PROCEEDINGS

OF THE

AMERICAN ACADEMY OF ARTS AND SCIENCES.

PROCEEDINGS

OF THE

AMERICAN ACADEMY

OF

ARTS AND SCIENCES.

NEW SERIES.
Vol. XXII.

WHOLE SERIES.
Vol. XXX.

FROM MAY, 1894, TO MAY, 1895.

SELECTED FROM THE RECORDS.

BOSTON:

UNIVERSITY PRESS; JOHN WILSON AND SON.

1895.

xfio i

CONTENTS.

Page

I. On the Determination of Sulphur in Volatile Organic Com-

2)ounds. By Charles F. Mabeey 1

II. Double Haloid Salts of Antimony, Calcium, and Magnesium,
with Observations on the Remarkable Dissociation of these
Compounds. By Francis Gang Benedict, A.M. . . 9

III. The North American Ceuthophili. By Samuel H. Scudder 17

IV. Neio Plants collected by Messrs. C. V. Hartman and C. E.

Lloyd upon an Archceological Expedition to Northwestern
Mexico under the Direction of Dr. Carl Lumholtz. By
B. L. Robinson and M. L. Fernald 114

V. On the Constitution of the Nitroparaffine Salts. By J. U. Nef 124

VI. On Bivalent Carbon. Second Paper. By J. U. Nef . . 151

VII. On the Properties of Batteries formed of Cells joined up in

Multiple Arc. By B. O. Peirce 194

VIII. On the Cell Lineage of the Ascidian Egg. A Preliminary

Notice. By W. E. Castle 200

IX. Wave Lengths of Electricity on Iron Wires. By Charles

E. St. John, A.M 218

X. A Heat Method for Measuring the Coefficient of Self-induc-
tion. By p. G. Spalding and H. B. Shaw . . . 247

XI. Researches on the Complex Inorganic Acids. By Wolcott

GiBBS, M.D 251

VI CONTENTS.

Page
XII. On the Blastodermic Vesicle of Sus Scrofa Domesticus. By

A. W. Weysse 283

XIII. On Ternary Mixtures. First Paper. By "Wilder D.

Bancroft 324

XIV. A Revision of the Atomic Weight of Strontium. First

Paper: The Analysis of Strontic Bromide. By Theo-
dore William Richards 369

XV. On the Electrical Resistances of certain Poor Conductoi's.

By B. O. Peirce 390

XVI. Variability in the Spores of Uredo Polypodii {Pers.) DC.

By B. M. Duggar 396

XVII. Trinitrophenylmalonic Ester. By C. Loring Jackson

AND C. A. SocH 401

XVIII. Action of Sodic Alcoholates on Chloranil. Acetals derived
from Substituted Quinones. By C. Loring Jackson
AND H. S. Grindley 409

XIX. On the Cupriammonium Double Salts. Second Paper. By
Theodore William Richards and Andrew Hen-
derson Whitridge 458

XX. Notes on Laboulbeniacece, ivith Descriptions of Neio Species.

By Roland Thaxter 467

XXI. Experiments and Observations on the Summer Ventilation and

Cooling of Hospitals. By Morrill Wyman . . . . 482

XXII. Experiments on the Relation of Hysteresis to Temperature.

By Frank A. Laws and Henry E. Warren . . 490

Proceedings 503

Biographical Notices : —

Josiah Parsons Cooke 513

Oliver Wendell Holmes 555

Edward Jackson Lowell 562

CONTENTS. Vll

Page
Biographical Notices (continued) : —

Robert Charles Winthrop 566

William Holmes Chambers Bartlett 570

Ezekiel Gilman Robinson 572

William Dwight Whitney 579

Charles Edouard Brown-Sequard 589

Hermann Ludwig Ferdinand von Helmholtz 592

Gaston, Marquis de Saporta 598

List op the Fellows and Foreign Honorary Members . . 601

Statutes and Standing Votes 609

Index 621

PROCEEDINGS

OF THE

AMERICAN ACADEMY

OF

ARTS AND SCIENCES.

VOL. XXX.
PAPERS READ BEFORE THE ACADEMY.

Aid in the work described in this Paper was given by the Academy from the
C. M. Warren Fcnd for Chemical Research.

CONTRIBUTIONS FROM THE CHEMICAL LABORATORY
OF THE CASE SCHOOL OF APPLIED SCIENCE.

XIX. — ON THE DETERMINATION OF SULPHUR IN
VOLATILE ORGANIC COMPOUNDS.*

By Charles F. Mabery.

Presented April 11, 1894

The great quantity of products introduced into the petroleum
industry from the fields in Ohio and Canada yielding the sulplmr
oils has involved many sulphur determinations, and the necessity
of a rapid method capable of affording results of extreme accuracy,
especially in oils containing a small fraction of one per cent of
sulphur. Several of tlie older methods leave nothing to be desired
in point of accuracy, but they are not sufficiently expeditious for ser-
vice in manufacturing operations, or in investigations which depend
upon immediate information concerning the percentage of sulphur.

The first attempt to determine sulphur in organic compounds by
combustion in oxygen was made by C. M. Warren, f the sulphuric acid
formed being absorbed within the combustion tube in plumbic peroxide.

* This paper is one of the series on the composition of tlie sulpliur petroleums.
t These Proceedings, VL 472.

VOL. XXX. (n. 8. XXII.) 1

2 PROCEEDINGS OF THE AMERICAN ACADEMY.

The oxides and acids formed by combustion were first distilled and
collected in bromiue water as an oxidizing agent by Sauer * and this
method was still further improved by Mixter, f who avoided the use of
a rubber cork in the forward end of the combustion tube, carried for-
ward the volatilized substance by a current of carbonic dioxide, and
suggested more efficient means for oxidation by bromiue and absorp-
tion. All these methods depend upon the formation of sulphuric acid
and precipitation as baric sulphate, which involves considerable labor
when a large number of determinations are necessary in a limited
time. To overcome this difficulty Burton j suggested a modification of
the method of Sauer, which consists in absorbing the oxidized sulphur
in a standard solution of potassic hydrate and titrating the excess of
alkali with standard sulphuric acid.

Besides these methods the only other suitable means for the deter-
mination of sulphur in oils with large percentages of sulphur is the well
known method of Carius, in which the substance is oxidized in a closed
tube by means of fuming nitric acid. In its applicability to all classes
of compounds, and in the accuracy of results of which it is capable, this
method leaves little to be desired except perhaps in the analysis of
oils containing less than one hundredth of one per cent of sulphur. On
account of the limited weight of substance that can be oxidized in a
Carius tube another method must be selected for substances containing
less sulphur. Our experience has shown that the Carius method may
be relied upon in sulphur determinations to yield concordant results
within a few hundredths of one per cent. Oxidation of the less vola-
tile oils containing a small percentage of sulphur, without doubt, may
be accurately accomplished in an open vessel, but with larger amounts
of sulphur the action of nitric acid is so violent that it must entail
loss by volatilization, unless indeed the sulphur oil is considerably
diluted by a sulphur-free oil, in which case the solvent must be com-
pletely oxidized.

The great number of sulphur determinations in crude oils and
products obtained from them, connected with the extended examina-
tions which have occupied my attention during several years past, has
demanded a careful comparison of the various methods as to their
efficiency and economy of time. Particular attention has been given
to details of the Carius method, with the precautions necessary in its
successful application to the analysis of sulphur oils. The first requi-

* Fres. Zeit. Anal. Chem., XII. 32.

t Amer. Cliem. Journ., II. 396. J Ibid., XI. 72.

MABERY. — DETERMINATION OP SULPHUR. 3

site is a furnace of suitable construction to maintain an equal tempera-
ture, easily controlled in all the tubes within the furnace, without a
great loss of heat by radiation. For this purpose and for Carius
analyses in general I have recently had a furnace constructed which
differs in certain features from any other 1 have seen, and it shows such
a high degree of efficiency that a brief description may not be entirely
devoid of interest. The body is of tlie ordinary cylindrical form, 75 cm.
long and 25 cm. in diameter, of heavy sheet iron, and it is surrounded
by two outer jackets of sheet iron each enclosing a half-inch space,
and extending beneath on either side to within 6 cm. of the heating
tube ; it is supported upon legs of strap iron three sixteenths of an
inch thick and two inches wide, each entirely encircling the body at
either end for rigidity. These two air spaces retain the heat so effectu-
ally that the hand may be borne on the outside of the furnace when
the thermometer within indicates a temperature of 200°. The iron
tubes are as usual of gas pipe, with threads at either end with caps
easily movable by the fingers. With a small hole in each cap for
the escape of gas, these tubes retain all glass in the most violent
explosions. When several tubes are in the furnace at the same time a
record of them may conveniently be kept by suspending metal tags
numbered consecutively from the holes in the caps by means of bent
wire.

Figure 1 shows the arrangement of the outer air spaces with the
position of the heating tube. The furnace is heated by means of a
gas stove heater 45 cm. in length, with thirty-two
gas jets that will burn continuously with a flame
2 mm. high, giving a temperature within the fur-
nace of less than 60° ; by interposing an asbestos
or an iron plate a considerably lower tempera-
ture may be maintained. The heating tube is
supported on two iron straps bolted to the legs,
one at either end of the furnace ; by means of it
the heat is very equally distributed with little ' ^^^ l

waste, and the glass tubes being thus evenly

heated there is less danger of loss by explosion. A temperature of
200° may be obtained within twenty-five minutes after lighting the
jets, and it may be maintained with jets fifteen millimeters in height,
requiring a small consumption of gas ; the hand may be held without
discomfort for some time directly beneath the heater. The variation
in temperature at different heights within the furnace is small ; with
the thermometer at 275° at the level of the upper tubes, the tempera-

4 PROCEEDINGS OF THE AMERICAN ACADEMY.

ture at the level of the lower tubes is about 9° higher. For tem-
peratures higher than 275° a second heating tube is necessary.

It is frequently convenient to be able to regulate within close limits
the flow of gas for the required temperature without further attention
after lighting tlie jets. The device shown in Figure 2, which sug-
gested itself for tliis purpose, consists in attaching to the end of the
gas valve by means of a screw thread a brass cap with an index of
stout copper wire moving in front of a graduated circle with a radius
of about six inches.

With glass tubes of large size, — those we use are l.o mm. inside
diameter, — well sealed and with strict adherence to certain conditions
which have elsewhere been described by A. W. Smith and me,* there

is little danger of an explosion. The
quantity of nitric acid should not be
in excess of twenty times the weight
of the substance taken, and after heat-
ing to 175° for fifteen hours the tubes
are opened, — best without remov-

^ ing from the furnace, — resealed and

Fig. 2. . ' .

heated aofain to 250 during five to

ten hours. The serious objection to the Carius method for sulphur is
the slow process of oxidation, and it seems hardly possible to hasten
the operation by raising the temperature, since glass tubes will not
stand the great pressure.

In studying various methods depending upon the oxidation of sul-
phur by combustion I have found that nothing less than complete
oxidation gives reliable results. Many experiments on fractional
combustion have shown clearly that compounds with high percentages
of sulphur do not yield concordant results, even when the sulphur
compound is diluted with a sulphur-free oil. I have found Burton's
adaptation of the Sauer method reliable and expeditious, and with
certain modifications presently to be described it is perfectly satisfac-
tory for the analysis of oils of high as well as low percentages of
sulphur. In Figure 3 the inlet tube for oxygen or air is shown as enter-
ing through the rear stopper, as proposed by Mixter, and extending
just to the centre of the constriction. In the combustion of some of
the oils which we have under examination, the temperature must be
maintained as high as the most infusible Bohemian glass will stand,
and at such temperatures the smaller tube within is distorted if it is

* Amer. Chem. Journ., XVI. 83

MABERY. — DETERMINATION OF SULPHUR. 5

placed in the forward portion of tlie combustion tiibe in the zone of
greatest heat ; if it terminates at the narrowest point of tlie constric-
tion, eontmuous combustion is insured by thorough admixture of the
volatilized substance with oxygen. Complete oxidation is still more
certain in rapid combustion if that portion of the tube in front of the
narrower part is left somewhat longer than is preferred by Sauer,
Mixter, or Burton. The tubing we have in use is somewhat thicker
in the wall than that in ordinary use, and larger, with an inside diame-
ter of 18 mm. It is important that the oxidation proceed as rapidly
as is consistent with complete absorption, and we find that this is best
accomplished in a large U tube partly filled with broken glass. Our
U tube is 34 cm. in height, 25 mm. inside diameter, and with 50 c, c. of
the absorbent solution a rapid gaseous stream may be passed through
without danger of loss. For low sulphur oils we use a solution of
sodic hydrate of such a strength that 1 c. c. equals 0.0010 gram of

ill

r

Fig. 3.

sulphur, and for higher percentages a solution in which 1 c. c. equals
0.0050 gram. Methyl orange has been used as an indicator in all
our determinations ; the change in color in titrating an alkaline solu-
tion with this indicator is well defined and exceedingly delicate. The
titrations may be made in the U tube without transferring the solution
after washing in the acid from the combustion tube. To carry for-
ward the volatilized substance it is advantageous to introduce a slow
current of carbonic dioxide, as proposed by Mixter, and we have some-
times used a combustion tube closed with a rubber cork in front and
sometimes a bent tube. With substances containing a high percentage
of sulphur it is doubtless safer, as Mixter suggests, to avoid the use of
a cork in front.

0 PROCEEDINGS OF THE AMERICAN ACADEMY.

On account of the large consumption of oxygen in burning rap-
idly a considerable weight of oil, — at least three times the quantity
theoretically required for oxidation, — and finding that the combus-
tion proceeds with equal facility in air, nearly all our determina-
tions have been made in a current of air supplied under pressure,
with the same means for exhaustion that Burton found advanta-
geous. The operation requires close attention and 0.5 to 1 gram
of oil may easily be burned in forty-five minutes to one hour, de-
pending upon the nature of the substance, the heavier oils especially
if containing much sulphur being the most difficult to burn. The
higher sulphides will not support a continuous flame, and dependence
must be placed upon a very hot tube ; with the naore volatile oils it is
sometimes difficult to maintain a continuous flame even in oxygen, the
combustion proceeding in long intermittent non-luminous flashes. If
the flame becomes luminous the rapidity of volatilization must be
instantly checked, and the flow of air increased. The appearance
of white fumes in the forward part of the combustion tube or the
absorption tube, indicating improper adjustment as to the temperature,
flow of gas, or rate of volatilization, is invariably attended with low
results. The completeness of the absorption in the U tube was tested
by placing a second tube beyond it containing a similar solution, but
no trace of acid was found in the second tube when the excess of
alkaline hydrate in the first at the end of the analysis was not less
than 15-20 c. c. With a smaller excess in rapid combustions there is
danger of loss. The oil for analysis is weighed in a bulb or tube of
hard glass, and it is sometimes convenient to transfer most of it to a
platinum or a porcelain boat, which may easily be accomplished with-
out loss within the combustion tube provided there is a gentle current
of air inward and the combustion tube in front has previously been
heated to the required temperature.

In the examination of Ohio and Canadian sulphur petroleums for
identification of the paraffine, aromatic, and unsaturated hydrocarbons,
sulphur compounds, and other constituents, with which I am at present
engaged, numerous determinations of sulphur have been necessary, and
the extreme convenience of combustion in air has greatly facilitated
the separation of the various products. As an evidence of the reli-
ability of this method, the following results are selected with parallel
determinations by the Carius method : —

MABEllY. — DETERMINATION OF SULPHUR.

Distillate from crude Canada oil collected at
89°-Ul^ after one distillation under 50 mm.
and seven under atmospheric pressure

Distillate from crude Ohio oil collected at
127°- 120° after one distillation under
50 mm. and seven under atmospheric pres-
sure

Distillate from crude Canada oil collected
at I15°-117° after one distillation under
50 mm. and seven under atmospheric pres-
sure

Distillate from crude Canada oil collected
at 120°-1.30° after one distillation under
50 mm. and five under atmospheric pres-
sure

The same after shaking five times with alco-
holic mercuric chloride

The same after shaking once with alcoholic
mercuric chloride with the addition of solid
mercuric chloride

Sulphur oil from Canada sludge acid . . .
Sulphur oil from Canada sludge acid . . .

Sulplmr oil from Canada sludge acid . , .

Canada sulphur oil

Canada sulphur oil

Crude sulphide separated by mercuric chlo-
ride from fraction 110°-115° of sulphur oil
after the fifth distillation under 50 mm,

A fraction of the same corresponding to pen-
tyl sulphide, percentage of sulphur, 18.39

Percentage of Sulphur.
Combustion in Air. Carius.

0.044 0 043

0.0343

0.173

0.505
0.07

0.086

18.85

0.036

0.0108

1. II.

6.3 6.3

6.47

17.36

17.31

I. 11.

16.67 16.76

6.15

6.01

13.67

13.70

I. II. 111.
18.53 18.55 18,67

These results were obtained by six persons working independently
of one another.

The oxidation of nitrogen to any considerable extent by the use
of air in the combustion of sulphur compounds is evidently excluded
by the close agreement of the results it yields with corresponding
determinations by the Carius method. In accordance with the sug-
gestion of a friend, from the fact that nitrous and nitric acids are
formed to a greater or less extent depending upon conditions in tlie
ordinary forms of combustion, it seemed of interest to ascertain
whether these acids were present at all in the alkaline absorbent. In
testing for the formation of nitrous acid, the exceedingly delicate color
reaction was applied which is produced in an acid solution of a nitrite
by the addition of sulphanilic acid and naphthylamine chloride. An

8 PROCEEDINGS OF THE AMERICAN ACADEMY.

examination of our reagents showed tiiat the purest commercial sodic
or potassic hydrate gives an intense color, and even hydrates prepared
from the metals are not free from color. Pure sulphuric acid gave no
reaction, and pure sodic carbonate only a faint color. We finally
obtained a solution that gave not a trace of color by dissolving metallic
sodium and boiling the solution for some time with metallic aluminum.
With this solution as the absorbent in a combustion of a suljjhur oil,
after the analysis the solution was as free from color as before when
it had stood half an hour after the addition of the reagents. Since a
pink color is distinctly visible in this reaction with one part of nitrogen
in the form of nitrous acid in one thousand million parts of solution,
it is safe to conclude that nitrous acid is not one of the products in
this form of combustion.

To determine whether nitric acid is formed, after the combustion a
portion of the sodic hydrate solution was neutralized, mixed with
ferrous sulphate, and concentrated sulphuric acid poured beneath the
solution. No color was visible at the junction of the two liquids.
In a second test another portion of the alkaline solution was nearly
neutralized with sulphuric acid, evaporated to dryness, and a few drops
of phenolsulphuric acid added. Ujion diluting to a definite volume,
no difference could be perceived between the color of this solution
and that given by phenolsulphuric acid alone in a blank experiment.
In the combustion of sulphur oils in air, therefore, the atmospheric
nitrogen is not affected.

For efficient aid in studying the details of these methods of analysis,
I should acknowledge my obligations to Mr. W. O. Quayle, and to my
assistants, Messrs D. B. Cleveland and G. M. Little.

BENEDICT. — DOUBLE SALTS OF ANTIMONY. 9

11.

CONTRIBUTIONS FROM THE CHEMICAL LABORATORY OF

HARVARD COLLEGE, UNDER THE DIRECTION OF

PROFESSOR JOSIAH P. COOKE.

DOUBLE HALOID SALTS OF ANTIMONY, CALCIUM,

AND MAGNESIUM, WITH OBSERVATIONS ON

THE REMARKABLE DISSOCIATION OF

THESE COMPOUNDS.

By Francis Gano Benedict, A. M-

Presented by J. P. Cooke, May 9, 1894.

In a recent paper,* we described the results of our study of the
double haloids of antimony and the alkaline metals. Since then we
have extended the investigation to the corrrespouding compounds
with calcium and magnesium, and, although the work is still in an
unfinished state, it must necessarily be interrupted for the present ;
and we therefore give here the results thus far obtained, the most
important of which is the complete dissociation of a definite crystalline
salt at the ordinary temperature of the air.

In the paper referred to,t a salt was mentioned having the composi-
tion SbCls . 2 KCl . 2 HoO, and the difficulties encountered in its prep-
aration, analysis, and crystallographic study were discussed. Chief
among these difficulties was the circumstance that the water of crystal-
lization was lost wholly or in part at temperatures above — 5° Cent.,
requiring the salt to be handled in a room below that temperature.
In dealing with these new compounds the necessity for cold weather
is even greater than in the case just mentioned. Hence the advancing
of the season has prevented further work on this line. The research
will be continued at the earliest opportunity.

Poggiale,t in 1845, was the first investigator to obtain double
haloids of antimony and the earthy alkaline metals : " Le chlorure de
barium, uni au chlorure d'antimoine, presente una particularite qui

* These Proceedings, XXIX. 212. % Comptes Rendus, XX. 1180.

t Loc. cit.

10 PROCEEDINGS OF THE AMERICAN ACADEMY.

merite d'etre mentionee. Si la solution de chlorure de barium n'est
pas concentree les deux sels separent par le refroidissement ; le
chlorure de barium cristallise en tables, tandis que le protochlorure
d'antimoine decompose I'eau. II faut done pour obtenir cette com-
binaison, coucentrer la solution de chlorure de barium, avant d'y
ajouter le protochlorure d'antimoine. La liqueur donne alors des
aiguilles fines disposees en groupes ^toiles. Ce sel double est
compose de

SbCls . 2 BaCl + 5 HO.

Le protochlorure d'antimoine se combine egalement avec les chlo-
rures de stroutium, de calcium et de magnesium."

SchiifFer, * in 1860, working on the double iodides of antimony and
the alkaline metals, described the double iodide of antimony and barium
as a yellow salt with a formula,

2 Ba I . Sbis + 18 HO.

Storer f gives a list of salts, viz. : —

2 BaCl : SbClg + 5 Aq.
2 CaCl : SbCla + 5 Aq.
2 MgCl : SbCls + 5 Aq.
2 SrCl : SbClg + 5 Aq.

Watts's Dictionary t gives the formula alone of a salt of this class,
i.e. 2 (BaClo.SbCla) 3 H2O.

Graham-Otto § makes the simple statement that antimouious chloride
forms crystalline compounds with the chlorides of the alkaline and
earthy alkaline metals.

Poggiale and Schiiffer, therefore, appear to be the only investiga-
tors wlio succeeded in obtaining compounds with the earthy alkaline
metals.

Although we have obtained a great many beautifully crystalline
compounds from various mixtures of the haloids of antimony with the
haloids of calcium, magnesium, barium, and strontium, only three of
these have as yet been investigated. As has been before stated, cold
weather is an absolute essential in the formation of the compounds,
and the season is so far advanced that no more work can be done on
them this year.

* Pogg. Ann., CIX. 611. J Edition of 1888, Vol. I. p. 287.

t Dictionary of Solubilities, p. 149. § Michaelis edition, Vol. II. p. 555.

BENEDICT. — DOUBLE SALTS OF ANTIMONY. 11

The following salts have been prepared and analyzed, and the
formula) deduced for them are : —

I.

SbClg . CaCla

. 8 H2O

II.

SbBrg . CaBr.

. 8 II„0.

III.

SbBrg . MgBro

.Slip.

The materials used in the preparation of these salts were obtained
as follows. The antimonious chloride and calcic chloride were the
'* chemically pure " products of the market. The antimonious bromide
was made by the direct union of finely powdered metallic antimony
and bromine in carbon bisulphide, after the manner described by Pro-
fessor Cooke.* The calcic bromide and magnesic bromide were made
by the action of pure hydrobromic acid upon pure calcic carbonate and
magnesic carbonate respectively.

No difficulty was experienced in obtaining the three salts just named
by mixing their components in approximately molecular proportions,
adding just enough free acid to effect the complete solution of the
antimony salt and evaporating the mixture in a crystallizing dish in
a vacuum over sulphuric acid. Fortunately there was a room in the
laboratory in which the temperature could be regulated quite easily so
as to keep it at about 0° Cent, and not let it fall low enough to solidify
the mixtures, thus offering the most favorable conditions to crystalli-
zation. The large isolated crystals were removed in the cold room,
crushed in a mortar, hastily rubbed between filter papers and placed
in glass-stoppered weighing bottles. Of necessity this operation re-
quired considerable dexterity to prevent any change in weight, but
experience has shown that the whole operation can be performed in
45 to 50 seconds, with no appreciable change in the composition of
the salt.

With but one exception the analysis of thesre salts presented no
great difficulty.

Antimony was determined in the usual manner, by weighing as
antimonious sulphide. All the precautions of this determination, as
advi.sed by Professor Cooke in his fundamental work on the atomic
weight of antimouy,t were closely observed.

Bromine and chlorine were determined as their respective silvei
salts. The presence of tartaric acid necessary for the solution of the
antimony salt interferes to some extent in this determination by pre-

* These Proceedings, XIII. 52.
t Ibid., XIII. 1-114.

12 PROCEEDINGS OF THE AMERICAN ACADEMY.

cipitating that crystalline salt " silver emetic," discovered by Wall-
quist * and further studied by Professor Cooke.f

However, if care is taken to have only a slight excess of silver
nitrate over the calculated amount, and to precipitate from dilute solu-
tions, the probable error is reduced to a minimum.

Calcium was determined by igniting calcic oxalate precipitated in
the usual way, and weighing as calcic oxide. This method was very
satisfactory. Magnesium was weighed as magnesic pyrophosphate
(MgoPoO;) formed by the ignition of the ammonic magnesic phos-
phate {NH4MgP04) precipitated in the usual manner.

The presence of tartaric acid evidently interferes to some extent
with the perfect working of this determination ; but as the per cent of
magnesium in the salt was so small the error was not prominent.

The determination of the water of crystallization presented the first
serious difficulty, for, drying the salt in an air bath at 98°-100°
showed rapid decomposition. In fact, no temperature was found at
which the water would all go off and the salt remain undecomposed.

On placing the salt in a vacuum desiccator the loss was considerably
greater than theory would require, till finally the residue amounted to
but about 24% of the whole amount of salt used. Even in an ordi-
nary desiccator there was a gradual loss in weight, and constancy was
only reached when the residue was about 24% of the total mass, as
before. At the suggestion of Professor Cooke the salt was intimately
mixed with a quantity of ignited oxide of magnesia (heavy) in a
crucible and heated to constant weight. In this operation it was
necessary to get the upper layer of magnesic oxide hot before heating
the lower part of the crucible containing the compound. Should any
antimony haloid be volatilized, it would be decomposed upon reaching
the hot layer of oxide of magnesium. This method served excellently
for the first salt, i. e. SbClg . CaClo . 8 HoO . The oxide of magnesia
seemed to retain the antimonious chloride readily, but when the same
process was applied to the analysis of the bromides it was found that
the magnesic oxide would not retain all of the bromide of antimony.
The escape of this salt was clearly observed by the color of the flame
held over the mouth of the crucible.

After several trials, a modification of the ajiparatus described by
Jannasch and Locke t was decided upon as giving the most satisfac-

* Gmelin, Handbook, Cavendish ed., X. 326.

t These Proceednigs, XVII. 5.

J Zeitschrift fiir Anorgan. Chemie, VI. 174.

BENEDICT. — DOUBLE SALTS OP ANTIMONY. 13

tory results. For this purpose some litharge was heated to constant
weifht, thereby expelling all the carbonic acid gas and moisture. The
weighed salt from a weighing bottle was mixed with several grams of
the ignited lead oxide in a porcelain boat large enough to fit a com-
bustion tube of two centimeteis internal diameter. This was placed
in a kerosene oven and dry air drawn through it. Upon heating, the
water expelled was absorbed in two weighed U tubes containing sul-
phuric acid and phosphoric pentoxide respectively. The apparatus
for drawing dry air through the combustion tube was devised, and
described at length by Professor Cooke in his paper on " A New
Method of Determining Gas Densities." *

This process for determining water is an ideal one, every trace of
the antimony haloid being retained, and tlie water passing off freely
at a moderate temperature, 250°. The results were surprisingly
constant.

Although these several analyses are not as concordant with theory
as one would wish, yet, when the instability of the compound, the
necessarily hasty drying of the salt (freeing from mother liquor), and
the difficulties of purification, are taken into consideration, the results
are not at all beyond a reasonable limit of error.

In all three cases we could deal with large isolated crystals. There
was no case of a complex crystalline precipitate, for all three com-
pounds are most perfectly crystalline, and the only sources of contam-
ination are occlusions of mother liquor and imperfect drying due to
the haste required in transferring the salt to the weighing bottle. All
three salts are decomposed by water, and are soluble in tartaric,
hydrochloric, and hydrobromic acids. The last two solvents must
be somewhat concentrated, as an excess of water decomposes the
antimony salt.

I. SbCls . CaCla . 8 H„0.

This is a beautifully crystalline salt, individual crystals often occur-
ring over one inch in length. They are large, colorless plates, appar-
ently belonging to the triclinic system. Their tendency to effloresce
and decompose prevented any very satisfactory crystallographic exam-
ination, although traces of biaxial structure were observed with a
polariscope. The salt loses all the water of crystallization and all
the antimonious chloride in a desiccator over sulphuric acid, leaving a
residue of nearly anhydrous calcic chloride.

* These Proceedings, XXIV. 213, and American Chera. Journal, XI. 521.

14 PROCEEDINGS OP THE AMERICAN ACADEMY.

a. 0.3607 gram of salt gave 0.1259 gram of autimouious sulphide.

h. 0.4342 gram of salt gave 0.052G yram of calcic oxide,

c. 0.2322 gram of salt gave 0.3499 gram of argentic oxide.

d. 1.0737 grams of salt gave 0.3154 gram of water.

Calculated* for
SbClg . CaCU . 8 HjO. Found.

Antimony 24.95 24.93

Calcium 8.31 8.65

Chlorine 36.82 37.26

Water 29.92 29.37

100.00 100.21

II. SbBrg . CaBro . 8 H2O.

This salt crystallizes well iu large tabular crystals, often exceeding
half an inch in length. Aside from the fact that the polariscope
showed no interference figure, no crystallographic study of the salt
could be made owing to its unstable nature. This salt, precisely as
its analogue above, loses all its water of crystallization and "also the
antimonious bromide in a desiccator, till finally a nearly anhydrous
residue of calcic bromide is left. Analysis gave the following
results : —

a. 0.3742 gram of salt gave 0.0896 gram of antimonious sulphide.

b. 1.1896 grams of salt gave 0.0909 gram of calcic oxide.

c. 0.3090 gram of salt gave 0.4191 gram of argentic bromide.

d. 0.8415 gram of salt gave 0.1720 gram of water.

Calculated for

SbBrg . CaBr, . 8 H,0.

Found.

Antimony

17.07

17.10

Calcium

5.68

5.46

Bromine

56.79

t57.72

Water

20.47
100.00

20.44
100.72

III.

SbBr, . MgBr„

. 8 HoO.

This salt crystallizes very well in large well defined tabular crystals,
apparently isomorphous with the preceding salt. Large well shaped

* Atomic weights used: Sb = 120; CI - 35.456 ; Ca = 40; H= 1.0075;
0 = 16; Br = 79.955; Mg = 24.36.

t This excess of 1 % of Br is probably due to the fact that the substance was
not perfectly freed from mother liquor rich in hydrobromic acid ; approaching
warm weather would not permit of purification by recrystallization.

BENEDICT. — DOUBLE SALTS OF ANTIMONY. 15

crystals gave uo interference figure with the polariscope. This salt,
as the others, loses all its water of crystallization and antimonious
bromide in a desiccator over sulphuric acid, leaving a residue of mag-
nesic bromide. Analysis gave the following results : —

a. 0.9131 gram of salt gave 0.2193 gram of antimonious sulphide.

b. 1.1178 grams of salt gave 0.2128 gram of magnesic pyrophosphate.

c. 0.5160 gram of salt gave 0.7044 gram of argentic bromide.

d. 0.7013 gram of salt gave 0.1469 gram of water.

Calculated for
SbBr3 . MgBr, . 8 HjO. Found.

Antimony 17.40 17.15

Magnesium 3.54 4.06

Bromine 58.07 58.09

Water 20.99 20.95

100.00 100.25

These three salts possess two important relations : —

1. Entire uniformity of structure, i. e. one molecule of the alkaline
haloid combining with one molecule of the antimony haloid, and the
resulting compound crystallizing in each case with eight molecules of
water.

2. Each salt completely dissociates at the ordinary temperatures in
a desiccator.

The most strikins; feature of this research is the above mentioned
phenomenon. On attempting to estimate the water of crystallization
by desiccation, an irritating odor first indicated a decomposition which
was conclusively proven by the continual loss in weight. When con-
stancy in weight was obtained, the residue on treating with water
gave a hissing sound, and dissolved to a perfectly clear solution. This
solution, on acidifying with hydrochloric acid and adding a solution
of hydrogen sulphide, gave no precipitate, indicating an absence of
antimony.

In the case of the salt SbCls . CaCl2 . 8 HgO, the per cent of residue
was 24.64, while the theoretical per cent of calcic cliloride in the salt
is 23.04. The excess would naturally be attributed to water which
the calcic chloride would not readily yield to the sulphuric acid in
the desiccator. The strong smell (volatilized antimony haloid) in the
desiccator was observed long before the theoretical amount of loss cal-
culated as water, i. e. 29.92^, had taken place. This showed that the
antimony haloid had escaped before all the water had left the mass.

16 PROCEEDINGS OP THE AMERICAN ACADEMY.

In the case of the double bromides, a singularly beautiful phe-
nomenon took place. The antimouious bromide would sublime and
cr^-stallize all over the edge of the powdered mass of salt in those
characteristic fine colorless needles measured and described by Pro-
fessor Cooke.* These crystals were for the most part of microscopic
size, but some attained a length of two or three millimeters. On fur-
ther desiccation they soon disappeared. As would be expected, a
direct experiment showed that the salt SbCls . CaCL . 8 HoO decom-
posed much more rapidly than the salt SbBrg . CaBrj . 8 HgO, under
precisely similar conditions.

Richards, t in 1890, described a tetra ammon-cupriammonium bro-
mide with a formula CuBro . 6 NH3, which loses four molecules of
ammonia in a desiccator, forming CuBra . 2 NH3. Although the
escape of ammonia from its compounds is not uncommon, yet we
believe this is the nearest case to the one in point, inasmuch as the
loss here is perfectly definite.

The escape of antimony haloids from these compounds at a low
temperature has a very important bearing 011 the question of molecu-
lar combination. It is almost universally admitted that the relation
of the water of crystallization to a salt is different from that of its
other components. A study of these compounds, however, shows
that there is apparently no greater affinity between the two haloids
than between the compound and the water of crystallization. Hence,
in whatever manner the latter is combined, it is reasonable to suppose
a similar union of the two haloids. If, therefore, the crystal water of
a salt is held in molecular combination, the evidence as set forth in
this research would be interpreted as signifying a molecular union of
the two haloids.

* Tliese Proceedings, XIII. 76.

t Berichte der deutsch. Cliem. Gesell., XXIII. 3790.

SCUDDEK. — NORTH AMERICAN CEUTHOPHILI. 17

III.

THE NORTH AMERICAN CEUTHOPHILI.
By Samuel H. Scudder.

Presented May 9, 1894

The Ceuthophili are wingless Locustarians in which the tarsi are
distinctly compressed rather than depressed, with no pulvilli,* the hind
tibicB furnished on the outer margins above with spines of two distinct
grades,t the fore femora without foramina or genicular spines, the
hind fiemora with the angle of their insertion on the inner and not on
the outer side beneath, and the antennas strongly approximated at
base. They are all apterous.

With the exception of the genus Troglophilus Krauss, with two
species from European caverns, and the genus Talitropis Bol., with a
single species from New Zealand, placed respectively at one and the
other end of the series, they are known only from America ; and with
the further exception of Heteromallus Brunner, with two species
from Chili, they are all peculiar to the United States and Northern
Mexico. Here they include six genera and sixty-seven species, the
genus Ceuthophilus alone containing above fifty species. The larger
proportion of them, if not all (excepting Udeopsylla nigra), frequent
dark places, such as burrows, pits, caverns, wells, hollow trees, and
especially the crevices beneath fallen logs.

They were first made known in this country by the descriptions of
Haldeman, Girard, and Harris, and before their time only a single
species from this counliy had been described, by Burmeister. Not a
species of the group, even the European, was known to Serville. My
first systematic paper, in 1861, was a study of " Rhaphidophora "
(Proc. Bost. Soc. Nat. Hist., VIII.) where seven of our species were

* Brunner states that Gammarotettix has a single pulvillus on the first tarsal
joint; but although the treading surface of tliis joint (as of the succeeding) is
broad, I can find no indication of a true pulvillus. »

t This feature is obscure in Gammarotettix, where there are alternating
longer and shorter spines of such slight inequality as easily to be overlooked,
and which in the Table of Genera given below is ignored.

VOL. XXX. (n. 8. XXII ) 2

18 PROCEEDINGS OF THE AMERICAN ACADEMY.

described or catalogued ; but their diversity was hardly fully recog-
nized when in the following year I published my Materials for a
Monograph of the North American Orthoptera (Bost. Journ, Nat.
Hist., VII.), where eighteen species and five genera were characterized
or indicated ; since then a few more species have been described, by
Thomas, Brunner, Bruner, Packard, Walker, Blatchley, and myself,
until now the number of nominal species is twenty-eight, which must,
however, be reduced by synonymy and by reference to other genera to
twenty.

In 1888, Brunner, in his Monographic der Stenopelmatiden und
Gyllacriden (Verb. Zool.-bot. Gesellsch. Wien), subjected all the spe-
cies known to him to systematic treatment ; but as the larger part of
our species and some of our genera were unknown to him, and the
number of separately described species has multiplied so greatly while
still not including, at least in Ceuthophilus, the half of our species, it
has seemed desirable to undertake a revision of the group, so far as
our native species are concerned, and in the genus Ceuthophilus to
redescribe all the older forms, as well as to publish the novelties.
Accordingly in the present paper thirty-eight additional species of
the group are characterized, together with a new genus, while I shall
further show the validity of Daihinia of Haldeman, which has been
called in question by Brunner, and shall point out first that one of the
genera thought to belong here should be separated as a member of a
distinct group. The total number of genera from North America is
therefore six, and of the species sixty-seven, while a number of other
species are known to me imperfectly by a single sex or poor examples.

TROPIDISCHIA ScuDDER.

TropidiscMa Scudd., Bost. Journ. Nat. Hist., vii. 440-441 (1862).

In his Monograph of the Stenopelmatidse, Brunner von Wattenwyl,
from the insufficient data given in my two statements regarding the
structure of this creature, incorrectly surmised that this genus should
be placed in the Ceuthophili, and was perhaps congeneric with Hetero-
mallus, a Chilian genus. Since, however, the hind tibiae are supplied
above with spines of one grade only, it is plainly more nearly related
to the Dolichopodae, from which it may be distinguished by the simi-
larly spined margins of the under surface. It seems to form a group
apart, between the Dolichopoda3 and Ceuthophili, and of equivalent
value. It appears to come nearer Hadenoecus and Dolichopoda than
to any other described genera.

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 19

In addition to the characters mentioned above and those given in
previous descriptions, I may add tliat all the legs are tetraquetrous,
with all the margins spined, the spines similar in character and uni-
formly crowded, excepting on the lower margins of the fore femora,
the inner carina of which is sparsely spined, the outer carina unarmed ;
also the lower margins of the middle femora, both carinae of which are
sparsely spined on the apical half , and the hind femora, the four
carinse of which, even on the swollen portion, are armed excepting at
the extreme base, though both the mferior caringe are rather sparsely
spined. There are no spines on the genicular lobes of the femora,
excepting a very slight one on the posterior side of the middle femora.
There are but two pair of calcaria on the hind tibiae, the upper the
longer and less than half as long as the first tarsal joint. The hind
tarsi are very strongly compressed, carinate beneath without pulvilli,
about two fifths as long as the hind tibia?, the first joint nearly as long
as the remaining joints together, the second and fourth joints of the
same length and either of them three times as long as the third.
Finally, the subgenital lamina of the male is ample, the hind margin
entire, with minute styles, consisting of a single bluntly conical joint ;
and the ovipositor is slender, gently arcuate, tapering and acuminate,
unarmed at tip.

Tropidischia xanthostoma.

Rhaphidophora xanthostoma Scudd.!, Proc. Bost. Soc. Nat. Hist.,
viii. 12 (1861).

Tropidischia xanthostoma Scudd.!, Bost. Journ. Nat. Hist., vii. 441
(1862).

Originally described from Crescent City, Cal. (A. Agassiz). I have
since received both sexes from Mendocino, Cal., through the favor of
Mr. J. Behrens.

20 PROCEEDINGS OP THE AMERICAN ACADEMY.

Table of the Genera of Ceuthophili.

a}. Last palpal joint cleft apically on the under side. Descending
lobes of the nit-sonotum but little longer than those of the pronotum ;
sides of fore and middle coxae externally laminate, the lamination
elevated to a denticle or compressed spine either mesially or (on middle
legs) apically, occasionally (Hadenoecus) wanting on middle legs. Fore
tibiEe not sulcate above ; hind tibi;\3 with spines of two grades on both
outer and inner margins of upper surface. Outer valves of ovipositor
unarmed above before the apex.

b'^. Palpi long. Hind tibia3 usually considerably longer than the
hind femora. Third hind tarsal joint only half or less than half as
long as the second.

c^. Vertex obscurely bituberculate at apex. Last palpal joint
DO longer or scarcely longer than the third, and cleft beneath
only apically. Middle coxa? unarmed. Middle femora with a
feeble genicular spine on posterior margin. Hind tibiie with more
than four pairs of spurs. First hind tarsal joint almost as long
as the others together. Subgenital plate of male triangular and
rather deeply and narrowly emarginate .... Hadenoecus.
(p-. Vertex not tuberculate. Last palpal joint distinctly longer
than the third, cleft beneath for almost its entire length. Middle
coxfE spined mesially. Middle femora with a distinct genicular
spine on posterior margin. Hind tibia? with only four pairs of
spurs. First hind tarsal joint generally a third shorter than the
rest combined. Subgenital plate of male ample and broadly

emarginate , Ceutliophilus.

IP'. Palpi short. Hind tibiae shorter or at most but little longer
than the hind femora. Third hind tarsal joint hardly shorter than
the second, or (in Daihinia) wanting. (Lamination of middle coxae
produced inferiorly to the semblance of a spine.)

c^ Third palpal joint as long as fifth, the inferior cleft of the
latter extending over only the apical half Middle femora un-
armed at tip or with a very feeble spine. Hind tibia? shorter or
at least no longer than the hind femora, with few spines of the
second grade on the upper surface, those of the first grade rela-
tively numerous, at least in the 9 , more or less irregularly placed
and of unequal length ; the calcaria three in number on each
side, the uppermost generally a little the longest and unusually
distant from the extreme apex, so as to appear rather as an addi-

SCUDDER. NORTH AMERICAN CEUTIIOPHILI. 21

tional pair of spurs. Subgenital plate of male greatly produced
and apically deeply fissured.

d^. Descending lobes of niesonotum slightly longer than
those of prouotuiu. Last larbal joint very much shorter tlian
the remaining joints together, the third joint normal, though
but little shorter than the second. Subgenital plate of male
ample, rather deeply and broadly emarginate, the sides extend-
ing backwards as slender threads . . . ■ . Phrixocnemis.
d-. Descending lobes of mesonotum no longer than those of
pronotum. Last tarsal joint about as long as the rest together ;
third tarsal joint wanting (as also on fore legs). Subgenital
plate of male immensely produced and so deeply fissured as to

form two tapering ribbons Daihinia.

&. Third palpal joint shorter than the fifth, the inferior cleft of
the latter extending its whole length. Middle femora with a
genicular spine on posterior side. Hind tibiae slightly longer
than the hind femora, with nuuierous spines of the second grade
uniform in length and pretty regularly separated ; calcaria three
in number on each side, the middle one much longer than the
others. (First hind tarsal joint a third shorter than the rest
combined.) Subgenital plate of male ample, apically bitu-

berculate Udeopsylla.

a^. (Vertex bituberculate. Palpi short), the last joint apically with
no inferior cleft. Descending lobes of mesonotum considerably longer
than those of pronotum ; sides of fore and middle coxa3 neither cari-
date nor spined. (Fore and middle femora unarmed.) Fore tibiae
sulcate above ; hind tibiae (of the same length as the hind femora)
with only one grade * of spines above on the lateral margins ; (calcaria
two in number on each side, subequal and not long. Third hind tar-
sal joint half as long as the second. Subgenital plate of male ample,
apically broadly and not deeply emarginate) ; outer valves of oviposi-
tor serrate above before the apex Gammarotettix.

* See introductory remarks.

22 PROCEEDINGS OP THE AMERICAN ACADEMY.

HADENCECUS Scudder.

Hadencecus Scudd., Bost. Journ. Nat. Hist., vii. 439-440 (1862) ;
Brunn., Monogr. Steuop., 66 (1888).

Table of the Species of Hadencecus.

Body pale testaceous. Ovipositor nearly or quite as long as the
body. Subgenital plate of $ broadly emarginate at apex.

cavernarum.

Body dark brown. Ovipositor only half as long as the body. Sub-
genital plate of Z narrovv^ly emarginate at apex . . puteanus.

Haden(ecus cavernarum.

Phalangopsis sp. Thomj^s., Ann. Mag. Nat. Hist., xiii. 113 (1844).

Rhapidophora cavernarum Sauss., Ann. Soc. Entom. France (4), i.
492 (1860).

Hadencecus cavernarum Scudd.!, Proc. Bost. Soc. Nat. Hist., xii.
409 (1869); xix. 38 (1877) ; Boliv. , Ann. Soc. Ent. France (5), x.
72 (1880) ; Riley, Stand. Nat. Hist., ii. 184, fig. 260 (1884) ; Comst.,
Intr. Ent., 114 (1888); Blatchl., Proc. Ind. Acad. Sc, 1892, 153.

Rhapidophora subterranea Scudd.!, Proc. Bost. Soc. Nat. Hist., viii.
8 (1861); Pack., Amer. Nat., v. 745, fig. 126 (1871) ; Cope, Ibid.,
vi. 409 (1872); Hubb., Amer. Ent., iii. 37 (1880).

Hadencecus subterraneus Scudd.!, Bost. Journ. Nat. Hist., vii. 441
(1862) ; Walk., Catal. Derm. Salt. Brit. Mus., i. 201 (1869) ; Pack.,
Guide Ins., 565 (1869) ; Glover, 111. N. A. Ent., Orth., pi. 8, fig. 6
(1872) ; Cope-Pack., Amer. Nat., xv. 882 (1881) ; Brunn., Monogr.
Stenop., 66, fig. 34 (1888); Pack., Mem. Nat. Acad. Sc. iv. 67-70,
83,116, fig. 16, pi. 17, fig. 3 (1888) ; Id., Psyche, v. 198-199 (1889);
Garm., Ibid., vi. 105, fig. (1891).

Early notices of this insect by Telkampf will be found in Muller's
Arch. Anat. Phys., 1844, 318, and Wiedemann's Arch. Naturg., 1844,
384 ; also by Schiodte in K. Danske Vid. Selsk. Skrift. 1849, 5 ; by
Agassiz in Silliman's Amer. Journ. Sc, 1851, 127; and by Lesque-
reux in the Actes Soc. Helv. Sc. Nat., 40 Sess., 52-53 (1855).

I have studied specimens only from the Mammoth Cave, Ky. It
is also reported by Packard from many other caves in the Mammoth
Cave region, as Dixon's, White's, Salt, Ice, Diamond, Grand Avenue,
Poynter's, Wetzel's, Haunted, and Emerson Spring Branch caves;
besides Mail Robbers', One Hundred Dome, Walnut Hill Spring,

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 23

Short, Proctor's, Little Lithographic, and Sugar Bowl caves, and a
cave under Gardiner's Knob, — all near Glasgow Junction ; also a
cave near Baker's Furnace, and John and Fred's Cave on the east
bank of Dismal Creek ; further in Carter County caves, viz. Gray
Tom's, Zwingle's, Bat, Van Meter's, Grayson Springs, and Burcliell's
caves ; and finally in Nickajack Cave, Tenn. Blatchley also reports it
from Wyandotte Cave, Ind., on the authority of Cope, but it is not so
given by Cope in the references quoted ; and Walker, of course in
error, from the " west coast of America" ! I have also seen specimens
in the Museum of Comparative Zoology, Cambridge, from Turner's
Caves, Pennington Gap, Lee County, Va. (H. G. Hubbard), and
Ely Cave, Lee County, Va. (N. S. Shaler).

Hadencecus puteanus.

Hudencecus puteanus Scudd.!, Proc. Bost. Soc. Nat. Hist., xix. 37
(1877).

On sides and under covering of wells in North Carolina ; also in
Mississippi.

CEUTHOPHILUS Scudder.

Ceuthophilus Scudd., Bost. Journ. Nat. Hist., vii. 433-434 (1862) ;
Brunn., Monogr. Stenop., 61 (1888).

This is one of the dominant American genera of Locustarise, con-
fined to North America and almost entirely to the United States,
embracing a large number of species in every section of the country,
of which fifty-five are here characterized. Several others are known
to me by single specimens or mutilated examples. The following
table is based principally upon the males. It has been impossible to
construct it so as to bring together the allied species^ whose relation-
ship is better shown by the order in which they are described, though
even here the arrangement is far from satisfactory, nearly allied
species being sometimes separated at considerable distances in order to
bring them in closer relation with other allies. Although I have had
six hundred and fifty examples to study at this time, besides others in
alcohol, the material is still insufficient to make a satisfactory disposi-
tion of our species, and I am confident that very many more yet
remain to be discovered.

24 PROCEEDINGS OP THE AMERICAN ACADEMY.

Table of the Species of Ceuthophilus.

a}. Second joint of hind tarsi at least half as long again, usually twice
or more than twice as long, as the third.

b^. Fore femora one third or more than one third longer than the
pronotum, at least in the $ ; hind tibiae of J almost always
straight, never greatly bowed.

c^. Hind tibise of J at least a tenth longer than the hind
femora.

d^. Ovipositor much shorter than the fore femora.

e^. Hind femora stout, not three times as long as broad,

at least m the ^ 1. variegatus.

e^. Hind femora slender, four times as long as broad in

the 9 .2. ensifer.

d}. Ovipositor much longer than the fore femora.

e^. Hind tibial spurs less than twice as long as the tibial
depth ; outer carina of hind femora of ^ generally with
some spines at least half as long as the tibial sjDurs.
f^. Fore femora of $ three fourths as long again as

the pronotum . 3. stygius.

f^. Fore femora of $ from one half to two thirds as
long again as the pronotum.

g^. Hind femora of $ much less than four times as
long as broad ; hind tibiae of $ very long and more
or less sinuous at base in old individuals.

h^. Largest spines of outer carina of hind femora
of $ simple and similar to the others.

4. gracilipes.
h^. Largest spines as above greatly tumid at base.

5. latebricola,
g^. Hind femora of $ much more than four times as
long as broad ; hind tibiee of $ scarcely more than
one tenth longer than the hind femora, straight.

6. grandis.

e^. Hind tibial spurs fully twice, generally much more

than twice, as long as tibial depth ; outer carina of hind

femora of $ with no spines a third as long as the tibial

spurs.

f^. Armature of outer carina of hind femora of J

developed as distinct spines rather than as serrations;

ovipositor arcuate 7. secretus.

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 25

f^. Armature of outer carina of hind femora of $
developed only as recumbent serrations ; ovipositor
almost or (juite straight.

g^. Hind femora of $ slender, almost or quite four

times as long as broad ; hind tibiae exceptionally long,

nearly or quite one sixth longer than the femora.

It)-. Hind femora of $ more than tveice as long as

the fore femora ; ovipositor very feebly arcuate,

only two thirds as long as the hind femora.

8. palmeri,

K~. Hind femora of $ less than twice as long as

the fore femora ; ovipositor straight, three fourths

as long as the hind femora ... 9. corticicola.

g^. Hind femora of $ less slender, being less than

three and three quarters times as long as broad ; hind

tibias but little more than one tenth longer than the

femora 10. varicator.

c^. Hind tibige of $ distinctly less than a tenth longer than the
hind femora ; ovipositor always longer than the fore femora.
d^. Hind tibiiB of $ straight ; outer carina of hind femora
of ^ never conspicuously spined.

e^. Hind tibial spurs nearly three times as long as the

tibial depth 11. latibuli.

e^. Hind tibial spurs at most less than twice as long as the
tibial depth, rarely half as long again.
f^. Prevailing colors blackish fuscous above, the lighter
colors being distinctly less extensive than the dark
(which is generally nearly black) and appearing as dots
or roundish spots, and sometimes also as a broad medio-
dorsal stripe.

g^. Fore femora of ^ at most scarcely more than a
third longer than the pronotum ; outer carina of hind
femora of ^ serrulate, not spined.

h}. Hind femora relatively long and slender, three
and three quarters times as long as broad.

12. sechisus.
h?. Hind femora relatively stout, not over three
and a half times longer than broad.

i^. Hind tibife but little longer than the femora,
the spurs not longer than the tibial depth, the
hind femora considerably more than twice aS
long as the fore femora.

26 PROCEEDINGS OF THE AMERICAN ACADEMY.

p. Hind femora less than three times as long

as broad 13. terrestris.

j'^. Hind femora three and a half times as

long as broad 14. celatus.

i^. Hind tibiae considerably longer than tlie
femora, the spurs half as long again as the tibial
depth, the hind femora only about twice as long

as the fore femora 15. brevipes.

g^. Fore femora of ^ nearly one half longer than
the pronotum ; outer carina of hind femora of male

spined, not serrulate 16. lapidicola.

f^. The lighter colors which are more massive prevail
above, the darker appearing principally as posterior
bands to the segments and rarely darker than fusco-
castaneous, rarely vfith a light mediodorsal line.

g^. Outer carina of hind femora of ^ armed with
only a few raised points.

Ji^. Hind femora slender, nearly three and a half
times longer than broad . . . 17. arizoiiensis.
h"^. Hind femora stout, about two and a half times

longer than broad 18. uniformis.

d'^. Hind tibi£8 of $ arcuate or sinuous; outer carina of
hind femora of ^ always conspicuously spined.

e^. Hind femora very long, four times as long as broad,
the fore femora fully three fourths as long again as the

pronotum 19. heros.

e^. Hind femora relatively short, not more than three and
a half times longer than broad, the fore femora consider-
ably less than half as long again as the pronotum.
f^. Inferior sulcus of hind femora of $ broadening

proximally 20. uhleri.

f^. Inferior sulcus of hind femora of ^ of uniform

width 21. hlatddeyi.

h^. Fore femora but little if any longer than the pronotum even
in the male ; hind tibiaj of male usually straight, but often bowed
or sinuate.

c^. Dorsal surface of abdomen of $ smooth and even.
d^. Hind tibiae of $ arcuate or sinuate in basal half.

e^. Hind tibiae of $ considerably longer than the femora;
hind tibial spurs usually at least half as long again as the
tibial depth.

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 27

/^ Hind femora of S relatively long, three and a half
times as long as broad ; no large spines on outer carina.

30. macvlntus.

f^. Hind femora of $ relatively stout, rarely exceeding

three, never three and a quarter, times as long as broad j

some spines on outer carina as long as the tibial spurs.

g^. Hind tibiai of $ at least a tenth longer than the

femora.

h^. Hind femora of $ two and a half times longer
than the fore femora ; hind tibial spurs only
slightly longer than the tibial depth.

28. meridionalis.

h"^. Hind femora of $ but little more than twice

as long as the fore femora ; hind tibial spurs nearly

twice as long as the tibial depth . 45. inquinatus.

g". Hind tibiae of $ less than one tenth longer than

the femora 22. spinosus.

e^. Hind tibire of $ at most scarcely longer than the

femora ; hind tibial spurs rarely longer than the tibial

depth.

f^. Hind femora of $ three or more than three times

as long as broad ; fore femora nearly or quite a fifth

longer than the pronotum.

g^. Hind tibiiB of $ at most feebly sinuate at base.

39. agassizii.
g"^. Hind tibiae of $ very strongly bowed.

34. valgus,
f'^. Hind femora of $ less than three times as long as
broad ; fore femora only an eighth longer than the pro-
notum.

g^. Hind tibise of ^ strongly bowed, armed below
with a row of spines mounted on nodules.

33. nodulosus.
g"^. Hind tibiae of $ faintly sinuate at base, normally

armed beneath 51. latipes.

cP. Hind tibiae of $ straight throughout.

e^. Outer carina of hind femora of ^ armed with prom-
inent conical spines, generally well separated.
f^. Hind tibitB of ^ less than one tenth longer than
the femora.

g^. Dorsal surface of body almost uniformly very
dark, almost black, the lighter markings themselves

28 PROCEEDINGS OF THE AMERICAN ACADEMY.

not very light nor extensive, and therefore incon<=
.. spicuous.

h}. Hind tibial spurs generally excessively diver-
gent, extending ia nearly opposite directions on the
two sides and set at a high angle with the tibia.

35. diver gens.
Jr. Hind tibial spurs rarely exceeding 120° in
divergence, and set at an angle with the tibia not
exceeding 50°.

^\ Smaller species, with pallid sides, luteous
legs, and narrow dorsal stripe, the hind tibise of
the $ a twelfth as long again as the femora.

23. ccecus.
i^. Larger species, with castaneous sides and legs
and broad dorsal stripe, the hind tibite of ^ not
a thirtieth longer than the femora . 26. sallei.
g^. Dorsal surface of body with conspicuously con-
trasted dark and light markings, neither prevailing

over the other 47. pallidm.

f^. Hind tibisE of (^ a tenth longer than the femora.

32. hicolor.
e^. Outer carina of hind femora of $ more or less deli-
cately serrate or armed with recumbent spines.
j"^. Body of male very compact, short subfusiform, not
or hardly more than two and a quarter times as long as
broad.

g^. Hind femora of $ relatively stout, considerably
less than three times as long as broad, the hind tibiae
longer than the femora, and the spurs only as long as

the tibial depth 24. nigricans.

g"^. Hind femora of $ relatively slender, three times
as long as broad, the hind tibise shorter than the
femora and the spurs nearly half as long again as the

tibial depth 25. fusiformis.

f^. Body of $ much more elongated, rarely distinctly
fusiform, over three and generally at least four times
as long as broad.

g^. Hind tibiee of $ at least a tenth longer than the
femora.

h^. Body without conspicuously contrasted colors ;
hind femora of ^ relatively slender, four times as
long as broad 36. occultus.

8CUDDER. NORTH AMEFJCAN CEUTHOPHILT. 29

h^. Body with conspicuously contrasted colors; hind

femora of ^ relatively slender, less than three and

a quarter times as long as broad . 46. discolor.

g^. Hind tibiae of $ less than one tenth longer than

the femora.

h}. Hind femora of $ with no raised points on the
upper distal half.

i^. Outer carina of hind femora of $ almost

unarmed ; markings of the body more or less

marmorate or maculate.

j^. A broad continuous light dorsal stripe on

pronotum, usually extending over the whole

thorax.

k^. Hind tibial spurs distinctly marked with

black at base ; ovipositor twice as long as

fore femora 27. latens.

P. Hind tibial spurs at most indistinctly
infuscated at base ; ovipositor shorter than

fore femora 31. tenehrarum.

j^. A narrow and very unequal light dorsal
stripe on pronotum, interrupted^ if present, on

rest of thorax 38. bruneri.

i-. Outer carina of hind femora of $ finely and
closely serrate ; dark markings of body confined
to transverse borderings of the segments.

48. vinculatus.
h'-. Hind femora of $ with a greater or less num-
ber of raised points on upper distal half.

^^ Hind femora of $ with only a few distant
recumbent spines on outer carina.
j^. Hind tibiae of c? a tenth longer than the
femora; spurs fully twice as long as tibial

depth 44. vinguis.

j'^. Hind tibife of $ less than a tenth longer

than the femora ; spurs much less than twice

as long as tibial depth . . 40. mexicanus.

p. Hind femora of ^ with numerous denticula-

tions on the outer carina, forming a more or less

close serration.

J^. Ovipositor relatively short, at most but

little more than half as long as hind femora.

30 PROCEEDINGS OP THE AMERICAN ACADEMY.

P. Hind femora of $ less than twice as
long as fore femora,

l^. Hind tibiffi of $ no longer than
femora ; spurs only a little longer than
tibial depth, and divaricating about 60° ;
inner carina of fore femora minutely ser-
ratulate .... 50. californianus.
P. Hind tibia; of c? a little longer than
femora ; spurs fully twice as long as tibial
depth, and divaricating about 90° ; inner
carina of fore femora simply spined.

49. testaceus.

¥■. Hind femora of $ two and a fourth times

as long as fore femora . . 29. neglectus.

j^. Ovipositor relatively long, two thirds as

long as hind femora or more.

F. Hind femora of $ relatively slender,
at least three times as long as broad.

l^. Hind tibiae of $ of same length as
femora ; colors moderately dark.

37. alpinus.
P. Hind tibia? of ^ considerably longer
than femora ; colors rather pallid.

41. pallescens.
P. Hind femora of ^ relatively stout,
hardly more than two and a half times as

long as broad 43. crassus.

c^. Dorsal surface of abdomen of ^ closely tuberculate ; hind
tibia? strongly arcuate.

d^. Both outer and inner caringe of hind femora of ^ armed
with a large compressed spine as long as the depth of the

genicular lobes 52. pacijicus.

d'^. Outer carina of hind femora of ^ elevated to a high
lamina, suddenly terminating acutely before the genicular

lobes 53. henshawi.

a^. Second joint of hind tarsi but little longer than the third.

v. Large species ; outer carina of hind femora considerably and

uniformly elevated throughout 54. devius.

6^. Small species ; outer carina of hind femora elevated distally

much more than proximally 55. neomexicanus.

The male being unknown to me, C, sylvestris does not appear in the
above table. It will be foun<l below as No. 41.

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 31

1. Ckuthophilus variegatus, sp. nov.

Blackish fuscous .witii a slight olivaceous tinge, marked with yel-
lowish luteous ; there is an interrupted dorsal stripe of the lighter
color especially interrupted on the anterior half of the pronotutn ; this
is heavily margined by subcoufluent dark blotches or spots, and the
dark color prevails over the rest of the thorax, with oblique patches of
the lighter tints on the meso- and metanotum, irregular verniiculate
blotches of greater or less extent on the pronotum and the lower
edges of the descending lobes of the thorax margined not very nar-
rowly with luteous ; the sides of the abdomen are prevailingly luteous,
but the anterior outer margins are mostly fuscous ; the hind femora
have the usual scalariform markings very pronounced, while the other
legs are prevailingly luteous and much streaked with fuliginous,
excepting the tarsi ; the longer spines are bright luteous, but black
tipped. The antennte are two or three times as long as the bodyj
moderately stout at the base and gradually tapering, and the legs
moderately short. Fore femora distinctly broader than the middle
femora, nearly half as long again ($) or scarcely a fourth as long again
(9) as the pronotum, and less than half as long as the hind femora,
the inner carina with three long spines, the distal subapical and very
long. Middle femora with 2-3 long spines on the front carina, one
subapical and very long, and on the hind carina 1-2 long spines besides
a long genicular spine. Hind femora slightly ($) ov considerably (9)
more than twice as long as the fore femora, very broad and stout, dis-
tinctly less than three times as long as broad especially in the male, a
few very distant and scattered raised points over the whole apical half of
the surface, excepting beneath and especially on the inner side above,
the outer carina with 3-4 very unequal spines in the apical half, one,
sometimes two, much lai'ger than the rest, coarse and as long as the
tibial spurs ( <J ) or with a single inconspicuous spine in the pregenicu-
lar sinus (9), the inner carina with half a dozen small uniform but
irregularly distant spinules, the intervening sulcus rather narrow.
Hind tibige straight in both sexes, moderately slender, scarcely ex-
panded distally, distinctly but not greatly longer than the femora,
armed beneath with a single subapical spine besides the apical pair ;
spurs subalternate, the basal before the end of the proximal fourth of
the tibia, half as long again as the tibial depth, set at an angle of 40-45°
with the tibia and divaricating about 50-60°, their tips considerably
incurved ; inner middle calcaria a little larger than the outer, twice as
long as the others or as the spurs, and nearly as long as the first tarsal

32 PROCEEDINGS OF THE AMERICAN ACADEMY.

joint. Hind tarsi considerably less than half as long as the tibia, the
first joint unusually prolonged below and as long as the rest together,
the second fully twice as long as the third and with it as long as the
fourth. Cerci moderately stout, regularly tapering, as long as the
pronotum. Ovipositor very short, not so long as the pronotura, rap-
idly tapering at base, beyond slender, the armature of the inner valves
consisting of moderately stout but rather prominent bluntly pointed
spines.

Length of body, $ 15 mm., 9 19 mm.; antennae (est.), ^ 30+
mm., 9 45+ mm.; pronotum, $ b.b mm., 9 6.5 mm.; fore femora,
$ 8 mm., 9 7.75 mm.; hind femora, $ 16.75 mm., 9 17.75 mm. ;
hind tibite, $ 19 mm., 9 18.5 mm.; ovipositor, 6 mm.

2 $,2 9 . Matamoras, Tamaulipas, Mexico, L. B. Couch ; Ringgold
Barracks at the lower end of the Rio Grande, C. A. Schott ; Carrigo
Springs, Texas, A. Wadgymar, through L. Bruner.

2. Ceuthophilus ensifer.

Ceuthophilus ensifer Pack.!, Amer. Nat., xv. 882, pi. 7, figs. 4, 4ab
(1881); Id.!, Mem. Nat. Acad. Sc, iv. 71-72, 83, figs. 17, 17ab (1888) ;
Blatchl., Proc. Ind. Acad. Sc, 1892, 153 (1894).

Body luteo-testaceous, heavily marked with blackish fuscous, which
broadly borders all the abdominal segments posteriorly and inferiorly,
as it does also (but more or less broken mediodorsally) the thoracic;
there are also two large subdorsal anterior blackish fuscous spots
on the meso- and raetanotum, and the pronotum has a large T-shaped
blackish median spot heavily mapped out with a basal expansion and
which is cut by a mediodorsal luteous line, bordered on either side
posteriorly by one, anteriorly by two luteous dots, transversely aligned ;
the inferior border is broadly margined with black, leaving in the
middle of either side a large irregular luteous blotch more or less
streaked with fuscous ; the legs are castaneous, the hind femora with
fuscous scalariform markings and apically broadly annulate with
fuscous ; the apical half of tibine and the tarsi pallid. The antennae
are about twice the length of the body and the legs long and slender.
The fore femora are not stouter than the middle femora, nearly twice
as long as the pronotura and somewhat more than half as long as the
hind femora, the inner carina with 3-4 spines of considerable size.
Middle femora with four spines on the front carina and on the hind
carina three besides a moderately long genicular spine. Hind femora
about as long as the body, somewhat less than twice as long as the
fore femora, slender, the apical third subequal, the inferior margin

SCUDDEIl. — NORTH AMERICAN CEUTHOPHILI. 33

nearly straight, the whole fully four times as long as broad, the dark
por'Lious of the surface, even of the inner side, with sliglit, equally
distributed raised points but none independent of them, the outer
carina (?) with delicate distant spinules especially beyond the middle,
the inner carina similarly armed, the intervening sulcus moderately
narrow. Hind tibia; considerably longer than the femora, slender,
armed beneath with a single preapical spine besides the apical pair ;
spurs rudely opposite, the basal well beyond the end of the proximal
third of the tibia, half as long again as the tibial depth, set at an
angle of 35° with the tibia and divaricating 90-100°, their tips strongly
incurved ; inner middle calcaria considerably longer than the outer,
much more than twice as long as the others or as the spurs, but much
shorter than the first tarsal joint. Hind tarsi almost half as long as
the tibise, the first joint as long as the rest together, the second almost
three times as long as the third and with it longer than the fourth.
Cerci tapering throughout, finely pointed, half as long again as the
femoral breadth. Ovipositor hardly three quarters as long as the fore
femora, stout in basal third, tapering in middle third, slender and sub-
equal in distal third, the apex produced and slightly upturned, the
inner valves with eight sharp but slight serrations.

Length of body, 9 19.5 mm. ; pronotum, 5.2 mm.; fore femora, 10
mm.; hind femora, 18.75 mm.; hind tibiae, 20.25 mm. ; ovipositor,
7 mm.

2 9 • Nickajack Cave, Tenn,

3. Ceuthophilds stygius.

Rhaphidophora stygia Scudd. !, Proc. Bost. Soc. Nat. Hist., viii. 9
(1861); Pack., Amer. Nat, v. 745 (1871).

Centhophilus stygivs Scudd.!, Bost. Journ. Nat. Hist., vii. 438
(1862) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 202 (1869); Pack.,
Guide Ins., 565 (1869) ; Riley, Stand. Nat. Hist., ii. 184 (1884) ;
Pack., Mem. Nat. Acad. Sc, iv. 70-71, 83 (1888); Brunn., Monogr.
Stenop., 05 (1888); Blatchl., Proc. Ind. Acad. Sc, 1892, 148-149
(1894).

Ceuthophilus sloanii Pack. !, Ann. Rep. Peab. Acad. Sc, v. 93-94
(1873) ; Id. !, Mem. Nat. Acad. Sc, iv. 71, 83 (1888). Immature.

Body pale brown, the segments bordered posteriorly with dark
brown or black, becoming gradually paler toward the hinder part of
the body and dotted with pale spots ; the markings in general closely
resemble those of C. gracilipes, but the dark colors do not generally pre-
vail to so great an extent as in that species. The antennae, moderately

VOL. XXX. (N. S. XXII.) 3

34 PROCEEDINGS OF THE AMERICAN ACADEMY.

coarse at the base, taper very gradually, and are of immeuse length,
being more than four times the length of the body. The legs are
very long and slender. Fore femora scarcely broader than middle
femora, very slender, three fourths as long again as the pronotum, yet
only about half as long as the hind femora, the inner carina armed
with 2-5 spines. Middle femora with 2-5 spines on the front carina
and on the hinder 1-3 spines besides a not very long genicular spine.
Hind femora about as long as the body and twice the length of
the fore femora, not very stout, about four times as long as broad,
tapering gracefully, the apical third being subequal, the darker por-
tions covered with exceedingly fine and subdued raised points, the
outer carina with more or less slight distant serrations or triangular
denticulations occasionally developing as spines, especially on the
apical half, the inner carina with a few slighter distant similar serra-
tions closest in the middle half, the intervening sulcus not very broad.
Hind tibise slender, straight in both sexes, fully a tenth longer than
the femora, armed beneath with 2-3 subapical spines besides the apical
pair ; spurs vaguely opposite or subopposite, the basal within the
proximal fourth of the tibia, about half as long again as the tibial
depth, set at an angle of about 40° with the tibia and divaricating
about 90°, their tips much incurved ; inner middle calcaria much
longer than the outer, more than twice as long as the others or as the
spurs and as long as the first joint of the tarsus, beset with short hairs,
as are also the upper calcaria. Hind tarsi fully two fifths the length
of the tibia, the first joint shorter than the rest combined, the second
twice as lono- as the third and with it shorter than the fourth. Cerci
rather long and slender, tapering to a fine point, fully half as long as
the hind femora. Ovipositor three fifths the length of the hind femora,
not greatly swollen at base, tapering gently in basal half, equal beyond
and not very narrow, the tip scarcely upturned and not produced, the
apex being nearly rectangular, the teeth of the inner valves feebly
crenate.

Length of body, S 17 mm., 9 19-5 mm.; pronotum, ^ 5.5 mm.,
9 5.3 mm.; fore femora, J' 9 9.75 mm.; hind femora, ^ 19.5 mm.,
9 20.1 mm.; hind tibia3, ^ 21.5 mm., 9 22.8 mm.; ovipositor,
13 mm.

1 ^,3 9 . Hickman's Cave, Ky., A. Hyatt ; cave in Crawford Co.,
Ind., W. P. Hay, through W. S, Blatchley. In the Museum of Com-
parative Zoology there are specimens taken at White's Cave, near
Mammoth Cave, Ky.; Fountain's Cave, A. S.Packard; and One
Hundred Dome Cave, near Glasgow Junction, Ky., F. G. Sanborn,

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 35

H. Garman. Packard, iu his Memoir on Cave Animals, reports it
also from Little and Great Wyandotte Caves, a cave in Washington
Co., and Georgetown, Floyd Co., all in Indiana, and also from the
following caves in Kentucky : Diamond Cave, near Mammoth Cave,
John and Fred Field Cave, near Dismal Creek, Bee Spring and
Laurel Caves, Carter Co. According to Brunner, specimens seen by
him come from Texas. G. sloanii was described from caves in Ken-
tucky and Bradford, Ind.

4. Ceuthophilus gracilipes.

Phalangopsis gracilipes Hald., Proc. Amer. Assoc. Adv. Sc, ii. 346
(1850) ; Walk., Cat. Derm. Salt. Brit. Mus,, i. 116 (1869).

Rhaphidophora gracilipes Scudd. !, Proc. Bost. Soc. Nat. Hist., viii. 7
(1861).

Ceuthophilus gracilipes Scudd. !, Bost. Journ. Nat. Hist., vii. 439
(1862) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 202 (1869) ; Scudd. !,
Rep. U. S. Geol. Surv. Nebr., 249 (1872) ; Brunn., Monogr. Steuop.,
62-63 (1888) ; Smith, Cat. Ins. N. J., 409 (1890) ; McNeill, Psyche,
vi. 27 (1891).

Ground color of body varying from luteous to dark castaneous, very
heavily marked with blackish fuscous, so that the latter is often or
perhaps generally the prevailing tint; the darker colors prevail always
on the hinder half of all the segments but the pronotum and some-
times, especially in young specimens, to such an extent that all parts
behind the pronotum are blackish fuscous, dotted with luteous ; in the
lightest colored specimens, the dark coloring prevails on the pronotum
along the anterior and especially the posterior margins, and is generally
present in a subdorsal posterior tongue emitted on either side from the
anterior margin ; the anterior edge of the dark posterior markings of
each segment, especially ni the front portion of the body, is exceed-
ingly irregular and broken, and the lightest parts are more or less and
irregularly clouded with fuscous ; the femora are usually of the jire-
vailing tint of the body, but, even when the body is dark, are some-
times luteous throughout as the tibice and tarsi always are, except for
occasional infuscation of the former at base ; the outer sides of the
hind femora have the characteristic markings of the genus more or less
distinct. Antennte moderately coarse at base, tapering with great
regularity, 3-4 times the length of the body. Legs very long and
slender. Fore femora no stouter than the middle femora, more than
half as long again as the pronotum, especially in the $, distinctly less
than half as long as the fore femora, the inner carina usually with 2-3

36 PROCEEDINGS OF THE AMERICAN ACADEMY.

spines, often rather long in old individuals, especially the distal ones.
Middle femora with 3-4 spines on either carina, the hind carina
with a not very long genicular spine. Hind femora as long as or
longer than the body, considerably more than twice the length of the
fore femora, very stout at base, but gradually diminishing in stout-
ness so that the distal third is slender and subequal and the whole
less than three and a half times longer than broad, the surface mostly
glabrous, but on the darker portions above beset not very sparsely
with feeble raised points, the outer carina with about thirteen distant un-
equal rather coarse spines, the longest shorter than the tibial spurs ( $ )
or almost unarmed (9), the inner carina much less elevated than
the outer, with equal abortive denticulations numerous in the i^, in-
frequent and equidistant in the 9, the intervening sulcus moderately
broad. Hind tibiae rather slender, straight or in old male specimens
gently subarcuate or slightly waved in the proximal third, nearly a
sixth longer than the femora, armed beneath usually with two aligned
preapical spines besides the apical pair ; spurs subopposite, the basal
pair near end of proximal fourth of tibia, less than half as long
again as the tibial depth, set at an angle of about 40° with the tibia
and usually divaricating about 60°, but sometimes to as much as
twice that, incurved especially at tip; inner middle calcaria much
longer than the outer, more than twice as long as the other calcaria,
about twice the length of the spurs, but much shorter than the first
tarsal joint. Hind tarsi much less than half as long as the tibia, the
first not so long as the rest together, the second nearly three times as
long as the third and with it fully as long as the fourth. Cerci stout at
base, tapering throughout, nearly a third as long as the hind femora.
Ovipositor with the basal third rather stout, beyond equal and rather
slender, nearly three fourths the length of the hind femora, the arma-
ture of inner valves acicular, arcuate, elongate.

Length of body, ,^19 mm., 9 23 mm. ; antennas, $ (est.) 75 mm. ;
pronotum, $ b.lb mm., 9 6.75 mm. ; fore femora, $ 10 mm., 9 10.6
mm.; hind femora, $ 21.5mm., 9 22 mm.; hind tibioe, $ 24.75mm.,
9 25 mm.; ovipositor, 15.5 mm.

22 (J, 11 9. Maryland, New Jersey, P. R. Uhler ; Ithaca, N. Y.,
Comstock ; Blockton, Florida (C. Caule, Jr.), J. H. Comstock ;
Southern Illinois, P. R. Uhler ; Illinois, Walsh, Webster ; Northern
Illinois, R. Kennicott ; Minnesota ; Red River, Manitoba, D. Gunn ;
Nebraska City, Nebr., F. V. Hayden. It has also been reported from
Pennsylvania by Haldeman, and from Georgia and Colorado by
Brunner.

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 37

5. Ceuthophilus latebricola, sp. nov.

Blackish fuscous, sometimes almost piceous, glabrous, profusely spot
ted with luteous or rufo-luteous and more or less blotched with the same
on the thoracic segments, though nowhere in large masses, but, except
the luteous bordering of the inferior margins, more as if through the
confluence of minute spots. There is always a narrow mediodorsal line
or stripe on the thoracic segments with slight expansions anteriorly and
posteriorly on the pronotum ; legs luteous with heavy blackish iufusca-
tions at the femoral tips, the hind femora heavily marked with fuscous
scalariform markings. The antennae are slender and about three
times as long as the body, and the legs moderately long and slender.
Fore femora no stouter than the middle femora, considerably less than
half as long as the hind femora, a little more (c?) or a little less (?)
than a third longer than the pronotum, the inner carina with a long
preapical spine and sometimes another much smaller. Middle femora
with 2-4 spines on the front carina and on the hind carina with 1-2
spines besides a long genicular spine. Hind femora about as long as
the body, considerably more than twice as long as the fore femora,
moderately stout, in the male somewhat strongly constricted before the
genicular lobes, about three and a quarter times longer than broad ($),
the surface with only a few raised points along the upper edge interi-
orly, the outer carina considerably elevated before the constriction,
armed with 6-9 unecpial teeth, the largest tumid at base and not so
long as the tibial spurs (^) or with 2-3 feeble serrations (9), the
inner carina with distant feeble minute spinules (9), the intervening
sulcus slender. Hind tibiae sinuate in the proximal half { ^) or straight
throughout (9), considerably longer than the femora (scarcely longer
in Eastern examples), armed beneath with a single subapical spine
besides the apical pair ; spurs subopposite, the basal just before the
end of the proximal third of the tibia, about half as long again as the
tibial depth, set at an angle of 45° with the tibia and divaricating
100°, their apical third incurved ; inner middle calcaria very much
longer than the outer, almost twice as long as the others or as the
spurs and nearly as long as the first joint of the tarsi. Hind tarsi
not a third as long as the tibiae, the first joint longer than the rest
together, the second fully twice as long as the third and with it at
least as long as the fourth. Cerci rather stout, rapidly tapering,
a little longer than half the femoral width. Abdomen roundly trun-
cate in the male. Ovipositor straight, two thirds as long as the hind
femora, gently tapering in basal third, beyond equal and slender, the

38 PROCEEDINGS OF THE AMERICAN ACADEMY.

tip considerably upcurved and very acuminate, the teeth of the inner
valves aculeate.

Length of body, $ 15 mm., 9 15.5 mm.; antennae, $ 52 mm. ;
pronotum, $ 5 mm., 9 4.75 mm. ; fore femora, (J 6.9 mm., 9 6 mm. ;
hind femora, $ 15.5 mm., 9 13.5 mm. ; hind tibia^, $ 17.5 mm.,
9 14.5 mm.; ovipositor, 9 mm.

4 (^, 6 9- Lexington and Tyrone, Ky. (S. Garman) ; Washington,
D. C, Wright; Centre Co., Peun., Shaler ; and Petroleum, Ritchie
Co., W. Va. (Mus. Comp. Zool.).

6. Ceuthophilus grandis, sp. nov.

Body dark luteo-castaneous very heavily marked with blackish or
blackish fuscous, which is heaviest at the posterior margins of all the
segments, along the front margin of the pronotum, and in a stripe
bordering the broad mediodorsal rufo-luteous stripe of the pronotum ;
the anterior lower angle of the pronotum, and to some extent that
of the other thoracic segments, are dull luteous, merging with the
luteous of the central portion of the descending lobes ; on the abdomen
the darker colors prevail above to such a degree that the luteous
appears to be maculate on a dark ground ; antennae and legs luteo-
testaceous, more or less though generally feebly infuscate, the hind
femora with fuscous scalariform markings, apically broadly marked
with fuscous but preceded by a broad more or less clearly marked
luteous annulation. The antennse are slender except near the base
and fully four times as long as the body, the legs very long and
slender. Fore femora scarcely stouter than the middle femora, barely
half as long as the hind femora, two thirds {$) or three fifths ( 9 ) as
long again as the pronotum, the inner carina with 3-4 spines none of
them very long nor very unequal. Middle femora similarly armed
on the front carina and on the hind carina 3-4 spines besides the
moderately long genicular spine. Hind femora as long as the body,
very little more than twice as long as the fore femora, pretty stout at
base, but with the slender portion much produced, the apical third or
in the female even more than that being subequal, the whole being in the
male nearly four and a half times longer than broad, the surface above
and on both sides just beyond the middle with a few scattered raised
points, the outer carina armed throughout all but extreme base with
8-12 distant, not greatly unequal, subequidistant spines, the longest
scarcely so long as the tibial spurs but tumid at base ( (J ) or with
similarly distant feeble serrulations (9)5 the inner carina sjiarsely {$)
or very sparsely ( 9 ) serrulate, the intervening sulcus narrow. Hind

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 39

tibia3 straight in both sexes, fully a tenth longer than the femora,
armed beneath with 1-2 subapical spines (one sometimes paired)
besides the apical pair ; spurs subopposite, the basal at about the end
of the proximal third of the tibia, slightly longer than the tibial depth,
set at an angle of 50-60° with the tibia and divaricating about 120°,
their tips much incurved ; inner middle calcaria very much longer than
the outer, fully twice as long as the others or as the spurs and nearly
as long as the first joint of the tarsi. Hind tarsi two fifths as long as
the tibiae, the first joint about as long as the rest together, the second
nearly three times as long as the third and with it as long as the
fourth. Cerci slender and delicately tapering, a quarter as long again
as the femoral breadth. Ovipositor more than half as long as the hind
tibite, the lower margin straight, not stout and gently tapering in the
basal half, slender and equal in the apical half, the tip upturned and
bluntly acuminate, the teeth of the inner valves triangular and rather
long, straight.

Length of body, ^ 19 mm., 923.5 mm. ; antennre (est), ^ 90 mm. ;
pronotum, (J 9 6.7 mm.; fore femora, ^ 11.25 mm., 9 10.75 mm.;
hind femora, ^ 22.8 mm., 9 23.4 mm.; hind tibiae, ^ 25 mm., 9 25.6
mm. ; ovipositor, 13.5 mm.

1 (?, 2 9. Chattanooga, Tenn., J. W. Martin (U. S. Nat. Mus.).

This species is not far removed from C. gracilipes in structural
details, though with much duller and less diversified markings.

7. Ceuthoi'hllus secretus, sp. nov.

In markings this species agrees altogether with C palmeri except
that the luteous colors are clearer and that the abdomen is more com-
pletely fuscous, the luteous being almost entirely confined to a narrow
stripe across the anterior margin, not seen when the segments are
contracted. The antennae are fully three times the length of the
body, slender and gradually tapering, the legs long and slender.
Fore femora scarcely stouter than middle femora, considerably more
than half as long again as the pronotum and about half as long as the
hind femora, the inner carina with 1-3 small spines. Middle femora
with 2-4 spines of varying length on the front carina, and on the hind
carina occasionally a single small spine besides the long genicular spine.
Hind femora nearly as long as the body, about twice the length of the
fore femora, tapering with no abruptness, nearly four times as long as
broad, the apical fourth subequal, with scattered but nowhere numerous
minute raised points on the upper apical half, the outer carina with
small but rather coarse unequal spines, mostly next the narrower por-

40 PROCEEDINGS OF THE AMERICAN ACADEMY.

tion of the femora, the longest less than a third as long as the tibial
spurs, the inner carina with similar but smaller and subequal spines
throughout its extent, on both far more delicate in the female than in the
male, the intervening sulcus decidedly narrow. Hind tibias straight in
both sexes, slender, about an eighth longer than the femora, armed
beneath with two subapical spines besides the apical pair ; spurs
scarcely subopposite, the basal at the end of the proximal third of the
tibia, almost or quite twice as long as the tibial depth, set at an angle
ordinarily of 30-40°, but sometimes of more nearly 80° with the tibia,
divaricating 100-160°, their tips incurved; inner middle calcaria con-
siderably longer than the outer, nearly twice as long as the others or
as the spurs, but much shorter than the first tarsal joint. Hind tarsi
almost half as long as the tibice, the first joint as long as the rest
together, the second three times as long as the third and with it longer
than the fourth. Cerci slender, tapering, half as long again as the
femoral breadth. Ovipositor fully three fourths as long as the hind
femora, gently and uniformly arcuate throughout, of equal width
throughout, the tip not sharply acuminate, the inner valves with a
feebly crenulate armature.

Length of body, J* 9 17.5 mm.; pronotum, ^ 4.6 mm., 9 4.9 mm.;
fore femora, ^ 8 mm., 9 7.8 mm. ; hind femora, ^16 mm., 9 14.75
mm.; hind tibiae, $ 18 mm., 9 16.5 mm.; ovipositor, 11.6 mm.

6 ^, 2 9. Dallas, Texas, Boll.

8. Ceutbophilus palmeri, sp. nov.

Dark fuscous heavily blotched and spotted with dull luteous, the
lighter markings consisting of a broken mediodorsal stri|)e of gener-
ally varying and greater or less width, of very irregular blotches and
tortuous streaks on the sides of the pronotum, of large anterior spots
on the sides of the meso- and metanotum, and of anterior transverse
daslies or belts on the abdominal segments ; the fore and middle legs
are fusco-luteous becoming more or less deeply fuscous at the distal
extremity of the femora and proximal end of the tibiae, the hind
femora fuscous except at base with the usual dull luteous markings, the
rest of the leg dull luteous, but the basal half of the tibiae more or less
infuscated. The antennae are three or four times as long as the body,
and very slender except toward the base, and the legs long and slen-
der. Fore femora no stouter than the middle femora, about three
fifths as long again as the pronotum and half or less than half as
long as the hind femora, the inner carina with 2-4 mostly long spines.
Middle femora with 1-2 spines besides a long subapical one on the

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 41

front carina, and on the hind carina 2-3 spines besides a very long
genicular spine. Hind femora nearly as long as the body, fully twice
as long as the fore femora, stout basally but rapidly tapering so that
the apical third or more is subecjual, nearly four times as long as
broad, with no raised points, both carinas distantly and finely serrulate
in the apical half, a little finer and more distant in the female than in
the male, the intervening sulcus not very broad. Hind tibite straight
in both sexes, fully a sixth longer than the femora, armed beneath
usually with two subapical spines besides the apical pair ; spurs sub-
alternate, the basal a little beyond the proximal fourth of the tibia,
nearly three times as long as tlie tibial depth, set at an angle of about
50° with the tibia and divaricating 110-130°, their tips considerably
incurved ; inner middle calcaria a good deal longer than the outer,
fully twice as long as the others or as the spurs, but shorter than
the first joint of the tarsi. Hind tarsi more than two fifths the length
of the tibicB, the first joint as long as the rest together, the second
three times as long as the third and as long as the fourth. Cerci
very long and slender, but shorter than the fore femora. Ovipositor
two thirds as long as the hind femora, very feebly arcuate, rather
slender, tapering gently throughout, a little upturned and very acutely
pointed at tip, the apical teeth of the inner ^jalves delicate and finely
pointed, but not very long, especially the proximal.

Length of body, $ 23 mm., 9 19 mm. ; pronotum, $ 6 mm. ;
9 5.75 mm.; fore femora, $ 9.8 mm., 9 9 mm.; hind femora, $ 19.5
mm., 9 18 mm. ; hind tibiae, $ 23.5 mm., 9 21 mm. ; ovipositor,
12 mm.

14 J, 14 9- From the darkest recesses of the side caverns of a
bat cave 48 X 20 feet in size, of which the roof had fallen in, in George-
town, Williamson Co., Texas, E. Palmer ; New Braunfels, Texas,
H. E. Scudder ; Texas, Schaupp in coll. S. Henshaw. The New
Braunfels specimen is referred to under C. californianus in Bost.
Journ. Nat. Hist., vii. 438.

9. Ceuthophilus corticicola, sp. nov.

Dark fuscous feebly marked, at least on the pronotum, with cloudy
dull luteous vermiculations, especially on the lower part of the descend-
ing lobes, which are generally edged more distinctly with luteous ;
legs of the color of the body or lighter, the anterior pairs more or
less infuscated near the femoro-tibial articulation, the distal part of the
tibiae and tarsi more clearly luteous ; hind femora with the usual
markings, growing luteous toward the base. The antennte are slender

42 PEOCEEDINGS OP THE AMERICAN ACADEMY.

and three or more times as long as the body, the legs long and slen-
der. Fore femora faintly stouter than the middle femora, more than
half as long again as the pronotum and fully half as long as the hind
femora, the inner carina with 2-3 long spines. Middle femora with
2-3 pretty long spines on the inner carina, and on the outer two small
ones besides a long genicular spine. Hind femora about as long as
the body, nearly twice as long as the fore femora, moderately stout in
the basal half, but the swollen portion short, the apical third being
subequal and the whole about four times as long as broad, the upper
half with a very few scattered raised points apically, the outer carina
feebly delicately and distantly serratulate on the distal half, more
delicately in the ? than in the <J, the inner carina similarly but more
closely spiued throughout, the intervening sulcus narrow. Hind tibiae
straight in both sexes and slender, nearly a sixth longer than the
femora, armed beneath with 1-2 subapical spines besides the apical
pair ; spurs subalternate, the basal just beyond the proximal fourth
of the tibia, fully twice as long as the tibial depth, set at an angle of
about 45° with the tibia and divaricating 100-120°, their tips in-
curved ; inner middle calcaria distinctly longer than the outer, more
than twice as long as the others or as the spurs, and nearly equal to
the first tarsal joint. Hind tarsi nearly half as long as the tibiae, the
first joint as long as the rest together, the second three times as long
as the third, and nearly equal to the fourth. Cerci very long and
slender, beyond the inflated basal portion tapering very gradually, as
long as the fore femora. Ovipositor long and straight, fully three
quarters as long as the hind femora, the base rather slender and taper-
ing, the distal half or more slender and equal, the extreme tip scarcely
upturned but very acute, the inner valves with an armature of fine
but not very long pointed teeth.

Length of body, $ 17.5 mm., 9 19.5 mm.; pronotum, $ 5.2 mm.,
9 5.75 mm. ; fore femora, $ 8.2 mm., $ 8.75 mm. ; hind femora,
$ 15.75 mm., 9 17 mm.; hind tibiae, $ 18.4 ram., 9 18.75 mm.;
ovipositor, 13 mm.

5 $,2 9 • Dallas, Texas, Boll. Texas, Belfrage, in woods under
bark, and coming to the light at night in September.

10. Cettthophilus varicator, sp. nov.

Dull testaceous, heavily infuscated especially on the thoracic seg-
ments which are more fuscous than testaceous, the latter appearing
on the pronotum principally as an impure fuscous-streaked blotch in
the middle of either lateral half, more or less connected posteriorly by

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 43

a transverse bar ; a transverse anterior series of four testaceous dots ;
on the other thoracic segments appearing in large anterior latei-al
spots more or less confluent ; legs fusco-testaceous, becoming luteous
apically, the hind femora testaceous with scalariform fuscous markings,
the other femora darker apically than at base. The antennie are
tolerably stout at base but soon taper to a delicate thread and are
about three times as long as the body, and the legs moderately long
and slender. Fore femora no stouter than the middle femora, nearly
half as long as the hind femora, and more than a third longer than
the pronotum (^ 9)i the inner carina armed with 2-3 spines, the
subapical very long. Middle femora similarly armed on the front
carina, and on the hind carina 1-2 moderate spines besides a very
long genicular spine. Hind femora a little more than twice as long
as the fore femora, moderately slender, being almost three and three
quarters times as long as broad ((^), the apical fourth subequal, the
surface with no raised points, the outer carina entirely unarmed except
for 4-5 very distant slight recumbent serrations on the apical half,
more distinct in the 9 than in the (?, the inner carina with a few
raised points, the intervening sulcus narrow. Hind tibiae straight in
both sexes, slender, fully a tenth longer than the femora, armed
beneath with two median subapical spines besides the apical pair ;
spurs subalternate, the basal at or beyond the end of the proximal
fourth of the tibia, more than twice as long as the tibial depth, set at
an angle of about 80° with the tibia and divaricating about 150°, their
extreme tips incurved ; inner middle calcaria very much longer than
the outer, about twice as long as the others, or as the spurs, and just
about as long as the first tarsal joint. Hind tarsi more than two fifths
the length of the tibiaj, the first joint longer than the rest together, the
second three times as long as the third, and as long as the fourth.
Cerci slender, tapering, a third as long again as the femoral breadth.
Ovipositor two thirds the length of the hind femora, faintly arcuate
throughout, equal from close to the base, moderately broad, the tip
scarcely upturned, acutangulate (about 40°), the inner valves feebly
crenulate, the prominences slightly accentuated.

Length of body, ^ 17 mm., 9 20 mm. ; antennae (est.), ^ 50 mm.,
9 58 mm. ; pronotum, ^ 5.25 mm., 9 6.4 mm. ; fore femora, ^ 7.5
mm., 9 8.9 mm. ; hind femora, ^ 15.75 mm., 9 18 mm. ; hind tibiae,
S 18 mm., 9 20 mm. ; ovipositor, 12 mm.

1 (?, 1 9. Waco, Texas, July 13 (Mus. Comp. Zool.). 3 9 from
Columbus, Texas, are in the Riley collection (U. S. National Museum).

44 PROCEEDINGS OF THE AMERICAN ACADEMY.

11. Ceuthophilus LATIBULI.

Ceuthophilus latibuli Scudd.!, lus. Life, vi. 313-314 (1894).

Dark brownish fuscous, heavily blotched with ferrugineo-testaceous,
largely in the form of small longitudinally ovate spots more or less
regularly disjiosed on the dorsum, but inclined to become confluent on
the sides, and forming blotches on the pronotum, the hind femora dark
with two series of longer and an intermediate series of shorter oblique
testaceous lines, forming scalariform markings, all the tarsi and at
least the distal half of the tibiie pallid luteous. The antennte are
slender and fully three times as long as the body, and the legs long
and slender. Fore femora slightly stouter at base than the middle
femora, half as long again as the pronotum, considerably less than half
as long as the hind femora, the inner carina armed with 2-4 longer or
shorter spines on the distal half. Middle femora with two or three
usually long spines besides a subapical long spine on the front carina,
and on the hind carina a very long genicular spine, besides sometimes
an additional spine. Hind femora about as long as the body, con-
siderably more than twice as long as the fore femora, rather stout, but
more than the distal fourth slender and subequal, the whole three ((^)
to three and a half { 9 ) times as long as greatest breadth, the surface
very finely and uniformly scabrous with delicate raised points on the
darker portions, the outer carina slightly prominent, furnished with
8-9 rather unequal inequidistant short spines, the longest not half
the length of the tibial spurs (^$) or unarmed (9), the inner carina
with 13-16 small inequidistant ((?) or 6-8 inconspicuous (9) spines,
the intervening sulcus rather deep but of moderate width. Hind tibise
much longer than the femora, straight in both sexes, slightly com-
pressed at the base, armed beneath with 1-2 median subapical spines,
besides the apical pair ; spurs not opposite, the basal generally at or
before the end of the proximal fourth of the tibia, nearly or quite three
times as long as the tibial depth, set at an angle of about 60° with the
tibia and of about 120° more or less with each other, slightly incurved
at tip ; inner middle calcaria very slender, considerably longer than the
outer, twice as long as the others or as the spurs and considerably
longer than the first tarsal joint. Hind tarsi distinctly less than half
as long as the tibite, the first joint not nearly so long as the rest com-
bined, the second twice as long as the third and with it shorter than
the fourth. Cerci slender, delicately tapering, about as long as the
femoral breadth. Ovipositor straight, rather slender, from a third to
more than one half as long as the hind tibice, the tip hardly upcurved

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 45

and exceedingly acute, the denticulations of the inner valves triangular,
hardly aculeate.

Length of body, c? 18 mm., 9 17 mm.; antennge, ^ 55-|- mm.,
9 (est.) 65 mm. ; pronotum, ^ 5 mm., 9 G mm. ; fore femora, cj 8
mm., 9 8.5 mm.; hiud femora, (J 9 18 mm.; hind tibise, (J 9 19.5
mm. ; ovipositor, 10 mm.

7 (^,5 9 . Crescent City, Fla., in burrows of the gopher ( Gopherus
polyp he mus), H. G. Hubbard ; Georgia, H. K. Morrison.

12. Cedthophilus seclusus, sp. nov.

Glabrous, blackish fuscous, heavily and irregularly marked with
luteous becoming rufo-luteous dorsally, the whole surface about equally
divided between the fuscous and luteous, but the fuscous prevails
dorsally, the luteous laterally ; there is an interrupted and irregular
broad rufo-luteous mediodorsal band on the thoracic segments, and the
inferior margins of at least the pronotum are bordered with luteous,
but the other luteous markings are mostly in the form of rather
irregularly scattered, more or less irregularly confluent small round
spots, often becoming blotches of great irregularity on the thorax ; legs
dull luteous, the femora infuscated especially apically and the hind
femora heavily marked in a scalariform pattern as well as apically
annulate with fuscous. The antennae are slender and apparently about
twice as long as the body, and the legs slender and moderately long.
Fore femora not stouter than the middle pair, varying greatly in
length in the sexes, in the male being only a little less than half as
long as the hind femora and more than a third as long again as the
pronotum, in the female very much less than half as long as the
hind femora, and not a fifth longer than the pronotum, the inner
carina with two spines, at least the subapical rather long. Middle
femora with 2-4 spines on the front carina and on the hmd
carina 1-2 spines besides a not very long genicular spine. Hind
femora about as long as the body, a little more than twice ((^) or
considerably more than two and a half times (9) as long as the fore
femora, slender and very gradually tapering, about three and three*
quarters times as long as broad, the apical fifth subequal, with no
raised points upon the surface, the outer carina minutely and inequidis-
tantly spinulate or subserrate, in the female the serrations much sub-
dued, the inner carina similarly but more finely armed in both sexes, the
intervening sulcus narrow. Hind tibiae straight, scarcely longer than
the femora, slender, armed beneath with a single preapical spine besides
the apical pair; spurs subalternate, the basal about the end of the

46 PROCEEDINGS OP THE AMERICAN ACADEMY.

proximal fourth of the tibia, less than twice as long as the tibial depth,
set at an angle of 70-80° with the tibia and divaricating about 90°
(^) or 150-170° (9)5 their tips incurved; inner middle calcaria
distinctly longer than the outer, much more than twice as long as the
others or as the spurs and as long as the first tarsal joint. Hind tarsi
much less than half as long as the tibise, the first joint as long as the
rest together, the second more than twice as long as the third and
nearly as long as the fourth. Cerci short, being hardly longer than
half the femoral breadth. Extremity of the abdomen roundly truncate
in the male. Ovipositor straight beneath, the upper margin broadly
arcuate, nearly two thirds as long as the hind femora, tapering in basal,
equal and slender in distal half, the tip upcurved and finely acuminate,
the teeth of the inner valves aculeate, only the last one arcuate.

Length of body, ^ 12 mm., 9 16 mm.; pronotum, ^ 3.5 mm.,
9 5.25 mm.; fore femora, ^ 0 mm., 9 6.1 mm.; hind femora, ^ 10.9
mm., 9 16 mm. ; hind tibiae, ^^ 11 mm., 9 16.3 mm. ; ovipositor, 10.5 mm.

3 $,7 9. Dallas and Crawford Cos., Iowa (J. A. Allen) ; "West
Point, Nebr (L. Bruner).

13. Ceuthophilus terrestris, sp. nov.

Rhaphidophoi-a lapidicola Scudd. ! , Proc. Bost. Soc. Nat. Hist.,
viii. 7 (1861).

Ceuthophilus lapidicolus Scudd. !, Bost. Journ. Nat. Hist., vii. 435
(1862); Walk., Catal. Derm. Salt. Brit. Mus., i. 201 (1869); Glov.,
111. N. A. Entom., Orth., pi. 7, figs. 4, 5 (1872); Prov., Nat. Canad.,
viii. 75 (1876); Ril., Stand. Nat. Hist., li. 184 (1884); Smith, Cat.
Ins. N. J., 409 (1890) ; Osb. ?, Proc. Iowa Acad. Sc, ii. 119 (1892) ;
Blatchl., Proc. Ind. Acad. Sc, 1892, 147-148 (1894).

Phalangopsis lapidicola Bess., Rep. Iowa Agric. Coll., vii. 206
(1877).

Glabrous, mottled with luteous and blackish fuscous, both colors
varying in tint in different individuals ; there is often, but not always, a
mediodorsal light stripe on the thorax bordered by dark tints, and the
lower portions of the sides are always lighter than the rest ; the inter-
vening portions of the thorax may be described as fuscous, heavily
sprinkled and blotched irregularly with luteous, sometimes one, some-
times the other prevailing ; on the abdomen the darker colors prevail
and the lighter appear as a tolerably regular and profuse sprinkling of
often confluent luteous dots, most abundant on the posterior portions
of the segments ; the hind femora have the usual markings, and are
feebly and narrowly iufuscate apically. The antenniB are slender,

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 47

fully twice as long as the body, the legs moderately short. Fore femora
not stouter thau the middle pair, a third longer than the pronotuni and
distinctly less thau half as long as the hiud femora, the inner carina
with a long preapical spine sometimes accompanied by a shorter one.
Middle femora with 1-2 spines on the front carina besides a preapical
spine, and on the hind carina usually two spines besides the genicular
spine. Hind femora somewhat shorter than the body, considerably
more than twice as long as the fore femora, less than three times as
long as broad, the swollen portion pretty stout, hardly more thau the
distal sixth of equal width, with a few feebly raised points on the
upper apical portion of the inner side only, the outer carina delicately
uniformly and densely serrate throughout ( J* ) or with a few apical
obscure serrations (9)5 ^^^ inner carina similar. Hind tibiae straight
in both sexes, rather stout in the male, scarcely exceeding the femora
in length, armed beneath with a preapical spine besides the apical pair ;
spurs subopposite, the basal beyond the end of the proximal third of
the tibia, hardly or no longer than the tibial depth, set at an angle
of 45° with the tibia and divaricating 90-100°, their tips incurved;
inner middle calcaria somewhat longer than the outer, twice as long as
the others or as the spurs, but not so long as the first tarsal joint.
Hind tarsi two fifths the length of the tibiae, the first joint nearly as
long as the rest together, the second twice as long as the third and with
it longer than the fourth. Cerci rather slender throughout, tapering,
pointed, as long as the femoral breadth. Ovipositor less than three
fifths as long as the hind femora, gently tapering in the proximal half,
equal and not very slender in the distal half, the tip upturned a little
and pointed at an angle of 45°, the teeth of the inner valves sharjD but
not aculeate.

Length of body, $ 13 mm., 9 15 mm.; pronotum, (? 9 4 mm.;
fore femora, ^ 5.3 mm., 9 5.6 mm. ; hind femora, ^ 12.3 mm.,
9 12.5 mm.; hind tibiae, ^ 12.5 mm., 9 12.75 mm.; ovipositor,
7 mm.

11 ^, 5 9. North Red Ri\^r, P. R. Uhler ; Chateaugay Lake,
Adirondack, N. Y., 2,000', F. C. Bowditch ; New Hampshire ;
Moosehead Lake, Me. ; Cambridge and Lowell, Mass., S. Henshaw ;
Maryland, P. R. Uhler. Specimens in the Museum of Comparative
Zoology are from Anticosti (Verrill), from Norway (Smith), Bethel
(Miss Edwards), and Gorham, Me., and from Nahant and Maiden,
Mass. (A. Agassiz). It is also reported, partly no doubt by mistake
for other species, from Iowa (Bessey, Osborn), Penn., Md., Geo., Ind.
(Walker), Canada (Provancher), New Jersey (Smith), Indiana
(Blatchley), and Nebraska (Bruner).

48 PROCEEDINGS OF THE AMERICAN ACADEMY.

14. Ceuthophilus celatus, sp. nov.

Body blackish fuscous, glabrous, liberally sprinkled with luteo-
testaceous giving it a speckled appearance in best marked specimens ;
some of these spots or dots are clustered in a more or less conspicuous
mediodorsal stripe, while others margin subequidistantly the posterior
border of all the abdominal segments or are submarginal ; on the pro-
notum and to a less degree on the meso- and metanotum they are liable
to coalesce and form vague and irregular patches and blotches ; the
fore and middle legs are luteous, more or less nifuscated especially at
the distal ends of the femora ; hind femora brownish fuscous, often
with an olivaceous tint, the scalariform markings nearly obsolete.
Antennae very slender, about twice the length of the body, the legs
rather short. Fore femora no stouter than the middle femora, about
a third ( ^) or a fourth (9 ) longer than the pronotum, and much less
than half as long as the hind femora, the inner carina with a subapical
spine sometimes accompanied by a few others near it. Middle femora
with a subapical spine sometimes accompanied by one or two others
on the front carina, and on the hind carina a not very long genicular
spine sometimes accompanied by two others. Hind femora, rather
slender, tapering almost regularly, about three and a half times as long
as broad, considerably more than twice as long as the fore femora,
with no raised points upon the surface, the outer carina very finely
denticulate ((?) or wholly or almost wholly unarmed (9), the inner
carina feebly and very finely serratulate, the intervening sulcus narrow.
Hind tibiee straight in both sexes, a little longer than the femora,
slender, armed beneath with a single subapical spine besides the apical
pair; spurs opposite or subopposite, the basal at the end of the proxi-
mal fourth of the tibia, no longer than the tibial depth, set at an angle
of about 45° with the tibia and divaricating about 60° ; inner middle
calcaria considerably longer than the outer, more than twice as long
as the others or as the spurs, but shorter than the first tarsal joint.
Hind tarsi a little less than half as long as the tibia, the first joint
scarcely as long as the rest together, the second much more than
twice as long as the third and with it longer than the fourth. Cerei
slight, tapering regularly, about three fourths as long as the femoral
breadth. Ovipositor straight, tapering on the proximal, slender and
equal on the distal half, somewhat more than half as long as the hind
femora, the tip very gradually attenuated and very slightly upcurved,
not very finely pointed, the inner valves rather feebly crenulate.

Length of body, ^ 9 mm., 9 13 mm. ; pronotum, ^ 3 mm., 9 3.5

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 49

mm.; fore femora, <? 4 mm., 9 4.25 mm.; hind femora, <J 9 mm.,
9 10 mm. ; hind tibiaj, (J 9.5 mm., 9 10.75 mm. ; ovipositor, 6 mm.
3(^,59. Behrens, Shaster County, Cal., San Francisco, Cal.,
Los Angeles, Cal., Cociuillett, all from L. Bruner ; and Siskiyou,
Placer, and Los Angeles Counties, Cal., mostly from Riley's collection
(U. S. Nat. Mus.).

15. Ceuthophilus brevipes.

Ceuthophilus brevipes Scudd. !, Bost. Journ. Nat. Hist., vii. 434
(1862); Walk., Cat. Derm. Salt. Brit. Mus., i. 201 (1869); Prov.,
Nat. Canad., viii. 75 (1876); Fern., Orth. N. Engl., 19 (1888);
Blatchl.!, Proc. Ind. Acad. Sc, 1892, 148 (1894).

Dull fuliginous brown, but glabrous, marked with very dull and pale
luteous dots, occasionally somewhat confluent ; there is sometimes, but
rarely, a mediodorsal luteous stripe on the pronotum ; the dots are
generally a little elongate and margin the segments posteriorly, often
turned obliquely inward and when accompanied by other dots in
advance these arranged to give an added obliquity to their general
course ; the pronotum is more or less marmorate with dull luteous ;
the legs have the general tone of the body and the hind femora the
usual markings of the genus, the darker colors generally the more
extensive, but the pattern obscured apically so that the distal exti-emity
of the femora, including more than the geniculation, is more or less
deeply iufuscated. The antennae are stout at base but immediately
become slender and are at least twice as long as the body. The legs
are short and rather slender. Fore femora no stouter than the middle
femora, a third longer than the pronotum and about half as long as
the hind femora, the inner carina with a subapical spine. Middle
femora with a subapical spine on the front carina and on the hind
carina 1-2 spines, sometimes wanting in the 9, besides a fairly long
genicular spine. Hind femora moderately stout and plump, regularly
tapering, about three and a half times longer than broad, the distal
fifth equal, the surface with no raised points, both carinte sparsely and
finely serrate in the $, almost unarmed in the 9> the intervening
sulcus of moderate breadth and V-shaped. Hind tibiae considerably
longer than the femora, unusually slender, straight in both sexes,
armed beneath with two preapical spines besides the apical pair ;
spurs subopposite, the basal at the end of the proximal fourth of the
tibia, nearly half as long agani as the tibial depth, set at an angle of
40-45° with the tibia and divaricating about 135°, their tips incurved ;
inner middle calcaria considerably longer than the outer, nearly twice

VOL. XXX. (n. S. XXII.) 4

50 PROCEEDINGS OF THE AMERICAN ACADEMY.

as loug as the others or as the spurs, but much shorter than the first
tarsal joint. Hind tarsi about two fifths the length of the tibia, the
first joint shorter than the others together, the second twice as long
as the third and with it as long as the fourth. Cerci rather slender,
regularly tapering, slightly longer than the femoral breadth. Oviposi-
tor gently tapering on proximal, equal on distal half, rather slender,
very slightly arcuate, two thirds the length of the hind femoi'a, the
tip acute but not produced, the armature of the inner valves a dull
and nearly obsolete serration.

Length of body, J" 14 mm., 9 15.5 mm. ; pronotum, ^ 3.9 mm.,
9 4.5 mm.; fore femora, ^ 5.5 mm.. 9 6 mm.; hind femora, ^ 11
mm., 9 13 mm.; hind tibice, ^ 12 mm., 9 13.5 mm. ; ovipositor,
8.4 mm.

3 ^,3 9. Grand Menan Isl., Me., A. E. Verrill ; Vigo Co., Ind.,
October, Blatchley. Specimens are in the Museum of Comparative
Zoology from St. Johns, N. B.

Provancher gives it from Canada with a query, and it appears, but
wrongly, in Bruner's list of the Orthoptera of Nebraska (Publ. Nebr.
Acad. Sc, iii. 32, 1893).

16. Ceuthophilus lapidicola.

Phalangopsis lapidicola Burm., Handb. d. Ent., ii. 723 (1838).

Locusto. {Rhaphidophorus) lapidicola De Haan, Bijdr. Kenn. Orth.,
178 (1842).

Body glabrous, blackish above and on upper part of sides, with a very
broad dark rufous mediodorsal stripe, narrowing on the abdomen and
disappearing in the middle of the same, the black portions sprinkled,
especially on the abdomen where it covers all the sides, with rufo-lute-
ous dots or small roundish spots, the lower portion of the sides of the
thorax and especially of the pronotum luteous, flecked and clouded to a
greater or less degree with fuscous ; antennse fuscous, very distantly and
narrowly annulated with luteous ; legs luteous, infuscated more or less
— and in this very variable — especially at the distal extremity of the
femora, the hind femora almost wholly blackish fuscous externally,
flecked, streaked, or stained, especially below, with sordid luteous.
The antennee are very slender and at least three and a half times as
long as the body, and the legs slender and pretty long. Fore femora
barely stouter in the basal half than the middle femora, somewhat less
than half as long as the hind femora, nearly a half ((?) or almost a
third (9) longer than the pronotum, the inner carina with two rather
short spines. Middle femoi'a with 2-3 rather short spines on the front

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 51

carina and on the hind carina two very feeble spines besides a moder-
ately long genicular spine. Hind femora about as long as the body,
somewhat more than twice as long as the fore femora, rather slender,
being fully three and a half times as long as broad, the distal third to
fourth subequal, the inner surface above and beyond the middle with
three or four distant raised points, both carina? feebly spinulate in the
distal half, the outer more strongly than the inner in the male, the
reverse in the female which as a whole is a little more feebly armed,
the intervening sulcus rather narrow. Hind tibiae straight in both
sexes, of the same length as the femora, armed beneath with 1-2 sub-
apical spines besides the apical pair ; spurs subopposite, the basal
before the end of the proximal third of the tibia, with sometimes a
supplementary spur still farther toward the base, fully half as long
again as the tibial depth, set at an angle of about 70° with the tibia,
and divaricating about 160°, the apical third incurved; inner middle
calcaria considerably longer than the outer, fully twice as long as
the others or as the spurs and scarcely shorter than the first tarsal
joint. Hind tarsi two fifths as long as the tibia?, the first joint some-
what shorter than the rest combined, the second more than twice as
long as the third and with it about as long as the fourth. Cerci
rather slender, scarcely shorter than the femoral breadth. Ovipositor
a little less than two thirds as long as the hind femora, straight,
feebly tapering on the basal third, equal and moderately broad beyond,
the tip a little upturned and acuminate (about 35°), the teeth not long,
aculeate.

Length of body, (^9 21 mm. ; antennae (est.), ^ 75+ mm., 9 68+
mm. ; pronotum, ^ 6.5 mm., 9 7 mm. ; fore femora, ^ 9.5 mm., 9 8.9
mm. ; hind femora and tibiae, ^ 20.25 mm., 9 20.4 mm. ; ovipositor,
12.75 mm.

1 c?9 2 9j and 3 immature specimens, N. Carolina, Morrison (Coll.
Henshaw, Bruner). A 9 fi'om Pennsylvania is in the Museum of
Comparative Zoology, and a 9 without locality in the U. S. National
Museum.

Burmeister's Phal. lapidicola came from Virginia and South Caro-
lina. The present species is the only one known to me from the
Southern Atlantic States which completely or approximately agrees
with his description, the species formerly referred by me and others
to this being a Northern form to which the description poorly fits,
and that described by Brunner under this name is a very different
insect.

62 PROCEEDINGS OP THE AMERICAN ACADEMY.

17. Ceuthophilus arizonexsis, sp. nov.

Pallid luteous, so heavily infuscated that behind the pronotum there
is only left a single series of luteous spots on each side, which on the
meso- and metanotum are transverse oval and rather large, and on
the abdomen are transverse anterior stripes, sometimes confluent with
those of the opposite side ; the pronotum is mostly fuscous, deepest
around the margin, more or less dotted and vermiculate with luteous
elsewhere, there being commonly a transverse row of dots bordering
the anterior fuscous margin, and the disk on either side more or less
heavily blotched with the same ; the legs are fuscous, varying in depth
in different individuals, the hind femora generally with sufficiently
conspicuous scalariform markings. The antennae are very slender and
fully three times as long as the body, and the legs are slender but not
very long. Fore femora slightly stouter than the middle femora, a
third longer than the pronotum and half as long as the hind femora,
the inner carina with one or two spines. Middle femora with 1-3
spines on the front carina, and the hind carina generally unarmed
except for a slight genicular spine, but sometimes with as many as
three other minute spines. Hind femora nearly as long as the body,
twice the length of the fore femora, moderately slender, being a little
less than three and a half times longer than broad, gradually diminish-
ing in size and yet with the distal fourth subequal, the surface with no
raised points, the outer carina with only a few raised points, mostly on
the distal half, the inner carina with most minute but sharp distant
spinules, the intervening sulcus narrow. Hind tibiag scarcely longer
than the femora, straight in both sexes, very slender, armed beneath
with a single preapical spine besides the apical pair ; spurs nearly
opposite, the basal beyond the end of the proximal third of the tibia,
about as long as the tibial depth, set at an angle of from 35-40° with
the tibia and generally divaricating about 70-80° (one example about
100°), their tips incurved ; inner middle calcaria a little longer than
the outer, fully twice as long as the others or as the spurs, but much
shorter than the first tarsal joint. Hind tarsi less than half as long
as the tibijE, the first joint fully as long as the rest combined, the
second twice as long as the third and with it as long as the fourth.
Cerci stout on the proximal, slender on the distal half, nearly as long
as the femoral breadth. Ovipositor four fifths the length of the hind
femora, slender, nearly straight, tapering slightly, the tip finely pointed
at an angle of about 30° and barely upturned, the armature of the
inner valves aculeate, only the terminal arcuate.

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 53

Length of body, c? 8 mmv 9 11-5 mm.; pronotum, (^ 2.7 mm.,
9 3.7o mm. ; fore femora, ^ 3.75 mm., 9 5 mm. ; hind femora,
^ 7.5 mm., 9 10 mm.; hind tibia?, ^ 8 mm., ? 10.2 nun. ; ovipositor,
tS mm.

3 c?, 99. St. George, Utah, April 1-12, E. Palmer; Prescott Mt.
district, Central Arizona, E. Palmer. One specimen was collected by
XantuS; locality not mentioned but not improbably Cape St. Lucas,
Lower California. In the U. S. National Museum are 3 ,^, 1 9,
from Ft. Wingate, N. Mex. (Shufeldt), in the Riley collection.

18. Ceuthophilus uniformis, sp. nov.

Ceuthophilus pallidus Scudd. !, Bull. U. S. Geol. Geogr. Surv. Terr.,
ii. 261 (1876) ; Id. !, Ann. Rep. Geogr. Surv. West 100th Mer., 1876,
279; Brum?, Bull. Washb. Coll.. i. 126 (1885), i. 194-195 (1886);
Id.?, Publ. Nebr. Acad. Sc, iii. 32 (1893).

Smoky luteo-testaceous with a slight olivaceous tinge, glabrous,
marked more or less deeply with fuscous along the posterior margins of
the segments and generally along the anterior margin of the pronotum ;
in this posterior infuscation are indistinct dots of luteous in a trans-
verse series ; generally there is also a mediodorsal luteous line over
all the segments but deepest and broadest on the pronotum, which is
also laterally irregularly streaked, clouded, or blotched with luteous ;
beyond the lighter more luteous bases of the femora, the legs are of
the body color, but the hind femora are considerably inf'uscated in a
scalariform pattern, apically confluent. The antenna? are slender and
nearly or quite three times the length of the body and the legs are
moderately short. Fore femora no stouter than the middle femora,
more than a third (cj) or less than a fourth (9) longer than the
pronotum and somewhat less than half as long as the hind femora,
the inner carina armed only with a subapical spine. Middle femora
with two spines on the front carina, and on the hind carina 2-3 (?)
or 3-4 ((^) spines besides a not very long genicular spine. Hind
femora nearly as long as (^$) or much shorter than (9) the body,
a little more than twice as long as the fore femora especially in the 9 ,
pretty stout, in the $ being but a little more than two and a half times
longer than broad, though in the 9 fully three and a quarter times as
long as broad, with no raised points on the surface, or at most four or
five scattered insignificant ones on the inner surface in the $, the
outer carina with a few spinous points on the distal half, the inner
carina similarly armed but in the $ weaker, the intervening sulcus
narrow. Hind tibite scarcely or no longer than the femora, straight

54 PROCEEDINGS OP THE AMERICAN ACADEMY.

in both sexes, slender, armed beneath with a single subapical spine
besides the apical pair ; spurs almost opposite, the basal rather beyond
the end of the proximal third of the tibia, scarcely longer ((^) or a little
longer (?) than the tibial depth, set at an angle of about 45° with the
tibia and divaricating 70-90°, their tips incurved; inner middle
calcaria distinctly longer than the outer, twice as long as the others
or as the spurs, but distinctly shorter than the first tarsal joint.
Hind tarsi nearly half as long as the tibite, the first joint fully (<?) or
nearly (9) as long as the rest taken together, the second more than
twice as long as the third and nearly as long as the fourth. Cerci
rather stout tapering from before the middle, shorter than the femoral
breadth. Ovipositor nearly twice as long as the fore femora and not
very much shorter than the hind tibite, beyond the extreme very
slightly swollen base slender and subequal but gently tapering, slightly
arcuate in the distal half, the extreme tip produced to a very fine
scarcely upturned point, the armature including the apical members
consisting of sharp minute reversed serrations hardly apparent until
mature.

Length of body, $ 10.7 mm., 9 16 mm.; pronotum, ^ 3.25 mm,,
9 4.1 mm. ; fore femora, ^ 5 mm., 9 4.9 mm. ; hind femora,
^ 10.2 mm., 9 11 mm. ; hind tibite, ^ 10.5 mm., 9 H mm.; oviposi-
tor. 9.4 mm.

5 (^, 9 9. Plains of Northern New Mexico, eastern slope, October
14 ; Beaver Brook, Col., 6,000', July 11, S. H. Scudder ; Empire City,
Col., E. Palmer. It has also been reported from Southern Colorado,
Manitou and Idaho, Col. (Scuddei'), Western Nebraska, and Topeka
and Berks Co., Kans. (Bruner).

19. Ceuthophilus herds, sp. nov.

Body castaneous, so heavily marked with black or blackish fuscous
as to appear rather as black marked with castaneous ; the latter
appears on the pronotum only in a very broad mediodorsal stripe of
unequal width, an impure blotch in the middle of the sides usually
connected with the former, and an inferior edging sometimes expand-
ing anteriorly ; in younger specimens, however, it extends over nearly
all the surface ; on the meso- and metanotum it margins the segments
anteriorly except below, separated from the black irregularly, and
extends mediodorsally across the segments ; on the abdomen it appears
as small spots dotting the surface and merging along the anterior mar-
gins ; the antennae are pale fuscous obscurely and distantly annulated
with luteous; the legs are castaneous, more or less infuscated, the

SCUDDER. — NORTH AMERICAN CEUTHOrHILI. 55

hind femora externally marked heavily with fuscous in a scalariform
pattern, with a broad obscure castaueous annulatiou well before the
genicular lobes. The antenna! are slender and exceedingly long,
about four times as long as the body, and the legs are very long though
only moderately slender. Fore femora no stouter than the middle
femora, a little less than half as long as the hind femora, and rather
more (<$) or rather less (9) than three fourths as long again as tlie
pronotum, the inner carina with 2-3 spines. Middle femora with
similar spines on the front carina and on the hind carina a couple of
similar spines besides a not very long genicular spine. Hind femora
fully as long as the body, a little more than twice as long as the fore
femora, the basal portion stout and swollen but delicately tapering so
that nearly or in the female quite the apical third is subequal, and the
whole is four times as long as broad, the upper edge of the inner sur-
face with 4—5 distant raised points, the outer carina with about ten
sub-equal spines, the longest much shorter than the tibial spurs (c?)>
or with about six slight and distant recumbent spines (9), the inner
carina rather bluntly denticulate, distantly in the outer half (^) or
like the outer carina but more closely denticulate (9)' the intervening
sulcus narrow. Hind tibi;e barely arcuate at base ( (?) or straight ( 9 ),
a very little longer than the femora, armed beneath with 1-2 sub-
apical spines besides the apical pair ; spurs subopposite, the basal at
the end of the proximal third of the tibia, a little longer than the tibial
depth, set at an angle of about 60° with the tibia and divaricating
about 130° (($) or 150-170° (9), incurved at tip; inner middle cal-
caria a little longer than the outer, twice as long as the others or as
the spurs, and as long as the first tarsal joint. Hind tarsi two fifths
as long as the tibite, the first joint much shorter than the rest together,
the second nearly three times as long as the third and with it fully as
long as the fourth. Cerci slender, nearly half as long again as the
femoral breadth. Ovipositor three fifths as long as the hind femora,
straight, tapering and not very stout in the basal, slender and equal in
the apical half, the apex obliquely truncate, upturned, and acuminate
but not much produced, the teeth of the inner valves rather short
and aculeate.

Length of body, $ 23.5 mm., 9 21 mm. ; antenna?, ^ 85 mm.,
9 92 mm.; pronotum, ^ 6.25mm., 9 7.2 mm.; fore femora, S 11-5
mm., 9 12 mm.; hind femora, ^ 24 mm., 9 25 mm.; hind tibiae,
^ 25.5 mm., 9 26 mm. ; ovipositor, 15 mm.

3 $,2 9- North Carolina, H. K. Morrison; over two hundred
were found in one old hollow tree when it was felled. 2 J and 2 9 •>

5Q PROCEEDINGS OF THE AMERICAN ACADEMY.

of what is apparently the same species, but smaller, are in the U. S.
National Museum from Washington, D. C.

20. Ceuthophilus uhleri.

Ceuthophilus uhleri Scudd.!, Bost. Journ. Nat. Hist., vii. 435 (18G2) ;
Walk., Catal. Derm. Salt. Brit. Mus., i. 201 (1869) ; Glov., 111. N. A.
Ent., Orth., pi. 8, fig. 8 (1872) ; Riley, Stand. Nat. Hist., ii. 184 (1884) ;
Brunn., Monogr. Stenop., 64-65, fiig. 33b (1888) ; Smith, Catal. Ins.
N. J., 409 (1890).

Ceuthophilus latisulcus Blachl.!, Proc. Ind. Acad. Sc, 1892, 146
(1894).

Dull luteo- or rufo-testaceous, very heavily flecked with dark fuscous
so as to produce a tolerably uniform mottled appearance, ordinaril}' a
little more open than elsewhere in a narrow mediodorsal streak on the
pronotum, and in the tolerably clear luteous or pallid luteous of the
inferior margin of the descending thoracic lobes ; the flecking is made
up of small more or less confluent dots, which assume a certain longi-
tudinal regularity on the abdomen only ; legs varying from luteous to
testaceous, more or less infuscated, especially on the apical portions of
the femora and in the distinct and heavy scalariform markings of the
hind femora. The antennae are moderately stout in the basal, but in
the apical half very slender, apparently only a little more than twice the
length of the body, the legs moderately long. Fore femora no stouter
than the hind femora, much less than half as long as the hind femora,
but considerably more than a third longer than the pronotum in the $
though only a fourth longer in the 9 , the inner carina with 2-3 spines,
the subapical not much longer than the others. Middle femora with
the front carina as in the fore femora, the hind carina armed with 1-3
spines besides a moderately long genicular spine. Hind femora
longer (^$) or shorter (9 ) than the body, considerably more than twice
as long as the fore femora (at least a third more in the male), stout, the
apical third or fourth subequal, about three and a third times as long
as broad in the male, the darker portions of the surface of the apical
half of the femora and the upper portion of the inner side rather
heavily {$) or very sparsely (9) scabrous with raised points, the
outer carina armed with 7-8 unetjual inequidistant coarse irregular ar-
cuate spines, the largest (just beyond the middle) as long as but much
stouter than the tibial spurs (<?) or almost entirely unarmed but for
some 3-4 raised points ( 9 ), the inner carina with about sixteen small
inequidistant coarse spinules covering the whole length {$) or a few
slight ones only on the apical fourth of the femora (9), the interven-

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 57

ing sulcus exceptionally broad. Hind tibise faintly and irregularly
sinuous (cJ) or straight (9), distinctly longer than the femora, slen-
der, armed beneath with 1-2 subapical spines besides the apical pair ;
spurs subopposite, the basal at or a little beyond the end of the proxi-
mal fourth of the tibia, a little longer than the tibial depth, set at an
ano-le of about 35° witli the tibia and divaricating 80°-'J0", the apical
half incurved; inner middle calcaria much longer than the outer, more
than twice as long as the others or as the spurs, but scarcely so long
as the first tarsal joint. Hind tarsi two fifths as long as the tibiae, the
first joint about as long as the rest together, the second nearly three
times as long as the third and with it fully as long as the fourth.
Cerc'i rather stout, shorter than the femoral breadth. Ovipositor only
slightly enlarged at base, the distal two thirds equal but not very
slender, straight, almost two thirds as long as the hind femora, the tip
considerably upcurved and finely acuminate, the teeth of the inner
valves triangular, increasing in length apically, only the terminal
arcuate.

Length of body, $ 9 15.5 mm.; antenna?, 9 32+ mm.; pronotum,
$ 5.1 mm., 9 4.6 mm.; fore femora, S 7.35 mm., 9 5.75 mm.;
hind femora, $ 11. lb mm., 9 13 mm.; hind tibia?, $ 18.5 mm.,
9 14 mm. ; ovipositor, 8.25 mm.

1$, 39. Maryland (P. R. Uhler) ; Middle States (R. Osten
Sacken) ; Vigo Co., Ind., (W. S. Blatchley) ; Georgia. It is also
reported from New Jersey (Smith) and Tennessee (Brunner). Bru-
ner quotes it doubtfully among Nebraska Orthoptera, but I do not know
to what species he refers.

Easily confounded with 0. hlatchleyi.

21. Ceuthophilus blatchleyi.

Ceuthophilus uhleri Blatchl.!, Proc. Ind. Acad. Sc, 1892, 1-44-145
(1894).

In color and markings this species is indistinguishable from O. uhleri.
The legs and especially the hind femora are slenderer. Fore femora
no stouter than the hind femora, much less than half as long as the
fore femora, fully a third {$) or scarcely a fourth (9) as long again
as the pronotum, the inner carina with 2-3 spines, the subapical long.
Middle femora armed on the front carina much as in the fore legs, the
hind carina with a long genicular spine sometimes accompanied by 1-3
other spines, often minute. Hind femora nearly two and a half times
as long as the fore femora, longer than the body in both sexes, slenaer
and tapering, nearly the apical third subequal, three and a half times

58 PROCEEDINGS OF THE AMERICAN ACADEMY.

as long as broad in the male and fully three and three quarters in the
female, the upper portion of the apical half of the inner surface and
to a less degree the upper surface near it with numerous raised points,
but not so pronounced as in G. uhleri^ the outer carina armed exactly
as there but with wider intervals between the larger spines and the
spines less stout {$), or with 2-3 scarcely noticeable spinules near
the apex (9 ), the inner carina with about 12-14 serrulations unequally
placed, slight, less numerous and distinctly slighter in the female than in
the male, the intervening sulcus only moderately broad. Hind tibiae with
a hardly noticeable arcuation or sinuatiou in the male, hardly ( c^ ) or
much ( 9 ) longer than the femora, slender, armed beneath with two
median subapical spines besides the apical pair; spurs subalternate, the
basal at about the end of the proximal fourth of the tibia, considerably
longer than the tibial depth, set at an angle of about 35° with the
tibia and divaricating 98°-100°, their apical fourth incurved; inner
middle calcaria considerably longer than the outer, more than twice as
long as the othei's or as the spurs, and fully as long as the first tarsal
joint. Hind tarsi about two fifths as long as the tibiae, the first joint
longer than the other joints together, the second much more tlian
twice as long as the third and with it longer than the fourth. Cerci
stout at base, beyond slender, about as long as the femoral breadth.
Ovipositor straight, almost two thirds as long as the hind femora, very
little enlarged at base, tapering almost throughout but very gently,
the tip upturned a little and finely acuminate, the armature as in
C. uhleri.

Length of body, $ 13.5 mm., ? 13 mm. ; pronotum, $ 4.7 mm.,
9 4.5 mm. ; fore femora, $ 6.4 mm., 9 5.5 mm.; hind femora, $\b.lb
mm., 9 13.5 mm. ; hind tibife, $ 9 16.25 mm.; ovipositor, 8.5 mm.

2 <?, 2 9- Vigo Co., Indiana (W. S. Blatchley) ; also from New
York, Riley (U. S. Nat. Mus.).

Distinguishable from C. uhleri by the slightly different and weaker
armature of the carinae of the hind femora, but especially by the slen-
derer hind femora, and the narrower inferior sulcus of the same. I
probably led Mr. Blatchley into his pardonable error by determining
this for him as C. uhleri.

22. Cedthophilus spinosus.

Ceuthophilus lapidicola Brunn., Monogr. Stenop., 63-64 (1888),
Body dark fusco-castaneous, glabrous, with irregular luteous spots

and blotches covering a considerable portion of the thoracic segments ;

the lower edges of the sides of the thoracic segments are sordid luteous

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 59

and the abdomen is mostly marked with alternate longitudinal bars
of luteous and fuscous, the latter prevailing dorsally; legs luteo-cas-
taueous, the hind femora distinctly but not heavily marked with fuscous
in scalariform patterns. Legs not very long. Fore femora broader
basally than the middle femora, much less than half as long as the
fore femora, and only a fifth longer than the pronotum, the inner
carina with a short spine besides a long preapical spine. Middle
femora armed with three spines on the front carina, the preapical very
long, the hind carina with only a couple of very short spines besides
the long genicular spine. Hind femora longer than the body, two and
a half times as long as the fore femora, very stout but with the distal
portion so produced that the apical fourth is equal, the whole three
times as long as broad, the surface covered everywhere on the darker
portions, but especially on the stouter part of the femora beyond the
middle and within as well as without, with raised points closely crowded,
the outer carina elevated, armed in the middle third with a series of
about five spines, sometimes iuequidistant, distally increasing in length,
the last and to some extent the others bent-arcuate, about as long as
the tibial spurs but coarser, followed by a rapid narrowing of the
femora and on this narrow portion by 4-5 minute serrulations, the
inner carina pretty regularly and minutely but not closely spinulate,
the intervening sulcus broad. Hind tibia? feebly arcuate, somewhat
longer than the femora, armed beneath with a single subapical spine
besides the apical pair ; spurs subopposite, the basal at the end of the
proximal fourth of the tibia, half as long again as the tibial depth, set
at an angle of about 45° with the tibia and divaricating 90-100°, their
tips incurved; inner middle calcaria considerably longer than the
outer, fully twice as long as the others or as the spurs, and as long as
the first tarsal joint. Hind tarsi about two fifths as long as the tibiae,
the first joint hardly as long as the rest together, the second twice as
long as the third, but with it scarcely as long as the fourth. C'erci
moderately slender, rather short, probably little exceeding in length
the femoral breadth.

Length of body, 13 mm. ; pronotum, 5 mm. ; fore femora, 6 mm. ;
hind femora, 15 mm.; hind tibiae, 16 mm.

1 ^. Georgia,

This species is very closely related to 0. uhleri, differing in its
markings, which are less sprinkled, and in the more pronounced spiuu-
lations of the hind femoral carinte in the male.

60 PROCEEDINGS OF THE AMERICAN ACADEMY.

23. Ceuthophilus c^cus, sp. nov.

Body glabrous, blackish fuscous above, pallid and more or less
sordid luteous ou the lower portion of the sides, with a mediodorsal
rufo-luteous Hue and dotted above faintly and rather sparsely with
rufo-luteous, some of the dots broadening the mediodorsal line, others
next the luteous sides becoming larger and sometimes more distinctly
luteous, and on the abdomen often becoming oblique dashes ; the very
edge of the inferior margins of the thoracic lobes castaneous ; antennae
fusco-luteous ; legs luteous, more or less infuscated, the hind femora
luteo-castaneous, with heavy and distinct blackish fuscous scalariform
markings, much heavier on distal than proximal half. The antennge
are slender and about three times the length of the body, the legs
moderately short. Fore femora slightly broader than the middle
femora, very much less than half as long as the hind femora and at
most ((?) only a fourth longer than the pronotum, the inner carina
with 2-3 spines, at io^st the preapical long. Middle femora with
2-4 long spines, the preapical very long, on the front carina,
the hind carina with 0-2 short spines besides a very long genicular
spine. Hind femora as long as the body, two and a half times as long
as the fore femora, very stout, scarcely more than three times as long
as broad, the stout portion rapidly tapering so that the apical fourth
is subequal, the inner surface of the male with a cluster of raised points
beyond the middle, above, the outer carina elevated, having on the
middle third a row of increasingly larger spinules, the largest still
very much shorter than the tibial spurs, followed distally by half a
dozen minute and equal spinules (^) or unarmed (?), the inner
carina with a few small subequal spinules in the distal half, smaller
and sparser in the 9 than in the ^, the intervening sulcus broad.
Hind tibiae straight in both sexes, a little longer than the femora,
armed beneath with a single preapical spine besides the apical pair;
spurs subopposite, the basal not much beyond the end of the proximal
fourth of the tibia, almost twice as long as the tibial depth, set at an
angle of 35-45° with the tibia, divaricating about 130° at least in the
9, their tips considerably incurved ; inner middle calcaria considerably
longer than the outer, nearly twice as long as the others or as the
spurs, and about as long as the first tarsal joint. Hind tarsi nearly
two fifths as long as the tibiae, the first joint fully as long as the rest
together, the second three times as long as the third and with it fully as
long as the fourth. Cerci moderately slender, bluntly pointed, much
shorter than the femoi-al breadth, Ovipositor scarcely longer than the

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 61

fore femora, feebly arcuate, tlie base moderately stout, the distal three
fifths equal and moderately slender, the tip considerably upturned and
very acuminate.

Length of body, (J 11.5 mm., 9 10 mm.; antenna} (est.), $ 32
mm., 9 31 mm. ; pronotum, $ 4 mm., 9 4.25 mm. ; fore femora,
$ 5 mm., 9 4.5 mm. ; hind femora, $ 12.5 mm., 9 11.25 mm.; hind
tibiaj, $ 13.5 mm., 9 ^1'' mni. ; ovipositor, 4.75 mm.

1 $ ,'2 9 . Lexington, Ky., June 28, S. Garman. A single imper-
fect $ in the National Museum without locality (Missouri?) probably
belongs to this species.

24. Ckuthophilus nigricans, sp. nov.

Body glabrous, blackish fuscous with obscure rufo-luteous markings,
becoming pallid luteous and more distinct on the abdomen ; they con-
sist almost wholly of a sprinkling of small roundish spots and dots,
more profuse and elongated on the abdomen, but there is besides a
very obscure mediodorsal line or stripe on the pronotum ; excepting
on the under sui'face of the femora, the femora and tibiae are dark
fuliginous and the outer side of the hind femora very dark castaneous,
heavily infuscated in the apical half, blackish at tip, and with deep
and heavy fuscous scalariform markings. The antennie are slender
and at least in the basal portion blackish fuscous, and the legs are
rather short, though the hind legs are relatively much longer in the
female than in the male. Fore femora not stouter than the middle
femora, much less than half as long as the hind femora, particularly
in the female, and very little longer than the pronotum, the inner
carina with one or two short spines. Middle femora similarly armed
on the front carina, the hind carina with one or two spines besides a
short genicular spine. Hind femora shorter {^) or longer (9) than
the body, somewhat more than twice ( (^) or about three times (9) as
long as the fore femora, in the male stout and tapering pretty regularly
to the genicular lobes, about two and three quarters times longer than
broad, the middle of the distal half of the inner surface above with a
small cluster of raised points, in the female much slenderer and with
the apical fourth subequal, the outer carina uniformly elevated, deli-
cately serratulo-spinous through most of its extent {$), or with a few
distant spinules in the outer half (9), the inner carina armed as the
outer but somewhat more delicately (J") or with a few raised points
(9)5 the intervening sulcus moderate. Hind tibiae somewhat longer
than the femora, straight in both sexes, armed beneath with a single
subapical spine besides the apical pair ; spurs subopposite, the basal

62 PROCEEDINGS OP THE A3IERICAN ACADEMY.

scarcely beyond the end of the proximal fourth of the tibia, about as
long as the tibial depth, set at an angle of about 50° with the tibia and
divaricating about 90°, faintly incurved ; inner middle calcaria much
longer than the outer, nearly tvpice as long as the others or as the
spurs, but much shorter than the first joint of the tarsus. Hind
tarsi not much less than half as long as the tibia;, the first joint almost
as long as the rest together, the second twice as long as the third and
with it as long as the fourth. Cerci very short and not very slender.
Ovipositor about a fifth longer than the fore femora, straight, not
stout and delicately tapering in basal half, the tip upturned and very
acuminate, the teeth of the inner valves aculeate, straight.

Length of body. $ 9 11.5 mm.; pronotum, $ 4.5 mm., 9 4.35
mm.; fore femora, $ 4.75 mm., 9 4.5 mm.; hind femora, S 10.75
mm., 9 13.4 mm.; hind tibiae, $ 11.1 mm., 9 14.5 mm.; ovipositor,
5.3 mm.

I S,\ 9. Tyrone, Ky., April 23 (S. Garman).

The single 9 has but one hind leg, and this has been attached
after breaking off. As the leg seems to be abnormally different from
that of the Si it is quite possible that it does not belong to this
specimen, and that the characters given above drawn from it should
be eliminated.

25. Ceuthophilus fusiformis, sp. nov.

Body testaceous almost wholly overlaid with black above, the
abdomen wholly, the meso- and metanotum all but an anterior mesial
spot, and the pronotum to such a degree that the testaceous is confined
to a large equilateral triangular patch on each side, the inferior mar-
gins for their base and a couple of small mesial jjatches, the larger
behind ; the lower half of the sides throughout, however, is pallid
testaceous ; the legs are testaceous and uniform except for rather faint
fuscous scalariform markings on the hind femora. The antennee are
slender and about three times as long as the very compact body, and
the legs short and not very slender. Fore femora distinctly stouter
than the middle femora, somewliat less than half as long as the hind
femora and but little longer than the pronotum, the inner carina
armed only with a strong subapical spine. Middle femora armed with
2-3 spines on the front carina, the distal scarcely or no longer than
the others, and on the hind carina 2-3 spines besides a moderate
genicular spine. Hind femora as long as the body, a little more than
twice as long as the fore femora, very stout, the subequal apical por-
tion not over one seventh of the whole, which is three times as long as

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 63

broad only, a few scattered raised points beyond tbe middle above, the
outer carina uniformly and rather closely serrulate, the inner carina
similarly but more delicately armed with a tendency to a biseriate
arrangement, the intervening sulcus rather broad. Iliud tibiae
straight, shorter than the femora, armed beneath with a single sub-
apical spine besides the apical pair ; spurs subopposite, the basal at
the end of the proximal fourth of the tibia, nearly half as long again
as the tibial depth, set at an angle of about 55° with the tibia and
divaricating about 100°, their extreme tips incurved; inner middle
calcaria barely longer than the outer, half as long again as the others
or as the spurs, and a little shorter than the first tarsal joint. Hind
tarsi almost half as long as the tibiae, the first joint about as long as
the rest together, the second fully twice as long as the third and with
it as long as the fourth. Cerci moderately slender, considerably
shorter than the femoral breadth.

Length of body, 1 0.5 mm. ; antenuie, (est.) 28+ mm. ; pronotum,
4.25 mm. ; fore femora, 4.75 mm. ; hind femora, 10.3 mm.; hiud tibiae,
9.75 mm.

1 $. Lincoln, Nebraska, L. Bruner.

26. Ceuthophilus sallei, sp. nov.

Dark mahogany brown, glabi'ous, marked with reddish luteous in a
more regular pattern than common, there being a moderately broad
mesial stripe of the brighter color, broader on the anterior than the
posterior part of the segments, the sides with regularly disposed flecks
and dots of luteous, becoming more numerous below, so that the luteous
prevails on the lower portion of the sides ; on the abdomen the luteous
spots are usually either circular or made of short oblique dashes ; the
legs are as dark as the upper surface, the hind femora with the usual
pattern, but the lighter portions subdued in tint. The legs are rather
short, the antennae not stout. Fore femora stouter than the middle
femora, especially on the proximal half, about a fifth longer than the
pronotum, at least in the $ , very much less than half as long as the
hind femora, the inner carina with a couple of spines, the subapical
long. Middle femora with two spines besides a long subapical spine
on the front carina, and on the hind carina 0-2 spines besides the long
genicular spine. Hind femora fully as long as the body, nearly two
and a half times longer than the fore femora, very stout, tapering so
that the distal fourth is subequal, nearly three times as long as broad,
the inner surface scabrous with a cluster of raised points near the
middle above, the outer carina with 8-10 distant unequal serrations or

64 PROCEEDINGS OF THE AMERICAN ACADEMY.

spines, one before the middle of the distal half longer than the others
and nearly as long as the tibial spurs, stout at base only (^) or
minutely and distantly denticulate in the distal half (9), the inner
carina with a similar number of small subequal and subequidistant
spines (^), or as in the male (9)> the intervening sulcus narrow and
deep. Hind tibiae slender and straight in both sexes, scarcely longer
than the femora, armed beneath with a single preapical spine besides
the apical pair ; spurs generally opposite, the basal at about the end of
the proximal third of the tibia, fully half as long again as the tibial
depth, set at an angle of about 50° with the tibia and divaricating
about 140° with each other, their tips incurved ; inner middle calcaria
very much longer than the outer, more than twice as long as the others
or as the spurs and fully as long as the first tarsal joint. Hind tarsi
almost half as long as the tibiaB, the first joint nearly as long as the
rest together, the second more than twice the length of the third
and with it not so long as the fourth. Cerci tapering throughout
equally, a little shorter than the femoral breadth, the tip not very
pointed. Ovipositor tapering gently in proximal, equal in distal
half, the tip upcurved and produced to a fine point, as long as the
fore femora, the teeth and apical hook of inner valves slender, long,
and arcuate.

Length of body, ^ 16 mm., 9 14.5 mm.; pronotum, ^ 5.7 mm.,
9 5.5 mm.; fore femora, $ 6.9 mm., 9 6 mm.; hind femora, ^ 17.5
mm., 9 14.8 mm.; hind tibise, (? 18 mm., 9 15 mm.; ovipositor,
6 mm.

1 (J, 7 9. New Orleans, Auguste Salle.

The species is noticeable for the length of all the spines.

27. Cedthophilus latens.

Ceuthophiluslatens Scudd., Bost. Journ. Nat. Hist., vii. 437 (1862) ;
Walk., Catal. Derm. Salt. Brit. Mus., i. 202 (1869) ; Brun., Publ.
Nebr. Acad. Sc, iii. 31 (1893) ; Blatchl.!, Proc. Ind. Acad. Sc, 1892,
143-144 (1894).

Body glabrous, with a broad mediodorsal stripe of dark rufo-luteous
"H the thoracic se2:meuts, bordered very broadly on either side with
blackish or blackish fuscous, fading out inferiorly, the lower portion of
the sides pallid luteous, more or less impure, the very margin luteo-
testaceous ; the abdominal segments obscurely continue these longi-
tudinal markings, but the black becomes brownish fuscous and is so
dotted with dull luteous as to give a very different appearance, the
segments being marked with alternate and frequent short longitudinal

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 65

or obliquely longitudinal bars of brovvnisli fuscous and dull luteous,
the darker parts often also dotted with luteous ; legs luteous, more
or less infuscated, especially the hind femora the outer surface
of which excepting at base is increasingly fuscous distally and
broadly annulate with blackish apically, the surface generally sprinkled
with luteous dots, with faintly different depths of color marking a
scalariform pattern. The hind tibial spines are distinctly blackish
at the base. The antennae are about three times as long as the body,
luteous, the joints at first feebly infuscated at the base, afterwards
wholly, and then interrupted by luteous for a single joint every few
joints irregularly, the legs moderately slender and not very long, the
hind tibial spurs distinctly infuscated or blackish at base. Fore
femora slightly stouter than the middle femora, considerably less than
half as long as the hind femora, nearly a third longer than the pro-
notum in the $, though but little longer in the 9, the inner carina
armed with 2-3 spines. Middle femora with generally 2-3 spines on
the front carina and on the hind carina 1-2 spines besides a moderate
genicular spine. Hind femora about as long as the body, at least two
and a quarter times longer than the fore femora, the swollen portion
very gradually tapering and of unusual length, the whole about three
and a quarter (^$) or three and three quarters (9) times as long as
broad, the surface with no raised points, both outer and inner carina in
both sexes almost unarmed, at most a few feeble spinules being seen
near the apex, the intervening sulcus narrow. Hind tibife scarcely or
no longer than the femora, straight in both sexes, slender, generally
armed beneath with two median subapical spines besides the apical
pair ; spurs irregularly opposite, the basal at the end of the proximal
third of the tibia, slightly longer than the tibial depth, set at an angle of
about 45° with the tibia and divaricating about 1 20°, slightly incurved
especially at tip ; inner middle calcaria much longer than the outer,
more than twice as long as the others or as the spurs, and as long as
the first tarsal joint. Hind tarsi about two fifths as long as the hind
tibios, the first joint as long as the rest together, the second more than
twice as long as the third and with it as long as the fourth. Cerci
rather slender, tapering, pointed, about two thirds as long as the
femora] breadth. Ovipositor twice as long as the fore femora, and
about two thirds as long as the hind femora, straight, gently tapering
in the proximal, rather slender and equal in the distal half, the tip
upturned and acute but not aculeate, the armature of the inner valves
consisting of deep denticulations.

Length of body, $ 14.5 mm., 9 1^ mm. ; antennae, 9 (est.) 44 mm.;
VOL. XXX. (n. s. xxii.) 5

66 PROCEEDINGS OF THE AMERICAN ACADEMY.

pronotum, (J 4.6 mm., ? 5 mm. ; fore femora, ^ 6 mm., ? 5.5 mm. ;
hiud femora, J" 9 14 mm,; hind tibiae, ^ 14.5 mm., ? 14 mm. ; ovi-
positor, 9 mm.

7 c?, 6 9 . Ithaca and Endfield Falls, N. Y. (Cornell Univ., Morse) ;
Vigo Co., lud. (Blatchley) ; Texas, Belfrage. Originally described
from Illinois. Said by Bruner to be found in Eastern Nebraska, but
I have seen no specimens from so far west.

28. Ceuthophilus meridionalis, sp. nov.

Whole dorsal surface of body dark, being mostly almost piceous
with dark mahogany brown markings consisting principally of a broad
mesial stripe of irregular width on the thorax, fully as broad as the
basal joint of the antenute and on the abdomen made up of numerous
spots and short longitudinal or oblique bars, which toward the sides
become tinged with luteous ; the sides dingy luteous, the femora fuseo-
luteous, the hind pair externally striped with clearer luteous above
and spotted below ; hind femoral geniculations blackish ; all the tibige
and antenna? dark luteous. The antennae are moderately slender, the
legs rather long. Fore femora scarcely stouter than the middle
femora, fully one fourth longer than the pronotum but only two fifths
the length of the hind femora, the inner carina with two spines, the
outer of which is hardly subapical but pretty stout. Middle femora
with three pretty stout spines on the front carina, and on the hind
carina from 1-4 small spines besides a long genicular spine. Hiud
femora of the length of the body, about two and a half times as
long as the fore femora, very stout, the ajiical fourth subequal, about
three and a quarter times as long as broad ; the upper half very
faintly but closely scabrous in the darker portions, the outer carina
elevated, with 5-6 unequal and inequidistant large or very large
spines, the largest just beyond the middle, coarse, especially at base,
and much longer than the tibial spurs, besides one or two spinules
in the constricted portion of the femora, the inner carina rather dis-
tantly and rather regularly spinulate throughout, the intervening sulcus
very broad. Hind tibiae gently arcuate on basal third, much longer
than the femora, not very slender, armed beneath apically with two or
three spines besides the apical pair ; spurs subalternate, the basal at
end of proximal third of the tibia, slightly longer than the tibial depth,
set at an angle of 45° with the tibia and divaricating about 100°, the
apical half incurved r (calcaria and hind tarsi lost in the only specimen
known). Cerci slender, gently tapering, about two thirds as long as
the femoral breadth.

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 67

Length of body, 20 mm. ; antennae, 25 X mm. ; pronotum, 6.5 mm. ;
fore femora, 8.25 mm. ; hind femora, 20.5 mm. ; hind tibias, 22.3 mm.
1 (J. Chihuahua, Mexico.

29. Ceuthophilus neglectds, sp. nov.

Ceuthophilus maculatus (pars), Scudd.!, Bost. Journ. Nat. Hist., vii.
434 (1862).

Glabrous, castaneous, more or less, often deeply, infuscated especially
above, the infuscation often but not always terminatmg below the
middle of the sides, which are there sordid luteous ; a broad more or
less and often very obscure mediodorsal rufo-luteous stripe on the
pronotum, sometimes extended farther back but then generally broken ;
the sides of the pronotum and to a lesser extent the meso- and meta-
notum are more or less blotched or vermiculate with luteous, and the
abdomen is more or less but generally feebly maculate with luteous ;
the markings and the coloring vary greatly, so that it is difficult to for-
mulate any general statement ; the female is apt to be darker than the
male, and specimens from New England are often almost uniformly
dark, even almost black, while the contrasts between the dorsum and
the lower portion of the sides are strongest in specimens from the
Middle Atlantic States, where they grow to a large size ; the legs are
generally luteo-castaneous, the tips of all the femora dark, sometimes
almost black, the hind femora with scalariform fuscous markings.
The antennae are not often infuscated and then generally more or less
or feebly annulate with luteous, slender and generally 2-3 times as
long as the body, the legs rather slender and moderately short.
Fore femora scarcely stouter than the middle femora, considerably less
than half as long as the hind femora and but very little longer than the
pronotum, the inner carina with a subapical spine, rarely accompa-
nied by another. Middle femora with 1-3 spines (largely depending
upon age) on the front carina, and on the hind carina 0-3 spines
besides a longer but short genicular spine. Hmd femora two and a
quarter times longer than the fore femora, about as long as the body,
stout and tumid, the upper and lower margms almost equally arcuate,
scarcely more than the genicular portion subequal, almost three times
as long as broad, the inner surface with a very few raised points next
or at the upper margin beyond the middle, scarcely perceptible or
absent from the female, the outer carina minutely, closely, and pretty
uniformly serrulate through all but the basal third, sometimes almost
imperceptible in the female, the inner carina a feebler repetition of the
outer, the intervening sulcus moderate in width. Hind tibiae slender.

68 PROCEEDINGS OF THE AMERICAN ACADEMY.

Straight in both sexes, barely or no longer than the femora, armed
beneath with 1-2 subapical spines besides the apical pair ; spurs sub-
opposite, the basal at the end of the proximal third of the tibia,
scarcely shorter than the tibial depth, set at an angle of about 45°
with the tibia and divaricating about 100-110°, their tips incurved;
inner middle calcaria considerably longer than the outer, about twice
as long as the othei-s or as the spurs, but shorter than the first tarsal
joint. Hind tarsi almost two fifths as long as the tibite, the first joint
not so long as the rest together, the second considerably more than
twice as long as the third and with it fully as long as the fourth.
Cerci moderately stout, tapering rather uniformly, about two thirds
as long as the femoral breadth. Ovipositor half as long as the hind
tibiffi, straight, tapering in basal half, equal and moderately slender,
the tip slightly upcurved and acutely pointed (about 35°), the inner
valves with aculeate, scarcely arcuate teeth.

Length of body, ^ 9 12.5 mm. ; pronotum, ^ 4.4 mm., 9 4.6 mm. ;
fore fiemora, c? 9 5 mm. ; hind femora, ,^12 mm., 9 11-7 mm. ; hind
tibiae, ^ 9 12 mm. ; ovipositor, C) mm.

31 c^, 29 9- Ithaca, N. Y., Comstock (Cornell Univ., Morse) ; Jay,
Vt. (A. P. Morse) ; Sudbury, Vt. (S. H. Scudder) ; side of Mt. Wash-
ington, N. H. ( S. H. Scudder) ; Forest Hills, Mass. (S. Henshaw) ;
Cambridge, Mass. (Mus. Comp. Zool.) ; Princeton, Mass. (S. H.
Scudder) ; Pennsylvania (Mus. Comp. Zool.) ; Maryland (P. R.
Uhler) ; Baltimore, Md. (Mus. Comp. Zool.) ; Washington, D. C.
Cornell Univ., L. Bruner) ; Virginia (L. Bruner) ; West Virginia
(Museum Comp. Zool.). In the U. S. National Museum, from C. V.
Riley's collection, are 3^, 2 9, from Maryland, District of Columbia,
and Virginia.

30. Ceuthophilus maculatus.

Rhaphidophora maculata [Say, MS.], Harr., Treat. Ins. Inj. Veg., ed,
1841-42, 126 ; Fitch, Amer. Journ. Agric. Sc, vi. 146 (1847) ; Pack.,
Rep. Nat. Hist. Me., 1861, 375 ; Thorn., Trans. 111. St. Agric. Soc,
V. 444 (1865).

Phalango'psis maculata Harr., Treat. Ins. Inj. Veg., ed. 1852, 137 ;
ed. 1862, fig. 73; Walk., Cat. Derm. Salt. Brit. Mus., i. 116 (1869).

