40
.39
38
38
38
34
.40
.41
.42
.42
.43
.44
.45
.47
.48
.47
.46
.45
.44
35
.46
.47
.48
.49
.50
.51
.52
.54
.56
.54
.53
.52
.50
(h) By areometric methods, as found on pages 65-67, Bulletin 107. If time permits
it would be well to determine the per cent of water in a number of sugar solutions by
methods (g) and also (h) and (6). The comparison being between results of (g) and
(6) and (h) and (6). The results could be reported as special samples under (g),
giving kind of sirup, also figures obtained by (g), (6), and (h).
(2) Polarimetric determinations. Effect of various clarifying agents on both samples.
Weigh out a normal weight and make up to 100 cc, or to such a multiple thereof as
may be necessary to secure an accurate polarization, after clarifying as follows:
(a) With lead subacetate solution. (Bull. 46, pp. 38-39; also Bull. 107, p. 40.)
Try at least two different quantities of the clarifying agents, reporting the separate
polarization.
(6) With normal lead acetate solution. (Saturated solution of lead acetate in
water.)
(c) With Home's dry lead subacetate. (J. Amer. Chem. Soc., 1904, 26 : 186.)
(d) With Herles' solution. No. 1, 250 grams lead nitrate to 500 cc water; No. 2,
25 grams sodium hydroxid to 500 cc water. Use equal parts of each solution,
either 5 cc each or up to 10 cc of each. Note whether increased amount changes the
polarization.
(e) WTith alumina cream and hydrosulphite (sodium Ijydrosulphite, B. A. S. F. or
"Blankit"). This with the dry subacetate can be obtained from any of the large
dealers in chemical supplies. In this clarification make solution up to required
volume, then add a few crystals at a time until decolorization is effected. Polarize
at once after filtering and again after standing for some time. Should the solution
become cloudy on standing add some kaolin and shake, filter. Also try the following
method of procedure: In a solution after clarifying with alumina cream and filter-
ing, just before screwing on cap of polarization tube, add a few crystals of the hydro-
sulphite and shake. Polarize immediately ; note whether on standing there is a change
in the polarization.
(J) Invert portions of a, 6, c, d, and e and determine the invert reading. Where
lead has been used take out the excess with some crystals of potassium oxalate or dry
sodium carbonate. Inversion can be accomplished by following (c), page 40, Bul-
letin 107, or (1), page 39, Bulletin 46, Revised. If the latter reference is used, the
equation should read:
a-b
S=-
142.66- s:
171
In this polarization take care to record all temperatures of polarization, dilutions
etc., that results mav be compared upon as uniform a basis as possible
It is als,, uijed that the work on the samples be begun immediately upon their
arrival. to avoid changes in composition which might result from fermentation.
A. HUGH BRYAN,
Rejeree on Sugar.
FRITZ ZERBAN,
Associate Referee.
A number of chemists signified their willingness to cooperate, and reports, in whole
or in purl, were received from them.
DETERMINATION OP TOTAL SOLIDS.
The work outlined was for the comparison of the vacuum method with the regular
method ,,f drying i-.r ten hours. But as ten hours is generally longer than the ordi-
nary lal.oratory day. a comparison was made of this determination conducted for ten
<-utive hours, and uls,, for six hours on one day and four the next. Together
with th.- c,,mpari.-..n of methods of determining moisture, the effect of mixing sand
with the material to be dried was studied in each case. The refractometer was tried,
and the specific gravity was also determined and the moisture calculated.
Determi nut inns nj moisture in sugar and molasses.
SUliAU.
Analyst.
Vacuum.
At boiling water temperature.
Refrac-
tom-
eter.
Spe-
cific
grav-
ity.
10 consecutive
hours.
6 and 4 hours.
Sand.
No
sand.
Sand.
No
sand.
Sand.
No
sand.
1'. 11. hnii.-riv. New Orleans, La..
Per ct.
Prrct.
Perct.
Perct.
'2. IJX
2.90
2.89
2.79
2.74
2.48
Perct.
2.87
Not
dry.
2.95
2.41
2.90
2.50
Perct.
2.76
2.70
2.97
2.37
2.75
2.49
Per ct.
2.60
&2.02
2.60
Perct.
1 . \\ . 1 tap MT, v\ ishnuMon. i
\s . I*, s LI ,111. New Orleans. I.a .
• 2.57
Not
dry.
t> 2. 10
2.68
2.09
2.87
2.22
John II i
2.60
•i. Florida...
TUV..
f2.52
e2.54
2.68 2.56
2.74
2.75
2.72
2.67
2.60
2.22
MOLASSKS.
1'. II. hoiiiTtv \.-\v Orleans, La
& 28. 06
27.67
27.99
27.37
27.04
26.36
K. U . !.;• ;.>IUT. \\ .ishiiiL,'t<iii. 1
\N 1' \ i<|iim \t-\v orlruiit 1
027.04
o27.17
27.35
27.38
27.48
625.55
27.84
27.94
27.15
27.86
26.27
27.04
24.30
26.36
J. 11. I'lirkin^ Ki. Inn. .n.| \ i
27.55
27.26
27. 77
27.24
28. 50
F. <;. Smith. \i-w i >rl.-.in>, l.;i
27.51
27.20
28.19
27.45
27.03
Average
27.04
27.17
27.45
27.40
27.94
27.41
27.17
25.78
o Constant at end of 31 hours.
t> Not (Minded in av«Tiii.v.
c Constant at end of 10 hours.
d By Westphal balance, 23.40.
It is noted here that the ten-hour drying gives higher results than the vacuum
method. This is due, no doubt, to a decomposition of the material at the temperature
of b.iiliiu» water. The ten consecutive hour results are lower than when the time is
dixi.led. The u-e of sand plays an important part in the drying, the determina-
lions being higher with sand present. The reason for this is self-evident. The
material forms a coating on the sand and between the particles and so presents a
i'arger surface to be affected by the heat. When not used, a hard, dry film forms on
172
the material and the under layer does not dry. When a small area of liquid is exposed
for drying, the amount of moisture going off will be smaller than when a larger surface
is exposed. Many chemists prefer and recommend the use of powdered pumice instead
of sand. This allows the material to be absorbed. In the referee's opinion, the
results so obtained are of no more value than those with the use of sand. Where
numerous determinations are to be made, it is an easy matter to wash and clean the
sand, while to clean the pumice stone and remove all traces of the sirup is not so easy.
Lately the use of a roll of filter paper has been recommended « as the absorbent. Wiley
(Bureau of Chemistry, Bui. 19, p. 49) recommended that in 1888, but it was thought
then to give low results. Mintz by this method reduced the time of drying from
seventeen hours to three. This method is practically the method of Adams for
milk, and should be given some consideration for next year. Finely flaked asbestos
as an absorbent material has been spoken of for drying milk. Browne & used it with
success in determinations of moisture in apple juices. It is further worthy of trial,
since the claim is made that it requires less time for drying than when sand or pumice
stone is used. The referee has made a few experiments with the Soxhlet oven,
where a current of dry air passes over the material, but the work has not progressed
far enough to make a report. A method that bids fair to supersede all others for
pure sugar solutions is the use of the refractometer. The comparison of this method
made by the collaborators shows its results to be nearer the vacuum results than those
of other methods. A second feature of the moisture work was a study of the effect of
increasing the time of heating or dryness on the determination. The following table
gives the average results obtained by the collaborators:
Determinations of moisture increasing the time of drying.
[Averages based on reports of five collaborators.]
SUGAR.
Modifications of method.
Pre-
scribed
time of
heat-
ing.
By heating.
12
hours.
14
hours.
16
hours.
18
hours.
20
hours.
22
hours.
24
hours.
On sand:
Vacuum
Per ct.
2.68
Perct.
Per ct.
Perct.
Perct.
Perct.
Perct.
Perct.
10 consecutive hours
2.58
2.72
2 56
2.78
2.79
2.91
2.86
2.89
2.92
3.04
3.01
3.06
3.06
No sand:
Vacuum
10 consecutive hours
2.75
2.67
2 45
2.85
2.70
2.87
2.81
2.97
2.84
3.05
2.97
3.00
2.97
fi and 4 hours _
MOLASSES.
On sand:
VarmiTn
27 04
10 consecutive hours
27 45
27.86
28.24
28.42
28.50
28.50
28.85
28.88
6 and 4 hours,, _ ...
27.94
28.19
28.53
28.67
28.82
28.78
29.02
No sand:
Vacuum
27 17
10 consecutive hours
6 and 4 hours
27.40
27 41
27.43
27 68
27.64
27 85
27.98
28 15
28.20
28 31
28.28
28 47
28.44
28 58
28.58
27 17
From these figures the importance of not allowing the length of time to exceed ten
hours is noted, as active decomposition sets in. This decomposition was greater when
sand was used than when it was not, a result one would naturally expect.
« Centrbl. Zuckerind., 1908, 16 : 1102; Chemical Abstracts, 1908, 2 : 2632.
6 J. Amer. Chem. Soc., 1901, 23 : 873.
173
i "i CLARIFICATION AGENTS ON POLARIZATION.
The work carried on was a continuation of that taken up a number of years ago.
The clarifying agents studied were neutral lead acetate, subacetate of lead, both wet
ami dry, 1 [cries' solution or basic lead nitrate, and hydrosulphites. An additional
feature was the comparison of the results obtained when using the necessary amount
of i hi- precipitant and when using an excess.
The results on the su-ar and molasses samples will be considered separately and for
a better comparison the results obtained by using the necessary amount of clarifying
air'-iit will be discussed. Following this the results of using an excess of clarifying
agent will be considered.
of sugar with different clarifying agents, using only amount necessary for
clarification.
(Normal weight to 100 cc; polarized in 200 mm tube; sucrose factor 142.66.]
St H.\i KTATE OF LEAD.
Anal
Amount of
clarifying
agent.
Dirtn-t po-
larization.
Corrected
invert po-
larization.
Tempera-
ture of po-
larization.
Sucrose by
Clerget
method.
r
•Y.
93 00
°V.
27 60
°C.
98
Per cent.
QQ 70
La
2
93.00
-28 60
27
94 14
o 1
92 80
29 86
25 5
94 43
' , II
• I
'(•' s."i
•79 20
°7
94 50
\\ i' Horn S >
u
c92.85
22
092 85
\\ I II. ".v. ii \, u Orleans, La
<1
93 40
26 20
30
93 69
W. P \* Orleans, La
1 II • hninn-l V.i
2
*5
K. i"-1
«90 00
-27.52
-29 04
30
28
94.66
C92 52
Orleans, La...
1
08. OB
-27.02
27.5
93 14
M II
aQ.5
92.55
-30 03
25 5
94 38
i: \ Wil
4
•« MI
27 W
27 4
94 14
1 >rk?ans LA
1
'i' MI
30 36
26 0
94 99
..'I'
93. as
94 18
I>KY SfBACKTATK OF I.KAD.
\ u It* i i-Tid.i
I* II Dohertj N--\V Orleans, I^a
Grams.
0.5
.5
08. v>
08.60
-27.40
29.92
28.0
24.5
93.46
93.94
j \ u ill Nen ¥ork< It;
.5
92.70
-29.86
25.5
94.35
i, II II n !;• \. . ': ••
.5
92.70
-29.15
27
94.34
U 1 • II ." \ >
|J
C92.70
29.00
22
c92.44
lla N.-W Orleans, La..
93.20
-26. 10
30
93. 45
U 1 '
j
;••_'. '.»•>
-28.40
29
94.67
J II i
93.40
-28.60
28
94.82
08.80
-27.07
27.5
93.09
M II
.5
92.50
-29.92
25.5
94.23
i: \
.5
93.41
-26.49
28.8
93.48
I>a
l.o
92.80
-29.15
26.5
94.24
Average
92.90
94.00
XKfTKAL I.KAD ACKTATE.
A. W. Blair. Florida
cc.
2
92.90
-27.40
28
93.58
I1 M I'M' , t", \.-\v Orleans, La
3
92.80
-28.60
27
93.98
l \ ;
2
92.60
-29.97
25.5
94.28
<i II II ir !;• \. A York Citv
5
92.80
-29.75
26.0
94.52
\\ l> MOM ,. y,, nkers \ Y
'3 6
92.40
22.0
\\ 1 lln\M-lN Ni-u orlr IM^ La
93.20
-26.50
30
93.77
u I • I .a
3
93.10
-27.85
29.3
94.48
1 11 I'-irkin*; Uichinoinl \':i
:,
<-92.00
-29.04
28.0
<-94.07
^niith \f\v orlr-in«j I a
n
93.14
-27.30
27.5
93.43
M 11 \Vilfv \t-\v York Citv
2
92.75
-30.03
25.5
94.38
i Florida
3
93.58
-27 03
28.8
94.04
F. Xerban, New Orleans. I.a
1
92.90
-28.82
26. 5
93.98
92.92
94.04
• M.Sbrix.
&56.0brix.
e Not included in average.
d 1.25 sp. gr.
« 10 per cent solution.
/20 per cent solution.
174
Polarizations of sugar with different clarifying agents, using only amount necessary for
clarification — Continued. .
BASIC LEAD NITRATE (HERLES' SOLUTION).
Analyst.
Amount of
clarifying
agent.
Direct po-
larization.
Corrected
invert po-
larization.
Tempera-
ture of po-
larization.
Sucrose by
Clerget
method.
P H Doherty New Orleans, La
cceach.
2
0^,
92.60
°V.
-29.70
°C.
24.5
Percent.
93.78
J A Hall New York City
2
92.75
-29.86
25.5
94.40
G H Hardin New York City
5
92.80
-29.86
26.0
94.60
W D Home Yonkers N Y
0 72
92.80
W L Howells New Orleans, La
5
93. .50
-25.50
30.0
93 21
W P Naquin, New Orleans, La
93.32
-28.82
28.6
95.16
J. H. Parkins, Richmond. Va
F G Smith New Orleans La
0
5
a92.22
93.44
-29.70
28.0
28.5
094.76
M H Wilev New York City
5
92.80
-30.14
•25. 5
9457
F Zerban New Orleans La
1
92.80
-30.47
26.0
95.07
92.98
94 39
ALUMINA CREAM AND SODIUM HYDROSULPHITE.
P H Doherty New Orleans, La..
92.20
W D Home Yonkers N Y
0.7
92.60
W L Howells New Orleans, La
93.10
-25.80
30.0
93.14
J H Parkins Richmond Va
092.00
-30.80
28.0
095.44
F G Smith New Orleans La
93.25
—26 90
29 0
93. 75
R N Wilson Florida
094.20
- 2f>. *<
28.8
094.37
F Zerban New Orleans La
92.50
-31.24
26.0
95 43
Average.
92.75 ..
94.11
o Not included in average.
The results of individual analysts on direct polarization compare very favorably
in each method of clarification. There are, however, some higher figures than the
average, but. in every case the polarization was carried on at a lower temperature or
an excess of the precipitant was used. With a few exceptions the results on sucrose
by the Clerget method do not differ so widely as the direct polarizations. This differ-
ence with the Clerget method is most likely due to the different methods of inverting
or to an error in calculation. As a check for the first error it is well to run a test on
pure sucrose with each set of determinations. This is especially wise in case of invert-
ing by heat, as the temperature may not be right or the time either too short or too
long, and, as a result, either all the sucrose has not been inverted, or the inversion has
been carried on so far that reversion products have been formed. Even in the stand-
ing method for inversion this blank is valuable in determining the completeness of
the inversion. There is a point in the cold inversion that should receive some atten-
tion. This is the question of the relation of time and temperature. In a few experi-
ments on the same sugar solution, one inverted by standing at 20° C. for twenty
hours showed — 12.3, while the other portion by standing at 32° for twenty hours
showed —12.08. These figures would make a difference in the Clerget sucrose.
The other point, error in calculation, is one that for some reason or other is rather
common. The inversion is carried on by taking 50 cc of the solution and adding
5 cc of acid and not correcting the reading for the increase of 10 per cent in volume.
Chemists not using the formula often should guard against this error, as the difference
amounts to nearly 3 per cent in high polarizations.
In comparing the average results of direct polarization it is noted that hydrosul-
phite gives the lowest reading, while wet subacetate gives the highest. The normal
acetate and Herles' solution give nearly the same results. Dry subacetate gives
readings that are lower than the two above mentioned and stands next to hydro-
sulphite.
175
.mis tin- dcrolorization effect, Herles' solution equals wet subacetate. The
,lry MllMkCetate gives solutions a little darker than the above, and next in order is neu-
tral acetate. 1 1 ylrosulphite gives a good decolorization, but under certain conditions
th«. Kdutionfl I •••« -,.me murky from the precipitation of sulphur and also, on standing,
th«- .-.,l..r rrturns again.
\\hrn the pivi-ipitutinii agents are used in excess, the readings are all higher, as
.-hewn l.y th<- folio win- table. This increase is no doubt due largely to the solution
l,r. -oiuin- more < onc«Mitratc(l from the increased amount of precipitation, and partly
al.-o in .in a < han-«- in rotation due to the salts.
Polarizations of sugar with different clarifying agents, using an excess ofclarifier.
[ Normal weight to 100 cc; polarized in 200 mm tube; sucrose factor 142.66.]
sr II ACETATE OF LEAD.
Ana!
Amount of
clarifying
agent.
Dinrt po-
larization.
Corrected
invert po-
larization.
Tempera-
ture of po-
larization.
Sucrose by
Clerget
method.
1'. 11. D.ih- ' in-, l.i
J. \ ii. ill. N-\V ^ orfc < 11 .
(i II lliii'lin. N'.-w Y<>r* ' ' .
cc.
3
• 4
•I
0 V.
93.00
92.95
92 95
0 V.
-28.60
-29.70
•79 20
0 C.
27
25.5
27
Per cent.
94.14
94.42
94 58
\\ . i>. Horn ^ ii -.• • N '
62
92.90
22
\\ 1 llnu. 11 S--W Orli'illl- 1 i
c2
'I'! "II
26 00
30
Q0 fifl
VV. P. 1 i
3
•i:; "1
27 56
30 3
94 74
Jill
c 10
d9l GO
99 04
28 0
d 93 77
2
93 15
27 30
27 5
93 44
M II
<>3
T' Ml
29 70
25 5
94 30
la
6
! I
94.00
02.80
92.90
-27.00
-30.25
—30.14
28.0
25.5
25.5
94.05
94.72
94.71
\ ViTUJJf
93 11
94 26
DKY I.KAIi SI I5.\< KTATE.
p II 1 '
Grama
1 00
92 60
29 70
24 5
93 75
U l>
.75
92.75
.ins I .a
50
'i.i "i,
28 53
28 8
94 95
•
1.00
93.61
-26.63
29.0
93.82
2 00
92.50
-29.15
26.5
94.00
• I.,'1'
,,, ,)}
94.13
RAL I.KAD ACETATE.
P. 11. l>..h.rtv. N- u «>,;
\\ 1 ' \ i jii; Ti New Ol
CC.
4
5
03.80
93.28
-28.60
-27.98
27.5
29.2
94.18
94.69
10
rf91.00
-29.04
28.0
d93.30
K. /i-rUui. N
2
92.80
-29.26
26.5
94.32
!(_'. «.HJ
94.39
BASIC I.KAD NITRATE.
P. II. hoh.Ttv. N.-w «»rl-:itH. L*.
\\ 1 Uowelb \' '.v ' M
cctoch.
,J
92.80
93.60
-29.70
-25.50
25.0
30.0
94.11
93.29
W. P. Naquln, New Oi la
10
93.20
-33.22
18.2
94.65
10
93 55
28.5
•'••an. X.-\v orl.ans. l.a
2
93.00
-30.47
26.0
95.22
93.23
94.32
' 54.3 brix.
656brix.
1.25 sp. gr.
d Not included in average.
The greatest diffen-nrc is in the Merles' solution, then comes the wet and dry sub-
acetate, which shnw about the same increase, and the least increase is with normal
176
acetate. This would naturally be expected, as the Herles' solution forms a precipi-
tate in itself, hence causing concentration, and the excess of wet lead subacetate
causes an increase and also a change of precipitate, thereby changing the concentra-
tion, while the normal acetate produces no more precipitate with an excess, and hence
no change of concentration.
As regards the danger of adding an excess, this is the least in case of the neutral
acetate, as an excess is indicated when no more precipitate continues to form. When
using wet subacetate a better clarification is reached before the point where more ace-
tate will produce a further precipitation. With dry lead it is difficult to determine
when enough has been added. To add by weight takes much time, but where many
determinations are to be made varying measures or cups could be used, the weight
of the contents having been previously determined. It has the fault of precipitating
reducing sugars in as large quantities as the wet subacetate, as noted in last year's
report; besides, an excess of this reagent increases the volume of the solution, thereby
lowering polarization. This effect is shown in the following experiment: Six hundred
cubic centimeters of a solution of pure sucrose were made up and five 100 cc flasks were
filled and the following quantities of the dry subacetate were added, shaken, and then
polarized, care being taken that the polarization was made at 20° C.
Polarization of pure sucrose solution with varying amounts of dry lead.
Number.
Dry sub-
acetate.
Polariza-
tion.
1
Grams.
0.0
°V.
81.25
2
.5
81.1
3
1.0
81.05
4
1.5
81.0
5
2.0
80.9
It is noted from the table that the polarization has been lowered 0.35° by the addition
of 2 grams of the dry lead.
The greater part of the lead subacetate went into solution even up to the 2 gram
quantity, and only a cloud was noted. The meniscus of the liquid in the flasks
containing the added lead subacetate was above the 100 mark in each case, showing
an increase in volume.
Experiments were tried to determine this increase in volume. Five accurately
graduated flasks with glass stoppers were used, and into these were weighed the varying
quantities of dry subacetate, as in the previous experiment. A 100 cc pipette was
used and an equal amount of solution of sucrose was added to each flask, the flasks
being shaken during the addition of the solution. \Vhen added, the flasks were
corked up and allowed to stand over night. The height of the liquid being marked
on the neck of the flasks, the contents were poured out and the flasks cleaned and
dried. By means of a Morse-Blalock pipette, capable of reading to 0.005 cc, the flasks
were filled to the mark. The results are tabulated below:
Volumes of solution of pure sucrose when adding various amounts of dry subacetate.
No.
Dry sub-
acetate of
lead added.
Content.
Calculated
to 100.
Grams.
cc.
cc.
1
0.0
99.90
100.00
2
.5
99.91
100.01
3
1.0
100.02
100.12
4
1.5
100.18
100.28
5
2.0
100.21
100.32
177
An increa.-e of 0.32 cc in volume by the addition of 2 grams of dry subacetateis
noted, ami, with a solution polarizing 81.25°, as in the experiment given above
tin- • -al< -ulaied polarization for this increase in volume would be 80.99°. The solu-
tion actually polarized 80.9°. Home « gives 0.22 cc as the increase in volume on 1
gram of Hiki.-.-tate. Pellet has shown it to be 0.37 cc. The referee's sugar sample
for this year, worked as above described, showed the following changes in volume in
two experiments:
•/' * in i nlunie using official sugar samples.
No.
Drv sul-
•eetata
lead added.
Experi-
ment 1.
Experi-
ment 2.
Urn in*.
1
0.0
100.00
100.00
2
.5
100.09
100.14
3
LO
100.25
100.19
4
1.5
100.32
100.34
2.0
100.53
100.58
An average increase in volume of about 0.55 cc is noted, this being due to the pre-
cipitate forim-d and also to the fact, as shown above, of the solution of the lead
subac.
From these experiment.- it is seen that clarification with dry lead introduces the
same errors an with wet lead, viz, a precipitation of the reducing sugars, and also
where u-ed to excess a change iii volume. The latter effect with wet lead acetate as
a rlarifier tends to raise the readings while with dry lead there is a tendency to lower
tin-in. However, in usim: the dry eubacetate of lead the errors are compensating,
the increase in volume tends to lower the reading and the precipitation of the
levulose to raise it, while with wet subacetate the volume is decreased by the forma-
tion ,,1" the pn-c ipitate. hence the reading increased, and this is again increased by the
pre< ipitaiion of the levulose. • Dry lead subacetate is a step in advance in the search
for the best clarifying agent, and further experiments are in progress; but so far the
i clarifying agent for dark-colored sugar solutions has not been found.
As to the use of hydrosulphites as a bleach for solutions to be polarized there are
serious objection*. When large quantities of reducing sugars are present in the sample
the reading is lowered. This was pointed out at last year's meeting by the writer.
The rotation of one of the sugars, dextrose, is decidedly lowered; hence the
polari/ation is lowered if the sample contains much dextrose. This change of
rotation of dextrose is due to the formation of an oxysulphonate which has a levoro-
tation. The dissociation of the glucose (dextrose) oxysulphonate can be measured
by this fact. In the experiments cited no inversion of sucrose by this substance
was noted, but later literal ure shows numerous cases of inversion by using commercial
hydros ulphite.
Where the quantity of reducing sugars is small, there is very little reduction in the
polarization due to the formation of this compound, and it has this merit, that readings
are not vitiated by a change in volume due to a precipitate. These compounds, hydro-
sulphites, while stable under most conditions, are very easily decomposed in moist
air and also on long standing, and hence lose their power of decolorization. And again,
their power of decolorization is limited, as they have no effect on caramel bodies
(those which give the dark color to molasses) but do bleach intermediate substances,
which on longer heating would yield caramel.
J. Amer. Chein. Soc., 1907, 29: 928.
73073— Hull. 1±>— 09 12
178
MOLASSES SAMPLE.
Unfortunately the sample of molasses selected for the collaboration work was of such
a consistency that fermentation started after shipping, and the results are not of such
value as they might have been had this not occurred. The reserve sample also was
found to be fermented, so that it was not possible to make check results.
The results as received from the collaborators are given here in tabular form.
Polarization of molasses with different clarifying agents, using only amount necessary
for clarification.
SUBACETATE OF LEAD.
Analyst.
Amount of
clarifying
agent.
Direct po-
larization.
Corrected
invert po-
larization.
Tempera-
ture of po-
larization.
Sucrose by
Clerget
method.
A W Blair Florida
cc.
5
°V.
42.56
0 V.
-20.00
•c.
22.0
Per cent.
47.51
P H Doherty New Orleans, La
8
43.00
-18.26
26.5
47.33
W L Ho wells New Orleans La
6
043.40
-15.80
23.2
a 45. 17
W P Naquin New Orleans, La
8
42.42
-20.59
22.6
47.90
J H Parkins Richmond Va
5
42.40
-17.60
26.3
46.33
F G Smith New Orleans La
6
43.72
-17.35
27.5
47.38
F. Zerban, New Orleans, La
5
a41.80
-19.36
27.0
a 47. 3.".
42.82
47.29
DRY SUBACETATE OF LEAD.
A W Blair Florida
Grams.
1.0
42.00
-19.04
22.0
46.37
P H Doherty, New Orleans, La
2.0
42.54
-17.82
27.5
46.86
W L Howells New Orleans La
a 43. 10
-16.60
23.2
a 45. 56
W P Naquin, New Orleans, La
2.0
42.36
-20.06
23.5
47.68
J H Parkins, Richmond, Va
a42.60
-19.80
26.5
o48.26
F. G. Smith, New Orleans, La
44.22
-16.85
27.5
47.37
F. Zerban, New Orleans, La
2.0
42.00
-20.02
26.0
47.82
42.63
47.22
NEUTRAL LEAD ACETATE.
A. W. Blair, Florida
cc.
2
42.00
-19.84
22.0
46.97
P. H. Doherty, New Orleans, La
12
42.80
-17.91
27.5
47.09
W. L. Howells, New Orleans, La.. .
6
042.90
-14.00
23.0
o 43. 42
W. P. Naquin, New Orleans, La
10
42.04
-20.10
23.4
47.45
J. H. Parkins, Richmond, Va
5
o42.00
-22.00
26.3
o 49. 49
F. G. Smith, New Orleans, La
6
43.47
-17.45
27.5
47.26
F. Zerban, New Orleans, La
5
42.00
-19.58
25.0
47.31
Average
42 46
47.22
BASIC LEAD NITRATE.
P. H. Doherty, New Orleans, La
cc each.
5
42.60
-18.26
27.5
47.22
W. L. Howells, New Orleans, La
5
44.00
-17.40
23.2
46.86
W. P. Naquin, New Orleans, La
5
42.46
-20.24
23.5
47.89
J. H. Parkins, Richmond, Va
F. G. Smith, New Orleans, La
5
5
43.20
43.90
-19.80
— 17.50
26.5
27.5
48.68
47.62
F. Zerban, New Orleans, La
5
o41.90
-20.24
24.0
o47.56
Average .
43.23
47.65
ALUMINA CREAM AND SODIUM HYDROSULPHITE.
P. H. Dohertv, New Orleans, La
42 00
W. L. Howells, New Orleans, La .
42.40
-18.20
23.2
46.26
W. P. Naquin,. New Orleans, La
41.96
—21.31
18.6
47.45
J. H. Parkins, Richmond, Va. . .
42.00
-18.48
26.5
46.73
F. G. Smith, New Orleans, La
42.97
. —17.53
29.0
47.21
F. Zerban, New Orleans, La
40 60
—21.34
24.0
47.41
Average
41.99
47.01
o Omitted from average.
179
A comparison «>f the average direct polarizations develops the fact that the hydro-
sulphitrs, as in the case of the sugar sample, give the lowest readings, neutral lead
acetate next, and then dry and wet lead subacetate, which are about the same. The
polarization with Herles' solution is the highest. The low polarization, when using
hydrooulphitee, has been already explained. Leaving that one out and the Herles'
polari/.ation, th«- other three agree fairly well. The calculations for sucrose by the
( l<-r-«-t f. >rmula give results that agree very closely. The highest is the Herles' result.
Wh.-ii i his n-au'«-iit is used, the factor is not 142.66, but 143.5, due to the fact of the
pn-rm-i- of a nitrate, instead of an acetate salt. Using this factor, the results would
hf lower.
I'nlnrr.ation of molasses vrith different clarifying agents, using an excess ofdarifier.
SUBACETATE OF LEAD.
\n •.;
Amount of
clarifying
•gwt.
Direct po-
larization.
Corrected
invert po-
larization.
Tempera-
ture of po-
larization.
Sucrose by
Clerget
method.
I' II l»..h.Ti \ \. ,\ iirlfiiiis, La...
U 1 Howell \-u ork.u... I.a
u i- Naqutai NewOrt
cc.
10
8
10
0 V.
43.24
043.50
42 50
°V.
-18.04
-15.12
19 75
°C.
27.0
23.2
24 2
Per cent.
47.44
a 44. 73
I 1! Parkin i: chmond, Vfa .
10
43 60
17 60
26 3
46 tt
i
g
43 92
17 33
27 5
F /rri>:m. New Orleans, La..
/
\ 10
42.00
42.30
-19.58
-18.81
27.0
26.0
47.68
47.13
ip
42 94
47 33
|.|;v <rn \n-T.\TK OF LEAD.
dram*.
r ii. DolMrti v u Ort •
\v i- -.
3.0
3.0
4.0
43.04
r-'. Bfi
42.40
-17.60
-19.05
-19.36
27.5
23.0
26.0
47.04
47.19
47.63
• ige
1' 7»i
47 29
NKTTKAL LEAD ACETATE.
1' II i>i .•'. \.-\v Orleans, La
cc.
U
43.00
— 18.26
27 5
47 52
U !• \ Ml till V--A ' '".• 1
J. II. I'.irkm- Kii-hrii.iii'1 V i
1.-,
10
42.16
o42.00
-20.28
22.00
23.0
26.3
47.60
« 49. 49
K./.Tt.i-i Net Orient, La
/ 7.5
\ 10.0
42.10
42.10
-19. ,58
-19. .58
25.0
25.0
47.39
47.39
Averaj;»>
42.34
47.48
BASIC LEAD NITRATE.
r M Dohertj N'-W <>rl«»ans, La
cc each.
10
43.40
-17.82
27.0
47.39
NV. I' N Mjuln Men • >rl<
\V 1. M.IW..US. N,-w nrl.-.irix. La
i
. 10
10
10
044.02
o 44. 40
44.30
-20.15
-15.40
-17.47
23.5
23.2
27.5
a 49. 02
a45.64
47.92
K. Xt'rMnn. NYu Orleans, La.
r 7.5
42.50
-19.03
26.5
47.55
\ 10.0
\ vonige
43.25
47.62
a Omitted from average.
When an excess of reagent is used all the polarizations are raised, as shown in the
• •ding tables. In the direct polarization, clarification with an excess of dry sub-
acetate gives the least increase in polarization, while the greatest is noted with Herles'
solution. Neutral acetate shows a lower reading when used in excess. The agreement
in the Clerget calculation here is closer than in the other cases.
180
Summing up the work, it can be said that where reducing sugar determinations
follow polarizations the clarifying agent should be neutral lead acetate. But for
ordinary polarization work, where the reducing sugar content is not high, either sub-
acetate or neutral acetate can be used. Where the content of invert sugar is high, a
double polarization is necessary to obtain the correct figure for sucrose, and then any
of the clarifying agents can be used, but care should be taken not to use an excess.
There is one point to which special attention should be called, namely, the
estimation ofreducing sugars. In Bulletin 107, Revised, page 53, under 6, Direct
Weighing of Cuprous Oxid, the weighing as cuprous oxid will give too high results if
the material under examination is high in nitrogenous matter or mineral salts; xanthin
bases and some other nitrogenous bodies are thrown down by the Fehling solution
along with the cuprous oxid. Also some baits are precipitated, and would be weighed
as cuprous oxid, thereby giving false results. This has been conclusively shown by
C. A. Browne in his reports as referee on sugar for the past two years, and is borne out
in all of the referee's work. In such cases the copper of the precipitate must be de-
termined direct either as cupric oxid or, better, by some volumetric method, as Low's,
where the cuprous oxid is dissolved, treated, and finally the copper estimated by
titration with thiosulphate. This is a longer procedure than the weighing as red oxid,
but it should be done if reliable and accurate figures are to be obtained.
RECOMMENDATIONS ON SUGAR.
It is recommended —
(1) That the question of the influence of precipitants upon the polarization of sugars
be further investigated.
(2) That the question of methods of determining moisture or dry substance be
further investigated.
(3) That the method of determining dry substance by means of the refractometer
and the table of Geerligs be adopted provisionally by the association.
(4) That under "Methods for the Determination of Copper contained in the Pre-
cipitate of Cuprous Oxid," pages 51-53, Official Methods, Bulletin 107, Revised (6)
"Direct Weighing of Cuprous Oxid," there be a limitation inserted, viz: "This method
should not be used in determining reducing sugars in commercial products, as other
substances are precipitated along with the cuprous oxid. In these products the
copper of the cuprous oxid should be determined direct by titration as in Low's
method (ibid., 241) or as cupric oxid."
DETECTION OF SMALL PERCENTAGES OF COMMERCIAL GLUCOSE
IN SIRUPS AND HONEY.
By A. H. BRYAN, Referee.
The provisional method of this association is the one described on page 70 of Bulletin
107, Revised. It calls for a polarization of the inverted solution at 87° C. A dextro-
rotary reading at this temperature is said to be due to commercial glucose. And to
obtain the percentage of glucose, the method divides this reading by the factor 163
and multiplies by 100.
C. A. Browne, in his report on honey, Bulletin 110, shows that normal honey
naturally has a dextrorotation at 87° C. and hence the results of a determination by this
method would not express the truth. The dextrorotation of a honey is due to honey
dextrins. These are of a different character from those obtained by acid hydrolysis of
starch, or such as occur in commercial glucose. One point of difference is the fact that
honey dextrin is not colored by iodin solution, while the dextrins of glucose, except in
cases of a high conversion product, are colored by iodin. By means of this test, Beck-
181
man's test,a as it is called, one can distinguish between these dextrins, and hence
• •;ui say whether commercial glucose has been added. Browne called attention
to the importance of this test. He also gave methods for the determination of the
perrenta-e ,,f -rlurose present in mixtures. In the following table are given analyses
of mixtures .if different amounts of glucose and honey:
Analyses of mixtures of commercial glucose and clover honey.
Mixture
Invert polariza-
tion -
Invert sugar—
Calculated glucose.
QtMOK.
Constant
dir.vt
polari-
zation
at 20* C.
At20»C.
At87°C.
Polari-
zation
differ-
ence
(87e-
20°).
Before
in-
version .
After
in-
version.
Invert
polari-
zation
at87°-i-
Invert
polari-
zation
at (20°
C.-
100-
(cor-
rected
polari-
zation
differ-
1.63.
17.5) •*-
encex
1.93.
100-s-
26.7).
Perct.
100
Per*.
" V.
+ 153.8
• v.
+ 153.34
T.
+ 144.32
•F.
Perc*.
30 02
Ptrct.
30 45
Perct.
88 5
Perct.
88 5
Perct.
50
SO
-1- 67.0
+ 65.67
+ 73.81
8.14
53.67
54.50
45.3
43.1
56.9
20
80
+ 15.4
+ 33.00
19.58
69.00
70.35
20.2
16.0
19.2
10
90
- 2.4
- 4.84
+ 18.59
23.43
74.42
74.12
11.4
6.6
8.8
&
95
- 11.5
- 14.30
+ 11.66
2596
75.74
77.80
7.2
1.6
3.8
3
97
- 14.2
- 16.94
+ 9.13
26.07
76.62
78.01
5.6
.29
3.7
2
98
- 16.0
- 18.70
+ 8.14
J«. M
76.64
78.34
5.0
.00
1.2
1
99
- 18.2 - 20.90
+ 6.93
•21 n
77.20
78.87
4.2
.00
.0
100
- 19.5
- 22.11
+ 5.94
28. 05
77.68
78.93
3.2
.00
.0
In the direct and invert polarizations it is noted that there is a gradual change from
a "plus" polarization to a "minus" polarization, due to the increase of the glucose
{ •« n outages. With reducing sugars before and after inversion there is again a large
inrrease with the decrease of glucose. The difference in polarization of the inverted
solution at 20° and 87°, as shown in column 4, increases from 8.14 to 28.05. C. A.
Browne found that nearly 95 per cent of his samples of pure honey showed a difference
rangn >aml the lowest was about 20. Taking 23 as a low figure, a mixture
"i I" |"T i -i -tit «'f -jlurose with honey would not be considered adulterated. If, how-
ever, the natural honey had not shown such a high difference, viz, 28.05, then 10 per
rent would be easily detected by this figure; but by adding up to 5 per cent this
difference is not noticeable, and also the other analytical figures would not indicate
the presence of glucose. It is, however, easily distinguishable when Beckman's test
is applied t«> the honey In fact, with the addition of as low as 1 per cent of glucose,
its presence .an I.e recognized by this test, especially if the dextrins are precipitated
by alrohol and then <li>sol\ed in water, thereby concentrating them.
In the la.^t three columns of the table the results of determining per cents of glucose
by the three different methods are given. It is seen that the method proposed by
Browne gives the figures closest to the actual mixture. Obviously in honey work
Beckman's test should l>e employed in all cases, and in the hands of ordinary chemists
after a few trials it will give good results.
As to the need for such a test, it is a well-known fact that where commercial
insert su-ar is used in a mixture of honey, also where honeys that crystallize are
used, a small percentage of glucose is quite often added to prevent this crystallization.
Cases are on record of such mixtures where less than 1 per cent of glucose was added.
The ii Klin test will indicate the presence of glucose down to that amount.
A I 'ii LT this line the same question comes up in the examination of sirup and molasses.
As is well known, glucose is added to these products in large quantities, and again in
aZts. anal. Them., 1896, 35 : 267.
182
other cases it is added in smaller quantities for the same purpose as in the case of honey.
To be able to determine the small quantity is the problem.
In the first place, molasses or sirup from cane may show some polarization at
87° C. on the inverted solution. This polarization is generally to the right, though
there are cases where it was to the left. This dextrorotation may be due to a pre-
ponderance of dextrose in the reducing sugars of the sample due to the easy decompo-
sition of the levulose or may be due to the decomposition products formed when the
raw juice is being defecated with lime, or by chance it might come from a special fer-
mentation of the sample forming dextran. However; it can be said not to be due to
dextrins. The normal polarization of sirups and molasses has been studied in samples
of known purity from Louisiana and is given in the following table:
Polarization of Louisiana molasses and sirup.
MOLASSES.
Corrected invert
Direct po-
larization
at 20° C.
polarization—
Dry sub-
stance.
At20°C.
At 87° C.
°F.
°F.
°V.
Per cent.
40.8
-20. 24
+2.2
80.8
24.6
-20.9
+2.2
7«.8
26.0
-18.26
+3. 52
76.8
42.4
-16.94
+2.42
78.2
52.4
-16.28
+2.20
69.1
55.6
-13.59
+4.18
69.6
39.6
-18.04
+2. 20
80.8
39.6
-17.82
+2.20
79.0
44.0
-17.16
+2.64
72.0
42.0
-17.60
+2.42
73.8
42.4
-17.27
+3.52
76.1
41.6
-16.94
+3.%
74.0
52.4
-17.60
+3.52
76.1
26.6
-19.8
.00
78.1
50.8
-25.08
+1. 10
87.5
22.6
-16.72
+3.96
84.1
41.6
-14.74
+ 1.10
75.0
45.6
-15.4
+2.20
78.0
SIRUP.
48.4
54.0
50.2
-17.6
-18.7
-12.1
+1.98
+3.30
+6.16
74.3
68.3
50 4
— 14 3
+ 1 76
61.8
-16.5
+2.20
Average . .
+2.65
Maximum
+6.16
Minimum
0.00
It is noted that the average is +2.65, the minimum 0.00, and maximum +6.16.
The sample giving +6.16 was badly fermented, hence its high figure. There remain
about 100 samples to be examined, and when these are finished more definite figures
can be obtained. As far as the work has progressed, about +5.5 is the maximum for
the invert reading at 87° C. The iodin method spoken of in the honey work can be used
here, but the sample must receive some previous treatment before applying the test.
Ten grams of the sample can be diluted with a little water (if the sample be a molasses),
and shaken with 95 per cent alcohol, adding a little at a time with shaking. The pre-
cipitate settles on standing. When settled, pour off the alcohol, add a little water to
dissolve the precipitate, heating if necessary, and then reprecipitate with 95 per cent
alcohol. Repeat a number of times. If the solution of this material in water is still
dark in color, filter through charcoal, or, better, add a drop of hydrochloric acid and
183
reprccipitate the dextrins with alcohol. Wash the precipitate with 95 per cent
alcohol, finally dissolve in water, and then test with iodin. A blank of pure water
should also be treated with the same quantity of iodin solution and run with the test.
A positive test of erythro-dextrin or amylo-dextrin is sufficient proof of the presence of
commercial glucose.
Mr. Davidson, as chairman of the committee to present the ques-
tion of the unification of terms to the International Congress of
Applied Chemistry, stated that the committee would present the
question according to their instructions at the meeting to be held
Max _".>, 1909, and report the results to the association at its subse-
quent annual meeting.
REPORT OF COMMITTEE A ON RECOMMENDATIONS OF REFEREES.
By R. J. DAVIDSON, Chairman.
NITROGEN.
Two recommendations (Nos. 2 and 4, Circular 38, p. 1) made by the referee in 1907,
and referred to the referee for 1908, in regard to the use of copper sulphate in the
Kjeldahl and ilunnini: methods, were again recommended for final action and were
adopted. These changes in the official methods read as follows:
(1) Bull. M in i()7, revised, page 6, line 4, under "(3) Determination," after the
words "sulphuric arid." insert: "From 0.1 to 0.3 gram of crystallized copper sulphate
may also be used in addition to the mercury or in lieu of it."
(2) Bulletin 107, revised, page 7, line 4, under "(3) Determination," after the
words "sulphuric arid." insert: "FromO.l to 0.3 gram of crystallized copper sulphate
may also be added."
Recommendations (3) and (4) offered by the referee for adoption were modified as
follows and proposed by the committee for further work, which latter recommendation
was adopted:
Bulletin 107, revised, page 8, fourth line, after the word "time" insert: "Allow
i he Hawk to stand without heat for not less than six hours or for a shorter time with
shaking at n -iilar interval-."
(4) Bulletin 107, n-vised, page 8, under "(3) Determination," fifth line, after the
word "and." insert the same sentence as in recommendation (3). The sentence then
\.Id •") u'ram- ..i' thiosulphate and allow the flask to stand without heat for not
less than six hours or for a shorter time with shaking at regular intervals; then heat the
solution for five minutes." ete.
POTASH.
It H recommended
(1) That the cobalti-nitrite method for potash be tested during the coming year.
(See p. li'l
Adopted.
(2) That there be a further trial of the method involving the use of ammonium
h\ droxid and ammonium oxalate in the preparation of the solution in the determina-
tion of the potash in potash salts, as compared with the present method of direct
precipitation of the potash without the use of the reagents mentioned.
Adopted.
The referee stated that he had not been able to take up the extensive investigations
thai would be necessary in attempting to define available potash, and offered the
following resolution, which was adopted by the association:
Resolved, That in view of the fact that practically the entire available time of the
referee on potash is needed for the study of analytical methods, the investigation of
184
the question of determining what should be designated as "available potash," pro-
vided for in a resolution adopted in 1906, be undertaken by a special referee or associate
referee.
PHOSPHORIC ACID.
It is recommended —
(1) That the recommendation of 1907 be repeated, namely, that the referee on
phosphoric acid shall take up for report, at the next meeting of the association, methods
applicable under American conditions to the official examination of basic slag
phosphates.
Adopted.
(2) That the referee make a further study of methods for the preparation of neutral
ammonium citrate.
Adopted.
(3) That the referee investigate the amount of wash water to be employed in the
treatment of the residue from the ammonium citrate digestion.
This recommendation was amended to include a study of the manner of filtering
and was so adopted.
INORGANIC PLANT CONSTITUENTS.
It is recommended —
(1) That the method for the separation of iron and aluminum offered as an official
method be referred to the referee for 1909 for final recommendation. (See p. 93.)
Adopted.
(2) That further work be done on the sodium peroxid method for the determination
of total sulphur in plants and plant products (Bulletin 107, p. 23).
Adopted.
SOILS.
It is recommended —
(1) That the modified J. L. Smith method for total potassium be adopted as a pro-
visional method and be further studied. (Circular 32, p. 4.)
This recommendation was adopted in the modified form, as presented by the com-
mittee, the referee having recommended its adoption as an optional method.
(2) That the sodium peroxid fusion for total phosphorus be continued as a pro-
visional method and be further tested. (Bulletin 105, p. 145.)
This recommendation also was adopted in the form presented by the committee,
the referee having recommended the adoption of the method as official.
(3) That the magnesium nitrate method for total phosphorus be adopted as a pro-
visional method and be further tested. (See p. 115.)
Adopted.
(4) That the Knorr method for the determination of carbonates in soils be further
studied. (Wiley's Principles and Practice of Agricultural Analysis, vol. 1, ed. 1894,
p. 338; ed. 1906, p. 380.)
Adopted.
CONVERSION TABLES.
Five conversion tables, submitted by W. J. Gascoyne, of Balti-
more, Md., for the consideration of the association, were referred to
Committee A, which recommended that the whole question of the
adoption of such tables be referred to a special committee, and after
some discussion the matter was referred to the standing committee
on revision of methods.
185
REPORT OF COMMITTEE ON FERTILIZER LEGISLATION.
Tin- report of thr committee of last year could not be sent out to interested parties
until Saturday, .November 7, 1908. This, of course, rendered it impossible to get
any definite statements respecting the tentative definitions of fertilizers and of mis-
branding and adulteration. A number of replies have been received, however, a
few of which, representing their general tenor, are submitted.
In tin- , -in •mnstam •«•>, therefore, the committee begs to report that it is desirable
to postpone further action in regard to this important matter until the next meeting
of tin- association. By that time the views of state officials, manufacturers, and
farmers on the tentative definitions, etc., can be received and fully digested and
placed in shape for consideration. The committee therefore recommends that it be
continued with this report of progress for the purpose of a further study, in view of
the criticisms which may be received on the definitions which have been submitted.
H. W. WILEY.
H. B. MCDONNELL.
B. B. Ross.
[The t. -iitativc definition.- referred to in the report are as follows, together with
•nuiH'iits <>n the same received at the time of the meeting.]
I i \i.\n\ K I M:UM i I..NS OK FKKTILIZERS AND OP MISBRANDING AND ADULTERATION.
A fertili/.er shall be defined as any simple, compound, or mixed material,
prepared f,,r the purpose of selling, or sold, or offered for sale, to be applied to the
-.>il it-* nouri-hment for plants, or a» a modifier of the soil in any respect in its relation
ti. i In- LT"\\ th of plant.- Th.- term "fertilizer material" (or ingredients) shall include
plant -food material which is utilized, or intended to be utilized, in the manu-
re, preparation, or mixing of the fertilizers defined above.
(2) A lertili/.er, or fertili/.er material (or ingredient), shall be deemed to be adulter-
ated
(a) If the percentage of any of its ingredients fall materially below the professed
standard under which it is sold, whether this standard appear as a label upon the
package or at* a guaranty in any other way by the vendor thereof.
(b) If any of the ingredients thereof have an origin other than that indicated upon
the ; r guaranteed in any other way by the vendor thereof.
(c) If any "t the iujn-dicnts of the fertilizer, or fertilizer material, be in a state of
combination dim-rent from that indicated by the label or guaranteed by the vendor
ther-
\ fertili/er, or fertili/er material, shall be deemed as misbranded:
(a) I f any false name or misleading statement or design or device be affixed to any
package thereof ..r used in any way as a representation of the materials thereof by the
vend
(b) If any false or misleading statement respecting the origin of the material be
made UIHUI the label, or any statement or guaranty of the vendor.
(c) If any false or misleading statement be made upon the label, or by the vendor,
n'spectini: the country or origin of the materials of which the fertilizer is composed.
(d) If any fal-e ..r inisleadiiu: statement be made on the label, or by the vendor,
tin-.: the virtues or qualities of the fertilizer or the materials composing it.
(e) If sold umlerany false name or appellation, whether such name appear upon the
package or label or be given to the article by the vendor thereof .
I f it be an imitation of or offered for sale under the name of another fertilizer or
fertili/.er material.
COMMENTS.
(1) Definition (1) includes land plaster, ground limestone, etc. I would hardly
r- the including of such materials, as any additional cost attached to such a sub-
stance as ground limestone would operate seriously against its use. In this State we
do not consider ground phosphate rock (raw rock) among the commercial fertilizers,
although its sale is in no way restricted.
186
(2) Would not the association do well to set a limit, or at least to suggest a limit, for
each of the important plant-food elements, below which a guaranteed constituent
would be considered as "materially" low? — C. A. MOOERS, Tennessee Station.