Ceuthophilus maculatus Scudd. ! (pars), Bost. Journ. Nat. Hist.,
vii. 434 (1862); Pack., Rep. Nat. Hist. Me., 1862, 196; Smith,
Proc. Portl. Soc. Nat. Hist., i. 145 (1868); Pack., Guide Ins., 565
(1869) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 201 (1869) ; Id., Ibid.,
Suppl., V. 23 (1871) ; Smith, Rep. Conn. Bd. Agric, 1872, 359, 380;

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 69

Glov., Til. N. A. Ent., Orth., pi. 3, fig. 5 (1872) ; Scudd., Ilitchc,
Rep. Geol. N. II., i. 366 (1874); Prov., Nat. Canad., viii. 75, fig. 5
(1876) ; Putu., Proc. Dav. Acad. Sc, ii. 11 (1876) ; Bol., Ann. Soc.
Ent. France (o), x. 72 (1880) ; Ril., Stand. Nat. Hist., ii. 184, fig. '2o9
(1884); Bruu.?, Bull. Washb. Coll. i. 126 (1885); Caulf., Can. Ent.,
xviii. 212 (1886); Id., Rep. Ent. Soc. Ont., xviii. 63, 69 (1888);
Brunn., Monogr. Stenop., 63 (1888) ; Pack., Mem. Nat. Acad. Sc,
iv. 72, 116 (1888); Fern., Orth. New Engl., 19 (1888); Pack.,
Psyche, v. 198 (1889) ; Davis, Ent. Amer., v. 80 (1889) ; Smith,
Cat. Ins. N. Jers., 409 (1890); Charlt. ?, Ent. News, i. 64 (1890);
Cock.?, Can. Ent., xxii. 76 (1890); McNeill, Psyche, vi. 27 (1891);
Osb., Proc. Iowa Acad. Sc, i. ii. 119 (1892) ; Towns. ?, Ins. Life, vi.
58 (1893); Blatchl., Proc. Ind. Acad. Sc, 1892, 142-143 (1894);
Cock.?, Trans. Amer. Ent. Soc, xx. 336 (1894).

Phalangopsis lapidicola Uhl, Harr. Treat. Ins. luj. Veg., 155 (1862).

Ceuthophilus lapidicolus Brun. ! , Publ. Nebr. Acad. Sc, iii. 32
(1893).

Color and markings abnost precisely the same as in C. terrestris, so
that imperfect and immature specimens are exceedingly difficult to
separate ; but the darker markings in this species are as a rule darker
and cover the surface to a greater extent, and when the mediodorsal
stripe is present it is often broader and extends upon the meso- and
metanotum ; on the other hand, the maculation of the abdomen with
luteous is usually more striking in the present species (partly from
the darkness of the ground) and forms sometimes a tolerably regular
pattern, consisting on each joint of an anterior mediodorsal triangular
spot, a central subdorsal oblique dash, and posterior spots farther from
the middle line. The antennas are from two to three times as long as
the l)0(ly, and slender except at extreme base, and the legs are
moderately long. Fore femora no stouter than the middle femora, a
little more than a fourth longer than the pronotum and much less than
half as long as the hind femora, the inner carina with a long subapical
spine and occasionally an additional one. Middle femora with 0-2
spines besides a rather long subapical spine on the front carina, and
on the hind carina an occasional small spine besides a long genicular
spine. Hind femora of about the length of the body, three and a half
times as long as broad, about two and a third times as long as the fore
femora, moderately stout at base, the distal fifth subequal, with no
raised points on the upper or inner surface, the outer carina with
about thirteen unequal coarse spines, the longest hardly half as long as
the tibial spurs {$)ov with minute distant inconspicuous spinules ( 9 )>

70 PROCEEDINGS OF THE AMERICAN ACADEMY.

the itiuer carina with similar but uniform spinulation, none so large
as on the outer carina (J') or with a few minute spiuules on the
apical half (9 ), the intervening sulcus not very broad. Hind tibiae
feebly undulate in the basal half in the male, slender in both sexes, dis-
tinctly but not greatly longer than the femora, armed beneath with a
single preapical spine or occasionally with two minute unaligned
spines besides the apical pair ; spurs rudely opposite, the basal at the
end of the proximal third of the tibia, more than half as long again as
the tibial depth, set at an angle of about 40° with the tibia and divari-
cating 90-100°, their tips incurved; inner and outer middle calcaria
sube(|ual, more than twice as long as the others or as the spurs, and as
long as the first tarsal joint. Hind tarsi about two fifths as long as
the tibiae, the first joint shorter than the rest together, the second twice
as long as the third and with it longer than the fourth. Cerci stout
in the proximal half, tapering beyond, about two thirds as long as the
femoral breadth. Ovipositor nearly two thirds as long as the hind
femora, shaped and armed as in G. terrestris.

Length of body, ^ 14 mm., 9 16? mm.; pronotum, ^ 5 mm.,
9 5.1 mm. ; fore femora, ^ 6.6 mm., 9 6.7 mm. ; hind femora,
$ 15.25 mm., 9 16 mm.; hind tibia?, ^ 16.25 mm., 9 17 mm.;
ovipositor, 10 mm.

18 ^,9 9. Montreal, Canada, Caulfield ; valleys of the White
Mts., N. H.; Chateaugay Lake, Adirondacks, N. Y., 2,000', F. C.
Bowditch ; Itliaca, N. Y., Pearce, Pettit (Corn. Univ.) ; Michigan,
J. G. Jack ; Cape Elizabeth, Me., E. S. Morse ; Blue Hills, Milton,
Mass., S. Henshaw; Mass., F. G. Sanborn; Conn., E. Norton;
New York ; S. Orange, N. J. : Moline, 111., McNeill ? Vigo Co., Ind.,
W. S. Blatchley; Iowa City, Iowa, Shimek (Bruner). I have also
seen specimens in the Museum of Comparative Zoology from Norway
(Smith), Gorham, Cape Elizabeth (Morse), Maine, Vermont, Maiden
(Higgins), House Island (Cooke), Feltonville (Jilson) and Nahant,
Mass. In addition to the districts mentioned above it has been
reported (but may often have been erroneously taken for another
species) from Howe's Cave, N. Y. (Packard), Missouri (Brunner),
IMcPherson Co., Kansas and Nebraska (Bruner), and Colorado
(Charlton, Cockerell, Townsend).

31. Ceuthophilus tenebrarum, sp. nov.

Ceuthophilus latens McNeill !, Psyche, vi. 27 (1891).
Body glabrous, brownish or blackish fuscous, heavily marked with
luteo-castaneous, often more or less pallid, sometimes with a rufous

SCUDDER. —NORTH AMERICAN CEUTHOPHILI. 71

tiuge ; the markings consist of a mediodorsal stripe of varying w»dth
but usually rather broad on the pronotum, especially a little before
either bonier, generally reduced to a line on the abdomen, a large
lateral patch on either side of the pronotum. sometimes confined to the
inferior margin, sometimes extending half way to the mediodorsal Hue,
and a conspicuous and liberal sprinkling of roundish spots, generally
more or less elongated longitudinally, especially on the abdomen ; the
antennas are pale fuscous and the legs sordid luteous more or less
infuscated, the hind femoia with heavy fuscous scalariform markings,
leaving roundish dull luteous spots in the openings of the upper half.
The antennie are slender and apparently only about twice the length
of the body or a little more, and the legs short though slender, t'ore
femora of the same slenderness as the middle femora, much less than
half as long as the hind femora and a little more (cj) or a little
less (9) than a fourth longer than the pronotum, the inner carina with
1-2 small spines. Middle femora with 1-3 spines on the front carina,
the subapical the longest but not long, the hind carina with rarely
more than the moderately short genicular spine. Hind femora some-
what shorter than the body, about two and a half times longer than
the fore femora, moderately slender, being about three and a third
times as long as broad, fully the apical fourth subequal, the surface
with no raised spines, the outer carina with a few distant serrations
or recumbent spines on apical half ((?) or unarmed (9), the inner
carina similar to the outer, the intervening sulcus narrow. Hind
tibifB straight in both sexes, not a great deal longer than the femora,
armed beneath with a single subapical spine besides the apical pair ;
spurs subalternate, the basal at the end of the proximal third of the
tibia, scarcely if any longer than the tibial depth, set at an angle of 45°
with the tibia and divaricating about 110°, their tips incurved; inner
middle calcaria much longer than the outer, more than twice as long
as the others or as the spurs, and nearly as long as the first joint of
the tarsus. Hind tarsi fully two fifths as long as the tibiae, the first
joint almost as long as the rest together, the second twice as long as
the third and with it fully as long as the fourth. Cerci slender, taper-
ing regularly, three fourths as long as the femoral breadth. Ovipositor
as long as the fore femora, straight, the apical three fifths equal and
moderately slender, the apex a little upturned and subacute but not
very much produced, the teeth of the inner valves consisting of blunt
pointed crenations.

Length of body, ^ 13.5 mm., 9 12.5 mm. ; pronotum, J 3.75
mm., 9 3.8 mm. , fore femora, ^ 4.8 mm., 9 4.25 mm. ; hind femora.

72 PROCEEDINGS OP THE AMEEICAN ACADEMY.

^ LI. 75 mm., 9 10.25 mm. ; hiud tibife, S 12-5 mm., 9 10.6 mm.:
ovipositor, 4.25 mm.

7 c?, 4 9 . Port Byon, III., July 7 (McNeill) ; S. Illinois (Keuui-
cott) ; Lexington, Ky., May, June, August (S. Garman) ; Bee Spring,
Ky., June, Sanborn (Mus. Comp. Zool.); Beaufort, N. C, Shute
(Mus. Comp. Zool.). 2 S, 2 9, from Ohio are in the collection of
Riley (U. S. Nat. Mus.).

32. Ceuthophilus bicolor, sp. nov.

Body glabrous, luteo-testaceous, with a broad subdorsal blackish
fuscous baud on either side, leaving between them a broad bright stripe
the whole length of the body, next the stripe sharply delimited, later-
ally more or less broken, ragged and fading away, uan*ow on the pro-
notum where it is infringed upon by a large central luteous spot on
the sides, broader and profusely spotted with luteous posteriorly, the
lower portions of the sides almost wholly pallid luteous with cloudy
iufuscations, the extreme margin testaceous ; legs luteo-testaceous, the
hiud femora feebly marked with fuscous in a scalariform pattern and
tipped with fuscous. The antennae are slender and at least three times
as long as the body, and the legs slender and rather short. Fore
femora no stouter than the middle pair, much less thau half as long
as the hiud femora, a fifth as long again as the pronotum, the inner
carina with two or three spines, the preapical much longer than
the others. Middle femora with the front carina similarly armed
and the hind carina with one or two spines mesially situated besides
a long genicular spine. Hind femora as long as the body, two and
a half times longer than the fore femora, stout, tapering with great
regularity to the slightly enlarged genicular lobes, scarcely more than
three times as long as broad, the inner surface above beyond the
middle with a small cluster of raised points, the outer carina armed
on the stouter part of the femora with an open series of serrula-
tions, developing distally into spines, the last two much larger than
the others and half as long as the tibial spurs, followed by 3-4 slight
spines just before and on the genicular lobes, the inner carina
equally but inequidistaiitly and rather sparsely spinulate, the inter-
vening sulcus broad. Hind tibiae straight, slender, more than a tenth
longer than the femora, armed beneath with a single subapical spine
besides the apical pair ; spurs subalternate, the basal before the end of
the proximal third of the tibia, nearly or quite twice as long as the
tibial depth, set at an angle of about 50° with the tibia and divaricat-
ing about 1 10°, their tips incurved ; inner middle calcaria greatly

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 73

loiiiier than the outer, more than twice as long as the others or as the
spurs, and fully as long as the first tarsal joint. Hind tarsi barely
two fifths as long as the tibiiv;, the first joint as long as the rest together,
the second three times as long as the third and with it as long as the
fourth. Cerci not very slender, blunt tipped, about two thirds as
lonn as the femoral breadth.

Length of body, 11.5 mm.; antennae, (est.) 32+ mm.; pronotum,
3.75 mm.; fore femora, 4.5 mm.; hind femora, 11.5 mm.; hind tibise,
13 mm.

1 (J. Bee Spring, Ky., June 14, F. G. Sanborn (Mus. Comp.
Zool.).

33. Cbuthophilus nodulosus.

Ceuthophilus nodulosus Brunn., Monogr. Stenop., 64, fig. 33a (1888).

Luteo-castaneous, heavily marked with blackish fuscous especially
along the posterior borders of all the segments and the anterior border
of the pronotum, and the latter also flecked with it in an obscure
fashion upon the whole disk ; legs luteous, the hind femora almost
lacking the usual scalariform markings. The antennae are slender,
but are apparently less than twice the length of the body, the legs
short. Fore femora very slightly stouter than the middle femora,
slightly ((J) or no (9) longer than the pronotum and distinctly less
than half as long as the hind femora, the inner carina with a feeble
subapical spine, at least in the male. Middle femora generally with
3-4 small spines on the front carina, and on the hind carina 0-1 ( 9 )
or 3-8 {$) short spines besides a short genicular spine. Hind femora
pretty stout, a very brief apical portion equal, a little less than three
times as long as broad, considerably more than twice as long as the
fore femora, all the scalariform dark portions of the surface, especially
in the male, scabrous with raised points, which are also clustered about
the upper portion of the inner side just beyond the middle, the outer
carina elevated, with three or four inequal and irregularly distant
large and rather coarse more or less arcuate spines, the longest nearly
or quite as long as the tibial depth, placed in the middle half, besides
a few minor spines beyond them ( J*) or with 4-5 small distant spines,
most of them in the constricted part of the femora (9), the inner
carina with a series of closer but in no way crowded smaller and uni-
form spinules, subobsolete in the female, the intervening sulcus moderate
in breadth. Hind tibiae strongly bent or bowed near the middle and
subsinuate, on the middle of the proximal half compressed to form a
triangular denticle on the under surface, from which a regular curve

74 PROCEEDINGS OP THE AMERICAN ACADEMY.

sweeps to an inferior slight spiniferous swelling just before the middle
of the distal half ((?), shorter than the femora in both sexes, armed
beneath on the distal half with a series of about three recumbent
spines (in the ^ arising from slight elevations) besides the apical pair;
spurs subopposite, the basal well beyond the end of the distal third of
the tibia, hardly more than half as long as the tibial depth, set at an
angle of about 45° with the tibia and divaricating about as much;
inner middle calcaria somewhat longer than the outer, twice as long
as the others or as the spurs but much shorter than the first tarsal
joint. Hind tarsi less than two fifths the length of the tibiae, the first
joint nearly as long as the rest together, the second fully twice as long
as the third and with it as long as the fourth. Cerci very short, not
very slender, rapidly tapering, hardly more than half as long as the
femoral breadth ( 9 ) or developed basally as a single stout sub-
clavate apically upturned blunt joint, surmounted by a brief conical
multiarticulate appendage, the only portion which surpasses the supra-
anal plate (S)- Ovipositor brief and slight, no longer than the fore
femora, tapering in proximal, equal in distal half, the apex and arma-
ture as in G. inquinatus.

Length of body, $ 13.5 mm., 9 12 mm.; pronotum, J 4 mm.,
9 3.8 mm.; fore femora, ^ 4.5 mm., 9 3.6 mm.; hind femora,
^ 10.5 mm., 9 8.5 mm. ; hind tibiae, $ 9.6 mm., 9 8 mm. ; oviposi-
tor, 3.5 mm.

2 ^,2 9' West Point, Nebr. ; McPherson Co., Kans., Run^strom,
all from L. Bruner. Subsequently to the description of the above
I received from the U. S. National Museum 3 (J, 1 9? from Dallas,
Texas, of considerably larger size, like that described by Brunner,
also from Texas.

34. Ceuthophilus valgus, sp. nov.

Dark luteo-testaceous, more or less infuscated especially along the
hind borders of all the segments and the front border of the pronotum ;
occasionally a few indistinct luteous dots occur in a transverse series
on the abdominal segments, but most of the varied markings are con-
fined to the pronotum, where they are not pronounced and consist of
a dull luteous mediodorsal stripe and vague and irregular streaks or
clouds of luteous upon either side, more or less extensive ; the legs
are generally lighter than the body, but are more or less infuscated
beyond the base of the femora, the hind pair of which scarcely show
any scalariform markings. The antennae are not very slender, two to
three times as long as the body, and the legs are moderately long and

SCUDDER. NORTH AMERICAN CEUTIIUPHILI. 75

slender. Fore tetnora no stouter than the middle femora, less than a
quarter longer than the pronotum and somewhat less than half as long
as the hind femora, the inner carina with a single minute spine, at least
in the cT, besides a distinct preapical spine. Middle femora with a
single spine (9) or 2-4 spines (J") on the front carina, and on the
hind carina about four spines (generally fewer in the ?) besides a
short genicular spine. Hind femora nearly as long as the body,
distinctly more than twice as long as the fore femora, not very stout,
being about three and a quarter times longer than broad, glabrous, the
surface with no raised points, the outer carina elevated, armed with
about ten unequal and inequally separated spines, the largest stouter
than and about as long as the tibial spurs (J*) or scarcely elevated and
unarmed (9), the inner carina with distant raised thick points, occa-
sionally becoming minute spines (c^) or unarmed (9), the interven-
ing sulcus narrow. Hind tibije as long as the femora, straight in the
9 , sti'ongly bowed on proximal half in the $ (unless immature),
armed beneath with a single preapical spine besides the apical pair ;
spurs subopposite, the basal at about the end of the proximal third of
the tibia, scarcely if at all longer than the tibial depth, set at an angle
of about 50° with the tibia and divaricating about 100°, their tips in-
curved ; inner middle calcaria about a third longer than the outer,
twice as long as the others or as the spurs, but hardly more than half
as long as the first tarsal joint. Hind tarsi less than half as long as
the tibite, the first joint nearly as long as the rest together, the second
more than twice as long as the third and with it fully as long as the
fourth. Cerci stout, tapering, pointed, hardly more than half as long
as the femoral breadth. Ovipositor almost as long as the hind tibiae,
rather slender, equal from close to the base to near the tip, gently
arcuate, the tip barely upturned and pointed at an angle of not less
than 50°, the inner valves scarcely armed, the teeth being barely in-
dicated by a slight crenulation.

Length of body, J 13 mm., 9 10 mm, ; pronotum, $ 4.7 mm.,
9 3.65 mm. ; fore femora, $ 5.5 mm., 9 4.5 mm. ; hind femora and
tibife, each, $ 12.9 mm., 9 9.4 mm.; ovipositor, 8.5 mm.

6 c? , 3 9 . Colorado 7-8,000', H. K. Morrison ; South Park, Col-
orado, 8-10,000', August 11-16, S. H. Scudder. I also place here an
immature 9 taken by me at Pueblo, Colorado, 4.700', August 30-31.
Since the description was written, Mr. L. Bruner has sent me \ $ ,
2 9, from Brush Creek, Custer Co., Colorado, 10,000'. and Granite,
Colorado.

76 PROCEEDINGS OF THE AMERICAN ACADEMY.

35. Ceuthophilus divergens.

Ceuthophilus divergens Scudd.!, Bost. Journ. Nat. Hist., vii. 436
(1862) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 201 (1869) ; Thorn. ?,
Proc. Acad. Nat. Sc. Philad., 1870, 77 ; Id. r, Ann. Rep. U. S. Geol.
Geogr. Surv. Terr., ii. 265, 269 (1871) ; Id.?, Bull. U. S. Geol. Geogr.
Surv. Terr., iv. 485 (1878) ; Ril., Stand. Nat. Hist., ii. 184 (1884);
Blatchl., Proc. lud. Acad. Sc, 1892, 153 (1894).

Body subglabrous, dark blackish fuscous above, passing on the sides
into rufo-testaceous more or less tinged with luteous, and with blotches
and irregular spots of the same above ; especially to be noted are a
mediodorsal rufo-luteous interrupted stripe and on the sides of the
pronotum a large spot of the same much vermiculate with fuscous ;
the abdomen is also more or less spotted with the same ; the legs are
dingy luteous, all the femora tipped with fuscous and the hind femora
heavily marked with fuscous in a scalariform pattern. The antennae
are moderately slender and three or four times as long as the body, and
the legs are rather long and slender, with jjrominent spines. Fore
femora no stouter, but in the male slightly shorter, than the middle
femora, much less than half as long as the hind femora and but little
longer than the pronotum, the inner carina with 2-3 spines, the sub-
apical long. Middle femora with 2-3 spines on the front carina, the
subapical longest, and on the hind carina two small spines besides a
long genicular spine. Hind femora about as long as the body, about
two and a half times longer than the fore femora, moderately stout
particularly in the male, where they are less than three and a half times
while in the female they are nearly four times as long as broad, the
middle of the inner surface in the male with a considerable cluster of
raised points on the upper half, the outer carina with about ten unequal
stout teeth the largest shorter but stouter than the tibial spurs (J* ) or
apically with a series of subdued serrulations (9 ), the inner carina in
9 armed like the outer carina but very inconspicuously, in the $ as in
the 9 but more conspicuously, the intervening carina narrow. Hind
tibia3 scarcely longer than the femora, straight in both sexes, slender,
distinctly though feebly constricted at the base, faintly enlarging above
toward the apex, armed beneath with a single subapical spine besides
the apical pair ; spurs subalternate, the basal at the end of the proximal
fourtli of the tibia, nearly or quite twice as long as the tibial depth, set
at an angle of about 70° with the tibia and divaricating from 130° to
180°, their tips incurved; inner middle calcaria much longer than the
outer, fully twice as long as the othei's or as the spurs, and as long as

SCUDDEll. — NORTH AMERICAN CEUTHOPHILT. 77

the first tarsal joint in the S, scarcely so long in the 9. Hind tarsi
less than half as long as the hiiul tibi;e, the first joint almost equalling
the rest together, the second much more than twice as long as the
third and with it about as long as the fourth. Cerci rather stout and
short, hardly exceeding in length half the femoral breadth. Ovipositor
nearly straight and short, shorter than the fore femora, the basal half
tapering, the apical half slender and equal, the tip more than usually
upturned and produced to a very acuminate point, the teeth of the
inner valves long, aculeate, arcuate.

Length of body, (J 1"2 mm., 9 13 mm. ; antennse, (est.) ^ 40 mm.,
9 48 mm. ; pronotum, ^f 4.5 mm., 9 5 mm. ; fore femora, ^ 5.4 mm.,
9 5.25 mm.; hind femora, ^ 13.5 mm., 9 12.75 mm.; hind tibiae,
(J 13.75 mm., 9 13 mm. ; ovipositor, 4.75 mm.

1 (J, 2 9. Nebraska, A. Agassiz (Mus. Comp. Zool.). Thomas
reports it from several localities in Colorado, Wyoming, Dakota, and
Montana, but it is quite as likely as not that some other species was
mistaken for it. The one reported by Osborn and Bruner from Iowa
and Nebraska is the one here described as C brunerl.

36. Ceuthophilus occdltus, sp. nov.

Body castaneous, more or less and irregularly blotched above with
feeble fuscous markings, most conspicuous on the pronotum and absent
from a narrow irregular and sometimes broken median stripe of the
ground color, which does not extend upon the abdomen ; abdomen
obscured with fuscous on the posterior margins of the segments. Legs
luteo-castaneous, the outside of the hind femora with the usual mark-
ings nearly obsolete. Antennas very long and slender, the legs
moderately long. Fore femora a little stouter than the middle femora,
about a sixth longer than the pronotum, and half or less than half as
long as the hind femora, the inner carina armed with a long preapical
spine and sometimes with another short one. Middle femora with a
long preapical spine on the front carina, sometimes accompanied in
the 9 hy 1-2 others, the hind carina with a long genicular spine
accompanied by 2-3 spines in the $. Hind femora of about the
length of the body in the (J, about twice (9) or distinctly more than
twice ((^) as long as the fore femora, rather slender, being nearly
four times as long as broad, without conspicuous raised points on the
surface, the outer carina elevated, with 5-6 distant spinules, the largest
very small (^) or not elevated, vpith many minute serrulations on the
apical half (9 )> the inner carina with numerous delicate spinules (1^) or
similar to the other carina (9). Hind tibiiB straight, distinctly longer

78 PROCEEDINGS OP THE AMERICAN ACADEMY.

than the femora, beneath with a single preapical spine besides the
apical pair ; spurs subopposite, the basal before the end of the proximal
fourth of the tibifs, long and delicate, being nearly twice as long as
the tibial depth, set at an angle of about 45° with each other and
divaricating about 110°, their tips incurved. Inner middle calcaria a
little longer than the outer, twice as long as the others and nearly
twice as long as the spurs, as long as the first tarsal joint. Hind tarsi
two fifths as long as the tibite, the first joint as long as the others
together, the fourth about equalling the second and third together.
Cerci pretty stout at base, tapering throughout, pointed, longer than
the femoral breadth. Ovipositor nearly two thirds as long as the hind
femora, pretty stout at base, the distal two thirds equal and rather
slender, the apex produced to a fine spinous point and the teeth of the
inner valves prominent and sharp, the jjroximal subdenticulate, the
others acicular and arcuate.

Length of body, J* 11 mm., 9 12 mm.; antennae, (est.) ^ 30 mm.,
9 25 mm. ; pronotum, ^ 4 ram., 9 3.75 mm. ; fore femora, J 4.7
mm., 9 4.5 mm.; hind femora, ^ 10.5 mm., 9 8.5 mm.; hind
tibige, ^ 11.5 mm., 9 9 mm.; ovipositor, 5.25 mm.

1 <J, 2 9. Georgia, Morrison.

37. Ceuthophilus alpinus, sp. nov.

Luteo-testaceous, traversed by distinct and rather broad fuscous
bands at the incisures of all the segments (about equally on the
anterior and posterior margins) which fade out more or less on the
lower portion of the sides ; pronotum with two broad subdorsal longi-
tudinal fuscous bars, extending across at least the anterior half of the
segment, leaving between them a slender mediodorsal luteous stripe ;
legs luteo-testaceous, scarcely at all iufuscated excepting on the hind
femora which sometimes show coarse and obscure scalariform mark-
ings. The antennae are moderately slender and probably do not twice
exceed the length of the body, and the legs are short. Fore femora
scarcely if at all stouter than the middle femora, but very little longer
than the pronotum, about half as long as the hind femora, the inner
carina with a subapical spine only. Middle femora armed with 1-2
(9) or 3-4 ((J) spinules on the front carina, and on the hind carina
with 1-2 spinules besides a sl)ort genicular spine. Hind femora very
much shorter than the body, twice as long as the fore femora, moder-
ately stout, being scarcely more than three times as long as broad, and
the enlarged portion long, the surface with exceedingly few scattered
raised points on the upper half beyond the middle, the outer carina

SCUDDER. — NORTH AMERICAN CEUTHOPHILl. 79

uniformly and rather finely serrulate, more finely in the 9 than in the
$, the inner carina with similar but finer and less frequent serrulations
or spinules, the intervening sulcus narrow. Hind tibiae as long as
the femora, straight in both sexes, armed beneath with two distant
median spines besides the apical pair; spurs opposite for the most part,
the basal at the end of the proximal third of the tibia, no longer than
the tibial depth, set at an angle of 45° to the tibia, and divaricating
about 60°, their tips incurved ; inner middle calcaria of about the same
length as the outer, less than twice as long as the others or as the
spurs, and fully two thirds as long as the first tarsal joint. Hind tarsi
almost half as long as the tibiae, the first joint distinctly shorter than
the rest together, the second twice as long as the third, and with it as
long as the fourth. Cerci stout on the basal half, tapering beyond,
shorter than the femoral breadth. Ovipositor stout at extreme base,
suddenly narrowing to a slender almost straight blade, nearly two
thirds as long as the hind tibiae, the teeth of the inner blades aculeate,
arcuate, and long.

Length of body, $ 13 mm., 9 12.5 mm.; pronotum, c? 3.9 mm.,
9 3.4 mm. ; fore femora, $ 4.4 mm., 9 3.8 mm. ; hind femora and
tibias, each, ^ 9 mm., 9 7.6 mm. ; ovipositor, 4.85 mm.

2 ^, 2 9. South Park, Colorado, 8-10,000', Aug. 11-16, S.'H.
Scudder; Mt. Lincoln, Colorado, 11-13,000', above timber, Aug. 13,
S. H. Scudder.

38. Cedthophilus bruneri, sp. nov.

CeutJiophihis divergens Osb., Proc. Iowa Acad. So., i., li. 119 (1892) ;
Brun.! (pars), Publ. Nebr. Acad. Sc, iii. 32 (1893).

Obscure brownish fuscous, with luteous markings which are very
dull and inconspicuous except in the bordering of the inferior margins
of the thoracic segments ; they are mostly found in large blotches of
very irregular form on the sides of the pronotum and in smaller lateral
and dorsal anterior spots on the other segments, sometimes confluent
and the lateral often crossing the abdominal segments ; there is some-
times an interrupted mediodorsal thread ; legs luteous, much infuscated
especially on either side of the femoro-tibial articulation, the hind
femora very broadly marked with blackish fuscous in a scalariform
pattern. The antennae are slender and about three times as long as
the body, and the legs slender but not very long. Fore femora no
stouter than the middle pair, much less than half as long as the hind
femora and only about a sixth longer than the pronotum, the inner
carina with a long preapical spine sometimes accompanied by a shorter

80 PROCEEDINGS OF THE AMERICAN ACADEMY.

one. Middle femora with 2-3 spines, the preapical long on the front
carina, the hind carina with a very long genicular spine and sometimes
an additional shorter one. Hind femora considerably more than twice
as long as the fore femora, about as long as the body, the upper margin
more arcuate than the lower moderately slender, about three and a
quarter times longer than broad, less than the apical fourth subequal,
the surface with no raised points, the outer carina with two or three
very feeble distant serrulations in the apical third ( c? ) or unarmed
(9), the inner carina with distant raised points, the intervening sulcus
narrow. Hind tibia3 straight in both sexes, very slender, slightly
longer than the femora, armed beneath with 1-2 median spines besides
the apical pair ; spurs subopposite, the basal at the end of the proximal
fourth of the tibia or a little beyond it, usually fully twice as long as
the tibial depth, set at an angle of about 60° with the tibia and
divaricating about 130° (rather less in the 9), their tips incurved;
inner middle calcaria considerably longer than the outer, more than
twice as long as the others, about twice as long as the spurs and a
little longer than the first joint of the tarsi. Hind tarsi more than
two fifths as long as the tibije, the first joint as long as the others
combined, the second more than twice as long as the third and with it
as long as the fourth. Cerci tapering throughout, but especially in the
basal half, nearly as long as the femoral breadth. Ovipositor fully
two thirds as long as the hind femora, straight, tapering strongly in
basal half, beyond equal and slender, the tip strongly upcurved and
very acute, the teeth aculeate, arcuate.

Length of body, J* 11 mm., 9 14 mm.; pronotum, ^ 3.9 mm.,
9 4.25 ram. ; fore femora, ^ 4.5 mm., 9 5 mm. ; hind femora, ^ 10.5
mm., 9 11 mm.; hind tibiae, J 11 mm., 9 11.4 ram.; ovipositor,
7.5 mm.

4 (^,5 9 • Lincoln, West Point, and Chadron, Dawes Co., Nebr.
(L. Bruner, Corn. Univ.) ; Sedgwick Co., Kans., S. S. Tucker (Univ.
Kans., through L. Bruner) ; Gulf Coast of Texas, S. F. Aaron. Os-
born also reports it from Iowa.

Mr. Bruner has also sent me from Carrizo Springs, Texas, two
males of a much larger size, in which the body is almost com-
pletely infuscated, so that the markings of the thorax cannot or can
scarcely be seen. The following measurements are taken from one of
them: length of body, 16.5 mm.; pronotum, 5,5 mm.; fore femora,
6.9 rara. ; hind feraoi'a, 15.5 mm. ; hind tibiae, 16.5 mm.

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 81

39. Ceuthophilus agassizif.

Rhaphidopliora agassizii Scudd.!, Proc. Bost. Soc. Nat. Hist., viii.
11 (1861).

Ceuthophilus agassizii Scudd.!, Bost. Journ. Nat. Hist., vii. 439
(1862) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 202 (1869) ; Brunu.,
Monogr. Stenop., 65 (1888).

Ceuthophilus zonarius Walk., Cat. Derm. Salt. Brit. Mus., i. 203
(1869).

Body luteous, more or less infuscated iu irregular patches which
especially form broad bands on the posterior margins of the segments
and leave the pronotum irregularly blotched, the fuscous portions
occupying the anterior and posterior and usually also the lateral mai'-
gins, sometimes broken along the middle line, and running backward
from the anterior margins in a pair of large subdorsal stripes, the
fuscous portions often dotted with distinct luteous dots. The hind
femora are marked in the usual compound scalariform manner with
tuscous, which unites distally in two elongate patches on the lower half
of the outer surface. Antennne more than twice as long as the body,
not very slender. Legs moderately long. Fore femora distinctly
broader than the middle femora, a tiftli longer than the pronotum, iind
at least in the ^ considerably less than half as lono- as the hind
femora, the inner carina with a preapical spine, and at least in the ^
with 3 or 4 other unequal spines. Middle femora with 4-5 unequal
spines on the front carina besides a preapical spine, and on the hind
carina numerous unequal spines, especially in the male, besides a
rather long genicular spine. Hind femora as long as the body, stout,
the apical fifth subequal, about three times as long as broad, with
scattered raised points on the distal half, especially above, the outei*
carina with a tolerably uniform series of very short spines or serra-
tions, the inner carina with similar but finer serrations. Hind tibioe
of the same length as the femora or (^) scarcely longer, straight in
both sexes or feebly sinuate in old males, moderately stout, armed
beneath with 1-2 preapical spines besides the apical pair ; spurs sub-
opposite, about the length of the tibial depth, set at an angle of 35-40°
with the tibia and divaricating about 80°, their tips incurved ; inner
middle calcaria a little longer than the outer, fully half as long again
as the others or as the spurs, but much shorter than the first tarsal
joint. Hind tarsi about two fifths the length of the hind tibige, the first
joint about as long as the rest together, the second twice as long as
the third and with it shorter than the fourth. Cerci tapering regu-

VOI-. XXX. (n. s. xxh.) 6

82 PROCEEDINGS OF THE AMERICAN ACADEMY.

larly, from a half to two thirds as long as the femoral breadth. Ovi-
positor fully tuo thirds as long as the hind femora, rather slender and
equal in the distal half, the distal teeth of the inner valves long,
slender, and arcuate, the proximal obsolescent.

Length of body, J 1 ' mm., 9 12.5 mm. ; antennae, ^ circ. 36 mm. ;
pronotum, S C.25 mm., 9 4.6 mm. ; fore femora, $ 7.5 mm., 9 6.2
mm.; hind femora, $ 18 mm., 9 I'^-S mm.; hind tibiae, $ 18.5 mm.,
9 12.5 mm.; ovipositor, 9.5 mm.

10 (J, 1 9- Islands in the Gulf of Georgia, between Vancouver
Isl. and the State of Washington, A. Agassiz ; Vancouver Isl., H. Ed-
wards ; Oregon; British Columbia, G. AV. Taylor in Bruner's coll.
Through misunderstanding Brunner von Wattenwyl has credited this
also to the State of Georgia.

40. Ceuthophilus mexicanus, sp. nov.

Pallid, probably in life luteous, heavily overlaid with dark fuscous
markings ; pronotum mostly fuscous, with a mediodorsal luteous
thread, expanding near anterior and posterior margins into a small
rhomboid spot and with a large posterior central luteous spot in the
middle of each side, the extreme inferior margin also luteous ; meso-
and metanotum with a large central luteous spot on either side often
reaching the border posteriorly and a posterior median similar spot,
the two sometimes confluent and often very irregular ; abdominal seg-
ments, when darkest, with a large luteous spot on each side and a
median anterior one, but the fuscous is often largely reduced ; legs
luteous, more or less infuscated, especially on the distal halves of
the fore and middle femora, the hind femora rather heavily marked
with fuscous in a scalariform pattern. Antennae very slender, at least
three times as long as the body, the legs slender and rather long.
Fore femora scarcely stouter than middle femora, a fourth longer than
the pronotum and half as long as the hind femora, the inner carina
with two spines, both long but especially the subapical. Middle femora
with 1-2 spines besides a very long subapical spine on the front carina,
and the hind carina with 1-2 spines besides a long genicular spine.
Hind femora as long as the body and twice as long as the fore femora,
rather stout at base but slender in the distal third, nearly thi'ee times
as long as broad, with a few feeble raised points on the distal half of the
extreme upper surface, the outer carina with 1-4 very small distant
spines on the apical half, the inner carina with 8-10 minute points,
the intervening sulcus narrow. Hind tibi® straight, slender, somewhat
longer than the femora, armed beneath with a single subapical s{)ine

SCUDDER. NOUTH AMERICAN CEUTHOPHILI. 83

besides the apical pair ; spurs subopposite, the basal at the end of the
proximal fourth of the tibia, considerably longer than the tibial depth,
set at an angle of 35-40° with tlie tibia and divaricating about 100°,
their tips incurved ; inner middle culcaria considerably longer than
the outer, more than twice as long as the others or as the spurs, and
nearly or quite as long as the first tarsal joint. Hind tarsi about
two fifths the length of" the tibiae, the first joint as long as the rest
together, the second fully twice as long as the third and with it rather
longer than the fourth. Cerci rather long and tapering, fully as
lonsr as the femoral breadth.

Length of body, 10 mm.; pronotum, 4 mm.; fore femora, 5 mm.;
hind femora, 9.8 mm. ; hind tibiie, 10.5 mm.

6 (J. San Pedro, Coliahuila, Mexico, May 20 ; San Lorenzo, Coha-
huila, Mexico, found in a cave among mummies, E. Palmer.

41. Ceuthophilus pallescens.

CeutJiophilus pallescetis Brun.!, Can. Ent., xxiii. 37-38 (1891) ;
Id.!, Publ. Nebr. Acad. Sc, iii. 32 (1893).

Very pallid luteous, marked with fuscous and blackish fuscous, the
latter in the posterior bordering of all the segments, the former in
obscure blotches on the pronotum and along its front margin, more
obscure in some specimens than in others ; a mediodorsal luteous
thread breaks most of the fuscous markings of the body ; the legs are
very pallid luteous, sometimes infuscated on the distal portions of the
femora and especially in scalariform markings, never deep, upon the
hind femora ; the spines of the legs are all dusky tipped ; eyes black.
Tlie antennie are slender and from twice to thrice the length of the
body, and the legs are rather long and slender. Fore femora scarcely
if any broader than the middle femora, about a fifth longer than the
pronotum and half as long as the hind femora, the inner carina with a
subapical spine sometimes accompanied by a shorter spine. Middle
femora with 4-5 delicate spines, the subapical longer than the others
on the front carina, and on the hind a similar series besides a not very
long genicular spine. Hind femora much shorter than the body, twice
as long as the fore femora, rather slender, being about three and a half
times longer than broad, tapering pretty regularly to the tip with no
genicular swelling, the surface with a few very scattered raised points
especially on the inner side and above beyond the middle, both carinae
minutely and rather distantly serrulate, the intervening sulcus slender.
Hind tibite straight in both sexes, considerably longer than the femora,
rather slender, apically armed beneath with a series of three recum-

84 PROCEEDINGS OF THE AMERICAN ACADEMY.

bent spines besides the apical pair ; spurs subopposite, the basal beyond
the end of the proximal third of the tibia, fully as long as the tibial
depth, set at an angle of about 50° with the tibia and divaricating
about 90°, feebly incurved at tip ; inner middle calcaria considerably
longer than the outer, twice as long as the others and nearly twice as
long as the spurs, but very much shorter than the first tarsal joint.
Hind tarsi fully two fifths the length of the tibia, the first joint fully
equal to the rest together, the second twice as long as the third and
with it as long as the fourth. Cerci slender and regularly tapering,
about as long as the femoral breadth. Ovipositor of exceptional
length, being nearly as long as the hind femora, very feebly arcuate,
slender throughout but especially beyond the proximal third, the tip
scarcely upturned more than the uniform arcuation and produced to
an angle of only about 40°, the teeth of the inner valves more distant
than usual, aculeate but not long, arcuate.

Length of body, S 8.5 mm., 9 18 mm. ; pronotum, ^ 3 mm., 9 5
mm. ; fore femora, ^ 3.5 mm., 9 6.1 mm. ; hind femora, ^ 7.5 mm.,
9 12 mm. ; hind tibia;. S 8 mm., 9 13.5 mm. ; ovipositor, 11.25 mm.

1 <^, 29. Hat Creek, Nebr., in wells; Pine Ridge, Nebr., Aug. 4,
under timber ; Hecla, Wyo. ; all from L. Bruner. The ^ from Pine
Ridge is rather immature.

42. Ceuthophilus sylvestris.

Ceuthophilus sylvestris Brun.!, Bull. Washb. Coll., i. 126-127
(18H5).

Nearly uniform mahogany brown, glabrous, very faintly and
broadly infuscated at the hinder margins of all tlie segments and on
the front margin of the pronotum, the lateral margins of the thoracic
segments very i'aintly bordered with obscure luteous ; legs uniformly of
a lighter tint than the body, the hind femora without scalariform mark-
ings. Antennae slender, more than twice as long as the body, the legs
moderately short. Fore femora no stouter than the middle femora,
scarceh'^ longer than the pronotum, half as long as the hind femora,
the inner carina with a short subapical spine. Middle femora with
only a single small spine or occasionally a second on either carina
besides the posterior genicular spine. Hind femora moderately stout,
tapering regularly to the tip with no pregenicular constriction or genic-
ular enlargement, fully three times as long as broad, twice as long as
the fore femora, with no raised points upon the surface, both carinas
(9) vfith the most delicate possible uniform and not crowded serrula-
tion, the intervening sulcus narrow. Hind tibiae considerably longer

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 85

tJiaii the femora, slender ; if armed beneath, so slightly as not to be
seen with an ordinary hand-glass ; spurs suboppo.-^ite, the basal at
about the end of the proximal third of the tibia, rather longer than
the tibial depth, set at an angle of about 35° with the tibia and divari-
cating about 70°, their tips scarcely incurved ; inner middle calcaria
considerably longer than the outer, twice as long as the others or as
the spurs, but shorter than the first tarsal joint. Hind tarsi almost
half as long as the tibiae, the first joint not so long as the others com-
bined, the second about twice as long as the third and with it shorter
than the fourth. Cerci slender, tapering, finely pointed, slightly
longer than the femoral breadth. Ovipositor straight, considerably
more than two thirds as long as the hind femora, gently tapering in
proximal, slender in distal half, the tip upturned to an excessively fine
point, the teeth produced, triangular, subaculeate.

Length of body, 9 7 mm. ; pronotum, 3 mm. ; fore femora, 3.1 mm. ;
hind femora, 6.1 mm. ; hind tibia?, 7 mm. ; ovipositor, 4.4 mm.

2 9 . Topeka, Kans., F. W. Cragin, through Lo Bruner.

43. Ceuthophilus crassus, sp. nov.

Specimens preserved after immersion in alcohol are dark fuscous
and very dull castaneous, the former prevailing, the latter seen on the
anterior borders of the abdominal segments in a median thoracic line,
irregular transverse bands on the middle of the meso- and metanotum,
and irregular blotches on the pronotum, mostly sublinear and very
angular ; the legs are prevailingly dusky except at base. Antenna?
imperfect in all specimens but probably twice as long as the body.
Legs rather short. Fore femora distinctly broader than the middle
femora, but little longer than the pronotum and much less than twice
as long as the hind femora, the inner carina with two small semi-
recumbent spines, one of them subapical. Middle femora with 3-4
small spines on the inner carina, one subapical, and on the hind carina
3-4 similar spines besides a small genicular spine. Hind femora con-
siderably more than twice as long as the fore femora, much shorter
than the body, stout, tapering to the tip with no pregenicular constric-
tion, scarcely more than two and a half times longer than broad, with
a very few scattered raised points on the upper surface apically, the
outer carina finely and sparsely serrulate throughout, more densely in
the (J than in the 9 , the inner carina similar, the intervening sulcus
narrow. Hind tibia? straight in both sexes, scarcely or no longer
than the femora, moderately stout, armed beneath with a single sub-
apical spine besides the apical pair ; spurs subopposite, the basal pair

86 PROCEEDINGS OF THE AMERICAN ACADEMY.

at the end of the proximal fourth of the tibia, not much longer than
the tibial depth, set at an angle of 30-40° with the tibia and divari-
cating about 60°, faintly incurved ; inner middle calcaria somewhat
longer than the outer, nearly twice as long as the others, twice as long
as the spurs, and as long as the first tarsal joint. Hind tarsi much
less than half as long as the tibiaj the first joint hardly equalling the
rest taken together, the second twice as long as the third and with
it a little shorter than the fourth. Cerci rather short and slender.
Ovipositor two thirds the length of the hind femora, rapidly tapering
at base, the distal half sleudei', the armature of the inner valves acicu-
lar, arcuate.

Length of body, ^ 13 mm., 9 17.5 mm.; pronotum, $ 4.5 mm., ?
5.6 mm. ; fore femora, ^ 5 mm., 9 6 mm. ; hind femora, ^ 11.25 mm,,
9 13.5 mm.; hind tibia?, ^J 11.5 mm., 9 13.5 mm.; ovipositor, 9 mm.

1 (?, 3 9- Locality unknown; probably from one of the South-
western States. It is a very robust species.

44. Ceuthophilus pinguis, sp. nov.

Of mingled fuscous and luteo-castaneous, sometimes one, sometimes
the other prevailing ; when it is the latter, the fuscous shows itself on
either side of the mediodorsal line in a series of subtriansular sub-
dorsal patches seated upon the posterior margin of the segments, much
larger on the thoracic than on the abdominal and partially or wholly
absent from some of the latter ; besides there is a series of lateral
blotches, just failing to reach the lower margins of the nota and more
extended on each segment anteriorly than posteriorly ; on the pro-
notum these two sets blend irregularly, so that here the darker colors
prevail ; the hind femora are more or less infuscated with the mark-
ings common to the genus, more or less distinct, the geniculations
laterally blackish. Antennae moderately stout. Legs not very elongate.
Fore femora basally somewhat stouter than the middle femora, con-
siderably less than half as long as the hind femora, about a fourth
longer than the pronotum, the inner carina with 2-3 spines, the sub-
apical and sometimes one or both the others pretty large. Middle
femora with the front carina as in the fore femora, the hind carina
with 1-2 spines near the middle besides a very long genicular spine.
Hind femora a little shorter than the body, considerably more than
twice as long as the fore femora, very stout and broad, being con-
siderably less than three times as long as broad, with a preapical
broad constriction, so that the distal fourth is subequal, the apical half
covered very sparsely except beneath with raised spinous points

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 87

of a reddish color, the outer carina armed with 3-4 very small subequal
irregularly distant spines, the inner with a dozen spinules irregularly
placed, the intervening sulcus not very broad. Hind tibia; straight,
about a tenth longer than the femora, armed beneath with a single
preapical spine besides the apical pair ; spurs subofiposite, the basal
at end of basal fourth of the tibia, fully twice as long as the tibial
df^pth, set at an angle of about 30° with the tibia and divaricating
scarcely more than 90°, their tips incurved distinctly; inner middle
calcaria twice or more than twice as long as the others or as the
spurs and as long as or longer than the first tarsal joint. Hind tarsi
fully two fifths the length of the tibise, the first joint almost or quite
as long as the rest together, the second more than twice as long as the
third and with it as long as the fourth. Cerci pretty stout at base,
tapering delicately, probably as long as the femoral breadth (broken in
all specimens seen).

Length of body, 16 mm. ; antenna?, 28+ mm. ; pronotum, 5.1 mm. ;
fore femora, 6.5 mm.; hind femora, 14.6 mm.; hind tibiiB, 16 mm.
One imperfect specimen is nearly half as large again.

4 (?, Eagle Pass, Texas, C. O. Schott.

45. Ceuthophilus inquinatus, sp. nov.

Ceuthophilus divergens Brun. ! (pars), Publ. Nebr. Acad. Sc, iii.
32 (1893).

Deep blackish fuscous, almost black, marked slenderly with luteous
which dorsally is tinged with reddish ; there is a mediodorsal line, ex-
panding near the postei'ior margin of the pronotum, on the middle of
the meso- and metanotum, and on the anterior margin of the abdominal
segments into small subtriangular or sublozenge-shaped patches, and
crossed near the anterior margin of the pronotum by a short transverse
bar sometimes forming a rhomb ; the sides of the segments and particu-
larly of the pronotum are marked in the middle by irregular luteous
blotches and the lateral margins of the thoracic segments are bordered
with the same more or less conspicuously ; the hind femora are dark
luteous with heavy scalariform markings of black and with longi-
tudinal streaks of blackish fuscous on either side of the submedian
clear stripe apically ; other femora luteous like the rest of the legs,
but more or less infuscated, especially apically. Antennae moderately
slender and probably long ; legs moderately long. Fore femora not
stouter than middle femora, less than a fourth longer than the pro-
notum and distinctly less than half as lonsf as the hind femora, the
inner carina with a very long subapical spine, sometimes accompanied by

88 PROCEEDINGS OF THE AMERICAN ACADEMY.

one or two others. Middle femora with the front carina armed as in the
fore femora, the hind carina the same but the apical spine genicular and
very long. Hind femora broad but not heavy, scarcely more tLan three
times as long as broad, tapering rather rapidly so that the distal fourth is
subt'qual. considerably more than twice as long as the fore femora, with
half a dozen raised points on the upper surface beyond the middle, the
outer carina with tour or five serrations next the narrowest portion of
the femora and before it half a dozen widely separated inequidistaut
spines, of which two or three just beyond the middle of the femora
are larger than the others and rather coarse, the longest no longer
than the tibial spurs (J*) or wholly unarmed except for two or three
inconspicuous pregenicular spinules (9), the inner carina with a series
of rather distant slight spinules, slighter and less frequent in the 9 than
in the ^, the intervening sulcus moderate. Hind tibiae straight in
both sexes or with the faintest possible arcuation in the ^, distinctly
though not greatly longer than the femora, armed beneath with a
single preapical spine, besides the apical pair; spurs subalternate,
the basal placed before the end of the proximal fourth of the tibia,
nearly or quite twice as long as the tibial depth, set at an angle
of about 50° with the tibia and divaricating about 110'^, their tips
feebly incurved ; inner middle calcaria but little longer than the
outer, considerably more than twice as long as the others, nearly
twice as long as the spurs, and slightly longer than the first tarsal
joint. Hind tarsi two fifths the length of the tibiae, the first joint
about as long as the rest together, the second twice as long as the
third and with it about the length of the fourth. Cerci rather stout
at base, tapering beyond, not so long as the femoral breadth. Ovi-
positor more than three fifths the length of the hind femora, straight,
tapering on proximal half or less, beyond moderately slender, the tip
upturned and produced to an extremely acute point, the teeth of the
inner valves aculeate and more or less arcuate.

Length of liody, ^ 13.5 mm., 9 13 mm.; pronotum, ^ 4.3 mm.,
9 5 mm.; fore femora, ^ 9 5.5 mm.; hind femora, (^ 12.25 mm.,
9 12.5 mm. ; hind tibisE, ^ 14 mm., 9 13 mm. ; ovipositor, 8 mm.

2 (J, 1 9- Fairbury, Nebr., Dr. Eaton; Lincoln, Nebr. ; both
through Mr. L. Bruner.

46. Ceuthophilus discolor, sp. nov.

Body blackish fuscous, almost black with luteous markings, as fol-
lows : a mediodorsal series of moderately large roundish spots, two
on the pronotum and one on each of the succeeding segments more or

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 89

less distiuctly connected by a luteous thi'ead ; on the middle of each
side of each segment a transverse dash, on the abdominal segments
more elongated than on the thoracic, and generally partly merged in
the mediodorsal spot, on tlie pionotum larger than elsewhere and ac-
companied by some ontlying dots ; also as an inferior margining of the
thoracic segments ; but all these markings may become so enlai-ged as to
make the surface prevailingly luteous ; the femora are fuscous, becom-
ing lutescent toward the base, on the hind pair as heavy scalarit'orm
markings, on the anterior pairs as slender stripes. The antennae are
brownish luteous, rather slender and apparently about three times
the length of the body, the legs rather short and slender. Fore
femora no stouter than the middle femora, less than a fourth longer
than the pronotum, much less than half as long as the hind femora,
the inner carina with a long subapical spine, sometimes accompanied
by another minute spine. Middle femora with a very long subapical
spine accompanied by a smaller one on the front carina, and the hind
carina with a long genicular spine only. Hind femora much shorter
than the body, but about two and a quarter times longer than the fore
femora, rather slender, being nearly three and a quarter times longer
than broad, the apical fourth subequal, the surface with a few raised
points scattered here and there beyond the middle of the upper
half of the femora both inside and outside, the outer carina with seven
or eight small unequal and inequidistant recumbent denticulations on
the apical half ((J) or apparently unarmed (9), the inner carina with
some very distant and very slight serrulations, the intervening sulcus
slender. Hind tibiae straight in both sexes, distinctly longer than the
femora, slender, armed beneath with a single preapical spine besides
the apical pair ; spurs subopposite, fully twice as long as the tibial
depth, set at an angle of about 35-45° with the tibia, and divaricating
about 90-100°, their tips considerably incurved ; inner middle calcaria
scarcely longer than the outer, more than twice as long as the others,
nearly twice as long as the spurs and about as long as the first tarsal
joint. Hind tarsi two fifths the length of the tibiae, the first joint fully
as long as the rest together, the second more than twice as long as the
third and with it nearly or quite as long as the fourth. Cerci rather
slender, tapering regularly, about as long as the femoral breadth.
Ovipositor more than two thirds as long as the hind femora, straight,
beyond the proximal third very slender, the tip upturned abruptly
and produced to an aculeate point, the teeth of the inner valves acu-
leate, pretty long and arcuate.

Length of body, ^ 10.5 mm., 9 12.5 mm. ; pronotum, ^ 3.5 mm.,

90 PROCEEDINGS OF THE AMERICAN ACADEMY.

9 3.75 mm.; fore femora, ^ 4.25 mm., ? 4.1 mm.; hind femora,
(^ 9 9.5 mm. ; hiud tibia?, ^ 9 10.5 mm. ; ovipositor, 6.75 mm.

1 (J, 1 9 . West Point, Nebr., L. Bruner ; Ellis, Kansas, Watson
(Mus. Comp. Zool.).

47. Ceuthophilus pallidus.

Ceuthophilus pallidus Thorn.!, Ann. Rep. U. S. Geol. Geogr. Surv.
Ten-., V. 434 (1872); Id., Proc. Dav. Acad. Nat. Sc, i. 264 (1876);
Glov., 111. N. A. Ent., Orth., pi. 18, fig. 18 (1874) ; Towns., Can. Ent.,
xxiv. 197-198 (1892) ; [Ril.], Ins. Life, i. 282-283 (1893); Towns.,
Ins. Life, vi. 58 (1893).

Body bright luteous, heavily marked with blackish fuscous ; on the
pronotum the markings are very irregular, but consist in the main of
the following: ,on either side of the front margin a large transverse
fuscous spot, which reaches neither the mediodorsal line nor the lateral
margin and is interrupted below by a roundish spot and above by the
incursion from the anterior margin of a short narrowing dash ; in
the middle of the dorsum a quadrate spot divided by a mediodorsal
luteous line into a pair of longitudinal bars, each connected anteriorly
with the before mentioned anterior spot, and leaving a luteous sub-
marginal anterior mediodorsal spot ; an infero-posterior black spot not
touchinjr the margin ; and a laterodorsal subtriangular spot on the
posterior margin ; on the succeeding thoracic segments, and on the
abdominal there is a series of large irregularly triangular laterodorsal
spots on the posterior margins, and another lateral series of roundish
or transverse spots generally not reaching any margin ; the legs are
luteous, the fore and middle femora more or less infuscated in longi-
tudinal streaks, the hind femora dull luteous with scalariform fuscous
markings. Antennge moderately slender, about twice the length of
the body, the legs moderately long. Fore femora scarcely stouter
than the middle femora, less than a fifth longer than the pronotum,
much less than half as long as the hind femora, the inner carina with
a tolerably long subapical spine sometimes accompanied by another
minute one. Middle femora with a long subapical spine on the front
carina, accompanied at least in the male by a couple of others smaller,
and on the hind carina one or two short spines at least in the male,
accompanied by a long genicular spine. Hind femora moderately
slender, fully three times as long as broad, two and a third times
longer than the fore femora, the surface with a few scattered raised
points on tlie distal half and especially along the upj^er edge of the
inner surface, the outer carina with 6-8 very unequal and inequidistant

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 91

spines, the longest about as long as the tibial spurs (<?) or wholly
unarmed or with a few raised points apically (9), the inner carina
very distantly and subequidistantly serrulate, finer in the 9 tban in
the (J, the intervening sulcus moderate. Hind tibia? straight in both
sexes, sliglitly longer than the femora, armed beneath with a single
subapical spine, besides the apical pair ; spurs subalternate, the basal
near the end of the proximal fourth of the tibia, about half as long
again as the tibial depth, set at a varying angle with the tibia, the
outer series at least in the ^ being directed outward, the inner series
both inward and posteriorly, divaricating about 120°, the tips incurved ;
inner middle calcaria considerably longer than the outer, more than
twice as long as the others or as the spurs, and nearly as long as the
first joint of the tarsi. Hind tarsi fully two fifths as long as the tibise,
the first joint fully as long as the remaining joints together, the second
three times as long as the third and with it as long as the fourth.
Cerci very slender and tapering in their distal half, stouter and sub-
equal in their proximal half, scarcely so long as the femoral breadth.
Ovipositor about half as long as the hind femora, straight, slender and
equal beyond the basal third, the tip produced, acuminate and up-
turned, the teeth long, aculeate, arcuate.

Length of body, (^ 15 mm., 9 12 mm. ; pronotum, ^ 9 4.5 mm. ;
fore femora, $ 5.25 mm., 9 5.1 mm. ; hind femora, S 12.2 mm.,
9 11.5 mm.; hind tibia?, ^ 13.1 mm., 9 12 mm.; ovipositor, 5.5 mm.

1 (^,39. Hot Springs, Dak. ; Denver, Col., Beales ; Las Cruces,
N. Mex., C. H. T. Townsend ; Silver City, N. Mex., C. H. Marsh ; —
all through L. Bruner. In the U. S. National Museum, mostly from
the Riley collection, are 2 <?, 5 9 •> from Laramie and Red ButtPS,Wyo.,
Custer, Colorado (Cockerell), Colorado, and New Mexico. Thomas
reported it from S. E. Colorado, Empire, CoL, and Red Buttes, Wyo. ;
Townsend from Colorado and New Mexico.

48, Ceuthopiiilus vinculatus, sp. nov.

Pale testaceous, nearly uniform, the posterior margins of all the seg-
ments infuscated, the apices of the hind femoral geniculations touched
with fuscous, and the pronotum more or lei^s blotched with pale fus-
cous, particularly with a pair of short submedian stripes on the anterior
half. Antenna? slender and nearly three times as long as the body,
the legs short but not stout. Fore femora distinctly stouter than
the middle femora, but very little longer than the pronotum, less than
half as long as the hind femora, the inner carina with a preapical
spine. Middle femora with 1-4 spines on the inner carina, and on the

92 PROCEEDINGS OF THE AMERICAN ACADEMY.

hind carina 1-2 spines besides the genicular spine. Hind femora
moderately stout, tapering regularly to the very tip with no pre-
genicular contraction, considerably more than twice as long as the fore
femora, less than three times as long as broad, glabrous, with no raised
points on any part, the outer carina pretty uniformly and finely serrate,
especially in apical half, the inner carina similarly but more sparsely
serrate, the intervening sulcus narrow except distally. Hind tibiae
straight in both sexes, slender, no wider in the middle than at base,
equal to or scarcely so long as the hind femora, armed beneath with
one or two preapical spines besides the apical pair ; spurs subopposite,
not so long as the tibial depth, set at an angle of about 45° with the
tibia and divaricating at even a less angle the extreme tips incurved;
inner middle calcaria scarcely longer than the outer, nearly twice as
long as the others or as the spurs, and much shorter than the first joint
of the tarsi. Cerci rather stout, tapering, about two thirds as long as
the femoral breadth. Ovipositor rather stout and uniformly ta2Dering
on the basal half, uniform and slender on the distal half, somewhat
longer than the fore femora, the extreme tip prolonged to a spine, the
teeth of the inner valves aciculate, arcuate.

Length of body, J" 12 mm., 9 13 mm.; antennae, $ (est.) 30 mm.;
pronotum, ^ 3.75 mm., 9 3.6 mm. ; fore femora, $ 4.2 mm., 9 4
mm.; hind femora, $ 9 mm., 9 7.65 mm.; hind tibiae, $ 8.5 mm.,
9 7.65 mm.; ovipositor, 5 mm.

4 $, \ 9. Nevada, H. Edwards; North Pacific R. R. Survey
below Lake .Jessie at Fort Benton, Dr. Suckley. Since description I
have received 2 <^, 5 9, from West Point, Lincoln, and Holt Co.,
Nebraska, from L. Bruner ; and have seen in the Museum of Compara-
tive Zoology at Cambridge a $ and 9 from Santa Barbara, Cal.
(Osten Sacken), which apparently belong here, although there are no
indications of any transverse banding. There are also 2 ^ in the
U. S. National Museum from California and Washington, both from
the Riley collection.

This species is closely allied to C. call foryii anus, but has slenderer
hind tibiaB and a longer ovipositor ; its general appearance is very
similar.

49. Ceuthophilus testaceus, sp. nov.

Light fusco-testaceous, with a faint mediodorsal luteous stripe and
obscurely dotted with luteous (sometimes obsolete), the lower sides of
the body growing gradually pallid luteous, and the pronotum more or less
mottled or clouded with fuscous ; legs testaceous, sometimes slightly

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 93

infuscated, the hind femora with feeblest possible fuscous scalariform
markings. AntenuiE very slender, two or three times as long as the
body, the legs short. Fore femora slightly broader than the middle
femora, a very little longer than the pronotum (relatively longer in the
9 than in the c?), a little more than half as long as the hind femora,
the inner carina with a rather long subapical spine and sometimes an
additional one. Middle femora with 2-4, usually three, subequal
spines on the front carina, and on the hind carina generally four spines
besides a moderately long genicular spine. Hind femora moderately
slender, tapering with almost exact regularity to the tip, somewhat
more than three times as long as broad, rather less than twice as long
as the fore femora, the surface just beyond the middle with very
scattered raised points on the whole upper half of the femora outside
and inside, both carinte distantly and delicately serrulate in both sexes,
the intervening sulcus narrow. Hind tibiae straight in both sexes, a
very little longer than the femora, at least in the male, slightly
enlarged apically as viewed from the side, armed beneath with a single
subapical spine besides the apical pair ; spurs subalteruate, the basal
set far before the end of the proximal fourth of the tibia, fully twice
as long as the tibial depth, set at an angle of 30-40° with the tibia and
divaricating at not above 90°, their extreme tips scarcely incurved ;
inner middle calcaria of about the same length as the outer, nearly
twice as long as the others and half as long again as the spurs, but
shorter than the first joint of the tarsi. Hind tarsi almost half as long
as the tibite, the first joint as long as the rest together, the second more
than twice as long as the third and with it equal to the fourth. Cerci
moderately slender, at least as long as the pronotum. Ovipositor
slender, straight, tapering at the base, equal from before the middle,
longer than the fore femora, the tip produced to an aculeate spine
projecting a little upward, the teeth of the inner valves pretty long,
aculeate, arcuate.

Length of body, c? 10 mm., 9 9 mm.; pronotum, $ 4 ram., 9 3.6
mm. ; fore femora, ^ 4.25 mm., 9 4.2 mm. ; hind femora, ^ 8 mm.,
9 7.7 mm. ; hind tibiee, ^ 8.5 mm., 9 7.8 mm. ; ovipositor, 4.5 mm.

2 (?, 2 9. West Point, Nebr. ; Sheridan, Wyo., C. Y. Smith, all
from L. Bruner ; St. Louis, Engelmann.

50. Ckuthophilus californianus.

Ceuthophihts califorjiianus Scudd.!, Bost. Journ. Nat. Hist., vii. 438
(1862) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 202 (1869).

Ceuthophihts castaneus Thom.!, Rep. U. S. Geol. Geogr. Surv. Terr.,

94 PROCEEDINGS OF THE AMERICAN ACADEMY.

V. 435 (1872) ; Glov., 111. N. A. Ent., Orth., pi. 18, fig. 17 (1874> ;
Fletch., Rep. Exp. Farms Can., 1888, 63 (1889).

Geuthophilus denticulatiis Scudd.!, Aun. Rep. Geogr. Surv. West
lOOth Mer., 1876, 279 (1877).

Varying from light to dark castaneous with very feeble markiogs,
excepting usually a greater or less degree of infuscation along the
posterior margins of all the segments and the anterior margin of the
pronotum ; the pronotum is also sometimes feebly enlivened with ver-
miculate fuliginous markings and not infrequently a faint luteous line
may be traced along the middle of the dorsum, often conspicuous on
the pronotum and always slender ; the legs are concolorous with the
body. The antenme are rather coarse, tapering throughout uniformly,
the eyes small, distinctly smaller than the autennal scrobes, the legs
short and stouter than usual. Fore femora distinctly stouter than the
middle femora, arched superiorly, about a fifth longer than the prono-
tum and slightly more than half as long as the hind femora, the inner
carina with a single subapical spine besides being minutely serrulate
throughout. Middle femora having a variable number of spines but
usually 3-4 on the front carina, and on the hind carina a variable but
generally considerable number of minute spines or serrations besides
a short genicular spine. Hind femora about two thirds as long as the
body ((J) or a little less than that (9)? almost twice as long as the
fore femora, moderately stout, regularly tapering to the very apex with
no pregenicular constriction, about three times as long as broad,
glabrous, with a few feeble distant raised points above just before the
geniculation, the outer carina uniformly and lather delicately serrulate
except at base, more feebly in the female than in the male, the inner
carina similarly but more delicately serrulate, the intervening sulcus
tolerably broad apically but not at base. Hind tibiiB of male straight,
unusually stout, on the upper surface twice as broad in the middle as at
base, of the same length as the femora, armed beneath with a single
preapical spine besides the apical pair ; spurs subopposite, about equal
to or a little longer than the tibial depth, set at an angle of about 45° to
the tibia and diverging at an angle of 60° or less with each other, their
tips incurved ; inner middle calcaria slightly longer than the outer,
half as long again as the other calcaria, twice as long as the spurs and
nearly as long as the first joint of the tarsus. Hind tarsi nearly half
as long as the tibise, the first joint nearly as long as the others com-
bined, the second twice as long as the third and with it not so long as
the fourth. Cerci rather stout, tapering throughout, not much longer
than half the femoral breadth. Ovipositor as long as the pronotum,

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 95

tapeiiiii; ill the basal half, beyond equal, not very slender and straight,
the tip strongly upcurved, the armature of the inuei- valves formed of
long, bluntly pointed, arcuate teeth.

Length of body, $ 19 mm., 9 16.25 mm. ; antenufe, $ (est.) 40
mm.; pronotum, $ b.'Ib mm., 9 4.75 mm.; fore femora, $ 6.75 mm.,
9 5.3 mm.; hind femora and tibias, each, $ 13 mm., 9 10.25 mui. ;
ovipositor 4.75 mm.

19 (J, 4 9. California (Edwards, Behrens, Crotch, Osten Sacken,
Palmer, Bruner), and in particular San Francisco, Pescadero, Gilroy,
Sonoma and Marin Counties, Santa Barbara, June, and San Ber-
nardino, Feb.; Beaver Dam, south of St. George, Utah, in the most
desert region, April 20-28, E. Palmer ; Ehrenberg, Colorado River,
Arizona, E. Palmer. It has also been reported from Vancouver Isl.
by Walker and Fletcher, In the U. S. National Museum, from the
Riley Collection, ai-e 4 ^ from California, Martinez, Cal. (Turner),
Los Angeles Co., Cal., and no locality (A. E. Bi ush) ; also a single $
with extraordinarily broad hind tibia3 from Alameda Co., Cal.

51. Ceuthophilus latipes, sp. nov.

Nearly uniform dull luteo-testaceous, with the usual fuscous slender
scalariform markings on the hind femora and short longitudinal fuscous
dashes on the posterior portions of the abdominal segments, repeated
vaguely as cloudy markings on the meso- and metanotum ; pronotum
slightly infuscated anteriorly and posteriorly. Antennse moderately
slender, the legs exceptionally short. Fore femora distinctly though
only sliglitly stouter than the middle femora, scarcely longer than the
pronotum and much less than half as long as the hind femora, the
inner carina unarmed. Middle femora with a single preapical spine
on the front carina, and on the hind carina a single small spine or none
besides a tolerably long genicular spine. Hind femora somewhat
shorter than the body, exceptionally broad, aboitt two and a half times
longer than broad, almost two and a half times longer than the fore
femora, strongly arcuate beneath, strongly and sharply constricted be-
fore the geniculation, with a very few raised point:* on the middle of the
inner side above, the outer carina closely serrulate, the inner carina dis-
tantly and finely denticulate, the intervening sulcus moderately broad
and uniform. Hind tibire with the extreme base briefly arcuate, beyond
straight, of the same length as the femora, slender, armed beneath
with a single delicate subapical spine (sometimes two) besides the
apical pair ; spurs opposite, the basal at the end of the proximal
third of the tibia, scarcely longer than the tibial breadth, set at an

96 PROCEEDINGS OF THE AMERICAN ACADEMY.

angle of about 60° with the tibia and divaricating about 80°, their tips
incurved ; inner middle calcaria considerably longer than the outer,
fully half as long again as the others or as the spurs, but much
shorter than the first joint of the tarsi. Hind tarsi considerably less
than half as long as the tibiae, the first joint hardly so long as the rest
together, the second fully twice as long as the third and with it as long
as the fourth. Cerci rather stout, tapering rapidly, somewhat shorter
than the breadth of the femora.

Length of body, 11 mm. ; antennae, IS-f- mm. ; pronotum, 3.25 mm. ;
fore femora, 3.65 mm. ; hind femora, 9 mm. ; hind tibiae, 9 mm.

1 ^ , Sierra de la Miguelito Mexico, E. Palmer.

52. Ceuthophilus pacificus.

Ceuthophilus pacijicus Thorn.. Ann. Rep. U. S. Geol. Surv. Terr., v.
436 (1872) ; Glov., 111. N. A. Ent., Orth., pi. 14, fig. 8 (1872).

Ceuthophilus unispinosus Brunn., Monogr. Stenop., 64 (1888).

Luteous, heavily irrorate with more or less confluent fuscous dots,
giving it, as Thomas well expresses it, a mossy appearance ; the
amount of confluence and accordingly of infuscation varies somewhat
in diflferent individuals, and is usually deepest on the pronotum, which
also often shows on either side a larger or smaller rufo-luteous patch
free from dots ; the hind femora retain the usual scalariform markings,
which are narrower than common. Antennae moderately stout at
base, very slender beyond, three or four times as long as the body.
Legs rather short. Fore femora scarcely stouter than the middle
femora, about a fourth longer than the pronotum and much less than
half as long as the hind femora, the iimer carina with a long subapical
spine. Middle femora with a long subapical spine on the front carina
sometimes accompanied by 1-2 shorter ones, the hind carina with a
single subapical spine besides the genicular spine. Hind femora
almost as long as the body, considerably more than twice as long as
the fore femora, very stout, apically tapering rapidly especially in the
^ , the distal fifth subequal, about two and a half times longer than
broad {^), tlie darker portions heavily scabrous with raised points,
besides a sparse sprinkling of the same on the apical half of the inner
surface, the outer carina minutely and bluntly bi- or tri-serrulate,
sometimes with a large preapical triangular dentiform spine serrulate
on its proximal edge ( (^ ) or unarmed (9), the inner carina similar
but in the distal half more coarsely uniserrulate, the serration stopping
abruptly before the apex with a distinct denticle, sometimes produced
to a stout triangular spine, serrulate on the proximal edge ((?) or with

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 97

a few feeble raised points or spinules on the apical half (9 ), the inter-
vening sulcus broad and V-sliaped. Hind tibiae strongly and sharply
bowecJ just before the middle, and on the proximal portion prominently
and roundly laminate beneath, by reason of the bow no longer than
the femora {^) or straight and simple, slightly longer than the fem-
ora ( 9 ) , armed beneath with a single preapical spine and an apical pair ;
spurs suboj)posite, the basal pair but little before the middle of the
tibia, about as long as the tibial depth, set at an angle of about 45°
with the tibia and divaricating but little more than that, the tips feebly
incurved ; inner middle calcaria slightly longer than the outer, more
than twice as long as the others or as the spurs, and as long as the first
tarsal joint. Hind tarsi about two fifths the length of the tibiae, the
first joint fully as long as the rest together, the second nearly three
times as long as the third and almost equal to the fourth. Cerci stout
in the basal half, beyond tapering, not more than half as long as the
femoral breadth, except in the female. Ovipositor gently tapering in
the basal half, slender beyond and finely pointed, scarcely upturned at
tip, about two thirds as long as the hind femora, the inner valves
feebly and bluntly serrulate apically with no apical hook.

Length of body, (^11.5 mm., 9 12-5 mm. ; pronotum, ^ 3.75 mm,,
9 4.1 mm. ; fore femora, S 4.4 mm., 9 5 mm.; hind femora, ^ 10
mm., 9 11'7 mm.; hind tibiae, ^ 10 mm., 9 12.25 mm.; ovipositor,
7.5 mm.

9 (?, 13 9. California, P. R. Uhler, J. Akhurst, H. Edwards,
Behrens ; Nevada, H. Edwards ; Mountains about Lake Tahoe, Cal.,
Oct., H. W. Henshaw in Capt. Wheeler's ExpL, 1876. The U. S.
National Museum also contains 5 (^,3 9, from Martinez, Cal., H. W.
Turner, and Los Angeles Co., Coquillet and others, mostly through
the collection of C. V. Riley.

The dorsal surface of the abdomen of the male of this species
somewhat resembles its next neighbor, C. hensliawi, in its sculpture,
the several segments being somewhat uniformly and rather closely
covered with blister-like elevations, largest and closest next the dorsal
line. Neither Thomas nor Brunner has noticed this peculiarity.

53. Ceuthophilus henshawi, sp. nov.

Mostly brownish fuscous above, but very minutely and abundantly
irrorate with luteous, increasingly so in passing down the sides, so that
the luteous prevails on the flanks ; the pronotum is also usually
marked with a broad prevailingly luteous mesial band, and the meso-
notum and raetanotum often but not always with a similar broad trans-

VOL. XXX. (n. S. XXII.) 7

98 PROCEEDINGS OF THE AMERICAN ACADEMY.

verse patch above ; occasionally in young individuals these thoracic
markings are reduced to a narrow mesial luteous stripe ; the hind fem-
ora are similarly speckled in place of the usual markings, though these
sometimes prevail. AntenniE very slender, probably about twice the
length of the body. Legs rather short and not stout. Fore femora
no stouter than the middle femora, about a fourth longer than the pro-
notum in the (^ , less than that in the 9 , and in both considerably less
than half the length of the hind femora, the inner carina with an ex-
ceedingly minute preapical spine. Middle femora with 2-3 minute
spines (sometimes obsolete in the 9 ) an the front carina, and the hind
carina similarly armed besides a small genicular spine. Hind femora
stout and broad, the lower margin straight by the posterior elevation
of the outer carina almost to the geniculation, when it terminates
abruptly and subacutely, as long as the body and about three times as
long as broad (^) or stout and broad, normal, about three fourths as
long as the body, with a few raised points clustered above the depressed
middle line of the femora ( 9 )? the outer carina closely serrulate through'
out ( J ) or simple and unarmed (9)- Hind tibiae abruptly and con-
siderably bent just beyond the base, but still nearly a tenth longer
than the femora, beyond the bend nearly straight {S )■, or straight
throughout and similarly longer than the femora (9), beneath with a
series of raised points and 1-2 recumbent subapical spines besides a
preapical and apical pair {^) or with a single subapical spine and an
apical pair ( 9 ) ; spurs subopposite, the basal pair situated not far
before the middle of the tibia, no longer than the tibial depth, set at
an angle of 45° with the tibia and divaricating about 90°, their tips
incurved ; inner middle calcaria considerably longer than the outer,
more than twice as long as the others or as the spurs, but shorter than
the first tarsal joint. Hind tarsi about one half the length of the
hind tibijB, very slender, the first joint not so long as the rest together,
the second fully twice as long as the third, and with it longer than the
fourth. Cerci greatly swollen in the basal half, beyond slight, the
whole about half as long as the femoral breadth. Ovipositor consider-
ably less than two thirds as long as the hind femora, tapering through-
out, the tip pointed but hardly upturned, the inner blades obsoletely
serrulate with 7-8 elevations.

Length of body, ^ 9 12 mm.; antennae, J" 9 15+ mm.; pro-
notum, (^ 4 mm., 9 3.5 mm. ; fore femora, ^ 5.2 mm., 9 4 ram. ; hind
femora, ^ 11.5 mm., 9 8.9 mm. ; hind tibise, $ 12.25 mm., 9 9.4 mm. ;
ovipositor, 5.25 mm.

6 (J, 2 9 . Sanzalito, Cal., California, Vancouver Isl., Washington,

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 99

II. K. Morrison, coll. S. Henshaw ; 1 (^,4 9, Oregon, and Placer,
Kern, and Los Angeles Counties, Cal., mostly from the Kiley collec-
tion (U. S. Nat. Mus.).

The male of this species is remarkable for the surface sculpture of
the dorsum of the abdomen, the first seven segments of which, but
particularly the second to the sixth inclusive, are densely covered with
minute strongly elevated tubercles, besides which on the anterior por-
tion of the lirst to the fifth segments and almost crossing the segment
is a mesial series of large slightly transverse tumid elevations, rounded
anteriorly, truncate posteriorly. I have seen nothing resembling it in
any other species, excepting to a less degree in its next neighbor,
G. pacijicus ; this and the peculiar characteristics of the outer hind
femoral carina make this a very striking species, which I take pleasure
in dedicating to my colleague, Mr. Samuel Henshaw.

54. Ceuthophilus devius, sp. nov.

Nearly uniform brownish testaceous, subglabrous, with very feeble
infuscated obscure blotches especially upon the pronotum, and a fine
mediodorsal luteous thread running the length of the body ; surface,
especially in $ and particularly on the thorax, very finely sub-
corrugate. The antennte are coarse at base (beyond broken), the
joints more or less thickened apically. The legs are rather short.
Fore femora much less than half the length of the body, hardly a fifth
longer than the pronotum, a little stouter than the middle femora and
a little less than half as long as the hind femora, the inner carina with
a preapical spine and a few (9) or many (<^) spinous points; the fore
tibiae with a single median spine on the inner side above, and beneath
with 3 (9) or 4 {$) pairs of stout spines. Middle femora with 5-6
(9) or H-9 (cj) spines on the fropt carina, the preapical small, at least
in the J", the hind carina similarly armed and with a small genicular
spine. Hind femora considerably shorter than the body, distinctly
more than twice the length of the fore femora, nearly straiglit above
in the $ where they are of nearly equal breadtli on the proximal two
thirds and are then somewhat abruptly emarginate beneath, less than
three and a half times as Ion" as broad in both sexes, the surface
glabrous with no raised points excepting sparsely scattered ones on
the upper surface in the middle half, the outer carina of both sexes
with equal slight denticulations on the constricted jaortion of the
femora, the inner carina with larger denticulations throughout (except
at base) much larger and more unequal in the ^, where the largest
are as long as the tibial spurs, the inferior sulcus narrow. Pliud tibiae

100 PROCEEDINGS OF THE AMERICAN ACADEMY.

straight, of the same length as the femora, stout, basally constricted,
beneath with a row of distant spines besides the apical pair ; spurs sub-
opposite, the basal pair at the end of the proximal third of the tibia,
scarcely longer than the tibial depth, set at an angle of 45° with the
tibia and divaricatina; 70-80° ; inner middle calcaria but little lonsfer
than the outer, about half as long again as the others or as the spurs,
shorter than the first joint of the tarsus. Hind tarsi about one third
as long as the tibiae, the first joint scarcely longer than the fourth and
less than twice as long as the second and third together, the sec-
ond but little longer than the third. Cerci rather slender, tapering
throughout, pointed, much shorter than the femoral breadth. Ovi-
positor nearly straight, scarcely longer than the fore femora, the basal
half tapering, the apical slender and equal, the tip pretty strongly
upcurved to a fine point, the teeth and especially the apical tooth very
long, slender, and arcuate.

Length of body, ^ 17 mm., 9 17 mm.; pronotum, $ 6.25 mm.,
9 5.5 mm. ; fore femora, $ 7.65 mm., 9 6.5 mm. ; hind femora and
hind tibiae, each, J' 16.25 mm., 9 13 mm. ; ovipositor, 7 ram.

\ S, \ 9. Explorations of the Upper Missouri and Yellowstone
under Lt. Warren, F. V. Hayden. I also find in the U. S. National
Museum from the Riley collection 1 (?, 2 9 , from Nebraska, the
Platte River, Nebr. (McCarthy), and Ft. Riley, Kans.

By the brevity of the first and second hind tarsal joints and the
slight enlargement of the fore tibiae in the male, this species approaches
the genus Phrixocnemis, but the normal development of the armature
of the hind tibiae forbids placing it there.

55. Ceuthophilus neomexicanus, sp. nov.

Dark testaceous or castaneous, glabrous, broadly but gradually
infuscated, especially above, on the posterior margins of all the seg-
ments, and on the anterior portion of the pronotum, which is otherwise
more or less slightly mottled, beneath and on the lower portions of the
sides invariably lighter and generally more nearly unicolorous. Legs
testaceous, the hind femora externally with a feeble median longi-
tudinal infuscation sometimes visible only on the distal half, where it
is often diffused and accompanied by feeble slender herring-bone
infuscations on either side, the hind tibial spines feebly infuscated at
apex. The antennae are not very slender and the legs short. Fore
femora distinctly stouter than the middle femora, but little longer than
the pronotum and less than half as long as the hind femora, the inner
carina with a subapical spine, sometimes accompanied at variable

SCUDDER. NORTH AMERICAN CliUTHOl'lULI. 101

distances by a smaller oue. Middle femora with 1-4 spines on the front

carina, most numerous in the 9 and the subapical the largest, the

hind carina similarly armed, but one spine genicular and the others as

numerous in the $ as in the ^. Hind femora much shorter than the

body, considerably more than twice as long as the fore femora, stout,

being in the ^ less than three times as long as broad, with hardly any

subapical constriction, that is, tajaering almost regularly to the apex,

the surface with no raised points, the outer carina pretty regularly and

rather minutely denticulate in the distal half or less, exclusive of the

geniculation {$), or minutely denticulate throughout (9)) the inner

carina similar to the outer, but in the $ more extensively denticulate

than the outer, the intervening sulcus narrow. Hind tibiae straight in

both sexes, distinctly shorter than the femora, the upper surface

rather broad in the $ and basally constricted, beneath with a longer

{$) or shorter (9) series of median spines, besides the apical pair;

spurs subopposite, the basal pair at the end of the proximal third of

the tibia (c^),"* about as long as the tibial depth {$), or two to three

times as long as the tibial depth (9), set at an angle of about 50°

(J) or 30° (9) with the tibia and divaricating as much, their tips

scarcely incurved ; inner middle calcaria not greatly longer than the

outer, less than half as long again as the others or as tlie {^) spurs,

nearly as long as the first tarsal joint. Hind tarsi much less than

two fifths as long as the tibia, the first joint not so long as the rest

together, the second but little longer than the third and with it a little

shorter than the fourth. Cerci rather slender and regularly tapering,

pointed, considerably shorter { ^) or considerably longer ( 9 ) than

the liind femoral breadth. Ovipositor about two thirds as long as the

hind femora, its upper margin feebly arcuate, the apical two thirds

subequal, the apex slightly upturned and very acuminate, the teeth of

the inner valves long, aciculate, the distal arcuate.

Length of body, $ \2 mm., 9 H.o mm, ; pronotum, $ 3.5 mm.,
9 3.25 mm.; fore femora, ^ 4 mm., 9 3.6 mm. ; hind femora, $ 8.75
mm., 9 7'.6 mm.; hind tibiae, $ 8.3 mm., 9 7.25 mm.; ovipositor,
5.2 mm.

4 ^, 1 9. Ft. Wingate, N. Mex. (Shufeldt), U. S. Nat. Mus.

The species is most nearly allied to G. devius, from which it difi\;rs
principally in its smaller size and the armature of the femora.

* The single 9 I have seen has four pairs of spurs on one tibia, the basal
pair at the end of the proximal fourtli of the tibia, while the other tibia has but
a single non-opposite pair in the middle of the tibia. It is further anomalous in
the excessive length of the spurs, in contrast to the $.

102 PROCEEDINGS OP THE AMERICAN ACADEMY.

The following species have not been seen by me.

56. Ceuthophilus scabripes.

Phalangopsis scabripes Hald., Proc. Acad. Nat. Sc, Philad., vi.
364 (1853) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 116 (1869).

Rhaphidophora scabripes Scudd., Proc. Bost. Soc. Nat. Hist., viii. 7
(1861).

Ceuthophilus scabripes Scudd., Bost. Journ. Nat. Hist., vii. 436
(1862) ; Walk., Cat. Derm. Salt. Brit. Mus., i. 201 (1869).

I cannot find any species which corresponds sufficiently with Halde-
man's description to apply this name to it. When we are better
acquainted with the forms occurring in the South, west of the
Alleghanies, we may be able accurately to fix it. It was described
from Selma, Alabama.

57. Ceuthophilus utahensis.

Ceuthophilus utahensis Thom., Proc. Dav. Acad. Nat. Sc, i. 264,
pi. 36, fig. 8 (1876).

None of the species I have seen can be referred to this. It seems to
resemble G. valgus. It comes from Mt. Nebo, Utah. (See Appendix.)

Note. — Ceuthophilus cnhaensis Walk. {Locusta Rliaphidophora cuhensis De
Haan), of Cuba, is a Plierterus, according to Bolivar and Brunner, belonging
to the Anostostomata.

PHRIXOCNEMIS (^bpt^d?, Kv-qiiij), Gen. nov.

Closely allied to Ceuthophilus, and having its general aspect, though
the legs are stouter than is commonly the case in that genus. Head
rather large, the vertex well rounded and deflexed, barely interrupted
from continuation into the frontal costa by the confluence of the
antennal scrobes. Eyes small, subpyriform, as large as the antennal
scrobes. Antennse as in Ceuthophilus. Palpi very small, the ante-
penultimate joint but little shorter than those on either side of it.
Pronotum sub-semicylindrical, the inferior margin of the descending
lateral lobes arcuate, the anterior and posterior angles equally or
almost equally rounded ; those of the meso- and metanotum similarly
rounded without the posterior obli(jue truncation common in Ceutho-
philus, or present in the slightest degree. Anterior coxjb compressed
and elevated to form a median denticle. Less short and rather stout.
Fore femora stout, or at least broad by compression. Middle femora
unarmed apically, or, when armed, only by an inferior and brief spine

SCUDDER. NORTH AMERICAN CRUTHOPHILI. 103

on the posterior side, the genicular lobes very small. Hind femora
very broad aud iucrassate, even the extremity stout, both inferior
carinte feebly denticulate, rarely vj^ith any conspicuous spines. Fore
tibite unarmed above, enlarged in the male ; middle tibiae armed above
with several pairs of spines besides those beneath ; hind tibiae stout, no
longer than hind femora, armed beneath with a single apical spine
besides the apical pair and above with lateral spines of two classes :
a larger series of generally long stout spines, longer than the calcaria,
and, especially in the 9 ? becoming longer and more crowded apically,
the 4-6 spines of one row not greatly divergent from those of the
other ; and minute denticulations occupying the interspaces, at least on
the proximal half of the tibia and the proximal free portion, but, at
least in the 9 , commonly absent from the distal half of the tibia ; the
three pairs of apical calcaria are not widely different in length. Hind
tarsi short, much less than half as long as the tibias, the first and fourth
joints, and the second and third joints, respectively subequal, the latter
together much shorter than either of the others. Ovipositor equal in
breadth throughout, when viewed laterally scarcely or not tapering in
the basal halfc

Table of the Species of Phrixocnemis.

Hind tibiffi of male strongly bowed ; distal hind tibial spurs of male as
widely separated as the proximal „ trv.culentus.

Hind tibiie of male straight or almost straight ; distal hind tibial spurs
of male much more closely approximated than the proximal.
Nearly uniform in coloring; vertex at tip, between upper bases
of antenna3, bituberculate ; four pairs of hind tibial spurs in

the male validus.

Distinctly particolored ; vertex at tip, between upper bases of
antennae, not bituberculate ; five pairs of hind tibial spurs in
the male , bellicosus.

Phrixocnemis truculentus, sp. nov.

Extreme apex of vertex with a slight depression. Body glabrous,
pale luteous, becoming rufo-luteous on the dorsum, where it is heavily
marked with blackish or blackish fuscous, particularly on the posterior
margins of the segments, the abdominal segments almost wholly
brownish fuscous with only an anterior luteous stripe, the meso- and
metanotum more rufo-luteous than blackish fuscous, and the pronotum
rufo-luteous above, luteous on the sides, with heavy fuscous markings,

104 PROCEEDINGS OP THE AMERICAN ACADEMY.

particularly an anterior bordering not reaching the lower margins and
thrusting back subdorsal stripes which are broadly separated by rufo-
luteous, all of which is sometimes very obscure ; legs luteous, the hind
femora externally tinged with rufo-fuliginous, in which fuscous scalari-
form markings moi'e or less feebly appear. The antennae are moder-
ately slender and the legs short. Fore femora considerably stouter
than the middle femora, as long as ((J) or less than a fifth longer than
( 9 ) the pronotum, and considerably less than half as long as the hind
femora, the inner carina with two or three feeble denticulations ; fore
tibiae subuUate, considerably stouter than the middle tibiae. Middle
femora with 1-3 short spines on the front carina, the hind carina with
4-0 very short but not very slight spines ($ ) or 1-2 feeble denticula-
tions (9), besides a very short inferior depending genicular sjjine, at
least in the ? . Hind femora much shorter than the body, but con-
siderably more than twice as long as the fore femora, stout and heavy,
being in the ^ about two and a half, in the 9 about two and three
quarters time as long as broad, with a rather strong pregenicular con-
striction beneath in the ^, the upper carinate margin of the inner
surface with a series of distant denticulations, the outer carina almost
angularly elevated in the middle, armed, mostly beyond the middle,
with a strong serration and just before the genicular lobes with a short
arcuate compressed rather blunt triangular spine, serrate on its
proximal edge, as long as tlie tibial depth, followed by a nearly similar
but smaller tooth upon the genicular lobe ( J" ) or with a post-median
spine much shorter than the shortest tibial spurs, another pregenicular
spine of smaller size, and between them 6-8 spinules (9), the inner
carina with a uniform series of raised points ($), or with small den-
ticulations throughout, similar to these of the outer carina but with
no large spines (9); the intervening sulcus moderate. Hind tibiae
strongly and pretty regularly bowed (i^) or faintly arcuate (9), tri-
quetral, deeper than broad, only three fourths ( 9 ) or a little more
than three fourths {^) the length of the hind femora, armed beneath
with a single preapical spine besides the apical pair ; spurs sub-
opposite, in the ^ four pairs in number, the basal at about the end of
the proximal third of the tibia, markedly increasing in length toward
the tarsi, so that the proximal are only half as long as the distal, the
middle ones slightly longer than the tibial depth, set at an angle of
about 70° with the tibia and divaricating about 45° ; in the 9 six
pairs in number, the basal placed before the end of the proximal fourth
of the tibia and jnst beyond a slight but distinct constriction of the
tibia, the distal series as long again as the proximal, the inner series a

SCUDDER, — NORTH AMERICAN CEUTHOPHILI. 105

little longer than the outer, the shortest not exceeding in length the
tibial depth, the proximal more recumbent than the distal and tlieie-
fore set at an angle with the tibia varying from 40° to 75°, divaricat-
ing 20°-30°, the whole faintly incurved ; inner middle calcaria of $
scarcely longer than the others or than the distal spurs and much
shorter than the first tarsal joint; calcaria of 9 subequal but decreasing
in length from above downward, those of opposite sides subec^ual, the
longest no longer than the shortest tibial spurs and much shorter than
the first tarsal joint. Hind tarsi about two fifths as long as the tibiaj,
the first and fourth joints subequal, and either nearly twice as long as
the second and third, which again are subequal, and all but the last
apically produced beneath in the 9 to a spinous point. Cerci slender,
tapering regularly, about three fourths as long as the femoi'al breadth.
Ovipositor short, hardly as long as the fore femora, straight, broad
even at apex, the extreme upper tip of which is feebly produced ; teeth
of inner valves aculeate, arcuate.

Length of body, ^ 15 mm., 9 16 mm. ; pronotum, ^ 5 mm., 9 4.5
mm. ; fore femora, ^ 5 mm., 9 5.25 mm. ; hind femora, ^ 12.5 mm.,
9 11.25 mm.; hind tibia?, ^ 10.5 mm., 9 8.5 mm. ; ovipositor, 5 mm.

2 ^, I 9. Peru, Nebr., Professor Townsend ; Colorado, July,
Snow, Coll. Univ. Kans., — all through L. Bruner.

Phrixocnemis validus, sp. nov.

Nearly uniform testaceous, glabrous, with feeble infuscation in
clouds upon the sides of the pronotum, and to a scarcely perceptible
degree upon the whole dorsum, made more evident by a fine medic-
dorsal luteous thread down the whole body, the legs of the body color,
but the apical half of the femora more or less though at most feebly
infuscated and the hind femora tipped narrowly with fuscous ; the
hind femora have also a faint rufous tinge. The antennae are moder-
ately stout and probably at least three times as long as the body, and
the legs short and stout, the vertex rudely bituberculate. Fore femora
distinctly stouter than the middle femora, a sixth longer only than the
pronotum and half as long as the hind femora, the inner carina fur-
nished with a row of minutest denticles but with no subapical spine.
Middle femora with three subequal spines on the front carina, the hind
carina unarmed and apparently with no genicular spine. Hind femora
very much shorter than the body, twice as long as the fore femora,
very stout, being not over two and a half times longer than broad,
with only two or three raised points on the inner edge of the upper
surface beyond the middle, the outer and inner carinas similarly armed

106 PROCEEDINGS OP THE AMERICAN ACADEMY.

with minute denticulations, the intervening sulcus not broad. Hind
tibife considerably shorter than the femora, straight, stout, armed
beneath with a single small preapical spine, besides the unusually long
apical pair ; the four pairs of spurs are opposite or subopposite, the
basal near the end of the proximal third of the tibia, regularly increas-
ing in length distally, so that the last are as long as the nearest calcaria,
while the proximal are but little more than half that length or than
the tibial depth, set at an angle of 70-80° with the tibia and divaricat-
ing only about 20°, the whole feebly incurved, the tips not more so ;
the spurs are also more closely crowded on the distal half of the tibia
than before it, and indeed so crowded as to have no intervening spines,
which even between the others are few in number and irregular, the
two distal spurs with the proximal calcaria being at uniform distances
apart, a distance hardly one half that which separates the preceding
spurs ; all the calcaria are subequal in length, those of opposite sides
similar, but they decrease slightly from above downwards, and the
longest is as long as the first to third tarsal joints combined. Hind
tarsi hardly more than a third as long as the tibiae, the first and fourth
joints subequal and either of them much longer than the subequal
second and third joints combined. Cerci moderately stout, equal and
single jointed in proximal half, tapering pointed and multiarticulate
beyond, the whole about as long as the width of the hind femora.

Length of body, 15 mm. ; antennae, 29+ mm. ; pronotum, 4.3 mm. ;
fore femora, 5 mm. ; hind femora, 10 mm. ; hind tibiae, 9 mm.

1 c? California, H. Edwards.

Phrixocnemis bellicosus, sp. uov.

Vertex smooth. Rather bright luteo-testaceous, subglabrous, very
broadly marked with blackish fuscous especially in a broad anterior
bordering to the pronotum, and a broader or narrower posterior bor-
dering to all the segments, relatively broader on the abdominal than
on the thoracic segments, but on the latter sometimes reinforced by a
stout mediodorsal stripe deeper in color posteriorly than anteriorly ;
the interior edges of the anterior and posterior borderings of the pro-
notum are very irregular, and particularly show subdorsal posterior
thrusts of the anterior, and laterodorsal anterior thrusts of the posterior
bordering ; the lower borders of the thoracic segments are broadly
luteous and immaculate ; the legs are luteous, the femora infuscated
more or less especially beyond the middle, the hind pair with more or
less distinct scalariform markings. The antennae are slender and
about three times as long as the body, and the legs short. Fore

SCUDDER. NORTH AMERICAN CEUTHOPHILI. 107

fetnora distinctly stouter than the middle femora, very little longer
than the pronotum and uiucli less than half as long as the fore femora,
the inner carina, at least in the male, with a couple of minute sub-
apical spines ; fore tibiie much stouter in the (J than in the 9 •
Middle femora with two ((J) or 0-1 (9) spines on the front carina,
the hind carina quite unarmed, even wanting a genicular spine. Hind
femora about two and a third times longer than the fore femora but
much shorter than the body, very stout, being about two and three
quarters times longer than broad (narrower in the 9 ), the upper surface
with 3-4 raised points on its inner edge, the outer carina in the male
elevated, arcuate, with about eleven subequal small triangular spines in
the distal half, in the female hardly elevated with similar but very
feeble spinules, the inner carina with a series of smaller denticulations,
the intervening sulcus narrow, but in the male deep. Hind tihia3 very
stout, much shorter than the femora, broadly and faintly arcuate, but
in the female this is scarcely perceptible, armed beneath with a single
subapical spine besides the apical pair; the five {^) or six (9) pairs
of spurs are subalternate, the basal at about the end of the proximal
fourth of the tibia, increasing in length from the first to the penulti-
mate, the ultimate and the three calcaria then decreasing in reverse
order, the proximal not much more than half as long as the distal and
much shorter than the tibial depth, the distal spurs more closely
crowded than the jjroximal, and lacking between them the few and
irregular spines of the second order found between the proximal, all
set at an angle of 60-70° with the tibia and divaricating 20-30° only,
the whole feebly incurved, their tips perhaps slightly more ; calcaria
of opposite sides subequal, the longest (uppermost) shorter than the
first tarsal joint. Hind tarsi much less than half as long as the tibiae,
the first and fourth joints subequal and either of them more than twice
as long as the subequal second and third joints together. Cerci slender
and no longer than the width of the hind f<^mora. Ovipositor slender
and of uniform width excepting a slight apical expansion, about as long
as the hind tibias, the tip acutangulate, at an angle of about 40°,
slightly upturned, the inner valves crenato-denticulate with four
projections which face posteriorly.

Length of body, ^ 11.5 mm., 9 9.5 mm.; antenna?, ^ 31+ ram.,
9 (est.) 18+ mm. ; pronotum, ^ 4 mm., 9 3 mm. ; fore femora,
S 4.3 mm., 9 3.35 mm.; hind femora, ^ 9.9 mm., 9 8 mm.; hind
tibiae, $ S..') mm., 9 6 mm. ; ovipositor, 6 mm.

1 ^,1 9 . Colorado, li. K. Morrison, the S at an elevation of
7,000', the 9 at one of 5,000' (the ^ therefore probably in the Ute
Pass, the 9 on the plains between Denver and Colorado Springs).

108 PROCEEDINGS OP THE AMERICAN ACADEMY.

DAIHINIA Haldeman.

Daihinia Hald., Proc. Amer. Assoc. Adv. Sc, ii. 346 (1850) ;

Girard, Marcy Expl. Red River, 257 (1853) ; Scudd., Bost. Journ.

Nat. Hist., vii. 443 (1862).
Not Daihinia Sauss., Orth. Nova Amer., i. 14-15 (1859), <

Tliis genus is remarkable for lacking the third tarsal joint of the
fore and hind legs. Brunuer (Monogr. Stenop., 60, foot-note) pre-
sumed this to be an abnormal condition found in a single specimen
seen by me ; but it was seen and specially remarked upon both by
Haldeman and Girard before me, and I have examined fourteen speci-
mens of both sexes, all of which agree in this particular except that
in two or three of them the fore or hind tarsi, or both, are broken,
so that it cannot be affirmed of them. There can be no question that
it is normal as no specimen of the two species has been found in which
the condition was different.

Table of the Species of Daihinia.

Hind femora of male about two and a half times longer than broad,
armed with 3-4 very large spines on the apical half of the outer
carina much larger than the others, the inner carina much more
feebly armed ; hind tibife armed beneath with a single subapical
spine brevipes.

Hind femora of male fully three times as long as broad, the spines of
the outer carina nearly uniform and much less prominent than
those of the inner carina ; hind tibias armed beneath with a row
of spines . gigantea.

Daihinia brevipes.

Phalangopsis {Daihinia) brevipes Hald. ! , Proc. Amer. Assoc. Adv.
Sc, ii. 346 (1850) ; Walk., Catal. Derm. Salt. Brit. Mus., i. 116
(1869).

Daihinia brevipes Girard, Marcy Expl. Red River, 257, pi. 15, figs.
9-13 (1853); Id., Ibid., 246, pi. 15, figs. 9-13 (1854); Scudd.!,
Bost. Journ. Nat. Hist., vii. 443, fig. 3ab (1862) ; Walk., Catal.
Derm. Salt. Brit. Mus., i. 205 (1869) ; Glover, 111. N. A. Entom.,
Orth., pi. 7, figs. 14, 15 (1872) ; Brunn., Monogr. Stenop., 60 (1888) ;
Brun., Publ. Nebr. Acad. Sc, iii. 31 (1893).

Upper waters of the Red River of Arkansas (Girard) , Platte River
above Ft. Laramie, Wyo. (Haldeman, Scudder) ; Sand Hills, Western
Nebraska, and other points in Nebraska, as Sugar Canon and Thed-

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. 109

ford, Thomas Co. (Brunei-) ; Ft. Hays, Ellis Co., Kans., J. A. Allen
(Mus. Comp. Zool.) ; Ellis, Kansas, Watson (Mus. Comp. Zool.) ; Kan-
sas (Bi'uner) ; Black Hills, South Dakota (E. P. Austin) ; a" specimen
was also obtained during the Pacific R. R. Surveys under Lt. E. G.
Beckwith, U. S. A., near Lat. 38°, presumably in Southern Colorado,
and it was taken by Snow in Colorado (Bruner). The species there-
fore extends along the eastern margin of the Rocky Mts. from Lat.
34° to 44° N.

Daihinia gigantea.

Daihinia gigantea Brun.!, Bull. Washb. Coll., i. 127 (1885)^
i. 195 (1886).

Udeopsylla gigantea Brun.!, Can. Ent., xxiii. 39 (1891) ; Id.,
Publ. Nebr. Acad. Sc, iii. 31 (1893).

Labette and Berber Cos., Kans. (Bruner). Bruner also reports it
to be found in Nebraska and the Indian Territory.

Note. — Daihinia mexicana Sauss. is not a Daihinia, nor one of the Ceutho-
phili, but has been placed by Brunner in the genus Glaphyrosoma among the
Anostostomata

UDEOPSYLLA Scudder.

Udeopsylla Scudd., Bost. Journ. Nat. Hist., vii. 442 (1862) ; Brunn.,
Monogr. Stenop., 59 (1888).

Table of the Species of Udeopsylla.

Body piceous, occasionally with faint rufous spots .... nigra.
Body varying in color from dark testaceous to mahogany brown.

robusta.
Udeopsylla nigra.

Udeopsylla nigra Scudd.!, Can. Nat., vii. 284-285 (1862) ; Id.!.
Bost. Journ. Nat. Hist., vii. 443, fig. 2 (1862) ; Walk., Catal. Derm.
Salt. Brit. Mus., i. 205 (1869) ; Thom., Rep. Geol. Geogr. Expl.
Surv. 100th Mer., v. 902 (1875) ; Broadh., Trans. St. Louis Acad.
Sc, iii. 345 (1876) ; Caulf., Rep. Ent. Soc. Ont., xviii. 63, 69
(1886) ; Brun., Bull. Washb. Coll., i. 195 (1886) ; Brunn., Monogr.
Stenop., 60 (1888) ; McNeill, Psyche, vi. 27 (1891) ; Osb., Proc. Iowa
Acad. Sc, i. ii. 119 (1892) ; Brun., Publ. Nebr. Acad. Sc, iii. 31
(1893); Blatchl., Proc Ind. Acad. Sc, 1892, 153 (1894).

Ceuthophilus niger Scudd.!, Bost. Journ. Nat. Hist., vii. 437 (1862) ;
Walk., Catal. Derm. Salt. Brit. Mus., i. 202 (1869) ; McNeill, Psyche,
vi. 27 (1S91) ; Blatchl., Proc Ind. Acad. Sc, 1892, 153 (1894).

110 PROCEEDINGS OF THE AMERICAN ACADEMY.

The specimens described by me as a Ceuthopbilus beloug to this
species, though separately described at the same time.

Specimens are recorded as having been taken, or have been seen
by me, from Perry Co., 111., Dr. E. R. Boardman (Uhler) ; Illi-
nois (Uhler, Comstock, McNeill) ; Southern Illinois and Rock
Island, 111. (Uhler); Red River, Manitoba (Caulfield) ; Carbery,
Manitoba, in the gizzard of a sparrowhawk (Fletcher) ; Northern
Minnesota, leaping about in the grass at midday (Scudder) ; Denison,
Crawford Co., Iowa, July 13, 15, 20 (J. A. Allen) ; Iowa (Osborn) ;
Nebraska City and the Platte Valley, Nebr. (F. V, Hayden) ; Ne-
braska City, West Point, and Pine Ridge, Nebr. (Bruner) ; Northeast
Nebraska (Bruner) ; Berber Co., Kans., and Topeka, Kans., Cragin
(Bruner); Missouri (Broadhead) ; Sedalia, Mo. (U. S. Nat. Mus.) ;
Dakota (Bruner), and Colorado, 5,000' (Morrison) ; so that its general
range appears to be between the Mississippi River or a little east of
the main stream to the Rocky Mountains between Lat. 37° and 50°
North. But I have two specimens in my collection, one from North
Carolina (Shute), the other from El Dorado Co., Calif., 4,000' (Giss-
ler), both of them far beyond the otherwise known limits of the
species. Of the latter locality I entertain no doubt, especially as I
have recently found in the Museum of Comparative Zoology a single
specimen collected by Morrison in Arizona; but as to the former I am
inclined to believe the label became accidentally attaclied to the wrong
insect, particularly as Shute's collection was made on the seaboard.

Udeopsylla robusta.

Phalangopsis (Daihinia) robustus Hald. !, Proc Amer. Assoc. Adv.
Sc, ii. 346 (1850) ; Walk., Catal. Derm. Salt. Brit. Mus., i. 117
(1869).

Daihinia robusta Girard, Marcy Expl. Red River, 1853, 257
1854, 246.

Udeopsylla robusta Scudd.!, Bost. Journ. Nat. Hist., vii. 442 (1862)
Walk., Catal. Derm. Salt. Brit. Mus., i. 205 (1869) ; Pack., Guide
Ins., 565 (1869) ; Thorn., Proc. Acad. Nat. Sc. Philad., 1870, 77
Glov., Rep. [U. S.] Dep. Agric, 1871, 79 ; Thom., Ann. Eep. U. S
Geol. Surv. Terr., ii. 265 (1871), v. 437 (1872); Scudd.!, Rep
U. S. Geol. Surv. Nebr., 249 (1872); Glov., 111. N. A. Ent., Orth.
pi. 8, fig. 9 (1872); Scudd.!, Ann. Rep. Geogr. Surv. West 100th
Mer., 1876, 279 ; Thom., Bull. U. S. Geol. Geogr. Surv. Terr., iv. 485
(1878) ; Scudd.!, Rep. U. S. Ent. Comm., ii. App. 23 (1881) ; Brun.,
Bull. Washb. Coll. i. 127 (1885); Brunn., Monogr. Stenop., 59-60,

SCUDDER. — NORTH AMERICAN CEUTHOPHILI. Ill

fig. 31 (1888) ; Osb., Proc. Iowa Acad. Sc, i. ii. 119 (1892) ; Brun.,
Publ. Nebr. Acad. Sc, iii. 31 (1893).

Udeopsylla compacla Brun.!, Cau. Ent., xxiii. 38-39 (1891); Id.,
Publ. Nebr. Acad. Sc, iii. 31 (1893).

Specimens have been seen by me from Clifford, N. Dak. (Bruner),
explorations in Dakota under Gen. Sully (Rotbhammer) ; Sheridan,
Wyo. (Bruner) ; Ft. Fettermaun, Wyo. (U. S. Nat. Mus.) ; above
Ft. Laramie, Wyo.; Denison, Crawford Co., Iowa, July 15 (J. A.
Allen) ; Holt Co., Pine Hills, Lincoln, and Broken Bow, Nebr.
(Bruner) ; Nebraska City and the banks of the Platte (Hayden) ;
Nebraska (P. R. Uhler and Miss Walker) ; Republican River, Nebr.
or Kans. (W. T. Wood) ; Syracuse, Kans. (U. S. Nat. Mus.) ;
Pacific R. R. Surveys, Lat. 38° (Lt. Beckwith) ; Colorado (U. S. Nat.
Mus.) ; Albuquen^ue, N. Mex., Wickham (Bruner) ; Texas (Uhler) ;
Pasadena, Cal. (Bruner). From the same States or Territories it
has also been reported as follows : Dakota and Wyoming (Thomas) ;
Holt and Wheeler Cos., Nebr. (Bruner), New Mexico (Bruner,
Scudder), and Texas (Brunner). It has also been credited to the
following: Montana, Southern Idaho, and Bloomiugtun, 111., — the
last probably in error (Thomas) ; Missouri (Bruner) ; Bourbon Co.,
Kans. (Bruner); Colorado (Scudder); and "open sections of the
Rocky Mt. region " (Thomas) ; besides Utah (Glover, Thomas).

GAMMAROTETTIX Brunner.

Gammarotettix Bruun., Mouogr. Stenop., (50, Gl (1888).

Gammarotettix bilobatus.

Ceiithophilus bilobatus Thom. ! , Ann. Rep. U. S. Geol. Surv. Terr.,
V. 437 (1872).

Gammarotettix califomicus Brunn., Monogr. Stenop., 61, fig. 32
(1888).

California (Brunner, Behrens) ; Marion and Sonoma Cos., Cal.
(Osten Sacken) ; Lakeport, Lake Co., Gilroy, Santa Clara Co., Chrys-
tal Springs, San Mateo Co.. and San Diego, Cal. (Crotch) ; Santa
Cruz Mts., Santa Clara Co., Los Angeles Co., Cal. (U. S. Nat.
Mus.).

112 PROCEEDINGS OF THE AMERICAN ACADEMY.

APPENDIX.

After this paper was in type, I received from the Davenport Academy
of Natural Sciences, through the kind intervention of Prof. Herbeit
Osborn, of Ames, Iowa, the single type of Ceuthophilus utuhensis
Thorn, (see p. 102), and append a description of it to render this paper
mi)re complete. It is not so closely related to C. valgus as I had sup-
posed from the description and figure, but belongs rather in the near
vicinity of C uhleri and C. blatchleyi^ though with the inferior sulcus
of the hind femora not so exceptionally broad as in those species, and
also with very different markings, in which respect it recalls rather
C.pallidus. The measurement of the hind tibiie given by Thomas
is too great. The specimen was collected in alcohol, but has since
been pinned.

Brownish fuscous with dull luteous markings ; on the pronotum the
fuscous borders all the margins broadly, the anterior and lateral mar-
gins very broadly, sending backward from in front a broad mediodorsal
stripe nearly meeting the posterior bordering, and through it runs a
faint median luteous thread ; the posterior bordering throws forward
on either side a subdorsal tooth embracing the posterior end of the
mediodorsal stripe and leaving between the two a U-shaped luteous
mark which connects the luteous disks of either side, the latter of
which are more or less mottled with fuscous lines ; the meso- and
metanotum are heavily spotted anteriorly with partly confluent luteous
spots, and the abdominal segments are more regularly margined an-
teriorly with luteous ; legs warm luteous, the hind femora with the
usual scalariform infuscations. The antennai are moderately slender
and more than twice, probably thrice, as long as the body, and the
legs moderately long. Fore femora no stouter than the middle femora,
a little less than half as long as the hind femora, scarcely more than a
third longer than the pronotum, the inner carina with a moderately
long preapical spine preceded by a shorter one. Middle femora with
a single moderately long spine on the front carina and on the hind
carina 1-2 short spines besides a moderate genicular spine. Hind
femora nearly as long as the body, somewhat more than twice as long
as the fore femora, moderately stout, only the distal sixth subequal,
about three and a quarter times as long as broad, the surface with a
very few raised points along the upper edge of the inner side, the
outer carina considerably and subequally elevated, with about fifteen
coarse but rather small subequal and inequidistant spines, the longest

SCUDDKU. — NORTH AMERICAN CEUTHOPHILI. 113

not a third as long as the tibial spurs, the inner carina with a series of
rather distant short spinules partially biseriate, the intervening sulcus
broad, equal, and deep. Hind tibia? rather feebly and broadly sinuate
(this point is exaggerated in the original figure), a very little longer
than the femora, armed beneath with a single long jjreapical spine
besides the apical pair ; spurs subalternate, the basal beyond the end
of the proximal third of the tibia, nearly twice as long as the tibial
depth, set at an angle of about 35° with the tibia and divaricating
about 80°, their apical third or fourth considerably incurved ; inner
middle calcaria considerably longer than the outer, fully twice as long
as the others or as the spurs, but somewhat shorter than the first tarsal
joint. Hind tarsi about two fifths as long as the tibiae, the first joint
as long as the rest together, the second and fourth suhequal, and each
about twice as long as the third. Cerci rather stout, tapering regu-
larly, about as long as the femoral breadth.

Length of body, 14.5 mm. ; antennas, 31+ mm. ; pronotum, 4.4 mm. ;
fore femora, 6 mm.; hind femora, 13 mm. ; hind tibiae, 13.5 ram.

1 J , Mt. Nebo, Utah, August, Putnam (Dav. Acad. Nat. Sc).

July 20, 1894.

VOL. XXX. (n. S. XXII.)

114 PROCEEDINGS OF THE AMERICAN ACADEMY.

IV.

CONTRIBUTIONS FROM THE GRAY HERBARIUM OF HARVARD
UNIVERSITY, NEW SERIES, NO. VIII.

NEW PLANTS COLLECTED BY MESSRS. C. V. HART-
MAN AND C. E. LLOYD UPON AN ARCHiEOLOGICAL
EXPEDITION TO NORTHWESTERN MEXICO UNDER
THE DIRECTION OF DR. CARL LUMHOLTZ.

By B. L. Robixson and M. L. Fernald.

Presented May 9, 1894

Crossosoma parviflora. a shrub, 4-8 feet high: branches
covered with gray bark ; brauchlets slender, elougated, and often
flexuous, sometimes straight and a little rigid ; cortex yellow : leaves
elliptic-oblong, obtuse and mucronulate at the apex, pale green upon
both surfaces, thickish, l-nerved, 4-6 lines long, 1|^-2| lines broad :
sepals 5, broadly oblong or suborbicular, 1|-2| lines long: petals 5,
oblong, 3 lines in length: stamens 15-20: carpels 3-4; follicles
glabrous, reticulated, only 3-3|^ lines long. — Collected in the Grand
Canon of the Colorado, by Dr. Gray, February to May, 1885, but
referred to Glossopetalon Nevadense, Gray ; and at La Tinaja, Sonora,
at 3,700 feet, by Mr. Hartman, 19 November, 1890 (no. 245).

Eriodendron acuminatum, Wats. (Proc. Am. Acad. xxi. 418).
Specimens apparently of this species, but representing other stages
than those shown by the type, were collected in Western Chihuahua
but without more exact locality. The older branches are armed with
stout spreading spines 3-4 lines in length, while the younger ones, as
Dr. Watson states, are unarmed ; the young shoots and leaves are
densely tomentose : the calyx deeply campanulate, an inch long, slial-
lowly 5-toothed, glabrous and glaucous upon the outer surface, densely
sordid tomentose within ; teeth rounded, often split (perhaps in dry-
ing) : petals linear, 5 inches long, 4 lines broad, very appressed silky
upon one side of the outer surface, tomentose upon the s-'de covered
in the bud; glabrate upon the inner surface : stamens included. — The
Mexican name is " Pochate." The fleshy white roots are eaten, the

ROBINSON AND FERNALD. — MEXICAN PLANTS. 115

fine cotton is used for making wicks for tapers of wild beeswax. Thi8
species is to be distinguished from E. tomentosum, Robinson, by its
glabrous calyx and relatively broader leaflets.

EsENBECKiA Haktmanii. A shrub, 6-10 feet high : twigs thick,
woody, covered with gray bark, leafy chiefly near the end : leaves
simple, alternate, oblong or somewhat obovate, entire, rounded or re-
tuse at the apex, somewhat narrowed below to an obtuse or rounded
base, thickish, green, nearly smooth and finely reticulated above,
tomentulose and scarcely paler beneath; the largest ones 16-20 lines
long, 8-11 lines broad; the others considerably smaller (8-9 lines in
length) ; petioles short, soft pubescent, 1-1 J lines long: inflorescences
short, terminal upon the branchlets ; fruiting pedicels 1-3 together, ^
inch or less in length : the capsule tuberculately roughened, 9-10 lines
in diameter ; pericarp white, thin and chartaceous, rather irregularly
ruptured upon dehiscence; seeds subglobose, smooth, black, 3^ lines
in diameter ; scar white, narrow, linear, h line in breadth. — Collected
in fruit at La Tinaja, Sonora, at 3,700 feet, by Mr. Hartman, 19 No-
vember, 1890 (no. 240). This species much resembles the Lower
Californian E. Jlava, Brandegee, but differs in its smaller greener
shorter-petioled leaves, and its smaller fruit with chartaceous and not
cartilaginous pericarp. The seeds of E. jiava also are larger and
have a much broader scar.

Ilex rubra, Wats. (Proc. Am. Acad. xxi. 422). Flowering
specimens of tliis species, which was originally described in fruit, have
been collected in an arroyo near Coloradas, by Mr. Hartman, May,
1893 (no. 513), and add the following characters : flowers numerous,
in small aggregated thyrses, greenish white, 4-parted: calyx lobes
ovate, obtuse, % line long : corolla nearly 4 lines in diameter, about
equalling the stamens ; the lobes rounded.

Dalea Lumholtzii. Stems many, slender, puberulent, punctate
with yellow glands, simple or sparingly branched, erect from a decum-
bent much branched sufFrutescent base : upper leaves erect or ascend-
ing, 1-1| inches long, leaflets 17-27, linear, 2-2^ lines long, nearly
\ line in breadth, obtuse, slightly narrowed to very short petiolules,
glabrous, glaucous and glandular-punctate upon both surfaces ; the
basal leaves numerous, shorter, and with considerably smaller almost
filiform leaflets, silky under a lens : spikes ovate, capitate, 3-7 lines in
length, becoming oblong, very densely flowered, covered with closely
imbricated persistent bracts ; the latter ovate or obovate, very ab-
ruptly pointed, silky upon the margins and especially near the some-
what narrowed base ; glabrate and glandular-punctate upon the back,

116 PROCEEDINGS OF THE AMERICAN ACADEMY.

1 ^ lines long : calyx striate, sparingly silky, entirely obscured by the
bracts : petals white or nearly so, oblong, obtuse, attenuate below to
slender claws: stamens 10. — Collected at Las Pinitos, Sonora, at
6,100 feet, by Mr. Hartuian, 14 October, 1890 (no. 133). A species
with the habit of a Petalostemon rather than a Dalea y the fresh leaves
very aromatic when crushed.

Sedum Lumholtzii. Hoary puberulent: roots fibrous: stems
herbaceous, decumbent, 5-10 inches high, ancipital, simple below the
spreading cymose inflorescences : leaves soft pubescent and ciliated ;
the basal ones crowded, spatulate, 4-6 lines long ; the cauline spatu-
late-oblong, obtuse, somewhat narrowed to a slightly extended base,
about an inch in length, 2-3 lines broad : flowers numerous, pedicel-
late, white: sepals lance-oblong, obtusisb, \\ lines long, not at all
extended at the base: petals lanceolate, acute, 2^- lines long: carpels
5, pruinose, erect, attenuate ; styles persistent ; scales small, truncate,
bright red ; seeds oblong, \ line in length. — Collected at Nacory,
Sonora, at 3,700 feet, by Mr. Hartman, 4 December, 1890 (no. 287) ;
and at Huchuerachi, Sonora, by Mr. Lloyd, 8 December, 1890
(no. 389).

SiCYOS COLLINUS. Stem slender, glabrous, furrowed : tendrils
2-3-parted : leaves thin, 5-lobed, scarcely paler beneath, li-2i inches
long, usually narrower, roughened upon both surfaces with minute
whitish tubercular hairs ; lobes ovate to lanceolate, acute or acuminate,
sharply dentate or denticulate; the terminal ones often elongated;
petioles 4-12 lines long: $ peduncles 1^-3 inches in length, smooth
or nearly so ; inflorescences slender, usually simple, slightly puberulent
or quite smooth, ^-1^ inches long, 10-35-flowered ; pedicels very
slender, spreading, smooth, equal, slightly thickened at the apex, l|-2
lines in length : calyx teeth very minute or obsolete : corolla rotate-
campanulate, 2^3 lines in diameter, finely granular ; lobes broadly
ovate, obtusish : staraineal column (including the anthers) | line long:
9 peduncles 2 lines long, smooth ; fruits 2-5 in a head, ovate, acumi-
nate, compressed, nearly 3 lines long, sparingly setose, otherwise nearly
glabrous; setae H lines long. — Collected on hills near Chihuahua,
by Mr. C. G. Priugle, 23 October, 1S85 (no. 568) ; and in the Canon
de San I^iego, Chihuahua, by Mr. Hartman, 17 September, 1891
(no. 773). A species near S'. Deppei, Don, but with leaves smaller
and somewhat more acutely lobed ; peduncles and inflorescences nearly
or quite glabrous ; petioles and pedicels shorter ; and male flowers a
little smaller.

Galium Wrightii, Gray, var. latifolium. Pubescent below as

ROBINSON AND FERNALD. — MEXICAN PLANTS. 117

in the type, but the branches nearly smooth ; leaves elliptic-oblong, ^
inch long, 2 lines broad ; fruit hisi)id, but the bristles fewer and shorter.
— Collected on the Sierra de las Gronillas, Sonora, at 5, HOC ieet, by
Mr. llartmun, 2 October, 1890 (no. 58) ; the same thing seems to have
been collected by Prof. Lemmon near Fort Huachuca, S. Arizona?
1883. Some of Mr. Hartmau's specimens show a tendency to inter-
grade with the type.

Bellis orthopoda. Perennial; rootstock short, thick, erect,
giving off several tough fibres : stems 1-5, decumbent or suberect,
4—5 inches high, simple, mouocephalous, appressed pubescent, very leafy
to above the middle : leaves thick, entire, appressed pubescent ; the rad-
ical ones numerous, spatulate, obtuse, 9 lines long, 11-2 lines broad,
the cauliue linear-oblong, erect, ciliate, becoming gradually smaller and
acutish: peduncles 1-1^ inches long, appressed cinereous pubescent:
heads rather large for the genus, a little over an inch in breadtli ; in-
volucral bracts lanceolate, acuminate, cinereous pubescent upon the
membranaceous margin, 2^-3 lines long : rays about 30, light blue in
a dried state, 6 lines long. — Collected at Guachachic, Chihuahua, by
Mr. Hartraan, 25 June, 1892 (no. 523). This species resembles
closely the low and coarse forms of -S. integrifolia, Michx., but is
to be distinguished by its vertical perennial caudex and few simple
stems.

Aster lepidopodus. Perennial : root a cluster of simple fibres :
stems several, slender, a foot high, scaly upon their spreading distinctly
decumbent bases, hirsute, simple or bearing several erect slender nearly
naked monocephalous branches: reduced basal leaves narrowly deltoid,
acute, entire, scarious, glabrate except upon the ciliated margins ; foliar
leaves of the stem oblong-linear, acutish, entire, erect, nearly an inch
in length, \\ lines broad, glabrous, except upon the strongly ciliated
margin and occasionally upon the midrib : heads about an inch in diam-
eter ; scales of the involucre 2(-3)-seriate, subequal, linear-lanceolate,
acuminate ; the dark herbaceous middle portion hirsute : rays 20-25,
narrow, pale rose-colored: achenes columnar, hirsute, 4-ribbe{l. — Col-
lected in pine forests about Chuchuichupa, Chihuahua, by Mr. Hart-
man. 14 June, 1891 (no. 697). A species apparently of the § Mega-
lastriim as regards involucre and achene, but more slender and less
rigid in habit than the other species of this group.

Franseria nivea. Finely white tomentose or pale cinereous
throughout, 1-4 feet high : pubescence persistent except upon the base
of the stem: leaves alternate, 2 inches long, somewhat broader, 3-parted
to the base; parts deeply pinnately lobed; segments acutish, toothed;

118 PROCEEDINGS OF THE AMERICAN ACADEMY.

petioles 1^-1^ inches loug, often somewhat winged or lobed near the
summit: terminal inflorescences about 2 inches long, rather closely
flowered, staminate, except at the very base ; inflorescences springing
from the upper axils several, very short, chiefly fertile ; $ pedicels
flexuous, 2 lines long, white tomentose and not at all glandular ; invo-
lucres cinereous, rotate, 2 lines in diameter, unequally 9-10-toothed, 20-
flowered ; teeth obtuse ; 9 involucres at first ovoid, acute, 2-beaked,
2-celled ; spines (scales) about 24, appressed, imbricated ; achenes sol-
itary in each cell ; fruit 2i lines long, puberulent and finely glandular,
corrugated toward the narrowed base ; the spines spreading, | line long.
— Collected on plains near Casas Grandes, Chihuahua, by Mr. Hart-
man, 10 October, 1891 (no. 813).

Encelia oblonga. Fruticose, 2-3 feet high : branches grayish,
nearly or quite smooth, finely striated ; branchlets glabrous or hirsute,
resiniferous : leaves attenuate, subsessile, oblong or oblanceolate, puber-
ulent, green upon both surfaces, scabrously ciliolate-denticulate, rounded
or obtuse and mucronate at the apex, cuneate at the base, l:j-2^ inches
long, 6-12 lines broad ; veinlets translucent : peduncles solitary, termi-
nal, sparingly hirsute, 2-3 inches in length, with 2-3 reduced leafy bracts
and a solitary head about an inch in diameter exclusive of the rays :
involucral bracts in two series, subequal, lanceolate, caudate-attenuate,
ciliolate, 5-6 lines long: rays 12-15, yellow, nearly half an inch in
length : disk corollas with throat cylindrical, 2 lines long, much exceed-
ing the short proper tube and still shorter glabrous limb : achenes
2\ lines long, appressed silky villous and crowned with two weak un-
equal readily deciduous ciliolated awns ; the larger one, on the side
opposite the enclosing palea, two thirds as long as the corolla. —
Collected on plains near Casas Grandes, Chihuahua, by Mr. Hartman,
10 October, 1891 (no. 812).

Leptosyne Arizonica, Gray, var. pubescens. Soft pubescent
throughout : leaves tending to have somewhat broader segments : not
otherwise differing from the glabrous type. — Collected at Granados,
Sonora, at 2,950 feet, by Mr. Hartman, 15 November, 1890 (no. 222);
near Huchuerachi, at 4,000 feet, by the same collector, 5 December,
1890 (no. 296) , and at Cardovas, Sonora, by Mr. Lloyd, 9 December,
1890 (no. 406).

Perityle Lloydii. Suffruticose, branching from the base. 4-10
inches high, cinereous-pubescent, very glandular and aromatic :
branches slender, terete, more or less decumbent : leaves opposite
below, subalternate above, ovate-deltoid, acute, somewhat doubly
dentate, 8-12 lines long, pubescent upon both surfaces; petioles

ROBINSON AND FKRNALD. MEXICAN PLANTS. 119

sleuder, 5-9 lines in length : peduncles springing from the upper axils,
about 2 inches long, slightly thickened upward : heads large, radiate,
5 lines high, including the rays 9 lines broad ; scales of the involucre
narrowly linear, J- line wide, caudate-attenuate, 4 lines in length : ray
flowers 18-20, pale yellow; ligules 3 lines long, 3-toothed at the apex ;
disk flowers including acheaes 4h lines long : style branches of the lat-
ter with attenuate hispid appendages, those of the former smooth ;
achf nes oblong, black with thickened white margins, puberulent, scarcely
ciliolate, li lines long. — Collected in niches of dry rocks at Bade-
huache, Sonora, by Mr. Lloyd, 2 December, 1890 (no. 400). A
species nearly related to P. leptoglossa, Gray, and P. Palmeri, Wats. ;
distinguished from the former by its much more copious pubescence,
more attenuate involucral scales, and larger flowers ; from the latter
by its slender terete branches, and by its achenes which are scarcely
ciliolate instead of having a copious ciliation.

Cacalia globosa. Caudex short, horizontal, giving off numerous
fibres : stem simple, flexuous, 8 inches in height, glabrate, except near
the somewhat fuscous-tomentose summit : leaves thickish, nearly or
quite glabrous, somewhat glaucous, cartilaginous upon the crenate-
dentate margins, obtuse, pinnately veined ; the radical ones deltoid,
1^- inches long, nearly as broad, cordate with a broad shallow sinus;
their petioles 1^ inches long, slender above, dilated below; the cauline
leaves for the most part consisting of ovate clasping cartilaginous
dentate phyllodia ; only the lower ones surmounted by an ovate or
deltoid crenate blade : heads about 6-flowered, densely packed together
in a globular inflorescence (9 lines in diameter) : involucral scales
obovate-oblong, 3 lines in length, with ciliate margins and tip, thickened
in the middle, especially near the summit : corollas 2:^ lines high ; the
linear lobes little exceeding the tube : pappus sparing. — Collected in
a moist meadow, Guachuchic, Chihuahua, by Mr. Hartman, 25 June,
1892 (no. 522).

Philibertia ctnanchoides, Decsne., var. subtruncata. Leaves
narrow, attenuate, abrupt at the base or subcordate with a very
shallow open sinus and spreading auricles. — Collected at Fronteras,
Sonora, at 4,550 feet, by Mr. Hartman, 25 September, 1890 (no. 4),
The type both by description and authenticated specimens has deeply
cordate and usually broader leaves. No other differences have been
noted.

Phacelia rupicola. Perennial, hirsute, subacaulescent : leaves
springing from an elongated thickish ascending caudex, deeply
pinnatifid ; blade oblong in outline, 2-3 inches long, equalling the

120 PROCEEDINGS OP THE AMERICAN ACADEMY.

petiole ; segments 15-19, broadly oblong, acutish, generally 1-2-toothed
upon the lower margin, 5-7 lines long, 2.V-4 lines broad; the upper
ones approximate ; the lower becoming smaller and more or less
scattered : inflorescence exceeded by the leaves, loose below, the lowest
jjedicels being 1^ inches long: calyx lobes oblong-lanceolate, acute,
slightly unequal, 2-3i lines long : corolla pure white, i inch in
diameter; lobes rounded, cleft half-way to the base ; appendages linear,
folds free at the tip and forming pairs alternating with the stamens :
filaments equalling the corolla, hirsute below : style 2-parted for two
thirds of its length and easily divided to the base ; ovary hirsute ;
ovules about 20. — Collected on cliffs in a pine forest of Strawberry
Valley, Chihuahua, by Mr. Hartman, 8 June, 1891 (no. 686). A
species of the § Eutoca.

Ltcium retdsum. Stems glabrous, smooth, dark brown or grayish,
sometimes armed with short slender spines ; branchlets divaricate .
pulvini white, pubescent ; leaves obovate, cuneate, usually retuse,
pubescent upon both surfaces : pedicels filiform, glandular-pubescent,
3-5 lines long : calyx tubular, glandular-pubescent, ''Ih lines long ; teeth
triangular-lanceolate, erect, acute, a third as long as the tube : corolla
trumpet-shaped, about 4 lines in length; teeth short, retuse, a fourth
as long as the tube : style and stamens exserted ; the latter unequal ;
filaments bearded at the base : fruit not seen. — Collected at Opata,
Sonora, at 3,450 feet, by Mr. Hartman, 1 November, 1890 (no. 212).

Maurandia (?) GENicuLATA. Densely glandular pubescent and
viscid : stems zigzag : leaves distichous, orbicular, cordate, coarsely
crenate, 1-2 inches broad, green upon both sides, 5-nerved ; petioles
spreading, 5-9 lines long : peduncles axillary, \-\ inch in length,
ascending in anthesis, somewhat thickened and recurved in fruit : calyx
narrowly campanulate, subequally 5-cleft to near the middle, 6 lines
long; segments narrowly ovate, obtusish, 1-nerved, somewhat plaited
at the sinuses: style simple, filiform, nearly or quite an inch in length ;
ovary superior, 2-celled ; ovules numerous, upon axial placentEe : fruit
capsular, about equalling the calyx ; seeds oblong, barely a line in
length, two thirds as thick, black, irregularly roughened with relatively
large tubercles but not at all winged : corolla and stamens not seen. —
Collected on cliffs at Nacory, Sonora, at 3,750 feet, by Mr. Hartman,
1 December, 1890 (no. 272). Closely resembling in foliage and
pubescence M. erecta, Hemsl., but with a very geniculate stem and
wingless seeds. Until the corolla and stamens are discovered the
generic position must remain somewhat doubtful.

MiMULUs DENTiLOBDS. Very pubpscent Or glabrate : stems slender,

ROBINSON AND FKRNALD. — MEXICAN PLANTS. 121

weak, loosely mattotl, decumbent, much branched, rooting at the johits,
3-6 inches in length : leaves small, suborbicular, broader than long,
shallowly sinuate-dentate, cartilaginous margined ; the largest 3 lines
in diameter, abruptly contracted into a short winged petiole : pedicels
axillary, opposite, filiform, 9-12 lines long: calyx in authesis 2^ lines
in length, slightly accrescent and loosely surrounding the fruit: corolla
yellow, spotted with purple ; lobes fringe-toothed ; the median lobe of
the lower lip somewhat retuse : anther cells not confluent: capsule
compressed, obtusish, 1] lines in length. — Collected at Nacory,
Sonora, at 3,750 feet, by Mr. Hartman, 4 December, 1890 (no. 288) ;
and on the Bavispe River, Sonora, by Mr. Lloyd, 23 December, 1890
(no. 440). Habit of M. Madrensis, Seem., but with fringed corolla.

Salvia rubropunctata. SufFrutescent : stems branched, gray-
ish; branches brown, slightly scabrous, pulverulent: leaves ovate-
oblong, obtuse or rounded at the apex, abruptly contracted to a cu-
neate base, finely crenate-serrate, punctate with dark red dots, at first
strongly rugose above and white-tomentose beneath, becoming nearly
smooth and glabrous; the largest IJ inches long, half as broad; many
smaller ones clustered in their axils : spikes subcapitate, terminal, soli-
tary, or 2-3 together, short-peduncled ; floral leaves lanceolate, slightly
exceeding the calyx ; verticels about 6-flowered, approximate : calyx
2^ lines long, covered with dense bluish wool, obscuring numerous
bright scarlet glandular dots ; the upper lip shortly 3-toothed ;
teeth acuminate : corolla blue, 6 lines in length, punctate with red
glands ; the lower lip about equalling the tube ; the upper lanate on
the outer surface. — Collected in the Canon Huehuerachi, Sonora, by
Mr. Lloyd, 12 December, 1890 (no. 451). The species appears to
belong to § Erianthoe. It is noteworthy for the bright red glands
which cover all parts of the flower, but are nearly or quite hidden by
the enveloping bluish wool.

Arceuthobium sp. Staminate plant very robust, 6-7 inches long,
profusely branched : stem terete at the base, 5-6 lines in diame-
ter, sheaths short, campanulate, truncate ; branches more or less
sharply quadrangular, bright yellow : spikes very numerous, short,
few-flowered : flowers 3-4-parted ; segments obtuse, ovate-oblong,
arched over the stamens ; the latter inserted near the middle of the
segments. — Collected on pines at Pine Ridge Pass, Sonora, at 3,200
feet, by Mr. Hartman, 17 December, 1890 (no. 340). This interest-
ing plant may be the staminate form of A. robustum^ Engelm., or of
A. campylopodium, var. (?) /3, Engelm. From the specimens of both
species at hand the present plant differs in its considerably greater

122 PROCEEDINGS OF THE AMERICAN ACADEMY.

size. These species, however, are too poorly known, especially in the
staminate forms, to permit satisfactory determination in this case.

Ficus Jaliscana, Wats. (Proc. Am. Acad. xxvi. 150). Addi-
tional material of this species, collected at Granados, Sonora, at 5,700
feet, by Mr. Hartmau, 15 November, 1890 (no. 217), shows that the
plant has leaves often 6 inches long ; also fascicled aerial roots a foot
and a half (or more) in length.

Spikanthes velata. Roots clustered, tuber-like : leaves (at least
at the time of flowering) none : stems 1-2, erect, 9-12 inches high,
thickish and enveloped in loose white scarious brownish-veined ovate-
oblong attenuate bracts ; the floral bracts similar, smaller but exceed-
ing the flowers : spike dense, oblong, 2-3 inches in length : sepals
subscarious ; the lateral ones oblong-lanceolate or linear-lanceolate,
acuminate, 3-nerved, 4 lines long ; the upper one free nearly half its
length, attenuate : petals acutish, narrowly ovate, nearly as long as the
upper sepal, also subscarious and brownish nerved ; lip rhombic,
roHnded at the tip, crenulate throughout, thickish, about 6 lines long,
finely granulated above and bearing two small oblong hoary-pubescent
callosities at the base. — Collected in a caiion parallel with the Carion
de los Alamos on Rio San Miguel, Chihuahua, by Mr. Hartman, 28
June, 1891 (no. 710).

Bravoa densiflora. Root of many spreading thickened fibres ;
bulbs loose, oblong, becoming 2 inches long and an inch or more in
thickness : radical leaves linear, attenuate, 3-4 inches long, a line wide ;
the cauline reduced to bracts, 1-2 inches long, with broad scarious and
attenuate tips ; the floral similar : spike short, dense ; flowers single in
each bract, slender, tubular, spreading, curved, 17-22 lines long, dull
yellow in a dried state, pulverulent-tomentulose upon the outer surface ;
limb oblique; segments ovate, obtuse, only 1-1 i- lines long, erect,
bearing a tuft of short white hairs at the tip : anthers inserted high up
in the scarcely ampliate throat : fruit (immature) ovate, over 3 lines
in diameter. — Collected on dry mesas near Varogachic, Chihuahua,
by Mr. Hartman, 5 July, 1892 (no. 536).

Finds Lumholtzii. A tree, 30-40 feet in height: branchlets
elongated, ] inch in diameter : leaves in 3's, springing from the
lower surface of the branchlets, pendulous, 10-13 inches long, | line
in breadth, nearly flat and shining upon the dorsal surface, carinate
upon the ventral ; margins scarcely involute : sheaths quite obsolete :
bud scales lanceolate, attenuate, tawny, somewhat lacerate-ciliate, 3^
lines lono- : aments and cones unknown. — Collected near Coloradas,
by Mr. Hartman, May, 1893 (no. 541). A beautiful species, striking

ROBINSON AND FERNALD. — MEXICAN PLANTS. 123

in habit on account of its dense pendulous foliage, and figured in
Scribner's Magazine, xvi. 38.

Mausilia mollis. Closely tufted, densely villous and cinereous
throujiliout ; hairs fine, silky, persistent or very tardily deciduous, finely
warted under a compound microscope: internodes and stems in the
numerous specimens at hand (terrestrial form) not at all developed •
root a cluster of delicate fibres : petioles filiform, reddish brown, flexu-
ous, 8-12 lines long, commonly nodding at the apex ; leaflets deltoid-
obovate, entire, rounded at the apex, broadly cuneate at the base, 1|
lines in length, equally broad : peduncles borne singly but in great
numbers and closely crowded, 2^-3 lines long ; conceptacles horizon-
tal, broadly oblong, compressed, 1| lines long, 1] lines broad, densely
white-villous, dull brown on the removal of the pubescence, finely 8-9-
wrinkled upon each surface, or smooth, often punctate ; rhaphe h line
in length; basal teeth very obscure ; sori 16-18. — Collected at San
Diego, Chihuahua, at 6,000 feet, by Mr. Hartman, 20 April, 1891
(no. 604). A very small and remarkably pubescent almost lanate
species.

124 PROCEEDINGS OP THE AMERICAN ACADEMY.

V.

CONTRIBUTIONS FROM THE KENT CHEMICAL LABORATORY
OF THE UNIVERSITY OF CHICAGO.

ON THE CONSTITUTION OF THE NITROPARAFFINE

SALTS.

By J. U. Nef.

Presented May 9, 1894.

Victor Meter, who discovered the nitro fatty compounds, has, as
is well known, shown that the primary and secondary nitroparafEnes
differ from the corresponding tertiary derivatives, as well as from the
aromatic nitro bodies, especially in the fact that they possess acid
properties. He has explained this very noteworthy character by the
assumption that the introduction of the nitro group exerts an " acid
making " influence on the molecule, which, however, extends only to
hydrogen atoms bound to the same carbon atom as the negative radi-
cal. He therefore supposes * sodic nitroethane to possess the consti-
tution represented by the formula

CHg-CHNa
I
NO,,

and, in an analogous manner, he represents the sodium salt of secon-
dary nitropropane by the formula

CHg^

CNa
CHa-^ I

NO2.

The fact that these salts, when treated with bromine, are converted
into bromnitroethane,

CHgCHBr
I
NO2,

* Ann. Chem. (Liebig), CLXXL 28, 48.

NEF. NITROPARAFPINE SALTS. 125

a Stroll!; acid, and into bromuitropropane,

CH3. .Br

en/ ^NOa,

a neutral body, seems at first to be an argument in favor of this
hypothesis. I have, however, already pointed out * that one is not
justified in drawing from this reaction such a conclusion with regard
to the nature of the sodium salts, and have further demonstrated t
that the hypothesis of the acid making influence of negative groups or
radicals has absolutely no justification, and is entirely illogical. That
this hypothesis is no longer tenable in many cases where it has hith-
erto been accepted is clear. That the sodium salts of acetoacetic
ether and of malonic ether possess a structure which must be repre-
sented by the formulae

CHg-CONa RO-CONa

II and II

HC-CO2R HC-COOR,

and not, as previously supposed, by the formulae

CH3-CO RO-CO

I and I

NaCHCOgR NaCHCO-.R,

can now be regarded as settled experimentally beyond a doubt. J

For these reasons it is almost self-evident that the metal in the
nitroparafiine salts cannot be bound directly to carbon, and is in all
probability bound to oxygen ; and the following experiments prove
this in a most satisfactory manner.

I. Decomposition of Primary and Secondary Nitro-

PARAFFINE SaLTS BY MEANS OF ACIDS.

Assuming that nitroethane possesses the constitution

CH3~CH,N ; ^ ,

* Amer. Cliem. Journal, XIII. 427.
t These Proceedings, XXVII. 157.

t Ann. Cliem. (Liebig), CCLVIII. 261, CCLXVI. 52, CCLXXVI. 200, and
CCLXXVII. 59.

126 PROCEEDINGS OF THE AMERICAN ACADEMY.

it is very well possible * that on treating it with sodic hydrate or with
sodium ethylate, an addition of these reagents to the nitro group takes
place, forming thus the products,

CH3-CH,-N^^^ and CHa-CH^-N^^^^a'
O O

which by loss of water or alcohol must give sodic nitroethane of the

constitution

CH3CH = NONa.

II
O

This reaction is entirely analogous to the formation of sodic malonic
ether from malonic ether and sodium ethylate,t the only difference
being in the fact that sodic malonic ether is instantly decomposed by
water, regenerating the ester and forming sodic hydrate,! whereas
sodic nitroethane dissolves in water without decomposition.

In favor of this interpretation of salt formation can be adduced the
fact that many higher members of the nitroparaflSne series, which
ought, like nitroethane, to possess acid properties, dissolve only with
great difficulty and on prolonged treatment in very concentrated sodic
hydrate ; § i. e. they possess very weak acid properties and were con-
sequently long considered to be neutral substances, || — a fact which,
as V. Meyer also observes,1[ is very noteworthy. If, however, the
salt formation depends on the addition of sodic hydrate to the nitro
group and subsequent loss of water, the peculiar and unexpected
behavior observed in these cases is easily comprehensible ; the first
members of the nitroparaffine series are soluble in water, and thus
more easily attacked by sodic hydrate, whereas the higher members
are insoluble in water.

Since, according to this conception of the nitroparaffine salts, they
do not possess a constitution analogous to that of the free nitro com-
pounds, it does not of necessity follow, especially since the salts are
soluble without decomposition in water, that these salts can be con-

* These Proceedings, XXVII. 150-158.
t Ann. Chem. (Liebig), CCLXVI. 67, CCLXXVI. 244.
t Ibid., CCLXVI. 113.

§ Ibid., CLXXV. 135, 144; Ziiblin,Ber. d. chem. Ges., X. 2083; Konowalow,
Ber. d. chem. Ges., XXV. Ref. 108.

II Ber. d. chem. Ges., V. 203; Ann. Chem. (Liebig), CLXXI. 44.
1[ Lehrbuch, p. 205.

NEF. — NITROPARAFFINE SALTS. 127

verted back again completely into the free nitro bodies from which
they were obtained. The first problem therefore was to determine
this point by experiment, and it was found that under no condition is
it possible to convert these salts back again completely into the cor-
responding free nitro compounds. On adding an aqueous solution
of a sodium salt of a nitroparalfine to cold dilute sulphuric or
hydrochloric acid, not a trace of the nitroalkyle is regenerated,
but a more or less smooth decomposition into nitrous oxide and an
aldehyde or ketone takes place, according to one of the following
equations :

I. 2 R-CH = NONa + 2 HCl

O

Sodium Salt of a Primary Nitroparafflne.

N^ / NOHv

= 2 R-CH : O + II O from II +2 NaCL

N'^ V NO 11/

11. 2 ^^C = NONa + 2 HCl
R/ II

O

Sodium Salt of a Secondary NitroparaflSne.

R\ N^ / NOHx

= 2 ;C:0+ll O ( from II ) + 2 NaCl.

R/ N^ \ NOH/

This new very noteworthy decomposition of nitroparaffine salts,
which always takes place, no matter how the experiment is carried
out, has been overlooked by V. Meyer and by all who have worked
with these compounds. V. Meyer states repeatedly that it is possible
to regenerate the free nitroparaffine from its sodium salt or from a
caustic alkaline solution, — a fact which is only true to a limited ex-
tent (see below). Decomposition always takes place according to one
or the other of the above equations, and this fact alone proves that the
nitroparaffine salts cannot possibly have a constitution analogous to
that of the free nitroalkyles.

If, for example, sodic nitroethane possessed the constitution

CHgCHNa

I
NO,,

it ought to be possible to convert it quantitatively into CH,— CHoNO.j
by addition to dilute sulphuric acid, just as sodium acetate goes over

128 PROCEEDINGS OF THE AMERICAN ACADEMY.

completely into acetic acid on similar treatment. As a matter of fact,
not a trace of uitroethane is formed.

Decomposition of Sodic Nitroelhane by Acids. — Sodic nitroethaiie
can be obtained from nitroethane by treating it in absolute etheicd,!
scjlution with sodium wire, or by means of alcoholic sodic hydrate,
according to the method of V. Meyer.* It is, however, best formed
by addition of au alcoholic solution of sodic ethylate to an alcoholic
solution of nitroethane. The salt is filtered off, well washed with
alcohol, and dried on clay plates and over sulphuric acid in a vacuum ;
30 grams nitroethane gave regularly 33 grams sodium salt. A com-
plete analysis of the salt is not possible, because it explodes on hciuing
with cupric oxide.

0.3035 gram substance gave 0.2225 gram NagSO^.

Theory for

CoIIiNOoNa.

Found.

23.71

23.74

Na

On adding quickly an aqueous solution of sodic nitroethane (1 part
to 10 parts H2O) to cold dilute sulphuric acid (1 : 5), using for one
gram salt about 15 to 20 c.cm. of the acid, decomposition takes place
into nitrous oxide and acetaldehyde ; the reaction takes place with
much evolution of heat, the solution becomes colored green, and not
a trace of nitroethane is regenerated. The experiment can be carried
out quantitatively as follows : 15 to 20 c.cm. of dilute sulphuric acid
are brought into a small distilling flask which is provided with a
separatory funnel, and is connected on the one hand with a carbonic
acid generator, and on the other with a Schiff's nitrometer. Air is first
expelled from the apparatus by means of carbon dioxide (passed over
heated copper), and then the aqueous solution of sodic nitroethane
is quickly added by means of the separatory funnel and well washed
down with water. The distilling flask is then heated to boiling and
the nitrous oxide driven over, by a current of carbonic acid, into the
azotometer. The aldehyde which is formed is absorbed by the caus-
tic potash solution (1:2) in the nitrometer, which was saturated
previous to the experiment with nitrous oxide.

0.7 gram substance gave 77 c.cm. NgO at 15° and 754 mm., corre-
sponding to 89.4% of the theoretical amount.

1.0 gram substance gave 105 c.cm. N2O at 16° and 748 mm., corre-
sponding to 84.6% of the theoretical amount.

* Ann. Chem (Liebi^), CLXXI. 29.

NEF. NITROPAllAPFINE SALTS. 129

That nitrous oxide was present was shown by its characteristic
reactions, and by passing a known volume of the gas over heated cop-
per, whereby au equal volume of nitrogen was obtained.

In order to determine the amount of acetaldehyde quantitativi ly,
the same apparatus is used except that the distilling flask, instead of
being connected with an azotometer, is connected with a condenser
and a well cooled receiver containing water. About one half of the
solution in the distilling flask is then boiled off, and the distillate in
the receiver is treated with powdered calcic carbonate to remove
traces of acetic acid, and then again distilled over. The second dis-
tillate thus obtained is perfectly neutral to test paper, and is heated
for four hours in a sealed tube at 100° with an excess of silver oxide.*
The silver acetate formed is boiled out with water, and the amount
determined by evaporating the aqueous solution.

1.5 grams sodic nitroethane gave 1.8 grams silver acetate, or G9.7%
of the theoretical amount.

A portion of the silver acetate, recrystallized from water and dried
at 80-90°, gave the following result on analysis :

0.3552 gram substance gave 0.2297 gram silver.

Theory for

CIIaCO^Ag Found.

Ag 64.67 64.67

Sodic nitroethane has thus been split pretty smoothly, on treatment
with an acid, according to the following equation :

2 CH3CH = N-ONa + H2SO, = 2 CH3CHO + NsO-f HgO + NagSO,.
II
O

The amount of acetaldehyde obtained (69.7% of the theory) is
undoubtedly somewhat less than the actual amount formed in the
reaction, since a slight loss of aldehyde can hardly be avoided in the
above operations. It was shown qualitatively that nitrous acid, acetic
acid, and hydroxylamine are side products in the above reaction.
Entirely analogous results are obtained if hydrochloric acid, instead
of sulphuric acid, is used in the reaction.

* A preliminary experiment with pure acetaldehyde showed that this method
is well adapted for the quantitative determination of aldehyde. 1 gram acetal-
dehyde (bpt. 23°), 20 c.cm. water, and 8.3 grams silver oxide, heated in a sealed
tube at 100° for one hour, gave 3.1 grams silver acetate corresponding to 81.7 per
cent of tlie theory. Traces of unchanged aldehyde were noticed on opening the
sealed tube.

VOL. XXX. (n. S. XXII.) 9

130 PROCEEDINGS OF THE AMERICAN ACADEMY.

The followiug explanation of this noteworthy decomposition of
sodic uitroethane is extremely probable, especially because of facts to
be presented later in this paper. On the addition of sodic nitroethaue,

CH3CH = NONa,
II
O

to a dilute acid, there is first formed the product

CH3CH = NOH,
11
O

which must be a strong oxidizing agent, and which therefore splits,
just as in analogous cases to be presented below, by intramolecular
oxidation into

NOH
2 CH3CHO and II

NOH.

V. Meyer states * that on addition of an acid to aqueous sodic nitro-
ethane, or to a caustic alkaline solution of nitroethane, free nitroethane
is formed. Later he mentions f that acids never regenerate the
entire amount of nitroethane from a solution of this substance in
caustic potash, and that ethylnitrolic acid is always formed in small
quantity. He seems never to have noticed a decomposition into acet-
aldehyde and nitrous oxide, which however always takes place, as is
evident from the following experiments.

20 grams nitroethane are dissolved in a solution of 20 grams caustic
potash (1^ molecules) in 300 c.cm. of water: the smell of nitroethane
is still distinctly noticeable. To this solution is added very slowly
dilute sulphuric acid, taking care to cool well with water. As soon
as the solution becomes acid, it is colored greenish, and a gas evolution
(N2O) and strong smell of acetaldehyde are noticed. Since no nitro-
ethane separates out, the sglution is extracted three times with ether.
The ethereal solution, after drying with calcic chloride, is then care-
fully fractionated; the lower boiling portions smell strongly of acetal-
dehyde. 7.2 grams oil were obtained, boiling between 112° and 118°,
which, redistilled, gave 5.2 grams, boiling between 112° and 116°.
The oil, although it smells of aldehyde, undoubtedly consists chiefly

* Ann. Chera. (Liebig), CLXXI. 27-30. Cf. also Ber. d. chera. Ges., V.
514-516.

t Ann. Cliem. (Liebig), CLXXV. 88-90.

NEF. — NITROPARAFFINE SALTS. 131

of nitroethane, since on treatment with sodic nitrite 5 grams of ethyl-
nitrolic acid were obtained from it.

An entirely analogous result is obtained on adding very slowly
dilute sulphuric or hydrochloric acid to an aqueous solution of sodic
nitroethane (made by means of sodium ethylate).

It is also possible to obtain traces of nitroethane on adding very
slowly an aqueous solution of the sodium salt to dilute sulphuric acid,
cooled with pieces of ice. The chief reaction in this case is, however,
decomposition into acetaldehyde and nitrous oxide.

Decomposition of Nitroethane-mercuric-chloride by means of Acids.

Nitroethane-mercuric-chloride was obtained by addition of corrosive
sublimate (one molecule) to an aqueous solution of sodic nitroethane.
Since V. Meyer determined only the percentage of chlorine and mer-
cury in the salt,* the substance, after drying for 24 hours in a vacuum,
was analyzed for carbon and hydrogen.

0.6849 gram substance gave 0 1949 gram CO2 and 0.0813 gram HgO.

Theory for
CaHiNOaHgCl. Found.

C 7.75 7.76

H 1.30 1.34

The former statements concerning the properties of this salt could
be confirmed except in one particular. V. Meyer mentions * that
acids regenerate nitroethane. I found it impossible, under any condi-
tion, to obtain from this salt even a trace of nitroethane.

Dilate nitric acid and sulphuric acid act upon the salt very slowly
in the cold, forming acetaldehyde and nitrous oxide : dilute hydro-
chloric acid reacts with great violence upon it, decomposing it into
nitrous oxide and acetaldehyde. A large amount of the mercury salt,
suspended in water, was treated in the cold with hydrogen sulphide,
and thereupon the solution was partially distilled off. The distillate
contained an oil which is neutral and smells strongly of thioaldehyde,
but in which not a trace of nitroethane could be detected by means of
the very delicate ethylnitrolic acid reaction.

As mentioned above, nitroethane-mercuric-chloride is decomposed
by addition of dilute hydrochloric acid into nitrous oxide and acetalde-
hyde ; the reaction is accompanied by a decided evolution of heat, and
a greenish-colored solution is obtained. The quantitative determina-

* Ann. Chem. (Liebig), CLXXI. 31.

132 PROCEEDINGS OP THE AMERICAN ACADEMY.

tions were carried out in the same apparatus as that used above in the
case of the sodium salt. The mercury salt is placed in the distilling
flask, and 10-15 c.cin. water added; after removing the air, dilute
hydrochloric acid is added by means of the separatory funnel, and the
solution is then heated to boiling. In the case of the aldehyde de-
termination, the distillate is treated with powdered calcic carbonate,
in order to remove the hydrochloric acid carried over, and then
redistilled.

1 gram salt gave 39 c.cm. NgO at 23° and 748 mm., corresponding to

98 per cent of the theory.
1 gram salt gave 38 c.cm. NoO at 22° and 748 mm.^ corresponding to

95.6 per cent of the theory.
4.5 grams salt gave 1.77 grams silver acetate, i.e. 72.9 per cent of the

theoretical amount.

The analysis of the silver acetate, recrystallized from water, gave
the following result.

0.3831 gram substance gave 0.2468 gram silver.

Theory for

CHgCOoAg. Found.

Ag 64.G7 64.42

Nitroethane-mercuric-chloride has thus been split by the acid, chiefly
according to the following equation :

2 CHs-CH = N-OHgCl + 2 HCl
II
O

= 2 CH3CHO + N2O + HoO + 2 HgCV

Nitrous acid and hydroxylaminehydrochloride (0.4 gram crude salt
from 10 grams) are side products formed in this decomposition.

Decomposition of Sodic Nitromethane by means of Acids.