I have no suggestion or criticism to make with regard to the "tentative definitions
of fertilizers and of misbranding and adulteration." They cover the ground fully to
my mind. It is impossible to so frame definitions that there will not be a chance for
difference of opinion as to what constitutes "misleading statement, or design, or
device," and the best a law can do, it seems to me, is to lay down the general principles
and leave it to the judgment of the individual officer in charge of the inspection work
to decide whether the law in special cases has been Violated as to misbranding. The
recommendation of the committee as to work in the future would seem to be along the
lines that give most promise of carrying the matter to a successful issue. — F. W. WOLL,
Wisconsin Station.
Owing to the brief time in which to mak3 a reply, I have only a few suggestions to
make.
Definition 1 is more comprehensive than in most of the state fertilizer acts, and is
evidently framed to include not only all materials sold as fertilizer, but, as well, air
amendments. I confess I have considerable doubts about the wisdom of legislation
so comprehensive at this time lest it too greatly encumber purely domestic exchanges.
My present inclination is to prefer rather a law that takes into account only what are
commonly recognized as commercial fertilizers.
I realize that there is considerable interstate traffic in certain lime products, as
amendments, and that there is a possibility that abuse may spring up in this trade, but
could it not be reached specifically rather than indirectly by including all amend-
ments. The definition proposed is so broad that a carload of sand becomes a fertilizer
if the sand is to be applied to affect the condition of the soil. The same is true of a
carload of coal ashes applied for purely physical effects.
I do not believe it is a wise principle to enact police legislation far beyond present
needs.
In making the above statements, I realize that the definitions for adulteration and
misbranding which follow definition 1 are such that the objections I have offered to
the definition for the word "fertilizer" may seem to be unnecessary-, but I take it
that if these definitions are adopted it will be for the purpose of advocating their
incorporation in future state and national legislation, and that, in such setting, they
will be accompanied by other clauses specifying the fertilizer materials that must be
matters of guaranty. As soon as such clauses are introduced, the embarrassments I
have in mind are likely to appear.
I desire to add that, in my judgment, the association, which is not specifically an
organization charged with the execution of fertilizer acts, should not undertake the
formulation and recommendation of a national fertilizer law, at least, until a full and
formal conference shall have been had with the fertilizer control executive officials
of the several States. — WM. FREAR, Pennsylvania Station.
* I certainly think this law would be an advantage, especially to the manu-
facturers, as there would be uniformity in all of the States. As the case is now many
of the fertilizer manufacturers are required to get out separate printed matter for
many of the States. However, I do not believe the control of sale of fertilizers should
go outside of the State in which sold, as I believe it can be looked after much better by
men who are in close proximity to the places where fertilizers are handled. * * * —
T. L. CALVERT, Ohio Department of Agriculture.
On most of the recommendations I am heartily in accord with the views of the com-
mittee. In section 1, which defines a fertilizer and fertilizer material, it seems to me
that some specific exemptions should be made. For instance, there are on sale in
this State for the purpose of soil improvement prepared lime, limestone, land plaster,
and marl, and hence our law expressly exempts barnyard manure, lime, wood ashes,
and plaster when sold under their respective names. From the definition prepared
by the committee there would no doubt arise the question as to whether such materials
should not properly be included under a fertilizer law based on this definition. This
point may not be well taken. I merely offer it for your consideration.
In a under 2 the question would naturally arise as to what is meant by "materially
under the guaranty," and the interpretation of this term would be left solely to the
judgment of the official in charge of fertilizer control. If it is possible to do so, I
believe some definite statement as to what should be considered a material deficiency
in any ingredient should be made, such a statement being based on the guaranteed
content. That is, if the fertilizer was guaranteed to contain a certain percentage of
ammonia, available phosphoric acid, and potash, a deficiency exceeding a certain per
187
..f the 'guaranty would be considered as indicating intent to defraud. — W. J.
JDSKS. Jr., Imliana Station.
My main criticism, other than those which are incorporated in the reprint
as emanating from me, would be as to 2a. I believe that there should be added a
I>n>\ i-ii as follou.-:
•• 1'roi ulxl, That if there should be a sufficient excess of other ingredients over the
LMiaranty statement to make good the commercial equivalent of the promised plant
food, the material may not be deemed adulterated." You will notice that I have
put the verb in the permissive rather than the mandatory form, so as to leave it in
the discretion of the inspecting officer to say whether the proviso should or should not
hold in a given case. I should strongly urge, however, before any goods are branded
as adulterate.! under this act, that resampling and reanalyzing should be resorted
to. .1. !.. HIII.S, Vermont Station.
\Ve are heartily in favor of the enactment of a national fertilizer-control law, that
would furnish a broad, scientific, and economical guide on this subject to state law-
makers. The law should provide for actual experiments so that the relative value
of plant food from all sources could be accurately shown without prejudice. The
state system of fertilizer control is all wrong, for the reason that the men who frame
the laws have not a sufficient knowledge of the subject. * * * The great need of
both the fertili/er industry and agriculture is positive knowledge without selfish
influence or opinions not founded on facts. Terms should not be misleading, and the
e from which the plant food is derived should be plainly stated. To leave these
<|ui -tions to the officials of the various States and the fertilizer manufacturers is a case
.if allowing the tail to \\:i.r the dog, and will prove a very unsatisfactory guide. —
AMI i 'UcrioN COMPANY.
REPORT OF COMMITTEE ON THE REVISION OF METHODS.
I'.y .1. K. HAYWOOD, Chairman.
The < •onunittee on the revi.-ion of methods presents as its report Bulletin 107,
e,l, which \\a- i-ueol in July, 1908. The committee was empowered at the last
meeting to make -u< h changes in their first revision (Bui. 107) as were necessary
to coordinate the method* and eliminate obsolete procedures. Such changes, together
with the correction of typographical and other errors in Bulletin 107, were made in
i-uin- the final n-\ itton. In submitting this report, I wish to thank the members of
the committee and all thone who have cooperated in the work, much patient and
detaile.l lal..,r having been put on it.
Tin- iv|>mt wafl :irrr|>t«'d and a vote of thanks passed in recogni-
tion ..f ihr tlion»u«rli manner in which the committee had discharged
it- .'Hire.
REPORT OF COMMITTEE B ON RECOMMENDATIONS OF REFEREES.
P.y B. B. Ross, Chairman.
MKDK INAL PLANTS AND DRUGS.
It i.- r.M •oiimiendcd .
(1) That the present provisional method for assaying opium be made official.
(Bui. ID:, Rev., p. L'oi
Adopted.
That the methods included in the referee's report be made provisional.
A.lopted. (These methods were made provisional in 1907, and are only slightly
modified in this year's report. (See p. 129.)
(3) That the method outlined in this year's report for acetanilid mixtures be further
,1. and that additional mixtures be tested by this and such other methods as
may be found desirable. (See p. 100.)
Adopted.
188
(4) That macroscopical and microscopic methods for examining drug products be
studied during the coming year.
Adopted.
(5) That microchemical methods for the identification of alkaloids in drug products
be further studied.
Adopted.
~ (6) That other microchemical methods be tested to determine the possibility of
thus identifying medicinal plant principles.
Adopted.
(7) That pharmacological methods for testing the quality of drug products be
investigated.
Adopted.
(8) That two associate referees on medicinal plants and drugs be appointed for the
ensuing year.
Adopted.
SUGAR.
It is recommended —
(1) That the question of the influence of precipitants upon the polarization of
sugars be further investigated.
Adopted.
(2) That the question of methods of determining moisture or dry substance be
further investigated, giving special attention to the method suggested by W. D.
Home and reported in the proceedings of 1907 (Bui. 116, pp. 22-23).
Adopted.
(3) That the method of determining dry substance by means of a refractometer and
Geerligs' table be adopted provisionally.
Adopted.
(4) That under the method for the determination of copper contained in the pre-
cipitate of cuprous oxid, pp. 51-53, Bulletin 107, Revised, limit section (6), "Direct
Weighing of Cuprous Oxid," page 53, by the following insertion: "This method
should not be used in determining reducing sugars in commercial products, as other
substances are precipitated along with the cuprous oxid. In these products the
copper of the cuprous oxid should be determined direct by titration as in Low's
method (Bui. 107, Rev., p. 241) or as cupric oxid."
Referred to the referee for 1908-9 for investigation, with the further recommenda-
tion that the term "commercial products" be more closely defined.
FOODS AND FEEDING STUFFS.
It is recommended —
That the referee for 1908-9 take up the question of acidity in cattle feeds and con-
sider how the results obtained by current methods can be applied to agricultural
problems.
Adopted.
DAIRY PRODUCTS.
It is recommended —
(1) That the following methods given in the referee's report (p. 153) for the analysis
of condensed milk be adopted as official, namely: (1) Preparation of sample; (2) total
solids; (3) ash; (4) protein; and (5) lactose.
These methods were referred to the referee for 1908-9 for final recommendation and
action by the association as to their adoption as official.
(2) That the methods for the determination of sucrose in condensed milk by inversion
with citric acid and by inversion with hydrochloric acid be investigated by the
referee for the ensuing year.
Adopted.
189
(3) That the determination of fat in condensed milk be studied, special attention
beinir given to solutions of less than 20 per cent concentration.
Adopted.
That the New Babcock standard, proposed by E. B. Holland and referred to
Committee B, be referred to the referee for 1908-9.
Adopted.
This contemplated standard" is as follows:
NKW BABCOCK STANDARD.
SECTION 1. The unit of graduation for all Babcock glassware shall be the true
cubic centimeter lO.'.c.^x, gram of water at 4° C.).
With bottles, the capacity of each per cent on the scale shall be two-tenths
cubic centimeter.
(6) With pipettes and acid measures, the delivery shall be the intent of the gradua-
tion and the graduation shall be read with the bottom of the meniscus in line with
the mark.
SKC. '2. The official method for testing Babcock bottles shall be calibration with
men -ury i !:;."> 17 I _' rams of clean, dry mercury at 20° C., carefully weighed on analytical
balances, to be equal to 5 per cent on the scale), the bottle being previously filled to
/..-P. \\iih mercury.
< >pti'>nal m.-ihod-: The mercury and cork, alcohol and burette, and alcohol
and brass plunder methods may be employed for the rapid testing of Babcock bottles,
but the accuracy <>f all que>tionable bottles shall be determined by the official method.
1. The ..llii ial method for testing pipettes and acid measures shall be calibra-
tion by meaMiriiiL: in a bun-He th«' quantity of water (at 20° (\) delivered.
Tin- limit >i error I '»r Babcock bottles, it shall be the smallest gradua-
tion <>ii tin- -ale, hut in ii<> case -hall it exceed five-tenths (0.5) percent, or for skim
milk b-.nl.- «.ni- hundredth (0.01) percent.
(6) Kor full quantity pip.-ti.-. it shall not exceed one-tenth (0.1) cubic centimeter,
and I'T fractional pipette- li ve-hundredths (0.05) cubic centimeter.
(c) For acid i it -hall n<>t exceed two-tenths (0.2) cubic centimeter.
REPORT OF COMMITTEE ON RESOLUTIONS.
1.. I.. VAN SLYKE, Chairman.
(1) Jton/m/, That we express to Professor Snyder our appreciation of the able
and rourt i< manner in which he has presided over the deliberations of the con-
vention.
AV.SO/M./. That whereas a national bill to regulate the composition and sale of
iiiMM-tiri.l** and fun-ji. i,l,-< has been recently drawn up by a committee composed of
members of the ASS.H -iation of Kconomic Entomologists, manufacturers of insecticides,
and a-ricultural «-h,-mi.-t- int.-r.-te<:l in insecticide and fungicide analysis, which bill
will be presented to Coi^ren I'-T approval and passage; the Association of Official
A-ricultural < h.-miM- doefl lu-reby express its approval of national legislation on this
Mil.je.-t. which lei:i>lati..n it is believed will be of inestimable service in protecting
the farmin- community a< well as the legitimate manufacturer and in unifying state
und fungicide laws.
ivpot-t «.f tlir c..tniiiittee was approved.
a For further discussion of this standard, see Twentieth Annual Report of the
Mawachusetts Agricultural Experiment Station, January, 1908, p. 113.
190
APPOINTMENT OF COMMITTEE ON THE REVISION OF METHODS
AND RECOMMENDATIONS OF REFEREES.
Mr. BIGELOW. It seems best in appointing this permanent com-
mittee to consider first the members of the editorial committee
which had charge of the revision of the methods last year, and to
appoint those who have so served for a^hort time and the newer
members for a longer period. With this in view I will appoint —
To serve one year, J. K. Haywood, F. P. Veitch, and L. .M. Tolman.
To serve two years, J. P. Street, F. W. Woll, and A. L. Winton.
To serve three years, B. B. Ross, E. M. Chace, and C. D. Howard.
Mr. Haywood will serve as chairman of the whole committee, \vhich
is to be subdivided as follows:
Committee A — Messrs. Haywood (chairman), Street, and Ross.
Committee B — Messrs. Woll (chairman), Veitch, and Chace.
Committee C — Messrs. Winton (chairman), Tolman, and Howard.
Mr. W. H. Bowker spoke at some length, urging the association to
adopt some method for the estimation of available potash, as had
been done in the case of available phosphoric acid, calling attention
to the necessity for such action in conserving valuable by-products
and furthering the interests of economic agriculture. The impor-
tance of this question had been already recognized by the association
by creating a special refereeship for the consideration of the question
of available potash, as recommended by the chairman of Com-
mittee A.
The place and time of meeting for the convention of 1909 was
referred to the executive committee.
As it appeared from the special programme prepared for Monday
that nearly all of the papers were on the subject of food adulteration,
it was moved and carried that the association meet as a whole, not
in sections, as originally contemplated.
The association adjourned to meet at 9 o'clock on Monday.
KOLJRXH DAY.
MONDAY— MORNING SESSION.
The a>s(M-iatioji convened at 9 o'clock for the reading of special
papers in accordance with the resolution adopted in 1907. Mr.
Toll nan, as chairman of Section C, presided.
METHODS RELATING TO THE RATE OF DECOMPOSITION
OF ORGANIC MATTER IN THE SOIL.
By JACOB G. LIPMAN.
< 'hemi- -ally con-ideretl, humus is a comparatively inert substance; biologically con-
-idere.l. n i0 readily Buaceptible to a wide range of modification. The host of bacteria,
fun-i. aii-1 yeasta that inhabit it find no difficulty in inducing its transformation, which,
in t urn, reacts mi the growth <if crops. In so far as the bacteria and other microorgan-
i-m~ 'i ih- - il titnl suitable conditions of moisture, temperature, aeration, and chem-
ical • -Mil.-! inn ii in, tin- humus will decay rapidly. In so far as these conditions are
unsuitable, the decomposition will he slow; and the supply of available nitrogen, and
prohahh «>i' phosphorus and potassium also, will be but meager. This fact was well
appreciated even bef,,r«- the function of bacteria in the soil was recognized, as may be
seen, for instance, from some experiments by Boussingault and Loewy « published in
Tin- recognition of humus OH an important factor in crop production & has led logically
to tin- analytical study of its decomjxwition products and their quantitative deter-
minatioii. Carbon dioxid. anunonia, and nitrates seemed important among these de-
< •<mi{>ositio!i products not merely because of their indirect or direct action as sources of
plant I'M id. but because of their value as indicatorsof quantitative reactions. Students
:1- tried t" establish a possible relation between the productive power of soils and
their content <>f carbon dioxid, ammonia, or nitrates. We need only mention here in
passing the investigations ..f Iloiissingault and Loewy,c and of von Fodor,<i as bearing
on the pr. .irbon dioxid in soil air; the rather careful work of Baumann f on
the determination ami presence of ammonia in soils; and the examination by Bous-
singault ' of various soils for their content of nitrates.
oMemoire sur la Composition do 1'Air Confine dans la Terre Vegetale, Ann. chimie
physique. 1853 (3), 50:3.
tebig, I Me < 'hemie iii ihrer Anwendung auf Agricultur und Physiologic, 9th ed.,
Kraunschwei-. |s7ii, p. •_»»;.
cLoc. cit.
<l Deutsche Vierteljahrschrift offentl. Gesundheitspflege, 1875, 7:205-237.
' Ueber die Bestimmung des im Boden enthaltenen Ammoniak-Stickstoffes und
iiber die Menge des assimilierbaren Stickstoffes im unbearbeiteten Boden, Habilita-
tions-Schrift. Berlin, 1886.
/ Agronomic, chimie agricole et physiologic, 3d ed., 2 :40.
(191)
192
The evidence gathered by these earlier investigators shows a distinct, though not
always uniform, relation between the productive power of soils and their content of
carbon dioxid, of ammonia, or of nitrates. We note that the air of fertile soil usually
contains more carbon dioxid than the air of unproductive soil. Similarly, the fertile
soils contain, as a rule, more ammonia and more nitrate than unproductive soils. But
even admitting this, it seems hardly practicable to draw definite conclusions as to the
future behavior of a soil from its content of the substances in question. The amount
of carbon dioxid in the soil air is an indication of oxidation changes already accom-
plished, but not necessarily a guide to future oxidation intensity. The organic con-
stituents of the humus, as well as the character of the microorganisms, may have been
modified to preclude rapid oxidation. In the same way the quantity of ammonia in
the soil is only a measure of past performance, and a very inadequate measure at that.
As a transition product ammonia may be speedily oxidized to nitrates, or it may be
transformed into protein substances by plants or fungi. Hence the quantity of am-
monia present at any time in cultivated soil can not even serve to indicate past intensity
of ammonia formation. As to nitrates, they, too, are not stable in the soil. Like am-
monia, they may be utilized by higher plants, or by bacteria, yeasts, and molds for the
production of new protein compounds. They may likewise be destroyed by denitri-
fying bacteria, or they may be leached out of the soil by excessive rainfall. In a word
then, the amounts of carbon dioxid, ammonia, and nitrates in field soil are but an
incomplete measure of past performance and a very inadequate guide as to future
efficiency.
The better understanding of the functions of humus, which has gradually come in
the wake of bacteriological investigations, has suggested new methods for the study of
organic matter and its transformation in the soil. In experiments like those of
Wollny,0 or in the more recent experiments of Stoklasa and Ernest, & the evolution of
carbon dioxid from soils kept under definite experimental conditions has been em-
ployed as a measure of the activities of the soil bacteria and of the susceptibility of the
humus to decay. The same purpose has been accomplished in the experiments of
Russell, c and of Darbishire and Russell,** by measuring the absorption of oxygen
instead of the evolution of carbon dioxid. These methods enable us, therefore, to
study the possible future behavior of the humus compounds under given conditions.
In other words, we are enabled to secure some information concerning the relative
availability of the constituents in the soil humus. For instance, it was found by
Stoklasa and Ernest in a comparison of several soils that the average daily production
of carbon dioxid in 1,000 grams of soil ranged from 17.5 to nearly 60 milligrams. More
carbon dioxid was produced by the soil than by the subsoil, the aerobic activities being
more prominent in the former, the anaerobic activities in the latter. Similarly, at
35° C. about twice as much carbon dioxid was produced as at 20° C. Darbishire and
Russell found that in a number of untreated soils examined the absorption of oxygen
in nine days ranged from 6 to 27 millimeters.
Analogous attempts at measuring the rate of decay of soil humus and of other
organic materials have been made, not by determining the oxidation products of
the carbon but of the nitrogen in the soil humus. It was well known that ammonia
almost invariably appears as one of the products in the oxidation of nitrogenous
materials of organic origin. It was likewise recognized after the convincing experi-
ments of Miintz and Coudon « that ammonia formation in the soil is a biological
« J. Landwirtsch., 1886, 34 :222.
&Centrbl. Bakt. Para., 1905, pt. II, 14:723; also Zts. Zuckerind., Bohmen, 1907,
57:291.
cj. Agr. Sci., 1905, 1:260.
dlbid., 1907,2:305.
< Compt. rend. acad. sci. Paris, 116 : 395.
193
ami distinct from nitrification proper. Further information was supplied
l.y Man-hal « in his demonstration of the intense oxidizing activities of B. mycoides
involving the formation of carbon dioxid and of ammonia. It was perceived at
the same time that the quantitative estimation of ammonia in the soil could lead
to no definite conclusion because of the further changes which ammonia undergoes
in the soil. The same may be said also of the quantitative estimation of nitrites.
On the other hand, the determination of nitrates in soils kept under definite con-
ditions promised to give valuable information not only as regards the rate of decom-
position of the soil humus, but also as regards the availability of various nitrogenous
fertili/.ers. It is not surprising, therefore, to find in agricultural literature a vast
amount of data hearing on the formation and accumulation of nitrates in the soil.&
We owe to these investigations a broader point of view and a deeper insight into
condition.- .if <..il. climate, and cropping in so far as they affect the oxidation of
organic mutter in the soil.
Tin- many intcre-iing facts brought to light by various nitrification experiments
served to emphasize, among other things, the necessity of distinguishing the indi-
vidual factor- more or less prominent in the formation of nitrates. It seemed evi-
dent that, apart from conditions of moisture and temperature, the process of nitri-
tieation is dirertly ufferted by at least three important factors, viz, the physical
ami chemical cnniputution of the inorganic constituents of the soil; the physical
ami chemical composition of the organic constituents of the soil; the character of
the nitrifying, and perhaps of other bacteria present in the soil. Without going
iteld, wo may note in this connection the interesting experiments of Withers
and Fraps.c
We find, in the first place, decided differences in the rate of oxidation of sub-
stances like dried blood, cotton-seed meal, dried fish, tankage, bat guano, bone,
ami ammonium sulphate. Not only were these differences maintained, but they
were in more or leas close agreement with the corresponding differences brought
out by digestion tests and vegetation experiments. We find also that the same
nitro^enoii- .-ul»-iaiicw were nitrified to a very unequal extent in different soils. <*
:n live different soils the proportions of nitrate nitrogen formed from
n-eeed meal under the conditions of the experiment were 4.4, 17.6, 22.9, 41.2,
and 54.8 JMT cent, respectively. Evidently there were wide divergences in the
phy-ical. chemical, ami Bacteriological make-up of these soils.
Hut, intere-iini: ua are the facts just noted, we encounter in the work of Withers
and Frap- ' a fad which is even more significant in its bearing on the physiology
of nitrification, namely, that in different soils ammonium sulphate and cotton-seed
meal are not nitrified in the same order. The authors are therefore led to conclude
that there may exi.-i in tin- soil an organism or organisms capable of oxidizing or-
ganic matter (they should have said ammonia) directly to nitrites or nitrates. This
assumption has been strengthened since by the investigations of Kaserer,/ who
believe- he has fntiml an organism capable of changing ammonia directly into nitrate.
It would hardly be safe to theorize too much with these meager facts as a basis,
hut for our purpose we may accept them at their face value in so far as they tend
to -h..w the need of differentiation in the study of decay processes. The nitrates
nt in the soil at any time may be but a small fraction of the total amount ac-
« Bui. soc. beige microsc., 1893, p. 83.
6 t'. S. Dept. Agr., Office of Experiment Stations, Bui. 194, p. 57.
•rth Carolina Agr. Exp. Sta., Bui. 176, p. 19.
«' North Carolina Agr. Exp. Sta., Report of the Chemist, 1902-3, p. 6.
e North Carolina Agr. Exp. Sta., Annual Report, 1901-2, p. 37.
•:trbl. Bakt. Para., 1906, 16 [2] :681.
7::';7:J— Hull. l£i— 09 13
194
tually produced. It is well known that processes are constantly at work in the soil
unfavorable to the accumulation of nitrates. Entirely apart from possible losses
by leaching, there is the more or less remote but still real danger of denitrification.
In addition to this there is the constant draft on the store of soil nitrates by bac-
teria, molds, yeasts, and algae, not to mention higher plants when these are included
in the experiment.
In view of these facts the more recent investigations on the decay of organic matter
in the soil frequently attempt at least a partial differentiation of the single stages
of the processr I am not aware of systematic attempts to determine albumoses and
peptones among the fragments of protein decomposition in the soil. There are,
however, systematic studies of ammonia formation as something independent of
nitrite or nitrate formation. Indeed, we have come to accept the term ammoni-
fication (or ammonization) as expressing a definite change or series of changes.
However, before taking up the discussion of methods relating to the study of am-
monification, nitrification, and denitrification in the soil itself, it would be proper
to consider here certain methods a which deal with the same reactions from a some-
what different standpoint.
The methods in question are based on the changes which occur in solutions of
known composition when inoculated with a given weight of soil. For instance,
a sterile solution of peptone or of gelatin, when inoculated with soil, will undergo
decay, and a portion of the organic nitrogen will be split off as ammonia, which can
be readily distilled off and estimated. Now, it happens that in equal quantities
of the same solution inoculated with equal weights of different soils the amounts
of ammonia produced may differ widely. Otherwise stated, soils vary in their
ammonifying power. But since ammonification is a biological process, we are
forced to the conclusion that the differences noted are due either to the unequal
numbers of bacteria introduced into the sterile solutions by the different soils, or
to differences in the species or vigor of the organisms, or perhaps to both. Be it
as it may, the ammonification coefficients show fairly constant characteristics bear-
ing a more or less definite relation to the productive capacity of the corresponding
soils. Similarly, solutions have been prepared to favor the growth of nitrifying,
denitrifying, or nitrogen-fixing bacteria looking toward the determination of the
nitrifying, denitrifying, or nitrogen-fixing coefficients of soils. The latter methods
have not, on the whole, proved as consistent in their results as have the ammonifica-
tion methods. However, it would be out of place here to discuss them in detail, par-
ticularly since they have been considered elsewhere.6
On the other hand, it would be well worth while to consider here the fundamental
differences between the methods just outlined and those based on the study of bac-
teriological processes in the soil itself. We can well appreciate, of course, how 10
grams of one soil might cause the production of more ammonia in peptone solutions
than 10 grams of another soil under identical experimental conditions. One soil
might have two or three times as many ammonifying bacteria as another; or it might
have not only larger numbers, but also species and individuals with a particularly
well-developed power of ammonia formation. Moreover, it appears quite logical to
assume that large numbers and vigorous species may produce large quantities of
ammonia in the soil itself as well as in the culture solutions. Hence the analogy
between the changes in suitable culture solutions and the returns from pot or field
experiments.
Theoretically, however, this analogy could not always be expected to exist. It
must be remembered that we are dealing here with micro-organisms entirely detached
«U. S. Dept. Agr., Office of Experiment Stations, Bui. 194, p. 10.
*>New Jersey Agr. Exp. Sta., Bui. 210; Annual Report, 1905, p. 225; 1906, p. 119;
1907, p. 186.
195
from their normal medium, the soil. By placing a portion of the latter in an artificial
cult ure solution we create entirely new conditions for the growth of the bacteria. Free
play is iriv.-ii thereby to the establishment of new group relationships, and species
obscure in the soil itself may come to the front. Hence it may often happen, as it
often does happen, that the ammonification coefficients of two soils, as indicated by
experiments in solution, ' ' umsetzungsversuche, " as the Germans would call them,
do not at all correspond to actual conditions. We must therefore distinguish here
between ammonifying power as referring to the numbers and species of the bacteria
th.-ms.-lv.-. and what Fraps" has recently designated as ammonifying capacity, as
referring to the physical and chemical constitution of the soil as well as to the number
and species «>f its bacteria.
Th.' differentiation of the various bacteriological changes in the soil itself is not a
simple matt.-r. As already noted, the activities of the decay bacteria in the soil can
not be measured by estimating the quantity of ammonia formed under normal con-
ditions. Thr ammonia nitrogen does not accumulate, for reasons already noted. We
can, however, create conditions in the soil precluding the further oxidation of ammonia.
This may be accomplish. -<1 by the addition to the soil of a sufficient quantity of dextrose
or of other soluble carbohydrates, or salts of certain organic acids. The same purpose
may be achieved, iH>rhaps, by skillfully adjusting the reaction of the soil. By these
means the ammonifying bacteria are permitted to grow while the nitrifying bacteria
are suppressed. The ammonia accumulates in the soil and may be readily estimated.
Th.- d.-f.-ct of this method lies in the fact that the formation of ammonia from the
soil humus is, analytically, a comparatively slow process. A further defect is due to a
probable rearrangement in the numbers and kinds of the decay bacteria, due to
th«- materials added or the artificial conditions created. As will be seen presently,
i he first of these defects may be remedied without difficulty. The second can not be
.•liminat«-«l so easily. \»-t is not necessarily fatal to the successful application of the
method.
Ammonia formation in the soil maybe greatly intensified and the simultaneous
suppression ..f nitrification effected in still another way. By mixing with the soil
certain quantities of peptone, of urea, or of other nitrogenous organic substances we
supply to the bacteria something from which ammonia may be produced readily and
in comparatively large quantities. At the same time, the presence of these substances
stops the growth of the nitrifying bacteria. In the practical application of this method
in our laboratory we thoroughly mix 0.5 gram of peptone or 0.25 gram of urea with
KM) grams of fresh noil, transfer the mixture into a beaker, adjust the moisture content
by the addition of sterile water, cover the beaker with a glass dish, and place it in the
incubator or closet. \\V usually sterilize the beaker, peptone, and urea before they
are brought in contact with the soil. The latter is drawn with the customary pre-
cautions a -a in- 1 -ross contamination. At the end of three or four days the contents
of the beaker are transferred to a 2-liter copper flask, about 150 cc of water added, and
a sufficient quantity of magnesium oxid. The distillation and titration of the ammonia
are performed in the customary manner.
Similarly, we may study nitrate formation in the soil itself by placing weighed
quantities of the latter in beakers and maintaining suitable moisture and temperature
conditions. At the end of four weeks (or of longer intervals, if desired) the soil is
leached ami the nitrites and nitrates determined in the teachings. In order to in-
tensify the nitrification processes we may add to the soil weighed quantities of ammo-
nium salts or of organic nitrogenous substances. The quantities of nitrate, which is the
end product of various bacteriological activities, may serve to gauge the comparative
rate of oxidation of the organic matter. This method may be employed — has, indeed,
a Texas Agr. Exp. Sta., Bui. 106.
196
been repeatedly employed — for the study of the comparative availability of different
nitrogenous substances as a source of nitrogen to plants.
Comparative studies of denitrification and nitrogen-fixation may be made by the
same method. It is merely necessary to modify the cultural conditions by the addi-
tion of certain substances. In the case of denitrification, for instance, we add a
known amount of potassium or sodium nitrate, leach the soil at the end of ten days,
and determine the ammonia, nitrite, and nitrate nitrogen in the leachings and the
total nitrogen in the residue. The initial nitrogen content of the soil being known,
we have the complete data required.
The methods just outlined may be still further differentiated. We may find means
to distinguish the single phases of ammonification as due to urea bacteria, spore or
nonspore-forming aerobes, spore or nonspore-fonning anaerobes. In the case of
nitrification, we may attempt to distinguish the single phases of oxidation; in the case
of denitrification the single phases of redaction; in the case of nitrogen-fixation the
aerobic and anaerobic phases of the process. The applications suggested may enable
us to gain an insight into the decay processes in the soil, which are imperfectly under-
stood at present. Moreover, we shall not only gain in our ability to interpret past
reactions as revealed by analysis, but also be enabled to forecast future reactions and
quantitative changes of importance to plant food production and its assimilation by
the growing crop.
An interesting paper on the determination of sulphurous acid and
sulphites or sulphur dioxid in food products was submitted by Mr.
Edward Gudeman. The paper comprised a comparison of the
method adopted by the association and a modified method suggested
by the author, the modification consisting in driving over the volatile
products with low-pressure steam rather than by direct distillation,
as in the association method. The steam is generated from distilled
water and passed directly into the mass through a glass U-tube.
The details of the paper are to be found in the Journal of Industrial
and Engineering Chemistry for February, 1909.
THE POSSIBILITIES OF MUSCOVADO SUGAR AS AN ADULTERANT
FOR MAPLE PRODUCTS.
By R. E. DOOLITTLE and A. F. SEEKER.
Occasionally there have been presented for entry at the port of New York shipments
of a brown-colored sugar from Venezuela designated as ''Melada" or "Melado." The
product is generally in the form of rectangular cakes about 1 inch thick by 5 inches
long by 4 inches wide. The cakes vary somewhat in color, but in general closely
resemble maple sugar in appearance. Their use as an adulterant or substitute for
the maple product seemed quite probable, and the finding of a large quantity of this
grade of sugar in the factory of a dealer in maple products by one of our inspectors
showed the necessity of making a careful examination of the product. We were
surprised to find on employing the usual methods for determining the purity of maple
sugar that the brown sugar gave practically the same results as does pure maple sugar.
These figures, together with those of a pure maple sugar run at the same time, are
given in the table:
197
Composition of muscovado and maple sugars.
pi'tiTinination.
N.Y. 10676,
light
muscovado
sugar.
N.Y. 10677,
dark
muscovado
sugar.
I. S. 758-a,
Vermont
maple
sugar.
Moisture ({XT cvnt)
7 35
Ash (per cvnt)
1 33
1 30
I'olari/atiim ilin-ct, at room temperature (° V.)
+80 0
+82 4
Polarization, iuvi-rl. at. room temperature (° V.)
-27 0
26 8
2q 5
I'olun/ -vtion it Mi"3 (° V )
db 0 0
;.. r rent)
81 4
83 1
85 6
WiDton lead nuintxT
2 08
2 12
Malic arid value
1 19
1 24
An analysis of tho ash, however, showed a distinct difference, as is shown by the
following data:
Analysis of the ash of muscovado and maple sugars.
nnination.
N.Y. 10676,
light
musco-
vado
sugar.
N.Y. 10677,
dark
musco-
vado
sugar.
I. S. 758-a,
Vermont
maple
sugar.
Average
of four
samples
of maple
sugar.o
Insoluble in (wiling nitric acid (1 : 3)
Per cent.
2.55
50.08
4.85
5.77
2.20
.29
1.96
22.16
4.02
6.12
Per cent.
3.41
49.89
2.32
5.66
2.63
.26
1.34
23.21
3.68
7.60
Per cent.
8.9
23.6
1.6
35.9
3.0
Slight trace.
Trace.
None.
.45
26.55
Per cent.
Potassium ' '
26.49
24.98
' ' • • • i
Chlorm
Siilplnir if
1.82
•iiiii-il
K«O
Ratio xioo
868
m
44
70
881
410
47
65
66
106
7
7
Ratio S<>' . mi
Ratio * v hi)
1
« Jours. Kightit'iitli Annual Report, Vermont Agr. Exp. Sta., 1905, p. 331.
Tin- a-h ..I ili«- l.rown sugar consuls mostly of potassium sulphate, while over 80
p.-r •-.-nt ..I" that ..i inaph- sugar is composed of carbonate of potassium and calcium,
t I,,.-,, i «.xistini: in approximately equal parts. From these facts one is led
t.» l>«'licv<> that a drti-rmination of water-soluble and water-insoluble ash, their ratio,
and thrir alkalinity would furnish the necessary evidence as to whether the product
un.lrr rxatiiinatiuii was composed of maple sugar or muscovado sugar. As a matter
Q| fa, i. il. l,-trn.iiiiati..iis when carried out on one of the samples gave the results
shown in tlu« following t-.ible:
198
Ash determinations and ratios of muscovado and maple sugars indicative of aduUeration.
[All results reduced to a moisture-free basis.]
Determination.
N. V. 10677.
muscovado
sugar.
I. S. 758-a,
maple
sugar.
Maple
sugars.*
Water-soluble ash (per cent) .
1.23
0 50
0 53
Water-insoluble Bsh (per cent) ? . . .
.17
.64
.48
Ratio water-soluble ash
7 7
8
1 i
"° water-insoluble ash "~
\lkalinity of water-soluble ash (cc tenth-normal acid)
11
49
08
\lkalinity of water-insoluble ash (cc tenth-normal acid)
.03
1 47
1 01
a Average of a number of analyses made by Jones, Vermont Agr. Exp. Sta. Report, 1905.
Unfortunately a sirup prepared from the muscovado sugar fermented before time
could be found to make the usual determinations, and no more of the sample remained
for further work. However, it^ seems reasonable to assume that the sirup as well as
the sugar could be detected by the high ratio of insoluble ash to soluble ash, and the
low alkalinity of both. As confirmatory evidence an ash analysis should be made
wherein a high percentage of potassium oxid and sulphur trioxid, together with a
small amount of calcium oxid, would indicate the adulteration. It would appear
also as if the phosphoric-acid content gave useful information, both of the muscovado
sugars possessing notable amounts and the maple sugar little. These data are also
given in the table in the form of ratios, which serve better to emphasize the contrast.
As there is good reason to suspect that the brown sugar under discussion is being used
by manufacturers of maple products, it seems highly important that an examination
of the ash should be included in all routine analyses of these goods.
Acknowledgments are due to Mr. W. A. Bender for the ash analyses here given and
to Mr. A. E. Taylor for many of the other determinations.
NOTES ON THE WINTON LEAD NUMBER OF MIXTURES OF CANE
AND MAPLE SIRUP.
By R. E. DOOLITTLE and A. F. SEEKER.
Among a number of samples of cane and maple sirup mixtures examined during the
past year were a few which had been mixed in the presence of one of the officials of the
laboratory and were known to contain 10 per cent of maple sugar. Upon analysis it
was found that these sirups gave no precipitate whatever with basic lead acetate when
making the lead number determinations according to Winton's method.
A sample of the same maple sugar from which the sirups had been prepared was
examined at the same time and gave a lead number of 2.31, besides other results which
indicated the purity of the product, and therefore the negative results obtained with
the 10 per cent mixtures caused some surprise.
Upon carefully repeating the determination it was observed that a precipitate was
formed when the lead subacetate solution first came in contact with the sirup, but
this was later redissolved when the whole of the reagent had been added. It was
judged, therefore, that so great an excess of basic acetate prevented the usual precipi-
tation with mixtures of this strength.
A number of portions of 5 grams each were accordingly taken, diluted to 15 cc with
water, and placed in test tubes. To each of these were added different amounts of
the standard basic acetate solution, varying from 0.1 to 5 cc, and after thorough shaking
the turbidity noted. The tubes to which the smaller amounts of reagent had been
added were perfectly clear, but a turbidity appeared as the quantity approached 0.5 cc,
then came a slight precipitate, which reached its maximum at 1 cc and gradually
decreased again to only a slight opalescence with 5 cc. Winton's method calls for 25 cc
199
of reagent for 25 grams of sugar or sirup, a proportion of 1 cc per gram of substance. The
maximum precipitate was in this case produced by 1 cc to 5 grams of substance. A
lead number determination was accordingly made on the 10 per cent maple sirup in
question with a lead subacetate solution five times weaker than that prescribed by
\Viutoii, and the figure 0.137 obtained. This solution is much too weak to be used
with pure maple sirups, as it contains only about 0.8 gram of lead (figured as metal)
per KM) cc, whereas 100 grams of an average maple sugar will precipitate in Winton's
in. -i hod over 2 grams of lead. To show that a large excess of lead reagent is necessary
to produce a normal precipitate, a sirup containing 30 per cent of cane sugar and 30
per cent of maple sugar was prepared and the lead number determined, using both the
\Vinton solution and the one diluted five times. With the weak subacetate a lead
number of 0.29 was obtained, with the strong, 0.72. In the former case there was just
enough basic -uku-etate in the 25 cc of solution added to have precipitated all of the
lead if a normal precipitation had occurred, and no lead would have appeared in the
filtrate. Actually the amount of lead was insufficient for maximum precipitation and
the l.-a.l number was accordingly too low. On comparing the amount of lead remain-
ing in solution with that added it was seen that the former was 62 per cent of the latter.
I'.y the regular meth(xl the excess of lead producing a normal lead number was found
to be 81.7 per cent. In the case of the 10 per cent maple sirup in which no precipita-
tion was produced by the regular solution and in which a lead number of 0.137 was
obtained with the I in ."> dilution, it was found that the excess of lead was 82.1 per cent.
AB a conclusion it would appear that at least 62 per cent excess of lead is necessary
for a complete precipitation, an excess of lead much greater than 80 per cent tends to
prevent precipitation, and that a zero lead number obtained by the regular method
doe* not indicate that so-oalled cane and maple sirups contain no maple sugar.
It ha _:>-ste<l that the lead number of the mixture containing 10 per cent of
maple -uu'ar mL'lit '-,'i ve normal results if the solution after addition of the lead reagent
allowed to stand longer than two hours, as was done in the previous determina-
tion- i >n standing for twenty-four hours the opalescence which formed on adding
the l«-ad suhacetate had collected into a very slight precipitate, which was matched
in the blank by one of similar proportions, though boiled distilled water had been used
in all C*0ea, After filtering in the usual way and determining the lead number zero
values were obtained as before.
THE DETERMINATION OF FUSEL OIL BY ALKALINE
PERMANGANATE.
By A. S. MITCHELL and C. R. SMITH.
I oil Ci .Heists chiefly of a mixture of normal and isopropyl, normal and isobutyl,
active amyl and isoamyl, and hexyl alcohols. The Allen-Marquardt method is in
reality an "estimation in terms of amyl alcohol of the higher alcohols which are dis-
>olv»-<"l and retained by carbon tetrachlorid, under fixed conditions, and converted
into volatile acids by oxidation with a chromic acid mixture.
This paper is the result of an effort to learn the conditions necessary to produce
definite oxidation of the various alcohols by alkaline potassium permanganate solu-
tion. 1 1 was hoped to avoid prolonged digestion with the oxidizing agent and, later,
t he subsequent distillation with the attendant concentration of the oxidizing mixture,
ordinary amyl alcohol, which consists of iso and active amyl alcohols, was first
experimented upon. In the first effort the manganese dioxid and unreduced per-
manganate was not removed after acidifying for the distillation of the free acids.
The mixture bumped so badly that the distillation could not be completed. It
became necessary to remove the manganese dioxid and permanganic acid. Oxalu
a.i.l vai t m,l and rejected. Hydrogen peroxid was finally selected for this purpose.
200
In the experiments recorded in the following table the amyl alcohol used had been
dried and fractionated at boiling points between 128° and 132° C. After the oxidation
50 cc of sulphuric acid (1:4) was added and then an excess of hydrogen peroxid, and
the mixture was boiled under a reflux condenser for fifteen minutes to remove any
carbon dioxid. The mixture was then distilled until bumping occurred due to the
separation of salts from the solution; 80 cc of water were added and distillation repeated
to the same point. The valeric acids were then titrated with tenth-normal sodium
hydroxid with the following results:
Amyl alcohol estimated under varying conditions, using alkaline potassium permanganate.
Time
of oxi-
dation.
Total
dilution
during
oxida-
tion.
Temperature of oxidat-'on.
Potas-
sium
hy-
droxid.
Potas-
sium
per-
man-
ganate.
Amount of amyl alcohol.
Quan-
tity
used.
Quan-
tity
found.
Per cent
found.
Minutes.
30
10
10
20
20
20
a20
10
10
30
30
30
30
30
cc.
60
60
CO
60
160
160
260
160
160
160
160
160
160
160
Room
Grams.
5
5
5
5
5
5
5
5
5
5
5
5
5
Grams.
3
3
3
3
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
Grams.
0. 1170
.1347
.1190
.1245
.1080
.1181
.1259
.1161
.1090
.1099
.1156
.1545
.1631
.1986
Grams.
0.1047
.0959
.0833
.0471
.0960
.0915
.1093
.1040
.0903
.1091
.1126
.1522
.1566
.1909
89.5
71.2
70.0
37.8
88.9
77.5
86.8
89.6
82.9
99.2
97.4
98.5
95.4
96.1
Boiling-water bath
do
Boiled free flame
Room ...
Boiling-water bath
Room
do
..do...
0°
0°
0°
0°
0°
« Hours.
At a temperature of 0°C. the oxidation of amyl alcohol to valeric acid appears to be
quantitative and at higher temperatures the yield of valeric acid is decreased.
Variations in time within the above limits have little influence upon the reaction.
When the oxidation is too vigorous destruction occurs and the results are low. If the
reaction is controlled by decreasing the temperature the oxidation is arrested at the
production of the corresponding acids. The acids when produced are not easily
altered and may be allowed to stand with the oxidizing agent at room temperature
without appreciable change.
THE OXIDATION OF NORMAL PROPYL AND ISOBUTYL ALCOHOLS.
Similar experiments were made upon normal propyl and isobutyl alcohols, following
the same procedure as in the case of amyl alcohol, and with the following results.
Estimation of propyl and isobutyl alcohols, using alkaline potassium permanga nnh .
Alcohol.
Amount
used.
Amount recovered.
Quantity
Percentage
found.
Propvl
Grams.
0. 1151
.1151
.1005
.1005
Grams.
0.1156
.1190
.0981
.1039
100.4
103.4
97.6
103.4
DO.::
Isobutyl
Do.
201
Tin l-:\n:vcnov OF PROPYL, ISOBUTYL, AND AMYL ALCOHOLS FROM ETHYL ALCOHOL
BOLUTHHff
A few trials were made upon tin- extraction of these alcohols by carbon letrachlorid.
In each ca.-e l(M) OC of \-'> per ''''ill by volume alcohol, containing known amounts of one
of th«« alcohols, was diluted to 115 <•<•. -alted, and saturated so<lium chlorid solution
added in bring the Bpecific gnviiy to I.IO, extracted with four siic.-es-i\e portions of
in. :;•». I'D, and 10 <•<•, respectively. The carbon tetrachlorid was washed with three
portions of saturated salt solution 50 cc each, and with one portion of 50 cc of saturated
sodium sulphate solution. The alkali was added to the carbon tt>trachlorid solution
contained in a separator}- funnel and cooled in an ice bath toO°C. The permanganate,
previously cooled, was added and allowed to remain in the bath thirty minutes, with
p-peated shaking. The dist illat ion was conducted as pre\ioii>ly described.
'ili-ittinls, '/ m t.trnrtilnnil.
Alcohol.
IJIMIllilV
,t,ty
bond.
nUge
foiui.l.
T1,
.' "U.
ii. r.-ij
drams.
i: :.
""•:,:,
Ann
;5
\ «
.mtt
.mm
.1747
56.7
Atlempts (.. extra, i .im\ I al«,.h,,| in.m eth\l al. ,,h,.| >(,|iiii..n~,
ether as a -.|\eni.
1 M ri UMI\ \ V\»\
AMVI. Air. nun I.
\ "I I \ll rid- '
petroleum
Isoitl r\\, A\l>
• •ated attempt :nade during the course of this- work to estimate
prop} I. i-obut}l. and am\l alcohol-, depending mi the amount of permanganate
n-duceil. hut without success until sati .ndition- had been determined for
the oxidation. T|,,. jM-n: lined was greatly in excess of the lheoretic.il
amount. The unused permanganate was d.-termined |,\ adding a known amount of
ox. ill. acid in e\r.-» and titrating back with perm.!
Tin-alcohol- Iknlved in'.". . in \\ hich hi cc • .1 potas-
sium hy.lroxid were added and the whole rimled in an ice bath. < Hie hundred OCOffli
aipieoii- -olution containing' 'J -rain- of pota.->ium |M*riiiaii<r.inate and pre\ inu-l\ cooled
in the i.e |,;iih were then added and the mixture wa- allowed to -tand for thirty min-
utes. It was then relinked from the bath, acidified with "»0 cc of iM percent sulphuric
acid, a known excess of oxalic a«id wan added, the mixture was then warmed and the
excessoi oxalic a« id titrated bark with standard p««rmanganate. The follow! n-j factors
were used as calculated from the theoretical oxidation of the alcohols to their acids
b\ potassium perniaiiiran. MIII ..f permanganate equal.- <>. i;:, .jram of pn.pyl
alcohol. «,r o ">v> irniin «•! i-obutyl aleohol. or 0.1»!M> gram nt am\ 1 alcohol. The n-ult.-
follow:
•>r -y trial* for lh, > »l>un> tnr determination of alcohol*.
Alcohol.
Amount
Amount
loun.l.
i'. r<
lolllHl.
(train.
Gram.
Propyl o ll.vi
I1M
!l24«
108
106
ISO.'HII \ 1 . . IINL'I
. 11)94
1119
Hi71
I'.Mii
.1400
130
130
202
These figures seemed fair in the cases of propyl and isobutyl alcohols, but poor for
amyl alcohol. They apparently indicate the complete destruction of a portion of the
latter at some stage of the process. Varying the amount of alkali made no improve-
ment.
That the results were slightly high, as in the case of the propyl and isobutyl alcohols,
might be expected, for permanganic acid and manganese dioxid are produced on
acidifying and are present together for several minutes during reduction by oxalic
acid. The excessive destruction of permanganate .with amyl alcohol points to other
causes.
As oxalic acid acts very slowly in reducing the manganese dioxid, it was decided
to substitute hydrogen peroxid. Sulphuric acid was added to hydrogen peroxid and
the mixture resulting from the oxidizatica was poured slowly into it. This gives the
permanganate little opportunity to react with free organic acids, as it is reduced by
the hydrogen peroxid as it is acidified.
Determination of amyl alcohol, substituting hydrogen peroxid for oxalic acid.
Amyl
alcohol
used.
Perman-
ganate
consumed.
Amyl
alcohol
found.
Per cent
found.
Gram.
Gram.
Gram.
0.1276
0.1850
0. 1287
100.9
.1276
.1830
.1274
99.8
.1276
.1827
.1272
99.7
.1536
.2173
. 1512
97.1
.2042
.2971
.2067
101.2
A series was run in which isobutyl and propyl alcohols were used instead of amyl
alcohol.
Determination of isobutyl and propyl alcohols, substituting hydrogen peroxid for oxalic acid.
Alcohol.
Amount
used.
Perman-
ganate
consumed.
Amount
found.
Percent
found.
Isobutyl
Gram.
0.1005
Gram.
0.1640
Gram.
0.0959
95 0
Do
Do
.1005
1407
.1645
2240
.0960
1300
95.0
92 4
Do
.1608
.2525
1477
91 8
Propyl... .
.1150
1625
0770
67 0
The results indicate incompletion of the oxidation at 0°, so the procedure was
adopted of starting the oxidation at 0° and allowing the mixture to warm slowly to
room temperature. The mixture was allowed to remain ten minutes in the ice bath
and taken out and warmed so that it reached room temperature (about 23° C.) in twenty
minutes. The experiments reported below were conducted with propyl alcohol.
Determination of propyl alcohol after warming solution to room temperature.
Propyl
alcohol
used.
Perman-
ganate
consumed.
Amount
found.
Per cent
found.
Gram.
Gram.
Gram.
0. 1215
0.2490
0.1183
97.4
.1458
.3050
.1449
99.4
.1701
.3600
.1710
100.5
.1215
.2495
.1185
97.4
. 1215
.2530
.1202
98.9
.1458
.3040
.1444
99.0
203
That it should !»«• nece<-ury to warm the solution to room temperature seems incon-
.-i.-tent \\ith the results obtained on propyl and i>obutyl alcohols where the acids
formed wen- distilled. The explanation probably lies in the fact that delay occurred
before the destruction of the permanganate with the hydrogen peroxid. Hence it
•BOM a Decent?? condition in the ((iiantitative oxidation of mixture* containing
isobutyl ami anul alcohols by alkaline permanganate, that after the' oxidation of the
ainyl alcohol at 0° the solution be allowed to warm to room temperature.
That ainyl alcohol in carbon tetrachlorid solution should be quantitatively oxidized
by alkaline permanganate was quite probable, providing the alkaline permanganate
could reach the alcohol. Knowing that the oxidation of the amyl alcohol is quite
rapid, and de-inn- to.-horten the t ime of shaking as much as possible, it was thought
live minutes of continual shaking would be sutlicient. The following table indicates
the amount of amyl alcohol dissolved in 100 cc of carbon tetrachlorid and the amount
found:
l>rtrrminntinn <>f nnii/l <tlmfi»l ,n curium t< truchlorid solution .
Amvl
o&oi
B -I
Ainuiuit
bond
IVrtvnt
found.
Onm
Urnin.
Q iml
B un
lirj 4
.1704
101.9
MM
.1031
102.1
.•'..-.;
BOM
IQO B
MM
MR
100.7
The extraction of amyl alcohol from alcoholic -olution \\as m-xt subjected to experi-
ment In the aiuilysi- of di-tilled liquors \\e are dealing \\ith »•"» to '^ per cent by
volume alcohol solutions which are extracted \NJth tetrachlorid and the tetrachlorid
washed with saturated w>luti' .um chlorid and siwlium sulpliate to remove
the eth\l alcohol. eMimatin- the higher alcohol- extracted under fixed conditions.
1 1 \\a- llmiiu'ht of importance t«> learn how thoroughly the washing of the ethyl alcohol
from the tetrachlorid was accomplished by the cii-tomary method of wa.-hin^ three
time* with thn- rtiooi "t" -aturated -odium <-hlorid solution, and lastly with
one .">o cc jMirtioii of .-aturaied -«.dium sulphate solution. The extraction was made
from IIMI ( c of »:. p.-r i-ent b> \olum.-aliohol. The temperature of the HoluUoot WM
In four experiment- the follouini: amounts (grams) of perman-anate \\crv
coa-uined: 0.0080, 0.0114, 0.0090, 0.0065; average, O.OOs: Thkimdicated thereten-
tion in the carb.m tetrachlorid of approximately 0.0033 gram of ethyl alcohol.
-action of known amounts of amyl alcohol from eth\l alcoholic solution, 45
percent by volume, \\ere made \\ith the follouin- re-ult-
knniin <ln><»i,it.< »/ niiii/l nlrntinl Jrnin •tfti/l nlrnfmf solution (23° C.).
££i
present.
.1 j»-r-
maiiganAte
('orni-tiou
for.-thvl
alcohol.
ivrmanga-
nut»> con-
siiiiH-d by
amyl
alcohol.
Auivl
alcohol
brad.
Kx trac-
tion.
On*
B oon
.1480
Gram.
. \n*
.2725
lint in.
0.0087
,0087
.oon
dram.
O.OM8
.1581
. Mi
Gram.
0.0873
.1100
.1826
Per cent.
68.2
74.3
740
204
Extraction of simihr known amounts of amyl alcohol at 17.5° C., using 100 re of a 50
per cent by volume solution of ethyl alcohol.
Permanga-
Amyl I Total per- Correction
alcohol manganate for ethyl
used. consumed. alcohol.
nate con-
sumed by
amvl
Amyl
alcohol
found.
Extrac-
tion.
alcohol
Gram.
Gram.
Gram
Gram.-*
Gram.
Per cent.
0.0)87
0.1205
0.0087
0.1118
0. 0778
78.8
.1481
.1810
.0087
.1723
.1199
81 0
.1481
.1730
.0087
.1643
.1143
77.2
.1974
.2295
.0087
.2208
.1537
77:9
For the estimation of ethyl alcohol by alkaline permanganate a solution of fusel-
free alcohol containing 24.75 grams per 100 cc as determined by the pycnometer was
diluted with water one hundred times. Portions of this solution were then diluted
to 50 cc and estimated by the same method as used in the case of the other alcohols.
The oxidation was quite rapid, and the time allowed was ten minutes. Using the
factor 0.3636 for oxidation to acetic acid the following results were obtained:
Estimation of ethyl alcohol by alkaline permanganate.
Perman-
ganate
used.
Ethyl alcohol.
Amount
present.
Amount Per cent
found. found.
Gram.
0.1392
.1673
.2072
.2045
.2070
.2812
.3405
Gram.
0.0495
.0619
.0742
.0742
.0742
.0990
.1237
Gram.
0.0506
.0608
.0753
.0743
.0753
.1021
.1237
102.2
98.2
101.4
100.1
101.4
103.1
100.0
Similar trials were made with methyl alcohol. Methyl alcohol was purified by
drying with calcium chlorid, heating with anhydrous oxalic acid to convert into
dimethyl oxalate, the crystals drained and pressed dry, and finally decomposed with
slight excess of dilute alkali and distilled. The specific gravity of the distillate was
taken and the methyl alcohol present obtained from Dittmar's table. In the first series
of experiments the oxidation was allowed twenty minutes at the temperature of the
ice bath. Considering formic acid to be the end product of the oxidation, the factor
would be 0.253; if the formic acid were completely oxidized to carbon dioxid the factor
would be 0.1686.
Estimation of methyl alcohol by alkaline permanganate at 0° C.
Methvl
alcohol
Perman-
Methyl alcohol found.
present.
consumed.
Factor 0.253. Factor 0.1686.
Gram.
Gram.
Gram.
Per cent.
Gram.
Per cent.
0.0196
0.1145 ,
0.0289
147.5
0 0193
98.5
.0392
.2150 !
.0544
143.9
.0362
92.4
.0589
.3130 ;
.0791
135.0
.0527
89.5
.0981
.4115
.1041
106. 1 . 0693
70.8
•ji »:.
It will !.«• inferred thai t he react i..n proceeded tocarUn dioxid. l»ut was not com-
plete when lari:«' amounts of methyl alcohol were oxidi/ed. There is no need of
cooling th«- solutions if complete oxidation is intended, so a scries of trials wen- made
in temperature, time of oxidation thirty minutes, and using the factor 0.1686.
The results follow:
xit'nm "f ,,nth til alcohol by alknl'inr /Mrmnnyanatf nt room tfin jurat aw.
Methyl IVnnun-
alcohol tranaii-
M.Mhvl
alcohol
IVr
cent
present, consume 1.
found.
found.
Gram. Gram.
Gram.
0 (AM n. ll'<>
a 0196
100.0
0 ;''-'
.900
.0888
:••_'
MM
.00}
,j»o
.MN
97.1
When warmed in a water l>aih af t'4)° for five minutes and eooled to room tempera-
ture and titrated, ().(>:;!•:; -ram of methyl aleohol UM\,- i» (i.;(i:> ,,r KMl.s percent of the
amount pr-
I-'or the appli< ai i«'u of I he alkaline perinanu'anale met In x I to the < arhon tetraehlorid
I of the higher al- oh,,U from di-tilled li«|iiors, the following pn.<-edure is su«-
>..ii ii..
I. A .-iroriir'T -oluiion of pota— ium pern • •nitainini: appn.\imai.
^ram- to the liter
\ hydrogen peroxid solution .,f a -rren-th sliu'lnlx in e\e.-ss of thai of solution
V standard permanganate nolut ion containing I" ill to the liter,
the \aliie of which has l>een accur 'laltied
I \ -oluiion of [...lassium h\dro\id"of 1 : I strength.
\ -ulphuri. a. id solut ion' containing ap|»n»\iinaiel\ j.'i p,-r c.-nl of arid.
v i i;
•he . arl.on teirarhlorid • niain«'d in I he separatorv funnel, add Ml cc
of ih. :i h\dro\id ,-oluiion \o I < IM,| i he mixt ure in i<e \\ater to approxi-
mate!) (» < Similarly cool KM) cc of the -t n.n-er soluiion of jiotas.-iiiin |.erman-anale
iiratel\ ni.-a-ured, in a flask.
hr ronirnt- "I the .-eparatory funnel add the l>ulk of the permanganate .-oliition,
l.ut without rinsing the tla.-k and retaining the n-.-idiir- lo I.e added ai a latersia^'.
:io\e the mi \t ure from the l.ath and -hake \ i'jori»u-l\ f<>r a |»eriiKl of li\e minute-;
set aside for tliirty nunute<. with occasional .-hakinu', permiitinur the Injuid to warm
to room temperature - ('.).
urately niea.-iiro 100 re of hydrogen pep.\id -olution into a 1-liter lOrlenmeyer
lla.-k. A- idulate tliis with KM) .-I- of sulphuric-acid solution. Slowly add the c,~>n-
lents of the separator}' funnel with « •on.-iani -hakini:. keepin- the arid H.lulion «-«»n-
.-tant 1\ in '-veSB.
Kin-e the M -parafory funnel and flask containing ihe residue of permanganate with
water and add to the peroxid solution.
Titrate the excess of hydrogen peroxid remaining with the standard potassium per-
man-anate.
Run a blank determination, IHUIL: 'he same amounts of the stronger permanganate,
-ium hydrate, hydrogen peroxid, and sulphuric-acid solution and titrating tin;
rer-idtial poroxid with ! he standard perman-janate as before.
The difference in amount ol permanganate consumed in grams lim< - 0.606
the result in terms ot aim 1 alcohol.
206
METHODS OF ANALYSIS OF DISTILLED SPIRITS.
By L. M. TOLMAN and W. E. HILLYER.
The methods of the association for the analysis of distilled spirits, as given in
Bulletin 107, Revised, of the Bureau of Chemistry, are for the most part the best
methods available; but a few modifications and some new methods have been found
to be of value.
DETERMINATION OF COLORING MATTERS.
The method which has proved to be the most satisfactory in the Bureau of Chemistry
for distinguishing between natural and artificial coloring matters in distilled spirits
is the qualitative Marsh test. This depends on the relative solubilities of coloring
matters in ethyl alcohol, amyl alcohol, and water. The addition of amyl alcohol,
when in sufficient quantity, to a mixture of 50 parts of ethyl alcohol and 50 parts
of water will cause a separation of the liquids into two layers, the lower layer being
largely water and the upper one a mixture of ethyl alcohol, amyl alcohol, and some
water. As a result of this separation, water-soluble coloring matter can be separated
from alcohol-soluble coloring matter; that is to say, caramel can be separated from
the natural coloring matter of whisky. Up to the present time this has been used
as a qualitative test of the greatest value, but it now appears that the method can
be adapted for quantitative determination, the amount of added coloring matter
present in relation to the natural coloring matter being determined. The following
method has been developed and found to be entirely satisfactory:
AMYL INSOLUBLE METHOD (QUANTITATIVE MARSH TEST).
Evaporate 50 cc of the whisky just to dryness on the steam bath in a porcelain
evaporating dish. Add 26.3 cc of 95 per cent alcohol to dissolve the residue, and
transfer to a 50 cc flask, using water and making up to volume with water. This
gives a 50 per cent alcoholic solution from which to make an extraction. [It is nec-
essary that the extraction should be made from a solution of definite alcoholic
strength, as it can be readily seen that variations in the percentage of ethyl alcohol
would make a decided difference in the amount of amyl alcohol to effect the proper
separation.] Place 25 cc of this 50 per cent alcoholic solution in a separatory funnel,
add 20 cc of the Marsh reagent, then shake lightly so as not to emulsify. (The Marsh
reagent consists of 100 cc of amyl alcohol, 3 cc of sirupy phosphoric acid, and 3 cc
of water; shake before using.) Allow the layers to separate; repeat this shaking and
standing twice more, and after the layers have clearly separated the last time, draw
off the lower or water layer containing the caramel or water-soluble coloring matter
into a 25 cc cylinder and make up to volume with 50 per cent alcohol. Compare
this portion in a colorimeter with the remaining 25 cc which has not been treated
with the Marsh reagent, thus directly giving the percentage of color not soluble in
amyl alcohol.
The following table gives the results obtained by applying this method to straight
and imitation whiskies:
Amyl alcohol tests for color in whiskies.
Description of sample.
Insolu-
ble in
amyl
alcohol.
Soluble
in amyl
alcohol.
Description of sample.
Insolu-
ble in
amyl
alcohol.
Soluble
in amvl
alcohol.
Straight American whiskies:
Average
Per cent.
10
Per cent.
90
Imitation whiskies bought
Ptr cent
Maximum
12
88
86
14
Minimum
7
93
Scotch whiskies (straight)'
Straight whiskies bought in
Average
7
93
market:
Maximum
8
92
Average...
9
91
5
95
207
It will !>«• seen f ru in this table that in an\ .-trakdit American whisky !M) per cent
i.i the ( •«.!,, riim matter is soluble in the amyl alcohol and ethyl alcohol layer, while
in an imitation whisky 1 I JMT cent is soluble in the upper layer. This method gives
a much more complete separation of the coloring matter taken from wood and from
caramel than either the water-insoluble method or the ether-soluble method, and
[•eems to be the iii<i.-t reliable and satisfactory test that we now have for the detection
ol added coloring matter and its estimation.
Further, if a whisky contains a certain amount of caramel this method will give a
partial separation, and the percentage of caramel added can be approximate!) e-ii-
mated. The present provisional method, known as the '-' Crampton and Simons test."
for caramel depending on the insolubility of caramel in ether, is not nearly so satis-
factory as the method here presented, as the separation of the coloring matters is
much less complete. The ether-soluble method, as given in Bulletin 107, Ke\i>«-d,
lul, i.- i-iimbersoine, and calls for unnecessary special apparatus. Accurate
practical re-nils ha\e always been obtained by the following procedure:
i : HI K-OOl UBXI OO] OI MI rinu».
' CC of the sample just to dryness mi the water bath; wash into a 50
<•<• lla.-k with _'• «. ,,i alcohol and dilute !•• mark with water. Transfer -'•> cc with a
pipette (.» a -eparatory funnel and add 50 <•<• of ether. Shake at intervals for half
an hour, let -ettle, draw off the aojueoii- layr, and make up to -^ cc with water.
Mix thi- latter and compare with the •_'."• .. ,,t the solution which were not treated
with ether Kxpre-.- the amount of color removed on the |>errentai:e basis as ether-
soluble color.
Thi.- modification -imply eliminates the social Hpunwell apparatus, and the
method i- but little u.-ed in the Bureau «•! < hemi.-try, but the change is presented
as essential in appUing the meth'Nl. \Ye do, how«-\er, u.-e the method of determin-
ing' the color insoluble in water, caramel, ,,f OOU ;-erfectl\ .-..luble ami tin-
coloring matter of whi-kv beiipj praeiically in-oluble in water. Thi- uri\e> a method
of separation which i- \er\ .-.it i.-fai-t«>r\ , the ppM-ediire outlined in this laboratory
U-INSOl I HI I . ..| in: MM ll»l>
i .-ample ju-t to drynetw. Take up with < old water, u-ii
.Miately l"i CC, and tiller, washing "with water until nearly •_'"> cc of filtrate i.-
obtained. Add about •_'•• .dcoh-.l. and coni|>lete the volume to the
mark by tlie addition of water. Mix thoroughly and compare in a colorimeter
with the color of the original sample, -tatin-j r«-ult- as percentage of color insoluble
in water obtained by .-ubtraetiiu; the pen entage soluble color, reading from 100.
The following table compare- the re-ulis obtained by the determination of water-
in- .bible color with the ether-soluble color on a number of -trai^ht whiskies and on
spirits colored with caramel:
' '<ni'/> nt, I, rnlnr nnil ft fur-soluble color on different type* o
Water-
Ether-
Description of samples.
insoluble
coloring
soluble
coloring
matter.
matter.
Per cent.
Percent.
-ht ryt» whiskies of known source and age
^lit hoiirl>on whiskies of known source and age.
IHHIIK! whiskies bought in open market
71.0
• >v I
12 2
35.0
29.5
19 3
:.; IIIH i at ion whiskies bought in open market
6 7
7 3
This table shows that results obtained by the ether-soluble method do not show
enough difference between the straight whiskies and those artificially colored. That
i- to - 1\ . iu ether the difference in solubility between whisky color and caramel is
208
not large enough to make a satisfactory separation, while the water-insoluble method
shows a much wider difference and gives the same information, but is not so valuable
as the amyl alcohol test, which makes the most complete separation of the two kinds
of coloring matter. In a study of the water-insoluble method it was found best to
evaporate just to dryness, and, further, that the manner of evaporation did not affect
the results. It also appears that the amount of sugar present as caramel does not
affect the solubility of the whisky coloring matter.
DETERMINATION OF FUS«L OIL.
The determination of fusel oil or higher alcohol is undoubtedly one of the most
important ones made in the analysis of distilled spirits, giving more information as
to the methods of distillation in the manufacture of the spirit than any other factor.
When the examination of distilled spirits was begun, an extensive investigation was
made of the Roese method as given in the official methods of the Association of Offi-
cial Agricultural Chemists,0 and it was found that a great many difficulties were
encountered in employing the apparatus and method as there directed. This method,
depending as it does upon the relative solubilities of alcohol, chloroform, and fusel
oil in each other, requires that the conditions of temperature and concentration must
be very carefully controlled. The first difficulty encountered was the leaking of the
stopcocks in the apparatus adopted by the association, known as the Bromwell tube,
and after many experiments it appeared that this could not be overcome. The
chloroform solution would invariably leak through the ground-glass stoppers, so that
it became necessary to return to the older form of apparatus as designed by Roese,
which has no stopcock, but is extremely difficult to fill. With this form of appa-
ratus, however, somewhat satisfactory results were obtained.
It was found also to be absolutely necessary that the apparatus be perfectly clean
and free from any oily material, and in order to insure this it was heated in a sulphuric-
acid-bichromate solution after almost every determination. Unless this is done
drops of water will stick to the sides of the chloroform bulb and increase the volume
of the chloroform and the amount of fusel oil shown. Also it is absolutely necessary
that during the whole determination the solutions and apparatus should be kept
exactly at 15° C., and to this end a large constant temperature bath was built deep
enough so that the tubes could be immersed completely and the shaking could be
carried on in the bath itself. It was found that if the tubes were removed from the
bath and shaken in the air the results were entirely inaccurate, a much larger blank
being obtained. This is easily explainable. If the temperature of the room is very
much above that of the bath, the shaking will raise the temperature of the solution
and change the relations between the solubilities of the various liquids in each other,
thus yielding results of little value.
A regular procedure was adopted in regard to the shaking. The apparatus was
filled according to directions and immersed in the constant-temperature bath until
all the solutions had reached the same temperature. The tube was inverted in the
bath and shaken vigorously 150 times, then reversed and allowed to stand in the tank
until all the chloroform had settled back into the bulb, after which a reading was
made.
By using this apparatus and carefully following these details fairly satisfactory
results were obtained, but at the same time the Allen-Marquardt method was tested
and found to be much more convenient and accurate. In a recent paper by Doctor
Dudley, of Vanderbilt University, on "The comparison of results obtained by the
Roese and the Allen-Marquardt methods, "& these same difficulties and errors in the
Roese method were noted, so that it seems advisable to abandon the old Roese method
and direct our attention to the Allen-Marquardt method, which apparently gives
much more satisfactory results.
a Bui. 107, Revised, p. 97. 6 J. Amer. Chem. Soc., 1908, 30 : 1271.
209
In the \v<>rk of the Bureau of Chemistry for the pa.-t year nr more much work lias
been done to perfect the Allen-Mar<|iuirdt method, and it will be discu»ed some
what in detail, as some of the moditicatioiis deviled improve the method and have
not been published, but are of great importance in obtaining accurate results.
The method as used at the present time is the same as is given in Bulletin 107,
Ke\ i.-cd. but it has been found necessary to have the proof of the sample under exami-
nation not much above 100 in order that the volume when made up to 1.12 specific
gravity will not be too great for the separatory funnels used. In the analysis of hi^h
proof spirits, therefore, 50 cc of the sample are used for analysis and 50 cc of water
added, making the product approximately 100 proof.
( )ne point which is extremely important is that the carbon tetrachlorid used must
be of the hi.irhe-t purity. \Ve have found that most of the ('. 1'. carbon tetrarhlorid
on the market is entirely un.-ati-factory for this determination until it has been puri-
fied by oxidation with bichromate and sulphuric acid, as called for in the present
provisional method. In the projKT control of this purification a renewal of the
bichromate and sulphuric acid mixture is necessary and often makes the procew a
lengthy one \\here the carbon tetrachlorid is very impure. For this reason the fol-
lowing new method, devised by A. M. Breckler, is used:
Mix the crude carbon tetrachlorid with strong sulphuric acid in the proportion of
of acid to e\ery :i,IMM) cc of the carbon tetrachlorid. Shake this mixture thor-
oughly at freoiient inter\al- and allow to stand over niijht. Then run \\ater through
the mixture continuou-l\ . l.y means of a glass tube inserted to the bottom of the
bottle and .--.nn.'. t with the water tap, until thoroughly washed free from .i.-i.| and
impurities. Draw oft the water or upper layer by means of a siphon, the last por-
tion- li.-ini: removed as bu :'•!«• by a pi|H-tte. Add an excess of soda solution
and di.-til the carbon tetrarhlorid from it.
II) "t tin- method is that a good blank can be obtained, the process of
purification i- decidedly shorter, and it may be adapted to cruder carbon tetrachlorid
than can the present pn>\ isional method, thus allowing cheaper material to be used.
A blank should always be run on each set of determinations and if thin amount- in ihe
end to more than 0.2 to ().:; DC "t i. nth-normal alkali due to the carbon tetrachlorid,
the reagent i- not pure enough for this determination. The impurities present in
some samples of bichromate also gave trouble It i- absolutely necessary in this
method t hat reagents of all kinds -hall be entirely free from organic contami nut ion.
In the extraction jx»rtion of the method the followim: precautions are necessary :
(1.) A shaking machine gives more regular condition- for extraction, each shaking
• ntinned for a period of two minu
It i- of advantage to h.i\e perfectly saturated sodium chlorid and sodium -ul-
phaie, and for this purpo-c the solutions are kept standing over an excess of the salt
and continually agitated by a current of air.
(3) It h. • iM-rimeniully determined that a colder temperature gives a more
efficient extraction.
It i- al-o HIM es-ary to take special care to remove by complete washing with
sodium sulphate all the sodium chlorid from the carbon tetrachlorid extract ,,n account
of the formation of chlorin in the oxidi/ini; process with bichromate and sulphuric
a<i,| and the danger of this chlorin interfering with the titration by bleaching the in-
dicator The pre-ent pr- 1\ i-i« -mil method calls for one washing with sodium sulphate
to accomplish this result, but it has been found by experiment that two are not suffi-
cient to remo\ e the sodium chlorid. < h\ the other hand, it may be that more than
two wa-hiiiL'- would abstract some of the higher alcohols, therefore it appears that the
it directions in the provisional method should be changed from one to two
(5) It is necessary in carrying on the oxidation that the boiling of the carbon tetra-
chlorid with the oxidi/in^ solution should be slow and regular, and that a high con-
« 1 en -er should be n.-ed to insure the complete condensation of all the products. Espe-
cially i- rlii- slow boiling necessary in the following modified method which de-
pends on the estimation of the potassium bichromate reduced during the oxidation.
T::I;T:I— Hull. 1±J— O9 - 14
210
The Allen-Marquardt method, modified according to these suggestions, reads as
follows:
MODIFIED ALLEN-MARQUARDT METHOD.
Reagents.
Solutions of sodium thiosulphate. — Two solutions of sodium thiosulphate are used,
one an approximate three-fourths-normal not standardized, and the other a tenth-
normal standardized against pure potassium bichromate whose value has been ob-
tained against pure iron. ^
Carbon tetrachlorid. — The purification of this reagent is a fundamental necessity.
(See Breckler's method, p. 209.)
Potassium iodid solution. — Dissolve 1 gram in every cubic centimeter of water
taken.
Bichromate oxidizing solution. — Dissolve 200 grams of pulverized potassium bichro-
mate in 1,800 cc of water and add 200 cc of concentrated sulphuric acid.
Determination.
Proceed with the Allen-Marquardt method for determining fusel oil, as given in
Bulletin 107, page 98, to the point of adding the oxidizing mixture. Add exactly 50
cc of the oxidizing solution to the blank and the samples by means of a pipette or
burette and then oxidize under a high reflux condenser for eight hours. During the
oxidation, shaking the flask with a rotary motion will prevent any isolation of spots
of bichromate on the flask below the carbon tetrachlorid. Decomposition from over-
heating is prevented by placing between the wire gauze and the flask two thicknesses
of one-fourth inch asbestos board.
Remove the flask from the reflux condenser and separate the bichromate from the
carbon tetrachlorid in a separating funnel. Care must be taken that in this process
no bichromate is lost and that the carbon tetrachlorid is washed free from it. Make
up the bichromate solution thus obtained to 500 cc.
Measure 200 cc of this solution into a liter flask. Add 50 cc of the potassium iodid
solution, 50 cc of the approximately three-fourths-normal solution of sodium-thio-
sulphate, and then 20 cc of concentrated hydrochloric acid. Titrate the excess of
bichromate with the standard tenth-normal thiosulphate solution. If a high content
of fusel oil was present in the original sample, the addition of 50 cc of the three-fourths-
normal thiosulphate solution may be excessive and if such is the case a smaller amount
should be added and the blank titrated in the same manner.
Treat blanks containing exactly the same amount of the reagents used in running
each series of commercial samples in the same way, starting them at the point where
the carbon tetrachlorid is washed with sodium chlorid. The titration of this blank,
to which has been added the same amount of the three-fourths-normal thiosulphate
solution, gives the value of the oxidizing mixture. The difference between this
value in cubic centimeters of tenth-normal thiosulphate and that obtained on the
reduced oxidizing mixture of the commercial sample in each case gives the amount
of bichromate used up by the oxidation of the fusel oil present. This difference is
then calculated to grams of amyl alcohol using the following factor: 1 cc of tenth-
normal thiosulphate equals 0.001773 gram of amyl alcohol.
The factor used is an average one obtained by three manipulators in making 60 runs
on standards containing amounts of pure amyl alcohol, varying from 0,05 to 0.5 gram
as follows:
Development of factor in the oxidizing process of the Allen-Marquardt method.
Analyst.
Content of
afnvl alco-
hol.
Number of
determina-
tions.
Maximum.
Minimum.
Average.
Boyle...
Gram.
0 05+
9
0 001885
0 001652
0 001751
Do...
10+
g
001885
001637
001785
Albrech .
10
5
001847
001806
001806
Palmore
10+
4
001790
001634
001726
Boyle
15+
9
001824
001721
001776
Do
20+
g
001840
001762
001799
Palmore
20+
5
001751
001710
001710
Boyle
31+
4
001754
001719
001736
Palmore
30+
5
001725
001819
001771
Boyle
42+
4
001830
001800
001810
Do
53+
001818
001818
.001885
.001634
. 001773
211
The maximum and ininiiniiin figures >ln.\v thai the oxidizing process carried out
under normal laboratory conditions is practically uniform with respect in tin- varying
amount- of fusel oil present. It was found that the reactions taking place Between
the liii hromateand the amyl alcohol were little understood, and that it was iuipossililc
to calculate a factor which gave anything like the actual results obtained; so that the
results of the experiments given above were made, and the surprising closeness of the
figures obtained by the various analysts shows that there is a definite reaction taking
place; and, while this reaction has not been figured out, the writers feel entirely justi-
fied by the results in adopting this factor.
This change in the method was developed as it was found that the final distillation
of the volatile acids was not satisfactory, on account of the fact that only a portion is
distilled over when the present provisional method is followed. The following table
of experimental data develop* the conclusion just stated and shows on an average for
all contents of amyl alcohol that the percentage yield is raised from 7S to !)L' per cent
if the w;i-hiii'_' pr< " • timie.l
<//.« nlthiim-t fnj tin- .\lltn-.\Iiiniinirilt
Ainyl:ili-ohol |iivs»'Mt.
Cram.
1). UN)
II. l.M)
ILM
II. llNI
". Im
1). 1IKI.
II. UN) .
0. UNI
\ m. .nuts of amyl alcohol recovered by
additional washings (expressed as oo
n-normal alkali ).
Total vi.-l.l l.v;i.l-
ditional washing.
\aioimts
|1 : .::;.•.:
.
"-.
.>
.00
..,
.Ill
m
.145
.179
.190
.184
171
.085
M
OH
.087
OH
on
.074
.070
.190
:;•'
. J7J
i'.-r,.-::'-
';:;;:,:
• Second.
Th.r.l.
Fourth.
Amount.
I'ercent.
96
98
103
96
H
97
97
H
H
H
H
82
Ml
89
^7
81
71.0
i ..,
! «
HLO
V 0
87.0
740
70.0
95.0
79.0
VIII
M 0
OLO
7x 0
".7 a2
-
6
.' 1 9
1
2
4 4
4 1
:i
1 1 r,
4 8
5 3
0.1
.0
.2
• o
.:<
.1
.2
'.'<,
.2
.2
Gram.
0.096
.OH
.103
.OH
.098
.097
.097
.099
.196
.246
.250
._'!'.
. :u:<
.HI
. Jx:',
0.5
!i
.2
.2
'.2
a.2
.1
1). UK)
0.300
7s.u
92
> By the fifth washing 0.3 cc were obtained.
212
The curves plotted in fig. 5 show the relationship between the percentage yields
of the present provisional method, of the impractical prolonged washing method, and
of the proposed modified Allen-Marquardt method. Only the figures obtained in
testing the portion of the Allen-Marquardt method which follows the beginning of the
oxidation process are represented.
3 /OS
\
O./SO
0.3SO
0.400
FIG. 5.— Comparison of three methods for the determination of amyl alcohol.
The curve shows that uniform results can not be obtained by the present provisional
method, and that if the washing and distillation method, an impractical procedure,
be adopted, high yields will probably only be obtained on the low-content samples.
The curve developed by the runs on varying amounts of amyl alcohol by the pro-
posed modification of the Allen-Marquardt method gives a higher and more uniform
yield for all amounts and one which approximates closely to 100 per cent. The work
of developing this latter curve represents 62 runs on varying amounts of amyl alcohol
from 0.05 to 0.53 gram, and the manipulation of three analysts.
The fact of obtaining a higher and more uniform yield caused us to prepare and send
out to 18 collaborators, 11 of whom reported, the samples described in the report of the
associate referee on distilled spirits for this year (see p. 25). The comparison of the
old and the modified method and the results of the collaborative work are there pre-
sented by the table and curves, and distinctly show the advantages of the proposed
modified method.
213
DETERMINATION OF THE IODIN NUMBER OF THE NONVOLATILE
ETHER EXTRACT OF PAPRIKA.
i;\ \v. i>i
As in this laboratory much difficulty was experienced in obtaining concordant re-
sults on determinations of the iodin number of the nonvolatile ether extract <>t' pap-
rika, 8 samples of ground paprika sent in as suspected of being Bduttentod with olive
oil, and I sample composed of the shells of Hungarian paprika .ground in the labora-
tory were examined, various methods of extraction being used.
Method 1. — This consisted in digesting 10 grams of paprika over night with 100 cc
of ordinary ether in a stoppered flask. The next morning all ether was decanted off
through a double filter and the residue thoroughly washed with 200 cc more ether.
The ether was then distilled off and the residue dried to constant weight at 100° ('.
and calculated as nonvolatile ether extract, the iodin number of the same being
deter ruined on portions of i hi- residue by the official method, using the Ha tins solution.
Mtihml '. Manipulation the same as in method 1 except that petroleum ether I'.. 1*.
50-60° was substituted for sulphuric ether
Method .*.— The official method for the determination of nonvolatile ether extract
in spice* as L'i\'-n in r.iilletin 107.
.\ffthml ;. The Doolittle-< >gden method of extraction with cold anhydrous ether."
All four <>f the above methods proved unsatisfactory. Methods I and 2 were at
once discarded because it was found after repeated trials to he absolutely impo-.-ihle
by these methods to obtain portions of identical compo-nion from one lot of ether
extract, due to the fact that on standing for a few minutes at 100° in the water oven
several drops of a colorless oil appeared on the sidesof the container, while on standing
at room temperature needlc-haped «T\ -tals. which on microscopic examination proved
tobecry-t al- of fai, were seen in the deep red re-idue. It was also frequently found
that in spite of careful tilt rat ion minute quant it ies of some body difficultly soluble in
chloroform were present in the extract, thus further interfering \\iih the accuracy
of the result-
l'.\ i he otlicial method also it was found ditlicult to obtain duplicate results, appar-
ently due to the fact that a drying oil is present in the extract which may oxi.li/c
to varying degrees depending on slight difference- in manipulation during the long
period of extra- the l>oolittIe-< )-jden method some difficulty, although not
so much as with the three preceding methods, was experienced in obtaining
duplicate determinations of the iodin number; and in addition this method has the
disadvantage of allowing only one determination of the iodin number to be made
on the product of a .-in-le extraction. The following modification of the Dooliitle-
Ogden method was finally devised, and so far has given satisfactory results. Diving
duplicates on iodin number determinations agreeing to within 0.2 per cent.
Method No. 5. — Ten grams of paprika spread in a thin layer on a flat -bottomed dish
are dried for two hours in a vacuum oven at fit)0 and L'"> mm. The material is then
transferred to a double filter and \\ashed with :)<)<) <<• of cold anhydrous alcohol-free
ether. After distilling off the ether the residue is taken up with fresh ether and
filtered into a -mall tared beaker, the filter paper being carefully washed with ether
to remove all trace of oil. After again evaporating off the ether t lie residue is dried
to con-taut wei_rht at 100°. After the final weighing the residue is washed with
chloroform into a 100 < . flask and made up to volume with this liquid. Determina-
ti..n- ot the iodin number are made on 10 cc portions of this solution, thus making
{possible -e\erai duplicate determinations on the residue obtained in a sample extrac-
tion.
oj. Amer. Them. Soc. 1908, 30. MM.
214
The following points are noted as having been brought out by the limited data
obtained :
(1) Any method in which portions of the extract are poured off into shell vials, etc.,
for the determination of the iodin number, as is customary in the determination of
this constant with oils and fats, should be avoided, for as before stated it is absolutely
impossible by this method to obtain two portions of identical composition.
(2) Iodin numbers determined on the nonvolatile ether extract of paprika, which
by the high value of this constant would appear not to be adulterated with olive oil,
are found when made on the product obtained by the official method of extraction
to be considerably lower than those obtained on the product produced by extraction
with cold solvents, indicating perhaps the presence of drying oils; while, as is to be
expected, the percentage of nonvolatile ether extract is lower. On the other hand,
with commercial paprikas adulterated with olive oil the difference between the iodin
numbers obtained by the two methods of extraction is not so marked. Extraction
with cold petroleum ether, boiling point 50°-60° gives a nonvolatile extract about
1 per cent lower than is obtained by the use of an equal volume of sulphuric ether
under identical conditions. In the following table samples Nos. 1 to 8 are commer-
cial paprikas sent in on suspicion of adulteration with olive oil while No. 9 is a pure
product prepared by grinding the shells of Hungarian paprika.
Comparison of methods for determination of iodin number and nonvolatile ether extract.
No.
Iodin number.
Nonvolatile ether extract.
Official
method.
Method
No. 5.
• Official
method.
Method
No. 5.
Method
No. 1.
Method
No. 2.
1
2
3
4
5
6
7
8
9
127.1
121.6
108 0
124 4
107.7
109.0
107.3
139.0
127.3
113.6
130.2
113.3
114.5
114.4
130 3
Per cent.
15.8
17.5
21.3
15.8
21.75
20.1
20.6
Percent.
9.64
12.29
15.14
11.52
17.00
15.74
15. 63
13.66
2.84
Per cent.
11.99
13.84
16.76
13.21
18.73
17.38
17.28
Per cent.
11.07
12.98
12.57
17.97
16.54
16.36
127.0
139.0
5.04
I
DETERMINATION OF STARCH IN COCOA PRODUCTS.
By W. L. DUBOIS.
The provisional method for the determination of starch in cocoa and cocoa products
requires grinding of the sample in a mortar repeatedly with ether and pouring the
solution through filter paper each time until the fat is extracted. With sweetened
material the fat-free residue is then rubbed in a mortar to a paste with water and
filtered on the same paper, the process being repeated until all the sugar is removed,
which requires about 500 cc of water. This process is a very slow and tedious one.
The manipulation of the sample in the mortar with ether both in the grinding and
subsequent pouring requires extreme care to prevent loss. The filtration in many
cases is very slow and with sweetened samples it often takes two days to wash with
500 cc of water. In order to overcome this objection the following procedure was tried :
Four grams of the unsweetened sample or 8 grams of the sweetened goods are shaken
with 100 cc of gasoline in an ordinary 8-ounce, short neck, nursing bottle until the
material is completely disintegrated; the bottle is whirled in a centrifuge until the
supernatant liquid is clear and the gasoline drawn off with a small tube attached to
vacuum pump and the process repeated. This procedure removes practically all the
215
fat ami prepare-; (lit- sample for the next operation. In case of unsweetened material
this merely enti-i.-is in washing the same into a 500 cc Erlenmeyer flask with 200 cc of
water ami proceeding with the hydrolizing and determination of starch as directed
in the provisional method. With the sweetened goods alter the extraction of fat with
gasoline LOO CC of water WO added to the residue ami the bottle shaken thoroughly and
whirled in the centrifugal machine. If the speed of the machine In- sufficiently liigh
a dear water solution may be obtained, although as a rule a thin layer of chocolate
will float on the top. A small pipette may be passed through this layer into the water
.-olutioii and the same withdrawn from the bottom. Where such high speed can not
be oiitained, however, it is necessary to pass the water solution through filter paper to
remove the suspended particles. The process is repeated and the residue transferred
i.. the filter paper and washed with sufficient water to make a filtrate of 500 cc. This
-s requires a very much shorter time than that outlined by the provisional
method.
From the table it will be seen that the extraction of fat and sugar is apparently com-
plete, the results \\here comparisons were made with the provisional method being
slightly higher than those obtained by that method, duplicates agreeing fairly well.
r»//i/Miri*rm of methods J<> »i nut inn nf starch in cocwi product*.
Sample.
B •:... ;.
in. tho.l.
fiainplf.
Mo.lili.-«l
Illi-tllixl.
Pro-
visional
lllctluxl.
/• | • M
Percent.
Percent.
Percent.
..
\ 10.77
Bit t«-r chocolate
I l:<.:u
: . _ ' -^
\ 1J. /.i
lilll.T rhiM't.l Lt<
1 II si
1 I'.' II
} U.M
Sw. -.•lrlnM-ol.il.-
N m
\ 8.22
7. 42
iiUt«T chiK-ol.it.-.
1
1 8.51
\ Lost.
7.40
MONDAY— AFTERNOON SESSION.
EXAMINATION OF OYSTERS.
W. I> P.I..KI.OW.
There has \m\\z been a pra< n. •• .uiion^' tho-e .-hipping oyster-^ in the shell to place
ihem for a day or two in a -treaiu or fresh or brackish water. This process is corn-
men iall> term.'. I •-.Irinkiiu'." and i- practiced for the purpo>e of plumping the
oysten. h d -iat.-d that at the I.e-innin-jof the ebb tide the oysters open their .-hell-
ami "drink." What really happen- is that the fresher waterdiffuses into the oyste'ra
:n..-i- ami u'ives them a fictitious appearance of plumpness.
This practice of ••.Irinkin- in the shell has been largely di.-continued.
I'rai-tically the same thing i- a<-( ..mplished, however, by soaking them for a consider-
able time in fre.-h water after their removal from the shell. As the purity of the water
can be better I -oiitrollcd by this means, it is to be preferred to the older process of
'•drinkini; " tlie <.\-ter before -hu« kiii'j In either case, the plumping of the oysters
is stated by .-hippers t<> be f. .r the purpose of improving the product. This improve-
ment, however, i- entirely fictitious, the increased plumpness being due merely to the
addition of water which is given off on cooking.
1 1 is believed that the unnecessary addition of water to oysters, either directly or by
objectionable on two grounds: First, it produces a fictitious appear-
ance of plumpness; and, second, the weight of the oysters is increased by a substance
216
whifch does not add to their nutritive value; that is, a substance (water) is mixed with
them N« such a manner as to reduce their quality or strength.
WheuHne oyster is removed from the bed by dredging or tonging, the inside of the
shell contains a considerable amount of dirt and sand. In order to remove this the
oysters are sometimes placed on floats at some convenient place in the salt water.
Here, probably at the beginning of the ebb tide, they open their shells and "drink."
Since the water in which they are placed is at the same concentration as that of the
bed, however, there is no plumping or other change in their appearance except that
during this process they appear to blow the dirt and sand from the shell and if the water
be clean the oyster is fairly clean. They are then taken to the oyster house, shucked,
and washed to remove the slime with which they are covered. It is said by shippers
that this slime will rapidly produce decomposition and must be removed before the
oysters are shipped. This washing, however, should not be prolonged more than is
absolutely necessary for proper cleansing.
During the last season a study was made of the oysters in various parts of the country
in order to secure data, if possible, by which oysters that had been properly treated
might be distinguished from those which had been treated with an excessive amount
of water. Seventy samples of oysters were taken from beds in various sections of the
seacoast of the United States and sent to the laboratory without any treatment what-
ever. Other samples from the same beds were merely washed with water for a suffi-
cient time to remove sand and dirt; while still other samples were soaked in water for
a length of time varying from one hour to twenty-four hours.
When the samples arrived at the laboratory they were examined as follows: First,
the total weight was taken, then the sample was strained through a colander and the
solid meats and liquors weighed separately. Fifty grams of the oysters were then
placed in a beaker with 200 cc of cold water and the whole heated in such a manner
that the water was brought to the boiling point in about fifteen minutes. The boiling
was continued for fifteen minutes, wrhen the water was poured off as completely as
possible, the oysters were cooled five minutes and weighed. From the figure thus
obtained the per cent loss on boiling was determined. It was found that by con-
tinuing the boiling for a longer period than fifteen minutes the results were not greatly
increased.
Another portion of the solid meats was passed through a meat chopper and the total
solids, ash, and sodium chlorid determined in the usual way. The percentages of
total solids and ash and sometimes of sodium chlorid were also determined in the
liquor. From the figures obtained by the examination of the solid meats and liquors,
together with their respective weights, the per cent of total solids in the original
sample was calculated. In the majority of cases samples of the salt water were taken
from the respective oyster beds and their content of sodium chlorid determined.
SIMPLE TESTS FOR DETECTING BLEACHING IN FLOUR.
By A. L. WINTON and E. J. SHANLEY.
The Griess-Ilosvay method for determining nitrites," originally designed for water
analysis, is generally recognized as the best means of detecting artificial bleaching in
flour. Commercial unbleached flour contains no appreciable amount of nitrous acid,
free or combined, while that bleached with nitrogen peroxid contains amounts increas-
ing with the degree of bleaching. The quantitative process of determining nitrous
acid, although not a tedious one, is, however, unnecessarily laborious when only
qualitative results are desired. It involves the preparation of a standard nitrite
solution and comparison of the intensity of the color produced in this solution with
aSutton: Volumetric Analysis, 9th ed., 1904, p. 449.
217
NTY
that produced in the water extract of the sample in question, all of which can
di.- pe used with when the purpose is merely to learn whether or not the flour is 1 .1
ami whether the bleaching is light, moderate, or excessive. Then- has also been a
demand not only for a simple and rapid method for detecting bleaching in the
laboratory, but also tor one which flour buyers, bakers, and consumers can carry out
without special training ami with simple apparatus.
The tests here described are, first, a simplification of the Griess-Ilosvay method and,
second, a confirmatory test based on the observations o£ Alway a and others that the
petroleum ether solution of unbleached flour is yellow, while that of bleached Hour,
if not excessively overbleached, is nearly colorless. The Griess-Ilosvay test is the
more reliable, but the gasoline test, which depends on an entirely different principle,
namely, the nature of the coloring matter of the fat, is useful for confirmation. A
description of the teet£ in popular language follows:
I ' METHOD.
Place a heaping teaspoonful (10 grains of the flour to be examined in a wide-
mouthed, glass-stoppered l-otince bottle. Nearly till with distilled water, or tap
water five from an appreciable amount of nitrites, and add a teaspoonful (-1 eo of the
t'-t ^olution prepared as .lirected In-low, measured with a glass spoon. Cork the
bottle and shake vigorously for a few minutes, then allow to settle for from fifteen to
twentv mil.
Under the above conditions bleached flour will impart to the liquid a color ranging
from a liirht pink to a deep red, depending on the degree of bleaching. With un
bleached Hour the liquid i- n»t colored a red tint, provided water free from nitrite* i-
used. Always run, for comparison, a parallel t«-t with a -ample of unbleached (lour,
so that allowance can be made for any nitrites in the water.
Test solution. — 1. Dissolve 0.5gram of sulphanilic acid in 150 cc of dilute acet i. :,cid
(about •_'(> percenJ . Keep u.-n t-ppered.
Dissolve 0.2 gram of alpha-naphthylamin bydrochktid in 20 cc of -iron- acetic
Doc of dilute acetic acid (20 per cent). Keep well stoppered.
I an«l _' for use. The mfxed reagent keeps for several weeks, and possibly
much longer.
II (.A HO LINK METHOD.
Place two heaping teaspoonfuk (20 grams) of the flour in a wi<ic-inoiithe<l, ^lass-
stoppcred i-on:. . add sufficient gasoline to nearly till the bottle, .-hake. ;m I
allou to -ettle If the flour is unbleached, the ura.-oline will become distinctly yellow;
if bleached, it will remain nearly colorless. «',,nduci a parallel test on unbleached
Hour for comparison.
A MODIFICATION OF THE BAMIHL TEST FOR DETECTING WHEAT
FLOUR IN RYE FLOUR.
\ I. \\INTON.
This test depends on the presence of gluten in wheat flour and its absence in con-
siderable amounts in rye and other flours. The original test, devised in 1852 by
Bamihl,b a Prussian customs official, consists in rubbing up a small amount of flour
with water on a microscopic slide by means of a cover glass and noting under the mi-
croscope whether or not gluten strings or rolls are formed. The objections to the test
in its original form are that the microscope reveals the presence of traces of gluten in
pure rye flour and under the microscope it is not possible to compare at a glance the
amount found in pure rye flour with that from a suspected sample.
The writer's modification of the test consists in employing a dilute solution of eosin
in place of water and dispensing with the microscope entirely. The gluten greedily
"braska Agr. Exp. Sta., Bui. 102.
& Poggendorff, Annalen Physik Chemie, 1852, 86; 161.
218
absorbs the dye, and on a white background becomes very conspicuous because of its
beautiful pink color. A description of the procedure follows:
Place side by side on a microscopic slide 1.5 mg of the flour and a drop of water
containing 0.2 gram of eosin in 1,000 cc. Allow the slide to rest on a sheet of white
paper and carefully mix the flour with the liquid by means of a cover glass, held
between the thumb and finger in such a manner that it is raised slightly above the
slide taking care that none of the flour escapes from beneath it. Finally, allow the
2 3
FIG. 6.— Bamihl gluten test (X4): 1, Pure rye flour showing only trace of gluten; 2, a mixture of 60
per cent rye and 40 per cent wheat; 3, pure wheat flour showing gluten masses.
cover glass to rest on the slide and rub it back and forth until the gluten, if present,
forms into rolls or masses. Conduct parallel tests for comparison on pure wheat and
pure rye flour. Proceeding in this manner, wheat flour yields an abundance of gluten,
which is stained a beautiful pink color by the eosin, whereas rye flour yields none, or
else only traces which are scarcely visible to the naked eye. Mixtures of rye and
wheat flour yield variable quantities of gluten, depending upon the proportion of the
two flours and their source.
In testing graham flour, buckwheat flour, and other cereal products containing
considerable quantities of bran tissues or coarse lumps of any kind, the flour should
be sifted through a bolting cloth before applying the test. The bolting is conveniently
219
carried 'tut by placing a small quantity of flour in a beaker, covering the top with the
bolting doth held in place by means nt' a rubber band, inverting and shaking. <>p.-i
aliiii; "ii tin- .-in f.l mati-cial. as little as •> per cent of wheat Hour in buckwheat flour
may be detected . In pure buckwheat flour 1 have n«-\ er obtained a visible amount
of gluten.
Figure <;, reproduced from photograph-; ma«le by Mr. 15. .) . Howard, Thief of the
Microchemical Laboratory, IJurcau of < hemistry, shows the gluten obtained by this
te-t in pure rye Hour, a mixture of »>() |>er cent rye flour and 40 per cent wheat flour,
and pure wheat Hour, iiiairniu'ed 1 diameters. As has been stated, in practical work
no nuiLMiilication whatever is necessary to bring «>"t the gluten strings or masses.
MOISTURE DETERMINATIONS WITHOUT THE AID OF HEAT.
p.y r. i' TI:I>\VIII{II><;K.
For more than a year at the Missouri experiment station the moisture determina-
tions on meats have been made without the aid of heat, by drying in vacuum OV6T
sulphuric acid. At tit>t the ordinary brass filter pump wa< u-ed for obtaining a
vacuum, aided by the u-e of about 10 cc of ether i Benedict method). A vacuum of
I or _' mm is ea.-ily obtained \\ith 'jood water pre.-sure. but in warm weather many of
the samples would show some putrefaction I n was complete enough
to cheek decomposition. It was n..ted that the water formed with the acid an upper
Mntod < ,,11-iderable heat when mixed by rotation. This suggi-ted
the frequent agitation of the sulphuric arid in the bottom of the desiccator-, with
the result that twel\e hour- \\as sullicient to dry fresh meat samples so that they
would not putrefy. Ha\ . :• -rabh- difficulty with the water pressure, a (Jer\ k
duplex vacuum pump was procured, and without tl iier a vacuum of less than
1 mm was secured in two .,r three minutes.
SubstanceseU' in and II\«T gavt much trouble by frothing out. of the mois-
ture i i usted, but the difficulty was ob\ iated by freezing
lhe.-e -ample- al'lel" |h--> U-!,- 'A . • IJ 1 1 . • I ^l!llllall\ . .M -\\.iter e\!ra,t- o| i.rel U elV
i and e\a|»orate<! to dry ness in the vacuum without e\er thawing, lea\ in-j tin-
dry substance as a web-like mass the full .-i/.e of the original : Tact.
The inoi-niM- ir.-e samples are UBt'd for d«- terminal ion of the ether-.-oluhle material.
:d, horn-like mass, BO that it is necessary to^rind
them and make a sen >i id extraction in onler to obtain all of the ether-soluble mat. rial.