Sodic nitromethane can be obtained from nitromethane by treating
it in absolute ethereal solution with sodium wire, or by means of
alcoholic sodic hydrate according to the method of V. Meyer. It is,
however, best formed by addition of an alcoholic solution of sodium
ethylate to an alcoholic solution of nitromethane. 30 grams nitrome-
thane yield thus regularly from 45 to 50 grams of the sodium salt,
which at first contains, as V. Meyer has shown, one molecule of
alcohol,

CHgNOsNa + C.HgO ;

NEF. — NITROPARAFFINE SALTS. 133

the salt slowly loses its alcohol ou standing over sulphuric acid in a
vacuum, but never completely. An analysis of a salt, which had been
kept 14 hours in a desiccator, gave the following figures

0.2500 gram gave 0.1791 gram NaaSOi.

Theory for Theory for

CIIoNOoNa. CHaNO^Na + CaHeO. Found.

Na 27.71 17.83 ' 23.21

The constitution of this alkoholate is very probably

/OC0H5
CH3-N

II \ONa,
O

formed by the addition of the sodium ethylate to the nitro group.
Sodic nitromethane, free from alcohol,

O

II
CHo = NONa,

which is best obtained by treating nitromethane in ethereal solution
with sodium, is a very unstable and remarkable body, whicli seems to
exist only under great tension. On adding a small amount of water
to it, spontaneous decomposition, with tremendous evolution of heat
and ofttiraes explosion, takes place.* On allowing an aqueous solu-
tion of the salt to evaporate spontaneously, it is decomposed chiefly
into sodic carbonate and sodic nitrite (besides other products). The
alcoholate of sodic nitromethane is much more stable than the pure
sodium salt, but behaves otherwise in an entirely analogous manner.
On adding an aqueous solution of either of these salts to dilute sul-
phuric acid or hydrochloric acid, decomposition into nitrous oxide,
formaldehyde, nitrous acid, carbonic acid, and hydroxylamine takes
place, and not a trace of nitrnmethane is regenerated.

The amount of nitrous oxide formed is small, as is evident from the
following determinations.

2 grams sodium salt, made by means of sodium ethylate and kept a

long time in a vacuum, gave 20 c.cm. N2O at 20° and 752 mm.,
corresponding to 7.44 per cent of the theory for CHgNOoNa,

3 grams sodium salt, made by means of sodium ethylate and used

directly, gave 26 c.cm. NoO at 22°, and 748 mm., correspond-
ing to 7.48 per cent of the theory for CHgNOgNa -f ^ CoHcO.

* Ann. Chem. (Liebig), CLXXI. 34.

134 PROCEEDINGS OF THE AMERICAN ACADEMY.

In the decomposition of sodic nitromethane by acids, a splitting
takes place, but in subordinate amount, according to the equation

2 CH2 = NONa + 2 HCl = 2 CH2O + N2O + HgO + 2 NaCl ;

II
O

which is entirely analogous to the decomposition of nitroethane salts.
The reason for this difference is also perfectly clear and will be ex-
plained farther on.

It is possible, but only under very special conditions and in subordi-
nate amounts, to regenerate nitromethane from its sodium salt;* in all
cases a very decided decomposition takes place, as will become evident
from the following experiments, 10 grams sodic nitromethane, made
by means of sodium ethylate and kept 10 hours in a vacuum over
sulphuric acid, are dissolved in water containing pieces of ice, and then
dilute sulphuric acid is added very slowly. As soon as the solution
becomes acid, a smell of formaldehyde is noticed, as well as the pres-
ence of nitrous acid and of nitrous oxide and carbon dioxide. 20 c.cm.
of the solution f is then distilled off (until no smell of nitromethane
can be noticed in the flask) and the distillate extracted with ether.
The ethereal solution, carefully fractionated, gave 1.9 grams nitrome-
thane, boiling between 99° and 101°. An entirely analogous result is
obtained from a solution of nitromethane in caustic soda or potash.

Decomposition of Secondary Sodic Nitropropane by Acids.

Secondary nitropropane was made according to the directions of
V. Meyer.j The yield is very poor. The sodium salt was made by
means of alcoholic sodium ethylate, and dried over sulphuric acid in a
vacuum.

On treatment of an aqueous solution of this salt with dilute acids, a
fairly smooth decomposition into acetone and nitrous oxide, according
to the equation

CH CH

2 '^C=:N-ONa+2HCl = 2 '^CO-f N2O+ HgO -h2NaCl
CH3/ II CH3/

O

takes place, — a reaction which is perfectly analogous to the decompo-
sition of salts of primary nitroparaffines.

* No statements concerning this point could be found anywhere.
t Preibisch, Journ. f. prakt. Chemie, [2.], VIII. 311.
\ Ann. Chem. (Liebig), CLXXT. 40

NEF. — NITROPARAFFINE SALTS. 135

0.7 gram sodium salt, dissolved in water and added in the above
apparatus to 15 c.cm. dilute sulphuric acid, gave (the solution becomes
colored greenish) 51 c.cm. NoO at 21° and 754 mm., corresponding to
66.52 per cent of the theory.

The formation of acetone in this reaction was proved as follows.
1.9 grams secondary sodic nitropropane are dissolved in water and
added to 15 c.cm. dilute sulphuric acid. The bluish green solution is
heated to boiling and partially distilled off. The distillate is filtered
from a small amount of solid and treated with powdered calcic car-
bonate and then redistilled. The solution thus obtained, which smells
distinctly of acetone, is treated with a solution of 0.6 gram hydroxyl-
amine hydrochloride and 0.34 gram caustic soda in 2.5 c.cm. water.
After standing for an hour, the solution is extracted three times with
ether, and after getting rid of the dried ether 0.35 gram residue is
obtained. This whs recrystallized from ligroine (bpt. 40°-60°) and
found to melt at 62°-63°, and to consist of pure acetoxime, identical in
every respect with a product made for comparison.

II. Synthesis of Mercury Fulminate, C : NOhg, from Sodic

C : N-ONa„

NiTROMETHANE, Hg II

o

With the exception of nitroethane-mercuric-chloride, no heavy
metal salt of a simple nitroparaffine has been obtained and analyzed.
Victor Meyer and Rilliet obtained from sodic nitromethane and
mercuric chloride a yellow very explosive mercury salt, which they
regarded as mercury nitromethane,

/CH„N02
\CH2NO2,

•

but which, on account of its very dangerous properties,* was not
further investigated or analyzed.

Since such heavy metal salts might perhaps be especially well
adapted for a determination of the constitution of the nitroparaffine
salts, a study of this salt was therefore again taken up, and it soon
became evident that it is not a salt of nitromethane at all because it
contains no hydrogen.

On adding quickly an aqueous solution of sodic nitromethane to a
solution of corrosive sul)limate, or vice versa, a white precipitate is first

* Ber. d. chem. Ges., V 1030. Cf. Ann. Chem. (Liebig), CLXXI. 36.

136 PROCEEDINGS OF THE AMERICAN ACADEMY.

formed, which very soon becomes colored yellow, and which in all
probability is the mercury salt of nitromethane,

CH2 = N-Ohg*

II
O

This white salt exists, however, only a few moments, since it is a
very powerful oxidizing agent capable of intra-molecular oxidation.
It therefor^ loses water almost instantly,

C : N - Ohg = C : NOhg + H,0,
H2 II
O

forming mercuric fulminate ; and since the constitution of fulminate
of mercury is definitely proved in the following paper to be C : NOhg,
it follows at the same time that the nitromethane salts must have the
constitution represented by the general formula

H.,C : NOM.

II
O

An aqueous solution of sodic nitromethane (10 grams) is added
rapidly to a cold mercuric chloride solution (containing 16 grams
HgClo). After standing 15 minutes, the solution (300-500 c.cm.) is
heated to boiling and quickly filtered from the yellow precipitate, which
is then boiled out once with hot water. On cooling, a grayish white
heavy crystalline precipitate separates out from the filtrate. In order
to get rid of traces of adhering mercury, it is dissolved in dilute cya-
nide of potash and reprecipitated with dilute nitric acid.f In this way
perfectly pure fulminate of mercury is obtained, which is absolutely
identical in every respect with the product made in the ordinary way.
The yield is 1 gram to 1.6 grams pure salt from 10 grams sodic nitro-
methane.

0.2221 gram substance, dried over H2'^04 in a vacuum, and dissolved
in dilute hydrochloric acid, with addition of KCIO3, and precipi-
tated with HoS, gave 0.1815 gram HgS.

0.4005 gram substance, mixed with cupric oxide, gave 0.1248 gram
CO., and 0,0074 gram HoO.

0.1968 gram substance gave 17.5 c.cm. Ng at 16° and 747 mm.

* hg represents a half-atnm of bivalent mercury,
t Steiner, Ber. d. cliem. Ges., IX. 787.

NEF. — NITROPARAFFINE SALTS. 137

Theory for

HgOoNoCj.

Found.

Hg

70.42

70.45

C

8.45

8.49

H

0.205

N

9.86

10.18

The following very simple reaction therefore takes place in the
formation of mercuric fulminate from sodic nitromethane :

C : NONa + hgCl = C : NOhg + NaCl = C : NOhg + HgO + NaCl.
Ha II U, II

o o

It follows clearly, however, that the mercury salt of nitromethane,

H^C : N-Ohg,

' II
O

formed as the intermediate product, must be a strong oxidizing agent,
which at first, for want of anything else present, acts on itself, form-
ing by intra-molecular oxidation fulminate of mercury, C : NOhg.
Since, however, the fulminate of mercury thus formed, in consequence
of its containing unsaturated or bivalent carbon, possesses an enor-
mous reactivity (see following paper) and can therefore most readily
take up oxygen, (this explains the reducing action of carbon monoxide,
C : O, of cyanide of potash, KN : C, as well as of the fulminates,
C : NOM,) It follows very clearly that the strong oxidizing agent
present, mercury nitromethane,

H2C : N-Ohg,
II
O

can act also on the mercury fulminate formed (in the nascent state),
converting it into mercuric carbondioxidoxirae, O : C : NOhg, whereby
the mercuric nitromethane itself is reduced to mercuric formoxime,

/H2C : NOhg \

CH2 : NOhg ( II = CH2 : NOhg + O j .

This explanation suffices completely in clearing up the nature of
all the products which are formed by the interaction of sodic nitro-
methane and mercuric chloride. The yellow salt obtained by V. Meyer

138 PROCEEDINGS OF THE AMERICAN ACADEMY.

and Rilliet * is, in all probability, basic mercuric carbondioxidoxime,

Hg; ;C:NOhg.

A yellow compound insoluble in water is, in all cases, the chief pro-
duct of the action between aqueous solutions of sodic nitromethane
and mercuric chloride ; in fact only by the above mentioned method is
it possible to obtain fulminate ot mercury in ajipreciable amounts.
If the corrosive sublimate solution is heated, before adding the sodic
nitromethane solution, or if the former solution is added to the latter
solution, not a trace of mercuric fulminate can be isolated, and much
yellow insoluble mercury salt is formed. The composition of this yel-
low salt varies also according to whether the mercuric chloride solution
is added to a solution of the sodium salt, or vice versa. In the latter
case, the salt obtained contains much more carbon and nitrogen.

Basic Mercuric Carbondioxidoxime, Hg C : NOhg.

On the addition of a solution of mercuric chloride (containing
16 grams HgCl2) to a cold aqueous solution of sodic nitromethane
(10 grams), a white precipitate is formed which, after an hour's stand-
ing, has become perfectly yellow. The solution is decanted, and the
residue is repeatedly treated with boiling water, and then dried on
clay plates, and finally at 100°. The latter operation must be carried
on with all possible precautions, since it happened several times that
the salt exploded, demolishing the air bath and the windows of the
hood. The yield from 10 grams sodium salt was regularly from
8 to 10 grams. The salt is, at ordinary temperatures, not quite so
dangerous as mercuric fulminate, but it often explodes by friction.
It is absolutely free from chlorine and contains no hydrogen : digestion
with dilute sulphuric or with dilute nitric acid, in which it is insoluble,
does not change the composition of the salt.

0.4698 gram, mixed with cupric oxide, gave 0.0612 gram COo and

0.0129 gram l\0.
0.1818 gram, mixed with cupric oxide, gave 6.5 ccm. Ng at 19°

and 747 mm.
0.2195 gram, dissolved in dilute hydrochloric acid, with addition of

little KCIO3 and precipitated with HgS, gave 0.2045 gram HgS.

* Ber. d. cliem. Ges., V. 1030. Cf. Ann. Chem. (Liebig), CLXXI. 35.

NEF. NITROPARAFPINE SALTS. 139

Theory for
Hg(0)c : NOhg

Found.

c

3.21

3.34

H

0.305

N

3.74

4.04

Hg

80.20

80.31

The salt is instantly decomposed by dilute hydrochloric acid, form-
ing calomel, carbonic acid, and a substance having a smell like prussic
acid, but not a trace of nitrous oxide is formed. Concentrated hydro-
chloric acid decomposes the salt into carbonic acid and hydroxyl-
aminehydrochloride (proved by conversion into acetoxime). The salt
is very soluble in dilute cyanide of potash, and on addition of dilute
nitric acid no precipitate is formed. It was at first long suspected
that the salt was basic fulminate of mercury, but it is not possible
in any way to convert this salt into normal fulminic acid salts. Thus
a large quantity of it was added to hydrochloric acid (one part cone,
acid 1.18 to one part water), and the solution thereupon extracted
with ether, but not a trace of formylchloridoxime (see following
paper) was obtained. On treating the salt suspended in water with
sodium amalgam, mercury is formed, and a solution obtained free
from mercury, in which, however, not a trace of sodium fulminate
could be detected.

That the salt possesses the constitution,

Hg; X^:NOhg,

is very probable, but not yet proved with absolute certainty. It will
therefore be further investigated, especially since its behavior towards
alkyliodides and its conversion into carbondioxidoxime, O : C : NOH,
may be of interest.

As mentioned above, there is formed, on addition of aqueous sodic
nitromethane to a mercuric chloride solution, besides fulminate of
mercury, a yellow insoluble salt, which is richer in carbon and in
nitrogen than the yellow salt just described.

This yellow salt, precipitated from hot mercuric chloride solution,
was repeatedly digested with boiling water and then dried, first on
a clay plate, and then carefully at 100°.

The substance is likewise free from chlorine and hydrogen and
explodes very readily by friction.

140 PKOCEEDINGS OP THE AMERICAN ACADEMY.

0.6731 gram, mixed with cupric oxide, gave 0.1487 gram COg and

0.0236 gram H2O.
0.2776 gram gave 16 c.cm. Ng at 15° and 749 mm.

Theory for

Theory for

Hg(g)c : NOhg

0 : C : NOhg

Found

c

3.21

7.59

6.03

H

0.39

N

3.74

8.86

6.65

This salt behaves in every respect — towards dilute nitric, hydro-
chloric, and sulphuric acid, towards concentrated hydrochloric acid,
sodium amalgam, and cyanide of potash — in exactly the same man-
ner as the mercury salt just described. It probably consists therefore
of a mixture of much mercuric carbondioxidoxime, 0 : C : NOhg and
of the basic salt,

Hg ^ ^ C : NOhg.
^O^

It is natural that in this case much less basic salt should be formed
than in the former case, where the corrosive sublimate solution was
added to the sodic nitromethane solution.

The above experiments have made it clear that the heavy metal
salts of nitromethane, e. g. a mercury salt,

H^C = N-Ohg,
II
O

are not capable of existence, but are immediately decomposed by intra-
molecular oxidation. An investigation of the precipitates formed by
adding copper sulphate or lead acetate to an aqueous solution of sodic
nitromethane showed that these consist in great part either of copper
carbonate or of lead carbonate (the lead salt obtained is yellow and
explodes, and probably contains some

Pb C : NOpb).

For these reasons it is obvious that sodic nitromethane itself,

H2C = NONa,
II
O

NBF. — NITROPARAPFINE SALTS. 141

which, as is known^, exists ouly under great tension, must be a strong
oxidizing agent which can easily, by intra-molecular oxidation, go
over into O : C : NONa and CH2 "• NONa,* which products in turn
are readily split into carbonic acid, hydroxylamine nitrous acid, and
other compounds. This explains therefore most clearly the intensely
violent decomposition of this salt on addition of a small quantity of
water, as well as its decomposition, in dilute aqueous solutions, into
sodic carbonate, sodic nitrite, and other products.

On adding sodic nitromethane to dilute acids, the product

U,C = N-OH

II
O

is in all probability first formed, which must readily go over, by
intra-molecular oxidation, into 0:C;NOH and CH2 : NOH, or into
their decomposition products. A slight decomposition, however, into
2 CH^O and N2O also takes place, — which in the case of the other
primary and the secondary nitroparaifine salts is the chief reaction
(see above) .

The formation of the above mentioned remarkable decomposition
products of nitroparaffiue salts, which, as is clearly seen, is due solely
to intra-molecular oxidation, find further on their complete analogy in
the decomposition products of esters of the formula,

RCH : NOC2H5 and R-CH : NOCH3 .

II II

o o

These substances also decompose (some spontaneously) by intra-mo-
lecular oxidation mto RCH : NOH and CH3CH : O or CH2O.

* The fulminate of soda, C : NONa, which is first formed as an intermediate
product,

H2C • NONa = C NONa + H2O,
II
O

must naturally be converted immediately by the excess of sodic nitromethane
present into O : C : NONa, and thus it in turn be reduced to CHo : NONa. It
was not possible at any rate, under any condition, to convert sodic nitrome-
thane by loss of water into sodium fulminate, — a fact which in view of the
enormous tendency of this salt to take up oxygen is almost self-evident.

142 PROCEEDINGS OF THE AMERICAN ACADEMY.

III. The Action of Alkyliodides on Silver Dinitroethane,

CHg - C = NOAg.

I II
NOo O

Preparation of Dinitroethane. — After many experiments, the fol-
lowing method of preparing dinitroethane was found to give the best
results.* 50 grams bromnitroethane (bpt. 140-145°, prepared accord-
ing to the directions of Tscherniak f), 50 c.cm. alcohol, and a solution
of 56 grams potassic nitrite in 56 grams water, were kept shaken up
very thoroughly in a shaking apparatus for 24 hours. The potassium
salt of dinitroethane separates out slowly in yellow crystals, which,
when filtered off and well washed with alcohol, are sufficiently pure.
The yield is from 13 to 14 grams. The salt is dissolved in warm
water and treated directly with silver nitrate (one molecule), and
the silver salt obtained in glistening heavy yellow leaflets, which are
filtered off and dried in a vacuum.

Ter Meer J has already studied the behavior of this salt towards
methyliodide and obtained thereby an oil, which, on treatment with
alcoholic potash, is partially converted back again into potassic dini-
troethane. Very recently Duden has studied the behavior of silver
dinitromethane towards alkyliodides, § and shown that, for example, it
is converted by means of methyliodide into dinitroethane.

The reaction which takes place, however, on treating the silver salt
of dinitromethane and of dinitroethane with alkyliodides, is far more
complicated than either ter Meer or Duden have surmised ; the very
remarkable and peculiar reaction is cleared up fully by the following
experiments.

50 grams silver dinitroethane are added slowly to 100 grams methyl-
iodide, taking care to cool well with water. Reaction quickly takes
place, with formation of silveriodide, and, towards the end, a strong
smell of formaldehyde is noticed. After standing one hour, ether is
added and the excess of methyliodide as well as the ether is removed
from the filtrate by heating in a distilling flask at 50 mm. pressure to a
temperature of 50°. The residual oil is taken up with ether, and treated
with cold dilute sodic hydrate and the deep red colored alkaline solu-

* Ter Meer, Ann Chem. (Liebig), CLXXXI. 6; Chancel, Jahresber,, 1883,
p. 1039.

t Ann. Chem. (Liebig), CLXXX. 126. t Ibid., CLXXXI. 16.

§ Ber. d. cliem. Ges., XXVL 3003.

NEF. NITROPARAPPINE SALTS. 143

tion immediately acidified with dilute sulphuric acid and extracted
with ether. After drying the ethereal solutious with calcic chloride,
and getting rid of the ether at reduced pressure, 10.1 grams of neutral
products and 9 grams of acid products are obtained.

On allowing the oily acid portion to stand in the air, crystals of
ethylnitrolic acid (1 gram) separated out, and the oil gave, on treat-
ment with alcoholic potash, 5.3 grams of potassic dinitroethane, which
was filtered off. The deep red colored filtrate gave, on acidifying and
extracting with ether, 0.4 gram more of ethylnitrolic acid. The acid
products formed in the above reaction are therefore dinitroethane and
ethylnitrolic acid. The latter substance melted at 88°, and was iden-
tical in every respect with a preparation made from nitroethane.*
This substance gives on treating in alkaline solution with benzoyl-
chloride f a characteristic insoluble benzoate.

Ethylnitrolic Acid Benzoate, CHg — C = NOCOCeHs-

I
NO,

12.1 grams ethylnitrolic acid, dissolved in 46 c.cm. sodic hydrate
(1 : 10), and shaken with 16.4 grams benzoylchloride gave 21.6 grams
crude benzoate (calculated 24.2 grams). Crystallized twice from
benzene, and twice from alcohol, it is obtained in colorless flat needles,
melting at 135° ; it is easily soluble in hot benzene and alcohol, and
very slightly in ether. It is insoluble in water, and is decomposed
slowly on standing with sodic hydrate into benzoic acid and ethyl-
nitrolic acid.

0.1585 gram, dried at 70°. gave 0.3001 gram COg and 0.0604 gram HgO.
0.1995 gram, dried at 70°, gave 24 c.cm. Ng at 16° and 750 mm.

Theory for Cc,H8N„04

Found.

c

51.92

51.64

H

3.85

4.23

N

13.46

13.84

The above mentioned portion (10.1 grams), insoluble in alkalies, is
also a mixture of two substances. It was first distilled with steam,
whereby all but a trace of yellow sticky material is easily carried
over ; the first portions of the distillate contain oil drops, which do not
solidify, and the latter portions contain a substance which solidifies in

* Ann. Chem. (Liebi^), CLXXV 94, CLXXXI. 2.

t Baumann and Udranzsky, Ber. d. chem. Ges., XXI. 2744.

144 PROCEEDINGS OP THE AMERICAN ACADEMY.

the condenser, so that it is possible ah-eady at this point to accomplish
a partial separation of the two products. The distillate was, however,
extracted with ether; and the ethereal solution was washed with dilute
sodic hydrate, and, after drying with calcic chloride, the ether was dis-
tilled off. 9.2 grams of oil were obtained, which was fractioned under
reduced pressure. The first portions boiled between 78° and 85° at
30 mm. pressure and were oily ; as soon as the distillate begins to
solidify, the operation was discontinued, and the residue in the distil-
ling flask (4.25 grams) poured out. On cooling, this solidified com-
pletely. It was transferred to a clay plate, and washed with a small
amount of ligroine, and thus 2.8 grams perfectly pure fi dinitropropane,
melting at 55°, were obtained, identical in every particular with the
product obtained by V. Meyer and Locher.*

0.2185 gram, dried over H2SO4 in a vacuum, gave 0.2141 gram COg

and 0.0941 gram HoO.
0.2272 gram gave 43.5 c.cm. N2 at 24° and 753 mm.

Found.

26.72

4.79

21.27

The lower boiling oil, which is not volatile without decomposition
at ordinary pressure, and which is more volatile with steam than
jB dinitropropane, was not analyzed, as it still contained traces of
/? dinitropropane. That it consists, however, of ethyluitrolic acid
methylester,

CH3-C=NOCH3,
I
NO2

is very probable, and a number of experiments were therefore carried
out with the object of isolating this substance directly from the silver
and lead salts of ethylnitrolic acid by means of methyliodide, which,
however, failed on account of the great instability of the ethylnitrolic
acid salts in the presence of water. f

On adding 11 grams of silver dinitroethane to 50.5 grams ethylio-
didi!. reaction sets in immediately, and at the end a very strong smell of
acetaldehyde is noticed. Both neutral and acid products are formed :

* Ann. Chem. (Liebig), CLXXX. 147.

t V. Meyer, Ann. Chem. (Liebig), CLXXV. 103.

c

Theory for
(CH3), :C(N02)2.

26.86

H

4.48

N

20.90

NEP. NITROPARAFFINE SALTS. 145

the presence of ethylnitrolic acid and of dinitroethane in the acid
portion was proved as in the above case. The neutral portion was an
oily mixture, boiling between 105° and 130° at 30 mm. pressure.
The amount of material at hand was, however, insufficient lo admit of
its further study, although a portion boiled at ordinary pressure at
about 200°, and consists therefore probably of ^ diuitrobutane,

CHsv

C(N0,)2.*
C2H5/

The results obtained above prove that the reaction which takes place
on treating silver dinitroethane with alkyliodides is the following.

I. Direct replacement of the metal (chief reaction) :

CH3-C = NOAg + CH3I or C2H5I

I II
NO2 O

= CH3C = NOCH3 or CHg-C = NOC2H5 + Agl.

I II I II

NO2 O NO2 o

A B

The esters A and B, which are first formed, are however very un-
stable compounds, and just as the nitromethane salts,

CH2 : NOM,

II

O

are strong oxidizing agents. An intramolecular oxidation therefore
takes place, and ethylnitrolic acid and either formaldehyde or acetal-
dehyde is formed, according to the equation :

CH3-C = N-CH2H or CH3-C = N-OCHHCH3

I II I II

NO2 O NO2 o

= CH3-C ; NOH or CH3-C : NOH

I I + CH2 ; O or CH3CH • O.

NO2 NO2

Ethylnitrolic Acid.

The ethylnitrolic acid thus formed reacts upon silver dinitroethane,
present in excess, setting free dinitroethane and forming the silver salt
of ethylnitrolic acid,

* V Meyer, Ber. d. chem. Ges., IX. 701.

VOL. XXX. (N. 8. XXII. J 10

146 PEOCEEDINGS OF THE AMERICAN ACADEMY.

CH3-C : NOAg,
I

which then reacts with the iodide of methyl or ethyl, forming either
the methyl ester or the ethyl ester of ethylnitrolic acid,

CHg-C : NOCH3 or CH3C : NOC^Hg-

That this explanation of the reaction is the correct one, is proved

with certainty by the following fact : fulminuric acid is, as will be

shown in the paper presented directly after this one, identical with
nitrocyauacetamide,

CN-CHNOo.
I
HOC : NH

On treating the silver salt of this substance,

CN-C == NOAg,
I II

HOC : NH O

with'ethyliodide, there is formed, by direct replacement of the silver,
the ester,

CN-C = NOC2H5,
I II

HOC : NH O

which, in this case, can be isolated. This compound is, however, very
unstable, and shows, just as the above assumed intermediate products
(A and B) and as the nitromethane salts, great tendency to intra-
molecular oxidation. On boiling with water it is split quantitatively
into acetaldehyde and cyanisonitrosoacetamide (see following paper).

CN-C = NOCHHCHs = CN-C : NOH

I II I + CH3CH : O.

HOC . NH O HOC : NH

Cyanisonitrosoacetamide.

This decomposition is perfectly analogous to those above.

Tlie formation of /? dinitropropane from silver dinitroethane and
methyliodide is in all probability to be explained T)y an addition of
methyliodide to tlie silver salt of dinitroethane ;

II.

NEP. — NITliOPAKAPFlNE 8ALTS. 147

CHa-C = NOAg + ICHs
I II
^O^ o

CHs I CH3. /NO2

= CH3-C-N0Ag= C + Agl.

I II CH3/ ^NOa

NO2O
Addition Product.

There are now so many cases known, where, by the interaction of
silver salts with alkyliodides or acid chlorides, no direct or only par-
tially a direct replacement of the silver takes place,* that this explana-
tion is not at all improbable, — especially also when one considers the
remarkable behavior of silver fulminate towards hydrogen sulphide
and towards hydrochloric acid (see following paper).

The formation of formic aldehyde, ethylnitrolic acid, dinitroethane,
/:? dinitropropane and of a fifth compound, probably ethylnitrolic acid
methylester, on treating silver dinitroethane with iodide of methyl, is
therefore perfectly cleared up by the above considerations.

IV. The Action of Acid Chlorides on Nitroparaffine

Salts.

The former experiments on the action of acetylchloride and of
benzoylchloride on sodic nitromethane and on sodic nitroethane t
have led to no positive results. Kissel has shown J that in these
reactions some dibenzhydroxamic acid and diacethydroxamic acid is
formed, but these can only have been formed, however, by a complete
destruction of the nitroparaffine molecule.

I have also carried out many fruitless experiments on these salts
with acetylchloride and benzoylchloride, and also with chlorocarbonic
ether; both neutral and acid products are formed, which cannot be so-
lidified, and which do not distil under reduced pressure without decom-
position. Entirely analogous results were obtained by the action of
acetylchloride and benzoylchloride on nitroethane-mercuric-chloride,

* Ann. Chem. (Liebig), CCLXX. 329, 331 ; CCLXXVI. 232 ; (TLXXVII.
73 Tlie experiment with silver afet3'lacetone lias been carried out here by
Dr. Curtis8 witli larger quantities of material, and both products have been
analyzed.

t V Meyer and Rilliet, Ber. d. chem. Ges., V. 1030; VI. 1168.

t Ber. d. cliem. Ges., XV. Ref. 727 and 1574.

148 PROCEEDINGS OF THE AMERICAN ACADEMY.

CH3CH ; NOHgCl ;

II
O

both these reagents, and especially the former, act with explosive
violence on this salt, so that it is necessary to dilute with ab-
solute ether.

The above results with silver dinitroethane, which have shown that
neutral ethers of the constitution

RCH : NOR

II
O

must be strong oxidizing agents, encourage one to undertake a renewed
study of the action of acid chlorides on nitroparaffine salts, and experi-
ments will therefore very shortly be taken up again. Of especial
interest is the behavior of chlorocarbonic ether towards sodic nitro-
methane. It is to be expected that the ester

HaC = NOCO2C2H5

II

O

will at first be formed, and this compound must, by intramolecular
oxidation, lose water, and be converted into carbyloximecarbonic ester,

H2C : NOCO2C2H5 = C : NOCO2C2H5 + H2O,

II
O

which then will be further oxidized by the ester

CH2 = N-OCOOC2H6

II
0

to carbon dioxydoximecarbonic ester, O: C: NOCOjCoHs, and at the
same time thus formoximecarbonic ester, CH2 : NOCO2C2H5, will be
formed.

Concluding Remarks.

The above experiments suffice to prove, witli absolute precision,
that the metal in the nitroparaffine salts is bound to oxygen, and not,
as has been previously supposed, to carbon ; and in consequence, the
hypothesis that there are organic substances of an acid nature, in
whose salts the metal is bound to carbon, is no longer tenable. Its

NEF. NITROPARAPFINE SALTS. 149

conception has been shown to be illogical,* and th«j work that 1 have
carried out during the last six years has proved, by incontrovertible
experimental evidence, the erroueousness of this hypothesis in all
cases where it has been applied.

The only instances of organic compounds now known which con-
tain a metal bound directly to carbon are the metallic carbides, the
metallic alkyles, and the metallic derivatives of the true acetylene
compounds. No one would however be willing to assert that these
substances are salts of acids. Acetylene, for example, is not an acid,
for it is not absorbed with salt formation by even concentrated caustic
alkalies. The peculiar formation of the metallic acetylene deriva-
tives, e. g. of acetylene silver or copper, depends, in all probability,
upon an addition of metaUic hydroxide to the triple bond present in
acetylene, and the subsequent splitting off of water.

As regards the constitution of the free nitroparaffines, the presence
of a true nitro group in these compounds can hardly be seriously ques-
tioned, especially in view of the experiments of Victor Meyer t and
the late syntheses carried out by Be wad. J

The formuli^ suggested for nitroethane by Geuther,§ Kissel, ||
Alexejeff,1[ and Thomsen,** owe their existence chiefly to the very
noteworthy decomposition of nitroethane into acetic acid and hydrox-
ylamine, when treated with concentrated hydrochloric acid. ft

This decomposition of nitroethane can now, because of the above
experiments, be easily explained. An addition of hydrochloric arid
to the nitro group, analogous to the addition of sodic hydrate or sodium
ethylate, first takes place, forming

CI
CHs-CHo-Nq^,
CI
which then loses hydrochloric acid

CH3C = Nqjj 5

* These Proceedings, XXVII. 157.
t Ann. Cliem. (Liebig), CLXXI., etc.
i Journ f prakt. Cliemie, [2.], XLVIII. 346.
§ Ann. Chem. (Liebig), CCXLIII. 105.
II Journ. russ. chem. Soc, XIV. 40.
H Ber. d. chem. Ges., XIX. Ref. 874.
** Journ. f. prakt. Chemie, [2.], XLVIH. 348.
tt V. xMeyer and Locher, Ann. Chem. (Liebig), CLXXX. 163.

150 PROCEEDINGS OF THE AMERICAN ACADEMY.

and then again adds hydrochloric acid

CI H
CH3-C : NOH.
OH

This product can then easily split into acetic acid and hydroxylamine,

CI H OH

CH3-C : NOn + IIoO = CII3C : O + H2N0M,HC].
OH

In the above experiments I have been most ably and zealously
assisted by Dr. M. Ikuta, to whom I wish here also to express my
warmest thanks.

NEF. — BIVALENT CARBON. 151

VI.

CONTRIBUTIONS FROxM THE KENT CHEMICAL LABORATORY
OF THE UNIVERSITY OF CHICAGO

ON BIVALENT CARBON.

SECOND PAPER*
By J. U. Nef.

Presented May 9, 1894.

The bivalent carbon atom in methyl- and in ethyl-isocyanide shows
itself much more reactive, as was to be expected, than in the case of
the aromatic isocyanides. The reactions, however, are otherwise
entirely analogous to those obtained in the case of the aromatic com-
pounds, as is evident from the following experiments.

I. On Ethyl and Methyl Isocyanide.

CeHsCO— COH

Benzoylformic Methylamide^ II

NCHg.

The methylisocyanide used was made according to the method of
Gautier,t by heating 100 grams silver cyanide and 100 grams methyl-
iodide for two hours on a water bath (with reversed condenser and with
a mercury valve). This substance unites with benzoylchloride slowly
already at ordinary temperatures, as is recognized by the yellow color-
ation which sets in. 10.2 c.cm. methylisocyanide and 27 grams ben-
zoylchloride (one molecule) are mixed and heated for half an hour at
100° in a sealed tube. No more isonitrile is left, and longer heating
is harmful, since much formation of resin (polymerization) then takes
place. The crude product is taken up with absolute ether, filtered off
from brown resinous flakes, and the residual oil, after getting rid of
the ether, treated with water, whereby on standing, or rubbing with

* First Paper, tliese Proceerlings, XXVII. 102-162.
t Annales de Chim. et de Phys., [4.], XVII. 216.

152 PROCEEDINGS OF THE AMERICAN ACADEMY.

a glass rod, it becomes solid. The substance is recrystallized from a
mixture of ether and ligroine (bpt. 40° to G0°), using animal charcoal,
and obtained in pale yellow heavy many-sided crystals, melting at
74°. It is little soluble in cold, but readily soluble in hot water, and
comes out on coolini;- in prisms. In organic solvents, except ligroine,
it is easily soluble.

0.1970 gram dried over H2SO4 in a vacuum gave 0.4775 gram

COo and 0.1044 gram U^O.
0.2034 gram gave 15.5 c.cm. N2 at 4° and 735 mm.

Theory for CgHgNGj. Found

C 66.25 66.11

H 5.52 5.88

N 8.59 9.05

Benzoylformic-methylamide has thus been obtained from the addi-
tion product

CgHsCO— CCl
II
NCH3

first formed. The substance is easily soluble in cold dilute sodic
hydrate, but on addition of dilute sulphuric acid it is not precipitated
again. Ether extracts an oily substance soluble in water, which
slowly, on standing over sulphuric acid in a vacuum, gets solid. The
solid product is insoluble in water, and crystallizes from acetic ether
in needles melting at 1 43° ; this is probably a polymer, whereas the
oily substance is a hydrate,

OH

CgHs— C,

I
CH3N=C0H.

The substance shows thus in its behavior great resemblance to ben-
zoylformic-amide, which Claisen has shown* exists in two modifications
(probably polymeric), and also forms a low melting hydrate. t

Be7izoylformic-methylamide-phenylhydrazonhydrate,
CH3N : COH

On treating benzoylformic-methylamide in concentrated ethereal solu-
tion at 0° with an ethereal solution of phenylhydrazine (one molecule),

* Ber. d. chem. Ges . XII 6:18

t Ann Chem. (Liebig), CCLXX. 295, 300, 316.

NEF. — BIVALENT CARBON. 153

a white voluminous precipitate separates out in flukes, which, after
being well washed with ether, dried on a clay plate and a short time
over sulphuric acid in a vacuum, was directly analyzed.

0.20.56 gram substance gave 0.5037 gram CO., and 0.1202 gram II^O.
0.1551 gram substance gave 20.5 c.cm. Ng at 6° and 745 mm.

Theory for CijUnNsO, Found.

C 66.42 66.77

H 6.27 649

N 15.50 15.78

Phenylhydrazine has thus simply added itself to the carbonyl group
present in benzoylformicmethylamide, giving rise to a hydi'azonehy-
drate. It is insoluble in water, and is not split into its components by
cold sodic hydrate, but possesses a great tendency to lose water,
becoming thereby yellow and sticky.

In this connection I would like again to point out that the product
which W. Wislicenus * has obtained from oxalacetic ether and phenyl-
hydrazine cannot possibly be a hydrazonehydrate,

ROsC-Cria.

because it possesses entirely different properties from the hydrazone-
hydrates obtained by myself,t which under no condition can be split
into their components by means of alkalies. The substance obtained
by W. Wislicenus shows a totally different behavior; it is, just as
phenylhydrazine hydrochloride, a salt-like compound, and is therefore
split immediately by alkalies into its components.

Benzoylformic-'phenylhydrazone from henzoylforinic-methylamide.

That the compounds just described are derivatives of phenyjglyoxy-
lic acid is very probable. The pooof of this is furnished as follows • 3
grams benzoylformic-methylamide-phenylhydrazonehydrate are warmed
on a water bath for half an hour with 80 c.cm. dilute ten per cent sodic
hydrate (the hydrazonehydrate dissolves readily on gentle warming).
A strong smell of methylamine is noticed, and on adding dilute hydro-
chloric acid a yellow flaky precipitate (1.4 grams) comes down, which
is dissolved again in soda and reprecipitated by acids. The method of

* Ber. d. chem Ges., XXIV. 3007

t Ann. Chem. (Liebig), CCLXX. 292, 300, 319, 333.

154 PROCEEDINGS OF THE AMERICAN ACADEMY.

purification used by Elbers * does not yield an absolutely pure product;
it is much better to recrystallize from benzene, wherein the substance
is readily soluble on heating, but practically insoluble in the cold.
Yellow needles melting at 163° (Elbers gives mpt. 153°) were thus
obtained.

0.1661 gram substance, dried at 90°, gave 0.4259 gram COg and

0.0750 gram HgO.
0.1008 gram substance, dried at 90°, gave 11 c.cm. Ng at 25° and

739 mm.

Theory for CuHijNjOj- Found.

C 70.00 69.93

H 5.00 5.02

N 11.66 11.82

Molecular Rearrangement of Etiiylisocyanide to Propionitrile.

Ethylisocyanide was made according to the method of Gautier,t by
heating 100 grams silvercyanide and 115 grams ethyliodide for one
and one half hours on a water bath (with reversed condenser and
with a mercury valve). The substance (bpt. 79°) can be kept for
fifteen months without the slightest change. It can be heated without
any essential change for many hours to 210° ; a slight yellow colora-
tion only is noticed, t The first statements of Gautier § concerning
this substance, which he does not mention in his later paper, || are
therefore to be corrected. On heating ethylisocyanide, however, to
a still higher temperature, molecular rearrangement to ethylcyanide
takes place almost quantitatively. 7.5 c.cm. ethylisocyanide are
heated in a sealed tube for three hours between 230°-255°, and the
contents of the tube, which are colored brown and smell slightly of
ammonia and isocyanide, distilled off. Everything came over except
a slight residue between 94° and 98°. In order to remove ammonia
and traces of isonitrile, the oil was washed with a chloride of calcium
solution containing hydrochloric acid, and then dried with solid calcic
chloride. On distilling, a pleasant ethereal smelling oil, boiling con-
stant at 97°, was obtained (4 c.cm.), which was identical in every
respect with propionitrile.

0.1528 gram substance gave 0.3608 gram COg and 0.1278 gram HgO.
0.1530 gram substance gave 33.5 c.cm. Ng at 9° and 741 mm.

* Ann Chem. (Liebig), CCXXVII. 341.

t Lor. r,i , [4.], XVII. 233. § Loc. at., [4.], XVII. 236.

t Comptcs Rendus, LXV. 862. || Ibid., 203-260.

NEP. BIVALENT CARBON, 155

Theory for CaUjN.

Found.

c

65.45

65.46

H

9.09

9.29

N

25.45

25. GG

The Action of Sulphur on Ethylisocyaiiide.

l.b c.cm. ethylisocyauide, 3.1 grams crystallized sulphur, and 15
c.crn. carboiibisulpliide were heated in a sealed tube at 110°-120° for
two hours. The reaction is complete, and the mustard oil formed is
driven over with steam, extracted with ether, and, after drying with
calcic; chloride, is fractionated. It boils constant at 131°, and is iden-
tical with ethyl-mustard oil first isolated by Hofmann.*

0.2040 gram burnt with lead chromate gave 0.3063 gram COo and

C.1016 gram H2O.
0.2544 gram substance gave 0.6771 gram BaSO^ (Carius).

Theory for CoHsNCS. Found.

c

41.38

40.95

H

5.75

5.50

S

36.78

36.55

The Action of Hydrogen Sulphide on Ethylisocyanide.

Tliioformethylamide, CoHsNrCqrr- 10 c.cm. ethylisocyanide

were dissolved in 200 c.cm. absolute alcohol, saturated at 0° with
hydrogen sulphide, and then heated for 4 hours in a sealed tube
at 100°. Tiie isonitrile smell was entirely gone, and, after distilling
off the alcohol, the brown oily residue was fractionated under reduced
pressure. The chief portion boiled at ]40°-150° at 40 mm. pressure,
and, on the second distillation, a yellow oil, smelling of sulphur, and
boiling at 125° at 14 mm. pressure was obtained.

0.1996 gram substance, burnt with lead chromate, gave 0.2980 gram

CO., and 0.1468 gram H,0.
0.2034 gram substance, gave 29.5 c.cm. No at 18° and 737 mm.
0.2885 gram substance gave 0.7529 gram BaSOi (Carius).

Found.

40.71

8.17

16.23

35.84

* Ber. d chem. Ges., I. 26.

Theory for C3H7NS

c

40.45

H

7.87

N

15.73

S

35.95

156 PROCEEDINGS OF THE AMERICAN ACADEMY.

Ethylisocyanchloride or Ethylimidocarbonylchloride, CoH5N=CCl2.

On passing dry chlorine over a solution of 10 c.cm. ethylisocyanide
in 40 c.cm. chloroform, the gas is absorbed instantly, without the
slightest trace of hydrochloric acid or of coloration being noticeable.
As soon as the solution is colored yellow, or smells of chlorine, it is
directly fractionated. It was possible to obtain a small amount of a
colorless, very sharp-smelling oil, boiling at 99°-100°. Since, how-
ever, the separation from the large amount of chloroform can only be
accomplished with much loss of material, the ethylisocyanchloride is
better prepared as follows : 5 c.cm. ethylisocyanide, diluted with four
times its volume of absolute ether, are cooled to — 15° and 5.5 c.cm.
sulphurylchloride are slowly added. An energetic reaction takes
place, and the solution becomes colored yellow and smells strongly of
sulphurdioxide. After ten minutes' standing, the solution is washed
with dilute sodic hydrate, and then dried with calcic chloride. Ou
fractionating, a colorless, intensely sharp-smelling oil, boiling at 102°,
is obtained.

0.2994 gram substance gave 0.3183 gram CO2 and 0.1101 gram H^O.
0.2450 gram substance gave 0.5536 gram AgCl (Carius).
0.1575 gram substance gave 14.5 c.cm. Ng at 8° and 745 mm.

Theory for C3H5NCI2.

Found.

c

28.57

28.99

H

3.97

4.09

N

11.11

10.90

CI

56.35

55.90

Hie Action of Acefylchloride on Ethylisocyanide.

CgHsNiCOH

Pyruvic-ethylamide-phenylhydrazone, I

CHsC.NNHCFTs.

Ethylisocyanide (7.5 c.cm.) and acetylchloride (6.5 com., one
molecule) react on each other when mixed together readily at 0°, and
the solution becomes colored yellow. After standing for twelve hours
at ordinary temperature, a dark brown liquid is obtained, which
was divided into two portions, a and b. On fractionating a, it all dis-
tilled over between 50° and 60° at 15 mm. pressure, as a yellow oil
which, redistilled at ordinary pressure, boils at 100°-130°. In both
cases the oil smells of isonitrile, so that a dissociation of the ethylimi-
dopyruvylchloride,

NEP. — BIVALENT CARBON. 157

CHfiN : CCl
I
CII3CO,

into its components must take place on distillation, and an analysis of
the substance would therefore be of no value. One encounters here,
as has also been observed in the case of many other addition products
of the isocyanides,* the remarkable property that these are easily
split into their components, either at higher temperatures, or on stand-
ing in the cold, or on treatment with sodic hydrate ; whereas, on the
other hand, these components either at — 20° or at ordinary or higher
temperatures often unite with explosive violence. Bivalent carbon
therefore behaves exactly like trivalent nitrogen in ammonia and the
amines, since also the last named compounds unite often with explosive
violence with acids, e. g. hydrochloric acid, forming addition products
containing quinquivalent nitrogen, which in turn, either by heating or
by treating with alkalies, are split into their components.

That the above distilled oil a , however, still contains much ethyl-
iraidopyruvylchloride, is shown by decomposing it with water: it is
converted thereby into pyruvic-ethylamide,

C^HgN : COH
I
CH3CO,

the presence of which in the aqueous solution, since it cannot be ex-
tracted therefrom by ether, is best shown by adding phenylhydrazine-
hydrochloride, which precipitates an insoluble hydrazone (3.5 grams).
The above mentioned portion b was not distilled, but decomposed
directly with ice water, and the reddish-colored solution treated with
phenylhydrazinehydrochloride, and thus 7.7 grams insoluble hydrazone
were obtained. The hydrazone is obtained, when recrystallized from
alcohol, in colorless many-sided heavy crystals, melting at 165°. It
is insoluble in alkalies and in water.

0.2002 gram substance, dried at 100°, gave 0.4731 gram CO2 and

0.1387 gram H^O.
0.1494 gram substance, dried at 100°, gave 27.5 c.cm. Ng at 20° and

747 mm.

Theory for C„H,

,5N30.

Found.

c

64.39

64.44

H

7.31

7.69

N

20.49

20.69

* Ann. Chem. (Liebig), CCLXX. 297, 298, 322.

158 PROCEEDINGS OF THE AMERICAN ACADEMY.

The Action of Phosgene on Ethylisocyanide.

On adding slowly 5 c.cm. phosgene (cooled to — 15°) to 10 c.cm.
ethylisocyanide (cooled to —19°), reaction takes place always with
explosive violence. Even when the isocyanide is diluted with an
equal volume of absolute ether and the solution is cooled to — 19°,
a very energetic union takes place on adding the phosgene, which
makes it difficult to regulate the reaction. A yellow sharp-smelling
liquid is formed, which does not boil without decomposition. On
pouring it into water a brown solution containing much hydrochlo-
ric acid is formed, from which ether extracts nothing, and which
gives no precipitate with phenylhydrazine. The products, which are
in all probability all derivatives of mesoxalic acid,* were not further
investigated.

The Action of Chlorocarbonic Ether on Ethylisocyanide.

An addition of fhlorocarbonic ether, or of alkyliodides or chlorides,
to aromatic derivatives of isocyauogen could not be accomplished, be-
cause a reaction takes place only at high temperatures, and this must
result in the formation of much resinous polymeric products, as well
as in the decomposition of the addition products first formed. t

An addition of chl(M'Ocarbonic ether to ethylisocyanide has, however,
been accomplished, and with the following experiences. Chlorocarbonic
ether reacts, already, at ordinary temperatures, on ethylisocyanide and
the mixture becomes colored yellow. On heating at 100°, complete
reaction takes place in a very short time, but the addition product first

formed,

C2H5N : CCl
I
OiCOCsHj,

is completely split into carbondioxide, ethylchloride, and ethyliso-
cyanide, C2H5N : C, which, generated in the nascent state, mostly
polymerizes. Klinger has already observed an entirely analogous
decomposition in the case of oxanilethane-imidechloride,

CeHjN : CCl
I
O : COC0H5,

on heating it to 120°. J

* Ann. Chem. (Liebig), CCLXX. 286-29.5 and 315

t Ibid., CCLXX. 280, et seq. Cf. also Wallach, Ibid., CLXXXIV. 8C, 108,
CCXIV 283

J Ibid., CLXXXIV. 283

NEP. — BIVALENT CARBON. 159

That in the above case au iutermediate formation of the imide-

chloride

C2H5N : CCl
I
O : COCgHg

takes place was proved as follows. 5 c.cm. ethylisocyanide and 7.8
grams chlorocarbonic ether were heated for 6 hours at 6(>°-70°,
whereby a c()[)ious evolution of carbondioxide and of ethylchloride
takes place. The very dark residue was treated with absolute ether
and much polymerized ethylisocyanide separated out in brown flakes
The ethereal filtrate gave a small amount of an oil (free from chloro-
carbonic ether), which was warmed gently with lime water. After
getting rid of the excess of lime by means of carbonic acid, the filtrate
gave, on concentration, crystals of calcic ethyloxaminate, which sepa-
rated out in needles. The free ethyloxarainic acid obtained from this
salt melted at 123°, and was found identical in its properties (as well
as also the salt) with the previous statements of Wallach* The yield
of calcic ethyloxaminate is very poor, — never over 0.2 gram ; its
source can only be explained through the intermediate formation of
the imidechloride

C2H5N • CCl
I
O : COC2H5

in the above reaction this substance must necessarily, by saponifica-
tion, yield ethyloxamiiiic acid,

C2H5N COH
I
O : COH.

A better yield of the imidechloride could, in all probability, be ex-
pected on allowing molecular proportions of ethylisocyanide and
chlorocarbonic ether to stand at ordinary temperature for a week or
more.

From the above experiments, it is clear that the aliphatic isocyano-
gen derivatives behave in a manner entirely analogous to the corre-
sponding aromatic derivatives, and differ from these only in the fact
that they react more energetically. It was further shown that carbon
tetrachloride reacts with ethylisocyanide at 180°, benzolsulphochloride
at 85°, benzylchloride at 120° ; it was not possible, however, to iso-
late any definite addition products.

* Ann. Cliem (Liebig), CLXX-XIV. 68.

160 PROCEEDINGS OF THE AMERICAN ACADEMY.

It is a noteworthy fact that ethylisocyanide can be heated in a
sealed tube for one hour to a temperature of 130° -170° with sodium
ethylate (free from alcohol) without the slightest change. For this
reason, it seems to me that in the action of caustic potash or sodium
ethylate * on the inert carbonic oxide,t an addition of these reagents
to the carbouylgroup t must first take place, as follows :

/OH /ONa

C : 0 + HOK or NaOCgHs = C or C

^OK ^OC^Hs.

The bivalent carbon atom present in these addition products must,
according to the ideas heretofore developed in these Proceediugs,§ be
far more reactive than the unsaturated carbon atom present in the
isocyanides ; and, in consequence, a further addition of sodic ethylate
or of caustic potash takes place, giving rise to the ortho derivatives,

C2H5. .ONa H. OK

C and C

NaO^ ^OC^Hs KO^ OH,

which naturally, on treatment with water, go over into propionic acid
and formic acid salts, respectively.

II. FuLMiNic Acid is identical with Carbyloxime, and
CONTAINS Bivalent Carbon, C : NOH.

TT

Formylchloridoxime, HON : C,,, . The synthesis of fulminate of

mercury from sodic nitromethane, described in the preceding paper,
leads directly to the conclusion that this substance must be identical
with mercuric carbyloxime, C : NOhg. The behavior of the salt
towards concentrated hydroclilnric acid is also in favor of this conclu-
sion ; there is formed, as Steiner,|| Carstanjen and Ehrenberg,1[ and
especially also Divers and Kawakita,** have shown, not a trace of
oxalic acid, but only formic acid, corrosive sublimate, and hydroxyl-
amine hydrochloride.

* Berthelot, Ann. Chem. (Liebig), XCVII. 125 , Geuther and Frohlich, Ann.
Chem. (Liebig), CCII. 290.

t Ann. Chera. (Liebig), CCLXX. 267. J Ibid., CCLXX. 322.

§ Vol. XXVII. pp. 102-104.
II Ber. de. chem. Ges., XVI 1484, 2419
IT Journ. f. prakt. Chem., [2.], XXV. 232; XXX. 38.
** Journ. chem. Soc, XLV. 13-30, 75.

NEF. — BIVALENT CARBON. 161

Notwithstanding this, all the formula) yet proposed for fulminic
acid, as, fur example, that of

C : NOH HOC = N\ HC = N-0

Steiner,* II of Divers, f I O, of Scholl,| I )

C:NOH, HC = N/ HC = N-0,

and many others, have originated from the assumption that this sub-
stance contains two carbon atoms in the molecule, because it was
regarded as proved by the experiments of Liebig and Gay-Lussac §
that the fulminic acid molecule contains two hydrogen atoms possess-
ing entirely different functions. The behavior of mercury fulmi-
nate towards bromine || and towards iodine,1[ whereby products are
formed which unquestionably contain two carbon atoms in the mole-
cule, as well as the decomposition of this salt, by means of chlorine,
into cyanogen chloride and chlorpicrine,** seem also to be in favor of
this conclusion. Only very recently has Scholl ft thought of the
possibility of the simple carbyloxime formula, C : NOH, but he still
gives the polymerized formula of Steiner,

C:NOH /C\

II , or HON II NOH, the preference. ^

C : NOH \ C /

I have succeeded in proving experimentally, with absolute precision,
that fulminic acid is identical with carbyloxime, C : NOH, and that
the bivalent carbon atom present in this substance possesses a most
surprising and enormous reactivity, so that in all reactions shown by
fulminic acid salts the unsaturated carbon atom is the point of attack ;
and, since we now possess some light on the nature of bivalent carbon,
the entire chemistry of the fulminic acid derivatives is very simply
and completely explained, as will become evident from the following
experiments.

It has for over seventy years been considered as settled that, on
treating fulminic acid salts with dilute hydrochloric acid, a complete
destruction of the fulminic acid molecule takes place, and that among

* Ber. d. chem. Ges., XVI. 1484, 2419.

t Journ. cliem. Soc, XLV. 21.

t Ber. de chem. Ges., XXIII. 3497, 3507.

§ Annales de Chim. et de Phys., XXIV. 294-317, XXV. 285-310.

II Kekule, Ann. Chem. (Liebig), CV. 280.

IT Sell and Biedermann, Ber. d. chem. Ges , V 89.
** Kekule', Ann. Chem. (Liebig), CI. 206
tt Ber. d. chem. Ges., XXIII. 350fi-3509.
tt Ber. d. chem. Ges., XXIV. 581.

VOL. XXX. (N. 8. XXII.) 11

162 PROCEEDINGS OF THE AMERICAN ACADEMY.

other products prussic acid is set free : this observation has repeatedly
been confirmed. Not a trace of prussic acid is formed, however, hut

formylchloi'idoxime, HON : C^, , a substance which, in dilute aqueous

solution, — probably because of a slight dissociation into hydrochloric
acid and carbyloxim, C : NOH, — has an odor which cannot be dis-
tinguished from that of prussic acid.

This is the reason why, among others,* Liebig and Gay-Lussac, as
well as Schischkoff, state that prussic acid is formed in this treatment
although, as they themselves add, the presence of prussic acid could
not be proved. Gay-Lussac and Liebig write : f " Dans I'intention
d'obtenir quelques lumieres a cet egard, nous avons essaye d'evaluer la
quantite d'acide hydrocyanique qui se degage lorsqu'on traite le fulmi-
nate d'argent par I'acide hydrochlorique, etc. Nous esperions obtenir
du cyanur d'argent ; mais, a notre grande surprise, il ne s'est fait
aucune precipitation, quoique nous nous fussions assures que la meme
dissolution d'argent donnait un abondant precipite lorsqu'on y versait
de I'acide hydrocyanique."

Schischkoff says : % " Fiir das Knallsilber war bereits beobachtet,
dass es bei der Einwirkung von Chlorwasserstoffsaiire Cyanwasserstoff
entwickelt ; ich versuchte dieselbe Reaktion mit Knallquecksilber, uud
war zuerst sehr erstaiint, dass ich nicht ein analoges Resultat nachwei-
sen konnte. Ich schrieb dieses abweichende Verhalten dem Umstande
zu, dass sich, in letzterem Falle, ein Quecksilberverbindung von unbe-
kaiinter Natur bilden moge, welche den Cyanwasserstoff zuriickhalten
moge. Und, in der That, wenn man vorher etwas schwefelsaures Ei-
senoxydul der Chlorwasserstoffsaure zusetzt, so lasst sich leicht eine
reichliche Entwicklung von Cyanwasserstoff constatiren. Durch das
zugesetzte Eisenoxydulsalz wird vermuthlich die den Cyanwasserstoff
gebunden zuriickhaltende Verbindung zersetzt."

Formation of Formylchloridoxime from Sodic Fulminate. — The ful-
minate of mercury used in these experiments was made according to
the method of Lobry de Bruyn ; § 32 grams of dry salt were regularly
obtained from 25 grams of mercury used. Carstanjen and Ehrenberg
were the first to show that this salt can be converted quantitatively

* Cf. Ehrenberg, Journ. f. prakt. Cliem., [2.], XXV. 241 ; Scholvien, Ibid.,
XXXII. 46.3.

t Annales de Chim. et de Phys., XXV 308.
\ Ann. Chem. (Liebig), Suppl. Vol., I. 108
§ Ber. de chem. Ges., XIX. 1370.

NEP. — BIVALENT CARBON. 163

into sodic fulminate by means of sodium amalgam.* It is possible to
convert 32 grams of mercury fulminate in 20 minutes into an aqueous
colorless solution of sodic fulminate (free from mercury) as follows.
The salt is suspended in about 125 c.cm. water and treated with
75 grams of 8 per cent sodium amalgam,! (5 grams more than the
theory). The operation is first carried out in a flask, cooling well
with water, and then in a flask, having a well fitting glass stopper,
taking care to shake thoroughly until the solution contains no
mercury.

The sodium fulminate solution thus obtained (about 150 c.cm.) is
cooled to 0°, and added slowly, taking care to cool well, to a solution
of hydrochloric acid at 0° (114 parts concentrated acid 1.18, and 114
parts water) and thereupon extracting immediately three times with
ether. The ethereal solution is placed in a distilling flask and concen-
trated to one third its volume by distilling off the ether in a stream of
dry air at a low temperature (40°), and the solution is then concen-
trated further at reduced pressure. A very concentrated solution of
formylchloridoxime in ether is thus obtained, from which the pure
substance is isolated by pouring on a watch-glass and evaporating rap-
idly in a vacuum desiccator. To insure success in these operations,
a very cold winter temperature is essential, and the concentrated ethe-
real solutions must be kept at 0°. On evaporation of the ether, per-
fectly transparent veiy long colorless needles, clear as glass, separate
out, which are first transferred to a clay plate (cooled at 0°) and
quickly powdered with a platinum spatula, and then weighed as
quickly as possible at a low temperature.

0.1235 gram substance, poured directly after weighing into water,
and treated with silver nitrate and concentrated nitric acid, gave,
after digesting on a water batli, 0.2128 gram AgCl.

0.6585 gram substance gave 1.1006 grams AgCl.

Theory for CH.,N0C1. Found.

CI 44.65 42.63 41.35

* Journ. f. prakt. Chem., [2], XXV. 241. Cf. also Scholvien, Ibid., XXXII.
462.

t Sodium amalgam is best made by adding 80 grams sodium to 400 c.cm.
toluene in a two-litre flask, and then slowly adding 920 grams of mercury. The
toluene heats up to its boiling point, and, after about one half of the mercury
has been added, the mass gets solid. The toluene is poured off, the residue
melted in a crucible, and then poured out on clay plates. In this way large
quantities of sodium amalgam can be made without danger, and with the
greatest ease. Cf. Chem. Zeit., 18G4, p. 720, and Gmelin, Kraut, III. 857.

16-4 PROCEEDINGS OF THE AMERICAN ACADEMY.

Preparation of Formylchloridoxime from Silver Fulminate. — Fulmi-
nate of silver is best obtained as follows. 5 grams of silver are dis-
solved in 100 grams nitric acid (sp. gr. 1.34), and the warm solution
is poured into 150 c.cm. alcohol (90 per cent) and then heated for
5 to 10 miuutes on a water bath until a reaction sets in. The reac-
tion then continues very energetically, of its own accord, and silver
fulminate separates out in beautiful needles. The yield is regularly
6.5 grams or more, and the filtrate contains only traces of silver. The
salt is much less soluble in boiling water than Liebig states.* In the
dry state it is far more dangerous than the mercury salt : it explodes
instantly, and with tremendous violence, on touching it very care-
fully with a platinum spatula. It can, however, be dried without the
slightest danger on filter paper, and collected therefrom by means of a
camel's hair brush. A silver determination of the salt, dried over
sulphuric acid in a vacuum, gave the following result.

0.2013 gram substance, digested with dilute hydrochloric and nitric
acids, gave 0.1925 gram AgCl.

Theory for AgONC. Found.

Ag 72.00 71.92

In order to convert silver fulminate into formylchloridoxime, 12
grams salt are added to 80 c.cm. hydrochloric acid (one part concen-
trated acid to one part water) containing pieces of ice, and then, after
decanting or filtering from the chloride of silver, proceeding as above
in the case of the sodium salt. A small portion of the concentrated
ethereal solution of formylchloridoxime was evaporated as above, and
the substance immediately analyzed : the chief portion was treated
directly with 12.5 grams of aniline (2 molecules) and thus converted
smoothly into phenylisuretine (see below).

0.4478 gram substance gave 0.7758 gram AgCl.

Theory for CH,N0C1. Found.

CI 44.65' 42.68

Properties of Formylchloriiloxime. — The formylchloridoxime ob-
tained in these two ways is a very reactive and remarkable substance.
In the solid condition, or in concentrated ethereal solution, it can be
kept at 0° for some time unchanged. It volatilizes very quickly and
completely, in small portions, at ordinary temperature, and this serves
as a good means of determining its purity. It often happens, when all
possible precautions in its manufacture are not observed, that a pro-

* Annales flc Chim. et de Phys., XXIV 297

NEF. — BIVALENT CAUBON. 165

duct is obtained which is only partially volatile, and leaves au amor-
phous opaque residue. This can.^ however, be seen immediately by
the ai)pfarauce of the lorn)ylchloridoxime itself when prepared ; if
the crystals are clear as glass, the substance is pure ; if, on the other
hand, the crystals are turbid or opaque, the product is impure. In
larger amounts (a few decigrams) formylchloridoxime decomposes
very soon at ordinary temperature ; it at first becomes colored green,
and then puffs up with tremendous evolution of heat and a hissing
noise. The same decomposition takes place instantly by the heat of
the hand, or on heating the substance in a vacuum at 40°. Carbon
monoxide is given off and the puffed up sticky residue consists chiefly
of hydroxylamine hydrochloride.

The substance thus possesses a tremendous tendency to decompose
into hydrogen chloride and carbyloxime, C : NOH, and the latter com-
pound is then split by the hydrochloric acid into carbonmonoxide and
hydroxylamine. Formylchloridoxime possesses very poisonous prop-
erties, has a very sharp pungent smell, and diluted with air or in
dilute aqueous solution has an odor which cannot be distinguished
from that of prussic acid ; this is probably due to a partial dissociation
into hydrogen chloride and carbyloxime, C ■ NOH. Also the action
of the substance on the human system, producing a flow of saliva, an
irritation in the throat, and violent headaches, is entirely analogous to
that of prussic acid. Formylchloridoxime possesses also a very sharp
pungent smell, and acts violently on the eyes, the action is not at first
very noticeable, but sets in after a time. Thus, for example, after
being exposed to the influence of the vapor of the substance for about
one hour on an afternoon, my eyes were only colored intensely red,
but in the evening a most violent inflammation set in, so that I could
hardly see for twenty -four hours. The consequences, however, are
only temporary.

Formylchloridoxime, when brought on the skin, causes white blis-
ters and deep wounds, which heal only very slowly. The substance is
not decomposed either by water or by alcohol, — a noteworthy prop-
erty for a soluble acid chloride ; in this respect it resembles the acid
chloride, benzenylethoximchloride,

C6H5C = NOCoH5,
CI

obtained by Tiemann and Kriiger,* which is stable even towards caus-

* Ber. d. chem. Ges., XVIII. 732.

166 PROCEEDINGS OF THE AMERICAN ACADEMY.

tic potash. The constitution of the substance as formylchloridoxime,

HON : c;„ ,

3

is proved by its behavior towards silver nitrate, ammonia, and espe-
cially towards aniline.

Behavior of Formylchloridoxime towards Silver Nitrate.

Synthesis of Silver Fidminate, C : NOAg. — On treating an aqueous
solution of formylchloridoxime with two molecules of silver nitrate, a
quantitative interaction takes place, forming silver fulminate and chlo-
ride of silver according to the equation :

HON : C^j + 2 AgNOs = C : NOAg -j- AgCl + 2 HNO3.

This shows what a great tendency exists in this formic acid derivative
to split oiF hydrogen chloride and generate carbyloxime, C : NOH.
Some analogous facts to show that this same tendency exists, have
already been presented in the previous paper : * whereas the oxime of
formylchloride,

/H
HON: C

^Cl,

can be isolated, formylchloride itself,

C: O,

does not exist even at 0°, l)ut decomposes spontaneously into hydro-
gen chloride and into carbon monoxide.

The separation of the chloride of silver and silver fulminate formed
in the above reaction can be accomplished very readily. The precipi-
tate, after some standing, and addition of cold dilute nitric acid, is
filtered off, well washed, and then boiled out three times with small
quantities of aqueous potassic chloride. On cooling, or on concen-
trating the filtrates, the double salt, AgONC, KONC, discovered by
Liebig.t separates out in long glistening flat needles. This salt, after
recrystallizing from water, is dissolved in warm water and poured
into an excess of cold dilute nitric acid, whereby regenerated silver

* Ann. Chem. (Liebig), CCLXX. 307. -308, 822.
\ Annales de Chim. et de Phys., XXIV. 315.

NEF. — BIVALENT CARBON. 167

fulminate comes down iu very fine colorless needles. Liebig and
Gay-Lussac* have regarded this precipitate as " acide fulminique/'
QliAgNaO^, which is incorrect.

0.2097 gram substance, dried over H2SO4 in a vacuum, gave 0.1988
gram AgCl.

Theory for AgONC, Found.

Ag 72.00 71.37

That silver fulminate, and not "acide fulminique," CgHAgNgOa,
is always formed on treating the double salt AgONC, KONC, with
nitric acid, was further proved by making the double salt from silver
fulminate (made in the ordinary way from silver, nitric acid, and alco-
hol), and treating it as above, with nitric acid.

0.2129 gram substance, dried over H2SO4 in a vacuum, gave 0.2031
gram AgCl.

Theory for AgONC. Found.

Ag 72.00 71.80

The conclusion of Liebig and Gay-Lussac that the fulminic acid
molecule contains two hydrogen atoms, possessing entirely different
functions, is therefore not justifiable. In exactly the same way as
cyanide of potash gives with silver cyanide a soluble double salt,
AgN : C, KN : C, the entirely analogously constituted silver ful-
minate gives with potassic fulminate a corresponding double salt,
AgOX : C, KON : C. The analogy between the salts of fulminic
acid and those of prussic acid is altogether a surprisingly close one, —
which can now hardly be considered strange, because both these acids
are quite analogous derivatives of isocyanogen. It will be shown fur-
ther on that a double salt, sodium ferrofulmiuate, Na4Fe (ON : C)(5,
exists, corresponding thus in every respect to the yellow prussiate of
soda, sodic ferrocyanide, NaiFe (N : C),-,. The physiological proper-
ties of the soluble prussic acid salts, MN : C, and those of the soluble
fulminic acid salts, MON : C, are so much alike that it is impossible,
as far as we now know, to distinguish between them. Schischkoff
is only one of the many observers who have worked with salts of
fulminic acid who observed the poisonous properties of these salts (the
enormous explosive properties are mentioned by all). He remarks:!
" Die Knallsauresalze sind ganz so giftig wie die Cyanmetalle.
Die Heftigkeit der Wirkung hangt von der Loslichkeit ab, aber

* Annales de Chim. et fie Phys., XXIV. 302, XXV. 289.
t Ann. Cliem. (Liebig), Suppl. Vol., I. 109.

168 PROCEEDINGS OF THE AMERICAN ACADEMY.

die VergiftuDgssymptome sind ganz dieselben wie sie durch die
Cyannietalle hervorgebracht werden. So ist das Kuullzink, welches
eines der loslichsten unter den Knallsauresalzen ist, zugleich das gif-
tigste. Ich bemerke noch dass die isocyanursauren Salze [die Fulmi-
nurate] gar nicht giftig sind."

E. Davy * first obtained zinc fulminate from mercury fulminate
by means of zinc dust and water, and made therefrom, by double de-
composition with the metallic hydroxides, many salts of the alkali
and alkaline-earth metals. That the majority of these salts are not
simple but double salts, e. g. that Davy's baric fulminate is a zinc
barium fulminate, baON : C, znON : C, was first shown by Fehling t
E^hrenberg is the first who obtained sodic fulminate pure and analyzed
the product, t

Other Syntheses of Silver Fulminate. — The behavior of silver ful-
minate towards the calculated amount (one molecule) of dilute hydro-
gen chloride and of hydrogen sulphide is very remarkable, and is
fully cleared up by what follows. On adding one molecule of dilute
hydrogen chloride to silver fulminate, suspended in water and kept
cold by means of pieces of ice, an energetic reaction immediately
takes place, and a strong smell of formylchloridoxime is noticed. The
mixture is well stirred, and as soon as it can be filtered clear, this is
done. The perfectly clear filtrate is found to contain two substances,
formylchloridoxime,

C:NOH,

which can easily be extracted from the solution by means of ether,
and silver formylchloridoxime,

C : NOAg,

which is soluble in water. The solution, therefore, contains much
chlorine and silver, which for a long time seemed very enigmatic : on
addition of hydrochloric acid, silver chloride is precipitated, and on
addition of nitric acid a precipitate consisting of silver fulminate and
silver chloride is formed.

* Trans. Roy. Soc. Dublin, 1829; extract in Berzelius's Jahr., XII. 97, 120.

t Ann. Chem. (Liebig), XXVII. .30.

t Journ. f. prakt. Chem., [2.], XXXII. 231.

NEF. — BIVALENT CARBON. 169

It follows from the above that on treating silver fulminate with
dilute hydrochloric acid (one molecule) an addition of hydrogen chlo-
ride to the unsaturated carbon atom in this salt takes place,

AgON : C + HCl = AgON : C^j •

The addition product, which is soluble in water, is then, in the second
stage of the reaction, further acted upon by some of the hydrogen
chloride present, aild converted partially into silver chloride and for-
mylchloridoxime,

AgON : C^j + HCl = HON : C^j + AgCl.

This experiment demonstrates, therefore, in a very pretty manner,
that an organic silver salt can react with hydrogen chloride, leaving
the silver present in the molecule entirely intact. The bivalent carbon
atom present in fulminate of silver is so reactive, that the metal is
not affected at all. I have already repeatedly, in other cases, drawn
attention to similar reactions ; the double bond present in sodium

acetacetic ether,

CHg - CONa
II
HCCO.R,

is so reactive that, on treatment of this salt with alkyliodides and acid
chlorides,* exclusively or chiefly an addition of these reagents to the
double bond takes place, and the sodium atom remains entirely intact
in the whole reaction. The same phenomenon has also already been
proved to take place with many other silver salts, t
The isolation of the intermediate product,

C:NOAg,

in the above instance therefore furnishes a further very important
experimental confirmation of the processes which I have shown
take place in the interaction of acetacetic salts with alkyliodides and
acid chlorides. A further entirely analogous example of addition is
furnished by the study of the action of hydrogen sulphide on silver
fulminate. On adding to silver fulminate, suspended in water con-

* Ann. Chem. (Liebig), CCLXVI. 52, CCLXX. 331, CCLXXVI. 200.
t Ann. Chem. (Liebig), CCLXX. 329, CCLXXVI. 234, CCLXXVII. 73
Of. also page 147 of tlie preceding paper.

170 PROCEEDINGS OF THE AMERICAN ACADEMY.

taining pieces of ice, an aqueous solution of hydrogen sulphide (one
molecule), reaction sets in immediately, and a strong odor resembling
very closely that of prussic acid is noticed. The clear colorless fil-
trate contains both silver and sulphur ; on addition of silver nitrate, a
brown precipitate consisting of silver fulminate and silver sulphide
is obtained ; hydrochloric acid precipitates chloride and sulphide of
silver. On treating silver fulminate with hydrogen sulphide, an addi-
tion must therefore take place as follows :

AgON : C + H^S =r AgON : C^^ ,

forming silver thioformhydroxamate, which, like silver formylchlorid-
oxime, is soluble in water; this salt is then further acted upon by
hydrogen sulphide, and partially converted into silver sulphide and
thioformhydroxamic acid,

HON ; C^jj •

The above facts suffice also to explain fully the former experiments
of Ehrenberg* and of Scholvien.f Scholvien believed he had ob-
tained free fulminic acid on adding aqueous sodic fulminate to cold
dilute sulphuric acid and extracting immediately with ether, for he
obtained by shaking the ethereal solution quickly with silver nitrate
a precipitate of silver fulminate. t He describes the " free fulminic
acid " as a volatile compound, which affects the eyes and mucous mem-
brane of the nose in an intolerable manner.

It is now clear that Scholvien's compound was nothing else than

XT

formylsulphate-oxime, HON: Cqo/-) qtt formed by an addition of sul-
phuric acid to the unsaturated carbon atom present in sodic fulminate,
as follows :

NaON : C -f H^SO^ = NaON : C^gQ ^^ (I.)

2NaON : C^Q Qjj -H HaSO^^ SHONiC^g^ ^j^ + Na,S04. (H.)

Formylsulphate-oxime is a substance which is far less stable than
the analogous formylchloridoxime described above, which is not sur-
prising. It possesses, just as formylchloridoxime, only to a far
greater extent, a tendency to split into sulphuric acid and carbyl-
oxime, C:NOH. This is the reason why Scholvien always noticed

* Journ. f. prakt. Cliem., [2.], XXX, 43. \ Ibid., XXXIL, 463, 481.

t Ibid., XXXII. 463, 480.

NEF. BIVALENT CARBON. 171

in an ethereal solution of the substance after a few moments a rise
in temperature, " which often is so great that the ether begins to
boil." * The carbyloxime formed in the nascent state polymerizes to
a great extent, just as has often been noticed in analogous cases with
isocyanides. For this reason it seems to me highly probable that
Scholvien's isocyanuric acid f consists simply of polymerized carbyl-
oxime, and probably possesses the constitution

OH

C-N-C

I I

HON-C-NOH.

All the properties of the substance can easily be explained by this
formula, and a further study of it will be taken up very shortly ;
especially also because Scholvien states that on treating the silver
salt CgHNgOsAga with ethyliodide, " a filtrate was obtained smelling
strongly of carbylamine." $ It is very likely that in this reaction no
ethyl isocyanide, but ethylcarbyloxime, C2H5ON : C, is formed, — a
substance which, as will be shown farther on, cannot be distinguished
from ethyl isocyanide in respect to odor.

Ehrenberg has already had an ethereal solution of formylchlorid-
oxime (containing also mercuric chloride and hydrogen chloride) in his
hands. He obtained it by passing dry hydrogen chloride over mercu-
ric fulminate suspended in absolute ether; and he assumes that free
fulminic acid may possibly be present in the solution. He describes
the ethereal solution § as a "strong-smelling liquid, bringing teai's to
the eyes, and affecting the mucous membrane, and causing an intensely
bitter taste in the mouth. The smell reminds one^of prussic acid, but
this could not be detected in the solution. On attempting to distil
off the ether, the mass all at once decomposed with violence and with
a hissing noise."

Ehrenbeig was, in consequence, unable to isolate the product, and
studied only the action of aqueous ammonia upon the ethereal solution
of the substance. The nature of the compounds which he obtained in
this way is cleared up by the experiments mentioned below.

Fulminic acid salts can therefore be obtained synthetically in four
different ways, as follows.

1. From sodic nitromethane :

H2C : N-ONa + hgCl = C : NOhg + NaCl + n„0.

II
O

* Journ. f. prakt. Chem., [2.], XXXII. 463. | Ibid., XXXII. 473.

t Ibid., XXXII. 464. § Ibid., XXX. 44

172 PROCEEDINGS OF THE AMERICAN ACADEMY.

2. From formylchloridoxime :

g ) C : NOH + 2AgN03 = C : NOAg + AgCl + 2 HNO3.

3. From formylsulphate-oxime :

HON : CQgQ Qjj + SAgNOg = C : NOAg + Ag2S04 + 3 HNO3.

4. From thioformhydroxamic acid :

HON : Cgpj + SAgNOs = C : NOAg + AgsS + 0 HNO3.

Behavior of Formylchloridoxime towards Aniline.

The constitufion of formylchloridoxime is proved by the fact that
aniline coverts it quantitatively into phenylisuretine, according to the
reaction ;

NHCeHs

HON: C^j + 2C6H5NH2 = HONH-C-Cl + CeH^NHa

H

Addition Product.

= ^^^J^)C:NC6H5 + C6H5NH3CI.

Phenylisuretine

On adding: an ethereal solution of aniline (2 molecules, 12.5 grams)
to a concentrated ethereal solution of formylchloridoxime (obtained
from 12 grams silver fulminate), a clear solution at first takes place,
but very soon a white salt begins to separate out in large quantity.
After standing for one hour, much ether is added, and the salt filtered
off. The residue, 9.2 grams, consists of a mixture of aniline hydro-
chloride and phenylisuretine, which, since the latter substance is insol-
uble in cold water, can readily be separated. The ethereal filtrate
gives, on evaporation, phenylisuretine and traces of aniline. Alto-
gether 6.5 grams of phenylisuretine were obtained. It is purified by
crystallizing from ether, and obtained in flat colorless needles, melting
with decomposition at 138°. The substance crystallizes from water in
long fibrous colorless needles, or, if the solution is dilute, in leaflets.
A slight decomposition into phenylisocyanide and hydroxylamine,
according to the equation,

CeH.N : C^^LOR = ^«"=^ '' ^ + H.,NOH,

NEF. — BIVALENT CARBON. 173

always takes place on recrystallizing the substance from water. Phe-
nylisuretine shows altogether a great tendency to decompose in this
manner. On melting the solid substance, a strong smell of phenyl-
isocyanide is noticed ; also on warming with sodic hydrate, in which
it first dissolves. The compound possesses strong basic properties,
and dissolves immediately in cold dilute acids. It gives a deep purple
red coloration with ferric chloride, and reduces silver solutions on
warming. Because of its decomj)osition into phenylisocyanide, the
substance burns with great difficulty.*

0.1435 gram substance, dried over H2SO4 in a vacuum, gave 0.3202

gram CO2 and 0.0799 gram HgO.
0.1549 gram substance, dried over H2SO4 in a vacuum, gave 0.3452

gram CO2 and 0.0848 gram HgO.
0.1526 gram substance, dried over HjSO^ in a vacuum, gave 0.3428

gram CO2 and 0.0843 gram H2O.
0.1544 gram substance gave 28.5 c.cm. N, at 20° and 755 mm.

Theory for C,Il8N„0.

C 61.76

H 5.89

N 20.59

In order to prove absolutely that the substance was really phenyl-
isuretine it was necessary to obtain it synthetically from a formic
acid derivative. To effect this, two ways were open ; the substance
could, in the first place, easily be formed from phenylisocyanide and
hydroxylamine, by addition,

C,H,N : C + H2NOH = C,H,N : C ^jjQjj

In the second place, it could probably easily be obtained from isuretine
by means of aniline hydrochloride.

The second method was first chosen, and since this succeeded
directly and quantitatively, the first way, which m all probability
would also yield phenylisuretine, was not tried.

Preparation of Isuretine, HN : C TVTTjfvTT • — Lossen and Schiffer-

decker have obtained this compound from prussic acid and hydroxyl-
amine.f The following slight modification of their method gives a
very good yield of isuretine. A solution of 30 grams of cyanide of

* Ann. Cliem. (Liebig), CCLXX. 276.
t Ibid., CLXVI 295.

Found

60.87

60.78

61.27

6.18

6.08

6.14

20.97

174 PROCEEDINGS OF THE AMERICAN ACADEMY.

potash in 60 grams of water, is added to a solution of 31.5 grams
hydroxylaminehydrochloride (one molecule) in 60 c.cm. water ; great
care must be taken that the temperature never rises above 5°. The
solution is kept for 48 hours at 5°, and then allowed to evaporate
spontaneously in flat dishes. The dry residue is boiled out with
absolute alcohol, and on cooling and evaporating the filtrates, isuretine
separates out in colorless needles, melting at 114°— 115°. The last
portions separating out are best crystallized from acetic ether, from
which the substance is obtained perfectly pure and beautifully crys-
talized. With the exception of the melting point (Lossen and SchilFer-
decker give mpt. 104°-10o°), the former statements concerning its
properties could be confirmed.

The yield is 84 grams pure isuretine from 142 grams cyanide of
potash used.

0.2531 gram substance, dried over HoSO^ in a vacuum, gave 0.1872

gram COj and 0.1571 gram HjO.
0.1369 gram substance, dried over HgSO^ in a vacuum, gave 56.7 c.cm.

No at 21° and 753 mm.

Theory for CNoHiO.

Found.

c

20.00

20.17

H

6.67

0.89

N

46.67

46.71

PhenyUsuretiiie from Isuretine. — On heating isuretine (1 gram)
and aniline hydrochloride (one molecule) in alcoholic solution, an inter-
action with formation of phenylisuretine and ammonium chloride very
soon takes place. After distilling off the alcohol, and treating the
residue with cold water to get rid of ammonium chloride, it is crystal-
lized from ether; 1.7 grams of phenylisuretine were obtained, crystal-
lizing in flat needles, melting at 138°, and in every respect identical
with the compound obtained from formylchloridoxime.

0.0687 gram substance, dried over HoSO^ in a vacuum, gave 13 c.cm.

Ng at 24° and 755 mm.

Theory for CiHgNjO. Found.

N 20.59 21.07

Behavior of Formylchloridoxime towards Ammonia.

CN-C : NOM

Oyanisonitrosoacefhydroxamic Acid., \ — In view of

HOC : NOH.
the results with aniline, it was at first expected that, on treating for-

NEF. — BIVALENT CARBON. 175

mylchloridoxime with ammouia, isuretine and ammonium chloride
would be formed. The reaction takes place, however, in a different
manner, no matter whether the ethereal solution of formylchloridoxime
is treated with concentrated aqueous, or with dry gaseous ammonia.
It is best to proceed as follows. The ethereal solution, obtained by
extracting the acidified sodium fulminate solution, is treated directly,
without concentrating it, in a separatory funnel with small quantities
of concentrated aqueous ammonia (30 per cent), taking care to shake
well and to cool thoroughly with water. A yellow powder separates
out in large quantity, which settles on shaking in the lower portion
of the funnel. A portion from 32 grams of mercuric fulminate was
always worked up at a time, and about 40-50 c.cm. concentrated
ammonia used (until a strong smell of ammonia is apparent). The
aqueous solution with the yellow powder suspended in it, is then
drawn off and filtered, and the filtrate again brought into the sepa-
ratory funnel, and the operation repeated until all the yellow powder
is brought on the filter ; it is then dried on clay plates. The filtrate
contains much ammonium chloride and also some of the yellow sub-
stance, which is sparingly soluble in cold water. 25 grams of the
yellow powder were regularly obtained from 96 grams of mercury
fulminate: it consists of the secondary ammonium salt of cyaniso-
nitrosoacethydroxamic acid ; it cannot be crystallized from hot water
however without some decomposition. The yellow powder is there-
fore converted directly into the free acid. 25 grams of the salt are
suspended in 40 c.cm. water, and 120 c.cm. dilute hydrochloric acid
(16.5 per cent) added, and thereupon the resulting solution is extracted
35 times with ether. After drying with chloride of calcium, the ethereal
solution is distilled off and 15 grams of a colorless solid remains,
which already consists of practically pure cyanisonitrosoacethydrox-
amic acid. The substance is recrystallized from ether with addition
of a small amount of ligroine (bpt. 70°-80°), and obtained in colorless
cubes or in 4-sided prisms, clear as glass, and melting, with decompo-
sition, at 117°-118°.

0.1555 gram substance, dried over HoSO^ in a vacuum, gave 0.1490

gram COg and 0.0438 gram HgO.
0.1125 gram substance, gave 30.5 c.cm. Nj at 20° and 751 mm.

Theory for C.5II3N3O3.

JH2O.

Found.

c

26.09

26.13

H

2.90

3.13

N

30.43

30.64

176 PROCEEDINGS OF THE AMERICAN ACADEMY.

The substance is readily soluble in water, and in organic solvents
with the exception of benzene and ligroine. It crystallizes from acetic
acid in transparent quadratic pyramids with basal planes. The sub-
stance has a strong acid smell, and gives both primary and secondary
salts, which are colored yellow. An aqueous solution of the acid gives
with ferric chloride an intense blood-red coloration.

Primary Silver Salt, CsHgNaOsAg. — This salt separates out slowly
in yellow flat prisms on addition of silver nitrate (one molecule) to a
concentrated aqueous solution of the acid. The filtrate gives, on long
standing, a brownish red precipitate.

0.1948 gram substance, dried over H2SO4 in a vacuum, gave 0.1172
gram AgCl.

Theory for CsH^NjOgAg. Found.

Ag 45.76 45.29

Secondary Potassium Salt, C3HN303K2> HaO. — This salt is obtained
quantitatively on adding an alcoholic solution of the acid to an alco-
holic solution of potassic hydrate (two molecules). It separates out
as a yellow crystalline powder, which, after being well washed with
alcohol and dried over sulphuric acid in a vacuum, was analyzed.

0.2038 gram substance gave 0.1596 gram K0SO4.

Theory for C3HN3O3K2H2O. Found.

K 34.98 ' ' 35.11

Behavior of the Acid towards Ammonia. — On adding concentrated
ammonia solution to an aqueous solution of cyanisonitrosoacethydrox-
amic acid, the secondary ammonium salt separates out as a yellow
amorphous powder, identical with the salt obtained directly from
formylchloridoxime and ammonia. If, however, much ammonia solu-
tion is used, a yellow solution results, in which, after some standing,
no longer the original substance, but its decomposition products are
present. These are the products which Ehrenberg (see above) ob-
tiiiued on treating his ethereal formylchloridoxime solution with a
large quantity of aqueous ammonia. The primary product of the
reaction, the ammonium salt of cyanisonitrosoacethydroxamic acid,
was obtained by him only in traces, and was not further investigated.*
It simply remained dissolved in the aqueous ammonia solution, be-
cause he used a very lai'ge amount of the solution. He obtained, on
allowing this solution to stand in the air, three compounds. First, a
substance,! C3H4N4O2, which separates out in yellow needles ; on

* Journ. f. prakt. Chem., [2.], XXX. 47. t Ibid., XXX. 49.

NEP. — BIVALENT CARBON. 177

acidifying and extracting with ether, two other compounds were
obtained : one of these, which is far less soluble in cold ether, he
calls isofulminuric acid,* and its composition as C3H3N3O3 was deter-
mined by many analyses ; the other substance was a syrupy acid from
which he obtained a small amount of a crystallized ammonium salt,

CII.NsO^.t

These three substances are all obtained by allowing an ammoniacal
solution of pure cyanisonitroacethydroxamic acid to stand in the air,
and proceeding according to the directions of Ehrenberg. It is to be
noted that Ehrenberg's compound of the formula C3H4N4O2 possesses
weak acid as well as also strong basic properties ; it dissolves there-
fore instantly in cold dilute hydrogen chloride. It also gives with
ferric chloride an intense blood-red coloration.

Behavior of Cyanisonitrosoacethydroxamic Acid totvm-ds Water. —
Whereas a solution of the free acid in concentrated hydrochloric acid
or in concentrated sulphuric acid can be kejit without essential change
for twelve hours in the cold, an aqueous solution of the acid (2 grams)
is completely decomposed after two hours heating on a water bath.
The solution no longer gives a yellow but a white precipitate with
silver nitrate. On extracting with ether, and drying the ethereal
solution with calcic chloride, two substances are obtained which are
identical with Ehrenberg's isofulminuric acid and his syrupy acid.
The former can easily be separated from the latter by washing with
a small amount of ether. It was crystallized (1 gram) from a small
amount of water, and obtained as a white spongy powder identical in
its properties and its behavior with Ehrenberg's isofulminuric acid.
The fact that the substance gives with ferric chloride a deep blood-red
coloration is worthy of mention.

0.1687 gram substance, dried at 100°, gave 0.1725 gram CO2 and

0.0386 gram H.O.
0.0780 gram substance, dried at 100°, gave 23 c.cm. N2 at 22° and

750 mm.

Theory for C3H3N3O3.

Found.

c

27.91

27.89

H

2.33

2.54

N

32.56

32.94

The syrupy acid which is formed at the same time is identical with
the corresponding compound obtained by Ehrenberg, but for the pres-
ent has not been further studied.

* Journ. f. prakt. Chem., [2.], XXX. 55. t Ibid., XXX. 59.

VOL. XXX. (n. S. XXII.) 12

178 PROCEEDINGS OF THE AMERICAN ACADEMY.

Behavior of the Acid C3H3N3O3, ^ HgO, towards concentrated Caus-
tic Potash. — Id the expectation that cyanisonitrosoacethydruxamic
acid must, by treatment with caustic potash, yield potassic isonitroso-
malonate, it was heated (1 gram) with concentrated potassic hydrate
(6.9 grams KOli and 10 grams water) for three quarters of an hour
on a water bath. Ammonia is given off copiously, and the solution is
then treated further according to the method of Baeyer.* On addition
of alcohol to the solution, acidulated with acetic acid, an oily precipitate
is obtained, which, on rubbing with a glass rod, solidifies. Recrystal-
lized once from water and alcohol, it is obtained (0.5 gram) in colorless
leaflets, which give with ferric chloride a deep red coloration, and
wliich resemble very closely potassic isonitrosomalonate. The analy-
sis of the salt, dried over sulphuric acid in a vacuum, shewed, however,
that another substance is at hand, and that the original acid has lost
only one atom of nitrogen as ammonia in the above treatment.

0.2498 gram substance save 32.5 c.cm. N, at 20° and 746 mm.
0.2024 gram substance gave 0.0988 gram K2SO4.

Theory for CgHNjOiK.HsO.

Found.

N

15.04

14.61

K

21.04

21.89

Behavior of the Acid C3H3N3O3, ^ H2O, towards concentrated Hydro-
gen Chloride. — 2 grams of the acid are heated in a sealed tube for
five hours with concentrated hydrochloric acid (10 c.cm. of sp. gr. 1.18).
On opening the tube, the presence of carbon dioxide was noticed ; and
on evaporating the contents on a water bath, 2.5 grams of residue are
regularly obtained. On digesting this with ether, the oxalic acid
formed in the reaction (proved by its tests and properties) was re-
moved, and the residue (2 grams) consists of a mixture of much
ammonic chloride and of little hydroxylamine hydrochloride. A
quantitative determination, carried out by means of Fehling's solution,
showed that the residue (2 grams) consists of 1.6 grams ammonium
chloride and of 0.4 grams hydroxylamine hydrocliloride.

It follows from these experiments that cyanisonitrosoacethydroxamic
acid is decomposed by hydrogen chloride into oxalic acid, carbon
dioxide, ammonium chloride, and oxyaramonium chloride ; and that
more than two thirds of its nitrogen is eliminated in the form of am-
monic chloride.

* Ann. Clieni. (Liebig), OXXXI. 292.

NEF. — BIVALENT CARBON. 179

Tlie Constitution of the Acid. — That the acid, C3H3N3O3, ^ IlgO,
obtained from formylchloridoxime by means of ammonia, is identical
with cyanisonitrosoacethydroxamic acid cannot at present be deter-
mined with certainty from its decomposition products. The consti-
tution of the acid as given is however extremely probable because of
its quantitative formation from sodic fulminate (two molecules) and
formylchloridoxime.

The action of formylchloridoxime on sodic fulminate can, because
of the entirely analogous results obtained with phosgene on isocya-
nides,* take place only in the following manner.

TT HON : CH C^N

HON : Cp, + C . NONa = I = | + HoO. (I.)

^^ Cl-C : NONa CIC : NONa

Addition.

C-=N
I
NaON:C-Cl-|-C:NONa

CN

I -t- H2O = CN-C : NONa
= NaON:C I -1- HCl. (H.)

I HOC : NONa

CIC : NONa

Addition . Sodic-cyanisonitrosoacethydroxamate

The reaction which takes place on treating formylchloridoxime with
ammonia is entirely analogous : a decomposition of the formylchlorid-
oxime into ammonium chloride and ammonic fulminate first takes
place as follows:

^j^ C : NOH + 2 NH3 = C • NONH, + NH4CI.

The ammonic fulminate thus formed (two molecules) then reacts with
unchanged formylchloridoxime (just as in the above equations does so-
dic fulminate) and ammonic cyanisonitrosoacethydroxamate is formed.
As can easily be seen, cyanisonitrosoacethydroxamic acid,

CN-C: NOH
I
HOC : NOH,

can readily go over by loss of water into a furazane derivative,

CN-C = N\

I o,

HOC = N/

* Ann. Chem. (Liebig), CCLXX. 286, 315.

180 PROCEEDINGS OF THE AMERICAN ACADEMY.

and this suffices to explain fully all the reactions and decomposition
products of this acid. That the t'urazaue ring is a very stable one is
clearly evident from the experiments of Wolff.* Ehrenberg's product,
CaH^N^Og, is therefore very probably

/ N = C-C-NH2
O^ I

^N = C-OH;
his isofulminuric acid is identical with oxyfurazaue-carbonicamide,

^N = COH,

whereas the syrupy acid obtained by him is probably oxyfurazane-

cyanide,

, N = C-CN

^ N = COH.

The product obtained by myself, by means of concentrated potassic
hydrate, CgHNgO^K, H2O, is, on the other hand, probably identical
with potassic oxyfurazanecarboxylate,

/ N = C-CO,K

\N = C0H;

it must therefore be obtained from all three of Ehrenberg's com-
pounds by saponification. Further experiments, with a view of
proving more sharply the constitution of these decomposition products
of cyauisonitrosoacethydroxamic acid, will be taken up again shortly.

III. Desoxtfdlmincric Acid is identical with Ctanisonitro-

CN-C : NOH

soacetamide,

HOC:NH.

Liebigt and SchischkofFJ have shown that on boiling mercuric ful-
minate with ammonic chloride, or with potassic chloride and water,
a monobasic acid, HCsHaN^Og, is formed which, at present, is known
by the name of fulminuric acid. Ehrenberg § obtained the same acid

* Ann. Chem. (Liebig), CCLX. 101. Cf. Ber d. chem Ges., XXIV. 1167.
t Ann. Chem. (Liebig), XCV. 282. t Il'id.. XCVTI. 53, CI. 213.

§ Jourii. f. prakt. Chem., [2.], XXXII. 98.

NEF. — BIVALENT CARBON. 181

by boiling fulminate of mercury with water. Among the manj for-
mula' which have been advanced as representing the constitution of
this acid, the one proposed by Steiner,*

CN-CHNO2
I
HOC : NH,

possesses the greatest probability. It explains very simply the forma-
tion of nitroacetonitrile, CN— CH2NO2, from it by means of sulphuric
acid,t as well as the formation of trinitroacetonitrile, CN— C (N02)3 5
by means of sulphuric acid and nitric acid, t

It follows directly from the above experiments, that, on boiling mer-
curic fulminate with water and either ammonic chloride or potassic
chloride, an addition of water or of hydrogen chloride to the unsatu-
rated carbon atom present in this salt must at first take place, and
thus the products

hgON : C ^ and hgON : C ^

must be formed. These can then act further, in the second stage, on
unchanged mercuric fulminate in exactly the same way as formyl-
chloridoxime acts on sodic fulminate (see above). It was therefore
suspected for a long time that cyanisonitrosoacethydroxamic acid
must be an intermediate product in the formation of fulminuric acid
(its isomer). After, however, many fruitless attempts were made to
convert this substance into fulminuric acid, by oxidation, by boiling
with mercuric oxide, or with ammonia and oxide of mercury, etc.. it
seems to me impossible that this is formed as an intermediate product.
If fulminic acid is identical with nitrocyanacetamide,

CN-CHNOo
I
HOC : NH,

and this is proved to be the case farther on, it must be formed
from mercury fulminate in a manner entirely analogous, for instance,
to the formation of mesoxanilide from phenylisocyanide, phosgene,
and water, § or also to that of cyanisonitrosoacethydroxamic acid
from formylchloridoxime and soluble fulminic acid salts. The fol-
lowing explanation of the reaction which takes place in the formation

* Ber. d. chem. Ges., IX. 784.

t Steiner, Ber. d. chem. Ges., IX. 782.

t Schisclikoff, Ann. de Chim. et de Phys., [3.], XLIX. 310.

§ Ann. Chem. (Liebig), CCLXX. 291.

182 PROCEEDINGS OF THE AMERICAN ACADEMY.

of fulminuric acid seems to me at present to be the most plausible
one. The product first formed by the action of ammonic chloride
on mercury fulminate,*

hgON:C^,

reacts first on the unchanged salt, giving by addition

hgON : CH

I (I.)

hgON : CCl.

Mercury formylchlorid-oxime is, however, as is readily understood
and has also been proved,! a strong oxidizing agent, which can easily
go over, with loss of oxygen, into cyanide of mercury,

hgON : C ^^ = hgN : C + HCl + O.

The cyanide of mercury thus formed, can then react with the addi-
tion product (I.) as follows :

hgON : CH hgON : CH

I I

hgON : CCl + hgN : C = hgON : C (II.)

I
hgON : CCl ;

and this product is then oxidized to

hgON : CH
I

C = N-Ohg (III.)

I II
hgON ; CCl O

from which, by means of ammonia, the ammonium salt of fulmmuric
acid,

O
11
CN-C : NONH4,

I

HOC : NH

* The reaction with water is entirely analogous ; it is only necessary to
substitute OH for CI.

t An aqueous solution of formylchloridoxime oxidizes, for example, ferrous
salts in acid solution immediately in the cold, and prussic acid is set free. Cf.
also Schischkoff, Ann. Chem. (Liebig), Suppl. Vol., I. 108.

NEF. — BIVALENT CARBON. 183

can readily be formed. It is, however, also possible that the addition

product 1.,

hgON : CH

I
hgON : CCl,

first goes over, by oxidatioo, into

hgON : C-H

CI-C : NOhg,

II
O

which then can add itself to cyanide o^ mercury, C : Nhg, present,
giving directly the addition product III., which, with ammonia, gives
mercuric oxide and ammonic fulminurate.

CN-C : NOH

Synthesis of Cyanisonitrosoacetamide, I

HOC : NH.

Seidel * has recently obtained, on treating silver fulminurate with
ethyliodide, a substance, C3H2N303(C2H5), which, on boiling with
water, decomposes into acetaldehyde, C2H4O, and a substance having
the formula C3H3N3O2, which he therefore calls desoxyfulminuric
acid. If fulminuric acid is identical with nitrocyanacetamide,

CH-CHNO2
I
HOC : NH,

it follows, by reason of the experiments on nitro compounds presented
in the preceding paper, that, on treating the silver salt of fulminuric
acid,

O
II
CN-C : NOAg,
I
HOCNH.

with ethyliodide, an ester of the constitution

O

II

CN-C : N-OC2H,

I
HOCNH

must be formed.

* Ber d. chem. Ges., XXV. 431 and 2756.

184 PROCEEDINGS OP THE AMERICAN ACADEMY.

This ester must then, on boiling with water, be split by intra-molec-
ular oxidation into cyanisonitrosoacetamide,

CN-C : NOH
I
HOC : NH,

and into acetaldehyde, CHgCH : O. These considerations lead to the
conclusion that desoxyfulmiuuric acid must be identical with cyaniso-
nitrosoacetamide, and the following experiments, which have led to
a synthesis of this compound, prove that in fact both products are
absolutely identical.

Cyanisonitrosoacetic ether, as well as cyanisonitrosoacetic acid, have
recently been obtained by Muller * from cyanacetic ether. I also
have made both these compounds in this way, and can confirm the
statements of Muller completely, except that the melting point of
cyanisonitrosoacetic ethylester was found to be 133° instead of 128°-
129°, when the substance is crystallized from benzene. Both com-
pounds were analyzed, and gave figures agreeing well with the theo-
retical ones. It is somewhat noteworthy that the ester melts higher
than the free cyanisonitrosoacetic acid.

On heating cyanisonitrosoacetic ethylester (2 grams) in a sealed
tube with 10 c.cm. of alcoholic ammonia for four hours at 100°, a salt
separates out, on cooling, in yellow heavy nodules. It is filtered ofP,
well washed with alcohol, dissolved in hydrochloric acid, and extracted
with ether. After drying the ethereal solution with calcic chloride,
and concentrating, colorless heavy plates separate out. which, recrys-
tallized once more from ether, melt at 184° and are perfectly pure.

0.1997 gram substance, dried over Hg'^Oi in a vacuum, gave 0.2325

gram CO^ and 0.0520 gram H^O.
0.15i5 gram substance, gave 50.2 c.cm. Ng at 19° and 744 mra.

Theory for C3H3N3O2. Found.

C 31.86 31.75

H 2.66 2.89

N 37.17 37.27

The substance crystallizes either in needles, or in heavy many-
sided flat crystals, and is identical in every respect with Seidel's
desoxyfulmiuuric acid. In order to be absolutely certain, this sub-
stance was made according to Seidel's directions, and compared in
every detail with the synthetic product ; no difference could be de-

* Annales de Cliim. et de Phys., [7.], I. 504.

NEF. — BIVALENT CARBON. 185

tected between them. Furthermore, desoxyfulminuric acid made
from mercury fulminate is converted quantitatively into cyanisonitro-
soacetic acid and into isonitrosomalouic acid, as is evident from the
following experiments.

3 grams desoxyfulminuric acid were heated on a water bath for one
hour with 2.2 grams sodic hydrate and 40 c.cm. water, whereby a
copious evolution of ammonia was noticed ; the solution was acidified
with dilute sulphuric acid, and extracted with ether. After evaporat-
ing the ether, the residual oil (1.6 grams) slowly solidifies. It was
twice crystallized from a mixture of ether and benzene, and obtained
in colorless needles, melting at 103°. The substance was identical
with cyanisonitrosoacetic acid prepared from cyanacetic ether.*

0.2048 gram substance, dried over H2SO4 in a vacuum, gave 0.2190

gram CO2 and 0.0495 gram HgO.
0.1251 gram substance gave 25.2 c.cm. N2 at 19° and 752 mm.

Theory for C3H2N4O3, J HjO. Found.

C 29.27 29.16

H 2.44 2.68

N 22.76 22.97

It is noteworthy that cyanisonitrosoacetic acid, which has now been
obtained in four different ways.f always contains half a molecule of
crystal water.

0.8 gram desoxyfulminuric acid, 2.5 grams caustic potash, and
5 c.cm. water, were heated for 3 hours on a water bath, and then
worked up according to the method of Baeyer t for potassic isonitro-
somalonate. The salt was recrystallized twice, and 0.95 gram was
obtained. The analysis agrees with theory for anhydrous salt.

0.2250 gram substance, dried over H2SO4 in a vacuum, gave 0.1844

gram K2SO4.
0.2520 gram substance gave 16 c.cm. N, at 24° and 744 mm.
0.3030 gram substance gave 0.1906 gram CO2 and 0.0175 gram H2O.

Theory for CsHOjKjN Found.

C 17.22 17.15

H 0.48 0.64

N 6.70 6.96

K 37.32 36.74

* Annales de Chira. et de Phys., [7.1, I. 604.
t Ann. Chem. (Liebig), CXXXI. 295.

J Wolff and Gans, Ber. d. chem. Ges., XXIV. 1169; Soderbaum, Ber. d. chem.
Ges., XXIV. 1231 and 1989 ; Muller, Annales de Chim. et de Phys., [7.], I. 504.

186 PROCEEDINGS OF THE AMERICAN ACADEMY.

Seidel obtained by heating silver fulminurate * with ethyliodide at
100°, instead of at 80°, a second compound of the formula,

CsH^NgOaCQHs),

melting point 155°. f This is in all probability formed from the

normal and original ester,

O
II
CN-C : NOQHg
1
HOC:NH,

by a molecular rearrangement, especially since we now know that
such esters are unstable compounds, capable of intramolecular oxida-
tion. It is very probable that this second compound, C3H2N303(C2H5),
possesses the constitution

CN-C : NOC2H5
I
HOC:NOH.

It is a strong acid, — a fact which Seidel does not mention.

IV. SODICFERROFULMINATE, Na4Fe(0N : C)6 + I8H2O,

The remarkable resemblance of fulrainic acid, C : NOH, and its
salts, C : NOM, to prussic acid, C : NH, and its salts, C : NM, has
become very evident by reason of the facts presented above. This
resemblance is so great, that many observers have been led astray in
working with fulmiuic acid compounds. For this reason it seems to
me that no longer the slightest doubt can exist concerning the nature
of prussic acid and its salts. $ They are unquestionably all derivatives
of isocyanogen,

* It need hardly be mentioned that many fruitless experiments were carried
out in the hope of synthesizing fulminuric acid, which, according to the above
results, must be identical with nitrocyanacetamide,

CN— CHNO2

I
HOC:NH.
Bromcyanacetamide,

CN— CHBr

HOC NH,

mpt. 122°, can easily be made from cyanacetamide, bromine, and water, but
all attempts to convert it, by means of potassic or silver nitrite, into nitrocyan-
acetamide were attended with negative results.

t Ber. d. chem. Ges., XXV. 2756.

t Ann. Chem. (Liebig), CCLXX. 329.

NEP. — BIVALENT CARBON. 187

N:C
I

N:C,

and not, as has so long been supposed, derivatives of cyanogen,

I

Tlie analogy between fulminic acid and prussic acid is further
shown by the isolation of a double salt, sodic ferrofulminate,

Na4Fe(ON.C)6

corresponding completely with sodic ferrocyanide,

Na4Fe(N:C)6.

Carstanjen and Ehrenberg have already drawn attention to the very
peculiar behavior of sodic fulminate towards iron salts, and shown
that solutions result in which the presence of iron can no longer be
detected,*

On adding to an aqueous solution of sodic fulminate containing
some sodic hydrate, and obtained as stated above from mercuric
fulminate (32 grams), a solution of ferrous sulphate (one molecule
to six molecules sodic fulminate), a yellowish solution is obtained,
in which the presence of iron cannot be detected either by means
of sodic hydrate or of ammonium sulphide. The filtered solution
is allowed to evaporate spontaneously ui flat dishes in the air, and
after some time beautiful yellow needles, often over an inch in length,
separate out. It is easily possible to obtaui 11 grams of this sub-
stance in a perfectly pure state from the above amount of mercury
fulminate taken. The crystals are filtered off, washed with a small
amount of cold water, and then dried between filter paper ; they do
not contain a trace of sodium sulphate.

On further evaporation of the mother liquors, more of the salt sepa-
rates out, but mixed with Glauber's salt. The sodic ferrofulminate
thus obtained is freely soluble in cold water, and gives with ferric
chloride an intense purple-red coloration, which is incredibly delicate.
The pure substance is, however, unstable in aqueous solutions or in a
moist condition,- and soon gets colored purplish red ; the presence of
sodic hydrate increases its stability, and for this reason it is well to
recrystallize in the presence of a small amount of sodic hydrate. The

* Journ. f prakt. Chem., [2.], XXV. 246, 247.

188 PROCEEDINGS OF THE AMERICAN ACADEMY.

salt contains 18 molecules of crystal water, a portion of which goes
off quickly in the air or over sulphuric acid in a vacuum, and the
substance changes its color first to white and then slowly to red. A
concentrated aqueous solution of the salt is precipitated by alcohol,
first in yellow needles, and on addition of more alcohol these are
suddenly transformed into a colorless white powder with loss of a
portion of the crystal water.

Whereas, the double salt. AgON : C, KON : C, is far more stable
than the corresponding prussic acid double salt, AgN : C, KN : C, in
this case the ferrofulminate of soda is far less stable than the analo-
gous sodic-ferrocyanide. It does not give an acid, ferrofulminic acid
corresponding to ferrocyanic acid, and, even on losing its crystal water,
the salt Na6Fe(0N : C)6 + 18 HgO dissociates completely into sodic
fulminate, NaON : C, and into ferrous fulminate, Fe(ON : C)2.

On treating the salt in the cold with dilute hydrochloric acid, it is
converted into formylchloridoxime. Also on boiling it in aqueous
solution with sodic hydrate or with ammonium sulphide, it is slowly
decomposed, with separation of iron hydrate or iron sulphide.

An aqueous solution of the salt gives with lead acetate, silver ni-
trate, or mercuric chloride, white very explosive precipitates, which
appear to consist exclusively of the corresponding fulminic acid salts.

As mentioned above, the yellow salt easily loses a portion of its
crystal water and becomes colored white ; on addition of water, it
is again transformed completely into the original salt. After long
standing over sulphuric acid in a vacuum, the white salt becomes
tinged red, and finally is converted into a red powder, which no longer
consists of ferrofulminate of soda, but of a mixture of sodic fulminate
and ferrous fulminate ; it then dissolves only partly in water, leaving
behind a red powder, and the solution does not contain a trace of sodic
ferrofulminate. On adding sodic hydrate, however, union of the com-
ponents again takes place, and the solution contains sodic ferrofulmi-
nate, which can be obtained on allowing the solution to evaporate.

The red dissociated salt just mentioned possesses very explosive
properties. It is just as dangerous as sodic fulminate,* and on this
account it was never possible to carry out a complete analysis of the
salt ; even when mixed very carefully with oxide of copper, on heat-
ing invariably a violent explosion took place. t The quantitative

* Journ. f. prakt. Cliem., [2.], XXXII. 231.

t The explosion is so sudden that not a gas bubble appears in the potash bulb
(5 times noticed), and the combustion tube is shattered completely only where
the substance was present.

NEF. — BIVALENT CARBON. 189

determination of the iron and sodium offered at first some difficulty,
because, on decomposing the salt with hydrochloric and nitric acids,
always a small amount of substance crystallizing in green leaflets is
formed, which is msoluble in aqua regia. The salt was finally decora-
posed by treating first with a small amount of dilute sulphuric acid,
and then evaporating to dryness and igniting. The residue was then
dissolved in hydrochloric acid, with addition of a small amount of
nitric acid, and the iron and sodium determined in the usual way.

4.754 grams yellow salt, dried between filter paper, lost on stand-
ing over II2SO4 in a vacuum, after two days, 1.5806 grams HgO; after
four days, 1.8167 grams U^O , after six days, 1.8996 grams HgO ; on
further standing, no further loss of weight was noticed.

Theory for Na^Fe (ONC)„ 2 HjO + 16 HjO. Found.

I6H2O 39.80 39.96

The red powder remaining is very hygroscopic, and still contains
two molecules of crystal water.

1.0073 grams substance gave 0.1760 gram FcoOs-

0.8154 gram substance gave 0.5380 gram Na2S04.

0.6999 gram substance gave 0.1282 gram FeaOg and 0.4609 gram

NaaSOi.

Theory for Na^Fe (ONC)o 2 H„0 Found.

Na 21.10 21.36 21.33

Fe 12.84 12.12 12.73

An attempt was made to obtain, by oxidation of this salt with bro-
mine and water, a fulminic acid double salt corresponding to sodic
ferricyanide, but without success.

V. On Fulminic Acid and its Esters. — The Carbyloxim-

ESTERS, C : NOR.

The experiments described above make it clear that it is not possible
to obtain free fulminic acid from its salts by treatment with acids,
because the acids always react first on the tremendously reactive biva-
lent carbon atom present in these salts ; and for this reason oximes of
formic acid derivatives are invariably obtained, which, although they
can readily be converted back again into fulminic acid salts, never
yield, when they decompose, the free fulminic acid. In this connec-
tion an experiment carried out with isuretine is of interest. On heat-
ing alcoholic solutions of isuretine and hydroxylamine hydrochloride
(in molecular quantities) an interaction with formation of ammonium

190 PIIOCEEDINGS OF THE AMERICAN ACADEMY.

chloride and of oxyisuretine very quickly takes place. Ou attempting
to distil off the alcohol, white fumes are noticed, which decompose
with some violence and the solution has an odor resembling very
closely that of prussic acid. On evaporating the solution over sul-
phuric acid in a vacuum, a yellow coloration is noticed (after most of
the alcohol has disappeared), and after a short time the residue de-
composes spontaneously with a hissing noise and tremendous evolution
of heat. It follows from this experiment that oxyisuretine,

HON : cHjjoH^

is a very unstable substance, and decomposes probably at first into
carbyloxime, C : NOH, and into hydroxylamine. This decomposition
is entirely analogous to that of phenylisuretine,

CeHgN : Cj^jjQjj^

and also especially to that of formylsulphate-oxime,

HON : C^gQ Qjj^

and of formylchloridoxime,

HON : C^j

The sum total of the results presented in this paper lead to the
conclusion that the free fulminic acid is a very unstable compound,
which possesses a smell that cannot be distinguished from that of
prussic acid. It follows further, however, that a series of ethers of
this acid must exist of the general formula C : NOR, which must in
their properties and their odor show the greatest resemblance to the
esters of prussic acid, the alkylisocyanides, RN : C. Although I have
not yet succeeded in isolating and analyzing a carbyloximether,
C : NOR, the following observations are sufficient to make it ex-
tremely probable that such esters do exist.

The Action of Ethyliodide on Silver Fulminate. — Calmels * states,
that on treating silver fulminate with ethyliodide, a and /3 nitropropy-
lene and ethylisocyanide are formed. I have repeated his experi-
ments, and observed that, on heating silver fulminate with ethyliodide
and absolute ether to 50°, or on allowing these substances to stand at

* Comptes Rendus, XCIX. 794

NEF. — BIVALENT CARBON. 1<J1

ordinary temperature, after a time most tremendous explosions take
place ; these can be entirely avoided as follows. 28.7 grams silver ful-
minate, 50 grams ethyliodide, and 38 grams absolute ether are brought
into a flask, which is constantly kept m cold water, and allowed to
stand thus for three weeks, takuig care to shake well from time to time.
At first, in the course of the reaction, a very strong smell of ethylcya-
nate is noticed (Calmels says smell of chlorpicrin) and towards the
end a smell resembling that of ethylisocyanide is noticed.

The investigation of the products formed has shown that they con-
sist chiefly of ethylcyanate and its polymer ethylcyanurate, whereas very
little of the substance smelling like ethylisocyanide is formed. It
seems to me, however, extremely probable that this product is not
ethylisocyanide, but ethylcarbyloxim, C : NOCgHg, the formation of
Avhich from silver fulminate, C; NOAg, and ethyliodide is self-evident.
The formation of ethylcyanate, or of its polymer, which is the chief
product of the above reaction, is easily explained by an addition of
ethyliodide to the unsaturated carbon atom present in silver fulminate,

AgON : C 4- IC2H5 = AgON : cj. „

The addition product is then converted by Beckmann's rearrange-
ment into ethylcyanate and silver iodide.

TT

Formation of Ethoxyformamidine, C2H5ON : C^rx

26 grams isuretine w^ere heated, in alcoholic solution, with one
molecule of sodium ethylate and ethyliodide (1^ molecules), for three
hours with reversed condenser; the alcohol was thereupon distilled
off, and a strong smell of isonitrile and ammonia was noticed. The
residue was dissolved in water and repeatedly extracted with ether.
After distilling off the ether, and fractionating the liquid remaining,
3 grams of an ethereal weak basic smelling oil were obtained, which
boils without decomposition at 170°-175°. Up to the present only
7 grams of this oil have been obtained, which, in view of an analysis
of a platinum double salt obtained from it, must be regarded as ethoxy-
formamidine. It is easily soluble in water; a portion was dissolved in
hydrochloric acid, and the evaporated solution takeo up in alcohol
and treated with platinic chloride. On addition of ether a yellow oil
separates out, which, on rubbing with a glass rod, solidifies. The
salt was recrystallized from alcohol and ether, and obtained in yellow
quadratic plates, melting at 153°

192 PROCEEDINGS OF THE AMERICAN ACADEMY.

0.3055 gram substance dried at 100° gave 0.1013 gram Pt.
0.3018 gram substance dried at 100° gave 26.6 c.cm. Ng at 17° and
749 mm.

Theory for(C3H8N,0,HCl)2PtCl4. Found.

Pt 33.16 33.16

N 9.57 10.07

The remaining ethoxyformamidine was dissolved in 4 molecules
dilute hydrochloric acid and treated, in the cold, with 1 molecule of
sodic nitrite.* A copious evolution of nitrogen is noticed, and after
standing for thirty minutes the solution is extracted with ether, and
the ethereal solution washed with dilute sodic hydrate and then dried
with calcic chloride. An oil is obtained which contains much chlorine,
and seems to boil without decomposition, and at higher temperatures
possesses a very sharp odor. It is very probable that it consists of
ethoximformylchloride,

C2H50N:C^j

On heating the oil, which is soluble in water, with concentrated caustic
alkalies, a strong smell of isonitrile is observed, which can only be due
to the formation of ethylcarbyloxime. Ethoximformylchloride seems,
however, in comparison with formylchloridoxime, to be remarkably
stable, and is split, on treatment with alkalies, chiefly into formic acid,
ethoxylamine, and potassic chloride.

The Action of Chloroform and Alcoholic Potash on a Benzylhy-

droxylamine.

The esters of carbyloxime ought, however, to be obtained most easily
from M alkylated hydroxylamines by means of Hofmann's reaction,

RONH, + CHClg + 3 KOH = RON : C + 3 KCl + 3 HjO.

On adding a mixture of a benzylhydroxamine f (10.4 grams) and
chloroform (17.3 grams) to a solution of 19.2 grams potassic hydrate
in 70 grams alcohol, an energetic reaction takes place, and a strong
smell of isocjanide is noticed. Benzylcarbyloxime, C7H7ON : C, has,
however, been formed only in minute quantities, and 7 grams unchanged
a benzylhydroxylamine were recovered. The reason for this seems
to me to be due to the fact that the intermediate product,

C7H7ON : C^j

* Tieraann and Kriiger, Ber. d. chem. Ges., XVIII. 1732.
t Behrend and Leuchs, Ann. Chem. (Liebig) 257, 205.

NEP. — BIVALENT CARBON. 193

which must be formed in the reactiou,* is very stable, just as is the
case with ethoximformylchloride mentioned above, and therefore it is
split chiefly into a benzylhydroxylamine, formic acid, and potassic
chloride.

In the above work on bivalent carbon, which will be continued in
various directions, I have been assisted with great skill and with
remarkable perseverance by Dr. M. Ikuta, to whom I wish also here
to express my warmest thanks.

* Ana. Chem. (Lieblg), CCLXX. 308.

VOL. XXX. (N. S. XXII.) 13

194 PROCEEDINGS OF THE AMERICAN ACADEMY.

VII.

ON THE PROPERTIES OF BATTERIES FORMED OF
CELLS JOINED UP IN MULTIPLE ARC.

By B. O. Peirce.

Presented May 9, 1894.

If three galvanic cells the electromotive forces of which are ei, e^,
and 63 respectively, and the internal resistances, bi, b^, and 63, be joined
up parallel to each other, the battery thus formed is equivalent — so
far as its ability to send electricity through an external circuit is
concerned — to a single cell of electromotive force e,,, and of internal
resistance 6q, where

eo =

ei b^ bs + ^2 bi bs + €3 bi b^ , 61 b^ b

b,=

bo bs + bsbi + bi b^ 5, b^ + ^i ^3 + ^i b.^

A similar statement * may be made about a battery of any number
of cells connected in multiple arc. It is evident, however, that the
efficiency f of such a battery of unlike cells is less than that of a single
cell which would do the same amount of useful work under the same
external circumstances.

I have had occasion of late to consider some relations between the
strengths of the currents which pass through the different members of
a given battery of unlike cells joined up in multiple arc. Many per-
sons must have used the equations which I found convenient in this
work, but I cannot find that any one % has taken the trouble to print
them all. I therefore give a few of them here, with some well
known formulas introduced for the sake of clearness.

Let the internal resistances of n cells, which are joined up in mul-
tiple arc with each other and with a conductor of resistance r, be
^n ^2> ^3 • • • respectively, and the electromotive forces be e,, €•>•, e„ . . .

* Stepanoff, Journal Russ. Phys. Chetn. Soc, XII. 38.
t Slouginoff, Journal Russ. Phys. Chem. Soc, XIV. 2.

X I have not had access to the papers of Messrs. Stepanoff and Slouginoff
quoted above.

PEIRCE. — BATTERIES IN MULTIPLE ARC.

195

Let C be the current which flows through the outside resistance r,
and let C^. be the current which flows, in the same cychc direction
as C, through the /;th cell. Then, if \ — X^ r,

k = I

p = n

p = i

(1)

(2)

Let the determinant of the coefficients of the C's in the set of n
linear equations of which (2) is an example, be denoted by A„ ; then

A„ = /•«

1 + Ai 1 1 1

1 1 + Aa 1 1

1 1 1 + A, 1

1 1 1 1 + A4

1 + K

or

A = r" S

It is evident that 8„ ^ , would be equal to the product of X„ + ^ and
8„ plus the product of all the X's from Xj 10 X„.

Let 3f„ represent the product of all the b's.

Let N„ represent the sum of the n products of the 5's taken n — 1
at a time.

Let P„ J represent the sum of the n — 1 products formed of all
the b's except b^ taken ?^ — 2 at a time.

Let Q,^ represent the sum of the n products formed by multiplying
every e by all the ^'s except its own.

Let S„^^. represent the sum of the products obtained by multiplying
every electromotive force except that of the kih cell by all the b's
except its own and b^.

Then A^ = M;, + r iV„. (3)

The determinant formed from the determinant of the coefficients
(A„) of the C's in the n linear equations of which (2) is a type, by sub-
stituting the corresponding e's for the elements of the ^th column shall
be called A„ j.

196 PROCEEDINGS OF THE AMERICAN ACADEMY.

Hence,

The current in the Z,th cell may be positive, zero, or negative accord-
ing to circumstances. If the electromotive forces and the internal
resistances of all the cells are given, C^ will be positive if r be made

less than -^ p — .

*^/i, ft ^k -^ n. ft

The currents in all the cells will be positive if r be made sufficiently
small. If the electromotive forces of the cells are unequal, and if r is
very large, the currents in the weakest cell or cells will be negative.
If the outside conductor be removed so that the poles of the battery
are not connected externally, the current in the i'th cell will be positive
if gj is greater than S^ ^ -i- P„ ^. Thus, if the battery consists of three
unlike cells numbered in order of descending electromotive force,
Cj^ must be positive and C^ negative, but 0^ will be positive or not

• • , ^1 ^1 H~ ^3 ^1

according as e., is or is not greater than -^,- — .

The case of a number of cells of the same internal resistance but of
different electromotive forces joined up in multiple arc is of some in-
terest when one has to use a number of unequally charged storage
cells to send a very heavy current through an outside circuit of
extremely low resistance. When the b's are all equal,

b (b + n r) b

^ — \- r

n

so that the equivalent cell has an electromotive force equal to the
average of the electromotive forces of the given cells, and an internal
resistance equal to ~th of that of each cell. This case also throws
some light on the properties of a thermal junction of large area formed
of two plates of metal soldered together flatwise when, as is sometimes
the case in practice, it is impossible to keep the whole junction at
exactly the same temperature.

Equations (1) and (5) give the equation

PEIRCE, — BATTERIES IN MULTIPLE ARC. 197

Ci.

Q

h I N

which defines Stepanoff's equivalent cell * already mentioned. 'Ihe
difference of potential between the poles of the battery is

V= "^ (7)

When r is made to increase indefinitely, F approaches as a limit the
electromotive force Q I N^oi the equivalent cell, and (7^ approaches

— — 2i^r= — , the current in the ^'th cell when the poles of the battery

are not connected by any external conductor.

If there is a battery of electromotive force E in the external circuit,
r, the quantity JiJ must, according to the direction of this external elec-
tromotive force, be added to or subtracted from the second member of '
each of the equations of which (2) is an example. If a battery of n
cells joined up in multiple arc be itself connected up parallel with a
cell of electromotive force £J and of internal resistance B, E -^ B must
be added to the numerator of the fraction which forms the second mem-
ber of (6), and r -i- B to the denominator. Upon an examination of
these cases, it appears that, if a battery of cells joined up in multiple
arc be itself connected up parallel or in series with another battery,
or if it be used for compensation purposes, it will exert the same in-
fluence upon the currents and diff'erences of potential in parts of the
circuit external to itself as its equivalent cell would exert.

The internal work done m the battery when its poles are connected
by the external resistance, r, is

W,Ji\c,H,). (8)

k = 1

The internal work done in the equivalent cell would be

2(Q

(9)

Let v) be the difference between W^ and W(, and in the equation
found by subtracting the members of (9) from the corresponding mem-

* See also SlouginofE, Carl's Repertorium, XVI. 539.

198 PROCEEDINGS OF THE AMERICAN ACADEMY.

bers of (8), let e^ — Gr be substituted for its equal Ck hk. It will tlien
be found that all the terms which contain r disappear, since the co-
efficients of Cr and of 0^ r^ vanish identically, and that

^^^....(^.^ 00)

iV„ 4 = 1 b^ b^

where the si2,n of summation introduces once only every value of
{eic — Cj)'^, in which k is ditfereut from^, and neither k nor / is greater
than n.

Since w does not involve r, it {w) is the work done inside the
battery when its poles are not connected by any external resistance.
Equation 10 shows that w cannot be negative, and that it is different
from zero unless all the cells in the battery have equal electromotive
forces. The expression for w may be written in a form due to
Slouginoff,

* = "'"" '/, (H)

where Cq and h^ are the electromotive force and the internal resistance
respectively of the equivalent cell.

It is known that if the poles of a battery formed of n cells be con-
nected by an outside resistance r, the current in the external circuit
will be tlie same, whether the cells be joined up in series or in multiple
arc, provided that

iV„ 2 (e,) - Q^

(12)

or, if the cells are all alike, provided that r =z b. It is worthy of
notice, however, that the efficiencies of the battery are different in
the two cases. If the cells are joined up in series, the efficiency of
the battery is

r

but if they are joined u)) in multiple arc the efficiency is

C- r

so that

F, C^r+C'^ib,)

(15)

PP:IRCE. — BATTERIES IN MULTIPLE ARC. 199

If the cells are all alike, and if r = b, this ratio has the value
1 -i- n, aud the arrangement in jiarallel is n times as efficient as the
arrangement in series. In the case of unlike cells, if the currents in
the cells are all positive, ^^ is always less than i^. It is easy, how-
ever, to find cases where -^ is less than F^, for this is true when

2(C^.^,)<[2(C,)7.2(6,).
Cambridge, July, 1894.

200 PROCEEDINGS OF THE AMERICAN ACADEMY.

VIII.

CONTRIBUTIONS FROM THE ZOOLOGICAL LABORATORY OF

THE MUSEUxM OF COMPARATIVE ZOOLOGY, UNDER

THE DIRECTION OF E. L. MARK, XLII.

ON THE CELL LINEAGE OF THE ASCIDIAN EGG.

A PRELIMINARY NOTICE.

By W. E. Castle.

Communicated by E. L. Mark, June 14, 1894.

The following paper is based on an uncompleted study of the early
stages in the development of C'iona intest'malis, the material for which
I was enabled to collect at the Newport Marine Laboratory in the
summer of 1893, through the kindness of Mr. Alexander Agassiz.

Tunicate embryology has been studied from the standpoint of cell
lineage to a greater or less extent, by Van Beneden et Julin ('84),
Seeliger ('85), and Chabry ('87). The first named authors have
followed the segmentation of the egg of Clavelina Rissoana as far as
the 32-cell stage in a manner that admits of no question as to its
accuracy. Every cell division is evidenced by karyokinetic figures
that prove beyond doubt the actual genetic relationship.

The cell lineage of a single additional stage is given, one of forty-
four cells. This stage must have been derived from the preceding by
twelve cell divisions, six in each of the equivalent halves of the egg.
Of these six, three are clearly indicated by spindles in the 32-cell
stage. The other three were apparently determined by conjecture,
and it is my purpose to show that by yielding themselves to conjec-
ture in so small a matter as these three cell divisions, the eminent
authors fell into an error which invalidates the most important con-
clusions of their otherwise excellent work. For in correlating the 44-
cell stage with the 32-cell stage they have changed the orientation, so
that they have identified the dorsal side of one with the ventral side
of the other, the endodermal half of one with the ectodermal half of
the other. Their orientation of all the stages prior to the A^-cell stage

CASTLE. — CELL LINEAGE OP THE ASCIDIAN EGG. 201

is accordingly ivrong. Their terms ectodermal and endodermal, ven-
tral and dorsaly as employed up to this stage, must he interchanged.

I shall iu the present paper reproduce the figures of the 32-cell
and 44-cell stages given by Van Beueden et Juliu, with the proper
orientation and tlie probable cell lineage as inferred from that actu-
ally determined in Ciona.

Chabry, iu a paper concerned chiefly with teratology, traces the
cell lineage of Ascidiella aspersa to a stage with thirty-two cells, and
finds it identical, cell for cell, with that of Clavelina as given by Van
Beneden et Julin. He however adopts, apparently without question,
the orientation given by them, and makes accordingly, in his early
stages the same error, calling dorsal (endodermal) that side of the
egg which is really ventral (ectodermal).

He gives in pai't the cell lineage of the ectodermal side of a single
older stage, in which five additional divisions are represented as hav-
ing occurred in each of the equivalent halves of the egg. (See his
Fig. 20.) These agree exactly with the divisions I have found
occurring in Ciona subsequent to the 32-cell stage.

Seeliger studied an undetermined species of Clavelina, the same
genus on which Van Beneden et Julin worked. It has been more
than once observed by writers on tunicate embryology, that, though
engaged with the study of forms so nearly related, these authors diflfer
widely in their conclusions.

In discussing the 4-cell stage, for example, Van Beueden et Julin
state that the two larger cells give rise to the anterior portion of the
embryo, and in this I fully agree, whereas Seeliger contends that
they produce the posterior portion. Seeliger however gives little
evidence in support of his view, for his determination of the cell lin-
eage IS in most cases so manifestly a matter of mere conjecture that it
hardly merits a serious consideration. But it may be worth while to
point out where he has made the mistake that led to his false conclu-
sion. It is in passing from the 16-cell stage to the next succeeding
stage, the number of cells in which he did not take the pains to
determine. In doing this he has reversed the poles anterior and pos-
terior.. For his 16-cell stage (his Figs. 14 and 15), if its anterior
and posterior poles fe reversec?, corresponds unmistakably, both in the
characteristic arrangement of its cells and in their relative size, with
the 16-cell stage figured by Van Beneden et Julin (their Figs. 8 and
8a), and that figured by Chabry (his Figs. 17 and 24), and I can
add from my own observations that it also corresponds with that of
Ciona.

202 PROCEEDINGS OF THE AMERICAN ACADEMY.

Seeliger's next stage (his Fig. 16) is oriented correctly, the poste-
rior end being clearly indicated by the smaller marginal cells (left
unshaded in his figure). This criterion for the posterior end of the
embryo had been previously pointed out by Van Beneden et Julin,
has since been recognized by Chabry and by Davidoflf for the forms
they studied, and holds good for Cioua also.

Seeliger speaks of his Figure 16 as representing a stage with four-
teen " eudoderm " cells (that is, cells which have been derived from
the four dorsal cells of the 8-cell stage). It is highly probable that
he should, have represented as *' endodermal " also a pair of lateral
marginal cells left unshaded in his figure, thus bringing the number of
descendants of the four dorsal cells of the 8-cell stage up to sixteen,
the nixmber we should expect as the result of two successive divisions
in that hemisphere. The two cells in question correspond in position
with the cells c®"^ and d^-^ of Figure 4 of this paper, except that in the
egg of Ciona figured the cells named do not reach the margin, but lie
a little more central.

Interpreted thus, Seeligex-'s Figure 16 corresponds closely with a
similar view of the 32-cell stage of Van Beneden et Julin (reproduced
in Figure 8 of this paper), and with Chabry's Figure 26, and with the
same stage of Ciona (Figure 4 of this paper).

From this stage on, all investigators are agreed as to which is the
anterior and which the posterior end of the embryo. If then the ori-
entation of Seeliger's later stages is correct (and this will be conceded
by every one), that of his 16-cell stage is ?'??correct ; and unless he again
reversed the poles m passing from the 4-cell to the 1 6-cell stage, his
A:-cell stage is also wrongly oriented. This l)eing so, the two larger
cells of the 4-cell stage are really anterior in the Clavelina studied by
Seeliger, just as in the one studied by Van Beneden et Julin.

Another point of difference between the authors mentioned, appears
in their discussion of the 8-cell stage. Seeliger states that the larger
cells belong to the ventral (ectodermal) half of the egg, whereas Van
Beneden et Julin state that they constitute the dorsal (endodermal)
half.

I shall i)resently show that Van Beneden et Julin were mistaken
in their determination of the dorsal and ventral faces of the 32-cell
and earlier stages. It follows that the larger cells, which they called
dorsal, were really ventral, as stated by Seeliger for the form studied by
him. If this is so, another point of difference is removed, for in both
the species of Clavelina that have been studied the larger cells of the
8-cell stage are ventral with reference to the axes of the future larva.

CASTLE. — CELL LINEAGE OF THE ASCIDIAN EGG. 203

In any extended work on cell lineage it is desirable to have some
system of naming the individual cells which will indicate readily the
exact history of each, — from vvliat part of the matured ovum it has
been derived, by how many divisions it is removed from the ovum,
and from what other cells these divisions have separated it.

Wliat system one adopts is a matter of choice, but not of indiffer-
ence. Chabry has employed a fnirly good one in his work on Ascidi-
ella. It is too cumbersome, however, for advanced stages, and limited
in its applicability. Van Beneden et Juliu have simply employed
numerals, which give no information whatever as to the derivation of
cells. Seeliger has followed no system at all beyond the 16-cell
stage, except that of arrows joining cells of the same parentage,
which serves to mark the lineage for only one generation.

So far as I know, only one system capable of general application
to different types of cleavage has been proposed, that introduced by
Kofoid ('94) in his recent work on Limax. As this seems to me
to embody several distinct advantages over other systems, I shall
follow its general features in this paper.

1. Each cell will be designated by a letter with two exponents.

2. The letter indicates the quadrant of the egg from which the cell
in question has been derived, or, in other words, that cell of the 4-cell
stage from which it is descended. Viewing the egg from the ventral
or ectodermal side, the left anterior quadrant is A, the right anterior
B, the right posterior C, and the left posterior D. In dorsal views,
right and left are of course reversed.

As the third cleavage plane is equatorial and separates a ventral
from a dorsal hemisphere, I shall designate the cells of the former by
capitals and those of the latter by small letters.

3. The first exponent indicates the generation to which a cell
belongs ; that is. the number of cell divisions by which it is removed
from the unsegmented ovum.

The ovum is generation one, the 2-cell stage two, the 4-cell stage
three, etc.

4. The second exponent indicates the niiviber of a cell in a genera-
tion, the cells of each quadrant being numbered independently of the
other quadrants from the centre of the ventral (ectodermal) toward the
centre of the dorsal side.* If in any case two cells of common de-

* In tliis I do not follow Kofoid, who numbers from the ventral (in his case
endodermal) toward the dorsal (in liis case ectodermal) pole. His system of
nomenclature I have treated throughout as being, for my purposes, not an index
to homologies between blastomeres, but a convenient method of notation.

204

PROCEEDINGS OF THE AMERICAN ACADEMY.

scent lie in an equatorial position, that one which is nearer the median
plane will be given the lower numeral.

It will be noted that I follow the accepted usage, orienting the egg
with reference to the future axes of the embryo, and using the terms
dorsal and ventral in this sense. I have regarded the egg as viewed
from the ventral rather than the dorsal sitle, because, as is rightly
held, the ventral side corresponds to the ectodermal pole.

Below is a table, the first six columns of which show the complete
cell lineage of the right half of the egg of Clavelina, Ascidiella, or
Ciona through the sixth generation (32-cell stage). The terminology
of Van Beneden et Julin for the 32-cell stage is given in the seventh
column, for purposes of comparison. In the next column is given, in

Cell Lineage of the egg of Clavelina, Ascidiella, or Ciona,
right half only, through the 32-cell stage.

First
Gen.

ABCD

1-celI
stage.

Second
Gen

Third
Gen.

Fourth
Gen.

Fifth
Gen.

[As-i

■A4-1

-

A5-'

A3

•

C a5-3

, i&-^

aS-*

f AD^

"

1)5.1

D^i

D3

-

D5-2

I Lbc^]

/=leftx
\ halfj

d* -i

rd5-3

(J5-4

2-cell

4-cell

8-cell

16-cell

stage.

stage.

stage.

stage.

Sixth
Gen.

( A6-1
\ A6-2

. A«-3
I A«-^

j a6-5
\ a6.6

I '■'■'

D6.1

DO-'
D«3

Y)M

,16.5
flG.6
(l>;-7

d6-«

.32-cell
stage.

CLAVELINA.

Termi-
nology
of V B.
et J.

Sixth
Gen.

XIV

1

XV

10

2

3
9
4

XVI
XIII

VIII

11

12

6

5

.32-cell
stage.

Interpretation of
V. B. et J.

Their
Terminology.

6th, 7th,

and 8th

Gen.

20
14
1
21
15
10

17

11

12

6

5

44-cell
stage.

My
Termi-
nology

6th,7th.

and 8th

Gen.

A"-l
AT.2

AS-2

A7.5

A'-6

A6.4

q6-5

a6-7

I>8.1

1)8-2
D7-2
D7-3
D7-4

D63
D77

d«-5

d8-6
d6.7
^6.8

My In

terpre
tation

6th &
7th
Gen.

a6.t>
a'i.5

A'i-2
n.B-8

A7-2

A7.1

A7-7

A7-5
dti.8
(16.7

D«-3

d6-«
DV4

D7-2

D"-8

D7-7
d6.5

A7.6

D"-3

44-cell 44-ceIl
;age [stage.

CASTLE. — CELL LINEAGE OP THE ASCIDIAN EGG. 205

the terminology of Van Beneden et Julin, the cell liueage of the
44-cell stage as interpreted by tliem ; and in the succeeding column
this interpretation is repeated in terms of the nomenclature adopted
hv me. Finally, in the last column is given my own interpretation
of the same stage.

The cell lineage for the left half of the egg would be expressed by
substituting, in the table, B, b, for A, a, and C, c, for D, d, where
my terminology is used ; and where the terminology of Van Beneden
et Julin is used, by adding a (') to each of the numerals.

To ascertain the designation of the mother cell of any particular
cell, its first exponent must be diminished by one ; and its second
exponent, if an even number, must be divided by two, but if an odd
number it must first be increased by one and then divided by two.

In order to determine the daughter cells of a particular cell, simply
reverse this process ; that is, increase the first exponent by one and
double the second exponent. The result will be the name of the
daughter cell having an even second exponent. To determine the
other daughter cell, diminish this second exponent by one. Thus the
daughter cells of a^* are a®'^ and a'^-^

This system I have applied to the 32-cell stage of Van Beneden
et Julin in Figures 7 and 8, reproduced from their Figures 9 and 9a,
the orientation being corrected to agree with my interpretation.

Similar views of the same stage of Ciona are given in Figures
3 and 4.

It will be seen that this stage of Ciona corresponds cell for cell
with the one of Claveliua figured.

In both, the posterior end is marked on one side (Figs. 3 and 7) by
the superficially, if not actually, largest pair of cells in the Qgg at this
stage, while underneath them, best seen from the other face of the
egg, is the smallest pair of cells (Figs. 4 and 8). The only thing in
the egg of Ciona figured which is not perfectly typical is the position
of the cells a*'-^ and b*'-^, which in other specimens examined lie
anterior quite as often as lateral to their sister cells, a^^ and b*'®
respectively.

A nearly median optical section parallel to the sagittal plane of the
egg exhibited in Figures 7 and 8 is reproduced in Figure 13, and an
actual transverse section of the same stage of Ciona is represented in
Figure 15. It will be seen that in both cases the cells of one face,
which are apparently very large when viewed from the surface, are
really thin and superficial ; while the apparently small cell? of the
other face are really high, columnar, and of considerable volume.

206 PROCEEDINGS OF THE AMERICAN ACADEMY.

These figures leave no doubt that the view of the Ciona egg given
in P^igure 3 corresponds with that of" the egg of Claveliua given in
Figure 7, and that the view of the Ciona egg given in Figure 4 cor-
responds with the view of the Clavelina egg given in Figure 8. If then
it can be sliovvn by a detailed study of later stages that the orientation
given for the egg of Ciona in Figures 3 and 4 is the correct one, it
follows that the orientation given for the egg of Clavelina in Figures
7 and 8 is also correct, and that the orientation given to this stage by
Van Beneden et Julin is consequently wrong; for they call Figure 7
a dorsal, and Figure 8 a ventral view.

An examination of Figure 3 shows that the thin superficially large
cells seen in this view of the egg are preparing for division. These,
as the lettering indicates, are derived from the four veutrally situated
cells of the 8-cell stage, and will be referred to collectively as the
ventral or ectodermal half of the %gg. The latter term must not be
understood, however, to imply that all the cells derived from this
hemisphere become ectoderm, but merely that ectoderm is its prin-
cipal derivative.

The other half of the egg, composed of high, columnar cells, will be
called the dorsal or endodermal half of the egg, with the same restric-
tion on the term endodermal as has been made for ectodermal.

Figure 4 shows the cells of the endodermal half to be quiescent,
while those of the ectodermal half are preparing for division. A
similar acceleration in division of the ectodermal over the endodermal
half of the egg was to be observed at the 24-cell stage (Figs. 1
and 2). Here the cells of the ectodermal half are seen to have passed
into the sixth generation, while the cells of the endodermal half are
only in the spindle stage, preparatory to the division which will carry
them into that generation.

Figure 5 represents a ventral view of a stage of forty-six cells, and
shows accomplished the divisions foreshadowed in Figure 3. All
the cells of the ventral half of the egg, except the pair of small
posterior cells, have divided either completely or partially, thus pass-
ing into the seventh generation. I should add that no one of the
divisions indicated is a matter of inference, but spindles have been
observed in every instance ; where they were not to be seen in the
specimen figured, they have been observed in other specimens not
quite so advanced in development.

Figure 6 gives a view of the opposite face of the same egg. The
cells of the dorsal half are here seen to be in the sixth generation,
and still quiescent. In a single cell, b®•^ a pair of astral radiations

CASTLE. — CELL LINEAGE OF THE ASCIDIAN EGG. 207

it visible. This fact does uot, however, foreshadow an immediate di-
vision of the cell, as these radiations often exist some time before the
division actually occurs. It does indicate, however, as the sequel will
show, that this cell with its mate, a^-^, will be among the earliest
cells ot the eiidodermal half of the egg to divide.

In Figures 9 and 10 are reproduced Van Beneden et Julin's fig-
ures of the 44-cell stage of Clavelina (their Figs. 10 and 10a). The
lettering on the left half of Figure 9 and the right half of Figure 10
indicates what I believe to be the correct interpretation of the cell
lineage of this stage. The interpretation of Van Beneden et Julin
is indicated (in terms of my own nomenclature) on the right half of
Figure 9 and the left half of Figure 10.*

It .will be seen that at this stage, according to my interpretation,
exactly the same divisions, with one exception, have occurred in the
egg of Clavelina as in the Ciona egg shown in Figures 5 and 6.
The exception mentioned is m the case of the most anterior cell of the
ectodermal half, on each side of the median plane (A'^'^ and its mate,
Figs, 8 and 9). This cell has not yet divided, but has remained
in the sixth generation, whereas in Ciona it has given rise to A^-^
and A^ ■*.

Not only has division occurred in corresponding cells in the egg of
Clavelina and that of Ciona, but this division has taken plate in the
same direction in every instance.

There is, however, in the two eggs, a slight difference in the ar-
rangement of the cells resulting from this division, due perhaps to a
difference in the order of division. In the egg of Clavelina (Fig. 9,
left half), the cells A''^ and D'^"^ have been pushed toward the me-
dian plane so that they are in contact with their mates in the other
half of the egg, and separate A"-^ from D"'-^ ; but in the egg of Ciona
(Fig. 5) A'^*^ and D'''' do not reach the median plane, so that A^-^ is
left in contact with D'^*^.

Van Beneden et Julin identify the face of the egg represented in
Figure 9 with that seen in Figure 8, and that in Figure 10 with the
one seen in Figure 7. In doing so they are forced into several very
strange correlations. For example, the small posterior cell C®'^ of
Figure 8 is identified with the rather large cell D'^-^ of Figure 9 ;
while the real C^-^ (D^-^ of Fig. 10, left half) is derived from D^-^
(Fig. 7), and its sister cell is supposed to have divided again, so that

* It will facilitate a comparison with the lettering of the original, if the
reader will make use of the table on page 204.

208 PROCEEDINGS OP THE AMERICAN ACADEMY.

the other derivatives of D^-^ (D^-^ aud D»-"^ of Fig. 10, left half) are
in the eighth generation.

Finally, the nearly median optical section of this egg, reproduced in
Figure 14, shows at a ijlance the absurdity of Van Beneden et Julin's
interpretation. Here the relatively large columnar cells d®-'', d®-^,
a®-®, and a®*^ of my interpretation,* are derived by them from the thin
superficial cells D®*^ and A*^'^ of the preceding stage (Fig. 13), the
first two together with D®-^ as a result of two successive divisions of
the single cell D"--^. On the other hand the small cubical cells D''^
D'-^, A^*^, A'^"\ and A''*^ are taken by them to represent, undiminished
hy division, the voluminous columnar cells d*^"'', d^-^, a^***, a^*^ and
a^"^ respectively, of the preceding stage.

It is thus seen from an examination of Van Beneden et Julin's own
figures, that they have reversed the dorsal and ventral relations in
passing from the 32-cell to the 44-cell stage, and have identified the
endodermal half of one with the ectodermal half of the other. This
fact has been overlooked by all subsequent writers on tunicate em-
bryology, for all have accepted as correct the results obtained by Van
Beneden et Julin.

The question next arises, Is the orientation given by Van Beneden
et Julin for the 32-cell stage, or that given for the 44-cell stage, the
correct one ? A strong presumption that the latter is the case exists
in the close correspondence in form and size between the endoderm
cells of the gastrula figured by them (their Fig. lid) and the columnar
dorsal cells of their 44-cell stage. This presumption becomes as
strong as anything except direct observation of Clavelina can make
it, when one follows the cell lineage of Ciona through to a stage which
marks the beginning of gastrulation, such as I have represented in
Figures 11 and 12.

In order to avoid the extension of this paper to an undesirable
length, I have not figured the stages intervening between the 46-cell
stage and gastrulation. A detailed study of these stages, however, al-
lows me to speak with confidence of the changes which have occurred.

In the 32-cell stage (Figs. 3 and 4), all the cells of both hemi-
spheres were seen to be in the sixth generation, though, as has been
stated, the cells of the dorsal half had divided a little later than those
of the ventral half. These dorsal cells now remained quiescent, while
all the cells of the ventral or ectodermal half, except the small pos-
terior cells C®^ and D®^, divided, and thus brought about the 46-cell

* See Explanation of Plates, Figure 14.

CASTLE. — CELL LINEAGE OP THE ASCIDIAN EGG. 209

stage. Before the division (Figs. 3 and 4), it will be noted, the cells
of the ectodermal half were so arranged that twelve of them were
marginal and in contact with cells of the eudodermal half, while four
(A*'-^ B*'\ C'S and D'^'S Fig. 3) were entirely surrounded by cells of
the ectodermal half. These four now divide along planes perpendicu-
lar to the sagittal plane, so that both the daughter cells of each still
abut on the median plane. All the marginal cells, however, except
the small posterior pair, which remains quiescent, divide in such a way
that only one of the daughter cells of each is still marginal and in
contact with cells of the endodermal half (Fig. 5, A^-*, A^-^ A''-^, D'^\
D'''^, and the corresponding cells in the right half of the figure).

The nest division again involves those cells of the ectodermal half
of the egg which are marginal, including this time the small posterior
cells C^-^ and D^*^, which have lagged one generation behind the other
cells of the ectodermal hemisphere, but now give off toward the
median plane each a peculiar flattened cell of minute dimensions, un-
doubtedly the '' petites cellules cuneiforraes" of Van Beneden et Julin.
This division also passes through two other cells of the ectodermal
half, C"'' and D"-'', and six anterior and marginal cells of the endo-
dermal half, namely, a®-^, a^*'', d®"^ and their mates b^*®, h^-'', and c®**.

Concomitantly with this division of marginal cells, and to a greater
or less extent in consequence of it, the endodermal face of the egg
becomes flat, its cells being crowded together at their superficial ends
and expanding club-shaped beneath the surface. The ectodermal face
at the same time becomes more convex, its cells growing thinner and
spreading out so as to cover a greater area. The marginal cells gradu-
ally extend around on to the endodermal face, and thus gastrulation
begins.

At this stage (66-cell) the ectodermal half of the egg consists of
forty-four cells, of which twenty-four, the more marginal ones, are in
the eighth generation, and the remaining twenty, centrally or pos-
teriorly situated, are in the seventh generation.

The endodermal half of the egg, on account of its less rapid cleav-
age, is composed of fewer cells, viz. twenty-two, just half the number
in the ectodermal portion. Of these, twelve — lying anterior and
marginal — are in the seventh generation, and ten — central or pos-
terior — in the sixth generation.

It will thus be seen (1) that the cells of the dorsal half have lagged
just one generation behind those of the ventral half, and (2) that cell
division has been more active in the anterior and lateral marginal
portions of the egg. As a consequence of the first mentioned fact, a

VOL. XXX. (n. 8. XXII.) 14

210 PROCEEDINGS OF THE AMERICAN ACADEMY.

gastrula is formed with a dorsal blastopore by a process " intermediate
between epibole and invagination " ; and because of the second, the
blastopore closes from the sides and anterior end, so that it ultimately
becomes pear-shaped and lies in the posterior half of the embryo.

The part which particular cells take in forming the organs of the
larva is reserved for discussion in a later paper, as that part of my
work is still incomplete. One thing may, however, be stated posi-
tively. The entire endoderm and mesoderm are not derived as stated
by Van Beneden et Julin from the twelve cells of the 44-cell stage
a«-5, a«-«, a'^-^ a*'-'*, d*'-^ d«-^ b«•^ b«•^ b«•^ b^-^, c«•^ and g^-\

Conclusions.

1. The conflicting statements of Van Beneden et Julin on the one
hand, and Seeliger on the other, regarding the segmentation of the
ascidian egg, are explained by the detection of a fundamental error
in the work of each.

Seeliger has determined the dorsal and ventral sides of the egg
correctly, but reversed the anterior and posterior ends in all his figures
of the early stages. Van Beneden et Julin have determined correctly
the anterior and posterior ends, but have reversed dorsal and ventral
in all stages previous to the 44-cell stage. These errors are clearly
indicated by a critical examination of the authors' own figures, and a
careful study of the cell lineage of Ciona leaves no doubt of their
existence.

2. The correction of Van Beneden et Julin's unfortunate change
of orientation necessitates fundamental changes in their conclusions.

(a) It is stated by them that the four smaller cells of the 8-cell
stage give rise to ectoderm only, while the four larger cells produce
both endoderm and ectoderm. On the contrary, neither the four
smaller cells nor the four larger ones produce ectoderm exclusively ;
but it is the four larger, not the four smaller ones, which give rise
to the greater portion, perhaps all, of the ectoderm.

(b) I cannot at present assent to the statement of Van Beneden
et Julin that the separation of the germ layers is complete at the
44-cell stao-e.

3. In Ciona, from the sixth to the eighth generations at least, cell
multiplication is more rapid in the anterior and lateral portions of the
egg, and this fact is an miportant element in determining the shape
and position of the gastrula mouth.

Cambridge, May 9, 1894.

CASTLE. — CELL LINEAGE OF THE ASCIDIAN EGG. 211

Postscript.

Since the foregoing was written I have had the opportunity of mak-
ing further observations upon the Hviug egg of Ciona immediately
after fertilization and during the early stages of segmentation. I have
repeatedly seen the polar globules and observed continuously the
cleavaee staares following their formation. These observations lead to
the surprising but unavoidable conclusion, that the point on the sur-
face of the egg at which the polar globules form becomes later the
centre of the dorsal or endodermal half of the egg. The evidence for
this conclusion will be presented and its significance discussed in a
future paper.

September 29. 1894.

Postscript No. 2.

After the preceding was already in print, Paul Samassa's recent
paper was received (Zur Kenntniss der Furchung bei den Ascidien.
Arch. f. mik. Anat., Bd. XLIV. Heft I. pp. 1-14, Taf. I. und II.
Ausgegeben 15 Sept., 1894).

Samassa's conclusions agree in a ^ratifying manner with my own,
that Van Beneden et Julin on the one hand, and Seeliger on the other,
were mistaken in their orientation of the Ascidian egg. Here, how-
ever, the agreement ends, for my own interpretation of the cell lineage
differs radically from that of Samassa.

In the earlier part of this paper I have pointed out how fatal to the
conclusions of Van Beneden et Julm was their conjecture as to the
manner of division in only three pairs of cells in the egg of Clavelina.
I cannot forbear .saying that a more apt illustration of the utter un-
trustworthiness of this method of determining cell lineage could not
have been offered than is found in Samassa's paper, where the method
of conjecture seems to have been followed in a wholesale and entirely
unjustifiable manner.

In his account of the 32-cell stage Samassa makes D^-^ (his ell) the
sister cell of D®^ (his c 12) both in Ciona and in Clavelina. In doing
so he contradicts, though without giving a particle of evidence in sup-
port of his views, the recorded observations of Van Beneden et Julin
on Clavelina and of Chabry on Ascidiella, and this too in the face of
the fact that Van Beneden et .Julin offer the absolutely incontroverti-
ble evidence of karyokinetic figures in support of their interpretation.

212 PROCEEDINGS OF THE AMERICAN ACADEMY.

In the living egg of Ciona I have myself repeatedly seen the cell di-
visions leading to the 32-cell stage take place, and my observations
agree perfectly with those of Van Beneden et Julin on Clavelina, and
of Chabry on Ascidiella, viz. that the cell D®-^ (Samassa's ell) is the
sister cell of D''-^ (Samassa's c 21) and D^-^ (c 12) that of D«* (c 22).
If Samassa expects his statement to stand against all these independent
observations, he must present some evidence in its support.

After discussing the 48-cell stage of Ciona, Samassa says : " Die
vi^eiteren Theilungen habe ich nicht Zelle filr Zelle verfolgt, da dies
fiir die Losung der mich interessirinder Frage nicht von Bedeutung
ist." Yet, again without a particle of evidence and confessedly without
detailed observations, he calmly proceeds to declare the ancestry and
fate of the individual blastomeres of subsequent stages ! The history
cell for cell of the cleavage subsequent to the 48-cell stage is precisely
the critical point in deciding the question with which Samassa is con-
cerned, viz. the origin of the endoderm, and in stopping where he
did he has stopped short of solving his problem. Worse than this,
by his guesses at the cell lineage he has fallen into positive error.
For example, the cells 8 and 9 of his Figure 10, wh'ich he says are
ectoderm, are not so at all, but are mesoderm. They with their mates
in the left half of the egg ultimately form the greater part, perhaps all,
of the lonoitudinal musculature of the tail, being derived from cells
corresponding to D^-^'^ and d®*^ of my Figure 12. There is no mis-
taking the identity of these cells , the large size of the nucleus, which
Samassa has observed for his cell 8, and would have found to hold
good at a slightly different stage for 9 also, is one of their distinguish
ing characteristics; their peculiar stainability under proper treatment is
another. Samassa assures us that these cells are derived from the
ventral or ectodermal cells of the 8-cell stage, and represent, with a
few cells posterior to them, " die erste Anlage der Medullarwiilste."
With these statements I squarely take issue. Of those under con-
sideration, only the cell 8 (my D^-^*') with its mate in the left half
of the egg, is derived from the ventral cells of the 8cell stage, the
other cell (9) is derived from the dorsal cells of the 8-cell stage ; and
both 8 and 9 form, not ectoderm, but mesoderm, beincj invasinated with
the endoderm cells at gastrulation.