In order to avoid this difficulty, the meat samples are mixed with ignited .-and. and
such good results are obtained that a desc -riptioii of the method may be of interest.
l-'..r the ni"i-Mire and fat tubes use either the S. & S n -hell- ,,r the glass
tubes w ith filter-paper bottom-. Fill the tube about one-third full of ignited
and then stuff in a liberal amount of fat free cotton. l>rv the tube- thus prepared i they
should be numbered) for several hours intheovenat L03°C., and place in a vacuum
ie\v hour- i'_'hiii_- U'l-i'/h ill a glass-stoppered \\ej./hin^ bottle and
.'lit of the tube and bottle o .n.-erut i \ el\ . This Uei-hilP_' is done in
advance of a ?-lau.i;hterin'.r experiment, and several hun<lred tubes are prepared.
IMace the finely Around and thon.u^hlv mixed samples of meats in wei'/hiii^ bottles
Erovidetl with ihorl aluminum scoops (a heavy piece of stirring ro«l will do , and weigh
y difference, usin-r fn-m ."> to 10 Drains for a sample. K»-ino\e the cotton from one of
the lan-d tabes, placing it mi the side of a flat inaUow p<»n-elain dish, and carefully
pour out the -and into the dish. Place the sample of the meat upon thesandand mix,
u-ini: a -patula and a stirring n»«l. When the sand and sample are thoroughly mixed,
tran.-fef the ma.-s to the tube, u-iiii: the <-otti>u to wipe all trace- from the dish, the
spatula, and the stirring r«id. Loss of any particles ..f sand is prevented by working
over black glazed paper. The last of the unused cotton is placed in the top Of the tube
as a plu'j.
Make the determinations in triplicate and place them in separate desiccators. (We
use a good U-inch vacuum desiccator. Larger desiccators were tried, but several of
them broke, owinir to the hiu'h pres.-ure. i Wire-gauze baskets are used, which set on
the porcelain desiccator plate. In this basket from eight to twelve tubes can be
placed. The desiccator coven and stopcocks must be well ground and a lubricant
220
used which will hold and yet permit the easy removal of the cover. A mixture of
3 parts paraffin (hard) and 5 parts vaselin is satisfactory. These are melted together
and then cooled slowly, with continual stirring. If the work is to be done during
continued cold weather a little more vaselin may be used, or in summer a little more
paraffin. The addition of rubber or Venice turpentine to the lubricant has been dis-
continued on account of the difficulty in removing the covers.
After the filled desiccators have been exhausted, rotate them carefully every three
or four hours to mix thoroughly the acid and the water which has been absorbed into
the upper portions. Care must be used not to spatter the acid upon the tubes. At
the end of twenty-four to forty-eight hours, a? is convenient, allow air to bubble slowly
through concentrated sulphuric acid into the desiccator and transfer the tubes to a
desiccator provided with fresh acid. Chemically pure sulphuric acid must be used,
as the commercial acid discolors the samples.
Exhaust the freshly filled desiccators and hold for another twenty-four to forty-eight
hours, as is convenient. During this interval mix the acid three or four times. Next
weigh the tubes and place them in a vacuum again for twelve hours or longer and
again weigh, to prove that the drying is complete. If any of the tubes do not show
constant weight they are placed in vacuum again with fresh acid. The acid employed
for the first drying 'is used for commercial acid; that with which the drying is com-
pleted is used as the first acid with fresh samples.
With blood the freshly drawn sample is rapidly poured into tared tubes filled with
fat-free cotton, each tube being placed in a tared weighing bottle. The tui>e and
stoppered bottle are weighed to get the weight of the sample, and the moisture is
obtained as with meat samples.
We have demonstrated that this method is capable of practical application to
agricultural analyses in general, and is especially to be recommended where a determi-
nation of the fat or ether-soluble constituents is to be made. The most marked
differences have been noted in fat determinations upon samples of fresh bone (skeleton
of beef). When heat has been used in drying the samples by the official method the
extracted fats are frequently very dark colored. By using the vacuum method with-
out heat the extracted fat is almost snow white. This method has been compared
with the regular official method upon numerous other samples, as butter, milk, soil,
feed stuffs, honey, soap, etc. A few results are given in the following tables illustrat-
ing several phases of the work.
Moisture determinations on various animal substances by vacuum method without heat.
Sample.
Results in triplicate.
Sample.
Results in triplicate.
(1)
(2)
(3)
(1)
(2)
(3)
Blood
Per cent.
79.23
82.29
68.77
68.82
Per cent.
79.25
82.73
68.74
68.82
Per cent.
79.55
82.83
68.96
68.41
Round lean
Kidney fat
Per cent.
72.67
5.52
8.95
12.51
Per cent.
73.22
5.51
8.74
12.29
Per cent.
72.61
5.42
8.34
12.43
Do
Liver
Do
Do
Offal fat
Moisture determinations on blood by vacuum method without heat.
[Using absorbent cotton and showing effect of second drying in the vacuum.]
Weight of
Loss in
Weight of
sample.
sample,
tube, and
weighing
First dry
weight.
Second dry
weight.
weight
second
time in
Total loss
in mois-
ture.
Moisture.
bottle.
vacuum.
Grams.
Grams.
Grams.
Grams.
Grams.
Grams.
Per cent.
a 4340
46.3238
41. 1025
41.0984
0.0041
5.2254
81.216
3.7002
43. 3378
40.3335
40.3324
.0011
3.0054 81.223
6.3934
44. 0746
38.8884
38.8860
.0024
5. 1886 81. 156
5.3474
44.5125
40.1695
40.1685
.0010
43440
81.236
i
±21
.tuition* nit n .vim/tie <>f linr, nirunni method nifhoitt mi.n'ny n ith sand,
shoving gradual loss of moist it/,
Grams. Gm. Gms. Cm.
Grams. Grams. Grams.
45,6373 40.7115 40.0977
45.4085 40.4024 40.3888
46.1368 40.5963 40.5435
Gm. Grams. Gm.
0.0138 40.687:
Gms.
4.8528 70. Jin
:.. i '•-':;:, 70.439
ro.2so
0m.
., 'Uls
7. 1317
8.0140
0138 40.38501
..'I.') .0240
4n.:.r.'l .009440.5070 O.OOol
<>f mnixtnn- <i> firm inntioiu made by '/a
the ojfirinl method.
method uith those made by
Sample.
By vacuum
method.
Hv official
method.
W heat stubble, air <!
Soil, air
( 'orn chop uir «lrv "
Percent.
i. M
j H
n .M
hi .!-»
• -..,
Per cent.
J in
i.« .->:
it n
.tj n
PttMt
., 971
i M
1.5 M
.U 11
s.. 71
PajrtfMf,
1948
I s:?
IJ vs
•M M
N.,. 7..
I'.lllt. !
I ll, •«••>.•
Milk*
a The corn chop was placed In vacuum a fourth time twfore it ceased to lose In weight.
'• The milk and butter were mixed with amnd and were dry by the vacuum method at the end of twelve
THE UNIFICATION OF SACCHARIMETRIC OBSERVATIONS.
By C. A. BROWNE.
In an article u{>on the Control of SacchariuM'trm by Otto Srliimrork." it is <lm\vn
that the differences in rotation for sugar solutions ili.sappear for clitf»-rvn
and dit'tVrrnt sources of whitr li-^ht only \vh«-n th«- li^'ht is lilt.-n-d thn.u-h ;i I .."• . m
of 6 percent potassium bichromate solution in water ( >n th< l..i-i- <>i ih.-.-
Schdnrock recommends that the use of this liirht tilt. -r be adopted in
tin- MX) point of tin- \Vntzke scale. This recommendation, which has l.ren
followed by the Iinpt-rial Il»-ii -hs Anstalt of German \ an«l th.- I S. Cureau of
Standard.-, s.-.-m-, h«i\\i-\.-r. i<»be more or lew disregarded by many < h«-nii~is who work
with -ac« -harim-
Tin- nifthods of the Association of utfirial Agricultural ( 'ht-mistM say nothing as to
tin- use of potassium liirhromate solution in sacchari meters, it heirrj deemed perhap-
a necessity too well known to require mention. \\ e know, however, of chemiHts
pun hasing sacchari meters and using them for years blL-vfully iirnorant of the presence
of the empty cell in the end of their instruments or of the purpose for which the cell
was intended to be used. Their mistake, which is due usually to inability to read
the German directions which accompany the instrument, in perhaps pardonable.
Leas pardonable is the attitude of tho><- < hemi-ts who, knowing of the cell and the
purposes of its u<e, yet wilfully neylect it. One very common and mont fallacious
argument advanced against using the cell is that standardi/ed quartz plates polarize
correctly without it and that its use is therefore wholly unnecessary. Another reason
uiven is that the bichromate renders the polari/ation of dark colored solutions so
difficult that it is more convenient to eliminate it altogether.
«Zts. Ver. d. Zuckerind., 41: 521-58.
222
The directions of instrument makers as to the use of bichromate and the strength of
solution to be employed are not at all explicit. One maker directs merely that the
bichromate cell must always be filled with bichromate solution, which, however, can
be more or less concentrated, according to the character of the liquid under examina-
tion.
The purpose of the bichromate solution insaccharimetric work is, of course, to correct
the difference in rotation dispersion between cane sugar and quartz. The rays of
light in the bljue and violet which cause the greatest Amount of rotation dispersion are
absorbed by the bichromate. To gain more exact information as to the effect of elim-
inating the bichromate solution in the polarization of raw sugars I have recently com-
pared the absorption spectra of bichromate solution with those of different clarified
sugar solutions. Molasses sugars when clarified give a brownish yellow liquid, which
absorbs practically all of the light in the blue and violet part of the spectrum. Solu-
tions of such sugars act themselves as light filters and absorb the rays producing the
greatest dispersion disturbances. They show upon polarization but little difference
between filtered and unfiltered light. Clarified solutions of several low-grade beet
sugars were found to absorb all of the violet but only a part of the blue. Slight rotation
dispersion was obtained without the bichromate cell. Ninety-six degree centrifugal
sugars give usually straw-colored solutions, which absorb most of the violet, but prac-
tically nothing of the blue. Rotation dispersion with these sugars is usually well
marked without bichromate. Java and other high-grade sugars give upon clarification
nearly colorless solutions which show very pronounced rotation dispersion without
the bichromate. With such sugars the difference in reading with and without bichro-
mate was in some cases nearly 0.2 per cent for the same observer.
The error due to rotation dispersion was found by Schonrock to be variable with dif-
ferent observers, a circumstance due perhaps to some physiological difference in the
pigment of the eye. Comparisons which I have made on five sugars polarizing over
96°, using no bichromate and 1 and 3 per cent solutions of bichromate in a 3 cm cell,
showed that the discrepancies in the readings of the same solution between four
observers were augmented six and one-half times, when no bichromate was used, as
compared with the 3 per cent bichromate, and two and one-half times when 1 per
cent bichromate was used, as compared with the 3 per cent. Using a 3 per cent solu-
tion of bichromate in a 3 cm cell the average difference between the readings of the
lowest of the four observers and the other three was only 0.03° V., using a 1 per cent
solution the average difference was 0.08° V., and using no bichromate 0.22° V. The
3 per cent bichromate in a 3 cm cell gives the same effect as the 6 per cent bichro-
mate in a 1.5 cm cell advocated by Schonrock. The use of bichromate of the above
concentrations according to the length of cell should therefore be prescribed and
rigidly adhered to in the polarization of sugars.
These concentrations apply, however, only to cane sugar. With substances of
greater rotation dispersion such as commercial glucose, dextrin, malt products, etc.,
it will be found necessary to increase the strength of the bichromate considerably, as
may be seen from the following:
Polarizations of starch conversion products with and without bichromate (°V.).
Starch conversion products.
No bi-
chro-
mate.
Strength of bichro-
mate, 3cm cell.
0.5 per
cent.
3 per
cent.
fi per
cent.
Dextrin...
253. P5
195.80
179.90
172. 10
253.50
195.50
179. 70
171. 85
253.40
195. 40
179. 70
171. 75
253.00
195. 15
179.55
171.55
Maltsirup
Glucose sirup...
Do ....
223
With starch conversion products it is possible to secure concordant readings between
different ohr-erver- only when (i per cent bichromate is used in a 3 cm cell. With
substances df higher <lispersii.ii than dextrin it would seem advisable tn use only
-odium light for polari/.ation. With all carbohydrate materials it would seem thai
the dispersion disturbances of white li-jht may In- eliminated by means of bichromate
solution. The results show, however, that the direct ions for operating saccharimeters
should specify the exact >ttvn<:th of bichromate solution to he used.
A second and very discordant element in the unification of saccharimetric observa-
tions is in the use of clarifying agents. The several errors resulting from the use of
lead salts in clarifying sugar solutions have long been recognized. There is, first, the
volume of precipitate error; second, the precipitation of levulose error; third, the forma-
tion of -oluble lead levulosate of lower specific rotation than levoluse; and, fourth,
\\hen dry defecation is used, the error of dilution or change in volume.
In .-fudyiiiir these various questions m\ attention was directed first of all to the
vrreat difference in composition of the • •, .minercial preparations of lead subacetale and
abo "l the solutions of this salt as ordinarily prepared for laboratory use. IVepara-
• -f the anhydrous subacetate of lead sold by reliable chemical firms, and all
iruaranteed as to purity according to the food and drugs act. were found to var\ in
their c'-ntent of ba-ic lead ox id : • - In lion- ..f lead subacetate
prepared by di <_:<•.- tini: litharge with the normal acetate of lead, according to the metho<l
of the association or other directions, will also vary greatly in composition, accord ini'
to the time and temperature ..f digestion. Solutions of the same specific ^raviiy thus
trad were found to \ary in the ratio of combined to basic PbOof from 5:2 to 1 : 1.
These \ariaiions in composition are not surprising when it is remembered that three
well-defined -ubacotatcfl have been prepared by the diu'i-.-tion of lithaire with normal
lead acetate. These are SPbvtf- I'M ), t he stihacetate ordinarily prescribed for clarifi-
cation; I'b.l'TbO, the monob.t .and I'b. lr_Tb< >, the diabasic acetate
The ottinal dil r preparing basic lead acetate are explicit .•- to i|,,. -p.-ejfie
V'ra\ ity of lea<l solutions to be used, but are nil. ..• point -t' -reaie-t importance,
the content of ba.-ic lead. The differences which may result in saccharimetric work
from the u.-e of lead -olution- of \ar ;t\ may be seen from the follow M:L; polar-
n- made upon a sirup and a sugar u.-ini: three different .-...luii-'iis of lead subace-
tate and "ne solution of the normal acetate all "i I _' \ specific LT:I\ ity.
li/rrrnt solution* of lend subacetate.
MulAriid
Quaiiliiy
V,n: d
U- (
1
,.,i nAMtta«
J.
rwMTBnt.
i,,.l It.-
5PbAc2PbO
3PbAc2PbO
PbArlM.n
Sirup.
^11 ' I!
«.
8
10
•v.
II. M
Sl V',
T.
I", -.1
v ,;n
•v.
r. ..„-,
v in
T.
».', .INI
82 50
The solutions of greatest basicity have the greatest clarifying power and give the
highest polarizations owing to the greater precipitation and lowering of polarization
of the levulose and consequent increase in dextro-rotation. The 3:2 subacetate is
the one usually prescribed, and since this compound can be obtained of satisfactory
purity from one chemical house at least it might be well for chemists desiring uniform-
ity to prepare these solutions directly from this salt. The important point, however,
i- that in \\hate\er way prepared the solutions of basic lead used in saccharimetry
should have not only a constant specific gravity, but a uniform content of basic lead.
The errors due to the volume of lead precipitate, a most serious one in the polariza-
tion of low-grade saccharine products, have been very largely eliminated by the ingen-
224
ious method of dry defecation proposed some years ago by W. D. Home. The ques-
tions of change in volume and precipitation of levulose, when the dry subacetate is used
in large amounts, as is always necessary with low-grade products, have given rise,
however, to some uncertainties, and the method has not met with universal approval.
To determine exactly the amount of error due to change in volume and precipitation
of levulose, mixtures of sucrose and invert sugar, with mineral and organic salts pre-
cipitable by lead, were prepared and the effects produced upon the polarization of
these solutions by different quantities of the dry acetate and dry subacetate of lead
noted. It was found that in quantities up to 0.5 gram but very little change could be
detected in the polarization of the original solution when either the dry acetate or
dry subacetate of lead was used. Using more than 0.5 gram of substance the dry
acetate invariably reduced the polarization owing to the increase in volume produced
by the dissolved salt; the effect of increased quantities of the dry subacetate, however,
was variable. Where but little invert sugar was present there was the same decrease
in polarization owing to increase in volume. Where considerable invert sugar was
present, however, this dilution error was counterbalanced, and often more than
counterbalanced, by the precipitation and lowering of the specific rotation of the
levulose and there was either no change in the reading of the original solution or an
increase. Used in very large excess beyond the precipitation of the levulose the dry
subacetate produced a continuous lowering of the polarization through dilution.
The same facts were noted in connection with the polarization of commercial sugars,
as may be seen from the following polarizations made in New York by M. H. Wiley:
Effect produced by different quantities of acetate and subacetate.
Sample.
Subacetate
solution.
Dry lead acetate.
Dry subacetate.
1 . Java sugar
cc.
1
3
1
4
°F.
98.10
88.95
90.75
86.15
Gram.
0.3
1.5
0.5
2.0
°F.
97.95
88.45
90.60
85.55
Gram.
2.0
3.0
2.0
4.0
°F.
97.65
88.15
90.40
85.30
Gram.
0.5
1.5
0.5
2.0
°F.
97.90
88.65
90.65
85.70
Gram.
2.0
3.0
2.0
4.0
°F.
97.75
88.65
90.55
85.70
2. Philippine mats
3. Cuba molasses
4. Do
The dry normal acetate by the addition of excess produced dilution in every instance
as is seen by the diminished polarization. This same dilution is noticed by the dry
subacetate, but to a much less extent on samples 1 and 3; on samples 2 and 4 doubling
the quantity of dry lead subacetate caused no change in the polarization through the
compensating effect of the levulose precipitation. It is needless to add that the
double quantity of lead used was beyond that necessary to secure clarification, so
that an idea may thus be formed of the probable errors due to excess.
In some interesting clarification experiments by J. A. Hall in the New York Sugar
Trade Laboratory the effect of adding varying amounts of dry lead subacetate was
studied in another way. Starting with a minimum quantity of the salt, this amount
was increased and the effect upon the polarization and the amount of lead dissolved
in the clarified filtrate noted. By calculating the dissolved lead to the subacetate
it is possible to estimate the dilution, allowing 0.22 cc increase of volume to 1 gram of
subacetate as determined by Home. Only one experiment upon a No. 2 Philippine
mat sugar is cited:
225
>inl 1-inn/Hirison of effects of varying ijimntitim <>f rltirifi/im/ <i<jmtx on dilution and
polarization.
Clarifying agent.
In 100 cc filtrate.
Estimated
dilution.
Polarization.
PbO.
I'l.sul-
;u-,'tat(>.
SubacetatP uvy
.TO
Grams.
0.2678
Trace.
.1530
.7203
•_'. H»7S
Gram.
cc.
•r.
86.70
Too dark to read.
86.50
86.60
86.50
Dry subac6tat6 (grams)
Trace.
0.05
0.20
0.60
Do
..1.0
(0.20)
(a 94)
(2.73)
Do
2.0
Do
4.0
a Sp. gr. 1.259.
It will he noted that with an estimated dilution of 0.2 cc instead of a decrease in
polarization as would be expected there is an increase. With an estimated dilution of
0.6 cc the reading is the same as that first obtained, so that the combined effect of the
dry lead upon the precipitation of levuloe*«» and upon the lowering of the rotation of
fhe lex iil-ise in solution is seen to be most pronounced. It will be noted that when
an excess of dry lead is added not til i this passes into solution. Adding 1 gram excess
caii-cd an increase in the filtrate of only 0.74 gram, and _' Lrram< an increase of only
1.8 grams. After the -olution is sufficiently clarilied for reading addition of more
I'-ad will continue to form a precipitate, so that the rule of adding lead until no more
precipitate forn. d ways a safe one to follow. An interesting fact mthi-. .M
nection i- that the addition of much lead subacetate beyond the point of maximum
darificat ion for low-grade cane products will produce a darkening of the solution.
Thi- is due to the well-known color reaction between reducing .-u-ar- and alkalies.
If the minimum amount of dry lead subacetate necessary to secure satMa< t<>i\
clarification l>e carefully determined for each grade of commercial product and excess
•id this lie avoided there is no <|iieMion but what this method «,f clarification
polan . r to the true polarization than any other method thii- far
pp.po-.-d The DM Q! dr\ I.-.M! -uha« •••tat«- and -uhar.-tate >oluli»n a> d«-fecat im;
agents in the determination of reducing sugars should of course be avoided.
A third and one of the greatest causes of the hick of agreement in saccharimetrie
observations between different chemists is variation in temperature. As regards the
effect of temperature U|N>H the polarization of pure sucrose nearly all chemi-t.- an- in
• •lose agreement. l-'..r (juart /.-wedge sacrhari meters the research i-s of Andr.-\\>.
Wiley. Schonrock, Watts and Tempany, and other chemists show that for each degree
Centiirrade increase in temperature there is a falling off in the polarization of pure
sucrose of about 0.031° Ventzke. The question now arises, with this variation in the
specific rotation of sucrose with temperature, what correction, if any, should be applied
to the polarization of commercial products.
In my report as associate referee on sugar, made to the association" in 1905, it was
shown that the applieation of temperature corrections to low grade cane sugars was
not advisable, for the reason that the polarization of a sugar is an expression not
merely of the ncroM alone hut of all the optical constituents present and since some of
these optical constituents, more especially the levulose, are affected by temperature
in a manner contrary to sucrose, it is not permissible to make a temperature correction
for one constituent without at the same time correcting for the others.
This view of the question has been recently contested by Dr. Francis Watts, govern-
ment chemist, and Mr. H. A. Tempany, assistant government chemist, for the Leeward
Islands of the British West Indies, in a recent number of the West Indian Bulletin. &
«U. S. Dept. of Agr., Bureau of Chemistry, Bui. 99, p. L'<).
73673— Bull. 122—00 15
61908, 9: 127.
226
They advocate for the purpose of securing greater uniformity and exactness among
analysts the application to all polarizations of a correction formula " JV + 0.00031 tN,
where N is the observed reading on the Ventzke scale and t is the difference
between the temperature of observation and that at which the polarimeter was stand-
ardized." In answer to my criticisms of such a correction when applied to raw cane
sugars Messrs. Watts and Tempany reply as follows:
While not disputing the accuracy of the statement concerning the effect of tempera-
ture on levulose, we would point out that the process of determining the polariscopic
test of a sugar js purely arbitrary and conventional. We take it that the polariscopic
test of any sample of sugar is the rotation produced t>y it when tested in such a way
that a sample of chemically pure sucrose tested under precisely similar conditions would
give a reading of 100°. The 100 point of the Ventzke, or any other sugar scale, is based
on the rotation of a standard weight of sucrose, dissolved in a standard volume of water,
at a standard temperature. If at any oth-T temperature this weight of pure sucrose
will not give a rotation of 100° on the scale, the scale has been altered; consequently,
allowance must be made for this alteration in the scale when polarizing commercial
sugars under these conditions.
The above criticism of my previous article is, however, not a valid one. We could
say with equal justice: Consequently, allowance must be made for this alteration in the
scale when polarizing molasses or honey or condensed milk or glucose or any other sub-
stance which is polarized upon a saccharimeter. The only scientific conclusion which
could be drawn is — allowance must therefore be made for this alteration in the scale
when polarizing pure sucrose; to include commercial sugars and other substances is
too sweeping and unwarranted a generalization. It is true that the 100 point of the
sugar scale of a saccharimeter is based upon the rotation of a standard weight of c. p.
sucrose under certain standard conditions; this sucrose, however, is a means of stand-
ardization and nothing more. A definite weight of milk sugar can be made to read
100 upon any saccharimeter and this weight is used for the estimation of milk sugar in
milk products. To apply a correction formula for sucrose in such cases would of course
be an absurdity.
Quartz may also be used for standardization, and is so used, the 100 point of the
French sugar scale being based upon the rotation of a plate of quartz 1 mm thick. It
might be said, following the same line of argument as that of Messrs. Watts and Tem-
pany, that because a standard plate of quartz always polarizes 100° irrespective of
temperature upon a quartz-wedge saccharimeter, the scale has not been altered and
consequently no allowance at all should be taken of temperature in the work of polari-
zation, a conclusion of course perfectly true as regards quartz but not of other sub-
stances. Similarly the conclusions worked out for chemically pure sucrose -for a given
type of saccharimeter are true for chemically pure sucrose but for nothing else, neither
for mixtures of sucrose with other substances nor for products which contain no sucrose.
The International Commission for Uniform Method of Sugar Analysis in 1900 decided
that it was permissible, as in tropical countries, to adjust saccharimeters to a higher
standard temperature than 20° C. This adjustment may be made by changing the
quartz wedges of the instrument, by increasing the normal weight of sugar, by increas-
ing the length of the observation tube, or in other ways. When only local comparisons
are involved it is advisable and advantageous to make such an adjustment; there is
a serious objection, however, against having several separate standards for universal
work, since comparisons are no longer possible upon a large class of low-grade sac-
charine products. Two saccharimeters, for example, one standardized for the rotation
of sucrose at 20° and one standardized for the rotation of sucrose at 30°, will give, of
course, identical results for pure sucrose, but not for a raw cane sugar, nor for a cane
molasses, nor for a large class of other products. Having adjusted our saccharimeter
to any desired standard temperature, this standard temperature must be rigidly
adhered to if identical observations are to be always obtained between different
227
The true polarization then of a raw sugar, a.- «>f other saccharine producis, is a con-
ventional arbitrary figure represent!!!'.: tin- sum of the polarizations of the various
optical constituents u in It-r certain fixed conditions of temperature.^ -eight of substance,
volume of solution, length of tulx-, and quality of liurht. If the temperature of polar-
i/.ation of a u'iven sii'jar is different from the standard the correction, if correctly
applied, must restore the reading obtained upon this same simar under standard con-
dition-. Now. the correction advocated by \\'atts and Tempany and that used by the
I'nii.-d Staie^ Treasury Department in the Division of Customs will do this for pure
M, hut it will not do it for a very large class of raw cane sugars for the reasons
already iriven.
Since the publication «>f my previous paper upon this subject I have had occasion to
study the effect ,,f temperature upon the polarization of many sugars and other cane
product- and have been more thoroughly convinced than ever of the futility of apply-
• •ctioii for the purpose of securing greater concordance in the sacchari-
metric observations .,f different ch.-n
The '.'eneral results of this work I have condensed into tabular form, showing the
I'olari/at ion and of reducini; sugars for raw cane sugars, and for -e \eral
• >f ni.i~-.-ciiit.-s and molannnn with the corrections necessary to obtain the polari-
x.ation at standard temperature. The theoretical sucrose corrections according to the
formula of Watt- and Tciiipany are apjM-nded for purjH>se of comparison The values
of the table have been made up fn>m averaged, aome variation was obtained for indi
vidual ola-.-e. of raw Hgpl :iple. those of I.oiii-iana which are \er\ hi-h
in rediK n louer c.-rn-ct imi. It i.- bclie\ed,
however, that i: D the whole, i- a fair a \erage.
TuMi jo,- correcting polfriuiwtu ndard temperature.
[Cornvtlon for «nu-h T. :I)M>VI> standard temperatur.-.]
-,, 0
n •»,
M •
ta tora
u,, ,,;
sa
,s ...
• n
Prr crnt.
I lit I. 141
I •-. | _1(
I .1. ; m
i ... .; *n
1 si. I.NI
\ -> I 10
'• .!•
I .11 7 >••
7.00 7.80
7 M> > .4,
x n i .,
•r.
> 0.024
4-aou
. -. a t
. I. l.n
. II ,.,..
n in.;
.1 1.17
-0.011
0 ni»
MAS8ECUITK.
A 00-10. 00 I -0.016
U in 14.00 n n.;,,
[.,.(»> is ... o 0§7
;» .ai
Ifl .11
Is ,,, .1, i,,
.•s i,, n ,,1
-0.070
u ,r.x
n 11.,
•r.
. n n.;.»
. u Q90
. .. m
MI on
. n tat
. n irj:,
• n ir.'l
• n n.-:(
+ O.M2
.1, m
+ 0.014
.u mo
• o 0.17
. n .«..
It will be noted that for very high-grade sugars which polarize over 96 an addition
of about 0.03° V. for each ° C. increase in temperature will practically restore the
reading obtained under standard conditions. The percentage of impurities is too
small to affect appreciably the temperature correction for sucrose. As the polarization
falls below 96 and the percentage of reducing sugars increases, the effect of the tempera-
228
ture upon the rotation of the levulose begins to lower the theoretical sucrose correc-
tion, until at a point usually about 80 to 86 the two influences — that of the tempera-
ture upon the levulose and other impurities and that of the temperature upon the
sucrose and quartz wedges of the instrument — counterbalance one another. Two
chemists polarizing such a sugar, one working at 30° C. and one working at 20° C.,
other conditions being equal, will obtain concordant and correct readings; the appli-
cation of the theoretical sucrose correction would place the observation of the chemist
working at 3Q° C., 0.25° V. too high.
Below 80 the effect of increase in temperature is usually to elevate rather than
diminish the reading, this influence becoming more and more pronounced in the
massecuites and molasses; the levulose correction more than counterbalances the
theoretical one due to sucrose. Every chemist knows how pronounced this influence
is on the polarization of sirups and molasses, how the simple handling of the observa-
tion tubes will increase the readings. It is the same with low-grade sugars which
consist simply of sucrose crystals contaminated with varying amounts of molasses.
When such sugars are polarized above 20° C. a correction would have to be subtracted
to secure the reading that would be obtained under standard conditions. To add a
correction, as required by a sucrose correction formula, would manifestly only further
increase the error of observation.
The solution of the temperature question then resolves itself simply into this: If
we are to make temperature corrections in the polarizations of commercial products,
we must correct for variations in the specific rotation of all the ingredients therein
present. If it is impossible to do this, no temperature corrections at all should be
applied; instead of this we should strive to make our polarizations as nearly as possible
under standard conditions. Custom-house laboratories, arbitration laboratories, and
all other laboratories, upon the results of which great interests are involved, should be
equipped with cooling and warming apparatus for maintaining a constant uniform
standard temperature. The great testing laboratories of Germany are so provided
and similar institutions in this country should do as much. For chemists who are
unable to provide themselves with this equipment much can be done by moving
the laboratory to cooler quarters, as from a hot upper room to a cool basement. By
such a change the New York Sugar Trade Laboratory has lowered the temperature
of testing from 25° C. to 21.5° C. in hot weather.
The services rendered to science by the researches of the many chemists who have
investigated the influence of temperature upon the specific rotation of sucrose are
great; the results of their labors are lasting and will stand the test of time. The appli-
cation, however, of what they have established for pure sucrose to the polarization
of all grades of saccharine products is a misapplication. It is a great mistake. It
will increase rather than diminish the errors between many of the sacchari metric
observations of different analysts and is bound to work great injustice when applied
commercially.
A paper on the influence of glycerin, acetanilid, and certain other
drugs in the estimation of alcohol by L. E. Warren and H. C. Fuller
of the Division of Drugs, Bureau of Chemistry, was presented by
Mr. Warren. This work, bearing especially upon the drug investiga-
tions, has been printed elsewhere for greater accessibility.0
The associate referee presented a lengthy paper by S. H. Baer on
the colorimetric method for the determination of citral, dealing
largely with the chemistry of that substance. The portions on
criticisms of the method are reported in abstract.
oAmer. J. Pharm., 1909, 81: 66.
229
CITRAL AND ITS ANALYSIS IN TERPENELESS EXTRACT OF
• LEMON.
By SAMUEL H. BAER.
The analyses were made by three chemists, including the writer, and as all three
judged the colon, it would seem that the analyses are as accurate as the colorimetric
method permits. Acknowledgment is due S. E. Shaffner for assistance rendered.
I>> termination of citral in lemon c.rtnu-1 hi/ the rnlnri metric method.
Sample
No.
Description.
Cltral.
mated
amount
present.
Amount
found.
H)
11
12
13
14
15
16
17
18
Terpeneless oil of lemon solution (dissolved in cologne spirits, 190 proof, or
95 per rent, and colored with loinun t«-H
Prr cent.
a 42
a
u
. !_•
Per cent.
0.19
.18
.10
.40
.10
.19
.07
.08
Terpeneless oil of lemon solution (dissolved in cologne spirits. 190 proof, or
95 per cent and colored with turmeric)
Terpeneless oil of lemon solution (dissolved in 38 per cent cologne spirits
and city water and filtered through magnesia)
Cltral solution (dissolved in cologne spirits of 190 proof, or 95 per cent)
MI.IS oil of lemon, 19 gallons cologne spirits. 33 gallons water (col-
ored with lemon peel and filtered through magnesia)
\i< nil > proof, generally used t>y manufacturers) .
1*1 spirits, 190 proof
50 per cent cologne spirits with citv water
50 per cent cologne spirits filtered through magnesia
m these analyses it is seen that \\li.-u the colorimetric method is applied t<> the
< ts of commerce, the correct result i- n»t trained. On sample N . I :;. a . -nr.il
solution, the analysis was reasonably close; samples No. 10 and 1 1 ate ter[>en<>lc*4 oils
of lemon and the low results on citral may be due to the fact that the sample pun 1
was not pure terpeneless oil of lemon, hut a product containing only 50 per cent <>i
the citral that should be tl
Most iif the extraet manufacturers use 188 proof alcohol, that is, 94 per cent alcohol,
which always contains a certain amount of aldehydes, and the sample used in this
test, treating the alcohol the same a* the lemon extract, showed 0.1!» per rent of < itral,
when there was no citral there at all. If only cologne spirits are used, the results
obtained are not so far wrong as if 94 per cent alcohol is used.
Since, then-tore, the presence of the impurities in alcohol throw the results off to
such an extent. _ri\ ing too high a per cent of citral, would it not be possible that the
impurities in tin- alcohol at certain times and also in the water, and the very change
of one or two ingredients in the lemon oil, might make the result inaccurate, rev*
the analysis and showing a smaller per cent of (itral than is really present?
The colorimetric method is applicable if the manufacturer used chemically pure
citral, distilled water, and aldehyde-free alcohol in the manufacture of his extracts,
l>ut such ideal conditions never exist. Further, any manufacturer could discreetly
add another aldehyde, even acetaldehyde, to the extent of 0.2 per cent, which would
give all the reactions of citral in the extract of lemon by the colorimetric method.
The method is not without use, but if the presence of citral could be determined
and estimated quantitatively by a sodium sulphite or carbazone method, then the
colorimetric method might be used as a check. Before adopting the colorimetric
method as official a committee should be appointed from the association members to
test it carefully, under the conditions that the manufacturer must meet since he can
not use aldehyde-free alcohol, nor is he always in a position to use distilled water.
230
Further, suppose the method is accurate, how would the analyses show that the citral
used was obtained from lemon oil or the commercial citral obtained from lemon grass
oil?
AN OUTLINE TO ASSIST IN THE IDENTIFICATION OF CERTAIN
WATER-SOLUBLE COAL-TAR COLORS.
By C. B. COCHRAN*.
The reactions given by the coal-tar colors listed in the following outline were all
obtained with solutions as dilute as they could be made and still give reactions suffi-
ciently clear and definite to furnish a ba^is for positive contusions. Because of the
degree of dilution the results here tabulated will, in some cases, appear contradictory
to those given by Schultz and Julius. For example, these authors may report a color
precipitated by a certain reagent when the precipitation is only partial and therefore
does not appear in dilute solutions such as have been used in the preparation of these
tables.
The sodium bisulphite reagent is prepared by saturating a 5 per cent solution of
sodium hy droxid with sulphur dioxid . The absorption tests with aluminum hydroxid
were made by adding between 2 and 3 cc of well-washed aluminum hydroxid (from
which the excess of water has been drained through the filter) to 10 cc of the color
solution.
The tests with the fuller's earth were made by adding 2 cc of the earth to 10 cc of
the color solution. In these absorption tests the aluminum hydroxid and fuller's
earth are shaken with the color solution. If, after setting, the supernatant liquid is
colorless or very nearly so, the result is recorded as color absorbed. In the majority
of cases the results obtained with aluminum hydroxid and fuller's earth are definite
and sharp. There are many colors belonging to Class I (Rota's classification) which
are much more readily absorbed from their water solutions by aluminum hydroxid
than by fuller's earth, while the reverse is true of many colors belonging to Classes
II, III, and IV.
In the dyeing tests sodium carbonate was used for making alkaline and hydrochloric
acid for acidifying. The alkali solution was very weak and the acid bath about one-
half the official strength (1 cc strong hydrochloric acid to 50 cc).
The numbers following the names of the colors refer to the 1904 edition of Green's
tables.
COAL-TAR COLORS OF CLASS I.
Solution reduced and in most cases decolorized by ptannous chlorid. Original
color not restored by hydrogen dioxid.
DIVISION I.— COLOR ABSORBED BY ALUMINUM HYDROXID.
Dye wool red.
SECTION I. — Color precipitated by sodium bisulphite reagent.
Congo red (A) (240) dyes wool and unmordanted cotton red from neutral or faintly
alkaline bath, but not from acid bath. Oxalic acid or acetic acid gives a blue precipi-
tate and colorless filtrate.
SECTION II. — Color not precipitated nor solution changed by sodium bisulphite
reagent.
Fast red A (102), hydrochloric acid gives a brown precipitate and colorless filtrate.
Dyes wool and unmordanted cotton red from acid, alkaline, or neutral bath. Color
precipitated by barium chlorid solution.
231
Azo rubin S (103), color only partially precipitated by hydrocholoric acid. Dyes
wool red from acid hath luit not from alkaline bath. Does not readily dye unmor-
danted cotton in either hath. Color not precipitated by barium chlorid.
Dyes wool yclloir.
Chrysamin R (269), hydrochloric acid gives a brown precipitate, sodium hydroxid
a red solution. Barium chlorid and .-odium bisulphite reagent each uri\es a yellow
precipitate and colorlrs< filtrate. Dyes wool pale yellow from a neutral bath and
unmordanted cotton orange yellow from a neutral or alkaline bath.
nool and unmordanted cotton brownjrom <i<'i<l bath.
Bismarck brown IT, . decolori/.ed by stannous chlorid and on adding hydrogen
dioxid a color somewhat redder than the original color appears. Color precipitated
by tannin rea-ent. Color absorbed from alkaline solution by ether, and on adding
dilute acetic acid to th«- ether solution, the color is taken up by the acid.
Kc.-orrin brown l:',7 . decolori/ed by stannous chlorid. No color returns on add-
ing hydrogen dioxid. No? precipitated by tannin rrau'rnt. Color absorbed by
fuller's earth.
M OOi : r\Kii\i.M tMOmmi in AiiMiNUlf
HVDHOXID.
Dye ' bath.
SECTION I. — Sodium hydroxid causes a distinct .han-c in color of water solution.
>dium hydroxid tun -Union violi-t.
Ponceau i>»-d W.K.I is blui-h rtxl, turned blue by hydrochloric acid or
sulphuric a<id. color in wo<,l ,: lution. Hydro-
chloric acid turns water solution \iol.-i. more turns it blur.
(2) Sodium hydroxid turns water solution brown.
P.rilliant rrorein lit, . hydrochloric acid produces little change in color of water
solution
Crystal ponceau (A) ((H>, d\.-,| wool turned violet by hydnx-hlorir arid and blue
;lphuric arid.
• •in -<arlct .; l: \ HI: . . 1 . , d wtM.l turned red \ iolet by hydrochloric acid or by
sulphuric acid.
V) (106), color of dyed wool not changed by hydrochloric acid.
dium hydroxid turns watrr solution yellow.
Palatin scarlet (53), dyed I !<>r not much changed by hydro-
chloric acid, but sulphuric acid turns it violet and u'ivrs a violet eolation. < )n <lilution
wool has nearly original «
DON II. — Sodium hydroxid does not cause a distinct change in the color of the
water solution.
Group I. — Sulphuric acid turns dyed wool blue or violet and gives a blue or violet
solution. Dyed wool is bluish red.
Bordeaux B (A) (65), hydrochloric acid turns dyed wool violet.
x S (A) (107), scarlet B K K . P) closely related to Bordeaux S.
Group II. — Sulphuric acid has little or no effect on color of dyed wool. Dyed wool
is scarlet.
Ponceau G (A) (55), barium chlorid gives an orange red precipitate, wool dyed
orange red.
Ponceau 3 R (A) (56), barium chlorid gives a red precipitate. Dyes wool more red
than (55).
232
Dye wool yellow or orange.
SECTION I. — Hydrochloric acid added to strong acidification precipitates the color
or decolorizes the solution (the nitro colors).
Group I. — Color extracted by ether from solution acidified with hydrochloric acid.
Victoria yellow (2).
Martius yellow (3), water solution plus potassium cyanid gives a brown color on
warming.
Group 11. — Color not extracted by ether from solution acidified with hydrochloric
acid.
Naphthol yellow S (4).
SECTION II. — Hydrochloric acid causes a decided change in the color of the water
solution (many of the tropceolins).
Group I. — Hydrochloric acid turns dyed wool violet.
Dyed wool is yellow.
Brilliant yellow S (Sch.) (89), dyed wool is yellow turned violet by hydrochloric
acid.
Metanil yellow (Sch.) (95), dyed wool is orange yellow turned violet by hydro-
chloric acid.
Group II. — Hydrochloric acid turns dyed wool brown.
Chrysoidin R (18). This color is absorbed by fuller's earth and partially absorbed
by aluminum hydroxid.
Group III. — Hydrochloric acid turns dyed wool red.
Fast yellow (8).
SECTION III. — Color of water solution not decidedly changed by hydrochloric acid.
(If a precipitate appears only a part of the color is precipitated.)
Dyed wool is yellow.
Naphthol yellow S (4), dyed wool is decolorized b'y hydrochloric acid.
Tartrazm (94), color of dyed wool not changed by hydrochloric acid.
Dyed wool is yellow orange to orange.
Tropoaolin 0 (84).
Tropceolin 000 (85).
Orange G (14).
Dyed wool is red orange.
Mandarin G (86), dyed wool is turned red violet by hydrochloric acid or sulphuric
acid.
Ponceau 4 G. B., color of dyed wool not changed by hydrochloric acid nor by sul-
phuric acid.
COLORS OP CLASS II.
Solution decolorized by stannous chlorid, original color returns on addition of
hydrogen dioxid. (Bismarck brown, which might be referred to this class, is included
under Class I.)
(1) Dyes wool and cotton bluish red (most readily from an alkaline bath).
Safranin (584), much hydrochloric acid turns water solution blue violet. Color
absorbed by fuller's earth, precipitated by tannin reagent. Sulphuric acid turns
dyed wool green, solution green, hydrochloric acid blue.
(2) Dyes wool blue from alkaline or neutral bath, cotton a paler blue from neutral
bath.
Methylene blue (650), color absorbed by fuller's earth precipitated by tannin;
hydrochloric acid turns dyed wool robin 's-egg blue, sulphuric acid green.
COLORS OP CLASS III.
Stannous chlorid produces no further effect on the color than hydrochloric acid.
Sodium hydroxid produces a precipitate or decolorizes the solution. All the colors
given in this class except auramin (425) are decolorized by sodium bisulphite reagent.
233
The color reappears on heating and disappears on cooling. With the exception of
acid magenta (A) (462) they are all absorbed by fuller's earth.
I hi, iion/ ml.
(1) Dye wool from acid bath only, do not dye unmordanted cotton in either bath.
Acid magenta (462), color absorbed by aluminum hydroxid. Dyed wool is decol-
orized by hydrochloric acid, sulphuric acid, sodium hydroxid, or ammonium hydroxid.
Tannin reagent gives no precipitate.
(2) Dyes wool and also unmordanted cotton most readily from a neutral bath.
Fuchsin (448), color not absorbed by aluminum hydroxid. Dyed wool turned red
brown by hydrochloric acid or sulphuric acid. Tannin reagent gives a precipitate.
. I>ves wool yellow from neutral or alkaline bath. Does not dye unmordanted cot-
ten. Auranin (425).
Dye wool green.
Dye from acid bath: Guinea green B (A) (433) and acid green (434) do not dye rot ton.
Dye from neutral or alkaline bath : Kthyl green (428) dyes unmordanted cotton
more readily than mahn-hite green.
Malachite green (427 >. dyed \v..,,l i> blue urrv«-n. turned at tirst <_:ra>< «rern by hydr..-
chlorir ai id <>r -ulphuric acid, then \ellow; mi dilution, blue
I>ye wool violet from neutral or alkaline bath.
Methyl v j..let (451), sodium hydroxid gives a brown precipitate and brown solution
Ethyl violet (453), sodium hydroxid gives a white precipitate, < •••lories.-* on warming
Either dyee unmordanted cotton ir-.m alkaline bath
Dye* wool blue from acid bath.
China blue (480), color absorbed by aluminum hydroxid Solution decolori/.-d
by sodium bisulphite reagent. Color does not readily return on heating, but d»«-
return on adding a drop of hydrochloric acid. Dyed wool de< ••>!.. ri/.-d by ammonium
hydr<>\id, turned reddish brown by sulphuric acid.
COLORS or CLASS IV.
Colors not reduced by stannous chlorid. Solution not de.-.-|,,n/e.| and . ..|..r not
completely precipitated by sodium hydr
Dye wool red from neutral bath .
Dyed wool is red orange to orange red :
Eosin (512), color not absorbed by fuller's earth nor by aluminum hydroxid. \Vat«-r
solution yellow to omnge with green fluoren em •»• Ihdr.M h|,,rir ;,<-jd ,,r sodium
bisulphite reagent gives an orange precipitate.
Dye wool bluish red from neutral bath:
(a) Color completely absorbed by fuller's earth. Sodium bisulphite reagent gives
no precipitate, but causes only a loss of fluorescence.
Rhodamin G (502), water solution red violet with red fluorescence.
Rhodamin B (504), water solution bluish red with orange brown fluorescence.
(6) Color only partially absorbed by fuller's earth. Sodium bisulphite reagent
precipitates the color.
Krythrosin (516), water solution cherry red. (Green's tables give no fluorescence.
A sample marked "Qrubler" gave green fluorescence.) Hydrochloric acid gives an
orange brown precipitate. Sodium bisulphite reagent gives an orange-red precipitate.
Rose bengal (520), water solution cherry red. No fluorescence. Hydrochloric
acid gives a brown-red precipitate. Sodium bisulphite reagent a pink precipitate.
Phloxin (521), water solution bluish red with green fluorescence. Hydrochloric
acid gives an orange precipitate. Sodium bisulphite a pink precipitate.
OFFICERS, REFEREES, AND COMMITTEES OF THE ASSOCIATION
OF OFFICIAL AGRICULTURAL CHEMISTS FOR THE YEAR 1908-9.
President.
W. D. BIGELOW, Washington, D. C.
Vice-presiden t .
W. A. WITHERS, Raleigh, N. C.
Secretary.
H. W. WILEY, Washington, D. C.
Additional members of the executive committee.
E. F. LADD, Fargo, N. Dak.
E. B. HOLLAND, Amherst, Maas.
Referees.
Phosphoric add: W. F. Hand, Agricultural College, Miss.
Nitrogen:
Determination of nitrogen: C. H. Jones, Burlington, Vt.
Separation of nitrogenous bodies: P. F. Trowbridge, Columbia, Mo. (meat pro-
teids).
Potash: B. B. Ross, Auburn, Ala.
Soils: S. D. Averitt, Lexington, Ky.
Dairy products: J. M. Bartlett, Orono, Me.
Foods and feeding stuffs: J. P. Street, New Haven, Conn.
Food adulteration: H. E. Barnard, Indianapolis, Ind.
Sugar: A. H. Bryan, Washington, D. C.
Tannin: F. P. Veitch, Washington, D. C.
Insecticides: C. C. McDonnell, Washington, D. C.
Inorganic plant constituents: F. WT. Robison, Lansing, Mich.
Medicinal plants and drugs: L. F. Kebler, Washington, D. C.
Water: J. K. Haywood, Washington, D. C.
Associate referees.
Phosphoric acid: H. D. Haskins, Amherst, Mass.
Nitrogen:
Determination of nitrogen: J. W. Kellogg, Harrisburg, Pa.
Separation of nitrogenous bodies:
Milk and cheese: G. E. Patrick, Washington, D. C.
Vegetable proteids: R. Harcourt, Guelph, Canada.
Potash:
E. L. Baker, Geneva, N. Y.
Jas. A. Bizzell, Ithaca, N. Y. (special associate referee on available potash).
(234)
238
ils: J. <i. I.ipman, New Brunswick, X. J.
jirnt/urts: I.. (J. Michael. Ames, Iowa.
Foods tiiulj'ft iliinj sin/*: V. \\ . Morse, Durham. X. II.
Food adu Item t io ns:
Color.-: II M. Loomis, Seattle, Wash.
Saccharine products: Chas. D. Howard, Concord, N. II.
Fruit products: C. B. Cochran, Westche>t. r. I 'a
Wine: Julius Ilortvet, St. Paul, Minn.
I'.- -I II. E. Barnard, Indianapolis, I ml.
Distilled liquors: I.. M. Tolman, Washington. I> «
Vim-ar: K. \V. Balcom. Xe\v V,.rk. X V
Flax orinur extracts: F. M. Chare. Washington, D. C.
Spices: A. F. Seeker. Xe\v York. X. V
Baking powders and baking chemicals Kdmuml C. Clark. Boston. Ma —
Meat and Mi I c. Weber, Washington, D. C.
Fats and oils: T. J. Bryan, Chicago, 111
Dairy products: Hermann C, I- ythgoe, Boston, Ma-
il products F I Lftdd, \_-ricultural «'"!!•••• \ I»ak.
Vegetal. i«- \v i Dubofe, r.un'ai •. \ ^
Condiments other than spicen: II I. l>i-h<>p, Indianapolis, hid.
Cocoa and cocoa products: A (J. \V oilman, Bowton, M«M.
Tea and coffee A <• \\ »><liuan, Boston, Mass.
Pre*. I' II. hunhar. \\a.-hin-i..n. I
••riniiiatii.ii of water in fo<>d-: I' I . TV .\\!.n.L" . « olumliia, M,,.
Molaaees methods: II. P. Agee, New Orleans
( h.-inical meth.-d- A II l'.r\.m.
I Sainmet, \\ a.-hin-t'-n. h •
II ,. .• : K \\.itkin-, \\a-liiri'_'fon. D. C.
:nii- i>lnnt rnns' 0. M. fi 1. I .'• \ iiiirt '-n.
' II I .. Wall. Philadelphia, Pa.
Medicinal plant* ,, ,, , A y rk
Water. \\ . \\ . Skinner, \\a~hin-t-n. h '
SPECIAL COMMITTKi
Foodtimdardt.
Mr. William Frear, State ( 'olle.je, |'a . chairman.
Mr. II. W. Wiley, \\a~h
Mr II A • »hio.
Mr M. A. Scovcll. I.exiiiL'ton
Mr M II Jenkins. Xe\v Haven, Conn.
tizer legislation.
Mr. II. W. Wiley. \\'a-hini;tt>n. h 0., chairman.
Mr is. W Kilgore, Kalei-h. x •
Mr. H. I'.M.honnell. College Park, Md.
Mr. J. L. Hills, Hurlin-ton. \'t.
Mr B. B. Ross, Auburn, Ala.
Testing chemical reagents.
Mr I.. F. Kehlor. Washington, D. C., chairman.
Mr. A. I.. Winton. Chicago. 111.
Mr. B. W. Kilgore, Raleigh, N. C.
236
Committee to present the question of the unification of terms to the International Congress
of Applied Chemistry.
Mr. R. J. Davidson, Blacksburg, Va., chairman.
Mr. C. G. Hopkins, Urbana, 111.
Mr. W. D. Bigelow, Washington, D. C.
Mr. G. S. Fraps, College Station, Tex.
Mr. B. W. Kilgore, Raleigh, N. C.
Mr. H. J. Wheeler, Kingston, R. I.
Mr. J. T. Willard, Manhattan, Kans.
Committee on standardization of alcohol tables.
Mr. L. M. Tolman, Washington, D. C., chairman.
Mr. M. E. Jaffa, Berkeley, Cal.
Mr. A. B. Adams, Washington, D. C.
Mr. R. J. Davidson, Blacksburg, Va.
Mr. H. E. Barnard, Indianapolis, Ind.
Committee on the unification of methods of analysis offals and oils.
Mr. L. M. Tolman, Washington, D. C., chairman.
Mr. P. H. Walker, Washington, D. C.
Mr. A. Lowenstein, Chicago, 111.
Standing committee on recommendations of referees and revision of methods.
(The figures in parentheses refer to number of years appointee is to serve.)
Committee A: B. B. Ross (3), J. P. Street (2), J. K. Haywood (1), chairman, Bureau
of Chemistry, Washington, D. C.
Committee B: E. M. Chace (3), F. W. Woll (2), chairman, Agricultural Experiment
Station, Madison, Wis.; F. P. Veitch (1).
Committee C: C. D. Howard (3), A. L. Winton (2), chairman, U. S. Food Inspection
Laboratory, Chicago, III.; L. M. Tolman (1).
COXSTITIT10N' (IF THE ASSOf IATIOX OF OFFICIAL AGRICULTURAL CHEMISTS.
1 This association shall be known as the Association of Official Agricultural
Chemists of North America. The objects of the association >hall he ( 1 ) to secure uni-
formity and accuracy in the methods, results, and modes of statement of analysis
of fertilfters, soils, cattle foods, dairy products, and other materials connected with
lU'ricultural industr\ ; i 'J • to afford opjM.rtunity for the discussion of matters of interest
to agricultural chem;
_' Analytical chemists connected with the United States Department of Agri-
culture, or with any State, Pn>\ in« ial, or National agricultural experiment station
or agricultural college, or with an\ Slat P» -vim-ial. or National institution or body
in North America charged with official control of the materials named in section 1,
shall alone he eligible to membership; and one such representati\ e f..r each ol' these
institutions or hoards, when properly ac< redited, shall In- entitled to enter motions
or \ote in the association. Only such chemists as an- connected with institutions
.-ini? official fortili/.er control shall vote on questions involving methods of
analy/.ini: fertili/.ers. All person.-, eligible (•• membership shall become members
ex ofhcio and shall be allowed the privileges of membership at any meeting of the
association after prescntim: proper credentials. All members of the association who
lose their rii;hi to such membership by retiring from positions indicated as requisite
for membership -hall be entitled to become honorary members and to have a'l privi-
leges of membership save the right to hold office and vote. All analytical < -In -mi-is
ami others interested in the objects of the association may attend its meetinu'- and
take part in its discussions, but shall not be entitled to enter motion- , ,,- vote,
(3) The officers of the association -hull consist of a president, a vice pre-idcnt,
and a secretary, who shall also act as treasurer; and these officers, together with two
other member* to }„• ••[••cted by the association, -hall ci.n.-titute the executive com-
miu.. When any officer ceases to be a member by reason .-i withdrawing from a
department or board whose members are eligible i,, membership, his office shall be
lered vacant, and a successor may be appointed by the executive committee,
to continue in nffice till the annual meeting next following.
(4) There shall be appointed by the executive committee, at the regular annual
meeting, from among the members of the association, a referee and such associate
referees for each of the subjects to be considered by the association as that committee
may deem appropriate.
It shall be the duty of these referees to prepare and distribute samples and
standard reagents to members of the association and others desiring the same, to
furnish blanks for tabulating analyses, and to present at the annual meeting the
results of work done, discussion thereof, and recommendations of methods to be
followed.
(5) The special duties of the officers of the association shall be further defined,
when necessary, by the executive committee.
<6) The annual meeting of this association shall be held at such place as shall be
decided by the association, and at such time as shall be decided by the executive
committee, and announced at least three months before the time of meeting.
(237)
238
(7) No changes shall be made in the methods of analysis used in official inspection,
except by unanimous consent, until an opportunity shall have been given all official
chemists having charge of the particular inspection affected to test the proposed
changes.
(8) Special meetings shall be called by the executive committee when in its
judgment it shall be necessary, or on the written request of five members; and at
any meeting, regular or special, seven enrolled members entitled to vote shall con-
stitute a quorum for the transaction of business.
(9) The executive committee will confer with the 'official boards represented with
reference to the payment of expenses connected with the meetings and publication
of the proceedings of the association.
(10) All proposed alterations or amendments to this constitution shall be referred
to a select committee of three at a regular meeting, and after report from such com-
mittee may be adopted by the approval of two-thirds of the members present entitled
to vote.
I X DEX.
Acetanilid determinat i«m in headache mixture-, methods 101
A< •etonitrile. biological testing 103
A«id. ben/oic. S,r l&en/oir acid.
caffetannic. See Cat'fetannic acid.
cinnamic. >>'»>• Cinnamic acid.
pho-phoric. See Phosphoric acid.
salicylic. See Salicylic acid.
Acidity, determination in <"attl< port by John Fttillip« Street, veJeiee I'i" 111:1
•riuten feed. . i»J">
indicator-. di~cu~-ion .. Mil*
A. id-. determination in \\im-. method-, compare | I.;. Is -j |
mineral, te~t method-, di-u--i ii .... Kii'
\\ine, determination method- i I, Is •_' |
Aconite P--I ;i-.i\ iiiL'. mcttiMd- and r«--ult- I:1. 1 132,184 L35
Icookin, bioloffioU tc-iin-
. \dii- and \\'...,d. method .,|' p..ta-h <l.-i,-rminat i"ii I'JI. I'J.'i
Adrenalin, l»i.»l.^i. al i.-iui- ... MM
Adulteration, ilru-, detr.ti,, n hv pli> M-al ••\ainin . l.'.i; !:',!»
plai/ . di-cii.s-ion 94-97
fertili/.er. delinit ioi; l,s.">
11 I L'
Alcohol estimation, naper I. \ 1 I \y. .-••:..• L'L'S
tables*, standardi/ati'.n. c.,mmitte.- f.-r 1908-9, p«i>"im«-| and din-ri..i
.\|C-,||M|-. di-terrninati''!! in fu-el ..il hy \ariinis methods
e-iimati..!! in i'u-i-1 .-il l.y \.iri-u- mrth L'lM). U04
Alkaloid determination in drui:-, nu-ih' l.'.n
Alkaloidal druu's. a.--a\ inj, pap«T !••. « 1 I' •!.•• 120
Alkaloids, mi.-rochemical anal\-is and identiticati«»n. preliminar> .-tnd> ... 97-100
precipitate.-, chancier ol.raine.l " ' 98
Allen-Marquardt, method, fusel oil determination, compari-.n
mcxlitie.i d det.-rminati"n -JloJlL'
Alumina cream and sodium hvdp>-ulphite. suirar and n»o|a.-ses polari/at imi-.
tabl. I;K ITS, ITT, i -
determination in pho-pl :in-tb<>dsaiid result- 140-146
Aluminum h\dp>\i, 2:iO-232
American Kedurtion Coinpanv. comments ..n iVrf ili/«-r
Ammonia i..riuati..n in >..il- a D ••.•«, studies 192-195
Ammonium citrate solution, examinations for neutrality 147-148
Amyl alcohol determination by A llen-Manpiardt method J 10-212
te-t i'or «ol,,r in \vhi-ki.- _'nti
Analysis, citral in terpenoless extra< t of lemon 229
distilled BpiHtB, methods, paper l.y I.M T..lmanand \\ Iv Ilillyer. U06-212
insecticide-. metho<l8and resulUi 105-110
methods, n.-ed of uniformity, remark.- 12
milk, methods and results " 153-158
M'li-, instructions, tables, comments and recommendation* 115-120
vinegar, method and re-ults 27-29
wine, mi -thods, proposals, suggestions and discussion 13-25
Animnl experimentation with drugs, for testing strength and purity, necessity. 103-105
Arsenate, lead, analy-e-. table and discussioi, 108
Arsenic oxid, determination in London purple, methods 106-107
Asafa'tida import-, adulteration- 95
Ash constituents of plants, anah.se- and comments by analysts 93
Assaying, alkaloidal drugs, paper by C. £. Parker ." 129-136
(239)
240
Page.
Association, members, names of attendants at meeting 7-11
of Official Agricultural Chemists, constitution 237-238
officers, referees, and committees
for 1908-9 234-236
Attendance, members and visitors, list of names 7-11
Averitt, S. D., report as referee on soils 114-120
Babcock standard, new, recommendation 189
Bacteria, function in soils, studies and discoveries 192-195
Baier and Neumann method for detection of calciu«a sucrate in milk or cream. 52-53
Baer, Samuel H., abstract of paper on citral analysis : 229
Bailey, E. M., work on vinegar analysis 28, 29
analyst, comments on milk analysis : 155
Baker, E. L., analyst, comments on potash determination 123
work on potash determination 124-125
Ballard, H. F., report as referee on food adulteration 11-12
Bamihl gluten test, modification 217-219
Barnard, H. E., report as associate referee on beer 25
Bartlett, G. M., analyst, comments on cocoa products 81
Bartlett, J. M., report as referee on dairy products 152-159
Basic slag, phosphoric acid valuation, paper 151-152
Bassett, H. P., method of determination of fat and moisture in cereal products. 55, 58
Beckman's test for glucose 180-181
Beef analysis, tables 63
Beer, report of H . E. Barnard, associate referee 25
salicylic acid determination 67-68
Belgian slag. See Thomas slag.
Belladonna leaves assaying, methods and results 132-133, 134-135
root adulteration, detection with microscope 138
assaying, methods and results 133-135
Benzoic acid determination methods 68-77
Bichromate, use in saccharimetric work 221-223
Bigelow, W. D., paper on "Examination of oysters" 215-216
report as referee on preservatives 64-78
Biological testing of drugs, necessity 103-105
Bleaching, detection in flour, simple tests 216-217
Blood, moisture determination by vacuum without heat 220
Bradshaw and La Wall, methods for determination of benzole acid 70-72
Breakfast foods, salicylic acid determination 67-68
Breckler, A.M., method, purification of carbon tetrachlorid 209
Brennon, VV. A., analyst, comments on milk analysis 155
Brinton, C. S., analyst, comments on lemon extract 30
paprika 37
Brown, Lin wood A., analyst, flavoring extracts, comments 30, 32
Brown, P. E., analyst, comments on potassium determination in soils 119
Browne, C. A., paper on "The Unification of Saccharimetric Observations". 221-228
Bryan, A. H., report as referee on detection of small percentages of commercial
glucose in sirups and honey 180-183
sugar 168-180
Caffein determination in headache mixtures, method 100-101
estimation in coffee 83-84
Caffetannic acid determination in coffee, methods 79-80
estimation in coffee 82-83
Calcium carbonate determination in soils, report by Jacob G. Lipman, associ-
ate referee 120-121
sucrate, detection in milk and in cream 52-53
Calvert, T. L., comments on fertilizer legislation 186
Cane and maple sirup mixtures, Winton lead number, notes 198-199
Cannabis, biological testing 104
Canned peas, report of W. L. Dubois, associate referee 58-61
Carbon cfioxid determination in soils 120-121
evolution from soils, studies and experiments 192
tetrachlorid, purification method by A. M. Breckler 209
solution, alcohol extraction and determination 201, 203, 205
Carlyle, E. C., analyst, comments on potash determination 123
Carpenter, F. B., analyst, comments on nitrogen work 89
Casein determination in milk, method, results, and recommendation 167-168
241
Page,
Can le feeds, acidity detenrdnation, report by John Phillips Street, referee... li;o li;:>
: I products analysis methods 53-56
fat determination methods and results 55-57
mint-iii Unions 127
report of F . F. 1 .add, associate referee 53-58
Chace, E. M., report as a— ociate referee on flavoring extracts 29-35
Chemical reagents te-tin:, committee for 1908-9, personnel and directory 235
» heini.-i. au'ricultural. training, address by President 11. Snyder 110-114
Chemistry Bulletin 107, revision re poi t by coiiunittee 187
< 'hen lists, American, work in advancement of industries 112
Chicken meat, fresh, cold-store. 1, and preserved, analyses
nitrogen determination, tallies ." 46-50
Cinchona hark, a<sa\ iii',', methods and details l:U)
Cinnamic acid detection, methods
( 'itral analy-is in ti-rpem-lcss extract of lemon, colorimetric method •_"_'!»
determination in lemon • .md oil, with comments of anal
.-, ammonium, solution, examinations for neutrality I ;
Clarification a^ent-. effect on polari/ation 17:'. l^ti. '_':.'
t method su',rar polari/.ations. table-* and discussion 1,
C|i.ver honey. N" lioii.
:i)le. identification 2:'.
ri-nitrite method of potash determination |-_>1 IL>;,
leavefl a-a> in/. metOoda and results 1
I 'I.1,
cr. ined with different reagenti ... 99
Cochineal red, 39
Codr paper on coal tar color-, identification
i products analyse-* and comm.':'- SO-81
starch determination . •_'! i i>|.->
recomni' • lL'7
•nan. a^s..c 78-82
and r.nnii:- I I 79-80
M, and tea, report '• ... 78-82
•nation of cati.-fannie a- id a: S2-84
mmendation- ...127
addition to .jl'. Hii;
reaction-, uine, r-'-ult- \\ith ili:'ferent -tandard- .... 18
< olorin- i: in di-till-
natural, in \\ i: i.ition 1»; |s
imetric method of oitral <|et,-niiination in terpeneless . lemOD 229
Color-, co., ilde. identification 2:iO-233
id'-ntiticati«.n. report of 11 M I
II \2
r_'7
Committee A. rep..rt .>n reconunendatioi i^:i-184
. port on re. ommendatio: 187-189
[>ort on i 1 ail ul i' "mmendation- 126-127
Committee^, appointmen^ i;}, !>•_'. IJH, 190
onel and directory.. 2:>5-236
Condensed milk >-- Milk.
Con-titutioti A-«x-iat ion of Official Agricultural Chemists 237-238
184
C. 1. . analy-t. tla\ orin,' extract ~. comment- 34
< o pa ilia import<, adult era 'ion- 95
Copper l>. : rmiriation of benzoic acid 72-74
Goto bark imital 138
Coumarin determination in vanilla extract 31
Cream, detection of calcium sucrate 52-53
Dairy products adulteration, report of Hermann 0. Lythgoe, associate referee.
•nmendation- ll'fj, 188
report by J. M. I '.art let t, referee 152-159
Davidson, R. J., analyst, comments on formaldehyde analysis 110
London purple analysis methods 107
report a< chairman of Committee A on recommendations... 183-184
on unification of terms .:... 183
73673— Bull. 122—09 16
242
Page.
Decomposition of organic matter in the soil, rate and methods 191-196
Denia, W., paper on "Determination of the iodin number of the nonvolatile
ether extract of paprika " 213-214
Digitalis adulteration detection with microscope 138
biological testing 104
leaves, adulteration 96
Dips, sulphur, analysis, table 110
Directory, names of members, officers, referees, and committees 7-11, 234-238
Distilled liquor*; fusel oil determination, recommendations 27
test of methods 25-27
recommendations 126
report of L. M. Tolman as associate referee 2-5-27
spirits, analysis methods, paper by L. M. Tolman and W. E. Hilly er. 206-212
fusel oil determination, methods 208-212
Donk, M. G., analyst, comments on potash determination 124
Doolittle, R. E., and A. F. Seeker, paper on "The possibilities of muscovado
sugar as an adulterant for ma-
ple products" 196-198
" Winton lead number of mixtures
of cane and maple sirup " . . 198-199
Doolittle and Woodruff, method for extract of tea 80
Doolittle-Ogden method of iodin number determination 213
Drug adulterations detection by physical examination 136-139
plant adulterations, need of stricter supervision, discussion 94-97
Drugs, alkaloid determination methods 130
alkaloidal, assaying, paper by (\ E. Parker 129-136
and plants, medicinal, recommendations 187-188
report by L. F. Kebler, referee 94-97
dilution with inert substances 95
macroscopy and microscopy, paper by H. H. Rusby 136-139
Drushel, method of potash determination 124-125
Dubois, W..L., analyst, flavoring extracts, comments 34
paper on "Determination of starch in cocoa products " 214-215
report as associate referee on vegetables 58-61
Dunbar, P. D., methods of determination of cinnamic acid 77-78
Dyes, coal-tar, wool and cotton, identification 230-233
Ellett's method pentosan determination 159-160
Emery, W. O., report on cooperative work on headache mixtures 100-102
Ergot, biological testing 105
Erythrosin, "testing for pure color 39
Ether extract, nonvolatile, of paprika, iodin number determination, methods. 213-214
Ethyl alcohol estimation by alkaline permanganate 204, 205
solutions, extraction of alcohols 201, 203. 204
Experiments on animals for testing strength and purity of drugs, necessity. . . 103-105
Extract, paprika, iodin number determination, methods 213-214
Extracts, flavoring, recommendations 126
report by E. M. Chace, associate referee 29-35
meat, cold water, preparation and examination 61-62
Farnham, G. S., analyst, comments on potash determination 123
Fat determination in cereal products, methods and results 55-57
condensed milk 158
Fats and oils analysis methods, unification, committee for 1908-9, personnel and
directory '. 236
Feed, gluten, manufacture, paper by T. B. Wagner 164-166
Feeding stuffs and foods, report of Fred W. Morse, associate referee 15.9-160
recommendations 188
Feeds, cattle, acidity determination, report by John Phillips Street, referee. 160-163
Fertilizer adulteration and misbranding, definitions 185
definition 185
legislation, committee for 1908-9, personnel and directory 235
report : 185-187
Fertilizers, rate of oxidation in different soils 193
Fetzer, Lewis W., analyst, comments on milk analysis 155
Fish and meat, report of F. C. Weber, associate referee 42-50
recommendations 126
243
Page.
Flavoring extracts, See Extracts.
Florida rock. determination of iron and alumina, table ....................... 143
Flour, analysis methods, results ami recommendation .........................
blea.-hn; .n. simple tests .................................. L'HJL'17
fat determination, methods and results ................................
moisture determination, methods and results ..........................
rye, detection of \vheat tloiir, modification of Bamihl test ............ 217 I'll*
it, d. -t <•<•! ion in rye Hour, modification of Uamihl test ............ -JI7 L'l!)
Food adulteration, repcrt ol H. E. Jttarnafti ai ...................... n IL'
col, .rs, identification, recommendations ................................ IU
j)roducts, determination of sulphurous acid, sulphite or sulphur dioxid.
paper submitted ................................................... Imi
standards, committee for 1908-9, personnel and direetory ............... I':1,".
report of com; ........... ' ................ ll'^
. report of !•>••« I \\ . Morse, associate rrfnvr ......... !.">:» II;M
recommendations ................................................... 1^
Formaldehyde anid\>is. table and comments .............................. ID.' Ill)
laments on fertilizer legislation ............................... I si;
Fuch -in Dilution formula ...... ................................ 32
Fuller, II. t . and I.. I'.. Warren, article on alcohol estimation, reference .....
Fuller's earth tot for coal-tar « .................................... i_':ii)
. <>il rompo-inon ---- ...........................
•ruination by alkaline permanganate. paper ................... !!)!> L'o:>
irison of meth ..... 26
in d Milled li.| .
'IK L'l'J
.lil.- for dry sir ••'> 170
< iladdin/ in- -t h- >d, dcterminat ii >n • :' ir»n ami alumina in phosphatr roek ....... Ill
Glaser method, determination of iron and alumina in phosp' I II
(iluc. - analyK*. 1^1
.leireiion in bj A II I -
(iluten cattle i. ... Iti:'>
in.")
manufacture, paper K\ T I1, \\ If, I |i;i;
iihl, m.. di lira t ion..
letennination in winoo, methods.... ........ M l">
• rmination in - ... 84
Method for determining nitrites, use in deirrtion of Meachiiii; in
Hour. ..
(irindley and Fmmett. n ... lil ij'J
( iudeman. IMuard. submission of pajHT on determination of .-ulphuroiis ;.
. in food priwln I'Mi
buig's reagent, lor addity detennii ........... i<.
M. A \\ . IDA] ......... ... 34
Haskii; II 1'. paper on •• \aluation of j.h.^phoric ai-id in ' I.I I •"»-'
rep i inoriranic plant constiti;
• "i. .! l\ dfman of committee on re vkioo ol method*.
• •he mix' . \ s<>s ................ .......... . IOJ
coop by \\ . ( ). Fmrr\ . . 100-102
Henbane adulteration. a< ............. i:;s
Hnlrs's solution, 1. polarization -. table .......... 171. I7.">
Bickey, Charles B . <• on vinc-ar ....... ... 27-29
HilK .1 . I. , comments on lertili/er legislation ...............................
Hiltii ii flavoring extracts ...................... 34
K \\ '., analyst, comments on cocoa pro. ...................... 81
flavoring extracts ....................... 34
Holland. F. II. . anal aonts on milk analysis .......................... IV)
Honey, clover, and glucose mixtures, analyses .............................. 181
glocose detection, report b'y A. II .' Bryan as referee ................. 1SO-183
Homer, Julius, report as referee on wine ____ ! .............................. 12-25
Howard, B. J., and C. 11 S». -phenson, paper on analvsis and identification of
alkaloids ................... ......... . ...97-100
Hydrochloric acid, eiYert on pyrites in phosp! ..................... 146-147
Hydrogen t>ero\id, use in determination of alcohols ......................... 202
HydrOBUlpoite (sodium) and alumina cream, sugar and molasses polarix.ation . . 171,
175, 177, 178, 179
244
Page.
Imus, Genevieve, analyst, comments on paprika 37
statement on examination of coloring matter in wine 16-18
Inorganic plant constituents, report by H. D. Haskins, referee 92-94
Insecticides, report of C. C. McDonnell, referee 105-110
lodin, number of nonvolatile ether extract of paprika, determination methods. 213-214
Iron determination in phosphate rock, methods and results 140-146
Jones, C. II., analyst, comments on milk analysis 156
Jones, W. J., jr., comments on fertilizer legislation. . . i* 186
Kebler, L. F., report as chairman, committee on testing of chemical reagents. . 127-128
referee on medicinal plants and drugs 94-97
Kelley, W. P., analyst, comments on potassium determination in soils 119
Ketchup, sodium benzoate determination by different methods 71, 74, 75, 76, 77
Krauch method for extract in tea 80
Krug method, determination of caffetannic acid in coffee 79-80. 83
La Wall and Bradshaw, methods for determination of benzoic acid 70-72
Ladd, E. F., report as associate referee on cereal products 53-58
Le Clerc, J. A., analyst, comments on inorganic plant constituents 93
Lead arsenate analyses, table and discussion 108
number, determination in vinegar 28
solutions, polarization of sugar and molasses, tables 173,
175-177,178,179,223,225
use as clarification agents : 173-180, 223-225
Legislation, fertilizer, committee for 1908-9, personnel and directory 235
report 185-187
Lemon extract, terpeneless, citral determination, colorimetric method 229
extracts and oil, citral determinations 30, 32-35
Lindsey, J. B.. paper on Thomas slag 148-151
Lipman, Jacob G., paper on "Methods relating to the rate of decomposition of
organic matter in the soil " 191-196
report as associate referee on the determination of calcium
carbonate in soils 1 20-121
Liquors, distilled. See Distilled liquors.
Litmus, use as indicator for wine acids, comparison with phenol phthalein 24
in acidity determinations 160-163
Liver, moisture determination by vacuum without heat 220, 221
London purple, analysis methods, comments and discussion 106-108
Loomis, H. M., report as associate referee on colors 38-42
Lott, C. I., analyst, comments on paprika 38
Lythgoe, Hermann C., report as associate referee on adulteration of dairy
'products. 51-53
Macroscopy and microscopy of drugs, pape*- by H. H. Rusby 136-139
Malic acid, determination in vinegar 28
Malt extracts, salicylic acid determination 67-68
Maple and cane sirup mixtures, Winton lead number, notes 198-199
products, adulteration with muscovado sugar ' 196-198
sugar. See Sugar, maple.
Marsh quantitative test for color in distilled spirits 206
Matico, genuine, identification by microscopic examination 139
McCandless, J. M., report as referee on phosphoric acid 140-148
McDonnell, C. C., report as referee on insecticides 105-110
Meat analysis, methods and Vesults, discussion '. 43-45
and fish, report of F. C. Weber, associate referee 42-50
proteids, recommendations • 127
separation, report of P. F. Trowbridge, associate referee 61-64
recommendations 126
Meats, cold water extracts, preparation and examination 61-62
Medicinal plants and drugs, recommendations 187-188
report by L. F. Kebler, referee 94-97
Melada. See Sugar, muscovado.
Merrill, F. D., analyst, flavoring extracts, comments 34
Methods, revision committee report 187
Methyl alcohol estimation by alkaline permanganate 204, 205
Microscopy and macroscppy of drugs, paper by H. H. Rusby 136-139
Milk, casein determination, method, results, and recommendation 167-168
245
Page.
Milk, condensed, analysia instroctioiM .................................... !•">
analyses. tallies, comments and diseus.-ion ................ 15-1 l~>s
hit determination ......................................... 158
mmendations ....................................... 158-159
••• linn of calcium suerate .......................................... .YJ ."»:>
-••rum preparation methods, comparison .............................. 51
Mi-brandinur fertili/er. definitions .............................. ............. 185
Milehell. A. S , and t '. II. Smith, paper on "The determination of fusel nil by
alkaline permanganate " ............................................... 199-205
ire determinations. su-ar and molasses .............................. 171 17'J
without the aid of heat, methods ................. L'lii •_"_' I
Molasses, glucose detection ................................................. Is-
Loui-iana. normal polari/at ion ................................... 182
moi-ture determination ........ ................. ............... 171 171'
polari/ation with different clarifying a-jeni-. table- ........... 17s. 17!). L'L'1
M oniniento on fertiliser legislation ............................ IM;
I'red \\".. re|M>rt as associate rrh-rer on l ..... 1.- and feeding Stuftl ....... !">!)- HID
\a«lo -iiL'ar. 8*6 Snirar.
; 'i attendance on met ......... .' ....... 711
NapMhol Yell- ii- for pun- color. . ..................
Nehi- ' . lla\orii, .-oinnient- .........................
te formaiioii i-. ... 193-195
Nitrogen determination, chicken ni' ;• .o
I 85-91
work for i!M)7. instrueti.'.ns ......... .............. 85
iimendation- . ... 91, 183
Niir- -.-paratioii: milk and • h. •••-•-. r.-port of 1.. I.. Van Sl\k.-,
refej . n;7 n;s
Noiiniii'i i.>ns, report ui' . i. mii::1 ......... l:>
-K-iation for 1!M)S '», ,|ire. ; •
( M-rii :-l
:i i'-n. niflhod-. pa|" i |!l I |!Hi
riments .
2
30
Paprika anal\- nd ilisciission .....
Mm volatile ether ( Q ofiodin number, methodi . L.'|:;L'II
with oli\,- nil. analvM-- :U^38
ontheasBayingofalkaloidaldrtieB.... i
I'a t it-ii, Andrew .1 . a I it n«-nts ..........
< -aimed. r«-p..rr of \\ I. I >i:l.
I't-nriN . (}. on deti-rminalion el mt( •
an determination. ! ' ,:» Hio
iv-rin alkaline, fo0el oil determination, ] ................. i1'
n berry ei -lini; i"r pun- ml >r . .............. to
I'heiiolphthalein. u.-e a> : uit l;tmu> ...... -_M
in aeidity det.-rii:! ........... li,i-
Phloxin, testing for pore coloi ........ 40
i of in.n and alumina, method- ............... 1 10-142
pyn • ..I h\.lr-M-l.!.,rn- a.-id ____ .......... I Mi 117
anq value as fertiliser ............ ........... 150-151
riio-ph.iri< a. i.l determination in '1 hi. mas .-1 1- .............................. 140
184
report by J. M. if cGand .................... 140-148
valuation in I a ............................. 151 |.V_'
riio-ph,iru< <li -termination in M-il.r « ........... 1 i
IMant <-oii.-titurnt-. inorganic, reeommei ........................... 184
rep,,rt by II. 1>. II;,- ree ...............
Plants and druirs, medicinal, recommeodationfl ............................. 187-188
report by I.. I'. Kebl.-r. n-feree ................. 94-97
Polarisation, normal, of Louisiana molasses and sirup ......................... 182
su«;ar and niola.-ses with different clarification air<-nt-. . 17:; M>. L'L'3-225
Polarizations of starch conversion products with and without bichromate ..... 222
246
Page.
Ponceau, testing for pure color 40
Potash work, instructions 121-122
recommendations 183
report by B. B. Ross, referee . 121-125
Potassium determination in soils, comparison of methods, tables 119
Preservatives, report of W. D. Bigelow, referee 64-78
Proteids, meat, separation, report of P. F. Trowbridge, associate referee 61-64
Pyrites in phosphate rock, effect of hydrochloric acid. 146-147
Quartz, use in saccharimetric work 226
Reagents, chemical, testing report of L. F. Kebler, chairman of committee.. 127-128
Recommendations, determination of acids in wine 24-25
casein in milk 168
f usol oil in distilled liquors 27
of referees, report of Committee A 183-184
B 187-189
C 126-127
on condensed milk 158-159
' . flour analysis 58
identification of colors in foods 42
method for separation of iron and aluminum in ash of
plants 93
nitrogen work 91
paprika analysis 38
soils analysis 119-120
sugar 180
tea, coffee, and cocoa work 81
Reducing sugars, determination in wine, methods 15-16
Referees and associate referees for 1908-9, directory 234-235
Resolutions committee report (. 189
Rhodamin, testing for pure color 39
Richardson, W. D., analyst, comments on potash determination 124
Robb, J. Bernard, analyst, comments on nitrogen work 89
Rockweed, pentosan determination 159-160
Rose, Bengal, testing for pure color 40
Ross, B. B., report as referee on potash 121-125
Rudnick, Paul, analyst, comments on nitrogen work 89
potash determination 123
Yon Grueber method analysis of phos-
phate rock 146
Rusby, H. H., paper on "The Macroscopy and microscopy of drugs " 136-139
Rye flour. See Flour.
Saccharimetric observations, unification, paper 221-228
Saffron adulteration, dangers 138
testing for pure color 39
Salant, William, paper on animal experimentation with medicinal prepara-
tions 103-105
Salicylic acid determination, methods 64-68
solvents, comparative efficiency 65
Saponins, biological testing 104
Seeker, A. F., analyst, comments on lemon extract 30
and R. E. Doolittle, paper on "The possibilities of muscovado
sugar as an adulterant for maple products " 196-198
and R. E. Doolittle, paper on "Winton lead number of mix-
tures of cane and maple sirup' ' 198-199
Sellier apparatus, for acid determination in wine, description 20-21
Shanley, E. J., and A. L. Winton, paper on "Simple tests for detecting bleach-
ing in flour " 216-217
Shedd, O. M., analyst, comments on inorganic plant constituents 93
potash determination 124
Silver benzoate method of determination of benzoic acid 74-76
Sirup, cane and maple mixtures, Winton lead number, notes 198-199
Sirups, glucose detection, report by A. H. Bryan, referee 180-183
Slag, basic, valuation of phosphoric acid, paper by H. D. Haskins 151-152
Thomas. See Thomas slag.
Page.
Smith, K II., analyst, comments on lemon extract 30
Smith. C. K .. :i*id A. s. Mitchell, paper on "The determination of fusel oil by
alkaline permanganate" 199-205
Snyder. II., president's address on "The training of the agricultural chemist " . no ill
iye anal >>K m*-t ho Is and table 10S !()!»
Sodium bencoate, determination in ketchup, by different methods 71, 71, 7-"). 7li, 77
bicarbonate, determination in headache mixtures 101
bi-ulphite, usf in coal- tar color test
Boil, organic matter, aition rate, methods relating to, paper mi UMS
M<!ruction-., iat.lt-. comment- ;umendations 115-120
calcium carbonate (It-termination, report by Jacob (I. I.ipman, associate
n-teree 120-121
carbon dioxi.i determination 120- 121
recommendation
report bj eritt, referee in -121)
: I2i>
n-p«irt. by A. L. \Vint «»n. a<s«x-iate reh-ree ^ 35-38
Spirits, distilled. -s'" Distilled spirite,
<\\ produ. • Hand \vitliout bichromate
detrrmii'at i Hi in COC.M j»rM,i 2 1 I '_' I •">
. <litlerei!t iiL'f- and COndltiODI
II . and I'- .1 . Howard, paper <m analysis and identification of
Stramonium, detection \\ ith DUdOBCOpe
iiillips, report as reieree on j in
'
;nd. dele, i, :
imin, bi ..
•ti in milk or cream
H; solution, polarization, with different amount.- of lead. . . 170
I analyses
musco\.id ., | !.- pr.Mluct.-. .
polari/a: • nt N-ad .-oluiinns. .
- I | xs
.-. and I r 168-180
worl
Sugar-house products, dry niib 1'.
ng to standard tern;
.:ure.
nxlucts, paper submit ted l!x;
<lipsan ... 110
Sulphuric acid met! -ilaiion 76-77
Sulphur.. i; Miatimi in IO.H! pr.Hlucf-, paper submit t
>n tla\'-n:
A., analy.-t, comments on flavoring extracts. 30
39
dman, pa; 'letannic acid
and caffein in coff. . 82-84
79-80
i man. a-- 78-82
-imendatioii^ |-_>7
Temperature variat; -ion 225-228
lessee rock, determinati": :id alumina table I \~2
<\*-\>-^- e\ • •••rmination, colorimetric methixl 229
iii; aridity a of indicators and method .. i»;o-n;:j
I.. 1'. Ki-bler, chairman of committee. . . I27-I2S
That.'her. i{. \\'.. at. : .n nurple analy.-is method-. 107
Thoi; in posit ion. value, and use as fertiliser, paper 148-151
Thyroid <_:ljnd extract.-, biological • 103
rminat.on 162, 163, 165
. 1.. M., report as aasoi ee on distilled li*juors
chairman of Committee C (fooa adulteration) 126-127
248
Page.
Trescot, T. C., analyst, comments on nitrogen work 89
Tropaeolin O O, testing for pure color 39
Trowbridge, P. F., paper on ''Moisture determinations without the aid of
heat' ' 219-221
report as associate referee on separation of meat proteids . 61-64
Unification of terms, committee for 1908-9, personnel and directory 236
report of committee 183
- T*
Vacuum method of moisture determinations 219-221
Van Slyke, L. L., report as chairman of the committee on resolutions 189
referee on separation of nitrogenous bodies: milk
and cheese proteids 167-168
Vanilla extract analyses, and comments of the analysts, 1907
Vanillin determination in vanilla extract 31
Vegetables, canned, recommendations 127
report of W. 1;. Dubois, associate referee 58-61
Vinegar analyses, tables 29
report by Charles H. Hickey, associate referee 27-29
Volatile acids in wines, table of results 19
See also Acids.
Wagner, T. B., paper on ' ' The manufacture of gluten feed " 364-166
Warren, L. E., and H. C. Fuller, article on alcohol estimation, reference 228
Weber, F. C., report as associate referee on meat and fish -12-50
West, R. M., method of determination of benzoic acid 76-77
Wheat flour. See Flour.
Whiskies, color determination by different methods 206-208
Wilson, C1. P., analyst, comments on paprika 38
Wilson, S. H., analyst, comments on analysis of phosphate rock 146
Wine, acids, determination and methods.' 13-14, 18-25
coloring matter, natural, examination 16-18
determination of acids, recommendations 24-25
glycerol, determination 14-15
reducing sugars, determination 15-16
report of Julius Hortvet as associate referee 12-25
Wines, recommendations 126
salicylic acid determination 66-67
Winton, A. L., paper on "A modification of the Bamihl test for detecting wheat
flour in rye flour" 217-219
report as associate referee on spices 35-38
and E. J. Shanley, paper on "Simple tests for detecting bleach-
ing in flour " 216-217
Winton lead number of mixtures of cane and maple sirup, notes 198-199
Woll, F. W., comments on fertilizer legislation 186
Woodman, A. G., and W. C. Taylor, paper on "Estimation of caffetannic acid
and caiiein in coffee ? ' 82-84
report as associate referee on tea, coffee, and cocoa 78-82
Woodruff, F. O., analyst, comments on tea and coffee analyses 79-80
Woods, 0. D., analyst, comments on lead arsenate analysis 108
London purple analysis methods 107
paprika 37
Wool dyes, coal-tar, identification 230-233
Zerban, Fritz, report as associate referee on sugar 168-180
o
.1 June;
%U. S. DKPARTMKXT OF AGRICULTURE,
BUREAU OF CHEMISTRY- BULLETIN No. 123.
11 \V. \VILKV. Chid ui Bui
MKTA HOLISM OF OWiAXK1 AND
ir PHOSPHORIC:
A KKKDIM. KXIM-KIMKNT I >LM; niVTIN
AND SUDITM IMInsiMIATKS.
F. • >K.
WASH i N<. i «
»,(.\ i i: \ M i \ T M: I \ I i i ICE.
1 '.'
H. W. WILEY, Chemist and Chief of Bureau.
F. L. DUN LAP, Associate Chemist.
W. D. BIGELOW, Assistant Chief of Bureau.
F. B. LINTON, Chief Clerk.
A. L. PIERCE, Editorial Clerk.
M. W. TAYLOR, Librarian.
Division of Foods, W. D. BIGELOW, Chief.
Food Inspection Laboratory, L. M. TOLMAX, Chief.
Food Technology Laboratory, E. M. CHACE, ('//ief and Assistant Chief of I)-
Oil, Fat, and Wax Laboratory. LXot appointed.]
Division of Drugs, L. F. KEBLER, Chief.
Drug Inspection Laboratory, G. W. HOOVER, CVuV/.
Synthetic Products Laboratory, W. O. EMERY, C/?/f/.
Essential Oils Laboratory. [Not appointed.]
Pharmacological Laboratory, WM. SALANT, Acting.
Chief Food and Drug Inspector, W. G. CAMPBELL.
Miscellaneous Division, J. K. HAYWOOD, Chief.
Water Laboratory, W. W. SKINNER, Chief.
Cattle-Food and Grain Laboratory, J. S. CHAMBERLAIN, Chief.
Insecticide and Fungicide Laboratory, C. C. MCDONNELL, Chief.
Trade Wastes Laboratory, under Chief of Division.
Contracts Laboratory, P. H. WALKER, Chiif.
Dairy Laboratory, G. E. PATRICK, Chief.
Food Research Laboratory, M. E. PENNINGTON, Chief.
Leather and Paper Laboratory, F. P. VEITCH, Chief.
Microchemical Laboratory., B. J. HOWARD, Chief.
Sugar Laboratory, A. H. BRYAN, Acting.
Nitrogen Section, T. C. TRESCOT, in Charge.
Special Investigations:
Physiological Chemistry (Animal), F. C. WEBER, in Charge.
Physiological Chemistry (Vegetable), J. A. LE CLERC, in Charge.
Bacteriological Chemistry, G. W. STILES, in ('hur<}< . *
Enological Chemistry, W. B. ALWOOD, in Charge.
Food and Drug Inspection Laboratories:
Boston, B. H. SMITH, Chief.
Buffalo, W. L. DUBOIS, Acting.
Chicago, A. L. WINTON, Chief.
Cincinnati, B. R. HART, Acting.
Denver, A. E. LEACH, Chief.
Detroit, H. L. SCHULZ, Acting.
Galveston, T. F. PAPPE, Acting.
Honolulu, Hawaiian Islands, R. A. DUNCAN, Acting.
Kansas City, Mo., A. V. H. MORY, Actimj.
Nashville. " [Not appointed.]
New Orleans, C. W. HARRISON, Chief.
New York, R. E. DOOLTTTLE, Chief.
Omaha, 8. II. Ross, Acting.
Philadelphia, C. S. BRINTON, Chief.
Pittsburg, M. C. ALBRECH, Acting.
Portland, Oreg., A. L. KNISELY, Acting.
St. Louis, D. B. BISBEE, Acting.
St. Paul, A. S. MITCHELL, Chief.
San Francisco, R. A. GOULD, Chief.
Savannah, W. C. BURNET, Acting.
Seattle, H. M, LOOMIS, Acting.
.1 .Inn.-
U. S. DKI'AkTMKNT OF AGRICULTURE,
BUREAU OF CHEMISTRY BULLETIN No. 123.
II. W. \\II.KV, Chief of r.urvuu.
METABOLISM OF
1NOU(JANI(1
AND
A FEEDING KXrKKIMKM I'SIMi IMIYTIN
AND SnDH'M IMlnsiMIATKS.
I . < . TOOK.
WASHINGTON:
QCn RRV M BH1 PB1 OFFICE.
LETTER OF TRAXSM1TTAL
U. S. DEPARTMENT OF AGRICULTURE,
BUREAU OF CHEMISTRY,
'\Yas7iington j D. C.} January 1-5, 1909.
SIR: I have the honor to submit for your inspection and approval
a report on a phosphorus metabolism experiment conducted by
F. C. Cook under the supervision of the Chief of Bureau. The report
covers an experiment in rabbit feeding, extending over a period of
six months, during which organic and inorganic phosphorus were fed,
and includes calcium, magnesium, and total and ether-alcohol soluble
phosphorus balances. At the conclusion of the experiment, com-
plete analyses were made of the bodies of the rabbits, also of normal
rabbits, which furnish some valuable data. Although the number
of experiments is limited, -the complete review of the literature bear-
ing on the subject, which is included in this paper, greatly enhances
its value and the interest both in this country and abroad in the
relative value of the organic and inorganic forms of phosphorus,
iron, etc., in the body economy makes the issuance of this contribu-
tion on the subject advisable.
I recommend that the manuscript be published as Bulletin 123 of
the Bureau of Chemistry.
Respectfully,
IT. W. WILEY, Chief.
Hon. JAMES WILSON.
Secretary of Agriculture.
2
CONTEXTS
K' \ i- \\ ' >t i he literature ...................................................
Phosphorus compound- ............................................... •">
iiin- ................... ............................ 0
Xudro-protrins ................................................... 7
Nucleius ......................................................... 7
:>ho-Ljluco-prot«'in.- ........ .......... N
Inorganic phosphoric ....... .............
!»
............... .........
un coiiip4iund
: illlrlil \S I '
Pn-p-ir.ii i'>n of f :
Mt-ih :;:;
l'n-1:
N i t n •
.'!7
I'rin
Niir«ccn balai 38
lit
• liiMc pho.-j.h..riH I. 42
irn an<l ina^ncsium '• . 46
( 'h.-niii-..; i lln- l>odii- ol tin- r |>.
Is
l.iv.-r . 51
52
53
53
54
54
Summary ..... .",:,
Find in-.:- of an
:,!»
Conclu-i- CO
IVflimin. • .................. GO
Principal fccdi: ..... 01
in «-x tmin Mi«.i. ......... 61
Li-t of lal.N-... 63
ILLUSTRATIONS.
Page.
PLATE I. Liver sections of organic-phosphorus-fed rabbit No. 1. Fig. 1. — Mag-
nification 60 diameters. Fig. 2. — Magnification 175 diameters 60
II. Liver sections of organic-phosphorus-fed rabbit No. 2. Fig. 1. — Mag-
nification 60 diameters. Fig. 2. — Magnification 175 diameters 60
III. Liversections of inorganic-phosphorus-fed rabbit No. 4. Fig. 1. — Mag-
nification 60 diameters. Fig. 2. — Magnification 175 diameters 60
4
METABOLISM OF ORGANIC AND INORGANIC
PHOSPHORUS.
REVIEW OF THE LITERATURE.
Much \\ork ha- already heen done on phosphorus metaholi-m.
hoili in regard to the inorganic and organic forms of phosphorus, and
many in\ e>t iirat ion- have hern recorded showing the advantages of
the varioii- organic forms, such as lecithin, irlveero-phosphoric acid,
phytin. etc. Mo>t of this work ha- heen done abroad, although
some ha- heen puhlished in this country, notahly the ivscaivhe- ,.f
Jordan. Patten, and Hat;; Mendel and I'mh-rhill ;'' and Le Here
and < :ued nd\i-ahle. therefore, to present a irenem!
survey of the Contributions previously made on this mooted question.
PHOSPHORUS COMPOUNDS.
In -peaking of pho-phorn- compounds. Bimire ' -tales that cer-
tain of them pmhahly -hould h mic food
-uh-taiice- fi.r man: aUo that in all animal and veiretahle tissues,
in every cell are found t\\o emnplrx organic compounds which are
ri<-h in pho-ph«»ni-. namely, the lecithins and the nuclein^.
According to the recent recommendations of the joint commi;
of the American l*h\ -ioL.^ical Society and the American Society
of Hio|,,._ri«-al Cliemi-t> on protein iK.menclat lire, the word " jn-oteid "
should he ahandone<| and the word M protein " >h<»uld «|e>iurn:ite that
irroiip of >nh^tanees uhich consists e>-entially of comhination- of
M-amino aci.U an<l their derivati^
The conjugated protein- are divided into (»/) nucleo-pr.,tein., (h)
i:l\co-prntein-. v phospho-proteins, (//• liemoLrlohin>. d i lecitho-
protein-. The nucleo-proteins are compound- of one or more pro-
tein molecule- with a nucleic acid. The phofipho-proteina are
compound- of the protein molecule with some, as yet unidentified,
phosphorus-containing .-uh-tance other than a nucleic acid or
lecithin. The lecitho-proteins are compounds of the protein molecule
with lecithins (lecithans, phosphat ids).
J. PhvMol . l!Mir,
17 :
Bioi, Chcin., I'.MMi. : • 203.
rf Physiologic and Pathologic <'h»-inistry. iM ed., 1902.
6 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
LECITHIN-.
The lecithins are ester compounds which may be regarded as having
been formed by the union of one molecule of glycerol with two mole-
cules of a fatty acid (stearic acid, palmitic acid, or oleic acid), one
molecule of phosphoric acid, and one molecule of cholin, with the
loss of four molecules of water. The formula for lecithin is
C^H^NPOj,. The lecithin radical contains one atom of nitrogen
for every atom of phosphorus.
Cholin is an ammonium base, the composition of which is accu-
rately known. When heated it splits into glycol (ethylene alcohol),
and trimethylamin. Its synthesis corresponds with this decomposi-
tion. Wurtz a produced it by the action of ethylene oxid and
\\ater on trimethylamin. In the animal kingdom cholin has, up to
the present time, been found only in lecithin. It was first obtained
by Strecker6 from the bile, which contains lecithin, and hence was
called cholin. Liebreich c found it among the products of the decom-
position of phosphorus compounds from brain tissue. Diaconowd
showed that it was a product of the decomposition of lecithin. In
the new tissues of plants cholin is found in other combinations as
well as in lecithin. At present Jbut little is known about the part
which the lecithins play in the vital functions.
An important question is whether the lecithins of the body tissues
are produced from the lecithins of the food or by synthesis from
other materials such as fat, protein, and phosphoric acid. It has
been ascertained from experiments on artificial pancreatic digestion
that the lecithins take up water and readily split up into glycero-
phosphoric acid, fatty acids, and cholin. It is not yet known whether
this decomposition . is complete in normal digestion, or a portion is
absorbed unchanged, and if so, how large a portion; whether only
the undecomposed part, when absorbed, can be utilized in the build-
ing up of the tissues, or the products of decomposition which are
absorbed again become united; or finally whether lecithin may also
be formed from other material. The absorption of lecithin or of its
products of decomposition is complete, according to Bunge, as he
states that neither lecithin nor glycero-phosphoric acid can be found
in the feces. More recent work, however, by Long e seems to show
that the feces sometimes contain lecithin in considerable quantities.
The presence of lecithin in milk, eggs, and many other foods indi-
cates that this substance is essential in nutrition.
« Centrbl. med. Wissensch., 1868, 6 : 69, 431.
& Ann. Chem. Pharm., 1862, 123 : 353; 1868, US : 77.
clbid., 1865, 134: 29.
d Centrbl. med. Wissensch., 1868, 6:97, 434.
« J. Amer. Chem. Soc., 1906, 28 : 704; Long and Johnson, ibid., 1499.
IIKVIKW Of LFFKBATUBB. 7
\i ( 1.1. < >-IM;« >i i i\-.
Ry this name are designated those compound proteins which yield
true nucleins on pepsin digestion and which, on cleavage with alkali,
yield protein and nucleic acid. The nucleo-proteins seem to be
widely distributed in the animal body. They occur chiefly in the
cell nuclei, but they also often occur in the protoplasm. They may
p8Sfl into the animal fluids on the destruction of the cells; hence
nucleo-proteins have also been found in blood scrum. They may be
con-idered as combinations of a protein nucleus with a side chain
which Kossel" calls the "pro.-ietic irroup." This side chain, which
contains the phosphorus. yield> on tin4 decomposition of many nucleo-
proteins. >iich as that from the yeasl cell ' or from the panen
besides nuclein ha>e>. al-o reducing substances, \N hich form crystalline
combinations with phenyl-hydra/.in. The nucleo-protems contain
from ()..") to l.ii per cent of phosphor
The nucleo-proteins >plit into a nuclein and an albumin radicle and
the nuclein radicle i^ fnrt her split into nucleic acid and albumin. The
nucleic acid- on e yield in addition to the purin bases three
simple pyrimidin derivative-, uracil. r\t«>Mn. and thymin. In a
receni article by ( Kbornc and lle\l it appears ihat all but one-
sixteenth of the nitrogen of nucleic acid probably belong to ^uanin,
adcnin. c\ t«>rm. and ura«-il. of \\ Inch one molecule of each i> present
for even four atoms of pho>phoru->.