In view of these facts, and others which need not be presented at
this time, I am forced to take issue with Samassa's main conclusion,
"dass bei Ciona und Clavelina durch die dritte Furchung die Tren-
nung der beiden primiiren Keimbljitter erfolgt." For Ciona at least
this is not true, and the close correspondence which Samassa himself

CASTLE. — CELL LINEAGE OF THE ASCIDIAN EGG. 213

has recognized between the early stages of Ciona and those of Clave-
liua renders its occurrence in Claveliua exceedingly improbable.

Davidoff's belief that the first equatorial cleavage separated the two
primary germ layers can have no weight une way or the other in de-
ciding the (juestion, for Davidoff did not profess to have traced cell
by cell the history of the cleavage subsequent to the 8-cell stage.

If my statements in this Postscript seem to the reader to be as dog-
matic as Samassa's, I can only say that they rest, not on confessed
inference or conjecture as to the cell lineage, but on repeated observa-
tions made on dozens of embryos, only continuous observations of the
living egg or the presence of karyokinetic figures in preserved speci-
mens being admitted as sufficient evidence of the genetic relationships
of cells. The evidence afforded by my figures will be presented, and
a more exhaustive discussion of the subject made, in a subsequent
paper.

October 5, 1894.

LITERATURE CITED.

Chabry, L

'87. Contribution k rembryogenie normale et teratologique des
Ascidies simples. Journ. Anat. et Physiol., Tom. XXII. pp. 167-

319, PI. xvm.-xxii.

Davidoff. M. v.

'89-'91 Untersuchungen zur Entwickiungsgeschichte der Distaplia
magnilarva, Delia Valle, einer zusammengesetzten Ascidie. Mitth.
Zool. Stat. Neapel, Bd. IX. Theil I. pp. 115-178, Taf. V., VI.,
und Theil 11. pp. 533-651, Taf. XVIII.-XXIV.

Kofoid, C A.

'94. On some Laws of Cleavage in Limax. Proc. Amer. Acad., Vol.
XXIX. pp. 180-200, 2 Pis.

Seeliger, O

'85. Die Entwickiungsgeschichte der socialen Ascidien. Jena. Zeit-
schr , Bd. XVIII. pp 45-120, Taf. I.-VIII.

Van Beneden, Ed., et Julin, Ch.

'84. La segmentation chez les Ascidien et ses rapports avec I'or-

ganisation de la larve. Arch, de Biol., Tom. V. pp 111-126, Pi.

VII., VIII.
'86. Recherches sur la morphologie des Tuniciers. Arch, de Biol.,

Tom. VI. pp. 237-476, PI. VII.-XVL

21-i PROCEEDINGS OF THE AMERICAN ACADKMY.

EXPLANATION OF PLATES.

Arrows joining cells indicate divisions tiiat have occurred since the last stage
figured or described.

A = Anterior. P — Posterior. R — Right. L = Left. D = Dorsal. V =
Ventral. For the system of lettering employed to mdicate cell lineage, consult
the text, pp. 203, 204.

PLATE 1.

Ciona intestindlis.

All the figures of this plate are drawn to the same magnification, 400
diameters.

Figure 1. Egg of Ciona, 24-cell stage, ventral view. The cells of the ventral
half of the egg number sixteen, and are all in the sixth generation.
The most recent division is seen to have been that resulting in the
posterior cells D»-3, D"^-"*, and C«-3, C*>i.

" 2. The same egg, dorsal view. The cells of the dorsal half of the
egg are still in the fifth generation, and consequently number
only eight. They are, however, about to divide, and the spindles
indicate the directions in which divisions will occur.

" 3. Egg of Ciona, 32-cell stage, ventral view. (Divisions which were
already completed at the 24-cell stage are again indicated by
arrows, for convenience in comparison.)

" 4. The same egg, dorsal view.

" 5. Ess of Ciona, 46-cell stage, ventral view. All the cells of the
ventral half of the egg are seen to have divided more or less
completely since the 32-cell stage, except the small posterior cells
C6-3 and W'^.

" 6. The same egg, dorsal view. All the cells of the dorsal half of the
egg are still in the sixth generation, as in Figure 4.

Castle -AsciDiAN Egg

Pt t

E Mfisel.iith.Boston

216 PROCEEDINGS OF THE AMERICAN ACADEMY. (

PLATE II.

Figures 7, 8, 9, 10, 13, and 14 are copied from Van Beneden et Julin's figures
of Clavelina Rlssoana. The otliers are of Ciona ; magnification, 400 diameters.

Figure 7. Egg of Clavelina, 32-celI stage, with corrected orientation, ventral
view. (After Van Beneden et Julin's Fig. 9a).

" 8. The same egg, dorsal view. (After Van Beneden et Julin's Fig. 9.)

" 9. Egg of Clavelina, 44-cell stage, ventral view. (After Van Beneden

et Julin's Fig. 10.) On the left side of the figure is given the

corrected cell lineage, on the right side, the cell lineage according

to Van Beneden et Julin.

" 10. The same egg, dorsal view. (After Van Beneden et Julin's Fig.
10a.) On the right side of the figure is given the corrected cell
lineage, on the left, the cell lineage according to Van Beneden et
Julin.

" 11 Egg of Ciona, 66-cell stage, ventral view. Only the marginal cells
of the ventral half have divided since the stage shown in Figures
5 and 6.

" 12. The same egg, dorsal view. By more rapid division in the ventral
half of the egg certain of its marginal cells have been shoved
around on to this face of the egg Six marginal and anterior cells
of the dorsal half have also divided since tlie 46-cell stage.

" 13. A nearly median optical section, parallel to the sagittal plane,
of the egg of Clavelina shown in Figures 7 and 8, with corrected
orientation. (After Van Beneden et Julin's Fig. 9c.)

" 14. A nearly median optical section, parallel to the sagittal plane, of
the egg of Clavelina shown in Figures 9 and 10. (After Van
Benenen et Julin's Fig. lOc.)

" 15. An actual transverse section of an egg of Ciona in the 32-cell stage.

.f'Tu- - AscidianEgg

PlII

B '■Ifiacl.liihBosion

218 PROCEEDINGS OF THE AMERICAN ACADEMY.

IX.
WAVE LENGTHS OF ELECTRICITY ON IRON WIRES.

By Charles E. St. John, A. M.

Presented by Professor John Trowbridge, May 9, 1894.

Since the experimental demonstration of the existence of the oscil-
lating electric discharge, it has been an interesting field of investiga-
tion to ascertain whether the magnetization of iron and nickel can
follow such rapidly alternating impulses as are obtained by the oscil-
lating discharge of a condenser through a circuit of low self-induction,
and, if magnetization does follow, in what way and to what extent
can it affect the character of an electric wave propagated along wires
of masfnetic material.

The results of investigation have shown considerable disagreement,
as will be seen from the following brief resume of the investigations
bearing upon these points. The questions referred to did not dis-
tinctly appear in all the investigations, as they have arisen since ; but
results were obtained and published which directly relate to at least
one of the points under consideration.

M. Savary announced, as early as 1826, that, when a needle was
placed in a spiral through which a Leyden jar was discharged, rever-
sals of polarity were obtained by varying the quantity of discharge
through the spiral ; and Faraday * adduces the magnetizing of needles
and bars by common (static) electricity as evidence of its identity
with Voltaic electricity, and in his ex[)eriment to show that common
electricity can deflect the magnetic needle, when a Leyden battery is
discharged through the galvanometer, he states the fact that the mag-
netism of the needle may be removed or reversed by the discharge.

Professor Henry f repeated the experiments of Savary with great
skill and care. He obtained reversals of polarity by increasing
the quantity of electricity discharged through the spiral in which the
needlp was placed, while the direction of the discharge remained the
same, and by varying the distance between the primary and secondary.

* Experimental Researches on Electricity. 1833.
t Writings of Joseph Henry, p. 201. 1842.

ST. JOHN. WAVE LENGTHS OF ELECTRICITY. 219

This anomalous result was referred by Professor Henry to an action of
the discharge of a Leydeii jar never before recognized. He here first
describes the oscillating character of such a discharge as follows : —

" The discharge, whatever may be its nature, is not correctly rep-
resented (employing for simplicity the theory of Franklin) by the
single transfer of an imponderable fluid from one side of the jar to
the other ; the phenomena require us to admit the existence of a
principal discharge in one direction, and then several reflex actions
backward and forward, each more feeble than the preceding, until
equilibrium is obtained. All the facts are shown to be in accordance
with this hypothesis, and a ready explanation is afforded by it of a
number of phenomena which are found in the older works on elec-
tricity, but which have until this time remained unexplained."

The ap[)arent change in the direction of the induced currents with a
change in distance between the primary and secondary circuit, as
indicated by a change in the direction of the magnetization of the
needle, was shown to be due to the fact that the discharge of the
Leyden jar does not produce an induced current in a single direction,
but several successive currents in opposite directions.

There can be no doubt that these discharges were oscillatory in
character, and that steel needles and bars were magnetized by them,
sometimes by the direct discharge, sometimes by the current induced
in a neighboring circuit, sometimes by the first impulse, sometimes by
the second or return impulse.

Feddersen * was of the opinion that iron might show some devia-
tion from the behavior of copper and lead ; of the last two he says,
that the time between two consecutive like-directed current maxima
is independent of the cross section and the specific conducting power
of the wires forming the circuit, and also of the density of the accu-
mulated electricity. And in regard to iron he adds the following note :
" Beim Eisen konnte in Folge der Magnetisirungen eine Abweichung
hervortreten: indess zeigt der Versuch dass dieselbe keinenfalls be-
deutend ist, librigens in dem Sinne erfolgen miisste, als wenn die
Electricitat beim Eisen ein grosseres Hinderniss fande als bei den
iihrigen Metallen."

Tlie rate of oscillation obtained by Feddersen was one million per
second.

The late Professor Hertz f gives in his first paper some experi-
ments that bear upon this subject. He was of the opinion that an

* Poggenaorff, Annalen, CVIII. 499. 1859. t Ibid., XXXI. 429. 1887.

220 PROCEEDINGS OP THE AMERICAN ACADEMY.

iron wire in an oscillating circuit might be eciuivaleiit to a copper
wire of greater length, owing to the higher self-induction of iron. He
based his opinion upon the known fact that for slowly oscillating cur-
rents the self-induction of iron is eight or ten times greater than that
of a copper wire of the same dimensions.

He says : " I therefore expected that short iron wires would pro-
duce equilibrium with longer copper wires. This expectation was
not confirmed ; the branches remained in equilibrium when the
copper wire was replaced by an iron wire of equal length. If the
theory of the observations here given is correct, this can only mean
that the magnetism of iron is quite unable to follow oscillations so
rapid as those with which we are here concerned, and that it there-
fore is without effect." *

The rate of oscillation here used was approximately one hundred
million per second, and the diameter of the wires was two millimeters.

In the same paper, he gives another experiment of like tenor.
He brought the primary and secondary into resonance, and then in
one instance he surrounded one side of the rectangular secondary by
an iron tube, and in a second instance he replaced this side by an
iron Arire of the same diameter as the copper wire. In each case he
found the secondary still in resonance with the primary, and was con-
firmed in his former conclusion. The secondary employed was a
rectangle 180 cm. long and 75 cm. wide, and only a length of 75 cm.
out of the total length of 510 cm. was changed. The diameter of the
wires was 2 mm., and the spark micrometer was used to test for
resonance.

In a later paper t on the " Finite Velocity of Electromagnetic
Actions," he compares the rate of propagation along copper wires
of various diameters, and also the rate of propagation along copper
wires with that along iron wires.

He says : " If we replace tlie copper wire previously used (diam.
1 mm.) by a thicker or a thinner copper wire, or by a wire of an-
other metal, the nodal points are found to remain in the same posi-
tions. Thus the rate of propagation in all such wires is the same,
and we are justified in speaking of it as a definite velocity. Even
iron wires are no exceptions to this general rule ; hence the magnetic
properties of the iron are not called into play by such rapid disturb-
ances." t (100,000,000 reversals per second.)

* Electric Waves, p. 36. J Electric Waves, p. 113.

t Poggendorff, Annalen, XXXIV. 551. 1888.

ST. JOHN. — WAVE LENGTHS OP ELECTRICITY.

221

Professor Oliver J. Lodge remarks as follows in his " Modern Views
of Electricity" (page 101, 1889) : "I might go on and say that iron
makes an enormously worse conductor than copper for rapidly alter-
natintr currents. So it does for currents that alternate with moderate
rapidity — a few hundred or thousand a second — like those from a
dynamo or telephone ; but, singularly enough, when the rapidity of
oscillation is immensely high, as it is in the Leyden jar discharges and
lio-htning, iron is every bit as good as copper, because the currents
keep to the extreme outer layer of the conductor, and so practically
do not find out what it is made of."

And again in more detail on
page 46 of his " Lightning
Conductors and Lightning
Guards" (1892) we find the
following: "But every one
will say — and I should have
said before trying — surely
iron has more self-induction
than copper. A current going
through iron has to magnetize
it in concentric cylinders, and
this takes time. But experi- '''
ment declares against this view j
for the case of Leyden jar \.

-o o-

-o a-

B

discharges. Iron is experi-

L

Fig. 1.

mentally better than copper.
It would seem, then, that the

flash is too quick to magnetize the iron ; or else the current con-
fines itself so entirely to the outer skin that there is nothing to
magnetize."

The experiment given to substantiate this conclusion is that of the
alternate path, as shown in Figure 1. The Leyden jars are charged
by an electrical machine, and when a spark occurs at A the charges
on the outer coatings may combine by sparking across B or flowing
around L. For the path L was used a strip of tinfoil 21 feet long
and 3 inches broad, in one case zigzagged backwards and forwards
with paraffine paper insulation to abolish self-induction as far as
possible, and in the other case wound upon a glass tube to produce
as much self-induction as possible.

When the path L was made by the tinfoil zigzag, the critical dis-
tance at B, when sparks sometimes passed and sometimes failed for a

222 PROCEEDINGS OF THE AMERICAN ACADEMY.

given spark distance at A, was 0.6. When the zigzag was replaced
by the spiral, the critical spark length at B rose to 6.4. A bundle of
finely divided iron was now inserted in the spiral, and the critical
length continued still to be 6.4,

He remarks on this result as follows : '* Here is magnetic time-
lag raised to an extreme. ... It may be said that the iron fails to
get magnetized because of the opposing action of the inverse ' Fou-
cault ' current induced in it, just half a period behind the inducing
currents. I thought this would be so, of course, with thick iron rods,
but with a bundle of thin wires I felt doubtful. . . . Whatever the
explanation, the fact of time-lag is patent. Yet there is something
strange about it, for that a steel knitting-needle can be magnetized by
discharging a Leyden jar round it is mentioned in every text-book,
and it is certainly true. There are points here requiring further
examination." *

So far the investigations that had in view the effect of iron upon
extremely rapid rates of oscillation have given but negative results,
though both investigators quoted expected to find that the magnetic
properties of the iron would be shown under such conditions. Some
positive results showing that the magnetic properties of iron still have
some effect upon rapid electric discharges have been obtained by the
following observers.

Professor John Trowbridge has proved f that the magnetic char-
acter of a conductor is by no means unimportant with 1,000,000
double oscillations per second. In brief the experiment and the
results were as follows. The oscillating circuit consisted of a Leyden
jar and two parallel wires 30 cm. apart and 510 cm. long. These
parallel wires could be replaced by others of different diameter and
material. A spark micrometer with tin terminals was included in
the circuit, and when the discharge occurred the spark w^as photo-
graphed by means of a rapidly revolving mirror.f

The following results bear upon the subject under investigation.
When the parallel wires were of copper (diam. 0.087 cm.), the number
of double oscillations on the negative averaged quite uniformly 9 or
9.5 ; but when an annealed iron wire (0.087 cm. diam.) was substi-
tuted, only the first return oscillation was distinctly visible, with
sometimes a trace of the first duplicate.

* Lightning Conductors and Lightning Guards, p. 48.
t Proceedinfrs of the American Academy, XXVL 115.
t Ibid., XXV. 10':),

ST. JOHN — WAVE LENGTHS OF ELECTRICITY.

223

With copper wire (diam. 0.027 cm.) five complete oscillations
were quite uniformly visible, but with irou wire (diam. 0.027 cm.)
only the first return discharge after the pilot spark was faintly
visible.

The time of the double oscillation for the large-sized copper wire
was 0.0000020 sec, and for the small copper wire 0.0000021 sec.
The author concludes that the magnetic permeability of iron wires
exercises an important influence upon the decay of electrical oscilla-
tions of high frequency, and

O O-

D

that currents of such frequency
as occur in Leyden jar dis-
charges magnetize the iron.
The data were not sufl&cient
to determine whether there was
a change of period, but showed
that it must be small if such
an effect was produced.

Professor J. J. Thompson
has stated that the presence of
iron can affect the rapidly
oscillating electric discharges
through a rarefied gas. His
method of showing the phe-
nomena is given in Figure 2.
C and D are Leyden jars with
a spark-gap in the circuit join-
ing their inner coatings, and
A and B are two loops in the
circuit joining their outer coat-
ings. In the loop A is placed
a bulb exhausted to such a

degree of sensitiveness that a small change in the electromotive
intensity acting upon the bulb produced a considerable effect upon
the appearance presented by the discharge. If, when the bulb at A
is brilliantly illuminated by the discharge through it, an iron rod be
placed in B, the discharge in A ceases ; but if a brass rod is placed
in B, the discharge in A is unaffected.

The author says : " A striking illustration of the difference be-
tween iron and other metals is shown when we take an iron rod
and place it in B, the discharge in A immediately stops ; if now we
slip a brass tube over the iron rod, the discharge in A is at once

Fig. 2.

224 PROCEEDINGS OP THE AMERICAN ACADEMY.

restored. If, on the other hand, we use a brass rod and an iron tube,
when the rod is put in without the tube the discharge is bright. If
we slip the iron tube over the rod, the discharge stops." *

In a paper upon the " Absorption Power of Metals for the Energy
of Electric Waves," t Bjerknes has given some results which show
the great damping power of magnetic metals upon electric oscillations
of very high frequency (100,000,000 double oscillations per second) .
The apparatus used was, in a slightly modified form, the Hertz vibra-
tor and circular resonator, but in place of the spark micrometer in
the resonating circuit he used a much more exact and sensitive arrange-
ment, — a kind of quadrant electrometer with two quadrants to which
the ends of the resonating circuit were directly joined. He employed
among others resonators of copper, iron, and nickel identical in size and
construction. The length of wire in each case was 123 cm. and the
diameter 0.5 mm. The length of wire joining the plates of the Hertz
vibrator could be varied at pleasure. By varying this, the length of
wire necessary for best resonance was found in each case, and the
electrometer throws were observed for five different lengths of the
primary circuit, including the one for best resonance effects. The
graphic representation of these results shows plainly that the metals
differ greatly in their power of damping electric oscillation. The
electrometer throws were much smaller for the iron and nickel than for
the copper, and the curves for iron and nickel come less sharply to a
maximum. He further conclusively shows that the damping power
of the metals experimented upon increases with their resistance and
magnetic susceptibility, and concludes that the magnetic properties of
iron and nickel are called into play by their extremely rapid alternations
of the magnetizing forces. He notes the fact that the maxima for iron
and nickel seem somewhat displaced to one side, which may indicate a
greater period, but says that such a displacement of the maxima enters
iu case of greater damping, so that best resonance does not corre-
spond to exactly equal periods of the two circuits, and adds that a
quantitative investigation is necessary to determine to which of the
two causes the effect may be referred.

From this brief survey of the field, it is seen how, with more exact
and refined means of measurement, some of the results expected, when
magnetic metals replaced copper in circuits through which rapid
electric discharges were taking place, have finally been observed.

* Pliil. Mag. (5.), XXXTI. 456. July, 1891.
t Poggendorff, Annalen, XL VII. 69. 1892.

ST. JOHN. — WAVE LENGTHS OF ELECTRICITY. 225

Thompson has shown that iron absorbs more energy than brass when
subjected to rapidly alternating magnetizing forces, while Trowbridge
and Bjerknes agree in showing that iron and nickle conductors damp
out electric waves much more rapidly then copper, and all agree that
the magnetic properties of iron are called into play under such
conditions.

It has seemed to the writer that it was still an interesting and
profitable field to investigate whether the magnetic properties of
iron were acted upon sufficiently, and in such a way as to produce a
change in self-induction that would affect the rate of propagation
of electric waves along iron wires. With this end in view, it was
sought to simplify some of the apparatus hitherto employed, and to
arrange it so that the effect, if observed, could not be due to any other
cause than the magnetic properties of the metals experimented upon.

Description of the Apparatus.

For producing the oscillations, the ordinary Hertz vibrator (Fig. 3)
was employed, consisting of two plates of zinc, each 40 cm. square,
61 cm. apart, and mounted upon insulated wooden supports. These
supports had square wooden bases that could slide in a grooved plank,
so that their distance apart could be easily varied, and by turning the
supports through a quarter revolution the plates could be made to face
each other or to stand m the same vertical plane. The plates were
joined by a conductor of brass 0.5 cm. in diameter, which was connected
to the plates by sliding with friction into* brass tubes 15 cm. long sol-
dered to the plates. The conductinij wire was broken by a spark gap,
provided with brass balls 3 cm. in diameter. Tin balls were tried, and
had perhaps a little greater effect in exciting oscillations in the secon-
dary ; but they required polishing fully as often as the brass balls.
Finally brass balls with platinum faces were used, and were found to
be much more constant in effect than either brass or tin. A circular
piece of platinum 0.025 cm. thick and 2 cm. in diameter was wedged
into a shape to fit the front of the ball and there countersunk so that the
joint was smooth. At first a piece of platinum 1 cm. in diameter was
tried, but this was too small, and frequently the sparks jumped from
the edge of the platinum or brass. These were discarded, and the
larger platinum faces employed. In a very few minutes after polishing
they would often reach a state that would remain constant through a
long series of observations, but frequently several trials would have to
be made before such a satisfactory condition was obtained. All the

VOL. XXX. (n. S. XXII.) 15

226 PEOCEEDINGS OF THE AMERICAN ACADEMY.

observations given below were made with the platinum-faced balls.
For polishing the balls a chamois skin with a very small amount of
rouge was used, and sometimes they were finally cleansed with alcohol,
but this seemed to be no great advantage.

On each side of the spark gap was a hard rubber vertical rod,
through which the conducting wire was jjassed and clamped by a
screw. These made a firm support, and held the balls rigorously at
the fixed distance apart. The leading wires from the induction coil
were soldered to closely fitting short brass tubes that were passed
over the conducting wires and rested against the rubber supports.
They always remained in the same position, and did not need to be
disturbed when the balls were removed for polishing.

A large induction coil (53 cm. long and 19 cm. in diameter) was
used to charge the plates of the vibrator. To excite the coil five
storage cells were employed, which woi'ked with uniformly good re-
sults. The coil was capable of giving a spark 15 cm. long with this
source of electromotive force. A sparking distance of 4-6 ram.
was found most effective in producing oscillations in the secondary
circuit.

The particular feature of the apparatus that applied directly to
the investigation was the secondary circuit. In the previous deter-
minations of the wave length due to the Hertzian vibration, the
arrangement originated by Hertz and modified by Lecher * and by
Sarsiu and De la Rive f has been generally employed. In this
arrangement secondary disks were placed face to face with the plates
of the vibrator, and to each secondary disk a long wire was attached,
and these wires then carried through the air parallel to each other,
with sometimes an additional disk on the free ends.

With such an arrangement no exact adjustment of the length of
the secondary circuit was required in order to excite vigorous oscilla-
tion in it, for the direct electrostatic induction between the plates of
the primary and the disks on the ends of the secondary wires was so
great that powerful oscillations were produced along the secondary
wires, whatever their length might be, and several systems of waves
could be detected which seemed to give experimental grounds for
believing that the wave system sent out from the Hertzian vibrator
was very complex.

The capacity of the vibrator is increased by the presence of these

* Poggendorff, Annalen, XLI. 850

t Archives des Sciences Physiques, XXIII. 113. 1890.

ST. JOHN.

WAVE LENGTHS OP ELECTRICITY.

227

secondary disks so near to the plates of the vibrator, so that the wave
length found under these conditions is not due to the simple Hertzian
vibrator, but to a very heavy complex oscillating system with some-
what obscure internal reactions. Lecher calls attention to the change
in the sound of the spark when the two parallel wires of the secondary
circuit are bridged across by a conductor, and there is a very marked
difference in the spark when the secondary circuit is removed entirely,
the spark losing much in body and explosive character. The second-
ary under these circumstances must exert a strong reaction upon the
primary.

It seemed desirable to devise some arrangement depending more
directly upon the principle of electrical resonance, and one whose use
would not increase the capacity of the vibrator and whose reaction
upon the vibrator would be a minimum. This was accomplished by
omitting the secondary disks and using simply one wire, as shown in
Figure 3.

O

^'59 cm

p

0

R

S

Fig 3

The secondary circuit consisted of the long rectangle P Q R S,
which was carefully adjusted to resonance by placing the exploring
terminals of the bolometer (described later) at P S, and then cutting
off the ends of the wire until the length was found that would give
the maximum effect. Such a maximum was found when P Q was
859 cm. long. The maximum was sharp and unmistakable, the effect
falling off rapidly when the wire was either lengthened or shortened.
The result is shown graphically in Figure 4, where, as in all the curves
given, distances from Q are used as abscissas and deflections of the
galvanometer as ordiuates.

228

PROCEEDINGS OF THE AMERICAN ACADERIY.

Of

60

w

/

\ \

40

/

\

/

\

SO

/

\

1

1

\

\

20

/

1

\

1

800

90 0

Fig. 4.

To determine the character of the vibration along the wire, the
lengths P Q and R S were fixed at 859 cm., the exploring terminals

were moved along the rec-
tangle, and the bolometer
reading taken for each position
of the exploring terminals.
The graphic representation of
the results is shown in Figure 1
of the Plate. The character
of the curve indicates a simple
form of vibration. The total
length of the wire is equiv-
alent to seven half wave
lengths. The minimum points
are very nearly the same dis-
tance apart, and the distance
from the minimum occurring
at 748 cm. to the centre of the side Q R may be taken as three half
wave lengths. This furnishes a ready means of calculating the half
wave length ; —

Q R =z 30 cm. 748 X 15 = 763 cm.

763 -f- 3 — 254.3 cm. = a half wave length.

The distance from this minimum to the end of the wire at P should
be one fourth wave length, or 127. 15fm. The actual distance is
859 — 748 =111 cm., so that the correction due to the free end of
the wire is about 16 cm.

To adjust the length of the wire under this arrangement was a
work of considerable difficulty ; for in finding the points of maximum
effect many trials had to be made, and the wire cut off a few centime-
ters at a time and then renewed many times. To remove this source
of inconvenience, the ends P and S were wound on wooden bobbins,
so that shortening and lengthening could be produced without cutting
the wire. This was a marked improvement, but the changing size of
the coils, as the wire was shortened or lengthened, varied the capacity
at the end slightly, and somewhat irregularly. This led to the adop-
tion of the arrangement shown in Figure 5.

The secondary circuit consisted of the rectangle K L M N. The
side L N was open, and the lengths of the sides K L and M N could
be varied between a few centimeters and ten meters. The ends of
the wires K L and M N were in reality formed by the small copper

ST. JOHN. — WAVE LENGTHS OF ELECTKICITY.

229

230 PROCEEDINGS OP THE AMERICAN ACADEMY.

boxes L and N. These were 10 cm. square and 4 cm. thick, and
mounted upon the wooden bar E by insulating supports. Within the
boxes were wooden bobbins fixed to a hard rubber axle, and each
capable of holding 10 m. of the largest wire experimented upon. In
the front of each box was a small opening for the passage of the
wire, but, to assure a firmer contact between the wires and the boxes,
a brass block was soldered on the inner side of the front and a bind-
ing screw passed in from the outer side of the box. The bar E was
fastened to a wooden support resting upon the car, which ran on a
wooden track extending the entire length of the room. The car car-
ried a brake, so that the wires could be drawn taut, and the wooden
screw held the axle from turning. With this arrangement the length
of the wires could be varied at will, while the end capacities would
remain constant. The end capacities are not a feature desirable for
their own sake, as they destroy the perfect simplicity of the plain rec-
tangle and seem to detract somewhat from the sharpness of the maxi-
mum ; but the gain in convenience, and the possibility of obtaining a
large number of observations whose average values can be used, quite
overbalance these considerations in most cases where the apparatus
may be applied.

In the early part of the investigation the " Foucault " mterruptor
was used, but it was extremely irregular in its action, and caused
endless annoyance. It ran at an ever varying rate, and required
repeated adjustment and constant attention. To remedy at least
some of these defects, an interrupter actuated by a small electric motor
was devised.* The results obtained from this motor-interruptor were
so satisfactory that a detailed description is added.

A Porter's motor. No. 1 (Fig. 6, M), was used to produce the mo-
tion. This was actuated by the current from two storage cells, and it
ran at a fairly constant speed. The armature of the motor was wound
in three sections, and was thus free from dead points, giving it the
great advantage for the present purpose that it could be set in motion
simply by closing the circuit, making it possible to control it from the
observer's station. The motor was geared to the two-crank shaft K
by means of a wheel and pinion. The wheel and pinion liad the
ratio of 144 to 24 in the following investigation, but the motor could
slide on the brass bed-plate so that pinions of other sizes were avail-
able. The speed of the shaft K was about 750 revolutions per min-

*This and the other apparatus especially prepared for this investigation, and
requiring nmch technical skill in its construction, was made by the mechanician
of the laboratory.

ST. JOHN.

WAVE LENGTHS OF ELECTRICITY.

231

ute, and about 25 breaks were produced per second. The plunging
rods were thinned down at 0 so tliat they were flexible and gave the
required freedom of motion ; they ran through the bed-plate and the
brass bar below, which served as guides. The plunging rods carried

Fig. 6.

lock-nuts by which the flexible coils leading the current from the
brass post Q were attached. The lower ends of the plungers were of
platinum wire, No. 18. The glass mercury cups had brass bottoms
that screwed into the brass arm N, which was adjustable by means of
the collar and binding screw L along the pillar P. At P was
attnched one pole of the battery actuating the coil, and also one pole
of tlie conden'ser in the base of the coil, and at Q was attached one
pole of the coil and the other pole of the condenser.

232 PROCEEDINGS OP THE AMERICAN ACADEMY.

The cups were filled with mercury to a height of about 8 mm., and
then filled with alcohol to withiu a few millimeters of the top. They
usually required cleaning only after several hours' use, when the
surface of the mercury consisted of very fine globules, and sharp breaks
of the circuit were not made at each stroke of the plunger, as was
indicated by the occasional failure of the spark. The length of the
spark was kept constant during the observation, and the character of
the spark depended much upon the exact adjustment of the height of
the mercury cups of the interruptor. While it and the coil were both
in action, the height of the cups was adjusted until the sparks came
regularly with a peculiar crashing snap, and showed the bluish white
thick body that Professor Hertz described. Both the ear and eye
were soon so trained that they gave quick and sure information of the
character of the spark, but the ear was better than the eye. The ex-
act height of the mercury cups was of the utmost importance, a slight
difference in height changing the character of the spark greatly. The
exact point was best found by concentrating the attention upon the
sound, and then slowly raising or lowering the cups, when suddenly
there would seem to be a rhythm between the sound of the interruptor
and the snap of the spark, which would disappear with further motion
up or down. This rhythm would indicate that for every break of
contact there was a corresponding pilot spark between the microm-
eter balls.

For measuring the effects produced in the secondary circuit, the
bolometer as designed by Paalzon and Rubens * was used with most
satisfactory results. The bolometer was constructed according to
the description given by them in the paper referred to, and differed
only in minor details arising from the circumstances and the materials
obtainable. The accompanying diagram is theirs, but the following
description applies in all its details only to the instrument constructed
for this investigation.

The bolometer is in reality a double Wheatstone bridge. The four
arms of the bridge are the resistances W^, Wg, Wg, W4, of which
Wi and W2 are quadrilateral circuits of equal resistance, and Wg and
W4 are coils of equal resistance. The quadrilateral A B C D, or Wg,
is really a small Wheatstone arrangement, used as one branch of the
main bridge. For convenience in description, Wo will be called the
" bolometer branch," and the term bridge limited to the Wheatstone

* Anwendiing des bolometrischen Princips auf electrische Messungen.
PoggendorfE, Annalen, XXXVII. 529.

ST. JOHN.

WAVE LENGTHS OP ELECTRICITY.

233

Fig. 7.

net, of which Wo is a portion. If in the quadrilateral A B C D the
sides are of equal resistance, and if then a current be led in at B and
out at D, or vice versa, no difference of potential will be produced
between A and C ; in the same way, a current can be led in at A and
out at C without producing
any potential difference be-
tween B and D. The two
currents can traverse the rec-
tangle simultaneously and ex-
ert no effect upon each other
arising from difference of po-
tential. If, after the bolom-
eter branch and the bridge
are both balanced, a current,
alternating or direct, is sent
through the bolometer branch
W2 from B to D, none of the
current will pass through the
galvanometer ; but the resist-
ance of the branch Wg will be increased by the evolution of heat,
and the bridge thrown out of balance, as indicated by the deflection of
the galvanometer.

The resistances W3 and W4 were coils of fine German silver wire
double wound on wooden spools, and of three ohms' resistance each.
The quadrilaterals W^ and W^ were of iron wire, radius 0.035 mm.,
and each side had a resistance of three ohms. The arms of the
bolometer branch Wg were balanced before use by means of the slid-
ing mercury contact D, so that no deflection was produced in the gal-
vanometer when a steady current was passed from B to D. The
sliding mercury contact consisted of 20 cm. of No. 18 German silver
wire, L M, and a sliding block of brass, D, which contained in its
upper surface a small cup-shaped cavity filled rounding full with
mercury. The German silver wire was amalgamated to insure a good
contact. The contact G was of similar construction. The connections
were of No. 18 copper wire, whose resistance was negligible in com-
parison with the bridge arms.

The adjustment of the bolometer branch, once made, remained
constant through the series of observations, but the bridge adjustment
by means of the sliding contact G had to be made frequently. To
supply the bridge current a Daniell cell was used with a resistance
of 5 to 30 ohms in circuit.

234 PROCEEDINGS OF THE AMERICAN ACADEMY.

The galvanometer was of the Thompson type and had a resistance
of 56.9 ohms, and a figure of merit of 2.3 X 410~*, with a scale
distance of 1 m. and scale divisions of 1 mm. The time of a half
vibration of tlie needle was 7 seconds.

The bolometer resistances were attached to the under side of the
cover of a well made box of cherry (33 cm. long, 26 cm. wide, and
8 cm. deep). The resistances Wi and Wg were supported on
slender posts, so that they came nearly in the middle of the box, and
were equally exposed to the air on all sides. On the upper side of
the cover were the binding posts and sliding contacts. This box was
placed inside another one of similar construction (47 cm. long, 39 cm.
wide, and 23 cm. deep), and the space between was packed with
cotton wool. Cords from the sliding contacts were led through the
sides of the outer box, so that adjustments of the arms could be made
without exposing or touching the bolometer. Even with this pro-
tection from thermal changes, much difficulty was experienced when
the hot weather came, and the temperature of the room could not be
kept constant. It was found, however, that early in the morning very
little disturbance was experienced, and most of the observations
whose results are reported were recorded before the heat of the
morning was much felt in the room containing the bolometer.

To use the bolometer for measuring the energy at all places on the
wires forming the secondary circuit, the arrangement devised by
Rubens* was used. Over the two wires KL and M N (Fig. 5),
were slipped thick-walled capillary tubes of glass, about 5 cm. long,
and these were held by a small wooden bar, so that they could be
slipped along together. This arrangement is spoken of hereafter as
the exploring terminals. The ends of the lead-wires to the bolometer
were wound once around the tubes and fastened by sealing wax.
These formed two Leyden jars of extremely small capacity, and
the oscillations of charge on their inner coatings, which were formed
by the wires KL and MN, produced rapidly oscillating currents
through the bolometer resistance Wo. For leading wires to the bolom-
eter silk covered copper wire No. 36 was used that had been drawn
through hot paraffine. Larger wires were tried and wires with rubber
insulation, but with these the apparatus was less sensitive.

The following method was pursued in taking the observations.
The interruptor was set in action, the circuit closed through the
induction coil, and an observation taken of the first swing of the

* Ueber stehendc electrische Wellen in Draliten und deren Messungen.
Poggendorff, Annak'n, XLII. 154

ST. JOHN. — WAVE LENGTHS OP ELECTRICITY. 235

needle. The circuits were broken as soon as the needle reached
the end of its first swing, and the extent of this excursion was the
readino- recorded. In accordance with the experience of Paalzow
and Rubens, it was found that a steady deflection could not be
obtained, but this first swing was, under like conditions, quite
constant, and a preliminary calibration of the instrument by passing
currents of known strength through the bolometer branch W^ showed
that the square root of the deflection was in a constant ratio to the
current. The needle was quickly damped by making and breaking
the circuit through the induction coil, with the interruptor in action.

The rooms at disposal were very suitable for such an investigation.
The main room was 18 ra. long, 6 m. wide, and 5.5 m. high, and it con-
tained a very small amount of metal, and as it was in the non-magnetic
part of the laboratory that small amount was of brass and bronze
except the temporary addition of a small steam radiator in the corner
back of the oscillator. The oscillator was placed at 4.5 m. from one
end, and the parallel wires ran through the middle of the room at a
distance of 1.6 m. from the floor. The leading wires carrying the
currents from the batteries were of twisted cable and placed high up
against the walls. The bolometer and galvanometer were in an
adjoining room, where the observation table was equipped with the keys
necessary for complete control of the interruptor and induction coil.
By this means it was possible for one person to carry on the in-
vestigation, though it was very trying. Not only were the observer's
eyps in use, but it was necessary to listen intently to the sparking of
the oscillator, as after some experience very slight changes could be
detected and a close judgment formed of the steadiness of the spark ;
besides, it was necessary to note the sound made by the interruptor,
as small variations in its sjieed were easily noticed. The only time the
interruptor was likely to sliovv much change in speed was when the
battery was beginning to fail, or the brushes had become worn.

The theory of the investigation was based upon the principle of
electrical resonance.

Bjerknes has shown, in the paper previously noted, that, if damped
electromotive impulses obeying a sine law be assumed to act upon a
secondary circuit, there will be produced in the secondary circuit oscil-
lations of the period belonging to the primary impulses, and at the
same time oscillations proper to the secondary circuit, and that these
induced oscillations will reach their maximum amplitude when the two
circuits have the same period. His investigations also show that the
oscillations of the Hertz vibrator damp out much more rapidly than

236 PROCEEDINGS OF THK AMERICAN ACADEMY.

the oscillations in the secondary, at least when there is no spark gap
in the secondary circuit.

The sides of the rectangle (Figure 5) were reduced to a few centi-
meters in length, so that it could be safely assumed that its period was
much shorter than that of the vibrator. The plates of the vibrator
were fixed at 61 cm. apart, and the side KM of the rectangular
secondary was placed at 6 cm. from the conductor joining the plates
of the vibrator, with its centre 0 opposite the spark gap. The sides
K L and M N lay in the horizontal plane through the axis of the
vibrator, and were held by the end supports at 30 cm. apart. The ap-
paratus was symmetrical about a vertical plane through its spark gap
normal to the axis. The exploring terminals were kept at L N and
bolometer readings taken for each small addition to the length of the
sides K L and M N. When best resonance was obtained with the
shortest length of the secondary circuit that gave a maximum, it was
assumed that the secondary had the same period as the primary, and
that its equivalent length was a half wave length, its actual length
depending upon the effect due to the free ends. The occurrence of
resonance is a very marked phenomenon, even with a vibrator that
damps as rapidly as the Hertzian. The following table shows two
series of readings for the first maximum when an iron wire was
used : —

Length of side of rectangle 15
Deflections ...... 107

Deflections 94

There can be no free motion of the electricity at the ends of the
secondary circuit, but an accumulation alternately positive and negative
and the resulting alternation of potential, the phase at L being always
opposite to the phase at N. Elsewhere along the circuit the electri-
city moves with more freedom and less accumulation. The point O
may be called the electrical middle of the circuit, where the accumula-
tion is least and the movement most restrained. The electromotive
impulses from the vibrator act directly upon the side K M, so that O
remains a point of free motion, or the central segment of the wave,
while L and N are always places of no electric motion, or the nodal
points. The nodes under this view are the places of greatest poten-
tial difference, so that in the graphic representation of tlie results the
maximum points of the curves correspond to the nodes, the bolometer
throws being the largest when the exploring terminals are placed
where the potential difference is greatest. The shortest circuit being

25

35

40.0

42.5

45.0

50

60

75

145

156

194.n

199.2

181.5

140

81

42

119

161

185.0

191.0

178.0

136

76

34

ST. JOHN. — WAVE LENGTHS OF ELECTRICITY. 237

a half wave length long, a second resonating circuit ought to be fouud
by increasing each side of the rectangle by a half wave length, making
the circuit 3 half wave lengths long, and a third when the circuit is
5 half wave lengths long, and so on.* This is evident from a con-
sideration of the accompanying diagram. O is the center of a central
segment and the points marked 1, 3, 5, are always nodes.

0

O

O

Fig. 8.

From the results that he obtained, Bjerknes concluded that the
change of period, if there was such a change, by the use of iron in
place of copper, could not exceed two per cent.

The difference in length between a copper and an iron circuit of
the same period would be very small with circuits a half wave length
long, but this difference would be three times as great with circuits
3 half wave lengths long, and there might be a cumulative difference
that would finally become measurable by the use of circuits of still
greater length. This theory was tested in the following way. A
copper wire (diameter 0.1201 cm.) was used as the secondary circuit
in Figure 5. The sides were taken 15 cm. long, and then gradually
lengthened to 875 cm., and bolometer readings observed for each
addition. The results are shown graphically by the upper curve in
Figure 4 of the Plate. The critical points in the curve are the re-
sults of many separate determinations. The unsteadiness of the spark
in the vibrator made the determinations somewhat laborious, though a
single series of observations would locate a maximum very closely.
After this had been done, a space of about a meter including the
maximum point was worked over forward and back, changing its length
2.5 to 5 centimeters at a time in the region of the maximum. To assure
the steadiness of the spark during such a series of observations, some
convenient length of circuit was chosen as a point of reference, and
observations taken before and after the series ; if these showed that
the activity of the spark was practically the same, the rendings of the

* J. J. Thompson, Recent Researches in Electricity and Magnetism, § 297.

238

PROCEEDINGS OF THE AMERICAN ACADEMY.

ST. JOHN. WAVE LENGTHS OP ELECTRICITY. 239

series were retained. The results here given rest upon such
readings.

An examination of the curve shows four maxima, E, F, G, H,
occurring when the sides of the rectangle were 45, 306, 562.5, and
818 cm. long. The additions of wire for the successive maxima
after the first were 261, 256.5, and 255.5 cm. These additions should
be a half wave length ; the last two are nearly the same, but the first
differs by 5 cm. from the average of the last two, which is 256 cm.
With the sides fixed 818 cm. long, the wave form along the circuit
was determined by sliding the exploring terminals over the wires by
short steps, and observing the bolometer throws for each position.
The result is shown in Figure 3 of the Plate. The critical points
were determined several times, and a method similar to that described
above was used to assure the constant activity of the spark. The
curve shows three minima, occurring at 240, 496, and 752 cm.
Starting from the point O these give half wave lengths of 255, 256,
and 256 cm., with an average of 255.6 cm. The third minimum at
752 was determined with care, as it was to be used as a basis for
calculating the half wave length. A small error in determining the
position of this miniumm would be divided by 3 in obtaining the
result, since its distance from O was 3 half wave lengths. The total
length of the circuit was 7 half wave lengths. From the third min-
imum to the end it was one fourth of a wave length, the capacities
bring each equivalent to 62 cm. of the wire. By fixing the length
of the rectangle at 562.5 and 306, a similar investigation showed the
circuits to be respectively 5 and 3 half wave lengths long.

An explanation of the fact mentioned above, that the distance
between the first and second maxima was anomalously large, may
possibly be this : the sides of the rectangle for the first maximum
were but 45 cm. long, so that the effect of the closed end in increas-
ing the self-induction was relatively large, and the maximum appeared
earlier than it otherwise would ; but when the rectangle was 300 cm.
long, the influence of the closed end became relatively small, and
the second and future maxima came in the normal positions. In
the first case the capacity was mostly local, while in the second it was
largely distributed, and the length of the circuit was greater than
the wave length. This same effect appeared in every case, and seemed
to be a constant phenomenon.

The maximum I, omitted from the above discussion, was not con-
stantly present, but appeared when the primary spark was particularly
active, and seemed to belong to a circuit whose period was to the

240 PROCEEDINGS OF THE AMERICAN ACADEMY.

period of the primary as 5 to 3. The side of the rectangle was 127.5
cm., and the end capacities equivalent to 62 cm. of wire. The half
wave length was

30 + 127.5 X 2 + 62 X 2 =: 409. 409 -^ 255.6 = 1.6, nearly.

This was the only indication observed of complexity in the vibra-
tion of the oscillator. It appears that, when the oscillator is especially
active, it can excite a circuit having this ratio to itself, or that the
vibration is not a simple one. Time was not at disposal sufficient to
decide this point, which is left for future investigation.

A comparison of the curve (Fig. 1 of Plate) obtained from the plain
wire circuit with the curve (Fig. 3 of Plate) obtained when capaci-
ties were fixed on the free ends shows a quite satisfactory agreement
in the results, which tends to create confidence in both methods. The
half wave length by the first is 254.3 cm., by the second it is 255.6 cm.,
values which differ by about one half of one per cent. There is
a marked difference, as was to be expected, in the form of the curve
for the quarter wave length next the free ends. When end capaci-
ties were used, the accumulation of charge seemed mainly confined
to those out of reach of the exploring terminals, while with the plain
wire it seemed distributed over a greater distance, and could be
detected by the exploring terminals. In each case the effect of the
ends was to make the curve depart from its normal form along the
free wire.

An annealed iron wire (diameter 0.1186 cm.) was put in place of
the copper, and the same series of observations was made as with the
copper. The results are shown graphically in the lower curve of the
upper pair in Figure 4 of the Plate. The maxima E, F, G, H, appear
at 42.5, 301, 553, and 805 cm. ; in each case before the corresponding
maxima with the copper, and the difference increases with the length
of the circuits, as is evident from an examination of the curves. The
successive additions after the first maxima are 258.5, 252, and 252
cm. ; the last two agreeing, while tlie first, as with the copper, is
larger. With the sides of the rectangle fixed at 805 cm., the form of
the wave was found as shown in Figure 2 of the Plate, The third
minimum occurs at 740 cm. Calculating its half wavelength as before,
740 + 15 = 755. 755 ^ 3 = 251.6 cm. This agrees well with the
value 252 cm. given above by the last two additions, but differs by
4 cm. from the value found when the copper was used.

The same series of observations was repeated with a second pair
of finer wires (diameter of copper wire 0.07836 cm., diameter of iron

ST. JOHN, — WAVE LENGTHS OF ELECTRICITY.

241

0,07850 cm.). The results are shown in the lower pair of curves in
Figure 4 of the Plate, the upper one, as before, being the copper. A
comparison of the curves shows the same general result, which appears
more distinctly from the following table.

1st Maximum.

2d Maximum.

3d Maximum.

4th Maximum,

Cu

Fe

Differ-
ence.

2.5

Cu

Fe
301

Differ-
ence

Cu

Fe

Differ-
ence.

Cu

Fe

Differ-
ence.

Upper pair

45
40

42.5

306

5

562.5

553

9.5
12.0

818

805

13

Lower pair

57.5

2.5

300

294

6

552

540

799

784

15

The successive differences should be in the ratio of 1,3, 5, 7, if the
theory of the investigation is correct. The differences for the first two
maxima are very small, so that the experimental error in their deter-
mination would be relatively large.

In the case of the fourth maximum, the damping was so great that
it was difficult to fix the point with certainty. The difference for the
third maximum was relatively large, and the determination of the
maximum point was sharp. Taking this difference as a point of ref-
erence, the calculated and observed values are shown in the following
table.

1st Maximum.

2d Maximum.

3d Maximum.

4th Maximum.

Calcu-
lated.

Ob-
served.

Calcu-
lated.

Ob-
served

Calcu-
lated

Ob-
served

Calcu-
lated.

Ob-
served

Upper pair

1.9

2.5

5.7

5

9.5

9.5

13.3

13

Lower pair

2.4

2.5

7.2

6

12.0

12.0

16.8

15

The observed half wave lengths for the four wires were as follows: —

( Copper (diameter 0.1201 cm.), 255.6 cm.
(Iron (diameter 0.1126 cm.), 251.6 cm.

j Copper (diameter 0.07836 cm.), 251.6 cm.
i Iron (diameter 0.07850 cm.), 246.8 cm.

The wires in each pair were as near the same diameter as could be
found, the iron of the larger pair having slightly the smaller diameter,

VOL. XXX. (n. S. XXII.) 16

242 PROCEEDINGS OF THE AMERICAN ACADEMY.

but the copper being the smaller one in the second case. In other
respects the circuits compared were as nearly identical as possible.
The capacity per unit length being the same for wires of the same
diameter, the shortening of the wave length when iron displaced cop-
per of the same diameter must be caused by an increase in self-induc-
tion due to the magnetic properties of the iron. If this is true, it
means that the magnetization of iron can be produced and reversed
115 million times per second. This reduces the " time-lag" of mag-
netization to a very small (quantity, if magnetizing forces of such
duration are capable of bringing the magnetic properties of the iron
into play.

In the case of extremely rapid oscillations, Prof. J. J. Thompson has
shown (Recent Researches in Electricity and Magnetism, § 295) that

2 v"

approximately y^ — 77-7^? where — -g is the square of the frequency,

and L' is the self-induction for any rapid oscillations, and G the
capacity of the system. It is easy from this to calculate an approxi-
mate value for the ratio between the self-induction per unit length of
the iron and the copper.

Let L = the self-induction of the copper per unit length.
Let L' = the self-induction of the iron per unit length.
Let C = the capacity of either per unit length.

Usins: as a basis of calculation the data from the third maximum
G of the curves of Figure 4 of the Plate, the total length of the copper
circuit (diameter 0.1201 cm.) is: —

The sides, 562.5 x 2 = 1125 cm.

The closed end, = 30 cm.

The equivalent of the end capacities. 02x2= 124 cm.

1279 cm.

For the iron (diameter 0.1186 cm.) the length is : —

The sides, 553 X 2 = 1106 cm.

The closed end, = 30 cm.

The equivalent of the end capacities, 61 X 2 = 122 cm.

1 258 cm.

Since the two circuits have the same frequency, the products of the
self-induction by the capacity are equal.

12532 Z' Q^ 1279' LO.
^ = 1.034.

ST. JOHN. — WAVE LENGTHS OF ELECTRICITY. 243

In the same way, for

j Copper (diameter 0.0884 cm.) Z^ _ ^ ^^^

(Iron (diameter 0.08847 cm.) L~ '

\ Copper (diameter 0.07836 cm.) L' _

( Iron (diameter 0.07850 cm.) L

By the use of Lord Rayleigh's formula for induction under very
rapid oscillations, it is easy to calculate the permeability of the iron,
since the ratio between the self-induction of the iron and copper are
given by the previous calculation.

Lord Rayleigh's formula is

Z' = /

where / is the total length of the circuit ; A^ a constant depending
only on the form of the circuit, or / ^ is the self-induction of a similar
copper circuit; p., the permeability; i?, the resistance; /> = 2 7rre,
where n is the number of complete oscillations per second.
The value ol 'p ^ 1 irn = 360,000,000.
R for iron wire diameter 0.1186 cm. = .1328 ohms per sec.
" " " 0.08847 cm. = .227 " "

" " " 0.0785 cm. = .301 " "

For iron diameter 0.1186 cm.

L! ^ \m\L = l

{'-^O'

L + M4L= L + ly^,,

^ 2pl

V 2vl'

- >

Calculating the value of L for a copper circuit / units long, substi-
tuting the value in the above equation, and solving, we find : —
For the iron wire diameter 0.1186 cm. ft = 430
" « " 0.08847 cm. fx = 389

'^ « " 0.0785 cm. fx = 336

These values for the permeability all fall within a reasonable limit,
and have for an average /* = 385. These are the values found for
different specimens of wire made by the same company, but the speci-
mens were wound and unwound and stretched many times during the
series of observations.

244 PROCEEDINGS OP THE AMERICAN ACADEMY.

Besides the shortening of the wave length due to the increased
self-induction of the iron, there is shown a decided increase in the
damping, as has already been observed by Trowbridge and Bjerknes.
In Fiirure 4 of the Plate the curves for iron fall below the corre-
spondiug ones for copper, but owing to the change in the activity of
the primary spark no exact measurement was made. It was only ob-
served that the bolometer throws with the copper circuit were always
greater than those with the iron circuit of same dimensions when the
spark was constant as far as the eye and ear could judge.

A value for the damping factor €~27. can be calculated for the iron
and the copper. Lord Rayleigh's formula for the resistance under
very rapid oscillations is;

R = ^/^plfxR.

For iron wire circuit (diameter 0.1186 cm.),

I = 1258 ; fji = A30; R= 1.67 X 109 . p = Ux lO^;

whence

72' = 403 X 109; Z' = 34 X 10^

The damping factor becomes e"*' ^ ^" '.

The time required for the amplitude to fall to one half of its max-
imum value is found from the equation | = e"^'^^" ':

t = .000000115 sec.

On the basis of 115,000,000 alternations per second, the number of
complete oscillations in this time is 6.5. A similar calculation for the
corresponding copper circuit gives nearly sixty times as many.

It has been suggested that the greater damping of the iron might
give an apparent change of wave length. If the iron circuit is chosen
too short, and the maximum point is sought by adding to the length of
the wire, the increase of length would increase the damping and tend
to diminish the bolometer throws while the approach to the point of
resonance would tend to increase the effect on the bolometer ; the two
in fact would work against each other. If, on the other hand, the
circuit be chosen too long, and resonance is sought by shortening the
wire, the two would work together.

If the damping plays an important part we might expect different
results under these conditions. Iron wire (diam. 0.08847 cm.) was used,
and the circuit shortened until the sides were 15 cm. long and the first

ST. JOHN.

WAVE LENGTHS OF ELECTRICITY.

245

maximum poiut was found by
gradually lengthening the wire;
It was then found by gradually
shortening the wire from an
initial length of 60 cm. for tlie
sides of the rectangle. The
results are shown in Figure 9
where the upper curve is based
on the data found when short-
ening the wire, and the lower
on the data found when length-
ening it. The two differ by
less than a centimeter, which
is as near as two determina-
tions could be expected to agree.
In all determinations of the crit-
ical points of the curves shown,
reading's were taken both for-
ward and back, and the averages
used as data for the curves.

Another result of the investigation is apparent when copper circuits
are compared in which wires of different diameters are used.

3d Max G

Copper wire, diameter 0.12010 cm.
" " " 0.08840 cm.

« « " 0.07836 cm.

'* " " 0.03915 cm.

O

2ry

o

Fig. 9.

562.0
553 5
552.0
535.0

The half wave lengths calculated from this maximum are : —

Copper (.01201 cm.) ' 255.8 cm.

" (.08840 cm.) 252.2 cm.

" (.07836 cm.) 251.6 cm.

(.03915 cm.) 244.8 cm.

These are found by taking the total length of the circuit, and
dividing by 5.

535 X 2 = 1070 cm., length of wires.

30 cm., length of closed end.
62 X 2 — 124 cm., equivalent of end capacities.

1224 cm.
1224 -^ 5

244.8 cm.

The results here presented differ from those hitherto given, and
particularly from those of the late Professor Hertz ; but his investiga-

246 PROCEEDINGS OP THE AMERICAN ACADEMY.

tions were made with the spark micrometer as a measuring instru-
ment, and the same is true of Dr. Lodge's work with the alternate path.
The adaptation of the bolometer principle to this purpose furnishes a
much more accurate means of determining wave lengths and the
occurrence of resonance. It is not surprising that a change of wave
length of less than two per cent escaped detection by the spaik
micrometer method. The difference between copper and iron
increases as the diameter of the wires diminishes ; with wires 2 mm.
in diameter, the size mostly used by Hertz, the difference would be
exceedingly small.

The range of wires suitable for the study of the phenomena is
rather limited. If the wires are larger than 1 mm. in diameter, the
difference between iron and copper is slight ; while with wires less
than 0.5 mm. in diameter the damping is so great that long wires can-
not be used and advantage cannot be taken of the cumulative effect
which is the basis of the present method. There is no disagreement
between the results here given and those reported by Trowbridge
and Bjerknes. The circuits Trowbridge used were so long that the
iron damped the oscillation too rapidly, and the circuits used by
Bjerknes were so short that the difference between the copper and
iron could not be determined with certainty.

I wish to express my great obligation to Professor John Trowbridge
for the encouragement and suggestions that I have received from him,
and for his kindness in placing the resources of the Jefferson Physical
Laboratory so completely at my disposal.

Conclusions.

1. The self-induction of iron circuits is greater than that of similar
copper circuits under very rapid electric oscillations (115,000,000
reversals per second). This change in self-induction varies from 3.4
to 4.3 per cent in the present investigation, and increases with decreas-
ing diameters.

2. The increase in self-induction produces greater damping, and a
shortening of the wave lengtli of between 1.5 and 2 per cent.

3. The permeability /m of annealed iron wires under this rate of
alternation is about 385.

4. For oscillations of the same period, the wave length along
parallel copper wires varies directly with the diameter of the wires.
Range of wires used 0.03915 cm. to 0.1201 cm. The maximum de-
crease observed is 5 per cent.

Jeffkrsox Physical Laboratory,
July 24, 1894.

SPALDING AND SHAW. — COEFFICIENT OF SELF-INDUCTION. 247

X.

A HEAT METHOD FOR MEASURING THE COEFFI-
CIENT OF SELF-INDUCTION.

By p. G. Spalding and H. B. Shaw.

Presented by Professor John Trowbridge, May 9, 1894.

The coefficient of self-induction of a coil having an iron core and
traversed by an alternating current depends upon the permeability of
the iron, and therefore upon the current strength, in a manner which
can be seen by examining the hysteresis curves of Ewing and others.

If the coil has no iron core, its coefficient of self-induction is con-
stant for all current strengths, and may be measured by some method
where the current used is small, " Rayleigh's bridge method," for
instance.

If we try to calculate the coefficient of self-induction when a coil
with an iron core is subjected to an alternating current, we have a
practically impossible problem ; but if we regard the effects as a
whole, we can measure the effective coefficient of self-induction for
any given impressed electromotive force.

The effective coefficient of self-induction of a coil having an iron
core may be defined as the equal of the constant coefficient of that
coil which would give the same integral current flow as the former
under the given conditions.

Let us first examine the case theoretically. Given a simple
branched circuit and an impressed electromotive force which varies
as the ordinate of a sine curve, we obtain the following for the values
of the currents in the two branches : —

(1) «i = sin (jo < -f ^i) ;

(2) ^2 = , sin {p t -{■ B^)',

248 PROCEEDINGS OF THE AMERICAN ACADEMY.

where, according to Figure 1, i?i and R^ are the resistances ; L^ and
L^ the constant coefficients of self-induction, in the two branches ;

/f. Ir

Fig. 1.

p ^= 2 IT n\ I, I\, and I^ are the maximum values of ^, ?'i , and ^2, or
the square root of their mean square values multiplied by the square
root of 2.* Formula? (1) and (2) may be written

z\ — /i sin {j) t + ^i),

i2 = I2 sin {p t -\- 6^;
where

(3) A= iVR^ + fW

V(Ri + R,r+p'{L, + L,y

(4) i,= iVB^+rL^

Dividing (3) by (4), we obtain

(5)
whence

= 0,

I, _^/R,^ + p^L,^

h VR^' + p'L^

and if Lg

(6)

^' = l^RHr\ -'>-'■'

so that by measuring p, Ri, Ro, and -y? , we can calculate the value
of L,. " ^'

Now, considering the practical case, we see that, though the current
curve is distorted by the varying permeability of the iron core and

* See Fleming, Alternate Current Transformer, I. 133.

SPALDING AND SHAW. — COEFFICIENT OF SELF-INDUCTION. 249

the armature reactions of the alternator, yet a definite current passes
through each of the two branches, so that equations (5) and (6) still
hold, though Li is no longer constant throughout an alternation but
is the effective coefficient of self-induction defined above.

The practical proof of our conclusion is an easy one. A constant
Zi is measured, first by Rayleigh Bridge and then by our heat
method.

The experiment was briefly this. An alternating current was
divided between two circuits, both of which had known resistances ;
one circuit contained a coil with no iron core whose coefficient of
self-induction was to be measured ; the other branch, for simplicity,
had no self-induction. The ratio of the currents was determined by
the amounts of heat generated in known parts of the two circuits'
The connections are shown in Figure 2.

.4 is a suitable alternator, the one used had a frequency of 200 '^'.
a and c are heat coils of German silver wire wound non-inductively ;
the resistance of each was 1.288 ohms, and they were placed in oil
in order to measure the heat generated, h is the coil whose coefficient
of self-induction is to be measured ; it had no iron core. (^ is a resist-
ance coil, proportioned to make the currents in the two branches
about equal ; it was wound non-inductively and placed in oil to keep
it cool. A known standard of variable self-induction might be used
and would be less trouble to adjust. The heat developed in the two
heat coils, was measured by a thermoelectric junction and a delicate
galvanometer ; one end of the junction was kept in melting ice, and
the other end measured the heat of each coil in turn. The quantities
of oil in the two were equal, so that the ratio of the galvanometer
readings gave the ratio of the heat generated in the two.

We found it desirable to protect our lead-wires from air currents,
and to pack the jars containing the heat coils.

250 PROCEEDINGS OF THE AMERICAN ACADEMY.

^ The periodicity was measured by taking the speed of the alternator
continuously during the test, it being necessary that the speed be
constant, or nearly so.

The value of the coefficient of self-induction as measured by a large
number of trials with Rayleigh's Bridge and the heat method com-
pared as follows : —

Rayleigh's Bridge. Heat Method.

.0157 henrys. .0159 - .0164 henrys.

We then tested the effect of permeability and periodicity by putting
an iron core into this same coil. The results were : —

p = 629 Li = .066 henrys.

p = 1332 Zi = .029 "

These last results have to be considered with caution, as the im-
pressed electromotive force is changed by changing the periodicity.

This gives an easy practical method of determining the coefficient
of self-induction under the ordinary conditions of use, which, so far as
we know, none of the various methods attempt to do. The method
was suggested by Professor Trowbridge.

Jefferson Physical Laboratory,

March 1, 1894.

GIBBS. — COMPLEX INORGANIC ACIDS. 251

XI.

RESEARCHES ON THE COMPLEX INORGANIC ACIDS.

By Wolcott Gibbs, M. D.,

Rumford Professor Emeritus in Harvard University.

Presented August 1, 1894.
(Continued from Vol. XXI., page 128.)

Platino-Tdngstates.

In a notice of these and corresponding compounds of molybdenum
published some years since,* and intended to be only preliminary, I
pointed out the analogy between them and the silico-tungstates of
Marignac. The notice in question requires correction in several par-
ticulars, and I shall here give the results of a more complete investiga-
tion, conducted with better facilities for work and with a much wider
acquaintance with the whole class of complex acids.

Platiuic hydrate, like silicic hydrate, dissolves when boiled with
solutions of alkaline tungstates belonging to the meta-tungstic series.
Platiuo-tungstates are formed under these circumstances, but various
conditions require to be considered. In general I have been accus-
tomed to prepare the hydrate Pt(OH)^ by Fremy's method, that is, by
boiling a solution of platinic chloride with a large excess of sodic
hydrate for some time and then adding acetic acid in small excess,
when the platinic hydrate separates as a pale buff-yellow slimy com-
pound to be washed by repeated decantation with cold water. When
the last portions of saline matter have been removed the wash-water
becomes turbid and settles only after very long standing. The hydrate
obtained in this way sometimes dissolves very readily in hot solutions
of alkaline tnngstates, sometimes only after long boiling, and sometimes
IS almost insoluble. The process is therefore an uncertain one at best.
The platino-tungstates formed have a yellow or orange-yellow color
and in many cases crystallize well. By the process which I have
given it is usually difficult to obtain perfectly saturated compounds

* Berichte der deutschen chemischen Gesellscliaft, X. 1384. 1877.

252 PROCEEDINGS OP THE AMERICAN ACADEMY.

unless a rather large excess of platinic hydrate is employed. When
this is the case a greater or less quantity of a deep orange-red solution
is sometimes formed, which on standing deposits a dark tarry mass in
case the sodic tungstate is employed. In place of sodic hydrate I have
also used baric hydrate in prejjaring a soluble form of the platinum
compound, but in this case also the platinic hydrate, according to
varying conditions, varied very much in solubility.

When platinic hydrate is boiled with a solution of 10:4 sodic tung-
state the latter being in large excess, yellow solutions are sometimes
formed which on evaporation and standing yield large crystalline
masses with a fine yellow color and strong lustre. These crystals con-
sist essentially of the 10 : 4 sodic salt, 10 WO3 . 4 NagO + 23 aq., but
they contain a greater or less proportion of a platinic compound
which — water of crystallization apart — has probably the formula
10 WO3. PtOa . 4 Na^O, and which appears to be isomorphous with
the tungstate. A compound of this kind gave on analysis figures which
corresponded very closely with the formula,

10 WO3 . PtOa . 4 Na.O + 2 {10 WO, . 4 NagO} + 72 aq.

We may have here a combination of two isomorphous salts, hav-
ing respectively the formulae, IOWO3. PtOg . 4 Na^O + 26 aq., and
10 WO3 . 4 NaoO + 23 aq. The analyses of two different preparations
of the salts correspond very closely.

The difficulty of obtaining definite compounds by direct solution of
platinic hydrate led me to another method, which may be used with
much advantage. Pure crystallized sodic tungstate is to be dissolved
in water, a rather large excess of sodic hydrate added, and a neutral or
nearly neutral solution of platinic chloride added to the boiling solution
in small portions at a time. Platinic hydrate is formed and instantly
dissolved. The chloride is to be added until a distinct excess of
Pt(0H)4 is present. Acetic acid is then to be added in small excess.
Alcohol then often throws down a dark tarry mass which contains one
or more saturated platino-tungstates. When the projjortion of platinic
chloride necessary happens to be exact, a beautiful orange-colored
clear solution is formed which on cooling or evaporation deposits an
abundance of beautiful yellow needles or prisms easily purified by
recrystallization. By this process a definite salt may be prepared in a
very short time and in large quantity. Different salts are, however,
formed under different conditions, and further investigations must show
whether it is possible by using definite quantities of platinic chloride
and of sodic tungstate to obtain uniform results as regards the constitu-

GIBBS. — COMPLEX INORGANIC ACIDS. 253

tion of the salt formed. It is indispensable to employ pure platinic
chloride or chlorplatinates. Even traces of iridium give a greenish
tint to the platino-tungstates formed, a fact which misled me in my
earlier experiments. Contrary to my preliminary statement, I now
find, on more prolonged study, no isomeric platino-tungstates.

10:1:6 Sodic Platino-tung state. 12:5 sodic tungstate very readily
dissolves platinic hydrate in its soluble form, and gives a fine deep
orange-colored solution which on standing yields a mass of ill defined
dull orange crystals. These may be redissolved, recrystallized, and
dried on woollen paper. Of these crystals :

1.1460 grams gave 0.8430 gram Pt + WO3 — 73.56 per cent.
1.1806 grams gave 0.0686 gram Pt + WO3 = 73.57 "
1.1806 grams gave 0.0706 gram platinum = 5.98 "
1.1460 grams gave 0.8695 gram platinum ^= 6.06 "
1.8770 grams gave 0.7774 gram WO3 = 67.83

0.8770 gram lost on ignition 0.1397 gram oxygen and water,
= 15.93 per cent.

The analyses lead to the formula,

10 WO3 . PtOa. 6 NaaO + 28 aq.,
which requires : —

Calculated. Mean. Found.

10 WO3 2320 67.79^ 67.65) 67.56 67.83

\ 74.40 } 74.65

PtOa 226.5 6.61 ) 7.00 j 6.96

6 Na.O 372 10.87 ) 10.51

V- 25.60
28 H2O 504 14.73 ) 14.94

3422.5 100.00

The soda being estimated by difference. It is remarkable that this
salt contains six molecules of base instead of four, all known silico-
tungstates being tetrabasic. The solution of this salt when shaken
with a solution of potaSsic bromide gives an amorphous pasty mass
with a deep orange-red color. In the analysis of this class of com-
pounds it is best to determine the platinum by ignition with sodic
carbonate. On treatment of the fused mass with water, the plati-
num remains as metal, and the tungsten may then be determined
in the filtrate in the usual manner. Nearly all the analyses were
made in this way, sodic oxide being determined by difference. In
some cases, however, tungstic and platinic oxides were precipitated
together by mercurous nitrate and mercuric oxide.

254 PROCEEDINGS OF THE AMERICAN ACADEMY.

20 : 1 : 9 Sodic Platino-tung state. In one experiment in which I
boiled a portion of pure sodic tuugstate with a considerable excess
of sodic hydrate, and added to the boiling solution chlorplatinic
acid (PtClglia) in small portions at a time, a fine yellow solution was
formed, after addition of an excess of acetic acid, which soon deposited
a mass of topaz-yellow crystals. This could be redissolved and re-
crystallized without decomposition. The mother liquor appeared to
contain one or two other salts. Of this salt :

(1) 1.4847 grams lost on ignition 0.2453 gram = 16.52% 0+ H2O.
(4) 1.4154 grams lost on ignition 0.2349 gram = 16.61 % O + HgO.

(2) 1.4847 grams gave 0.0466 gram platinum = 3.73% PtOg.

(3) 1.0976 grams gave 0.0345 gram platinum := 3.65% Pt02.
x-N ( 1.4154 grams gave 1.0467 grams platinum ^= 3.83%.

\ 1.4154 grams gave 1.0129 grams WO3 = 71.57%.
(6) 1.4847 grams gave 1.0619 grams WO3 = l\.bO%.

The analyses lead to the formula,

20 WO3 . PtOa . 9 Na^O -\- 58 aq.,
which requires ;

Calculated,

Mean.

Found.

20 WO3

4640

71.73

71.53

71.57 71.50

PtOa

226.5

3.50

3.74

3.73 3.65 3.83

9 Na^O

558

8.63

8.68

8.67

58 H.O

1044

16.14

16.05

16.00 16.09

6468.5 100.00

The solution of this salt has a strongly acid reaction with litmus. It
gives with ammonic chloride beautiful colorless scaly crystals, slightly
soluble in cold but soluble in boiling water, exactly resembling in
appearance the sodio-ammonic tungstate, 12 WO3 . IS^a^O . 4 (NHJgO?
and containing nd platinum. This reaction seems to support the view
that the compound is a double salt, and we may perhaps assume that it
is represented by the formula,

10 WO, . 4 NaaO + 10 WO3 . PtOg . 5 NagO + 58 aq.

The principal reactions of this salt are as follows : —

With AgN03 ^ white fine grained crystalline precipitate settling slowly.
With TINO3 a similar precipitate in rather coarser grains.
With SO^Cu a very pale blue or bluish white fine grained precipitate.
With HgNOg a bright yellow amorphous precipitate.
With Co(NH3)f,Cl3 a pale bull precipitate quickly becoming crystal-
line in leaves.

GIBBS. — COMPLEX INORGANIC ACIDS. 255

A quantity of this platino-tungstate was precipitated by a solution of
mercurous nitrate. The fine yellow mercurous salt was well washed
and then decomposed by dilute chlorhydric acid, the platino-tungstate
being in very small excess. The clear yellow filtrate on spontaneous
evaporation deposited a pale yellow substance which may prove to be
the corresponding acid.

30:2:15 Sodic Platino-tungstate. This salt was obtained under
the same conditions as the last, and formed granular efflorescent dull
yellowish crystals readily soluble in water. Of this salt :

1.3231 grams gave 0.9787 gram WO3 + Pt == 73.97 per cent.
1.3231 grams gave 0.0510 gram platinum = 4.49 per cent PtOg.
1.0144 grams gave 0.0410 gram platinum = 4.70 per cent PtOg.
1.5776 grams lost on ignition with WO^Nag 0.2657 gram 0 + HgO

= 16.71 per cent.
1.5776 grams gave 1.1059 grams WO3 = 70.06 per cent.
1.3231 grams gave 0.9271 gram WO3 = 70.03 per cent.

The analyses lead to the formula,

30 WO3 . 2 PtOa . 15 NaoO + 89 aq.,
which requires :

Calculated.

Found.

30 WO3

6960

69.98

70.03 70.06

2 PtOa

453

4.56

4.49 4.70

15 Na^O

930

9.35

9.24

89 H2O

1602

16.11

16.18

9945

A solution of this salt also gives white scaly crystals with potassic
and ammonic salts. It gives a white flocky precipitate with baric
chloride, and a pale yellow flocky crystalline precipitate with mercurous
nitrate. The compound is probably, like the last described, a double
salt and may have the formula,

10 WO3 . 3 NaaO . H2O + 2 {10 WO3 . PtOg . 6 NaaO} + 88 aq.

The solution of the salt is acid to litmus. Analysis by Dr. Morris
Loeb.

30 : 1:12 Sodie Platino-tungstate. I obtained this salt by boiling
platinic hydrate with 10:4 sodic tungstate for some time in a plati-
num vessel. It formed very large masses of honey-yellow heavy
crystals, very easily soluble in water. Of this salt ■

256 PROCEEDINGS OF THE AMERICAN ACADEMY.

1.1441 grams lost on gentle heating 0.1583 gram water = 13.84%.
0.9383 gram lost on gentle heating 0.1313 gram water ^ 13.99%.
1.8069 grams gave 1.4033 grams WO3 + Pt = 77.66%.
0.8809 gram gave 0.6847 gram WOg+Pt = 77.72%.
* gram gave gram platinum == 2.46% Pt02.

The analyses agree with the formula,

30 WO3 . PtO^ . 12 NaaO + 72 aq.,
which requires :

Calculated.

Found.

30 WO3

6960

75.44

75.53 75.43

PtOa

226.5

2.45

2.46

12 NaaO

744

8.06

8.15

72H2O

1296

14.05

13.84 13.99

9226.5 100.00

In the analyses the water was determined by heating in an air-bath,
and not by ignition. No correction for oxygen of PtOg is therefore
applied. The solution of the salt gives the characteristic white scaly
crystals with NH4CI and KCl, and as in the last two cases we may
safely assume that the compound is a double salt. The most probable
formula considering the mode of formation is,

10 WO3 . PtOa . 4 NasO + 2 {10 WO3 . 4 NagO} + 72 aq.

From the above it appears that, strictly speaking, none of the com-
pounds described correspond to the silico-tungstates of Marignac, all
of which appear to contain four molecules of basic oxide. Such plati-
num compounds may, however, exist in combination, as seems to be
shown in the salts last described.

The other metals of the platinum group will probably be found to
form similar compounds. Want of material has prevented a careful
study of the subject, but a number of qualitative tests made with small
quantities of salts of iridium, ruthenium, palladium, and osmium ap-
peared to show clearly that these metals also form compounds with
tungstic and raolybdic oxides analogous to those of platinum.

8:2:3 Platino-mohjbdate of Ammonium. When freshly prepared
sodic platinate NaoO . 3 Pt02 is boiled with a solution of 14 : 6 am-
monic molybdate, it readily dissolves to an orange-yellow liquid, which
after a time deposits beautiful lemon-yellow crystals, which may be
easily purified by recrystallization. The salt dissolves rather easily in

* The data of this analysis were accidentally lost.

GIBBS. — COMPLEX INORGANIC ACIDS. 257

cold, and very readily in hot water. The solution gives with argentic
nitrate a pale yellow flocky precipitate which becomes crystalline on
standing. With mercurous, mercuric, and thallous nitrates it gives
pale yellow flocky precipitates not distinctly crystalline and settling
quickly. With nitrate of croceo-cobalt the solution gives a beautiful
bright yellow crystalline salt. The formula of the ammonium salt is,

8 M0O3 . 2 PtOo. 3(NH,)20 + 12 aq.,

as the following analyses show :

1.7831 grams gave 0.3554 gram Pt = 19.94% = 23.21% Pt02.

0.5425 gram gave 0.1075 gram Pt = 19.82% = 23.09% PtOg.

0.4354 gram gave 0.0868 gram Pt = 19.92% = 23.15% PtOg.

1.0407 grams gave 0.0535 gram NHg =z 5.14%.

0.5149 gram gave 0.0405 gram NH3 = 5.14%.

0.5878 gram gave 0.0459 gram NHg = 5.14%.

1.2015 grams lost on ignition with WO^ Nag 0.2663 gram 22.17%

H^O + NH3 + O.
0.8368 gram lost on ignition with WO^ 0.1876 gram 22.42% HgO +

NH3

+ 0.

Calculated.

Mean.

Found.

8 M0O3

1152

58.27

57.83

2 PtOs

453

22.91

23.15

^23.21 23.09 23.15

6 NH3

102

5.16

5.14

5.14 5.14 5.14

15 H2O

270
1977

13.66
100.00

13.88

13.76 14.01

Other salts of this series may be prepared from the ammonium salt
by precipitating its solution with mercurous nitrate and decomposing
the well washed mercurous salt by solutions of the chlorides of other
metals.

4:2:2 Platino-molyhdnte of Ammonium. The solution from
which the yellow ammonium salt first described separated by crystalli-
zation gave on evaporation a dark colored liquid over a heavy oily
deep brown-red substance. This last was washed with a little ice-cold
water and gradually dried to a transparent dark brown-red ma§s which
broke up into clean sharp brilliant fragments. Of this salt :

0.4502 gram lost on careful heating 0.1297 gram = 28.81% HoO

+ NH3 -f O.
0.4502 gram gave 0.1226 gram platinum — 31.63% PtOo.
0.5398 gram gave 0.0402 gram (NH,).,0 = 4.91 % NHg.
0.4917 gram gave 0.0369 gram (NHJ2O = 4.87% NHg.

VOL. XXX. (n. S. XXII.) 17

258 PROCEEDINGS OF THE AMERICAN ACADEMY.

The analyses lead to the formula,

4 M0O3 • 2 Pt02 . 2 (NH4)20 + 19 aq.,
which requires :

Calculated.

Found.

4 M0O3

576

40.03

39.56

2 PtOa

453

31.48

31. G3

4NH3

68

4.72

4.91 4.87

19 H2O

342

23.77

23.97

1439 100.00

As in the last case the molybdic oxide is estimated by difference
which in the present state of our knowledge of analysis is the most
accurate method. The salt can hardly have been absolutely pure.
Water decomposes it and gives an opaque buff-yellow compound which
I have not examined. It will be seen from the above that the platino-
molybdates described do not correspond in general composition with the
only silico-molybdates known in which the ratio of molybdic to silicic
oxide is as 12:1,

Rammelsberg * has described a molybdate of the dioxide and ammo-
nium which has the formula,

4 M0O3 . 2 MoO., . (NH,).,0 + 9 aq.

lu endeavoring to prepare a class of stanno-tungstates I obtained a
sodium salt the solution of which gave on evaporation a hard nearly
colorless glassy mass. This gave on analysis results which did not
correspond very well, but the mean of several led to the formula,

4 WO,, . 2 SnOs . NaoO + 7 aq.

The compound deserves further study, and is not without interest in
connection with the two salts noticed above.

60 : 1 : 1 0 Platino-molybdate of Potassium. This salt was obtained
by boiling potassic molybdate with an excess of potassic hydrate, and
adding a solution of PtCl,;H2 ""til platinic hydrate which at first dis-
solves as fast as formed, was in small excess. Acetic acid was then
added to an acid reaction. On standing fine granular yellow crystals
were formed in quantity. These were dissolved in hot water and
recry stall i zed. Of this salt :

0.5191 gram gave 0.0098 gram Pt = 2.20% PtOj.
0.5191 gram gave 0.5665 gram M0S3 = 81.85% M0O3.

* Poggendoff, Annalen, CXXVII. 291.

GIBBS. — COMPLEX INORGANIC ACIDS.

259

0.6459 gram lost on ignition with WO^Na^ 0.0447 gram = 6.92%

O + H2O = 6.61 H2O.
1.2241 grams lost on ignition with WO^Na^ 0.0872 gram = 7.12%
O + H2O = 6.81 H2O.
The analyses lead to the formula,

60 M0O3 . Pt02 . 10 K2O + 40 aq.,
which may be written provisionally as

1 2 M0O3 . PtOs . 2 ICO . 4 HoO + 4 {1 2 M0O3 . 2 Kp . 3 H^O} + 24 aq.
The formula requires :

Calculated. Found.

60 M0O3 8640 82.04 81.85

Pto/ 226.5 2.16 2.20

10 KOo" 994 8.97 9.24

40 H26 720 6.83 6.61 6.81

10530.5 100.00

This salt is readily soluble in hot water without apparent decompo-
sition. It gives a very pale yellow crystalline precipitate with argentic
nitrate and a pale greenish blue precipitate with cupric sulphate, which
is soluble in an excess of this last.

Rosenheim has recently described * another platind-tungstate with
the empirical formula,

7 WO3 . 2 PtO. . 5 NaoO + 35 aq.,
and regards it as a double salt,

7 AVO3 . 3 NaoO + 2 {PtO., . Na^O} + 35 aq.

This salt was obtained by boiling normal sodic tungstate, WO^Naj,
in concentrated solution with platinic hydrate, and presented small
yellow needles which could not be recrystallized without decomposition.
He did not succeed in obtaining platino-tungstates by boiling platinic
hydrate with various meta-tungstates, and suggests that the three salts
which I described in my preliminary notice were mixtures of meta-
tungstates (para-tungstates) and platinic oxide. They were, on the
contrary, perfectly well defined and crystallized, as were also the
platino-tungstates and platino-molybdates described in this paper.
Further investigation will probably show that a number of other salts
can be obtained by the method which I have described in which the

* Berichte der deutschen chera. Gesellschaft, XXIV. 2397.

260 PROCEEDINGS OP THE AMERICAN ACADEMY.

platinic hydrate is brought in contact with acid tungstates or molyb-
dates in the nascent state. Phospho-platino-tungstates and similar
molybdenum compounds appear also to exist. A solution of 24 : 1 : 2
phospho-tungstate of sodium readily dissolves platinic hydrate on boil-
ing, and gives an orange-colored solution which after filtration and
evaporation deposits ill defined orange crystals. When a solution of
ammonic chloride is mixed with the solution obtained as above, a beau-
tiful orange crystalline salt is thrown down. In a preliminary notice
published in 1877,* I have described the preparation and properties
of platiuo-tungstates having respectively the formulas

10 WO3 . PtO, . 4 NaaO 4- 25 aq ; 10 WO3 . PtOa . 4 K2O + 9 aq. ;
10 WO3 . PtO. . 4 (NH,). O + 12 aq. ;

and of a platino-molybdate with the formula

10 M0O3 . PtOa . 4 NagO + 29 aq.

All of these tungstate compounds were obtained by boiling

10WO3.4Na2O + 23aq.

•with the soluble form of platinic hydrate. The molybdenum compound
was obtained in a similar manner, but I am not now able to state
what acid molybdate of sodium was employed. I have not succeeded
in obtaining these compounds a second time, and in the long interval
of time which has elapsed since the publication of my preliminary
notice the notes of description and analyses have been lost. I can
only express my conviction that more extended investigations will
show that no error has been made, and that the compounds unite as
described. I will further remark, that, taking the analyses which I
have given in this paper, it may be possible to give simpler formulas
for some at least of the salts described. The formulas given represent
I believe most accurately the results of the analyses, but as the per-
centages of platinum are relatively small the quotients of these per-
centages by the atomic mass of platinum are very small divisors. Ou
the other hand, the quotients obtained by dividing the i)ercentages of
tungstic or molybdic oxide by the molecular masses of tungstic or
molybdic oxide are relatively very large, and the ratio between the
two quotients in question becomes somewhat uncertain. The com-
pounds which I have obtained by the method which I have given of
bringing platinic oxide in statu nascenti into contact with the solutions

* Rerichte rler deutschen chem. Gesellschaft, X. 1384. Am. Journ. of Sci-
ence, [3.], XIV. 61.

GIBBS. — COMPLEX INORGANIC ACIDS. 261

of acid tuugstates or molybdates gives such well defined and beautifully
crystalline salts that the subject will doubtless attract the attention of
other chemists. I will make the suggestion that possibly the salts
which I described in my preliminary notice may be obtained by add-
ing ammonic chloride to solutions of the double salts described in this
paper, so as, in the case of the tungstic compounds at least, to pre-
cipitate the tungstic oxide not combined with platinic oxide in the
form of

10 WO3 . 4 Na^O + 4 {10 WO3 . 4 (NHJ.O} + ,50 aq.,

or an analogous salt. The solution should then contain only a platino-
tungstate. The application to the platiuo-molybdates described is less
probable.

Second Series of Pyrophospho-Tungstates and Pyrophos-

pho-molybdates.

When sodic pyrophosphate is added in excess to a solution contain-
ing a metallic salt, the precipitate which is at first found is in many
caseg redissolved with formation of a double salt of sodium and the
metal in question. In a certain number of cases, the heavier metal
in the new compound is not replaceable under ordinary conditions, and
does not exhibit its characteristic reactions with tests. These facts
are of course familiar to all chemists. Persoz supposed that these
salts might be represented, in the case of divalent metals, by the
general formula, as we should now write it,

PAR" + P20,Na„

and that the group P2O7R" was to be regarded as electro-negative to
the group PoOjrNa^, so that the compound would be simply analogous
to ClNa. If we write the double salt PsO-R'^Na,, we may regard
the complex PoO-R" as playing the part of a relatively electro-
negative group, as in the case of double cyanides, so called. Whether
this view is to be considered as identical with that of Persoz, is a
question about which opinions may differ, and wliich is not important
for my present purpose. Admitting that the groups PgO-R" or
P2O-R'" are transferable as such in their relatively simple alkaline
salts, we may inquire whether they enter into the composition of com-
plex acids, and if so, whether the compounds so formed differ from
ordinary pyrophospho-tungstates and pyrophospho-molybdates. As
the initial point in this investigation I have selected mangano-disodic
pyrophosphate, PgO^MngNaa .

262 PROCEEDINGS OF THE AMERICAN ACADEMY.

Mangano-sodic Pyrophospho-Molybdate .

In another part of this memoir I have described several salts be-
longing to the group of pyrophospho-tuugstates. As these were
peculiar in their constitution, it became a matter of interest to deter-
mine whether the pyrophospho-molybdates had a similar constitution,
or, in other words, whether they contained the pyrophosphoric group
22 RO3 . 9 P2O7 found in the salts of the tungstic series.

Molybdic teroxide boiled with sodic pyrophosphate, care being taken
to keep the oxide in excess, is dissolved with much facility and in large
quantity. The colorless solution may be evaporated to a syrup with-
out yielding crystals on standing, and gives no precipitates with salts
of potassium or ammonium. The solution, however, gives precipitates
with salts of most of the heavier metals. Of these I selected the
mangauous compounds for special study, supposing that all the manga-
nese would be present as base, and that a comparison could be made
between salts of this type and those in which manganese exists in the
pyrophosphoric molecule, and which I shall describe further on.

When a solution of manganous chloride is mixed with one of sodic
pyrophospho-molybdate prepared as above, a dull bufF-colored ajipar-
ently amorphous precipitate is formed. On standing with an excess
of the sodium salt, this was gradually converted into a mass of beauti-
ful bright yellow crystals. These were well washed with cold water,
and then dissolved in boiling water. The filtered solution gave on
cooling a mass of sulphur-yellow crystals, which were again dissolved
and recrystallized. The salt was then dried on woollen paper. It
was analyzed by Mr. G. W. Patterson.

1.3289 grams gave 0.1065 gram PAMg, = 5.13% PgOg.
1.3289 grams gave 0.2486 gram PoO^Mna r= 9.36% MnO.
0.9538 gram gave 0.1819 gram P.OyMua = 9.53% MnO.
0.9538 gram gave 0.5934 gram P.O5 + M0O3 = 62.22%.
1.0960 grams lost with Wo4Na2 0.2037 gram = 18.56%.
0.9445 gram lost with WoiNaj 0.1743 gram = 18.45%.
The analyses lead to the formula

22 M0O3 • 2 P2O5 . 7 MnO . 9 NaaO -t- 57 aq.,
which requires :

Calculated. Found.

^ 62.29

19.20

18.45
5533 100.00

I

22 MoOg
2P2O5

3168

284

^^•26162.39
5.13)

57.16)
5.13)

7 MnO
9 NaoO

497
558

^•^n 19.07
10.08)

9.36)

9.84)

57 H2O

1026

18.54

18.58

GIBBS. — COMPLEX INORGANIC ACIDS. 263

The salt is nearly insoluble in cold water. Boiling water dissolves
it, but the salt is decomposed, giving a jjide yellow fiocky precipitate
and a sherry wine colored solution. On standing a short time, the so-
lution as it cools becomes pale yellow, and finally almost colorless,
while the precipitate gradually becomes brighter yellow and crystal-
line, and the original salt appears to be again formed by recombination.
Both the precipitate formed in the decomposition by boiling water and
the wine-yellow solution give reactions with argentic nitrate which
differ from one another as well as from the yellow crystalline silver
salt formed by digesting the pyrophospho-molybdate of manganese
and sodium with argentic nitrate.

In the analysis the solution of the salt was boiled with mercurous
nitrate and mercuric oxide. The precipitate contained only molybdic
and phosphoric oxides, and was free from manganese. There is
therefoi-e reason for assuming, as I have done, that all the manga-
nese is basic, and that none is present in the form of the molecule
PaO^Mn.

Mangano-ammonic Pyrophospho-Molybdates.

When manganous pyrophosphate is digested for some time with a
strong solution of 14:6 acid ammonic molybdate, a buff-yellow very
slightly soluble compound is formed. This is to be well washed,
dried on woollen paper, and afterward in pleno over sulphuric acid.
Of this salt, analyzed by Mr. G. W. Patterson:

0.7830 gram lost on ignition with WO^Nag 0.0778 gram NHg -f H„0

= 9.94%.
0.6554 gram lost on ignition with WOiNao 0.0645 gram NHg -f H2O

= 9.84%.
0.8590 gram gave 0.0338 gram NH3 = 3.92%.
0.7191 gram gave 0.0285 gram NH3 = 3.97%.
0.8725 gram gave 0.0881 gram PoOyMg, = 6.46% P0O5.
0.8725 gram gave 0.2841 gram PAMug = 12.62% MnO.

The analyses lead to the formula,

20 M0O3 . 2 PA . 10 MnO . 5 (NH^)^© -\- 10 aq.,
which requires :

264 PROCEEDINGS OF THE AMERICAN ACADEMY.

Calculated.

Found.

20 MoOs
2P2O5

2880

284

66.76)
6.58 [

73.34

67.27 Ug
6.46 j

10 MnO

710

16.46

16.30

IONH3

170

3.94

3.92 3.97

15 H^O

270

6.26

5.94

3.73

4314 100.00

In the analyses the salt was digested for some time at a boiling
heat with mercurous nitrate and mercuric oxide. The mercurous salt
formed contained mangauous oxide. The precipitate was fused with
a mixture of potassic and sodic carbonates to separate manganous
oxide. The filtrate from this last gave the phosphoric pentoxide.
Molybdic teroxide was determined by difference. As the salt could
not be recrystallized, the defects in tbe analysis are doubtless chiefly
due to traces of impurity. The formula of the salt should be written,
according to my view :

20 M0O3 . 2 P^TMn . 2 (NH^)^© . 8 MnO . 3 (NH4)„0 + 12 aq.

We may have here a double salt, as, for instance,

10 M0O3 . P,07Mn(NH4)2 . 4 MnO . (NH4)20 . H^O

+ 10 M0O3 . P20^Mn(NH4)2 . 4 MnO . 2 (NH4)20 + 12 aq.,

but of course other arrangements are possible.

The manganese in the molecule containing P0O7 may be called,
for convenience, the internal or fixed manganese, to distinguish it from
the external or basic manganese. To determine if possible the ratio
between the external and internal manganese, I digested a weighed
portion of the salt in the cold for twelve hours with mercurous nitrate,
and then boiled, adding a little mercuric oxide in the usual manner.
In the filtrate, after separating the mercury, the manganese was
determined as PoOtMuo. In this manner,

1.2306 grams gave 0.3520 gram PAMn = 11.08 %.

From this it appears that about {h of the manganese was precipi-
tated by mercurous nitrate, in place of 1%. If, therefore, we consider
^(f of the manganese to be present in the salt as PgOyMn, we must
suppose that this molecule is broken up, to a certain extent at least, by
boiling with mercurous nitrate, and it is very doubtful whether the
manganous oxide exists in any other form than as a base. Certainly

GIBBS. — COMPLEX INORGANIC ACIDS. 265

there is no sufficient evidence that it forms here an integrant molecule
Po07Mn, as in sodio-mauganous pyrophosphate, PgOyMn . Na^. I re-
gard the question, however, as still an open one, since the molecule
PoOjMn, assuming its existence, may be decomposed by mercu-
rous nitrate and give a corresponding mercurous integrant molecule
P207Hg2, and since the salt is decomposed by water like the other
salts of this series. It appears also from the above that the pyro-
phospho-molybdates do not correspond in composition to the pyro-
phospho-tungstates. At least I have not found in them the molybdenum
molecule corresponding to the tungstic molecule, 22 WO3 . 9 P2O7.
It must, however, be remarked that, as I shall show, the pyrophospho-
tuucrstates which contain manganese do not contain this molecule.

Mangano-sodiG Py7-ophospho- Tungstates.

These salt? are very easily formed by boiling manganous pyrophos-
phate with acid tungstates. Dark sherry-wine colored solutions are
formed, which in cooling deposit crystals in abundance.

14 : 1 : 3 : 6 Mangano-sodic Pyrophospho-7\ingstate. This salt is
formed more conveniently by mixing a solution of 12 : 5 sodic tung-
state with manganous pyrophosphate and digesting for some hours in
a closed bottle heated in a water bath. The pyrophosphate must be
in excess. It dissolves rather slowly to a fine deep orange-colored
li(;[uid, which after evaporation deposits beautiful crystals, which may
be redissolved and recrystallized. In spite of the employment of an
excess of manganous pyrophosphate, it is rather difficult to obtain a
solution of the salt which is perfectly saturated with the manganous
salt. The crystals have a brownish orange color. They effloresce in
dry air, though not rapidly, but in pleno over sulphuric acid they lose
water in relatively large quantity. Of this salt, analyzed by IMr. G.
"VV. Patterson:

1,4176 grams lost on ignition with WOiNao 0.2032 gram - 14.34^
water.

1.2375 grams gave 0.0611 gram PjO^Mgo = 3.16% PA .
\ 1.0476 grams gave 0.1041 gram PAMn., = 4.97% MnO.
( 1.0476 grams gave 0.7650 gram WO, -F PA = 73.05%.

The analyses lead to the formula,

14 WO3 . P0O5 . 3 MnO . 6 NagO -f- 36 aq.,
which requires:

266 PROCEEDINGS OF THE AMERICAN ACADEMY.

Calculated.

Found.

14 WO3

3248
142

70.25 > ,332
3.07)

''■>'' I 73.05
3.16 J

3 MdO

6 Na,.0

213

372

^•^•^ 1 12.66
8.04)

7.68)

36 H2O

648

14.02

14.34

4623

100.00

We may give this salt the formula

14 WO3 . 6 Na^O + PAMn3 + 36 aq.,

if we suppose that the pyrophosphate of manganese has become ortho-
phosphate. Both constituents are then normal salts.

The ammonium salt was prepared by double decomposition between
the sodium salt and ammonic chloride, and repeated crystallization.
It presented orange-colored prismatic crystals, very soluble in both hot
and cold water. Of this salt :

0.7846 gram gave 0.01715 gram NH3 = 2.19%.
0.6556 gram gave 0.01394 gram NH3 = 2.13%.
0.4886 gram gave 0.0594 gram NH3 + HjO = 12.16%.
1.0895 grams gave 0.1162 gram PoOyMn^ = 5.83% MnO.

The analyses correspond well with the formula,

28 WO3 . 2 PA • 6 MnO . 5 (NH,)oO . 2 NaoO + 48 aq.,

which requires :

Calculated.

Mean.

28 WO3

6496

77.67

77.76

Z7.84 77.69

2 PA

284

3.40

3.13

3.13

6 MnO

426

5.09

5.39

5.33 5.45

IONH3

170

2.03

2.16

2.13 2.19

2Na,0

124

1.48

1.56

1.56 (diff.)

48H26

864

10.33

10.00

10.00

8364 100.00
We may formulate this salt as

{14 WO3 . 4 MnO . 2 NaoO + P20vMn2}

+ {14 WO3 . 5 (NH^y.b . HoO -f PAH4} + 45 aq.,

the type being 14 WO3 . 6 RO + P207R'4, so that so far as the em-
pirical constitution is concerned the salt may be regarded as a double
salt of two normal constituents. The analyses were made by Mr. G.
W. Patterson.

GIBBS. — COMPLEX INORGANIC ACIDS. 267

Auramin Pyrofliospliales,

When a solution of double chloride of gold and sodium AuCl4Na is
made as nearly neutral as possible and then boiled with sodic pyro-
phosphate P207Na4 , a very pale yellow solution is formed, which con-
tains the auro-sodic salt discovered by Persoz, the formula of which
we should now write PaOyAu'^'Na. The solution of this salt gives
with ammonia a white precipitate which quickly becomes yellow and
crystalline. With argentic nitrate it gives a pale yellow flocky crys-
talline precii^itate, which is very insoluble and does not blacken readily
in the light. With mercurous nitrate it gives a greenish gray flocky
crystalline precipitate. A nearly white curdy precipitate is formed
with sulphate of luteo-cobalt ; none with sulphate of croceo-cobalt.
With Pt (NH3)4Cl2 gold is reduced.

The crystalline precipitate formed by ammonia in the auro-sodic
pyrophosphate solution was well washed, dried at 150°, and analyzed.

0.9665 gram gave 0.6756 gram gold = 78.44% AugOs.
0.9031 gram gave 0.7003 gram gold = 78.34% AuoO,.-
0.9665 gram gave 0.1621 gram P-AMgo = 10.73% PA-
1.0031 grams gave 0.1703 gram PAMga = 10.86% PA-
0.7375 gram gave 0.02286 gram NII3 = 8.10%.
0.7691 gram lost, at 150° C, 0.0420 gram water = 5.46%.

The analyses lead to the formula

14 AU.O3 . 6 PA • 14 NII3 . 3 Na^O -f 24 Aq.,

which requires

14 AuA

6 PA

14 NH3

3 NaoO

24 H.,6

Calculated.

Found,

6178

78.34

78.44 78.34

852

10.80

10.73 10.86

238

3.02

3.10

186

2.36

2.26 (difif.)

432

5.48

5.46

7886 100.00

The analysis is due to Dr. Morris Loeb, who assisted me in this
part of my work most efficiently.

The salt does not explode at low temperatures, but on heating to a
little above 170° C. a violent explosion takes place. This shows
clearly that part at least of the gold is in the form of an auramin, or
compound with ammonia.

268 PROCEEDINGS OF THE AMERICAN ACADEMY,

The auramin pyrophosphate of sodium, on boiling with baric chlo-
ride, gives a yellow crystalline salt; with mercuric chloride, a fine pale
yellow crystalline salt which becomes very distinct on boiling.

When the auramin salt is*boiled with mercurous nitrate, some mer-
cury is reduced to metal, and at the same time very characteristic
white prismatic crystals are formed. Chlorhydric acid does not sensi-
bly dissolve the pyrophosphate, but changes it to a pale yellow flocky
crystalline body. Chloride of luteo-cobalt gives on boiling an orange
crystalline salt.

When the crystalline yellow or dull orange baric salt is well washed
with hot water and then filtered off, the colorless filtrate on evaporation
gives with sodic hydrate a very distinct reaction for ammonia. Part
of the ammonia in the salt must therefore have been in the form
of ammonia, unless we admit that the auramin is decomposed under
the circumstances. When treated with a cold solution of argentic ni-
trate reaction sets in at once, and a fine yellow flocky crystalline salt is
formed ; but no trace of ammonia is obtained from the filtrate after
washing the salt with cold water and separating the excess of silver.
Both the barium and silver salts were partially analyzed.

The barium salt was analyzed by Mr. G. W. Patterson :

0.6472 gram gave 0.1015 gram BaS04 = 10.30% BaO.
0.6472 gram gave 0.1426 gram PoOyMg., = 14.09% PA •
0.6472 gram gave 0.3900 gram gold = 67.63%.

Here the ratios are 9 AU2O3 : 6 P2O5 : 4 BaO.
In the silver salt (Patterson) :

0.7718 gram 0.0915 gram AgCi = 9.58% AgA
0.7718 gram 0.4470 gram gold = 64.98%.

0.7718 gram 0.1584 gram PaO^Mga = 13.13% PA-

The ratios are approximately 16 AuAs '■ 10 P2O5 '■ 5 AgoO.

The analyses of the barium and silver salts are at least sufficient to
show that no simple double decomposition takes place in either case.
The formula which I have given for the gold salt is to be regarded
as purely empirical, and does not explain the explosive character
of the salt. No compounds falling under the general expression
Au2(NH3)n03 are at present known. Dumas and Raschig give to
fulminating gold the formula NIIo • Au'" . NH, which may be written
N2II3AU'". This is equivalent to 2NHr; the corresponding ammo-
nium must be NgHsAu^'Ha, and the oxide of this (N2H5Au'")0. If

GIBBS. — COMPLEX INORGANIC ACIDS. 269

we assume that this oxide is present in the auramin pyrophosphate
which I have described, we may write the formula

8 AuA . 6 P^OTAu'^Na . 6 {(N^H^Au^OO} (NH4)20 . 2H2O + 24 aq.,

which is reducible to the type

8 R2O3 . 7 RO + 6 P207R'4 + 26 aq.

As regards the deduction of the formula from the analyses, it may
be worth while to give also the equations

G P2O5 + 3 Au.Og + 3 NaoO = 6 PaO^Au'^N ;
3 AU2O3 + 12 NH3 = 6 {(N^HjAu^OO} + 3 HA

In the determination of the ammonia by boiling with KHO or
NaHO, we have

6 NJIsAu'" + 3 H2O = 12 NH3 + 3 AU2O3.

Auro-pijrophospho-MoIyhdates.

When a solution of chloro-aurate of sodium, AuCLNa, is mixed
with one of pyrophospho-molybdate of sodium, a dull orange-colored
fine-grained crystalline precipitate is thrown down, which is almost
certainly an auro-pyrophospho-molybdate of sodium. When a solution
of auro-pyrophos]ihate of sodium, PoOvAuNa, is boiled for some time
with 14:6 molybdate of ammonium, a pale buff-colored crystalline
precipitate is formed, which is sligiitly soluble in boiling water, giving
however only a turbid liquid. After washing with cold water this
precipitate was dried in pleno over sulphuric acid. Of this salt:

0.5581 gram lost by ignition with W04Na2 0.0841 gram = 15.07%
H.,0 + Nil, + O.
f 0.8123 gram gave 0.3489 gram gold = 42.94% = 48.18% AU2O3.
1 0.8123 gram gave 0.0837 gram P.O^Mgo = 6.59% P2O5.

0.6133 gram gave 0.2615 gram gold = 42.13% = 47.85%.

0.2746 gram gave 0.01558 gram NH3 = 5.65% NH3.

0.4774 gram lost by ignition with WO^Nag 0.0744 gram = 15.58%.

In this last analysis the salt had probably absorbed a little water.
The same is true for the next;

0.6133 gram gave 0.0624 gram PaO^Mga = 6.51%.
If we calculate the analyses for an anhydrous salt, we find:

270 PROCEEDINGS OF THE AMERICAN ACADEMY.

Calculated.

Found.

11 M003

1584

36.07

5 AU2O3

2206

50.25

50.29 50.27

2 PA

284

6.46

6.87 6.83

15 NH3

255

5.81

5.89

Na.O

62

1.41

4391 100.00

In the hydrated salt the ratios are nearly

1 1 M0O3 . 5 AU2O3 . 2 P2O5 . 15 NH3 . Na^O + 10 aq.

The formula requires 3.93% of water. The mean of the water in
the two analyses is 4.18. It is to be borne in mind that the salt
could not be recrystallized, and was probably not absolutely pure.
The salt does not explode on heating, but merely " puffs." Hot
dilute chlorhydric acid readily dissolves it. Ammonia water does not
sensibly dissolve it, but gives an orange-colored substance which may
be the corresponding auramin compound. The formula may be writ-
ten provisionally

22 MoO,, . 4 P^OvAu^'Na . 6 AU2O3 . 15 (NH^).,© + 5 aq.

More extended investigations are necessary to fix the formulas of
this and analogous compounds. Analysis by Mr. G. W. Patterson.

Auramin-pyrophospho-Molyhdates.

When the orange-colored flocky precipitate formed by adding am-
monia to auro-pyrophosphate of sodium is boiled for some time with
14: 6 ammonic roolybdate, and the whole allowed to stand with the
supernatant liquid, a pale yellowish crystalline salt is formed. After
thorough washing with cold water, the salt was dried on bibulous
paper and in plena over sulphuric acid. For analysis it was boiled
for a short time with a mixture of chlorhydric and sulphurous acids.
The phosphoric acid was determined in the filtrate from the gold by
magnesia mixture, in the manner which I have pointed out in treat-
ing of the analysis of the phospho-molybdates.* The filtrate from
the ammonio-magnesic phosphate, after adding (NH^jaS, was evapo-
rated, filtered to separate free sulphur, and then treated with cold
dilute chlorhydric acid. The precipitated M0S3 was filtered on a
Gooch filter, washed, dried at 106° C, tlien washed several times
with carbon disulphide, dried, and weighed. Ammonia was deter-
mined by boiling with sodic hydrate and titration.

* Proceedings of tlie American Academy, XXIX. 64.

GIBBS. — COMPLEX INORGANIC ACIDS. 271

(1) 0.3969 gram gave 0.0217 gram NH^ = 5.47%.

(2) 0.5733 gram gave 0.3612 gram gold = 70.68%.

(3) 0.5733 gram gave 0.1168 <,^ram PaO^Mg, = 13.03% P2O5.

(4) 0.5733 gram gave 0.0426 gram M0S3 = 5.57% MoO,.

(5) 0.3499 gram lost on ignition with WOiNao 0.0703 gram = 20.09%.

The salt explodes on heating, but not violently. There appears to
have been a slight loss on heating with sodic tungstate, and I have
accordingly calculated the water by difference, all the other constitu-
ents having been determined directly. The analyses correspond to
the formula 12 Au.Os . 3 M0O3 . 7 P2O5 . 24 NH3 + 21 aq. Analysis
by Mr. G. W. Patterson :

Calculated.

Found.

12 Au.O.

5297

70.54

70.68

3 M0O3'

432

5.75

5.57

7P2O5

994

13.23

13.03

24NH3

408

5.44

5.47

21 H2O

378

5.04

5.25

7509 100.00

Here, as in the cases of the other gold compounds, part of the am-
monia is present as ammonic oxide and part is directly combined with
gold ; but the proportions remain to be determined. The careful
study of this class of compounds appears likely to lead to verj' inter-
esting results. I have classed them only provisionally with complex
acids.

As it may not be possible for me to return to the subject,* I will
here give the results of some preliminary work, which will at least
serve as starting points for further investigation.

Molyhdico- Tnngstates.

When acid molybdate of ammonium is boiled with chlorhydric acid
and potassic iodide, and the deep orange-colored liquid is precipitated
with ammonia, a brown precipitate of Mo(OH)4 is thrown down,
which after thorough washing is readily soluble in a solution of 12:5
sodic tungstate, forming a deep orange-red liquid. Potassic bromide
gives a bufF-colored crystalline precipitate, which is soluble in boil-
ing water, and ci-ystallizes on cooling in small pale brown scales.
Ammonic chloride gives a similar salt, as do also the chlorides of
barium, strontium, and calcium. All these salts are soluble in hot
water, and separate from the solution in pale brown crystals. In

* "A rebus gerendis senectus abstrahit." — Cicero, Cato Major.

272 PROCEEDINGS OP THE AMERICAN ACADEMY.

preparing the potassium salt a large excess of potassic bromide should
be used : the bromide in this, as in many other cases, appears to be
preferable to the chloride and nitrate. In these salts the molybdic
dioxide may be easily and accurately determined by titration with
permanganate, after adding sulphuric acid. The solutions of the mo-
lybdico-tungstates readily absorb oxygen from the air, forming molybdic
teroxide, a fact which must be taken into account in analysis.

Molybdic hydrate, Mo(OH)4, quickly reduces M0O3 "^ ^ solution
of 14:6 ammonium salt, and gives a fine blue liquid, which probably
contains M02O5 or M0O2 + M0O3. When a very cold solution of
ammouic molybdate is employed, and molybdic hydrate is added in
small portions at a time, the solution becomes yellow, then quickly
green, and finally blue. It is possible that a molybdico-molybdate,
OTM0O2 . nMoOg . joRoO, is formed at first. Molybdic hydrate reduces
both molybdic and tungstic teroxides in phospho-molybdates and
phosplio-tungstates. Analyses of the potassium, calcium, and barium
molybdico-tungstates were made with salts which perhaps were not
absolutely pure. Tiie formulas obtained appeared to be respectively
12 WO3 , M0O2 • 5 KoO + 16 aq. ; 12 WO3 . M0O2 . 5 CaO + 32 aq. ;
and 12 WO.j . M0O2 . 6 BaO + 30 aq. ; but these are given with much
reserve. In these the molybdenum was determined by titration with
permanganate, and the sum of the molybdic and tungstic teroxides,
after oxidation, by precipitation of the neutral solution with calcic
or baric chloride. Tungstic teroxide could then be determined by
difFierence.

It seems at least probable that tungstico-molybdates corresponding
to molybdico-tungstates, as, for example, 1 2 M0O3 . AVO2 . x RO, also
exist.

Uranoso- Tungstntes.

When uranic oxide is dissolved in dilute sulphuric acid, and the
solution is treated with metallic zinc, a solution of sulphate of uranic
dioxide is formed which after a time deposits a gray-green powder
insoluble in cold water, and probably a basic sulphate. This body
treated with a solution of 12:5 sodic tungstate gives at once an olive-
green crystalline salt very insoluble in hot water. The supernatant
liquid has a peculiar reddish tint. The dark olive-green salt is
oxidized by boiling with nitric acid and gives a yellowish white mix-
ture, or possibly compound, of uranic and tungstic teroxides, easily
decomposed by boiling with caustic alkalies, with separation of uranic
oxide and formation of sodic tungstate. A solution of 12:5 potassic

GIBBS. — COMPLEX INORGANIC ACIDS. 273

tungstate acts in the same manner upon the uranious salt, giving also
an olive-green crystalline salt and a brown-red solution. Similar
results were obtained with acid ammonic tungstate. After drying for
some days upon paper, the sodium salt was analyzed by Dr. Loeb:

0.4436 gram lost with WO4NO0 0.0331 gram = 7.46%.

( 0.9861 gram gave 0.3954 gram WO. = 40.09%.

\ 0.9861 gram gave 0.3360 gram UOo and KMnO^ = 34.08%.

The analyses lead to this formula,

8WO3.

. 6 UO2 . 12 Na,0 +

25 aq.

Calculated.

Found.

8 WO3
6UO2

1856
1626

39.69 I 74^g
34.77 )

40.09 I ^^^^
34.08 J

12 Na,0

744

15.92

16.46 (diff.)

25 11,0

450

9.62

9.47

4676 100.00

The water determination was made by heating with sodic tungstate
and determining the loss of weight. In the fusion the UO, is com-
pletely reoxidized to UO3. Hence a correction must be applied to the
water, which in the above case amounts to 2.01% to be added. As the
salt could not be recrystallized, it was doubtless not perfectly pure.

The olive-green potassium salt is also insoluble in hot water and in
chlorhydric acid. It reduces silver and mercury from their nitrates,
and appears to undergo double decomposition with baric and calcic
chlorides. This salt was also analyzed by Dr. Loeb:

( 1.3260 grams gave 0.4997 gram WO3 = 37.69%.
1 1.32G0 grams gave with KMn04 gram UO2 = 33.21%.
0.9275 gram lost on ignition with WO^Nag 0.0833 gram = 8.98%.

The analyses lead to the formula,

8 WO3 . 6 UO2 . 9 K2O H- 34 aq.

Calculated. Found,

37-^n 70.50 S^-^n 70.90
32.92) 33.21)

17.12 16.60 (diff.)

12.38 12.50

8W03

1856

6U02

1626

9 K2O

846

!4H20

612

4940 100.00

The potassic salt corresponds in constitution to the sodic salt if we
write it :

8 WO3 . 6 UO2 . 9 K2O . 3 H2O + 31 aq.

VOL. XXX. (n. S. XXII.) 18

274: PROCEEDINGS OP THE AMERICAN ACADEMY.

Silico-Molyhdates.

The existence of definite silico-molybtlates appears to have been
first observed by Parmentier,* who obtained potassium, sodium, and
ammonium salts by the action of alkaline silicates upon alkaline mo-
lybdates in presence of* nitric acid. The free acid has the formula
12 M0O3 • Si02 + 26 aq. I have devised another method of prejjar-
ing this class of salts, which may perhaps be generalized in its appli-
cation. When a solution of fluosilicic acid is poured into one of 14 : G
molybdate of ammonium, no precipitate is formed, but the solution be-
comes yellow. On evaporation a bright yellow crystalline body sepa-'
rates in large quantity. When normal sodic molybdate, Mo04lS[a2, is
strongly acidulated with chlorhydric acid, the addition of fluosilicic acid
gives at once a bright yellow color. The solution obtained in this
manner gives no precipitate in the cold with ammonic chloride, but on
boiling and shaking for a few minutes a beautiful bright yellow crystal-
line precipitate is thrown down in abundance. Tiiis is slightly soluble
in hot water to a yellow liquid. A solution of fluosilicic acid mixed with
one of an acid potassic molybdate forms no precipitate, but the mix-
ture is yellow, and on evaporation to dryness upon a water bath yields
a highly crystalline yellow powder. Much molybdic teroxide is at
the same time reduced to blue oxide. The yellow solutions of the
silico-molybdates of potassium and sodium give with nitrate of croceo-
cobalt a beautiful orange crystalline precipitate, which is insoluble in
cold water and readily washed and dried. The bright yellow silico-
molybdate of ammonium after careful washing was analyzed :

0.7963 gram lost on ignition with WOiNaa 0.0750 gram NH3 and

H.O = 9.42%.
0.5279 gram left on ignition 0.0158 gram S : O2 = 2.99%.
0.6504 gram gave 0.0339 gram (NH4)20 = 5.22%.

0.5817 gram gave 0.03045 gram (NH4)20 = 5.23%.

The analyses correspond to the formula,

12 M0O3 • SiOa .

, 2 (MH4)2C

► -f 5 aq. ;

which requires :

Calculated.

Found.

12 M0O3

1728

87.18

87.58 (diff.)

SiO.

60

3.03

3.00

2 {m\,),o

104

5.24

5.22 5.23

5 H2O

90

4.55

4.20

1982

100.00

* Comptes Rendus, XCII. 1234, and XCIV. 213.

GIBBS. — COMPLEX INORGANIC ACIDS. 275

The silica was determiued by igniting the salt with free access of
air until all the molybdic oxide was exjielled. The reactions of a so-
lution of the sodium salt were as follows. No precipitate with baric
and calcic chlorides. None at first with potassic bromide, but on
standing bright yellow crystals formed. A sulphur yellow crystalline
precipitate with mercuric nitrate and a beautiful bright orange-yellow
highly crystalline precipitate with mercurous nitrate. A very pale
yellow crystalline precipitate with argentic nitrate and a pale yellow
line-graiued crystalline precipitate with thallous nitrate. Pechard *
has obtained the same salt by precisely the same process as that
which I have employed, and has priority in publication. I have
also obtained a titanio-molybdate and a zirconio-molybdate by similar
methods, but have not analyzed them. Pechard has described beau-
tiful salts of the two series, and rendered further work on my part
unnecessary.

Selenoso-Molybdates.

When 24 : 1 phospho-molybdate of potassium is boiled with a solu-
tion of potassic selenite SO.Ka it readily dissolves to a perfectly clear
and colorless liquid, which after an hour deposits beautiful large gran-
ular colorless crystals in abundance. These are readily soluble in hot
water, and crystallize from the solution without change, except that
large transparent colorless crusts are obtained. Of this salt, analyzed
by Mr. G. W. Patterson :

1.1360 grams gave 0.1503 gram of selenium = 13.23% = 18.09% SeOa-
1.1360 grams gave 0.7772 gram PtCleK, = 13.27% K,0.
0.9570 gram lost up to 175° C. 0.0058 gram HoO = 0.61%.

Deducting the small percentage of water, the analyses correspond to
the formula.

17 MoO, . 6 SeO, . 5 KoO.

1

Calculated.

Found.

17 MoO,

2448

68.81

68.45

6 SeOa

648

18.16

18.20

5 K^O

472

13.23

13.35

3568 100.00

The formula may also be written,

6 {SeOa . 2 M0O3} -f 5 M0O4K0.

* Comptes Rendus, CXVII. 691-694. Cited in Zeitschift fur anorg Chemie,
VI. 200.

276 PROCEEDINGS OF THE AMERICAN ACADEMY.

The selenium was determined by reduction with sulphurous acid and
the molybdic oxide by difference. In spite of the mode of prepara-
tion, the salt did not contain phos^shoric pentoxide. On repeating
the preparation of the salt I obtained different results, the pro-
portions used being probably not the same. The solution deposited
first groups of colorless crystals, and then gave after further evapora-
tion a white granular crystalline salt. The grouped crystals seemed
at first to be quite insoluble in water, but when boiled dissolved, and
then crystallized out very readily. Perhaps more than one salt was
formed in this operation. The solution of the salt analyzed gave pale
yellow crystalline precipitate with argentic and mercurous nitrates.

Selenoso- Tungstates.

When ammonic tungstate is boiled with a solution of SeOgHo it
readily dissolves to a pale yellow solution, which almost immediately
gives beautiful shimmering scales in a pale yellow mother liquor.
These pass at once through a filter and are difficult to separate and
wash. Potassic tungstate also readily dissolves in a solution of sele-
nious acid, forming a pale yellow solution which on heating suddenly
becomes opaque, while a pale yellow precijiitate is thrown down.
'When washed by decantation with cold water, both the ammonic and
potassic salts have a distinct pale yellow color. When a solution of
selenious acid is mixed with one of 12:5 sodic tungstate and a solu-
tion of potassic bromide is added, a white precij^itate m very minute
granular crystals is formed, settling rather slowly, and very slightly
soluble in hot water. A solution of argentic nitrate gave, with the
well washed salt, large very pale yellow crystalline flakes. Mercu-
rous nitrate gave a pale yellow crystalline precipitate. A solution of
selenious acid mixed with one of 24 : 1 : 2 sodic phospho-tungstate
gave a white granular precipitate very slightly soluble in hot water.
After careful washing, this gave, on boiling with argentic nitrate, a
perfectly white crystalline salt, a bright yellow crystalline precipitate
with mercurous nitrate, and a white crystalline precipitate with baric
chloride. It is possible that phospho-seleuoso-tungstates are formed in
this manner.

Pechard * has recently described salts of two series of molybdo-
eelenites, as he terms them, having respectively formulas which
would indicate that they are derivatives of the acids ;

4 ILO . 3 SeOg . 10 M0O3 , and 2 HoO . SeO,, . 5 M0O3.

* Comptes Rendus, CXVI. 1441-1444; also, CXVII. 104-106.

GICBS, — COMPLEX INORGANIC ACIDS. 277

The same chemist has also described a very interesting series of
salts, which he terms molybdo-sulphites, embraced under the general
formula,

4H2O . 3SO2. IOM0O3.

Telluroso-Mulyhdates and Tungstates.

Klein * many years since also observed the existence of complex
acids containing tellurous and telluric oxides and tungstic oxide. So
far as I am aware, no analyses have been published. A preliminary
notice of my own work was communicated to the Harvard Chemical
Club, February 12, 1884.t

When a solution of TeBrgKo is formed with a large excess of
water, the salt is completely decomposed into bromhydric and tellu-
rous acid TeO,H,. A solution of 14: 6 acid molvbdate of ammonium
readily dissolves this last on boiling, and the clear filtered solution
soon deposits beautiful granular colorless crystals in quantity. It is
best to use an excess of tellurous acid. The telluroso-molybdate is
much less soluble than the acid molybdate of ammonium, and may be
redissolved and recry stall ized without apparent decomposition. When
a solution of the TeBr6K2 is mixed with one of the acid molybdate, •
a very pale yellow precipitate is formed. After standing, small bright
yellow crystals also appear. The white precipitate is probably only
tellurous acid. When freshly precipitated tellurous acid is boiled with
a strong solution of an acid potassic tungstate, it does not dissolve, but
changes character and becomes more distinctly crystalline. A solu-
tion of TeBrcKa gives with one of 24 : 1 : 2 phospho-tungstate of
sodium a very white granular precipitate, which is insoluble, and may
be washed with boiling, but then settles slowly. The tellurium em-
ployed was the best commercial product, and doubtless not absolutely
pure. If, as has been supposed, two different metals are embraced
under the name, it is possible that the compounds of the two oxides
with molybdic and tungstic oxides may afford means of separation in
consequence of differences in composition and properties. Should
tellurium be hereafter found to possess a technical value or interest, an
abundant supply can be furnished by the mines of Colorado. The
very high cost of the metal at present has prevented further study on
my part.

* Bull, de la Societe Chimique, [2.], XLII. 169.

t See also Berichte der deutschen chem. Gesellschaft, XVIII. 1089. August,
1884.

278 PROCEEDINGS OF THE AMERICAN ACADEMY.

Cerico-Molyhdates.

When eerie fluoride, CeF4, is boiled in a platinum dish with 14 : 6
molybdate of ammonium, the solution quickly becomes yellow, and
soon deposits a fine yellow crystalline salt, which may be washed with
cold water, in which it is but slightly soluble. It contains molybdic
teroxide, eerie oxide, and ammonia. Basic eerie nitrate treated with
a solution of hydro-potassic fluoride, KFoH, changes character at once
and becomes flocky-crystalline. After washing with cold water, boil-
ing with 14:6 molybdate of ammonium dissolves but little, but the
salt becomes bright sulphur-yellow and crystalline and is practically
insoluble in water. The best method of preparing this salt consists in
first preparing pure basic nitrate of cerium* free from lanthanum
and didymium (neo-dymium and praseo-dymium). This is to be dis-
solved in nitric acid and the solution diluted. Acid potassic fluoride
then precipitates a nearly white flocky salt, which dissolves readily in
a boiling solution of 14 : 6 molybdate of ammonium to a yellow solu-
tion, and crystallizes from this. It will probably be better to boil with
a solution of an acid sodic molybdate, as this yields a soluble sodic salt,
the solution of which gives with ammonic chloride a yellow crystalline
precipitate of an ammonium salt, which will make a good starting
point for further investigations.

When the eerie fluorine salt, prepared as above with KFoH, is
boiled with 10:4 sodic tungstate, a fine bright yellow solution is
formed which gives a beautiful orange crystalline precipitate with
nitrate of croceo-cobalt. In preparing the fluorine compound it is
best to add a cold filtered solution of KFgH to the basic eerie nitrate
diffused in cold water, and not to heat at all. Ceric hydrate dissolves
with difficulty in solutions of acid tungstates and molybdates, more
easily when precipitated from cold solutions.

Note on Certain Tungstates, and on a new
Phospho-Tungstate.

In other instalments of my work I have endeavored to show f that
there exists a special class of metatungstates, of which the lowest term
has the general formula 4 WO3 . RO, and the highest the general
formula 24 WO, . 11 R^O. This view appeared to be supported both
by my own work and by that of Marignac, but has not found favor

* See my paper in American Journal of Science, XXXVII. 352.
t Proceedings of tlie American Academy, XV. 15.

GIBBS. — COMPLEX INORGANIC ACIDS. 279

with chemists, and has in fact, so far as I am aware, passed wholly
unnoticed. The highest term actually obtained by me * appeared to
have the formula :

16 WO3 . 3 Na^O . 4 (NH4)20 + 18 aq.

The only complete analysis made agreed well with this formula,
and differed very materially from that of the 12 : 5 ammonia-sodic
tungstate. As it has been asserted, however, that the two are iden-
tical, Mr. Charles D. Smith has made in my laboratory four analyses
with portions of the salt which had been preserved. The analyses
are as follows :

0.7226 gram gave 0.6038 gram = 83.55% WO3.

1.1598 grams gave 0.9687 gram = 83.54% WO3.

1.3281 grams gave 1.1091 grams = 83.51% WO3.

1.4740 grams gave 1.2309 grams == 83.50% WO3.

1.2726 grams gave 0.0604 gram (NH4)20 = 4.75%.

1.0901 grams gave 0.0508 gram (NH4)20 = 4.66%.

1.1360 grams gave 0.0532 gram (NH4)20 = 4.67%.

0.6756 gram gave 0.0318 gram (NH4)20 = 4.72%.

4.4687 grams lost on ignition 0.5292 gram = 11.84% NH3 and H2O.

3.0697 grams lost on ignition 0.3638 gram = 11.84% NHgandHgO.

4.6030 grams lost on ignition 0.5444 gram = 11.82% NHgand H2O.

3.3885 grams lost on ignition 0.4014 gram = 11.84% NH3 and HgO.

The analyses correspond to the formula,

24 WO3 . 5 NaaO . 6 (NH4)20 + 27 aq.,

which requires :

Calculated.

Mean.

I.

II.

III.

IV.

24 WO3

5568

83.40

83.52

83.55

83.54

vS3.51

83.50

6 (NH4)20

310

4.68

4.70

4.75

4.66

4.67

4.72

5 Na20

312

4.65

4.65

27H2O

486

7.27

7.13

7.08

7.14

7.16

7.11

6676 100.00

The sodic oxide is determined by difference. The analyses agree
rather more closely with the new formula than with that formerly
given, which I will cite for the sake of comparison:

16 WO3 . 4 (NH4)20 . 3 Na20 + 18 aq.,
requires ;

* Ibid., XVI. 76.

280 PROCEEDINGS OF THE AMERICAN ACADEMY.

Calculated.

Found.

16 WO3

3712

83.77

83.94

4 (NHO2O

208

4.69

4.64

3 NaaO

186

4.20

4.21

I8H26

324

7.32

7.21

4430

100.00

It is certainly difficult to decide between these two formulas, only
it must be observed that the higher formula is derived from the mean
of four analyses, which agree well with each other, and has therefore
the weight of analytical evidence in its favor until further research
shall prove its inaccuracy. Still another formula has been proposed
by Von Knorre,* who writes 12 WO3 . 3 (NH4)2 . 2 Na.O + 13 aq.,
which requires 84.41% WO3, 4.73% (NH4)A 3.76% NaA and 7.10%
HgO. The correspondence between the results of the analyses and
the data required by the formula is much less than with the formula
which I first gave and which Von Knorre rejects, and of course still
less than with the new formula.

New Phospho- Tungstate.

Pure normal sodic tungstate was mixed in solution with sodic ortho-
phosphate, P04Na2H + 12 aq., in the proportion of twelve molecules
of the first to one of the second salt, and chlorhydric acid added in
small excess. A phospho-tungstate crystallized from the solution,
and was redissolved and twice recrystallized. The new salt was in
fine colorless crystals, less soluble than the now well known salt
which has the formula, 24 WO3 . P0O5 . 2 NajO + 27 aq. The salt
was dried on paper for analysis. It effloresced or became opaque in
dry air. Mr. Charles D. Howard obtained the following results on
analysis.

1.4941 grams lost on ignition with WOiNa. 0.1078 gram = 7.21% \\0.
1.4502 grams lost on ignition with WO^Nao 0.1046 gram = 7.21% HgO.
1.0950 grams gave 1.0019 grams WO3 + PA = 91.49%.
1.1950 grams gave 1.0975 grams WO, + PoOj = 91.58%.
1.6782 grams gave 0.0720 gram WO, + PA = 2.74% PA5.

The analyses lead to the formula,

20 WO3 . PA • NasO . 2 II.O + 19 aq.,
which requires:

* Berichte der deutschen chem. Gesellschaft, XIX, 823.

GIBBS. — COMPLEX INORGANIC ACIDS, 281

Calculated.

I II,

20 WO3

4640

88.85

88.75 88.84

P2O5

142

2.73

2.74

Na^O

62

1.18

1.25

21 II2O

378

7.24

7.21 7.21

5222 100.00

The only 20 : 1 phospho-tungstate which I have hitherto described *
contained 6 molecules of base (BaO), and perhaps the new salt
should be written 20 WO3 . P2O5 . Na^O . 5 H2O + 16 aq. With re-
spect to its formation with the propoitions given, I may remark that
1 have in repeated trials failed to obtain the salt

24 WO3 . P2O5 . 2 NaoO + 27 aq.

by mixing sodic tungstate and phosphate in the exact theoretical pro-
portions and adding chlorhydric acid to the mixed solutions. The
quantity of phosphate necessary to be added is much more than one
molecule for twelve molecules of the tungstate. This remark appears
to have been made by other chemists also.

Kehrmann t has recently described phospho-tungstates which come
under the general formula 18 WO3 . P2O5 . 3 RO, the salts being

18 WO3 . P2O5 . 3 K2O + 14 aq., and 18 WO^ . PA • 3 (NHJO -f 14 aq.

He gives to the acid the name " Phospholuteo-wolframsaure " ; but
though there is little doubt that there is here a hitherto undescribed
series, the analyses are not satisfactory.

In another part of this paper I have described three salts of a
phosphotungstic acid which would have the formula,

18 WO3 . P2O5 . 6 H2O,

the salts themselves having respectively the formulas,

18 WO3 , P2O5 . 6 K3O + 23 aq. ; 18 WO. . P2O5 . 6 K^O -F 30 aq. ;

and 18 WO3 . P2O5 . K2O . 5 H.^O + 14 aq.

These salts are however colorless, and if we admit the accuracy of
Kehrmann's formulas, there must be two isomeric series. Kehrmann
appears to have been wholly unacquainted with my work.

Experiments to determine the relations of WS4K2. M0S4K2, and
WS2O2K2, to phosphates and arsenates have not led to definite results,

* Proceedings of the American Academy, XVI. 127, and Am. Chemical
Journal, II. 282.

t Zeitschrift fiir anorganische Chemie, IV. 138, 386.

282 PROCEEDINGS OP THE AMERICAN ACADEMY.

though there seemed to be a relation of some kind. The same state-
ment applies to the various oxyfluorides of molybdenum and tungsten.
In a communication made to the British Association * at the Mont-
real meeting, in 1884, I stated that complex acids existed into which
platinum chloride entered, as, for instance, compounds of the type
2 PtCl.2 . R2O.J. Since then I have made various communications on
the same subject to the Harvard Chemical Club. I regard these com-
pounds as respectively phosphoric, arsenic, and antimonic oxides, in
which 2 PtClg replaces Og. A great amount of work on the subject
has been done, but as it is at least possible that a very different view
of the subject may be taken, I will reserve the results of my work for
another occasion.

Newport, R. I., August 1, 1894.

* Report for 1884, p. 670.
{To he continued.)

WEYSSE. — BLASTODERMIC VESICLE OP SUS SCROPA. 283

XII.

CONTRIBUTIONS FROM THE ZOOLOGICAL LABORATORY OF

THE MUSEUM OF COMPARATIVE ZOOLOGY, UNDER THE

DIRECTION OF E. L. MARK, XLIII.

ON THE BLASTODERMIC VESICLE OF SUS SCROFA

DOMESTICUS.

By A. W. Weysse.

Communicated by E. L. Mark. Receiyed August 10, 1894.

Page

I. Introduction 283

1. Subject 283

2. Material 28i

3. Technique 285

11. Description of the Embryos . . . 287

1. General Characteristics of the
Blastodermic Vesicle . . . 287

2. Detailed Account of Observations

on the Germinal Disk . . . 289

1st Stage, Figs. 7-9, Plate II. . . 289
2d Stage, Fig. 1, Plate I. ; Fig. 10,

Plate II 292

3d Stage, Fig. 2, Plate I. ; Figs.

21 and 26, Plate IV 293

Page

4th Stage, Figs. 3-5, Plate I. ; Figs.
11-13, Plate II. ; Figs. 14-19, Plate
111. ; Fig. 20, Plate IV. ... 294
5th Stage, Fig. 6, Plate I. ; Figs.

22-25, Plate IV 299

3. Summary of Observations . . . 300
lit. Historical and Theoretical .... 303

1. Consideration of Observations on
the Blastodermic Vesicle in Gen-
eral 303

2. Interpretation of the Bridge . 311

3. Summary 315

Literature cited 317

Explanation of Plates 321

L Introduction.
1. Subject.

In the latter part of the summer of 1893 the opportunity was opened
to me of obtaining young embryos of Sus scrofa domesticus. So I let
the work rest which I had in hand on the development of some other
mammals and began investigations on this. I was fortunate enough
to secure a number of embryos several days younger than the youngest
of the six, from fourteen to fifteen days old, which Keibel ('93) has
recently described so elaborately ; and since these present phenomena
of development unusual in the ontogeny of the Mammalia, it has seemed
best to record them, in the hope that they may possibly lead to similar
discoveries in allied forms.

The incompleteness of our knowledge of the early stages in the
■embryology of the higher viviparous animals is due largely, of course,

284 PROCEEDINGS OF THE AMERICAN ACADEMY.

to the difficulty of securing sufficient material in successive stages of
growth, and there is the further difficulty that it is impossible to deter-
mine iu the great majoiity of cases the exact age of the embryos, since
spermatozoa may remain for several hours, days, or even months, within
the body of the female before fertilization takes place. And further,
it has long been known that, especially during the earlier phases of de-
velopment, ova which were apparently fertilized at the same time grow
at very different rates, so that within one uterus we may find embryos
illustrating several stages of ontogeny. For these reasons I cannot
give exact ages for the embryos 1 am about to describe, though in
almost every case I can give the period which has elapsed between
coitus and the time when the sows were killed and the embryos
obtained.

2. Material.

The present paper is based on the results obtained by the study of
thirty embryos taken from four sows. In all I had nine sows served
at different times, and these were killed at from nine to eleven days
after coitus. Only three of the nine proved to be pregnant at the
time they were killed, and of these three, two were killed ten days
and the other eleven days after copulation. P^ach of the two sows
killed on the tenth day contained eleven embryos in varying stages of
development, though all the embryos in one were much less advanced
than those in the other, as I conclude from the difference in the size
both of the embryos and of the cells of which they are composed, and
from the difference in the size and structure of the germinal disks.
The third sow, killed on the eleventh day, contained only four em-
bryos, two of which were as old as the oldest of those from the first
two sows ; the other two were younger. The remaining four embryos
of the thirty were found in a sow which had been served before coming
under my control, and were apparently in about the same stage onto-
genetically as some of the older embryos in the first two cases men-
tioned above. The uterus in which these last embryos lay, contained
six in all, but two were so badly folded as to be unavailable as far as
the study of the germinal disk was concerned. These embryos were
obtained by opening a large number of apparently empty uteri ; in this
way 1 have found about 3% of the individuals examined pregnant, but
all of the embryos with the exception of the six just mentioned were
in a much more advanced stage of devolopment, so that they afford no
information on the subject matter of the present article, and I shall
reserve the consideration of them for a future paper.

WEYSSE. — BLASTODERMIC VESICLE OP SUS SCROFA. 285

3. Technique.

In the case of the first uteri which I opened, I followed with some
variations one of the methodo which Keibcl ('93) has described in his
work on the pig. When the uterus had been removed from the animal,
it was cut open along the side opposite the mesometrium and placed
in a flat-bottomed glass dish containing Kleinenberg's picro-sulphuric
mixture and resting on a black tile. Then, by carefully spreading out
the complicated folds of the inner wall of the uterus and gently agitating
them, the embryos readily floated out into the fluid, and could be dis-
tinguished at once against the black surfi^co of the tile. They were
then carefully removed on a spatula to a smaller vessel of the picro-
sulphuric mixture, where they remained several hours and were then
transferred to 70% alcohol, and after twelve or fourteen hours to 90%
alcohol, which was gently warmed and changed several times until all
trace of the acid had been washed out. But this method had some
minor disadvantages which seemed avoidable ; the action of the acid
mixture on the instruments used, and the staining of the hands, were
at least undesirable, and to be avoided unless absolutely necessary.
Accordingly, in my later work, instead of using Kleinenberg's mixture
as a medium for floating out the embryos from the uterus, I employed
normal salt solution (0.75% NaCl in water), at a temperature of about
40° C. Keibel ('93) says that he did not use this because it is said to
injure the embryos, and Bonnet ('84) found that, if embryos lay a long
time in this solution, they became swollen. This is doubtless true, if
they remain in the fluid as long as is necessary to detach such com-
plicated embryos as Keibel worked with, some of which were more
than a meter long and greatly folded amongst the plications of the
uterine wall. The same may be true for the embryos of the sheep, —
upon which Bonnet worked, — which at a corresponding stage of de-
velopment closely resemble those of the pig, hut in the case of such small
embryos as those which I have been concerned with the very short
time during which it is necessary for them to remain in the salt solu-
tion has absolutely no effect either on the general form of the embryo or
on the histological conditions, as my sections clearly demonstrate. As
soon as the embryos were floated out from the uterus, they were at
once transferred as before to Kleinenberg's picro-sulphuric mixture.
All the embryos which I have studied have been fixed in this fluid.
Had my supply of material been larger, I should have employed
several other fixing reagents, but my work on young embryos of other
mammals, as well as the results of the experiments of other embry-

286 PROCEEDINGS OF THE AMERICAN ACADEMY.

ologists, gave me complete confidence in the reliability of this reagent
for the material in hand. The results in this case wei-e in the highest
degree satisfactory.

After the specimens had been entirely freed from acid, drawings of
them as opaque objects seen against a black background were made
with the aid of an Abbe camera lucida ; they were then returned
to 70% alcohol, and from this transferred to Kleineubers's alcoholic
hcEmatoxylin (70%) diluted with twice its volume of his solution ot
calcium chloride and alum. Here they remained for a few hours, the
time varying according to the size of the embryos, and were then
transferred to a 0.1% solution of hydrochloric acid in 70% alcohol,
the process of decolorizing being carefully watched under the micro-
scope until the object had attained the proper color. It was then
placed in 70% alcohol containing a slight trace of ammonia, which
made the stain permanent by neutralizing the acid. I have found that
washing simply in neutral alcohol, though it be never so carefully done,
will not always prevent an ultimate fading of this stain ; the addition
of ammonia is an absolute essential if one wishes to be perfectly sure
that the sections will not fade. Objects which I have treated thus have
always preserved their color. In my work on the pig I have not as
yet used carmine stains. On the embryos of both the rat and the
mouse I have obtained very brilliant results, both with borax carmine
and with hydrochloric carmine, but, so far as I could see, they had no
advantage over ha3matoxylin. The last is valuable because of its
high alcoholic grade, and because, when properly decolorized, it be-
comes a most highly differential stain for these embryonic tissues.
Small semi-transparent objects, like the embryos of the pig at this
stage of development, can readily be decolorized in toto, for the extent
of the decolorizing can be determined by the aid of the microscope ;
but opaque objects, like the uterus of the mouse, have to be decolorized
largely after sectioning.

When the embryos had been stained and decolorized, they were
cleared in chloroform, embedded in paraffine, and cut on the Minot-
Zimmerman microtome into sections 10^ thick. They were then
spread on the surface of distilled water, which rested on a thin film of
albumen affixative covering the slide. The slide was gently warmed
in an alcohol flame, until the sections became perfectly smooth.
Finally the water was removed, the paraffine dissolved out in xylol,
and the sections mounted in Canada balsam.

I have given this rather extended account of my technique in order
to show that there has been no lack of care in this direction which

WEYSSE. BLASTODERMIC VESICLE OP SUS SCROPA. 287

could affect the histological coudition of my specimens. I will now
give a description of the embryos themselves, and then proceed to a
consideration of the investigations of other authors, and to the theo-
retical interpretation of the phenomena described.

II. Description of the Embryos.
1. General Oharacteristics of the Blastodermic Vesicle.

The embryos are all in more or less advanced stages of the so-called
blastodermic vesicle or didermic blastocyst, as it has been described
by Balfour ('81), Van Beneden ('80), Hubrecht ('90), Bonnet ('91),
and others. They consist in general of at least two well defined
layers, — an outer of more or less isodiametric cells, and an inner, in
contact with the outer, of greatly flattened cells, which are very much
larger than thos3 of the outer layer. There is no trace of cells lying
between these two layers at any point. At one region of the embryo,
the outer layer of cells is thickened, forming the germinal disk. For
the sake of convenience this region may be spoken of as the germinal
or embryonic area, and the rest of the vesicle as the extra-germinal or
extra-embryonic region. In most cases there is evidence of a third
layer of cells, which is outside the two layers just mentioned, and is in
a more or less disintegrated condition. I shall later refer to this more
at length.

It has not seemed to me necessary to give figures of the whole
blastocyst. In each case it consists of a hollow vesicle with a double
wall, which if fully distended would be about spherical. I have never
found the vesicles completely distended, and often they are greatly
folded, so that it is not always possible to make sections in just the
plane one wishes ; for if the germinal disk lies on the edge of a fold, it
is usually necessary to cut at right angles to the fold in order to avoid
getting sections oblique to the surface of the disk. Something of an
idea of the general appearance of the vesicle can be gained from Bon-
net's ('84, Taf. IX. Fig. 2) figure of a sheep embryo of the thirteenth
day, which has the same general characters as the pig embryos which
I have studied.

The germinal disk of this stage can be detected by the naked eye,
even before staining, as a very small opaque white spot on the surface
of the vesicle. The smallest vesicle which I have examined is about
1 mm. in diameter, while the largest is about 4.5 mm. In the latter
there is no trace whatever of the beginning of the excessive elongation

288 PROCEEDINGS OP THE AMERICAN ACADEMY.

which takes place before the fourteenth day, and has been well figured
by Keibel ('93) ; this growth undoubtedly takes place very rapidly,
for Bonnet ('91) has estimated that in the sheep, where a similar
though less extensive growth occurs, the embryo must elongate at the
rate of more than 1 cm. per hour, and that in the pig the growth is
still more rapid. The germinal disk varies in size from 0.1 mm. in
the smallest to 0.265 mm. in the largest embryo here considered.

In describing the embryos more at length 1 shall speak of the layer
of nearly isodiametric cells as the ectoderm, and of the inner layer of
flattened cells as the entoderm ; the relation of these to the outer dis-
integrating layer, which with Rauber ('75) is best designated as the
" Deckschicht," I shall discuss later. The two prominent layers
(ectoderm and entoderm) are distinguished from each other not only
by the shape of their component cells, but also by the shape of their
nuclei, and by the chromatic reaction of their protoplasm. The nu-
clei of the extra-germinal region of the ectoderm are nearly always
perfectly spherical ; those of the germinal disk, especially in later
stages of development, are more often slightly elongated or ellipsoid,
with the longest axis at right angles to the surface of the disk ;
there are significant exceptions to this last rule which will be con-
sidered later. The entodermal nuclei in the extra-germinal region
are generally flattened parallel to the surface of the embryonic vesicle ;
those in the region of the disk also have this shape in the younger
embryos, but in the older stages they are spherical, and the cells
in which they lie are essentially isodiametric. Furthermore, when
properly decolorized the hgematoxylin gives three distinct shades of
blue to the embryonic cytoplasm. The extra-germinal ectoderm is
stained a lip-ht blue, the ectoderm of the germinal disk is sharply
marked off from this by a deeper shade, and the cytoplasm of the ento-
dermal cells stains uniformly a still deeper blue. This diiferentiation
in color, which is often of very great value, does not appear before the
embryo is decolorized, and it disappears if the process of decolorizing
is carried too far, for in that case the whole vesicle becomes a uniform
light blue. In almost every instance, these three shades of blue are
manifest in my preparations. The chromatic substance of the nucleus
stains deeply throughout the vesicle, both in resting nuclei and in those
undergoing karyokinetic changes. In the latter, when cut at the
proper angle, the nuclear spindle and the protoplasmic radiations
around the centrosomes can be clearly seen. It should further be
noted, that this stain brings out the cell walls with great distinctness,
especially in the ectoderm. In the entoderm the cells are extremely

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROFA. 289

attenuated at their regions of contact, appearing spindle-shaped in
section, the nucleus occupying the swollen portion, so that the dividing
walls are apparent in the region of the germinal disk only, where the
axes of the cell are nearly equal. In my oldest embryos there is no
sio-n of the formation of mesoderm, or of the medullary groove. With
this description of the embryonic vesicle in general, I now proceed to
the consideration of the more detailed structure of several embryos
which I have selected for illustration here. I have chosen these because
they show in a typical manner the phenomena which all present, and
with drawings from them I can explain intelligibly any variations from
the type.

2. Detailed Account of Observations on the Germinal Dish
First Stage. (Plate II Figs. 7, 8, and 9.)

The first embryo which I shall describe is represented by drawings
(Plate II. Figs. 7, 8, and 9) of three sections of the germinal disk.
This embryo was taken from a sow killed ten days after coitus, which
contained eleven embryos. The embryo in question was with one
exception the smallest found, but it should be noted here that the ratio
between the size of the embryo and that of the germinal disk is not
constant for different embryos ; and furthermore, that the ratio of the
size of the disk to its degree of development varies; e. g. Figs. 11, 12,
and 13, Plate II., were drawn from an embryo much larger than that
from which Figs. 7, 8, and 9 were made ; the two embryos came
from the same uterus, and yet the former disk is slightly smaller
than the latter ; on the other hand, it represents a much later stage of
development, as I shall show hereafter, and this fact is doubtless suffi-
cient to account for the difference, in size. The whole vesicle from
which Figs. 7, 8, and 9 were drawn measured about 1.25 mm. in
diameter. As I have already said, the vesicles are flattened out and
greatly wrinkled, so that such measurements are at best approximate
only, though they serve to give a general idea of the relative sizes
of the embryos. The germinal disk, which lies on a part of the vesicle
that is not folded, is slightly elliptical in outline, the chief and trans-
verse axes being about 0.11 mm. and 0.167 mm. long respectively;
the sections were made nearly at right angles to the shorter axis,
which, as I think I can show later, represents the chief axis of the
future embryo.

The ectoderm consists of the characteristic large cells with spherical
nuclei already described. The entodermal cells form a complete layer
VOL, XXX. (n. s. xxii.) 19

290 PROCEEDINGS OF THE AMERICAN ACADEMY.

on the inner surface of the ectodermal layer, and are more numerous in
the region of the germinal disk than in tlie extra-germinal area, but they
everywhere retain their elongated flattened outline. Tlie germinal disk
was cut into ten sections, of which Figs. 7 and 8 represent respectively
the second and third, and Fig. 9, the sixth. According to my method
of orientation the two former are at the posterior end of the future
embryo, the latter nearer the anterior end. It will be seen from the
figures that the ectodermal cells of the germinal disk are slightly elon-
gated in a direction at right angles to the surface of the disk, and
show a tendency to arrange themselves in two interlocking layers. At
the margin of the disk the transition from disk ectoderm to extra-
germinal ectoderm is abrupt, but the general characteristics of the
cells in the two regions is such as to suggest an identity of origin at
least, — the differences being merely the slight variation in the chro-
matic affinity of the cytoplasm, which I have already mentioned, and
the change in shape, which would necessarily attend a difference in
cell arrangement. The exposed surface of the disk is pretty uniformly
even, except at one very significant point. Two sections through this
point are shown in Figs. 7 and 8, Plate II., where in the centre of
each section a cell is seen to project above the general level of the
disk, and in Fig. 8 to be slightly cut off from it. The same appear-
ance is present in the two sections which intervene between Fig. 8 and
Fig. 9, and the whole projection running through the four sections
contains three cells, which are without any question true ectodermal
cells of the germinal disk, which have assumed this new position.
These cells represent a very early stage in the development of a
structure which I shall later designate as the bridge, and for that
reason 1 shall call these bridge cells. It should be noted here that
there is no evidence whatever of a third layer of cells, i. e. a " Deck-
schicht," outside the ectoderm in the region of the germinal disk,
though in the extra-germinal region there are a few widely separated
cells attached to the outer surftice of the ectoderm ; these differ from
the ectodermal cells in having very small nuclei ; they resemble the
cells of the entoderm in general outline. By an enumeration of the
nuclei I have ascertained approximately the number of cells in the
area of the germinal disk, which is as follows : cells in the ectoderm
proper, 188; in the entoderm, 48; in the bridge, 3. The presence
and position of this bridge supply the criterion on which I have deter-
mined the chief axis and its poles for the future embryo. It should be
further noted here, that in the two sections immediately succeeding
Fig. 9, i. e. sections seven and eight of the series through the disk,

WEYSSE. — BLASTODERMIC VESICLE OP SUS SCROFA. 291

there is a slight elevation of the ectodermal cells at the margin of the
disk on either side. The significance of this fact will appear in my
further description of the bridge. Moreover, in sections seven, eight,
and nine of the disk there is a distinct groove or furrow in the upper
surface of the ectoderm ; this runs along the median line, and is there-
fore in a line continuous with that of the bridge cells described above.
And now a word as to similar stages in embryos which I have not
figured here.

The ten other embryos which came from the same uterus as the one
I have just described vary in size from 1 mm. to 1.9 mm. in diameter,
and represent very diverse stages of development. Only two of these
are in about the same stage as the one mentioned above, the others
being clearly much more advanced, and of these two I consider one
further developed than the other, since it has many more bridge cells
on the disk. The younger embryo measured 1.4 mm. in diameter,
while its germinal disk was 0.11 mm. in diameter and very nearly
circular in outline. An enumeration of the nuclei shows approxi-
mately 117 cells in the ectoderm proper, 33 in the entoderm, and 6
in the bridge. It is somewhat difficult to determine with absolute cer-
tainty the number of cells in the bridge in this case, for some cells are
just in process of passing over from the true ectoderm of the disk to
the bridge ; the direction of the spindle in the karyokinetic figures
makes this point indisputable. The mass of bridge cells appears, as in
the specimen already described, nearer one margin of the germinal disk,
and for that reason I term the margin near the bridge cells the
posterior end of the embryo. Anterior to this point there is the same
lateral or marginal uprising which I mentioned in the first case. The
entoderm consists of greatly flattened cells with widely separated
nuclei, but so far as I can determine they are all connected by delicate
protoplasmic masses, which often appear like a thin membrane lying
across the rounded inner boundaries of the ectodermal cells. One may
therefore pass through several sections without finding an entodermal
nucleus on a certain area of the embryonic vesicle, but I should not
feel justified in assuming that the entoderm fails to cover any portion
of the interior surface of the ectoderm of this vesicle.

The second embryo to which I referred in connection with this was
but 1 mm. in diameter, and therefore the smallest in my collection.
The germinal disk is, however, clearly in a more advanced stage of
development, for the reason which I have already given, and the vesicle
also has a larger number of entodermal cells, so that there can be no
doubt in this case that they form a complete layer on the inside of the

292 PROCEEDINGS OF THE AMERICAN ACADEMY.

ectoderm. On the outside of the vesicle are a very few " Deckschicht"
cells. Beyond these facts the embryo presents no characteristic differ-
ences from the embryos already described.

Second Stage. (Plate I. Fig. 1 ; Plate II. Fig. 10.)

I will now take up a stage which shows a distinct advance in the
development of the embryo. Fig. 1, Plate I., shows the portion of
the blastodermic vesicle containing the germinal disk. This embryo
came from the uterus of the sow which was served before coming under
my control, so that I do not know the time which elapsed between
coitus and the killing of the animal. The stage of development, how-
ever, clearly places it at this point in my series. The whole vesicle,
which was somewhat wrinkled, was about 2.65 mm. in diameter, while
the germinal disk measured 0.205 mm. in its longest axis and 0.18 mm.
in its transverse axis, thus having an elliptical or slightly ovate outline,
which is shown in the figure. The drawing (Fig. 1) was made from
the whole object before staining, and is represented as seen by reflected
light against a black background. In sections the entoderm shows the
characteristic spindle-shaped cells in the extra-germinal region, while
in the area covered by the germinal disk it consists of cells lying closely
together and showing sharply defined cell boundaries. On the outside
of the blastodermic vesicle are a large number of " Deckschicht " nuclei
in the extra-germinal region, all with little chromatic substance and
with ill defined cell boundaries. But it is the ectoderm of the germinal
disk which presents the most interesting phenomena in this embryo.
Fig. 10, Plate II., shows a median longitudinal section through the
disk shown in Fig. 1, Plate I. Here the general surface of the disk is
seen to be somewhat depressed, thus leaving a raised margin, while at
one pole of the longest axis there is a large upgrowth or overgrowth
of ectodermal cells forming the bridge to which I have already re-
ferred. The beginning of the formation of this overgrowth is at what
I hope to establish as the posterior end of the germinal disk. The
bridge consists at this stage of practicalfy two layers of cells, which
are essentially the same in structure as the remaining ectodermal cells
of the germinal disk. Clearly this overgrowth is only a later stage in
the growth of the structure which was seen in its first stage of develop-
ipent in Figs. 7 and 8, Plate II., and the raised lateral margins seen
here I hold to be comparable with the raised margins described in the
previous embryos, while the depressed area seems to be due to a
broadening of the median groove of the vesicle, described in detail
above. It may be noted here that the germinal d;.sk is unusually

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROFA. 293

large for a bridge which has developed to so small an extent, and
furthermore the bridge is more widely separated from the underlying
ectoderm than it is in many embryos of this stage.

Third Stage. (Plate I. Fig. 2 , Plate IV. Figs. 21 and 26 )

In Fig. 2, Plate I., is shown a surface view of a germinal disk from
an embryo taken from still another sow, which was killed ten days
after copulation. The blastodermic vesicle was almost completely
distended, there being but one marked fold, and measured 1.95 mm.
in diameter. The germinal disk was about 0.15 mm. in diameter
and circular in outline. It was cut into fourteen sections ; these were
all drawn with the aid of the camera lucida to an enlargement of 275
diameters, and from these drawings a reconstruction of the surface
was made and then reduced to an enlargement of 100 diameters, as it
appears in P^ig. 2. A reconstruction in wax was also made as a surer
means of control to guard against any error in the graphic reconstruc-
tion. Two sections of this embryo are shown on Plate IV., Figs. 21
and 26, made through the region of the germinal disk and the extra-
germinal area respectively. The sections are oblique to the antero-
posterior axis of the disk, cutting it at an angle of about 45°, and run-
ning on the reconstruction drawing from the lower right-hand corner
to the upper left, Fig. 2, Plate I. Of the fourteen sections into which
the disk was cut. Fig. 21, Plate IV., represents the seventh, and
passes through the deeper portion of the depression which lies just
beneath the central point of the free margin of the bridge, as seen in
Fig. 2. In this specimen the two lateral elevations mentioned in the
embryos already described are seen to have increased in size until
they have come into contact with the posterior overgrowth, with which
they have fused at two points, thus giving the bridge three points of
attachment to the ectoderm proper and leaving three openings from
the depression or cavity beneath it to the outside. This bridge, then,
has manifestly three points of origin, one posterior and two lateral.
Further evidence in corroboration of a similar method of formation
will appear in the course of the description of the other embryos.

Before leaving the ectoderm of the germinal disk, it should be added
that it is relatively very thick in all these younger embryos, consisting
of two or even three interlocking layers of cells, m addition to the
bridge cells, which are usually two layers deep. This great thickening
of the ectoderm of the germinal disk is not, however, the earliest con-
dition ontogeneiically, for in younger stages of development, as, for
example, those represented by Figs. 7-10, Plate II., it is much thinner

294 PROCEEDINGS OF THE AMERICAN ACADEMY.

than in either the stage under discussion or that represented by the
figures on Plate III.

The cells of the entoderm are essentially the same in structure in
the region of the germinal disk as they were over the same area in the
embryo represented in Fig. 1, Plate I., and Fig. 10, Plate II.; but
there is a further thickening or increase in number of the entodermal
cells immediately surrounding the germinal disk, and extending on all
sides of it for a distance about equal to the diameter of the disk itself,
so that the diameter of the entodermal thickening is at this stage about
three times the diameter of the germinal disk. The normal distribu-
tion of the entodermal nuclei in the remainder of the extra-germinal
area can be seen from Fig. 26, Plate IV. A possible explanation as
to the significance of this thickening of the entoderm has occurred to
me, which I will mention in the theoretical considerations concerning
the interpretation of the vesicle.

Fourth Stage. (Plate I. Figs 3-5, Plate II Figs 11-13; Plate III.
Figs 14-19 ; Plate IV. Fig. 20.)