It is important to dMin.uuUh between the nuele«.-pniieins and the
{)seu.|(» nucleo-pn»tein^. The latter bodies are obtained as an insolu-
ble residue on diircMion of certain nudeo-albumins or phospho-glyCO-
proieins with pepsin hydrochloric acid. They contain phosphoru-
but yield no nuclein bases. Amoni: the pseudo QUCleo-proteillS mav
be mentioned phospho-proteins and lecitho-proteins. The-e >ub-
stain -I'ten fed in the form of casein or vitellin in metabolism
experiment-.
M < 1.1 :
The ireneric name of nuclein has been bestoued uj»on a larire number
of very ditrerent orLTanic pho.sphonis compound.-, which are to be
found in all animal and vegetable tissues, beinir e>|)ecially abundant
in the nuclei of cells. The nuclein- contain about .') per cent of phos-
phorus and are formed by the cleavage of nueleo-protcin. The
nucleins are acids, and the phosphorus is given oil' as phosphoric acid
on boiling with water, and more rapidly on boilinir with alkalies or
acids. But the organic substances which are combined with the
" An-h. Anal. Ph\>i<>l., Physiol. AM.. |V):j. j,. |."»7.
*> Il)i«i., 1S!H. j>
• ILuuiiutr-ien. Xt>. Ph\>i..l. Cli.-in . ISMI. /.'; : 19.
'/ Anu-r. .1. Phy<i..l.. L908, .'/ : 157.
8 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
phosphoric acid appear to be of varying characters. Most nucleins
are protein compounds, although a few do not contain protein.
Nucleins appear to occur mostly in the tissues, not in a free state, but
as compounds with protein as nucleo-albumins, and perhaps also
with lecithin, and the gastric digestion separates them from these
bodies.
Whether the nucleins of the body tissues arise from the nucleins
of food (in which case they would rank among the number of essential
food substances), or whether the nucleins are formed in the body by
synthesis, is a question of great importance, about which, as in the
case of the mode in which the lecithins originate, very little is known.
The extensive observations by Miescher ° on Rhine salmon seem
to show that the nucleins as well as the lecithins arise in the animal
body by synthesis.
PHOSPHO-GLUCO-PROTEIXS.
This group includes the phosphorized gluco-proteins. These com-
pound proteins are decomposed by pepsin digestion and split off para-
or pseudo-nuclein substances, similar to nucleo-albumins. They
differ from the nucleo-albumins in that they yield a reducing sub-
stance on boiling with acids, and from the micleo-proteins in that
they do not yield purin bases.
Only two phosphorized gluco-proteins are known at the present
time. Ichthulin, which occurs in carp eggs and was studied by
Walter,6 was considered by him as vitellin for a time. In regard to
solubilities, ichthulin behaves like a globulin. Walter prepared a
reducing substance from the para-nuclein of ichthulin, which gave a
crystalline combination with phenylhydrazin. The other phospho-
gluco-protein is helico-protein, obtained from the glands of the small
snail Helix pomatia.
INORGANIC PHOSPHOR I >.
4
In regard to phosphoric acid Hammarsten c states that there seems
to be no doubt that its importance lies chiefly in the fact that it takes
part in the formation of nucleins and thereby indirectly makes pos-
sible the processes of growth and division which are dependent upon
the cell nuclei. Loew d has shown, by means of cultivation experi-
ments on the alga Spirogyra, that only by supplying phosphates (in
this case potassium phosphate was used) was the nutrition of the cell
nucleus made possible, and thereby the growth and division of the
cells. The cells of the Spirogyra can be kept alive, and indeed produce
« Cited in Hammarsten 's Textbook of Physiological Chemistry, New York, 1908.
& Zts. physiol. Chem., 1891, 15 : 477.
c Physiological Chemistry, 2d ed., 1898.
<*Biol. Centrbl., 1891, 11: 269.
Ki:vn.\v <>F i.rn.i; A i < 9
March and proteins for sonic time, \\ithout a supply of phosphate-.
hut their growth and propagation suffer. Phosphoric acid is also
without doubt <>f importance in the formation of the lecithin.- and
other organic phosphorus compounds. The inorganic forms of phos-
phorus occur in the bones and teeth as calcium phosphate and mag-
nesium phosphate.
A small part of the phosphorus of the food is in the form of inor-
ganic salts, a- in meat, hut i- mostly in organic combinat ion, a- in
milk etc., as nucleo-albumin. nucleins, casein, lecithin, and
vitellin.
PHOSPHORUS METABOLISM.
Ivohmann " and his follo\\«-i-. Marcu-e. Sieinit/..1 Leip/.iger,'7
Zadik. Klirlieh.'' mid (iou>tein,'/ favor the organic forms of phos-
phorus, and the opinion of the majority is that the nuclein.-.not be in*;
ea-ily >plit by the di.LTeMive jmV. bsorhed with dilliculty; con-
se()iiently the body builds it- organic compound- from the more
-imple organic phosphorus bodie-.
The ti Salkou-ki. I'mber. and the Bre-laii -chool i- that
the body ha.- not the pouer to build from j>ho-phoi ii--frce protein
and inorganic p! organic phosphorus combinations essen-
tial to the life of the cell. Lack of plm^phato in the food is u ithout
influence on pho.-ph .-utioM. and exec— ive feeding of organic
pho-phoni-> c : ion of more pho-phoi-ii- than ti
sive feeding of him L.M nic pin -pha t «•>. 'I'he a.lvaii' ; OlgaDlC
pho^)!iMm> over inorganic phos] luring the period of Drouth
is >h.)\\n by (Yonheim and Miiller b\ i-\p«-riments pci f..nned on
li\" inl'ant> and a l» •• problr: .. determine \\hether the
two f. •!•! ^ani.- ph.ivphorus, j)rotein-ph<»phorus and fat-phos-
phoi'ii-. exert the same inlluence on the a»imilation of phosphorus
and iiitrojren. Tin- I were Q pre|>arat ion from
-kiiiimed milk and a lecithin preparation from the yolk of eggs.
The f.., id containing lecithin apjx'ared i ution of cal-
cium, most of which ua- fniiiul in th- l^xperiments wei'e also
made u|>on ! 3 old at the beginning of the experi-
ment. Thef ..... ! ^nsisted of milk, rice, flour, and butter. Three
diet phi -Ik. and t u o n-ceived plasmon
rlin. klin. NV.M-h.'ii-
ft Aix-h. gesam. rhy-iol
!l»id., 1898.
d Ibid., 1899, 78: K>_'
1., 1899, ?
/Stoffwechselv.TMirh,-. Imuiir. I»i m, 1900.
^Ibid., 1901.
*Zt.-v -liat. j.hysik. TluTapi.-. 1903
10 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
together with sodium phosphate. The amount of food given was
calculated according to the following formula: (^/Body weight)2.
One dog which was fed on egg yolk died, the histological section
showing that death was due to pneumonia. There was no difference
in the appearance of the dogs and all grew equally well. The marrow
of the bones of the dogs fed on egg yolk was yellow and richer in fat,
while the marrow of the bones of the plasfnon-fed dogs was red and
richer in blood but poorer in fat. On aging, the red marrow became
yellow, proving that the dogs which were fed with egg yolk made
more progress.
The same experiment was tried with four guinea pigs and one of
those fed on egg yolk died of pneumonia in three months. The pigs
so fed also showed fatty livers, which weighed more than the other
livers. The increase in weight was greater in the case of the pigs fed
on egg yolk than in the case of those which were fed plasmon. In
all cases the phosphorus content of the brain was the same.
The general conclusion was that the growth of nitrogenous tissue
is facilitated if phosphorus is ingested in the form of egg 3rolk; that
is, in organic form. The daily amount of phosphorus needed by the
average man, according to Siven,a is from 0.7 to 0.8 gram, and
according to Ehrstrom,6 from 1 to 2 grams. He states that phos-
phorus is necessary for the proper nourishment of the bones, nervous
system, body proteins and cells, and that the body strives to retain
the phosphates more than other salts. Other investigations along
this line were carried out by Tigerstedt,c Renvall,d and Schlossmann. e
Slowtzoff/ in studying the action of lecithin on metabolism, found
a plus nitrogen balance accompanied by a diminished excretion of
phosphorus and also of purin bases. Where the nitrogen balance
was minus, the case could be otherwise explained.
Loewi^ investigated the metabolism of nucleins. He experimented
on himself and found that a part of the nuclein was split in the
intestine, the phosphorus of the split portion going into the feces,
while the nitrogen was absorbed. The part not split was nearly all
absorbed and consequently the phosphorus remained in organic com-
bination. It is possible by nuclein feeding to bring the body into
the same nitrogen and phosphoric-acid relation as exists in the
nucleins themselves, since nuclein ingestion increases the retention
of nitrogen and slightly increases that of the phosphorus.
aSkand. Arch. Physiol., 1901, 11 : 308.
*> Ibid., 1903, 14 : 82.
c Ibid., 1904, 16 : 67.
dlbid., 1904, 16: 94.
eArch. Kinderheilk., 1905, 40 : 1.
/Beitr. chem. Physiol. Path., 1906, 8 : 370.
9 Arch, exper. Path. Pharm., 1900, 44 : 1; 1901, 45 : 157.
REVIEW Of LITKllATfUK. 1 1
and Berjvll"' studied the influence of nuclein food on the
blood and metabolism and found that it increases the number of the
leucocytes. Briicke'' conducted experiments to show tliat the benefit
derived from e^ yolk was due to lecithin. Danilewsky' determined
that lecithin had ^reat influence on the growth of youn^ animals.
I'mikoH'-' at about the same time showed that rats and doves died
when fed on a phosphorus-free diet and also when fed on an inorganic
phosphorus diet pli; Ibnmin, and barely lived on a nuclein-
phosphorus diet, but thrived when lecithin was fed. Selensky also
demon>! rated the valuable efl'ect> of lecithin. Seroim \\as the first
•iject lecithin into a human subject, and the experiment uave
-ults. Danilewsky showed that lecithin increased the
number of red blood corpu- the hemoglobin: also that the
'ite, body v ;id growth increa>ed. Moreover, the resist-
ance of i he bod\ bCF after lecithin feeding, and the
• »f body \\eijjlit duri -d. \Yildiers,' how-
. did im:
'.merited \\ ith LTiiinr.- and
LCood results \\ere obtained t'.-i four and one-half months after the
lecithin f --ped. In the urine there uas more nitroLreu
but le» phnsphorus than in the controls. A larvvr part of the urine
niti' i in lecithin-fed animal> and a more com-
plete devtniction «>f the protein \\a> brouu'hl about ifi the.-
(Jilbei- ' Claude and and othei-s
carried OH clinical 6X] ith lecithin and found a resultant
in appetite, number of red corpuscles, hemoblast>, and
hemoglobin*
(diken' made a Mudy of the lecithin content mur animals
born blind and helplox and of i ! that the
yoiiULT anii' m a higher lecithin content than do mature
animaU: that the lecithin contei: with the growth and
of the animal, and that the • --ome into the world with
a larire relative amount "f li-cithin in their bodies.
J, .;- : 1:1.
-
JM! l-'ouniirr. ( ..nipi. n-ml BOC, l.i-.l, }'.*<)l , .>.i : [\r>.
pCompt. n-n.I.. 1904,759:819.
80C. biol.. 1'Hil. ; ; : 1 \7>.
<Compt. n-n.l.. 1!«)1.
:io<i»itaiix .-ivils milir.iin-. l')i)|. \,,. 11:;. p. 1084.
i. Zt.-.? 1907-8, 7 :286.
12 METABOLISM OF ORGANIC AND INORGANIC PHOSPHOR rs.
Xerking0 studied the lecithin distribution in animal organisms, and
quotes the lecithin content of the organs of various animals as varying
from 0.55 per cent in the pancreas to 1.5 per cent in the liver.
Schulze6 investigated the lecithin content of various plant seeds,
and found from 0.5 to 1.5 per cent. This author also determined the
lecithin content of various portions of the bodies of rabbits, from
which it appeared that the average lecithin content equaled 0.45 per
cent of the living weight of the rabbits. In the case of a hedgehog
the average per cent of lecithin was 0.82 per cent of the rive weight.
A study of the stability of egg ard brain lecithins has recently been
made by Longc and a further study of lecithin emulsions was made
by Long and Gephart.d
In making determinations of the deposition of lecithin and its con-
tent in organisms Franchini6 found that feeding lecithin to rabbits
increased the content of this substance and also of glycero-phosphoric
acid in the liver and the muscles, but not in the brain. Lecithin
remains in the liver sometimes for fifteen days after its ingestion has
been stopped. The feeding causes a slight increase of glycero-
phosphoric acid and of formic acid but not of cholin. Most of the
ingested lecithin is absorbed, since only a very small increase is noted
in the feces.
According to observations made by Merservizky/ lecithin forms
15.35 per cent of fresh hens' eggs. After six days the lecithin content
diminishes. The lecithin of the yolk is a storehouse of food for the
developing germ, and is used in the development of the skeletal phos-
phoric acid, in the building up of the phosphorus of proteins, and for
the liberation of energy, after which the fat radical is oxidized.
According to Kiittner/ the influence of lecithin on the activity of
the digestive ferments varies with different enzyms, having a favor-
able effect upon the activity of the gastric and pancreatic enzyms,
but a retarding effect upon others. How lecithin itself is affected he
could not determine.
Koch and Reed,* in an article on the relation of the extractive to
the protein phosphorus in the Aspergillus niger, express the view
that protein, or in the case of Aspergillus niger, nuclein phosphorus
is the most important form of phosphorus for cell life. It is formed
at the expense of the other forms of phosphorus, excepting lecithin,
and its formation is not diminished even in extreme starvation. In
building up the nucleins lecithin probably takes no direct part.
When lecithin is metabolized some or all of its phosphoric acid may be
built up into nucleins as a matter of economy to the organism. The
« Biochem. Zts., 1908, 10 : 193. * Biochem. Zts., 1907, 6 : 210.
& Zts. physiol. Chem., 1908, 55 : 338. / Russky Uratch, 1907, No. 9, p. 302.
<• J. Amer. Chem. Soc., 1908, 30 : 881. 9 Zts. physiol. Chem., 1906-7, 50 : 472.
<Ubid., p. 895 hj. Biol. Chem., 1907, 3 : 49.
KKVIKW OF i.i i I.I;A i TIM:. 13
extractive. \\ater-soluhle forms of phosphoric acid are (ho oiu .s t'mm
which tin- others ait> built and represent tin1 intermediary .steps
betueen the phosphates and the more complex phosphorus combi-
nation^.
KalaroukoH' and Terroine n studied the inlluence ol' lecithin on the
action of the pancreatic lipa>e and found very little, if any, increased
activity when lecithin was present.
in his experiment on phosphorus liberation from nuclein
compounds, determined that it is more ditlicult to cause phosphorus
to pass from its nucleic acid combination to an inorganic condition
than ha> been BUppOSed.
Michel ih cd the Duality of woman's milk and found
that the utili/ation of its nutritive materials by infants is nearly
complete. The -alt- \\eiv least utili/.ed. In per cent of ca.lcium and
K) per cent of phosphoric acid be !e(l in the IV
Keller studied the metabolism of phosphorus by determining
the phosphoric acid in the urine of infants fed with woman's ,-md
with cow's milk, and found loss phosphoric a« id 90 excreted in the
of the b d children. Whether this \\a- due ater
excretion in the t«» a better assimilation of the phosphorus
of the mother's milk remains t.. be determined.
In the experiment d out b\ Jordan. Hart, ami Pair
it \sas found in th.- AS fed on a hiirh phytin diet that
when the amount of phytin fed was reduced the amount of fat
in the milk uas reduced, although there uas no ell'ect mi the total
solids and casein. Thei. -mailer excretion of urine and a
tendciK \ -tip:itioii. In these experiments fhere \\as a consid-
erable [oes of body phosphorus f,,r da\s, \\hen the COWS \\ere fed (»n
u low phosphorus diet, \\ith no apparent ill ellVcts. The amount
of phosphorus in \\ ., ,1 l,ut litth' by the
of the phoephoi C phosphor^ the
all'ecte«l. if any <• en produce«l at all.
:ne e\])eriinents bt\ M,( ollum and Hart/ indicate that theli\cr
and blood have the proper! \ of dca\ in«_r the >alts of phytic acid \\itli
the production of inor'_rani«- phosphoric acid. 'I'he wide distribution
of inosite in the it impossibi- whether
it is also a produet of this cleavage. The>e results are in aeconl
witli those of Mendel and Underbill,' who sln,ur(| that the intestine
i> not necessarily involved in the excretion of the metabolic products
of phytin in certain animals, and aU.. with the conclu>ions of Scof
that the en/.\ ins of the digest ive t met do not alter phytin. Kxami-
aipt. n-iid. BOC, l»i«»l.. l'M>; • ADI.T. .1. I'hy-ii)I.t 1!M)»), in
.1 Biol. ch.-i,... inns. 4
i/Ain.-r. .1. Piiy-inl.. |!»n.
<*Abe., Ch«-in c.-ntrU., 1899, 70 : * Ab*., Bioc-hem. Centrbl., 1905, .;
14 METABOLISM OF ORGANIC AND INORGANIC JMlnsi'HORUS.
nations of the action of ptyalin, pepsin, and trypsin have confirmed
Scofone's results.
Experiments made with extracts of muscle and kidney did not
give results which pointed toward the presence of a phytase in these
tissues.
Suzuki and Yoshimura* studied the distribution of anhydroxy-
methylene -phosphorus (phytin), and giva a method for extracting
the compound, which is a calcium or a magnesium salt. In the
juice of tubers and fruit more inorganic than organic phosphorus
is found.
Suzuki, Yoshimura, and Takaishi* made an investigation of the
enzvm which decomposes anhydroxymethylene diphosphoric acid,
and state that when rice bran and water are allowed to stand the
organic compound will be decomposed and the amount of soluble
inorganic phosphoric acid increased. When boiled this action does
not take place. The same change takes place when barley and rape
seeds are used. No other enzym will do this.
As opposed to the beneficial results of organic phosphorus Keller0
got very favorable results from feeding normal milk plus inorganic
phosphates.
Ivochniamid studied the changes in the inorganic constituents
in the tissues of rabbits poisoned by phosphorus, lie made iron,
calcium, magnesium, phosphorus, potassium, and sodium estima-
tions in the liver, heart, muscles, and bones and compared them with
similar estimations in normal animals. His conclusions are that a
definite effect was produced on phosphorus metabolism and that the
use of phosphorus in bone affections and as a stimulant is well
founded. Calcium, potassium, and sodium replace one another.
The magnesium metabolism is also affected in the cases of phosphorus
poisoning, and the excretion of phosphorus and calcium run parallel.
More recent work by Hart and McCollum c on feeding inorganic
phosphates to growing pigs has been conducted for two years.
According to the abstract published by the authors, the results clearly
indicate that inorganic phosphates, such as bone ash, finely ground
rock phosphate, or precipitated calcium phosphate (a mixture of
di- and tri-calcium phosphates) can be used by^ these animals in
connection with rations containing insufficient phosphorus. Young
animals of 40 pounds weight, receiving inorganic phosphates,
together with other salts as supplementary to a ration very low in
mineral constituents, grew to be animals of 280 pounds weight,
Al.<.. Chem. Centrbl., 1907, 78 : 1636.
b Ibid., 1637.
c Abs., Zts. diat. .physik. Therapie, 1901, -5 : 147.
* Arch, gesam. Physiol., 1907, 119 : 417.
« Abs., Science, 1908, 28 : 217.
i;i:vu:\v OF LI i I;I;A rn;i.. 1,)
and bore litters of fairly vigorous pi^s. which on the Stone ration
completed the cycle hack to SI) pounds, while, animals on the same
ration, without the inorganic phosphates, collapsed in three months,
losing weight and the u>e of their leir>. Other important observa-
tions made are a- follows: (1) Animals on a ration extremely low
in phosphorus made as lap up to 7~> to 100 pounds, as did
animals receiving an ahundtince of this element, hut after reaching
this point the v. is reduced :ind colhipse followed. . ('J) When
such low j)hosphorus rations as induced these symptoms \\ere
supplemented hy inorganic phosphates, no unfavorable results ap-
peared. Animals fed a low phosphorus diet, supplemented by
inorganic phosphates, made as vigorous a development a,s other
animal> receiving all the phosphorus in the organic form. (:>} Deter-
minatioi ''ium and phosphorus in the principal organs and
tissues of the animals fed on the low phosphorus ration showed that
they maintained their normal bod\ comj)osit ion. The per cent
of a-h in the skeleton of pi'/- on .-. depleted phosphorus ration uas
reduced to > .ue-half that of pij/s uhich received a normal
mtion. or the phosphorus-,- plus inorganic phosph,
When the anin ir\in/ for phosphorus they derived it
fr their hones, hut alu.-iy- remo\«'d calcium and phosphorus in the
proportion- found in tricalcium phosph;
PHOSPHORUS ELIMINATION.
In Mudyini: i i »n of j)ho>j)horu- and
other Bill the inllucnr, of ih,- n-a.-tion- of the ira-t ro-intcs-
M impo! .'haracirr of th<> a-h of
•«l. All of the conditions influencinir acidiiv and
fret the a1 :i and the pa«h <»f • i of
pho-ph.i' iiim. and m.^nc-iu:;, In t he ca-e of herl>i\ ora
a larire portion of the- Inated in the feees, no
ah-orptioii haxini: taken place. This i- likelv to happen when the
food ml -ullicient ca'citim ami mairnesium are present
• mbine \\ith the phosphoric aci<l. There ifi then an excivtiori of
these elemrnt.s through the intestines as well as through the ki«ln-
and when all. KUltesI inal tract
the eiiminalion through the hcwel i< likely to exceed that through
the urine. In onmivorou- animals a larger portion of the phos-
phorus, calcium, and ma^nesium, as \\-<dl as t he nitrogen, is eliminated
hy the kidneys than is the case with herbivorous animaU.
The subject of phosphorus elimination has been studied under
many pathological condition-, and especially in hunger, in the cases
Hreihaupt/' and otl
r and Miillcr: Yin-how's An-hiv. Suppl.. 1893, 131 :'2.
1'ilh-r: \ irchou-'s Art-hiv. Suppl., 1893, 131 : 52.
16 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORIC.
A phosphoric-acid diabetes, noted by Tei>sier,a and Ralfe,6 showed
a resulting polyurea where as much as 12 grams of phosphoric acid
were eliminated per day by the kidneys. In diseases of the kidneys
the activities of these organs in eliminating the phosphates may be
considerably diminished. In meningitis, on the contrary, a marked
increase in the phosphates eliminated is observed in the urine. The
statements in regard to the quantity of phosphates in the urine in
rachitis and in osteomalacia are somewhat contradictory. A phos-
phaturia is described, which is more correctly called an alkalinuria,
where the phosphates settle out owing to an alkaline reaction. A
pathological phosphaturia is also noted. Sendtner c showed that
there was an increased calcium excretion in cases of phosphaturia.
This condition is due to a perversion of metabolism, but serves to
illustrate the close relationship which exists between calcium and
phosphoric acid.
Voit d found that the feces of starving dogs contained phosphates.
The subject of phosphorus elimination has been quite fully investi-
gated by Paton, Dunlop, and Aitchison/ In the case of dogs fed on
a vegetable diet a large proportion of the phosphorus of the food is
not eliminated in the urine. The same thing is true when the phos-
phorus (inorganic) is injected subcutaneously.
In the case of goats none of the subcutaneously injected phos-
phorus is found in the urine, neither is any of the body or food phos-
phorus found in the urine. During lactation the excretion of phos-
phorus by the bowel is diminished to meet the requirements of milk
formation. In the case of dogs there is a diminished excretion of
phosphorus in the urine during lactation. The milk of goats contains
a large amount of total phosphorus, but a small percentage of organic
combined phosphorus.
On giving a soluble glycero-phosphate of calcium by the mouth
no increased excretion of phosphorus was detected in the urine of
dogs or in the urine or milk of goats.
The excretion of inorganic constituents in the urine was studied
by Cathcart and»Fawsitt f during a fourteen-day fasting period. The
excretion of phosphorus fell off gradually. There was a decreased
output of calcium, magnesium, sodium, and potassium. The normal
ratio of sodium and potassium is reversed in starvation.
Fitz, Alsberg, and Henderson's ff determinations of phosphoric-
acid excretion during experimental acidosis in rabbits are to the
a Lyon Medical, 1875, 19 :307.
& Lancet, 1887 (2), p. 1243.
c Munch, med. Wochenschr., 1888, 35: 671.
d Hermann's Handbuch der Physiologie, 1881, 6 : 345.
« J. Physiol., 1900, ,'.5:212.
/ Ibid., 1907, 36:27.
9 Amer. J. Physiol., 1907, 18 : 113.
KKVIKW < >!•' I.I I i.KA IT UK. 17
cll'ect that feeding hydrochloric acid produce, first an increa-^ : nd
then a decrea-e in the phosphorus (P,O5) excreted in the urine. The
determination favor* the view that the body phosphates are con-
cerned with neutralizing the acid and wilh its removal from the body.
U >os(i on feeding thyroids to dogs got an increased phosphoric
acid excretion and alter extirpation of the thyroids found that the
elimination of phosphoru- was decreased. Phosphorus elimination
-eems to be regulated, in part at least, by those glands, the relation-
ship being similar to that A\hich probably exists between calcium
and pho-phnric acid and the ovaries, and that between iron and the
spleen.
I is dillicult to give a typira: urine analysis «>n account of its \ aria-
tious. Tin- follow-in. may be of ue, though only ap-
proximate li for the quantities of the most important
inorganic constituents which are e'iminated by an a
• •II on a mixed diet in tin* course of twenty-four hours in a quan-
tity of ! .
Grams.
.Hill rhloi. .......................... 16. 0
Sulphur: ..........
Phofpho: ........
Pot i
Aiiimoni ... .7
IfagnOU M_<> ..... ....... :,
Lin ..... .3
.lining i normal. ... .2
... 25.0
Phosphoric acid ••«-. . id urin< u double MHiPO4y and
pal! .iple M.ilPO,, botli of the>e plu^phales being found ill
acid Ulinee at fcbie -aim- time. On found that on an average 60 per
M|' the total pi d \\as double, and 40 per cent was
simple acid phosphate. The total quantity of pho>phoric acid is
d)le and depend- on the kind and th- ;\ M|' the food. The
p!iM-p!iMi-ie acid eliminated by man i.> in round
numb«-i> 2.5 a rial ion of from 1 to ."> grams per twenty-
four hour-. A -mall j.ait of the phosphoric acid of the urine origi-
nate- from the burn :iic compounds such as nuclei n, pro-
:i, and lecithin within the organi-m. The greater part originate-
fro! 11 the phosphates of the food, and the quantity of eliminated phos-
phoric acid i r when the food is ridi in alkali phosphate.^ in
o the quantity of lime and magnesium phosphates. If
iitain^ much lime and magnesium, large quantities
.rthy plio-phat. iiminated in th<4 excrements; and even
though the food contain- con>iderabie amounts of phosphoric acid in
. riu-in., ; J!>. 6Zte. i.h\M'.l. < h.-in., iss(i, 10:1.
:«M)_l{ull. 12:5— 09 - 2
18 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
these cases, the quantity of phosphoric acid in the urine is small.
Such a condition is found in herbivora, whose urine is habitually poor
in phosphates. The extent of the elimination of phosphoric acid by
the urine depends not only upon the total quantity of phosphorus in
the food, but also on the relative amounts of alkaline earths and the
alkali salts in the food. According to Preysz0 and Klug6 and Olsav-
szky, the elimination of phosphoric acid is considerably increased by
intense muscular work.
From the transformation of tissues rich in protein or phosphorized
nerve substances in the body, an equal relation between the nitrogen
and the phosphoric acid in the urine might be expected. Many
investigations have been made on this point, but the conditions which
affect the elimination of phosphoric acid are not yet sufficient ly
known to permit any definite conclusions being drawn from the obser-
vations thus far made.
Of the various forms of phosphate compounds which appear in the
urine the following may be mentioned: Tricalcium phosphate,
Ca3(PO4)2, which occurs only in alkaline urines; calcium diphosphate
(CaHP04 + 2H2O) occurs in neutral or only in very faintly acid
urines; ammonium magnesium phosphate, triple phosphate, may
separate, of course, from an amphoteric urine in the presence of a
sufficient quantity of ammonium salts, but it is generally charac-
teristic of a urine which has become ammoniacal through alkaline
fermentation; amorphous magnesium triphosphate, Mg,(PO4)2, occurs
with calcium triphosphate in urine rendered alkaline by a fixed
alkali, and crystalline magnesium phosphate (Mg2(PO4), + 22 H2O)
which has been observed in a few cases in human urine, and in horses'
urine.
Phosphate calculi may consist of a mixture of the normal phos-
phate of alkaline earths with triple phosphate. They also are
composed of a mixture of earthy phosphate, triple phosphate, and
ammonium urate, surrounding a foreign bod}' as a nucleus. Calculi
consisting of triple phosphates alone and stones of simple acid calcium
phosphate are seldom obtained.
SALTS IN THE ORGANISM.
The body contains in its tissues and liquids a considerable amount
of inorganic material. When an}T organ is incinerated this material
remains as ash. If the bones, which are rich in mineral material, are
omitted the average amount of ash in the human body amounts to
about 0.1 per cent of its weight. It consists of clilorids, phosphates,
sulphates, carbonates, fluorids, silicates of potassium, sodium, calcium,
« Maly's Jahres-Ber., 1891r Ji
b Arch, gesam. Physiol., 1893, 54 :21.
KKVIKW (>K LJTERATUBE, 19
magnesium, and iron: iodin occurs also, especially in the thyroid tissues.
In the liquids of the body the main salts are sodium chlorid, sodium
carbonate, sodium phosphate, and potassium and calcium chlorid or
phosphate. In considering the organic foodstull's. their value as
sources of eneriry, as well as their function in constructing tissue, is
emphasized. The salts have4 no importance from the former point of
view. Whatever chemical changes they undergo are not attended
by the liberation of heat ener<:y — none at least of sullicient impor-
tance to be couriered. They have, however, most important func-
tions as they maintain a normal composition and osmotic pressure
in the liquids and tissues of the body, and by virtue of their osmotic,
procure pla\ an important part in controlling the How of water to
and from the ti- Moreover, these -ah- constitute an essential
part of the composition of living matter. In some \\ ay they are
bound up in the structure of the living molecule and are necessary to
its normal reactions or irritability. I'ven the proteins of the body
liquids contain definite amounts of ash. and if this ash is remo\c<!
their proper <>usly altered, as i- -ho\\ n b\ the fact that-
native protein- \\hen made practically a>h-free |o-e their properl \ of
ion by heat. The globulin- are precipitate<l from their solu-
tions \\lien the >alts are removed. Th- I importance of the
ealci oairulation of the blood and the curdling «,f milk
also the peculiar part played b\ the calcium,
pot.-i- :iid sodium salts in the rhythmical cont ract ion- of the
heart mu-cle and the irritability of musc,ular and nervon- tissues.
The -pecial importance of the it for the production of hemo-
globin i- ill knoun. The nutritive impor the salt- in
diet ha> been ileinon-traled by direct exjieriinent .
D" fed b\ FoTSter* upon a die! com|>i»^ed of a-h-free fats
and earboli\ drates. and meats which had been extracted with \\ater
until the salts had been reduced. The animals were in a dyini: con-
dition at the end of twenty-six t o t hirt \ ->ix da \ >. It i> pro!>able that
they would have live.l longer if deprived of food entirely, with the
;>tion of ualer. since the metabolism of the abundant diet pro-
vided aided in increasing the los> ,,f ^alts from the body. Lunin'' has
described experiments which in<licate that some at least of our salts
must be provided for us in organic combination- >uch a- ai'e found
in plant and animal food-. In hi- experiments he found that mice
fared well on a diet of dried row's milk. If fed, however, on a diet
containing the oriranic but ash-free constituents of milk, namely,
siiLTar. fat. and casein, together with t he ext racted salts of cow's milk,
they died in from twenty to thirty day-.
ii. Ily-h'iM'. L8£ i, j)hy,i..l. <'h.-n,.. 1881, .-7:31.
20 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
In a recent article on alkali salts in the ash of human and cow's
milk, Kastlea states that the practices which have for their object
the reduction of the amount of fat in cow's milk, or the addition
thereto of mineral matter available for neutralizing the acids result-
ing from the processes of metabolism are based on sound practical
experience, the important difference between the two kinds of milk as
to mineral constituents being as follows :,,(!) Human milk contains
relatively more of its mineral matter in utilizable form than cow's
milk; (2) it can supply the organism of the child with relatively
larger amounts of available alkali in proportion to the protein than
cow's milk.
The idea is advanced that in the milk of various animals the inor-
ganic constituents are present in the same proportion as in the ash of
the young animals. Bunge 6 shows that there is a very close relation
between the composition of the ash of young rabbits, dogs, and cats,
and that of dog's milk, dog's blood, and dog's blood serum. He also
makes the statement that the epithelial cells of the mammary glands
select from the blood and give to the milk all the inorganic constitu-
ents in the proportion needed by the young animal.
Phosphoric acid is an important constituent of milk. According
to the same author woman's milk contains 0.31 to 0.45 gram of phos-
phoric acid per liter, and cow's milk 1.81 to 1.97 grams. It is an
important fact that the food of the young furnishes the phosphoric
acid in organic combinations.
Many investigators have shown that the phosphorus of cow's milk
is not so weh1 absorbed as that of woman's milk. Stoklasac claims
that the lecithin phosphorus content of woman's milk is 0.35 per cent,
as compared with 0.5 per cent in cow's milk. Blauberg<* fed a child
on mother's milk and studied the metabolism of the salts contained
therein. He compared his results with the results obtained by other
investigators and concluded that the constituents of mother's milk
seem to be better utilized by the system than the constituents of
cow's milk.
Xo complete analyses of the mineral substances of pure, blood-free
muscle substance were found. The ash remaining after burning the
muscle (which amounts to about 10 to 15 parts per thousand, calculated
on the moist muscle) is acid in reaction. The chief mineral constitu-
ents are potassium and phosphoric acid. Next in amount are sodium
and magnesium, and lastly calcium, chlorin, and iron oxid. Sul-
phates only exist as traces in the muscles, but are formed by the burn-
ing of the proteins, and, therefore, occur in abundant quantities in the
ash. The muscles contain such large quantities of potassium and
" Amer. J. Physiol., 1908, 22 : 284. c Zts. physiol. Chem., 1895-6, n : 79.
&Zts. Biol., 1874, 10 : 111, 295. d Abs., Chem. Centrbl., 1897, 68 : 957.
HKVIKW <>!•• LFFEBATUBE. 21
phosphoric arid that potassium phosphate seems to he uiupiestioii-
al)ly the predominating salt. C'hlorin is found in such insignificant
<juantitie> that it is perhaps derived from a contamination with Mood
or lymph. The (piantity of magnesium is ahout douhle that of cal-
cium. The>e two hodies, as well as iron, occur only in very small
Amounts.
Sherman" in making a determination of the amount of mineral
matter required hy the human hody, examined twenty Amerieau
dietario for ash and compared the amount of mineral matter contained
in them with the estimated maintenance4 requirements as found in
metaholi.xm experiments. lie concludes that iron and protein run
parallel and that calcium and phosphoric acid vary; further that the
diets do not >upply a sullieieiit amount of either calcium or
phosphoric acid, and as much attention should he paid to the supply
ilcium, pho>phoric acid, and iron *& t-» protein. Milk and d.
mi^ht he sui»tituted for a part of the meat of the ordinary diet and
the use of fruitx and veirelahles >hould supply a part of the 813
Btarchj and minerals. Several other worker- ha\«- viudied ash-free
diets.
CALCIUM COMPOUNDS.
The metaholism of calcium has heeii extensively studied. There
are two form- of ralcium which enter into the composition of our food
and drink, the organic form in milk, e^.irs, plant seeds, etc., an<l the
inorganic f'-nn. whi<-h consists principally of ralcium carhonate, cal-
cium sulphate, and calcium pho>phate. Both forms are ahsorhahle,
the amount ahsorhed depending on the food taken simultaneously
AIIIOIIL: other factor- intlurnciiiL' tin- calcium al^orption may he men-
tioned sodium chlorid, which in.-: ,nd the alkali-, \\hich dimin-
i-h. the amount ,.f calcium al»orhed. A- noted hefore, there exists
a clo-e relatioii-hij) l)et\\eeii calcium and phosphoric aeid.
.•ordini: to Hun-.- • and l»ertramr the euleium in plant food
is not so \\ell al>-oi!.>d a- that in animal food. Many foods lack
calcium, the daily need of which for the human hody is, in the
opinion of ( )herndorifer, ' !."» grains, \shile Bun^e' claims douhle
that aiiH»um. mi- per diem. The yoiin;: need milk rich in cal-
cium. Hui lire >ays calcium forms 0.04 per cent of the hlood, while
Alhu and Neul)er.L:; cite experimenis >ho\viug that calcium forms as
much as 0/J7 per cent of the hlood. In arterio sclerosis, Gazert^
o Lake Plari.l r.,1,-- coo. Proc., 1907,9 : 114.
• Al.~.,< h.-m.< . ntrbl.,1879, J0 :•
d Berlin, klin. W-H-h.-n-hr.. 1904,4^:1068.
Biol., 1-7'.. i : : r.'l.
/Mineral Si.,n\v,-«-h-..l. 1',,-rlin, 1906.
'••ut*-h. An-h. klin. M«-<1., 1S9S, t;..' :H90.
22 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORTS.
found from fifteen to twenty times as much calcium in the blood as in
normal health. More calcium is absorbed from natural food than
from artificial, and in the latter case more calcium is likely to be ex-
creted by the bowels unaltered than normally. The amount of cal-
cium retained b}r the tissues and its manner of combination depend
both upon the quality of the food and the amount of calcium in it
With the exception of the importance* of the alkaline earths as
carbonates, and especially as phosphates, on the physical composition
of certain structures, such as the bones and teeth, their physio-
logical importance is nearly unknown. The occurrence of earthy
phosphates in all proteins, and their great importance in the passage
of the proteins from a soluble to a coagulable state, make it probable
that the earthy phosphates play an important part in the organiza-
tion of the proteins. An insufficient supply of alkali earths in the
food raises an interesting question as to the effect of this lack on the
bony structure.
CALCIUM SALTS AND COAGULATION.
The property which is the most characteristic of casein is that it
coagulates with rennet in the presence of a sufficiently great amount
of lime salts. In solutions free from lime salts the casein does not
coagulate with rennet, but if lime salts are added it is changed so that
the solution (even if the enzym is destnyyed b}7 heating) yields a
coagulated mass, having the properties of curd.
According to Soxhleta the soluble lime salts are only of essential
importance in coagulation, wliile the calcium phosphate is without
importance. According to Courant6 the calcium casein compound
on coagulation may cany down with it, if the solution contains di-
calcium phosphate, a part of this as tricalcium phosphate, leaving
monocalcium phosphate in the solution. The chemical process wliich
takes place in the rennet coagulation has not been thoroughly investi-
gated.
The fibrin ferment, wliich was called thrombin by Schmidt,0 is pro-
duced, according to Pekelharing,d by the action of soluble calcium
salts on a preformed zymogen existing in the noncoagulated plasma.
Schmidt admits the presence of such a mother-substance of fibrin
ferment in the blood and calls it prothrombin.
Briicke* showed long ago that fibrin left an ash containing calcium
phosphate. The fact that calcium salts may facilitate or even cause
a coagulation in liquids poor in fibrin ferment has been known for a
« Munch, med. Wochenschr., 1893, 40 : 61.
& Arch, gesam. Physiol., 1891, 50 : 109.
c Zur Blutlehre, Leipzig, 1892.
<*Zts. physiol. Chem., 1896-7, ..'.' : 245.
« Vorlesungen tiber Physiologic, 2nd ed., 1875, 1 : 270.
RI:VII:\V or i.iiT.RA in;r. 23
years through the researches of ( liven," Ringer and Sains-
hury/' and others. Tin1 necessity of the lime salts for coagulation
was lirst >hown positively by the important investigations of Arthus
and Paircs.' In regard to the manner in which the lime .salts act
a conclusion has been reached by Freund,d who claims that the sep-
aration of the excess of calcium phosphate is the cause of a part of the
protein becoming insoluble— that is, a cause forcoagulation. Weighty
objections to this view can be raided, and it is refuted by Latschen-
berirer and Straiich.' According to Pekelharinjj:." the process is as
follows: The prothrombin is converted into thromhin by the action
of the >oluble lime salts, aiuf iluids which are in all other respects
kbfe of coagulation, but contain onlyprothrombin and no thromhin,
can therefore be coagulated by the addition of soluble lime salts.
Thromhin is ,( lime combination of j)rothrombin, and the proce» of
illation con-i-t- in the thromhin carrying the lime to the lihrino-
\\hich is converted into the insoluble combination of librin and
lim.-. S :.d impoi-talil papers have appeared, notably those of
Field/ Mora\\it/.' and L«.eb..' de.-dini: \\ith the role of calcium in the
-illation of the hlood. While the literature on this subject lias
not hem fully covered in this report, its importance demands more
than a pas-ini: reference in a paper dealing with calcium metabolism.
It has be«-n vj|,,\Mi by the in ve>t i-jat ions . >f ( 'a \ a/./.aiii ' t hat the lime
salt- an of importance ill the coagulation of the muscle-pla-ma M
well as in that of the blood.
The inorganic OODfltituentfl of the bony st nu-ture, the so-called bone
<»arths. \\hicli remain after the complete calcination of the organic
.substance a> a white, hrittl ; u-i-t chielly of calcium and phos-
phoric acid, but 'bon dioxid and, in smaller amounts,
Medium, chloi'in. and thiorin. Alkali sulphates and iron, which
have b;-eii found in h«»nc ash, d-; not -eem to hrlon.cr to the bone tia8U€
it - If, but to the nutritive fluid or ot he r parts of the bones. According
to Gabriel' pota-Murn and -odium aiv e^niti.-d con-f it iieni s of bone
a-h. The opinions of ini >rs differ somewhat as t<> the manner
,8:372.
6 I bid , 1S<K), //:
' .-MtrM.. 1S!»1 , I , p. :,ll.
•Ubiil., 1889(1), p.
«AI>- • :•!•!. 1S!H) (I , ],. ir,'».
/ Bhrtgerinntiiigstbeorie. I>iss., I>or|>:it, 1889.
PAbs. Chem. C.-ntrbl., 1S«»2 (J
*CentrbI. I'hy<i..I., 1!M):
It. An h. klin. MIM!., 190;i-4, 47!' : 1.
/Beitr.chem. I'hy.<i.)l. Path., 1903-t,.x l!)l, liK)i Arch, Path. Anat. Phy-
siol., 190.i 1906, 7&5:160; J. Mod. Research, !!*):{, 7^:407.
j 'sJahiw-Ber., \w, j/:346.
. ph:
24 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
in which the mineral bodies of the bony structure are combined with
each other. Chlorin and fluorin are present in the same form as in
apatite (CaFl2, 3Ca3P2O8). If the magnesium, chlorin, and fluorin be
eliminated, the last according to Gabriel occurring only as traces, the
remaining mineral bodies form the combination 3(Ca3P2O8)CaCO3.
According to this author the simplest expression for the composition
of the ash of the teeth is (Ca2(PO4)2 + Ca5HP3O13 + H2O), in which 2 to
3 per cent of the lime is replaced by magnesia, potash, and soda, and
4 to 6 per cent of the phosphoric acid by carbon dioxid, chlorin, and
fluorin. Analyses of bone earths have shown that the mineral con-
stituents exist in rather constant proportions, which is nearly the
same in different animals. The diverse quantitative composition of
the various bones of the skeleton depends probably on the varying
quantities of other formations, such as the marrow, blood vessels, etc.,
which they contain. This probably also explains the larger quantity
of organic substance in the spongy parts of the bones as compared
with the more compact parts. Schrodt a has made comparative analy-
ses of different parts of the skeleton of the same animal (dog), and
has found an essential difference. The quantity of water in the fresh
bones varies from 138 to 438 parts per thousand. The composition
of bones at different ages has not been definitely determined, but
according to the analyses made by Voit6 of bones of dogs and by
Brubacherc of the bones of children it appears that the skeleton be-
comes poorer in water and richer in ash with increase in age. Grafen-
bergerd has found that the bones of rabbits from 6^ to 7J years old
contained only 14 to 17 per cent of water, while the bones of full
grown rabbits from 2 to 4 years old contained 20 to 24 per cent. The
bones of old rabbits contain more carbon dioxid and less calcium
phosphate than do those of young ones.
CALCIUM METABOLISM.
A great many experiments have been made to determine the change
in the bone constituents, for instance, when a ration rich in lime
and one deficient in lime is fed, but the results have always been inde-
cisive or contradictory. The attempts to substitute other alkaline
earths or clay for the lime of the bones have also given unsatisfactory
results. Weiske e has shown that when young and still rapidly grow-
ing rabbits are fed wTith oats, which are poor, in acid and lime, plus
magnesium and strontium carbonate, these substances in part pass
into the skeleton, but a physiological replacement of lime by magne-
sium or strontium is not to be expected. On the administration of
« Maly's Jahres-Ber., 1877, 6 : 207. * Maly s Jahres-Ber., 1891, 21 : 290.
1> Zts. Biol., 1880, 16 : 55. e Abs., Chem. Centrbl., 1892 (2), p. 590.
e Ibid. /1890, 27:517.
HKVIK'.V OF LITERATURE. k2;)
madder the Ixmes of the animal are found to he colored red after a
few days or weeks; but these experiments have not led to any posi-
tive conclusion in regard to the growth or metabolism of the boues.
I'nder pathological conditions, as rachitis and softening of the
bone-, an o-sein has been found which does not jrive any typical
gelatin on boiling with water. Otherwise pathological conditions
seem to all'ect chiefly the quantitative composition of the bones, and
especially the relationship between the organic and inorganic ^\\\>-
-tanee-. Attempts have been made to product4 rachitis in animals
by the u-e of foods deficient in lime. From experiments on fully
developed animals contradictory results have been obtained. In
vounir, undeveloped animal- Vbil produced, by lack of lime salts
in the food, a change similar to rachitis. In full-thrown animals the
hones were changed afler a loin: time because of the lack of the lime
sail- in the food, but did not become -oft , onlv thinner (osteo-porosis).
The experiment- in which the lime -alts were removed from the bones
by t he addit ion of la< >d ha\ c led to no posit ive results
(Ileit/mann. Heiflfl !>ai:in-kv . W. >ntrarv, has
>hi»wn by admini-ieri[r_r dilute siilpliurir acid or moiiosodium phos-
phate with the f-.od (pre-uppo-ini: that the food u'ave no alkaline
ash] to -herp and rabbit-, that the quantity of mineral matter in the
bone- miirht be dimini-hed. A i'.-u investigators are of the opinion
that in rachiti-. ifl in OSteomalacia, a solution of the lime salt- by
mean- OJ Thi- W*J -ted by the fact
that \Veber and Schmidt' found lactic acid in the ey-t-like altered
born nee in osteomi Well-known inve-t i_Mtor- have
di-pnted the po»ibility of the lime -.-dt- bein/ wa-hed from the hours
in OSteomalaCOSlfl by mean- ..f lactic acid. The recent investigations
i he -obit ion of lime -alt- by
lactic arid b alacia. lie has found that the normal relation-
ship r.T < Ifl retained in all part- of th -malacia,
which would n<>t be the ca-e if the ! -olved by an
acid. The decrease in pho.-phate- occur- in the >ame (plant it at ive
relationship as the carbonate: and, according to Levy, in OSteo-
malacia the exhau.-tion of the bone take- plarc by decalcilicat ion, in
which one molecule of pho.-phate and calcium after the other is
removed.
''Mi ,1873,3:
51.
«* Yin-how's Archiv. ISS'J. 07 :901.
. rh««n. C.-ntrl.! . i- 590.
s;i, j». t,
phynol. « h.-m.. 189
26 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
The relative amounts of calcium and phosphoric acid in the teeth
are, according to the analysis of Hoppe-Seyler,a about the same as
in bone earths.
The importance of calcium for the activity of the nervous system
and the muscles has been the subject of study by many investigators.
The conclusions drawn are that if the, amount of calcium is decreased
nervous and muscular irritability will result and, conversely, that an
increase of the calcium will diminish the irritability of the nerves and
muscles. Ringer proved that the frog's heart can be kept beating
for long periods upon a mixture of sodium chlorid, potassium chlorid,
and calcium phosphate or chlorid, and he laid especial importance
upon the calcium. The calcium ions are present in relatively small
quantities in the blood, but they are absolutely necessary to con-
tractility and irritability. When present in quantities above normal
or when in proportional excess over the sodium or potassium ions
they cause a condition of tonic contraction that has been designated
as calcium rigor. The calcium promotes a state of contraction, the
sodium and the potassium a state of relaxation.
Tigerstedt in his text-book states that calcium salts favor the con-
traction of the heart, while potassium salts are important for its
relaxation. Calcium favors muscular movements of low forms of
animal life — the contractility of both skeletal and smooth muscles.
He cites the experiments of Voit,6 who fed pigeons with food con-
taining no calcium, and found that the bones which were used for
movements were normal for calcium, while the sternum and skull
bones were brittle and even perforated in places.
Falta and Whitney c showed that after extirpation of a dog's
pancreas, the calcium elimination was increased, though the nitro-
gen, phosphoric acid ratio remained unchanged. The excretion of
uric acid in these cases was doubled.
The importance of calcium salts for the growing organisms is dis-
cussed by Aron and Sebauer.d Special attention was given to the
calcium content of the bones, brains, nerves, muscles, and blood.
Dogs and rabbits were used, half of them being fed on a calcium-poor
diet. The young animal requires at least 1.2 per cent of its body
weight of calcium; a diet supplying a smaller amount is called a
calcium-poor diet. Under such conditions .nervous and other dis-
orders follow, a condition like rickets being established after con-
tinued feeding of such a diet; in these cases the bones contain more
water than is normal, that is, a water-rich bone is developed whose
« Hammarsten, Textbook of Physiological Chemistry, New York, 1908, p. 440.
&Zts. Biol., 1880, jftf :55.
c Beitr. chem. Physiol. Path., 1908, 11 : 224.
d Biochem. Zts., 1908, 8:1.
I;KVII:\\ o? LJTEBATURE. 27
organic framework is poor in calcium. The calcium content of tlic
ilesh and blood sliows no variation and the brain but a slight vari.i-
tion from the normal.
Following some experiments made by Sanford and Lnsk at the
Vale Medical School on new-born pijrs. Wilson" studied the influence
of diet on the irrowth of yonn^ piles. Three piirs were killed and
analy/ed at birth and three were reared on a skim-milk diet. To the
diet of one piir, lacto-" W8fl added; to that of the second, dextrose:
and the third was i^iven the skim milk without any added substance.