The next two embryos in the series are shown in Figs. 3 and 4,
Plate I. I have given no sections of these, as the surface views show
the more important characteristics, and because they are essentially the
same as sections of other embryos which I have figured farther on.
Fig. 3 shows that the bridge has a nearly circular margin bordering
the opening into the cavity beneath. There is no evidence on the sur-
face of the germinal disk or in the sections — which are taken at right
angles to the longer (i. e. transverse) axis — as to whether the bridge
arose at three points, as mentioned above, and then became one by a
fusion of the three parts, or whether it arose as one continuous over-
growth from the margins towards the centre of the disk. The vesicle
to which this germinal disk belongs was 2.25 mm. in diameter and very
little folded. The disk itself measured 0.19 mm. in its longer axis and
0.15 in its shorter or antero-posterior axis. It will be observed that
tlie elliptical outline of the germinal disk is the same with regard to
the chief axis of the future embryo, as in the case of the first embryo
described.

Figure 4 represents a disk which is a little older than that shown in
Fig. 3. The bridge covers a larger portion of the germinal disk than
in the preceding case, and if we assume that the disk had at first the
shape shown in Fig. 3, it has begun to elongate in the direction of its
chief axis, until it is now nearly circular in outline. The right-hand
side of the figure shows a lateral opening into the cavity beneath the

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROPA. 295

bridge, where the lateral overgrowth has not as yet entirely fused with
the overgrowth from the posterior end to form a continuous bridge
such as exists in Fig. 3. The left-hand side, however, is complete,
exactly as in Fig. 3. This germiual disk might be considered as illus-
tratinor a stajre intermediate between Figs. 2 and 3, so far as the
fusion of the various parts of the bridge is concerned ; it is, however,
clearly more advanced, not alone on account of the greater size of the
germinal disk, — for this may vary greatly, as we have already seen,
— but because of the greater extent and degree of development of
the bridge. The embryonic vesicle in this case was only slightly
folded, nearly circular in outline, and about 2.75 mm. in diameter;
the germinal disk measured 0.2 mm. in diameter.

Figures 11, 12, and 13, Plate II., represent sections through a
germinal disk in which the bridge has reached about the same stage of
development as in the two cases last described. The embryo from
which these three sections were taken came from the same uterus as
that of Figs. 7, 8, and 9, and the sow was killed therefore on the tenth
day after coitus. This vesicle measured about 1.-55 mm. in diameter,
while the disk, which was slightly elliptical, measured 0.145 mm. in
its longer axis (the sections shown in Figs. 11, 12, and 13 are parallel
to this axis), and 0.11 mm. in its shorter axis. This shows, then, a
still greater elongation than the preceding germinal disk in the direc-
tion of the chief axis of the future embryo. The disk was cut into
eleven sections, of which Fig. 11 represents the fifth; it is, therefore,
a little to one side of the median plane. This section shows well a
phenomenon which is present in all sections of bridges that have devel-
oped to some extent, and seems to point to a double origin of this
structure. It will be noticed that the extra-germinal ectoderm appears
to extend as a continuous layer over the right-hand portion of the disk
and to constitute the upper layer of bridge cells, while the lower layer
is clearly derived from the true ectoderm of the germinal disk itself, as
we can see from the position of the nuclei at the region of contact of
the bridge with the underlying ectoderm. It should be observed,
however, that this apparent extension of the extra-germinal ectoderm
over the ectoderm of the germinal disk occurs in the region of the
bridge only. The whole appearance suggests an upfolding of the mar-
gin of the disk, which carries both the extra-germinal and the germi-
nal ectoderm with it. Figs. 12 and 13 represent the eighth and ninth
sections respectively through the same disk. Fig. 12 is a section at
the extreme lateral margin of the opening of the bridge, the cavity
beneath it appearing as a somewhat triangular space in the section.

296 PEOCEEDINGS OP THE AMERICAN ACADEMY.

Fig. 13 lies beyond the region of the cavity, and the bridge is here in
contact with the underlying ectoderm.

I am so fortunate as to have another embryo from the same uterus
from which this came, which is in almost precisely the same stage of
development, and is cut very nearly at right angles to the chief axis of
the germinal disk. This gives a series of sections transverse to those
which I have just described. The general relation of the overgrowth,
or bridge, to the underlying ectoderm will be plain, if I describe
briefly two or three of the sections. Beginning with the second sec-
tion in the series, which lies at what I term the posterior end of the
embryo, a condition is found which is very like that represented in
Fig. 13, Plate II,, consisting of a layer of true, somewhat columnar
ectodermal cells, with the long axis perpendicular to the surface of the
disk, and overlaid by a layer of bridge cells, slightly elongated in a
direction parallel to the surface of the disk. The next section anterior
to this shows the bridge passing across the germinal disk from one
side to the other, and separated from it in the central region by a cavity ;
the structure here resembles an arch spanning the disk from side td
side. Taking next a still more anterior section, the bridge is repre-
sented by an upfolded region at either side of the germinal disk,
overhanging the true ectoderm, and presenting very much the appear-
ance that Fig. 10, Plate II., would present if there were also an
upfolding at the right-hand side of the drawing similar to that at the
left. The succeeding sections simply show these lateral upfoldings
diminishing in size until they disappear near the anterior margin of
the germinal disk. Thus this series of sections, together with the series
described just before it, gives the basis for a very complete conception
of the bridge as it appears at this stage.

Returning now to the figures, we find a condition somewhat more
advanced than the preceding, represented by Fig. 5, Plate I. The
vesicle from which this germinal disk came was taken from the ute-
rus on the eleventh day after coitus, together with three others, which
were all manifestly older. The vesicle was somewhat wrinkled, and
measured 3.4 mm. in its longest diameter. Tlie disk lay near one
margin in an unwrinkled area, and was ovate in outline, the long axis
being 0.23 mm. and the greatest transverse axis 0.2 mm. in length.
At the broad or anterior end the crescent-shaped free margin of the
bridge appears sharply marked off from the underlying ectoderm by a
cavity which extends to within a short distance of the margin of the
disk on all sides except at the anterior end, where the bridge is wanting.
At this point the ectoderm is slightly thicker than in the region beneath

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROFA. 297

the bridge, and this thickening appears on the surface as a slight ele-
vation, which I have tried to show by the shading in the drawing.
This germinal disk illustrates the form and structure of the bridge so
clearly and so typically, and represents almost, if not quite, its maxi-
mum development as a free and independent structure, that I have
thought best to illustrate it more fully by sections than I have done in
the case of the preceding embryos.

The sections were made in a direction very nearly parallel to the
long axis of the germinal disk, which at this stage corresponds to
the anterp-posterior axis of the embryo. The disk was divided into fif-
teen sections, and of these, Figs. 14-19, Plate III., and Fig. 20, Plate
IV., represent respectively the first, second, fourth, sixth, seventh,
eighth, and ninth ; the sections beyond these simply present the same
phenomena in reversed order. Little need be said in explanation of
the first two sections. Figs. 14 and 15, Plate III. Figure 14 is taken at
the extreme lateral margin of the disk and is consequently nearer the
anterior than the posterior end, because of the ovate outline of the disk.
The section immediately preceding this consisted merely of a layer of
typical ectodermal cells on the outside with a layer of characteristic
entodermal cells a short distance beneath. Figs. 14 and 15 show the
great rapidity with which the ectoderm increases in thickness in
passing from the lateral margin of the disk towards its centre. The
third section in the series has not been represented here, since it shows
no new features beyond those represented in Fig. 15, except ah ex-
tension of the ectodermal cells in a posterior direction. The next
section is represented by Fig. 16, in which occurs the first appear-
ance of the cavity which marks off the bridge from the rest of the
germinal disk. The bridge itself consists of several irregular layers of
cells, the outei'most of which is made up of cells considerably flattened
in the plane of the germinal disk. As to the general characteristics of
the disk in section, it should be noted that the anterior (in the figure,
the right-hand) end is thicker and more rounded than the posterior,
which is rather attenuated. It will also be seen that the lower or inner
boundary of the ectodermal cells of the disk is marked by a relatively
sharp line due to the presence of a very delicate membrane. At
the margin of the germinal ectoderm, — where, between the extra-
embryonic ectoderm and entoderm, a space (triangular in section)
occurs which completely surrounds the disk, — this membrane loses
its connection with the ectoderm of the germinal disk and stretches
across the space to meet the extra-embryonic portion of the outer layer
at some distance from the margin of the disk. The whole entoderm is

298 PROCEEDINGS OF THE AMERICAN ACADEMY.

normally in close contact with the ectoderm, but in the region of this
membrane it seems to be more loosely attached than elsewhere, or else
the cells are less resistant, for we often find that here they are some-
what torn away, as though by some mechanical injury, possibly due to
the effect of the fixing or the hardening reagents, which necessarily
produce a slight shrinking of the vesicle. This membrane will be
more fully discussed farther on.

I have not introduced the figure of the next section in the series,
since it merely shows a condition intermediate between the preceding
and following sections. Fig. 17 passes near the lateral margin of
the free edge of the bridge, and shows that the cavity beneath the
bridge extends much farther towards the posterior end of the germinal
disk, and also that the bridge itself is thinner just at this point than in
the preceding and the succeeding sections. By comparing this with
both Figs. 18 and 19, it will be readily seen that this diminution in
thickness results in a ring or crescent very near the inner margin of
the under side of the bridge, which in Fig. 17 is cut nearly longitu-
dinally, and in Figs. 18 and 19 transversely near the posterior point
of attachment of the bridge to the underlying ectoderm. Fig. 18
shows the first section which passes through the free anterior margin
of the bridge.

Figures 19 and 20 may best be considered together. Fig. 19 repre-
sents the section which lies in the median plane of the embryo, and con-
sequently here the free edge of the bridge is farthest removed from the
anterior end of the disk. In Fig. 20, Plate IV. the free margin of the
bridge has begun to advance towards the anterior end of the disk again.
The phenomenon of greatest significance in these sections, however, is
found at the point where the bridge comes in contact with the ectoderm
of the germinal disk near the posterior pole of the chief axis. In Fig.
19 it will be noticed that the cavity beneath the bridge appears to
extend between the cells posteriorly as a narrow opening for a short
distance. In Fig. 20 we find a continuous canal passing from the
cavity beneath the bridge into the space between the ectoderm and the
entoderm of the extra-germinal area just at the margin of the germinal
disk. This canal appears to arise in the median plane of the embryo,
and to pass between the ectodermal cells into the cavity just mentioned
in a direction slightly oblique to that plane. At least that must be the
conclusion, provided the sections are exactly parallel to the median
plane of the disk; but if the sections were only very slightly oblique,
they would make a canal as small as this appear to have an oblique
direction, even though it were actually parallel to the chief axis of the

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROFA. 299

embryo. This phenomenon is not confined to this embryo. A pre-
cisely similar canal can be traced in the embryo figured ou Plate I.
Fio-. 3, and in two or three other cases there are suggestions of a
similar condition, but not sufficiently well marked for me to put much
stress upon them. It will be readily seen that unless the section
should pass in exactly the right direction, i. e. very nearly through the
lono- axis of the canal, it would be impossible to establish its presence
except in extremely thin sections. Its occurrence in Fig. 20 is be-
yond question ; I shall discuss its possible morphological significance
later.

The fact that the free surface of the germinal ectoderm shows no
trace of cells resembling the ectoderm of the extra-germinal area, such
as are present on the upper surface of the bridge, may be mentioned
here again in passing.

Fifth Stage. (Plate I. Fig. 6 ; Plate IV. Figs. 22-25.)

"We now come to the last stage in the history of the bridge. This
can best be shown in two phases, the first of which is represented by
Figs. 22 and 23, Plate IV. These are from sections of an embryo
taken from the same uterus as that represented by Fig. 2, Plate I.
The blastodermic vesicle was small in comparison with the size of the
germinal disk, being but 3.1 mm. in diameter, while the disk, which
was ovate in outline, measured about 0.3 mm. in its long diameter, and
in its greatest width 0.29 mm. It was cut into thirty sections in a
direction nearly perpendicular to the long (chief) axis. Fig. 22
represents the thirteenth section in the series, which begins at the
narrower or posterior end, and Fig. 23 represents the seventeenth,
which is therefore somewhat more anterior. Fig. 22 shows that the
germinal disk consists of cells whose nuclei lie at varying distances
from the surfoce of the disk, and that it has a rather broad median region
pretty clearly marked off from a marginal region on either side, by the
fact that it contains more nuclei, and also because the general surface
of the median region is here slightly elevated above the lateral portions
of the disk. This median elevation is more or less marked in the sec-
tions which precede this in the series, maintaining about the same
relative extent. In the succeeding sections, however, it is no longer
marked, so that the surface of the ectoderm is pretty uniformly flat.
At the same time there is to be noticed at the margin a layer of cells
cut off from the underlying ectoderm by a narrow cavity. This occurs
on each side of the disk, but owing to the obliquity of the sections it
appears in Fig. 23 at the left-hand side only, while it is seen at the

300 PROCEEDINGS OF THE AMERICAN ACADEMY.

right as well in the sections immediately following. The stage of de-
velopment represented by these sections can, I think, be readily shown
to be only a more advanced condition of the phenomena presented by
the germinal disk of Fig. 5. The change is brought about by a simple
obliteration of the cavity between the disk and the bridge, produced by
the siukins down of the bridge until it comes in contact with the sur-
face of the disk, with which it fuses. The cavity which appears at the
left in Fig. 23, and on the right in succeeding sections, is in all
probability the last trace of the marginal groove which I mentioned in
the description of the preceding embryo as running around the under
surface of t^e bridge.

Another embryo shows a second and later phase in the disappearance
of the bridge. Fig. 6, Plate I., represents the germinal disk of an em-
bryo taken from the same uterus as that of Fig. 5. The blastodermic
vesicle was nearly circular in outline, slightly folded, and measured
3.9 mm. in diameter. The germinal disk was distinctly ovate in outline,
as shown in Fig. 6, and measured in its long axis 0,265 mm. and in
its greatest breadth 0.23 mm., thus exceeding in size the disk of Fig. 5
by just 0.03 mm. in each diameter. Though somewhat smaller than
the disk just described, it is clearly older, as the description of tlie sec-
tions will show. It was cut into thirty sections in a transverse direction,
i. e. at right angles to the long axis of the embryo. Starting from the
broader end of the disk, Fig. 24 represents the fourth section in the
series, and Fig. 25 the seventh. Here the only evidence we have
that a bridge has been present is in the shape and position of some of
tlie more superficial cells and their nuclei. In Fig. 24 several of the
surface cells show the characteristic elongated outline with flattened
nuclei which the more superficial cells of the bridge present in its
greatest development, and in Fig. 25 two cells near the centre show,
for the same reason, an undoubted origin from the bridge.

3. Summary of Observations on the Blastodermic Vesicle of the Pig.

I have given above in some detail the principal jihenomena which
my material presents, and now I wish to give in a more compact form
what I take to be the typical changes which occur in the period of
development which these embryos cover, and to point out one or two
variations from the type which serve to throw some light upon its
meaning.

The earliest sta^e which I have, shows a blastodermic vesicle con-
sisting of a sharply defined inner layer of flattened cells, — the ento-
derm, — which forms a closed sac. In contact with the outside of this

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROFA. 301

is a layer of nearly isodiametric cells, — the ectoderm, — which at one
point is thickened to form the germinal disk, both by an increase
in the diameter of the cells at right angles to the surface, and by an
increase in the number of cell layers. On the outside of the ectoderm
is found here and there a " Deckschicht " cell, apparently in process
of disintegration. In short, the blastodermic vesicle has seemingly
completed only recently the so-called first phase in mammalian gas-
trulation, as advocated by Hubrecht ('88 and '90) and Keibel ('89
and '93).- The germinal disk is slightly elliptical in outline ; not far
from one pole of the siiorter axis a proliferation of ectodermal cells
has taken place, so that three cells have come to lie above the general
surface of the disk. Consequently, and for additional reasons which
I shall give later, I consider the shorter axis to be the chief axis of
the embryo, and the pole where the proliferation of cells takes place
the posterior pole. There is, furthermore, anterior to this prolifera-
tion, a slight elevation at the two lateral margins of the disk, while
along the median line between them there is a depression.

As the embryo develops, the germinal disk grows by a multiplication
of cells ; the area covered by the disk is, however, augmented slowly,
the tendency being, for a certain period, to an increase in thickness.
Thus the germinal disk, sections of which are shown in Figs. 14
to 21 on Plates III. and IV., is relatively much thicker than those
represented by Figs. 7 to 10 on Plate II. While the disk increases
thus in thickness, the proliferation of cells at the posterior end con-
tinues, producing a distinct upfolding or overgrowth in that region,
and at the same time a similar process has been going on at the two
lateral margins. Soon these three overgrowths meet and fuse, form-
ing one continuous bridge, at first attached at only three points, but
later coming in contact with the disk at all points of the margin, save
the anterior. There is present also a depression on the surface of the
ectoderm of the disk immediately beneath the bridge, and the cavity
which lies between this surface and the under surface of the bridge
is connected by a narrow canal with the cavity which surrounds the
disk between the extra-germinal ectoderm and the entoderm. The
bridge, furthermore, seems to grow not only by a proliferation of the
ectodermal cells of the germinal disk, but also by additions from the
adjacent cells of the extra-germinal area.

There is strong evidence of such a method of development as I
have just traced, not only in the figures which I have reproduced
here, but also in the case of several embryos in which the disk is
much larger than at this stage, and has clearly made a greater

302 PROCEEDINGS OF THE AMERICAN ACADEMY.

ontogenetic advance. In these a large well developed bridge is
found, overlying a depression in the germinal disk below, to which
it is attached at only three points, one of these being usually larger
than the others, and apparently representing the posterior overgrowth,
which seems to develop slightly in advance of the lateral prolifera-
tions. An anomalous condition of the bridge is interesting. In
one embryo measuring 4 mm., with a germinal disk 0.28 mm. in
diameter, the lateral proliferations seem to have been entirely sup-
pressed, and we have an overgrowth from only one region, the
posterior, extending forward along the median line of the disk.

The fate of the bridge seems to be, that its free anterior margin
finally meets the true ectoderm of the disk ; the structure then sinks
down until it comes in contact with the underlying ectoderm, with
which it finally fuses. At the same time the disk increases in area,
this being largely due to a rearrangement of the cells of the disk in
consequence of the addition received from the bridge. This method
of increasing in size at this stage was first suggested to me by the
fact that few nuclei are found in a karyokinetic condition. Accord-
ingly, in the case of the two germinal disks represented by Figs. 5 and
6, Plate I., which correspond to the two stages of development in
question, I counted the number of nuclei in each, as seen in sec-
tions, to determine the numerical relations of the cells. In the disk
of Fig. 5 I found 1067 cells, in that of Fig. 6, 992 ; although em-
bryos in their early development grow at very different rates, still
the facts which these numbers present, together with the absence of
nuclear figures, would seem to point to a simple rearrangement of
existing cells as the principal factor in the increase in area of the
germinal disk at this stage, rather than to an active multiplication
of cells.

The oldest embryos considered in this paper consist, then, of a
blastodermic vesicle, composed of a continuous inner sac of entoderm
closely surrounded by a layer of ectodermal cells, which in the ger-
minal disk are thickened into a flat, ovate expanse, without jirimitive
groove or streak, with no signs of any mesoderm, and with a few
widely scattered " Deckschicht " nuclei on the extra-germinal area.
The entodermal cells are thickened in the region of the germinal
disk until they become nearly isodiametric, and they are also
thickened, though to a less extent, in an area all around the ger-
minal disk, the diameter of which is about three times as great as
that of the disk itself. With this summary I now pass to a consider-
ation of the observations of other investigators on the mammalian

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROPA. 303

blastodermic vesicle, and to the theoretical interpretation of some of
the phenomena which occur in the embryo of the pig, as I have
described them.

III. Historical and Theoretical.

1. Consideration of Observations on the Blastodermic Vesicle in

General.

On account of the incompleteness of our knowledge of the facts con-
cerning the blastodermic vesicle of the Mammalia, there are naturally
several theories with regard to the exact method of its formation, and
the interpretation of the vesicle when once it has been formed. Since
my own material begins with the completely formed blastodermic
vesicle, I cannot from an actual observation of the process of develop-
ment add anything to our knowledge of the method of it formation ;
but the phenomena which the vesicle at this stage presents, taken in
connection with the observations of other investigators on mammalian
embryology, serve to throw not a little light on several of the mooted
points of its development.

Although the accounts of mammalian cleavage are few, and not in
accord with one another, it seems to be pretty well established that
cleavage results in the formation of a hollow sphere of cells, contain-
ing on the inside, at one pole, a more or less irregular mass of cells.
These facts have been recorded by various authors ; as, for example,
Lieberkiihn ('79), Van Beneden ('80), Van Beneden et Julin ('80),
Heape ('83), Hubrecht ('90), Duval ('91), Robinson ('92), Christian!
('92), and others. The method of formation of the germinal layers
from these structures is in much dispute, however, I will consider
briefly four theories which have been advanced on this subject, upon
which my own investigations seem to throw some light ; but I would
not be understood as trying to make all the observed methods of
mammalian development conform to one type, — there certainly are
not as yet sufficient data for that ; and besides, many reasons exist
for supposing that there may be several types of development, con-
forming to the varied conditions under which the very young embryo
is placed in different mammals.

The first theory is that which Van Beneden ('80) formulated for
th« rabbit. He found a well defined outer layer of cells, just beneath
this in the region of the germinal disk a layer of flattened cells
lining a limited area, and within this a layer which had extended
partially around the inner wall of the outer layer, and these three

304 PROCEEDINGS OF THE AMERICAN ACADEMY.

layers he believed to represent the ectoderm, mesoderm, and entoderm
respectively.

Other investigators have found different conditions, hovrever,
which disprove this theory. I merely mention it ; first, because
my own embryos show clearly a marked outer layer, which I have
termed ectoderm, lined with a flattened layer, the entoderm, and
outside of all, unmistakable " Deckzellen," which would have to be
derived from the outermost layer of cells at a stage such as Van
Beueden described ; and, secondly, because not long ago Duval ('91)
found, as described in his work on the rat and the mouse, young
embryos to which he gave an interpretation very similar to that of
Van Beneden for the rabbit. He describes a hollow vesicle, consist-
ing of an outer layer of nearly isodiametric cells (see Duval, '91, Plate
I., Figs. 73 and 74), with a number of larger, somewhat irregular
cells inside, attached to the outer layer at one pole. He considers
these two sets of cells ectoderm and entoderm respectively. As
Duval describes the subsequent development, it is difficult to interpret
these otherwise ; but it should be remembered that Selenka ('83)
considei'ed the outer layer a " Deckschicht," and that Robinson ('92),
working on the same animals, has reached conclusions widely different
from those of Duval. I should like further to call attention to
Duval's Figs. 75 and 79, Plate I., which resemble strongly those of
other investigators on the rabbit, the mole, and the shrew, and which
would seem to represent a vesicle consisting of an outer layer of
somewhat flattened cells, and an inner mass differentiated into two
distinct regions, very much as Heape ('83, Plate XXIX. Fig. 20)
has shown it in the mole.

The second theory is held by a larger number of investigators,
perhaps, than any other. It maintains that the flattened cells of the
outer layer become columnar and form the ectoderm of the extra-
germinal region. The inner mass of cells differentiates into two
superposed parts; the inner becomes the entoderm and comes to line
the inner surface of the ectoderm ; the cells of the outer part be-
come columnar, and, fusing with the cells of the outer layer, form the
ectoderm of the germinal disk. Balfour ('81), in conjunction with
Heape, thought he was able to trace the actual process of transforma-
tion of the flattened into columnar cells. Essentially the same views
are advocated by Rauber ('75), Lieberklihn ('79), Kolliker ('80), aid
Hubrecht ('90).

My material supplies no evidence whatever of any transformation
of the outer layer of cells, or " Deckschicht,'' into true ectodermal

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROFA. 305

cells ; on the other hand, these " Deckzellen " show unmistakable
signs of disintegration. The embryos represented in part in Figs. 1, 3,
and 4, Plate I., have these cells in a better state of preservation than
most of the others figured here. Fig. 27, Plate IV., is from a
section through the extra-germinal area of the embryo of Fig. 3.
Here, at the left and the centre, we see two " Deckschicht " cells,
which are entirely characteristic, the boundaries rather indistinct, the
nuclei round and with very little chromatic substance, the whole cell
flattened, in the plane of the surface of the ectoderm ; these occur all
over the vesicle at about the same distance apart. At the right-hand
side of the figure I have shown several such cells in contact with one
another ; this is the only place in my material where I have found
this phenomenon ; it suggested a possible earlier condition of these
cells. The cell boundaries, however, are very indistinct ; the cyto-
plasm is scarcely stainable at all, while the contents of the nucleus
stain a nearly uniform light blue. I am inclined, then, to regard
these cells as belonging to a purely transitory layer, which may for a
time serve some protective or other function, and then disappears
by the disintegration of its elements as it gradually becomes of no
further use. Bonnet ('91) says that this layer disappears early in the
sheep and in the pig, and he finds no trace of it in the youngest
sheep embryo he has described (Bonnet, '84, Taf. IX. Figs. 2 and 3.)
It should be remarked that in my oldest embryos, e. g. Fig. 6,
Plate I., there is scarcely any evidence that a " Deckschicht " has
been present, — only here and there a small nucleus attached to the
surface of the ectoderm.

The third theory mentioned is that advocated by Minot ('85 and
'89) and at the same time by Haddon ('85 and 87) and later by
Keibel ('87). This theory starts, like the others, with an outer layer,
and at one pole an inner attached mass, and assumes that the whole
outer layer is entoderm, while the inner mass differentiates into two
superposed layers, an outer, which becomes the true ectoderm when
the entoderm outside of it, as a Rauber's " Deckschicht," disappears,
and an inner, which becomes the entoderm of the germinal disk. Mi-
not ('89) further suggests a complete inversion of the layers for all pla-
cental Mammalia. Earlier stages than mine are necessary for a full
discussion of this question, but the three-layer condition which I have
found over the greater part of the blastodermic vesicles of the pig,
seems to me an insurmountable objection to this theory. If the primary
vesicle is of entoderm, and the ectoderm later grows around it to pro-

VOL. XXX. (n. S. XXII.) 20

306 PROCEEDINGS OF THE AMERICAN ACADEMY.

duce the dulermic blastocyst, to what origin are we to ascribe the
outer layer of " Deckzelleu " which I have described ?

The last theory which I shall mention is that suggested by Robin-
son ('92). His studies on the embryos of the rat and the mouse have
led him to believe that the portion of the outer layer lying beyond
the germinal disk is entoderm, while the ectoderm is limited to the
outer layer of the germinal disk region. In the rat and the mouse
he does not find the ectoderm overgrowing the entoderm. However
correct this theory may be for the rat and the mouse, (my own work
on these animals leaves me still undecided on this point,) my investi-
gations on the pig show conclusively that the entodermal vesicle
becomes entirely surrounded by ectoderm.

I can add little towards determining whether in the pig the extension
of the entoderm over the inner surface of the ectoderm takes place by
a growth proceeding from the margin of the entodermal portion of the
germinal disk, as in the rabbit, mole, etc., or whether this entodermal
mass of the germinal disk becomes a hollow vesicle, which reaches the
ectodermal wall by a multiplication and expansion of its cells, such
as would seem to take place in the hedgehog (Hubrecht '89, Figs.
7, 8, and 9, Plate XV.) and in the cat (Scliafer '76, Fig. 1, Plate X.).
The youngest embryo which I have described, from which Figs. 7 , 8,
and 9, Plate II., were made, showed, as I have already said, an area at
the end of the vesicle farthest from the germinal disk, where for several
sections no entodermal nuclei appeared. If I had had several embryos
presenting this same phenomenon, I should be inclined to think that
the entoderm was in process of lining the ectodermal vesicle and had
not yet completed its work; but, as I said in my description of this
embryo, the entodermal cells are so widely separated over the whole
vesicle that 1 do not feel justified in asserting that there is a space
really free from entoderm at this stage. Bonnet ('84), in his descrip-
tion of a sheep embryo of thirteen days, finds the entoderm in very
much the same condition ; he says : " Die Keimblase ist, wie audi die
Schnitte beweisen, durchweg doppelblattrig. Die Entoblastzellen bilden
aher in einiger Entfernung vom Schild keine continuirliche Lage,
sondern eine netzformig durchbrochene Membran anastomosirender
Zellen von 15-24 /xLange." Van Beneden ('80) finds that it is absent
at one pole of the vesicle, and the same condition has been observed by
both Heape ('83, Figs. 20-23, Plate XXIX.) and Keibel ('89, Fig. 46 a,
Taf. XXIV.). Hubrecht ('90) quotes Hensen (76, Fig. 18,Taf. VIII.)
as authority for the presence of the entoderm at this region, and the
figure would certainly seem to suggest this ; but we should at least not

WEYSSE. — BLASTODERMIC VESICLE OF SU3 SCROFA. 307

Ignore Hensen's own statement of the case when he says, " Die innere
Keimhaut eeht nur iiber das obere Drittheil des Eies ; wenn an audere
Stellen die Keimhaut zweischichtig erscheint, so moge man dies aus
der Dreliung beim Uebergang von der Flachen- in die Kauteuansicht
erklaren." The figure, however, does give the appearance of two
layers at the region under discussion. While such observations as
those of Heape ('83) and of Schafer ('76) would seem to point to two
distinct methods of the extension of the entoderm in Mammalia, I can-
not affirm with certainty that either occurs in the pig ; what evidence I
have, I am inclined to interpret in support of the phenomenon as it is
said to occur in the rabbit, the mole, etc. ; i. e. as a pi-ocess of marginal
growth from the inner mass of cells of the germinal disk.

The process of entoderm formation from the inner mass of cells
would seem to be primarily, then, a separation of certain cells from
the general group, and I cannot help drawing attention here to the
fact that there may be an homology between this process and the
method of entoderm formation described by Robinson and Assheton
('91) in the frog; furthermore, the formation of the didermic stage in
the rat, as interpreted by Robinson ('92), is comparable with this, for
he finds first a mass of irregular cells, in which a cavity develops sep-
arating a single layer of cells at one pole from a mass of cells at the
other ; the single layer he considers ectoderm, and the cells at the
opposite pole the entoderm, or, as he calls them, epiblast and hypoblast
respectively. I am not, however, sure in the light of the results of
Selenka ('83) and Duval ('91), that this interpretation is correct.

Before leaving the general consideration of the blastodermic vesicle,
there are two or three other points to which I wish to refer. Schafer
('76) found in the embryo of the cat a clearly defined non-cellular
membrane over the outer surfiice of the entoderm in the region of the
germinal disk ; this he calls the " membrana limitans hypoblastica,"
and compares it to the " membrana prima" desciibed by Hensen ('76)
in the first part of his paper on the rabbit (see Hensen, Fig. 19, Taf.
IX.). In the second part of his paper, Hensen figures the membrane
as in contact with the entoderm in the region of the primitive streak
only, and as then passing over the dorsal side of the mesodermal
somites, and coming in contact with the ectoderm laterally (see his
Fig. 37, Taf. X.). In Hensen's eai'lier figure, and in Schafer's, this
membrane is clearly an entodermal structure, and I hold it comparable
to the membrane which I have found between the ectoderm and the
entoderm of the germinal disk, which leaves the ectoderm at the margin
of the disk and passes off to meet the extra-germinal ectoderm farther

808 PROCEEDINGS OF THE AMERICAN ACADEMY.

on. This membrane would be of great assistance, it seems to me, in
determining the origin of the mesoderm within the germinal area.
Many authors have not figured this structure, as, for example, Kolliker
('82), Heape ('83), Bonnet ('84), Hubrecht ('90), and others. In the
rat and the mouse I have noticed a sharp line between ectoderm
and entoderm, which is probably the same structure, and it has been
figured by other investigators of these animals (see Duval '91, Robin-
son '92, and others).

There is another point to which I wish to draw attention, without
however attaching too great significance to it. In the description of
my younger embryos I mentioned the fact that the germinal disk was
elliptical in outline, and that, according to my orientation, the shorter
axis of the ellipse lay in the plane of bilateral symmetry of the future
animal. Though it may be of little morphological significance, it is
certainly very interesting to note that in its earlier stages the blasto-
derm in teleosts (which must be held to be homologous with the ger-
minal disk of the mammalian embryonic vesicle) is also elliptical in
outline, and furthermore that the shorter axis of the ellipse corresponds
to the chief axis of the future fish, as established by Agassiz and
"Whitman ('84). This elliptical outline, which seems to be constant
in teleosts (see Ryder '84, Agassiz and Whitman '85 and '89, Wilson
'91, etc.), is produced in the first place by the first cleavage plane,
which divides the protoplasmic mass at the active pole of the egg into
two parts, each circular in outline, so that as they lie side by side the
blastoderm is elongated ; this condition persists for some time.

If the first plane of cleavage in the teleost is not identical with the
plane of bilateral symmetry, my comparison, of course, has no validity.
So far as I am aware, there has been but one series of experiments
whose results would seem to disprove this theory ; and these were
conducted by Miss Clapp ('91), who worked on the eggs of Batrachus
tau. These eggs — attached by means of their thick outer membrane
to the vessel in which they were placed — were artificially fertilized,
and the position of the first plane of cleavage noted. Some seven days
later the chief axis of the future fish was clearly visible, and was super-
posed on the line of direction of the first cleavage plane. In only
three cases out of twenty-three did the two lines coincide ; in the rest
the second line made a greater or less angle to the right or left of the
first, — never greater than 70° however. But I think there is a possi-
ble source of error here, which makes my comparison still permissible.
The author states that rotation is impossible, since the yolk is at-
tached to the egg membrane at the point where the membrane attaches

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROPA. 309

itself to the vessel, but offers nothing in evidence of this statement.
Ryder {'86), however, infers that the yolk does not become attached
until " after the vitellus has been covered by the blastoderm." During
last summer, when through the courtesy of Dr. Alexander Agassiz I
had the privilege of studying several weeks at the Newport Marine
Laboratory, I collected material of the cleavage stages of Batrachus
tau. This material was fixed without puncturing the egg membrane,
and a careful examination of it shows no trace of any attachment of
the yolk to the membrane, although the contents of the egg are every-
where in contact with it. It should further be remembered that the
contents are in a semi-fluid condition, and during the seven days men-
tioned abundant opportunity is furnished for a rotation of the yolk
within the egg membrane.*

Before leaving this matter of the shape of the germinal disk, I wish
to refer to a young disk of the shrew, which Hubrecht ('90) has figured
(Plate XXXVII. Fig. 17) as elliptical, very much as I have described
the disks of the pig. From the position of the figure on the plate I am
left to infer that the shorter axis of the disk becomes the principal axis
of the embryo. In the later development he finds the disk ovate, but
he places the narrow end anterior and the broad end posterior, except
in one case (Plate XXXVII. Fig. 21), where the broad end is anterior,
just as I have placed it in my descriptions of the pig. This ovate out-
line, oriented thus, is certainly characteristic of slightly later stages,
and has been figured many times ; e. g. by Kolliker ('82) in the rabbit,
Duval ('89) in the chick, Keibel ('93) in the pig, etc.

I now come to the last point which I wish to consider before taking
up the interpretation of the bridge. In the embryo represented by
Fig. 2, Plate I., and in all the following embryos figured on this plate,
there occurs a thickening of the entoderm, not only in the region of
the germinal disk, but also in a considerable area immediately sur-
rounding it. By a thickening I do not mean that the entodermal
cells have multiplied so as to be superimposed upon one another to
form a mass more than one layer of cells deep, but simply an increase

* Very recently Morgan, (Experimental Studies on the Teleost Eggs, Pre-
liminary Communication, Anat. Anzeiger, Jahrg. VIII. pp. 803-814, 1893,)
working on the eggs of Ctenolabrus and Serranus, has arrived at the conclusion
that " there is no relation whatsoever between the cleavage planes of the egg and
the median plane of the adult body." Dr. Morgan bases this statement on the
observation of the axes of twenty-two eggs, and his method of determining the
position of the axes appears to be satisfactory. I cannot, however, enter upon a
fuller consideration of the subject here.

310 PROCEEDINGS OP THE AMERICAN ACADEMY.

in the number of cells over a certain area, so that they come to lie
more closely together, and in consequence give the appearance in sur-
face view of a thickened entpdermal area. The question of course
concerns the significance of this circum-germinal thickening. An ex-
planation has suggested itself to me, which rests, however, on a theory
which I do not feel at all sure is established. The theory concerns
the origin of the mesoderm. Hubrecht ('90) gives three sources for
the mesoderm : the protochordal plate, the primitive streak (" gastrula
ridge " and " KoptFortsatz "), and " an annular zone of hypoblast situ-
ated just outside the limits of the embryonic shield, and thus enclos-
ing — but at the outset independent of — the protochordal plate." The
annular zone according to Hubrecht does not arise until after the first
stages in the development of the primitive streak, and therefore is
a later differentiation in the hypoblast than is the protochordal
plate.

Concerning this third source there has been much dispute. Bonnet
('84) has found it in the sheep, and Robinson ('92) in the rat and the
mouse. But many authors find no evidence of such an origin for any
part of the mesoderm, as, for example, Kolliker ('82), Heape ('83),
Fleischmann ('89), Keibel ('91 and "93), Hertwig ('93), and very
many others. It has occurred to me that this circum-germinal thick-
ening might be the first evidence of a later (ontogenetically) formation
of mesoderm in this region. Since Keibel's ('93) youngest pig embryo
has the mesoderm already well advanced in development and covering
the area in question in two layers, somatic and splanchnic, it is impos-
sible to say what the stages intermediate between his and mine may
have been, and I merely mention the above suggestion as a possible
explanation of an interesting phenomenon. There is, as I have al-
ready said, no trace in my specimens of mesoderm in any region of
the vesicle, and no sign, either in surface view or in section, of a
thickening of entodermal cells in any part of the germinal disk, like
the protochordal plate which Hubrecht ('90) describes for the shrew.
To make sure that this was not merely a subjective impression I
enumerated the nuclei in each section of the germinal disk of Fig. 6,
Plate I., beginning at the broader end, and the result was as follows :
3, 8, 10, 10, 14, 15, 18, 18, 20, 23, 28, 24, 23, 25, 24, 31, 30, 23, 22,
17, 15, 12, 10, 9, 10, 11, 6. A comparison of these figures with the
shape of the disk will show an almost uniform distribution of entodermal
cells.

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROPA. 311

2. Interpretation of the Bridge.

I now have to consider the interpretation of the structure which I
have called the bridge. There are two structures which have been
described in vertebrate ontogeny with which it may perhaps be possi-
ble to compare it. One of these has been figured by Heape ('83, Plate
XXIX. Figs. 20-28) in the blastodermic vesicle of the mole. He here
shows a thickened ectoderm in the region of the germinal disk, with a
layer of entoderm beneath but not extending far beyond it, and above
it a cavity (his " secondary cavity ") which is roofed over by a bridge
of cells from the " Deckschicht," or, as he calls it, the " outer layer."
The history of the structure, as he gives it, is briefly this. The
blastodermic vesicle consists of a closed sac of flattened cells, the outer
layer, and of a mass of rounded cells within at one pole, the inner
mass. The latter differentiates into two parts, which become ectoderm
and entoderm. The ectoderm becomes continuous at its margin with
the outer layer, from which it is separated over its central area by a
shallow cavity. The ectoderm increases in extent and becomes some-
what cup-shaped, so that the cavity increases in depth, but it is filled
with amoeboid cells derived from the outer layer. Later the ectoderm
of the disk flattens out, and the cells of the outer layer above it fuse
with it and become a part of the true germinal ectoderm. The inter-
pretation which Heape puts on these phenomena is, that they are a
transitory representation of the inversion of the germinal layers which
is carried to such a great extent in some rodents. I see no reason
why Heape's observations and conclusions are not entirely correct.
A similar phenomenon has been figured by Hubrecht ('89, Plate XVI.)
in the hedgehog. Here, however, the portion of the outer layer, or
" trophoblast," which is separated from the germinal disk ectoderm,
does not become fused with the disk later, but remains in contact with
the uterine mucosa. This roof-like structure, where it comes in con-
tact with the ectoderm of the disk, is clearly continuous with the cells
of the " trophoblast " and also with those of the disk, so that Hubrecht's
('89) Fig. 20 B, Plate XVI., resembles my figures of sections through
the posterior attachment of the bridge in the pig.

The condition in the pig, although it seems at a casual glance to
resemble the structure in the mole embryo, is not directly comparable
with it. In the first place, the structure in the mole forms from the
beginning an uninterrupted covering to the ectoderm of the germinal
disk, and continues to do so through the subsequent development, up
to its complete obliteration through fusion with the disk. During the

312 PROCEEDINGS OP THE AMERICAN ACADEMY.

whole process no stage occurs where there is any trace of an over-
growth, such as I have found in the pig, or of an external opening into
the cavity which lies between the two layers in question. Moreover,
this cavity in the mole is largely filled with a loosely arranged mass of
amoeboid cells, except in one case, where, as Heape ('83, Plate XXIX.
Fig. 25) says, their absence is due to mechanical injury in the process
of preparing the sections. Furthermore, it may be noted that this
bridge-like structure appears at a much earlier ontogenetic stage in
the mole than in the pig. In the former the entoderm covers the area
of the germinal disk only ; in the latter I find a complete didermic
vesicle when the first trace of the bridge cells appears. It is true, we
need not be surprised to find an inversion of the layers in other mam-
mals than those in which it has already been established, especially
in the light of Mall's ('93) paper on a human embryo of the second
week, m which he explains the conditions as the result of inversion ;
but, for the reasons I have given, I do not consider the bridge in the
pig as even a potential inversion, — the less so as the explanation
I am about to offer is to my mind a much more satisfactory inter-
pretation of the phenomena. If it should be urged that the bridge is
homologous with the roof-like structure over the germinal disk of the
hedgehog (Hubrecht '89), it would be necessary to assume the ex-
istence of a potential opening through this structure into the cavity
beneath it from the very beginning of its formation, but the facts, as
recorded for the hedgehog, seem to furnish no grounds for this assump-
tion. Moreover, in this animal the roof-like structure never comes in
contact with the ectoderm of the germinal disk, but contributes to the
formation of the placenta, a very different fate from that of the bridge
in the pig.

I am inclined to compare this bridge with the overgrowth which
occurs in the development of Amphioxus just after gastrulation and
the elongation of the embryo have taken place. We knew through
the investigations of Kowalevsky ('67 and '76) and of Hatschek ('81)
that at this time there is a sinking of both ectoderm and entoderm
along one side of the gastrnla, the future dorsal or neural side of the
animal, which forms the so called medullary plate, and at about the
same time a proliferation of cells begins at the posterior margin of the
blastopore, and, growing forward over the blastopore and the medullary
plate, meets lateral elevations on either side, and fusing with them
forms a continuous roof over the dorsal depression, with an opening at
the anterior end, which persists for a considerable time as the neuro-
pore. The neural tube is later formed from the medullary plate,

WEYSSE. — BLASTODERMIC VESICLE OP SUS SCROFA. 313

which is iu this way cut off from the rest of the ectoderm, but the
overgrowth itself takes uo part in the formation of the tube, as we see
clearly from Kowalevsky's (76) Figs. 11, 12, and 13, Taf. XV., where
the cells of the medullary plate grow across under the roof, and thus
separate the roof from the lumen of the neural tube. Kowalevsky
says on this point : " Die Riickenrinne, obgleich von aussen voll-
stiindig bedeckt, innen — unter der Haut — noch offen ist. Die Quer-
schnitte der Gastrula und der zuletzt angefilhrte Querschnitt auf der
Fig. 11 erkliiren uns diese P^rscheinuug ganz einfach. Querschnitte
der etwas weiter ausgebildeten Larve, Figg. 12 u. 13 zeigeu uns nun,
dass die oberen Riinder der Medullarplatten sich bald verbinden, an-
fangs vermittelst einer sehr feinen und platten Briicke, welche sich
aber bei den weiter ausgebildeten Larven bedeutend verdickt und so
ein Verhaltniss annimmt, wie bei dem ausgewachsenen Amphioxus."

Now the development of the bridge in Sus scrofa domesticus, as
I have traced it iu the present paper, corresponds in many important
points with the development of the dorsal overgrowth in Amphioxus.
In the first place, it begins by a marked proliferation of cells at
one pole of the chief axis of the germinal disk, and at the same time
by a slight elevation laterally on either side of this axis and nearer
the opposite pole. The median growth is more rapid than the
lateral growths, and gives a condition like that of Fig. 1, Plate I.,
which is much the same as that figured by Kowalevsky ('7G, Taf.
XV. Fig. 3) and by Hatschek ('81, Taf. III. Fig. 37) for Amphi-
oxus. The overgrowth continues in the direction of the median axis,
and the three parts fuse to form the continuous bridge, as already
described for the subsequent stages, represented by the figures on
Plate I. These correspond with the phenomena as they have been
described by Kowalevsky in Amphioxus : " Die jetzt beginnende
Scliliessung der Riickenfurche geht hier, so wie bei den anderen
Wirbelthieren, von hinten aus, wobei die ganz hinteren Riinder,
welche die Einstiilpungsoffnung riickwiirts begrenzten, sich aufheben,
eine Art Dach uber diese OefFnung bilden und immer mehr und
mehr nach vorne wachsend und mit den seitlichen Randern der
Riickenfurche verschraelzend den Riicken, resp. das Nervenrohr,
zu bilden beginnen."

It is for these reasons that I have oriented my embryos in the
way already described. The opening into the depression below the
bridge corresponds, I believe, to the neuropore of Amphioxus, and I
am inclined to carry the homology of the two forms still further, and
suggest that the canal which I have shown in Fig. 20, Plate IV.,
corresponds to part of the neurenteric canal of Amphioxus.

81-1 PROCEEDINGS OF THE AMERICAN ACADEMY.

There are several objections to this theory which suggest them-
selves at once. In the first place, as to the structure of the two
overgrowths ; that in Amphioxus is figured as consisting of but one
layer of ectodermal cells ; the bridge in the pig, on the contrary, is
from two to three layers of cells thick. This seems to me but a
minor point, however, readily explained by the morphological differ-
ences between the larva of Amphioxus and the blastodermic vesicle
of the Mammalia. In the former case there is no part which may not
be said to develop directly into some important tissue or organ of the
adult animal ; in the latter, it is essentially the germinal disk only of
which this is true. Here, then, we have a germinal and an extra-
germinal region, and in the process of rapidly increasing the number
of cells in the disk the extra-germinal cells of the ectoderm, as well
as the cells of the disk, apparently contribute to the development
of the bridge, thus producing an overgrowth two or three cells
thick. Again, it may be urged that I have not shown a blastopore
around which the overgrowth should take place. I have found in my
youngest embryos no trace of an opening through the germinal disk
which could be compared with wnat Hertwig ('93) says may pos-
sibly be a blastopore, as figured by Heape ('83), Selenka ('86-'87)j
and Keibel ('89). But the blastopore in Amphioxus becomes the
neurenteric canal, which leads from the posterior end of the cavity
beneath the overgrowth into the gastrula cavity. It is at just this
point in several of my embryos that I find a canal leading from
the cavity beneath the bridge to the cavity located at the margin
of the disk, between ectoderm and entoderm. To be a true neuren-
teric canal, it should be continued into the gastrula cavity, i. e. the
cavity within the entoderm ; but on account of the loose connection
of the entodermal cells, it is impossible here to trace any such pas-
sage. I do not, however, think we should be justified in asserting
on this account that it does not exist. There ought, however, to
be at least a fusion of the two primary germ layers in this region,
such as always occurs, I believe, in the case of a true neurenteric
canal.

Still another objection may be raised to this theory, and that is
the extremely remote relationship existing between Amphioxus and
the Mammalia. If the bridge of the pig is really a reappearance of
a structure which occurs as far back in phylogeny as the lowest
representative of the Vertebrata, why may we not justly look for its
presence in intermediate groups ? The question is certainly a fair
one, and I can only say that, so far as I am aware, no structure

WEYSSE. — BLASTODERMIC VESICLE OP SUS SCROFA. 315

having so marked a resemblance to the overgrowth iu Amphioxus
has been recorded in any intermediate group. I am tempted, how-
ever, to call attention here to a parallel case. The early cleavage in
mammals, as described especially by Tafani ('89), bears a striking
resemblance to the early cleavage of Amphioxus. Why, then, do we
not find the same type of cleavage occurring in intermediate groups
of vertebrates? Here asfain it must be admitted that we do not
find it, but iu this case the reason is plain ; it is because the whole
structure of the ovum is so changed by the accumulation in it of
nutrient material, that cleavage on the type of Amphioxus is impos-
sible, and it is not until we reach the Mammalia that the conditions
are such as to admit of total equal cleavage. But is it not for the
same reason that the steps which lead up to the formation of the neu-
ral tube have been modified, and that the overgrowth in Amphioxus
finds its first striking recurrence in the mammalian embryo ? The
lumen of the canal is often extremely small in other mammals, and
has in some cases been represented by a single line, e. g. Robinson
('92, Plate XXIII. Fig. 13 A, Plate XXIV. Fig. 15 D, and Plate
XXVI. Fig. 17).

A more serious objection exists in the fact that the cavity beneath
the overgrowth in Amphioxus becomes the neural canal, whereas, as
I have traced it in the pig, it becomes obliterated by a fusion of the
bridge with the ectoderm of the disk. I would not be understood as
considering the canal which I have compared to the neurenteric
canal decisive evidence in favor of this theory ; it is, however, a sig-
nificant phenomenon occurring in a significant position. To my mind
it occupies the position of the neurenteric canal in Amphioxus ; that
it is certainly the neurenteric canal of the pig, I would not presume
to say ; the descriptions of this canal in mammals are varied ; the
bridge and canal which I have described have never before been
recorded in the Mammalia, so far as I am aware.

3. Summary.

My conclusions as to this bridge may be briefly summarized as
follows. Two interpretations of the structure have presented them-
selves as in some measure probable. The first homologizes it with
the thickening of the " Deckschicht " or Rauber's layer, or, as
Heape ('83) calls it in the mole, the outer layer, which through the
development of a secondary cavity becomes separated from the true
ectoderm of the germinal disk and forms a sort of roof over it.
That this structure is not homologous with the bridge seems to me

316 PROCEEDINGS OP THE AMERICAN ACADEMY.

evident from the fact that in the case of the bridge there is always
an opening leading from the outside into the cavity beneath the
bridge, and this cavity is never filled with amoeboid cells as is the
cavity in the mole. Furthermore, on the bridge there are found in
some cases " Deckzellen," — or rather their remains, consisting of
homogeneously staining nuclei and little cytoplasm, -^ which clearly
can take no part in the formation of either bridge cells or true
ectodermal cells. Again, the roof of overlying cells in the mole
makes its appearance and finally fuses with the germinal disk ectoderm
at an earlier stage in ontogeny than that at which the bridge in the
pig develops.

The second theory, which seems to me the more probable, ho-
mologizes the bridge with the overgrowth along the dorsal side of
Amphioxus. The reasons for this comparison are that the two struc-
tures develop at about the same time in ontogeny in the two cases,
i. e. just after the formation of a didermic vesicle ; that, further, a
process of growth can be traced for the bridge which corresponds
closely to the method of growth in the case of the structure under
consideration in Amphioxus ; and, finally, that there is a median
thickening of the germinal disk corresponding topographically to the
medullary plate of Amphioxus, a free margin to the bridge corre-
sponding to the neuropore, and a canal at the opposite pole which
may, perhaps, be compared with the neurenteric canal of the primitive
vertebrate. From my present knowledge of the bridge in the pig,
I cannot homologize it with the roof-like structures in the shrew and
the mole, and if it is not comparable with the overgrowth in Amphi-
oxus, it seems to me necessary to regard it as a structure hitherto
undescribed in vertebrate embryology. Whatever the interpretation
of the bridge may be, we have the fact of its existence, and it is
reasonable to expect that it will be found in other mammals as well,
as, for example, in the sheep, in which the immediately succeeding
stages of development are so similar to those of the pig.

I wish to express my thanks to Dr. Alexander Agassiz, to whom
I am greatly indebted for the opportunity of studying at his private
laboratory at Newport and for the privilege of using his library, and
to Dr. E. L. Mark, who has very kindly followed all my work and
examined my preparations with great care, and also to the employees
of the abattoir, who have given me much assistance in securing
material.

Cam BRIDGE, April 18, 1894.

WEYSSE. — BLASTODERMIC VESICLE OF SUS SCROFA. 317

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Selenka, E.

'83. Studien iiber Entwickelungsgeschichte der Thiere. Heft L
Keimbliitter und Primitivorgane der Maus, pp. 1-23, Taf. I.-IV.

'86 u. '87. Studien iiber Entwickelungsgeschichte der Thiere. Heft 4.
Das Opossum (Didelphys virginiana), L pp. 101-132, Taf. XVII.-
XXIV., XXVI; II. pp. 133-172, Taf. XXV., XXVII.-XXX.

Tafani, A.

'89. La fecondation et la segmentation etudiees dans les oeufs des
rats. Arch. Ital. de Biol., Tom. XI. pp. 112-117.

Wilson, H. V.

'91. The Embryology of the Sea Bass (Serranus atrarius). Bull.
U. S. Fish Com., 1889, pp. 209-277, Plates LXXXVIII.-CVII.

WEYSSE. — BLASTODERMIC VESICLE OF BUS SCROFA. 321

EXPLANATION OF PLATES.

All the drawings were made with the camera lucida directly from the object
itself, with the exception of Fig. 2, Plate I., which is a graphic reconstruction
made from sections drawn with the camera. In the case of all transverse sec-
tions it is the posterior face of the section that is shown, so that right on the
figure corresponds to the right side of the disk. The embryos came from four
uteri, and may accordingly be grouped as follows : A, Figs. I, 3, 4, 10, 27 ;
B, Figs. 2, 21, 22, 23, 26 ; C, Figs. 5, 6, 14-20, 24, 25 ; D, Figs. 7, 8, 9, 11, 12, 13.

VOL XXX. (n. S. XXII.) 21

PLATE I.

All figures magnified 100 diameters, and oriented on the plate with the chief
axis vertical and the anterior pole towards the top.

Figure 1 A portion of the blastodermic vesicle containing the germinal disk.
The posterior overgrowth is marked, and the marginal elevations
and median depression are apparent.

" 2. A later stage than the preceding, with the posterior and the lateral

overgrowths fused at two points.
" 3. One continuous overgrowth or bridge, with no trace remaining of the

fusion of parts.

" 4. A later stage showing a more extensive bridge with a lateral opening
at the right, where the lateral and the posterior overgrowths have
not completely fused.

" 5. A germinal disk with ovate outline and highly developed bridge.
The broad end of the disk is anterior.

" 6. Enlarged disk, ovate, with no separate bridge. Sections show that
the bridge has fused with the ectoderm of the disk.

ASTODt

:;SICLE.

vv-.v

PLATE II.

All figures magnified 400 diameters, ectoderm uppermost.

Figure 7. Transverse section of a very young germinal disk, showing one cell
at the centre projecting above the general level of the ectoderm,
but clearly an ectodermal cell.

" 8. Section immediately succeeding that of Fig. 7, and showing essen-
tially the same phenomena.

" 9. More anterior section of the same disk showing the even surface of
the ectoderm and the general arrangement of the cells. No " Deck-
schicht " cells.

" 10. Longitudinal section, nearly median, through the germinal disk of
Fig. 1. At the left hand or posterior end is seen an early stage in
the development of the bridge, which here consists of two layers of
cells, the outermost resembling the extra-germinal ectoderm, the
inner the germinal ectoderm. Note the dividing nucleus at the
base of the bridge.

" 11. A nearly median longitudinal section of another germinal disk in a
little later stage of development.

" 12. More lateral section through the same embryo as Fig. 11, showing
lateral continuity of the bridge and the cavity beneath it.

" 13. A still more lateral section of the same disk as the two preceding, in
which the cavity has disappeared, but the bridge cells are readily
distinguished from the true ectodermal cells of the disk.

WeyssetBlastodeumig Vesicle .

Plate H.

A.W.V/.,del.

BMeisel I

PLATE III.

All figures magnified 400 diameters, and all drawn from longitudinal sections
through tlie germinal disk of Fig. 6. Tiie anterior end is at the right.

Figure 14. First section of the disk ; the disk cells first appear near the anterior
end on account of the ovate outline of the disk.

15. Second section in the series ; merely shows an extension of the
germinal-disk ectoderm.

16. Fourth section. First appearance of the bridge, marked off by a
distinct cavity.

17. Sixth section through the disk. Extension of the cavity and decrease
in thickness of the bridge.

18. Seventh section, showing free margin of the bridge at the anterior
end, with posterior attachment.

19. Eighth or median section ; here we have the most posterior point of
the free margin of the bridge. The cavity beneath extends a short
distance towards the posterior pole, between the cells.

Weys s e rBLASTODERMic Vesicle .

Plate DI.

^^m:^zB

PLATE IV.

Figures 20 and 27 magnified 400 diameters, all others 275 diameters. Ecto-
derm in every case uppermost.

Figure 20. The ninth section in the same series as those of Plate III. The free'
margin of the bridge is again nearer the anterior pole, while the
cavity beneath extends by a narrow canal completely through the
ectoderm of the disk into the extra-germinal space between ecto-
derm and entoderm.

" 21. Somewhat oblique longitudinal section nearly through the centre of
Fig. 2, Plate I. The ectoderm of the disk is greatly thickened, the
cavity beneath the bridge is rather shallow, but there is a marked
depression just in front of tiie free edge of tiie bridge. Tlie ento-
derm is thickened beyond the area of the disk in the extra-embryonic
region.

" 22. A nearly transverse section through a much older germinal disk,
which shows the decrease in thickness of the ectoderm attending
an extension in area and the fusion of the bridge along the median
portion.

" 23. A slightly more anterior section of the same disk as Fig. 22, where
we see at the left lateral margin the fusion of the bridge not quite
completed.

" 24. Transverse section, the fourth from the anterior end of the germinal
disk of Fig. 6, showing the bridge cells in contact with the germi-
nal-disk ectoderm.

" 25. Seventh section of same disk as the preceding, showing near the
median line the last trace of the fusion of two bridge cells with the
ectoderm.

" 26. Section through the extra-germinal region of the blastodermic vesi-
cle of Fig. 2, Plate I. On the upper side are a few " Deckschicht "
cells, flattened and disintegrating; then a layer of typical ecto-
dermal cells, and, below, the normally distributed entodermal cells
of this stage.

" 27o Section through the extra-germinal region of Fig. 3, Plate I. The
" Deckschicht " cells are more numerous than in the preceding case,
and at one point several are in contact with one another, — an un-
usual condition. The entodermal cells are more numerous tlian
in the preceding, since this is a later stage of development.

WeYS S E rBlASTODE-RMIC VeS IGLE .

Plate N.

STT?

xwPl'^'.^^TCI^v^

V ^f

^^ • - ^ZoE^^--^^-^^

. i-

A WYiT..

EMeisel.Iidi.Boslor.

324 . PROCEEDINGS OF THE AMERICAN ACADEMY.

XIII.

CONTRIBUTIONS FROM THE CHEMICAL LABORATORY OF

HARVARD COLLEGE.

ON TERNARY MIXTURES.

FIRST PAPER.

By Wilder D. Bancroft.

Presented by C. L. Jackson, May 9, 1894.

Following out tlie analogy between dissolved substances and
gases, Nernst deduces the law that, when two dissolved substances
have no common ion and do not react chemically, the influence of
each on the solubility of the other is zero, within certain undefined
limits. He says : * " Die Analogic zwischen der Auflosung und Sub-
limation bezw. Dissociation fester Stoffe zeigt sich nun auch deutlich
ausgesprochen, was den Einfluss fremden Zusatzes betrifft. Ebenso
wenig wie die Sublimatiousspannung bei Gegenwart fremder indiffe-
renter Gase sich iindert, wird die Loslichkeit eines festen Stoffes durch
Zusatz eines zweiten (in nicht zu grosser Meuge) beeinflusst, wofern
der hinzugefiigte fremde StofF nicht chemisch auf jenen einwirkt; und
ebenso wie die Dissociationsspannungim hochsten Maasse durch Zusatz
eines der gasformigen Zersetzungsproducte beeinflusst wird, so variirt
entsprecheud auch die Loslichkeit derjenigen Stofi^e, bei welchen die
Auflosunw mit einem mehr oder wenisrer vollstiiudigen Zerfall verbun-
den ist, die also bei ihrer Auflosung mehrere Molekiilgattungen liefern,
wenn eine dieser letzteren der Losung hinzugefiigt wird." There are
several things in this statement which are open to criticism. If taken
literally, the author implies a fundamental difference between solu-
tions of liquids in liquids, and solids in liquids, a distinction which is
not in accordance with the view that in dilute solutions the solute.t

* Theor. Cliemie, p. 383.

t Tliere seems to me a need for a word denoting the dissolved substance.
In future I shall use tlie word "solute," meaning the substance dissolved in the
solvent. Instead of the phrase "infinitely miscible liquids," I propose " con-
solute " liquids.

BANCROFT. — TERNARY MIXTURES. 325

whether liquid or solid in the pure state, behaves like a gas at that
temperature. If applied to any dissolved substance, the statement
just quoted is too inaccurate to need any comment. The precipitation
of salts by alcohol is a well known instance where it does not apply,
and, in general, adding to a solution a substance in which the solute is
practically insoluble diminishes the solubility of the latter. This is
recognized by Nernst, for he has based a method for determining re-
acting weights upon it.* Even if limited to solids, the proposition can-
not be admitted. We have the precipitation of lactones by potassium
carbonate as an intermediate step, and the precipitation of salts by
phenol as a definite case of diminished solubility without the presence
of a common ion. Other cases could be cited, if necessary, and there
are also examples where an increase of solubility takes place when a
solid substance is added to a solution containing another solid as solute.
The explanation usually offered under these circumstances is, that
" double molecules " are formed, a mode of getting round the facts
which is not always entirely satisfactory.

Since in the application of the gas laws to solutions there has been
observed no difference between a solid and a liquid when dissolved,
I am inclined to think that the general statement should be, that in
all cases where a third substance, B, is added to a solution of ^ in S, the
solubility of A undergoes a change. This variation may be large or
small, positive or negative, depending on the nature of the three sub-
stances A, B, and S. When both A and B are liquids, or even when
only one of them is, the effect is so marked as to be familiar to all ;
when both are solids, the effect is not yet recognized by so competent
an authority as Nernst.

The work of the last few years on solutions has been devoted to
bringing out the analogy between the dissolved substance and gases.
In the cases of changed solubility, no common ion being present, the
analogy is no longer with gases, but with liquids. The added sub-
stance acts as a liquid, precipitating the solute more or less in propor-
tion as the dissolved substance happens to be more or less soluble in it.
The laws governing these displacements are entirely unknown, with
the exception of Nernst's Distribution Law,t which is only a first ap-
proximation, in that it takes no account of the changing mutual
solubilities of the hypothetically non-raiscible liquids. Under these
circumstances it seemed to me desirable to investigate the laws gov-
erning systems composed of three substances, and the experiments

* Zeitschr. f. ph. Chem., VI. IG. 1890. t Teilingssatz.

326 PROCEEDINGS OF THE AMERICAN ACADEMY.

which I communicate in this paper have been made on the simplest
form of ternary mixtures, that where all three substances are liquids.
The subject has been very little studied, the only researches known to
me being by Tuchschmidt and Folleuius,* Berthelot and Jungfleisch,t
Duclaux, t Nernst, § and PfeiiFer. || Of these, all except the first and
last deal with the equilibrium between two liquid phases ; the paper
of Tuchschmidt and Follenius contains but one series of measurements,
while Pfeiffer remarks, apropos of his own extended investigations,
that " there is very little to be made out of them." In this he does
himself an injustice, for, as I shall show, his results are very satisfac-
tory and astonishingly accurate when one remembers how they were
made.

The simplest case of three-liquid systems is when one has two prac-
tically non-miscible liquids, and a third with which each of the others
is miscible in all proportions; for then any complication due to the
mutual solubility of the two dissolved liquids is avoided. It is pos-
sible to say something a priori about the law which governs these
saturated solutions. Let A and £ be two non-miscible liquids, S the
common solvent with which A and B are miscible in all proportions
when taken singly, and let the quantity of S remain constant, so that
we are considering the amounts of A and B^ namely x and y, which
will dissolve simultaneously in a fixed amount of S. It is known,
experimentally, that the presence of A decreases the solubility of B,
and vice versa ; it is required to find the law governing this change of
solubility. This, being a case of equilibrium, must come under the
general equation of equilibrium.

where dx and dy denote the changes in the concentrations of A and
B respectively.

This equation, though absolutely accurate, is of no value practically
so long as the differential coefficients are unknown functions. In re-
gard to them we may make two assumptions. Tlie decrease in tlie
solubility of A may be proportional to the amount of B added, and inde-
pendent of the amounts of A and B already present in the solution.
The differential equation expressing this is :
(2) a dx + b y = 0,

* B. B., IV. 583. 1871.

t Ann. chim. pliys., [4.], XXVI. 396. 1872. | Ibid., [5.], p. 264. 1876.

§ Zeitschr. f. pli. Chein., VI. 16. 1890. || Ibid., IX. 469. 1892.

BANCROFT. — TERNARY MIXTURES. 327

where a and h are proportionality factors and constants. This equa-
tion may be rejected on a 'priori grounds, because it does not show that
when B is absent, the miscibility of A with S is infinite, and also
because it has no similarity with the other equations representing
chemical equilibrium. The second assumption is that the change in
solubility may be a function of the amounts of A and J5 already
present. This is the usual condition of chemical equilibrium, and is
known as the Mass Law. Its mathematical expression is

a dx , B dy ^

+ - — - — 0, or

X y

(3) a d log X -\- 13 d log y = 0,

where x and y denote the amounts of A and B in a constant quantity
of S, a and /3 are proportionality factors, and the logarithms are natural
logarithms.

If a and /3 are constants, this equation is integrable, and gives when
cleared of logarithms :

(4) x"/ = Constant.

If we make — = w, we Ishall have :

(5) x-y^C,

where C is of course different in value from the constant in equa-
tion (4).

Before we proceed to test equation (5) experimentally, it remains
to be seen in what unit x and y should be expressed. It is obvious
that the nature of the unit has no effect on the general form of the
equation, nor upon the exponential factor n. The only change will be
in the value of the integration constant log G, so that the measurements
may be expressed in any form that is convenient, as chemical units,*
for example, grams per litre, volumes, reacting volumes, or anything
else. It is not even necessary that x and y be expressed in the same
unit, though it would probably always be more practical. In my own

* I have adopted the following nomenclature for molecular and atomic
weights, viz. reacting and combining weights. As the reacting weight is pro-
portional to the chemical unit experimentally, I propose that the gram molecule
in the unit of volume (reacting weight in grams per litre) be called the chemical
unit, or simply the unit. Tlie object of these arbitrary changes in our chemical
terms is to do away with everything involving or implying the assumption of
the existence of molecules and atoms.

328 PROCEEDINGS OP THE AMERICAN ACADEMY.

experiments x and y are expressed in cubic centimeters because they
were measured directly as such, and in this way it was not necessary
to make determinations of the densities of the liquids used, nor any
assumptions in regard to their reacting weights. Equation (o) will
not remain unchanged if the reacting weight of ^ or ^ varies, that is,
if the ratio of the active mass to the actual mass changes as x ox y
changes. The converse of this is also true, that if the system follows
the law ic" y = C, the common solvent remaining constant, the react-
ing weishts of the substances A and B cannot have varied with the
concentration.

I have found that the equation, x'^if^ Constant, is the expression
representing the saturated solutions of two non-miscible liquids in a
constant quantity of a consolute lic^uid. I find, however, that in most
cases the concentrations cannot be given by one curve, but involve
two, so that for one set of concentrations I have the relation x"^y= Ci,
for the other set off^y =0^. This cannot be true unless the two sets of
saturated solutions correspond to different conditions. This is the
case. Duclaux* found that a saturated solution of amylalcohol and
water in ethylalcohol became turbid on adding a drop either of amyl-
alcohol or of water. In other words the solution was sensitive to an
excess of either liquid. f, I have confirmed this result, and it is per-
fectly general. It is not proper, however, to draw the conclusion that
the solution is saturated' in respect to both liquids. If to a given
saturated solution of chloroform, water, and alcohol, for instance, one
adds a drop of water or of chloroform, the solution becomes turbid ;
but what separates out is the same in both cases. It is analogous to a
saturated solution of salt in a mixture of alcohol and water. It is in-
different whether one adds alcohol or salt to the solution. In either
case, there is a precipitate ; but in both cases the precipitate is salt, and
the solution is saturated in respect to salt, not in respect to alcohol.
It is not so easy to see what takes place in a system composed of
liquids because the precipitate, being itself a liquid, dissolves part of the
solution, and the new phase is not composed of pure substance. This
need not trouble us, for, theoretically at any rate, the precipitate may
be treated as pure liquid, and the final equilibrium looked upon as due
to a subsequent reaction. One of the two curves represents, then, the
set of solutions which is saturated in respect to chloroform, and not in
respect to water. Whether one adds water or chloroform, to these
solutions, the precipitate is chloroform. Tne other curve represents

* Ann. chim. phys , [5.], VII. 264. 1876. t Ostwalcl, Lehrbuch, I. 819.

BANCROFT. — TERNARY MIXTURES. 329

the mixtures which are saturated in respect to water, and not in respect
to chloroform. Either water or chloroform, when added to these solu-
tions, produces a precipitate of water. These two sets of solutions :ire
easily distinguishable qualitatively, because in the first case the new
phase, containing a large percentage of chloroform, is denser than the
mixture from which it separates, while in the second case the new
phase, containing chiefly water, is lighter than the original solution.
The point where the new phase changes from being denser to beino-
lighter than the first phase is the point of intersection of the two curves.
At this point only is the nature of the precipitate determined by the
nature of the infinitely small excess added. The intersecting point
represents the concentration at which, were chloroform and water
solids at that temperature, both could be in equilibrium with the solu-
tion and its saturated vapor. It corresponds to the concentration of a
solution containing two salts with a common ion which is in equilibrium
with the two solid salts, formation of a double salt being excluded. In
one respect the analogy between a system having three liquid compo-
nents and one composed of two solids and a liquid does not hold. If
to a saturated solution of silver bromate silver acetate is added, the
precipitate is silver bromate, and, conversely, the precipitate is silver
acetate if silver bromate be added to a saturated solution of silver
acetate. The salt with the less concentration precipitates the one with
the greater, up to a certain point. In a chloroform-water-alcohol mix-
ture in which chloroform is present in large quantities, the precipitate
is water, or the substance with the greater precipitates the one with the
lesser concentration. This difference of behavior is due to the new
phase being a solid in the one case and a liquid in the other. By a
suitable choice of the three components, and by varying the tempera-
ture, the substance in respect to which the solution was saturated
could be made to separate either as a liquid or a solid phase, and this
difference could be made zero. The transition point would come
when the equilibrium was between four phases, one solid, two liquid,
and one gaseous.

There is no apparent theoretical reason why the two curves should
not be prolonged beyond their intersection ; but there is a very good
practical one. Beyond the point of intersection the curves denote
saturated but labile solutions, and a supersaturated system composed of
liquids is almost impossible to realize. When I come to the study of
ternary mixtures having one or more solid components, I hope to be
able to follow one of the curves at least beyond the intersecting point;
but in the present work I have made no such attempt.

330 PROCEEDINGS OF THE AMERICAN ACADEMY.

I will now describe the method used in my work, and then take up
the experimental data obtained. As pairs of non-miscible liquids, I
have taken chloroform and water, benzol and water ; and as consolute
liquids, ethylalcohol, methylalcohol, and acetone. The next point was
how to determine the composition of the saturated solutions. The
methods of quantitative analysis are useless in this case ; but the
problem is solved without difficulty by quantitative synthesis. In-
stead of making a saturated solution and analyzing it, I measured the
quantities required to make a saturated solution at the required tem-
perature. Definite amounts of the consolute liquids were put in test
tubes by means of a carefully graduated pipette ; varying quantities
of one of the non-miscible liquids were run in from a burette, and the
second non-miscible liquid added from another burette to saturation.
The test tubes were corked, warmed just above the temperature at
which the final readings were made, so that there should be a single
homogeneous liquid layer, and placed in a constant temperature bath.
If the tube clouds, it is beyond the saturation point; if it remains
clear, it is not up to it, the required value lying between the two.
By making a series of experiments one can bring the limiting values
very close together, and thus determine the saturation point with great
accuracy. The constant temperature bath was at 20° C. No correc-
tion was made for the amounts of the three liquids evaporating off
into the vapor space in the upper part of the test tubes ; but by using
different sized test tubes this space did not vary much, being about
five cubic centimeters, so that the error due to this may be neglected.

The chloroform used (Squibb's) was treated with sodium bisulphite
solution to free it from acetone, washed thoroughly with water, dried
over calcium chloride and fractionated, twelve hundred grams going
over within one quarter of a degree. Kahlbaum's crystallized benzol
was recrystallized twice and fractionated to constant boiling point.
The ethylalcohol was dried over lime and copper sulphate and frac-
tionated. The lot used distilled within half a degree. Part of the
acetone (from Eimer and Amend) was converted into the bisulphite
compound, back again, dried over potassium carbonate and calcium
chloride, and fractionated. Another portion was treated direct with
calcium chloride and fractionated. I could detect no difference be-
tween the two lots. I tried to purify a sample of acetone from Cutler
Brothers, purporting to be manufactured by Merck in Darmstadt; but
it was so bad that I used none of it in my experiments. The methyl-
alcohol (from Kahlliaum) was dried over anhydrous copper sulphate
and fractionated.

BANCROFT. — TERNARY MIXTURES. 331

The measurements in the tables are the mean of at least four
determinations, and the error is probably not more than b% except in
the cases where the quantity of one component is less than 0.20 c.c,
when it may easily rise to 10%. The values for n are accurate
to within 2% without much question. The values for log C are
more untrustworthy, being much affected by a slight variation in ?«,
while the term G is liable to even greater fluctuations, and is not
given, as being too uncertain. Under the headings " Calc." are the
values required by the formula to correspond with the experimental
data for the other component. The figures in the column marked
logC are Briggsian logarithms. As will be noticed, I have not always
taken the mathematical mean of this column as the value of log C in
the formula. It seemed better to take the value which best satisfied
the experimental data, and to ignore numbers which were obviously
faulty.

TABLE I.

X c.c. H2O; y c.c. CHCI3; 5 c.c. Alcohol. Temp. 20°
Formula x«i y=:C-^; n-^ = 1.90 ; log C]_ - 1.190.

Water. CHCl,

Calc.

Found.

Calc.

Found.

logC,.

9.94

10.00

0.195

0.20-

1.195

8.99

9.00

0.24

0.24

1.192

7.98

8.00

0.30

0.30

1.193

7.14

7.00

0.385

0.37

1.174

6.00

6.00

0.515

0.515

1.190

5.00

5.00

0.73

0.73

1.191

3.97

4.00

1.12

1.13

1.197

Average, 1.190
Formula x\f^ - Co; n^ — I-IH; log Cg = 0.742.

3.00

1.99

1.01

0.92

0.755

0.635

0.55

0.48

0.43-

0.20

0.127

3.00

1.73

2.00

2.49

1.00

4. 66

0.91

5.07

0.76

5.96

0.63

7.06

0.55

8.00

0.49

8.86

0.425

10.06

0.20-

20.00

0.125

30.24

logCj.

1.73

0.741

2.51

0.745

4.60

0.737

5.00

0.736

6.00

0.745

7.00

0.738

8.00

0.743

9.00

0.750

10.00

0.739

20.00

0.742

30.00

0.738

Average,

0.741

332

PROCEEDINGS OF THE AMERICAN. ACADEMY.

TABLE II.

X c.c< Water; y c.c. CHCI3; 5 c.c. Methyl Alcohol. Temp. 20°
Formula x^^y - Cj; n^ = 2.30; log Cj = 1.291.

Water.

CHCI,

Calc.

Found.

Calc.

Found.

logCj.

9.91

10.00

0.10

0.10

1.300

5.01

5.00

0.48

0.48

1.288

4.03

4.00

0.81

0.80

1.283

1.99

2.Q0

3.97

4.00
Average,

1.294

1.291

Formula x"" y =

Cy,

«2 = 1.25;

log C.2 = 1.061.

log Cj.

1.49

1.49

7.00

7.00

1.061

1.34

1.35

7.93

8.00

1.005

1.12

1.12

10.00

10.00
Average,

1.061

1.062

TABLE III.

a: c.c.

Water

; y c.c. Chloroform ; 5 c.c.

Acetone. Temp. 20°.

Formula x»i y =

Cxi

wi =r 1.415

; log (7^ = 0.194.

Water.

Chloroform.

Calc.

Found.

Calc.

Found.

logC.

5.01

5.00

0.16

0.16

0.193

4.00

4.00

0.22

0.22

0.194

3.47

3.50

0.266

0.27

0.201

3.00

3.00

0.33

0,33

0.193

2.49

2.50

0.43

0.43

0.196

2.01

2.00

0.586

0.58
Average,

0.189

0.194

1.50

0.74

1.20

0.83

1.00

0.955

0.93

1.00

0.79

1.12

0.71

1.20

0.58

1.40

0.i53

1.50

0.505

1.60

0.38

2.00

0.30-

2.50

0.25

3.00

0.21

3.50

0.19

s

4.00

0.16

5.00

0.12

10.00

BANCROFT.

TERNARY MIXTURES.

333

TABLE IV.

a; c.c. Water; yc.c. Benzol ; 5 c.c. Alcohol. Temp. 20°.
Formula x" y - C ; n =z 1.60 ; log C - 0.554.

Benzol,

Calc.

X.

Found.

19.87

20-00

10.65

10.00

7.94

8.00

4.97

5.00

4.00

4.00

3.02

3.00

2.01

2.00

1.72

1.72

1.50

1.50

1.44

1.45

1.00

1.00

0.605

0.605

0.526

0.525

0.34

0.34

Cale.

Found.

logC.

0.03

0.03

0.557

0.09

0.08

0.503

0.13

0.13

0.559

0.273

0.275

0.557

0.39

0.39

0..554

0.61

0.61

0.558

1.18

1.17

0.550

1.50

1.50

0.553

1.87

1.87

0.554

K98

2.00

0.559

3.58

3.57

0.553

8.00

8.00

0.554

10.04

10.00

0.552

20 J 4

20.00
Average,

0.551

0.551

TABLE V.

a; c.c. Water; r/c.c. Benzol ; 5 c.c. Methyl Alcohol. Temp. 20°.
Formula ar»i y = Cj ; wi = 1.48 ; log Ci = 0.216.

Water.

Benzol.

Cale.

Found.

Calc.

Found.

logC,.

5.05

5.00

0.15

0.15

0.211

3.95

4.00

0.21

0.215

0.223

3.01

3.00

0.32

0.32

0.211

2.00

2.00

0.59

0.59

' 0.216

1.40

1.40

LOO

1.00
Average,

0.216

0.215

Formula x^^y = C

'2; »2 = 2.00;

log C.2 = 0.28L

logQ.

1.13

1.13

1.50

1.50

0.282

1.00

1.00

1.91

1.90

0.279

0.80

0.80

2.99

3.00

0.283

0.69

0.69

4.01

4.00

0.280

0.49

0.49

7.96

8.00
Average,

0.283

0.281

334 PROCEEDINGS OF THE AMERICAN ACADEMY.

TABLE VI.

arcc. Water; yc.c. Benzol; 5 c.c. Acetone. Temp. 20°.
Formula a: 'i y = Ci; «i = 1.40 ; log C^ = 0.262.

Water. Benzol.

Calc.

Found.

Cale.

Found.

logC,.

7.97

8.00

0.10

0.10

0.264

7.00

7.00

0.12

0.12

0.262

5.04

5.00

•0.19

0.19

0.258

4.03

4.00

0.26

0.26

0.258

2.99

3.00

0.393

0.395

0.264

2.49

2.50

0.51

0.51

0.265

2.18

2.20

0.61

0.615

0.269

2.01

2.00

0.69

0.69
Average,

0.260
0.2625

Formula x y^-^ z=. C

2; "2 = 1-35;

log (?2 = 0.114.

JogC,.

1.67

1.67

0.8.33

0.833

0.114

1.50

1.50

0.90

0.90

0.114

J. 30

1.30

1.00

1.00

0.114

1.005

J. 00

1.215

1.21

0.112

0.65

0.65

1.67

1.67

0.114

0.51

0.51

2.00

2.00

0.114

0.38

0.38

2.49

2.50

0.116

0.295

0.295

3.00

3.00

0.114

0.20

0.20

4.00

4.00

0.114

0.15

0.15

4.96

5.00
Average,

0.119
0.1145

There is but one exception, in the chloroform- water-ace tone series.
As chloroform and water behave normally with alcohol (Table I.),
water and acetone with benzol (Table VI.), the disturbing effect must be
due to chloroform and acetone in presence of each other. I have not
yet had time to investigate mixtures of chloroform and acetone in the
absence of water, to determine whether they are abnormal in respect
to any other physical properties. In the other five cases the agree-
ment between observed and calci^lated values is a remarkable one, well
within the limits of experimental error, and this in spite of the wide
range that the measurements cover. In the benzol- water-alcohol
series the ratio of benzol to water varies as one to forty thousand ; in
the chloroform-water-alcohol series the ratio chloroform-water varies as
one to twelve thousand. In the last measurement of Table I. the
chloroform forms over 809^ by volume synthetically of the solution,
so that in this instance we are well beyond the realms of the " dilute

BANCROFT. — TERNARY MIXTURES. 335

solutions," without noticing any disturbing effect due to " variations
from the gas laws." The series benzol-water-alcohol is represented by
a single curve ; but it must not be thought that in this it forms a real
exception to the other mixtures. Theoretically, there are two curves
for this series ; but the two happen to have the same direction, and
therefore appear as one. The point where the precipitate ceases to be
less dense tlian the original solution lies between the mixtures benzol
2.00 c.c, water 1.45 c.c, and benzol 3.57 c.c, water 1.00 c.c.

The formula x°- yP= Constant is not satisfactory, because it contains
no term expressing the variation of the consolute liquid in case one of
the non-miscible liquids is kept constant, and also because a change in
the units in which x and y are expressed or a change in the amount
of the consolute liquid taken affects the constant of the formula. This
can be remedied by the following reasoning. According to Gibbs and
to experiment, the absolute mass of a phase has no effect on the equi-
librium. Therefore increasing the quantities of x and y ?n-fold in-
volves inC'reasing the quantity of the consolute liquid m-fold if the
solutions are to remain at the saturation point. This would increase
the value of the constant m='+^ times. If then x and y denote the
values in cubic centimeters of the non-miscible liquids A and B, z the
corresponding value for the consolute liquid S^ we have as equation of
equilibrium for saturated solutions the expression :

If, as was done, z is kept constant, this simplifies to formula (4), which
I will renumber la .

la. - a^"/ = (^1-

\i y is constant, x and z varying, we have :

lb. -^ = c

And if X is constant, y and z varying, we have :

In equation I the value of C is a function of the nature of the units
in which x, y, and z are expressed ; but independent of the size. Thus
grams and kilograms give the same result, cubic centimeters and litres ;
but the weight constant is different from the volume constant, and the
constants for reacting weights or reacting volumes would have still

336 PROCEEDINGS OF THE AMERICAN ACADEMY.

Other values. C is also dependent on the absolute value of the expo-
nential factors a and /3. We can however eliminate this effect by
writing

(6) G = K-+^,

in which case K remains entirely unchanged, when we substitute

— = n. In Table VII. I ijive in the first two columns the values for

log (7 according to the general formula -;^^ — C, when a:, y, and z are

expressed in volumes. Since 2: = 5 in all these measurements, Table
VII. gives the constants of the preceding tables less the corresponding
values of (n + 1) log 5. It would have been better to calculate the
integration constant using the rational exponents a and /3 ; but only
their ratio can be determined by a study of equilibrium in one liquid
layer, and the case of two liquid layers will form the subject of a
separate communication. In columns three and four are the corre-
sponding values of K^ and A'o according to equation (6). They are
the constants of the preceding two columns divided by the appropriate
values of n -\-\.

TABLE

VII.

Mixtures.

logC,.

log C.

log K, .

log^,.

HoO,

CHCI3, CoHsOH

1.163

T.266

T.711

1.652

HoO,

CHCI3, CH3OH

2.984

1.489

1.692

T.773

H.,0,

CHCI3, CH3COCH3

2.506

• • • •

1.381

• • • •

H.,0,

CfiHe, C.HjOH

2.737

2.737

T.514

T.514

H.O,

CeHg, CH3OH

2.482

2.184

T.388

T.395

H2O,

C.Hfi, CH3COCH3

2.584

2.471

1.410

T.349

The values given under x and y in Tables I.-VI. are amounts of the

liquids A and Birnx given quantity of S, — in this case 0 c.c. A glance

at the tables will show that these figures are very far from expressing

volume concentrations, i. e. quantity of substance in a given volume of

the solution. As most theoretical generalizations in chemistry are

expressed in volume concentrations, it will be necessary to see what

effect such a change would have on general Formula I. If there is no

contraction or expansion on mixing, the volume of the solution will be

the sum of the component volumes, or V=x + y-^z, and the volume

. ... , X y z . .

concentrations will be ; — 1 , — ; , respectively.

x^yA^z x-Vy^z x+y + z

This simple case may be said never to occur, and the volume of the
solution is an at present unknown function of the component volumes

BANCROFT. — TERNARY MIXTURES, 337

represented by the expression V^= F (x,y,z). While the knowledge
of the form of this function is necessary to enable us to calculate the
volume concentrations of a given solution from our experimental data,
it is superfluous in the present discussion. We have (from Formula I.) :

a log X + /3 log y — (a + /3) log z = log C.

Now a log F + i8 log F — (a + /3) log V=0,

alog - + y8 log - - (a + /5) log- = log (7;

x"-^

or

^a + P

^ = C, if X, y, and z denote volume concentrations instead of

having their previous significance. Since a, 3, and C remain unchanged,
we find that Equation I represents the series of saturated solutions
obtained at constant temperature with any two non-miscible liquids,
and a third liquid miscible in all proportions with each of the other
two, provided no chemical reaction takes place and provided the react-
ing weights of the liquids remain unchanged. It is immaterial whether
X, y, and z denote volume concentrations, or concentrations of two of
the substances in a constant quantity of the third.

As has been said, volume concentrations are generally looked upon
as the only scientific way of expressing data. This is perfectly nat-
ural when we remember that our theoretical ideas have been formed
almost entirely upon a study of the gaseous state. It is not a neces-
sary method, and in this particular case it is decidedly disadvantageous
practically to use volume concentrations. It involves a determination
of the density of each solution, increasing the work and bringing in a
new source of error. When expressed in volume concentrations all
three components vary, and while it is a simple matter to plot three
variables in a plane,* I know of no way in which this can be done for
the logarithms of these variables. By the method which I have fol-
lowed, one constituent can be kept constant, no density determinations
are necessary, and there are only two variables. The formula being
hyperbolic, by plotting the data on logarithmic co-ordinates one gets a
straight line, any variation from which is easily seen, while the con-
stants of the curve can be determined from the diagram with more
speed and accuracy than by substituting the experimental values in
an equation and solving for two unknown quantities.

The next case to be considered is when we have two partially miscible

* Gibbs, Tliermodynamisclie Studien, p. 141 ; Eoozeboom, Zeitschr. f. ph.
Chem., XII. 369, 1893.

VOL. XXX. (n. S. XXII.) 22

338 PROCEEDINGS OF THE AMERICAN ACADEMY.

liquids, and a third miscible in all proportions with each of the others.
Formula I cannot apply here, because it was deduced for two non-mis-
cible liquids, and this condition is no longer fulfilled. There are two
ways of treating a problem like this. One is to change the conditions
of the experiment until they agree with the formula. The other is to
change the formula till it conforms to the conditions of the experi-
ment. I have done both. I will suppose, for the sake of clearness,
that the two partially miscible liquids are ether and water. Saturated
solutions of water in ether are absolutely non-miscible at the tempera-
ture for which they are saturated, being thus an improvement over
benzol and water, which are slightly miscible theoretically. If x and
y in equation la mean quantities of saturated water and saturated
ether solutions, instead of pure water and pure ethei*, the conditions
are satisfied for which this formula was deduced, and the equation must
apply. I have found that it did, and the experimental i^roof is given
in Tables IX. and XI,

This being settled, we can attack the second part of the problem.
Let X denote cubic centimeters of saturated solution of ether in
water, Y cubic centimeters of saturated solution of water in ether
which saturate a given quantity of a consolute liquid. It is found
experimentally that

(7) Z«r^=. Constant,

or, if we set — = n, we shall have

(8) x» r= c.

If Sj is the solubility of ether in water, s^ the solubility of water in
ether, both expressed in volumes per cubic centimeter of the solvent
synthetically, we shall have, if no contraction or expansion takes place
in forming the saturated solutions of water in ether and ether in water :

(9) X=^ + 5iJ; Y^B^s.^B;

(10) {A-\-s^AY{B^s^B)= G;

where A = c.c. water in X, Bo = c.c. ether in Y As we must assume
some contraction or expansion, let the ratio of the actual volume to
the sum of the component volumes be a-y in the saturated solution of
ether in water, and a-2 in the saturated solution of water in ether. We
have then:

(11) X=a-^(A-\- s,A); Y=cT„_{B+ SoB)',

(12) {<j, (A + s, A)y {a, (B + s, B)} = C, ;

BANCROFT. — TERNARY MIXTURES. 339

which can be rewritten :

(13) (A + si Ay (B +s,B) = -^.

(Ji 0-2

If X and y denote cubic centimeters of pure water and pure ether
dissolved in a given quantity of the consolute liquid, we have :

(14) x = A+s2B; y = B+SiA.
Solving for A and B: —

(15) ^ = -^^l^; i? = p^^.

i — Si $2 1 — Si s^

Substituting these values in (13) : —

Since cTj, o-o, Si, S2) ^^e constants for constant temperature, we can
simplify equation (16) into:

(17) (^^-s,^jy(y-s,x)= C^,

where the relation between Ci and C^ is

nR-\ ^1 _ CTl" 0-2 (1 + S,Y (1 + So)

Eliminating the effect due to the arbitrary quantity of consolute liquid

used, we have :

n Q\ {x - SoyY iy - sr oc) _

(ly; 2„+i — —^3,

Q

where Cg = ^^ . Reverting to the most general form, so as to make
the equation correspond in form to Equation I.,
n (a: - Sa yT {V - Si ^Y ^ g^

Equation II. is more general than Equation I., the latter being merely
a special case of the former, where the terms representing the mutual
solubilities are so small that they can be neglected.

In testing these equations I took, as pairs of partially miscible
liquids, ether and water, ethylacetate and water. The ether was
distilled over sodium, the ethylacetate dried with calcium chloride and
fractionated, the boiling point rising a full degree for a litre distilled
off. I think however that no essential error was introduced in this
way, and that, for my purposes, it was sufficiently pure. The solubili-

340 PROCEEDINGS OP THE AMERICAN ACADEMY.

ties were determined volumetricallj. In all cases I took 1 0 c.c. of the
solvent in a test tube and ran in the solute from a burette till the solution
clouded. One can determine this point to 0.01 c.c. without difficulty.
In Table VIII. I give the solubilities at 20° expressed in cubic centi-
meters of solute in ten cubic centimeters of solvent. The solubilities
of ether and ethylacetate in water decrease with increasing tempera-
ture ; the solubilities of water in ether and ethylacetate increase with
increasing temperature. This behavior is well known for ether ; but
I have not found it stated anywhere for ethylacetate.

TABLE VIII.

Solute

Solvent.

Solubility.

Ether

Water

1.03-4*

Water

Ether

0.08

Ethylacetate

Water

0.926

Water

Ethylacetate

0.294

It will be remembered that, when two liquids were practically non-
miscible, the series of saturated solutions formed by these with a con-
solute liquid were expressed by two curves of the same general form,
but having different constants ; and it was found that these two curves
represented, the one the sei-ies of solutions out of which liquid B is
precipitated on addition of either A or JB ; the other, the converse
series, when the solution was saturated in respect to A but sensitive to
an excess of either A or B. When the liquids A and B are partially
miscible, the case becomes apparently more complicated, for we have
four curves instead of two. These refer to four distinct sets of equi-
librium, there being the following four series of saturated solutions.

1 . The solution is saturated in respect to B. Excess of A produces
no precipitate.

2. The solution is saturated in respect to B. Excess of ^ or 5
produces a precipitate of B.

3. The solution is saturated in respect to A. Excess of ^ or ^
produces a precipitate of A.

4. The solution is saturated in respect to A. Excess of B produces
no precipitate.

Series 2 and 3 correspond to the two series observed with two non-
miscible liquids. In these two series the consolute liquid is the solvent,
whereas in series 1 and 4 we have, in addition, A and B respectively

* Schuncke finds 1.04-5, Zeitschr. f. ph. Chem., XIV, 3.34. 1894.

BANCROFT. — TERNARY MIXTURES. 341

as solvents, In Tables IX.-XIII. I give the measurements made
with ether and water, ethylacetate and water with the consolute liquids
alcohol, methylalcohol, and acetone. In Tables IX. and XI. the ex-
periments were made with saturated solutions ; in Tables X., XII., and
XIII., with pure liquids. The first method has the advantage that the
readings obtained are final, involving no correction and no knowledge
of the mutual solubilities. On the other hand, it is necessary to keep
the solutions in the burettes at the same temperature as that at which
one makes the determinations, a very difficult thing to do usually, so that
the second method is to be preferred. The exponential factors are the
same according to both methods, as I have already shown. The inte-
gration constants are diff'erent, standing to each other in the relation
given in Equation (18). It would have been well if I had determined
the densities of the saturated solutions so that they could be recalculated
into cubic centimeters of the pure liquids ; but I shall have to make
an extended series of density determinations in connection with the
equilibrium between two liquid phases, and I have postponed these
others till then. The measurements in Tables IX.-XIII. are about as
accurate as those in Tables I.-VI., with the exception of the solutions
when water is part solvent. The precipitate in these cases is lighter
than the solution, consists of a few drops only, and is very difficult to
distinguish from air bubbles, especially in the ether solutions, where the
clouding at best is very slight. For this reason the first series in each
table must be considered as very doubtful as the absolute measure-
ments go. The determination of the saturation point for these cases
depended on the light, the state of my eyes, and the mood which I
happened to be in on the days when the measurements were .made.
So difficult are the determinations sometimes, that I give no results for
ether-water-acetone because I obtained different measurements every
day. The agreement between the observed and the theoretical values
is no test of the absolute accuracy of either ; but merely shows that the
solutions follow the same general law, the constants, exponential, and
integration varying with the degree of cloudiness which the observer
takes as denoting the point of saturation. The values of n are not so
accurate as in the first set of tables, because the curves cover a more
limited extent, and therefore the variations are smaller, and because
when the value of n is large, say over 2, a very slight change in the
direction of the logarithmic curve produces a very large corresponding
change in n. The amounts of ethylacetate and water which dissolve
in 5 c.c. of alcohol, methylalcohol, or acetone were so large that I was
forced to work with one cubic centimeter of these liquids as solvent.

342

PROCEEDINGS OP THE AMERICAN ACADEMY.

TABLE IS.

Xc.c. Sat. Water; Fee. Sat. Ether; 5c.c. Alcohol. Temp. 20°.
Formula Xy»i - Ci; n^- 2.60; log C^ =: 1.994.

Sat.

Water.

Sat. Ethei

Calc

Found.

Calc.

Found.

logCi.

49.89

50.00

1.30

1.30

1.995

24.89

25.00

1.70

1.70

1.996

10.02

10.00

2.41

2.41
Average,

1.993
1.995

Formula X«2 Y =

Ca; n.2 =

1.49;

log C2 = 1.867

,

log Gj .

9.04

9.00

2.79

2.77

1.864

7.96

8.00

3.33

3.35

1.870

7.72

7.70

3.52

3.50

1.865

6.00

6.00

5.10

5.10
Average,

1.867

1.867

Formula XY- C^;

logQ

= 1.493.

lOgCg.

5.19

5.21

5.97

6.00

1.495

4.45

4.45

7.00

7.00

1.493

3.99

4.00

7.78

7.80

1 .494

3.89

3.87

8.03

8.00

1.491

3.11

3.10

10.05

10.00

1.491

2.08

2.08

14.95

15.00

1.495

1.78

1.77

17.58

17.50
Average,

1.491

1.493

Formula X"4 y =

: C4 ; 7?4 =

:1.73;

log Ci = 1.66E

).

logQ.

1.62

1.61

20.28

20.00

1.661

1.43

1.43

24.95

25.00

1 .673

1.09

1.10

.39.27

40.00

1.666

0.96

0.95

50.47

50.00
Average,

1 .659

1.G65

TABLE

X.

arc.c. Water; yc.c. Ether; 1 c.c. Methyl Alcohol. Temp. 20°.
Formula {x - 0.008 3/) {jj - 0.103 r)"' = Cj ; n^- 1.50 ; log C^ - 1.502.

Water.

Ether.

Calc.

Found

Calc.

found.

logCi.

10.05

10.00

1.13

1.13

1..500

9.00

9.00

1.04

1.04

l..^)02

7.03

7.00

0.85

0.85

I. .300

4.97

5.00

0.68

0.68

T.505

4.00

4.00

0 60

0.60

1.502

1.502

BANCROFT. — TERNARY MIXTURES. 343

inula (x - 0.008 y)»"-

iy-

-.0.103 x) =

C,;

«2 = 1.13;

log a, = 1.

Water.
Calc. Found.

Calc.

Ether.

Found

log Cj.

2.95 3.00

0.555

0.56

T.936

2.50 2.50

0.56

0.56

T.928

2.03 2.00

0.60

0.59

1 .920

1.80 1.80

0.63

0.63

T.929

1.50 1.50

0.70

0.70

T.929

1.928
Formula {x - 0.008 (/)"3 {y - 0.103 x)^Cs; i^ = 2.04 ; log Cg = 0.045.

logCs.

1.20

1.20

0.90

0.90

0.047

1.00

1.00

1.23

1.23

0.045

0.90

0.89

1.53

1.50

0.035

0.83

0.83

1.79

1.80

0.047

0.78

0.78

2.00

2.00

0.046

0.64

0.64

3.01

3.00

0.043

0.57

0.57

3.99

4.00

0.047

0.52

0.52

5.00

5.00

0.045

0.47

0.47

6.89

7.00

0.053

Formula (x — 0

.008 y)"

0.44

0.44

0.45

0.45

0.45

0.45

0.045

0.008 ?/)"i (y - 0.103 x) = Q ; Wi = 4.4 ; log C^ = 1.057.

log Ct .
10.30 10.00 T.044

11.62 12.00 T.071

15.04 15.00 T.0.56

1.057

TABLE XI,

Xc.c. Sat. Water ; Yc.c. Sat. Ethylacetate ; 1 c.c. Alcohol. Temp. 20° .
Formula X y«i = Ci ; ni = 2.86; log C^ = 1.280.

Sat.

Water.

Sat.

Ethylacetate.

Calc.

Found.

Calc.

Found.

log C,.

10.05

10.00

0.25

0.25

1.278

8.07

8.00

0.27

0.27

T.276

7.11

7.00

0.28

0.28

1.263

5.97

6.00

0.30

0.30

1.282

4.97

5.00

0.32

0.32

1.283

3.94

4.00

0.34

0.3.5-
Average,

T.286

T.278

344

PROCEEDINGS OF THE AMERICAN ACADEMY.

Formula X"-^ Y

= C.2; n.2= 1.80;

log C, =.

0.549.

Sat. Water.

Sat. Etbylacetate.

Calc. found.

Calc.

Found.

logC^.

3.00 3.00

0.49

0.49

0.549

2.50 2.50

0.68

0.68

0.548

2.00 2.00

1.02

1.02

Average,

0.550

0.549

Formula X"^ Y

= Q; «3=1.36;

log a, =

: 0.433.

log C3 .

1.45 J. 50

1.56

1.59

0.445

1.25 1.25

2.00

2.00

0.433

1.06 1.06

2.51

2.50

0.432

1.00 1.00

2.71

2.72

0.434

0.93 0.92

3.04

3.00

0.428

0.75 0.75

4.00

4.00

0.432

Average,

0.434

Formula X"* Y -

= C4 ; ^4 = 1.765 ;

log Ci -

: 0.372

log Ct .

0.65 0.65

5.02

5.00

0.369

0.59 0.59

5.98

6.00

0.373

0.54 0.54

7.00

7.00

0.372

O.50 0.50

8.00

8.00

0.372

0.44 0.44

9.96

10.00
Average,

0.370

0.371

TABLE XII.

X c.c. Water ; y c.c. Ethylacetate ; 1 c.c. Methyl Alcohol. Temp. 20°.
Formula {x - 0.029 y) (y - 0.093 a:)«i = C\ ; n-^ - 1.20 ; log C-^ - 0.002.

Water.

Ethylacetate

Calc.

Found.

Calc.

Found.

log C, .

9.92

10.00

1.08

1.08

0.006

6.96

7.00

0.85

0.85

0.005

5.08

5.00

0.72

0.72

T.995

3.96

4.00

0.69

0.69

0.006

3.01

3.00

0.68

0.68

0.000

2.51

2.50

0.70

•

0.70
Average,

0.001
0.002

mula

(x- 0.029 (/)«= {y ■

- 0.093 x) =

2 J ^2

= 2.78 ; log

a, = o.e

log. C,.

2.03

2.00

0.83

0.82

0.637

1.80

1.80

1.04

1.04

0.630

1.72

1.70

1.19

1.15

0.617

1.49

1.50

1.63

1.69

0.644

1.41

1.41

1.99

2.00
Average,

0.633

0.632

BANCROFT. — TERNARY MIXTURES. 345

Formula {x - 0.029 y)"^ (y - 0.093 x)-Cs; n^ - 2.00; log Cg - 0.550.

Water.

Calc.

Found.

1.29

1.29

1.20

1.20

1.07

1.07

1.00

1.00

Formula (.r ■

- 0.029 y}"'

0.97

0.97

0.98

0.98

1.00

1.00

1.03

1.03

Ethylacetate

Calc.

Found.

log. Cs

2.51

2.50

0.549

2.99

3.00

0.551

4.03

4.00

0.547

4.88

4.90

0.552

Avert

ige,

0.550

0.029 y}"^ (y - 0.093 x)-Ci\ n^ = 7.00 ; log C^ = 0.078.

G.OO 6.00

7.02 7.00

7.61 8.00

9.98 10.00

log C,.

0.078

0.076

0.100

0.079

Average, 0.083

TABLE XIII.

xc.c. Water; yc.c. Ethylacetate ; 1 c.c. Acetone. Temp. 20°.
Formula {x - 0.029//) {y - O.OCS .r)"! = C^ ; «i = 1.54 ; log C^ =1.364.

Water.

Ethylacetate

Calc.

Found.

Calc.

Found.

logCi.

10.12

10.00

1.02

1.01

T.359

6.99

7.00

0.76

0.76

1.365

5.01

5.00

0.60

0.60

1.363

3.00

3.00

0.47

0.47

1.364

2.00

2.00

0.43

0.43
Average,

T.365

T.363

Formula {x - 0.029 //)«2 (// - 0.093 x) = C.j ; ng = 1.16 ; log Ca = 1.721.

logC„.

1.50

1.50

0.47

0.47

T.721

1.00

1.00

0.63

0.63
Average,

T.721
T.721

Formula (x - 0.029 y) {y - 0.093 t)''3 = Cg ; n^ = 1.26; log Cg = 1.653.

logCs

0.79

0.80

0.74

0.74

1.656

0.69

0.69

0.80

0.80

1.652

0.51

0.51

1.00

1.00

T.652

0.31

0.31

1.50

1.50
Average,

T.653
T.653

346 PROCEEDINGS OF THE AMERICAN ACADEMY.

Formula (x - 0.029 j/)"^ {y - 0.093 .r) = Q ; 714 = 3.00 ; log C4 = 2.135.

Water. Ethylacetate.

Calc. Found. Calc Found. log C^.

0.25 0.25 2.01 2.00 2.134

0.25- 0.25 2.48 2.50 2.138

0.286 0.285 3.01 3.00 2.134

0.29 0.29 5.00 5.00 5.1.35

Average, 2.135

In this set of tables, as in the first set, the amount of one non-miscible
liquid which will dissolve in the consolute liquid decreases as the
quantity of the other non-miscible liquid increases. In this case,
however, the non-miscible liquids are saturated solutions and it does
not follow that the quantity of one pure liquid decreases as the other
increases. There comes a point where the rate of increase of one
component in the solution in which it is solute is greater than its rate
of decrease in the solution in which it is solvent. If we take the
general Equation (17),

(x — So yY (y — s^x) = C^,

it is obvious that as x increases y will first decrease, pass through a
minimum, and then increase. If the same equation expressed the two
equilibria, the point where y was a minimum would be the point where
the solution is no longer sensitive to an excess of x. In general, the
equilibrium for this second stage is given by a second equation, and
all we can say in our present knowledge is that at the intersec-
tion of these two curves y should have a minimum value. This
does not seem to hold in Table XII., where the amount of ethylace-
tate soluble in 1 c.c. methylalcohol in presence of 2.50 c.c. water is more
than will dissolve when either three or four cubic centimeters of water
are added. I am inclined to attribute this to experimental error, as I
do not see how there can be two saturated solutions of the same sub-
stance in the same solvent. Such a case would be entirely new, and
would involve such consequences that it is not to be assumed on the
strength of a variation of two one-hundredths of a cubic centimeter on
measurements where the probable error is known to be very large. I
propose to repeat these measurements on a larger scale, so as to deter-
mine what the facts really are. There are also one or two things in
respect to the ether-water-methylalcohol curve which need to be gone
into more closely. In Table XIV. I give the values for log C when
cleared of the term for z, and the values for log A''when the effect of the
exponential factor has been eliminated. Both log (7 and log A' are

BANCROFT. — TERNARY MIXTURES. 347

calculated for x, y, and z being expressed in cubic centimeters. A
discussion of these values is not possible at present, and in any case
they should be reduced to reacting volumes or eacting weights before
a rational treatment could be thought of.

Mixtures.

log Ci .

TAB

logC,.

LE x:

lOgCg.

[V.

10gC4.

logiTi.

log ^2.

lOg^s.

log^i.

S .H2O, S. Ether, Alcohol

1.478

0.126

0.095

1.757

1 .855

0.051

0.047

1.911

H,0, Ether, Methylalcohol

T.502

1.928

0.045

T.057

T.801

T.966

0.015

T.825

S . HjG, S. Et. Ac, Alcohol

T.280

0.549

0.433

0.372

T.814

0.196

0.182

0.134

HjO, Et. Ac, CH3OH

0.002

0.631

0.550

0.078

0.001

0.167

0.183

0.001

HjO, Et. Ac, Acetone

T.364

1.721

T.653

2.135

T.749

T.871

1.894

T.534

The measurements already communicated would be sufRcent by
themselves to establish the general law governing this class of equi-
libria ; but I have in addition experiments by other investigators which
give the same result. In 1871 Tuchschmidt and Follenius *" noticed
that carbon bisulphide was not infinitely miscible with aqueous alcohol
and they made a series of experiments to determine the saturation
points when carbon bisulphide was added to alcohol of known strengths.
They expressed their results by means of a complex empirical formula.
This is not necessary, as the general equation for two non-miscible
liquids covers the case entirely. In Table XV. the first column gives
the number of cubic centimeters of carbon bisulphide which will dissolve
in ten cubic centimeters of aqueous alcohol of the percentage compo-
sition by weight given in column two. In column three is the strength
of alcohol as required by the formula.

TABLE

XV.

a: = g.

HoO; ,

y =

ce.

CS2 . Temp.

17°.

Formula

X y^ =

C;

; n ■-

= i; log (7-

1.345.

ra-

Alcohol.

y-

Calc.

Found.

logC.

18.20

9.88

9.85

1.457

13.20

9.80

9.815

1.318

10.00

9.70

9.695

1.345

7.00

9.50

9.354

1.456

5.00

9.15

9.137

1.350

3.00

8.43

8.412

1.324

2.00

7.40

7.602

1.310

0.20

• • • •

4.84

Average,

....

1.366

* B. B., IV. 583. 1871.

348 PROCEEDINGS OF THE AMERICAN ACADEMY.

When one considers that the carbon bisuljjhide was evidently deter-
mined very roughly, the agreement is an excellent one. Here, too,
we find the existence of two curves. The last measurement lies oa
the second curve when water is the precipitate, and not carbon bisul-
phide. As only one point on this curve was measured, it is impossible
to determine the constants even approximately. The object of this
investigation by Tuchschmidt and Follenius was to obtain a method
for determining the strength of aqueous alcohol quickly and easily.
Owing to the unpleasant properties of carbon bisulphide, their choice of
liquids was bad, though the method seems to me a good one. If one
were to make a complete table for benzol or chloroform and aqueous
alcohol at zero degrees, the rest would be simplicity itself. One would
take ten cubic centimeters of the alcohol to be tested and run m chloro-
form from a burette till saturated, when a glance at the table would
give the percentage composition of the alcohol. The method would
be quicker thau any except with a hydrometer, and more accurate than
that. An idea of the accuracy is given by the fact that at 20°, 5 c.c.
of 96% alcohol require about 20 c.c. chloroform, while the same amount
of 97.5% alcohol requires about 30 c.c. for saturation. For a weaker
alcohol the change for each per cent is much less ; but the measurements
can be made more accurately.

I will now take up the measurements of PfeifFer * on the miscibility
of various esters with alcohol and water. The measurements were
not made under the most favorable circumstances. A known amount
of the ester was poured into a beaker, a definite quantity of alcohol
added, and water run in till the saturation point was reached. Nothing
was done to prevent evaporation, nothing, so far as is mentioned, to
keep a constant temperature, and there was no means of warming the
solution above the final temperature in order to insure that equilib-
rium had been reached. The necessity of this last had already been
pointed out by Duclaux,t who found that, on cooling a solution below
its saturation point, it clouded at once ; but on warming, the equilibrium
was reached much more slowly. Given these untoward conditions,
the comparative accuracy of the measurements is remarkable. While
Pfeiffer has given us series upon series of valuable measurements,
showing the increase of miscibility of esters and water in presence of
alcohol, he has curiously enough omitted all determinations of the misci-
bility of water and esters when no alcohol is present. This is still

* Zeitschr. f. ph. Chem., IX. 469. 1892.
t Ann. chim. phys., [5.], VII. 264. 1876.

BANCROFT. — TERNARY MIXTURES. 349

more remarkable if one considers the uselessness of comparing the effect
of equal quantities of alcohol on ethylaoetate and water, amylacetate and
water, without allowing for the fact that ethylacetate is roughly forty
times as soluble in water as amylacetate. As these solubilities had to
be known at any rate approximately, in order to apply Equation II.
to Pfeiffer's experimental data, I have determined several myself.
Through the courtesy of Mr. Dunlap of the organic laboratory, I re-
ceived small quantities of ethylbutyrate, ethylisovalerate, and isoamyl-
acetate. I dried them over calcium chloride and fractionated. The
change of boiling point of the portions used was four degrees for
the ethylisovalerate and two degrees for each of the others. The
amounts at my disposal made it not worth while to attempt further
purification. In Table XVI. I give the solubilities in cubic centimeters
of the solute in ten cubic centimeters of the solvent at 20°. For pur-
poses of comparison I have also inserted in this table the values for
ethylacetate from Table VIII.

TABLE XVI.

Solute.

Solvent.

Solubility.

Ethylacetate

Water

0.926

Water

Ethylacetate

0.2D4

Isoamylacetate

Water

0.02

Water

Isoamylacetate

0.12

Ethylbutyrate

Water

0.08

Water

Ethylbutyrate

0.04-5

Ethylisovalerate

Water

0.02-

Water

Ethylisovalerate

0.04+

For these four esters I have found that the solubility in water
decreases with increasing temperature, while the solubility of water in
the ester increases with increasing temperature, both observations
being made at 20°. As there is no obvious reason why these four
esters should all be abnormal, it is more than likely that this behavior
is characteristic of all esters at ordinary temperatures. As it is im-
probable that the solubility of the esters in water can continue to
decrease indefinitely with increasing temperature, there must be some
point where it reaches a minimum, and it is quite possible that a deter-
mination of this temperature for different esters might give interesting
results. The experiments could be made with great ease as the
amount of saponification during the time necessary for a measurement
would be very small.

350 PROCEEDINGS OF THE AMERICAN ACADEMY.

Quite recently, de Hemptinne * has determined the solubilities of
several esters in water at 25°. His measurements are given in grams
of the solute per litre of solution. I have reduced his measurements
to cubic centimeters of solute in ten cubic centimeters of solvent by
dividing by the densities as far as I could get them out of Landolt and
Bernstein's tables and Roscoe and Schorlemmer's text-book, disregard-
ing the difference between a litre of solution and a litre of solvent.
The results which I give in Table XVII. are only rough approxi-
mations, but quite sufficient for my purpose. The figures in the second
column are the densities used in recalculating de Hemptinue's figures.

XVII.

Solute.

Solubility

Density,

Isobutylacetate

0.07

0.88

Amylacetate

0.02-

0.88

Methylbutyrate

0.115

0.94

Ethylbutyrate

0.08-

0.898

Amylbutyrate

O.OOG

0.85

Propylpropionate

0.06+

0.88

Amylpropionate

0.01+

0.88

Ethylvalerate

0.03

0.86

De Hemptinne did not measure the solubility of water in the esters,
and I have not been able to find any data on the subject beyond
the few measurements which I have made myself. In considering
Pfeiffer's results, this is not very serious, because he worked always
•with three cubic centimeters of esters, adding alcohol in varying quan-
tities, and water to saturation. As the solubility of water in the
different esters can be rarely more than one per cent, the error in
calculating the amount of water required to saturate will in no case be
more than a tenth of a cubic centimeter, and will rarely exceed two or
three hundredths. The solubilities of esters in water, which have not
been determined by de Hemptinne or myself, have been filled in as
best I could by analogy, remembering that increase of carbon means
decrease of solubility, and that among isomeric esters the one with the
smaller acid radical was rather the less soluble. In deciding where
between two limits an unknown solubility should be put, I have taken
the figure which satisfied the experimental data best. The solubilities
thus obtained lay no claim to being accurate ; but they are not very
far out, probably in no case more than 100%, and this rough approxi-

* Zeitschr f. ph. Chem., XIII. 561. 1894.

BANCROFT. — TERNARY MIXTURES.

351

mation is better than treating the esters and water as absolutely non-
miscible. In Table XVIII. I give the solubilities which I have used
in calculating Pfeiffer's results, expressed in cubic centimeters of the
ester in ten cubic centimeters of water.

XVIII.

Solute.

Solubility.

Solute.

SolubiUty.

Methylvalerate

0.20

Propylacetate

0.30

Ethylvalerate

0.03

Butylacetate

0.07

Methylbutyrate

0.12

Amylacetate

0.02

Ethylbutyrate

0.08

Propylformiate

0.40

Propylbutyrate

0.02

Butylformiate

0.10

Ethylpropionate

0.30

Amylformiate

0.05

Propylpropionate

0.065

Starting, a3 Pfeiffer did, with a constant quantity of ester, his results
necessarily lie almost entirely along the curve representing the equilib-
rium when addition of water or ester produces a precipitate of ester.
In a few cases there are a few measurements, never more than two, on
the curve where water or ester produces a precipitate of water. There
are not enough of these measurements to enable me to determine the
direction of this second curve, and in the tables I have therefore given
no calculated values in these cases. The point where, according to
Pfeiffer, infinite miscibility occurs is the beginning of the curve where
the solution is saturated in regard to ester ; but water produces no
precipitate. The corresponding curve where the solution is saturated
in respect to water, while addition of ester produces no precipitate, did
not come within the scope of Pfeiffer's investigations at all. It will be
noticed that in the last measurements of each series the amount of
water required to saturate is very generally greater than the theoreti-
cal quantity. I attribute this variation entirely to experimental error.
When one is working with one hundred cubic centimeters of solution
or more, it becomes almost impossible to determine the first appearance
of clouding with great accuracy. In Tables XIX. to XXXI. I give
Pfeiffer's results, with the values for the water calculated according to
the formula at the top of each table. It is only fair to Herr Pfeiffer to
say that, if I had arranged the exponential factors so that z should have
been raised to the first power only, the differences between the ob-
served and the calculated values would have been less than they now
are. I felt, however, that, as the water was the thing I was calculat-
ing, I would make its exponential factor unity instead of that of the
alcohol.

352 PROCEEDINGS OP THE AMERICAN ACADEMY.

TABLE XIX.

y = 3 c.c. Methylvalerate ; x = c.c. Water ; z = c.c. Alcohol.
Formula x {y - 0.02 z)0-^i / si-^? = C ; log C = 1.807.

z.

Cak.

Found

logC.

3

• • • •

1.66

• • • •

6

5.04

5.06

1.809

9

8.88

9.03

1.815

13

13.28

13.40

1.809

15

18.34

18.41

1.809

18

23.90

24.00

1.809

21

30.09

30.09

T.807

24

36.80

36.72

T.806

27

44.35

44.15

1.805

30

.')2.80

52.37

T.803

33

62.60

62.25

1.804

36

74.25

74.15

T.806

39

91.45

• • • •

91.45

1.807

42

T.807

TABLE

XX.

^ = 3 c.c. Ethylralerate ; x — c.c. Water ; z = c.c. Alcohol.
Formula x (y - 0.003)<>-«> / z^-io = C; log C = 1.682.

X.

e.

Cale.

Found.

logC.

3

• • • •

1.42

• • • •

6

3.81

4.14

T.718

9

6.73

7.18

T.710

12

10.07

10.51

T.701

15

13.81

14.13

1.692

18

17.80

18.09

1.688

21

22.15

22.40

1.687

24

26.80

26.83

T.683

27

31.65

31.70

T.6S3

30

36.70

36.62

T.681

33

42.15

41.81

T.678

36

47.65

48.00

1.685

39

53.40

53.13

1.679

42

59.40

58.35

T.674

45

65.55

63.60

T.668

48

71.90

69.97

T.670

51

78.50

76.90

T.672

54

83.25

84.25

T.688

57

92.40

90.53

T.673

60

99.50

98.60

T.678

BANCROFT. —

•TERNARY MIXTURES

1.

z.

Calc.

X.

Found.

logC.

63

106.80

105.20

T.675

66

114.70

112.80

T.674

69

122.40

121.90

1.(580

72

130.40

131.00

1.084

75

138,90

140.20

T.G87

78

148.00

158.70

T.712

81

157.50

180.00

T.740
T.687

TABLE XXI.

353

t/ — S c.c. Methylbutyrate ; x = c.c. Water ; z = c.c. Alcohol.
Formula a; (;/ - 0.012)0-52 / 2IJ2 = C; log (7 = 1.

z.

Calc.

Found.

logC.

3

2.33

2.34

T.889

6

6.75

6.96

T.902

9

12.67

12.62

T.886

12

19.90

19.45

T.878

15

28.38

28.13

T.884

18

38.76

38.80

. T.889

21

50.85

,55.64

1.927

24

• • • •

00

T.892

TABLE

XXII.

?/ =: 3 c.c Ethylbutyrate ; a: = c.c Water ; z = c.c. Alcohol.
Formula {x - 0.005y) {y - 0.008 a: )0*i / z^*^ -C; log C = 1.785.

z.

Calc.

Found.

logC.

3

• • • •

1.66

• • • •

6

4.90

5.00

T.794

9

8.73

8.81

T.789

12

13.08

13.10

T.786

15

17.95

17.82

T.782

18

23.50

23.25

1.780

21

29.24

29.04

T.782

24

35.55

35.16

T.784

27

42.35

41.75

T.779

30

49.40

49.05

T.782

33

57.12

57.00

T.784

36

65.69

65.73

T.786

39

75.25

76.02

T.790

42

84.05

86.58

T.798

45

94.50

100.57

(T.812)

48

106.00

115.40

(T.822)

51

I19..50

137.40

(T.846)

54 .... 00 T.786

VOL. XXX. (n. S. XXII.) 23

354 PROCEEDINGS OP THE AMERICAN ACADEMY.

TABLE XXm.

y = S c.c. Propylbutyrate ; x = c.c. Water ; z = c.c. Alcohol.
Formula x {>/ - 0.002 x)<'-378y ^iszs - Q; log C = 1.651.

z.

Calc.

Found.

logC.

3

• « • •

1.19

• • • •

6

3.49

3.55

1.658

9

6.11

6.13

T.652

12

9.05

9.05

T.651

15

12.31

12.31

T.651

18

15.92

15.90

1.650

21

19.68 .

19.68

T.651

24

23.72

23.72

T.651

27

27.92

27.84

1.650

30

32.20

32.10

1.649

33

36.71

36.71

T.651

36

41.66

41.55

1.650

39

46.64

46.49

1.649

42

51.56

51.60

T.652

45

56.80

56.90

T.652

48

62.64

62.40

1.649

51

67.84

68.00

T.652

54

73.93

73.85

T.650

1.651

TABLE XXIV.

y = S c.c. Ethylpropionate ; x = c.c. Water ; z = c.c. Alcohol.
Formula x (i/ - 0.03 x)0-^ / 2i-39 - C; log. C - 1.931.

s.

Calc.

Found.

logC.

3

2.36

2.32

T.924

6

6.89

6.87

T.930

9

12.38

12.35

T.930

12

19.10

19.17

T.933

15

27.12

27.12

T.931

18

36,84

36.84

1.931

21

50.35

50.42

T.932

24

• • . •

00

T.930

BANCROFT. — TERNARY MIXTURES. 355

TABLE XXV.

^ = 3 c.c. Propylpropionate ; x = c.c. Water ; z=.cc. Alcohol.
Formula x (jj - 0.0065 x)0-« / ^i-^ = C ^ \og C = 1.733.

z.

Calc.

Found,

logC.

3

• • • ■

1.58

« t • *

6

4.45

4.70

T.757

9

8.27

8.35

1.738

12

12.25

12.54

T.743

15

17.04

17.15

T.736

18

22.27

22.27

T.733

21

28.00

27.83

1.731

24

34.20

33.75

T.727

27

40.80

40.24

1.727

30

47.95

47.15

1.725

33

55.70

54.65

T.725

36

63.50

63.18

T.731

39

72.25

71.59

1.729

42

81.15

83.05

T.743

45

91.30

93.91

1.746

48

102.00

107.46

T.756

1.737

TABLE XXVI.

y = Z c.c. Propylacetate ; x = c.c. Water ; z = c.c. Alcohol.
Formula x{y- 0.03 .r )0-23 / gi-as - Q.iQg c- 0.166.

z.

Calc.

Found.

logC.

3

4.44

4.50

0.170

6

10.57

10.48

0.163

9

17.75

17.80

0.167

12

25.95

26.00

0.167

15

35.72

.35.63

0.165

18

46.50

47.50

0.178

21

59.00

58.71

0.164

24

....

00

0.168

356 PKOCEEDINGS OF THE AMERICAN ACADEMY.

TABLE XXVII.

y = S c.c. Butylacetate ; x = c.c. Water ; z — c.c. Alcohol
Formula x (y - 0.007 x)0-3 / zi.3 = C ; log C = 1.912.

z.

Calc.

Found.

logC.

3

• • • •

2.08

• • • *

6

6.06

6.08

T.914

9

10.29

10.46

T.920

12

15.04

15.37

1.922

15

20.10

20.42

1.918

18

25.64

25.60

T.911

21

31.49

31.49

1.912

24

37.60

37.48

1.911

27

44.05

43.75

T.909

30

50.74

50.74

1.912

33

58.00

59.97

1.927

1.916

TABLE XXVIIL

y = 3 c.c. Amylacetate ; x = c.c. Water ; z = c.c. Alcohol.
Formula x {y - 0.02x)0-294 / si.m - c-^logC- 1.861.

z.

Calc.

Found.

logC

3

• « • •

1.76

• • • •

6

■ • • •

4.24

• ■ • •

9

9.03

9.03

T.861

12

13.11

13.24

T.866

15

17.43

17.52

T.864

18

22.22

22.22

T.861

21

26 99

26.99

T.861

24

32.24

32.14

T.860

27

37.59

37.23

T.856

30

42.78

42.66

T.859

33

48.41

48.41

1.861

T.861

BANCROFT. — TERNARY MIXTURES. 357

TABLE XXIX.

y = S c.c. Propylformiate ; x = c.c. Water ; z = c.c. Alcohol.
Formula x (i/ - 0.04 x)0-s» / ^i-ss =: C ; log C = 1.967.

z.

Calc.

Found.

logC.

3

2.82

2.83

T.969

6

7..52

7.50

T.966

9

13.05

13.50

T.962

12

21.30

21.60

1.973

15

30.95

30.60

T.962

18

52.40

53.00

T.972

21

• • • •

00

T.967

TABLE

XXX.

y = S c.c. Butylformiate ; x = c.c. Water ; z — c.c. Alcohol.
Formula x{y- 0.01 x)^ / z^ - C ; log C = 0.057.

z.

Calc.

Found.

logC.

3

3.43

3.45

0.060

6

8.71

8.83

0.063

9

15.02

14.75

0.049

12

22.32

21.45

0.041

15

30.25

29.65

0.048

18

39.00

39.00

0.057

21

48.80

• • • •

51.80

03

0.083

24

0.057

TABLE

XXXL

^ = 3 c.c. Amylformiate ; x — c.c. Water ; z = c.c. Alcohol.
Formula x {y - 0.005 xf-35 / z^-^^ = C ; log C = 1.808.

z.

Calc.

Found.

logC.

3

• • • •

1.80

• • • •

6

4.92

5.17

T.829

9

8.54

8.77

T.820

12

12.63

12.64

1.809

15

17.10

17.01

1.806

18

21.90

21.86

1.807

21

27.06

27.06

T.808

24

32.50

32.31

T.805

27

38.31

38.31

T.808

358 PROCEEDINGS OF THE AMERICAN ACADEMY.

z.

Calc.

Found.

logC.

30

44.40

44.50

T.809

33

50.71

50.71

T.808

36

57.20

57.82

T.813

39

62.70

65.21

(T.830)

42

71.35

77.05

(T.842)

45

78.75

85.10

(T.842)

48

86.55

94.20

(T.845)

1.811

In addition to these tables, Pfeiffer made a few measurements on
amylalcohol, monochlor-, dichlor , and trichloracetic ester in the pres-
ence of alcohol and water. The solubility of amylalcohol in water is
given by Roscoe and Schorlemmer as two parts in a hundred, and I
have used this value. I could find no data whatsoever in rej^ard to
the chloracetic esters, so I have calculated the values on the false
assumption that they are non-miscible with water. The effect of this
error is seen very markedly in the case of the monochloraceticester,
which is undoubtedly the most soluble of the three. I give these tables
in spite of the known inaccuracy, because the absolute values of the
constants are, for the time being, of little value, whereas it is essential
to show that the same general law covers all substances and that the
substitution of chlorine for hydrogen does not affect the action of
the Mass Law. The coincidence of the three choraceticesters hav-
ing the same exponential factor is probably only superficial, as the
correction for the solubilities would alter the exponential factor
somewhat.

TABLE XXXII.

y = Z c.c. Amylalcohol ; x — c.c. Water ; z — c.c. Alcohol.
Formula x {y = 0.02 xf'^ / -i ^ = C ; log C = 0.100. Temp. 9.1o.

z.

Calc.

Found.

log. C.

3

3.81

3.21

• • . •

6

10.26

10.35

0.104

9

18.53

18.34

0.095

12

28.45

27.47

0.085

15

40.85

41.25

0.104

0.097

BANCROFT. — TERNARY MIXTURES. 359

TABLE XXXIII.

^ = 3 c.c. Amylalcoliol ; x = cc. Water ; z = c.c Alcohol.
Formula x (y - 0,02 xf-^ / z^* = (7 ; log C = 0 112, Temp. 19.2°

z.

Calc.

Found.

logo

3

3.93

3.50

• • • >

6

10.55

10.80

0.122

9

19.10

19.10

0.112

12

30.05

29.15

0.099

15

42.30

43.15

0.121

0.114

TABLE XXXIV.

.c Monochloraceticester ; x

— C.C Water

; z

— c.c. Alcohol

Formula x tf^"^ /

2.1,4.3 -

:C, log

C =

1.700.

Z. Calc.

X.

Found.

logC.

3 1.54

1.32

T.644

6 4.05

4.01

1.695

9 7.23

7.30

T.705

12 10.91

10.78

T.695

15 15.04

16.16

T.731

18 19.50

22.16

T.756

21 24.33

28.74

T.772

1.714

TABLE XXXV,

y = 3 c.c. Dichloraceticester ; x = c.c. Water; z = cc. Alcohol.
Formula x if-'^'^ I z^^ = C ; log C =^ 1.479.

X.

z.

Calc.

Found.

logC.

3

0.90

0.90

1.477

6

2.44

2.45

T.481

9

4.35

4..33

T.477

12

6.54

6.60

T.482

15

9.04

9.20

T.487

T.481

860 PROCEEDINGS OP THE AMERICAN ACADEMY.

TABLE XXXVI.

y ■= S c.c Trichloraceticester ; x = c.c. Water ; z = c c. Alcohol.
Formula x yO-« / z i-« = C; log C - 1.336.

X.

z.

Calc.

Found.

logC.

3

0.65

0.65

T.336

6

1.76

1.80

1.347

9

3.13

3.02

T.321

12

4.72

4.50

T.315

15

6.50

6.50

T.336
T.331

Tables XIX.-XXXI. fwrnish a striking confirmation of the way in
which the Mass Law applies to this class of phenomena ; while some of
the results are not as satisfactory, perhaps, as I should like, there are
some, notably those with propylbutyrate, where the agreement between
the observed and the calculated values is something marvellous, though
it is unfortunate that the solubility of propylbutyrate in water has
never been determined experimentally.

As it might be thought a mere assumption that the first measure-
ments in several series were determinations of another equilibrium,
namely, of a saturated solution from which water or ester precipitated
water, I have made a few measurements with the few esters I had on
hand. The object of these measurements was to show that the change
from one equilibrium to another did come at the point shown by
Pfeiffer's results, and to make sure that the variations in Pfeiffer's data
were due to experimental error. On this account I have made no
measurements on the end curves, where water and where ester are part
solvents, and in the case of ethylisovalerate I have measured only one
series. The results are given in Tables XXXVII.-XXXIX.

TABLE XXXVn.

X = c.c. HoO ; y = c.c. Ethylisovalerate ; 5 c.c. Alcohol. Temp 20°.
Formula (x - 0.004^)" (y -0.002 x) / 3" + ^ = C; n = 2.45; log C = 1.149.

Water

Et Val.

Calc. Found.

Calc.

Found.

log P.

9.98 10.00

0.15

0.15

T.152

8.05 8.00

0.24

0.23

T.142

6.01 6.00

0.46

0.46

T.147

4.99 5.00

0.72

0.72

T.152

4.00 4.00

1.23

1.23

T.I 49

1.148

BANCROFT. — TERNARY MIXTURES. 361

TABLE XXXVIII.

X = c c. H.,0 ; y = c.c Ethylbutyrate ; 5 c c. Alcohol, Temp. 20°.
Formula {x - 0.005 y)"^ {y - 0.008 x) / z«i + ' = Ci ; n^ - 244 ; log C, - 1.449.

Calc.

Found.

Calc

Found.

log Ci.

9.99

10.00

0.34

0.34

1.450

8.01

8.00

0.51

0.51

1.447

5.97

6.00

0.95

0.96

1.453

&.01

5.00

1.45

1.44

1.447

3.99

4.00

2.46

2.47

1.45'

1.449
Formula (x - 0.005 y)"^ (^ - 0 008 x) / s"* + ^= C^ ■,n.2 = 1.20, log Cg = 1.623.

log C,

2.96

2.96

3.99

4.00

1.624

2.46

2.48

4.94

5.00

1.628

2.12

2.10

6.07

6.00

1.618
1.623

TABLE XXXIX.

X = c.c. Water ; y = c.c Isoamylacetate; 5 c.c. Alcohol Temp 20°

Formula (x - 0.012 y)»> (y - 0 002 x) / s'" + 1 = Cj , ji^- 3.50 ; log C^ =1.414,

X. y.

Calc. Found. Calc. Found. log C,.

7.00 7.00 0.41 0.41 1.414

6.00 6.00 0.70 0.70 1.414

5.01 5.00 1.32 1.31 1.411

1.413

Formula (x - 0.012 y)"^ (// -

- 0.002 r)/ 2"'' +1 =

Co ; n^

= 1.50; log C.^

lOgCj

3.62 3.61

3.00

3.00

1.558

3.00 3.01

3.99

4.00

1.560

2.60 2.60

5.00

5.00

1.5.59

1.559

Although Pfeiffer does not say so, his araylacetate and ethylvalerate
are unquestionably iso- and not the normal compounds. We can now
take up the results given in Tables XXXVII.-XXXIX. and see how
satisfactorily they fulfil their object. Ethylbutyrate and amylacetate
show the change from one equilibrium to the other at the same point
that Pfeiffer found. The ethylbutyrate and ethylisovalerate mixtures
are perfectly regular at concentrations beyond those used by Pfeiffer,
and the isoamylacetate is normal throughout both in Pfeiffer's work

362 PROCEEDINGS OP THE AMERICAN ACADEMY.

and in mine, so that the variations in Tables XXIX.-XXXI. are due

to experimental error. The agreement in results between the two
sets is shown in Table XL., where I give in the first column the value
of the exponential factor w + 1 from the formula

i^-hy) {y-s,xyiz"+'=c,

and in the second column the values for the simplified integration

constant log K.

TABLE XL.

Ester.

« + l.

log K.

Ethylisovalerate

Pfeiffer

1.40

T.773

(<

W. D. B.

1.41

T.754

Ethylbutyrate

PfeifEer

1.41

T.847

iC

W. D. B.

1.41

T.840

Isoamylacetate

Pfeiflfer

1.294

T.893

**

W. D. B.

1.286

T.870

As will be seen, the values of w + 1 are identical, the values for los
-ff, though very close, are not quite the same. This may be due to
inaccuracies in the work, but I am more inclined to attribute it to differ-
ences in temperature. It is not known at what temperature PfeifFer
worked, and it would take only a slight difference to account for the
variation. In Table XLI. I have tabulated the w + 1 values from
Pfeiffer's results, together with log C and log K.

TABLE XLI.

Ester.

n+1.

log C.

log A-.

Methylisovalerate

1.37

T.807

T.H59

Ethylisovalerate

1.40

1.682

T.773

Ethylisovalerate *

1.41

1.653

T.754

Methylbutyrate

1.52

T.888

T.926

Ethylbutyrate

1.41

1.785

T.847

Ethylbutyrate *

1.41

T.774

1.840

Propylbutyrate

1.378

T.651

T.747

Ethylpropionate

1.39

1.931

T.878

Propylpropionate

1.45

T.733

T.816

Etliylacetate *

1.555

8 • • •

Propylacetate

1.23

0.166

0.135

Butylacetate

1.30

T.912

T.9.32

Isoamylacetate

1.294

T.861

T.893

Isoamylacetate *

1.286

T.832

T.870

Propylformiate

1.38

1.967

T.976

Butylformiate

1.333

0.0.57

0.043

Isoamylformiate

1.35

1.808

T.8.58

* My own measurements.

BANCROFT. — TERNARY MIXTURES. 363

The first thing that strikes one about this table is the way in which
so many of tlie h + 1 values approximate to 1.40. Why this should
be so is entirely unknown. In tiie log K values we notice that, for the
same acid, increasing the carbon atoms in the alcohol radical diminishes
the constant. There is only one exception to this, butylformiate, and
here the possible error is very large. It looks also as if the constants
might be additive, being made up of one factor for the alcohol and
another for the acid radical ; but the experimental data is too insuffi-
cient to Justify this hypothesis. It is very much to be hoped that
some one will make a careful series of experiments to settle this
point.

Formula II. was deduced for the case when the reacting weights of
the substances in equilibrium are not functions of the concentration.
The measurements of Pfeiffer and myself show that, with the possible
exception of the chloi'oform-water-acetone series, this condition has been
satisfied in all the cases studied, though the experiments extended over
a wide range of concentrations. This is in flat contradiction with
the determinations of the reacting weights by the boiling-point and
freezing-point methods. These methods give accurate results only for
very dilute solutions, and even then only for certain solutes in certain
solvents. To explain the variations, we are forced to assume "double
molecules " in some cases, polymerization with increasing concentration
in practically all cases, and " variations from the gas laws." I have
brought together a large series of measurements in which there is no
sign of any of these things. I see only two jjossible hypotheses to
account for this discrepancy : first, to enunciate a new and most in-
teresting law, to wit, presence of a third substance prevents " polymeri-
zation " and " variations from the gas laws " ; second, the formula for
the change of vapor pressure with the concentration is incorrect. Tlie
first hypothesis seems to me out of the question, and there remains
only the second. It is a bold thing to question so univei'sally accepted
a formula, but I feel convinced that it is not right, and that equal react-
ino- weights of different substances do not produce the same change of
vapor pressure. I think that the mistake in the past lay in assuming
that the work done in compressing a dissolved substance from the
volume Fi to the volume V^, by means of a semipermeable piston is
equal to f p d v between those limits, irrespective of the nature of
solute and solvent. I have already collected some experimental evi-
dence in favor of this view, and I hope before long to be able to
establish my point.

The facts brought out in this paper throw light on a research by

364 PROCEEDINGS OF THE AMERICAN ACADEMY.

Abegg * carried out under the direction of Arrlieuius. Abegg let
alcohol diffuse into a salt solution and found, to his surprise, that the
salt, instead of remaining equally divided throughout the liquid, diffused
somewhat into the part not yet reached by the alcohol. He concludes
that this extraordinary behavior can only be accounted for on the
assumption that alcohol increases the osmotic pressure of a dissolved
salt. What happens is very simple. When the alcohol has diffused
only a little way, one may consider the solution as composed of two
parts, one containing a large amount of alcohol, the other very little.
The dissolved substance, being in this case less soluble in the first
layer than in the second, diffuses into the second only to go back again
as the alcohol becomes more evenly divided throughout the liquid.
Except that the part containing much alcohol and little water merges
insensibly into the part containing much water and little alcohol, and
is not in equilibrium with it, the case does not differ from two layers
formed by ether and water, where it is well known that the concen-
tration of a third substance is not the same in the two layers. The
effect of the alcohol is not, as Abegg assumes, to increase the osmotic
pressure of the solute, but to diminish its solubility in that portion of
the liquid. If, instead of taking salts which were only slightly soluble
in alcohol, Abegs; had let water diffuse into water containin"; in solution
some substance very soluble in alcohol, slightly soluble in water, he
would have observed the opposite effect, and the dissolved substance
would have diffused partially into tlie layer rich in alcohol.

Another line of reasoning which is not quite defensible is that taken
by Wildermann,t in his paper, " Ueber cyclische Gleichgewichte."
His train of thought is something as follows. Suppose he has a system
of three phases, bromine, a solution of bromine in water, and the
vapor of bromine and water, it being assumed that the amount of
water which dissolves in the bromine can be neglected. He adds to
the aqueous solution some substance which does not dissolve in bromine
perceptibly, such as potassium bromide or sulphuric acid. The three
phases, when in equilibrium, have still the same concentration of liquid
bromine and of bromine vapor. Therefore the solubility of the bro-
mine in the liquid cannot have changed. It does change experimen-
tally ; therefore, in order to reconcile the reasoning with the facts, he
concludes that the apparent change, decrease or increase, is due to
chemical action, and that the amount of bromine dissolved as such
remains unchanged. This may be true in the special examples studied

* Zeitsclir. f. ph. Chem., XI. 248. 1893. t Ibid., XI. 407.

BANCROFT. — TERNARY MIXTURES. 365

by Wildermanii.* That I cannot say ; but it is not true that it is a
necessary theoretical conclusion, and there is no proof that it is correct
in any case. If, instead of adding potassium bromide, we add to the
water some liquid in which bromine is readily soluble, the amount of
bromine dissolved will increase without there being any reason to
assume chemical action in order to account for it. Bromine is not a
good substance to consider, because there are so few liquids soluble in
water in which it dissolves without decomposition, and also because we
cannot ignore the solubility of the added substance in it. Let us
rather treat the case when we have iodine instead of bromine. Sup-
pose we have the system, solid iodine, a solution of iodine iu water, and
vapor of iodine and water; we add alcohol to tlie solution. The con-
centrations of the solid iodine and the iodine vapor will remain prac-
tically unchanged ; therefore the solubility of iodine in the water, and
alcohol should remain unchanged according to Wildermann. As a
matter of fact it does change, and I do not see how this variation can
be attributed to chemical action unless all solution is defined as chemi-
cal action, which begs the question though very possibly true. There
may be a radical difference between the action of the alcohol and the
action of potassium iodide; but that difference has not been shown.
As far as I can see, Wildermann's conclusions require that adding
alcohol to a saturated salt solution should have no effect on the concen-
tration of the salt because the, equilibrium between the solid salt and
its own vapor would remain unchanged.

Early in this paper I proposed the word "solute" as something
distinct from " solvent," and it is necessary for me to justify that dis-
tinction. The usual way of looking at binary solutions is to consider
them as mixtures, and that it is purely arbitrary which of the two sub-
stances we consider as solvent and which as dissolved substance. The ,
following citations will show what the prevailing opinion at the present
moment is.

Lothar Meyer, after pointing out that in alcohol-water mixtures it
depends on the nature of the semipermeable membrane which sub-
stance exerts the osmotic pressure, says : t " Mit der Beschaffenheit
der Membran tauschen beide Stoffe die Rollen ; es ist daher eine
Willkiir wenn wir den einen als gelost, den anderen als das Losungs-
mittel bezeichnen." Ostwahl is consistent to the bitter end, saying :t

* See Jakovkin, Zeitschr. f. ph. Cheni., XIII. 539. 1894.
t Zeitschr. f. ph. Chem., V. 24. 1890.
t Ibid., XII. 394. 1893.

366 PROCEEDINGS OP THE AMERICAN ACADEMY.

" Losungsmittel ist derjenige Stoff des Gemenges, welclier bei dem
betrachteten Vorgange ausgeschieden wird." This view is heroically
logical, for it meaus that, when a salt crystallizes from a saturated
solution, the mother liquor consists of water dissolved in the salt.

Nernst's position on the subject is doubtful. He puts solutions un-
der the head of physical mixtures and remarks : * " Die verdiinnten
Losingen sind Gemische welche eine Komponente in grossen Ueber-
schuss zu den iibrigen enthalten ; erstere bezeichnen wir in diesem
Falle als das Losungsmittel, letztere als geldste StofEe." On the other
hand, he draws a distinction between freezing out the solvent and
crystallizing out the solute, f He does not accept the view that the
salt is the solvent in a saturated solution ; but he does not suggest in
any way that there may be different laws for the solute and the solvent.
Planck is very clear and precise ; he defines dilute solutions in almost
the same words as Nernst, and goes on : $ " Bei einer beliebigen Losung
kann jeder Bestandtheil derselben als Losungsmittel oder als geloster
Stoff aufgefasst werden." This means that in a mixture of two liquids
either may be considered as the dissolved substance, and will therefore
decrease the partial vapor pressure of the other, and this decrease of
the vapor pressure will be greater the greater the concentration of the
dissolved substance. This is not in agreement with the facts. A
saturated solution of ether in water has the same partial vapor pres-
sures as a solution of water in ether sajturated at the same tempera-
ture. § For the moment we will consider ether as the dissolved
substance. In the first solution, the volume concentration is roughly
10% ; in the second, about 99% at 20° ; and yet this enormous change
of concentration has no effect on the partial vapor pressures. The
figures are still more remarkable if we consider solutions of chloroform
, in water and water in chloroform, when one of the components is
present in infinitesimal quantities. We must assume one of two things :
either that our present formula for the change of the vapor pressure
with the concentration is all wrong, since it does not admit of the
vapor pressure of one of the components passing through a mini-
mum ; or that there is a difference between solvent and solute, and
that each has its own law expressing the change of its vapor pressure
with the concentration. This time I prefer the second assumption,
with all that it implies. The equations of van 't Hoff and Raoult are

* Tlieoretische Chemie, p. 115. t Ibid., p. 393.

I GrunJriss der Thermoclicmie, p. 131.

§ Wied. Ann., XIV. 219, 1881; Ostwald, Lelirbucli, I. 644.

BANCROFT. — TERNARY MIXTURES. 367

the rough statements of the laws for the solvent. The corresponding
expressions for the solute have not yet been worked out. The distinc-
tion between solvent and solute is very clear in solid solutions of
metals in metals. Starting from either of two pure metals a depres-
sion of the freezing point is noted when the other is added, the two
curves thus formed meeting at the melting point of the eutectic alloy.
Here there can be no question that along one curve the first metal is
solvent, while on the other it plays the role of solute. In the case of
two partially miscible liquids there is also no difficulty in determining
which is solvent and which solute. When ether and water are shaken
tosfether, the upper layer contains water as dissolved substance, the
lower ether. With completely miscible liquids having a maximum (or
minimum) vapor pressure at some concentration, such as propylalco-
hol and water (formic acid and water), it is probable that the change
of solvent occurs at the concentration corresponding to the maximum
(or minimum) vapor pressure. With such things as ethylalcohol and
water, which are infinitely miscible and which show no maximum or
minimum vapor pressure, it is impossible at present to say at what con-
centration alcohol ceases to be the solvent and water assumes that
duty. As soon as we have worked out the relation between the con-
centrations in the solution and in the va[)or, I feel certain that we
shall find that it requires two curves to express the relation, and not
one. The intersection of these curves will be the point where the
solvent changes. I look upon my own results with ternary mixtures as
very significant in this respect, the change from one curve to another
coming at the point where the precipitate or the solvent changed. It
is interesting to note that at the point, for instance, where an excess of
one of the partially miscible liquids first has no effect, the solubility
curve of the dissolved substance has a " break." The possibility of
such a case has always been denied except by the upholders of the
" hydrate theory."

The effect of temperature on the various equilibria will form the
subject of a special paper, and I shall reserve for it the discussion of
changes of temperature coefficient at the intersections of two curves,
one or two very striking instances of which I have come upon inci-
dentally in my work so far. I hope also to be able to present a
paper on equilibrium in two liquid layers, a subject which is of especial
interest because the theoretical treatment based on the experimental
work in this paper gives results which are not in accordance with the
assumptions on which Nernst bases his Distribution Law. Besides,
there is the application of the Mass Law to the case where one or more

368 PEOCEEDINGS OP THE AMERICAN ACADEMY.

of the components is solid, and to the instances where there is an
increase instead of a decrease of solubility.

The results of this paper may be summarized briefly as follows.

1 . The equilibria between two partially miscible liquids, and a con-
solute liquid follow the Mass Law.

2. There are four sets of equilibria corresponding to four different
series of solutions.

3. If the two liquids are practically non-miscible, there are only two
sets of equilibria.

4. The reacting weights of the liquids studied were not functions of
the concentration, — possibly with one exception.

5. There is a fundamental difference between the solute and the
solvent.

6. The solubility curve of a substance in a varying mixture of two
liquids at constant temperature has a break.

BICHARDS. — ATOMIC WEIGHT OF STRONTIUM.

369

XIV.

CONTRIBUTIONS FROM THE CHEMICAL LABORATORY OF

HARVARD COLLIiGE.

A REVISION OF THE ATOMIC WEIGHT OF

STRONTIUM.

FIRST PAPER: THE ANALYSIS OF STRONTIC BROMII)E.

By Theodore William Richards.

Presented June 9, 1894.
«

Table of Contents.

Earlier Work 364

Properties of Strontic Bromide . . 373

Preparation of Materials .... 375

Method of Analysis 380

PAGE

Ratio of Silver to Strontic Bromide . 384
Ratio of Argentic to Strontic Bromide 388
Final Averages 389

Earlier Work.

A GLANCE at published results shows that the atomic weight of
stroutiuin has not been investigated for thirty-five years. The early
determinations, good enough for their time, show variations which
render them quite unsatisfactory to-day ; and the case is parallel in
every respect to that of barium, which has formed the subject of two
recent papers.*

The oldest experiments of any note upon the atomic weight of stron-
tium are those of Stromeyer,t who measured, in 1816, the gas evolved
from strontic carbonate upon its decomposition by an acid. The
result, which is only of interest historically, gives Sr = 87.3, if a litre
of carbon dioxide weighs 1.977 grams under normal conditions.

At about the saine time Rose t found that 181.25 parts of argentic
chloride could be obtained from a hundred parts of strontic chloride, —
data which indicated Sr = 87.31. Twenty-seven years afterward, in

* These Proceedings, XXVIII. 1 ; XXIX. 55.

t Schweig. J., XIX. 228 ; Meyer u. K. Seubert's Atomgewichte, p. 123.
} Poggendorff's Annalen, VIII. 189.
VOL. XXX. (n. s. XXII.) 24

870 PROCEEDINGS OP THE AMERICAN ACADEMY.

1843, Salvetat * determined by loss of weight the carbon dioxide in
strontic carbonate, and concluded that the metal must be 88.0, — a
result which scarcely improved the situation.

Subsequently, in 1845, Pelouze f found the amount of silver neces-
sary to precipitate a weighed amount of ignited strontic chloride ; his
results give the value Sr = 87.70. Thirteen years later Marignac X
repeated these experiments, determining also the amount of crystal
water in crystallized strontic chloride, as well as the amount of stron-
tic sulphate obtainable from the salt. Thus he found that 15.000
grams of crystallized strontic chloride yielded 8.9164 § grams of the
anhydrous salt and 10.3282 grams of strontic sulphate ; moreover,
15.000 grams of hydrated strontic chloride required 12.1515 grams of
silver for precipitation. Another similar series of experiments upon
the water of crystallization made its amount appear three milligrams
more than before. These data give basis for a number of possible
values for the atomic weight of strontium, ranmns: from 87.17 to
87.55, the individual figures being tabulated below.

In 1859 Dumas || published another determination of the ratio of
strontic chloride to silver, the salt having been fused in a stream of
hydrochloric acid. Altogether, 27.3435 grams of strontic chloride
required in his hands 37.252 grams of silver, the individual values
for strontium varying fi'om 87.3 to 87.8. Since this time the sub-
ject has remained untouched.

Below is tabulated a list of the various determinations, grouped
according to the ratios determined.

The Atomic Weight of Strontium.

Oxygen = 16.000.

From the carbonate :

Stromeyer, 1816 87.30

Salvetat. 1843 88.00

Ratio of strontic and argentic chlorides :

Rose, 1816? 87.31

* Comptcs Eendus, XVII. 318.

t Ibid., XX. 1047.

X Liebig's Annalcn, CVI. 168.

§ Corrected V)y L. Meyer u. K. Seubert, Atomgewichte, pp. 78, 79.

II Liebig's Annalen, CXIII. 34.

RICHARDS. — ATOMIC WEIGHT OP STRONTIUM.

371

Ratio of anhydrous strontic chloride to silver :

Pelouze, 1845 87.70

Marignac, 1858 87.48

Dumas, 1859 87.53

Ratio of crystallized strontic chloride to silver :

Marignac, 1858 87.52

From the crystal water iu strontic chloride :

Marignac, 1858 87.35

Ratio of anhydrous and crystallized strontic chloride to strontic
sulphate :

Marignac, 1858 87.2 to 87.6

Selected by Clarke 87.58

Selected by Meyer and Seubert 87.5

Selected by Ostwald * 87.5

A critical review of the list reveals a great lack of trustworthiness
in all the figures. The values deduced from the carbonate, and those
involving water of crystallization, may all be thrown out at once ;
and the results yielded by the displacement of hydrochloric by sul-
phuric acid are but little better. The series upon which most chemists
have relied — the one based ou the titration of the chloride by means
of silver — is hopelessly vitiated by the imperfect execution of the
method of analysis.f If any further proof of this uncertainty were
needed, the following table, giving a comparison of the work of differ-
ent experimenters upon other chlorides, would furnish it.

Molecular Weights of Chlorides by the Method of Gat-Lussac.

Pelouze.

Marignac.

Dumas.

Stas.
1st. 2d.

NaCI

58.434

58.468

58.506

58.503

KCl

74.539

74.583

74.600

NH4CI

53.464

53.450

53 530

53.532

* Much assistance in preparing this list has been obtained from the well
known works of these authors. The figures have all been based upon the
most recently accepted atomic weights.

t Tliese Proceedings, XXIX. 80 et seq.

372 PROCEEDINGS OF THE AMERICAN ACADEMY.

Thus, Pelouze, Marigoac, and Dumas all obtained low results with
the method of Gay-Lussac ; in fact, the error sometimes exceeded the
tenth of one per cent. The cause of this error, which apjjeared also
in the work of these expeiimeuters upon barium, has already been
pointed out in another paper.*

We are thus led to infer that the true molecular weight of strontic
chloride must exceed the usually accepted value 158.4 by about one
tenth of one per cent, and that the true atomic weight of strontium
must be nearly 87.7. This inference is confirmed by the result of the
investigation now to be described.

The balance and weights, and the methods of weighing and of tabu-
lating results employed in the work recounted below have already
been described in sufficient detail. f The balance seems to have in-
creased slightly in sensitiveness during its four years' work, owing
perhaps to the smoothing of microscopic roughnesses in the bearings.
It is almost needless to say again that the weights were carefully stan-
dardized from time to time, and the small, surprisingly constant cor-
rections were always applied. The correction to the vacuum standard
was calculated by the usual formula :

( "-""'^"^ 0.000156^ 2L 2P\

\sp. gr. substance / t 60 273° + t°

= correction in grams for 1 gram of substance, j

The values thus calculated for the appropriate substances at 20°
and 760 mm. were as follows :

Correction to be applied to One Gram of Substance.

Gram.

Silver —0.000031

Argentic bromide +0.000043

Strontic bromide +0.000141

The general plan of the following work was similar to that adopted
in the case of barium. For obvious reasons the bromide of strontium
was chosen as the starting point ; and the investigation began with a
study of the properties of the salt, in order to determine its fitness for
the purpose.

The atomic weight of silver is assumed to be 107.93, and that of
bromine 79,955, unless a definite statement to the contrary is made.

* Tliese Proceedings, XXIX. 80.
t These Proceedings, XXVI. 242 ; also XXVIII. 5.

J H = atmosplieric pressure; <° = atmospheric temperature at the time of
weigliing ; 0.000156 = standard weiglit of air displaced by 1 gram of brass.

RICHARDS. — ATOMIC WEIGHT OP STRONTIUM. 373

Properties of Strontic Bromide.

The properties of the bromide of stiontium resemble very closely
those of the corresponding salt of barium. As is well known, how-
ever, the strontium salt usually crystallizes with six instead of with
two molecules of water. The crystals, unlike those of the barium
salt, are noticeably hygroscopic in ordinary air, so that they can-
not be weighed with great accuracy ; they melt easily in their own
water of crystallization at about 100°. This latter fact renders more
difficult the quantitative drying of the salts ; indeed, in the few cases
where the water of crystallization was determined, it was necessary to
allow the crystals slowly to lose their water in a desiccator before
ignition. Thus, it was found in the following experiment that five
molecules of water were given off, the sixth having very little, if
any, tension at ordinary temperatures.

Grams.

Initial weight of strontic bromide .... 1.3305

Constant weight after three weeks over H2SO4 .9926

Heated to 200° for three hours 9246

T n ■ u.- 1 • ( Found . . = 25.41

Loss of weight in dry air ■<

^ ^ \ Calc. for 5 HjO = 25.33

Additional loss on ignition \ ' '

(Calc. . . . = 5.06

A week's standing in the air of the laboratory sufficed to supply
again all the water which had been lost. These results point without
doubt to the existence of a definite substance having the formula
SrBi'g . HoO, which is hygroscopic in the air and corresponds to the
compound BaBr.^ . HoO, obtained in a similar way.* The existence
of this substance has already been inferred by Lescoeur f from obser-
vations of the vapor tension of the crystal water. Anhydrous strontic
bromide is perhaps even more hygroscopic than the corresponding salt
of barium.

Strontic bromide melts to a transparent liquid at 630° (Carnelly),
losing bromine in noticeable quantities if exposed to the air for some
time at this temperature. Fused in a current of dry hydrobromic
acid the salt soon recovers this lost bromine, and upon subsequent
solution in water shows itself to be wholly neutral both to phenol
phthalein and methyl orange. It will be seen that this fact is of the

* These Proceedings, XXVIII. 12, foot-note.

t Ann. de Chira. et de Phys., [6.], XIX. 553 (1890).

374 PROCEEDINGS OF THE AMERICAN ACADEMY.

utmost significauce. The cold fused transparent or trauslucent mass
is much less hygroscopic than the powder from which it was made.

The importance of driving out every trace of water from the salt
before weighing cannot be overestimated. Systematic experiments*
with baric bromide and chloride led to the conclusion that probably
neither of these salts retains water at a red heat, and it was to be ex-
pected that the same fact might be true of the substance in hand. In
order to test the jioint, four grams of very pure strontic bromide dried
at about 400° were fused in a stream of hydrogen bromide. The mass
gained nearly six milligrams in weight, showing that the loss of bro-
mine in the air at 400° much more than counterbalanced a possible
trace of water. Again, 11.2G10 grams of the same specimen, dried
at 305° until constant in weight, were found to weioh 11.2630 grams
after fusion as before. Since these gains corresponded closely with
losses of bromine found alkalimetrically in similarly heated but unfused
samples, it is evident that very little if any water can be held by the
dried salt. It has already been pointed out that no absolute proof of
such a fact is possible ;t and these experiments, together with the
analogy furnished by the more manageable barium salts, seem to be
the last resort. The apparatus used for these experiments v/ill be
described under the heading " Method of Analysis."

The specific gravity of anhydrous strontic bromide has been found
by Bodeker to be 3.96. Since no more recent data regarding this
constant could be found, another determination, described below,
seemed to be needed. 3.2560 grams of a pure specimen which had
been fused in the air and dried at 200° in the pycnometer were found
to displace 0.6678 gram of toluol at 24°. Since the specific gravity
of the toluol under these conditions, referred to water at 4°, was found
to be 0.8618, that of the strontic bromide referred to the same stan-
dard must be 4.203. Again, 2.3065 grams of strontic bromide which
had been fused in a stream of hydrobromic acid displaced 0.4699 gram
of toluol, thus having a specific gravity of 4.229. The mean of these
determinations, 4.216, was adopted as the basis of the reduction of the
weighings to the vacuum standard.

Strontic bromide, like baric bromide and chloride, may be evapo-
rated to apparent dryness over a free flame in a platinum dish without
losing a trace of halogen. Experiment showed that, upon mixing pure
bromide of strontium with small quantities of bromide of calcium and

* These Proceedings, XXVIII. 12; XXIX. 58.
t These Proceedings, XXVIII. 14.

RICHARDS. — ATOMIC WEIGHT OF STRONTIUM. 375

barium and crystallizing the mixture, both impurities tended toward
the mother liquors. Hence simple crystallization affords a method of
eliminating the two most likely impurities.

The other properties of strontic bromide do not pertain especially
to the present work.

Preparation of Materials.

Strontic Bromide. — Six different specimens of the salt were ana-
lyzed, in order to establish the presence or absence of accidental
impurities.

In the first place, five hundred grams of the purest strontic nitrate
of commerce were dissolved in two litres of pure water, and four times
in succession a cubic centimeter of pure sulphuric acid, diluted with
much water, was added to the solution. Each time only a small amount
of precipitate appeared at once, the rest appearing slowly. After
waiting in each case three or four days, the clear liquid was decanted.
No barium could be found even in the first precipitate of strontic
sulphate ; but it is true that the spectroscope is not a very satisfactory
means for the detection of barium under these circumstances. The
acid solution of strontic nitrate, which had been thus almost if not quite
freed from a possible trace of barium, was evaporated to small bulk,
filtered from the precipitated strontic sulphate, and twice successively
brought to crystallization. Each mass of crystals was washed three
times with alcohol upon the filter pump, to free it from the mother
liquor, which might contain calcium or magnesium. After having
been converted into pure carbonate by precipitation with ammonic
carbonate and long continued washing the strontium was combined
with bromine. For this purpose hydrobromic acid remaining from
the barium work, obtained by repeated fractional distillation of the
common acid, was used.

The strontic bromide was evaporated in a platinum dish. This was
slightly attacked, bromine having been set free by a little occluded
strontic nitrate in the carbonate. After evaporation to dryness the
bromide was fused at a bright red heat in platinum. The alkaline
solution of the fused cake was treated with hydric sulphide, filtered,
acidified with hydrobromic acid, warmed, filtered from the platinic sul-
phide, boiled to free it from sulphuretted hydrogen, again filtered, and
crystallized twice from water. The crystals were washed with alcohol,
and the strontic bromide thus obtained is numbered I. below ; it was
used for the three preliminary experiments, as well as for Analysis 13,

376 PROCEEDINGS OF THE AMERICAN ACADEMY.

The second sample of strontic bromide was prepared from similarly
treated strontic nitrate which had been recrjstallized four times in-
stead of twice. The nitrate was converted into oxide by ignition in a
nickel crucible ; and the dissolved residue was filtered to get rid of a
small amount of nickel. Ammonic sulphydrate gave no trace of color-
ation to a portion of the filtrate. Two recrystallizations in a platinum
bottle sufficed to free the strontic hydrate from a trace of undecora-
posed oxides of nitrogen, and the last crystals dissolved to form an
absolutely clear solution in pure hydrobroraic acid.* The solution of
strontic bromide was evaporated to crystallization, the crystals were
dehydrated, and the anhydrous salt was fused; finally, after solution,
standing, and filtration, a fresh crop of crystals was obtained. This
sample, labelled No. II., was used for Analysis 14.

Among several different methods for obtaining pure strontic salts,
that recommended by Barthe and Falieres j seemed to promise well
and accordingly the third preparation was based upon their work
The so called " pure " strontic chloride of commerce was dissolved in
water, treated with ammonic hydrate and a little carbonate, and filtered
from the precijjitate containing iron, aluminum, and so forth. To
the filtrate was added an excess of sulphuric acid, and the precipitated
strontic sulphate was thoroughly washed with dilute sulphuric acid and
then with pure water, in the hope of freeing it from magnesium and
calcium. When the wash water became neutral to methyl orange the
precipitate was treated with enough ammonic carbonate solution to
convert about half of it into carbonate, and the mixed precipitate was
then washed with water by decantation until only a very small con-
stant trace of sulphuri;' acid (due to strontic sulphate) was found in
the decantate. The carbonate was then decomposed by pure hydro-
chloric acid, and the solution was allowed to stand in a glass flask for
nine months over the undecomposed sulphate, with occasional shaking.
The strontic chloride was decanted, the sulphate was washed once
with water, and the filtered decanted liquid was evaporated in a plati-
num dish until most of the free hydrochloric acid had been expelled.
The dissolved residue was neutralized with ammonia, shaken with a
little ammonic carbonate, and then filtered. To the greatly diluted
filtrate was added an excess of pure ammonic carbonate, and the pre-
cipitate was washed until the wash water was free from chlorine.
The strontic carbonate was dissolved in nitric acid which had been

* See these Proceedings, XXVIII. 17, bottom of page.

t Journ. Chem. Soc, Abs. 1892, p. 1277. Bull. Soc. Chim., [3.], VII. 104

RICHARDS. — ATOMIC WEIGHT OF STRONTIUM. 377

twice distilled in platinum, and the nitrate was crystallized twice suc-
cessively in a platinum dish. Each quantity of crystals was washed
with small quantities of water and tliree or four additions of alcohol.
The first mother liiiuor, upon being fractionally precipitated by means
of alcohol, showed distinct traces of calcium in the extreme solution ;
thus Barthe and Falieres's method was not capable of freeing the
substance wholly from calcium. The second mother liquor showed
no trace of calcium upou the most careful scrutiny.

Two hundred grams of the purest crystals, after having been dried
at 130°, were dissolved in about a litre of the purest water and filtered
into a large platinum dish, into which was passed first pure ammonia
gas and then pure carbon dioxide through a platinum tube.* The
pure strontic carbonate was washed by decantatiou eight or ten times,
dried on the steam bath, and ignited in a double platinum crucible
over a spirit lamp.

Part of this carbonate was converted into bromide by means of the
purest hydrobromic acid,t and the product was digested for a long
time with a considerable excess of carbonate. After filtration and
evaporation the strontic bromide was fused in a platinum dish over
the spirit lamp, the salt being perfectly clear while liquid. The trans-
lucent cake was dissolved, allowed to stand, filtered, faintly acidified
with hydrobromic acid, and crystallized twice from water. Each time
the crystals were washed with the purest alcohol. The resulting bro-
mide of strontium was used for Analyses 1, 2, 3, 5, 6, 7, 12, 15, 16,
17, and 18.

The next sample was prepared from the strontic carbonate which
had been digested with the strontic bromide just described. It was
dissolved in the purest hydrobromic acid and purified much as before,
except that the salt was fused twice with intermediate crystalliza-
tions, instead of only once. This fourth preparation was used for
Analysis 9.

The fifth sample was made by the repeated crystallization of the
combined mother liquors obtained from the four previous preparations.
It was used for Analyses 4, 8, and 19.

The sixth preparation of strontic bromide was made from the stron-
tic sulphate remaining from the third. This residue was treated with
enough ammonic carbonate to convert all but about twenty grams of

* See page 379.

t Prepared from pure baric bromide and redistilled many times. See these
Proceedings, XXVIII. 17.

378 PROCEEDINGS OP THE AMERICAN ACADEMY.

the sulphate into carbonate. The washed strontic carbonate having
been dissolved in a slight excess of hydrochloric acid, the residual sul-
phate was allowed to remain in the solution for a week. After filtra-
tion, evaporation to dryness in platinum, solution, a second filtration,
treatment with a little ammonic hydrate and carbonate, and yet an-
other filtration, the strontic chloride was converted into carbonate by
means of purified ammonic carbonate.* After a very complete wash-
ing the strontic carbonate was dissolved in pure nitric acid in a plati-
num dish. The nitrate was crystallized, dried at 150°, recrystallized.
washed with alcohol with the aid of the pump, dried, dissolved, and
stirred with a little pure strontic carbonate for a week. The filtrate
containing pure strontic nitrate was diluted, brought to boiling in a
platinum dish, and poured in a fine stream into a boiling solution of
pure ammonic oxalate f also contained in platinum. The strontic
oxalate was washed with the purest water upon the filter pump,
until no ammonia could be detected upon boiling the filtrate with
sodic hydroxide. Nessler's reagent still showed a trace of ammo-
nia ; but since this could easily be expelled by ignition, and the pre-
cipitate was very hard to handle, the washing was not carried further.
After drying and powdering, the oxalate was converted into carbon-
ate by ignition at a full red heat. The product was now ground
in a mortar with an equivalent amount of pure ammonic bromide, J
and the whole was gently ignited in a large platinum dish until no
more ammonia was evolved. The hundred grams of strontium bromide
thus obtained formed a pure white translucent cake upon fusion in a
large platinum crucible. The cake was dissolved in water, and the
alkaline solution, after havingr been boiled for some time, was neutral-
ized with sulphuric acid. The clear filtrate from the strontic sidpliafe
was now evaporated to a volume of about a hundred and twenty cubic
centimeters, and diluted with two hundred cubic centimeters of the
purest alcohol. The mixture was allowed to stand for a day, in
order that the strontic sulphate and any trace of baric sulphate which
might remain should be precipitated, .and then filtered. After three
successive crystallizations from water, the substance was used for
Analysis 10; a further crop'of crystals from the purest mother liquor
served for Analysis 11.

Considering the pains taken in the purification of even the lea?t
pure sample, it is not surprising tliat all of these samples gave quan-
titative results which proved them to be essentially identical.

* See page 379. t See page 379. J See page 380.

RICHARDS. — ATOMIC WEIGHT OP STRONTIUM. 379

Siloe7\ — The preparation of pure silver has been repeatedly detailed.
The most elaborate method described iu the paper upon barium was
used in the present case.* A few improvements were introduced,
notably the purification of the sodic hydrate used for the reduction of
the argentic chloride by means of a strong galvanic current, instead of
by hydrogen sulphide. Little but iron was found in it, however. The
final crystals of electrolytic silver were usually fused upon pure sugar
charcoal or lime, in a reducing flame ; once however (for Analysis 10)
the crystals contained in a lime boat within a stout porcelain tube
were fused in a Sprengel vacuum by means of a Fletcher furnace.
Two holes bored through the furnace at right angles to the flame
entrance served to admit the tube. The heat was very gradually
applied, and after the silver had been melted all the apertures of the
furnace were closed and the tube was allowed to cool very slowly. A
wide glass tube set into the porcelain tube on one end served as a
convenient window for the observation of the fusion.

Ammonic Carbonate. — Two varieties of ammonia carbonate were
used for the work just described. The first consisted of ordinary pure
" ammonic carbonate," which had been dissolved, treated with a
small amount of a pure strontium salt, and filtered. This treatment
undoubtedly removed any substance which could seriously interfere
with the preliminary purifications for which this ammonic carbonate
was used. For the final stages of the purification of the strontium
preparations, ammonic carbonate was made by saturating the purest
water in a platinum vessel with ammonia gas obtained by boiling the
pure strong ammonia of commerce, and then passing into this saturated
solution pure carbon dioxide. This latter gas was prepared by the
action of dilute nitric acid on marble ; it was purified by passing
through washing flasks containing water and a meter of glass tube
packed with moist beads. Upon delivering the gas into a Bunsen
flame, no trace of calcium could be detected spectroscopically. Both
gases were conducted into the solution through a platinum tube made
for the purpose. The resulting ammonic carbonate undoubtedly con-
tained more or less of the amines common in ordinary ammonia, but
it could not have contained a trace of non-volatile impurity capable
of contaminating the strontic carbonate for whose preparation it was
designed.

Ammonic Oxalate. — This salt was made by neutralizing pure am-
monia water with pure oxalic acid, which had been still further

* These Proceedings, XXIX. 64, 65.

380 PROCEEDINGS OP TUE AMERICAN ACADEMY.

purified by many recrystallizations from hydrochloric acid and water.
The amnionic oxalate was crystallized twice in a platinum dish, the
crystals being thoroughly washed each time. The salt was wholly
free from chlorine.

Ammonic Bromide was prepared in the usual fashion from ammonia
prepared in platinum and bromine purified according to Stas. The
reaction was naturally conducted in a flask of hard glass ; but the
crystallization was carried on as usual in platinum. A slight excess
of the pure white substance precipitated 3.97970 grams of argentic
bromide (fused, reduced to the vacuum standard) from a solution
containing 2.28G16 grams of pure silver. From this experiment
AgBr : Ag = 100 : 57.4455. Stas found 57.445, hence the purity of
the ammonic bromide is proved.

A very simple and convenient platinum condenser was used for the
preparation work described above. The tube, almost a centimeter in
diameter and perhaps twenty-five centimeters in length, is bent, some-
what contracted near one end, and surrounded with a condenser jacket.
It is easy to draw out the neck of a round-bottomed flask to fit outside
of the conical end, and if the juncture is not absolutely tight a thin
film of condensed liquid soon makes it so. If the glass neck be pro-
longed somewhat above the point of juncture, evaporation from this
film is very slow. Of course pure filter paper may be used to tighten
the joint if water is to be distilled. The apparatus has the great
advantages of cheapness and transparency over the ordinary platinum
still. All the hydrochloric, hydrobromic, sulphuric, and nitric acids,
water, and alcohol used in the important stages of the work were
distilled with the help of this contrivance.

Platinum vessels have been used wherever it was possible to use
them in the work detailed above, although the fact is not always
mentioned. They were cleaned in the usual fashion.

Method of Analysis.

As in the case of baric bromide,* the silver required to precipitate
all the bromine in strontic bromide was determined, as well as the
amount of argentic bromide formed by the precipitation.

The chief problem which presented itself was the preparation of
pure dry neutral bromide of strontium for weighing. In preliminary
analyses the salt was ignited or fused in a platinum crucible, and

* These Proceedings, XXVIII. 23.

RICHARDS. — ATOMIC WEIGHT OP STRONTIUM. 381

weighed as the baric bromide had been. The decomposition of the
salt was so great, however, that the uncertainty of the alkalimetric
correction sometimes amounted to two or three tenths of a milligram ;
lience this method was clearly inadmissible.

The fusion of the salt in a platinum boat in a stream of nitrogen
gave much better results, and two or three further preliminary deter-
minations by this method gave promise of much greater accuracy.
It is probable that the slight decomposition which occurred even in
the atmosphere of nitrogen was due to the presence at 250°-300° of a
slight trace of moisture.

The presence of an excess of hydrobromic acid must necessarily
lessen or prevent this decomposition ; hence in three succeeding deter-
minations (Nos. 13, 14, 15, below) pure dry hydrogen bromide was
added to the nitrogen in which the combustion was conducted.

In these cases, however, the platinum boat, which had previously
remained quite constant in weight, was evidently attacked, since upon
one occasion (Exp. 15) it lost over two tenths of a milligram, and the
pure white strontic bromide became tinged with a brown color. The
weight of the boat after each fusion was taken as the true weight,
because the bromide of platinum, if formed, must precipitate nearly as
much silver as the bromide of strontium.

In order to avoid the corrosion of the boat, hydrogen was added in
small quantities to the mixture of gases. This, by preventing the
dissociation of the hydrobromic acid, effectually preserved the platinum,
and the boat remained constant in "weight. The pure translucent or
transparent colorlessness of the fused salt left nothing to be desired.
A somewhat complex piece of apparatus was needed for the purpose.
(See page 382.) A mixture of six volumes of pure nitrogen (made
by passing air and ammonia over red-hot copper) and one volume of
pure hydrogen was delivered from a gas holder through a succession
of tubes of red-hot copper, dilute chromic and sulphuric acids, concen-
trated alkaline pyrogallol, and fused potash, into the arrangement for
preparing hydrobromic acid. This, as well as all the apparatus fol-
lowing, was without rubber connections, the ground joints being made
tight by means of syrupy phosphoric acid (Morley) and flexible by
means of fine glass gridirons (Finkener). The pure dry nitrogen and
hydrogen were led in the first place into a flask containing bromine,
and then over asbestos and red phosphorus saturated with pure
fuming hydrobromic acid. The bromine and hydrobromic acid were
proved to be pure by the usual quantitative analysis, and the red
phosphorus was ground and washed many times with pure water to

382

PROCEEDINGS OP THE AMERICAN ACADEMY.

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RICHARDS. — ATOMIC WEIGHT OF STRONTIUM. 383

free it as much as possible from clilorine (Stas). The mixture of pure
slightly moist hydrogen bromide, nitrogen, and hydrogen was now
dried by calcic bromide free from chlorine and iodine, and thus
became ready for use.

The hard glass tube used for heating the platinum boat containing
the strontic bromide was ground very tightly into its socket of soft
glass, since it was not advisable to risk the presence of phosphoric
acid here. The powdered nearly anhydrous strontic bromide, haviug
been packed tightly into the boat and carefully pushed into position
in the fusion tube, was thoroughly dried at 200° in a stream of pure
air. The elaborate apparatus for preparing the mixture of gases was
now connected with the fusion tube, and when all the air had been ex-
pelled the boat was slowly heated to cherry-redness until the strontic
bromide was wholly fused. The temperature was then allowed to fall
a little below 600°, and the solidified bromide of strontium was freed
from any possible excess of hydrobromic acid by a current of dry hy-
drogen and nitrogen free from acid, delivered through a short-cut tube
(see page 382).

The almost red-hot boat was now transferred as quickly as possible
to the light weighing bottle, within which it was allowed to cool. In
the preliminary work (and in Analyses 13 and 14) this bottle was
stoppered at once and cooled in an ordinary desiccator. Subsequently
an improved desiccator was devised for this purpose. A wide glass
tube capable of containing the weighing bottle was drawn out at one
end to a fine tube, which was fitted with a ground-glass stopper. The
other open end was made slightly conical and ground into a recepta-
cle which was in its turn attached to a drying tube containing fused
potash. The following sketch supplements this description.

While the boat was still hot within the fusion tube, the stopper of
the weighing bottle was placed in the horizontal desiccator tube. The
moment after the transference of the boat into the bottle, both to-
gether were slid into the momentarily opened desiccator tube by
means of a glass rod which projected from the receptacle. The bot-
tle was held by means of a glass carriage during this manipul ition.

The open weighing bottle, with its stopper and fused contents, could
now be heated indefinitely in a current of pure dry air at any tern-

384 PROCEEDINGS OF THE AMERICAN ACADEMY.

perature below the softeniug poiut of soft glass. At the moment
when it was desired to close the bottle, it was only necessary to ele-
vate the desiccator tube from the horizontal to the vertical position,
and the hot stopper fell automatically into the equally hot bottle.
The desiccator tube was now closed above, and allowed to cool at least
four hours in the balance room. It is needless to say that before
taking the final weighing of the bottle its stopper was loosened.

Having thus obtained as nearly as possible the true weight of the
typical salt of strontium, the remainder of the analysis was conducted
in a manner essentially similar to that adopted in the case of baric
bromide.* Since it is unnecessary to describe again most of the pre-
cautions, nothing will be noted below excepting those particulars in
which the details of the work differed from those already given.
Two analyses, which were vitiated by knowu errors, are omitted from
the tables.

The Ratio of Silver to Strontic Bromide.

First Series. — In this series a slight excess of silver was taken, dis-
solved, and diluted with at least a hundred times its weight of water,
and added to the strontic bromide in a glass-stoppered flask. After
the usual long continued shaking, the precipitate was collected upon a
Gooch crucible, and the excess of silver in the evaporated filtrate and
first five or six wash waters was determined after Volhard's method. f
Upon subtracting this small excess of silver from the total, the
amount corresponding to the strontic bromide remains. This method
is not a very satisfactory one, the final result being probably too low,
because of loss of a portion of the slight excess of silver.

Second Series. — Here the end point of the reaction was determined
by titration after the method of Abrahall,t very weak solutions of
silver and hydrobromic acid being used to titrate backwards and for-
wards. The mean readinji was taken in each case, and the method of
procedure resembled exactly the work with barium. These results
are much more trustworthy than the last. In several cases the sample
of strontic bromide was first analyzed by this method, and subsequently
an excess of silver nitrate was added and the preceding method was
applied.

Third Series. — For this series a new method was devised. Accord-

* These Proceedings, XXVIII. 24. J These Proceedings, XXVIII. 24.

t These Proceedings, XXIX. 66.

EICHARDS. — ATOMIC WEIGHT OF STRONTIUM.

385

ing to Stas,* argentic bromide is wholly insoluble in water ; accord-
ing to Goodwin,! it is only very slightly soluble; while according to
Kohlrausch and Rose,f it is soluble to the extent of three tenths of
a milligram in a litre. The time during wliich chloride of silver is
shaken makes an enormous difference in the solubility, and it is not
impossible that a similar effect may occur here. Perhaps KoWrausch
and Rose did not agitate their precipitate so thoroughly as Stas did.
According to the present experience the purest silver bromide was
capable of yielding a filtrate which would give a very faint opalescence
with both silver and hydrobromic acid ; and this
effect usually diminished upon long continued agita-
tion. The method of determination used in this
series was based upon this fact. Somewhat less
silver than the amount required was added to the
strontic bromide, and a very weak standard solution
of argentic nitrate (the cubic centimeter contained
a milligram of silver) was dropped in until equiva-
lent solutions of silver and hydrobromic acid pro-
duced equal opalescence in two similar pipetted
portions of the supernatant liquid. Since the opa-
lescence was so faint that one could only with diffi-
culty see it at all under ordinary conditions, a piece
of apparatus, which may be named a " nephelome-
ter" (ve<ji4X7], a cloud), was devised for detecting it.
Two test tubes, holding each just thirty cubic cen-
timeters, were arranged in a wooden frame so that
two centimeters of the top of the tubes were in
darkness. The bottoms of the tubes were fitted
into the top of larger opaque tubes containing water,
and were provided with closely fitting cylindrical
shades, which could be raised or lowered independently over a gradu-
ated scale. All these contrivances prevented disturbing side reflections
from the «aeniscus at the top of the tube and the rounded glass at
the bottom. The two test tubes were slightly inclined towards one
another, so that the eye at a distance of eight inches could look directly
into both without change of position. Filled with pure water the
tubes appear absolutely black, even when exposed to a strong light ;
but an absurdly small amount of precipitate, which no ordinary means

u

JEm.

Nephelometer.

* Mem. de I'Acad. Belg., XLIII., Part II. Introduction.

t Zeitschr. f. phys. Chem., XIII. 645.

VOL. XXX. (n. S. XXII.) 25

t Ibid., XII. 234.

386 PROCEEDINGS OF THE AMERICAN ACADEMY.

could discover at all, makes a very evident cloudiness. By sliding
the shades up and down a point may be found where the two tubes,
containing solutions of different cloudiness, appear equal in depth of
tone. The reason of this is that only the portion of the opalescence
is visible upon which light is allowed to fall. Of course the intensi-
ties of the opalescence, and hence the quantities of precipitate, are
then inversely as the length of the lighted portions of the two tubes.

If care is taken to direct the light horizontally upon the tubes,
considerable accuracy may be obtained with the apparatus, especially
if the columns are nearly equal in cloudiness.

A pointed blackened roof with a small hole in the top for the eye
is useful in excluding light from the surface of the liquid, thus ren-
dering the comparison easier. The chief advantages of the apparatus
lie in the facts that the two disks of light to be compared remain equal
in size thi-oughout the comparison, and that the eye is not confused
by bright surface reflections. Two typical test series are given below.
In each case one shade was adjusted at ten centimeters, and the
other was run backward and forward until apparent similarity was
obtained.

(a.) One tube contained 0.010 milligram of silver, and the other
0.0125 milligram, measured by means of a very dilute standard solu-
tion. Both amounts were made up to twenty-five cubic centimeters,
and one cubic centimeter of hundredth normal hydrochloric acid was
added to each. The opalescence in each was then compared after a
thorough stirring and a short delay.

Heights of Columns appearing Alike.

stronger

Solution.

Weaker Solution,

8.7

cm.

10.0 cm.

7.9

<c

10.0 "

6.9

((

10.0 "

7.6

<(

10.0 «

8.4

((

10.0 «

8.6

u

10.0 "

8.9

<(

10.0 «

Found,

8.1

cm.

10.0 cm.

True value.

, 8.0

a

10.0 "

{b.) In a similar experiment one tube contained 0.025 milligram of
silver, the other 0.0225 milligram.

RICHARDS. — ATOMIC WEIGHT OF STRONTIUM

387

Heights of Columns appearing Alike

Stronger

Solution

88

cm.

8.9

K

8.2

l(

9.5

U

8.9

a

-

8.7

u

8.9

((

9.4

ii

Found,

8.9

cm.

True value,

9.0

a

Weaker S

oiutioa

10.0

cm.

10.0

kk

10 0

(

10 0

(C

10.0

«

10.0

ii

10.0

((

10 0

u

10.0

cm.

10.0

hi

Some series were more accurate, others less so, than these, which
serve to give a fair idea of the probable error of the method.

The details of the analysis must be evident from what has been said.
The method is similar to Stas's third method for the determination of
chlorine,* except that of course the opalescence is very much fainter.

Below are given the tables containiuor the data and results of the
three series ; these will be comprehensible without further remark.

Ratio of Strontic Bromide to Silvee
First Series. Volhard's Method.

No. of
Analysis.

No. of
Specimen

Weight of
Strontic
Bromide
taken.

Total

Weight of

Sliver

taken.

Excess

of
Silver

Weight of
Silver corre-
sponding to
Strontic

Bromide.

Ratio
SrBrj

Ag2

Atom e

Weight

Sr

1
2
3
4

III.

III.

Ill

V.

grams

1 499G2

2 41225

2 56153
6 15663

1 30893
2 10494

2 23529
5 3086

m. g
138

143

172

0 2

1 30755
210351
2.23357
5 3684

114.689
114 677
114 683
114 683

87 658
87 633
87 645
87 644

12 63003

11 01303

114 683

87 644

* See these Proceedings, XXIX 86.

388

PROCEEDINGS OF THE AMERICAN ACADEMY.

Eatio of Stroxtic Bromide to Silver.
Second Series Abrahall's MetliOQ

No of
Auaiysis

No of
Specimen.

Weight of
Strontic Bro-
mide taken.

Weight of
Silver required

Ratio

SrBr„

Agj

Atomic Weight
of Strontium.

5
6

7
8

III.
III.
Ill
V

grams.
1 49962

2.41225

5.24727

6 15663

grams.
1 30762

2.10322
4.57502
5.3680

114.683
114.693
114.694
114.691

87.645
87.667
87.668
87.663

15.31577

13.35386

114.692

87.663

Third Series. New Method.

9
10
11
12

IV
VI
VI.

Ill

grams.

2.9172
3.8946
4.5426
5.2473

grams.
2.5434

3.3957

3.9607

4.5750

114 697
114.692
114.692
114 695

87.675
87 665
87 664
87671

16 6017

14.4748

114.694

87.668

Ratio of Argentic to Strontic Bromide.

Id many of the preceding determinations the bromide of silver
resulting from the decomposition was weighed. In every case a slight
excess of silver nitrate was added, to render the argentic bromide
wholly insoluble in the filtrate. The very slight amount which may
have been dissolved by the wash water during its brief contact with
the precipitate was not considered. The precipitate was collected
upon a Gooch crucible; and the traces (0.04 to 0.2 milligram) of
asbestos carried through were collected upon a small washed filter,
ignited separately, weighed, and added to the gain in weight of the
crucible. From this was subtracted the loss in weight of the precipi-
tate upon fusion in a covered porcelain crucible. A description of
the dark room used for the experiments, and many other precautions
and details, will be found in other papers.* The results are tabulated
below.

* These Proceedings, XXVIII. 24; XXIX. 74.

RICHARDS. — ATOMIC WEIGHT OF STRONTIUM.

389

Ratio of Strontic and Argentic Bromides

First Series.

No of
Aualisis

No of
Specimen.

Weight of
Strontic Bro-
mide taken

Weight of fused
Argentic Bro-
mide found

Ratio
SrBrj
2 AgB^

Atomic
Weight of
Strontium.

13
14
15

I.

II

III

grams
160S6

18817

4 5681

grams

2 4415
2 8561
6 9337

65 886
65 884
65 883

87 669
87 662
87 657

8 0584

12 2313

65 8834

87 660

Second Series

16
17

18
19

III
III
III

V

grams

1 49962
241225

2 56153
6 15663

grams

2 27625

3 66140

3 88776
9 34497

65.881

65 883
65 887
65 882

87 652
87 660
87 674
87 654

12 63003

19 17038

65 883

87 659

It remains only to bring together the results into one table.

Final Averages
Oxygen =16.000

I.

2 Ag : SrBr^

First Series

II.

(( u

Second Series

III.

u ((

Third Series

IV.

2 AgBr : SrBrj

First Series

V.

U ((

Second Series
Total average

strontium equals

87.644
87.663
87.668
87.660
87.659

= 87.659
Average, rejecting I. above = 87.663

The last average is probably most nearly correct.

The analysis of strontic chloride has already been begun, and the
preliminary results indicate that the results given above are certainly
not too high. For the present, then, the atomic weight of strontium
may be taken as 87.66 if oxygen is 16.00, 87.44 if oxygen is 15.96,
and 87.01 if oxygen is 15.88.

390 PROCEEDINGS OF THE AMERICAN ACADEMY.

XV.

ON THE ELECTRICAL RESISTANCES OF CERTAIN

POOR CONDUCTORS.

By B. O. Peirce.

Presented October 10, 1894.

Since the subject of electricity began to be studied seriously, many
experimenters have made lists of substances arranged in the order of
their electrical conductivities. These lists have not agreed with
one another in all respects ; but at one end of every one of them
metals have stood, and at the other end such insulating substances
as ebonite, glass, paraffine, shellac, and mica. Somewhere between
these extremes have appeared the so called " half-conductors," * like
wood and some kinds of stone. How these latter are to be classed
depends very much, of course, upon the uses to which they are put.
For work with the small charges and high potentials of experiments
in electrostatics, we must generally consider wood as a conductor;
while, for practical purposes, we may regard the wooden base upon
which a telegraph instrument is mounted as a perfect insulator.

In makiug electrical measurements in the laboratory, it is often
necessary to be able to change quickly the connections of one's
apparatus, and for this purpose some kind of " switch-board " must
generally be provided. Sometimes a dry wooden board, into which holes
have been bored to form mercury cups, will suffice ; sometimes a plate
of ebonite or a non-combustible slab of slate or marble is required.

I have been obliged, during the last three years, to procure several
hundred more or less complicated switch-boards, and many of these
had to be used in making accurate measurements of electrical quanti-
ties. It has been necessary, therefore, to determine under what cir-
cumstances hard dry wood or red vulcanized filjre may safely be
used, and when marble or ebonite, or even a block of freshly scraped
paraffine, is required. For use with these switch-boards I have pro-
vided several hundred resistance coils of German silver, platinoid,

* Du Moncel, Annates de Chimie et de Pliysique, [5.], X. 1877 ; Addenbrooke,
Muir and Jamieson's Pocket-Book, p. 194.

PEIRCE. — ELECTRICAL RESISTANCES.

391

and manganhie wire, wound on spools two inches in diameter over all,
and from four to eight inches long. The coils are furnished with stout
copper terminals (Figure 1), and are protected by cylindrical shields
made of brass or pasteboard tube. The copper terminals are screwed,
with axes parallel to each other, and one inch
apart, into one end of each spool. Spools and
shields together act as shunts to the coils, and it
has been necessary to determine a lower limit for
the resistance which such a shunt could offer in
practice. It has been necessary also to measure
the insulation resistance between the two mercury
cups, on a switch-board, into which the terminals
of one of the resistance coils dip. These cups are
formed by holes three eighths of an inch in diame-
ter (Figure 2), and five eighths or three quarters
of an inch deep. The axes of each pair of holes
are one inch apart. The holes are bored, or
drilled, in a lathe, in the top of the switch-board,
with a FiJrstuer bit if the material be wood or
vulcanized fibre or ebonite, with a flat or twist
drill moistened with water if slate or marble be
used.

In order to get such information as I needed with respect to the

insulation resistance which might safelj^ be counted on in the case

of wood, marble, or vulcanized fibre, used for the purposes

Ojust described, I made a long series of measurements, with
the help of a battery of twelve dry cells, and an absolutely
calibrated high-resistance mirror galvanometer, on a large
number of specimens. Of course individual measurements
of this sort have little general value, but a large number of
experiments on different samples of material of a given kind

Omake it possible to set a lower limit to the resistance of
this substance when used in a given way, and such knowl-
edge as this is often useful when one is planning apparatus.
Fig. 2. For instance, my experience seems to show that it is per-
fectly safe to assume that the specific resistance per cubic
centimeter of an inch-thick slab of pure white Vermont marble, which
has been standing exposed to the air in a fairly dry room for three
weeks, is not less than 10® ohms, and is probably as much as 10^" ohms.
Eeally dry white marble has a far higher specific resistance than this.
It is safe also to set a lower limit for the specific resistance of sea-

FlG. 1.

392 PROCEEDINGS OF THE AMERICAN ACADEMY.

soned wood of a given kiod, but only in the sense that wood of resist-
ance as high as this can always be obtained without difficulty in the
market. Abnormal specimens occur. In measuring the insulation
resistances between the copper terminals of un paraffined maple and
birch spools, like or similar to the one represented in Figure 1, I ex-
perimented upon a large number of spools which had been lying for
about a year in a certain dry closet. The smallest resistance in any
case was 1,100 megohms, and the average resistance was more than
2,000 megohms. This is what one may expect to get in spools of this
kind. In the same closet were some spools of a different lot, bought
of the maker of the other spools, and in no way different in appear-
ance from them. These also had been seasoning beside the others for
a year, yet the average insulation resistance of these spools was only
a little over one megohm. This is an extreme case. The nearest
approach to it that I found in experimenting on other lots of spools
was that of some which had been standing for a long time in the
damp basement of the laboratory, and represent what the ordinarily
good dry spool might become if it were placed for months in a moist
place. Yet the lowest resistance in the case of these spools was more
than 100 megohms.

It is, of course, well known that the insulation resistance of a po-
rous half-conductor depends very much upon the amount of moisture
which it contains, and that this moisture may give rise to all manner
of anomalies, as Du Moncel has shown. Thus, white marble when
it comes from the mill is often a fairly good conductor, owing to the
water which it has absorbed in the process of manufacture, but a fort-
night's drying in the sun sometimes increases its resistance ten thou-
sand fold. It is now almost always possible to get kiln-dried wood,
and after wood or marble has once been thoroughly dried, an immer-
sion in a bath of hot paraffine tends to prevent the reabsorption
of moisture. Red vulcanized fibre absorbs hot paraffine greedily ; but
I do not think that it would be easy to saturate a piece of fibre so
thoroughly with paraffine that a drop of water allowed to rest on its
surface for a few moments would not begin to raise a blister.

Prolonged immersion in clean, hot, melted paraffine always in-
creases the insulation of a half-conductor, even if the bath leaves no
perceptible coating on the outside. This increase, however, is very
slight in the cases of some close-grained substances like rosewood,
though it may amount to three or four times the original resistance in
the case of a porous conductor. If while such a conductor is immersed
in hot paraffine the bath and its contents be placed under the receiver

PEIRCE.

ELECTRICAL RESISTANCES.

393

of an air-pump, and the air be alternately exhausted from and re-
admitted to the receiver, the resistance of the conductor is always
materially increased. This process is in common use for the purpose
of improving the insulation between the layers of covered wire in
galvanometer coils. A coat of shellac, when not thoroughly dry, often
lowers very much the insulation resistance of a porous half-conductor.
The followiuij table shows the results of measurements of the resist-
ance between the two members of each of a large number of pairs of
mercury cups of the size shown in Figure 2 bored in the tops of slabs
of different substances. The specific resistance of wood for currents
going across the grain is generally from 20 to 50 per cent higher
than for currents going with the grain. The figures given below may
be taken as referring to currents going with the grain. I procured,
wherever I could conveniently, a number of pieces of seasoned wood
of each variety named, rejecting none, and I believe that the numbers
in the table represent fairly what one may expect in practice. The
number in the second column of the table, in the same horizontal line
with the name of a substance, shows how many pairs of mercury cups
bored in slabs of this substance were experimented on, while the
numbers in the next two columns give in megohms the lowest and
the average resistance between the members of these pairs. Some-
times a single pair of cups only was bored in a slab, sometimes two or
three. The resistances between the members of pairs of mercury cups
bored in the single specimens of cypress and maple that I had were, in
the average, upwards of 2,000 megohms.

TABLE I.

Substance.

No. of Pairs of Cups.

Lowest Resistance
in Megohms.

Average Resistance
in Megohms.

Ash

13

550

920

Cherry

15

1100

4000

Mahogany . . .

14

430

730

Oak

17

220

420

Pine

24

330

630

Hard Pine ....

8

10

48

Black Walnut . .

30

1100

3000

Red Fibre ....

6

2

4

394

PROCEEDINGS OF THE AMERICAN ACADEMY.

Choice pieces of wood of each of the seven kinds named in the
table would yield insulation resistances far higher than those given in
the column of averages, and not less than 1,000 megohms even in the
case of hard pine.

TABLE II.

Substance.

Lowest Specific Resistance in

Megohms found among the

Specimens tested.

Average Specific Resistance
in Megohms of the Speci-
mens tested.

Ash

380

700

Cherry

2800

6000

Mahogany ....

310

610

Oak

1050

2200

Hard Pine ....

17

1050

White Pine . . .

360

1470

Black Walnut . .

320

2100

Vulcanized Fibre .

3

60

Slate

184

280

Soapstone ....

330

500

White Marble . .

2000

8800

Table II. gives the results of a great number of experiments upon
the electric resistances of slabs of different substances, throusfh which
currents were sent by means of mercury electrodes placed opposite
each other. Each electrode was contained in a cavity excavated in a
piece of ebonite (Figure 3), and was generally
about GO square centimeters in area. Compara-
tive measurements made with slabs of wood cut
across the grain were rather unsatisfactory, for
the reason that there seemed to be in every case
a resistance of contact ( Uebergangswiderstand) at
the common surface of the mercury and wood, and
the ma2:nitude of this resistance depended very much upon the rough-
ness or smoothness of the cut, and was sometimes greater than the
intrinsic resistance of the wood. In experiments made with currents
sent across the grain of the wood through slabs of different thick-
nesses cut from the same plank, the resistances seemed to follow

Fig. 3.

PEIRCE. — ELECTRICAL RESISTANCES. 395

Ohm's law so nearly that the contact resistances were of compara-
tively small importauoe. The contact resistance between two pieces
of wood pressed together seemed to be great, since the insulation
resistance of a compound slab formed of two in close contact was far
greater than the sum of the resistances of the two taken singly. To
avoid any disturbing effects that might arise from injury to the sub-
stance at tool-cut edges, slabs were sometimes used (see the shaded
portion of Figure 4) much

greater in area than the elec- X—X .1 I.

trodes, and this necessitated
the making of allowances
(based on experiments with
zinc electrodes in a tank of so-
lution of zinc sulphate) for
the effect of the spreading of
the lines of flow in the slab.

This process was not entirely satisfactory, but the results are doubt-
less quite accurate enough for the purpose in view. Tlie mercury
electrodes were effectively insulated from the brass clamping bolts
by the intervening slabs of ebonite.

All the slabs of stone were specially dried in the summer sun for
about three weeks before they were experimented on. Through the
kindness of Messrs. Bowker, Torrey, & Co. of Boston, I was en-
abled to test the specific resistances of a large number of pieces
of colored marble of different kinds. A vein in a piece of marble
used as a switch-board has been known to short-circuit a fire-alarm
system, and it was to be expected that the specific resistances of most
colored marbles would prove to be less than that of white marble.
In one instance, the specific resistance was as low as three megohms.
The single piece of sandstone which I had at my disposal had been
in a dry place in the laboratory for more than five years ; its specific
resistance was thirty megohms. The average specific resistance of
hard pine as given in Table II. means little. I have seen a piece of
this wood with a specific resistance as high as 4,000 megohms ; but
very resinous pieces of hard pine, however long they may have been
dried, seem to have low specific resistances. Some thin birch, of
the kind now used to separate from each other the successive plates
of one or two forms of storage cell, had a specific resistance, when
dry, of about 500 megohms.

Jefferson Physical Laboratory,

August, 1894.

396 PROCEEDINGS OF THE AMERICAN ACADEMY.

XVI.

CONTRIBUTIONS FROM THE CRYPTOGAMIC LABORATORY
OF HARVARD UNIVERSITY.

XXIV. — VARIABILITY IN THE SPORES OF UREDO
POLYPODII (PERS.) DC.

By B. M. Duggar.

Presented by W. G. Farlow, October 10, 1894.

Different opinions have been held as to the specific importance
of certain forms of Uredo occurring on various genera of ferns. Like-
wise an uncertainty has existed relative to the tvFofold nature of the
spores found in a single pustule. With a considerable amount of
material representing several host-genera, to vphich I have had access
through the kindness of Dr. Farlow, it has seemed of interest to give
the subject careful study, hoping thereby to reconcile some of the
views expressed.

Winter* has referred to Uredo Polypodii (Pers.) DC. all of the
Uredo forms reported on many genera of ferns, the spores of this spe-
cies measuring 19-52 X 12-22 jx. He distinguishes, however, a forma
Phegopteris, on Phegopteris, based on the more or less polygonal
character of the rather larger spores. Schroeter t includes under
the same species the forms on Cystopteris fragilis and Phegopteris
Dryopteris, recognizing, it seems, no essential differences for the forms
on the two hosts. He describes the species in language resembling
that of Winter, but with the exception that he mentions two kinds of
uredospores respectively distinguished by thin and thick walls. It
is suggested that perhaps the thick-walled spores are teleutospores.
Dietel,$ after examining some American and European collections,
principally herbarium material, concludes that the differences in size of
spores and the position of the sorus on the frond between the form on
Phegopteris Dryopteris and the form on Cystopteris fragilis and other

* Rabenhorst, Kryptogamenflora, Pilze I. Abth. I. p. 253.
t Kryptogamenflora von Sclilesien.

J Ueber Uredo Polypodii (Pers.), Oesterreichische Botanische Zeitschrift,
XLIV., No. 2, February, 1894.

DUGGAR. — UKEDO POLYPODII. 397

genera are sufficient to separate them. He would therefore refer the
form on Phegopteris Dryopteris to Uredo Aspidiotus Pk.,* which is
distinguished by having the sori on both sides of the leaf, but more
abundant on the upper side ; the spores are moi'e or less polygonal or
oval, measuring 36-56 X 27-40 /i, with from six to eight germ pores
iri'egularly distributed over the surface. Dietel also emphasizes the
constant appearance of thin-walled and thick-walled spores in both
Uredo Aspidiotus Pk. and U. Polypodii (Pers.) DC. He mentions
finding intermediate stages between the thin and the thick-walled
spores, which seem to show that the one is developed from the other ;
but he entertains doubts as to which might be the primary form.
Bearing in mind the suggestion of Winter as to the possibility of a
teleutosporic form, he made cultures of the thick- walled type, yet the
germination was that of true uredospores. It was then concluded that
there were two kinds of uredospores in each of these species. It was
also found that the thin-walled spores possess the constant character of
four germ pores equatorially arranged, but this will be discussed later.
As far as I can ascertain, no views have been advanced as to the
definite relationship of the thick-walled and thin-walled spores in re-
gard to the relative time of development. For this purpose, as well
as for a careful interj)retation of specific distinctions, fresh specimens
are essential. For the present study I was fortunate to secure from
Arlington, Mass., fresh material of Uredo Polypodii (Pers.) DC. on
Cystopteris fragilis ; and at Shelburne, N. H., I found a supply of the
form on Phegopteris Dryopteris described as Uredo Aspidiotus Pk.
Access to an abundance of herbarium material, to be mentioned later,
left no doubt as to the correct identification of the above named speci-
mens. These two forms were carefully examined and compared in the
fresh condition. In the form on Cystopteris fragilis the sori appear
only on the under side of the leaf, and the spores are often smaller
than in the case of the form on Phegopteris Dryopteris, but with
these exceptions the general characters are the same. In either case,
sections across the youngest sori show the thin-walled spores attached,
and no thick-walled spores are present. The thin-walled spores are
irregularly ellipticaP or oval (Figures 1, 2, 5, and 6), with very
little trace of the orange contents. The whole number of germ pores
is difficult to ascertain. In optical section one germ pore is often
visible on each side about half-way between the apex and base, but
more than one germ pore to a side is not infrequent, even in those

* Twenty-fourth Report of N. Y. State Museum, p. 88.

398 PROCEEDINGS OF THE AMERICAN ACADEMY.

spores possessing the thinnest walls. As I have stated, thick-walled
spores are rarely to be seen in the young sori ; but they are more
abundant with the increasing age of the sorus, and the best defined of
this type are always found unattached. These spores have orange-
colored contents in the fresh condition. They are more or less oval
in outline, with from four to eight germ pores generally indefinitely
distributed over the surface, as in Figures 4, 8, and 10, taken from
dried material. In every sorus showing both kinds of spoi'es it needed
little search to find connecting stages of every grade between the
irregularly elliptical thin-walled spores and the oval or polygonal thick-
walled spores. The cell wall is found in different degrees of thickness,
and the number of well defined germ pores manifestly increases in
proportion to this thickness of wall. Then from these results we de-
rive the necessary conclusion that the thin-walled spores are merely the
immature condition of the thick-walled mature uredo form.

The herbarium material utilized in this study represented a number
of host-plants, and the collections were made in widely separated
localities ; the diversity of material, therefore, should give a broad
basis for reaching definite results. I have examined Uredo Aspidiotus
Pk. on Phegopteris Dryopteris, Myc. Univ. 9oO, the material from
the author of that species; also Uredo Pulypodii (Pers.) DC. on the
same host from Krieger, Fung. Sax. 566, Syd. Ured. 746, and a speci-
men collected by Dr. Farlow at Shelburne, N. H. I have studied
specimens on Oystopteris fra gills bearing names as follows : Uredo
Polypodii (Pers.) DC, Krieger, Fung. Sax. 567, and Uredo Flllcum
Desm., Erbario Critt. Italiano, 889 ; also material from Switzerland col-
lected by P. INIagnus and by Winter, and from Granville, Mass., Manitou,
Col., Oregon, Gorham, N. H., and from near Boston, Mass. Other her-
barium material included a specimen on Phegopteris Dryopteris from
Thumen, Franconia, Germany; and Uredo Polypodii (Pers.) DC. on
Pulypodium Dryopteris, Eriksson, Fung. Paras. Scand., 70 b. I must
admit that with the examination of only a few preparations of herba-
rium material I might be inclined to agree with previous writers in
distinguishing two distinct kinds of uredospores, but the fresh material
showed beyond doubt that the two forms are but different phases in
the development. Likewise, this process of development was traced
in all of the herbarium specimens above enumerated. Figures 1 to 8
inclusive show two series in which this development may be traced.

In view of Dietel's mention of the four germ pores equatorially
disposed in the thin-walled spores, it was thought well to study this
further ; hence young sori were isolated, the spores cleared and stained.

DUGGAR. — UREDO POLYPODII. 399

The disposition of the germ pores thus made clearer is various, and
I failed to find any constant number relative to auy special zone.
Figures 11, 12, 13, and 14 are examples seen. At most, a study of
the germ pores of spores in such immature condition is unsatisfactory
on account of the slight differentiation of the walls.

We may now proceed to a more detailed consideration of what may
be the specific distinctions or likenesses in all of the specimens exam-
ined. It has been seen that the general characters of the mature spores
are the same, the number and distribution of the germ pores varies
within certain definite limits, and the process of development shows
the same peculiarity — if one may term it such — of thin-walled and
thick-walled spores. It remains for a comparison of measurements
to lend weight one way or another. As Dietel's results would indi-
cate, the form on Cystopteris fragilis is smaller than that on Phegop-
teris Dryopteris, but this did not prove entirely constant, nor is the
average difference great. The following are the full limits of the
spore measurements on the different genera : Phegopteris Dryopteris,
Krieg. Fung. Sax. 566, 30-52 X 17-35 /x ; Eriksson, Fung. Paras.
Scand. 70 b, 24-40 X 16-35 fx ; Phegopteris Dryopteris, from Germany,
26-40 X 18-24 /x ; Cystopteris fragilis, 20-40 X 16-27 /x. One speci-
men on Cystopteris fragilis from Massachusetts measured 20-30 X
16-21 /x, while another specimen on the same host and from the same
State gave 24-40 X 23-27 /x ; thus the extremes on the same host
showed a variation quite as marked as that characterizing the forms on
different hosts. From these results it seems conclusive that these forms
should all be referred to the same species, Uredo Polypodii (Pers.) DC.

The specimens on Cystopteris fragilis and Polypodium Dryopteris
often show a slight roughness on the outer wall, and this character was
more clearly seen in fresh specimens of the former. A Uredo on
Adiantum Capillus - Veneris from Cavara, Fung. Longobardige, and
one on Woodsia glabella from New Hampshire, have this roughened
appearance ; but the general characters of the spores seem undoubtedly
those of Uredo Polypodii (Pers.) DC. The limited material hardly
justifies a positive assertion. A Calif ornian form on Pteris aquilina
is distinctly echinulate, but in the general form and size of the spores
it agrees with others studied. If it belongs to the same species at all,
it is certainly an extreme form.* Fresh specimens are necessary for
accurate demonstration.

* Since the above notes were prepared for publication Dietel has described
in Erythea, Vol. II. No. 8, [August, 1894,] Uredo Pteridis D. & H., on Pteris aqui-
lina ; and from his description it is plainly the form to which I have referred.

400 PROCEEDINGS OF THE AMERICAN ACADEMY.

EXPLANATION OF THE PLATE.

All figures were drawn with the aid of an Abbe camera, using a Leitz objective
No. 7 and ocular No. 3, reduced one fourth.

Figs. 1-4. Stages in tlie development of the form on Phegopteris Dryopteris,
from Shelburne, N. H.
" 5-8. Similar stages as seen on Cystopteris fragilis, from Manitou, Col.
" 9, 10. Extreme sizes noted on Phegopteris Dryopteris, Eriksson, Fung.

Paras. Scand. 70 h.
" 11-14. Immature spores on Phegoptens Dryopteris, cleared and stained,
showing position of germ pores.
15. A spore of the form on Woodsia glabella.
" 16. From, specimen on Ad iantum Capill us -Veneris.

13

B.m.'Q 'it'^-

Duggar on Uredo Polypodii.

JACKSON AND SOCH. — TRINITROPHENYLMALONIC ESTER. 401

XVIL

CONTRIBUTIONS FROM THE CHEMICAL LABORATORY OF

HARVARD COLLEGE.

TRINITROPHENYLMALONIC ESTER.

By C. Loring Jackson and C. A. Soch.

Presented May 9, 1894.

At the end of bis paper on the action of sodium acetacetic ester on
picrylchloride, Dittrich* states that, in spite of many and varied at-
tempts, he had not succeeded in making a picrylmalonic ester from
picrylchloride and sodium malonic ester, but that he obtained in every
case sodic picrate and viscous products of the decomposition of the
malonic ester. This statement impressed us as a strange one, since
in work f done in this Laboratory it had been found that tribromdini-
trobenzol acted much more easily with sodium malonic ester than with
sodium acetacetic ester ; for whereas a good yield of the substituted
malonic ester could be obtained even when the reaction took place in
the cold, with the acetacetic ester the yield was small even after the
reagents had been boiled together. Accordingly, we took up the
study of this subject, and found, as we had expected, that the picryl-
malonic ester could be obtained without difficulty. It is a white sub-
stance melting at 59°, and forms a blood-red sodium salt, which is
tolerably stable, dissolving in water without decomposition. The
picrylbrommalonic ester CGH2(N0.2)3CBr(COOC2H5)2 was made by
treating the substituted malonic ester with an excess of bromine ;
it melts at 85°-86°. One object in undertaking this work was to
see whether any trinitrobenzol was formed in the action of sodium
malonic ester or sodium acetacetic ester on picrylchloride by the re-
placement of the atom of chlorine by hydrogen after the analogy of
such reductions, which have been noticed frequently in the work done
in this Laboratory upon tribromdinitrobenzol and tribromtrinitrobenzol.
Unfortunately the research was begun so late in the year that we

* Ber. d. ch. G., XXIII. 2720. t These Proceedings, XXIV. 2, 274.

VOL. XXX. (n. S. XXII.) 26

402 PROCEEDINGS OF THE AMERICAN ACADEMY.

have been unable to arrive at a definite conclusion on this subject,
and it is hoped that it will be possible to repeat the experiments on
a larger scale and with conclusive results early in the coming term.
A bromdinitrophenylbrommalonic ester corresponding to the picryl
compound mentioned above was also prepared. It melts at 72°-73°.

Trinitrophenyhnalonic Ester {Picryhnalonic Ester),
C6H2(N02)3CH(COOC2H5)o.

As Dittrich* states that the product of the reaction of picrylchloride
and sodium malonic ester is viscous, we first turned our attention to
the preparation of the sodium salt of the substituted malonic ester in
the hope that this might be purified more easily than the free ester.

Sodium Plcrylmalonic Ester, C6H.j(NOo)3CNa(COOC2H5)2.

The picrylchloride used in making this substance was prepared
according to the method of Clemm,t except that we crystallized the
chloride from a mixture of chloroform and alcohol, as we found that
the addition of the chloroform made it possible to work with much
smaller volumes of the solvent, and also seemed to prevent in great
measure the deposition of the picrylchloride in an oily form. A strong
cold benzol solution of 10 grams of this picrylchloride was mixed with
an alcoholic solution of sodium malonic ester made from 14 grams of
malonic ester and the sodic ethylate from 2.1 grams of metallic sodium.
The mixture, which took on at once a deep red color, was cooled at
first, and then allowed to stand for twelve hours at ordinary tempera-
tures ; after which it was diluted with about three quarters of a litre
of water. In this way a red aqueous solution was obtained, and a
supernatant layer of benzol which contained a portion of the picryl-
malonic ester formed, while the rest was dissolved as a sodium salt
in the red aqueous solution, in addition to some sodic picrate and the
sodic chloride. Upon acidifying the aqueous liquid with sulphuric
acid a yellow precipitate was thrown down, which as it settled from
the liquid collected in an oily state on the bottom of the beaker. To
the oily product a strong solution of sodic hydrate was added, which
imparted to it a dark red color, and after thorough mixing converted
it into a red crystalline solid. To remove any liquid or viscous
impurities from the salt, it was next dissolved in the smallest possible
amount of alcohol and treated with an excess of benzol, after which

* Bar. d. ch. G., XXIII. 2720. 1 Journ. Prakt. Chem., [2.], I. 145.

JACKSON AND SOCH. TRINITROPHENYLMALONIC ESTER. 403

the mixed solutions were evaporated cautiously on the steam bath
until crystals begau to form, when upon cooling the sodium salt was
obtained in fine red crystals ; these were washed with benzol, and after
drying in a desiccator gave the following results on analysis : —

I. 0.2400 gram of the substance after evaporation with sulphuric
acid gave 0.0427 gram of sodic sulphate.
II. 0.8331 gram of the substance gave 0.1429 gram of sodic sulphate.

Calculated for Found

CeH2(N0o)3CNa(C00C2H5)2. I. II.

Sodium 0.85 5.76 5.56

An additional quantity of the salt was obtained by the treatment
just described from the residue left after evaporating off the benzol
from the solution of picrylmalonic ester in this solvent obtained by
adding water to the product of the reaction.

Properties of the Sodium Salt of Picrylmalonic Ester. — It crystal-
lizes from a mixture of alcohol and benzol in dark red crystals often
a centimeter long. It is easily soluble in alcohol or ether ; some-
what less soluble in water than in alcohol ; nearly insoluble in benzol.
It does not seem to be decomposed by any of these solvents. Strong
sulphuric acid decomposes it, but without any explosion, which sur-
prised us, as it showed a tendency to explode when dry even at
comparatively low temperatures.

As the potassium salt of picric acid is so much less soluble than the
sodium salt, we prepared the potassium salt of the picrylmalonic ester
by treating the free ester with potassic hydrate in strong aqueous
solution ; but, although this salt was somewhat less soluble in both
water and alcohol than the sodium salt, the difference was not very
marked, and there would be no advantage in using the potassium salt
instead of the sodium salt in the purification of the substance.

The behavior of an aqueous solution of the sodium salt of picryl-
malonic ester with various reagents was also studied, and the following
more or less characteristic precipitates were obtained : —

Salt of magnesium, heavy reddish flocks.

Salts of calcium or barium, granular or crystalline precipitates of aa
amethyst color.

Salt of manganese, dirty yellow flocks.
Salt of nickel, light red flocks.
Salts of lead or silver, dark red flocks.
Salt of cadmium, reddish yellow flocks.

404 PROCEEDINGS OP THE AMERICAN ACADEMY.

Picrylmalonic Ester, C6Ho(NO,)3CH(COOC2H5)2.

Although in our earlier experiments we prepared this substance
through its sodium salt on account of the discouraging statements of
Dittrich, we soon found that this was unnecessary, as the substance
could be purified directly without difficulty, and in all our later work
we have adopted this direct method, which we are about to describe,
as it is much more convenient than the method of purification by means
of the sodium salt. To prepare the picrylmalonic ester we proceeded
according to the method described under Sodium Picrylmalonic Ester,
until by the addition of water the product had been divided into an
aqueous and a benzol solution. The aqueous solution after acidifica-
tion with dilute sulphuric acid was allowed to stand until the oily pre-
cipitate bad separated completely from the mass of the liquid ; part
of it settled, part floated on the surface, and even during this com-
paratively short standing the floating part was converted into crystals,
which could be used to promote the crj'stallization of the larger quan-
tity on the bottom of the beaker. This solidification of the main
portion of the oily product was effected without difficulty by cooling
with running water, one of the crystals from the surface of the water
laeing added if necessary ; and the solidified product, after washing with
cold water, was crystallized from alcohol. The benzol solution, which
had been separated from the aqueous solution, was acidified with dilute
sulphuric acid, and allowed to evaporate spontaneously, when it fur-
nished a rather large additional quantity of the oily product, which
however, did not solidify so easily as that obtained from the aqueous
portion, since it was necessary to allow it to stand for three or four
days with occasional stirring in order to bring it into a crystalline
condition. It was then pressed between layers of filter paper, which
removed an oily impurity, after which it was mixed with the crystals
obtained from the aqueous liquid, and the whole purified by crystalli-
zation from alcohol until it showed the constant melting point 59°,
when it was dried in a desiccator, and analyzed with the following
results : —

I. 0.2707 gram of the substance gave 28.6 c.c. of nitrogen at a
temperature of 25° and a pressure of 757.4 mm.
II. 0.2565 gram gave 25.9 c.c. of nitrogen at a temperature of 22°
and a pressure of 755.8 mm.

Nitrogen

Calculated for

Found.

CoH2(NO,)3CH(COOC2H5)j.

I.

II.

11.32

11.75

11.38

JACKSON AND SOCH. — TRINITROPHENYLMALONIC ESTER. 405

It is worthy of remark that, whereas Dittrich from the action of
picrylchloride on sodium acetacetic ester obtained a considerable
quantity of dipicrylacetacetic ester, our principal product was the
monopicrylmalonic ester, and only on one occasion have we observed
a trace of a substance with a much higher melting point, which we
took to be the dipicryl compound. We should add that, in applying
the same method to the action of sodium acetacetic ester on picryl-
chloride, we obtained almost exclusively monopicrylacetacetic ester.

Properties of Picrylmalonic Ester. — It crystallizes from alcohol in
white, long, rather slender rectangular plates, which develop into rather
thick prisms with blunt ends often as much as two centimeters long.
It melts at 59°, and is very soluble in chloroform, ether, benzol, or
glacial acetic acid ; somewhat less soluble in carbonic disulphide ;
soluble in cold alcohol, freely in hot ; rather more soluble in methyl
than in ethyl alcohol ; insoluble m ligroine or cold water, slightly
soluble in hot water. All the solutions of this substance except that
in glacial acetic acid have a pink color, which is the more marked the
stronger the solution, and the alcoholic solution imparts to the fingers
a crimson color not unlike rosaniline, although less purple. This
coloration of the fingers is much deeper than the color of the solu-
tion, and IS tolerably fast. The formation of these pink or crimson
colors from the white crystals is striking, and will be more carefully
studied.

Cold strong sulphuric acid dissolves it ; if this solution is warmed
it turns red, and gives off bubbles of gas ; dilution of the red solution
after it had cooled precipitated a yellow solid. Sti'ong nitric acid acted
in the same way, except that the picrylmalonic ester dissolves more
slowly in cold nitric acid than in sulphuric acid. Strong hydrochloric
acid did not dissolve it in the cold, but on warming the substance
melted, and then went into solution very slowly. The picrylmalonic
ester has well marked acid properties forming the red sodium salt
when treated with an aqueous solution of sodic hydrate. As is often
the case with substances of this class, the sodium salt is nearly in-
soluble in a strong solution of sodic hydrate. The sodium salt is
also formed by the action of a solution of sodic carbonate on the free
ester.

Trinitrophenylbrommalonic Ester {Plcrylhrommalonic Ester),
C6H2(N0o),,CBr(C00dH5)2.

This substance was made by dissolving some of the trinitrophenyl-
malonic ester described in the preceding section in a small quantity

406 PROCEEDINGS OF THE AMERICAN ACADE3IY.

of glacial acetic acid, and adding liquid bromine until it was present
in distinct excess, as shown by the reddish brown color of the liquid.
To make certain that the reaction was complete, the liquid was
warmed gently on the steam bath for a few minutes, and then allowed
to stand at ordinary temperatures for an hour, after which water was
added in excess, giving a pale yellow precipitate partly solid and partly
liquid. After this had settled, the supernatant liquid, colored red
with the excess of bromine, was poured off, and the liquid part solidi-
fied by cooling. It was then washed with water, dried by pressure on
filter paper, and purified by recrystallization from alcohol until it
showed the constant melting point 85°-86°, when it was dried in
a desiccator, and analyzed with the following result : —

0,1873 gram of the substance gave by the method of Carius 0.0789
gram of argentic bromide.

Calculated for
C6H2(N0,)3CBr(C00C2Hg)2. Found.

Bromine 17.78 17.93

It is obvious that this atom of bromine, the presence of which is
shown by the analysis, may have entered the molecule in one of two
different places, either replacing the hydrogen of the malonic ester
radical, as in the formula given above, or replacing one of the atoms
of hydrogen attached to the benzol ring. It is easy to determine
which position the bromine occupies, for, if it is attached to the
malonic ester radical, the substance will have lost all its acid proper-
ties, since the acid hydrogen has been replaced by 4he atom of bro-
mine. In the second case, where the bromine is attached to the benzol
ring, on the other hand, the acid properties will not be interfered with,
but on the contrary will be somewhat increased if the bromine atom
has any effect whatever. Upon treating our new substance with a
solution of sodic carbonate no change was observed, whereas the picryl-
malonic ester is converted at once into its red salt by this reagent;
as, therefore, this substance has no acid properties, it follows that the
bromine has entered the malonic ester radical, and the formula given
above is the correct one.

Properties of Picrylbrommalonic Ester. — It crystallizes from alcohol
in white plates, nearly but not quite square, and much striated ; these
plates are arranged in irregular rather long rosettes. Less commonly
it occurs in bladed or pennate forms. In general appearance it resem-
bles acetanilid. It melts at 85°-86°, and is very soluble in chloro-
form or benzol ; rather less soluble in ether, carbonic disulphide, or
glacial acetic acid ; soluble in cold alcohol, freely soluble in hot ; rather

JACKSON AND SOCH. — TRINITROPHENYLMALONIC ESTER. 407

more soluble iu methyl than in ethyl alcohol ; insoluble in cold ligroiue,
soluble in it when hot although with some difficulty ; essentially insol-
uble in water, whether hot or cold. The best solvent for it is alcohol.
Its alcoholic solution shows a faint pink color, similar to that given by
picrylmalonic ester, but less marked. Strong sulphuric acid dissolves
it in the cold with a yellow color; upon warming this solution it
becomes brownish black, and bubbles of gas are given off. Sirong
hydrochloric acid seems to have no action on it even when hot. In
cold strong nitric acid it is insoluble, but dissolves easily if the acid is
hot, and boiling this solution for a short time produces no signs of
decomposition. A strong solution of sodic hvdrate did not act upon
it in the cold, but, when heated with it, gave a red solution. The
solution here was undoubtedly preceded by removal of the bromine.
As has been stated already, sodic carbonate does not act on this
substance.

Bromdinitrophenylbromnialonic Ester^
CyH2Br(NOo)oCBr(COOC2H5)2.

This substance was made by dissolving the bromdinitrophenylma-
louic ester in glacial acetic acid and adding to the strong solution an
excess of liquid bromine. The bromdiuitrophenylmalonic ester was
made from tribromdinitrobenzol melting at 192° and sodium malonic
ester.* After an excess of bromine had been added, as shown by the
color, the liquid was warmed gently on the water bath for a short
time, and, if the color had disappeared, more bromine added. It was
then, after it was cool, precipitated with water, and the substance
obtained solidified by coolinsr, if necessary ; after which it was purified
by crystallization from alcohol, until it showed the constant melting
point 72°-73°. It is not wise, however, to rely on the melting point
as the only proof of purity, since the bromdiuitrophenylmalonic ester
from which it is formed melts at 75°-76° ; we have therefore always
tested our product also with a solution of sodic hydrate, which gives a
red salt with the mother substance, but has no effect in the cold on the
desired compound. After purification it was dried in a desiccator,
and analyzed with the following results: —

I. 0.3196 gram of the substance gave by the method of Carius
0.2451 orram of argentic bromide.
II. 0.1997 gram of the substance gave 0.1550 gram of argentic
bromide.

* These Proceedings, XXIV. 2.

408 PROCEEDINGS OF THE AMERICAN ACADEMY.

Calculated for

Found.

C6H2Br(NOo)2CBr(COOC.,U5)j

I.

II.

Bromine

33.05

32.64

33.02

The fact that this substance is not acted on by cold sodic hydrate
proves that it contains the second atom of bromine attached to the
malonic ester radical and not to the benzol ring.

Properties of Bromdinitrophenylhrommalonic Ester. — It crystallizes
from alcohol in long white prisms terminated by a single plane at an
acute angle and arranged in radiated groups ; these crystals are some-
times a centimeter long. It melts at 72°-73°, and is very soluble
in benzol, chloroform, acetone, carbonic disulphide, or glacial acetic
acid ; not freely soluble in cold alcohol, but easily in hot ; more
soluble in methyl than in ethyl alcohol ; insoluble in cold ligroine,
slightly soluble in hot ; insoluble in water, but if boiled with water
for some time, fresh water being added to take the place of that which
evaporates, it is finally brought completely into solution. This action
is undoubtedly due to the removal of the side-chain bromine as hydro-
bromic acid. It will be studied more carefully hereafter. Strong
sulphuric acid does not act upon it m the cold, and when hot it acts only
very slowly. Strong nitric acid also has no action when cold, but if
hot dissolves it. Strong hydrochloric acid does not act upon it in the
cold, and when hot has rather less effect than sulphuric acid. Strong
solutions of sodic hydrate and ammonic hydrate have little or no
action in the cold ; when warmed they convert it into a red substance,
probably a salt formed after the removal of the side-chain atom of
bromine. The whole subject of the replacement of this second atom
of bromine by other radicals must be studied more carefully before
any account can be given of it. It is hoped that this work can be
carried on in this Laboratory during the coming term.

JACKSON AND GKINDLEY. — ACETALS FROM QUINONES. 40&

xvm.

CONTRIBUTIONS FROM THE CHEMICAL LABORATORY OF

HARVARD COLLEGE.

ACTION OF SODIC ALCOHOLATES ON CHLORANIL.

ACETALS DERIVED FROM SUBSTITUTED

QUINONES*

By C. Loring Jackson and H. S. Grindley.

Presented May 9, 1894.

Introduction.

During the study of the action of sodic alcoholates, sodium malo-
nic ester, and similai* reagents upon tribromdinitrobenzol and related
substances,! carried on now for some years in this Laboratory, it has
been observed repeatedly that one of the atoms of bromine is replaced
by hydrogen. In all this work, however, the bromine replaced by
hydrogen has stood in the meta position to two other atoms of bro-
mine, and, as it was possible that this strange reaction depended on the
symmetrical position of the three atoms of bromine, we undertook the
study of a substance with a different constitution ; and for this pur-
pose selected chloranil, in which no one of the atoms of halogen is in
the meta position to two others. While this substance was well fitted
for our work, because the atoms of chlorine which it contains can be
replaced with comparative ease, on the other hand the action of most
of these reagents with it had been already studied by Stieglitz,+ Ikuta,§
Kehrmann.ll and others, and in no case could we find any mention of
a direct replacement of chlorine by hydrogen ; but still as it was

* The work described in this paper formed a thesis presented to the Fac-
ulty of Arts and Sciences of Harvard University for the Degree of Doctor of
Science, by H. S. Grindley.

t These Proceedings, XXIV. 1, 234, 256, 271, 288 ; XXV. 164 ; XXVII. 280 ;
XXIX. 228.

J Am. Chem. Journ. XIII. 38.

§ These Proceedings, XXVI. 295.

II Journ. Prakt. Chem., [2.], XL. 365.

410 PROCEEDINGS OP 'tHE AxMERICAN ACADEMY.

possible that the compounds formed by such a replacement might have
been overlooked among the secondary products of some of these
reactions, or might be formed under other conditions, we have carried
through our experiments. In fact, one of them has proved that, when
sodic methylate acts upon chloranil, a reduction takes place, but the
hydrogen, instead of replacing chlorine, reduces part of the chloranil
to the corresponding tetrachlorhydroquinonCo The work with clilor-
anil, therefore, did not throw light on the replacement of bromine by
hydrogen in tribromdinitrobenzol, because of the presence of the two
atoms of quinone oxygen, which seized upon the hydrogen before it
could replace the halogen. In the mean time, however, our experi-
ments have led to interesting results of another sort, which are
described in this paper.

The action of potassic phenylate on chloranil was the first selected
for study, and we found that, if the substances were mixed in the
proportion of two molecules of the former to one of the latter, the
product was dichlordiphenoxyquinone, CgCl2(OCgHj2C)2) which melts
at 243°, and gives a hydroquinone melting at 197°-198° when treated
with reducing agents. With the object of replacing the two remain-
ing atoms of chlorine we next treated the dichlordiphenoxyquinone
with aniline, but instead of acting on the atoms of chlorine this
reagent attacked the phenoxy groups, giving dichlordianilidoqiiinone
and phenol, behaving in this respect in the same way as dichlordime-
thoxyquinone, which, Kehrmann* found, was converted by treatment
with aniline into dichlordianilidoquinone. This action we found
was the normal one for our substance ; for example, sodium malonic
ester gave with the dichlordiphenoxyquinone the dichlorquinonedi-
malonic ester melting at 132° discovered by Stieglitz f ; and, strangely
enough, this indirect method of preparing the substance gives a better
yield than the direct action of sodium malonic ester on chloranil, for
while Stieglitz by this latter method obtained only about 10 per cent,
our yield was as high as 27 per cent. The beautiful bright blue
sodium salt CgCl202[CNa(COOC2H5)2]o was obtained, and analyzed ;
it is stable for a malonic ester salt. The " deep pure violet color,
resembling exactly a concentrated solution of potassium permanganate,"
obtained by Stieglitz upon the addition of sodic hydrate to the sub-
stance, is due, according to our observations, to some decomposition of
the salt brought about by an excess of the alkali. The solution of
the pure salt has the full blue color of aniline blue.

* Journ. Prakt. Chem., [2.], XL. 370. t Am. Chem. Journ., XIII. 38.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 411

Sodic inetliylate acted on the dichlordipheuoxyquiuoue like the two
reageuts ali'eady mentioued ; that is, the two pheuoxy groups were
replaced by two methoxy groups ; but this action was followed by
another and more interesting one, which formed a crystalline salt,
appearing as a precipitate, if the amount of methylalcohol used as the
solvent was small. Upon the addition of an acid to this salt a white
substance was set free having the followiug formula:

C,C\,(OCB.,).fi.,(CU,OH),.

The sodium salt was also analyzed, and proved to have the formula

C6Cl2(OCIl3)oO,(CH30Na)2(CH30H)2.

The two molecules of methyl alcohol appearing in this last formula
are evidently only alcohol of crystallization, as they could be easily
driven off by heat. The corresponding ethyl compound,

and the methylethyl compound,

C,Clo(OCH3)202(aH50H)2,'

were also obtained, and resembled the methyl compound most closely
in properties. In considering the way in which the two molecules of
methyl alcohol (or sodic methylate) are attached to the molecule of
CgCL,(OCH3)202, only two formulas seemed to us sufficiently probable
to merit discussion. In the first of these (I.) the double bonds of the
benzol ring are broken, and the radicals NaO and CHg added directly
to the ring after the manner of the bromine and chlorine addition
■compounds discovered by Nef.* In the second (II.) the NaO and CHg
have been added to the two carbonyl groups of the quinone, transform-
ing it into a substance closely related to the acetals.

I. II.

O CH3-O 0-Na

II \ /

c c

CH,-0\p/ \p/Cl / \

Na-0/'" ^\CH3 CH3O-C C-Cl

CH3\

/0-Na

ci ; c ^ / c c 6-hk ^^-\ /-OCH3

C

II

o

c

/ \
Na-0 OCH3

* Am. Chem. Journ., XII. 483; XIII. 422.

412 PROCEEDINGS OP THE AMERICAN ACADEMY.

The various isomeric forms of Formula I. need not be considered,
as the arguments which follow will apply as well to them as to this
one. From the properties of the substance, it is nut possible to decide
between these formulas. It is white, like Nef's bromine addition
products, but an acetal like Formula II. would also probably be white,^
as the colors of chloranil and its derivatives undoubtedly depend on
the fact that they are quinoiies, and in such an acetal as this the
quinone nature is obliterated. Its most striking property is the ease
with which the free substance loses the two additional molecules of
methyl alcohol, since it passes into dichlordiniethoxyquinone when
heated to temperatures from 160° to 195° ; the same change is brought
about by dilute sulphuric or hydrochloric acid, slowly in the cold.
more rapidly when the mixture is warmed gently. While this insta-
bility is in harmony with the second formula given above, it is
hard to connect it with the first, as it seems improbable that a methyl
group attached directly to the benzol ring, as in Formula I., could be
so easily removed. It must be remembered in this connection, how-
ever, that Stieglitz * by treating the dichlorquinonedimalonic ester
with dilute sodic hydrate in the cold obtained parachlorhydroxy-
quinone, CgC10HH202. As in this case carbon atoms attached to the
quinone ring were removed by a dilute alkali in a few minutes, it
might be that the methyl group in Formula I. could be removed under
the conditions observed by us. The objection to Formula I. mentioned
above might also be met by substituting for it one in which the
radicals added were Na and CHoO instead of NaO and CH., as in that
formula, but such an addition seems to us at the best improbable. It
should be remarked here that Nef's bromine addition compounds were
decomposed with the utmost ease by alkalies, but were very stable in
contact with acids, being crystallized from strong nitric acid ; our sub-
stances show just the opposite behavior, as they are rather remarkably
stable toward alkalies ; but this difference might be due to the differ-
ence in the nature of the radicals added (Br„ in one case, NaO and
CHg in the other) rather than to a difference in the structure of the
compounds.

Since, as explained above, the properties of our new substance
were not sufficient to prove the correctness of one or the other of the
two formulas proposed, we next turned our attention to some experi-
ments with derivatives of this substance, or rather of the correspond-
ing ethyl compound, which have settled the question conclusively.

* Am. Cliem. Journ., XIII. 38.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 418

To obtain material for this work, which would be possessed of the
requisite stability, we replaced the sodium in the salt of our substance
with the benzoyl radical forming a compound which must have one of
the following formulas, according as one or the other hypothesis about
these substances is adojjted.

I. II.

O C2H5-O O-COCsHs

II \ /

c c

aH,-0\^/ \r./Ci / \

J ..r. f^ .^ ^^ (.^pj^ C^H.-O-C C-Cl

CsH.CO-O/
C,H,.\

ci/-w-<olS&''^ ci-c^ ^c-o-cw.
c c

II / \

O CeHjCO-O O-C.Hg

In Formula I. the carbonyl groups are unaffected, and the body
should therefore retain the properties of a diketoue. In Formula II.,
on the other hand, the carbonyl groups having been transformed
into acetal groups, the body should have lost its diketone nature.
Accordingly, a substance constituted like Formula I. should be con-
verted by reducing agents into a substance containing secondary
hydroxyl groups, and by the chloride of hydroxylamine into a mono
or dioxime. Upon treating our substance with zinc dust and glacial
acetic acid, (which we have found the most efficient agent for con-
verting quinones into hydroquinones,) it remained entirely unaltered,
and the same result was obtained when we tried to act on it with
chloride of hydroxylamine. The substance therefore shows neither
of these characteristic reactions of the diketones and must be consti-
tuted according to Formula II. To meet the not overstrong objec-
tion that the diketone properties of the substance might have been
weakened or destroyed by the presence of radicals attached to the
ring, we treated dichlordiethoxyquinone with the reducing mixture,
and also with chloride of hydroxylamine, and in both cases obtained a
satisfactory quinone reaction. We tried also to determine the consti-
tution of our substance in another way. This consisted in making the
dichlordiethoxyquinone tetraethylacetal C6C12(OCoH5).t(OC.2H5)4 by re-
placing the sodium in the sodium salt C6Cl2(OC.2H5)2(ONa)2(OCoH5)2
by ethyl, and then treating this dissolved in chloroform with bromine
in the hope of making an addition product similar to those of Nef, The

414 PROCEEDINGS OP THE AMERICAN ACADEMY.

result of this experiment was negative, as no bromine was taken up,
but this cannot be accepted as an argument against Formula II., since
Nef * found that dichlordiethoxyquiuone itself gives no addition com-
pound with bromine, — a result which we can confirm. The failure
of the tetraethylacetal to form addition compounds must be ascribed,
therefore, to the presence of the two atoms of chlorine and two ethoxy
groups attached to the quinone ring, rather than to the absence of
double bonds.

It is perhaps worth noting that the formation of these hemiacetalg
is easily explained by the diketo formula of quinone, but cannot be
brought into harmony with the peroxide formula, so far as we can
find. Our work, therefore, would have been of value in determining
the constitution of quinone, if it had been done before this question
was finally settled by Nef's proof of the diketo constitution through
his work on the action of bromine on argentic chloranilate.j

Since, as we have just proved, our new substance has the two mole-
cules of methyl alcohol attached to the two carbonyl groups of the
dichlordimethoxyquinone, it belongs to the class of acetals, and we
propose to call it and similarly constituted bodies hemiacetals, because
only half of the hydrogen in the hypothetical mother group of the
acetals =C=(0H)2 has been replaced by the organic radical. Such
hemiacetals are not especially uncommon, the most familiar examples
being the alcoholates of ordinary chloral and of butylchloral. Jacob-
sen, | and later Renard,§ claimed tliat tliey obtained the corresponding
compound of acetaldehyd CH3CH(OH)(OC^H5), but do not agree in
regard to its boiling point, and apparently assign to it a much greater
stability than would be expected in such a substance. Without mul-
tiplying examples, we pass at once to some compounds more nearly
related to ours, recently obtained by Zincke with some of his scliolars.
Zincke and Arnst || by the action (if alcohol on tetrachlordiketohydro-
uaphthalin have obtained a compound,

OH

co-c(

cji.: I

CClo-CClo

6"4 \^

which is tolerably stal)le in the cold, but decomposed by heat, like our
hemiacetal. The corresponding para compound formed no such deriv-

* Am. Chem. .Tourn., XI 20, 24. § Rer. d. ch. G., VIII. 132.

t Il)i(l.. XII 4RC, II Ann. Cliem., CCLXVII. 319.

.t BtT. d. ch. G.,IV. 2ir>

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 4l5

ative. Zincke and Neumann,* by the action of alcohol on nitro-y8-
naphthoquinone, obtained a substance the formula of which was made
out as follows : —

O

II /OH

/ , ^wi^ng

/N(
\H

C6H4 ^ I -^Q_^

\ • /

C-C
/ \
H OCH

Still later, Zincke and Schaum f have made similar compounds from
the isomeric heptachlorketotetrahydrobenzols by the action of sodic
methylate. Although Zincke's work shows that ring ketones, ortho-
diketones, and orthoquinones are capable of forming such hemiacetals,
so far as we can find our compound is the first of this class to be made
from a paraquinone, and the compound of Zincke's which approaches
most nearly to it, the orthoquiuone derivative, differs from it strikingly,
for, whereas in our compound both carbonyls are converted into hemi-
acetal groups, in Zincke and Neumann's only one of the carbonyl
groups is thus affected, and at the same time a molecule of sodic
methylate is added to the ring by the breaking of a double bond. It
should be mentioned here that J. U. Nef $ has assumed the formation
of addition products of water or hydrochloric acid with the carbonyls
of quinone in explaining the formation of hydroquinone by the action
of water,§ or substituted hydroquinones by the action of hydrochloric
acid on quinone ; II but he supposes that these intermediate products
break up immediately, and none of them have been isolated.

The discovery of the hemiacetals of the quinones has suggested to
us a possible explanation of the constitution of quinhydrone and the
bodies related to it. The most important of these substances are
quinhydrone, formed from one molecule of quinone and one of hydro-
quinone; resorcinequinone, from one molecule of quinone and one of
resorcine ; phenoquinone, from one molecule of quinone and two of
phenol ; and quinhydronedimethylether, from one molecule of quinone
and two of the monomethylether of hydroquinone. The state of our

* Ann. Cheni., CCLXXVIII. 173.
t Ber. d. cli. G., XXVII. 5-37.

t Am. Cliem. -Journ., XIII. 427; Ann. Chem., CCLXX. 323; Clark, Am.
Chem. Journ., XIV. 55.3.

§ Hesse, Ann. Chem., CCXX. 367; Ciamician, Gazz. Chim., XVI. 111.
II Levy, Schultz, Ann. Chem., CCX. 133; Sarauw, Ibid., CCIX. 93.

416 PROCEEDINGS OF THE AMERICAN ACADEMY,

knowledge of the constitution of these substances is described in the
following quotation from a paper on this subject by Nietzki : * " Aus
vorstehenden Versuchen scheint hervorzugelien, dass das Chinhydron,
das Chinonresorcin, blosse Additionsproducte des Chinons mit phe-
nolartigen Korpern sind, und zwar scheint hierbei die Zahl der in
letzteren enthaltenen freien Hydroxyle stets den beiden Chinousauer-
stoiFen zu entsprechen. Eine Formel im Sinne der Structurtheorie
liisst sich ftir diese Korper wohl augenblicklich kaum aufstellen, denn
die von Kekule filr das Chinhydron vorgeschlagene Structurformel

/ OH HO ^

C6H4 H4C6

\o - 0/

lasst sich fiir die Verbindungen des Chinons mit einwerthigen Phenolen
nicht mehr anwenden. Aus dem von O. Hesse beobachteten Verhalten
des Chinhydrons gegen Essigsaureanhydrid scheint jedoch hervorzu-
gehen dass das Chinhydron keine freien Hydroxyle enthalt. Audi
das von Wichelhaus beobachtete Verhalten des Monomethylhydrochi-
nous spricht dafur, dass Substitutionsproducte des Chinhydrons in den
Hydroxylgruppen nicht existiren."

It appears from this quotation that there is no satisfactory theory
for the constitution of these compounds, since the statement that they
are addition products amounts to saying that we have no theory on the
subject. We would, therefore, advance the following theory in regai-d
to the constitution of these bodies : that they are hemiacetals similar to
those described in this paper ; in phenoquinone the phenol, in quinhy-
drone the hydroquinone, taking the place of the methyl or ethyl alcohol,
which is added to the substituted quinones in our new substances.
On this theory the graphical formulas of phenoquinone and quiuhy-
drone would be written as follows : —

OH

/

C 0 — c

/ \ / \

HC CH HC CH

II II II II

HC CH HC CH

\ / \ /

c o — c

\
OH

* Ann. Chem., CCXV. 1.36.

CeH.O

OH

\

/

c

1

/

\

HC

CH

II

II

HC

CH

\

/

C

/

\

HO

OCeHs

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 417

The principal argumeuts in favor of tliis theory are the following.
It requires the union of one molecule of quinone with one molecule of
a diatomic phenol such as hydroquinoue or resorcine, but with two of a
monatomic phenol like common phenol or mouomethylhydroquinone,and
is in this respect in accordance with the facts. Such substances would
not be formed when the hydroxyl groups of the phenols had been con-
verted into alkyloxyl groups, and dimethyl liydroquinone has no action
on quinone. The products should be unstable, as we have found that
the stability of our new hemiacetals depends on the number and strength
of the negative radicals attached to the (juinone ring, and in these cases,
where there are no negative radicals, we should expect a very slight
stability. As a matter of fact, these substances are not only decom-
posed by acids or alkalies, but quinhydrone even by solution in
neutral solvents.* The action of acetic anhydride giving diacetylhy-
droquinone and quinone,t which is brought up by Nietzki as a proof
of the absence of free hydroxyl, is really in accordance with our
theory, as our dimethyl hemiacetal with acetic anhydride gave methyl
acetate and the quinone from which the hemiacetal was derived.
All these observed facts, therefore, are in harmony with our theory.
Against it is the marked color of all this quinhydrone group, whereas
our hemiacetals are colorless. This may be due, however, to the
difference in the nature of the radicals attached to the carbonyl groups,
our hemiacetals containing methyl or ethyl, the quinhydrone group
aromatic radicals, which might well give more colored compounds. It
may be remarked in this connection, that, while the methyl or ethyl
ether of resorcine is colorless, the simple resorcine ether itself is red-
dish brown. An attempt will be made next year to find other parallel
cases. Another objection to our theory is, that no salts have been
obtained from phenoquinone, whereas the substance, according to our
formula, contains two free hydroxyls. Wichelhaus, who states that
he obtained no salts of it, adds that the substance turns blue when
treated with alkalies ; this may indicate the formation of a salt not yet
isolated. We have attempted to test our theory by experiment in this
direction, but so far with little result. By treating phenoquinone with
sodic ethylate, not in excess, we obtained a green salt; but, as much
phenol was found in the filtrate, we are inclined to consider this salt
at present rather a product of the action of sodic ethylate on the qui-
none formed by the decomposition, than a salt of the phenoquinone

* Clark, Am. Chem. Journ., XIV. 574.
t Hesse, Ann. Cliem., CC. 248.

VOL. XXX. (n. S. XXII.) 27

418 PROCEEDINGS OF THE AMERICAN ACADEMY.

itself. If this iuterpretation of the observation is true, it has no bear-
ing ou our theory, as it shows only that the phenoquinoue is easily
decomposed by alkalies, this decomposition taking place before it had
time to form a salt. We then tried the action of sodic phenylate on
quinone, as according to our theory this should act as well, or even
better than free phenol, and we have succeeded in getting an action in
this case, a strongly colored product being formed ; but these experi-
ments were undertaken so late in the year that we had no time to
isolate this substance for study. We should add that in the action
of potassic phenylate on chloranil, described at the beginning of the
experimental part of this paper, there are strong indications of the
formation of a diphenylhemiacetal, as the liquid took on a blue-black
color in the cold, which upon heating changed to the red of the di-
chlordipheiioxyquiuone. The isolation of this hemiacetal, if possible,
will throw a great deal of light upon our theory of the nature of
phenoquinoue. All these lines of work will be taken up in this Labo-
ratory during the next academic year, and we hope that by means of
these experiments we shall succeed in testing thoroughly our theory
that quinhydrone and phenoquinone are hemiacetals of quinone. The
curious addition compounds of the nitranilines and quinones * will also
be considered in this connection.

The dichlordimethoxyquinone dimethylhemiacetal

C6Clo(OCH3)o(OII),(OCH3)„ ,

although most conveniently made from the dichlordiphenoxyquinone
by the action of sorlic methylate, can also be obtained by the action of
the same reagent on diclilordimethoxyquinone, or even on chloranil.
In this last case the first product is a green sodium salt, which by treat-
ment with water yields the sodium salt of the hemiacetal and the
tetrachlorhydroquinone, mentioned at the beginning of this paper.
With sodic ethylate and chloranil we have not succeeded in obtaining
the cnrrespotiding ethyl compound ; it may be, however, that this
result was due to not finding the proper conditions for .the reaction.
The dichlordiethoxyquinone tetraethylacetal

C6Clo(OaH,,),(OCoH5), ,

alluded to in the discussion of the constitution of the hemiacetals, was
made by the action of ethyliodide in the cold on the silver salt of the
corresponding hemiacetal. The yield was exceedingly small, most of

* Hebebrand, Ber. d. eh. G., XV. 1973; Niemayer, Ann. Chem., CCXXVIII.
332.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 419

the hemiacetal dropping back to dichlordiethoxyquinone. Its proper-
ties were strangely unlike those of the correspoudiiig hemiacetal, for
whereas the dichlordiethoxyquinone hemiacetal was essentially in-
soluble in all solvents, the tetraethylacetal was so easily soluble in all
the common solvents except water, that it was hard to crystallize it
from any of them. The most striking property of the hemiacetal was
its instability, since it gave up ethyl alcohol at temperatures from
140° to 143°, becoming converted into the dichlordiethoxyquinone
(mekino- at 104°-10o°) ; the tetraethylacetal, on die other hand, melts-
without decomposition at 10r-102°, and from 205° to 275° sublimes
apparently unaltered. The hemiacetal is converted into dichlordie-
thoxyquinone when treated with acids, even more easily than by heat^
dilute sulphuric or hydrochloric acid acting on it slowly even in the
cold, rapidly when warmed. This is its most marked property ; in
fact, it is so susceptible to the action of acids that in our earlier prep-
arations we obtained a considerable amount of dichlordiethoxyquinone
by drying the hemiacetal at ordinary temperatures, when it had not
been washed enough to remove the last traces of acid. In order to
bring about a similar decomposition of the tetraethylacetal it is neces-
sary to boil it with sulphuric acid of specific gravity 1.44. A more
dilute acid does not act upon it, and even this rather strong sulphuric
acid has no action in the cold. With alkalies the hemiacetal forms
crystalline salts, which are comparatively stable, since they dissolve
in water without decomposition, and can be kept in the dry state for
a moderate length of time. The stability of the substance toward
alkalies is in marked contrast to its behavior with acids, as it is neces-
sary actually to boil it with sodic hydrate in order to convert it into
chloranilic acid. The tetraethylacetal can of course form no salts, as
it contains no hydroxyl. It is even more stable toward alkalies than
the hemiacetal, as sodic hydrate even when boiling or mixed with
alcohol does not decompose it. Finally the hemiacetal is amorphous,
the acetal crystallizes finely, so that almost the only property which
they have in common is their white color. The salts of the hemia-
cetals which are not derived from the alkalies are insoluble in water.
The dichlordiethoxyquinone dibenzoyldiethylacetal,

C6Cl2(OC2H5)2(OC2H5)o(OCOC6H5)2,

also mentioned in the discussion of the constitution of the hemiacetals,
was made by the action of benzoyl chloride on the sodium salt of the
corresponding hemiacetal suspended in alcohol. In this case the yield
is good, about 66 per cent of the theoretical, so that this substance is

420 PROCEEDINGS OF THE AMElilCAN ACADEMY.

much more accessible than the tetraethylacetal ; it crystalUzes well,
and melts at 170°. It is a curious fact that none of the benzoyl
compound is formed, it" the sodium or silver salt of the hemiacetal is
susjjended in ether instead of alcohol, and treated with benzoyl-
chloride. In order to obtain this benzoyl compound, therefore, it is
essential to use alcohol as the diluent. The reaction with ether is
apparently the same as that which occurs when the free hemiacetal
or its sodium salt is heated to 100° with benzoylchloride, the products
in this case beiug dichlordiethoxyquinoue and ethyl benzoate.

When the dichlordiethoxyquinone-dibenzoyldiethylacetal is heated
with sulphuric acid of specific gravity 1.44 it is converted into a
new substance, the analysis* of which gave numbers corresponding
to the formula C6Cl2(OC2H5),,(OCOCoIl5)20. This body must be
formed by the saponification of two ethoxy groups by the sulphuric
acid, whereas we should have expected that the acid would have
attacked rather the two benzoate groups. Our experiments have not
as yet given us any means of determining which pair of ethoxy groups
has been saponified. From the formula established by analysis we
should infer that, after the two ethoxy groups had been converted by
saponification into two hydroxyls, a molecule of water was eliminated,
leaving the atom of oxygen spanning the benzol ring between two
atoms of carbon in the para position to each other. Our substance,
therefore, would have some analogy to cineol, if the constitution
ascribed to it by Briihl f is correct. We realize fully, however, that
such an unusual constitution as this should not be considered estab-
lished without the most convincing proof, and, as at present we are
unable to give this, we propose it only as that which accords best
with the results of analysis and the method of preparation of the sub-
stance. We have made some attempts to prepare derivatives of this
substance in order to throw light on its constitution, and have found

* As our first analytical results approached the numbers calculated for the di-
chlordiethoxyhydroquinone dibenzoate CgCl^lOCaHgjoiOCOCgHsJo, we thought
that perhaps we had in hand this substance mixed with an obstinately adhering
impurity, and accordingly we made it from the substituted hydroquinone in
order to compare it with our substance, but found that the two were not iden-
tical, since it melts at 215°, while the melting point of our new substance is
142°. The bad results from our first analyses we found afterward to be due to
the diflSculty in securing a complete combustion of our saponification product,
and, after taking special precautions to insure this, numbers were obtained
from very carefully purified preparations agreeing excellently with those for
the formula given above.

t Ber. d. ch. G., XXI. 461. Compare also Ibid., XXVII. 810.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 421

that hydriodic acid converts it into a substance probably having the
formula C6Cl20C2H50H(OCOC6H5)o and melting at 164°, but we
have not yet studied this substance thoroughly enough to advance any
theory in regard to its constitution. Aniline also forms one or more
compounds with the saponification product, which we have not yet
succeeded in bringing it into a state fit for analysis. We must content
ourselves, therefore, at present with this preliminary statement of our
experiments on this subject, the study of which will be continued in
this laboratory during the next academic year.

The methyl compounds CgC]o(OCH3)2(OCH3)2(OCOC6H5)o, melt-
ing at 193°, and C6Cl2(OCH3),(OCOC6H5)20, melting at 205°-206°,
which agree with the corresponding ethyl compounds in every respect,
have also been prepared. In order to determine whether other acid
radicals would act like benzoyl we treated the sodium salt of the
-diethyl hemiacetal with chlorocarbonic ester, and obtained the dichlor-
diethoxyquinone diethylacetaldicarbonic ester

CeClaCOQHs) (OC2H5)2(OCOOCo 115)2 ,

which melts at 122°— 123°. In view of our experiments with the
benzoyl derivative, the saponification of this substance promises inter-
•esting results.

We have tried a number of experiments to determine the limits of
the formation of hemiacetals from quinones ; and have found that the
dibromdiphenoxyquinone, melting point 266°-267°, made from brom-
anil, forms a hemiacetal, which seems to be as stable as the one
made from chloranil. The chlordiphenoxyquinone, melting point
169°-170°, made from trichlorquinoue, also forms a hemiacetal, but this
is much less stable than that containinor two atoms of chlorine. Even
the diraethoxydiphenoxyquinone yielded a hemiacetal, but it was so
unstable that it decomposed spontaneously almost as soon as it was
formed. So that the stability of the hemiacetals seems to depend on
the number and strength of the negative radicals attached to the
benzol ring. It was not very probable, therefore, that a hemiacetal of
quinone itself could be isolated, but yet we felt it was necessary to try
the experiment ; and this has established the fact that quinone is acted
on by sodic ethylate, although the product — a green salt — has so far
resisted our attempts to purify it for analysis. Work with it is
especially hard because of its very slight stability ; it takes fire
spontaneously, if dried in the air at ordinary temperatures ; and
although, if dried first in hydrogen, it does not take fire on mere ex-
posure to the air, it glows like tinder when heated to temperatures as

422 PROCEEDINGS OP THE AMERICAN ACADEMY.

low as 40°. After we had abandoned for the present the attempt to-
analyze the green salt, we succeeded in throwing some light on its
composition by determining the proportion of quinone to sodic ethylate
necessary to form it, as we found that each molecule of quinone takes
up one molecule of sodic ethylate, but it must be left to future experi-
ments to decide whether the product is really a hemiacetal.

In all the work so far described in this paper only two of the atoms
of chlorine in chloranil have been replaced by other radicals; we
found, however, that the other pair of atoms of chlorine could be
replaced by phenoxy groups, if the dichlordiphenoxyquinone was
treated with sodic phenylate, or if chloranil was acted on by four
equivalents of sodic phenylate. The tetraphenoxyquinone thus formed
melted at 229°-230°, and offered a rather striking resistance to the
action of reducing agents, although zinc dust and glacial acetic acid
converted it into tetraphenoxyhydroquinone, C6(OCgH5)^OH, melting
point 219°-220°. Toward acids the tetraphenoxyquinone shows a
marked stability, but by boiling with a strong solution of sodic hydrate
it was converted into the diphenoxanilic acid, Cg(OCyIl5)o(OH)o02,
which melts at about 276°. Sodic methylate converts tetraphenoxy-
quinone into the dimethoxydiphenoxyquinone by replacing two of its
phenoxy by methoxy groups ; the substance melts at 171°. The
corresponding diethoxydiphenoxyquinone, melting at 128°, was formed,
instead of tetraphenoxyquinone, when chloranil was treated with sodic
phenylate made from phenol and sodic ethylate in alcoholic solution.
It is a noteworthy fact that bromanil acts differently with sodic phe-
nylate made in this way, giving the dibromdiphenoxyquiuone. One
other case was observed of the substitution of all four of the chlorine
atoms of chloranil. This was when the dichlorquinone dimalonic ester
of Stieglitz was boiled with alcohol and sodic carbonate, as it was
converted into diethoxyquinone dimalonic ester melting at 115°. It is
certainly strange that such a rather weak reagent should remove these
two atoms of chlorine, which in other cases have seemed very firmly
attached to the molecule. In all the reactions just described it is to
be observed that the chlorine atoms or phenoxy groups are replaced in
pairs, and this fact also appears in much of the work with chloranil
previous to ours. This replacement of the radicals two at a time can
probably be connected with the para position of the two atoms of
oxygen, which in this case serve to diminish the attraction of these
radicals to the benzol ring, and thus make it possible to replace them,
as in the case of tribromdinitrobenzol (BrNOoBrNOoBr), melting point
192°, where the loosening nitro groups are in the meta position, all
three of the bromine atoms are replaced in many reactions.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 423

Experimental Part.
Action of Potassic Phenylate on Chloranil.

In order to study this action, 25 grams of chloranil suspended in
50 c. c. of water were treated with au aqueous solution of pota-ssic
phenylate, made from 12 grams of potassic hydrate and 25 giams of
phenol, which gave the proportion of two molecules of potassic phe-
nylate to one of chloranil. To obtain a good result in this process it
was necessary that the chloranil should not be in too large crystals ;
if, therefore, the specimen used was well crystallized, it was reduced
to the hydroquinone with sulphurous acid, and then oxidized with
nitric acid, which left it in a finely divided form easily attacked by
the solution of potassic phenylate. The potassic phenylate was added
in small portions at a time, and the first few drops imparted to the
liquid a chrome-green color, which gradually changed to blue-black
as more of the solution was added, until at last the whole became very
dark blue or nearly black. In order to complete the reaction the
mixture was heated on the steam bath for thirty minutes, which
changed the color from black to red. In the cold there were no siirns
of the formation of this red substance, but it began to appear as soon
as the mixture was warmed. The solution was filtered, and the dark
red solid remaining on the filter, after washing thoroughly with water
and alcohol, was purified by crystallization from hot benzol until it
showed the constant melting point of 243°.

The analysis of the substance dried at 100° gave the following
results : —

I. 0.2138 gram of the substance gave on combustion 0.4692 gram of
carbonic dioxide and 0.0637 gram of water.
II. 0.1510 gram of the substance gave, according to the method of
Carius, 0.1206 gram of argentic chloride-
Found.

II.

Calculated for

C6Cl,(OCoIl5)202.

I.

Carbon

59.83

59.85

Hydrogen

2.77

3.32

Chlorine

19.67

19.75

From these results it is evident that the substance is dichlordiphe-
•noxyquinone. The yield is very good, 25 grams of chloranil giving as
a rule 26 to 30 grams of the new substance, that is, about 80 per cent
of the theoretical yield.

424 PROCEEDINGS OP THE AMERICAN ACADEMY.

Properties of Dichlordlphenoxyquinone, C6Cl2(C6H50)202. — The
substance crystallizes from benzol iu beautiful red needles arranged ia
rosettes. It melts at 243°, and is very slightly soluble in alcohol even
when hot, less so when cold, insoluble in cold and boiling water, diffi-
cultly soluble in boiling benzol, and only very slightly soluble in the
cold ; it is sparingly soluble in cold chloroform, more easily in hot,
slightly soluble in cold glacial acetic acid, but easily when the acid is
boiling; in ether, ligroine, carbonic disulphide, or acetone, it is insoluble.
The three strong acids have no visible effect on it, hot or cold. It is
readily saponified by a solution of sodic hydrate, forming chloranilic
acid. It is not affected by sulphurous acid at 100° under the ordinary
pressure, but is easily reduced to the corresponding hydroquinone by
warming with hydriodic acid, or by the action of glacial acetic acid and
zinc dust.

Dichlordiphenoxyhydroquinone, C6Cl2( C6H50)2(OH)2.

This substance was prepared by mixing dichlordlphenoxyquinone
with hydriodic acid (boiling between 123° and 126°), and heating for
some time on the steam bath. The product formed by this reduction
was purified by crystallization from boiling dilute alcohol (50 per cent)
until it showed the constant melting point of 197°. The analysis of
the substance dried at 100° gave the following results : —

I. 0.2147 gram of the substance gave on combustion 0.4678 gram of

carbonic dioxide and 0.0723 gram of water.
II. 0.1578 gram of the substance gave by the method of Carius 0.1244
gram of argentic chloride.

Found.
I. 11.

59.41
3.73

19.49

The change from the quinone to the hydroquinone is quantitative.

Properties of Diclilordiplienoxyhydroquinone. — It crystallizes from
dilute alcohol (50 per cent) in large colorless prisms, or in little needles
very much branched, forming thick arborescent masses which melt at
197°-198°, and are readily soluble in ethyl alcohol, methyl alcohol,
or acetone ; soluble in carbonic disulphide or hot glacial acetic acid ;
slightly soluble in chloroform, cold glacial acetic acid, or ether. It is
insoluble in water, either cold or hot, benzol, or ligroine. Dilute or
strong sulphuric acid or hydrochloric acid does not act on the di-

Calculated for

CeCloCGCnHjIJOH),,

Carbon

59.51

Hydrogen

3.31

Chlorine

19.56

JACKSON AND GRINDLEY. ACETALS FROM QUINONES. 425

clilordiphenoxydroquinone even when hot. It dissolves in alkalies and
is reprecipitated from the solution by acids. On long standing or
boilino- with sodic hydrate it is saponified, giving the sodium salt of
chloranilic acid which separates in long dark carmine red needles.

By the action of oxidizing agents, such as ferric chloride, dilute
nitric acid, or potassic dichromate in acid solution, it is easily changed
to the corresponding quiuone.

Action of Aniline on Dichlurdiphenoxyqidnone.

The dichlordiphenoxyquinone was treated with aniline in the expec-
tation of removing the two remaining atoms of chlorine. For this
purpose 1 gram of dichlordiphenoxyquinone was mixed with 5 grams
of aniline, and the mixture warmed on the water bath for a few min-
utes. When cool, the large excess of aniline was removed by dilute
sulphuric acid, and, after thorough washing, the dark-colored residue
was purified by dissolving it in aniline, and then adding a small quan-
tity of alcohol ; in this way well formed dark brown crystals were
obtained, melting at 287°-290°, and therefore probably the dichlor-
dianilidoquinone, the melting point of which is given as 285°-290°.
This substance was first prepared and studied by O. Hesse,* later by
Knapp and Schultz.t To confirm this inference the crystals were dried
at 100° and the chlorine determined.

0.1480 gram of the substance gave by the method of Carius 0.1174
gram of argentic chloride.

Calculated for

C6Ci2(c,,ir-,Nii),o,

Pound.

19.70

19.61

Chlorine

The reaction therefore took an unexpected course, since the anilido
groups replaced the two phenoxy radicals instead of the two atoms of
chlorine.

Action of Sodium Malonic Ester on Dichlordiphenoxyquinone.

It has been shown in the preceding section that aniline removes the
phenoxy groups instead of the atoms of chlorine from dichlordiphenoxy-
quinone. We therefore next turned our attention to the action of
sodium malonic ester upon it to see whether this reagent behaved in
the same way. In order to study this reaction 1 gram of dichlordi-
phenoxyquinone suspended in 10 c.c. of absolute alcohol was treated

* Ann. Chem., CXIV. 306. t Ibid., CCX. 187.

426 PROCEEDINGS OF THE AMERICAN ACADEMY.

with a little more than two equivalents of sodium malonic ester, which
was made by treating 0.15 gram of metallic sodium with about 10 c.c.
of absolute alcohol, and then adding 2 grams of malonic ester. On
adding tlie sodium malonic ester, the solution turned very dark blue,
and un standing a dark blue precipitate separated, which was filtered
off and washed with alcohol, in which it is only slightly soluble. The
precipitate dissolved readily in water with a beautiful blue color, and
on the addition of an acid a slightly yellow crystalline product sepa-
rated, which was purified by recrystallization from boiling dilute
ali-oiiol until it gave the constant melting point 132°. After drying
at 100°, it gave the following results on analysis: —

I. 0.2180 gram of the substance gave on combustion 0.3880 gram of
carbonic dioxide and 0.0994 gram of water.
II. 0.1654 gram of the substance gave 0.0964 gram of argentic
chloride.

Carbon

Calculated for
C6Cl2[CH(C00C,H5)2]20j.

48.68

I
48.53

Found.

II

Hydrogen
Chlorine

4.46
14.41

5.06

14

These results prove that ihe substance is dichlorquinonedimalonic
ester. Four grams of the dichlordiphenoxyquinone gave a yield of
about 1.5 grams of the malonic ester compound, that is, 27 per cent of
the theoretical yield.

It is evident that this body must be formed through the replace-
ment of the two phenoxy groups by two malonic ester radicals, and
in fact it was not hard to detect the phenol, which formed the second-
ary product of the reaction. For this purpose the alcoholic filtrate
from the sodium salt of the malonic ester derivative, after evaporation
nearly to dryness, was diluted with water, and treated with a dilute
acid, when the smell of phenol was very evident, and bromine water
gave a voluminous white precipitate. This easy replacement of the
phenoxy groups by the malonic ester radicals, even although the for-
mer are attached to a benzol ring, suggests other work in the same
line, which will be undertaken in this Laboratory,

This dichlorquinonedimalonic ester crystallizes from dilute alcohol
in long slender radiating needles of a yellow color, which melt at
132°, and are insoluble in cold or boiling water, soluble in cold or
warm alcohol. It is not affected by weak oxidizing agents, but hydri-
odic acid reduces it to a white crystalline substance, which melts at

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 427

159°-160°, the melting point* of the dichlorhydroquinonedimalonic
ester discovered by J. Stieglitz ; * our dichlorquinonedimalouic ester
is therefore identical with that obtained by him from the direct action
of sodium malouic ester on chlorauil. Our indirect method of pre-
paring it, however, gives a better yield than the direct method, 27 per
cent instead of 10 per cent. That we might not intrude on this field
of research already occupied by Stieglitz, we have confined our work
on this substance to that necessary for establishing its identity.

Sodium Salt of Dichlorqamonedimalonic Ester,
C6Clo(CNa(COOC2H5)2)202.

In order to prepare this salt the dichlorquinonedimalonic ester was
dissolved in ether, and treated with rather less than the required
amount of sodic ethylate in a strong alcoholic solution. The sodium
salt separated at once as a blue precipitate, which was repeatedly
washed with ether by decantation, and dried over sulphuric acid and
paraffine until the weight remained constant,* after which the sodium
was determined with the following result : —

0.2788 gram of the salt gave 0.0731 gram of sodic sulphate.

Calculated for
CgCljCCNaCCOOCaHjjo)^- Found.

Sodium 8.57" " 8.49

The sodium salt has a beautiful blue color, and is very easily soluble
in water, givino- a solution of a blue color as intense and strikinEf as
that of aniline blue. It is somewhat soluble in alcohol, but insoluble
in ether.

Diethoxyqidnonedimalonic Ester, C6(OC2H5)2(CH(COOC2H5)2)202.

In the first attempt to form the sodium salt of the dichlorquinone-
dimalonic ester, the substance was dissolved in absolute alcohol and
boiled with an excess of dry sodic carbonate. When the sodic car-
bonate was first added, the alcoholic solution was colored dark blue ;
but after filtering out the excess of sodic carbonate and evaporating
rapidly, the solution became nearly colorless, and left after the alcohol
had been driven off a residue of almost white crystals, which were
purified by crystallization from alcohol until the melting point re-
mained constant at 115°. The analysis of the substance dried over
sulphuric acid and paraffine gave the following results : —

* Am. Chem. Journ., XIII. 38.

428 PROCEEDINGS OF THE AMERICAN ACADEMY.

0.2010 gram of the suUstauce gave on combustion 0.4122 gram of
carbonic dioxide and 0.1242 irram of water.

Carbon

Calculated for
Ce(0C,Hj,[CII(C0OC2Hgy,02

56.25

Fouud.

55.93

Hydrogen

6.25

6.86

It gave no teat for chlorine. These results prove that the substance
is diethoxyquinonedimalonic ester, and it is certainly strange that this
substance sliould have been formed from the corresponding dichlor
compound by the action of sodic carbonate and alcohol, in view of
the fact that these two atoms of chlorine in other cases have proved
hard to replace. The substance crystallizes in beautiful yellowish
white needles melting at 115°, which are insoluble in water, readily
soluble in alcohol or ether.

Action of Sodic Methylate on Dichlordiphenoxyquinone. — Dlchlordime-
thoxyquinone DlmethyJhemiacetal, C6Clo(0 0113)0(011)0(00113)2.

In order to see whether the phenoxy groups in dichlordiphenoxy-
quinone would be removed by sodic methylate, as they were when it
was treated with sodium malonic ester or aniline, 10 grams of the
dichlordiphenoxyquinone were mixed with a methyl alcohol solution
of a little less than four equivalents of sodic methylate, made by treat-
ing 2.5 grams of metallic sodium with 60 c.c. of methyl alcohol. The
solution was warmed gently on the water bath, and stirred constantly ;
soon a white crystalline substance began to separate, and the red color
of the dichlordiphenoxyquinone disappeared entirely. The solution
was filtered, the residue washed with a little alcohol, dissolved in
water, filtered again, and then treated with dilute sulphuric acid in
excess, which set free a white insoluble compound. The proper-
ties of this substance indicated at once that the reaction bad not con-
sisted in a simple replacement of the phenoxy by methoxy groups,
as in that case the product must have been the dichlordimethoxy-
quinone discovered by Kehrmann,* which is red, melts at 141°-142°,
and is not insoluble in the common solvents. To prepare our new
body for analysis it was filtered off, washed with water, alcohol, and
then with water again ; after which it was dissolved in dilute sodic
hydrate, filtered, precipitated with dilute sulphuric acid, and washed
thoroughly as described above. This treatment was repeated two or
three times, until the substance was perfectly white and did not change

* Journ. Prakt. Chem., [2.], XL. 370.

JACKSON AND GRINDLEY. — ACETAL3 PROM QUINONES. 429

color vvheu washed with alcohol and ether, aud theu dried for a short
time over sulphuric acid aud paraffiue. It was then analyzed with
the following results : —

I. 0.2410 gram of the substance gave on combustiou 0.3459 gram
of carbonic dioxide and 0.1064 gram of water.
II. 0.2005 gram of the substance gave on combustiou 0 2943 gram
of carbonic dioxide and 0.9720 gram of water.

III. 0.1920 gram of the substance gave by the method of Carius

0.1851 gram of argentic chloride.

IV. 0.2372 gram of the substance gave by the method of Carius

0.2233 gram of argentic chloride.

Found.

IV.

Calculated for

C6CL(OCIIa)202(CH30H)2.

Carbon 39.87

I.
39.13

Found.
II. III.

40.02

Hydrogen 4.65

4.90

Chlorine 23.59

23.8

23.28

These results indicate that the substance is a dimethoxydichlor-
quinone, to which two molecules of methyl alcohol have been added.
To confirm this view of its composition the sodium salt was prepared
and analyzed as follows. An excess of the insoluble compound was
added to a solution of sodic methylate in a large ([uautity of methyl
alcohol. As the sodium salt formed is soluble in methyl alcohol,*
while the original compound is not, it was easy by filtering to obtain a
pure solution of the salt, from which it was then precipitated by
adding an excess of ether. The precipitate was repeatedly washed
with ether by decantation, transferred to a weighed platinum crucible,
dried over sulphuric acid and paraffine, and analyzed with the follow-
ino; results : —

'»

I. 0.2372 gram of the salt gave 0.0828 gram of sodic sulphate.
II. 0.2887 gram of the salt gave 0 1025 gram of sodic sulphate.

Calculated for Found.

CeCl2(0CH3)30„(Cn30Na)2(CH30H)j. I. II.

Sodium 11.24 11.31 11.50

As these analyses indicate that the salt contains two molecules of
methyl alcohol of crystallization, an attempt was next made to detei'-
mine the amount of volatile matter which it contained, with the
following result : —

* In the preparation of the original substance the sodium salt was obtained
as a precipitate, because the amount of methyl alcohol used was not enough to
dissolve it.

430 PROCEEDINGS OF THE AMERICAN ACADEMY.

0.3177 gram of the salt heated at 100° lost 0.0501 gram.

Calculated for
C6Cl2(0CH3)202(CU3ONa).(CH30H)2. Found.

Methyl Alcohol 15.64 15.77

Another sample of the sodium salt was then dried at 100° to a
constant weight, and a sodium determination was made in the dry
substance.

0.2422 gram of the salt gave 0.1018 gram of sodic sulphate.

• Calculated for

CeCUCOCHslAlCHaONajj. Found.

Sodium 13.33 13.61

These results show that, by the action of sodic methylate upon the
dichlordiphenoxyquinone in the first place the two phenoxy groups are
replaced by two methoxy groups, and then two molecules of sodic
metliylate are added directly to the molecule of dichlordimethoxy-
quinone formed by the first part of the action. The proof that these
two molecules of sodic methylate are attached to the carbonyl groups
of the quinone has been given in the introduction to this paper, and
the new substance therefore is dichlordimethoxyquinone dimethyl-
hemiacetal.

Other Mdliods of Preparing the DicJdurdimetJioxyquinone
Dimethylh emiacetal.

This body can be made also directly from chloranil by the action of
sodic methylate. When one equivalent of chloranil was treated with
five or six equivalents of sodic methylate dissolved in methyl alcohol,
a green salt containing sodium separated. This salt was dissolved in
water rendered alkaline by a little sodic hydrate, and the addition of
a dilute acid to this solution produced a dirty white precipitate, a
portion of which was soluble in alcohol, while the rest remained
undissolved. The insoluble part, after purification by dissolving in
sodic hydrate and filtering, was precipitated again with dilute sulphuric
acid, and washed with water and alcohol, after which it was dried in
a desiccator, and the chlorine determined : —

0.2060 gram of the substance gave by the method of Carius 0.1962
gram of argentic chloride.

Calculated for
CaCUCOCir.i i„0.,(CU30H)2. Found.

Chlorine 23.59 23.55

JACKSON AND GRINDLEY. — ACETALS FROM QDINONES. 431

That this product was the same as that prepared from the dichlor-
dipheuoxyquiuoiie was showu also by its properties, which agreed
with those observed for that substauce, especially by its very charac-
teristic reaction with dilute acids.

The other product obtained from the green salt formed by the
action of sodic methylate on chloranil was dissolved in the alcohol
used in washing the dirty white precipitate from dilute sulphuric acid ;
after evaporating off the alcohol, it was purified by recrystallizatiou
from dilute alcohol, and analyzed with the following result : —

0.2094 gram of the substance gave by the method of Carius 0.4841
gram of argentic chloride.

Calculated for CuCl4(OH)2. Found.

Chlorine 57.25 57.16

As it melts at 235°, there can be no doubt that it is the tetrachlor-
hydroquinone, the melting point of which is given by Sutkowski * as
232°. We are unable to determine at present whether this tetrachlor-
hydroquinone is due to a secondary reaction, or whether it proceeds
from that by which the hemiacetal is made. Sodic ethylate does not
act in this way with chloranil.

The dichlordimethosyquinone dimethylhemiacetal is also formed
when dichlordimethoxyquinone melting at 141°'-142° is treated with
two equivalents of sodic methylate dissolved in methyl alcohol.

Properties of the Dichlordimethoxyquinone Dimethylhemiacetal. — It
is a white amorphous solid, insoluble in all the common solvents.
It is very easily converted into the red dichlordimethoxyquinone,
melting at 141°-142°, discovered by Kehrmann.f This change can
be effected by heat alone, since in the neighborhood of 160° it begins
to take on a slight reddish color, which becomes darker very slowly at
this temperature, but when heated to 195° or higher the substance
melts to a red liquid, at the same time increasing very much in volume
and giving otF many bubbles of gas consisting probably of the vapor
of methyl alcohol. Tlie decompostion point is not a definite one, as
in different trials this action took place at temperatures sometimes as
much as twenty or twenty-five degrees apart. An easier way to
bring about this change is by treating the hemiacetal with dilute
sulphuric acid or dilute hydrochloric acid, to either of which it shows
itself remarkably susceptible, the decomposition taking place quanti-

* Ber. d. ch. G., XIX. 2316. t Journ. Prakt. Chem., [2.], XL. 370.

432 PROCEEDINGS OF THE AMERICAN ACADEMY.

tatively, slowly in the cold, but quickly on warming. The ease with
which it is attaclied by dilute acids is its most striking property.
Continued boiling witli water or with dilute alcohol or glacial acetic
acid brings about the same decomposition, as does also treatment of
either the free substance or its sodium salt with benzoylchloride in
a sealed tube at 100°, methyl benzoate being the secondary product.
Acetic anhydride decomposes it in the same way, but more slowly ;
on the other hand, neither methyl nor ethyl iodide acts on the sodium
salt or the free substance. The formation of the benzoic ester of
the substance is described below.

The hemiacetal is a weak acid, forming with sodic metliylate the
wliite crystalline sodium salt, the method of preparation and analyses
of which have been given above. This salt is soluble in water or
alcohol, insoluble in ether. With argentic nitrate a white non-
crystalline silver salt is formed, which is insoluble in water, and easily
decomposed.

Action of Sodic EthyJate on Dichlordiplienoxyquinone. — Dichhrdie-
thoxyquinone Diethylhemiacetal, C6Cl9(OC2H5)2(Ori )2(OC2Hs)2.

In order to study this action 10 grams of dichlordiphenoxyquinone
were treated with an alcoholic solution of little less than four equiva-
lents of sodic ethylate, which was made by treating 2.5 grams of metal-
lic sodium with 60 c.c. of absolute alcohol. When the sodic ethylate
was first added there was no apparent action, but on standing, even in
the cold, the red color of the dichlordiphenoxyquinone gradually disap-
peared, and a white crystalline sodium salt was formed. After warm-
ing gently on the water bath to finish the reaction, the solution was
filtered, the salt washed with alcohol, dissolved in water, filtered again,
and then dilute sulphuric acid added in excess, which gave a bulky
white precipitate. This was filtered off, washed with water, alcohol,
and then with water again. In order to purify the substance further,
it was dissolved in dilute sodic hydrate, filtered, precipitated again with
dilute sulphuric acid, and washed thoroughly, as above. This treat-
ment was repeated until finally the substance was perfectly white, and
did not change color when washed with alcohol and ether, and then
dried for a short time over sulphuric acid and paraffine. The product
was analyzed with the following results : —

I. 0.2205 gram of the substance gave on combustion 0.3802 gram of

carbonic dioxide and 0.1304 gram of water.
II. 0.2017 gram of the substance gave by the method of Carius 0.1614
gram of argentic chloride.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 433

Found.

U.

Calculated for

Cs Clj (0C2H5)2O2(02H5OH)j.

I.

Carbon

47.06

47.02

Hydrogen

6.16

6.57

Chlorine

19.89

19.78

These results show that the action of the sodic ethylate on the
dichlordiphenoxyquinone is analogous to that of sodic methylate, since
two phenoxy groups are replaced by two ethoxy groups, and then two
molecules of sodic ethylate are added directly to one molecule of the
dichlordietlioxy(|uinone thus formed, giving the sodium salt of dichlor-
diethoxyquinone diethylhemiacetal. The yield of the sodium salt from
10 grams of dichlordiphenoxyquinone was usually a little less than
10 grams, and therefore, as the change from the sodium salt to the
hemiacetal is nearly quantitative, we obtained over 75 per cent of the
theoretical yield.

Properties of the Dichlordiethoxyquinone Diethylhemiacetal. — It is
a white amorphous solid, which dissolves slightly in alcohol, but is
partially decom[)psed by this solvent, so that it cannot be recrystallized
from it. It is essentially insoluble in all the other common solvents.
By boiling with dilute sulphuric or hydrochloric acid it is decomposed,
and the same reaction takes place more slowly when it stands with
the dilute acid in tlie cold. The product of the action in either case
is a light red body melting at 104° -105°, after being purified by crys-
tallization from alcohol, which is, therefore, dichlordiethoxyquinone,
as this is the melting point ascribed to this substance by Kehrmann.*
Stenhouse,t who discovered it, gives its melting point as 107° ; but
even by repeated recrystallization we have not been able to raise the
melting point above 104°-105°, and therefore have come to the con-
clusion that Stenhouse's higher number must be due to an error. The
white insoluble hemiacetal melts at 140°-143°, or rather decomposes
at this temperature, changing into the red dichlordiethoxyquinone,
which then melts. From these properties it appears that the relation-
ship between the diethyl and dimethyihemiacetals is of the closest
sort.

Like the corresponding methyl compound the dichlordiethoxyqui-
none diethylhemiacetal has acid properties forming with sodic hydrate
a sodium salt. It shows toward sodic hydrate a stability in marked
contrast to its susceptibility to the action of dilute acids, as it is neces-

* Journ. Prakt. Chem., [2 ], XL. 365. t Ann. Cliera., Suppl. VIII. 14.

VOL. XXX. (n. S. XXII.) 28

434 PROCEEDINGS OF THE AMERICAN ACADEMY.

sary to boil it with a strong solution of sodic hydrate in order to
saponify it to chloranilic acid. The sodium salt of the diethylhemia-
cetal is white and crystalline, readily soluble in water^ slightly soluble
in alcohol, and insoluble in ether. The dried salt is slowly decom-
posed on standing in a closed bottle for several weeks, alcohol is given
off, and a solid product left, which contains some sodic chloranilate
and another body, or more than one, which we have not yet identified.
The silver salt is insoluble, and has a slight brownish yellow color.
It is blackened by light alcohol being set free. On warming with
water a red substance is formed, probably chloranilic acid. Insoluble
salts were also obtained with solutions containing barium, calcium,
lead, or zinc, but they were not studied. The details of the prepara-
tion of the sodium and silver salts will be found under the preparation
of dichlordiethoxyquiuone tetraethylacetal later in this paper.

Dichlordim ethoxyqidnone Diethylhemiacetal,

CeCl2(OCH3)2(OH)2(OC2H5)2.

This substance was made by treating 0.9 gram of dichlordimethoxy-
quinone with an alcoholic solution of sodic ethylate made from 0.2
gram of metallic sodium and absolute alcohol. After warming the
mixture for a few minutes, all the red dichlordimethoxyquinone disap-
peared, and a crystalline sodium salt was deposited. The liquid was
then cooled, the precipitate filtered out, washed with a little alcohol, and
dissolved in water, in which it is completely and easily soluble. The
aqueous liquid after filtration was treated with dilute sulphuric acid,
which threw down a white bulky precipitate of the free hemiacetal,
and this, after thorough washing with water, alcohol, and ether, was
dried over sulphuric acid and paraffine, and analyzed with the follow-
ing result : —

0.1892 gram of the substance gave by the method of Carius 0.1 G27
gram of argentic chloride.

Calculated for
CeCl, 0CH3)2(0H)2(0C2H6)2. Found.

Chlorine 21.58 21.26

The dichlordimethoxyquinone diethylhemiacetal, like those hemia-
cetals which have been described already, is an amorphous white solid,
essentially insoluble in all the common solvents. It is decomposed at
temperatures between 140° and 160°, forming a red substance, prob-
ably dichlordimethoxyquinone, and it is easily saponified by dilute
acids.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 435

Dichlordiethoxyquinone Tetraethylacetal^ C6Cl^(OC2H5)2(OC2H5)4.

It has been stated already that ethyl or methyliodide did not act
either on the free hemiacetal or its sodium salt ; if, however, the
silver salt of dichlordiethoxyquinone diethylhemiacetal vpas treated
with ethyliodide, the corresponding tetraethylacetal was formed. As
this compound could be obtained only in very small quantities and
with great difficulty, it was necessary to prepare the sodium and silver
salts of the hemiacetal on a large scale, which was done as follows.
40 grams of dichlordiphenoxyquinone were mixed with the sodic
ethylate made by treating 10 grams of metallic sodium with 150 c.c.
of absolute alcohol, and in order to complete the reaction the mixture
was warmed on the steam bath for a few minutes, and then allowed to
stand at ordinary temperatures for four or five hours. The sodium
salt of the dichlordiethoxyquinone diethylhemiacetal, which separated
in large amount, was filtered off, and washed thoroughly, first with a
mixture consisting of equal parts of alcohol and ether, and finally with
ether alone. In this way 40 to 42 grams of the essentially pure sodium
salt were obtained instead of the 44 grams required by the theory ;
the yield, therefore, was between 90 and 95 per cent of the theoretical.

In order to prepare the silver salt of the diethylhemiacetal, a
concentrated aqueous solution of the sodium salt was treated with
25 grams of argentic nitrate dissolved in a small amount of water.
The insoluble silver salt was filtered, washed thoroughly with water,
alcohol, and ether, and then dried as quickly as possible by sucking a
stream of air through it on the filter pump.

The silver salt of the diclilordiethoxyquinone diethylhemiacetal
was then suspended in ether, and treated in the cold with ethyl iodide,
when, in addition to a very small quantity of the tetraethylacetal, a
large amount of dichlordiethoxyquinone was obtained. The acetal
was separated from the quinone by treating the products of the
reaction with a dilute solution of sodic hydrate in 50 per cent alcohol,
which converted the dichlordiethoxyquinone into the sodium salt of
chlorani}ic acid, while the dichlordiethoxyquinone tetraethylacetal
was not affected by it. By washing with water it was then easy to
separate the freely soluble sodic chloranilate from the insoluble
acetal, which was purified by recrystallization from ligroine until it
showed the constant melting point 101°-102°, when it was dried in
a desiccator, and on analysis gave the following results : —

I. 0.2039 gram of the substance gave on combustion 0.3928 gram of
carbonic dioxide and 0.1335 gram of water.

436 PROCEEDINGS OF THE AMERICAN ACADEMY.

II. 0.2177 gi-am of the substance gave on combustion 0.4181 gram
of carbonic dioxide. The water determination was lost.
III. 0.1843 gram of the substance gave by the method of Carius
0.1304 gram of argentic chloride.
IV. 0.1 G20 gram of the substance gave 0.1135 gram of argentic
chloride.

Calculated for Found.

CoCl,(OC,,U.,),(OCaH5)i. I. 11 III. IV.

Carbon 52.30 52.54 52.37

Hydrogen 7.26 7.28 —

Chlorine 17.19 17.49 17.32

The yield, as has been already stated, is very small.

Properties of Dlchlordiethoxyquinone Tetraetliylacetal. — This sub-
stance can be obtained from ligroine in good-sized white rhombic
prisms, but when more rapidly crystallized it forms irregularly fan-
shaped groups of very much branched needles resembling certain
delicate seaweeds, or four-sided plates nearly but not quite rectangu-
lar and much striated. It melts at 101°-102°. Bv heating in a
ca[)illary tube it is ajiparently not decomposed even at so high a tem-
perature as 275°, but between 2G0° and 275° it sublimes, giving
beautiful white crystals in the upper part of the tube. It is very
easily soluble in ether, benzol, alcohol, chloroform, acetone, ligroine,
glacial acetic acid, carbonic disulphide, acetic anhydride, or methyl
alcohol, but is insoluble in water. Ligroine is the best solvent for it.

It is saponified by sulphuric acid of specific gravity 1.44, giving
the dichlordiethoxyquiuone melting at 104°-105°, and also a small
quantity of chloranilic acid. In the cold the acid produces little or
no effect on the acetal, but after warming on the steam bath for half
an hour the saponification is complete. A more dilute acid seems to
have no action upon it. Sodic hydrate, even when boiling or mixed
with alcohol, does not decompose the acetal.

The differences between the properties of the tetraetliylacetal and
the diethyllieraiacetal certainly are remarkable. The hemiacetal is
entirely insoluble, while the acetal is exceedingly soluble in all the
common solvents except water. The former is very unstable, being
readily decomposed by even very dilute acids, while the latter is sa-
ponified only slowly by comparatively strong acids when heated with
them. By heat also the hemiacetal is easily decomposed, whereas
the acetal sublimes apparently unaltered at high temperatures.

The action of bromine on the tetraetliylacetal might prove of great
interest, as the formation of addition products from it similar to those

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 437

obtained by J. U. Nef* from quiuone would prove that the four
ethoxy groups were attached to the carbonyl radicals of the quinone
molecule, and thus settle the constitution of this whole class of com-
pounds. The chances of the formation of such addition compounds
were, however, small, as Nef has shown f that dichlordiethoxyquinone
does not take up bromine, a result which we can confirm ; neverthe-
less we felt that it would be unwise to neglect this experiment.
Accordingly, 0.5 gram of bromine dissolved in chloroform was added
to 0.5 gram of the acetal also dissolved in dry chloroform. Even the
first drop of the bromine imparted a distinct yellowish red color to
the solution, showing that no bromine addition compound had been
formed. When all the bromine had been added, the solution was
allowed to evaporate spontaneously, and, although the residue was
colored slightly, it was found that the weight had not increased, and
after one recrystallization from ligroine it gave the melting point of
the unaltered acetal 101°-102°. In another experiment the chloro-
form solution was evaporated to dryness on the water bath, and the
same results were obtained. Under no conditions that we have found
could the acetal be induced to take up bromine. The negative out-
come of these experiments cannot be used^in deciding the constitution
of the acetal, since its inability to take up bromine is more likely to
be due to the presence of the two atoms of chlorine and two ethoxy
groups attached to the benzol ring than to the occupation of the
double bonds by the four additional ethoxy groups, since dichlordie-
thoxyquinone does not take up bromine, as has been already stated,

Dicldordiethoxyquinone Dihenzoyldiethylacetal,

When the diethylhemiicetal itself or its sodium salt was treated
with benzoyl chloride at 100° in a sealed tube, no benzoyl compound
was formed, but tlie main products were dichlordiethoxyquinone and
ethylbenzoate. A similar result was obtained when the sodium or
silver salt of the hemiacetal was suspended in ether, and then treated
with benzoyl chloride. When, however, the sodium salt was sus-
pended in alcohol instead of ether and benzoyl chloride added, the
dibenzoyl derivative was readily formed, and only a trace of dichlordie-
thoxyquinone was produced. The following method was found to be
the best for the preparation of this substance. To 10 grams of the
sodium salt of the dichlordiethoxyquinone diethylhemiacetal suspended

* Amer. Chem. Journ., XII. 483. t Ibid., XI. 20.

438 PROCEEDINGS OP THE AMERICAN ACADEMY.

in a small quautitj of alcohol 7.6 grams of benzoyl chloride were
added, which gave the proportion of two molecules of benzoyl chloride
to one of the sodium salt. There was but little action in the cold, but
when the raixtui-e was warmed on the water bath the reaction took
place readily, with the separation of sodic chloride. After cooling,
the solution was filtered, and the solid remaining on the filter washed
thoroughly with alcohol and water, and then crystallized from hot
alcohol until it showed the constant melting point 170°. The analysis
of the substance dried at 100° gave the following results : —

I. 0.2428 gram of the substance gave on combustion 0.5276 gram
of carbonic dioxide and 0.1230 gram of water.
II. 0.2173 gram of the substance gave by the method of Carius
0.1112 gram of argentic chloride.

Calculated for Found.

CeCi2(OC2U5),(oc,u^ocoCoH5)2. I. ir.

Carbon 59.47 59.27

Hydrogen 5.31 5.63

Chlorine 12.57 12.65

The yield of the dichlordiethoxyquinone-dibenzoyldiethylacetal from
ten grams of the salt is seven and one half grams, or about 66 per cent
of the theoretical yield.

Properties of Dichlordiethoxyquinone Dibenzoyldiethylacetal. — From
alcohol it crystallizes in short thick prisms, or, when crystallized more
rapidly, in rhombic crystals with a sharp terminal angle, often col-
lected into curving radiated or bladed groups. It is white, and melts
at 170°. It is easily soluble in chloroform, carbonic disulphide, ether,
or benzol ; also in hot ethyl or methyl alcohol, but only slightly soluble
in either of these liquids when cold ; soluble in warm glacial acetic
acid ; slightly soluble in hot ligroine ; insoluble in water. Sulphuric
acid of specific gravity 1.44 saponifies it, forming tlie compound de-
scribed in the next section. Sodic hydrate solution, even if boiling or
mixed with alcohol, does not decompose it.

The study of the action of reducing agents and of hydroxylamine
on the dichlordiethoxyquinone dibenzoyldiethylacetal was of especial
interest, because it threw so much light upon the constitution of this
whole class of substances. If this body was a true acetal, these agents
should have no action upon it ; if, on the other hand, the ethoxy and
benzoyl radicals were not attached to the two carbonyl groups of the
quinone molecule, but to the four other atoms of carbon, the substance

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 439

•would be converted into a secondary alcohol by reducing agents, and
into an oxime by hydroxylamiue. The reducing agent selected was
a mixture of zinc dust and glacial acetic acid, as this had proved
rather the most effective for the conversion of a quinone into a hydro-
quinone, and there was little or no danger that it would saponify the
compound. Even after long continued action there were no signs of
reduction, but the unaltered dichlordiethoxyquinone dihenzoyldiethyl-
acetal was recovered from the mixture. This experiment, therefore,
goes to prove that the substance is an acetal, and this proof is strength-
ened by the fact that dichlordiethoxyquinone is converted into the
corresponding hydroquinone quickly and easily by this reducing mix-
ture.

To try the action of hydroxylamine 0.2 gram of the dichlordiethoxy-
quinone dibenzoyhliethylacetal dissolved in alcohol was mixed with
an alcoholic solution of 0.5 gram of hydroxylamine chloride. The
solution was boiled over the free flame for half an hour, and then after
cooling treated with a large excess of water. The precipitate thus
formed after one crystallization from alcohol melted at 170°, and was
therefore the unchanged original substance. No other organic sub-
stance could be found in the precipitate, or in the aqueous filtrate.
The experiment was repeated with an alkaline solution, and again
with an acid solution, but in no case could any change in the original
acetal be detected. To prove that the indifference of the acetal to the
hydroxylamine was not due to the effect of the ethoxy radicals and
chlorine atoms attached to its benzol ring, we next studied the action
of the chloride of hydroxylamine on dichlordiethoxyquinone. For
this purpose 0.5 gram of it were treated with the chlori<le of hydrox-
ylamine in alcoholic solution, and the mixture warmed for sixteen hours
on the water bath. Water precipitated a black substance crystallized
in scales, which was thoroughly washed with water to remove all the
hydroxylamine salt. It dissolved easily in sodic hydrate, and from
this solution acids threw down a reddish gelatinous precipitate. It
gave a good test for nitrogen by the potassium method. There can
be no doubt, therefore, that the chloride of hydroxylamine acts on
dichlordiethoxyquinone and consequently the indifference of our acetal
to this reagent is not due to the presence of the radicals attached to
the benzol ring, but is caused by the occupation of the two carbonyl
groups by the ethoxy and benzoyl radicals. As we had accomplished
our purpose when we had proved that the chloride of hydroxylamine
acts on dichlordiethoxyquinone, we have not tried to study the product
more carefully.

440 PROCEEDINGS OF THE AMERICAN ACADEMY.

Saponification of Dichlordiethoxyquinone Dibenzoyldiethylacetal.

This substance was boiled with sulphuric acid of specific gravity
1.44 for half an hour in a tiask with a return condenser ; a certain
amount of gas was given off, and the solid finally went into solution
completely, but upon cooling crystals were deposited, the amount of
which was increased by diluting the acid with water. This crystal-
line precipitate was filtered out, washed repeatedly with water to
remove a little chloranilic acid which had been formed in tlie process,
and the residue recrystallized from alcohol until it showed the constant
melting point 142°, when it was dried for analysis. The analysis of
this substance gave a great deal of trouble ; by using a boat and a
stream of oxygen according to the usual method we were unable to
secure <;omplete combustion, and therefore were forced to mix the
compound with cupric oxide, and carry on the combustion in an old-
fashioned closed tube. This accounts for the fact that our jjercent-
ages of hydrogen are somewhat high.

I. 0.2119 gram of the substance gave on combustion 0.4558 gram
of carbonic dioxide and 0.0845 gram of water.
II, 0,20G2 gram gave 0.4452 gram of carbonic dioxide and 0.08G9
gram of water.
III. 0.2020 gram gave 0.4344 gram of carbonic dioxide and 0.0830

gram of water.
IV. 0.2063 gram gave 0.4451 gram of carbonic dioxide and 0.0837
gram of water.
V. 0.1947 gram of the substance gave by the method of Carius
0.1136 gram of argentic chloride.
VI. 0.2212 gram gave 0.1290 gram of argentic chloride.

Calculated for Fouud.

CeCl,(OC,Il5).(OCOC6H5)20. • I. II. III. IV V. VI.

Carbon 58.65 58.66 58.88 58.64 58.84

Hydrocren 4.07 4.43 4.67 4.56 4.51

Chlorine 14.46 14.42 14.41

The formula calculated from these analytical results is so strange,
that we were at first unwilling to accept it, and thought that perhaps
we had the dibenzoate of dichlordiethoxyhydroquinone in our hands,
the calculated percentages of hydrogen and chlorine for which agree
fairly well with those found by us, whereas the calculated percentage
of carbon is over two per cent higher. This difference we thought
might be due to an obstinate impurity, and accordingly we prepared

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES, 441

this dibenzoate from dichlordiethoxyhjdroquinone, and found that it
was entirely different from the saponification product, as it melts at
215° instead of 14:2°. The description of this substance is given
later in the paper. The supposition that the substance might contain
an obstinately adhering impurity was disposed of by frequent recrys-
tallizations. The sample for Analysis I. was crystallized only three
or four times, that for II. and III. ten times, that for IV. eight times.
There was no difference in the melting points of these three samples,
and, as the results given above show, no essential difference in their
percentage composition. We must therefore accept tlie formula
derived from these analyses, and the most probable Jiypothesis is that
the atom of oxygen spans the benzol ring between two atoms of
carbon in the para position, but we are unable to determine at present
whether this atom of oxygen proceeded from the saponification of the
ethoxy radicals of the acetal, and therefore lies between the two atoms
of carbon to which the benzoate groups are attached, or from the
two ethoxy groups of the chloranilic ester, and therefore spans the
ring between two other atoms of carbon. This latter supposition
seems to us the more probable, as it would give some explanation of
the ease with which the ethyls are removed. We wished to confirm
such an unusual hypothesis by studying the derivatives of this sub-
stance, but our work in this direction has not yet brought any con-
clusive evidence in regard to its constitution, and we therefore propose
this theory only as the most probable one, leaving to future work the
testing of its accuracy. It may be observed here that such a sub-
stance would be a natural product of the saponification of dichlor-
diethoxy(iuinone dibeuzoyldiethylacetal as shown by the following
reactions : —

C6Cl2(OC2H5)o(OaH5)o(OCOCcH5)2 + 2 HoS04 =

CeC]2(OC2H5)2(OH)o(OCOC6H5)2 + 2 C,H5HS04 =

C6C]2(OC.,H5)20(OCOC6H5)2 + H2O + 2 C2H5HSO4.

We would call the substance, in accordance with its provisional
formula, oxide of dichlordiethoxyhydroquinone dibenzoate, although it
may be instead the oxide of dichlorquinone ethylbenzoylacetal.

Properties of the Oxide of Dichlordiethoxyhydroquinone Dihenzoate.
— It crystallizes in white well developed six-sided prisms, often of
considerable size, belonjiing either to the hexafjonal or orthorhom-
bic system. When crystallized more quickly, it. forms rather loose
rosettes of prisms terminated by several planes forming a very blunt
end. It shows a strong tendency to separate from its solutions in the

442 PROCEEDINGS OF THE AMERICAN ACADEMY.

form of a varnish, this result being obtained, for instance, when the
alcoholic solution is evaporated to dryness on the water bath. It
melts at 142°, and is readily soluble in alcohol or chloroform ; soluble
in carbonic disulphide, glacial acetic acid, or benzol ; difficultly soluble
in ether ; insoluble in water. The best solvent for it is alcohol. With
aniline it gives two or more products, the study of which next year
we hope may throw some light on its constitution.

Reduction of the Oxide of Dichlordiethoxyhydroquinone Dihenzoate.

When the substance described in the preceding paragraph is moist-
ened with a concentrated solution of hydriodic acid, and heated on the
water bath until dry, a reaction takes place, as shown by the separation
of free iodine. In order to complete the action the moistening with
hydriodic acid and warming was repeated, and the product thus
obtained was purified by repeated recrystallization from a veiy small
quantity of alcohol until it showed the constant melting point 164°,
when it was dried at 100°, and analyzed with the following results: —

I. 0.2004 gram of the substance gave on combustion 0.4339 gram of

carbonic dioxide and 0.0812 gram of water.
II. 0.2301 gram of substance gave 0.5001 gram of carbonic dioxide
and 0.0825 gram of water.
III. 0.2274 gram of substance gave by the method of Carius 0.1462
gram of argentic chloride.
IV. 0.1998 gram gave 0.1276 gram of argentic chloride.
V. 0.1990 gram gave 0.1276 gram of argentic chloride.

Calculated for Found.

CeCljOCoHjOHlOCOCeHsJj. 1. II. III. IV. V.

Carbon 59.06 59.06 59.28

Hydrogen 3.58 4.50 3.99

Chlorine 15.89 15.90 15.79 15.85

These results ajjree best with those calculated for the formula given
above, although it is not impossible that the substance may contain
more hydrogen. It is obvious, however, that the formula of the sub-
stance cannot be considered as established, until the analytical data
have been supported by experiments with some of its derivatives. AYe
shall not at present indulge in any speculations on the constitution of
this substance. It crystallizes usually in balls of indistinct little
prisms, but occasionally slender short prisms terminated by a single
plane at a very sharp angle were observed. Like its mother sub-
stance, it has a strong tendency to come down from its solutions in the

JACKSON AND GRINDLh:Y. ACETALS FROM QUINONES. 443

form of a varuish. It melts at 164°, aud is very soluble in alcohol,
mnch more so tliau the oxide from which it was obtaiued ; easily
soluble ill acetone, or glacial acetic acid ; sparingly soluble in ether,
benzol, or chloroform ; insoluble in carbonic disulphide, or water. It
shows weak acid properties, since it dissolves in a solution of sodic
hydrate, and is reprecipitated by an acid. Aniline acts upon it, but
we liave not yet studied the products. Alcohol seems to be the best
solvent for it. The study of this substance will be continued in this
Laboratory next year, and we hope the results of this work will not
only definitely establish its formula, but also throw much light on the
constitution of the body we have called the oxide of dichlordiethoxy-
h}droquinone dibenzoate, from which it was obtained.

Dibenzoate of Dichlordiethoxyhydroquinone,

CeCl2(OC2H5)2(OCOCeH5)2.

This substance, which was made in order to compare it with the
oxide of dichlordiethoxyhydroquinone dibenzoate just described was
prepared as follows. The sodium salt of the substituted hydro-
quinone was treated with a slight excess of benzoyl chloride, and the
product boiled with water to decompose the benzoyl chloride which
had not entered into the reaction. After filtering hot the residue was
recrystallized from a mixture of alcohol and chloroform until it
showed the constant melting point 215°, when it was dried at 100°,
and analyzed with the following result : —

0.2000 gram of the substance gave by the method of Carius 0.1202
gram of argentic chloride.

Calculated for
C6Cl2(002H-,),,( 0C0CbH5)2. Found.

Chlorine 14.95 14.86

Properties of the Dibenzoate of Dichlordiethoxyhydroquinone. — It
crystallizes from a mixture of alcohol and chloroform in long white
prisms terminated by two planes meeting at an obtuse angle ; these
prisms show a tendency to unite longitudinally. It melts at 215°,
and is easily soluble in chloroform ; soluble in boiling benzol ;
sparingly soluble in alcohol even when hot, or in glacial acetic acid ;
insoluble in ether, carbonic disulphide, ligroine, or water. The dilute
acids do not act on it even when boiling, nor does strong hydrochloric
acid or strong nitric acid produce any visible effect ; strong sulphu-
ric acid also does not act on it in the cold, but when hot dissolves it,
forming a slightly dark-colored solution. Alkalies even in strong
boiling solution do not de'-ompose it.

444 PROCEEDINGS OF THE AMERICAN ACADEMY.

DlcJilordimethoxyquinone Dibenzoyldimethylacetal,
C6Cl2(OCH3)o(OCig2(OCOCeH5)2.

This substance was made in the hope that its saponification might
throw some additional light on the curious products obtained from the
corresponding ethyl compound, and described in the preceding sections.
For this jDurpose 17 grams of the sodium salt of dichlordimethoxy-
quinone dimethylhemiacetal were suspended in methyl alcohol, and
20 grams of benzoyl chloride added (this is a little more than the
calculated amount), after warming for a short time to finish the
reaction, the liquid was allowed to cool, the solid, which had separated,
filtered out, and washed first with alcohol and afterward with water.
The residue was purified by crystallization from a mixture of alcohol
and chloroform until it showed the constant melting point 193°, when
it was dried at 100°, and analyzed with the following result: —

0.2052 gram of the substance gave by the method of Carius 0.1163
gram of argentic chloride.

Calculated for
C6Cl2(0CH3)j(0CU3)2(0C0CgH5)2. Found.

Chlorine 13.95 14.02

The substance crystallizes from a mixture of alcohol and chloroform
in several different forms, which however may be produced by the
twinning of a single form in different ways. The simplest form ob-
served consisted of rather long plates terminated by two planes at an
obtuse angle to each other ; these frequently appeared as broad blades
in radiating groups, when less well developed. A second very common
form was white thick plates, square or nearly so, which showed evi-
dence of twinning, and finally mixed with these were sharp thick
rhombic crystals looking like very acute scalenohedra, and showing a
line of twinning along the diagonal between the two acute angles.
Whether these were different habits of the same form, or indicated
that the substance was not homogeneous, mattered little to us, as
the saponification with sulphuric acid of specific gravity 1.44 gave a
product which was evidently homogeneous, and this was the substance
in which we were especially interested. The dichlordimethoxyquinone
dibenzoyldimethylacetal is white, and melts at 193°. It is easily
soluble in chloroform ; soluble in benzol ; sparingly soluble in alcohol,
ether, glacial acetic acid, or carbonic disulphide ; insoluble in water
or ligroine. The best solvent for it is a mixture of alcohol and
chloroform.

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 445

Saponijication of Dichlordimethoxyqumone Dihenzoyldimethylacetal.

The substance was boiled with sulphuric acid of specific gravity
1.44, in the manner already described under the corresponding ethyl
compound, and the phenomena observed in this case were exactly
similar to those presented by the ethyl compound. The product of
the reaction was purified by recrystallization from a mixture of
chloroform and alcohol until it showed the constant melting point
205°-206°, when it was dried at 100°, and analyzed with the following;
result : —

0.2071 gram of the substance gave according to the method of
Carius 0.1288 gram of argentic chloride.

Calculated for
CfiCl2(OCH3),(O0OC6H5)2O. Found.

Chlorine 15.33 15.38

f-

This product therefore corresponds to that obtained by the saponi-
fication of the ethyl compound, and this view of its nature is confirmed
by the striking similarity between these two substances in crystalline
foi"m.

Properties of the Oxide of Dichlordimethoxyhydroquinone Diheii-
zoate. — It crystallizes from a mixture of alcohol and chloroform in
white well formed rhombic prisms, shorter than they are broad,
terminated by a very obtuse octahedron and a basal plane forming a
very blunt end ; the j^risms are frequently rendered six-sided by the
presence of two basal planes on the acute edges. It melts at 205°-
206°, and is readily soluble in chloroform ; soluble in glacial acetic
acid, or benzol ; slightly soluble in alcohol, acetone, or carbonic disul-
phide ; very sparingly soluble in ether ; insoluble in water. The best
solvent for it is a mixture of alcohol and chloroform.

Dichlordiethoxyquinone Di ethyl acetaldicarhonic Ester,

C6Cl2(OC2H5),,(OC2H5)2(OCOOC,H,)2. .

After we had succeeded in replacing the sodium in the salts of the
hemiacetals described in this paper with the benzoyl radical, it seemed of
interest to see whether other acid chlorides would act in the same way,
and we therefore tried the action of chlorocarbonic ester. Four sframs
of the sodium salt of dichlordiethoxyquinone diethylhemiacetal sus-
pended in absolute alcohol were mixed with a slight excess of chlorocar-
bonic ester, and warmed on the steam bath for a few minutes in order
to complete the reaction. The solution was filtered while still hot from

446 PROCEEDINGS OP THE AMERICAN ACADEMY.

the precipitate of sodic chloride, and the filtrate on cooling deposited
well formed crystals of the new substance, which was purified by
recrystallization from alcohol until it showed the constant melting
point 122°-123°, when it was dried, and analyzed with the following
result : —

0.1866 gram of the substance gave by the method of Carius 0.1075
gram of argentic chloride.

Calculated for
C6Cl2(OC2H5)„(OC2H5).>(OCOOC2H5)2. Found.

Chlorine 14.18 14.24

The substance crystallizes in white flat prisms, terminated usually
by a single plane at a very sharp angle, which is occasionally modified
by a sei-oud smaller plane. It melts at 122°-123°, and is readily
soluble in alcoliol, chloroform, benzol, or acetone ; soluble in glacial
acetic acid, or carbonic disulphide ; slightly soluble in ether; insoluble
in water. The best solvent for it is alcohol. In view of the results
of tlie saponification of the corresponding benzoyl compound the
decomposition of this substance with sulphuric acid of specific gravity
1.44 promises to be interesting. Unfortunately, it was prepared just
before the vacation, so that this work must be postponed until the
next college year.

Action of Potassic Phenylate on Dichlordiphenoxyqidnone. —
Tetraphenoxyquinone, Q>^^{OC^^ ^O^-

By treating 10 grams of pure dichlordiphenoxyquinone with a little
more than two equivalents of potassic phenylate, made by dissolving 4
grams of potassic hydrate and 12 grams of phenol in 150 c.c. of water,
tetray)henoxyquinone was formed. In order to complete the reaction
it was necessary to boil the dichlordiphenoxyquinone with the potas-
sic phenylate for twenty to thirty minutes. The product formed was
then filtered ofp. and after washing thoroughly with water and alcohol
was fturifiFd by crystallization from benzol until it gave the constant
melting p'«int of 229°-230°. After drying at 100°, the substance
gave the following results on analysis : —

I. 0.2198 gram of the substance gave on combustion 0.6122 gram
of carbonic dioxide and 0.0865 gram of water.

Calculated for Cp,(0C6H5)402. Found.

Carbon 75.63 75.97

Hydrogen 4.20 4.37

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 447

This body can also be formed by the action of four equivaleuts of
potassic pheuylate in aqueous solution on chloraml, or by the at-tion
of sodic phenylate on the dichlordiphenoxyquinone suspended in
benzol. In this latter case the sodic phenylate was prepared by
dissolving phenol in a rather large volume of benzol, and then adding
the required quantity of sodium, which disa|)peared completely alter
warminc the solution on the steam bath for some time. Neither of
these methods gives so good a result as the one described at the be-
ginning of this section. On the other hand, the tetraphcnoxyquinone
is not formed when the dichlordiphenoxyquinone is treated witli sodic
phenylate, which has been made by the action of metallic sodium on
absolute alcohol mixed with phenol, as in this case the principal pro-
duct is diethoxydiphenoxyquinone.

Properties of Tetraphenoxyquinoiie. — It crystallizes from benzol
in red prisms which, when well developed, have blunt ends formed by
a number of planes or by a single plane at an oblique angle. When
smaller they appear as long somewhat shuttle-shaped prisms, radiating
from a common centre, but not forming circular groups. It melts at
229°-230°, and is soluble in hot chloroform, boiling acetic anhydride,
or boiling benzol ; slightly soluble in carbonic disulphide, or boiling
glacial acetic acid ; very sparingly in warm acetone ; insoluble in
water, alcohol, ether, or ligroine. The best solvent for it is boiling
benzol.

The tetraphenoxy qui none is not easily attacked by reducing agents ;
sulphurous acid at ordinary temperatures, or in a sealed tube at 100°,
has no action on it ; hydriodic acid, or a mixture of stannous chloride
and hydrochloric acid, reduces it, but the action is very slow ; on the
other hand, it is easily reduced by glacial acetic acid and zinc dust.

Saponification of Tetraphenoxyquinone.

Toward acid saponifying agents the tetraphenoxyquinone shows a
remarkable stability. Sulphuric acid of specific gravity 1.44 has no
effect whatever, even after long continued boiling, but hot strong
sulphuric acid of specific gravity 1.83 dissolves it, giving a solution
from which nothing is precipitated on adding water. This may be
due to the formation of a sulphonic acid, but we have not as yet
studied the reaction carefully.

A better result was obtained by boiling the tetraphenoxyquinone
with a solution of sodic hydrate (one part in four) for ;ibout two hours,
as it was then completely dissolved, giving a dark purple color to the
solution, which on cooling deposited small black crystals of a sodium

448 PKOCEEDINGS OF THE AMERICAN ACADEMY.

salt. The alkaline solution, when poured into an excess of dilute
acid, gave a reddish yellow precipitate, which was filtered out, washed
with water, and, after purification by recrystallizatiou from alcohol,
dried, and analyzed with the following result : —

0.2224 gram of the substance gave on combustion 0.5436 gram of
carbonic dioxide and 0.0794 gram of water.

Calculated for

Cs(0C6H5),(0U),0j.

Found.

Carbon

66.68

66.65

Hydrogen

3.70

3.97

The substance was therefore formed from the tetraphenoxyquinone
by replacing two of the phenyl radicals by hydrogen, and is the
diphenoxyauilic acid.

Properties of Diphenoxyanilic Acid, C(;(OCgH5)2(OH)202. — It
forms glistening rather thick plates, either square or in rectangular
oblong forms, having a dark reddish brown color like that of ferric
citrate ; which the substance also resembles in lustre and general
appearance. It melts at about 276°, but the melting point is not
sharp, as it shows signs of softening even at 270°. If heated some-
what above its melting point, it puffs up filling the capillary tube with
a dark liquid. It is soluble in glacial acetic acid ; sparingly soluble
in alcohol or hot chloroform ; insoluble in ether, benzol, carbonic
disulphide, or ligroine. It dissolves slightly in boiling water, imparting
a pink color to the solution. It has distinct acid properties dissolving
in sodic hydrate to form a black crystalline salt, which dissolves in
water with a dark purple color. It is not acted on by acids dilute or
strong, cold or hot.