The lacto-e-fed pi-_r thrived best, while the pi^ fed on >kim milk alone
showed the lea-t pi- een days. The analyses showed
that the piir fed on skim milk used •'*- per cent of the calcium in the
food for irrowth: the lactose-fed |>i«r used 7>) per cent: and the dex-
tro-e-fed piiMil p.-; cent. The calcium content of the bodies of the
pigs at the end of the experiment \\ vn:j, and s.i:; per eent,
re-pect i\ el\ . Calcium 81 evidently depends on the develop-
ment of the animal rather than on any >pecilir influence of the milk
Constituents. lleiter'' found striking retardations in the develop-
meiit of th,- -keleton of oldn pi-- i'«-,| ,.n ^kiiu milk for many months,
but Ho rvidence of I'icket- \\a- ^een.
\V. Camei-er. jr.. iind- that the calcium content of motheis' milk
i- barely sullicicnl to < ,,\, i ilir QI lie nur-in-.: infant if the per-
centaLrc coinpo-ii ion ,,f the li\ e-mont h>-o|<| bal)\ \\ei~e the BEUU M
that of tin- n. -\\-born baby. The p. . of calcium in the !ie\\-
boi-M pi'j pet « -cut at birth and i- s.l."> per
cent at the end of two and one-half \\eek-' feeding. If the pi-- fed
on 1. lined '.». I pel- cent <-alcium at the end
of the t\\o and one-half \\ • I, an almost complete calcium
ab-oi pt ion would have taken j)la
t iliat when an animal i> <leprived of all inor-
-alt- in ii^ food profound constitutional disturbances, resulting
in <leath, are pioiincr.l. '1 he -alt> of the blood mii-t not only be
nt in Millicient (piantity to bi-ini: the o-motic pre— UK- of the
blood to ;, con-tant \alue.but they must also be present in certain
delimit' ratio ry li\ inir cell of the body must be washed by a
fluid containing -alt^ of certain moiiovalent and divalent metals in an
unvarying ratio. otherwi>e a disturbance in the int racellular ion-
protein- Loeb 01 colloidal salt- ( )-b<»i ne i- produced. Bearing
in mind this nece--it\ for a con-tant ratio between the various -alts
of the blood, a number of interest inir <pie-tion- are raided by Patter-
-on in reirard t<» the probable effect- of dej)rivinir an animal, coin-
" Ani.-r. .). I'll;. 1!)7. d\\ : 39.
.11 ter, \.-\v V..rk, 1906.
JJ. Phy-inl.. |!»(Mi. .; :84.
28 METABOLISM OF ORGANIC AND I X< MM !A X 1C PHOSPHORUS.
pletely or partly, of one particular metal, say calcium. If the proper
ratios are not maintained in the blood, then:
(a) Is the excretion of calcium checked wholly or partially? Dur-
ing the progress of his research an article appeared by Goitein0
which disposes of this question by showing that if a rabbit received
less than 0.16 grams of calcium per kilo per day in its food, there was
a stead}' loss of calcium from the bocly. Lehmann6 and others
have shown that in starvation the calcium excreted exceeds the
amount of this substance present in the drinking water taken.
(b) Are the other salts of the body reduced pari passu by increased
excretion? This would entail a considerable fall in the total molecular
concentration of the blood, and as the living cells of the body and also
the red corpuscles are extremely sensitive to osmotic changes this
question may also be answered in the negative.
(c) Is the deficiency in the food made good by certain tissues of
the body giving up a portion of their calcium to the blood and so
keeping the proper inorganic balance in this fluid ? That this would
be the most probable contingency may be inferred from a number
of facts. Forster/ who was the first to make observations on the
effect of insufficient calcium in the food, found that the muscles lost
56 per cent of their calcium content, while the bones also showed a
considerable diminution. Voitd found that on a calcium-poor diet
the bones were more brittle, the skeleton showed a smaller per-
centage of dry weight than in the normal animal, and that the
quantity of calcium in all organs of the body was more or less di-
minished.
In the experiments in which rabbits were fed on oatmeal and
maize meal, a diet which admittedly leads to calcium starvation,
the ratio of the calcium of the blood to the total ash of the blood
remained the same as that found in the normal animal. That is to
say, the blood underwent no loss of calcium relative to the other
salts in the time allotted to the experiment — a result which one might
anticipate from the immense importance of the salt ratios of the
blood. The ratio of calcium to the total mineral matter in the bones
was, however, inconstant, and showed fairly wide fluctuations even
in the normal animal. The bones can, without doubt, act as store-
houses of calcium and possibly of magnesium. That the}' lose
calcium when the animal is placed on a calcium-poor diet has been
proved conclusively. Voit's results, however, tend to show that the
bones can lose calcium relatively to the other salts, that is, by a
selective autolysis. The experiments on his own body metabolism
show that calcium can be readily stored during nitrogen retention.
« Arch, gesam. Physiol., 1906, 115 : 118. <• Maly's Jahres-Ber., 1873, 3 : 251.
& Abs., Maly's Jahres-Ber., 1894, 23 :497. <*Zte. Biol., 1880, 16 : 55.
IIKVIKW OK i.rn.iiA i n;i.. V29
interesting, however, arc the experiments involving rectal
feeding, calcium being stored despite a continuous drainage of nitro-
gen from the body. In the latter case, as the protein al)sorbed from
the food was insuilicient, tlie muscles and glands must have dimin-
ished in bulk, and yet calcium was retained. This fact rather points
to the bones as the place where calcium is Mored. In the experi-
ments on himself, and in those with rectal feeding, with a fixed diet
the urinary calcium varied but slightly, and the variations, such as
there were, ran parallel with the total amounts of urine excreted.
This result is not remarkable if it is assumed that the kidney, in
order to lighten its work against osmotic pressure, allows a fraction
of each of th. •!' the blood to escape into the urine. The greater
the volume of the urine, therefore, the greater the amount of salts
eliminated.
The following theories have been published by Albu and Neuberg"
concerning the cause <»f rick.
1. An in-ulHciftit amount <>f calcium in the food.
\n inadequate al.-..rptioii <>l tin' calcium sal <>d.
in thf hoM.'-buil.lin
.rkmcc "t" calcium :il»M,rjiti«.n in boD6fl them-
.•a rickets aii-l Mo<>,l pn^sure IM.-'-.! mi the thcnry tStfili/.-
ili. ii calcium inrtai by a secretion of the kidni
•iiilar theories a^ to the ca leomalacia \\ere enumerated by
the same author as follov.
I. A lack i'f calcium in
\ lack "t" Cftll iUBQ .1 -)d.
A decreased alk If in the •
which «Ii.-- ilciuin Kil-
I f mctal>ol: '• ri-sultiiu; from a .limini-h.-.l acti\ity
of the i»varii-. which in •
!{»cnnick>-' • last's. wteomalacia an a m(>ta>>«>li-m -li-.-.i-.-. (In- |.!i..-|.!n.ru- mcta-
1 >• in«r also affected.
In pathological cases tin- and opinions are maii\ and
iliver^e in regard to Calcium elimination. l-'«»r example, Px-n.
found increased calcium elimination in fever, while Senator'7 obtained
opposite results. lu charac t cri-t i«- bone diseax nialacia and
ricket^. the >ame ^tai md.
Calcium and magnesium occur in the urine for the nio>t part aa
phosphate-. The quantity of earthy phosphates eliminated daily is
'•:-• -1. Berlin, 11K)6.
::ch. m.-a. \V.M-h.-n>chr.. 1577,
.'nr.--l.uchf. Kin.lcrhcilkun.lc. HMMI. /,/
:.-k.. \^n I. SS : 17 172.
lin. klin. W.K-h.-nschr., 1!)04, .;/ : 11") L
Patholo^ie dee 8to£fwech0eI0, licrlin, 1874,
. me.!. \Visscnsch., 1877, /.7 .
30 METABOLISM OF ORGANIC' AND INORGANIC PHOSPHORUS.
somewhat more than 1 gram, and of this amount two-thirds is mag-
nesium and one-third calcium phosphate. In acid urines the simple
as well as the double acid earthy phosphates are found, and the
solubility of the former (among which the calcium salt, CaHPO4, is
especially insoluble) is particularly augmented by the presence of
double acid alkali phosphates and sodium chlorid in the urine (Ott).°
The quantity of alkaline earths in the uryio depends upon the com-
position of the food.
MAGNESIUM COMPOUNDS.
The relative ratio of magnesiui i to calcium as eliminated by the
body is 1 : 8 or 1:9, and consists largely of magnesium phosphate,
Mg3(PO4)2. The amount of magnesium required by the body per
duv is 0.6 gram. As in the case of iron, though magnesium is neces-
sary to health, but little magnesium is found in the child's food,
namely, milk. The need of magnesium in the system has been
studied by Bunge. b The magnesium balances have been studied by
Blauberg,c Cronheim and Miiller/ Bertram/ and Ren vail/ but are
not considered as important as the calcium. Moreover, little study
has been given to the elimination of magnesium under pathological
conditions.
The elimination of phosphoric acid, calcium, and magnesium de-
pends principally on the character of the food and the relative pro-
portion of animal and vegetable food digested.
A FEEDING EXPERIMENT WITH RABBITS.
PLAN OF THE EXPERIMENT.
In these experiments four female rabbits were used, the diet con-
taining as little phosphorus as possible. To two of the rabbits organic
phosphorus in the form of crude phytin was fed, and to the other
two an equivalent amount of phosphorus in the form of sodium
phosphates was given.
It was intended to keep these four rabbits on their respective diets
for three or four months, in order that they might become accus-
tomed to the added phosphorus and, further, that it might be com-
pletely anabolized, and then to mate them and feed the young rabbits
on the same kind of food and on phosphorus in the same respective
combinations as that fed to the mother rabbits. When the young
«Zts. physiol. Chem., 1886, 10 : 1.
bZta. Biol., 1874, 40 : 111, 295.
clbid., 1900, 40:1.
dZts. diat. physik. Therapie, 1902-3, 6 : 25, 92.
«Abs., Chem. Centrbl., 1879, 10 : 526.
/Skand. Arch. Physiol., 1904, 16 : 94.
1'LAN <>F KXl'KHl.MKNT. 31
ral)l)its had lived for several weeks on these diets, it was planned to
kill them and to examine their bodies in minutest detail 1'or various
eombinations of nitrogen and phosphorus. The same procedure
wa> to he carried out in the case of the four female rabbits, and in
addition, normal rabbits were to be examined as controls, Unfortu-
nately, it proved impossible to obtain young rabbits under these
abnormal conditions, that is, living in closely confined quarters
:iid fed on an artificial diet.
The work was begun early in November, 1(.M)7, and concluded
the middle of March, 1(.)()S. Complete nitrogen" and phosphorus
balancc> \\ere determined during a period of nearly live months.
Moreover, the inorganic phosphorus \\as estimated in the urine by
the uranium acetate method throughout the entire time. In addition,
during the last four \\eek>, calcium, magnesium, and ether-alcohol
soluble phosph. thin) balances were included to make the
study of the phosphorus metabolism more complete.
At the end of the period the rabbits were chloroformed, and the
bones, tc.-th, blood, liver*, nervo (including the spinal cord) and
hraii analw.ed for n total phosphoric a< id, lecithin-
phosphoric acid, calciuii, i, and ether extract.
Two normal female rabb; : ined and the same procedure
followed Bfl in the ca>e of the rabbits art ilicially fed. In all cases
pos|-morlciii examinat ions \\eie made and slides of t he various tissues
were prepared all<l hi>t • •logical changes n..te<|.
PREPARATION OF FOOD.
The food iiTots, gluten, a mixture of starch and
live oil, ami -lutioii. The above constituents seemed
to furnish a \\ell-rouiule.l ration, -Mipplying suilieieMt protein, fat,
and carbohydrate for the needs of the body. The rabbits to which
the ilioriranic phosphorus salts \\ere fed received daily 5 CC of a
standard >alt mixture ron>i>ting of {."in grains of sugar, 4 grams of
calcium chlorid, ! .", Drains of .sodium chlorid, 1*0 grains of potassium
chlorid. and < MUIU sulphate, made up to a volume of
1 CC and containing ' phosphoric acid, in the form
ot di-Midium hydrogen j)hosphate and sodium dihydrogen phosphate,
per cubic centiiiH
The rabbits to which the organic phosphorus was fed received daily
of a salt mixture made >o as to supply an e(|uivalent amount of
the above mineral salts, allowance being made for the presence of
calcium, magnesium, potassium, and phosphorus in the phytin. In
this way an equal amount of calcium, magnesium, potassium, and
1 th»« nitrogen work was done by th«- niiro^-ii laboratory, Mr. T. C. Trescot in
char
32 METABOLISM OF ORGANIC AND INORGANIC PHOSPIHUH
-odium was given to all four rabbits, and the total amount of phos-
phoric acid fed was practically equalized.
Gluten was selected as a food high in nitrogen but containing little
phosphoric acid. The usual method of washing out the starch from
coarse flour was employed. The moist gluten was spread out on
sheets of tin and dried on the steam bath. After several days of
this treatment the samples were sufficiently dried for grinding, and
contained from 12 to 13 per cent of nitrogen.
The organic phosphorus was supplied in the form of phytin, a cal-
cium-magnesiiim-potassium compound of anhydro-oxy-methylene-
di-phosphoric acid which was first isolated by Pasternak." This
was prepared by extracting wheat bran with 0.2 per cent hydro-
chloric acid, allowing the starch to settle, decanting off the clear
liquid, and to this adding a large volume of 95 per cent alcohol. A
heavy flocculent precipitate formed. This was allowed to settle and
after the clear liquid Lad been decanted off, the remainder was fil-
tered. The precipitate was then dried at room temperature by
blowing air over it by means of an electric fan. In this air-dried
condition the phytin contained from 22 to 30 per cent of phosphorus
(P2O5) in organic form. The uranium acetate titration method
showed that no inorganic phosphorus was present.
The nature of phytin has been investigated by Patten and Hart, 6
who gave to it the following composition: Calcium, 1.13; magne-
sium, 5.80; and phosphorus, 16.3 per cent.
Phytin on heating with mineral acids is decomposed into inosite
and phosphoric acid. The investigators just quoted claim there is
no decomposition of phytin by enzyms and the same conclusion was
reached by Mendel and Underbill,0 who also studied this ques-
tion. It is claimed that the proteolytic enzyms of the alimentary
tract do not alter phytin, but that the alteration is brought about by
the intestinal epithelium. The free acid phytin corresponds to the
formula C2H8P,O9. The alkali salts are freely soluble in water and
the calcium and copper salts are slightly soluble in water, while the
barium and strontium salts are but sparingly soluble in water. Phy-
tin has thus far been found in peas, beans, pumpkin seeds, and red
and yellow lupines. The carbohydrates of the food were supplied
by feeding a mixture consisting of equal portions of cane sugar and
cornstarch. The fat used w^as olive oil.
The food was prepared in the following manner: The carrots were
first chopped into small pieces and a portion was mixed with part of
the gluten-starch-sugar mixture. To this was added the phytin and
5 cc of the phosphoric-acid-free salt solution in the case of the rabbits
« Rev. gen. bot., 1900, 12 : 5.
&Amer. Chem. J., 1904, 31 : 564.
cAmer.-J. Physiol., 1906, 17 : 7.",.
METHODS OF ANALYSIS. 33
fed organic phosphorus. This was made into a thick paste and placed
on a Miiall tray in one corner of the cage. The same procedure \vas
followed in the case of the rabbits fed inorganic phosphorus, except
that instead of phytin the salt solution containing the inorganic
phosphorus was mixed with the food. Thus the rabbits wen4 com-
pelled to eat the food containing the phosphorus before the remain-
der of the food was given to them. The rest of the carrots, sugar
and >tarch mixture, and 2 <•«• of olive oil were made into a thick
paMe and given to the rabbits during the afternoon.
METHODS OF ANALYSIS.
Fach rabbit was confined in a suitable wire cage, which allowed
the feces and urine to be easily separated.
After establishing a nitrogen equilibrium, the experiments with
the rabbits were commenced. The focefl \\ere collected at fre(iueilt
interval- during the day. OWmg to the fact that the rabbits persist-
ently ate them. The urine and the food reMduo were collected
daily. All of the-e >ample- ueie composited and analy/ed; the
nitrogen in the food. fece-. and urine being determined according to
the (limning ' method a;nl the phosphoric acid in the food, feces,
and urine by Neumann'- '' method. The phosphoric acid in the
urine ua- determined aUo by the uranium acetate volumetric
method. In this \\-.i\- a check on the amount of phosphoric acid in
the urine was obtained, and further, this double determination
Sen <'d a- an indication of the presence of organic pho^phoru-.
The methods employed for \\ater and a-h. ami for calcium and
magnesium' were tho-e of the A»ociation of Ollicial Agricultural
Uicmi-K. From ~2 to :i gram- of the food- or fecefl wm a-hed; and
in the ca>e of the urine. 'Jnn <-.• \\ere e\ aporatecl to dryne-> iii a plati-
num di>h and allied. The ether-alcohol soluble phosphorus (lecithin)
determined in the following manner:
'I'r.in-i'.T MI,,- ,,r m ..f ih.- tiin-ly -^n.uinl .-nl».-lanc«- \n u :!(«»-<•<•
lla.-k: a-1'1 :'.'» OC "I al>-..lut.- .-ili.-r ami «-xira«-i iht- wh..|,- <,\.-r niu'hi. l-'iltrr
i thmuu'h a hanlfiit-d tiltrr pajn-r int<> an ordinary .Jnui flat-bottomed flask of
503-cc capacity ami ivttirn any |>articli- of ih,- r«->iilu«- fotind on the fill* r paper to the
Hrlenmeyer Jla.-k. Then a<l«l to th«- nh-T extract residue 60 cc of ab.sulute alcohol
.uul boil the solution for three hours, u.-in-j a reflux condenser. Filter this alcohol
extract while hot into the . I. -na tla-k containing the ether extract and wa.-h tin- re-idue
t\vic • with two separate port io;. f liot alcohol, adding the wa.-h in-^ to the
extract. In the combined fth»-r-ali-ohol filtrate determine the phosphoric acid by the
Neumann f> method.
o U. S. I)eju. A-r.. P.un-au of < 'h.-miMry, Hul. 107, Rev., p. 7.
ft Zts. pliv.Mol. Ch.-in.. 1 '.MIL'. 57 : 11").
c\ \-r.. Bureau. .f Chemistry, Hul. 107. R.-v., p. i:,. Hi.
77400— Hull. 123-09 3
34 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
PRELIMINARY FEEDING PERIOD.
The results recorded in Table I are especially valuable in view of
the fact that they cover a period of practically one hundred days.
During this time an attempt was made to mate the rabbits, each one
being removed from her cage every four days at 5 o'clock and placed
in a large box with a male rabbit and allowed to remain there until
the next morning at 9 o'clock. This .,was repeated fifteen or
twenty times in each case. Consequently some loss of feces and
urine must have resulted, which loss in the course of an experiment
extending over one hundred days would be practically uniform in
the case of each pah- of rabbits. Such a loss would naturally tend to
give somewhat larger apparent nitrogen and phosphoric acid bal-
ances. The rabbits had always eaten the food provided for them
before being removed from then* cages.
Throughout this work the rabbits fed organic phosphorus are given
the numbers 1 and 2, and those fed inorganic phosphorus the num-
bers 3 and 4.
The weight of the rabbits remained constant in the case of Nos.
1 and 4, while in the case of No. 2 a slight average loss of weight
resulted and No. 3 showed a gain in weight.
TABLE I. — Nitrogen and phosphorus metabolism — Preliminary period.
No. 1.— RABBIT FED ORGANIC PHOSPHORUS.
Date.
3
"o
1
Nitrogen (N). Phosphoric acid (P2O5).
In urine.
Absorbed
material
retained.
1
EH
Total
excreted.
>.
I
Gms.
-0.18
- .03
.35,
.5?
a
1
1
|
H
Gms.
0.66
1.81
2.37
3.13
Excreted.
i
>.
8
g
P.ct.
Phosphoric
acid.
Nitrogen.
Phosphoric
acid.
-1
•8J
"1
=1
1907-8.
November 17-23
November 24-30
December 1-7
Gms.
1,647
1,596
1,596
1,654
0m*.
3.34
5.35
8.22
9.33
Gms.
4.22
4.65
4.91
5.22
Gms.
0.40
.92
.83
.39
Gms.
0.95
.13
.77
.50
Gms.
0.28
.90
.76
.49
Gms.
-0.08
.11
.11
.30
P. ct.
P.cl. P.ct.
December 8-14
Average
1,623
1,656
1,663
1,677
1,623
1,616
6.56
10.10
10.10
3.54
7.44
7.03
4.75
.64
.17
Tes
.45
- .36
.25
.17
1.99
.59
. 61 . 11
72.40 29.65
December 15-21
December 22-28
December 29-Janu-
ary 4
4.78
6.33
5. 26
5.12
4.58
.60
.60
.85
.54
1.12
3.29
3.29
1.74
2.79
2.67
.68
1.00
1.12
.81
.63
.69
.69
.77
.44
1.95
.27
.22
- .02
.21
.14
January 5-11
January 12-18
Average
1,647
1,597
1,587
1,588
1,567
_^
9.56
10.06
10.19
10.60
5.21
.U
.24
2.76
.85
.91
.16
68.19
30.79
January 19-25
6. 40| 1. 08
6. 06i 1. 32
7.34) 1.02
8.11 1.33
.29
.38
.26
.16
3.27
3.24
3.27
3.23
.77
1.04
1.11
1.80
1. 01 . 21
1.05 .16
1. 02 .16
1. 1H . 03
January 26-Febru-
ary 1
February 2-8 . .
February 9-15
Average
69. 11
j
1,585
1,618
10.10
8.08
6. 98 1. 19 . 27
3. 25 1. 18
106 .14
34.71
Average for period .
5.65 .86 .23 2.67
|
.87
.86 .14' 69.901 31.72
22 53
1.42 grams of organic phosphorus per period were intimately mixed with the food.
PRELIMINARY FEK1MM; 1'KKIOD.
35
TABLE I. \itmtjin and fikotpkonu i/n'tuhnlism I'/rliniimiri/ ]>cri<nl- CoutimU'd.
l; M5BIT KKD n|;t; \\|( I'l K )S I'll « > li I >.
Date.
A 1, >,.rl. o.l
material
n-taitu'd.
1907-8.
November i.
1-30....
• r 1-7
\ vi-ra^'f
December l.v
December 22-28 —
December 29-Janu-
ary4
Jauuaj
ary I ....
i;iry9-15
Average
Average for period
59
No. 3.-RABBIT Ki iANK PHO8Pn<
• T 17 '23
7.53
6.48
1.20
710
n.«
1.02
t 30
9.10
7.4«
? IV
H
r 1 7
1. t»7
1» in
s v.
• 0&
M
Deoember 8- 1 •
1 l.i'.
10.06
7.20;
••
3.59
.99
1 I'.
.2C
Average..
1,460
9.27
7.51
1.41
.05
| •
|.Vi
1.24
.16
n.oj
J7 us
December 15-21...
1 ><>|
II 7n
-, IN
.,',
. :•>
.; 1.7
x»
..:-.
H
.: >'
1.54
•j:,
.2A
|).V.-|||».-r -."> J:lIUI-
ir\ t
1 -.-''.
In ,._•
4.73
i M
141
| M
..;
.99
.30
1 •
1 :,'ix
|n .. •
6.50
| >.»,
1.08
1.27
.18
January 12-1 N
Uftfl
10. tt
4.89
.V,
.89
.:.-.
.88
.27
Average...
1,532
11.05
5.55
1.07
.u-«
:!.M,
.98
.73
.27
50.23
26.78
.
January 19-25
11.06
5.82
1 Is
:,7
:; ' i
1.0»>
1 17
.20
January 2ti-Febm-
ary 1
1 7.4.
1 1 •
.61
3.61
1.58
. 1 '
1.77..
2.54
.37
1.28
1.97
February 9-15
1,778
12.08
7.65
2.54
..'.,
3.65
1.98
. 11
Average
1. •,'•-'
11. ..I
ft. 43
1.97
.45
3.63
1.09*
1.67
.12
55.38
:;ii. (r_»
AV»T.U'" lor |»-riii'l.
—
1,585
HLM
6.50
1.48
==
.38
3.51
Tw
1.37
" " ~
.18
62.21
27.96
2^
54
o 1.42 grams of organic phosphorus per period were intimately mixed with the food.
6 1.72 grams of inorganic phosphorus per period were intimately mixed with the food.
36
METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
TABLE I. — Nitrogen and phosphorus metabolism— Preliminary period — Continued.
No. 4.— RABBIT FED INORGANIC PHOSPHORUS.
Date.
Average weight of rabbit.
Nitrogen (N).
Phosphoric acid (P2O5).
In urine.
Absorbed
material
retained.
j
Total
excreted.
Daily balance.
Total ingested.o
Excreted.
j
Nitrogen.
Phosphoric
acid.
Nitrogen.
*t) Phosphoric
a acid.
"1
4
18 1
flj
1907-8.
November 17-23
November 24-30
December 1-7 . .
Gms.
1,950
1,960
1,960
1,985
Gms.
8.90
9.14
10.40
10.05
Gms.
8.89
7.91
4.81
3.71
Gms.
0.76
1.13
.42
.68
Gms.
-0.10
.01
.73
.80
Gms.
3.10
3.31
3.32
3.59
Gms.
1.54
.94
1.19
.36
Gms.
0.49
.94
.36
.51
Gms.
0.15
.20
.25
.38
P.ct.
P.ct.
P.ct.
December 8-14
Average
1,964
9.62
11.70
11.70
10.62
10.62
10.62
6. 33 . 75
5.16 1.06
8.63!. 1.06
8.89 1.28
6.44 .26
5.21 .46
.36
!32
.06
.55
.70
3.33! 1.34
3.67 T74
3.67 1.42
3.66J 1.44
3. 66 1. 02
3.66| 1.04
.58
.25
T28
.19
.11
.31
.29
65.80 40.24
December 15-21 ... .
=
I,y65
2.002
.90
.90
1.42
.42
.57
December 22-28
December 29-Janu-
arv 4
January 5-11
January 12-18
Average
1,979 11.05
6.86
.82 .48
3.66
1.13 .84
.24
62.08
30.88
Januarv 19-25
2,006
2,017
2,000
1,975
2,000
1,981
7.78
11.65
7.06
8.07
8.64
9.77
5.94
7.43
5.44
6.59
1.09
.72
.46
2.38
.10
.50
.16
- .12
3.20
3.61
2.28
1.45
1.55
1.29
1.48
1.03
L.
.77
.54
2.36
Tl9
s
.03
- .13
January 26-Febru-
ary 1
Februarv 2-8 . . .
February 9-15
Average .
50. 76
6.35
6.51
1.16 .16 2.64
. 91 . 33 3. 21
1.34
1.27
.04
.18
73.50
Average for period.
.87
67.12
40.63 26
42
o 1.72 grams of inorganic phosphorus per period were intimately mixed with the food.
NITROGEN BALANCES.
The rabbit which gained in weight, No. 3, received a larger amount
of nitrogen than the others. In fact, the amount of nitrogen ingested
in all cases varied somewhat, but the total during a period of seven
days was from 5 to 6.6 grams of nitrogen per 1,000 grams of body
weight, No. 3 receiving the largest relative amount. The average
figures show that relatively more nitrogen was excreted in the urine
in the cases of rabbits No. 1 and No. 2 (those fed organic phosphorus),
than in the cases of No. 3 and No. 4 (fed inorganic phosphorus).
The amount of nitrogen eliminated in the feces varied with the indi-
vidual rabbit. No. 1 eliminated 10.6 per cent and No. 2, 14.6 per
cent. No. 3 eliminated 13.8 per cent and No. 4 only 9.3 per cent in
this manner. Nos. 1 and 2 retained a smaller proportion of the
metabolized nitrogen than did Nos. 3 and 4, the figures being respec-
tively 22, 24, 29, and 26 per cent. This means that the rabbits fed
inorganic phosphorus retained a larger proportion of the absorbed
nitrogen than did those fed organic phosphorus; and it appears that
those fed organic phosphorus excreted in the urine a larger propor-
tion of the ingested nitrogen, but did not utilize this nitrogen so well
as did the rabbits fed inorganic phosphorus,
PRINCIPAL 1T.KIMN : PERIOD.
I'liosIMlolM S BALANCES.
37
-
In all cases, excepting rabbit No. :5, the average amount of phos-
phoric acid ingested during seven days per 1,000 grams of body
weight varied from !.<> to 1.7 grains; in No. 3 the amount was 2.2
grams. More phosphorus was eliminated by rabbit No. 4 through
the kidneys than in any other ease. Both of the rabbits fed organic
phosphorus and No. 3 fed inorganic phosphorus retained about the
same amounts of the absorbed pln»phorus (averaging 53 per cent),
while the figure for Xo. 4 is much lower, only 42 per cent. From
the average figures, it appears that the rabbits fed organic phos-
phorus eliminated a smaller percentage of the ingested phosphoric
arid in the urine than those fed on inorganic phosphorus/ It must
be remembered that the amount of phosphoric acid eliminated by
the kidneys dors not necessarily represent the amount melaholi/ed,
fur inorganic phosphorus ingested might and undoubtedly does pass
through the kidneys \\ithoiit undergoing any change. Of the total
phosphoric acid inge>ted. '•>- percent \\ a> found in the feces of No. 1
and :il per cent in the feces of No. \, \\hile No. 2 and No. 3 elimi-
nated in this manner .'17 and .'I'.' per cent . respect i vely. Although the
rabbits fed inorganic phosph,,nc excreted a larger amount of phos-
phorus in the urine than did the others, they retained on the average
less of the absorbed phosphoric.
The ratio of nitrogen !•• phosphorii acid in the food is but slightly
above :i:l. Thi- -ho\\s a much larger proportion of phosphoric acid
than c usually fed in a normal diet. The ratio of nitrogen to phos-
phoric acid in the urine TOU16fl from .', : 1 to 7..VI, being higher in the
of the rabbits fed organic phosphoric. o\\ ing to the relatively
• T elimination of phosphoric acid in the urine of those fed inor-
ganic phosphoric. The ratio in the fooefi i- rather constant , averaging
about 1.1:1 in all eases. The e\ad rat ios are given in Table IT.
T \ IM I 1 1 . /.'• /' - I mi i mini pa 'mtl.
i.it.
Food.
Urine.
Hem,
3.03:1
i, .'41 i
1.00:1
; .'.ti
1 27-1
», »..; i
1 08*1
0.91-1
PRINCIPAL FEEDING PERIOD.
The principal feeding experiment extended over a period of four
\\eeks, and during this time complete nitrogen, phosphoric' acid, cal-
cium, and magnesium balances \\ere determined, as well as the ether-
alcohol soluble phosphorus balance. In addition the inorganic phos-
phorus in the urine was determined by the uranium-acetate titration
method. Other salts, as well as the calcium and magnesium salts,
38 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
are important for the welfare of the organism, but in .phosphorus-
feeding experiments the two named stand out most prominently.
The second rabbit fed organic phosphorus was in poor condition
during the test and died of pneumonia at the end of the second week;
consequently the results in this case must not be given the same
weight as in the others. Throughout this period all of the rabbits
remained practically constant in weight. -,Nos. 3 and 4 received
more nitrogen and phosphoric acid than did Nos. 1 and 2 on an
average, but Nos. 1 and 4 received practically the same amounts.
The nitrogen and phosphorus balances were positive, except in the
case of rabbit No. 2, which died, and naturally would show a nega-
tive set of balances.
NITROGEN BALANCES.
The analytical data obtained during the experiment are recorded
in Table III.
TABLE III. — Nitrogen and phosphoric acid balances — Principal period.
RABBITS FED ORGANIC PHOSPHORUS.
Date.
Rabbit.
Total in-
gested.
Total excreted.
Ab-
Daily bal- T . sorbed
ance. n llnne- material
retained.
d
fe
•<
Nitrogen.
Phosphoric acid.
Nitrogen.
Phosphoric
acid.
fc
Phosphoric acid.
Nitrogen.
Phosphoric acid.
Nitrogen.
Phosphoric acid.
d
i— i
£
S
In urine.
1908.
February 17-23....
February 24-
Marchl
1
1
1
1
1
2
2
Gms.
1,565
1,551
1,551
1,533
Gms. Gm-s.
9. 891 |02. 824
10. 176W. 078
10.745o3.391
10. 589 «3. 483
Gms.
0.751
2.449
1.482
2.310
Gms.
6.471
6.680
7.560
6.470
Gms.
0.602
1.569
.998
1.461
Gms.
0.887
.970
1.146
.489
Gms.
0.381
.149
.243
.253
Gms.
0.191
.077
.178
.218
P.O.
P. ct. P.ct. P.ct.
March 2-8
March 9-15
Average
1,55010.349803.194 1.748 6.795
1.157
.876
.256
- .154
- .374
.166 65.65
27.4121.0
57.1
February 17-23....
February 24-
March 1
1,660
1,623
7. 583,o2. 626
8. 519|02. 451
1.572 7.087
3.284 7.480
.900
1.738
1.307
1.230
.060
-.085
Average 2 weeks.
General average.
1.1142 8.0.^102.539 2.828
7.284
1.319
1.269- .264
-.013 90.47
49 97
=
1,596 9. 200 a2.867 2.288
7.040
1.238
1.073
1
RABBITS FED INORGANIC PHOSPHORUS.
February 17-23
February 24-
Marchl
March 2-8
3
3
8
1,765
1,791
1 814
12.39863.688 2.378J 6.959
12.41463.688 2.434 7.429
12 149 63 944 2 632 7 882
1. 766J 1. 345
1.479' 1.495
1.328 1.295
.534 1.014
0.437
.363
.365
.421
0.082
.102
140
March 9-15
Average
3
1,814
11.96263.944 1.133 7.882
.342
1,796
12. 231 63. 788 2. 144; 7. 308
1.328
.592
.440
.760
.728
1.295
1.800
1.927
1.540
1.806
.397
.166 59.75 34
17 27. 5 47. 3
February 17-23....
February 24-
Marchl.."
4
4
4
4
1,986
2,028
2,011
1,971
9.15763.206 .5% 7.680
12.40163.688 .743'l0.211
12.24963.933 1.1981 7.520
7. 72 63. 222 1. 212 7. 360
.126
.207
.505
-.114
.116
\"
. 1891
March 2-8
March 9-15.
Average
.219
098
1,994
1,895
10.39563.487 .937 8.193
.630
1.768
.181 .1.56 78.82 50
.289j .161 69.29 42
7113.438.1
General average.
11.31363.638 1.521 7.751 .979
1.532
44 20. 5 42. 7
6 Including 1.42 grams of inorganic phosphorus added to the food per period.
PRINCIPAL FEEDIXfJ PERIOD.
39
The amount of nitrogen invested per 1,000 grams of body weight
for ;i seven-day period was as follows: No. 1, C-.7 grams; No. :;. (>.S
grams: No. 1. ">._ grains. The amount of nitrogen absorbed per
1,000 grains of body weight per period «»f seven days was likewise
very uniform, excepting for rabbit No. _\ being ">.(> grams for No. 1
and No. ."». l.s grains for No. 4, and •">._ grams for No. L\ The amounts
of nitrogen excreted in t he urine and feees show considerable variat ion.
the ratio of urine nitrogen to feces nitrogen being highest in No. 1,
that iBj v7:l, and lo\\e>t in No. _. -.i\:\. No. 1 showed a. ratio of
3.9:1, and No. :5 a ratio of 3.4:1,
In Table IV the ratios of nitrogen to phosphoric aeid. calcium to
magnesium, and phosphoric acid to calcium in food, feces, and urine
in given. The relation of urine nitrogen to urine phosphoric is
highest in the cases of the rabbit*. fVd organic phosphorus. This is
due to a larirer excretion of phosphorus in the urine of rabbits Nos.
:; and 1. fed on inorganic phosphorus. This ratio in the feces is very
regular, being !.">:! in thivr :;d for No. _> inereasing to 2.1:1.
A higher ratio of calcium to magnesium is noted in the feees of the.
r:ihhit> fed inorganic phosphorus. This ratio varies considerably in
the urine of the individual rabbit-.
T \IIIK 1\ /; • 'in. nn -/ phosphorus • **, and urine —
/
RABBITS IKI> OBG INK PHO8PHO3
Rshhit
In-
1
|
3. 2 :<. '•
i :,
3.0
H. 1
11.7
liAHIU! - 1 Fl> IS. i|t,; \SI< |'| loSIM I o I: I 8.
IfooA
2.9
4 2
;{
I.,,,'
LI
3.5
5 5
2 2
34 0
(Pood
2.9
2.9
4.0
4
PMM
:< 7
1.8
Urine
4 6
6.6
The figures show also that the phosphorus-calcium ratios of the
food of rabbit - N • ia 1 and J arc 1« »\\ er than in the food of rabbits Nos.
3 and 4: this is due to a larger iiiLTc-tioii of phosphorus in the latter
cases. The ratio of phosphoric acid to calcium in the feces varies
\vith the individual case. The phosphoric acid to calcium ratios in
the urine again show more phosphorus eliminated by rabbits Nos.
3 and \ than by rabbits NOB. 1 and 2. The nitrogen and phosphoric
acid eliminated in the urine are generally considered to represent the
40 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
amounts of the two substances metabolized by the system, but this
does not hold in all cases. Rabbit No. 2, for example, which died,
shows a much larger amount of katabolized nitrogen and phosphoric
acid, as indicated by an increased elimination through the kidneys,
but this does not indicate an increased metabolism of these two sub-
stances. The ratio of nitrogen to phosphoric acid excreted in the
feces shows equal average figures for all the rabbits, excluding the
figures for No. 2. If the figures for rabbit No. 2 are included, the
average ratio is lower for the rabbits fed inorganic phosphorus. The
bulk of the nitrogen (60 to 78 per c^nt) is eliminated by the kidneys,
whereas, on the other hand, only 27 to 50 per cent of the phosphoric
acid is thus eliminated. The percentage of absorbed nitrogen which
was retained in the system is the same for rabbit No. 1 as for the
average of Nos. 3 and 4, receiving inorganic phosphorus.
PHOSPHORUS BALANCES.
The study of phosphoric acid metabolism raises many questions, of
which the following are especially important:
(1) How is the phosphoric acid, ingested in different forms, taken
up by the body?
(2) How is the phosphoric acid changed in the body?
(3) In what manner is the phosphoric acid eliminated from the
body?
Many investigators have attempted to answer some or all of these
questions, but no definite answer has been obtained. The generally
accepted idea is that the phosphoric acid ingested in different forms
is taken up by the body partly in various forms of organic combina-
tion and partly, also, in the inorganic or phosphate form. Most of
the organic phosphorus taken up by the body — that absorbed from
the intestines — is changed to the inorganic or phosphate form, and
all such phosphorus is eliminated in the urine as phosphates. This
idea that organic phosphorus compounds are more valuable than
inorganic combinations of phosphoric acid has been promulgated in
the medical literature during the past few years. Nevertheless, many
practicing physicians continue to prescribe the inorganic forms, not
only of phosphorus, but of iron, calcium, magnesium, etc. Yellow
phosphorus is given solely as an alterative.
As the extent of the elimination of phosphoric acid is largely
dependent upon the character of the food and the absorption of the
phosphates in the intestines, it is apparent that the relationship
between the nitrogen and phosphoric acid in the urine can only be
approximately constant with a certain uniform food. Thus, on feed-
ing dogs with an exclusive meat diet, as observed by Voit,a when the
0 Cited by Hammarsten, A Textbook of Physiological Chemistry, rev. ed., New
York, 1908.
I'll! NCI I'M. FKKMlNi; PKHIOD. 41
nitro'/en and phosphoric acid of the food exactly reappeared in the
urine and the t'eees. the relationship was S.I :1. In these experiments
with rabbits the nitrogen and phosphoric acid ratio in the urine varied
from 4.C>:1 to 7.7:1. In starvation Wellmann" has shown that this
relationship is chanired, namely, relatively more phosphoric acid is
eliminated, which seems to indicate that besides flesh and related
tissues, aUo another tissue rich in phosphorus is largely destroyed.
The starvation experiments show that this is the bone tissue. Tiger-
stedt'' claims that only 0.1. 'II gr:,m of phosphoric acid is eliminated
in the feces of man daily. For some years it was claimed by many
investigators that the elimination of phosphorus and nitrogen should
run |>arallel. both substances heini: derived from protein, the usual
ratio of nitrogen to phosphorus helm: 7.5:1, In these experiments
there U a general tendency in the individual data toward parallelism
between the nitrogen and phosphoric acid excretion in the urine, but
this ratio U not maintained in the general average, as in the case of
the rabbit> fed inorganic pho^phom> a much larger proportion of the
phosphoric acid is ah-orhed and eliminated by the kidneys. Siven.1'
Khrst roin.'' and Me\ei have also shown no parallelism to exi-t.
I>ho>j)!n»rus i- u-cd in the formation of the bones and other bodies
where no nitrogen is pn-ent. Moreover, the ratio of nitrogen and
phos|)horic acid will ^'inctimes run a> low as 3:1.
The amount of phosphoric acid which was fed to all the rabbits \\as
considerably lusher than the amount present in their normal diet.
In fact, the food itself contained praetieally a .siiHicient amount to
supply the needs of the s\Mem. The result is that by adding all
excess of phosphoric acid metabolic changes \\ere induced in all
Casefl 1" a greater OI le-s extent, The amount of phosphoric acid fed
per se\en-da\ period per 1 .01 ill grains of body \\eight varied from
ram- in rabbit No. '_' to -J.l grains in the cases of rabbits N'os. 1
and :>. The amount of absorbed phosphorus pel1 1 ,000 grains of body
\\eiirht \\as ju-aet ieall\ eipial. 1 .-'I Lrram-. exce|)t inir in the case of rabbit
No. •_'. \\l-.ei-e the l'n:uies sho\\ O.7 Lrram of phosphoric acid per 1,000
grains of body \\ciLrht. The ratio of phosphoric acid in the urine to
that in the fece- >ho\\s that the individual eh-nient was the most
important factor, rabbit No. 1 eliminating a far larger proportional
amount by tlie kidneys than in the case of any other rabbit. The
percentage of phosphoric acid eliminated by the kidneys was higher
in the rabbits fed inorganic phosphoric acid than in rabbit No. 1, but
this simply means that more of the inorganic phosphoric acid passed
through the kidneys unaltered, for rabbit No. 1 retained a larger
proportion of it- absorbed phosphorus than did either No. 3 or No. 4.
-••h. gesam. Physiol., 1908, J^:508. <* Ibid., 190:*, / ; 82,
ft Skan.l. An h. Physiol., 1904, It; * Zts. phyeiol. Chem., 1904-5, 43 : 1.
., 1901, 11:30S.
42 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
According to Ehrstrom,0 who studied phosphorus elimination, from
50 to 88 per cent of the phosphoric acid is eliminated in the urine by
the human organism, but the average amount given by different inves-
tigators varies from 70 to 80 per cent. With animal food almost all
the phosphorus is eliminated in the urine, while with vegetable food
a larger proportion of the phosphorus is found in the feces. The
amounts of calcium and phosphorus present in the food stand in
close relationship to one another. The rabbits eliminated from 27
to 50 per cent of the ingested phosphoric acid in the urine, a con-
siderably lower percentage than ir the case of carnivorous animals.
ETHER- ALCOHOL-SOLUBLE PHOSPHORUS BALANCES.
The ether-alcohol soluble phosphorus balances were determined
during the principal feeding period. The amount of phosphorus
ingested in this form was practically the same in all cases. It is
interesting to note the small portion of the 29 per cent of organic com-
bined phosphorus in phytin, which is soluble in ether and alcohol.
The figures show that 0.59 per cent of the phosphorus was present in
phytin as ether-alcohol soluble phosphorus. This shows that the
ether-alcohol extracted phosphorus may represent but a small pro-
portion of the total organic combined phosphorus.
The presence of organic phosphorus in the urine has been discussed,
but it is interesting to note that the average figures in Tables V and
VI show a slightly larger amount of the so-called organic, or ether-
alcohol soluble phosphorus in the urine in the case of the rabbits fed
on inorganic phosphorus.
TABLE V .—Ether-alcohol-soluble phosphoric acid balances — Principal period.
RABBITS FED ORGANIC PHOSPHORUS.
Date.
Number of ral>iiil.
Phosphoric acid in-
gested.
Excreted as phosphoric acid.
"ci
^
TJ
lg
I
Total phosphoric
acid in feces.
Ether-alcohol soluble
phosphoric ;u-i<i of
feces in terms of to-
tal phosphoric acid.
|
a
a
|
§
1908.
February 17-23
1
1
1
1
Gram.
0.2890
.2923
.3081
.3080
Gram.
0. 0180
.0050
.0036
.0000
Gram.
0. 0146
.0795
.0992
.1188
Gram.
0. 0596
.0845
.1028
.1188
Gram.
0.2380
.2075
.2053
.1893
Grams.
0.6020
1.5680
.9976
1.4608
Per cent.
2.4
5.1
9.9
8.1
February 24-March 1
March 2-8
March 9-15
Average
.2994
.0067
.0848 .0914
.2100
1. 1571
6.4
February 17-23...
February 24-March 1
Average...
2
2
.2413
.2374
.0162
.0110
. 0X7.3 . 1035
. 1925 . 2035
.1378
.0339
.9000
1.7380
9.3
20.8
.2394
.2694
.0136
.0102
.1399
.1089
.1535
.0859
1.3190
1.2381
15.1
ioTs
General average
.1225
.1479
aSkan. Arch. Physiol; 1903, 14: 82.
1'KINCIPAL IT.KDINC I'KKHM).
43
T.UM.K V. I-:>l,,r-itl'-»}iol-x<>l>ihl, phoxitfmrim -ill fmlnnc. .v /V/w/ywi/ jx'riod — Continue*!.
KA1UUTS FKD INoU'JANIC 1' I l< >SI'I H )RUS.
Date.
1908.
K.-l.mary 17 S
February J4 March i.
M:in-h 2
March '»i:.
A\. r;u'.-..
K.-l.ruary 17 .
F.-hriiiirv.'l March 1..
"
-'
n»K»'
(i.-||. r:il :t\. r.l/'
Ormm.
0.2797
.2797
.2797
. _'7'. 7
Gram.
.0080
I N M N )
Gram.
ft 0173
i i •; ; '
.0848
,0000
Gram.
0.0308
.0370
. .U.'x
!OOM
.-_•:•• 7
. J7'.7
.J7''7
.0081
moo
i i i N i
O|M, .0502
.0030 .1110
,,..,.,
.S7U
..'77..
.0149
.iill-.i
Gram.
0.2481
.2707
.22M
.•Ji:«)
^^^=
Grams.
1.7664
1 I7"J
1.5308
.4400
. <..7s.x
I :,
U •_'
I I
4.1
Tin4 liirim-s also show that in tin- «'asi» «>f the rahhits fed 01
])hos|)honi> a r..M>i.|«-niM»' ani.Miii! ••!' rt h.-r-alcohol soluhle plios-
])ho!-ii- '.-(I in the frc<->. 'I'hi' aiial\-«^ ..f' th«« lVr.-> ,,!' the
rabbits fed in«>ruranie phosphorus show that there i> -mne ethei-
alcohol s«)lul)le j)ho>j)horus al\\a\v pn->eiit. 'I'his amount must
cnine from the ether-aleohol soluble phosphoric ..f the food, or from
the seeretions of the intestinal juiee>. There is nn doiiht that the
feediniT <>f ])hytin. \\hich eontain> n..V.i j>er rent of plmspbnnis in this
form, irreatly inciva>e> the amount of ether-aleohol soluble phos-
phorus in the fooes. The insoluble calcium phosphate formed in the
LTaM ro-inteMinal tract of the rabl>it> fed iimr-^anic phosphorus may
tend to irivc a higher ratio of ct hei -alcohol >oluble phosphni'iis in the
feoefl of the rabl>it> fed \\ith phytin. Fui'ther, the results indicate
that of the total pbn>plmrus eliminated in the fe068 the percentaLTe of
ether-aleohol soluble jilmspborus is much larger in the case nf the
rabbits fed on organic plinsj>lmru>. Thi> may indicate that when
phytin i> fed in lar«_re amounts the gastro-intest inal tract is not able
to >plit and absorb it all. ('oii>r<|uently the ]>ercontage of ether-
alcohol >oluble phosphorus in the feces is increased. The question
of the presence of organic phosphorus in the urine is still unsettled.
In the principal feeding period the phosphorus in the urine was
determined by the uranium acetate titration method, and, further,
the lecithin phosphorus, ether-alcohol method, was applied to the
urine after evaporating inn cc to dry ness. The figures which are
given in Table VI show that the urine results for phosphorus obtained
44 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
by the different methods are practically the same whether organic or
inorganic phosphorus is fed.
TABLE VI. — Various forms of phosphorus in urine — Principal period.
Date.
Number
of
rabbit.
Phosphoric acid per 100 cc of urine.
Dif-
ference
between
two
figures
for
organic
phos-
phorus.
Total
(by
Neumann
method).
Inorganic
(by
uranium
acetate
method).
Organic
(by dif-
ference).
Organic
(by ether-
alcohol
extrac-
tion).
1908.
February 17—23
1
1
1
1
2
2
3
3
3
4
4
4
4
Gram.
0.0986
Gram.
0.1009
.1153
Gram.
-0.0023
Gram.
0.0020
0005
Gram.
0.0043
February 24— March 1
March 2-8
.1080
.0303
March 9-15
.CXi70
.0000
February 17-23
.1376
.1230
.141(1
.1300
.1325
.2250
.1835
.1540
.1570
.1308
. 1181
.1277
.1287
.1290
.2039
.1740
.1340
.1290
.0068
.0046
.0139
.0013
.0035
.0211
.0095
.0200
.0280
.0017
.0011
-.0014
.0012
.0008
.0009
.0032
.0018
.0051
.0035
.0125
.0001
.0027
.0202
.0063
.0182
February 24— March 1
February 17-23 - . -
February 24— March 1
March 2-8
February 17-23
February 24-March 1
March 2-8
March 9-15
An ether-alcohol extraction of an inorganic phosphate solution
(100 cc of a r_iicrocosmic salt solution) was made containing 0.2 gram
of phosphoric acid and this gave 0.0054 gram of phosphoric acid by
the ether-alcohol extraction method, as large an amount of ether-
alcohol soluble phosphorus as was obtained in the average samples
of the urine examined. This fact points to the conclusion that no
ether-alcohol soluble phosphorus is normally present in the urine of
rabbits, even after the feeding of organic phosphorus for several
months.