Tetraphenoxyhydroqicinone, Cg (OCgHj) ^ ( OH) 2.

This body was made by reducing the tetraphenoxyquinone with
glacial acetic acid and zinc dust. Two grams of the tetraphenoxyqui-
none were warmed on the steam bath with these reagents until the red
color of the original substance had completely disappeared ; water was
then added, and the precipitated hydroquinone purified by recrystal-
lizing it from alcohol containing a little hydriodic acid to prevent
oxidation. On analysis the following results were obtained : —

0.2015 gram of the substance gave on combustion 0.5558 gram of
carbonic dioxide and 0.0862 gram of water,

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 449

Calculated for

C6(00,Il5),(OH)2.

Found.

75.32

75.21

4.60

4.75

Carbon
Hydrogen

Properties of the Tetraphenoxyhydroquinone. — It crystallizes from
alcohol in white well developed rather thick rhombic plates, with a
very acute angle, which sometimes show sharp notches in the two
ends. When seen on the edge the plates seem to be monoclinic, and
are often twinned on the basal plane. Larger crystals are apt to
have the form of sharp spear-heads. At 210°, it shows signs of
decomposition by beginning to turn red. This change of color
increases as the temperature rises, until finally it melts at 2 19° -220°
giving a light red liquid, which on cooling solidifies to a red body,
probably the quinone. It is readily soluble in acetone ; somewhat
more sparingly soluble in ethyl alcohol, methyl alcohol, or chloroform ;
sparingly soluble in cold glacial acetic acid, more readily in hot ;
very sparingly soluble in benzol or ether. It is insoluble in water,
carbonic disulphide, or ligroine. Alcohol is the best solvent for it.

Diethoxydiphenoxyquinone, Cg (OCgH.) 2( O CgH.) 2O2.

This substance was obtained in some of our earlier attempts to
make tetraphenoxyquinone by treating dichlordiphenoxyquinone with
sodic phenylate dissolved in absolute alcohol, 10 grams of dichlordi-
phenoxyquinone were mixed with two equivalents of sodic phenylate
made by treating 1.6 grams of sodium with about 20 c.c. of abso-
lute alcohol and then adding 8 grams of phenol. On the addition of
the sodic phenylate the dichlordiphenoxyquinone became dark-colored,
and a very black tarry solution was obtained, which after standing for
two hours was separated by filtration from the sodic chloride formed ;
water was then added to the filtrate, which precipitated an oily black
liquid. In order to purify this liquid it was repeatedly washed with
water by decantation, and then dissolved in alcohol, from which
beautiful silky orange-yellow needles were obtained, and these were
recrystallized from alcohol until they showed the constant melting
point 128°, when after drying in a desiccator they gave the following
results on analysis : —

0.2104 gram of the substance gave on combustion 0.5324 gram of

carbonic dioxide and 0.1004 gram of water.

Calculated for

C6(0C„H,),(0CeH5)202.

Carbon

69.47

Hydrogen

5.26

VOL.

XXX. (n. S. XXII.;

) 29

Found.

69.01
5.30

450 PROCEEDINGS OF THE AMERICAN ACADEMY.

The yield is small. The diethoxydiphenoxyquinone crystallizes
in long silky orange-yellow slender needles arranged in radiating
groups. It melts at 128°, and is readily soluble in alcohol or chloro-
form ; soluble in carbonic disulphide or benzol ; sparingly soluble in
ether or glacial acetic acid ; insoluble in ligroine or water. The
best solvent for it is alcohol.

Action of Sodic Methylate on Tetraphenoxyquinone. {Dimethoxy-
diphenoxyquiaone, C^^{OCH^.^{OC^^2^2')

When 5 grams of tetraphenoxyquinone were treated with a solution
of six equivalents of sodic methylate in methyl alcohol, it dissolved to
a colorless liquid, which on standing deposited a quantity of nearly
white needles. These were filtered off, and after washing with a little
methyl alcohol treated with water rendered alkaline by sodic hydrate,
when a portion of the substance was dissolved, and a yellow crystal-
line body was left as an insoluble residue. This latter substance was
purified by crystallization from a mixture of benzol and alcohol until
it showed the constant melting point 171°, when it was dried at 100°,
and analyzed with the following result : —

0.2043 gram of the substance gave on combustion 0.5068 gram of
carbonic dioxide and 0.08 G2 gram of water.

Calculated for

C6(0CH3),(0C„H5)20j.

Found

Carbon

68.19

67.66

Hydrogen

4.55

4. 69

The substance is therefore dimethoxydiphenoxyquiuoiie formed by
the replacement of two of the phenjl by methyl radicals.

Properties of Dimethoxydiphenoxyqulnone. — It crystallizes from a
mixture of alcohol and benzol in beautiful long golden-yellow needles,
which under the microscope are seen to be slender prisms arranged in
radiating groups. The terminations of these prisms consist of one
principal plane, sometimes at a right angle, sometimes at an oblique
angle to the sides ; in this latter case, when the crystals are large
enough, small modifying planes are also seen. It melts at 171°, and
is readily soluble in chloroform ; soluble in ethyl or methyl alcohol,
benzol, or glacial acetic acid ; sparingly soluble in ether or carbonic
disulphide ; insoluble in ligroine or water. It is reduced by zinc and
glacial acetic acid to a colorless hydroquinone.

It dissolves apparently with decomposition in a dilute solution of
sodic hydrate, and from this solution dilute sulphuric acid precipitates

JACKSON AND GRINDLEY. — ACETALS PROM QUINONES. 451

a non-crystalliue body insoluble in water, but soluble in sodic hydrate
with a fine purple color. We have not had time as yet to study this
substance more carefully.

When the yellow dimethoxydiphenoxyquinone was mixed with a
solution of sodic methylate in methyl alcohol, and the mixture stirred
vigorously, the yellow solid disappeared, and a white crystalline
sodium salt was precipitated. This precipitate dissolved in water
without residue, and from the solution the addition of a dilute acid
threw down a white amorphous solid, which decomposed almost
immediately into a yellow substance probably dimethoxydiphenoxy-
quinone. These observations show that in this case a hemiacetal was
formed, but a much less stable one than that obtained from the
quinones containing chlorine. It seems, therefore, that the stability
of the hemiacetals depends on the number and strength of the negative
radicals attached to the quinone ring.

Action of Sodic Phenylate on Bromanil.

In order to study this action 2 grams of bromanil, prepared accord-
inor to Stenhouse,* were treated with an alcoholic solutionf of sodic
phenylate made by acting on 0.3 gram of sodium with absolute alcohol
and then adding 3 grams of phenol. The bromanil began to turn
red as soon as the phenylate was added, but it was necessary to warm
the mixture in order to make the reaction complete. After this the
solution was filtered, and the solid remaining on the filter, after
thorough washing with water and alcohol, was purified by crystalliza-
tion from benzol until it showed the constant melting point 2G6°-
267°, when it was dried at 100° and analyzed with the following
result : —

0.1677 gram of the substance gave, according to the method of
Carius, 0.1393 gram of argentic bromide.

Calculated for
C6B^2(0CgHg^202 Found.

Bromine 35.56 35.36

The substance is, therefore, dibromdiphenoxyquinone, and it is to
be observed that bromanil behaves differently from chloranil with this

* Ann. Chem., Suppl. VIII. 13.

t This experiment was tried early in our work, before we had found that an
aqueous solution of the sodic phenylate acted better on chloranil than the
same reagent dissolved in alcohol. If we were to repeat this preparation,
therefore, we should use a solution in water instead of in alcohol.

452 PROCEEDINGS OF THE AMERICAN ACADEMY.

alcoholic solution of sodic phenylate, for the latter lost all four of its
atoms of chlorine, two being replaced by pheuoxy and two by ethoxy
groups. The bromanil, on the other hand, behaves with the alcoholic
solution of sodic phenylate as chloranil does with an aqueous solution
of this reagent, the action consisting in the replacement of two atoms
of halogen by two phenoxy groups.

Properties of Dibromdiphenoxyquinone. — It crystallizes from ben-
zol in rather short orange-red needles with blunt points, melting at
266°-2G7°. It is very slightly soluble in alcohol even when hot;
insoluble in ether or ligroine, or in water whether cold or hot;
sparingly soluble in carbonic disulphide or boiling benzol, and only
very slightly soluble in cold benzol ; more soluble in chloroform ;
freely soluble in hot glacial acetic acid, slightly in cold. The three
strong acids have no visible effect upon it. By the action of glacial
acetic acid and zinc dust it is reduced to a colorless hydroquinone. It
reacts easily with sodic methylate, ethylate, or phenylate, and also with
sodium malonic ester, or aniline, but we have studied only its action
with sodic methylate.

Dihromdimethoxyquinone Dimethylhemiacetal,
CoBr2(OCH3)2(OH)2(OCH3)2.

This body was formed by treating 1.4 grams of dibromdiphenoxy-
quinone with a solution of rather less than four equivalents of sodic
methylate in methyl alcohol, which was made by the action of a little
methyl alcohol on 0.3 gram of metallic sodium. When the sodic
methylate was first added, there was no apparent action, but after
warming on the steam-bath for a few minutes a white crystalline
sodium salt separated. The salt was filtered out, washed with a little
methyl alcohol, dissolved in water, filtered again, and then dilute
sulphuric acid added in excess, which gave a bulky white precipitate.
This was filtered off, washed with water, alcohol, and ether, and then
dried for a short time over sulphuric acid and paraffine. The product
was analyzed with the following results : —

0.2047 gram of the substance gave by the method of Carius 0.1966
gram of argentic bromide.

Calculated for
C6Br2(0CH,,)2(0H)2(0CH3)2. Found.

Bromine 41.03 40.88

The dihromdimethoxyquinone dimethylhemiacetal is a white amor-
phous solid insoluble in all the common solvents. It melts at 178"-

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 453

188°, at the same time changing to a red substance, probably dibrom-
dimethoxyquinone. This change can also be produced by treatment
with dilute sulphuric acid, or dilute hydrochloric acid. From this
description of the preparation and properties of this hemiacetal it is
evident that the action of sodic methylate on dibromdiphenoxyquinone
is similar in every respect to the action of this reagent on the corre-
sponding compound containing chlorine.

Action of Potassic Phenylctte on Trichlorqidnone.

By treating 5 grams of trichlorquinone suspended in water with
two equivalents of potassic phenylate, made from 2.7 grams of potassic
hydrate and 8 grams of phenol, a red serai-liquid substance was
formed. After the mixture had been heated on the steam bath for
twenty minutes in order to complete the reaction, the supernatant
liquid was poured off, and the pasty residue washed with water by
decantation, and then warmed with alcohol, which converted it into
a crystalline solid. These crystals were then separated by filtration,
washed thoroughly with cold alcohol, and recrystallized from alcohol
containing a small amount of benzol until they showed the constant
melting point 169° -170°, when they were dried at 100°, and analyzed
with the following results : — •

I. 0.1888 gram of the substance gave by the method of Carius 0.0818

gram of argentic chloride.
II. 0.1913 gram gave 0.0832 gram of argentic chloride.

Calculated for Found.

C6HC1(0C6H3)203. I n.

Chlorine 10.87 10.71 10.75

Properties of Monochlordiphenoxyqidnone. — It crystallizes from
alcohol in long, slender, pointed oval blades arranged in irregular
groups, — a very charactei'istic habit of crystallization. It has an
orange color, with a slight brownish tinge, and melts at 169°-170°.
It is easily soluble in benzol or chloroform ; difficultly soluble in alco-
hol ; slightly soluble in carbonic disulphide ; insoluble in water, ether,
or ligroine. It is easily reduced to a colorless hydroquinone by glacial
acetic acid and zinc dust.

To see whether it would form a hemiacetal 0.5 gram of the mono-
chlordiphenoxyquinone was treated with the sodic methylate made
by acting on 0.3 gram of metallic sodium with a few cubic centimeters
of methyl alcohol. The quinone dissolved in the cold, but, even when
allowed to stand for some time and stirred vigorously, no precipitate

454 PROCEEDINGS OP THE AMERICAN ACADEMY,

of a sodium salt was formed. When, however, it was warmed for a
few minutes, a heavy white precipitate was deposited, which, after
beiug watched with a little methyl alcohol, dissolved completely in
water, giving a clear solution. The addition of an acid to this solu-
tion produced a turbidity, which soon developed into a white precipi-
tate, undoubtedly the hemiacetal, but this passes so easily into a red
quinone derivative that we have not attempted to analyze it, especially
as its properties leave no doubt as to its nature. It follows from these
observations that the stability of the hemiacetals is increased by the
number of negative radicals, such as chlorine atoms, present.

Action of Sodic Ethylate on Quinone.

Although the results described in the last section made it probable
that the hemiacetal derived from quinone itself would be very unstable,
we have tried some experiments on the action of sodic ethylate on
quinone (0611402), and think it best to give a preliminary account of
them here, in spite of the fact that they have not led as yet to any
definite result. They have, however, proved that sodic ethylate acts
on quinone, but have by no means convinced us that the product is a
hemiacetal. On treating quinone dissolved in ether with an alcoholic
solution of sodic ethylate, a heavy flocculent dark green precipitate is
formed, which is insoluble in ether, but dissolves in alcohol or water
with decomposition. This precipitate does not seem to be homo-
geneous, as by fractional precipitation products were obtained unlike
in color, and also in their composition, as shown by analysis ; more-
over its study is rendered difficult by the fact that it takes fire spon-
taneously when dried at ordinary temperatures in the air ; if, however,
it is dried in an atmosphere of hydrogen, it can be exposed to the air
without taking fire at ordinary temperatures, but, if warmed to 40°,
it begins to glow, and burns like tinder. Before studying this rather
unmanageable substance further, we tried to get some idea of the way
in which the reaction ran by a quantitative study of it, based upon the
fact that all the quinone can be removed from its ethereal solution by
the sodic ethylate.

In the first trial, it was found that one gram of quinone required
0.2352 gram of sodium for complete precipitation.

In the second trial, one gram of quinone required 0.2460 gram of
sodium.

In the third trial, 3 grams of quinone required 0.6 gram of sodium.

These results indicate that each molecule of quinone acts with only
one molecule of sodic ethylate, as the amount of sodium needed in this

JACKSON AND GRINDLEY. — ACETALS FROM QUIN0NE8. 455

case for one gram of quinone is 0.213 gram, and the observed results
come as near to this number as could be expected, when the roughness
of the method is considered. This conclusion is confirmed by ilie
yield of the salt obtained from 3 grams of quinone, which vva.> 4.7
grams, whereas, if only one molecule of sodic ethylate had been ;ui<ied
to each molecule of the quinone, the yield should have been 4.9 grams.
The study of other parts of this research has occupied our tiim- so
completely that we have been unable to do more on this division of
the subject, but we hope that this work can be taken up again in tliis
Laboratory at an early date.

Experiments on Phenoquinone.

It has been suggested in the introduction that phenoquinone and
quinhydrone may be hemiacetals similar to those studied in this paper.
In that case phenoquinone should contain two hydroxyl groups, and
form salts. Accordingly, we have tried to obtain a salt of it, although
the chances of success were not great as Wichelhaus * has stated that
phenoquinone forms no salts, but is decomposed by alkalies. Still we
thought that possibly by using sodic ethylate in insufficient quantity
we might succeed, as the replacement of the hydrojjen by the metal
might take place in preference to the decomposition of the pheno-
quinone, especially as Wichelhaus also states that it gives a blue color
with alkalies. "We proceeded as follows. One gram of phenoqui-
none t was dissolved in ether, and treated with an alcoholic solution
of the sodic ethylate made from 0.1 gram of sodium; as 0.1 o4 ofram
of sodium would be required for two atoms of sodium to each mole-
cule of phenoquinone, there was a considerable excess of this latter
substance. As soon as the sodic ethylate was added, a heavy fioccu-
lent dark green precipitate was formed, which was filtered out, washed
thoroughly with ether, and dried over sulphuric acid and paraffiiip. We
hoped at first that this was the salt of phenoquinone, and three sodium
determinations seemed to confirm this idea, as they gave 13.14, 13,41,
and 14.31 per cent of sodium, which is not far from the > iimlier
calculated for a sodium salt of phenoquinone, since that is 13.52 per

* Ber. d. ch. G., V. 248.

t The phenoquinone was made by adding one equivalent of quinone dissolved
in hot ligroine to two equivalents of phenol dissolved in a small quantity of the
same solvent. The mixed solutions were wanned for a few minutes, and then
on cooling beautiful red crystals separated, which were purified by recrystalli-
zation from alcohol.

456 PROCEEDINGS OF THE AMERICAN ACADEMY.

cent of sodium ; but the study of the ethereal filtrate from the salt
threw a great deal of doubt on this conclusion, since it contained a
large amount of phenol. We think it more probable, therefore, that
the sodic ethylate decomj^osed the phenoquiuone into quinone and
phenol, and that the green salt was then formed by the action of the
sodic ethylate upon the quinone, the action being the same as that
described in the last section. This inference is strengthened by the
marked resemblance in appearance between the salts obtained in these
two cases, and also by the study of the proi^erties of the salt made
from the phenoquinone, since it dissolved completely in water, forming
a dirty green solution, and undoubtedly suffering partial decomposi-
tion, as ether extracted from this solution colorless crystals of hydro-
quiuone recognized by their melting point of 169°. The addition of
an acid to this solution gave no precipitate, and upon shaking out the
acidified liquid with ether, nothing was extracted but hydroquinone.
If the substance had been the desired salt of phenoquinone, phenol
should have been obtained from this filtrate. Although these experi-
ments tell against the formation of salts of phenoquinone, we do not
consider them absolutely final, but the study of the action of alkalies
on phenoquiuone under other conditions will be continued in this
Laboratory during the coming college year.

As we had not succeeded in making a salt of phenoquiuone we next
turned our attention to the action of sodic phenylate on quinone, as,
if the phenoquinone is a hemiacetal, this should act as well as free
phenol, whereas according to the other theories of the constitution of
phenoquinone, it is hard to see how there should be any action in this
case. Sodic phenylate was made by warming the proper amount of
metallic sodium with a solution of phenol in benzol until the sodium
had entirely disappeared. As the benzol cooled, the white crystalline
sodic phenylate separated abundantly, and, after filtering, any free
phenol was removed by washing with cold benzol. Upon adding the
solid sodic phenylate to a solution of quinone in absolute ether a dark
red crystalline substance looking like phenoquinone was formed.
After evaporating off the ether slowly, the residue dissolved easily in
water with a slight green color, and acids precipitated from this
aqueous solution a small amount of a dark reddish solid. The ethereal
solution showed a tendency to turn green round the edges during the
evaporation which may perhaps have been due to the action of the
moisture in the air. If benzol was used to dissolve the quinone in-
stead of ether, a pink substance was foimed, which changes to a dark
green body when warmed. With ligroine as the solvent, a dark green

JACKSON AND GRINDLEY. — ACETALS FROM QUINONES. 457

precipitate was obtained at first. Uufortuuately, this work was under-
taken at the very end of the term, so that a more careful study of
these products must be postponed until next year, but these prelim-
inary experiments show that sodic phenylate does combine with
quinone, and therefore lend a certain amount of countenance to our
suggestion that phenoquinone is a hemiacetal.

458 PROCEEDINGS OP THE AMERICAN ACADEMY.

XIX.

CONTRIBUTIONS FROM THE CHEMICAL LABORATORY OF

HARVARD COLLEGE.

ON THE CUPRIAMMONIUM DOUBLE SALTS.

SECOND PAPER.

By Theodore William Richards and Andrew Henderson

Whitridge.

Presented May 9, 1894:.

The continuation of the study of the cupriammonium double salts,
begun in 1891,* has led to the preparation of the following new
compounds : —

(1.) Cu(NH3)2CICH02.

(2.) Cu(NH3)3BrC.,H30o . HjO.

(3.) Cu(NH3)2BrC3H50.,.

(4.) Cu(NH3)2BrC3H503.

(5.) Cu(NH3)2ClC3H503.

(1.) Cupriammonium Formiochloride, Cu(NH3)2ClCH02.

The bromide corresponding to this chloride has been described
already by Richards and Shaw. The chloride itself was obtained at
the same time by these experimenters, but only in an impure state,
and the present problem was to determine the conditions necessary
for the preparation of the substance in a state of purity.

If any considerable amount of water is present in the materials,
basic salts of copper are certain to be precipitated, and to contaminate
the preparation. On the other hand, the slight solubility of cupric
formiate and cupriammonium chloride in alcohol makes it difficult to
avoid the admixture of these substances with the desired compound,
if alcohol is used in the anhydrous condition.

* Theo. W. Richards, Berichte d. d. ch. Gesell., XXV. 1492; T. W. Richards
and H. G. Shaw, These rroceedinp.s XXVIII. 247.

RICHARDS AND WHITRIDGE. — CUPRIAMMONIUM SALTS. 459

The following procedure was found to be the most successful, but
great care was needed to carry it out. Three grams of crystallized
cupric formiate were dissolved in just enough warm alcohol to effect
solution, and two grams of animonic chloride were added to the mix-
ture. The whole was then heated to boiling, and dry ammonia was
passed in until a very slight excess was present. Upon cooling and
evaporation in the air, fine blue prismatic crystals separated, which
were fairly pure, as the analyses show. The salt resembles in its
properties the formiobromide, being permanent in dry air, but at once
decomposed by water. In color it is a purer blue than the formi-
bromide, having much less of the greenish tinge.

In the analysis of the compound the copper was determined electro-
lytically after the substance had been evaporated with sulphuric and
nitric acids. The chlorine from a new portion was weighed as argen-
tic chloride, and the ammonia was distilled after the addition of pot-
ash. The formic acid was determined by combustion.

Analyses of Cu(NH3)2ClCH02.

I. 0.0862 gram of the substance gave on electrolysis 0.0305 gram

of copper.
II. 0.0997 gram of the substance gave on electrolysis 0.0356 gram

of copper.
III. 0.1258 gram of the substance yielded 0.0994 gram of argentic

chloride.
IV. 0.1285 gram of the substance yielded 0.1008 gram of argentic

chloride.
V. 0.1060 gram of the substance distilled with caustic potash re-
quired 11.75 cubic centimeters of a decinormal solution for

neutralization.
VI. 0.0984 gram of the substance yielded on combustion 0.0241 gram

of carbon dioxide.

Analyses III. and IV. were made from different samples; hence
they prove the definiteness of the compound.

460

PROCEEDINGS OF THE AMERICAN ACADEMY.

Copper.

Ammonia.

Chlorine.

Formic Acid.

I. . .

35.38

II. . .

35.71

III. . .

—

—

19.54

IV. . .

—

—

19.40

V. . .

—

18.91

VI. . .

—

—

—

25.05

Averages

35.54

18.91

19.47

25.05

Copper

Calculated for
0u(NH3)2ClCH03.

35.69

Found

35.54

Ammonia

19.15

18.91

Chlorine

19.90

19.47

Formic Acid

(CHO2)

25.26

25.05

100.00

98.97

(2.) Ammon-Cdpriammonium Acetobromide,
Cu(NH3)3BrC2H302 . HA

This compound is formed readily when cupric bromide is dissolved
in a mixture of alcohol and glacial acetic acid, and an excess of dry
ammonia gas is passed into the solution. It is essential to have the
solutions concentrated. For example, 2.5 grams of cupric bromide
were shaken with 13 cubic centimeters of glacial acetic acid and 25
cubic centimeters of alcohol. Upon cooling after the addition of the
ammonia, which raised the temperature of the solution, the desired
substance separated out. If when passing in the gas a black precipi-
tate (Cu3Br(;(NH3)io) falls after the solution has become dark purple,*
the supernatant liquid should be decanted before it is allowed to crys-
tallize. The precipitate shows the presence of an excess of cupric
bromide in proportion to the acetic acid.

Ammon-cupriammonium acetobromide had already been made by
Richards and Shaw ; but the analyses of the compound were so un-
satisfactory that no account of the substance was given in their paper.
This unsatisfactoriness was due, not to any difficulty in preparing the

* Richards and Sliaw, he. cit.

RICHARDS AND WHITRIDGE. — CUPRIAMMONIUM SALTS. 461

substance in a state of purity, as iu the previous instance, but rather
to the great difficulty of drying the substance enough without drying
it too much. The extra molecule of ammonia and the molecule of
water are held very loosely, mere exposure to the air allowing thera
to escape. Especially is this the case when the substance is placed
over sulphuric acid. 0.1242 gram of material, which had been ex-
posed thus until constant iu weight, yielded 0.0331 gram, or 26.65 per
cent, of copper upon electrolysis. This showed that the substance had
lost practically all of its extra ammonia and water, for the theoretical
per cent of copjDer in Cu(NH3)2BrC2H302 is 26.87. The new salt
consists of pearly flakes of a brilliant light blue color, somewhat less
intense than that of the normal cupriammonium acetobromide. It is
only very slightly soluble in alcohol, and is at once decomposed by
water, a little of the copper going into solution. In properties and
general appearance it resembles the ammon-cupriammonium aceto-
chloride prepared by Richards and Shaw, except that it is much less
stable.

The acetic acid was determined by distillation with phosphoric acid,
according to the well known method of Fresenius. Ilydrobromic and
a trace of phosphoric acid which come over in the distillate were pre-
cipitated with argentic nitrate from the neutralized solution, the result
being calculated as argentic bromide, since this is the greater part of
the precipitate.

Analyses of Cu (NH3) jBrC JI3O2 . H2O.

I. 0.3276 gram of the substance yielded 0.0774 gram of copper
upon electrolysis.
II. 0.3902 gram of the substance yielded 0.0896 gram of copper
upon electrolysis.

III. 0.3376 gram of the substance yielded 0.2365 gram of argentic

bromide.

IV, 0.2453 gram of the substance yielded 0.1732 gram of argentic

bromide.
V. 0.4214 gram of the substance yielded 0.2940 gram of argentic
bromide.
VI. 0.2600 gram of the substance distilled with caustic potash re-
quired 13.28 cubic centimeters of a decinormal acid solution
for neutralization.
VII. 0.1528 gram of the substance distilled with caustic potash re-
quired 16.29 cubic centimeters of a decinormal solution for
neutralization.

462

PROCEEDINGS OP THE AMERICAN ACADEMY.

VIII. The distillate from a mixture of 0.1469 gram of the substance
with phosphoric acid required 5.67 cubic centimeters of a
decinormal alkali for neutralization. Approximately cor-
rected for the alkalimetric equivalent of the argentic phos-
phate and bromide obtained from the distillate, this amount
becomes 5.47 c.c.

Copper

Ammonia.

Bromine.

C.HjO,.

I.

II.

III.

IV.

V.

VI.

VII.

VIII.

23.63
22.97

18.20
18.19

29.81
30.04
29.68

22.35

Averages .

23.30

18.20

29.84

22.35

Calculated for

above Formula.

Found.

Copper

23.40

23.30

Ammonia

18.84

18.19

Bromine

29.42

29.84

Acetic Acid

21.72

22.35

Water (by difference)

6.62

6.32

100.00

100.00

It is evident that most of the substance analyzed had lost some of
its ammonia and water. A few other determinations were made of
substance just prepared and not dried at all, in order to be sure that
the atomic ratio of the ammonia to the copper was not greater than
3:1. This point was proved beyond a doubt.

(3.) CuPRiAMMONiuM Propionobromide, Cu(NH3)oBrC3H50.2.

Ten grams of ammonic propionate, made by neutralizing propionic
acid with ammonia gas and allowing the solution to evaporate over
caustic potash, were mixed with two grams of cupric bromide, and

RICHARDS AND WHITRIDGE. — CUPRIAMMONIUM SALTS. 463

dissolved iu about fifty cubic centimeters of absolute alcohol. Dry
ammouia gas was passed into the solution, and on standing a precipi-
tate of cupriammonium bromide (Cu(NH3)2Br2) came down. Four
and a half cubic centimeters of strong propionic acid were added to
dissolve the precipitate, and more ammonia gas was added. Again
the same crystals appeared, showing that the tendency to form this
substance was much more decided than the tendency to form the sub-
stance desired. Since the addition of more propionic acid did not help
the matter, one and a half grams of precipitated cupric oxide were
added, and the whole was warmed until most of the powder had dis-
solved. After filtration and evaporation in the air, prismatic crystals
of a very strong blue color were deposited, proving to be the substance
sought. The crystals were washed with alcohol, and dried in the air,
iu which they are permanent. 0.5750 gram of the substance was
found to displace 0.2197 gram of toluol having a specific gravity of
0.8619 ; hence the specific gravity of cupriammonium propionobromide
is 2.255. The other properties resemble so closely those of the acetic
compound that it is not worth while to detail them.

Analyses o/ Cu(NH3)2BrC3H502.
I. 0.1017 gram of the substance gave on electrolysis 0.0262 gram

of copper.
II. 0.1061 gram of the substance gave on electrolysis 0.0270 gram
of copper.
III. 0.0825 gram of the substance yielded 0.0624 gram of argentic

bromide.
IV. 0.0788 gram of the substance distilled with caustic potash required
6.19 cubic centimeters of a decinormal acid for neutralization.
V. 0.1109 gram of the substance yielded 0.0588 gram of carbon
dioxide upon combustion.

Copper.

Ammonia.

Bromine.

Propionic Acid.

I. . . .
11. . . .

IIL . . .

IV. . . .
V. . . .

25.76
25.45

13.40

32.18

29.31

Averages .

25.60

13.40

32.18

29.31

464 PROCEEDINGS OP THE AMERICAN ACADEMY.

Calculated for
above Formula.

Found.

Copper

25.37

25.60

Ammonia

13.61

13.40

Bromine

31.90

32.18

Propionic

acid

29.12

29.31

100.00 100.49

(4.) CUPRIAMMONIUM Lactobromide, Cu(NH3)2BrC3H503.

This compound is easily obtained by dissolving syrujiy lactic acid
and about a third of its weight of cupric bromide in alcoiiol, and then
passing dry ammonia gas into the solution. Basic salts of copper do
not form readily here, but if an insufficiency of lactic acid is added,
Cu(NH3)9Br2 will crystallize out. The crystals are of a strong light
blue color, with a faint tinge of purple ; they may be obtained of great
size. They are permanent in the air, and at once decomposed by
water. 2.6377 grams of the substance were found to di.splace 1.0334
grams of toluol, indicating a specific gravity of 2.20.

For analysis the salt was washed twice with alcohol, and pressed
bet"veen filter paper.

Analyses of Cu(NH3)2BrC3Ho03.

I. 0.1742 gram of the substance gave on electrolysis 0.0418 gram

of copper.
II. 0.1108 gram of the substance yielded 0.0786 gram of argentic
bromide.

III. 0.1916 gram of the substance yielded 0.1360 gram of argentic

bromide.

IV. 0.0850 gram of the substance required on distillation G.25 cubic

centimeters of decinormal acid solution for neutralization.
V. 0.0987 gram of the substance required 7.38 cubic centimeters of

decinormal acid.
VI. 0.1634 gram of the substance yielded on combustion 0,0819
gram of carbon dioxide.

Analyses II. and III. were made from different samples of the
substance.

RICHARDS AND WHITRIDGE. — CUPRIAMMONIUM SALTS. 465

Copper.

Ammonia.

Bromine.

Lactic Acid.

I. . . .

II. . . .
III. . . .

IV. . . .

V. . . .

VI. . . .

23.99

12.56
12.84

30.19
30.20

33.79

Averages ,

23:99

12.70

30.19

33.79

Copper
Ammonia
Bromine
Lactic Acid

Calculated for
above Formula.

23.85
12.79

29.99
33.37

100.00

Found.

23.99
12.70
30.19
33.79

100.67

(5.) CupRiAMMONiDM Lactochloride, Cu(NH3)2C1C3H503.

Four grams of cupric lactate were dissolved in strong alcohol, and
when the solution was boiling, two grams of ammonic chloride were
added. Through this solution perfectly dry ammonia gas was passed
until slightly in excess. Upon filtering and evaporating the solution
fine crystals of cupriammonium lactochloride were deposited. A sim-
ilar method would have answered in the case of the bromine. These
crystals are of a somewhat lighter blue color than the lactobromide,
but otherwise their properties are similar. Because of this similarity,
determinations of the chlorine and copper were considered enough to
identify the compound.

Analyses o/Cu(NH3)oClC3H503.

I. 0.1751 gram of the substance gave on electrolysis 0.0496 gram

of copper.
11. 0.1341 gram of the substance gave on electrolysis 0.0382 gram

of copper.
III. 0.1314 gram of the substance gave on electrolysis 0.0378 gram
of copper.

VOL. XXX. (n. S. XXII.) 30

466

PROCEEDINGS OF THE AMERICAN ACADEMY.

IV. 0.1025 gram of the substance yielded 0.0659 gram of argentic

chloride.
V. 0.1015 gram of the substance yielded 0.0656 gram of argentic

chloride.

I.

II.

III.

IV.

V.

Copper

Chlorine

28.33

28.49

28.76

15.93

15.98

Average

28.52

15.95

Calculated for above formula

28.64

15.96

Attempts were made to make similar compounds of butyric acid
without success. Various different proportions, suggested by those
required ia the previous preparations, were tried with equal failure,
and the attempts were finally discontinued.

It was also hoped that such compounds as Cu(NH3)2ClN03 and
Cu(NH8)2N03 . C2H3O2 might be found. The results of a great
many experiments showed that under ordinary conditions nothing
but Cu(NHg)2Cl2, or Cu(NH8)4(N03)2, can be obtained. Further
attempts to combine cupriammonium sulphate with cupriammonium
acetate were also unsuccessful ; so that in these directions the field
seems to be limited. All of these facts, as well as the relative proper-
ties of those compounds which have been prej^ared, may be of some
use in the future when the structure of the cupriammonium com-
pounds comes under consideration. "Work upon the subject, as well
as upon similar investigation of products containing amines instead of
ammonia, is being continued here.

Cambridge, Mass., September 20, 1894.

THAXTER. — LABOULBENIACE^. 467

XX.

CONTRIBUTIONS FROM THE CRYPTOGAMIC LABORATORY OF

HARVARD UNIVERSITY.

XXVL — NOTES ON LABOULBENIACE^, WITH
DESCRIPTIONS OF NEW SPECIES.

By Roland Thaxter.

Presented November 23, 1894.

Laboulbenia pilosella Robin.

{Traitedu Miavscope, p. 912, Fig. 285.)

Through the kindness of Professor Giard the existence of a species
bearing this name has been brought to the writer's attention, and an
examination of the figure which accompanies its description leaves
little doubt of its identity with the form described by the writer on
European specimens of the genus Lathrobium under the name Acan-
ihomyces brevipes. The plant figured by Robin is said by him to occur
on a member of the same genus, and his drawing, though coarse, cor-
responds so closely in essentials that the two may be considered
synonymous. In selecting the name Acanthomyces, however, the
writer was not aware of its previous use by Lebert in a zoological
publication, the Acanthomyces aculeata * of this writer having escaped
the notice of compilers in recent years. In view of this fact a new
designation for the genus of Laboulbeniacete becomes necessary, and
the writer would suggest for this purpose the name Rhachomyces,
from the resemblance which the main axis of these plants beai's to a
vertebral column. The new name will therefore include the six de-
scribed species, Rhachomyces longissimus, R, lasiophorus, R. hypogczus,
R. Lathrobu, R. furcatus, and R. piloseUus (Robin), to which may be
added a seventh form, parasitic, like R. hypogceus, on a blind cave
beetle.

* Zeitschr. f. wissensch. Zoologie, 1858, Vol. IX. p. 447.

468 PROCEEDINGS OP THE AMERICAN ACADEMY.

RHACHOMYCES nov. nom. = ACANTHOMYCES Thaxter.

Rhacuomyces speluncalis, nov. sp. •

Perithecium more or less deeply suffused with brown ; short and
stout, with a broad bluntly rounded apex. Receptacle slender, the
main axis constricted strongly at the septa, its cells rather small, the
basal slender and cylindrical ; the remainder, about nine in number,
all evenly and rather deeply suffused with brown, and more or less
uniform in size. Appendages mostly opaque, more or less rigid,
hyaline-tipped, those surrounding the base of the perithecium hardly
equalling it in length, a few lower on the receptacle exceeding its
apex by the whole length of the plant : of the shorter median appen-
dages some are terminated by a peculiarly modified partly hyaline
(antheridial ?) cell, the neck-like tip of which curves strongly out-
wards, terminating bluntly. Perithecia 90 X 37 fx. Receptacle about
110 /A (when not proliferous). Longest appendages 300 /a. Total
length to tip of perithecium 185 fx to 260 /x (in proliferous forms).

On Anophthalmus jnisio Horn. West Virginia.

The smallest species of the genus, more nearly allied to R. lasio-
phorus in the form of its perithecium and the disposition of its appen-
dages around the base of the latter. It is quite distinct, however,
from any of the described species.

DIPLOMYCES, nov. gen.

Flattened antero-posteriorly, sub-triangular, bilaterally symmetrical,
furcate through the presence of a pair of prominent posterior projec-
tions. The receptacle consisting of two superposed cells, followed by
four cells placed antero-posteriorly in pairs, of which the posterior
produce the characteristic prominences ; the anterior a pair of short
stalked perithecia, near the base of which, within and above, arise two
or more pairs of appendages, and eventually a second pair of peri-
thecia. Appendages copiously branched, many of the branchlets ter-
minated by beak-like cells. Spores once-septate.

A singular genus, recalling Teratomyces, to which it seems most'
nearly allied through the presence of the characteristic terminal beak-
like cells of its appendages. The branching of the latter is not, how-
ever, sympodial in a single plane, as is the case in Teratomyces, and
the general structure of the receptacle is difficult to homologize with
that of any other genus. The second pair of perithecia arise in all
probability from secondary divisions of the pair of perithecia-bearing

THAXTER. — LABOULBENIACE^E. 469

cells above described ; but the exact structure in this region, behind
the stalk cells of the perithecia, has not been made out satisfactorily.
An obliquity in the septum which separates the basal and sub-basal
cells sometimes results in the apparent absence of any sub-basal cell.

DiPLOMYCES ACTOBIANUS, nov. Sp.

More or less faintly tinged with brownish. Basal cell of receptacle
triangular, sub-basal cell flattened or wedge-shaped ; the posterior
prominences peculiar to the genus nearly as long as the receptacle
itself, slightly divergent, two-celled, the terminal cell twice as long as^
the basal, tapering slightly towards its rounded extremity. On the
anterior side the two perithecigerous cells bear the first pair of peri-
thecia on short stalk-cells bent abruptly upwards, divergent, and suc-
ceeded by three small cells forming the base of the peritheciunu The
perithecia rather slender, curved towards the receptacle so that their
tips project beyond it, divergent, rather long and slender, tapering
slightly, the apex blunt with ill defined lips, the base of the old
trichogyne persisting conspicuously below the pore. Appendages
branching, arranged in pairs symmetrically like the perithecia ; a
smaller one arising just behind the stalk cell of the perithecium, a
much larger one above this followed by a few smaller ones less defi-
nitely arranged in the region whence a second pair of perithecia may
arise. All the appendages more or less copiously branched, the
branchlets terminating in many cases by the slender, curved and
sharply pointed cells characteristic of Teratomyces. Spores 32 X 2 /x.
Perithecia, including stalks, about 75 X 12 |x. Receptacle to tips of
prominences 75 /x. Total length to tip of perithecia 110 /x. Greatest
width 37 fx.

On Actobius nanus Horn. Massachusetts.

This species occurs rather rarely on the abdomen of a large brown
variety of Actobius nanus, but not as far as has been observed on the
normal form. A second form, perhaps distinct from the present, was
found on the abdomen of a small Philonthus, and is distinguished by
the presence of slender thread-like branches from the larger appen-
dages. Sufficient material of tbis form was not, however, obtained,
and it may prove to be nothing more than a variety of the one above
described.

Sphaleromyces occidentalis, nov, sp.

More or less evenly tinged with brownish. Perithecium large, sub-
fusiform, with faintly defined ridges at the divisions between- the wall

470 PROCEEDINGS OP THE AMERICAN ACADEMY.

cells, the apex made externally oblique through the outgrowth of oue
of the lip cells which forms a pointed projection beyond the pore ; the
stalk cell wholly free, tapering to a narrow base, and about as long as
the receptacle proper. Receptacle small, pointed below, its sub-basal
cell united throughout its length to the basal cell of the appendage, ita
basal and sub-basal cells separated by a horizontal septum. The ap-
pendage straight, rigid, tapering, composed of a series of usually four
superposed cells separated by oblique partitions, and bearing short
branches with flask-shaped antheridia from their upper inner angles.
Perithecia 200 X 45 /x. Length to tip of perithecia 350 fx. Length
to tip of appendage 200 /x. Length of receptacle 55 /a.

On Pinophilus densus Lee. Utah.

The occurrence of a second well marked species, abundantly dis-
tinct from the type, serves to settle any doubts which may have existed
concerning the validity of this genus. The present form was found
on the abdomen of its host, and is readily distinguished from S. La-
throhii by the peculiarly modified tip of its perithecium, as well as by
other important differences.

Laboulbenia Hageni, nov. sp.

More or less deeply tinged with brown. Perithecium slightly inflated,
tapering to the blunt outwardly oblique apex, which is blackened be-
low the hyaline lips. Appendages arising from an outer and an inner
basal cell, the outer of which is followed by a squarish cell of about
the same size, from the end of which project four rather short, rigid,
slightly divergent hyaline branches, which taper to blunt tips, and, as
a rule, hardly exceed the tip of the perithecium : the inner basal cell
gives rise to two squarish cells, one on either side, each of which
bears usually a pair of branches similar to those just described. Re-
ceptacle short and stout, normal in form, the lower portion of the basal
cell hyaline. Perithecia 55 x 18 /x. Appendages (longest) 65 fi.
Total length to tip of perithecium 100 jx.

On Termes helUcosus var. Mozamhica Hagen. Africa.

The occurrence of a most typical and decidedly insignificant looking
species of this genus on a larva of the worker of a species of white
ant is certainly quite unexpected in view of the wide difference which
exists between this Neuropterous host and the usual insects infested
by the genus. But for the four stiff branches arising from the sub-
basal cell of the outer appendage, and suggesting the roots of a molar
tooth, it would be difficult to specify its distinguishing characters.
The species is dedicated to the memory of the late Professor Hagen,

THAXTER. — LABOULBENIACE^. 471

by whom it was observed many years since on the same specimen ex-
amined by the writer, collected by Dr. Peters in Africa, from all parts
of which sufficiently abundant material was obtained.

Laboulbenia Kunkelii (Giard).

Thaxtena Kunkelii Giakd, Comptes Rendus Hebdomadaires des Seances de la
Socie'te de Biologie, Se'r. IX., Vol. IV. p. 156.

Through the kindness of Professor Giard, the writer Las had an
opportunity of examining specimens of this remarkable species, which
is by far the largest member of the family, measuring between three
and four millimeters from its base to the tip of the peritheciura. It
occurs with the succeeding species on the elytra and thorax of Mormo-
lyce phyllodes Hagenb., a carabid beetle, native in the East Indies.
The writer is unable to agree with Professor Giard in believing that
this form, however singular, should be separated generically from
Laboulbenia, to which it seems to correspond in every essential de-
tail. The type of cell arrangement, so characteristic in Laboulbenia,
is followed without deviation ; while the appendages also originate
in a manner much more typical than is found in very many species
of this genus. The elongation of the basal wall cells of the perithe-
cium to form a stalk-like base finds also an exact parallel in species
like L. Galeritce, L. longicoUis, L. melanotheca, and other forms, the
generic reference of which is not to be disputed.

Laboulbenia palmella, nov. sp.

Perithecium nearly straight, almost opaque, sometimes slightly in-
flated, its tip nearly symmetrical, truncate, its inner walls often having
a corrugated appearance, the four lower wall cells elongated and con-
tracted to form a short stalk below and about one third as long as the
ascigerous portion. Appendages arising from two small basal cells :
an outer which gives rise to a series of two or three opaque branches
placed antero-posteriorly, the inner of which alone reaches any con-
siderable size, branching sympodially in an antero-posterior plane, the
main axis opaque, successively inflated below the branchlets which
are usually about ten in number, opaque with hyaline tips: an inner
which gives rise to a single branch on either side consisting of a sub-
cylindrical basal cell, black below, nearly hyaline above and followed
by a series of sympodial branchlets like those of the outer appen-
dage. Receptacle short, tapering rapidly to the base, wholly black
and opaque with the exception of the whole or a portion of its basal

472 PROCEEDINGS OP THE AMERICAN ACADEMY.

cell which may be hyaline and is abruptly bent above the very large
hoof-like haustorium or blackened point of attachment. Spores 150 X
12 ya. Perithecium 580 X 75-100 /a, its neck 75-150 X 35-65 /x.
Receptacle 300-400 [x, its greatest width 75-100 jx. Appendages
(longest) 500 ^, the branchlets about 225-250 X 7-8 /x. Total length
to tip of perithecium, 1-1.1 mm.

On Mormolyce phyllodes Hagenb. Perak, Molucca, Java.

The writer is indebted to Professor Riley for abundant material of
this species found by Mr. Schwarz on a specimen of Mormolyce in the
National Museum labelled " Java," as well as to Mr. Beutenmueller
who has kindly sent material derived from a specimen in the Central
Park Museum labelled Molucca. Professor Giard has also most gen-
erously allowed him to examine the original specimen of Mormolyce
from Perak on which the types of L. Kunkelii were associated with
the present species. The two species are very closely allied, and
were found intermingled towards the base of the elytra, although the
smaller was much more abundant on the flattened margins where it
presents the appearance under a hand lens of a grove of little palm-
trees. The absence of any transitional forms between the two species
seems to render it unlikely that they should prove merely varieties of
a single form, while the much smaller size of L. palmella, its wholly
opaque and short receptacle, straight short-necked perithecium, large
hoof-like base, together with the absence of furcation in the main axis
of the two lateral branches of its inner appendage, afford constant and
sufficient specific differences. The antheridia appear to be repre-
sented by flask-shaped bodies borne on short hyaline branches near
the tips of the branchlets of the inner appendages. The trichogynes
are well developed and more or less copiously branched.

Laboulbenia melanotheca, nov. sp.

Tinged with pale reddish brown, except the nearly black perithe-
cium. Perithecium long, straight, symmetrical, subcylindrical or but
slightly inflated, narrowed abruptly to the symmetrical apex, its basal
wall cells elongated to form a neck-like stalk about one fourth as long
as its main body, projecting from the receptacle at an angle to its long
axis towards and beyond the appendages. Appendages as in L. mex-
icana, hardly exceeding the perithecium in length, consisting of two
basal cells ; the outer producing an outer and an inner branch either
simple or once branched ; the inner producing single branches on
either side. Receptacle elongate expanding very gradually from the
base, distally abruptly rounded and contracted below the insertion cell

THAXTER. — LABOULBENIACEiE. 473

on one side and the neck-like base of the perithecium on the other.
Spores 95 X 5.5 /a. Perithecium 220-245 x 60-65 /x, its neck-like
base about 75 X 30 /x. Receptacle about 515 x 100 /x. Total length
to tip of perithecium 800-835 /x.

On Galerita mexicana Chaud. Nicaragua.

This species has been previously referred to by the writer as a
possible hybrid between L. mexicana and L. Galeritce. It seems on
more careful comparison, however, to be abundantly distinct from
either. The neck-like base of the perithecium appears to be formed
from the elongated basal wall cells of the perithecium which lie wholly
below the ascogenic cells. The eight types were found on the elytra
of their host in company with L. mexicana.

Laboulbenia decipiens, nov. sp.

Perithecium nearly opaque, not punctate, large, slightly and evenly
inflated, tapering rather abruptly to the nearly symmetrical apex ; the
basal wall cells forming a short stout clearly defined neck ; the septa
separating the upper wall-cells deeper blackish and spirally twisted.
Appendages arising as in L. Galeritce from a conical cellular base
consisting of one outer and two inner rows of superposed cells, each
of which bears a single simple straight septate branch, its lower seg-
ments slightly inflated, hardly exceeding the tip of the perithecium.
Antheridia blackish, with a very long curved neck, borne singly or
two together from the sub-basal cell of the inner series of superposed
cells. Receptacle as in L. Galeritce except that cell (3) extends
upwards nearly to the black insertion cell of the appendages, cells (4)
and (5) being wholly included by it. Color sub-hyaline with brownish
suffusions especially in the region of cells (4) and (5). Perithecium
175-278 X 55 jtt (smallest 130 X 37/*), its stalk-like base 40-55 x 30 /x.
Receptacle (larger) 300 x 75 /x.

On Galerita cequinoctialis. Guatemala.

This species is remarkable for its close resemblance to L. Galeritce.
It is at once distinguished by the position of cell (3), and by the pecu-
liar twist of its perithecial wall cells which are not punctate as in the
latter species.

Laboulbenia Aspidogloss^, nov. sp.

Perithecium black, almost opaque, rather narrow, the inner margin
curved abruptly outwards to the rather large apex, its lips very
oblique outwards. Appendages arising from two basal cells which

474 PROCEEDINGS OF THE AMERICAN ACADEMY.

are nearly equal in size : the outer inflated and separated from the
cell above it by a blackened septum, this sub-basal cell roundish,
inflated, about as large as the basal cell and giving rise to two branches,
an outer and an inner ; the outer separated from it by a blackened
septum and consisting of a basal cell with three terminal brauchlets
the inner of which is deeply and broadly blackened at its base, while
the other two are wholly hyaline and fertile : the inner branch from
the sub-basal cell has no blackened basal septum and produces several
short branchlets bearing numerous antheridia. The inner appendage,
like the outer, consists of a roundish or squarish basal cell separated
from a sub-basal cell by a blackened sejDtum ; the sub-basal cell pro-
ducing a tuft of short branches bearing at their tips two to four
antheridia or becoming more elongate and sterile. Receptacle nor-
mal, the two basal cells rather slender, elongate, colorless ; the distal
cells suffused with blackish brown. Perithecia 110-120 X 40 /x.
Appendages (longest) 240 /x. Total length to tip of perithecium
333 /A, greatest width 63 /x.

On Aspidoglossa suhangulata Chaud. Kansas (M. A. Barber).

A species clearly marked by the peculiarities of its appendages,
which, unlike almost all other species of the genus, are fertile without
regard to their external or internal origin.

Laboulbenia macrotheca, nov. sp.

Amber-yellow. Perithecium large, evenly inflated, the curvature
from base to apex nearly symmetrical on either side, the apex rather
large, outwardly oblique, with a blackish basal shade ; the remainder
of the i^erithecium translucent, amber-colored, the walls thick, the
spore mass large. Appendages flexuous, thick, pale amber-colored
or tinged with purplish, arising from two cells, the inner small and
roundish, the outer much larger, two or three times as long, usu-
ally bearing a single cell with two terminal more commonly simple
branches; the inner producing two branches each several times
branched : the outer appendages especially more or less constricted
at the septa. Receptacle small, usually short and slender, the basal
cell long, narrowed towards its base, the sub-basal cell short, the
remaining cells relatively small. Perithecium 130-150 X 45-55 /x.
Spores GO x 5.5//, Appendages (longer) 185 /x. Receptacle 150-
165 X 35-40 /x. Total length to tip of perithecium 240 /x (longest
270 /x), greatest width 55-60 /x.

On Anisodactylns BaHimorensis Say. Maine. On Anisodactylus
sp.? Bathurst, N. B. (II. M. Richards).

THAXTER. — LABOULBENIACEiE. 475

This species occurs not rarely on the anterior legs of its host, less
frequently on the borders of the elytra. It may be distinguished by
its pale amber color, large evenly inflated perithecium, and slender re-
ceptacle, the distal portion of which is relatively unusually reduced.

Laboulbenia terminalis, nov. sp.

Perithecium deeply suffused with smoky brown, slightly inflated, the
inner margin evenly curved outwards, the outer more nearly straight,
but bent abruptly outwards to the large prominent apex, the lips of
which are well defined and outwardly oblique. Appendages arising
from two basal cells, a very large outer and much smaller inner : the
outer giving rise to two cells each of which bears terminally from two
to three long slender tapering flexuous branches tinged, at least
basally, with reddish brown : the inner bearing a single cell as a rule
followed by two terminal cells which give rise to groups of two or
three rather slender sessile antheridia : insertion cell placed just below
the middle of the perithecium. Receptacle pointed below, broad
above, nearly hyaline or evenly tinged with brownish, cell (7)
slightly prominent below the perithecium. Spores 55 X 5.5 fx, Peri-
thecia 120-150 X 45-50 /x. Receptacle 200-220 /x. Total length to
tips of perithecium 275-340 /x..

On Pterostichus luctiiosus Dej. Maine and Massachusetts.

This species occurs in tufts at the tips of the elytra or abdomen,
apparently never elsewhere. It is allied to forms of L. polyphaga
and L. Pterostichi, from which it is at once distinguished by its
perithecium.

Laboulbenia rigida, nov. sp.

More or less deeply tinged with olive-brown. Perithecium becoming
almost or quite opaque, somewhat inflated, a slight depression at its
base above the more or less bulging terminal portion of the receptacle,
its apex stout, snout-like, bent slightly inwards. Appendages arising
from two basal cells, the outer of which gives rise to a single simple
rigid branch, tapering slightly or not at all ; the inner producing two
similar somewhat shorter branches almost invariably simple and
bearing near the base solitary sessile antheridia. Receptacle nor-
mal, sometimes rather elongate. Spores 75 X 55 jx. Perithecia
125-150 X 10 /x. Appendages (longest) 300 /x. Receptacle 185-
300 /x. Total length to tip of perithecium (largest) 300 /x.

On Pterostichus patruelis Dej. Maine and Massachusetts.

476 PROCEEDINGS OP THE AMERICAN ACADEMY.

This sijecies may be distinguished by its rigid habit, straight single
outer api^endage aud the bluut suout-like apex of its peritheciuin. It
is one of the less well marked types of the genus, yet sufficient
material from the two localities mentioned indicates that its characters
are sufficiently well marked to warrant its specific separation from
other species of the flagellata type.

Laboulbenia confusa, nov. sp.

Becoming deeply suffused with smoky brown. Perithecium rather
small, inwardly inflated, the apex broad, slightly oblique outwards.
Appendages arising primarily from an inner and outer cell : the outer
bearing a second cell which bearS terminally a dense tuft of hyaline
flexuous tapering more or less divergent branches which are them-
selves more or less branched: the inner basal cell becoming several
times divided and giving rise to numerous branches densely crowded
and similar to the external ones. Receptacle consisting of a long
sub-cylindrical basal cell, the sub-basal cell shorter and broader, cells
(3-5) unusually large, causing this portion of the receptacle to bulge
outwards in an evenly rounded and characteristic fashion. Perithecia
166 X 55 /i.. Appendages (longest) 150 /x. Receptacle 215 yu long,
its basal cell 90-110 x 25-40 jx. Total length to tip of perithecium,
315 jx ; greatest width 75 fx.

On Bembidium sp. Connecticut.

This species although based on scanty material seems quite distinct
from its nearest allies, L. luxurians and L. compacta. Although the
general arrangement of the appendages is similar in the present
species, their flexuous divergent tapering habit is quite different from
those of the two forms just mentioned, from which it is also distin-
guished by its larger size and peculiarly shaped receptacle. It occurs
on the legs of a very small metallic-green Bembidium.

Laboulbenia cornuta, nov. sp.

Dark blackish brown. Perithecium tapering to a broad blunt apex,
from which projects a prominent straight dark brown appendage,
unicellular, bent abruptly outwards from its base, tapering slightly to
its nearly hyaline rounded tip. Appendages as in L. luxurians, the
branches fewer and stouter. Receptacle short, expanding somewhat
abruptly above the sub-basal cell, the basal cell becoming narrowed
and nearly hyaline towards its base. Perithecium 85 x 29 /x. Its
appendage 26 X 7 /x. Total length to tip of perithecial appendage
185 fx, greatest width 52 /x.

THAXTER. — LABOULBENIACE^. 477

On BemUdium cojnplanulum Mann. Wasliington (Miss Parker).

The five types of this singular species are all in poor condition, the
appendages being, for the most part, broken; but it seems safe to
describe it without regard to the termination of its appendages, since
the terminal projection from the perithecium distinguishes it from all
other known members of the genus, and finds a parallel only in
L. Gyrinidarum, with which it can by no chance be confused. It
was found on two specimens of the host, in each case growing ia
a definite position towards the base of the right elytron. The
beetles were among material kindly collected for the writer by Miss
A. M. Parker.

Laboulbenia Oberthuri Giard (in lit.).

Nearly hyaline except the brown or smoke-colored perithecium and
sub-basal cell of the receptacle. Perithecium large, inflated towards
the base, the narrower distal half abruptly rounded and contracted
below a rather narrow apex vath protruding lips bent outwards;
general color dark brown, much deeper below the apex. Appendages
numerous, crowded, slender, short, the lower segments inflated, arising
as in L. Guerinii. Receptacle elongate, consisting of a short curved
stout nearly hyaline basal cell, a very long sub-cylindrical sub-basal
cell smoky brown in color with deeper brown wart-like or scale-like
scattered prominences of varying size, the remaining cells normal
except that the insertion cells of the appendages are irregularly
divided. Perithecium 300-315 X 120 /a. Receptacle 1 mm.-900 /x ;
its sub-basal cell 370-425 x G5-75 ^. Total length to tip of
receptacle 1.225 mm.

On Orectogyrus heros, Reg. Madagascar.

This fine species has been kindly communicated to the writer by
Professor Giard, who has dedicated it to M. Rene Oberthur, its discov-
erer. It is with the exception of the two species described above on
Mormolyce by far the largest of the Laboulbenife, and is closely allied
to the form already known on Gyretes (Z. Guerinii Rob.), from
•■which, however, it is abundantly distinct.

Heimatomyces distortus, nov. sp.

Pale yellowish, more or less clavate in general form. Perithecium
inflated, its external margin strongly curved, becoming abruptly con-
stricted below a long slender tubular terminal mouth, which is usually,
but not always, bent abruptly outwards almost at right angles to the
nearly straight inner margin of the perithecium. A short straight

478 PROCEEDINGS OP THE AMERICAN ACADEMY.

bluntly pointed rather stout appendage arises on one side only of the
perithecium, just below this tubular apex beyond which it projects.
The basal and sub-basal cells of the receptacle about equal in length,
the latter broader : distal portion of the receptacle composed of the
usual four cells, the sub-terminal cell forming a distinct external
prominence below the terminal cell which is bent towards and partly
overlaps the perithecium. Perithecium (main body) 60 X 18 fx, its
tubular apex 18-25 X G /i. Spores 20 X 3 /x. Length of receptacle
110 IX.

On Laccophilus maculosus Germ. Connecticut.

A singular species appearing at first sight malformed or abnormal.
It occurs in company with H. uppendiculatus on the anterior legs of
its host.

Heimatomyces uncigerus, nov. sp.

Pale yellowish. Perithecium moderate, rather broad, its outer
edge straight, its upper fourth free from the receptacle, its prominent
bluntly tipped extremity bent abruptly outwards at right angles : a
slender hooked appendage arises from a point close to the receptacle
about two thirds of the distance from the base to the apex of the peri=
thecium, projecting from it obliquely outwards. Basal cell of the
receptacle large and long, the sub-basal cell small, sub-rectangular,
flattened: the distal portion composed of the usual four cells, the
terminal one not very prominent and bent strongly towards the peri-
thecium. Perithecia 80 X 22-25 p.. Spores 45 X 4 /x. Perithecial
appendage about 22 /x, long. Receptacle 132 ^ long. Total length to
tip of perithecium 135 yu,.

On Laccophilus maculosus Germ. Connecticut.

The more or less wedge-shaped apex of the perithecium of this very
distinct form projects outwards abruptly at right angles to the straight
outer perithecial margin. The hook-like appendage is quite unlike
that of any other species in form and position, and, occurring only on
one side, is not seen unless the perithecium lies at the right. It oc-
curs with H. spinigprus, H. hyalinvs, and rarely H. mai-ginatus, on
the posterior legs of its host.

Heimatomyces spinigerus, nov. sp.

Brownish yellow. Perithecium small, its tip slightly exceeding
that of the receptacle; its extremity blunt, lobed, curved outwards,
and bearing two projections just below the tip, unequal in size, one of
which extends outwards beyond the perithecial margin as a blunt

THAXTER. — LABOULBENIACEiE. 479

prominence. Basal cell of the receptacle often bent, expanding dis-
tally, much longer than the flattened sub-basal cell : the distal portion
of the receptacle with greatly thickened external walls, and consisting
of the usual four cells, the terminal one short, with a broad base and
bent towards the apex of the perithecium. Three small cells are dis-
tinct below the perithecial cavity, from the outer of which is produced
externally a prominent spur-like process. Peritliecia 55 X 15 //.,
Total length to tip of perithecium 88-90 fi. Spur-like process 12-
30 fji long.

On Laccophilus maculosus Germ. Connecticut.

Distinguished from all other species by the spur-like process from
the base of the perithecium. The septa are all defined with unusual
clearness, the external walls being greatly thickened. Apparently
among the rarest of the twelve species inhabiting this host.

DiCHOMTCES PRINCEPS, nOV. Sp.

Nearly hyaline, becoming slightly and uniformly tinged with pale
reddish brown, sometimes narrowly edged with blackish near the
base. Receptacle large, consisting of a single small squarish basal
cell, above which are three successive transverse rows of cells placed
side by side, the upper margin of each series convex : the lower series
consisting of a long narrow axial cell, with three or four more or less
obliquely superposed cells on either side : the middle series consisting
also of an axial cell, with five to eight cells on either side, which
extend obliquely upwards and outwards to form a free rounded pro-
jection, each cell of which bears a short bladder-like appendage, the
antheridia prominent at the base of each projection : the third or dis-
tal transverse series like the second, the cells often slightly more
numerous, forming projections in a similar fashion on either side
which bear the same bladder-like appendages. The axial cell of the
terminal series is followed by two small cells, each bearing a short
appendage, on either side of which a large somewhat flattened ?ell
forms the base of the perithecium. Perithecia two, more or less
divergent, elongate, slightly inflated and tapering gradually to the
blunt apex. Perithecia 110-165 X 22-30 fx. Spores 38 X 4 //. Re-
ceptacle 150-180 X 70-75 jx.

On PhilontJms sordidus Grav. Massachusetts.

A conspicuous species, occurring on all parts of the host, but espe-
cially on the inferior surface of the abdomen.

480 PROCEEDINGS OF THE AMERICAN ACADEMY.

EUCANTHAROMYCES, nov. gen.

Receptacle consistiug of two superposed cells, giving rise on one
side to a free stalked perithecium, on the other to a free appendage.
The appendage consisting of a basal and sub-basal cell terminated
by a compound antheridium. The antheridium formed from numer-
ous small cells, obliquely superposed in three rows, bordered exter-
nally by a sterile cell and terminated by a cavity from which the
antherozoids are discharged through a short irregular finger-like
projection.

EUCANTHAROMTCES AtRANI, DOV. Sp.

Pale straw-colored. Perithecium rather long, slightly inflated,
tapering to a blunt apex with rounded lips, its stalk consisting of a
single large free basal cell surmounted by three smaller cells. Basal
and sub-basal cells of the receptacle long and very obliquely super-
posed, lying almost side by side. The appendage consisting of a
basal cell not wholly free, but partially connected with the stalk cell
of the perithecium at its base, followed by a second sub-triangular
cell, the oblique upper walls of which separate it on the inside from
the body of the antheridium proper, and on the outside from the long
narrow cell which forms its sterile outer margin. Antheridium sub-
cylindrical, with rounded apex consisting of three series of obliquely
superposed cells decreasing in size from below upwards, and running
obliquely upwards and outwards, the lower series of six cells, the
middle of four, and the upper of two, the three series terminating in a
common cavity filled with antherozoids, which are discharged through
a terminal irregular finger-like projection which is bent strongly out-
wards. Perithecium 135 x 35 jx. Length to tip of perithecium 260 fx.
To tip of antheridium 150 jx.

On Atranus picbescens Dej. Virginia (T. Pergande).

Two specimens of this perplexing form were found in company
with Rhachomyces lasiophorus on an example of Atranus kindly sent
me by Mr. Pergande. The genus is based wholly upon the pecu-
liar compound antheridium, which seems quite different in character
from that of either Cantharomyces or Camptomyces, its nearest
allies.

Ceratomtces mirabilis Thaxter.

Abundant material of this species, collected in Maine and Massa-
chusetts, indicates that the writer has confused two closely allied
forms which were at first considered merely varieties of a single

THAXTER. LABOULBEKIACE^. 481

species. The type of C. mirabilis, which is the most common species,
is characterized by a stouter perithecium, the inner margin of which
is strongly curved, the curve being broken by a rounded prominence
on either side just below the apex, which is bent strongly to the base
of the perithecial appendage. The perithecial appendage is evenly
and distinctly inflated towards its base, and reaches a considerable
length. The main axis of the antheridial appendage is short and
stout, consisting of about a dozen superposed cells. From this type
may be separated a second species, which may be designated as
follows : —

Ceratomyces confusus, nov. sp.

General habit and color as in C. mirahilis. Perithecium hardly
inflated, its inner margin curving evenly to the prominent blunt apex
which stands out free from the base of the perithecial ajjpendage.
The perithecial appendage shorter than in C. mirahilis, without the
bulbous inflation at its base. Axis of antheridial appendage long and
slender, distally attenuated, with comparatively few short branches.
Receptacle as in 0. mirabilis. Spores 75 X 3.7 fx. Perithecia 235-
835 X 65 yu,. Axis of antheridial appendage 235 yu. (longest). Recep-
tacle 165 X 75 //,.

On Tropisternus glaher Hb. and T. nimhatus Say. New England.

This species is much rarer than O. mirahilis, and is at once distin-
guished by the absence of any prominences below the apex of the
perithecium, as well as by the differences presented by its perithecial
and antheridial appendages. Otherwise the two species are easily
confused.

VOL. XXX. (n. s. xxii.) 31

482 PROCEEDINGS OF THE AMERICAN ACADEMY.

Investigations on Light and Heat, made and published wholly or in part witb
Appropriation from the Rumford Fund

XXI.

EXPERIMENTS AND OBSERVATIONS ON THE SUMMER
VENTILATION AND COOLING OF HOSPITALS.

By ISIoRRiix Wyman.

Presented November 23, 1894.

In this climate, the sick in our hospitals often suffer much distress
from the excessive heats of summer. Their relief demands more
serious attention than it has generally received.

At first sight it would seem a simple matter by means of the cooling
processes known to the arts to surround a sick bed with a cool atmos-
phere ; but this atmosphere must be constantly renewed and the incom-
ing air as constantly cooled ; this cooling is a difficult problem, and has
not been satisfactorily solved by any of these processes. It is much
easier to warm our patients in winter than to cool them in summer.

The three principal ways in which our bodies lose heat are by con-
vection, radiation, and evaporation ; but they are efficient in very
different degrees.

Radiation, although effective in the open air with a clear sky, does
us but little good as a cooling agent on a warm and muggy day. In
our wards, when their walls are near the temperature of our patients,
or rather of their clothing, which is really the radiating surface, radia-
tion benefits them but little, for these walls of necessity return nearly
as much heat as is radiated to them. Neither is radiation sensibly
modified by any movement of the surrounding air.

Convection, as the name implies, is the carrying away of heat; it
increases inversely as the temperature of the surrounding air, and
directly v^'ith its moisture and velocity. We know well the agreeable
sensations on a hot summer's day of the sea breeze, which in a greater
or less degree combines these qualities. "We know too how much,
on a still, hot day, fanning, which changes neither the moisture nor the
temperature of the air, but simply causes more air to move over and
come in contact with us, adds to our comfort by displacing the hot and
moist air immediately around us.

WYMAN. — COOLING OP HOSPITALS. 483

The Cambridge Hospital is warmed by air heated in passing over
pipes in which hot water circulates, enclosed in heating boxes ; it is
obvious that the substitution of cold water for hot water in these pipes
would cool, more or less, the air on its way to the wards.

It was thought worth while to determine by experiment what influ-
ence this previous cooling might have on the comfort of our patients
as compared with air of the same velocity from the open, unchanged
in temperature or moisture.

An air-chamber extends under the whole ward ; it is devoted
exclusively to the purpose of receiving the air for ventilation and
distributing it equally through the heating boxes and ten registers to
the ward above. This air-chamber is well lighted, and is kept scrupu-
lously clean ; nothing is allowed to be placed in it under any pretence
whatever. It is generally cooler in the summer than the atmosphere ;
water from the city water service is also cooler by several degrees, in
the early summer, than the air. By connecting the city main with
the pipes in the heating boxes, and allowing the water flowing through
them to run to waste, they become in some degree air-coolers.

On the 21st of May, 1893, all windows and openings in the air-
chamber were carefully closed, and the water from the main let on.
At 3 p. M. the external thermometer was at 84° F. ; there was na
wind, and the patients were sufi^ering from the heat. The tempera-
ture of the air-chamber was 67" F. ; the water as it entered the cool-
ing boxes, 57-58°. The electric fan, 36 inches in diameter, driving
the air into the air-chamber, was put in motion, making 500 revolu-
tions with an air-moving power of 10,200 cubic feet a minute. At
4 p. M. the air entering the ward at the registers was at 71° F.

During this hour 400,000 cubic feet of air, as measured by a
Casella's air-meter, was thrown into the ward through the ten regis-
ters ; a quantity sufficient to fill the ward of 21,000 cubic feet twenty
times an hour, — once in three minutes.

The result was satisfactory ; the comfort of the patients was mani-
festly improved.

But it must be observed that the cooling surfaces were, first, the ten
cooling boxes of 30 square feet each at 57-58° F., and, secondly, the
floor and walls of the air-chamber, the two together amounting to about
3,300 square feet. The temperature of these walls could not well be
determined ; but as they had not been exposed to much increase of
heat since the winter, they may be assumed to have been about that
of the water supply, then 58° (in winter it is about 50°). At the out-
set then we had the air-chamber full of cool air and a cooling surface

484 PROCEEDINGS OF THE AMERICAN ACADEMY.

of about 3,000 feet along which the air, driven by the fan, was diffused
before it entered the ward. The cooling power of the boxes may be
assumed to be about oue tenth that of the walls.

These were the arrangements through the month of May, with the
same benefit to the patients. In June, the summer heats were greater
and more constant, and the fan more steadily used. The temperature
of the air-chamber and the air passing thx'ough it had increased, and
that of the water had already risen to 70°, and is usually somewhat
higher later in the season ; the quantity of water required was large
and expensive ; it was therefore shut off permanently. The same
amount of ventilation, however, was continued, and the conditions as
to the air-chamber and the admission of the air to the ward were
unchanged. During the summer, the ward temperature gradually
rose until it differed but little from that of the open air.

Still the comfort given to our patients and their nurses under both
these methods was immediate and decided. To those entering the
ward there was a feeling of freshness and freedom of air quite beyond
that of the other ward of similar construction, which had only the
usual summer ventilation.

At first the walls of the air-chamber to a degree acted as coolers,
but this ceased as they became warmer.

We may form some estimate of the probable effect of the boxes as
coolers in summer, by comparing it with their work as heaters in
winter.

The average boiler temperature in December and January is 200° F. ;
that of the return, 145° ; therefore, 55° of heat is lost iu heating
120,000 c.f. of air hourly supplied to the wards in winter.

From these data Professor Trowbridge has kindly made the follow-
ing computation : —

''Mean temperature of water = 172.5° (173°)

" « " air = ^ (30 + 70) = 50

Mean excess of water temperature available 173-50 =123
Excess per degree rise of air temperature ^^ — 3.07

" To cool the same amount of air from 80° to 70° (mean temperature
75") would require, if Newton's law hold, a mean temperature of
75° — 10 X 3.07 = 45° approximately."

Our boxes, therefore, as then constructed, with a water circulation
at 58° F., were inadequate to our purpose as cooling boxes. It is
true the boxes could be enlarged. It has been computed that, with a
constant flow of cool water at 50° through boxes 5.G times as large

WYMAN. — COOLING OF HOSPITALS. 485

as those we now have, we might keep a ward at 70° with an outside
air of 90°, and a ventilation reduced to 40,000 cubic feet an hour, —
one third of our winter supply, or one tenth of our summer supply.
But we have no reliable experiments to confirm this computation. Our
own experiments have shown that this previous cooling of the air is an
expensive and uncertain process, and would lessen the evaporation
upon which, as we shall see further on, we principally depend for
cooliug, and, what is more important, would probably not be hygienic.
No further experiments were made as to cooliug the air before its
entrance into the ward.

Our first experiment showed clearly enough the advantage of a
large supply of fresh and slightly cooled air ; but it is not so clear
how much was due to the temperature of the air, and how much to
the rapid evaporation caused by its velocity and dryness. But as the
comfort of the sick continued the same after the rise of temperature
of the cooling apparatus and the shutting off of the cold water, it is
probable that it was due more to the velocity and drying qualities of
the air acting upon the patients themselves, than to any change of
temperature in the ward generally, which, as we have already said,
differed but little from that of the open air. This is a point of the
first importance.

The most effective way of losing heat is that last mentioned, that is,
by evaporation. It is Nature's great consumer of heat. Evaporation
increases with the temperature of the air, with its dryness, and with
its velocity. Common observation teaches how rapidly wet clothing
and muddy roads dry in windy weather. If we are exposed to a warm
dry air, especially if it is in motion, we may feel cool, or even cold,
because of the rapid evaporation from the skin. In the heats of
summer the relative dryness of the air is of more importance to our
comfort than its temperature. The thermometer and our sensations do
not correspond. It is evaporation increased by the air put in motion
by his punkah that enables the Englishman to bear the heats of India
and keep his blood at its normal temperature.

Pettenkofer calculates that in twenty-four hours we lose heat, by
respiration alone, as follows : —

In dry air at 32° F.

« u 86°

A difference of about
In air completely humid at 32°

<.i ii a (; 86°

A difference of nearly

293,044 units of

he

274,050

ii.

a

19,000

a

a

265,050

a

u

105,390

ii

((

160,000

ii

a

486 PROCEEDINGS OP THE AMERICAN ACADEMY.

The cooling by respiration in moist air is therefore about one eighth
of that in dry air at the same temperature. But this is not all the
heat lost by evaporation, nor the greater part ; the loss by the skin
is nearly twice that by the lungs under the same conditions. Here
also the same law holds, the greater the relative moisture the less
evaporation and consequently the less cooling.

According to Lavoisier and Seguin, 900 grams of fluid per day
are discharged by perspiration, and 500 grams from the lungs,
making 1400 grams of fluid lost in twenty-four hours. The evapo-
ration of this quantity of water will consume 750 units of heat, or
about one fifth of all the heat produced in the body in twenty-four
hours.

The production of heat in the animal body, and its maintenance at
a normal standard, are two of the most important processes in the
living organism. The two chief means for regulating the temperature
of the body are the skin and the lungs. Of these the most direct and
simplest is that by the cutaneous perspiration. The relations of these
organs to the atmosphere, therefore, are of great importance in the
question now under consideration.

But the rate of evaporation and consequent cooling depends in great
measure on the aqueous vapor already in the atmosphere. That this
relative amount has a material influence on our individual comfort
there is no doubt. It is certain that on those days when the propor-
tion of humidity is greatest, even the healthiest feel an oppression and
languor, and that on other days when the humidity is less there is an
exhilaration of spirits and an increase of muscular energy.

It is worth while, then, to recall the laws governing this aqueous
vapor, for it pervades the atmosphere, is one of the main causes of its
movements, and the only fluctuating ingredient in its composition.

The evaporating power of air raised to a higher temperature is
increased. A quantity of air absolutely humid at 59° F. holds an
amount of vapor ecjual to g'^ of its weight ; at 8G^, ^^^ ! ^^ 113°, ^^ ;
at 140°, jL ; so that while the temperature advances in an arithmetical
progression, the vapor-difFusing power of the atmosphere rises with the
accelerating rapidity of a geometrical series having a ratio of two ;
with the same ratio, evaporation increases, and consequently the cooling
process.

It is upon this play of forces in the aqueous vapor and the air, and
the movements they bring about, that we must rely for the comfort of
our patients in the heats of summer. It is not a question of changing
the temperature of the air ; practically, we cannot alter that nor its

WYMAN. — COOLING OP HOSPITALS. 487

humidity, in the volumes required for ventilation. It is a question of
the rate of evaporation from a perspiring surface, which again is
governed in great measure by the velocity of the air ; and this by the
improvements in the arts we can control.

If, on the other hand, we attempt to attain our object by cooling
the air before it enters the ward, we are met with this fact. If air
absolutely humid comes in contact with warmer air also saturated, the
latter will be cooled, it will approach the dew-point, and, if its moisture
is condensed into visible vapor, will give out heat. Evaporation con-
sumes heat, condensation liberates heat.

In our first experiment the previous cooling of the air did not bring
it to the point of condensation, but its relative humidity was increased ;
the rate of evaporation was therefore diminished, and to that degree
it was a disadvantage.

The quantity of air required for our purpose cannot, as we have
already said, be determined by instruments of precision alone ; it must
be learned by experiment and the declared sensations of the sick.

The movement of the air around us, and it is never still, — the
natural ventilation as it is called, — is much greater than is generally
supposed. Repeated experiments have shown that at two feet a
second we first feel the air as a moving body ; less than that we con-
sider a perfect calm. And yet at this velocity air would move from
end to end of our ward of 60 feet in 30 seconds, and across, it in half
that time, quite unnoticed by us.

To give comfort during the excessive heats of summer the sick
require three or four times the air needed for satisfactory ventilation
in winter. It required 400,000 cubic feet an hour for our sixteen
patients, and yet while this large quantity was passing through the
ward it was only known, except at the registers, by the accompany-
ing sense of freshness and pleasant coolness ; it was never felt as a
draught.

" The great regulator of the heat of the body is undoubtedly the
skin." Physiology teaches that perspiration is a secretion, in a sen-
sible or insensible form, constantly going on. Increased heat increases
perspiration, and the evaporation of this increased quantity consumes
in work a large portion of the heat derived from the atmosphere, and
thus prevents an undue rise of the temperature of the bodily organs.
The very intensity, therefore, of the peripheral circulation, under the
action of heat, leads the way to relief.

Experiments made more than a hundred years ago prove that, if
the skin perspires freely and the perspiration be readily evaporated,

488 PROCEEDINGS OF THE AMERICAN ACADEMY.

the temperature of the body may remain nearly normal in an exces-
sively hot atmosphere, — even more than 200° F.

In the present atmosphere of mixed air and aqueous vapor, with
which it is never saturated, evaporation and convection must coexist.
So long as the expired air is loaded with moisture, and the skin per-
forms its perspiratory function, and the movement of the surrounding
air is under our own control, if, so to speak, we own a breeze, we may
confidently rely on our ability to dispense its comforting and refreshing
influences to the patients in our hospital.

The following observations with the wet and dry bulb thermometer
may serve to illustrate the cooling of a moist surface. June 17, 1894,
a thermometer in a still room was at 78° F. ; after covering the bulb
with a piece of thin cotton cloth moistened with water, and fanning it
for five minutes with a common fan, it fell to 72°, — a difference of 6°.
The same thermometer on the same day at 99°, treated in the same
way, fell to 77°, — a difference of 12°. A thermometer in the open air
in the shade, July 13, 1894, with a gentle breeze, was at 95° ; with a
moistened bulb, at 73°, — a difference of 12°. The relative humidity
at the same time was 53%.

But the air must be in motion. A perspiring patient in still air is
surrounded by an atmosphere permeated by much aqueous vapor; this
must be diffused and carried away from the neighborhood by the
continued arrival of fresh drier air, to get the full cooling effect due
to evaporation.

It is in this way that simple agitation of the air in a warm still
room brings relief, as with a common fan, or the rotary fan of the
shops, or the Indian punkah. So it is with a ride in the open elec-
tric car on a hot day ; the relief is immediate. There is no atmos-
pheric change either in temperature or in moisture ; it makes no
difference whether we move through the air, or the air moves by us,
the sense of cooling is the same. In both, we are surrounded by air
constantly renewed, bringing with it the pleasurable sensations and
invigorating influences belonging to a freely moving atmosphere.

What these influences are to those in health we know; what they
are to those languishing on beds of sickness, those only who have ex-
perienced them can fully appreciate. That the patients in our hospi-
tal have derived much comfort from them, their repeated declarations
fully prove. Besides the physical comfort they give, — like the sug-
gestions of flowers and music, with which the sufferings of the sick are
now so often soothed, — these large volumes of air fresh from the fields
seem to hold up to the mind of the convalescents suggestions of other

WYMAN. — COOLING OP HOSPITALS. 489

scenes, which displace, for tlie time at least, present surroundings,
and encourage the hope, so helpful to the sick, of a speedy return ta
their former enjoyments.

The experience of the Cambridge Hospital leads to these two con-
clusions : first, that fresh air directly from the open, in the quantity
and manner there supplied, can be made to give great comfort to the
sick during the heats of summer ; and, secondly, that pi'evious cooling
of the air so supplied is difficult and practically useless.

To this may be added, what is of much importance to charity
hospitals, that the method here adopted is the least expensive of the
cooling processes hitherto made generally known.

490 PROCEEDINGS OP THE AMERICAN ACADEMY.

Investigations on Lioht and Hkat. mabk and published wholly or in part with
Appropriation from the Rumford Fund.

XXII.

CONTRIBUTIONS FROM THE PHYSICAL LABORATORY OF THE
MASSACHUSETTS INSTITUTE OF TECHNOLOGY.

XLIIL — EXPERIMENTS ON THE RELATION OF
HYSTERESIS TO TEMPERATURE.

By Frank A. Laws and Henry E. Warren.

Presented by Charles R. Cross, October 10, 1894.

This paper gives an account of some experiments to determine the
effect of temperatures much above the normal on the dissipation of
energy by hysteresis in a specimen of steel.

At the time of the beginning of this research, in February, 1894,
there were no complete studies of this subject known to us. A casual
reference is to be found in the Proceedings of the American Institute of
Electrical Engineers, Vol. VII. p. 325, 1890, by Prof. Harris J. Ryan.
The tests there referred to were made on a cast-iron rinw. The maxi-
mum temperature employed was 360°. The details of the measure-
ments are not given. A short paper by Dr. Wilhelm Kuntz appeared
in the Electrotechnische Zeitschrift, Vol. XIII., May 6, 1892. In
this Dr. Kuntz showed that the hysteresis loss decreased with rise
of temperature. A second paper by the same author appeared in
the Electrotechnische Zeitschrift, Vol. XV., April 5, 1894. The
magnetometer method was used by Dr. Kuntz in this work. In this
paper tests of several ferrous materials are given, as well as some on
a specimen of nickel.

At the outset of this research it was decided that alternating cur-
rents should be used, and that the losses should be determined by a
Wattmeter, thus reducing the time required for observations to a mini-
mum. The instrument which we designed and used is shown in
Figure 1. We have decided to call the arrangement a Watt-balance.
Mr. A. E. Kennelly has given in the Electrical Engineer, December 21,

Figure i.

LAWS AND WARREN. — HYSTERESIS. 491

1892, a descriptioD of a "Differential Wattmeter." This instrument
gives the difference of the mean values of two definite integrals repre-
senting the primary and secondary energy in a transformer ; that is,
the losses. The Watt-balance measures the ratio of the mean values
of two definite integrals. It can therefore be used to measure the
efiiciency of a convertor, giving the result by a single reading.

The Watt-balance consists of two electrodynamometer Wattmeters,
one above the other. The movable coils are rigidly connected in our
instrument by a spiral-wound paper tube, and consist of 100 turns
of silk-covered German silver wire No. 32 B. & S. gage. The
resistance, including leads, is 103 ohms; the diameter of coils, 2 cm.
In series with the movable coils are two adjustable resistances, r^ and
^2, as shown in Figure 2. The stationary coils are arranged in pairs ;
each is 2.3 cm. in mean radius, and contains 130 turns of No. 12
cotton-covered wire. They are movable along their axes, so that the
factor of the instrument may be adjusted. The vertical distance
between the two dynamometers is 30 cm. The movable parts are
suspended by a silk thread inside a narrow paper tube to prevent
disturbance by air currents, and directive force is given by four spiral
springs, made of copper wire 0.005 cm. in diameter. These springs
serve as leading in wires for the movable coils. The instrument is
read by a telescope and scale.

In Figure 2 is shown the scheme of connections for a hysteresis test.
At the left the slide resistances for controlling the currents are shown.
By the proper insertion of the connection, G. either a direct or an
alternating current could be sent through the remainder of the appar-
atus, which in the main circuit consisted of an electrodynamometer,
one pair of stationary coils, the specimen under test, a known resist-
ance, R^ of German silver strip immersed in kerosene oil to keep it
at a constant temperature, and the second pair of fixed coils. At one
terminal of ^ a conn,ection was made by means of a short piece of
stout wire and a key, K; beyond the key the circuit branched, pass-
ing through the adjustable resistances r-^ and r,, the proper movable
coils, and returning one lead to the external terminal of the specimen,
and the other to the corresponding terminal of R. The resistance r^
was some hundreds of ohms, seldom falling below 300, and was more
frequently in the neighborhood of 1 ,000 ; rg was kept at a constant
value, 976 ohms. The resistances r^ and r^ were ordinary plug boxes,
and the assumption was made throughout the work that the resistances
of circuits r^ and r^, were so high in comparison with their inductances
that no correction factor need be applied to the indications of the

492

PROCEEDINGS OP THE AMERICAN ACADEMY.

O
111
PC?

CM

LAWS AND WARREN. — HYSTERESIS. 493

Watt-balance. It may be well to mention that the use of high resist-
ances constructed in the usual way by double winding may lead to
serious errors in alternating current measurements on account of
the capacity effects.

If the plug G be inserted so that a current flows in the apparatus^
and no deflection is observed, then the factors of the upper and lower
dynamometers are equal ; if the key K is depressed, there will in gen-
eral be a deflection, which may be reduced to zero by adjusting r^, as-
a zero reading means that the average values of the products of the
currents in the two coils of the upper and lower dynamometers are the
same. It is known that the work in S bears the same ratio to the
work in R that the total resistance in circuit 7\ does to the total resis-
tance in circuit r^. If the current is alternating, the work in S is of
course divided between hysteresis and heating losses. No allowance
has been thought necessary for the work done in the suspended coils.
If Wg and JFg represent the work in the specimen and in R, then

ri + 103x _P^(ri+l03)

^2+103 '

J^ is given by the electrodynamometer DYN.

To correct for the heating loss in S a direct current of any conve-
nient magnitude is sent through the circuit, and a second balance, r^,
obtained,

P
1000'

B = 1,079 ohms, r^ = 976 ohms ; so Ws= t-/^7^(''i ~ '"i^)-

It will be seen that the Watt-balance as used in the present case is a
Wattmeter with an electrodynamic control. The advantage derived
from obtaining this control by shunting a portion of the main current
is that any manipulation of the circuits does not disturb the equilibrium
of the instrument, and that it renders it possible to use the instrument
in a null instead of a compensation method.

As the hysteresis loss is a function of the maximum magnetization,
denoted by i?, it was necessary to provide some means by which the
maximum might be kept constant, and its value determined. The de-
vice sketched in Figure 3 was used for this purpose. In addition to
the magnetizing coil, the specimen was provided with a winding of 24
turns, which was connected in series with an adjustable resistance of
874 ohms during the tests, and a galvanometer of 126 ohms. Leads
were carried to the dynamo room, and terminated in brushes which
rested on the edge of an ebonite disk 11 inches in diameter, fastened
rigidly to the dynamo shaft ; the brushes were carried by a radial arm,

494

PROCEEDINGS OF THE AMERICAN ACADEMY.

the motion of which is controlled by a small magneto-motor driven by
three Leclanche cells. The motor was governed by a reversing key
in the testing room, about one hundred feet away. The alternator
used had ten poles, thus making the length of a wave 72°. A piece
of brass, 36° or one half a wave long, was set into the edge of the disk,
and the whole carefully trued up. When the dynamo was in action
the B current was closed once during a revolution, and for a time cor-
responding to one half a wave length. The galvanometer then per-
forms the operation ^ ^

fifteen hundred times a minute. The value of this integral will be a
maximum when it extends over the time between -{-B and — B. By

the use of the key K^ the brushes may be shifted, and the reading of
the galvanometer brought to its greatest value. With the dynamo
running at its normal speed a Leclanche cell, E.M.F. 1.4 volts was in-
serted in the circuit ; Rh was 1,374 ohms, and the deflection 21.2 cm. ;
with brushes short circuited and Rh equal to 14,874 ohms the deflec-
tion was 21.8 em., the ratio of deflection being .972. If the brushes
made perfect coutact, and there was no self-induction effect, the ratio
would be unity, the entire cycle of operation being performed in a time
short compared with the period of the galvanometer. During the tests
the reading with R h = 1,374 was frequently repeated in order that
the brushes might be kept in as uniform a condition as possible.

Owinfi; to the manner in which the specimen is constructed, the area
included in the B winding is but partially occupied by the iron. In cal-
culating the approximate values of B no allowance has been made for
this, as the permeability is high in the cases where B has been deter-
mined. If observations were taken at temperatures where the permea-

LAWS AND WARREN. — HYSTERESIS. 495

bility was very low, it would be necessary to apply a correction for this
unoccupied area. The values of B were calculated by the formula

E^RD

~ 20 A NnE^iy"- '

D is the deflection corresponding to the value of B to be found. R is
the resistance in circuit R h ; N, the number of turns on B winding.
n, the number of revolutions per second. A is the area of the iron in-
cluded in the B windings. D^ is the deflection of the galvanometer
when an E.M.F. of magnitude E^ and a resistance R^ are inserted in
the circuit R h, the dynamo turning at the normal rate.

The furnace used for heating the specimen was built of fire brick,
the external diameter was about 36 inches, height 18 inches. Inside
the fire brick was a layer of asbestos wool 2^ inches thick, kept in place
by asbestos board, which was protected by thin sheet iron. The box
containing the specimen was made of asbestos board about IJ- inches
in thickness, and lined with retort cement. During the tests it was
tightly closed. The furnace was heated by three blast jets made of
gas pipe, the external tubes were | inch inside diameter, the inner
tube I inch. The supplies of gas and air were regulated by slide
valves. The jets were directed into the furnace tangentially and with
a slight upward inclination, the eff"ect being to establish a good circu-
lation and keep the interior of the furnace at a uniform temperature.

The specimen upon which the following tests were made was com-
posed of so called French steel, which showed on analysis the follow-
ing impurities : —

Manganese 0.535 per cent.

Phosphorus 0.013 "

Silicon 0.085 "

Sulphur 0.018 "

Carbon 0.970

u

The mass of iron employed was 628 grams. From this material,
which was four one-thousandths of an inch thick, rings of 3 inches' out-
side and 2 inches' inside diameter were stamped, and the specimen
formed by piling them. Each was insulated from its neighbors by a
layer of pipe clay, applied as a sort of paint, the clay having been
moistened with alcohol. Every tenth layer was insulated with mica.
The pile so formed was wrapped with asbestos cloth, and the mag-
netizing coil of 36 turns of No, 14 copper wire wound on. The wire
was insulated by winding it with asbestos twine. Interwound with

496 PROCEEDINGS OF THE AMERICAN ACADEMY.

the magnetizing coil was the B coil of 24 turns. These two windings
formed on the outside of the specimen a single layer. The tempera-
tures were determined by a Le Chatelier pyrometer, calibrated by
known melting points. The hot junction was placed inside the asbestos
wrapping resting against the iron, the leads were brought out through
the usual double-cored fire clay tube ; this was surrounded by a piece
of gas pipe thoroughly wrapped in asbestos cloth, because in using this
pyrometer in a case like the present, where the leads pass from the
hot junction through a space at a higher temperature at a short dis-
tance from the junction, it is necessary to guard against conduction
along the leads, and consequent errors in the temperature.

The manner of making the tests and the subsequent calculation was
as follows. Owing to the construction of the furnace, the specimen
being well shielded from the heat of the fiames by the internal chamber,
the air insulation, and its own asbestos covering, the temperature of the
iron rises gradually ; consequently the specimen will be at very nearly
a uniform temi^erature. When a reading is desired, the alternating
current is turned on and the S deflection adjusted to< its maximum
value by J^^, and to its correct numerical value by varying the mag-
netizing current. Watt-balance resistance r^ is now adjusted, and the
pyrometer reading corrected for zero, and dynamometer reading and
time observed ; after a few minutes the observations are repeated, the
temperature having risen in the mean time. This process is kept up
until the iron loses its magnetism. Occasionally, a direct current was
sent through the apparatus and the Watt-balance, dynamometer, and
pyrometer readings taken ; these allow the value of r-^^ in the hysteresis
formula to be determined by making a plot, the co-ordinates being
Watt-balance and pyrometer readings, from the plot the value of
ri\ corresponding to any pyrometer reading may be read off. The
electrodynamoraeters were calibrated by sending a direct current
through them, and measuring the P.D. at the terminals of a known
resistance by projection against the E.M.F. of a Clark cell ; the values
of deflections and currents squared were plotted, giving straight lines.
j?^ was determined by reference to these plots. The zei'o errors of
the dynamometers employed were very variable, and were determined
after each reading.

The results of the measurements will now be given. They are
plotted as referred to at the beginnings of the several tables.

LAWS AND WARBEN. — HYSTERESIS. 497

TABLE I.
First Heating : Ascenbing Curve.
See Figure 4.
W^ = liysteresis loss in specimen.

B =

1970.

n = 125,

Wh-

Temp
o

.852

23

.834

45

.845

67

.845

98

.817

132

.809

181

,818

272

.742

347

Wh-

Temp.

o

.678

387

.526

440

.450

481

.331

546

.241

595

.130

672

.088

709

The specimen lost its magnetic properties so rapidly that furtliei
measurements could not be taken on the ascending curve.

TABLE L — Descending.

Wh-

Temp.

o

.0

787

161

576

.206

503

.255

445

,290

Power shut off.

417

VOL. XXX. (n. s. xxii.) 32

498

PROCEEDINGS OP THE AMERICAN ACADEMY.

/«0* 206'

906' tloo*

(too hoe' 76b'

LAWS AND WARREN. — HYSTERESIS.

499

TABLE

II.

Second

Heating :

Ascending.

See Figure 5.

B

^ 1974. n

= 125

^H

Temp.

Wh-

Temp

.516

o

20

.149

632

.520

75

.121

653

.519

1C8

.115

662

.522

160

.093

679

.440

269

.083

688

.407

310

.094

692

.378

345

.104

693

.340

397

.130

693

.321

423

.130

693

.311

438

.142

693

.293

470

.144

693

.258

511

.142

692

.228

555

.140

694

.167

593

'TOO

soc

Fl&.t.

60 c

500 PROCEEDINGS OP THE AMERICAN ACADEMY.

Inspection of the plots shows (Figs. 4 and 5) that for this sample of
steel a moderate elevation of temperature up to about 270° has but a
small influence on the hysteresis loss ; that at this point a change takes
place, and the diminution of hysteresis, with rise of temperature, is
much more rapid, the decrease being such that at 675° the loss is but
13 per cent of its value at ordinary temperatures. After heating
above the inflection point, the specimen shows on cooling a marked
decrease of the hysteresis loss from its value at the same temperature
on the ascending curve. If the specimen be heated again, a change of
direction of the curve takes place, but at a lower temperature. The
second plot (Fig. 5) shows an increase of the hysteresis loss after the
point of inflection has been reached. As only two heatings were made,
we were unable to verify these observations, the results of which became
apparent only when they were reduced. In addition to the experi-
ment at high temperatures, the following observations were made. A
specimen was made up and the loss measured at the ordinary tempera-
tures ; a mean of three measurements gave .289 Watts as Wh. The
specimen was then covered with a mixture of solid carbonic acid and
ether ; a mean of three measurements showed Wh as .288 Watts,
showing that there is practically no change of hysteresis for a diminu-
tion of temperature to about — 80°.

Between the ascending and descending observations of the second
heating, readings were taken for the purpose of finding whether the
temperature at which the iron becomes markedly magnetic on coolino-
is the same as that at which the sudden diminution of the mas:netic
properties occurs on heating. Simultaneous readings of the B gal-
vanometer and pyrometer were taken, the current remaining constant,
no adjustment for maximum was made. The readings, together with
some from the descending curve of the first heating, are given below,
and, after being corrected for zero, are plotted in Figure 6.

TABLE III.

First

Heating.

Second

Heating.

B Reading.

Pyr.

B Reading.

Pyr.

38.8

7.17

28.1

6.99

38.8

7.10

29.9

7.01

38.8

7.05

31.0

7.02

38.8

7.00

32.1

7.03

38.7

6.95

33.4

7.05

38.55

6.90

34.8

7.10

38.15

6.83

36.1

7.11

37.70

680

87.2

7.12

37.00

6.73

37.9

7.13

LAWS AND WARREN.

First Heating.

B Reading. Pyr.

36.3 6.69

33.65 6.51

31.2 6.45

- HYSTERESIS.

Second Heating.

B Reading.

Pyr.

38.3

7.14

38.6

7.15

38.7

7.15

38.6

7.19

38.8

7.14

38.75

7.10

38,75

7.03

38.7

7.01

38.65

6.98

38.55

6.95

38.25

6.93

37.85

6.90

37.1

6.85

36.5

6.84

34.1

6.76

32.7

6.73

30.7

6.70

501

<3

«3

Q

<

^4

Pyr..

610

6S0

/^/G 6.

700

502 PROCEEDINGS OP THE AMERICAN ACADEMY.

Figure 6 shows that the two points do not coincide, that on the
descending being about 12° lower than that on the ascending curve.
The diiFerence of form of the curves is noticeable, showing that the
regaining of magnetic properties on cooling is more gradual than their
loss on heating ; the sudden exaltation of magnetic properties occurs
at the same temperature in the first and second coolings.

At the time of this writing the research has not been fully com-
pleted. We are, however, now engaged on further experiments, and
hope to present additional data in the near future.

Rogers Laboratory of Physics,
June, 1894.

PROCEEDINGS.

Eight hundred and sixty-seventh Meeting.

May 9, 1894. — Annual Meeting.

The Peesident in the chair.

The Corresponding Secretary read the following letters :
from the Royal Society of London, on the project of making
a catalogue of scientific papers by means of international
co-operation ; from the Royal Society oi Canada, inviting tlie
Academy to send delegates to its Twelfth General Meeting
on the 22d of Ma}'' ; from Ad. de Marignac, announcing the
death of his father, Jean Charles Galissard de Marignac, a
Foreign Honorar}^ Member of the Academy ; and from
Francis M. Green and W. C. Sabine, acknowledging their
election into the Academy.

Voted, To accept the invitation of the Royal Society of
Canada, and the President was authorized to appoint a
delegate.

The Report of the Council of the Academy was read and
accepted.

The Reports of the Librarian, of the Treasurer, and of the
C. M. Warren Committee were read and accepted.

Notice of a proposed change in the statutes was given
by Charles L. Jackson, viz. to increase the number of
Vice-Presidents so as to have one from each Class. This
proposal was referred to a Committee consisting of C. L.
Jackson, S. H. Scudder, and F. W. Putnam.

The President appointed, as a Committee of Co-operation
on the project of making a catalogue of scientific papers,
C. L. Jackson, H. P. Bowditch, and Denman W. Ross.

504 PROCEEDINGS OF THE AMERICAN ACADEMY

H. P. Bowditcli presented a motion in regard to indepen-
dent nominations for the offices of the Academy, which was
referred to the Committee on the changes in the statutes.
On the recommendation of the Committee of Finance, it was
Voted, To make the following appropriations from the
income of the General Fund for the ensuing year : —

For the library $1,200

For general expenses 2,500

For publications 1,800

For the expenses of meetings . . . 200

Voted, That the assessment for the ensuing year be five
dollars.

Voted, That $1,000 from the Rumford Fund be placed at
the disposal of the Rumford Committee, to be expended in
aid of investigations on Light and Heat, payments to be
made on the order of the Chairman of the Committee.

In accordance with the recommendation of the Committee
on the proposed alteration of the statutes, it was

Voted, To amend Chapter V. of the Statutes by changing
the numbers of sections 4, 5, and 6 to 5, 6, and 7, respectively,
and inserting a new paragraph as follows : —

" 4. The C. M, AVarren Committee, of seven Fellows, to be chosen
by ballot, who shall consider and report on all applications for appro-
priations from the income of the C. M. Warren Fund, and generally
see to the due and proper execution of this trust."

The following gentlemen were elected members of the
Academy : —

Walter Gould Davis, of Cordova, to be an Associate Fellow
in Class 11., Section 1 (Geology, Mineralogy, and Physics of
the Globe), in place of the late William H. C. Bartlett.

Hermann Eduard von Hoist, of Chicago, to be an Asso-
ciate Fellow in Class HI., Section 3 (Political Economy and
History).

Ingram By water, of Oxford, to be a Foreign Honorary
Member in Class III., Section 2 (Philology and Archaeology),
in place of the late Benjamin Jowett.

OF ARTS AND SCIENCES. 505

Sir John Robert Seeley, of Cambridge, to be a Foreign
Honorary Member in Class III., Section 3 (Political Economy
and History), in place of the late Charles Merivale.

The annual election resulted in the choice of the following
officers : —

JosiAH P. Cooke, President.

Augustus Lowell, Vice-President.

Chaeles L. Jackson, Corresponding Secretary.

William Watson, Becordivig Secretary.

Eliot C. Clakke, Treasurer.

Henry W. Haynes, Librarian.

Councillors.

William R. Livermore,
Benjamin O. Peirce, \ of Class I.
Benjamin A. Gould,

Henry P. Walcott,

Benjamin L. Robinson, ) of Class H.

Henry W. Williams,

Andrew M. Davis,

Thomas W. Higginson, \ of Class III.

James B. Thayer,

Member of the Committee of Finance.
Augustus Lowell.

Rumford Committee.

John Trowbridge, Edward C. Pickering,

Erasmus D. Leavitt, Charles R. Cross,
Benjamin O. Peirce, Amos E. Dolbear,
Benjamin A. Gould.

C. 31. Warren Committee.
Francis H. Storer, Samuel Cabot,

Thomas M. Drown, Henry B. Hill,

Charles L. Jackson, Leonard P. Kinnicutt,
Arthur M. Comey.

506 PROCEEDINGS OF THE AMERICAN ACADEMY

The President appointed the following Standing Com-
mittees: —

Committee of Publication.

Charles L. Jackson, William G. Farlow,
Charles G. Loring.

Committee on the Library.

Henry P. Bowditch, Amos E. Dolbear,

Edward J. Lowell.

Auditing Committee.
Henry G. Denny, John C. Ropes.

On the motion of the Corresponding Secretary it was

Voted, That the thanks of the Academy be tendered to
Wolcott Gibbs for his long and valuable services as member
of the Rumford Committee.

The following papers were presented by title : —

On those Orthogonal Substitutions that are given by Cay-
ley's Expression, or by the Limiting Form of Cayley's Expres-
sion. By Henry Taber.

On the Measurement of Resistance by the Method of Sub-
stitution. By G. Le Clear.

On the Currents in Batteries made up of Cells joined up in
Multiple Arc. By B. O. Peirce.

On the Constitution of the Nitroparaffine Salts. Second
Paper. By John U. Nef.

On Ternar}'- Mixtures. First Paper : The Chemical Poten-
tial of Metals. By Wilder D. Bancroft.

Action of Alcoholates on Chloranil. By C. Loring Jackson
and H. S. Grindley.

Bromine Derivatives of Metaphenylene Diamine. By C.
Loring Jackson and S. Calvert.

Behavior of certain Derivatives of Benzol containing Halo-
gens. By C. Loring Jackson and S. Calvert.

A Revision of the Atomic Weight of Strontium. First
Paper: The Analysis of Strontic Bromide. By Theodore
W. Richards.

OF ARTS AND SCIENCES. 507

On the Cupriammonium Double Salts. Second Paper.
By Theodore W. Richards and A. H. Whitrido-e.

On the Cupriammonium Double Salts. Third Paper :
Compounds of Iodine. By Theodore W. Richards and G.
Oenslager.

On a Series of Cupraniline Compounds. By Theodore W.
Richards and F. C. Moulton.

Euglenopsis, a new Alga-like Organism. By Bradley Moors
Davis.

New Plants of Northwest Mexico, collected by Messrs. C.
V. Hartman and C. G. Lloyd upon the Lumholtz Archgeologi-
cal Expedition. By B. L. Robinson and M. L. Fernald.

On the Cell Lineage of the Ascidian Egg. A Preliminary
Notice. By W. E. Castle.

The North American Ceuthoj)hili. By S. H. Scudder.

Researches on Electrical Waves. By John Trowbridge.

On the motion of the Corresponding Secretary, it was

Voted, That the Rumford Committee be directed to defray
the cost of the publication of John Trowbridge's paper on
" Electrical Waves " from the income of the Rumford Fund.

Eight hundred and sixty-eighth Meeting.

October 10, 1894. — Stated Meeting.

The Vice-President in the chair.

The Corresponding Secretary read the following letters :
from the Scientific Alliance of New York, requesting the co-
operation of the Academy in the endeavor to obtain a reduc-
tion of postage rates on natural history specimens ; from the
Royal Society of New South Wales, offering its medal and
twenty-five pounds for the best communication containing the
results of original researches on a series of specified topics ;
from the Imperial Russian Geographical Society, enclosing
a copy of a pamphlet " Respecting the Necessity of an Inter-
national Agreement with regard to the Publication of Material
contained in Naval Meteorological Journals, a Memorandum
drawn up by Rear Admiral Makaroff, St. Petersburg," and

508 PROCEEDINGS OP THE AMERICAN ACADEMY

requesting the Academy to favor the Society with its views
thereon ; from the Royal Academy of Sciences of Turin, an-
nouncing the deaths of Commanders Frebretti and Lessona ;
and from H. von Hoist, John Donnell Smith, and Ingram
Bywater, acknowledging their election into the Academy.

The chair announced the death of Josiah Parsons Cooke,
President of the Academy ; of Oliver Wendell Holmes and
Edward J. Lowell, Resident Fellows ', of E. G. Robinson
and W. D. Whitne}^ Associate Fellows, and of H. L. F.
von Helmholtz, a Foreign Honorary Member.

The vacancy occasioned by the death of the President,
Josiah Parsons Cooke, was filled by the unanimous election of ^

Alexander Agassiz, President.

On motion of the Corresponding Secretary, it was

Voted, That the December meeting be devoted to addresses
in memory of the late President of the Academy, Josiah
Parsons Cooke.

Voted, To appropriate the sum of two hundred dollars
($200) from the income of the C. M. Warren Fund to Francis
C. Phillips, of Allegheny, Pennsylvania, in aid of his re-
searches relating to the Chemistry of Natural Gas ; and six
hundred dollars ($600) to Charles F. Mabery, of Cleveland,
Ohio, in aid of his investigations of the Sulphur Petroleums.

The following report was adopted : —

The Committee, appointed at the Annual Meeting to consider the
changes in the Statutes proposed by S. H. Scudder, and the amend-
ment offered by H. P. Bowditch to the rule for the nomination of
officers of the Academy, recommends the following alterations in the
Statutes : —

Chapter 11., Section 1, change the words "a Vice-President"
to " three Vice-Presidents, one for each Class." Change the words
"written votes" to "ballot."

Section 2, change the word " Vice-President " to " the three
Vice-Presidents."

Section 3, add at the end, "or at a meeting called for this purpose."

After Chapter II. insert a new Chapter III., "Of Nominations of
Officers," and alter the numbers of the following chapters to corre-
spond to this change. The new chapter to read as follows : —

OF AETS AND SCIENCES. 509

" Chapter III. — Of Nominations of Officers.

"1. At the stated meeting in March the President shall appoint
from the next retiring Councillors a Nominating Committee of three
Fellows, one for each Class.

"2. It shall be the duty of this Nominating Committee to prepare a
list of candidates for the offices of President, Vice-Presidents, Corre-
sponding Secretary, Recording Secretary, Treasurer, Librarian, Coun-
cillors, and the Standing Committees which are chosen by ballot ; and
to cause this list to be sent by mail to all the Resident Fellows of
the Academy not later than four weeks before the Annual Meeting.

" 3. Independent nominations for any office, signed by at least five
Resident Fellows and received by the Recording Secretary not less
than ten days before the Annual Meeting, shall be inserted in the
call for the Annual Meeting, which shall then be issued not later
than one week before that meeting.

" 4. The Recording Secretary shall prepare for use in voting at the
Annual Meeting a ballot containing the names of all persons nomi-
nated for office under the provisions given above.

" 0. When an office is to be filled at any other time than at the An-
nual Meeting, the President shall appoint a Nominating Committee, in
accordance with the provisions of Section 1, which shall announce its
nomination in the manner prescribed in Section 2 at least two weeks
before the time of election. Independeb„, nominations, signed by at
least five Resident Fellows, and received by the Recording Secretary
not later tlian one week before the meeting for election, shall be inserted
in the call for that meeting."

Chapter III. of the present Statutes, Section 1, change the word
"Vice-President" to "Senior Vice-President present," and insert
at the end of the section, " Length of continuous membership in the
Academy shall determine the seniority of the Vice-Presidents."

C. L. Jackson,

S. H. SCUDDER,

F. W. Putnam,

Committee.

The following report was presented and adopted : —

Report of the Committee to consider the Circular of the Royal Society
in regard to a Catalogue of Scientific Publications.

The Committee finds itself fully in sympathy with the desire of
the Royal Society to improve the methods of cataloguing scientific

510 PROCEEDINGS OF THE AMERICAN ACADEMY

literature, and is distinctly of the opinion that the establishment of
such a catalogue, to be compiled through international co-operation, is
both desirable and practicable.

It seems probable that this improvement in the methods of cata-
loguing may best be made by establishing some form of card catalogue
prepared by the co-operation of a central bureau with the various
publishers and editors of scientific literature in issuing with each
book and with each number of every periodical a set of cards of
standard size and type, each card to exhibit for a book or for a single
article in a periodical, —

1st. The name of the author.

2d. The title of the book or article.

3d. The date, place and house of publication of the book, or the
title, volume, and page of the periodical, in which the article appears.

4th. A brief statement, not to exceed eight or ten lines, to be pre-
pared by the author himself, setting forth the general purport of the
book or article so as to furnish the necessary data for cross references.

Such cards should be in duplicate, to permit of arrangement accord-
ing to subject or author, or both if desired, and additional cards
should be issued whenever the character of the title necessitates cross
references.

If thought desirable the type used in printing the cards could be
kept set up till the end of the year, and then, by arranging the material
according to subjects, an annual report in book form could readily be
published.

A central bureau charofed with the work as above outlined could
very properly be established under the auspices of the Royal Society.
In this central office subscriptions could be received from libraries
and individuals for cards relating to the articles published in certain
journals, or to the literature of certain departments of science, and a
subscriber would thus receive, in weekly instalments, a complete card
catalogue of all the literature in his own line of work.

The Committee present only a general outline of the plan for this
card catalogue, as it is understood that the details of the scheme will
be sent to the Committee of the Royal Society by Harvard Univer-
sity. They would further express the hope that some plan may be
successfully inaugurated at an earlier date than the year 1900, as
suggested in the circular of the Royal Society.

In accordance with the views above set forth the Committee re-
spectfully recommends to the American Academy the adoption of the
following votes : —

OP ARTS AND SCIENCES. 511

1. That, in the opinion of the American Academy of Arts and
Sciences, the establishment of a catalogue of scientific literature to
be maintained through international co-operation is both desirable and
practicable.

2. That a copy of this report be transmitted to the Royal Society,
as a suggestion of the way in which this plan may be best carried
out.

3. That in case such a card catalogue as that recommended in this
report be established, it is desirable that the American Academy co-
operate with the central bureau by forwarding titles and summaries
of the articles published in its Proceedings and Memoirs.

(Signed,)^

C. L. Jackson,
h. p. bowditch,
Denman W. Ross,

Committee.

The Corresponding Secretary read an abstract of C. F.
Mabery's paper, " On the Composition of the Ohio and
Canadian Petroleums."

The following papers were read by title : —

On the Electric Resistance of certain Poor Conductors.
By B. 0. Peirce.

On the Variability in the Spores of the Uredo Polypodii.
By B. M. Duggar.

Note on the Effect of Temperature on Hysteresis. By
Frank A. Laws and Henry E, Warren,

The Recording Secretary presented a copy of the Proceed-
ings of the International Congress on Water Transportation,
held at Chicago in 1893, and remarked that it contained a
memoir on Electric Haulage which anticipated two papers
presented this year at the International Inland Navigation
Congress at the Hague, at which he was present.

512 PROCEEDINGS OF THE AMERICAN ACADEMY

£iglit huudred and sixty-niuth Meeting.

November 23, 1894. — Special Meeting.

The Academy met at the house of the President, at
Cambridge.

The President in the chair.

The death of Robert C. Winthrop, a Resident Fellow, was
announced ; also, the death of James McCosh, an Associate
Fellow.

The President, after acknowledging his indebtedness to the
Academy for the high honor conferred upon him by his elec-
tion, proceeded to give an account of his explorations in
1891 in connection with the U. S. Fish Commission in the
Steamer "Albatross," commanded by Captain Z. L. Tanner.

This expedition opeued the deep water of the Panamic Region as
far west as the Galapagos and as far north as the Gulf of California.
He compared the deep water Panamic fauna with the abyssal fauna of
the Caribbean, as well as the primal conditions of life existing in the
ocean on the two sides of the Isthmus. When contrastinw the coral
fauna of the two seas he took occasion to refer to his recent explora-
tions of the coral reefs of the Bahamas and of the Bermudas^ and to
indicate their bearing on the Darwinian theory of the formation of coral
reefs. The exploration of the Bahamas took place in the spring of
1893, in the Steam Yacht " Wild Duck," owned by the Hon. John M.
Forbes. That of the Bermudas was made in March, 1894.

'5

Morrill Wyman read a paper entitled, " Experiments and
Observations on the Summer Ventilation and Cooling of
Hospitals."

The following papers were presented by title : —

Contributions from the Gray Herbarium of Harvard Univer-
sity. New Series, No. 9 : A Revision of the North American
Cruciferse. By S. Watson and B. L. Robinson.

Experiments on the Relation of Hysteresis to Temperature.
By Frank A. Laws and Henry E. Warren.

Notes on Laboulbeniacege, with Descriptions of New Species.
By Roland Thaxter.

OF ARTS AND SCIENCES. 513

Eight hundred and seventieth Meeting.

December 12, 1894.

The President Id the chair.

The President aunouuced the death of Ferdinand Marie
de Lesseps, Foreign Honorary Member.

On the recommendation of the Council, it was

Voted, That the use of the Academy's room be granted to
the Colonial Society of Massachusetts on the third Wednes-
day afternoon of each of the five months December to April,
in the same way as during the past year.

The meeting was devoted to a commemoration of the late
Josiah Parsons Cooke, President of the Academy.

ADDRESS OF CHARLES LORING JACKSON.

Josiah Parsons Cooke, for forty-one years a Resident Fellow
of the Academy, Librarian for eight years, Corresponding Secretary
from 1873 till 1892, and President in 1892, 1893, and 1894, was
born in Boston on October 12, 1827, and died in Newport on Sep-
tember 3, 1894.

He was descended from Major Aaron Cooke, who came in 1630 to
Dorchester, Massachusetts, from E^ngland, and aftei'ward was one of
the founders of Northampton, where he died in 1690. His son, also
named Aaron, lived in Hadley, and it was under his protection that
the regicides Goffe and Whalley lay in hiding in that town. Noah
Cooke, the fifth in descent from Major Aaron Cooke, after serving as
a chaplain in the war of the Revolution, moved to New Hampshire,
where a son, Josiah Parsons Cooke, the father of the subject of this
memoir, was born, in 1787. After a boyhood passed in Keene he
graduated from Dartmouth College in 1807, and then established him-
self in Boston as a lawyer, where, in 1826, he married Mary Pratt,
the eldest daughter of John Pratt, a well known merchant.

On October 12, 1827, a son was born, who was named Josiah
Parsons Cooke after his father. In 1833 Mrs. Cooke died in Santa
Cruz, and her little son, only six years old, and a younger sister, now
Mrs. Bennett Hubbard Nash, were left to the devoted care of a faith-
ful friend, who did all that was possible to replace the mother whom
they had lost.

VOL. XXX. (n. S. XXII.) 33

514 PROCEEDINGS OP THE AMERICAN ACADEMY

Youug Cooke grew up a quiet boy, little given to sports out of
doors, especially as early in his boyhood a course of lectures given in
Boston by the elder Silliman kindled in him an enthusiasm for
chemistry, which continued to blaze till the end of his life, and led
him to pass all his spare time, not on the playground, but in a little
laboratory which he had fitted up in his father's house. Here he
attacked the science by experiment, guided by the bulky volume of
Turner's Chemistry, and secured a mastery of the subject which
would have been highly creditable with a good instructor, but without
a teacher of any sort was most surprising. Yet, while a remarkably
able student in chemistry and also in mathematics, he had neither
taste nor aptitude for the dead languages, and it was only with much
difficulty that he surmounted the barrier of Greek and Latin which
guarded the approach to Harvard College.

Once fairly in College he distinguished himself in mathematics, but
found little instruction in his favorite science. Professor Webster,
then near the end of his service, gave the class two or three chemi-
cal lectures, which were brought to a sudden end by his show experi-
ment called the volcano, — a large heap of sugar and potassic chlorate
piled on a slab of soapstone. After he had lighted it with a drop of
sulphuric acid, he saved himself by dodging out of the room, and in
a very few seconds all the members of the class found themselves
obliged to jump out of the windows. Later, Professor Horsford, who
had just taken charge of the laboratory of the Lawrence Scientific
School, to till the gap gave a voluntary course of lectures on chemis-
try, which, however, did not extend beyond three, so that the teaching
of chemistry which he received in Harvard College did not percep-
tibly add to his knowledge of the science acquired by his own
exertions.

After his graduation, in 1848, a year was spent in European travel,
and on his return, in the autumn of 1849, he was made Tutor in
Mathematics at Harvard College; but the absence of all chemical teach-
ing in the College soon gave him more congenial occupation, since a
few weeks after his appointment he was asked to give instruction in
chemistry to the Freshmen, and in the following spring (May 25
1850) was appointed Instructor in Chemistry and Mineralogy, with
the following condition, — "he providing at his own charge the con-
sumable materials necessary in performing chemical experiments."
In this one does not know which to admire more, the liberality of the
arrangement or the elegance of the language. The materials to be
provided by him need not have been confined to those " consumable,"

OP ARTS AND SCIENCES. 615

however, since the College possessed no apparatus worth mentioning,
and his two courses of lectures given in 1850 were illustrated by
material brought from the small private laboratory which he had
fitted up at home when a boy.

At the end of this year it was decided to fill the Erviug Professor-
ship of Chemistry and Mineralogy, and the two most prominent candi-
dates were Cooke and David A. Wells, the first graduate in chemistry
of the Lawrence Scientific School, now so eminent for his work in
political economy. The election resulted in the choice of Cooke
on December 30, 1850, and he held this position till his death. He
was now only twenty-three years old, with barely a year and a half of
experience as a teacher, and a knowledge of chemistry the product of
his own studies unaided by any systematic instruction. With this
meagre outfit he was confronted with problems which would have
tasked the abilities of an old, experienced, and fully educated pro-
fessor. The chemical teaching in Harvard College had become
extinct, he must re-establish it. The College was wedded to methods
of teaching excellent for classics and mathematics, but entirely unfit
for a subject like chemistry ; he must displace these, and put in
their stead better methods, many of which were still to be invented.
Finally, he must help to raise science from its position as an unwel-
come interloper on the outskirts of the College course to an equality
with the humanities intrenched behind centuries of tradition.

His first step after his appointment was to obtain leave of absence
for the remainder of the College year, which was well spent in Europe
buying apparatus and chemicals, mostly at his own expense, accord-
ing to an agreement between the Professors of the Medical School ;
but he also found time to improve his intellectual equipment by
attending the lectures of Regnault and Dumas, whose influence can
be traced in his strong leaning to chemical physics, and the care and
accuracy of his later work upon atomic weights. Regnault espe-
cially inspired him with the warmest affection, as is pleasantly shown
by the enthusiastic reverence with which he is invariably mentioned
in his book on Chemical Physics. With this work his systematic
instruction in chemistry, if it can be called such, began and ended,
and it is hard to believe in view of his achievements that it was all
crowded into six months, broken by many other necessary occu-
pations.

On his return from Europe in 1851 he promptly accomplished his
first task, the re-establishment of chemical instruction in Harvard
College on its old recitation basis ; but it is a high tribute to his

516 PROCEEDINGS OF THE AMERICAN ACADEMY

peneti-ation aud judgment that he recognized from the first the insuffi-
ciency of this way of teaching, aud turned eagerly to the laboratory
naethod, invented by Liebig not many years before, aud brought to
the Laboratory of the Lawrence Scientific School by Horsford, a
pupil of Liebig, in 1847. The reason for this, Cooke tells us, was
that he had taught himself chemistry by experiment. His second
great task, the introduction of this laboratory method, proved no easy
one. A begiuning was made even in his first year of service as
Erving Professor by fitting up a small laboratory in the north end of
the cellar of Uuiversity Hall, under the lecture and apjiaratus rooms
assigned to the Chemical Department. Here Storer, Eliot, Dean,
just home from Wohler's laboratory, and many others, worked as
volunteers, but it took seven years of hard fighting to get this course
adopted by the College as anytliing but an extx'a. Meanwhile he was
striving to improve the regular courses by introducing into the two
weekly recitations Stockhardt's Chemistry as the text-book, since
this made a first though crude attempt to follow the experimental
method of presenting the subject, and by laying great stress on writ-
ing reactions, which, to use his own words, "served its purpose in
making the study respected in a literary community ; but it did this
at the sacrifice of all that is distinctive and peculiarly valuable in the
study of an experimental science." This led to the publication of
his first book, in 1857, which was a thin volume called " Chemical
Problems and Reactions," an admirable manual of tactics for this
recitation drill. Amid this arid desert of recitations the weekly lec-
ture was the one green spot, as here experimental demonstrations
were not only allowed, but required, and yet these lectures were sur-
rounded by difficulties before which most men would have given up
in despair. The apparatus which he had brought home from Europe
was bought for the Medical School; but, as the College had no chem-
ical collection, it was obliged to do double duty, and the frequent
transportation from Cambi-idge to Boston and from Boston to Cam-
bridge of these bulky and fragile pieces of apparatus used up much
time and energy, and must have been a constant strain upon his
nerves.

His duties at the Medical School, which at first divided his time
with the College, were irksome in the extreme. Chemistry was sys-
tematically neglected by the students, and the fact that he held no
medical degree caused a certain amount of friction with his colleagues,
but nothing could damp his youthful enthusiasm, and laboratory
courses in qualitative analysis and medical chemistry were established

OP ARTS AND SCIENCES. 517

by him, although tolerated in the School only as extras. It was at
this time that he prepared and delivered a long course of lectures on
organic chemistry to satisfy a wholly unintelligent demand on the
part of the medical students, to which he alludes later as a monument
of useless labor ; but this was not the case, as the familiarity thus
gained with a field so different from that which he cultivated in after
life had a most excellent effect in broadening his view of the science.
It was a great relief to him when, in 1857, he was freed from his duties
at the Medical School, the apparatus made its last journey over the
bridge, and henceforward he was able to devote his time and energy
to the development of the chemical department of Harvard College.

But it must not be inferred that during these early years all his
attention was given to teaching, as his first scientific paper, that on
the Classification of the Elements, dates from this period, since it was
published in 1854. It created a marked sensation when, in December,
1853, he presented it to our Academy, to which he had been elected
in the previous year. Benjamin Peirce in particular hailed it as a
wonderful discovery, and this, as Cooke once told me, had a bad effect
on his subsequent work for many years, both by keeping him from
many excellent researches because they did not promise far-reaching
theoretical results, and by making him try to find such results in all
the work that he did. These tendencies unfortunately were not coun-
teracted by association with other chemists, for, although he had many
scientific acquaintances, he was singularly unwilling to discuss chemi-
cal subjects with them, owing, it would seem, to a natural sensitiveness
and reticence inherited from his father, and not modified by study in
one of the large foreign laboratories, where a man learns among other
useful lessons that all scientific men are comrades. It took him
twenty years to shake off this habit of mind, and to grow into a better
and therefore more prolific mood in reference to research.

The year 1858 was a most important epoch in his life, as at this
time the proper method of chemical instruction was recognized by the
acceptance of the experimental course in qualitative analysis as a
regular elective study in the College, and also satisfactory laboratory
accommodations were provided by the erection of Boylston Hall.

In the ten years that followed no new courses were added, but that
already established was perfected, and its success gradually accus-
tomed the College authorities to the new method of instruction, and
prepared them for the further advance at the end of this period. But
although these years from 1858 to 1868 show no striking changes
in the curriculum or very important papers, they are rich in literary

518 PROCEEDINGS OP THE AMERICAN ACADEMY

activity. His first large book, the " Elements of Chemical Physics,"
was published in 1860, an excellent account of this branch of the
science as it existed at that day, which ran through three editions,
and was still used at Oxford within a very few years. At the very
end of this period his second important text-book appeared, the
" Chemical Philosophy," published in 1868 (four editions), a won-
derfully clear and complete exposition of the modern theories of
chemistry. Neither of these books was popular with the students.
They could not be, as they obliged their readers to think, and there is
no occupation more distasteful to the undergraduate. I can well
remember the utter despair which settled upon me when I attacked
my first problem in the Chemical Physics. I had never been called
upon to think unassisted before, and at first I doubted the possibility
of the process. But in this very demand on the thinking powers of
the student lay the chief usefulness of these books, and their educa-
tional value on this account can hardly be overestimated. Nor would
the fact that this work was distasteful have troubled him much, as he
often expressed his disapprobation of the sugar-coating now so gener-
ally considered essential on educational pills.

A book of au entirely different sort came out between the two
which I have just mentioned. This was " Religion and Chemistry, or
Proofs of God's Plan in the Atmosphere and its Elements" (1864,
and a new edition in 1880). It consisted of a course of lectures
delivered before the Brooklyn Institute, the Lowell Institute of
Boston, and the Mechanics' Association of Lowell, in 1861. In it
the argument of natural theology is worked out in great detail from
chemical data, and his stores of scientific knowledge are brouEcht to
the service of his sincere and earnest piety.

In 1860, he married Mary Hinckley Huntington, of Lowell, who
survives him. Some years later Oliver W. Huntington and his sister
(now Mrs. W. A. Pew, Jr.), a nephew and niece of Mrs. Cooke,
became members of his family ; and their presence did much to
brighten his life, and gave additional objects for his warm affection.

For many years before 1868, the Catalogue had contained the fol-
lowing announcement : " Mineralogy is taught to those who desire
to learn it by Professor Cooke." This was associated with a similar
announcement about Hebrew, and the number who desired either of
these incongruous companions was small. Enough however studied
mineralogy to prove to Cooke, " somewhat to his own surprise, that,
when made solely a subject for object lessons, the study of deter-
minative mineralogy was an admirable training of the powers of

OP ARTS AND SCIENCES. 519

observation, and therefore a disciplinary study of the highest value."
Accordingly a certain amount of mineralogy was crowded iuto the
single chemical elective, and when, in 1868, a second elective was
introduced, this was devoted entirely to that subject, leaving all the
time of the original course for qualitative analysis.

After this time there was a continual increase in the number of the
chemical courses, until, in 1871, the single laboratory of the original
building became overcrowded, and new accommodations were secured
by adding to Boylston Hall a story, which contained a large laboratory
for elementary students. At about the same time the chemical de-
partment of the, Lawrence Scientific School was merged in that of the
College, and all the chemical material was removed from the Scientific
School building to Boylston Hall. Cooke had now essentially accom-
plished the three tasks which confronted him when appointed Erving
Professor. Chemical teaching was established in the College ; the new
methods of instruction had been introduced ; and equal rights for
science had been gained after a hard struggle in the Faculty, in which
Cooke took a prominent part, and showed rare powers as a debater
and a strategist. It only remained for him to gather the fruits of the
victory.

In 1872 he was elected a member of the National Academy of
Sciences. In 1873 he was made Corresponding Secretary of our
Academy, and for twenty years after this he managed our corre-
spondence and publications, and to him is due the establishment of an
annual volume of the Proceedinsfs.

Of the many courses of popular lectures which he gave at this
time, one delivered before the Lowell Institute of Boston was em-
bodied in a book called " The New Chemistry " (1874), containing a
clear popular account of the modern chemical theories, which he had
already treated in a more technical way in his Chemical Philosophy.
This book had a striking success. It ran through five editions in
English in four years, and was translated into nearly all the civilized
languages of the globe. It still remains one of the best and most
readable statements of the theories of chemistry.

In 1876 he Avas elected an Honorary Member of the London
Chemical Society, and a few years later a Member of the Royal
Institution.

One of his principal amusements was photography, in which he
attained remarkable skill, and not only did he take excellent photo-
graphs himself, but he collected an enormous number of photographic
slides, and his frequent exhibitions of these to his friends or his classes

520 PROCEEDINGS OF THE AMERICAN ACADEMY

were most enjoyable, the beauty of the views being enhanced by his
vivid descriptions and comments. His own pleasure in these exhibi-
tions must have been as great as that of his audiences, since he was
never tired of giving them, in spite of the very considerable amount of
trouble and labor which they involved.

The manifold employments which I have tried to sketch left Cooke
little time for original investigation, and this, combined with the too
exaggerated conception of the dignity of research wliich he had formed
in early life, as I have already said, prevented him from publishing
before 1874 very many or very important jjapers, if we except his
discoveries of minerals in Rockport. All this time, however, his
chemical ability and insight were slowly ripening, and in 1874 the
harvest began with his paper on the Vermiculites, which was closely
followed by his researches on Antimony and on Oxygen, so that from
this time till 1889 his scientific production was continuous and
important.

This scientific activity did not interfere with his other occupations.
During this period the number of chemical electives was increased,
new laboratories were fitted up, and the growth of the Mineral Cabinet
was incessant. This collection of minerals was an object of such
affectionate care to him that no account of his life would be complete
without a sketch of its history. Starting in comparative insignificance
both in quantity and quality at the time he was made Professor, it
grew at first slowly, principally by the collections which he made in
vacation excursions, and by occasional purchases, until during one of
his earlier journeys to Europe he succeeded in buying the collection
of Count Liebener, rich in uncommon minerals from the Tyrol.
After this it increased steadily by quiet purchases, often paid for out
of his own pocket, until in 1875 it crowded Comparative Anatomy,
which originally shared Boylston Hall with Chemistry, into other
quarters; but in 1891 Mineralogy in its turn had to yield to Chemis-
try, which was left in undisputed possession of the whole building.
To provide new quarters for the minerals, a division of the University
Museum was built largely through bis exertions, and here the collec-
tion was installed, which in the mean time had risen to be one of the
first in the world so far as meteorites are concerned by the addition ot
the J. Lawrence Smith collection, partly left to the College by its
original owner, and partly bought with money raised or subscribed by
Professor Cooke. Since then the generous gifts of Mr. J. A. Garland
of New York and Dr. W. S. Bigelow of Boston have given the col-
lection a similar commanding position in regard to precious stones.

OF ARTS AND SCIENCES. 521

In 1877 he was made an associate editor of the American Journal
of Science, and contributed to it then and afterward several excellent
reviews of important papers.

In 1881 he collected a number of his essays and addresses in an in-
teresting little volume entitled " Scientific Culture and other Essays."
The address which gives its name to the book, and the two which fol-
low, " The Nobility of Knowledge," and " The Elementary Teaching
of Physical Science," display the penetrating insight and good judg-
ment which he brought to bear on the problems of education ; they
are full of wise advice and inspiration. The book also contains
appreciative biographical notices of Graham and W. H. Miller, and a
paper on the radiometer, dwelling on the scientific principles brought
out by this instrument. The careful and enthusiastic study of the
radiometer, which led to this article, is exceedingly characteristic of
the man. Whenever a striking new discovery was announced, he at
once threw himself into the study of it with the greatest ardor. Thus
he was probably the first to take calotypes in America, and later
became an expert photographer, as I have already said. Shortly
after Bunsen and KirchhofF's great invention, he constructed the most
powerful spectroscope of that time, inventing many ingenious contriv-
ances for making the necessary adjustments ; sevei'al of his papers
owe their origin to this work on spectrum analysis, and he was on
the point of making a discovery of the first order, the method of
seeing the solar prominences in spite of the full glare of the sun,
when he was anticipated by two other observers. In the same way
he mastered the new science of electrical measurements, procured the
necessary apparatus, gave instruction in this subject to voluntary
students, and wrote a popular account of its principles.

In 1880 his father died, at a great age, and in the following year,
after the graduation of his nephew 0. W. Huntington from Harvard
College, he went to Europe with his family, and passed the winter in
Egypt. This was the last and longest of his many foreign journeys,
and was rendered more noteworthy by the fact that on his return to
England in the summer of 1882 the University of Cambridge con-
ferred on him the honorary degree of Doctor of Laws.

In 1887 he returned to the field of Natural Theology in a course
of lectures before the Union Theological Seminary of New York,
which was repeated before the Lowell Institute of Boston, and pub-
lished in 1888 under the title, " The Credentials of Science the War-
rant of Faith." This book, which has passed through two editions,
was intended for students of divinity, and the argument therefore is

522 PROCEEDINGS OF THE AMERICAN ACADEMY

more technical than that in " Religion and Chemistry." It consists
in proving the thesis " that the inductions of natural theology are as
legitimate as the inductions of physical science." The illustrations
are drawn from astronomy and physics quite as often as from chemis-
try, and the strong metaphysical bent of his mind is very apparent.
Like all of his books whicli are not text-books, this one shows that
he was a devoted and appreciative student of Tennyson, " in whose
verses," he says, " he has discovered a truer appreciation of the diffi-
culties which beset " the relation of science and religion " than he has
ever found in the philosophy of the schools."

In 1889 he received the degree of Doctor of Laws from Harvard
University ; and now began the melancholy period when failing
health interfered with, though it could not stop, his various activity
and wonderful industry. Through it all he was supported by the
devoted help and affection of his wife's nephew, 0. W. Huntington,
who, as he often said, was in every respect the staff of his old age.

A severe functional trouble, which would have thrown most men
into retirement, and a serious affection of his eyes resulting in the
loss of one of them, were unable to overcome his persistent energy.
It is true that he was obliged gradually to abandon his own original
work, but he still directed that of a few advanced students, and gave
several courses of instruction, including the lectures on general chem-
istry, to the whole Freshman Class, a labor which would tax severely
the powers of a young and sound man. These lectures had continued,
with only occasional breaks of not more than two years at a time,
ever since he began teaching chemistry in 1850. In the latter years
of his life they ceased to be a systematic course in chemistry, and
became rather an inspiring statement of the methods, aims, and needs
of the science, thus admirably serving their purpose by awakening an
enthusiasm for scientific work among the students in their first year.
The attendance on these later lectures was voluntary, and it was
astonishing to see the crowd packed in the aisles of the old lecture-
room, filling the vacant space before the table, and even extending
well out into the entry, often with men standing on the stair-rail,
and peering over the heads of those in front. As a college lecturer
his style was striking and luminous, and his experiments uniformly
successful, in spite of his tremulous hand, which one would have
thought must have precluded any delicate manipulations. He has
enriched the stock of lecture apparatus with many excellent contriv-
ances, notably his arrangement for the projection of spectra, his form
of the lecture-table eudiometer, and his vertical lantern. In the

OP ARTS AND SCIENCES. 523

laboratory his explanations were clear and patient, and be always
bore in mind the necessity of making the student think for himself.
His students, whether elementary or advanced, regarded him with a
warm affection, whicli was well merited by his exceeding kindliness,
and his devotion to their interests.

In addition to these labors as a teacher he continued to serve as
Director of the Laboratory, and even published an eighth book,
" Laboratory Practice" (1891), a series of experiments to be used in
fitting students for Harvard College, and in the corresponding College
elective study, a course which he had founded, and in which he took
till the end the strongest interest.

In 1892 he was elected President of our Academy, but in spite of
a journey to Alaska, which gave him much needed change and recrea-
tion, he did not survive long to enjoy this well deserved honor. In
the summer of 1894, after a most harassing winter, he went to his
country house in Newport, where he had passed the summers for
more than twenty years, and as soon as the strain of the term's work
was removed broke down almost completely. Nevertheless, he man-
aged to make out the European order for laboratory material for the
following year in the midst of pitiable weakness, and then slowly, but
without pause, faded away, until he died, on September 3, 1894.

ADDKESS OF HENRY BAEKER HILL.

The scientific work of Professor Cooke began soon after his ap-
pointment to the Erving Professorship, and continued throughout his
life. At first he seems to have been drawn toward subjects which
were more or less intimately connected with mineralogy, his favorite
pursuit, but in later years he turned to problems which tax to the
utmost the patience and ingenuity of the investigator, and devoted
the last half of his scientific life to the determination of atomic
weights.

Forty one years ago, in December, 1853, he presented to the
Academy a preliminary sketch of an investigation into the numerical
relation of the atomic weights, and the Memoir uiDon this subject
which appeared a few months later is noteworthy in that it was one
of the early attempts to classify the elements through their atomic
weights. It is, however, to us especially interesting in that it con-
tained a discussion of the errors involved in the determination of
atomic weights, which in a way foreshadows the investigations which
occupied him in after life. The conclusions which he reached in this

524 PROCEEDINGS OF THE AMERICAN ACADEMY

early pai^er Professor Cooke was able to quote thirty years later as
the exi3ression of his riper judgment.

An investigation upon the alloys of zinc and antimony, which
followed soon after, in 1854, proved the existence of two definite crys-
talline compounds of the two metals. A subsequent study showed
that the crystalline form of these bodies remained constant with a
tolerably wide variation in percentage composition. This fact led him
at the time to suggest that perturbation of the law of definite propor-
tion could be effected by mass, and that these perturbations became
serious wherever chemical affinity was weak. Six years later he ap-
plied the same course of reasoning to the composition of minerals, and
came to the conclusion that the geneial formula in this case was but
the typical formula toward which the mineral tended, but which per-
haps was never realized with any actual specimen. Twenty-five years
afterwards, when Butlerow again discussed the possible variability of
the law of definite proportion, Professor Cooke, after referring to
his own earlier views upon the subject, wrote that he felt the weight
of evidence to be in favor of the atomic theory, and that absolute
definiteness of combining proportion which this theory involves.

In 1860 appeared the detailed account of the brilliant researches
of Kirchhoff and Bunsen upon spectrum analysis ; and with character-
istic enthusiasm Professor Cooke was soon absorbed in the study of
this new mode of chemical investigation. Several papers appeared
upon the construction of spectroscopes, the projection of the spectra
of the metals, and upon the aqueous lines of the solar spectrum.
While thus engaged in the study of the spectroscope, he found time to
make a crystallographic examination of the acid tartrates of caesium
and rubidium and of childrenite, and to investigate the dimorphism of
arsenic, antimony, and zinc. The results of these investigations were
published from time to time in the American Journal of Science.

For several successive years he was now engaged in the study of
new mineral species. In 1866 he described danalite from Rockport,
Massachusetts, and in the following year cryophyllite from the same
locality. He also described at this time two analytical processes
which had evidently been -^suggested by his work upon these minerals.
A few years later appeared a paper upon the vermiculites, in which
two new species or varieties, hallite and culsageeite, were described, and
this was supplemented in the following year by an account of the in-
vestigation, with F. A. Gooch, of two more varieties of the same
family. These researches, together with a note upon melanosiderite
and a crystallographic study of some American chlorites, were the last
of his purely mineralogical contributions.

OP ARTS AND SCIENCES. 625

Before the publication of these papers upon the vermiculites,
Professor Cooke had begun the study of antimony, and was able to
present to the Academy, in June, 1873, a preliminary notice of some
determinations of its atomic weight. So many ditficulties were en-
countered, however, that the extended paper upon the subject did not
make its appearance until four years later. In 1854 he had expressed
the opinion that the accidental errors affecting such determinations
could easily be eliminated, while the constant errors were the great
eri-ors involved. In 1877 he closes the account of his revision of the
atomic weight of antimony with the remark that the investigation
from the first had been a study of constant errors. It is not possible
to tell briefly the story of the persevering search for these constant
errors, — a search involving months of patient labor. I could but re-
peat the words with which Professor Cooke has himself described,
with painstaking fidelity, the steps which he took in surmounting the
successive difficulties. The hardest task, possibly, was to show the
constant error which vitiated the results obtained by Dumas twenty
years before, — results which had been welluigh universally accepted.

The careful study of the compounds of antimony with the halogens,
which was a necessary preliminary to the determination of its atomic
weight, established many interesting facts, the most important of
which, possibly, was the existence of three different crystalline forms
of antimonious iodide belonging, respectively, to the monoclinic, ortho-
rhombic, and hexagonal systems. The results of the quantitative
study of antimonious bromide, confirming the value of the atomic
weight of antimony which he had previously established, were given in
a paper which appeared a year or two later, and the advantage which
could be gained by the simultaneous determination of three atomic
ratios was here discussed. The evidence was now complete, and the
new atomic weight of antimony was adopted by the whole chemical
world. A series of less important papers appeared during the pro-
gress of this work upon antimony, describing new methods devised for
the work, or discussing details of the processes involved. Among
them may be mentioned " A new method for manipulating hydric
sulphide," '•' The process of reverse filtering," " Argento antimonious
tartrate," and " The solubility of chloride of silver in water."

Shortly after the completion of the work upon antimony. Professor
Cooke planned an investigation upon the relative values of the atomic
weights of oxygen and hydrogen. The necessary exploratory work
upon this research was delayed by failing sight and precarious health,
so that it was not until the autumn of 1886 that everything was ready

526 PROCEEDINGS OF THE AMERICAN ACADEMY

for the final decisive experiments. During the following winter, with
the co-operation of T. W. Richards, numerous determinations were
made, in which an accurately weighed quantity of hydrogen was
burned, and the weight of water which was formed determined. The
experimental difficulties involved were great although they were in
kind quite different from those which the work upon antimony pre-
sented. These difficulties were at last overcome, and the wonderfully
close agreement between sixteen successive determinations, made
with hydrogen prepared in three different ways, showed how perfectly
all sources of accidental error had been eliminated.

One source of constant error had been overlooked, however, which
affected not only these determinations but all the results which had ever
been obtained by the classic method of Regnault. Agamennone, and
afterward Lord Rayleigh, discovered that the volume of a glass vessel
was sensibly diminished when the air within it wa;^ exhausted, so that
the tare of the globe in which the hydrogen had been weighed had
been incorrectly determined on account of the diminished volume of
the air displaced. The amount of this error could easily be deter-
mined, and in a second paper the necessary small correction was ap-
plied. In order to avoid this change of volume, he devised an ingen-
ious method for determining the tare of the globe without exhausting
it ; and this method was the subject of his last communication to the
Academy, in June, 1889.

As an investigator Professor Cooke was clear in thought, perse-
vering amid difficulties, fertile in expedients, impatient of dogma, and
to the end he retained the keen curiosity and enthusiasm of his earlier
days.

ADDKESS OF AUGUSTUS LOWELL.

Tt is always interesting to trace the impulse which had determined
a man's life work. It is peculiarly so to me in the case of Professor
Cooke, because he himself was wont to attribute it in a large measure
to the impression made upon him as a boy by the lectures of Professor
Silliman, before the Lowell Institute. These lectures opened a new
horizon. He was intensely interested, repeating the experiments he
had witnessed with such imperfect appliances as he was able to pro-
cure, and from that moment there was no hesitation as to his future.
His life was to be devoted to the study of Chemistry.

There was nothing in his birth or surroundings to indicate such a
career. His father was a successful lawyer ; his maternal ancestors

OP ARTS AND SCIENCES. 527

devoted to commerce. The pursuit of Science for its own sake was
little understood or appreciated. There was no adequate teaching,
and those of us who can remember the lectures in Holden Chapel
will realize what must have been the difficulties of a young beginner.

When the College lost its Professor of Chemistry, it was not easy
to fill the position. The same necessity which had called a young
Divinity student to the Professorship of Physics, placed an untried
youth in the chair of Chemistry. The choice was justified, however,
by the result.

To a keen mind and power of analysis Cooke added a gift of lan-
guage and clearness of statement which made him a natural lecturer.
It was said of him that he recalled the manner of Faraday ; and
whether he was explaining the mysteries of Science, describing the
recently discovered Pharaohs, or treating of the higher issues of
religious thought, the same ciiarm marked his discourse. With uncer-
tain muscles which often seemed to imperil the success of an experi-
ment, there was no hesitancy in thought or utterance. All was clear,
logical, and convincing. I never had the opportunity of hearing him
at Cambridge, but I have often listened to his public lectures, and can
bear witness that few lecturers held the attention of their audiences
more completely than he, or gave more pleasure.

Professor Cooke did not confine himself to one subject of thought.
He was many-sided. His religious lectures were marked by the same
cogency of reasoning, purity of style, and apt illustration as any of
his scientific discourses.

Professor Cooke lectured eight times before the Lowell Institute,
and I cannot better indicate the breadth of his studies than by enumer-
ating the subjects of these lectures.

In 1855 and 185G he lectured on "The Chemistry of the Non-
metallic Elements."

In 1860 and 1861, on "The Chemistry of the Atmosphere as illus-
trating the Wisdom, Power, and Goodness of God."

In 1864 and 1865, on "The Sunbeam, its Nature and Power."

In 1868 and 1869, on "Electricity."

In 1872 and 1873, on "The New Chemistry."

In 1878 and 1879, on " Crystals, and their Optical Relations."

In 1887 and 1888, on ''The necessary Limitation of Scientific
Thought."

In 1892 and 1893, on " Photographic Sketches of Egypt."

This last course recalled his travels and embodied the study and
reflections of a cultivated mind amidst the monuments of that wonder-

528 PROCEEDINGS OF THE AMERICAN ACADEMY

ful country. To it he brought the same patient investigation and
broad generalization which marked his work elsewhere, and his treat-
ment of it before his audience was generous, persuasive, and attractive.
One word I may be permitted in regard to his personal qualities.
Professor Cooke was eminently simple, truthful, and earnest, kindly
and affectionate. Possibly my connection with the Institute, which
had done so much to determine his career and before which he had so
often appeared, may have influenced his feeling, but to me he was
always a kind friend, for whose attainments I had the highest respect,
and whose pure, honest, confiding nature was always attractive and
inspiring.

ADDRESS OF FRANCIS HUMPHREYS STORER.

I HAVE heard Professor Cooke say jokingly, but with a tinge of
honest pride, that he was a '• self-made chemist." The remark was
true in one sense, for beside listening as a boy to a few popular lec-
tures by the elder Silliman, and following for a brief period some of
the public lectures of Dumas and other Parisians, he never had any
definite, stated instruction in Chemistry. To the best of my knowl-
edge and belief, he never worked for an hour in any other laboratory
than his own. Many of the most familiar details of analytical manip-
ulation he learned from his assistants while teaching them and his
classes what Chemistry really is. It was from books and from his
own inner consciousness that chemical knowledge came to him. Yet,
thanks to native ability, to an excellent academic training, to inherited
wealth, a clear head and a tenacious will, he came at last to stand in
the fore-front of American chemists, and to command the attention of
the fraternity in every land. Even as a manipulator, he became
expert; in spite of a constitutional tremulousness, which, in his youth
at least, had placed him at a great disadvantage. Like tlie surgeon
with his knife, in the story, he had so mastered his trembling hand,
that the thing held in it should shake assuredly into the right
place.

But, although it is fair enough to say that as a chemist Cooke was
self-taught, no such statement would be true of him as a scholar.
There can, I think, be no question that a great part of the strength
of the man depended upon a scholarship distinctly superior to that of
most contemporaneous chemists. In point of fact, Professor Cooke
was very carefully trained at College, where he came under the
influence of many eminent men. Thanks to the teachings of Benja-

OP ARTS AND SCIENCES. 529

min Peirce and Joseph Lovering, he became accomplished in the
mathematics and in physics. Doctor Beck taught him Latin enough
for his purposes. Felton and Sophocles strove with him as to Greek,
and with Doctor Walker his relations were peculiarly intimate. He
long continued to look up to President Walker as to a counsellor and
guide. In the matter of rhetoric, he had the inestimable advantage
of Professor Chauning's drill. He was in contact also, to a certain
extent, with such teachers as Asa Gray, Jeffries Wyman, and Long-
fellow. . Incidentally, he obtained a good working knowledge of
French and German.

It was by his mathematical studies more particularly that Cooke
acquired that habit of thinking clearly and reasoning closely which
distinguished him through life. To his academic training I attribute
also much of that power of stating his thoughts clearly and forcibly,
which made him one of the best teachers of his time. No matter
what objection a purely literary person may be moved to urge against
the use of the word " scholarship " as here applied, or what criticisms
may occur to any one as to the style or manner of the man, it will
still remain true that Professor Cooke's knowledge was ample and
assured. In many respects it was profound ! His reasoning was
always cogent and his language plain.

I remember well the very favorable impression made by an address
which he delivered at the opening of the Harvard Medical School?
immediately after his appointment to a chair at that institution.
There had been murmurings in the land that one so young and so
inexperienced should have received the appointment. But they were
silenced then and there, absolutely and forever.

There is, indeed, a certain note of distinction in many of Cooke's
writiuiTS, such as is all too rare in scientific literature. Several of his
memoirs might well be set before the laboratory student as models of
clear presentation of a subject, in the same sense that, at an earlier
time, we turned for such illustration to the writings of Gay-Lussac
and Thenard, of Dumas, Boussingault, and Berzelius.

On looking beyond this immediate locality or centre, it will be seen
that there have been thus far, here in America, four great chemical
teachers ; the elder Silliman, Hare at Philadelphia, Draper in New
York, and Cooke at Cambridge ; and of these four Cooke undoubt-
edly deserves to be placed first and foremost, in view of the fact that
working and teaching chemists, trained by him, are scattered through-
out the land. Were it not for this circumstance, it might perhaps
justly be claimed that Draper's name should take precedence, because

VOL. XXX. (n. S. XXII.) 34

530 PROCEEDINGS OF THE AMERICAN ACADEMY

of the great influeuce he exerted duriug many years as a lecturer, a
writer, and an investigator.

After all has been said, however, as to talent innate, power inherited,
or wisdom acquired, it must still be remembered of our lamented
President that he ranked higher than most men, because of the indis-
putable fact, that occasionally — at not infrequent times and seasons —
his mind was illumined by divine sparks and flashes of genius.

ADDRESS OF CHARLES WILLIAM ELIOT.

Last spring an inquirer into the Department of Chemistry and
Mineralogy in Harvard University would have found a building called
Boylston Hall, one hundred and twenty feet by seventy, and three
stories in height, completely occupied with the laboratories, store-
rooms, and lecture-rooms for Chemistry, and a large section of the
University Museum devoted to mineralogical collections and labor-
atories. Turning to the College Catalogue he would have found a
series of elective courses in Chemistry, beginning with General Chem-
istry and Elementary Mineralogy, and rising through Qualitative
Analysis, Quantitative Analysis, Organic Chemistry, Crystallography
and the Physics of Crystals, Chemical Physics, and the Philosophy
of Chemistry, to original investigation in various branches of both
Inorganic and Organic Chemistry. Last year there were three hun-
dred and fifteen choices of these courses made by graduate and under-
graduate students ; so that this number of places had to be provided
in the laboratories of the department. The inquirer would also have
seen large illustrative collections of apparatus, chemicals, and min-
erals, — and particularly the mineral collection would have struck him
as extensive, well selected, and valuable. He would have found as
teachers in the department three full professors, three instructors, and
eight assistants. This elaborate and well equipped department of
instruction has grown up in the course of forty-four years under the
direction. of one man, Josiah Parsons Cooke. I shall endeavor to
show in some detail the strenuous, persevering, and well-directed
labor by which Professor Cooke developed this admirable instrument
of instruction and research. I might simply say in eleven words, —
Professor Cooke created the Chemical and Mineralogical Department
of Harvard University; but I should like to put before you some
faint picture of the intelligence, energy, persistence, and enthusiasm
which went into the accomplishment of that task. Mr. Cooke took
the degree of Bachelor of Arts in 1848, but when he was an under-

OP ARTS AND SCIENCES. 531

graduate at Harvard no Chemistry was taught there. I have often
heard him say that he got his best guidance and iucitement towards
chemical study from the lectures of Professor Benjamin Silliman, the
elder, before the Lowell Institute, in the early days of that invalu-
able institution. Although he had never received any systematic
instruction in either Chemistry or Mineralogy, Mr. Cooke had ac-
quired a considerable knowledge of the elements of both these subjects
by 1849, and what is more, he had determined to be a teacher and a
man of science. On the 3d of July, 1849, he was appointed Tutor in
Mathematics in Harvard College, at the usual salary of |G45 a year.
Such an appointment seems almost incredible to the present genera-
tion, for he cannot be said to have received any professional training
in Mathematics. In his view it merely offered an entrance into the
Faculty of Harvard College.

On the 24th of November following, " Mr. Tutor Cooke was ap-
pointed (by the Corporation) to teach Chemistry to the Freshman
Class next term. For this service, and for the apparatus and mate-
rials he may use, Mr. Cooke shall be paid $225." Such was the vote
of the Corporation. The edge of the wedge was very thin ; but it
made a sufficient entrance. At the same meeting the Corporation
voted, " As instruction in Chemistry for the undergraduates is no
longer to be required of the Erving Professor (J. W. Webster),
Voted,lLha.t for the rest of his services his salary be $1,000." Pro-
fessor Webster's salary from the College (he was Professor also in
the Medical School) had previously been |1,200. The Corporation
had therefore taken $200 from his salary and given it to Mr. Cooke.
It was an extraordinary coincidence that on the day before this
ominous vote was passed Dr. Webster had killed Dr. Parkman ; and
on the 30th of November he was arrested for the crime. . . . During
the ensuing term Mr. Cooke gave lectures to the Freshman Class,
and held recitations ; and then and there I, for one, first learned what
Chemistry was about, and what was the scientific method in observing
and reasoning.

On the 25th of May, 1850, the Corporation voted, "That Mr.
Tutor Cooke, for the ensuing academic year, teach Mathematics to
the Freshman Class, and Chemistry to the Sophomore and Freshman
Classes, and Mineralogy to the Seniors, and that his salary shall be
$1,000, he providing at his own charge the consumable materials
necessary in performing chemical experiments." The frugality and
prudence of the Corporation appear in these money votes. They had
no idea of taking any great risk on the cost of illustrative materials ;

532 PROCEEDINGS OF THE AMERICAN ACADEMY

but Mr. Cooke was fortunately indifferent on that subject. He had
resources which enabled him to provide all necessary furniture, appar-
atus, and materials ; and he used these resources with liberal good
sense. He got possession in this first year of the lower northern lec-
ture room in University Hall, and of a room about twenty by twenty-
five feet in area in the northwestern corner of the basement of the
same hall. There he fitted up the only chemical laboratory on the
premises of Harvard College. There was already a good laboratory
across Kirkland Street, in the new building of the Lawrence Scientific
School ; but with that the College had nothing to do. There was neither
gas nor running water in University Hall, and Mr. Cooke's nearest
neighbor on the adjoining corner of the basement was a baker's oven,
where considerable batches of bread were baked every morning and
every evening, and yeast was sold every afternoon. A pump in the
cellar yielded water for both bakery and laboratory, and within fifty
feet of the pump was a privy which served for the whole College.

On the 10th of July, 1850, Professor Webster's resignation was
accepted. The young tutor had completed his plans for the ensuing
year ; but, for some reason which cannot now be determined, he pro-
cured a vote of the Corporation to settle one part of his plan. On
the 31st of August, 1850, the President and Fellows voted, "That
Stockhardt's Principles of Chemistry be adopted as a text-book, in the
College." I know of no other instance within the last fifty years in
which the President and Fellows have passed a vote concerning the
adoption of a text-book.

On the 30th of December, 1850, Mr. Cooke was elected Erving
Professor of Chemistry and Mineralogy, at the age of twenty-three.
He had already demonstrated to the satisfaction of the Corporation
that he was an efficient and prudent manager in business details, an
interesting lecturer, and a zealous and singleminded College official.
His salary was fixed at $1,200, " he paying all the expenses of his
lectures, excepting that of fuel in Cambridge, the salary to commence
on the first of March next." Again, a frugal arrangement which did
not in the least discourage the youthful professor.

The vote describing his duties is an interesting one, for it illustrates
the extraordinary expectation which it was then held reasonable to
entertain concerning the teaching capacities of a youth of twenty-
three : —

" Voted, that he shall reside in Cambridge, and be a member of
the College Faculty, and that he shall give the lectures in the Medi-
cal College in Boston, and all the instruction required in Chemistry,

OF ARTS AND SCIENCES. 533

Mineralogy, and Geology to the undergraduates, and perform such
other duties as may from time to time be assigned him by the Cor-
poration not inconsistent with the duties of the office."