A review of this question of the presence of organic phosphorus in
the urine in general supports this conclusion. Ronald a was the
first to call attention to the presence of organic phosphorus in the
urine, and Rockwood b claims to have found phosphocarnic acid
present. Bergmann,c however, using glycero-phosphoric acid made
subcutaneous injections on sheep, but could not detect the same in the
urine. Patten, Jordan, and Hart d in their extensive experiments
with cows found no organic phosphorus eliminated in the urine, and
like results were obtained by Mendel and Underbill e and by Le Clerc
and Cook / working with rabbits and a dog.
« Philosophical Transactions, 1864, p. 461.
b Abs., Chem. Centrbl., 1895 (1), p. 1063.
c Arch, exper. Path. Pharm., 1902, 47 :77.
d Amer. J. Physiol., 1906, 16 :268.
e Ibid., 1906, .77:75.
/ J. Biol. Chem., 1906, 2 :203.
IMMM'II'AL FKKDlNd I'KKMM). 45
Mandel and Oertel " made some experiments on man alon^ this
line, feeding first food ])oor in phosphorus and later food rich in
phosphorus, hut found no ell'eet upon the amount of organic phos-
phorus in the urine. They conclude that the organic phosphorus of
the urine is of endogenous origin. The inorganic phosphorus \vas
determined by uranium acetate tit ration, the solution was boiled
with hydrochloric acid and retitrated, t ho difference being the organic
phosphorus.
Organic phosphoru- waa found in the human urine by Sotnits-
chewskv.'' Oertel/ usiiiLT the method of precipit at in.ir the inorganic
phosphorus with calcium chlorid in ammoniacal solution, found
organic phosphorus in the urine of seven men.
Keller '' undertook >ome extensive experiments aloiiLT thi- line in
the case of infant-, and he concluded that the food did not influence
the amoiinl of organic phosphorus in the. urine. He starved himself
and found the amount of organic phosphorus eliminated the first
three day- \\a- Constant, uhile then- \\a- an increased elimination
the fourth day. This indicated that >ome highly organic phosphor-
i/e<l ti — ue that i-. the lymphocytes were broken <lo\vn.
Symmers • -tudied thi- question in variou^ pathological Casefl
diseases of the nervous system, enteric fever, t uherculo-i-, diahctc-.
and lymphatic leucaemia and found laiire amounts of organ ie
])ho-|)lioru- in the urine.
In agreement \\ith nio-t invest JLrat"r- \\lm have >tudied phytin
and it- action on the |MM|V . Scofoin- ' and ( iiaco-a '; claim that pliytin
is principally eliminated in inorganic comhinat ion-.
There i- no doubt that in pat hol<»irical caSOB there i- con>i<lerabl««
organic combined phoaphonis eliminated, hul there is much doubt as to
\\ he i her any pho-phoru- in the organic form is eliminated normally in
the 11 line. The method- \\hieh ha\e been em ployed t o -epa ra t e t he t \\ o
forms of pho>|)horu- are far from Satisfactory, The -liirht difference
between two iv-ult- obtained by different methods, which in nianv
cases \\oiild be counted afl <blplicate-. ha- been cla— ed as <lue to the
pi-e-ence of organic- phosphorus. Moieo\cr. in this work, ether-
alcohol soluble phosphorus \\a- found in the urine. This is of little
-iirnificance. because a -olution of sodium hydrogen j)ho-phate yielded
an equivalent or greater amount of ether-alcohol soluble phosphorus
« N. Y. Univ. Bui. Med. Sci., 1901, 1 : 166.
physi-.l. Cli.'in., 1880, ^:'_'l t.
Ml.i.L. 1898-9, 26 : 1 •_':;.
dlbid., 1900.
fj. Path. Bact., 1904-5, in : i:,;». H'7.
/Abs., Biochem. (Vntrbl., l!H)r,. .; : ooo.
46 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
by this same method, which precludes the possibility of any phos-
phorus in this form being normally present in the urine of rabbits.
In Table VI, where the total phosphorus is determined by the
Neumann method and the inorganic phosphorus by tit ration with
uranium acetate, the difference is called organic phosphorus. That
the uranium acetate method is not absolutely correct is indicated
by the figures which in several cases show more phosphorus by this
method than by the Neumann method. *In the case of rabbit No. 4
and in one instance in the case of rabbit No. 3 the differences are too
large to be explained on the basis of experimental error. It is
certain from these results that the ingestion of organic phosphorus
does not cause an increased elimination of organic phosphorus in the
urine; but the fact that in the case of the rabbits fed inorganic phos-
phorus there should be an apparent elimination of organic phosphorus
in the urine in some cases must be explained on the basis of the
endogenous origin of the organic phosphorus of the urine which
appears to take place only in abnormal cases.
CALCIUM AND MAGNESIUM BALANCES.
During the principal metabolism experiments, lasting four weeks,
the calcium and magnesium balances were determined in addition
to those of nitrogen and phosphoric acid. The amount of calcium
ingested per seven-day period varied from 0.44 to 0.58 gram per
1,000 grams body weight, while that of magnesium varied from 0.15
to 0.21 gram, rabbit No. 1 receiving more than rabbits Nos. 3 and 4,
while rabbit No. 2, which died at the end of the first two \veeks,
received about the same amount as rabbits No. 3 and No. 4. Goitein °
states that unless a rabbit receives 0.16 gram of calcium per kilo body
weight, a loss of calcium will occur. The figures show that the rabbits
under this observation received far more than that minimum amount
and, therefore, were in no danger of calcium starvation.
The figures in Table VII show that the calcium excreted in the
urine was 9 per cent for No. 1, 10.8 per cent for No. 2, 4.2 per cent
for No. 3, and 4.9 per cent for No. 4. In the case of the rabbits fed
organic phosphorus, the average amount of calcium absorbed from
the intestinal tract or metabolized was higher than in the case of
those fed inorganic phosphorus. These figures agree with the theory
that the calcium and phosphorus in the inorganic form unite to form
the insoluble calcium phosphate, which is eliminated by the bowels
in unchanged form.
« Arch, gesam. Physiol., 1906, 115 : 118.
I'KUNCll'AL
I'KK 1» >t >.
47
TABLE Vll.-^Ctilcium niul ii'ttnjm'xtum btilnnrcs —Principal period.
KABHITS FKD oi:«}.\\lC l'H« >SPHOKUS.
Date.
o
x
\
-
1
1
Total in-
gested.
Kxcrete<l
in uriiu1.
Excreted
Total ex-
creted.
Daily
balance.
Daily
l.al-'
ance
ratio.
Kxcreted
in urine.
Absorbed
material
n-taiiu-il.
<'a.
M -.
Ca.
Mg.
,,
Ca.
Mg.
Oft.:'**
Ca.
Mg.
Ca.
M,'.
1908.
February 17-23.
Krhruarv L'4
M-m-li 1
Om.
II.VNS
863
Om.
Om. Om.
0.0290.006
iMi (l\{
771
Gm.
Gm. Gin. Gm.
0.4360.1450.065
.937 .310 .011
Gm.
0.08B
.002
1 : 0. 40
1 : 0. 18
P.ct.P.ct.
P.*.
I'.ct.
"
March 9- 15
Average
Februar
F»-l>ruarv 1M
Average
Cdl.T.lllU '.'••
1
1
1
•2
I
.910 .352
.mix .013
.551
.619 .257
.047
.049
.019
.014
1:0.40
1:0.2')
.893
•=
.858
.735
.279
.080
•
.118
.054
.irji
==
.ny
.043
.564
.363
.488
Tfss
MS
.644 .233
.481 .277
.037
.053
.031
.015
.000
1 : 0. 32
=====
9.0
6.2
75.6 81.8
1
"- '
.844
=====
.081
TosI
^
_•_•;
.216
.512 .301
T5J
-.008
T=
rrrprp::
i: MM;: NORG \\i« I-MMSI-II
Februai
M
'
Average
M
30.1
;; .
0. 307 0. 046 a 008 0. 609
.ma
.an
.107
.am
.an
. i.7
.an
. a.:
.am
.oat
,087
nil
,008
.008
.in:
.015
.081
OH
.011
.017
. 1 1.5
a 223 0.7 15 0.229 0.025
-
.
.an
I! ••
.100
.018
.OH
.OH
Ifl8
.on
.305
..HI
.431
.an
.103
.on
.l.M
.107
.11.-,
0.011
.OM
oaa
.023
I 0. ID
i .1 :;.'
1:0.40
1 .0. 44
1:0.40
i 0 '.'
,. in
t J
l ••
:, 7
i a s •••
•..I «i
Ml -I
91.5
91.7
91.6
111 ! li.- OU6 <>f man. I'rmn .". U> K ftl «>f the calcium i> rmniuiily
•ted in the urine; the remainder i- cxereied with the t'ece> either
directly, «.r a par; may he ahsoi-hed from the >mall intestine and
.-ted into the hiri:-- tnteel inc. n> >ho\vn hy Voit " in the ca>e of t he
dt>^. Some calcium may com,- irom tlie int*-iina' juice... Accord-
ing to Seheteli*:.'' \'on Xoordeii,' and Kumpf.1' the ainoiml of
calcium excreted in the urine incn-a-e, with the amount of water
taken into the >y>teni. \'arioii- uuihor> have increased the calcium
elimination hy addiiiLT aci(U (especially hydroch orie acid • and salt-, to
the food. lloppe-Seyler' and Yon Noordeii found an increased calcium
elimination during oomp . cium retention was found l>v
Kumpf, Ilirx-hler. and Terray^ in feeding milk (containini: 1.58
- of calcium per liter). The total vo'ume of urinr in each case
o Cited, Hammurst.'ii. T.-xtbook of Physiological Chemist ry, n-\ . <-.!., New York,
1908.
6\"irrh«)\v'.< An-hiv. Is-,.,
,ir. I..-hn- Sf..n\vi-i-li-,.| gQBtind. krunk. M.-n~«-h<-n. H.-rlin, 1902.
ll Ui-rlin. klin. \Vo<-hei»s<-Ur.. 1^.17. .;; :_•
phy.<i..l. riu-m.. isiti, 15: 1'Jl.
i:;:
48 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
was practically the same, varying only from 975 to 1,100 cc per
period on an average, and yet the calcium excreted was subject to
considerable variation even in the case of the same rabbit fed on the
same diet for several weeks. This fact is contrary to the findings of
Patterson,0 who found that on a fixed diet writh man the urinary
calcium ran parallel to the total amount of urine excreted. Although
there was a smaller amount of calcium metabolized by the rabbits fed
inorganic phosphorus, yet of this amount a larger proportion was
retained than in the case of those fed organic phosphorus.
By excluding the very abnormally high amount of magnesium
found in the urine in the case of rabbit No. 2 (which died), we find
a very close agreement in the case of the other three animals, though
there is a slight tendency for the rabbit fed organic phosphorus to
excrete more magnesium in the urine. The amount of metabolized
magnesium that was retained shows that the rabbits fed inorganic
phosphorus, while metabolizing a smaller amount of the magnesium
than did those fed organic phosphorus, retained a larger per cent of
the amount actually metabolized. In man from 29 bo 38 per cent
of the ingested magnesium is excreted in the urine, which is higher
than in the case of rabbits. The ratio of calcium to magnesium
eliminated in the urine is not constant in the cases studied. Accord-
ing to Bertram5 and Renvall,c 29 to 38 per cent of magnesium is
excreted in the urine and 62 to 71 per cent is eliminated in the feces.
It is more easily excreted through the kidneys than is calcium. The
ratio of calcium oxid to magnesium oxid excreted in human urine,
according to Klemperer and Tritschler/* varies from 1:0.8 to 1:1.2.
The ratio of calcium to magnesium excreted in the feces in the cases
of rabbits Nos. 1 and 2 is lower than in the case of Nos. 3 and 4. The
ratio of calcium to magnesium excreted by man is held to be 8:1, but
in the case of the rabbits the ratio is considerably lower. The amount
of magnesium required by man is placed at 0.6 gram per day. In all
cases of the rabbits experimented with, daily positive calcium and
magnesium balances were obtained.
CHEMICAL ANALYSIS OF THE BODIES OF THE BABBITS.
In all cases the analyses were made on composite samples of two
rabbits, and represent the average figures. All analyses were calcu-
lated to a water-free basis.
BONES.
The bones were freed from the adhering muscular and tendon
tissue and placed in a large kettle and boiled for several hours with
water until all the flesh could be easily removed. They were then
dried in a hot-air bath, again scraped, arid finally ground into a fine
powder. The bone powder in the case of the two normal rabbits was
« Bio-Chem. J., 1908, 3:39. cSkand. Arch. PhysioL, 1904, 16:94
b Abs. Chem. Centrbl., 1897, 68:957. d Zts. klin. Med., 1902, 44:337.
CHEMICAL ANALYSIS <>F RABBITS.
49
in color and did not have the oily feeling characteristic of iluit
of the phosphorus-fed rabbits. The water content of the normal
bones was lower than in the cases when4 phosphorus was I'ed. This
wax due to the higher fat content in those cases. The remainder of
the figures represent the results calculated to a water-free basis, and
are >hown in Table VIU.
TABI.K VIII. -' ')» //"'«// nnnln^'* »f bodies of rabbits (water-free basis).
HAHIUTS FKI> ORGANIC PHOSPHORUS, N'os. 1 AND 2.
Phosphoric aci'l.
Description ,,f ^
Ash.
CtaMuoi.
sitiiu.
Klh.T
extract.
Kthcr-
Ktht-r- alcohol
Total.
alcohol solul.lc
soliil'lr. in terms
•
<-f total.
Per cent.
Per cent.
Percent.
Percent.
Per cent. Per cent.
Per cent.
Per cent.
.v, .v.
* Ml
11
U n.V,
3.78 .00 .00
I'.XII
14.72
.00
mix i 07
Bnim
.. U
7.00
6. 54 ..1 .11
:; <N',
l>, ».
tan
2.390
59.34
r,» 'f.
BOOH
I r;x
a 15
0 ;.,
ji; :;.;
0.061
0 23
0.41
4.73 .00
.00
M »x
' .V,
.854
Trace
.00
Ir i. I
5
008
1 !'•
lit tin
••• H
7 17
.06
1 : v»
in
1 I-."
28.51
5.83 .28
.06
1 22
M 7n
, \\i> ,
I'.'.n.
li> 17
u • ;
II M,,..
10 27
11 •«.
oo
1 s;,
1 IMI
% 24
it u
4.55
.44
.19
1 r . '•
M
%£
t :-i
7 vj
-, ••:
44
.08
1 '
.IS /-I
lt.lt
; 'MI
1 7.-.0
75.17
N •.',
1 !:•
.;:, r,.;
The normal rabbit-; -h.»\\ a -lightly higher figure for total ash
in the bones than do the phosphoms-fed rabbit>. Several inve>ti-
LTat«>r> have pointed out the fad that I be skeleton becomes pot.rcr
inhaler and richer in ;->h uith a .ire. V«»it" slmwed this fact in the
case of dn.irs. and Brubacher'' in the < iiildren. There is a
coii>iderabl<' variation in the ratio of the calcium to the total a>li.
; in normal animals. \Vellmann that in ca866 "{'starved
ral>bits the bones -!i-»\\ a -mailer percentage of organic matter, that
i>. a higher ratio of ash. In the case of the normal rabbits, where
the hi.irheM ash is present, we expect to find the highest percentage
of ash constituents, and such is the case.
Hummaiv. -k 1.1 I>hy-i..l,,.;i,-ah 'hi-inistry, rev. ed., New York, 1908.
li..l.. 1S!M>, .'7 : :,17.
Mm. I'hy.M.,1., 1908, Ul :508. *
77 !<>() Hull. IL':;— 09 4
50 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
The amounts of ether-soluble matter present in the bones show
some very interesting results. Both when organic and inorganic
phosphorus were fed, the bones contained more ether-soluble matter
than the normal bones, evidently a case similar to the increased
percentage of ether-soluble material in the liver and presumably due
to the phosphorus fed. The bones of the .normal rabbits and of
those fed inorganic phosphorus show practically an equal amount of
total phosphorus, the figure for the rabbits fed organic phosphorus
being a little lower. The bones of the normally fed rabbits contain a
slightly higher percentage of ether-alcohol soluble phosphorus than
in the other cases. The conclusion is that feeding this large amount
of phosphorus has not materially affected the quantity of phosphorus
stored in the bones, nor has the form of that storage been appreci-
ably changed. There is 0.27 per cent of the total phosphorus as
ether-alcohol soluble phosphorus in the bones of the normal rabbits,
and 0.23 per cen£ in the other cases, but the difference, 0.04 per
cent, is not large enough to have any significance. In a matter of
this kind the age of the animal should be taken into account, for it
is known that there is less calcium phosphate and more carbonate in
the bones of old rabbits than in the bones of young ones; likewise,
less calcium, magnesium, and phosphorus in the bones of starved
rabbits, as shown by Wellmann.
On a fat-free, water-free basis the analysis of the bones, given in
Table IX, shows a slight variation in the ash content, the ash of
the rabbits fed organic phosphorus being slightly higher than that for
the bones of the rabbits fed inorganic phosphorus, which in turn is
higher than the normal. In regard to the calcium and magnesium,
the bones of the rabbits fed inorganic phosphorus contain the
smallest amount, while the highest percentage of calcium is present
in the normal bones. The total ash content in the cases of the
experimental rabbits was greater than in the normal rabbits. The
bones of the rabbits fed inorganic phosphorus show a higher phos-
phorus content than in the other cases; but the results as regards
ether-alcohol soluble phosphorus show little variation, the bones of
the normal rabbits containing the largest proportion and those of
the rabbits fed organic phosphorus the smallest proportion.
TABLE IX. — Analysis of bones calculated to a fat- and vmter-free basis.
Rabbits.
Calcium.
Magne-
sium.
Ash.
Phosphoric acid.
Total.
Ether-
alcohol
soluble.
Ether-
alcohol
insoluble.
Ether-
alcohol
soluble
in terms
of total.
Fed organic phosphorus
Per cent.
9.99
8.54
10.72
Per cent.
0.25
.17
.24
Per cent.
62.66
61.71
60.57
Per cent.
27.04
29.06
27.33
Per cent.
0.065
.067
.073
Per cent.
26.97
28.99
27.26
Per cent.
0.26
.23
.28
Fed inorganic phosphorus
Normal .
CHEMICAL ANALYSIS OF RABB11S.
51
LIVERS.
The livers of the rabbits were dried and powdered. The total ash
of tlu> livers of the normal rabbits is higher than the ash of the livers
of those fed inorganic phosphorus which, in turn, is slightly higher
than the ash of the livers of those fed organic phosphorus.
The changes produced in the livers do not seem to include any
large storage of phosphorus in the organ, for the livers of the rabbits
fed organic phosphorus which show the largest excess of fat contain
the lowest permit ago of total and ot her-alcohol-soluble phosphorus,
and the livers of the rabbits fed inorganic phosphorus, which have
a lower fat content, contain a lower percentage of phosphorus than
the normal rabbits' livers. Not onl\ i> there a diH'erence in the total
phosphorus content of the various liveis. but the livers of t he rabbits
fed organic phosphorus contain a lower percentage of ether-alcohol-
-oluble phosphorus than i> present in the other cases, the normal
livers >howing the highest figures. That there is an excess of fat
in tin- livers of the rabbit-* fed an excessive amount of phosphorus,
whether organic «»r inorganic. i> >hown by the figures for the ether-
>olublc matter. iKiiueh. H.'.»~> pel- cent in the case of t he rabbits fed
oruMiiie pho.xphorus, 34.48 per cent in the livers of those fed inor-
urani<- pho.xphorus. and only 14.47 per cent in the case of the livers of
the normally fed rabbit-.
TABLK X. A> > rs ( water-free b<>
.l.u.-.l to ;i fat-free
Mtof
Btafaooot-
posit
toal
amount^.
Nitrogen.
Phosphoric
acid.
g
-r:
Ration.
1
ll
ll
«
1
i
1
1
Total nit
fkm
I1
I
I1
H
§.*
ii
Om*.
Gm*.
Om*.
Om*.
Om.
QlM.
Om*.
Gnu.
Gm.
1
1,550
Organic p h o s -
phunis
91.0
36.1
7.64
1.98
44.95
2.76
0.72
5.01
3.23
1.31
0.85
3
1,800
Inorganic phos-
phor
81 5
I
9 41
2 56
34 48
2 58
?n
2 18
i n?
60
2,000
86.0
* 9.41
2.56
34.48
.90
2.50 1.37
.69
•-MO'
2,200
Noninl
50.0
60.0
11.90
1'.90
2.85
2.85
11.47
i .42
• . 43
LVIM l.(X)
2.09' .95
.49
.50
.24
.23
In Table X the results for the body weights, liver weights, total
nitrogen, total phosphorus, and ether extract found in the Livers of
the various rabbits are given. That phosphorus in the forms fed tends
to enlarge the livers is seen from the percentage of total weight of the
livers in terms of the body weight of the rabbits. In the case of Nos.
52 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
5 and 6 (the normal rabbits) the livers formed 3 and 2.8 percent, re-
spectively, of the total weight of the rabbits, while in Nos. 1, 3, and 4
the liver weight made 6.0, 4.5, and 4.4 per cent of the body weight.
More total nitrogen and phosphorus is present in the livers of phos-
phorus-fed rabbits than in the normal livers, and calculated to a
fat-free basis the differences are more evident. The tendency of
organic phosphorus to produce fat is especially striking; in these ex-
periments an increased amount of ether-soluble matter is seen in the
bones, livers, brains, and nerves of the phosphorus-fed rabbits.
Jordan, Patten, and Hart,a in their experiments with phytin, state
that when the, cows were reduced from a high to a low phytin diet,
the percentage of fat in the milk was reduced. The fact that phytin
tends to the production of fat in various organs and secretions
seems to be established by all of these experiments.
BLOOD.
The figures for blood analysis are given on a water-free basis. The
amount of ash is highest in the blood of the rabbits -fed organic phos-
phorus. The blood of those fed inorganic phosphorus and of the nor-
mal rabbits contain about an equal amount of ash. The variations
are not large enough to be of any consequence when the individuality of
the different rabbits is considered. The calcium content of the blood
of all the phosphorus-fed rabbits is reduced, showing only a trace,
while 0.44 per cent of calcium is present in the dried blood of the nor-
mal rabbits. The same holds true in the case of the magnesium, 0.19
per cent being present in the dried blood of the normal rabbits and
none being found in the blood of the phosphorus-fed rabbits. The pre-
vailing belief is that the composition of the blood changes but little if
any, no matter what changes may take place in the body tissues.
Patterson b found, in the case of animals kept on a calcium-poor diet,
that the ratio of the calcium of the blood to the total ash of the blood
was the same as that of normal animals. The amount of total phos-
phorus present in the normal blood is somewhat lower than in the
cases where phosphorus was fed. The ether-alcohol soluble (lecithin)
phosphorus is highest in the blood of the normal rabbits and the figures
show that 6.33 per cent of the total phosphorus is present in the dried
blood of the normal rabbits as ether-alcohol soluble phosphorus
against 1.07 and 1.16 per cent in the case of the experimental rabbits.
Here again we see that the constant ratio of the constituents of the
blood is not maintained. Only traces of ether-soluble matter were
found in any of the samples of blood examined. (Table VIII.)
aAmer. J. Physiol., 1906, 16 : 268. &Bio-Chem. J., 1908, 3 : 39.
CHI.MK AI. ANALYSTS OF RABBITS. 53
BRAINS.
The brains of the rabbits were completely removed and dried in
platinum dishes, then ground in a mortar and mixed as well as pos-
sible before analyzing. The a>h v.iried from 7.0 to 7.82 per cent,
being highest in the normal brains. As the age and other factors in-
fluence the asli content of all organs, this variation h.as no significance.
The percentage of calcium shows some variation and is likewise high-
est in the ash of the brains of the normal rabbits.
The percentage of magnesium remains fairly constant in all cases.
The ratio of calcium to magnesium in the brains is 6.3: 1 in the normal
rabbits. \.~>:\ in the brains of those fed inorganic- phosphorus, and
3.5:1 in the brains of those led organic phosphorus.
The total phosphorus found in the brains is about the same in all
CaaeS, but this i> not true of the ether-alcohol soluble phosphorus.
The brains of the rabbit-; fed organic phosphorus show 2.35 percent
]>ho>|)horus afl ether-alcohol soluble,' or ")«.).: 1-1 per cent of the total.
The brains of tlio-<- fed inorganic phosphorus show but 1.16 percent
pho>phorus as et her-alcohol soluble phosphorus, or LN..")1 per cent of
the t«»tal. This j. louer than the figures for brains of the normal rab-
bi is. which contain U.07 per cent of the phosphorus in a form soluble
in ether and alcohol. It appears from these figures that the brains of
the rabbits fed organic pho>phorus contain an appreciably larger
amount of ether-alcohol soluble phosphorus than do the brains of
rabbits fed on inorganic phosphorus or those of the normally fed rab-
bits. (Table VIII
\ i i : \ i >
The ash content on a water-free basis shows a fairly constant
percentage in al As in the brain, the calcium content of the
ncr\rs \s higher for the normal rabbits than in the other 08860.
The amount of magnesium in the nerves of the normal rabbits is
0. U per cent, 0.11 per cent, or practically the same, in the nerves
of those fed organic phosphorus, and one-half, or 0.06 per cent in the
nerves of those fed inorganic ph,»phoru-.
The ratio of the calcium to the magnesium is much lower in the
nerve< of the rabbits fed organic phosphorus than in the other cases.
The data for ether-soluble material are fairly uniform, being a trifle
lower for the nerves of the normal rabbits than for the experimental
rabbits.
The total phosphorus content varies from 3.72 per cent in the case
of the rabbits fed organic phosphorus to 4.28 per cent in the case of
those fed inorganic phosphorus. The amount of ether-alcohol soluble
phosphorus is lowest in the case of the rabbits fed on inorganic
phosphorus, the percentage of the total phosphorus in this form being
54 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
34.25 per cent against 64.26 per cent in the case of the rabbits fed
on organic phosphorus, and 59.23 per cent in the normal rabbits.
These results are similar to those recorded in the case of the brains.
(Table VIII.)
TEETH.
The teeth were freed from adhering bone and muscle tissue by
scraping and were dried in a hot-air oven at 100° C. The ash was
constant in all cases, averaging 75 per cent. There was somewhat
more calcium and a trifle less magnesium found in the teeth of the
normal rabbits than in the teeth of the phosphorus-fed rabbits.
These results run parallel with those obtained for calcium in the case
of the bones of the rabbits. The total phosphorus was practically
no higher in the normal rabbits than in the other cases. (Table VIII.)
INTESTINES.
Phosphorus was estimated in portions of the small intestines of the
various rabbits. The loops of intestine were well washed and dried
between filter papers and then in an air bath at 45° C. for five hours.
When sufficiently dry they were cut into small bits. Moisture and
total phosphorus were determined on a weighed quantity of this
substance and on another portion the following extractions were made :
One gram of substance was ground fine with pure sand in a porcelain mortar and
transferred to a 300 cc Erlenmeyer flask. Thirty cubic centimeters of absolute ether
were then added and the whole extracted on the water bath overnight, using a reflux
condenser. The ether extract was then filtered through a hardened filter into an
ordinary Jena flat-bottom flask. Particles of residue found on the filter paper were
scraped back into the Erlenmeyer flask. To this ether extract residue 60 cc of abso-
lute alcohol were added and boiled for three hours, using a reflux condenser. This
alcohol extract was filtered hot into the Jena flask containing the ether extract and the
residue washed twice with separate portions of 25 cc of hot alcohol and the washings
were added to the combined extract. Phosphorus was determined in the combined
ether-alcohol filtrate by the Neumann method.
The ether-alcohol extraction residue was next treated six times with 50 cc portions
of cold water saturated with chloroform, allowing ten hours for each extraction, using
the same hardened filter paper as before and scraping back the residue from the filter
paper into the flask. This solution was evaporated to dryness and the phosphoric
acid determined therein by the Neumann method. This is called the phosphorus
insoluble in ether and alcohol, but soluble in water. Phosphoric acid was then
obtained in the residue by difference and called the phosphorus insoluble in ether,
alcohol, and water.
In all cases a large amount of the phosphorus of the fresh sample
was soluble in water, fully 50 per cent being dissolved by this means
during the preparation of the sample. The amount of phosphorus
insoluble in alcohol, ether, and water was higher in the normal
rabbits' intestines than in the other cases. The amount of ether-
alcohol soluble phosphorus showed but little variation.
CHEMICAL ANALYSIS OF RABBITS. 55
SUMMARY.
There are many variations in the composition of the diiYerent
portions of the rabbits, apparently due to the feeding of phosphorus
in the two forms. The amount of ether-alcohol-soluble phosphorus
stored in the brains and nerves is much lower in the case of the
rabbits fed inorganic phosphorus than in the normal rabbits and
those fed organic phosphorus. The organic and the inorganic
phosphorus, fed in excess, caused an increased percentage of ether-
soluble material in the bones, and an indication of the same is noted
in the brains and in the nerves. No increased storage of calcium
or magnesium w<is imted ; on the contrary there isaslight decrease, as
compared with the normal, in bones, nerves, and brain. The ether-
alcohol soluble phosphorus of the blood was reduced in all eases
where phosphorus was fed. The increase in the fat of the livers was
marked in both cases of phosphorus feeding, but was greater for
the rabbits fed organic phosphorus. If a large percentage of ether-
alcohol soluble phosphorus in the brains and nerves is desirable,
then the rabbits fed organic phosphorus were in a better condition,
• the data, than were those led on inorganic phosphorus.
The nitrogen content was determined in all of the samples, and is
given in Table VIII calculated to a water-free basis. The percentage
of nitrogen found iu the bones varied from -l.il'J per cent in the
bones of the normal rabbits to Lt'.s per cent in the bones of the
rabbits fed on inorganic phosphorus. The percentage of nitrogen
found iu the livers of t he experimental rabbits \\ as considerably lower
than in the livers ,,f the normal rabbits, this agreeing with the
other dala >howing a ^em-rally poor condition of the livers of the
former. The percentage of nitrogen found in the blood was fairly
coiisi ant. as i> usually the case, and the same is true of the brains.
Just why we find a variation in the amount of nitrogen present in
the nerves and spinal cord is diliicult to explain. More, ash and
more ether-alcohol-soluble phosphorus are found in the samples of
nerves of the rabbits fed organic phosphorus, which also show the
highest percentage of nitrogen. The ratio ot phosphorus to nitrogen
in the liver of rabbits is 1:14.7, according to Wellmann.0 His
figures are higher than the results obtained in this experiment, the
ratio of phosphorus to nitrogen being, for normal rabbits 1:9.7, for
rabbits fed organic phosphorus i:S.8, and for those fed inorganic
phosphorus 1:8.6.
« Arch. ^-am. I'hysiol., 1908, 121:508.
56 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
FINDINGS OF AUTOPSIES.
At the conclusion of the principal feeding period the rabbits were
chloroformed, autopsies were made, and histological slides of several
of the organs prepared. Two normal rabbits were similarly treated.
The normal rabbits had been fed on corn, oats, and vegetables for
some time previously and had been kept in cages. There seems to
be no constant relationship between the total weights and the per-
centages of solids present in the various organs, blood, brains, and
nerves of the six rabbits examined. The autopsies showed the
following results: a
Rabbit No. 1, fed organic phosphorus.
Intestines: Normal, containing food. Some fat distributed along the intestines.
Lymphatics: Apparently normal.
Kidneys: Apparently normal.
Spleen: Apparently normal.
Liver: Very light in color, possibly fatty infiltration. Appearance similar to that
of No. 2.
Stomach: Contained food. Normal.
Heart: Normal.
Lungs: Showed a condition of anemia along edges.
After drying: Bones seemed oily. Much fat in liver; fat left in bottom of dish after
drying.
Rabbit No. 2, fed organic phosphorus.
Intestines: Normal, except colon distended with large amount of feces; no con-
gestion.
Lymphatics: Apparently normal.
Kidneys: Apparently normal.
Spleen: Apparently normal.
Liver: Somewhat enlarged, pale, with yellow tinge; seemed pathological.
Stomach: Full of food; appeared to have extended area of old hemorrhage on lessor
curvature.
Heart: Apparently normal; post-mortem blood clot.
Lungs: Left, apparently normal; right, partly congested.
Nervous system : Normal.
General appearance: Good.
Rabbit No. 3 , fed inorganic phosphorus.
Intestines: Apparently normal.
Lymphatics: Apparently normal.
Kidneys: There seemed to be slight irritation and congestion.
Liver: Light colored ; enlarged.
Spleen: Normal in size and color generally; better condition than Nos. 1 and 2;
yellow color; numerous small areas of what may be fatty degeneration or infiltration.
Stomach: Old hemorrhage around greater curvature.
Heart: Apparently normal.
Lungs: General appearance good, but apex of right lung had a small area of
congestion.
General appearance: Fairly fat and in good condition externally.
a-H. L. Amoss, of the Animal Physiological Laboratory, assisted in making the
autopsies and interpreting the histological slides which were prepared by E. A. Read,
of the Microcheinical Laboratory.
AUTOPSY FINDINGS. 57
Rabbit No. 4, fed inorganic phosphorus.
Intestines: Apparently normal.
Kidneys: Right, slight yellow color in cortex, pitted, congested; left, pitted over
external surface, slight congestion in medulla, very .-li-rht yellowish color in cortex.
Spleen: Apparently normal .
Liver: Light color, lighter spots seen. Gall bladder apparently normal.
Stomach: Capillaries of fundus darkened — apparently not post-mortem change.
Heart: Apparently normal.
Lungs: Left, apparently normal; right, lower half of lower l<>l>t> congested.
linbbltx Xnx. .'» tun/ H, nnrmalltj h <I.
The autopsies showed that in the ca-es of the two normal rabbits, Xos. ~> and »i. the
organs were apparently normal. The liver- had the normal dark-red color in contrast
with the pale liver- <•! \..<. 1. '_', :;. and -I.
Tin1 autopsies showed that none of the experimental rabbits was
in a normal condition. The livers \\ere especially affected, bein^
]>ale and abnormal, and indicating an ez068B of fat.
The relation of the liver to metabolism is a problem important to
both the phy-io|o-_:ist and the pathologist. For a loiuj time it has
been reeo'_:ni/ed that one .»!' the functions of the liver is connected in
.some \\ay \\itli the destruction or removal of poison from the hlo<,d,
e-pc-cially such poison-. as are produced in, or absorbed from, the
alimentary canal. It \\ a> earl\ :/.ed that the destruction of
the liver cells leads t.»serioiis p«»isoiiiii'_r. Jiiul this w&B experimentally
demonstrated b\ Kck, \\ho e\<-luded the liver from the circulation
b\ making a direct communication between the portal vein and the
inferior vena ca\ ;i. an oj)"ration Unou n as " KcU listula."
The ((uestioii of fatty degeneration has an ini|)ortnnt bearing from
the physioln-iral |M»i!it of \ie\\, for fa tt y de-eiieral ion is another
proof of the formation of fat from proteins. 1'Yom the investiga-
tions of Bauer" on do>_> and Leo on i'ro^ ur must admit that at
l«-a-t in acute poivoniii'.: by pho-plmrus fatly degeneration takes
place \\ith the formation of fats from proteins. Still, invest i^ators
an not unanimous <>n this point, and Pflii^er'' especially has raised
objections to these experiments.
The ideas of the fatty degeneration of protein in the old sense as
u-ed by these writers hav been changed by the work of Rosenfeld,d
etc.. who believe in the theory of fat transportation.
In the ca-e of a phosphori/ed du;:. Mandel' has shown that lactic
acid disappears from the blood and urine when phlorhizin glycosuria
Bid., 1871, 3
*>Zts. phy-i.,1. Chem.. 1885,9:469.
• Arch, iresam. IMiy.-i..! . \^.t\ 92,51:317.
«*Erg«-h. I'hysii:!.. Pi. I, Uiochemie, 1903,^:50.
eAmer. J. Physiol , Proc., 1905, l.i : 16.
58 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
is induced. Ltisk a offers the following general hypothesis as his expla-
nation of fatty changes in tissues:
The lactic acid which occurs is derived from the sugar formed in proteid metabolism.
In the above case the sugar is removed before its conversion into lactic acid. In
phlorhizin diabetes, dextrose does not burn; in phosphorus poisoning lactic acid
derived from dextrose does not burn. In both cases a sugar-hungry cell, or one where
carbohydrate is not oxidized, is found, and under these circumstances fat is attracted
to the cell, and in larger quantities than can be useful. Wherever sugar freely burns
this fatty infiltration is impossible. A reduced local circulation in a portion of the
heart may produce anemia of the part, an imperfect local combustion of lactic acid
normally formed and a fatty infiltration of the locality.
*******
It has been stated that the action of phosphorus is to induce autolysis (self-digestion)
of the body's protoplasm (Jacoby,6 Waldvogel c), since leucin, tyrosin, and other
amino acids may be eliminated in considerable quantity in the urine. Oswald &
thinks that phosphorus destroys or weakens the antiautolytic agents of the body.
That autolytic enzymes do not gain free control over the cells through the direct
influence of phosphorus is proved by the work of Ray, McDermott, and Lusk.«
These authors found that phosphorus injections raised the proteid metabolism of fasting
dogs to 250, 260, 283, 248, 183, and 164 per cent of that of the dog when normal. They
contrasted this increased proteid metabolism with that obtained in phlorhizin glyco-
suria, which is represented by increases to 540, 450, 340, and 340 per cent. When,
however, they gave phlorhizin and obtained the increased metabolism, and then
injected phosphorus, this was not followed by any marked increase in proteid metab-
olism. Under these circumstances phlorhizin glycosuria is the predominating factor,
removing the dextrose produced from proteid. As regards phosphorus poisoning,
Araki/ believes that lactic acid accumulation is due to lack of oxygenation of the
tissues caused by a slow heart beat, but not due to anemia. He does not believe the
oxygen deprivation to be very pronounced. The writer offers the explanation that
phosphorus may affect the enzyme which breaks up the lactic acid derived from dex-
trose, and the accumulation of this acid may prevent the action of some of the deni-
trogenizing enzymes; and further, its noncombustion may necessitate an increase of
proteid metabolism.
This theory is strengthened by the discovery of Schryver g that the addition of
lactic acid favors the accumulation of amino acids in autolysis of the liver.
In this connection we must recognize the fact that the presence of
amino bodies — leucin, tyrosin, etc. — in the liver in cases of phosphorus
poisoning is well established. Abderhalden and Bergell71 detected
glycocoll in the urine of a rabbit poisoned with phosphorus. Wohl-
gemut-J found phenylanin and arginin in the urine after a case of phos-
phorus poisoning. An altered quantitative relationship between
a The Elements of the Science of Nutrition, Philadelphia, 1906.
bZts. physiol. Chem., 1900, SO : 174.
cArch. klin. Med., 1905, 82 : 437.
<*Biochem. Centrbl., 1905, 3 : 365.
«Amer. J. Physiol., 1899, 3 : 139.
/Zts. physiol. Chem., 1893, 17 : 310.
0Bio-Chem. J., 1906, 1 : 123.
& Zts. physiol. Chem., 1903, 39 :464.
'Ibid., 1905, 44:74.
AUTOPSY FINDINGS. 59
ar^inin, lysin, and histidin was noted in the liver of a phosphorus-
poisoned do"; by Wakeman. * The amount of arginin was consider-
ably lower tban the amount present in the liver of a normal do^.
In tbe experiments here reported tliere is no doubt that, due to
organic and inorganic phosphorus, an alteration in the livers, brains,
and nerves has taken place, accompanied by the presence of abnor-
mally hijjh pen-entases of fat.
HISTOLOGICAL EXAMINATION.
The follow inir results were obtained from the histolo^ieal examina-
tion:
Kal)bit> Xos. 1 and L\ fed or^aine phosphorus.
Liver, No. 1: Kxien-ive areas of fuiiy d* -em-ration and fatty infiltration. Sec-
tion- -tained \\-iili hemotoxylin and ensin. Fleming's solution, and Soudan III.
I.i\t-r, \... •_'. Nt)t (juile as e\ien-i\e RTefU «.f faiiy de<_renerat inn and fatly infiltra-
tion a.- in the ca.-e of No. I. <'hn>nir inllammatory processes seen and general areas
of hemorrhages.
Lungs. No. | Several areas of focal neero-i- noticed stirronndinu' v.-in in a state of
passive conurr.-ii.,;i. Practically al! 'll;ip~'-d an<l \\ alls congested. General
red cell «-xir;i\;i.-;ition.
Stomach. > ~li«;ht congestion
liabbil^ NOB, 3 and 1. fed in< >fLranie pliospborUS.
l.i\ •«-r. No. :',: Inliliralion in certain an-as, hut not as far ^one as Noe. 1 and 2. Cer-
tain ar.-a.> .-hou.-d lntlc chanu'.-. Slight cloudy swi-llinir. Slight chronic inllainina-
tion, n, .1 BO mark'-d a.- N
I.i\.-r, No. I: Little difference <XMHpued with Nos. 1 and •_'. Somesubacuteinllarn-
niatory procoOBOB Been, al.-o .-oim- faiiy tli-irt-n. -ration. Soudan III stain shows more
iatt\ d> -cnrration than is sc.-n with i-'lcniin.
Ln: I'ncunionia in .-ta-jc- of ^ra\' hcpaii/alion.
I. in. Not normal. Inn in better general Condition than oih.-r-. l.umenof
art«-r\ m-arly obliterated hy iihrous tissue. Uronchilis. Slight ^i-in-ral congest ion.
Heart. No. 3: I'cricarditi- I fatty degeneration of myocardium,
Kidney-, No. 3: Marked conur'-tion. Slight parenchymatous degeneration.
!: I'aren<'h\ inatou- de-jetieral ion. Congestion more pronounced than
in case « <i N
Stoinacl: \pparently normal.
Stomach. No. t: Ap|)arently normal.
Rabbit s Nos, •"> and •'». imniially fed.
Livers: Practically normal. No fat pre-eni; .-mall areas in which few nuclei did
no, -lain as deeply as the n-si. prohaMy due to sectioninir.
Lnnirs: <'oime-ti.)n throughout. A few areas of hemorrhages with superimposed
intlammaiory j>rocesses.
Kidneys: Slight intertulmlar hemorrhage.
Hearts: Slight myocarditis.
Stomachs: Apparently normal.
The results of the histological examination confirm the opinions
formed at the time of the autopsy and show most marked fatty
"/is. phy>iol. ('hem., 1905, 44 :335.
60 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
degeneration of the livers of rabbits Xos. 1 and 2. The liver of rabbit
No. 4 also shows fatty degeneration, but less marked, while rabbits
Nos. 5 and 6 show normal livers. That the harmful effects noted
are due to the excessive amounts of phosphorus fed either organic
or inorganic, is proven from the cases of the normal rabbits which,
although likewise kept in cages, showed apparently normal livers.
In reviewing the phosphorus literature it was noticed that in several
cases rabbits fed on organic phosphorus were reported to have died
of pneumonia, as did rabbit No. 2 in the experiments here recorded.
Six photomicrographs0 are appended, which show sections of the
livers of rabbits Xos. 1, 2, and 4. The tissue in the case of rabbit
No. 3 was exhausted before an osmic acid slide was prepared and it
was therefore impossible to give a reproduction in this case. The
photomicrographs in which the fat is shown stained black in position
demonstrate that degeneration as well as fatty infiltration has taken
place in the livers of both of the organic and in one of the inorganic-
phosphorus-fed rabbits.
The author is indebted to Doctor Mohler, of the Bureau of Animal
Industry, for his interpretation of the microscopic slides, in regard to
which he makes the following statement:
The section in the case of rabbit No. 1 (PI. I) shows a more marked and advanced
lesion of fatty degeneration than do the three remaining cases. In this case fatty
infiltration is also present and occurs principally on the periphery of the lobules and
in the tract supplied by branches of the portal vein, while the fatty degeneration is
more abundant in the central zone around the hepatic vein. In fatty degeneration
the fat is usually in minute granules, which may coalesce to form small droplets,
but only in the most advanced stages do they form large drops as is the case in fatty
infiltration.
The sections in which the tissue has been treated with Fleming's solution show the
lesion best, as the contrast of the black-stained fat is so marked as compared with the
light hepatic parenchyma that photomicrographs may be readily made.- The Soudan
III sections, while valuable for demonstration purposes, can not be reproduced as well
on account of less contrast and the red color.
The section in the case of rabbit No. 4 (PI. Ill) shows a less advanced stage of fatty
degeneration; there is also not much fatty infiltration present. In the section in the
case of No. 2 (PI. II) there is still less fatty degeneration present, while the section of
rabbit No. 3 does not show any degeneration and only a little fatty infiltration.
CONCLUSIONS.
The somewhat limited experimental data here reported point to the
following conclusions, which may be altered by more extensive work
on the subject.
PRELIMINARY FEEDING PERIOD.
During the preliminary feeding period, the rabbits fed on organic
phosphorus excreted a slightly larger proportion of nitrogen in the
urine than did the rabbits fed on inorganic phosphates, but retained
°Made by B. J. Howard, Chief, Microchemical Laboratory, Bureau of Chemistry.
***9 w:r ^z^v-^v*:-. • - \. * - rjf*fj
^•vr^v^'-v^^v' Wm
>• *<«*•*»£&• ' '*•' ' "& " -•S;«**
i>^i • -*.~.Q . ;&-, •*&-**m\
• ° "• -*%. ' ' A-' - • -*^ • . ££ £ & •
.*-•• . • .^ . f'i i^r? •& _7- ' •aP-Xi.-.-» _ic
FIG. 2. — MAGNIFICATION 175 DIAMETERS.
LIVER SECTIONS OF ORGANIC-PHOSPHORUS-FED RABBIT No. 1
[Fat stained black with osmic acid.]
Bui. 123, Bureau of Chemistry, U. S. Dept. of Agriculture.
PLATE II.
I.— MAGNIFICATION 60 DIAMETERS.
JitfV
i
FIQ. 2. — MAGNIFICATIO
LIVER SECTIONS OF ORGANIC-PHOSPHORUS-FED RABBIT No. 2.
[Fat stained black with osmic acid.]
Bui. 123, Bureau of Chemistry, U. S. Dept. of Agriculture
»' * , -,«F * ^*«* . •" *4»»i«
>. "•«*%£l-i-/:Uvk •
FIG. 2. — MAGNIFICATION 175 DIAMETERS.
LIVER SECTIONS OF INORGANIC-PHOSPHORUS-FED RABBIT No. 4.
[Fat stained black with osmic acid.]
CONCLUSIONS. 61
a smaller proportion of the absorbed nitrogen than did the rabbits
fed inorganic phosphorus. AVitli a few exceptions, the daily balances
were positive.
The rabbits fed organic phosphorus excreted less phosphorus
through the kidneys than did those iVd inorganic phosphorus, but
they retained a larger proportion of the absorbed phosphorus.
PRINCIPAL FEEDING PERIOD.
The percentages of absorbed nitrogen retained in the case of the
rubbiis led inorganic phosphorus show a wide variation, the average
figure being practically the same as that for rabbit No. 1 fed organic
phosphorus, rabbit No. - being excluded from the average. Accord-
ingly, it is impossible to establish any ^ll'ect produced on the nitrogen
metabolism by the two forms of phosphorus fed.
A laiger proportion of the ingested phosphorus was eliminated by
the kidneys in the cases of tin rabhits fed inorganic phosphorus than
where the rabbits were fed organic phosphorus. The proportion of
• rhed pho-phonis retained is greater for the rabbits fed on organic
phosphorus. The d. QCCfl Wen positive with the c-xceptiou of
r:i!)l>it No. L', which died I w<> \\eeks before the close of the experiment.
The ether phosphorus balances show tliat more
phosph >ru> in this form wa> eliminated in the feces where phytin was
ilian \\hrre mop/aiiir pho-phorii- wafl fed.
\o r'li.T-;ilcohol-so!uble phosphor; .umd in the urine in any
. and it is doubtful if any organic phosphoric ia present in the
urine of a normal rabbit.
A smaller proportional B um of calcium was eliminated in the
urine by the rabbits fed on moriraiiie. phosphorus, hut . pro-
port iona1 amount \\ -ied in the hodv than in the ca>es of the
rabbits fed on organic phosphorus. The same >t atement is true of
iiesium.
IM»r-M<UM l.M 1. \\MIN MI<>\.
A large proportion of the phosphoric of (he fresh intestines of
rabbits is dissolved by water durinir the process of cleaning prepara-
The hone-; of rabbit x fed on phosphorus for several months, either
nic or inorganic, show a higher content of ether-soluble matter
than do the hones of normal rabbits, and they form a larger percent-
of the body weight than in the case of normal rabbits.
The livers of the rabbits fed on organic phosphorus for several
months sh,>\\ 1'aMv degeneration as well as fatty infiltration. Of the
livers of the inorganic phosphorus fed rabbits No. 4 shows both fatty
degeneration and fatty infiltration; in the case of No. 3, only slight
fatty infiltration is .shown. The livers are. enlarged and contain
62 METABOLISM OF ORGANIC AND INORGANIC PHOSPHORUS.
considerably more nitrogen and phosphoric acid than normal livers
when calculated to a \\ ater and fat-free basis. In these experiments
the degeneration and infiltration were most marked when organic
phosphorus was ingested.
The brains and nerves of the rabbits fed on organic phosphorus
yield a larger percentage of ether-alcohol soluble phosphorus than
those of normal rabbits, while the brains and -nerves of those fed
inorganic phosphorus show lower figures. " There is also a larger
percentage content of ether-soluble material in the brains and nerves
of the phosphorus-fed rabbits than is normal.
The tendency of organic phospnorus, especially in the form of
phytin, to produce fat was strikingly indicated in this experiment as
in the work of Jordan, Hart, and Patten. The autopsies showed that
all the phosphorus-fed rabbits were in an abnormal condition, the
livers being especially affected, and the histological examination con-
firmed the autopsy findings.
LIST OF TABLES.
1. Nitiragen and phoBpitorufl metabolism preliminary period 34
II. Ratio of nitrogen to phosphoric acid in food and excreta preliminary
peri :'.7
III. Niin>i;«'ii an.l phosphoric acid l>alance< principal period :!S
IV. Itatio- of ( al« iuin. niaL'in'>iuiii. and phosphorus in food, frees, and
urinr principal period 39
V. Kihrr-alcohol->olul)lc j)ho>phoii,- acid l>alanc<- principal period... -i'J
\ I . V'arioii- form- of pho-phoni- in urine principal period 44
VII. Calcium and magnci-ium halam-r.- principal period 17
VIII. Chemical analyik of bodies of rabbita (water-free 49
IX. .\iial\-i- alcolated to a fat- and water-free basie 50
X. . \n.tl\-i- of nil. I'it.-' li\er- \\aJ«-r-i'n-i- l.a.-i- • 51
63
O
UNIVERSITY OF CALIFORNIA LIBRARY
BERKELEY
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