Professor Cooke immediately resigned his Tutorship in Mathemat-
ics. He had now obtained the firm position from which he proposed
to carry on the long campaign for the introduction of Chemistry and
Mineralogy into the teaching of Harvard College. He held a per-
manent professorship ; he was a member of the College Faculty,
which - his predecessor had never been, and he had established a
small chemical laboratory in the middle of the College Yard. He
prevailed on the Faculty to announce Chemistry for Freshmen in the
second term of the year 1850-51, and Chemistry for Sophomores in
the first term of the year 1851-52; also lectures on Mineralogy to
Seniors in the first term of 1851-52. The introduction of these new
subjects into a prescribed curriculum, which was already overloaded,
is a subject for wonder and admiration. The present generation of
teachers finds it hard enough to get new elective courses announced ;
but Professor Cooke successfully invaded a prescribed course in which
the traditional subjects had long been securely intrenched.

In the second story of Harvard Hall was a large, miscellaneous, and
unassorted collection of minerals and fossils, with some curiosities,
which had been accumulating for years, but had received little care.
Within a few months of his appointment as professor, Mr. Cooke
made a survey of this inchoate collection. His knowledge of minerals
was mathematical and physical rather than chemical, and he had no
considerable experience in recognizing and determining them. He
did not feel competent, without assistance, to sort the collection, and
decide what to keep and what to throw away. He feared lest,
through ignorance, he might reject valuable specimens ; yet the sort-
ing of the collection was obviously the first thing to be done. Under
these circumstances he did a conscientious and coura2;eous thing which,
in my judgment, very few persons in his situation would have done.
He employed Professor Benjamin Silliman, Jr., of Yale College, to
sort the collection, and advise him what to keep and what to throw
away. Professor Silliman performed this task with prormptness and
discretion, and the specimens then selected for preservation, — which
naturally represented in the main the commoner species — constituted
the skeleton, as it were, of the rich and ample collection of to-day.
Out of this intercourse between Professor Silliman and Professor
Cooke there grew a life-long friendship. The collection remained in
Harvard Hall for eight years, being enlarged every year by Professor
Cooke's constant activity in buying and collecting.

534 PROCEEDINGS OF THE AMERICAN ACADEMY

The Corporation soon found that it was difficult to resist the fre-
quent demands of the young Professor. On the 25th of January,
1851, they granted "$200 to Professor Cooke for purchasing
chemical apparatus for the laboratory at Cambridge for the use of the
undergraduates." Observe the phrase, " the laboratory at Cambridge."
It was still that little room in the basement of University Hall. Oq
November 8th, 1851, by vote of the Corporation, Professor Cooke
was " made a member of the Faculty of the Scientific School to teach
Mineralogy to such students as may desire his instruction." His
membershijj of the Scientific Faculty was always for Professor Cooke
rather a security against the invasion of his precincts, than a means of
prosecuting any aggressive campaign on his own part. For ten years
there stood a notice in the Catalogue under the head of the Lawrence
Scientific School to the effect that Professor Cooke would receive
students in Mineralogy at his laboratory during the second term.
Then for ten years more an enlarged notice under the same head
invited scientific students to attend the course in Crystallography and
Mineralogy which he was really providing for College students. In
1871-72, when the Scientific School was reorganized, all special men-
tion of these opportunities was withdrawn.

The- very next month — that is, in December, 1851 — the Cor-
poration received a communication from the Serving Professor,
" respecting the accommodation at present afforded for the chemi-
cal apparatus of the College." This communication was referred
to President Sparks and Dr. Walker, two firm friends of Pro-
fessor Cooke. The result was that he got possession of a room
on the first floor of University Hall adjoining his lecture-room ;
and this room he immediately fitted up at his own expense with
counters and other conveniences. He also got rid of the baker
and occupied his quarters. On the 31st of January, 1852, the
" Treasurer was authorized to discharge the account of Professor
Cooke for apparatus in Chemistry and Geology procured by him in
Europe for a sum not exceeding $150, in addition to the appropria-
tion heretofore made for that purpose." In the following month they
voted " that the Treasurer be authorized to expend a sum not exceed-
ing $120, for the fitting up of the Eumford apparatus room." This
was the room of which Professor Cooke had just got possession. In
the mean time Professor Cooke had persuaded the Faculty to permit
him to give lectures on Mineralogy to Juniors in the second term, and
a course of lectures on Chemistry to Sophomores in the first term, —
these in addition to the recitations in Stockhardt's Chemistry in the

OF ARTS AND SCIENCES. 535

second term for Freshmen, and in the first term for Sophomores.
This was no inconsiderable amount of teaching for an inexperienced
young man who had on his hands also the giving of a course ot lec-
tures at the Medical School in Boston, from the 1st of November to
the 1st of March. At the building in North Grove Street, where he
found plenty of space, and very little else, Professor Cooke fitted up
ail excellent laboratory for lecture purposes and for research. The
Medical Class was turbulent, and always contained a considerable
proportion of rough, uneducated young men ; but the young professor
made his lectures so interesting by carefully prepared experiments,
that he rarely had trouble with his boisterous auditors. To the
methods and policy of the Medical Faculty, on the other hand, he
soon began to manifest a dislike, which before long became acute.

On the 26th of June, 18.'>2, the President and Fellows passed
a vote making " an annual grant of $200, half for minerals
and half for chemical apparatus, to be disbursed under the direc-
tion of the Erving Professor, who will account for the same at
the end of each academic year." That vote remains in force to this
day ; but the annual grant has risen from $200 a year to $800. It
gave Professor Cooke something on which he could depend every
year for the increase of apparatus and of the mineral collection.

In the following November, the Treasurer of the College laid be-
fore the Corporation " a catalogue of the Rumford and other appara-
tus belonging to the College, in charge of the Erving Professor of
Chemistry, which had been examined and verified by him and found
to be in good order." In less than two years Professor Cooke es-
tablished his reputation with the Corporation as a trustworthy custo-
dian of apparatus and other College property. This reputation stood
him in good stead throuo-hout his career. He had also secured labo-
ratories both in Cambridge and Boston, procured considerable quanti-
ties of fittings and apparatus, and pushed his subjects into the
prescribed curriculum of the College.

Let us turn now to consider what he did next in the Faculty. In
1852-53, he introduced a course of lectures on Chemistry, twice a
week, for Seniors in the second term. He had already got access to
the Freshmen, Sophomores, and Juniors. In the following year he
gave up the Freshman Chemistry in the second term, in order to
occupy both terms of the Sophomore year. The Senior lectures on
Mineralogy disappeared, but instead, notice was given that Mineralogy
is taught to those who desire to learn it by Professor Cooke. Con-
sidering that not a particle of Chemistry was taught to undergradu-

536 PROCEEDINGS OP THE AMERICAN ACADEMY

ates, in 1850, he had certainly obtained a good position for his sub-
jects in the College course by 1853. At the beginning of the
medical term in the autumn of 1853, he was ready to receive a
small number of medical students into his Boston laboratory, to pur-
sue the subject of qualitative analysis, and James C. White, subse-
quently adjunct Professor of Chemistiy in the Medical School, was a
member of this first class. It is believed that this was the begin-
ning in the United States of laboratory instruction in Chemistry for
medical students.

On the 23d of May, 1855, comes the first application of a method
which Professor Cooke afterward used often. The Corporation
voted, " That $500 be appropriated to supply deficiencies in the
cabinet of minerals, to be expended under the direction ' of Professor
Cooke, provided that the additional sum of $500 be raised by private
subscription for the same purpose." Nearly a year later Professor
Cooke informs the Corporation that $1470 (subsequently increased
to $1720) have been contributed by persons whose names are sub-
joined for the increase of the mineral cabinet, and he thereupon pro-
poses that he have leave of absence for the summer term of 1857 to
make purchases in Europe. In every summer vacation, and in some
of the long winter vacations of that period. Professor Cooke travelled
in search of minerals ; and for a period of six years I frequently ac-
companied him. I was the first student whom he admitted to the lit-
tle laboratory in the basement of University Hall, and Professor
Frank H. Storer and I were his first assistants, both at the Cambridge
laboratory and at the laboratory in the Medical School. I therefore
have a vivid recollection of the humbleness of the beginnings of both
the Chemical and the Mineralogical departments ; of the elementary
quality of the instruction given ; and of the great disadvantages under
which all the instruction was given, without any possibility of offering
laboratory practice to the students, except as a favor which could be
granted only to very few ; but I also have a clear vision of the indom-
itable industry, perseverance, and mental activity of the young Pro-
fessor. He threw himself body and soul into his work, and wanted
neither recreation nor leisure, neither ease nor pleasure, but only
work which would tell for the advancement of his department and the
satisfaction of iiis worthy ambitions.

Early in 1856, he begau to revolve plans for building a Chemical
Laboratory at Cambridge ; but a suggestion made to him by Mr.
John Eliot Thayer turned his attention to the Boylston Fund (then
amounting to nearly $23,000), which was held by the Corporation

OP ARTS AND SCIENCES. 537

for the purpose of ultimately building an Anatomical Museum and
Chemical Laboratory. This fund was to accumulate until it reached
the sum of ^35,000 ; but Mr. Thayer suggested that the fund be tilled
up by private subscription and the building contemplated by Mr.
Boylston be at once erected. Accordingly, on the 30th of August,
1856, we find this entry in the records of the President and Fellows :
" A letter from Professor Cooke having been read, the President,
Treasurer, and Dr. Hayward were appointed a Committee to confer
with Professors Wyman and Cooke on the subject of an Anatomical
Museum and Chemical Laboratory." This project being made known
abroad, a storm arose in the Medical Faculty, who feared the com-
petition of the proposed Cambridge establishment. On the loth of
September following " a memorial from the Medical Faculty on the
subject of certain proposed subscriptions was read and referred to the
same Committee to which the letter of Professor Cooke was referred
at the last meeting of this Board."

At a meeting of the President and Fellows on September 27th,
" on application of Mr. Cooke, Erving Professor of Chemistry and
Mineralogy, voted, that the Erving Professor be released from the
duty of delivering lectures at the Medical College in Boston." There-
upon Professor Cooke caused all the excellent fixtures and furniture
which he had provided in the building on North Grove Street to be
torn out, and removed with all his apparatus to Cambridge. This
vigorous procedure occurred shortly before the opening of the medi-
cal course of lectures, and threatened grave inconvenience to the
Medical Faculty. At the same time, Professor Morrill Wyman
resigned as a member of the Medical Faculty, because he was charged
with disloyalty to the Medical Faculty in promoting the building of
Boylston Hall. Altogether, the conflict waxed so warm, that Pro-
fessor Cooke proposed an adjustment, which was carried into effect.
By his advice I gave the first half of the course of chemical lectures
at the Medical School, and Professor Cooke lent me, as his friend,
all the apparatus and supplies necessary for the purpose. This sud-
den and unexpected disturbance led to two good results. It freed
Professor Cooke from distracting and uncongenial labors at the
Medical College ; and it caused the appointment of a separate Pro-
fessor of Chemistry for the Medical School, the first incumbent of
that professorship being the excellent Dr. John Bacon, who began
his labors in January, 1857. Thereafter, Professor Cooke was
entirely free to devote himself to the interests of his departments at
Cambridge.

VOL. XXX. (n. 8. XXII.) 37

538 PROCEEDINGS OF THE AMERICAN ACADEMY

In 1856 — the year now under consideration — Professor Cooke
obtained from the College Faculty a really extraordinary concession
for the ensuing academic year. He succeeded in introducing into the
Junior year a required course on Molecular Physics, the text-book
being the first volume of Graham's Elements of Chemistry. When
one remembers that the traditional subjects filled well the jirescribed
curriculum, it is a marvel that a wholly new subject should have been
inserted into the Junior year. Two years later the text-book for
Molecular Physics became Cooke's Chemical Physics, — a work which
showed the natural leaning of his mind to Physics rather than to
Chemistry, and which also showed what importance he attached to
exactness and thorough drill in undergraduate work. The book was
intended to be used with numerous problems of an arithmetical or
algebraic sort. The same year which saw the introduction of the
Chemical Physics, namely, 1858-59, saw also an additional chemical
elective for Juniors, — in the first term, Crystallography, and in the
second term Analytical Chemistry and Dana's Mineralogy, — but in
the meantime Boylston Hall had been built.

I must turn back for a moment to the year 1856. On the 25th
of October, 1856, the Corporation voted, " That the President, Dr.
Hay ward, and Mr. Lowell, be a Committee to consider and report
upon a plan and location for a building for the Anatomical Museum
and Chemical Laboratory," and three months later it was voted
" That the Committee on the new Anatomical Museum and Labora-
tory be authorized to make contracts for the erection of the same
whenever the subscriptions for the increase of the Boylston Fund
shall amount to $17,000." At the same meeting, "it appearing to
this Board that in the new distribution of studies for the present year
the proportion assigned to the Erving Professor of Chemistry and
Mineralogy has been largely increased, so that the work now required
of him equals the average of what is required of the other Professors,
therefore, Voted^ That the salary of the Erving Professor of Chemistry
and Mineralogy be raised to $2,200, until further order of this Board."
This vote, passed only seven years after the election of Mr. Cooke as
Erving Professor, established him on terms of perfect equality with
the Professors of the traditional subjects in Harvard College ; and he
was now only thirty years of age.

By the 31st of January, 1857, the necessary supplement to th*e
Boylston Fund had been raised and the contract made for the erection
of the building. On the 20th of May following. Professor Cooke
reported to the Corporation on the inception and completion of this

OF ARTS AND SCIENCES. 639

undertaking. The sum raised was $14,000. Thereupon it was voted,
" That the Corporation avail themselves of this opportunity to express
their sense of the efficiency and public spirit of Professor Cooke in
obtaining the above mentioned subscriptions, and of his devotion to
science and to his own department of instruction in the University, as
manifested in his willingness to commence this movement, and in the
unwearied efforts by which he has brought it to a successful issue."
Long before the building was finished, — namely, on the 29th of
Au<mst, 1857, " Mr. Lowell laid before the meeting a communication
from Professor Cooke in regard to the necessary furniture for the
new Anatomical Museum and Chemical Laboratory," whereupon it
was voted " That the Building Committee be authorized to contract
for the necessary furniture not exceeding the sum of $2,000," On
the 1st of January following, the " Building Committee was authorized
to pay a further sum, not exceeding $2,108, for altering, finishing,
and fitting up the new Museum and Laboratory."

All this time Professor Cooke had had no visible assistance in the
conduct of his department. He had himself paid for the services of
Francis P. Clary, for many years his only assistant at his lectures,
and he had received some volunteered assistance from students. In
February, 1858, Charles W. Eliot, Tutor in Mathematics, was elected
Assistant Professor in Mathematics and Chemistry, " to give such
assistant instruction in the Department of Chemistry as may be
agreed upon in the distribution of studies by the Faculty." The
duties of this officer continued, however, to be chiefly mathematical,
and it was not till January 26, 1861, that the Corporation voted,
" That the duties of Mr. Charles W. Eliot be limited to the Chemical
Department, and that he be designated accordingly."

On the 26th of June, 1858, a committee of the Corporation having
reported that Professor Cooke had given furnaces, counters, and cases
which originally belonged to him, and that part of the apparatus still
belonged to him, it was voted, " That the President be requested to
write a suitable letter of acknowledgment to Professor Cooke for his
liberal contributions towards the erection and furnishing of Boylston
Hall, and for his zeal and unremitting attention in overseeing the
progress and successful accomplishment of the whole work." There
are at this moment in Boylston Hall wooden counters and hoods with
cast-iron sashes which Professor Cooke caused to be made forty-three
years ago for the Laboratory which he first fitted up in the Medical
College on North Grove Street. Boylston Hall was originally two
stories high, and the western end was devoted to the Anatomical

540 PROCEEDINGS OP THE AMERICAN ACADEMY

Department, in charge of Professor Jeffries Wyman. About two
thirds of the building, however, were devoted to the Chemical
Department.

In 1858-59 the first laboratory instruction in Chemistry open to
Harvard undergraduates, was given in Boylston Hall, and in that
first class I find the following names, now well known in this
community : —

James A. Rumrill,
William Everett,
William R. Huntington,
S. W. Langmaid,
John Homans, Jr.,
Henry P. Walcott, and
Louis Cabot.

The number of students in this first class was twenty-three, part of
them graduates.

On the completion of Boylston Hall, the Mineral Cabinet was
moved into it, so that all Professor Cooke's interests were concen-
trated in that building. The completion of Boylston Hall made it
possible for Professor Cooke to teach mainly by the laboratory
method; but recitations and problem work, not accompanied by
laboratory practice, lingered, nevertheless, for seventeen years ;
although only in required courses. There was a required course in
the Junior year down to 1867-68, and in the Sophomore year down
to 1872-73. The required work was then moved into the second term
of the Freshman year, whence it disappeared in 1875-76, a brilliantly
illustrated course of lectures, always given by Professor Cooke, being
thereafter the sole remnant of required work in Chemistry. The
expansion of the elective work after the completion of Boylston Hall
went on as follows : In 1868-69 a Senior elective appears, which was
devoted in the first term to Crystallography and the Physics of Crys-
tals, and in the second term to Mineralogy and the Determination of
Minerals. In the year 1871-72 there are electives in Chemistry for
the Sophomore, Junior, and Senior years, and Organic Chemistry ap-
pears in the Senior electives. In 1873-74 the electives are: —

1. Descriptive Chemistry.

2. Qualitative Analysis.

3. Mineralogy.

4. Quantitative Analysis.

5. Organic Chemistry.

OF ARTS AND SCIENCES. 541

In 1876-77, two new electives were added, — namely, an advanced
coui-se in Inorganic Chemistry, and a course in Crystallography and
the Physics of Crystals, the second of these subjects having appeared
for the first time as a half course in 1868-69. In 1886-87 the ad-
vanced course in Inorganic Chemistry was more completely defined
as including Molecular Weights and Volumes, Thermo-Chemistryy
and Specific Refractive Power. This course, thus introduced by
Professor Cooke, has to-day a growing importance. In 1892-93, at
the age of sixty-five, Professor Cooke undertook a new elective
course in Chemical Philosophy and the History of Chemistry. This
was the last addition he made to the series of elective courses he had
successively introduced, the greater part of which he had delivered
over into the hands of younger men. "We cannot too much admire
the intellectual vitality which enabled him to keep in the van of the
onward movement in an extensive department which he had himself
filled with younger teachers full of zeal and ambition.

The picture of Professor Cooke's influence at the head of the
Chemical Department down to 1880, would be incomplete without an
enumeration of the names of the young men who served as his labora-
tory assistants during the first thirty years that he held the professor-
ship. Three of these gentlemen died young ; but the following
survive : —

Professor Frank H. Storer,
President Charles W. Eliot,

Professor William H. Pettee, of the University of Michigan,
Professor Charles L. Jackson,
Professor Henry B. Hill,

Professor Charles E. Munroe, of Washington,
Professor William Elder, of Waterville,
Professor Frank A. Gooch, of Yale University,
Professor M. E. Wads worth. Head of the Michigan Mining School,
Professor Charles F. Mabery, Professor in the Case School of Ap-
plied Science of Cleveland ;

and four gentlemen who have all been devoted to technical Chemistry,
— namely, Messrs. Charles S. Homer, William D. Philbrick, John
F. White, and Harry Blake Hodges- All these gentlemen wei-e em-
phatically Professor Cooke's assistants. A large number of younger
men have been trained as assistants in Boylston Hall during the last
fourteen years ; but many of them were brought into little immediate
contact with Professor Cooke, because they served in laboratories

542 PROCEEDINGS OP THE AMERICAN ACADEMY

which were chiefly directed by other Professors. Of late years he
used to complain that there were assistants in Boylston Hall whose
names he did not know, — an inevitable but unwelcome result of the
growth of the establishment.

The growth of the College and the increased teaching of Chemistry
by the laboratory method, made it necessary in 1871 to enlarge
Boylston Hall. This was done by adding a roof story, at a cost of
$13,500, of which sum Professor Cooke contributed $1,000 and his
father $500. Professor Cooke also devised all the improvements
himself, and zealously superintended their execution. For the uses
of the Chemical Department, two thirds of the roof story were avail-
able ; the trustees of the Peabody Museum hired the remaining third.
This enlargement of Bolyston Hall made it possible to carry all the
chemical teaching at Cambridge to that building, and, therefore, to
close the Chemical Laboratory in the Lawrence Scientific School.
This change was in part an economical measure, but was due, also, to
the desire of the Corporation to use Count Rumford's gift for teaching
the subjects of light and heat, and to make the Rumford Professor-
ship again a College professorship. The consolidation was naturally
a great satisfaction to Professor Cooke, and it was certainly an im-
portant step in the development, not only of the Chemical Depart-
ment, but of the Department of Physics as well.

After the lamented death of Professor Jeffries Wyman in 1874,
Professor Cooke began the process of acquiring for Chemistry the
whole of Boylston Hall. The rooms on the lower story of Boylston
Hall, which had formerly been used by Professor Wyman, wei'e fitted
up for a laboratory of Organic Chemistry. In the summer of 1877
the Peabody Collection was moved from Boylston Hall to the new
building erected by the trustees; and thereupon the two large and hand-
some rooms on the western side of Boylston Hall were appropriated to
the Mineral Cabinet, which had long outgrown its narrow quarters.
The rearrangement of this collection made manifest the results of
Professor Cooke's well directed and unremitting exertions for twenty-
six years. The collection had become not only an effective instrument
of instruction, but a beautiful and impressive representation of the
mineral kingdom, unusually complete, and of large money value.
From this date Professor Cooke had possession of the whole of
Boylston Hall, except that a lecture room on the western end was
still used for miscellaneous purposes. In 1887 this lecture room was
converted into a laboratory for elementary experimental Chemistry, —
again both planning and executing being Professor Cooke's. His

OF ARTS AND SCIENCES. 543

occupation of the hall thus became complete, twenty-nine years from
the date of its erection.

One year later, Professor Cooke entered on his last undertaking
for the enlargement of his domain. He began to make plans and
solicit subscriptions for a section of the University Museum on Oxford
Street to be devoted to Mineralogy. His primary object was to ob-
tain more space for the exhibition of minerals, and a new laboratory
of Mineralogy ; but a secondary object was to remove this valuable
collection from a building which was not fireproof, and which was sub-
ject to the risks of chemical experimentation. His efforts were soon
crowned with success ; and in 1889-90 a section of the Museum de-
voted to Mineralogy, with a floor area of 13,200 feet, was finished at
a cost of $35,000. This area provided not only an exhibition room,
but a lecture room, laboratory, and store-rooms. The Mineral Cabinet
having been removed from Boylston Hall, it became possible to pro-
vide in that building a large laboratory for Organic Chemistry, and a
new lecture room seating five hundred students. These changes were
made at the cost of the Corporation in 1891, Professor Cooke actively
superintending them in all their details.

When a man has started early in enthusiastic pursuit of a worthy
object, and has vigorously pursued it through all his active life, it is a
sincere satisfaction to all who have observed him, and particularly to
all who have been at any time his comrades or followers in the pur-
suit, to see him, before death comes, reach his goal. Professor Cooke
attained and gave this happiness. He himself saw his beloved science
taught in the only way he thought wise and effectual, and raised in
academic standing to an equal level with the oldest and most valued
subjects used in education. He saw large laboratories and lecture
rooms, which he had himself planned and built, filled with eager
students. And finally he saw the mineral collection, which had been his
care and delight for forty-four years, safely and handsomely established
in the principal University Museum. Few men see so many of their
objects attained, so many of their hopes fulfilled. He had other
sources of profound satisfaction, some of which have been already
pointed out to-night ; it was my part to describe his remarkable and
enduring administrative achievements as Erving Professor of Chem-
istry and Mineralogy in Harvard College.

544 PEOCEEDINGS OF THE AMERICAN ACADEMY

A LIST OF THE MORE IMPORTANT PUBLICATIONS OF
JOSIAH PARSONS COOKE.

Books.

1857. Chemical Problems and Reactions.

1860. Elements of Chemical Physics. New editions in 1866 and 1877.

1864. Religion and Chemistry or Proofs of God's Plan in the Atmos-
phere and its Elements. New edition in 1880.

1868. Principles of Chemical Philosophy. New editions in 1870, 1875,
and revised edition in 1881.

1874. The New Chemistry. New editions in 1876, 1877, 1884 and 1888.
Also translations in many languages.

1881. Scientific Culture and Other Essays.

1888. The Credentials of Science the Warrant of Faith. New edition
1893.

1891. Laboratory Practice. A Series of Experiments on the Funda-
mental Principles of Chemistrj-.

Papers on his Original Investigations.^

1852. Descri]3tion of a Crystal of Rhombic Arsenic. These Proceedings,

III. 86.
1852. Octahedral Crystals of Arsenic. These Proceedings, III. 204.
1854. The Relation between the Atomic Weights. Mem. Am. Acad.,

New Series, V. Am. J. Sci., [2.], XVIL 387.
1854. On two new Crystalline Compounds of Zinc and Antimony. Am.

J. Sci., [2.], XVIIL 229.

1854. On a new Filtering Apparatus. Am. J. Sci., [2.], XVIIL 127.

1855. On the Law of Definite Proportions in the Compounds of Zinc

and Antimony. Am. J. Sci., [2.], XX. 222.

1860. Crystalline Form not necessarily an Indication of Definite Chemi-

cal Composition. Am. J. Sci., [2.], XXX. 194. Phil. Mag., XIX.
405.

1861. On the Dimorphism of Arsenic, Antimony, and Zinc. Am. J.

Sci., [2.], XXXI. 191.

1862. On the Spectroscope. Am. J. Sci., [2.], XXXIV. 299.

1863. On the Cleavage of Galena. Am. J. Sci., [2.1, XXXV. 126.
1863. An Improved Spectroscope. Am. J. Sci., [2.], XXXVI. 266.

1863. Crystal] ographic Examination of Childrenite. Am. J. Sci., [2.],

XXXVI. 2.57.

1864. Crystallographic Examination of the Acid Tartrates of Caesia

and Rubidia. Am. J. Sci., [2.], XXXVII. 70.

1 Prepared by T. W. Richards.

OF ARTS AND SCIENCES. 545

1865. On a Spectroscope with many Prisms. Am. J. Sci., [2.], XL.
305.

1865. On the Projection of the Spectra of the Metals. Am. J. Sci., [2.],

XL. 243.

1866. On the Aqueous Lines of the Solar Spectrum. Am. J. Sci., [2.],

XLL 17.
1866. Separation of Iron and Alumina. Am. J. Sci., [2.], XLII. 78.

1866. Analysis of Danalite of Rockport. Am. J. Sci., [2.], XLII. 73.

1867. On Cryophyllite. Am. J. Sci., [2.], XLIII. 217.

1867. On Certain Lecture Experiments. Am. J. Sci., [2.], XLIV.

189.
1867. Crystallographic Examination of some American Chlorites. Am.

J. Sci., [2.], XLIV. 201.
1867. A Method of Determining the Protoxyd of Iron in Silicates not

Soluble in the Ordinary Mineral Acids. Am. J. Sci., [2.],

XLIV., 347.
1869. Atomic Pvatio. Am. J. Sci., [2.], XLVIL, 386.

1874. The Vermiculites. These Proceedings, IX. 35.

1875. Melanosiderite. These Proceedings, X. 451.

1875, On two new Varieties of Vermiculites. With F. A. Gooch. These

Proceedings, X. 453.

1876. On a new Mode of Manipulating Hydric Sulphide. These Pro-

ceedings, XIL 113.

1876. On the Process of Reverse Filtering. These Proceedings, XIL

124.

1877. Revision of the Atomic Weights of Antimony. These Proceed-

ings, XIII. 1.
1877. Re-examination of Some of the Haloid Compounds of Antimony.
These Proceedings, XIII. 72.

1879. The Atomic Weight of Antimony. These Proceedings, XV. 251.

1880. On Argento-antimonious Tartrate. These Proceedings, XIX.

393.

1880. On the Oxidation of Hydrochloric Acid Solutions of Antimony in

the Atmosphere. Am. J. Sci., [3.], XIX. 464.

1881. On the Solubility of Chloride of Silver in Water. Am. J. Sci.,

[3.]. XXI. 220.
1881. Additional Experiments on the Atomic Weight of Antimony.

These Proceedings, XVII. 1.
1881. The Boiling Point of Iodide of Antimony and a new Form of Air

Thermometer. These Proceedings, XVII. 22.
1883. A Simple Method for Correcting the Weight of a Body for the

Buoyancy of the Atmosphere when the Volume is Unknown.

Am. J. Sci., [3.], XXVI. 38.
1883. Possible Variability of the Law of Definite Proportions. Am.

J. Sci., [3.], XXVI. 310.

VOL. XXX. (n. s.) xxii. 35

546 PROCEEDINGS OF THE AMERICAN ACADEMY

1887. The Relative "Values of the Atomic Weights of Oxygen and

Hydrogen. With T. W. Richards. These Proceedings, XXIII.
149.

1888. Additional Note on the Relative Values of the Atomic Weights of

Oxygen and Hydrogen. With T. W. Richards. These Pro-
ceedings, XXIII. 182.

1889. On a New Method of Determining Gas- densities. These Pro-

ceedings, XXIV. 202.

Papers on Other Subjects.

1862. Review of Trollope's North America. No. Am. Rev., XCV. 416.
1865. On the Heat of Friction. These Proceedings, VI.
1871. Memoir of Thomas Graham. Am. J. Sci.

1871. Absolute System of Electrical Measurements. Collected Papers
from Journal of Franklin Institute.

1874, The Nobility of Knowledge. An Address delivered before the

Free Institute of Worcester. Pop. Sci. ISIonth., V. 610.

1875. Scientific Culture. Pop. Sci. jNIonth., VII. 511.
1875. "Gas." Johnson's Cyclopaedia.

1875. "Molecules." American Cyclopaedia.

1877. Chemical and Physical Researches by Thomas Graham. Am. J.

Sci,, [2.], XIV. 152.

1878. The Radiometer : a Fresh Evidence of a Molecular Universe.

Pop. Sci. Month., XIII. 1. Also Am. J. Sci., [3.], XIV. 231.
1878. Chemical Philosophy. Am, J. Sci., [3.], XV. 211.
1880. In Memoriam Josiah Parsons Cooke.

1880. Notice of Berthelot's Thermo-Chemistry. Am. J. Sci., [3. J, XIX.

261.

1881. Memoir of William Hallowes Miller. These Proceedings, XVI.

461.
1881. Notice of the Investigation of Dr. J. W. Briihl on the Relations

between Molecular Structure of Organic Compounds and their

Refractive Power. Am. J. Sci., [3.], XXI. 70.
1881. Notice of Julius Thomsen's Thermo-chemical Investigation of the
Molecular Structure of Hydrocarbon Compounds. Am. J. Sci.,

[3.], XXI. 88.
1883. The Greek Question. Pop, Sci. INIonth., XXIV. 1.
1883. Memoir of John Bacon. These Proceedings, XVIII. 419.

1883. Memoir of William Barton Rogers. Ibid,, 428.

1884. Memoir of J. B. A. Dumas. These Proceedings, XIX. 545.
1884. Memoir of C. A. Wurtz. Ibid., 568.

1884. Further Remarks on the Greek Question. Pop. Sci. Month.
188.5. Memoir of Benjamin Sillinian. These Proceedings, XX. 523.
1886. Descriptive List of Experiments for Use in Chemistry B.

OP ARTS AND SCIENCES. 547

1886. The New Requisitions for Admission at Harvard College. Top.

Sci. Month., XXX. 195.
1889. The Chemical Elements. History of the Conception which this

Term involves. Pop. Sci. Month., XXXIV. 733.
1889. Address at the Commencement Dinner.

1889. Concluding Address to the Freshman Class of Harvard College.

1890. Report of the Director of the Chemical Laboratory of Harvard

College. Presented to the Visiting Committee of the Overseers.
1890. A Plea for Liberal Culture.
1892. The Value and Limitations of Laboratory Practice in a Scheme of

Liberal Education.
1892. Memoir of Joseph Lovering. These Proceedings, XXVII. 372.

Also many Reviews and Reports, including Annual Reports as
Director of the Chemical Laboratory during many years.

Eight hundred and seventy-first Meeting.

January 9, 1895. — Stated Meeting.

The President in the chair.

The election of two Vice-Presidents to fill the vacancies
occasioned by the amendment of the Statutes adopted on the
10th of October, 1894, resulted in the choice of

Benjamin A. Gould, Vice-President for Class I.
George L. Goodale, Vice-President for Class II.

The following gentlemen were elected members of the
Academy : —

Robert Tracy Jackson, of Boston, to be a Resident Fellow
in Class II., Section 1 (Geology, Mineralogy, and Physics
of the Globe).

John Eliot Wolff, of Cambridge, to be a Resident Fellow
in Class II., Section 1.

Samuel Fessenden Clarke, of Williamstown, to be a Resident
Fellow in Class II., Section 3 (Zoology and Physiology).
' William Thomas Councilman, of Boston, to be a Resident
Fellow in Class II., Section 3.

Charles Benedict Davenport, of Cambridge, to be a Resi-
dent Fellow in Class II., Section 3.

548 PROCEEDINGS OF THE AMERICAN ACADEMY

John Sterling Kingsley, of Somerville, to be a Resident
Fellow in Class II., Section 3.

George Howard Parker, of Cambridge, to be a Resident
Fellow in Class II., Section 3.

William McMichael Woodworth, of Cambridge, to be a
Resident Fellow in Class II., Section 3.

Charles L. Jackson proposed certain changes in the Stat-
utes. This subject w^as referred to a committee, consisting
of C. L. Jackson, A. Lowell, and F. H. Storer.

Henry P. Bowditch, Chairman of the Committee on the
Librar}^, read a statement in reference to the expenditures on
account of the library, during the last live years. After some
discussion, the matter was referred to a committee, consisting
of the Librarian, the Treasurer, and the Chairman of the Rum-
ford Committee, with instructions to consider the advisability
of appropriating a portion of the income of the Rumford
Fund toward defraying the expenses of the library.

On the motion of Charles S. Minot, it was

Voted, To refer the matter of expenditures both for Publi-
cations and for the Library to a committee, consisting of the
Committee of Publication and the Committee on the Library,
the chairman of this committee to be the Chairman of the
Committee of Publication.

Edward L. Mark alluded to the " List of serial Publications
taken in the Principal Libraries of Boston and Cambridge,"
published in 1878, and spoke of the need of a new and revised
edition of this list. After some discussion, it was

Voted, To call the attention of the Trustees of the Boston
Public Library to this matter.

Franklin B. Stephenson read a paper entitled, " Congenital
Spots on Annamites, a Means of Racial Identification."

The following papers were read by title : —

Studies on Morphogenesis, III. On the Acclimatization of
Organisms to High Temperatures. By Charles B. Davenport
and W. E. Castle.

On the Occlusion of Baric Chloride by Baric Sulphate. By
T. W. Richards and H. G. Parker.

OP ARTS AND SCIENCES. 549

Eight hundred and seventy-second Meeting.

February 13, 1895.

Vice-President B. A. Gould in the chair.

The chair announced the death of Arthur Cayley and of
Sir John R. Seeley, Foreign Honorary Members.

The Corresponding Secretary read the following letters :
from S. F. Clarke, of Willianistown, acknowledging his elec-
tion as Resident Fellow ; and from the National Society of
Horticulture of Paris, announcing the death of its Secretary,
Pierre Etienne Simon Duchartre. He also read an invitation
circular from the organizing committee of the Sixth Inter-
national Geographical Congress.

Edward Atkinson described the application of heat to the
process of cooking according to the principle of Count Rum-
ford, illustrated by demonstrations.

He also exhibited a specimen of calcium carbide (CaCg).
This substance, being dropped into water, readily decomposes,
liberating pure acetylene with the formation of calcium
hydrate, the reaction being CaC.2 + 2 HjO = C2H2 + CaOaH.^.
The acetylene was lighted with a match, and burnt on the
water.

Eight hundred and seventy-third Meeting.

March 13, 1895. — Stated Meeting.

Vice-President B. A. Gould in the chair.

The chair announced the death of Sir Henry C. Rawlinson
and of the Marquis de Saporta, Foreign Honorary Members.

The chair appointed a Nominating Committee, consisting
of William R. Livermore, Henry P. Walcott, and Thomas
W. Higginson.

The report of the Committee on amending the Statutes was
read, and the committee discharged.

In accordance with the recommendation of the Committee,
it was

550 PROCEEDINGS OF THE AMERICAN ACADEMY

Voted,, To amend the second section of Chapter IX.
of the Statutes by omitting the words, "and any Resident
Fellow who shall remove hit* domicil from the Common-
wealth shall be deemed to have abandoned his Fellowship."

A recommendation to rearrange the sections in Class I.
was laid on the table until the next meeting.

The Committee on Appropriations for Publications and for
the Library made a report, and, in accordance with a recom-
mendation contained therein, it was

Voted, That the committee issue a circular to the Fellows
of the Academy, soliciting subscriptions to meet the expenses
of publication.

Voted, To discontinue the purchase of books for the library
excepting such as shall be approved by a vote of the Com-
mittee on the Library.

On the motion of the Corresponding Secretary, it was

Voted, To meet on adjournment on the second Wednesday
in April.

Charles L. Jackson tendered his resignation from the Com-
mittee on Appropriations for Publications and for the Library,
which was accepted, and the chair appointed Henry W.
Haynes member and chairman of the committee.

Henry W. Haynes read a report of the committee ap-
pointed to consider the advisability of appropriating a por-
tion of the income of the Rumford Fund toward defraying
the expenses of the Library.

The following gentlemen were elected members of the
Academy : —

Sir Henry Bessemer, of London, to be a Foreign Hon-
orary Member in Class I., Section 4 (Technology and En-
gineering), in place of the late Ferdinand M. de Lesseps.

Sven Lov^n, of Stockholm, to be a Foreign Honorary
Member in Class II., Section 3 (Zoology and Physiology), in
place of the late Pierre J. Van Beneden.

Sir Frederick Pollock, Bart., of Oxford, to be a Foreign
Honorary Member in Class III., Section 1 (Philosophy and
Jurisprudence), in place of the late Sir James F. Stephen.

W. R. Livermore gave an informal talk on the political

OF ARTS AND SCIENCES. 551

changes of Europe, from 350 to 1100 A. D., illustrated by a
series of seventy-five colored maps, showing the boundaries
of each tribe and nation for every ten years.

The following announcement by Henry Taber was read
by William E. Story : —

In Volume XVI, p. 130, of the American Journal of Mathematics
I have shown that certain conditions are satisfied hy every orthogonal
substitution which is given by the positive square of Cayley's symbolic
expression for orthogonal substitutions, in other words, by every
orthogonal substitution which is the second power of an orthogonal
substitution. I have since found that these conditions are sufficient
that a given orthogonal substitution shall be the second power of an
orthogonal substitution.

"»■-

The following papers were read by title : —

On the Action of Ammonia upon Cupriammonium Aceto-

bromide. By Theodore W. Richards and Robert J. Forsyth.
Velocity of Electric Waves. A direct Determination of

this Value and a Discussion of its Relation to the Velocity of

Light. By John Trowbridge.

Eight hundred and seventy-fourth Meeting.

April 10, 1895. — Adjourned Stated Meeting.

The President in the chair.

In the absence of the Recording Secretary, William R.
Livermore was appointed Secretary pro tempore.

The chair announced the death of James Edward Oliver,
of Ithaca, Associate Fellow.

The Corresponding Secretary read a circular from Emil
Diebitsch, soliciting on behalf of Mrs. Josephine Diebitsch
Peary subscriptions in aid of a proposed expedition for the
relief of Mr. Peary and the promotion of Arctic scientific
research.

On the motion of B. A. Gould, it was

Voted, That the Corresponding Secretary be directed to
express to Mrs. Peary the regrets of the Academy that the

552 PROCEEDINGS OP THE AMERICAN ACADEMY.

state of its funds do not permit it to contribute toward the
expenses of this expedition.

On the motion of the Corresponding Secretary it was

Voted, To take from the table the report of the Committee
on rearranging the sections in Class I.

Voted, To amend Chapter I., Section 1, of the Statutes by
changing "Section I. Mathematics;- — Section 2. Practical
Astronomy and Geodesy ; — Section 3. Physics and Chem-
istry," to "Section 1. Mathematics and Astronomy; —
Section 2. Physics ; — Section 3. Chemistry."

The Corresponding Secretary proposed that Chapter 9,
Section 2, line 8, of the Statutes be amended by changing
the word " eight " to " seven." This proposition was re-
ferred to a committee, consisting of C. S. Minot, S. C. Chan-
dler, and A. M. Davis.

A report on the subject of appropriations for the ensuing
year was read by H. W. Haynes, Chairman of the Joint
Committee consisting of the Standing Committees of Publica-
tion and on the Library. After discussion, it was

Voted, That the Committee of Publication, the Committee
on the Library, and the Treasurer be instructed to report to
the Committee of Finance estimates of expenses for the
coming year.

Voted, That the money recently raised by subscription be
appropriated to printing the current volume of Proceedings.

Alexander Agassiz and William M. Wood worth read a
paper entitled, " Some Variations in the Genus Eucope."

The following papers were presented by title : —

On Bivalent Carbon. Third Paper : The Chemistry of
Cyanogen and Isocyanogen. By J. U. Nef

A Eevision of the Atomic Weight of Zinc. By T. W.
Richards and E. F. Rosfers.

On the Automorphic Linear Transformation of a Bilinear
Form. By Henry Taber.

On the Types of Linear Substitution which transform auto-
morphically a Bilinear Form with Cogredient Variables. By
Henry Taber.

AMERICAN ACADEMY OF ARTS AND SCIENCES.

Report of the Council. — Presented May 8, 1895.

BIOGRAPHICAL NOTICES.

JosiAH Parsons Cooke See Page 513,

Oliver Wendell Holmes By Percival Lowell.

Edward Jackson Lowell Henry W. Haynes.

Robert Charles Winthrop ..... William Everett.

William Holmes Chambers Bartlett . . William R. Livermore.

Ezekiel Gilman Robinson Thomas D. Anderson.

William Dwight Whitney Thomas R. Lounsbury.

Charles Edouard Brown-Sequard .... James J. Putnam.

Hermann Ludwig Ferdinand von Helmholtz Henry W. Williams.

Marquis de Saporta Sir John W. Dawson.

Notices of Dana, McCosh, Newton, Oliver, Cayley, De Lesseps, Marignac,
Rawlinson, and Seeley are deferred to the next volume ; that of Bartlett, de-
ferred from last year, is given below.

KEPORT OF THE COUNCIL.

Since the Annual Meeting of the 9th of May, 1894, the
Academy has lost by death sixteen members; — four Fellows,
Josiah Parsons Cooke, Oliver Wendell Holmes, Edward Jack-
son Lowell, and Robert Charles Winthrop ; six Associate
Fellows, James Dwight Dana, James McCosh, John Newton,
James Edward Oliver, Ezekiel Oilman Robinson, and William
Dwight Whitney; and six Foreign Honorary Members, Arthur
Cayley, Hermann Ludwig Ferdinand von Helmholtz, Ferdi-
nand Marie de Lesseps, Sir Henry Creswicke Rawlinson, Bart.,
Louis Charles Joseph Gaston, Marquis de Saporta, and Sir
John Robert Seeley.

RESIDENT FELLOWS.

OLIVER WENDELL HOLMES.

Oliver Wendell Holmes was born on August 29, 1809, in the
first decade of the nineteenth century, and died on November 7, 1894,
in its last. The century's contemporary, he was essentially exponent
of the spirit of his time. But he was more. He was pre-eminently
the spokesman of the place in which he lived. Though born in Cam-
bridge, Massachusetts, his life was spent in Boston, and it was there
he died. Bostonian by birth, if not by birthplace, he was himself that
typical individual of whom, more than half in earnest, he recorded the
innate conviction that "Boston State- House" was "the hub of the
solar system."

It is usually considered necessary to preface an account of a man
with an account at some length of his ancestors, in a spirit truly
Chinese. For though every man be a part of all that have met to his

556 OLIVER WENDELL HOLMES.

eventual construction, it is precisely because he differs from any of
his progenitors that he is noteworthy. It is the combination he em-
bodies, to say nothing of the advance, that singles him out as a man
of mark.

Special stress, therefore, need not be laid on the fact that Holmes
was the lineal descendant of " The Tenth Muse, lately sprung up in
America," as Anne Bradstreet called her book of poems, since that
lady was the poet's great-great-great-great-grandmother. Nor must
we chronicle all the Dutchmen who appear with such safe wisdom in
the middle of his name. Yet is it pleasing to note that his father was
the Rev. Abiel Holmes, " a sunny old man," from whom, if from any
one, he inherited his own sunny disposition.

It is sufficient here to begin with the dame to whom Holmes early
went to school, whose Prentiss hand, armed with an enormous birch,
seems rarely or never to have been tried on the youngsters she under-
took to form, — a pleasing exception to the spirit of the times. From
this almost fossiliferous educational period it gives one something of a
start to find the subject of it five years later in all modernity at Phil-
lips Academy, Andover. It was there that Holmes began to write,
poetry of course and heroics, a translation of the first book of the
^ueid. In 1825 he entered Harvard, and started on that career of
verse for which we remember him, — verse called occasional; in
Holmes's case with certainly double-edged humor, as the occasions
were substantially continuous from the start.

He began very early to write well; some of his best pieces being
written for the Collegian, the college paper of the day, — among oth-
ers "The Height of the Ridiculous" and "The Spectre Pig." In
due course he became a member of the $ B K. On graduating he
coquetted with law, but soon gave it up for medicine, to which he
remained faithful for the rest of his life, non sine gloria, illumined by
facetice, for to him the funny-bone by definition bordered on the hume-
rus. Upon his valuable contributions to the profession, and upon his
all-pervasive scientific sense on the subject, it is not necessary here to
dwell. For thirty-five years he held the chair of Anatomy and Phys-
iolonry in the Harvard Medical School, delighting successive genera-
tions of students, and when at last he resigned, in 1882, the ovation he
received showed how dearly he was loved.

One episode in his medical career, however, is important, from a
literary standpoint. In 1833 he went abroad to study medicine in
Paris. The importance of this lies not in the fact, but in its effect
upon Holmes, and the importance of the effect not upon its positive,

OLIVER WENDELL HOLMES. 557

but upon its negative side. He got what was to be got without bar-
tering for it a tittle of his individuality.

" Ccelum non animum mutant qui trans mare currunt,"

was never truer than of him. Indeed, had Horace not written this line,
Holmes might have been counted on to do so. Both men were so whole
with their native surroundings as to preclude their becoming to any
transforming degree pai-t of any other they might meet. This was even
more tlie case with Holmes than with Horace. For Horace took much
from the Greek, while Holmes never followed the French. But to
both the great world without was corrective, not creative of that corner
of it each was respectively born to within. In both there was that same
tiresomeless carrier-pigeon flight across the waters from wherever the
body might be, flight ever mindful of home and never resting till it
reached there, which above all other traits is the characteristic of the
poet of his own time and place. At home both were pre-eminently
at home, which made them both delightful diners out. And if Horace
was somewhat more mindful of Chloe than of the Schoolmistress, to
the times is due the change. Plolmes could find the woman amid per-
haps the most austere society the world has ever known, unless it be
that of the same society's ancestors, in which to be human was itself
perilously near sin. So people wore masks, shocked by the sin in
sincerity. Holmes and Horace might well have sat at the same table.
And just as Quintus par excellence, Quintessence that he was of later
Roman life, reveals to us that life as much more human than our early
Latin text-books led us to suppose, so Holmes discovers charms in
the Schoolmistress unsuspected of her pupils.

Having gone abroad once at the beginning of his life, Holmes did
not go again till toward the close of it, a half-century later. The
half-century that intervened constituted his life, and that was spent to
all intents and purposes in Boston. His flights were chiefly limited,
like Apollo's, to annual migrations from his winter home in his own
temple in town to his summer sanctuary by the sea, and back again, —
Beverly Farms being his local Delos. Yet though he thus practically
never stirred from home, it was he who was always asked to welcome
his country's guests, — welcome which none could more gracefully
extend.

Of his honors the catalogue is long. He was elected into the
American Academy on November 14, 1838, and became its Record-
ing Secretary in 1845, an office he held till 1848. From 1880 to
1887 he was its Vice-President. In 1880 he was made an LL. D. by

558 OLIVER WENDELL HOLMES.

Harvard, and in 1886 an LL. D. by Edinburgh, a Litt. D. by Cam-
bridge, England, and a D. C. L. by Oxford. Not the least of the
marks of the regard in which he was held by his fellows is the fact
that when he died, as full of years as of honors, his death was felt as
a national loss.

According to a remark credited to Longfellow, — thongh one finds
it hard to conceive that he ever can have made it, — " Autobiography
is what biography ought to be." True as this is of any man, it is well-
nigh a truism of a man of letters. For, like the evening paper, the
autobiographer chronicles little that is not already told. In the case
of a man of action, even though that action take the intellectual form
of prying into nature's laws, it is possible to catalogue the subject's
deeds or "discoveries. But with a writer who, instead of doing, said
all that made his life important, a biographer has the doubtful choice
between apologetically transcribing his original, or boldly taking him
for a text to some disquisition of his own. If he have nothing to say,
he embraces the former alternative ; if something, the latter. Prop-
erly speaking, there is in the way of facts not much beyond the un-
avoidable birth and death, and usually unavoided marriage, together
with a list of dated honors duly bestowed. The real life of the
man was lived within, not without, and that the man has himself
already revealed in the best of all ways, — unsuspectingly. Espe-
cially is this true of Holmes. His biography is his own books.
There one shall find his life told better than any other will ever be
able to tell it.

One point I shall mention and only one, for it seems to me peculi-
arly to distinguish the man. Holmes's genius was that of broad-
minded localism. The term local may seem at first to carry with it
the inference of the limited, but in truth it involves no more circum-
scription than individuality itself, the one applying to the man, the
other to the community. An individual to be anybody must first of
all be himself. In like manner, one who represents a place must, to
start with, be permeated with the spirit of the place. In this sense he
must be local, and in this sense Holmes was. It was the local that
made the essence of the man, — the broad-mindedness that based it
inseparably upon the universal, and made it not a part-truth, but a
part of all truth. What is thus in the true sense local, tliough builded
in one place, is builded for all time, taking on, from the fact that it
once was, brevet of immortality. Thus did Holmes represent New
England during the middle of the nineteenth century. He was him-
self New Englander to the core ; so essentially so that he seemed not

OLIVER WENDELL HOLMES. 559

only to outsiders, but to New Englanders themselves, to stand for all
that was most their own. If a man can be said to be a community,
Holmes was New England.

Recognition began, unlike the proverbial prophet, with those near-
est him. Chosen class-poet before graduation, he remained class-poet
his whole life long, poet of the now historic Class of '29. Distin-
guished as the class was, Holmes's verses have carved for it a peculiar
niche in the long gallery of commemorated class fame. These poems
form a remarkable anthology. They extend over a period of sixty
years, but the most striking point about them is the way in which each
falls naturally into its place in the series as if designed to do so. There
could be no greater witness to the fundamental fitness of each to its
occasion. Reflected there we seem to see the class grow up, grow on,
grow old. Pleasantry at the beginning slowly gives place to pathos
toward the close. Yet, true mirror of life, neither is wholly absent ;
it is but a little more of the one, a little less of the other, as the pro-
cession of the years passes on. In these verses, too, we note with pe-
culiar force that apotheosizing of the local which seems so easy and is
so hard. Written for his fellows, their tellingness at the time loses
none of its appositeness when retold in print to another generation of
men. It is this carrying quality in his verse that marks, not afore-
thought, but something much deeper, the unconscious fulness of the
thought itself. It was not meant to be universal : but it was univer-
sal because it was meant.

Passing on to his poems generally, we find at every turn proof of
their New England stuff ; and, as New England was and largely still
is representative of America, proof of their national character. First,
in their wit. The New Englander is emphatically witty ; to him life
itself is a sort of do\ihle entente. " Maybe to say one thing and mean
another comes nat'ral to women " ; certainly to say a thing by not
saying it comes natural to the New Englander. Both quick and sen-
sitive, he shies from direct statement as being both dangerous and dull.
His conversation is of the nature of an intellectual wrestling match, in
which his chief object is to give no hold to his opponent. Further-
more, he lives in a new country, in which he is constantly encountering
the unexpected, and in consequence the unexpected reflects itself in
his speech. Now of this all-pervasive humor Holmes is the embodi-
ment. Of all our poets he most is the exponent of the unexpected.
Consult him passim for proof of it ; then compare him with others,
and the reader shall find that, to quote substantially unchanged his
own words about another,

560 OLIVER WENDELL HOLMES.

" Now we have lost him, our lament must be
We have five hundred — not as good as he."

That communities less witty should occasionally be shocked by his
play of fancy is, reversely, to be expected. Possibly, the New Eng-
lander himself is a mistake, and all life as serious a thing as the
statutes declare. But it tires one to think so.

Punuinw, unlike other crimes, is commonly denounced by such as
are themselves incapable of committing it. Doubtless there are puns
that are poorer than others, some of Shakespeare's being, by the
accepted standard, among the worst, — but even a pun is not always
hopelessly depraved. Still less so is humor which deals with the im-
pression rather than with the expression of the thought. Yet, I sup-
pose no humorist has lacked friendly critics to apologize to the public
for his wit. I have just read some very kind excuses made for
Holmes on this score, and am wondering why man is the only laugh-
ing animal if he must needs be so ashamed of his propensity. The
philosopher perceives the profound unimportance of things, including
his own opinions ; it is the Governor's aide who takes himself seriously.

Pathos and pleasantry are twins. The mind that conceives the one
feels the other. Even the funniest of Holmes's verse stands against a
background of feeling. He was so human. His set productions of a
pathetic character are singularly few, — as few as the actual occasions
in life that to a healthy mind call them forth. But all his verse is
touched by emotion hinted at, not expressed, as to any sensitive soul
is life itself. Even his " Last Leaf "is not primarily pathetic but
humorous, yet the stanza,

" The mossy marbles rest
On the lips that he has pressed

In their bloom,
And the names he loved to hear
Have been carved for many a year

On the tomb,"

brings a lump into the throat and a dimming of the eyes, no matter
how often one repeat the lines. It is to miss the point to consider
this poem, as I have seen done by a critic from across the sea, as a
pathetic production, and then explain away the humor in it as irrele-
vant. The humor it is that has the right of way, but makes way
insensibly for the feeling.

Another point in which Holmes stood representative of his unwrit-
ten constituents was his skill in apt simile. A shunning of the
positive leads the New Englander unconsciously into parable. Rather

OLIVER WENDELL HOLMES. 561

than blurt out bluntly what he means, he prefers to constrain consent
by a process of easy analogical admission. This may or may not take
the form of the comic. In the average Yankee it usually does so, but
his parabolic cast of thought is really something distinct from humor.
Witness the landlord in Fitz Adam's story, who described his son as

" A long slab-sided youngster with a gun,"

and whose recipe for cooking birds was

" Jes' scare 'em with the coals, — that 's my idee."

Of course this deviation from directness easily passes into the hyper-
bolic, as when we are told that a thing is as difficult as hunting in the
dark for a black hat which is n't there. Such hyperbolic intent is not
to be confounded with the conversational curve of pursuit — -but non
attainment — of the unconsciously blundering bull.

But though Holmes's wit was based on the broad foundations of his
country's wit, his was no rescript of it such as we are presented with
in real or fictitious dialect tales. These too are national in an ob-
jective sense. Holmes was subjectively so. He was always himself,
but that self was essentially the outcome of his surroundings. He
was typical and typical of the best, — the national poet of the edu-
cated class of his countrymen, to a degree which I do not recall ever
to have been matched.

New England air is conducive to a shi-ewd sort of philosophizing.
There is much pithy wisdom, if there be naught else, to be gleaned
from the hillsides of the boulder-strewn New England farm. All
this was Holmes's inheritance ; genius and culture did the rest. We
are given it capitalized in the " Autocrat of the Breakfast Table,"
and on in delightful instalments, till we sit with him at last " Over
the Teacups " in the sunset of his life. These books of practical
philosophy are probably without a peer in the world as a combination
of wisdom with wit. But their characteristic that most impresses one
is. like the poems, their remarkably genuine ring. They are delight-
fully humorous, without a hint of burlesque. You feel as you i-ead on
that this is no travesty of life seen through an astigmatic eye, however
keen-sighted, but the real thing mirrored in a singularly pellucid retina
that reflects without distortion. These books are most fittingly com-
memorative of their author. Poet always, his volumes of verse are
beautiful mosaics ; his essays are his monoliths.

In this brief attempt at tribute to one we shall all miss so long as
we live, I have tried simply to point out what seems to me the essence

VOL. XXX. (X. S. XXII.) 36 ■

562 EDWARD JACKSON LOWELL.

of his genius, the fact that it was not the genius of dissimilarity, but
the more uncommon one of supreme comprehensiveness of his kind.
And this word is touchstone to more, since in its other sense as well
it was so fully what he was, — whose like, like as he was to others,
we shall never look upon again, — our own Holmes, witty, genial,
kind.

1895. Percival Lowell.

EDWARD JACKSON LOWELL.

Edward Jackson Lowell was born in Boston on October 18,
1845. His father was Francis Cabot Lowell, one of a family note-
worthy among the founders of the cotton-manufacturing industry of
this country, and distinguished for acts of public beneficence. His
mother was Mary, daughter of Samuel P. Gardner, of Boston. The
youngest of five children, and having lost his mother before he was
nine years old, he was placed, in accordance with her wish, at an
excellent private school in Switzerland. The three years there spent,
and the knowledge of the French and German languages there
acquired, had doubtless a controlling influence upon the subsequent
occupations of his lifetime. After completing his preparation at a
private school in Boston, he entered Harvard College, and graduated
with the Class of 1867. At college he gained some distinction as a
writer of verse, both for the college paper and as occasional poet of
society anniversaries, and upon graduation was selected to write the
Class Ode. After spending some months in travel in Eui'ope, he
was married, on January 14, 1868, to Mary, daughter of Samuel G.
Goodrich, whose writings, under the name of Peter Parley, were the
delight of children of the last generation.

Mr. Lowell at first turned his attention to business, which he soon
abandoned for the study of law, and was admitted to the bar in Boston
in 1872. But having been so unfortunate as to lose his wife early in
1874, he thereupon determined to devote himrelf completely to the
care and education of his three young children, a daughter and two
sons, and to literary culture in general.

On June 19, 1877, he was married a second time, to Elizabeth,
daughter of George Jones, of New York, one of the founders and
principal directors of the New York Times, who survives him. Carry-
ing out his educational plans, in 1879 he took his family to Europe,
and passed two winters in Dresden and two in Paris, travelling exten-
sively in the summer.

EDWARD JACKSON LOWELL. 563

During his residence in Germany he became interested in the his-
tory of the German mercenaries employed by Great Britain in this
country during our Revolutionary War, and in consequence he under-
took extended researches among the archives of some of the smaller
German states. The most important of these are now preserved at
Marburg, in Hesse-Nassau, where are to be found many reports and
journals received by the Landgrave Frederick II. of Hesse-Cassel
from his officers during the entire course of the war. Others ai-e to be
found in the State library at Cassel, and in that of the Prince of
Waldeck, at Arolsen, and a few in other localities. Of many of
these documents, containing " original German accounts of every im-
portant engagement, and of almost every skirmish, of the Revolution-
ary War from the year 1776 to the end," he caused transcripts to be
made, and was thus enabled to make use of sources of information that
had never fallen under the eye of any American writer. The results
of these researches were first given to the world in a series of letters
to the New York Times, in the winter of 1880-81. After his return to
this country, in 1884, they were published in a more extended shape in
a volume entitled '' The Hessians and the other German Auxiliaries of
Great Britain in the Revolutionary War, with Maps and Plans," New
York, 1884. This was a genuine contribution to the history of our
country, and it attracted universal interest among our historical stu-
dents. It was, indeed, a surprise to learn that a force of between
fifteen and twenty thousand Gerraa'ns served for seven years against
us, and that more than twenty-nine thousand were brought to this
country for that purpose, of whom more than twelve thousand never
returned. As but a comparatively small portion of these were killed,
we are thus able to account for a goodly contribution to the number
of our German fellow citizens. The work was systematically con-
ceived and thoroughly executed, and it was enlivened with anecdotes
and adventures drawn from the experience of private individuals, in
accordance with the intention of the author "to give an idea of what
sort of people the auxiliaries were, and of what impression America
and the Americans made upon them." It had a decided success, and
as a speedy recognition of its merits the author was chosen a member
of the Massachusetts Historical Society, in November, 1884.

Besides contributing articles to some of the leading magazines, Mr.
Lowell's studies were now principally directed to the preparation for
Dr. Winsor's " Narrative and Critical History of America " of a chapter
upon " The Political Struggles and Relations of the United States with
Europe, 1775-1782," which appeared in 1888. This bears evidence

564 EDWARD JACKSON LOWELL.

of extended reading in English and French historical sources, in addi-
tion to his German studies. It is principally devoted to narrating the
attempts made by the United States during the earlier part of the
Revolutionary War to obtain recognition and aid from foreign coun-
tries, and to raise the money for carrying on the struggle. Inciden-
tall}^ the diplomatic situation in P^urope, so far as it affected us, is
portrayed, and the desperate financial straits to which we were re-
duced are well described. The result is a succinct and instructive
survey of our early foreign relations. Besides embodying the results
of his studies of the German auxiliaries, he became so deeply inter-
ested in the career of Lafayette that he formed the intention of writ-
ing his life. For that purpose, he began to collect materials, but
abandoned the design upon learning tliat a similar work by another
was on the eve of publication. He had intended to draw a contrast
between the American and French Revolutions, but he changed his
jjlan, and began the composition of what turned out to be his most
important literary undertaking.

This was published in 1892 under the title of " The Eve of the
French Revolution." It contains the ripe fruit of the studies and reflec-
tions of his life ; from it we can learn the manly strength that underlay
his singularly sweet and winning personality, and on it his reputation
will chiefly rest. Whoever wishes to obtain a clear idea of the hidden
causes that resulted in that fearful outburst of political passion cannot
fail of satisfaction if he will carefully study this small but weighty
volume. The author lays no claim to original research and pretends
to formulate no novel views, but relies upon the results reached by the
best historians and thinkers of France ; and the reader will find many
popular delusions in regard to the actual situation of that country
immediately before the meeting of the States General completely dis-
pelled. " The condition of the people," we are told, " both in Paris
and in the provinces was far less bad than it has often been repre-
sented." They were not crushed by the oppression of a dissolute and
tyrannical aristocracy, as many writers have asserted, nor was the
Bastille crowded with captives, so that a political hurricane was
needed to clear the moral atmosphere. But, on the other hand, we
are made to see clearly what were the inherent vices of that aneien
regime, which harassed and irritated every class in the community,
and in the language of De Tocqueville produced "a condition of society
which was detested by every one who knew it." In dififerent chapters
and with ample detail the author shows how the army had become
discontented, because only nobles were eligible to high rank ; how the

EDWARD JACKSON LOWELL. 565

magistracy had been for more than a generation engaged in a contest
with the crown ; how the men of letters without exception had become
hostile to the government ; how the taxationj though not so absolutely
burdensome as has been assumed, was so manifestly unequal as to
excite the bitterest indignation at the odious privilege of exemption
enjoyed by the nobles and the ecclesiastics ; and minor sources of dis-
satisfaction are brought to light in abundance. The author's summing
up is that, " while France was great, prospeious, and growing, and a
model to her neighbors, she was deeply discontented. . . . She had be-
come conscious that her government did not correspond to her degree
of civilization. . . . The financial situation was not the. cause of the
Revolution, but its occasion. All the machinery of the state needed
to be inspected, repaired, or renewed. The people entei-ed into the
task with good will and the warmest interest. But tliey were entirely
without experience. ... In their ignorance of the working of popu-
lar assemblies, they supposed them to be inspired with wisdom and vir-
tue beyond that of the individuals who compose them. . . . They accom-
plished for France much that was good, tliey prepared the way for
much that was evil."

For many years Mr. Lowell was a very efficient member of the
Board of Trustees of the Boston Athenajum, and. by his refined appre-
ciation and extended knowledge of art he was able to brino^ about a
most marked improvement and increase in the art collections of that
institution. In the winter of 1893 he again visited Europe, and passed
quite a long time in Athens in the congenial companionship of the
professors and students of the American School of Classical Studies,
to which he had given his services for several years as treasurer.
During this time he also procured additional treasures for the art col-
lection of the Athenaeum.

He was called home by illness in his family, and not long after-
wards developed that mysterious sickness, arising from a tumor in the
brain, which resulted in his sudden and regretted death at Cotuit, Mass.,
on May 11, 1894.

Mr. Lowell was elected a member of this Academy on March 9,
1887. He rendered the writer valuable assistance upon the Library
Committee, and contributed to Volume XXVIII. of the Proceedings
of the Academy, in May, 1893, a Memoir of Lord Tennyson, the last
of his literary productions. Of these a chronological list is appended,
so far as known to me.

1880-81. The Hessians. N. Y. Times.
1884. The Hessians; extended to a volume.

566 ROBERT CHARLES WINTHROP.

1887. Journal of Captain Pausch. — Introduction.

1887. German MS. Documents. Proc. Mass. Hist. Soc.

1887. Memoir of L. M. Sargent. Proc. Mass. Hist. Soc.

1887. Adventures of a Hessian Recruit. Proc. Mass. lli.st. Soc.

1887. Bayeux Tapestry. Scribner's Magazine.

1888. A Liberal Education. Atlantic IMonthly.

1888. The United States, their Political Struggles and Relations with

Europe. Nar. and Crit. Hist, of America.

1889. Life of Benvenuto Cellini. Scribner's Magazine.

1892. The Eve of the French Revolution.

1893. Clothes Historically Considered. Scribner's Magazine.
1893. Memoir of Lord Tennyson. Proc. Amer. Acad.

1895. Heney W. IIaynes.

ROBERT CHARLES WINTHROP.

The Hon. Robert Charles Winthrop died in Boston on the
16th of November, 1894, at the age of eighty-tive years and six
months, having been born on the 12th of May, 1809. He was the
son of the Hon. Thomas Lindall and Elizabeth (Temple) Winthrop,
and a descendant of Governor John Winthrop, founder of the Massa-
chusetts Bay Colony. Between this illustrious ancestor and himself
were interposed five generations. His father, Thomas Lindall Win-
throp, was for many years Lieutenant Governor of Massachusetts,
and also President of the Massachusetts Historical Society ; he was
universally esteemed as a man of courtly manners, social disposition,
and stainless character, rendering much more valuable service to
the community than many men of greater intellectual prominence.
Robert C. Winthrop was educated at the Boston Latin School and at
Harvard College, graduating with distinction in the class of 1828.
The social position of his parents at once introduced him to the most
cultivated circles in Boston, and he was conspicuous throughout his
life for the strictest devotion to all social duties. He always took
keen interest in the militia of the State, as a member and commander
of Company A of the First Regiment M. V. M., otherwise the Boston
Liglit Lifantry, or '' Tigers," and was afterwards an Aide-de-Camp on
the staff of Governor Everett.

Mr. Winthrop was admitted to the bar, and studied for a time in
the office of the Hon. Daniel Webster. But his attention was early
attracted to politics. At the period of his entering college the so
called " era of good feeling," which had culminated in the almost
unopposed re-election of President Motiroe, had come to a violent end

ROBERT CHARLES WINTHROP. 567

in the contest of 1824. Mr. Winthrop's college course nearly coin-
cided with the Presidency of John Quincy Adams, and, as he was
beginning active life, a new political [):irty was forming itself, com-
posed partly of old Federalists and partly of such Democrats as had
supported Mr. Adams against Crawfoid, Jackson, and Clay. This
party was for a short time dominated by the " Antimasons," a singular
association of those who distrusted the political and moral tendencies
of secret societies. It early, however, assumed the name of National
Republicans, and later settled down as the Whig party. To this
party Mr. Winthrop was devotedly attached for the twenty odd years
that it had any existence ; not merely its favorite candidate for State
and national offices, but its untiring organizer, alert every day and
every hour to extend its influence and deepen its hold upon the peo-
ple. He was a popular speaker at all its conventions, and a certain
fighting element in his nature, which could use the weapons of fun
and sarcasm as well as of argument and pathos, cannot be understood
without reading his speeches delivered on these political occasions.

Mr. Winthrop entered the General Court of Massachusetts as a
Representative when he was but twenty-five years old, and served in
that capacity for five terms, for three of which he was Speaker. In
1840 he was elected to the House of Representatives of the United
States, and represented the Boston district in five Congresses. In his
fourth term, he was elected Speaker of the Thirtieth Congress. It
was during his occupancy of the chair that the venerable John Quincy
Adams, rising to address the house, was stricken down at his place,
and, being carried into the Speaker's private room, died on the 23d
of February, 1848.

It had been Mr. Winthrop's intention to close his career as a Repre-
sentative with this Congress, but he yielded to the solicitations of his
friends to sit for another term. He was of course the Whig candi-
date for Speaker ; but after a contest of unprecedented duration, in
which the bitterest partisans, both from the North and the South,
united to make any election by a majority impossible, he was defeated
by Howell Cobb of Georgia, who received a plurality of two votes.

In 1850, Mr. Webster having resigned his seat in the Senate to
enter President Fillmore's Cabinet, Mr. Winthrop was nominated by
Governor Briggs to hold the Senatorship till the legislature could
meet. This body, on its assembling, was controlled by the " Coalition "
of Democrats and Free-Soilers, who elected Robert Rantoul, Jr.
Senator for the very few weeks of the Senatorial term then remaining,
and chose Charles Sumner for six years.

568 ROBERT CHARLES WINTHROP.

In 1851 Mr. Wiuthrop was the Whig candidate for Governor of
Massachusetts ; but, as the law then stood, an absolute majority was
required for a popular election, and, failing that, the Governor was
chosen by the newly elected legislature. Here again the Coalition
triumphed, no candidate having a majority of the popular vote,
though Mr. Winthroj) had by far the largest number ; and the legis-
lature elected George S. Boutwell.

Thus ended Mr. Winthrop's political service, which had reflected
the highest honor on his name, his State and his person. He was a
conservative in the truest and highest sense, deeply attached to his
country and her traditions, suspicious of everything which tended to
break up directly or insidiously the flourishing fabric which had been
constructed with such amazing rapidity in the generation that immedi-
ately succeeded the misery of Mr. Madison's war, but eager for every-
thing which could promote that wonderful development peacefully and
honorably. Those who have been trained to believe that his political
conduct showed a lack of moral courage would do well to read the
debates on the annexation of Texas and the Mexican war, in which
he gave voice completely and convincingly to the highest moral senti-
ment of Massachusetts. If the 2)resent laws of election had been in
force at the time he was defeated as candidate for Governor, he would
have been declared elected to that post, and probably had no diffi-
culty in securing several re-elections. He was a national patriot, who
would not for a score of Senatorships have renounced what he con-
sidered his duty to his whole country in submission to any sectional
feeling.

Particular attention should be drawn to his services as Speaker,
both in Boston and in Washington. It may be confidently asserted
that no occupant of those chairs ever discharged his duty with greater
dignity, courtesy, and understanding of its minutest details. That
be was entirely impartial is proved by the fact that fifteen of the very
bitterest and most irreconcilable extremists, equally divided between
North and South, voted to strike out that word from the vote of thanks
to him.

For the last half of Mr. Winthrop's life he occupied what is called
a private station. He had, indeed, allowed his name to head the
Democratic electoral ticket in 1864, with no idea that he could be
chosen. But thei'c have been very few men in any country, or
at any period, who have discharged so faithfully, usefully, and ac-
ceptably such multifarious public duties. The record of them is to be
found in the second, third, and fourth volumes of his public addresses,

ROBERT CHARLES WINTHROP. 569

the first being cliieHy occupied with those of a political character.
These addresses range over a great variety of subjects, charitable,
literary, historical, commemorative. One may select, as specially
worthy to be studied, those on laying the corner stone of the Wash-
ington Monument in 1848, on the dedication of the statue of Franklin
in 1856, and on the centennial anniversary of the surrender of York-
town in 1881. But, whatever the occasion, Mr. Winthrop was sui'e
to invest it with a richness of historical record, a tenderness of per-
sonal reminiscence, an appropriateness of local and contemporary
illustration, and a soundness of social philosophy, all conveyed in
faultless J-Cnglish, to which there are few parallels. The sense of
order and propriety was extremely conspicuous in all he did ; he
possessed a keeu sense of humor, and, as has been stated, in his earlier
years an entire willingness to fight ; but he objected to engaging in
any but clean warfare, and for many years before his death dealt only
with such things as make for peace.

The expression used above, that the record of his public service
may be found in his speeches, should be corrected; he was the soul
of many most important organizations, where his instinct and experi-
ence in transacting society business was of incalculable value. Of the
many charitable, religious, and antiquarian bodies that looked to him as
their guiding spirit, two, the Massachusetts Historical Society and the
Peabody Education Fund, were his chosen spheres of constant action.
To the Collections of the former he contributed precious stores from
his family papers; and his " Life and Letters of John Winthrop" is a
most important contribution to our national biography. The various
donations of the late George Peabody were made very largely from
Mr. Winthrop's direct suggestion ; and he threw himself heart and
soul into the work of making the Peabody Education Fund immedi-
ately and extensively useful for the most pressing need of the Southern
States. From this cause his name undoubtedly will be honored and
loved hereafter by whole commimities, who never heard of the
Arbella's voyage or the Antinomian Controversy, — the transit of
Venus or the Speakership election.

Mr. Winthrop was chosen a Fellow of this Academy on the 8th of
August, 1849, and between 1858 and 1881 he served upwards of
twenty years as Counsellor. In 1879 he was appointed Chairman
of the " Centennial Committee," and in that capacity was called upon
at twenty-four hours' notice to deliver the principal address at the
celebration of the one hundredth anniversary of the foundation of the
Academy, on the 26th of May, 1880, when it became evident that our

570 WILLIAM HOLMES CHAMBERS BARTLETT.

President, the lion. Charles F. Adams, was too seriously affected in
health to fulfil that duty. Impossible as it was in so brief a time for
the orator to do justice to himself or the occasion, he gave an eminently
graceful and ai)propriate discourse.

Mr. Winthrop was twice married, and three children survive him.
The memory of his character and services is among the precious
possessions of this century in Massachusetts.

1895. William Everett.

ASSOCIATE FELLOWS.

WILLIAM HOLMES CHAMBERS BARTLETT.

William Holmes Chambers Bartlett, for many years Pro-
lessor of Natural and Experimental Philosophy in the Military Acad-
emy at West Point, contributed as much as any man to impress
upon that institution its well known character. As a scientist, he
was one of the tlrst to base a system of physics on the principle of
the conservation of energy ; as a teacher, he was so clear and logical
that he made the most complicated laws of physics and astronomy
embraced in his course of instruction appear to be self-evident truths.
His genial manner and personal interest in his pupils will ever be
remembered with gratitude, and his magnetic influence helped to unite
the officers of the army and attach them to the Union at a time when
so many were tempted to join their native States.

He was born in Lancaster, Pennsylvania, in September, 1804, but his
parents moved to St. Louis, Missouri, while he was yet an infant. He
was appointed a Cadet at the Military Academy in 1822, graduated at
the head of his class in 1826, and promoted to the rank of Second Lieu-
tenant of Engineers. He served at the Military Academy as Assistant
Professor of Engineering from 1827 to 1829 ; as Assistant Engineer
in the construction of Fortress Monroe, Virginia, in 1828, and of
Fort Adams, Newport, Rhode Island, from 1829 to 1832; as Assist-
ant to the Chief of Engineers at Washington, from 1832 to 1834; as
Acting Professor of Natural and Experimental Philosophy from 1834
to 1836; and as full Professor from 1836 to 1871, when, on his
own application, he was retired from the active list for forty years of
continuous service. Since his retirement he has been Actuary of the
]\Iutual Life Insurance Company of New York. He died at Yonkers,
New York. Februarv 11, 1893.

WILLIAM HOLMES CHAMBERS BARTLETT. 571

lu 1829 he was married to Harriet Whitehouse, of Newport, Rhode
Island. Of eight children, three sons and two daughters survive him.
His eldest daughter was the wife of General J. M. Schofield, now in
command of the army, and his family has always been identified with
the army and navy.

In 1837 the degree of A. M. was conferred on him by the College
of New Jersey, at Princeton, and in 1847 that of LL. D. by Geneva
College, New York. He has been a corporator of the National
Academy- since 1863, an Associate Fellow of the American Academy
since 1845, and a member of the Philosophical Society of Philadel-
phia since 1840, and also of other societies.

He was the author of a Treatise on Optics, 1839 ; Synthetic Mechan-
ics, 1850-58; Acoustics and Optics, 1852-59; Analytical Mechanics,
1853-59 ; Special Astronomy, 1855-58 ; — all designed for the use of
the cadets of the United States Military Academy. He was also the
author of " Mortuary Experience" of the Mutual Life Insurance Com-
pany of New York from 1843 to 1874 ; and of official reports and
contributions to the publications of scientific societies.

His Analytical Mechanics passed through nine editions, and was
used extensively throughout the country. In his Preface he says :
" The design of the author is to give to the classes committed to his
instruction in the Military Academy what has appeared to him a
proper elementary basis for a systematic study of the laws of nature.
The subject is the action of force upon bodies, — the source of all
physical phenomena, — and of which the sole and sufficient foundation
is the comprehensive fact, that all action is ever accompanied by an
equal, contrary, and simultaneous reaction. Neither can have prece-
dence of the other in point of time, and from this comes that character
of permanence in the midst of endless variety apparent in tlie order of
nature. A mathematical formula which shall express the laws of this
antagonism will contain the whole subject, and whatever of specialty
may mark our perceptions of a particular instance will be found to
have its origin in corresponding peculiarities of physical condition,
distance, place, and time, which are the elements of this formula. Its
discussion constitutes the study of Mechanics. All phenomena in
which bodies have a part are its legitimate subjects, and no form of
matter under extraneous influences is exempt from its scrutiny. As-
tronomy, terrestrial physics, and chemistry are but its specialties; it
classifies all of human knowledge thac relates to inert matter into
groups of phenomena, of which the rationale is in a common principle ;
and in the hands of those gifted with the priceless boon of a copious

572 EZEKIEL GILMAN ROBI^'SON.

mathematics, it is a key to external nature." Twenty years later, in
the ninth edition of the same work, in referring to this formula, he
says : " That formula was no other than the simple analytical expi-es-
sion of what is now generally called the law of the conservation of
energy, which has since revolutionized 2:)hysical science in nearly all
its branches, and which at that time was but little developed or
accepted. It is believed that this not only was the first, but that it
even still is the only treatise on Analytical Mechanics in which all the
phenomena are presented as mere consequences of that single law."

His report of an inspection of the European Observatories, made in
1840, gave an impulse to astronomical work which resulted in the
establishment of observatories in all parts of the country.

1895. W. R. LlVERMORE.

EZEKIEL GILMAN ROBINSON.

EzEKiEL Oilman Robinson, an Associate Fellow of our Academy
since 1885, was born at Attleborough, Massachusetts, on March 23,
1815. It was not his good fortune to begin his life in a literary
atmosphere, or to spend any of his earlier days in tumbling about in
a library. His early instruction was poor, and what was bad in itself
was made worse by reason of frequent changes.

Entering Brown University in 1831, he was during his first year
interrupted in his work by sickness, and, discouraged by his manifest
inferiority to classmates who had been more thoroughly prepared, he
seemed to lose ambition. Later, however, the student's enthusiasm
was awakened under Professor H. B. Hackett in Latin, and under
President Wayland in ethics. But in addition to the inspiration
received from his teachers, he found a strong educational stimulus in
the debating society of which he was an enthusiastic and prominent
member. In his enthusiastic and successful work in this debating
society we discover the prophecy of the Socratic teacher and the great
pulpit orator of later days ; while in his choice of theme for Com-
mencement, "The Value of Metaphysical Speculations," we detect the
mental bias which was followed through scores of years of philosophic
study.

After a year spent in post-graduate work he determined to study
theology, and entered the Theological Institution at Newton Centre,
Massachusetts. Then, according to his own testimony, he " went to
work in earnest with a will and a purpose, giving his days to prescribed
work, reserving an hour or two for Oerman and associated readings

EZEKIEL OILMAN ROBINSON. 573

with fellow students, and devoting his evenings to philosophy and
literature."

After graduating from Newton in 1842, Mr. Robinson was ordained
and settled as pastor of a Baptist church in Norfolk, Virginia. Dur-
ing this pastorate he received leave of absence from his church, in
order to serve for the eight months of an academic year as chaplain
of the University of Virginia.

After pastoral service of three years at Norfolk and one year at
Cambridge, Massachusetts, the call came to leave the pastorate and to
devote himself to the instruction of students for the ministry, and he
became Professor of Biblical Interpretation in the Western Baptist
Theological Institute at Covington, Kentucky. This connection was
terminated after two or three years of service, and Mr. Robinson
again entered the pastorate in 1850, in the service of the Ninth Street
Baptist Church of Cincinnati, Ohio. Here his reputation as a great
pulpit orator was firmly established. He became the foremost preacher
of the city, and his reputation was rapidly extending throughout the
country. But the man was coveted for other positions, and having
received an invitation to accept the chair of theology in the recently
established Seminary at Rochester, New York, he, after three years of
ministerial service, again left the pastorate for the Professor's chair.

Although after leaving Cincinnati Dr. Robinson never re-entered
the pastorate, he continued to preach up to the time of his death. He
loved the work of the preacher ; he honored the preacher's office, and
in that office he was cons{)icuously successful. His sermons in Cincin-
nati and Rochester on Modern Skepticism, made deep and lasting
impression on the intelligent citizens who came in large numbers to
hear them ; and throughout his life he was an attractive, instructive, and
inspiring preacher. His pulpit presence was striking and effective ;
his conduct of worship was impressive and memorable ; but it was in
the sermon that his powerful personality came into fullest manifes-
tation. He was pre-eminently an instructive preacher. Not infre-
quently were his sermons packed with the results of the thinking of
months and years. On special occasions he appeared a veritable giant
in intellectual power. He chose the extemporaneous method of de-
livery ; but the extemporaneous method did not exempt him from
careful preparation. It was only through the most exacting mental
discipline and the most patient literary cultivation that he became the
consummate master of unwritten discourse that he was. As he said
liimself, " It is not the naturally fluent man who makes in the end the
best extemporaneous speaker."

574 EZEKIEL OILMAN ROBINSON.

His sermons in general were characterized by comprehensiveness of
thought, by keenness of analysis, by sharp discrimination in definition,
by clear, forceful, and elegant diction, by honesty and earnestness of
purpose, and on occasion by tremendous power of appeal. One other
characteristic of his preaching, which is worthy of special mention,
was what might be called his intellectual honesty. His moral honesty
was shown, as, shunning all hypocrisy, he preached level with his
convictions. His intellectual honesty he illustrated, as, guarding
against prejudice, he preached level with his thinking. He thought
as earnestly and as far as he could, and very few thought further ;
but where his thinking stopped, there his sermon stopped also. He
did not urge upon the minds of his hearers what had failed to gain the
assent of his own thinking mind. He knew but in part, ;ind he was
honest enough to prophesy but in part.

In accepting the chair at Rochester in the spring of 1853, Mr.
Robinson exchanged the work of the pastor for that of the tlieological
instructor, for which he was admirably fitted, and in which he was
pre-eminently successful. As a theologian he was pre-eminently an
investigator rather than a systematizer, or, to use his own word, a
" systemizer." He believed that investigation must be carried to
great lengths before the work of systemization can be satisfactorily
performed. He was too logical to be unsystematic ; but his critical
faculty was always hindering and interfering with the work of con-
struction. If, thi'ough his lack of complete system, and by reason of
his dominant tendency to emphasize one phase of truth at a time, he
sometimes laid himself open to the charge of inconsistency, he at least
escaped some of the faults of the systemizers. If his mind was too
critical hastily to construct a system, it was too honest to falsify facts
or to minify truths.

Dr. Robinson believed in and taught a rational theology. He cared
nothing for words except as they gave expression to reality. He was
constantly looking through the formula to the fact, and discarding tra-
dition for truth. He revered historic creeds, as statements of belief
which have been formed after profound experience, and which signal-
ize the victories and the progress of Christian truth ; but he scouted
the idea that any divine fact or truth can be exhaustively measured by
finite minds, or that there has been or ever can be an ultimate dogma
in theology. The Scriptures, as an organic whole, he considered as
authoritative ; but he reacted from that method of using particular
proof texts which prevents men from seeing the forest for the trees.
Discarding the rule that reason may guide us in examining the evi-

EZEKIEL OILMAN ROBINSON. 575

dences of Divine revelation, but must be scrupulously abjured the
moment we come to an examination of the truths which revelation
declares, he inquired, " To what does revelation address itself, if not
to our reason and our conscience ? In the name of reason, for what
was reason given us if not to be employed on the highest thoughts and
the noblest ends that can engage our attention ? "

Again, he believed in and taught a progressive theology. Before
the name became familiar, he represented the movement which has
since been denominated the New Theology. He was in advance of
most of his contemporaries in welcoming the discoveries and paying
earnest heed to the teachings of physical ^science. He was constantly
modifying his own views, was quick to detect the way to fresh dis-
covery, and anticipated the modifications which the new revelations of
the age have effected in theology. His ablest students affirm that, in
the modifications which they have been compelled to make within the
last twenty-five years, they have but followed the lines of thought
indicated by Dr. Robinson to his students from twenty to forty years
ago.

Great as was Dr. Robinson's work as a theologian, his work was
still greater as a teacher of theologj . The testimony of his pupils is
strong, concurrent, enthusiastic, and convincing with regard to his
transcendent ability as a teacher. Ilis method was Socratic. By his
keen questions he aroused his students from their dogmatic slumbers,
by his personal magnetism and strong intellectuality he led them to
discover themselves, and quickened them into newness of intellectual
life ; while the vital themes he presented sank dee^) into their hearts
and wei'e wrought into the very fibres of their moral and religious
nature.

This brilliant and eminent success in the chair of theology made
Dr. Robinson a marked man in educational circles ; and it is not sur-
prising that, when Brown University was looking for some able and
progressive man to become her head, she should turn with longing
eyes to the eminent teacher at Rochester. Alma Mater extended a
call to her brilliant and distinguished son, and he loyally responded,
assuming the duties of the Presidency in the fall of 1872.

The college at that time did not hold a very advanced position. la
its material and intellectual condition it needed regeneration, and de-
manded close attention and self-denying effort from the incoming
President. To the work which lay before him he consecrated all his
powers, under that stern conviction of duty which dominated his life.
The requirements of admission were raised, until at one time they

576 EZEKIEL GILMAN ROBINSON.

were said to be in a(l\ unce of the requirements in colleges generally ;
more room was provided in the curriculum for the modern languages
and the natural sciences ; and, in harmony with the insistent purpose
of the President, better equipment was provided for the application of
science to the arts.

Towards the latter part of his administration the President renewed
and urged more strongly his demand for an enlarged attention to the
study of English ; preseuted a plan by which young women might
share in the advantages of the University, and succeeded in extend-
ing its work so that students might pursue post-graduate studies
at their Alma Mater and receive from her the degree of Doctor of
Philosophy.

While these changes were effected in the inner life of the college, in
the outward condition improvements were made with accelerating
rapidity. Indeed, it showed greater material advance during the
administration of Dr. Robinson tlian at any other period of its history.
The grounds were greatly improved ; the University came to be much
better housed and equipped ; the educational plant was very greatly
extended, while the funds were almost doubled.

As the head of the college. President Robinson had a deep concern
for the moral welfare of his students, and if in specific cases of disci-
pline, he was not always happy, the general discipline of the institu-
tion during his administration was efficient and wholesome. For
if, owins to his natural reserve and his sternness of demeanor, the
President was not always able to win the affection and love of the
students, he exerted upon them a most wholesome disciplinary in-
fluence through the example of industry, high moral purpose, and con-
stant devotion to duty which he himself afforded. Under this inspiring
influence the aims of the students were heightened, and the spirit of
devotion to study was very greatly increased.

But the work of administration and discipline did not relieve Dr.
Robinson from special work in teaching. During his entire adminis-
tration he was engaged five or six hours a week in teaching. Very
few students, perhaps no earnest student, could fail to receive a deep
impression from Dr. Robinson's instruction in ethics. The teachings
most deeply impressed were the immutability of the moral law, and
penalty as a reaction from violated law ; the nature, and not simply
the will, of the Supreme Being as the ultimate ground of virtue ; and
conscience as, strictly defined, neither legislative nor prophetic, but
rather as the supreme, though not infallible, "moral judiciary of the
soul."

EZEKIEL OILMAN ROBINSON. 577

His careful efiuition was of great benefit in giving to the jDupil
solid ground on which to stand. The ethical universe remained no
longer chaotic, inchoate, an earth without form and void, illumined by
light transfused through an omnipresent mist ; but, under his teaching,
dry land began to appear in the midst of the waters, and sun, moon,
and stars shone out as distinct luminaries in the ethical firmament.
Students who have continued to prosecute their studies, for instance on
the subject of conscience, after being surprised to see how vaguely and
without precise definition that term is used even by writers of emi-
nence, have come to feel a deeper gratitude to their college instructor
for his sharp definition. They may perhaps think that the definition
given was not sufficiently comprehensive ; but that definition has
risen, amid the haze which seems to enwrap many ethical writers,
like the island which Kant saw outlined amid the restless waters, the
obscuring mists, and the dissolving phantoms of a wide and stormy
ocean.

But no estimate of the teaching would be adequate which failed to
take account of the teacher. The man was in his teaching, the living
truth was in the man ; therefore his teaching did not simply add to
the intellectual capital of the pupil, it became an element in that
pupil's moral life. In his best moods his class-room was a forge,
where, in the fires of his own intense thinking, heated seven times hot-
ter under the blast of free discussion, the cold iron of traditional notion
was fused and then taken out, hot and fluent, to be fashioned anew
under the hammers of master-workman and apprentice alike ; or, to
change the figure, that class-room was a palajstra where he who wres-
tled the best enjoyed the fullest discipline and received the richest
reward, as he carried away his " apples of gold in pictures of sUver."

The preacher, the administrator, the teacher, demands our admira-
tion ; but still more admirable is the man himself. Towering above
many in physical stature, he towered also in intellectual power and
moral character. On the physical side of his nature he was endowed
with a striking personal presence, and a wiry well knit bodily frame ;
but these were only the physical setting of pre-eminent intellectual
power.

His paramount mental characteristic was his power of analysis. His
mind was a crucible, in which, when heated by the intense fires of his
intellectual nature, thoughts were readily resolved into their constitu-
ent elements. But he was by no means lacking in synthetic power.
This was seen in his well constructed sermons and in the broad gener-
alizations and brilliant inductions of his theology ; but the analytic

VOL. XXX. (n. S. XXII.) 37

578 EZEKIEL GILMAN ROBLNSON.

dominated the synthetic, as is evident from the fact that his theology
was never thoroughly systemized.

But the moral man is grander than the man of intellect, and Dr.
Robinson's moral character demands a higher admiration than his
intellectual power. He had his faults; but his aim was higli, his
motives noble, and his heart sincere. His most prominent moral char-
acteristic was tremendous power of will. The man's whole counte-
nance betokened a dominant, imperious will ; but this mighty energy
was associated with a stern sense of moral obligation. This will was
not prostituted to low ends. It was not self-will. It recognized a law
to be obeyed, and it held the man in its grip until he rendered obedi-
ence. As in the tremendous energy of will we discover the centrifu-
gal force, so in the high moral ideal we discover the centripetal force,
which determined the orbit of his life.

The life which was characterized by this striking combination of
tremendous energy of will and high sense of moral obligation also dis-
played a not unhappy union of pride and humiHty. Probably no
human pride is virtue unalloyed ; but there is a pride which savors
more of virtue than of vice. Essential manhood is worthy of respect.
The Almighty has placed man's head erect upon his shoulders ; He
has " made him a little lower than God, and has put all things under
his feet " ; the great moral teacher of the ages inculcates self-respect,
as he instructs man to love his neighbor as himself. In the philo-
sophic Christian sense, Dr. Robinson was exceedingly proud. He had
abundant self-respect ; he had little self-conceit. His pride was akin
to the awe with which Kant reflected upon the moral law within, and
•differed heaven-wide from that Narcissus-like vanity which pines away
in admiration of its adventitious and ephemeral beauty.

This pride, however, retained its virtue, and was raised from the
level of the Stoic philosophy to the higher elevation of the Christian
religion, as it was mated to humility. Humility, with him, was not
cringing before one's fellows and asking their pardon for one's exist-
ence ; it was not an undue depreciation of self ; it was rather a just
appreciation of another and a worthier, in comparison with whom self
seems but little. Dr. Robinson bared his head before the Almighty.
He walked humbly before his God.

It was in the closing period of life that the strength and nobility of
his character found fullest and most beautiful expression. Although
Dr. Robinson was seventy-four years of age when he laid aside
his duties as President of P>rown University, his work was not yet
done. In response to the call of honor and of duty, the stern believer

WILLIAM DWIGHT WHITNEY. 579

in moral law again took up his burden and pressed on toward the
goal. Continuing his intellectual toil, he devoted himself to the work
of preaching and lecturing, until he again entered the teacher's chair
as Professor of Ethics and Apologetics in the University of Chicago,
where he remained until he was removed by death on June 13, 1894.
It was in this autumnal season that the peaceable fruits of righteous-
ness most rapidly matured. The character which had been steadily
and sturdily growing in early and more mature manhood, blossomed in
old age. Sorrows deep and distressing were experienced, but the dis-
cipline of sorrow seemed only to beautify the character which the dis-
cipline of work had made strong. The nature was mellowed, and the
heart which had been so jealously guarded through life now over-
flowed, and gave freer expression to its deeper feeling. The column
had been piled stone upon stone, with severe and unremitting toil, the
surface had been chiselled with painstaking diligence and skill, until,
as a finishing touch, the lily was carved at the top of the pillar, and
strength was crowned with beauty.

His chief literary remains are a translation of Neander's "Planting
and Training of the Christian Church," his "Yale Lectures on Preach-
ing," and his '' Principles and Practice of Morality," together with
shorter articles in magazines, notably in " The. Christian Review," of
which he was editor from 1859 to 1864. During the last year there
issued from the press a limited edition of his " Christian Theology,"
which is chiefly a republication of his lectures as prepared for the use
of his students in Rochester prior to the year 1872, and in the present
year have appeared his lectures on " Christian Apologetics."

Dr. Robiuson's scholarship was officially recognized by his Alma
Mater, which conferred upon him in 1853 the degree of Doctor of
Divinity, and in 1872 the degree of Doctor of Laws ; and by Harvard
University, which conferred on him the degree of Doctor of Laws in
1886.

1895. Thomas D. Anderson.

WILLIAM DWIGHT WHITNPZY.

W-iLLiAM DwiGHT Whitnet, an Associate Member of the Academy
since 1860, was born at Northampton, Massachusetts, on February 9,
1827. His early education he received in his native place. In 1842,
at the age of fifteen, he entered the Sophomore Class of Williams Col-
leg^. There he remained during' the three following years. While

580 WILLIAM DWIGHT WHITNEY.

thei'e, though he paid due atteution to the required studies of the
course, he did not coufiue himself to them. He had an inborn taste for
the natural sciences, and spent no small share of his time in botanical
excursions among the fields and wooded hills encompassing the college
town. There too and then he began the work of making and mount-
ing the collection of the birds of New England, which he subsequently
presented to the Peabody Museum of Yale University.

In 1845 he received his bachelor's degree. In spite of the time he
had given to studies outside of the regular curriculum, he had easily
maintained the position at the head of his class. At that period he
had little thought of what was to be the work of his life, and the bent
of his mind was certainly then rather towards the natural sciences than
languages. He at first contemplated pursuing the study of medicine,
but an accidental illness prevented him from carrying the scheme at
once into effect, and when laid aside it was discarded altogether. In
the uncertainty attending his future he remained in his native place,
and entei-ed as teller the bank of which his father was president. In
that position he continued for more than three years. Whitney was
by nature a man of method. It was that quality which enabled him
to accomplish with apparent ease so many things which lay outside of
the special pursuits to which he directed his main atteution. But
while under any circumstances he would have displayed this charac-
teristic, there can be no question that the business training which he
received during this most impressionable period of his life did much to
impart additional strength and efficiency to habits which had been im-
planted by nature. In no sense was the time thus employed wasted.
Nor were his business occupations so engrossing that he was prevented
from carrying on the pursuits in which he had already taken special
interest. He completed his collection of New England birds ; he
made botanical excursions in the neighborhood of his home ; he prose-
cuted vigorously the study of two or three modern languages. These
avocations furnished a by no means unsuitable preparation for the
work he was to accomplish in other fields.

Up to this time, as has already been intimated, his interests lay
mainly in the direction of the natural sciences. But an event was
now about to occur which was destined to change the course of his
studies and to determine his whole future. In 1847, his elder brother,
Professor J. D. Whitney, had returned from Germany, where he had
been devoting himself to the science in which he has become distin-
guished. Yet while there he had not limited his attention to it, but
had given iq) a good deal of time to language. Among the books he

WILLIAM DWIGHT WHITNEY. 581

brought back with him was a copy of the second edition of Bopp's
Sanscrit Grammar. This work attracted the attention of his youDger
brother, and aroused a keener interest than he had before felt in any
ijarticuhir subject. In the winter of tiie following year he began the
systematic study of Sanscrit. For him this was the parting of the
ways. In June, 1849, indeed, he joined an expedition sent out by the
United States government to explore the region about Lake Superior.
One of its two directors was his elder brother, and to the future philolo-
gist were assigned the barometrical observations, the botany, and the
charge of the accounts. But he took with him also this copy of Bopp,
and the leisure moments he enjoyed during the expedition were, as far
as possible, devoted to the fuller study of that work.

His progress in it at that time definitely decided his career. The
study of Sanscrit is a pursuit which in any country has never been
specially lucrative ; and in the United States at that time there was
certainly little to prompt any one to choose it as a profession. Whit-
ney's father, a business man, and naturally anxious for the success of
his children, saw this clearly ; but he was not disposed to stand in the
way of a pursuit upon which his son had set his heart. Accordingly,
the latter was allowed to follow his choice. The only instruction in
Sanscrit then offered in the United States was at Yale College, where
in 1841 Edward E. Salisbury had been created Professor of that
tongue and of Arabic. To New Haven, therefore, Whitney repaired
in the autumn of 1849, and to the study of Sanscrit he devoted the
following year. He had but one fellow student, Hadley, who had
been made in 1848 Assistant Professor of Greek, and whose compara-
tively early death Whitney was always wont to lament as the greatest
loss American scholarship had up to that time suffered.

After remaining a year in New Haven he sailed in the autumn of
1850 for Europe. He was absent for three years. Arabic, Persian,
Egyptian, and Coptic were attacked by him ; but his attention was
mainly given to Sanscrit, which he studied at Berlin under Weber, and
at Tubingen under Roth. In conjunction with the latter he began the
preparation of an edition of the Atharva-Veda, and with this object in
view spent some months before his return in Paris, in London, and in
Oxford, engaged principally in the collation of Sanscrit manuscripts.
He reached America in August, 1853.

In 1854 the chair of Sanscrit and Arabic, held by Professor Salis-
bury, was at his wish divided. At his suggestion, also, Whitney was
called to the newly created separate chair of Sanscrit. It was a posi-
tion the latter held to his death, though to the title was subsequently

582 WILLIAM DWIGHT WHITNEY.

added Comparative Philology. In 1856 appeared the text of the first
important work in the production of which Whitney bore a part, the
edltio princeps of the Atharva-Veda. It bears upon the title-page his
name, and tliat of his old instructor, Roth ; but the subsequent labors
bestowed upon this one of the Vedas were by him alone. It was in
18J:9 that an article of Whitney's had appeared in the August number
of the " Bibliotheca Sacra." It was an abridged translation of the
once popular treatise Das Alte Lidien of the orientalist Van Bohlen.
This was the beginning of a long career of literary activity, the records
of which can be found in the journals of Europe and America, in the
proceedings of learned societies, and in independent publications. The
list of his published productions numbers about one hundred and fifty
titles. They range all the way from comparatively brief pieces, which
appeared in weekly periodicals, to works involving immense time and
labor in their preparation, sucli as the text and translation of and
notes on the " Taittiriya-Pratifakhya," and its commentary, the '' Trib-
hashyaratna," for which the Bopp prize was awarded him by the Ber-
lin Academy of Sciences. A large part of what he produced in his
special field of investigation made its appearance in the successive vol-
umes of the " Journals and Proceedings of the American Oriental
Society," though it was by no means confined to that publication. In
particular should be mentioned his Sanscrit Grammar, and his contri-
butions to the great seven-volumed Sanscrit-German Lexicon, pub-
lished by the Imperial Academy of Sciences of St. Petersburg. Of this
latter work he was one of the four collaborators who faithfully assisted
the editors, Bohtlingk and Roth, during the twenty-tliree years taken
up with its progress through the press. Besides these purely technical
productions he contributed to a number of periodicals essays on various
Oriental and linguistic topics of more or less general interest. These
were collected by him and published in two volumes in 1873 and
1874; but the work of his that up to that time appealed most to the
public of educated men was his treatise on the principles of linguistic
'science, which came out in 1867 under the title of '•Lano-ua'T-e and
the Study of Language." An outline of this same science, cover-
ing essentially the same ground as the preceding work, was published
in 1875 in the International Scientific Series, under the title of '' The
Life and Growth of Language." It was then the only popular and at
the same time scientific exposition of the subject which can be found
in any tongue, and such it has remained to the present day.

AYliitnoy took up his residence in New Haven in 1854, and with
the exception of occasional visits abroad, New Haven remained his

WILLIAM DWIGHT WHITNEY. 583

abiding place until his death. In 1869 he was called to Harvard
University, and, had it not been for the prompt gift by Professor
Salisbury of the sum needed to endow fully his chair at Yale, he
would have felt bound, in justice to his family, to accept the similar
chair in the sister institution, now so ably filled by his pupil, Profes-
sor Lanmau. In 1856 he had been married to Elizabeth Wooster
Baldwin, the daughter of Roger Sherman Baldwin, once Governor of
and United States Senator from Connecticut. The union was a pecu-
liarly happy and helpful one, and the assistance he received from the
members of his family, as time went on, was an important agency in
enabling him to accomplish so much in so many different ways. Three
times he visited Europe, and once remained there fifteen months,
engaged in the preparation of his Sanscrit Grammar. In fact, all his
journeys abroad had as one of their principal objects the completion
or more successful prosecution of some work upon which he was at the
time employed.

The pay of his professorship was at first very small, and hi the coL
lege year of 1856-57 he was appointed Instructor in German in the
Academic Department. His duties, however, were limited to the
third term and to the Junior Class. In the following year French
was added to the then narrow list of electives, and in that tongue also
he was called upon to impart instruction. This duty of teaching these
two languages in the Academic Department Whitney continued to dis-
charge until 1867. Then he turned over this work to the Professor
of Modern Languages, for instruction in which a special chair had been
created three yeai's before. After 1871, however, he gave an elective
in linguistics to the students of the classical course.

It was while he was teaching French and German in the Academic
Department that I first came under his instruction, and made his per-
sonal acquaintance. Though then myself a mere boy, I could not fail
to be struck with the earnestness ancl thoroughness which he brought
to the performance of duties that most men of his grade would have
deemed the veriest drudgery ; with the breadth and accuracy of his
knowledge, and the lofty standard of scholarship he set before us all ;
but perhaps at that time more than with anything else, with the
patience which no indifference ever discouraged, no thoughtlessness
ever irritated, and no stupidity ever tired. All these feelings were
intensified when several years later I came to be his colleague and
personal friend.

In 1861, while still an instructor in modern languasres in the Aca-
demic Department, he was called upon to perform the same duties in

584: WILLIAM DWIGHT WHITNEY.

the Sheffield Scientific School, then a small part of the University,
but about to enter upon a rapid course of prosperity. With it he
speedily became identified in spirit, and his instruction in it did not
cease until 1886, when the disease manifested itself which eventually
struck him down. To the School his connection was of enduring
benefit. He was in the fullest sympathy with its objects and aims,
was profoundly interested in its success, and was unremitting in his
efforts for its advancement. It was largely, perhaps mainly, due to
his influence, that this department of the University never degenerated
into a merely technical institution ; that in it the study of language
and literature always occupied a position of equal prominence and
honor with the purely special subjects which it set out primarily to
teach. AYhile the School was small and the number of students few,
he gave instruction both in French and German. But it was not
many years before its rapid growth compelled him to confine himself
to one of these two subjects. From 1869 to 1872, he taught German
alone; after the latter year till 1886, French alone. It is, however,
to be added, that during the whole period of his connection with the
School he gave instruction in liuiruistics to the students of one of the
special courses.

He received then and subsequently a good deal of sympathy for the
time thus spent in elementary instruction, and to many it will seem a
waste of power to have so employed it. But it was largely his own
choice. He kept up the practice long after the necessity which led
him at first to assume it had passed away. Nor, in fact, did it
seriously encroach upon his leisure. Whitney, as I have observed
previously, was a man of method, and the hours of his day were so
regulated and disposed as to secure the largest results with the least
friction. A single incident will illustrate how carefully his time was
measured. French and German were compulsory studies upon all
students, no matter what their special courses. In order to get tliem
out of the way, the first hour of the morning was given up to recita-
tions in tliese two languages. This had been from eight to nine ; but
at one of the few meetings of the Governing: Board of the Sheffield
Scientific School, from which Whitney was absent, it was decided to
change the time, so that henceforth it should be from half-past eight to
half-past nine. But to this he felt obliged to refuse his consent. The
hour from eight to nine he was willing to give up to this instruction,
but nothing more. There was accordingly no other course left for the
Board, unwilling to lose his services, than to rescind promptly its
previous action.

WILLIAM DWIGHT WHITNEY. 585

The relation, furthermore, which he held to the Scientific School,
he felt was of advantage to himself in many ways. He has more than
once assured me that his connection with it, his intimate acquaintance
with the spirit which pervaded it, his knowledge of the work accom-
plished by it, had done more than any other one thing to broaden his
mind on the whole subject of intellectual training ; to dispel from it the
notion that there was but one kind of education in the world ; to free
it, in particular, from the illiberality which, in the case of some, is the
most conspicuous result of an exclusive devotion to what they desig-
nate as liberal studies. Another incidental result of this connection
with the School was that it led to the preparation of a series of excel-
lent text-books. These have played a most important part in putting
the instruction in modern languages on a higher and more scientific
plane than it had ever before enjoyed in this, or for that matter in any
English-speaking country. The list of these is somewhat remarkable
for one who accomplished so much in other fields. In 18G9 appeared
his German Grammar, in 1870 the corresponding German Reader, in
1877 his German-English Dictionary, in the same year his English
Grammar, and in 1886 his French Grammar, All these were worked
up with his usual thoroughness, and exhibit the latest results of lin-
guistic investigation. Had they taken his time from his special
studies, their preparation might have been a matter of regret. As it
was, it is nothing but a subject of congratulation.

The preparation of the French Grammar occupied a portion of the
earlier months of 1886. It was then that Whitney felt at times a
pain in his arms, occasionally so severe that he would be under the
necessity of keeping them for a while folded. It was naturally at-
tributed to rheumatism. The summer of that year was spent in
Kittery, Maine, and while there these pains extended to the chest.
Still they occasioned no serious alarm, and the physician whom he
consulted did not venture to speak positively as to their cause. It was
not until his return to New Haven in the autumn that the increase
in the frequency and violence of these symptoms led him, at the
suggestion of his family physician, to seek the advice of a specialist.
In October he went to New York and consulted Dr. Loomis. That
practitioner, after a careful examination, felt compelled to warn him
that the situation was exceedingly grave ; that in fact the heart
was so seriously affected that the chances were heavily against his
living more than six weeks ; and that, if his life should be protracted
beycnd that period, it could be done only by the immediate cessation
of all work, and by steadily conforming to a most exacting regimen

586 WILLIAM DWIGHT WHITNEY.

as regards labor and diet, which few are found willing or sufficiently
sell-controlled to maintain for any length of time.

In a man whose life had been spent in study and investigation, and
who had found in them supremest pleasure, this unexpected revelation
of his physical condition was necessarily a severe shock. He was in
the midst of work well advanced towards completion. He had formed
projects and made engagements for the future. His intellectual force
was unabated. It was hard for him to stop suddenly short, and play
the part of a confirmed invalid. But the situation had been too clearly
pointed out by the physician for him to doubt the correctness of the
diagnosis. He bore the blow, however, with the same quiet fortitude
with which he had met the various trials of a life in which he had never
shirked a duty however distasteful, or shrunk from a task however
irksome or onerous. Tiiough hardly hoping to survive the allotted
six weeks, he set to work to fight for life on the lines laid down for
him with the same calmness and courage with which he would have
attacked a delicate and difficult problem of scholastic investigation.
For the time being all work was laid aside. He conformed in the
minutest detail to the strict regimen which had been imposed. Every
effort was bent towards the restoration, so far as was possible, of health.
The task was made as easy for him as it could be by the members
of his family, all of whom devoted themselves with a single eye to
alleviating as much as lay in their power the monotony of this en-
forced idleness, and to scanning with jealous watchfulness the slightest
sign of approaching danger. Yet, in spite of all that ardent affection
could do and did do, it was necessarily a grievous burden. Still it
was a burden uncomplainingly borne. In time, too, it was lightened.
The self-restraint he exercised, the rigid rule he imposed upon him-
self, met with a partial reward. Though it could not avert the sen-
tence of death which had been pronounced ujjon him, it was sufficient
to suspend for several years its execution. When six months after
Dr. Loomis again saw his patient, he made no attempt to conceal
his astonishment at the improvement that had been made. The
necessity for the most rigid adherence to the rules that had been
laid down for his guidance was indeed as pressing as ever ; but,
with these closely observed, it was reasonable to believe that there
was still a chance for him to accomplish much which it had been in
his mind to undertake.

From this point on follows a period in Whitney's life of quiet hero-
ism, and, considering the situation he was in, of wonderful achieve-
ment. During all those years, in which I saw him not unfrequently,

WILLIAM DWIGHT WHITNEY. 587

I never knew him to utter the slightest coniphiint about the calamity
which had uuex{)ectedly falleu upon him in the fulness of his strength.
He preserved the same cheerful composure which had characterized
iiim in the days of his health and vigor. He gradually and cautiously
took up much of the work which he had been obliged to lay aside.
He resumed his instruction in his special department, though his classes
were now obliged to meet him in his own home. In fact, not a single
•duty remained uufultilled which it was in his power to accomplish.
Moreover, he carried on to conclusion several undertakings in which
he had been concerned, and in a few instances projected others. In
particular, during those years he went through the necessary drudgery
of reading twice over all the proofs of the Century Dictionary, of which
he was editor in chief, and of carrying on a correspondence, which may
be fairly called immense, with its numerous sub-editors and contribu-
tors ; he revised his Sanscrit Grammar, originally published in 1879 ;
and when he died, he was at work upon the second volume of the
Atharva-Veda, containing commentary and ti'anslation, which had been
promised forty years before. As time went on, indeed, his health
seemed to improve. It is possible that renewed strength gave renewed
confidence, and that he was at last led to venture further than his frail
physical condition could endure. These are considerations which are
sure to present themselves to those who live to lament him. But it
was inevitable that the stroke should fall sooner or later, and against it
no precautions could long prevail. In the latter part of May, 1894,
his disease assumed an acute and painful form ; on the morning of
Thursday, the 7th of June, he died.

Of the value of Whitney's services in the special fields of investiga-
tion to which he devoted his life, others can speak and have spoken
with an authority to which it would be presumption in me to lay the
slightest claim. Yet it is certain that down to the very close of his
career his eminence was undisputed. He lived long enough to see
the studies which he had been almost the first in this country to take
up pursued enthusiastically by hundreds. But the progress of their
investigations, the results of their researches, never once shook his
commanding position. To the younger linguistic scholars of the coun-
try he remained to the last the master. He was the friend to whom,
whether students of his or not, they came for advice and encouragement.
He was the leader to whom they looked for guidance. He had un-
doubtedly here his critics and opponents, but they were never found
among the men who stood highest in the department of study in
which he had been with us the great pioneer. They were almost

588 WILLIAM DWIGHT WHITNEY.

invariably the mere echoers of the views of his adversaries across "the
ocean, and not only were they never very numerous, they were never
very effective.

But without expressing any opinion upon the comparative value of
the work he accomplished, there were certain characteristics distin-
guishing his scholarship which can be read and known of all men,
and which naturally forced themselves upon the attention of any one
whose relations to him personally were close enough to render it fre-
quently necessary to seek his advice and to ask his direction. One of
these was his thorough intellectual independence. No one was ever
less influenced than he by the authority of great names. No one was
ever less affected by the general acceptation of plausible theories. He
came to the examination of every subject, not with any desire either
to adopt or to attack the conclusions of others, but to study it for him-
self in the light of truth. It was accordingly his good fortune to see
views, which he had unsparingly censured while they were widely held,
abandoned by the vast body of scholars. The controversies in which
he became engaged were, indeed, largely due to his severe and almost
contemptuous criticism of doctrines which had little to show in their
favor but superficial plausibility, though often presented in a capti-
vating form. His unhesitating rejection of theories which had wide
vogue, his exposure of the fallacies of men with wide reputations,
distressed always, and often irritated, that body of partisans attaching
themselves to noted names, who, while never possessing the courage
of their own convictions, display invariably the most unreasoning and
undaunted hardihood in upholding the convictions of others.

Joined with this intellectual independence was his thorough intel-
lectual sanity, if it be not more correct to say that the former was the
result of the latter. It is, at any rate, the one quality which will give
the greatest stability to the work he accomplished. The advance of
scholarship necessarily causes many previously accepted beliefs to be
reviewed, many statements to be modified, many received theories to
be exploded. It not unfrequently happens that the individual himself
lives to see the views he had imposed upon the world set aside as a result
of the fuller and clearer light furnished by later investigations. From
this too common calamity Whitney has been saved by the sanity of his
judgment. There are few scholars who have been called upon to
retract, or even modify, so little as he by the advance of knowledge.
From this cause his reputation never had to suffer during his life, and,
so far as the future can be foreseen, it is little likely to suffer in the
years to come.

CHARLES EDOUARD BROWN-SEQUARD. 689

There are other characteristics of his to which it is not within the
limits of the present notice to make more than a passing reference.
It is enough to say, in general terms, that those who knew him best
esteemed him most. The affectionate regard in whicli he always
continued to be held by the men once brought into close communiou
with him by the nature of their special studies was due full as much
to the respect inspired by his moral qualities as by those purely intel-
lectual. His sincerity, his disinterestedness, his unflinching devo-
tion to duty, could not fail to impress profoundly all with whom he
came into constant contact. Speaking for myself personally, I may
be permitted to say, in conclusion, after the intimate associations of
twenty-five years, that never have I known a man more unselfish in
his dealings with others, more loyal to his friends, more genuine
in profession, and more upright in every relation of life than he,
who held unchallenged during the whole of his career the position of
foremost of American philologists.

1895. Thomas R. Lounsbury.

FOREIGN HONORARY MEMBERS.

CHARLES EDOUARD BROWN-SEQUARD.

Charles Edouard Brown-Sequard * was born at Port Louis,
on the island of Mauritius, April 8, 1817, and died at Paris, April 2,
1894. His father was an American sea-captain, and his mother,
Madame Sequard, was a native of Provence. Left without resources
by her husband's death just before the birth of her child, she managed
to support herself and him by her needle, and to give him a care and
training which gained her his deep love and devotion, and doubtless
fostered the affectionate and domestic traits of his disposition which
characterized him throughout his life. The extraordinary industry
and singleness of purpose which he afterwards showed must have had
their root in fine inborn qualities of mind, but his early simple life.
with its traditions of hard work and self-reliance, was a good school for
virtues of this order.

As a young man, and while supporting himself as agent for a large

* For many interesting facts relating to his life and works, see an address
by Eugene Dupuy, published in the Transactions of the Socie'te de Biologic,
1894, which is my authority for most of the data here given.

590 CHARLES EDOUARD BROWN-SEQUARD.

colonial store, he is said to have tried his hand with local success at
polite letters, and soon afterwards to have made his way with his
mother to Paris, as an aspirant for literary fame, following in this
respect also in the footsteps of his great predecessor in the Chair of
Physiology, Claude Bernard.

But he was quickly disillusioned, and, gathering fresh courage, be-
gan to prepare himself for the practice of medicine. The next few
years covered a period of extreme poverty, in spite of which he dared
to devote himself to physiology, though there seemed to be no pros-
pect of support or advancement in its pursuit, and then began that
long course of tenacious, unflagging labor in scientific fields which was
checked only by his death.

Even the wandering life he led — for he crossed the ocean innumer-
able times, and planned at ditFereut periods to make a home for him-
self in various cities of Europe and America — did not for a moment
arrest his labors or his productiveness, or cause him even to change
materially his hours or methods of woik. He was in the habit,
from the period of his student years throughout the rest of his life, of
going to bed at eight o'clock in the evening and rising at two in the
morning, in order to have time for uninterrupted work, and even when
journeying by land or sea he continued to study and to write. His
whole mental attitude was characterized by an eagerness and intensity
which made a moment's conversation with him seem like a memorable
■event. It may be questioned whether his judgment might not have
been calmer, and his sense of proportion more just, if the fire of his
energy had burned less fiercely ; but it is doubtless true that the bril-
liancy of his scientific imagination, which, next to his tireless industry,
was his most characteristic trait, was ke^t at a glowing heat by this
flame.

His first scientific communication of consequence was his graduation
thesis, on the " Sensory Tracts in the Spinal Cord," presented m 1846,
and the investigations which he made with regard to this matter, both
at this time and subsequently, were among the most important of his
scientific life. In 1848 he took part in founding the Societe de Bi-
ologic, and up to the time of his death he remained one of its most
active members. In 18.52 he embarked in a sailing vessel for New
York, and, having utilized the voyage in studying English, he at once
began to teach experimental physiology in the medical schools of New
York, Philadelpliia, and Boston, at the same time writing papers in
the medical journals and eking out his small income by teaching
French and by practising obstetrics. In 1854 he returned to Mauri-

CHARLES EDOUARD BROWN-SEQUARD. 591

dus, and during the epidemic of cholera which shortly followed he
was put in charge of the hospital. In 1855 he was made Professor of
Physiology at the University of Virginia, in Richmond, but his life
there was not congenial. An ardent republican, and with the scenes
of the cuup d'etat of 1852, in which he had himself borne arms, still
fresh in his mind, the contact with Negro slavery impressed him very
unpleasantly, and iu 1856 he returned to Paris and established a
laboratory with his friend Robin. His researches, and especially
those relating to the spinal cord and to epilepsy, had by this time
made him famous, and he was welcomed as a lecturer in the Univer-
sities of England, Scotland and Ireland, which he visited in the course
of the next year. In 1858 he began the publication of his "Journal
de la Physiologic de FHomme et des Animaux." He next went to
London, where he was made Physician to the National Hospital for
Epileptics and Paralytics, and became busy with a large consulting
practice ; but in 1863 he again broke loose, and came to establish him-
self in Boston, the home of his first wife, whom he had married on
his earlier visit. In 1864 he was made Professor of Physiology and
Pathology of the Nervous System in the Harvard Medical School.
The loss of his wife, in 1867, determined him to change his plans and
return to Europe. In 1868 he founded the " Archives de Physiologie,"
in company with Charcot and Vulpian, By 1872 he had however
again crossed the sea, intending to establish himself in New York,
which was the home of the lady who became his second wife, and he
at once began together with Dr. E. C. Seguin to edit the "Archives
of Scientific and Practical Medicine," which had a brief but creditable
existence. The early death of his second wife again broke up his
home, and he returned to Europe once more. Within a few years he
married for the third time, and had agreed to accept a professorship
at Geneva, when the death of Claude Bernard, in 1873, brought him
a call to the Chair of Experimental Medicine at the Ecole de Medecine
(1878), and this position he held for the remaining sixteen years of
his life. His wife, to whom he had been deeply attached, died in
1894, and he survived her only a few months. He worked to the
last, and had taken an active share in the preparation of the issue of
his journal, the " Archives de Physiologie," which appeared shortly
after his death.

Brown-Sequard was the only person whose name appears succes-
sively in the three divisions of the American Academy. He was
elected a Fellow May 28, 1867, an Associate Fellow May 27, 1873,
and a Foreign Honorary Member February 9, 1881.

592 BARON VON HELMHOLTZ.

This IS not the place for a critical estimate of Brown-Sequard's
work, or au enumeration of his comniunicatious. The works by
which he will be longest remembered are, perhaps, first, the investi*
gations already referred to with regai'd to the sensory tracts in the
spinal cord ; secondly, his insistence on the complex nature of the cere-
bral functions, and the interaction of one pan on another, leading to
the phenomena of inhibition and reinforcement ; thirdly, his studies
on experimental epilepsy ; fourthly, his observation that many of the
organs of the body, such as the suprarenal capsules and other glands,
both ductless and secretive, exercise an important influence on the
nutrition of the body through the substances which they pour into the
blood. These are all still living problems, and the work which he
did on the last of them, though it has led to much adverse criticism,
partly just, partly unjust, has borne and will bear practical fruit.

It is true that in collecting materials for the support of the conclu-
sions which he reached he sometimes showed a lack of critical judg-
ment which carried him too far, and impaired the weight of his au-
thority in the eyes of many persons who were not in a position to know
the real merit of his work, and to select the grain from the chaff. It
is likewise true, however, that his researches gave birth to a sjjlendid
array of observations and generalizations, for which his name will be
gratefully remembered by every sincere student of physiology.

His friend and co-worker Gley says of him, " Brown-Sequard was
one of the greatest discoverers of facts that the world has ever seen."

1895. James Jackson Putnam.

HERMANN LUDWIG FERDINAND VON HELMHOLTZ.

Hermann Ludwig Ferdinand von Helmholtz, one of the most
illustrious of European savants and one of the most distinguished of
the Foreign Honorary Members of the American Academy of Arts
and Sciences, was born at Potsdam, Prussia, on August 31, 1821.

Admitted at the age of seventeen to the Royal Military School at
Berlin, he became Assistant Surgeon at La Charite Hospital, and
later, as full Military Surgeon, was stationed at Potsdam. But after
four years of service he relinquished the practice of medicine to enter
upon congenial pursuits in extended and accurate mathematical and
physiological researches, and in untiring investigations of various
intricate questions in physics and optics.

One of the earliest of his published scientific papers, " On the Con-

BARON VON HELMHOLTZ. 593

i^ervatioii of Force," gave him at once au acknowledged rank 2^s facile
princeps among the chief investigators in natural science. This was
accompanied by other notable contributions ; especially those on
"The Nature of Putrefaction and of Fermentation," published in
1843 ; " On Animal Heat " ; and on " The Consumption of Tissue dur-
ing Muscular Action," in which was considered the question whether
the living body gives off as much heat as is produced by the combus-
tion and change of the food it takes in.

In 1849, Helmholtz became Professor of Physiology in the Univer-
sity of Konigsberg, where he made notable investigations on " The
Rapidity of Propagation of Nerve Excitation." By ingenious methods,
of his own devising, for measuring extremely small differences of
time, he was enabled to demonstrate that thought is not instantaneous,
that it takes a definite period for us to become conscious of a fact, and
that a certain measurable time elapses between the willing of a move-
ment and the executing of it.

Helmholtz's original and intricate researches begun thus early and
including every department of physiology and of physics, are a record
of amazing originality, acuteness, and industry, largely in new fields.
They are especially remarkable for accuracy of observation, and quick
discernment in the interpretation of the phenomena investigated.
Nothing seemed so insignificant as to escape his notice, and little was
so obscure as to defy his explanation.

Among the fruitful practical results of Helmholtz's untiring activi-
ties, we do not exaggerate in placing a superlative value upon his
invention of the Opthalmoscope, — not only a most precious endowment
of science, but as bestowing immeasurable benefits upon the whole
human race.

We may well say, with Hasner : *' The ophthalmoscope is not only
the most valuable boon to ophthalmology, but is also one of the great-
est creations of our century. What the telescope is to astronomy,
the ophthalmoscope is to ophthalmology. The telescope owed its
existence to an accident, but the ophthalmoscope is absolutely the
mature offspring of theory, and is therefore a greater ornament than
the former, not only to Helmholtz, its originator, but also to the age
itself, which has not been here indebted to blind chance for great dis-
coveries, but has known how to deduce them from exact and laborious
scientific investigations."

Zehender, himself illustrious as an author and teacher, says of
Helmholtz : " For more than two hundred years physiologists and
mathematicians earnestly and with great sagacity sought for a solution

VOL. XXX. (n. S. XXII.) 38

594 BARON VON HELMHOLTZ.

of the mode in which the eye instantly and involuntarily adapts itself
for various distances, near and far. It was reserved for Helmholtz
and his collaborator, Cramer, to solve this problem, by proving that
an adaptive accommodation is effected by an increase of convexity of
the crystalline lens, and principally of its anterior surface, through the
agency of the ciliary muscle." The demonstration of these facts, by
means of oblique illumination, was in this wise.

In a darkened room, a lamp fiame, placed near the eye to be ob-
served at an angle of about 30° from its visual axis, gives, while the
eye looks at a distance, to an observer placed at about the same angle
at the opposite side of the visual line, three reflected images of the
flame: one erect, from the cornea; another, also erect, from the ante-
rior capsule of the crystalline lens; and a third, an inverted and
smaller image, from the posterior capsule of the crystalline. If now
the observed eye, instead of looking at a distance, accommodates itself
for a near object, say at twelve inches, the reflected image from the
anterior surface of the lens appears lessened in size and approaches
the corneal reflection, — a change which could result only from an
increase of convexity of the anterior surface of the crystalline. The
inverted image from the posterior capsule of the lens remains prac-
tically unchanged in size or position, proving that but slight, if any,
change of curvature occurs at this posterior surface of the lens during
accommodation for near objects.

Of all proof, we deem ocular evidence the most conclusive. Thanks
to Professor von Helmholtz, we possess, in his supreme inquisitor,
the opthalmoscope, an interpreter not only capable of revealing and
explaining hitherto unknown physiological laws of normal vision, but
which also affords clear and positive disclosures of previously unsus-
pected morbid processes, which, if unarrested, may imperil the most
precious of our senses, and our chiefest means of instruction and of
enjoyment. More than by any other faculty we live, and move, and
learn, and enjoy by that of vision. To our eyes we owe almost every-
thing we have, and are, and hope to become.

Were the revelations of the ophthalmoscope as to pathological and
physiological conditions limited to such as affect the eye itself, they
would still have an infinite value. But these disclosures have a still
wider range, showing, through changes discoverable by its means in
the retina and other internal structures of the eye, the advent of yet
graver disease in other remote and most important parts of the body,
— as, for instance, in the brain or the kidneys, — before the presence
of any morbid tendency has been suspected.

BARON VON HELMHOLTZ. 595

Fortunately for scieuce, Helmholtz was pre-eminently an observer
and an interpreter ; fortunately for science and for himself, he was
destined to fill positions, one after another, not only of preferment, but
of opportunity. When at an early age, in 1855, four years after his
invention of the ophthalmoscope, he was appointed Professor of
Anatomy and Physiology at Bonn University ; then, three years later
he became Professor of Physiology at Heidelberg University. Since
1871 he has been Professor of Physics at Berlin University, and in
1877 he became its Rector, becoming thus a veritable apostle of
natural science.

On his election to membership in the French Academy he was
hailed as " the foremost naturalist of his age, to whose glory nothing
was wanting, but whose admission conferred fame upon the Academy."
In 1873, the Copley Medal was awarded to him by the Royal Society
of Great Britain.

In 1856, when thirty-five years old, Helmholtz published one of
his works, modestly styled by himself a " Handbook of Physiologi-
cal Optics," but which is a book of more than a thousand pages, — a
stupendous monument of his patience, his alert and wise perception,
his industry, and his accuracy in a field where not only conditions^
but functions came to be investigated in the light of new revelations,
and where the observer must be a law unto himself.

It was this complete equipment of various knowledge, — in physi-
ology, in physics, in biology, in mathematics, in optics, — joined to
powers of quick and accurate perception and judgment, which so
greatly enhanced the glory of Germany's and Europe's most illus-
trious and honored savant. It is hoped that the work of the later
period of his career may be collected and published, to add yet further
contributions to scientific knowledge.

In 1883 an hereditary title of nobility was conferred by the Em-
peror of Germany upon Plelmholtz. In 1891, on his seventietli birth-
day, a jubilee ovation was tendered to him, where, in response to
enthusiastic testimonials of admiration and affection from the Ger-
man Emperor and other European sovereigns, from tlie President of
the French Republic, from numerous learned societies and the great
Universities, the Professor with great emotion referred to his disabil-
ity of health in his earlier years of childhood, and spoke of his strong
inclination, even from that period, for exact and experimental studies,
which he had most zealously pursued.

In 1893, Baron von Helmholtz, accompanied by the Baroness,
made a brief visit to this country, attending the Pan American.

o96 BARON VON HELMHOLTZ.

Medical Coagress at Washington, and making a trip to the Chicago
P^xposition and the Western States. Coming afterwards to Boston
and to Harvard College, they were greatly pleased with their visit.
In paying a visit of respect to them, I remarked, " Professor, we
know a hundred fold as much in opthalmology as before you gave us
the ophthalmoscope." With a deprecating smile and gesture, he
replied, " I was not even a Doctor of Medicine ! I was only Pro-
fessor of Physics at the University ! but I set myself this problem,
'To illuminate if I could the interior of the eye,' — and I succeeded ! "
Alas! but a few mouths have passed since the eclipse of that great
liofht which had done so much for those who sit in darkness, for
science, and for the world. As the creator of modern opthalmology,
substituting by means of the opthalmoscope certainty for surmise,
Helmholtz has bestowed an incalculable benefit upon mankind.
1895. H. W. Williams.

At the request of the late Dr. Williams the following account of
the original work of Helmholtz was prepared to be added to the bio-
graphical notice.

The work of Helmholtz as an investigator seems to have begun
while he was studying at Berlin in preparation for the profession of mili-
tary surgeon, and his first scientific paper was his Proraotionsschrift,
" De Fabrica Systematis Nervosi Evertebratorum," published in 1842.
Helmholtz's knowledge of mathematics, afterwards so profound, ap-
pears to have been at this time comparatively slight. His attention
was chiefly devoted to physiology, though he was especially interested
in physics for its own sake, as well as for the reason that accurate
physiological measurements could be made only by persons who were
able to devise and to use intelligently physical apparatus.

During most of the interval between 1842, when he became MilitJir
ArtZ; and 1847, when, through the kind intercession of Alexander
von Humboldt, he was honorably discharged from the army, Helm-
holtz was stationed in his native town of Potsdam, and there, besides
carrying on his researches in physiology, some of the results * of
which he published, he studied mathematics and physics, with the
help of books borrowed from the library of the Gymnasium, to such

* " Ueber das "Wesen der Faulniss und Gahrung," 1843. " Ueber den StoflT-
verbrauch bei der Muskclaction," 1845. " ]^ie Physiolog^ische Warme," 1845.
" B^icht iiber die Tlieorieder Physiolojjischen Warmecrsclieinungen furl845."
■" Ueber die Warmeentwickelung bei der Muskelaction," 1847.

BARON VON HELMHOLTZ. 597

good purpose that he was soon able to read easily the most abstruse
treatises on these subjects, and to write his famous essay, " Ueber die
Erhaltung der Kraft," in which the great doctrine of the conserva-
tion of energy was first forced upon the attention of physicists.
The seven papers which Helraholtz published before he left the army
had already (in 1848) given him a high reputation among physiolo-
gists, and after a year spent as teacher of anatomy at the Kunst-
akademie at Berlin, he was called to a Professorship of Physiology and
Pathological Anatomy at Konigsberg. During the six years which he
spent here Helmholtz published about twenty papers, mostly of great
importance, and of these almost all, except those on the velocity of
propagation of nerve excitation, and on the duration of induced elec-
tric currents, had to do with physical or with physiological optics.

These twenty papers, however, do not represent the whole of the
work which Helmholtz did at Konigsberg beyond his professional
duties, for he must have written here the greater part of his " Hand-
buch der Physiologischen Optik," the first edition of which appeared
in 1856. It was by this time clear that Helmholtz had become one
of the first of living physicists. Almost every one of his publications,
whatever its title, showed his mastery in some branch of physics, and
made some contribution to the world's knowledge of the subject.

From Konigsberg, Helmholtz went to Bonn, and thence, in 1858, to
Heidelberg, where he remained as Professor of Physiology until 1871.
While at Bonn and Heidelberg he published forty-three considerable
papers, besides his " Lehre von den Tonempfindungen," which ap-
peared in 1862, and which he says in his Preface is fruit of work
stretching over eight years,* though of the fourteen publications
which he wrote in the six years after he left Konigsberg at least
five have to do with matter foreign to acoustics and to tone-sensations.
One of - these was an epoch making paper in mathematical physics, in
which it was shown that vortex rings and vortex filaments in perfect
fluids under the action of conservative forces are indestructible, and
that such rings and filaments apparently attract or repel one another
according to the relative signs of their vorticities.

One may get some conception of the catholicity of Helmholtz's tastes
and of the extent of his knowledge by reading a list of the subjects
of the papers which he wrote at Heidelberg on Physiology, Physical
and Physiological Optics, Physical and Physiological Acoustics, the

* " Indem ich die Fruchte achtjahriger Arbeit der Oeffentliclikeit uber-
gebe," etc.

598 MARQUIS DE SAPORTA.

Theory of Perception of Geometrical Truth, the Doctrine of Energy,
Hydrodynamics, and Electrodynamics. Towards the end of his stay in
Heidelberg, his attention was more and more turned in the direction
of physics and away from physiology. He had certainly become the
greatest living German physicist, and when Magnus died, in 1871, it
was on all sides agreed that he should be called to take the Director-
ship of the Physical Laboratory of the University at Berlin, and
natural that he should accept the position. From this time on by far
the larger part of his own experimental work was in the domain of
jjhysics, though he suggested and helped on to success the researches
in physiology of other experimenters, and when it became necessary
to review the whole literature of physiological optics on the occasion
of the preparation of a new edition of his Handbuch, he spent much
time and energy in studying and in drawing conclusions from the work
of others in this field.

Some of the most important of the later contributions of Helm-
holtz to mathematical and experimental physics are contained in his
papers on, —

1. Possible Discontinuities in the Motion of a Frictionless Fluid.

2. The Theory of the Motion of Viscous Fluids.

3. The Thermodynamics of Chemical Processes.

4. The Theoretical and Practical Limits to the Resolving Powers of

Microscopes.

5. Electrolytical Processes.

6. The Fundamental Laws of Electrodynamics.

7. Electrical Oscillations and the Nature of Electricity.

In 1888 Helmholtz resigned his place at the head of the Berlin
Laboratory in order to take charge of the newly established Reiclis-
Anstalt at Charlottenburg, and the last years of his life were chiefly
spent in organizing the work of this institution.

GASTON, MARQUIS DE SAPORTA.

The Marquis de Saporta was born on July 28th, 1823, and died
at the age of seventy-one years on January 26th of the present year,
at his residence in Aix-en-Provence.

Since the appearance of his first paper on the Fossil Plants of
Provence in 1860, he has been a prominent palaeobotanist, and yields
to few cultivators of that science in the number, variety, and impor-
tance of his memoirs and larger works. His greatest and most impor-
tant work is that on the Mesozoic Flora of France, to which he added

MARQUIS DE SAPORTA. 599

last year a valuable report on the Mesozoic Plants of Portugal. A
summary of this last work, in connection more particularly with its
bearing on the paloeobotany of North America, from the pen of Pro-
fessor Lester F. Ward, a fellow laborer in the United States, has
lately appeared in " Science " ; and perhaps with the exception of
those of his great rival, Heer of Zurich, who passed away before him,
no European works on the botany of the Mesozoic period are m(»re
frequently referred to than those of Saporta.

Though a specialist in the floras of the later geological periods, he
could enter with enthusiasm into the whole history of the vegetable
kingdom, in a manner at once elaborate, careful, and attractive to gen-
eral readers, and with an enlightened grasp of the succession of plants
in time, and of their relations to the various changes of climate and
geography in the different periods. This is remarkable in his popular
work, " Le Monde des Plantes," which goes over the whole field of
geological botany, is written in a clear and vivid style, and illustrated
with geological maps and very clever restorations of the forests of dif-
ferent periods.

His memoirs also cover a wide geographical range, as specimens
from many regions were submitted to him, and he was always ready,
in the kindest and most genial spirit, to give the benefit of his advice
and information to his fellow laborers in every part of the world.
His work was characterized by much discrimination and care, and by
a judicious attention to the geological horizons of the plants he studied,
but, like many other paloeobotanists, he was occasionally carried
away by his enthusiasm, so as to recognize as plants mere imitative
markings. This was especially the case in the controversies in which
he took part respecting the nature of certain markings on rocks whose
algal nature had been maintained by Delgado and others, while to
Natherst, and to palaeontologists generally who were familiar with the
tracks of animals and the imitative tracings on the surfaces of aqueous
deposits, they were of animal or of inorganic origin.

In conjunction with Professor Marion, Saporta published a work on
the Evolution of Plants, which forms three volumes of the French
International Library of Science. It abounds with curious informa-
tion of a very suggestive character, but was perhaps too ambitious in
the present state of knowledge. This the authors frankly admit, stat-
ing, in conclusion, that they can but point out a few landmarks to their
successors, "who may decipher the inscriptions of which we can but
spell out some letters."

But though an evolutionist, Saporta was by no means an agnostic.

600 MARQUIS DE SAPORTA.

He saw in the grand succession of vegetable forms a great and pro-
found design, related to the inorganic world and its mutations on the
one hand, and to the animal kingdom on the other. He sums up this
conclusion in his " Le Monde des Plantes " in the following words,
which may serve as an example of his style and of his habit of thought
in the wider problems of his science : —

'•' Mais, si Ton remonte de phenomene en phenomene plus haut que
les appareuces mobiles et contingentes, il semble que Ton aboutisse
forcement a quelque chose d'entier, d'immuable et de superieur,
qui serait I'expression premiere et la raison d'etre absolu de toute
existence, en qui se resumerait la diversite dans I'unite, eternel pro-
bleme que la science ne saurait resoudre, mais qui se pose de lui-meme
devant la conscience humaine. La serait la vraie source de I'ideal
religieux ; de cette pensee se degagerait d'une fagon lumineuse, cette
conception de notre §-me a laquelle nous appliquons instinctivement le
nom de Dieu."

Saporta was Correspondant de I'Institut de France, a Foreign
Member of the Geological Society of London, a Foreign Honorary
Member of our Academy since 1885, and an honorary or correspond-
ing member of many other societies on both sides of the Atlantic.

1895. J. William Dawson.

Three Resident Fellows have been returned to the list of
Associate Fellows on account of removal from the Common-
wealth, and one Associate Fellow has been transferred to the
list of Resident Fellows.

The Academy has received an accession of eight Resident
Fellows, two Associate Fellows, and five Foreign Honorary
Members.

The Roll of the Academy cori'ected to date includes the
names of 195 Fellows, 95 Associate Fellows, and 67 Foreign
Honoraiy Members.

Mat 9, 1895.

LIST

OF THE

FELLOWS AND FOKEIGN HONORARY MEMBERS.

(Corrected to May 9, 1895.)

RESIDENT FELLOWS. — 195.

(Number limited to two liundred.)

Class L — Mathematical and Physical Sciences. — 71,

Section I. — 17.

Mathematics and Astronomy.

Solon I. Bailey, Arequipa, Peru.
Seth C. Chandler, Cambridge.

Alvan G. Clark, Cambridgeport.
J. Rayner Edmands, Cambridge.
Benjamin A. Gould, Cambridge.
Francis M. Green, Boston.
Gustavus Hay, Boston.

Henry Mitchell, Nantucket.

Edward C. Pickering, Cambridge.
John Ritchie, Jr.,
John D. Runkle,
T. H. Safford,
Edwin F. Sawyer,
Arthur Searle,
William E. Story,
Henry Taber,
O. C. Wendell,

Boston.
Brookline.
Williamstown.
Brighton.
Cambridge.
Worcester.
Worcester.
Cambridge.

Section H. — 20.

Physics.

A. Graham Bell, Washington.

Clarence J. Blake, Boston.
Francis Blake, Weston.

John II. Blake,
Charles R. Cross,
Amos E. Dolbear,
Edwin H. Hall,
Silas W. Holman,
William L. Hooper,
William W. Jacques,
Alonzo S. Kimball,
T. C. Mendenhall,
Benjamin O. Peirce,
Edward S. Ritchie,
A. Lawrence Rotch,
Wallace C. Sabine,
Elihu Thomson,
John Trowbridge,
A. G. Webster,
Harold Whiting,

Boston.

Boston.

Somerville,

Cambridge.

Boston.

Somerville.

Newton.

Worcester.

Worcester.

Cambridge.

Newton.

Boston.

Cambridge.

Lynn.

Cambridge.

Worcester.

Berkeley, Cal.

Section III. — 21.

Chemistry.

Samuel Cabot,
Arthur M. Comey,
Thos. M. Drown,
Charles W. Eliot,
Thomas GafReld,
Henry B. Hill,

Boston.

Cambridge.

Lehigh, Pa.

Cambridge.

Boston.

Cambridge.

602

RESIDENT FELLOWS.

Henry M, Howe, Boston.

Charles L. Jackson, Cambridge.
Leonai'd F. Kiunicutt, Worcester.

Charles F. JMabery, Cleveland, O.

Arthur Michael, Somerville.

George D. Moore, Worcester.

Charles E. Munroe, Washington.

John U. Nef, Chicago.

Robert H. Richards, Boston.
Theodore W. Richards, Cambridge.

Charles R. Sanger, St. Louis.

Stephen P. Sharjales, Cambridge.

Francis H. Storer, Boston.

Charles H. Wing, Ledger, N. C.

Edward S. Wood, Boston.

Section IV. — 13.

Technology and Engineering.

Eliot C. Clarke, Boston.

Gaetano Lanza, Boston.

E. D. Leavitt, Cambiudgeport.

William R. Livermore, Boston.
Hiram F. Mills, Lowell.

Cecil H. Peabody, Boston.
Alfred P. Rockwell, Boston.
Andrew H. Russell, Rock Island, 111.
Peter Schwamb, Arlington.

Charles S. Storrow, Boston.
George F. Swain, Boston.

AVilliam Watson, Boston.

Morrill Wyman,

Cambridge.

Class U. — Natural and Physiological Sciences. — 63.

Section III. — 24.
Zoology and Physiology.

Section I. — 13

Geology, Mineralogy , and Physics of

the Globe.

Thomas T. Bouve, Boston.

H. H. Clayton, Milton.

Algernon Coolidge, Boston.

William O. Crosby, Boston.

William M. Davis, Cambridge.

O. W. Huntington, Cambridge.

Robert T. Jackson, Boston.

Jules Marcou, Cambridge.

WilHam H. Niles, Cambridge.

John E. Pillsbury, Boston.

Nathaniel S. Shaler, Cambridge.

AVarren Upham, Cleveland, 0.
John E. Wolff,

Section II.
Botany.
William G. Farlow,
Charles E. Faxon,
George L. Goodale,
H. H. Hunnewell,
B. L. Robinson,
Charles S. Sargent,
Arthur B. Seymour,
Charles J. Sprague,
Roland Thaxter,

Cambridge.

— 9.

Cambridge.

Boston.

Cambridge.

AVellesley.

Cambridge.

Brookline.

Cambridge.

Boston.

Cambridge.

Alexander Agassiz, Cambridge.
Robert Amory, Boston.

James M. Barnard, Milton.
Henry P. Bowditch, Boston.
William Brewster, Cambridge.
Louis Cabot, Brookline.

W. T. Councilman, Boston.
Charles B. Davenport, Cambridge,
Harold C. Ernst, Boston.

J. Walter Fewkes, Boston.
Edward G. Gardiner, Boston.
Samuel Henshaw, Cambridge.
Alpheus Hyatt, Cambridge.

John S. Kingsley, Somerville.

Theodore Lyman, Brookline.
Edward L. Mark, Cambridge.
Charles S. Minot, Boston.
Edward S. Morse, Salem.
George H. Parker,
James J. Putnam,
Samuel H. Scudder,
William T. Sedgwick, Boston.
James C. White, Boston.

William M. Woodworth, Cambridge.

Cambridge.

Boston.

Cambridge.

RESIDENT FELLOWS.

603

Section IV. — 17.

Medicine and Surgery.

Samuel L. Abbot, Boston.
Edward H. Bradford, Boston.
Arthur T. Cabot, Boston.

David W. Cheever, Boston.
Benjamin E. Cotting, Roxbury.
Frank \V. Draper, Boston.
Thomas Dwight, Boston.

Reginald H. Fitz,
Charles F. Folsom,
Richard M. Hodges,
Frederick I. Knight,
Francis Minot,
Samuel J. Mixter,
W. L. Richardson,
Henry P. Walcott,
John C. Warren,
Henry W. Williams,

Boston.

Boston.

Boston.

Boston.

Boston.

Boston.

Boston.

Cambridge.

Boston.

Boston.

Class III. — Iforal and Political Sciences. — 61.

Section I. — 10.

Philosophy and Jnris^prudence.

James B. Ames, Cambridge.

Charles C. Everett, Cambridge.

Horace Gray, Boston.

John C. Gray, Boston.

G. Stanley Hall, Worcester.

Nathaniel Holmes, Cambridge.

John E. Hudson, Boston.

John Lowell, Newton.

Josiah Royce, Cambridge.

James B. Thayer, Cambridge.

Section II. — 20.

Philology and Archceology.

William S. Appleton, Boston.
Charles P. Bowditch, Boston.

Lucien Carr,

Franklin Carter,

Joseph T. Clarke,

Henry G. Denny,

Epes S. Dixwell,

William Everett,

WilUam W. Goodwin, Cambridge.

Henry W. Haynes, Boston.

Bennett H. Nash, Boston.

Frederick W. Putnam, Cambridge.

Edward Robinson, Boston.

Cambridge.
Williamstown.
Boston.
Boston.
Cambridge.
Quincy.

F. B. Stephenson,
Joseph H. Thayer,
Crawford H. Toy,
John W. White,
Justin Winsor,
John H. Wright,
Edward J. Young,

Boston.

Cambridge.

Cambridge.

Cambridge.

Cambridge.

Cambridge.

Waltham.

Section 111.-18.
Political Economy and History.

Charles F. Adams,
Edward Atkinson,
Edmund H. Bennett,
Mellen Chamberlain,
John Cummings,
Andrew M. Davis,
Charles F. Dunbar,
Samuel Eliot,
John Fiske,
A. C. Goodell, Jr.,
Henry C. Lodge,
Augustus Lowell,
Silas M. Macvane,
John C. Ropes,
Denman W. Ross,
Charles C. Smith,
F. W. Taussig,
Francis A. Walker,

Lincoln.

Boston.

Boston.

Chelsea.

Woburn.

Cambridge.

Cambridge.

Boston.

Cambridge.

Salem.

Nahant.

Boston.

Cambridge.

Boston .

Cambridge.

Boston.

Cambridge.

Boston.

604

RESIDENT FELLOWS.

Section IV. — 13.

Literature and the Fine Arts.

Francis Bartlett,
John Bartlett,
George S. Boutwell,
Martin Brimmer,
J. Elliot Cabot,

Boston.

Cambridge.

Groton.

Boston.

Brookline.

Francis J. Child,
T. W. Higginson,
S. R. Koehler,
Charles G. Loring,
Percival Lowell,
Charles Eliot Norton,
Horace E. Scudder,
Barrett Wendell,

Cambridge.

Cambridge.

Boston.

Boston.

Brookline.

Cambridge.

Cambridge.

Boston.

ASSOCIATE FELLOWS.

605

ASSOCIATE FELLOWS.

95.

(Number limited to one hundred. Elected as vacancies occur.)

Class I. — Mathematical and Physical Sciences. — 36.

Chicago.

San Francisco.

Baltimore.

Washington.

Washington.

San Jose, Cal.

Allegany, Pa.

Section I. — 15.

Mathematics and Astronomy.

Edward E. Barnard, San Jose, CaL

S. W. Burnhara,

George Davidson,

Fabian Franklin,

Asaph Hall,

George W. Hill,

E. S. Holden,

James E. Keeler,

Emory McClintock, New York.

Simon Newcomb, Washington.

H. A. Newton, New Haven.

AVilliam A. Rogers, Waterville, Me.

George M. Searle, Washington.

J. N. Stockwell, Cleveland, O.

Chas. A. Young, Princeton, N.J.

Section II. — 7.

Physics.

Washington.
New Haven.
Washington.

Carl Barns,

J. Willard Gibbs,

S. P. Langley,

A. M. Mayer,
A. A. Michelson,
Ogden N. Piood,
H. A. Rowland,

Hoboken, N. J.
Chicago.
New York«,
Baltimore.

Section IH. — 8.

Chemistry.

Wolcott Gibbs, Newport.
Frank A. Gooch, New Haven.
S.W.Johnson, New Haven.
M. Carey Lea,
J. W. Mallet,
E. W. Morley,
J. M. Ordway,
Ira Remsen,

Philadelphia.
Charlottesville, Va.
Cleveland, O.
New Orleans.
Baltimore.

Section IV. — 6.

Technology and Engineering.

Henry L. Abbot, New York.
Cyrus B. Comstock, Washington.
W. P. Craighill, Washington.
F. R. Hutton, New York.

George S. Morison, Chicago.
William Sellers, Philadelphia.

Class II. — Natural and Physiological Sciences. — 32.

Section I. — 15.

Geology, Mineralogy, and Physics of
the Globe.

Cleveland Abbe,
George J. Bru.sh,
Edward S. Dana,
Walter G. Davis,
Sir J. W. Dawson,
G. K. Gilbert,

Washington.
New Haven.
New Haven.
Cordova, Arg.
Montreal.
Washington.

James Hall,
Clarence King,
Joseph LeConte,
J. Peter Lesley,
J. W. Powell,
S. L. Penfield,
R. Pumpelly,
A. R. C. Selwyn,
G. C. Swallow,

Albany, N.Y.
New York.
Berkeley, Cal.
Philadelphia.
Washington.
New Haven.
Newport, R.I.
Ottawa.
Columbia, Mo.

606

ASSOCIATE FELLOWS.

Section II. — 4.

Botany.

A. W. Chapmau, Apalachicola, Fla.
D. C. Eatou, New Haven.
W. Trelease, St. Louis.
John D. Smith, Baltimore.

Section III. — 8.

Zoology and Physiology.

Joel A. Allen, New York.
W. K. Brooks, Baltimore.
George B. Goode, Washington.

O. C. Marsh,
H. N. Martin,
S. Weir Mitchell,
A. S. Packard,
A. E. Verrill,

New Haven.
Baltimore.
Philadelphia.
Providence.
New Haven.

Section IV. — 5.

Medicine and Surgery.

John S. Billings, Washington.
Jacob M. Da Costa, Philadelphia.
W. A. Hammond, New York.
Alfred Stille, Philadelphia.

H. C. Wood, Philadelphia.

Class III. — Moral and Political Sciences. — 27.

Section I. — 6.

Philosophy and

T. M. Cooley,
D. R. Goodwin,
A. G. Haygood,
Charles S. Peirce,
T. R. Pynchon,
Jeremiah Smith,

Jurisprudence.

Ann Arbor,Mich.
Philadeli^hia.
Oxford, Ga.
New York.
Hartford, Conn.
Cambridge.

Section II. — 6.

Philology and Archceology.

A. N. Arnold, Pawtuxet, R.I.
Timothy Dwight, New Haven.

D. C. Gilman, Baltimore.

A. C. Kendrick, Rochester, N.Y.

E. E. Salisbury, New Haven.
A. D. White, Ithaca, N.Y.

Section III. — 9.
Political Economy and History.

Henry Adams,
G. P. Fisher,
M. F. Force,
H. E. Von Hoist,
Henry C. Lea,
Edward J. Phelps,
W. G. Sumner,
J. H. Trumbull,
David A. Wells,

Washington.
New Haven.
Cincinnati.
Chicago.
Philadelphia.
Burlington, Vt.
New Haven.
Hartford, Conn.
Norwich, Conn.

Section IV. — 6.

Literature and the Fine Arts.

James B. Angell, Ann Arbor, INIich.
L. P. di Cesnola, New York.
F. E. Church, New York.

R. S. Greenough, Florence.
William W. Story, Rome.
W. R. Ware, New York.

FOREIGN HONORARY MEMBERS.

607

FOREIGN HONORARY MEMBERS. — 67.

(Number limited to seventy-five. Elected as vacancies occur.)

Class I. — Mathematical and Physical Sciences. — 23.

Section I.

— 10.

Section HL

— 8.

Mathematics and

Astronomy.

Chemistry

f.

Arthur Auwers,

Berlin.

Adolf Baeyer,

Munich.

Francesco Brioschi,

Milan.

Marcellin Berthelot,

Paris.

J. H. W. DoUen,

Dorpat.

Robert Bunsen,

Heidelberg.

H. A. E. A. Faye,

Paris.

August Kekule,

Bonn.

Hugo Gylden,

Stockholm.

Mendeleeff, St. Petersburg

Charles Hermite,

Paris.

Victor Meyer,

Heidelberg.

William Hoggins,

London.

Sir H. E. Roscoe,

London.

Otto Struve,

Pulkowa.

Julius Thomseu,

Copenhagen.

J. J. Sylvester,

Oxford.

H. C. Vogel,

Potsdam.

Section IV

— 3.

Section H

2.

Technology and E

ngineering.

Physics

•

Sir Henry Bessemer,

London.

Lord Rayleigh,

Witham.

Lord Kelvin,

Glasgow.

Sir G. G. Stokes,

Cambridge.

Maurice Levy,

Paris.

Class II. — Natural and Physiological Sciences. — 25.

Section I. — 6.

Geology, Mineralogy, and Physics of
the Globe.

H. Ernst Beyrich, Berlin.
Alfred Des Cloizeaux, Paris.
A. E. Nordenskicild, Stockholm.
C. F. Rammelsberg, Berlin.
Henry C Sorby, Sheffield.

Heinrich Wild, St. Petersburg.

Section II. — 6.
Botany.

J. G. Agardh, Lund.

E. Bornet, Paris.

Sir Joseph D. Hooker, London.
Baron von Mueller, Melbourne.
Julius Sachs, Wiirzburg.

Eduard Strasburger, Bonn.

608

FOREIGN HONORARY MEMBERS.

Section III. — 10.
Zoology and Physiology.

Du Bois-Reymond,

Berlin.

Ludimar Hermann,

Konigsberg

Thomas H. Huxley,

London.

Albrecht Kolliker,

Wiirzburg.

Lacaze-Duthiers,

Paris.

Rudolph Leuckart,

Leii^sic.

Sven Loven,

Stockholm.

C. F. W. Ludwig,

Leipsic.

Class III.

— Moral an

Louis Pasteur,

J. J. S. Steenstrup,

Paris.
Copenhagen.

Section IV. — 3.

Medicine and Surgery,

Sir Joseph Lister, London.

Sir James Paget, Loudon,

Rudolph Virchow, Berlin.

Moral and Political Sciences. — 19.

Section I. — 3.
Philosophy and Jurisprudence.

James Martineau, London.

Henry Sidgwick, Cambridge.

Sir Frederick Pollock, Oxfoi-d.

Section II. — 6.

Philology and Archceology.

Ingram Bywater, Oxford.

Sir John Evans, Hemel Hempstead.
Pascual de Gayangos, ]\Iadrid.
J. W. A. Kirchhoff, Berlin.
G. C. C. Maspero, Paris.
Max Miiller, Oxford.

Section III. — 7.

Political Economy

and History

Due de Broglie,

Paris.

James Bryce,

Oxford.

Ernst Curtius,

Berlin.

W. E. Gladstone,

Hawarden

Theodor Mommsen,

Berlin.

Jules Simon,

Pai'is.

William Stubbs,

Oxford.

Section

lY

. — 3.

Literature and

the

Fine Arts.

Jean Leon Gerome, Paris.
John Ruskiu, Coniston.

Leslie Stephen, London.

STATUTES AND STANDING VOTES.

STATUTES.

{Adopted May 30, 1854 : amended September 8, 1857, November 12, 1862,
May 24, 1864, November 9, 1870, May 27, 1873, January 26, 1876,
June 16, 1886, October 8, 1890, January 11 and May 10, 1893, April
11, iJfai/ 9, a?id October 10, 1894, a«o? March 13, ^;jn7 10, an(£ 3Iay
8, 1895.

CHAPTER I.

Of Fellows and Foreign Honoeary Members.

1. The Academy consists of Fellows and Foreign Honorary Ifem-
hers. They are arranged in three Classes, according to the Arts
and Sciences in which they are severally proficient, viz. : Class I.
The Mathematical and Physical Sciences ; — Class II. The Nat-
ural and Physiological Sciences ; — Class III. The Moral and
Political Sciences. Each Class is divided into four Sections, viz. :
Class I., Section 1. Mathematics and Astronomy ; — Section 2.
Physics ; — Section 3. Chemistry ; — Section 4. Technology and
Engineering. Class II., Section 1. Geology, Mineralogy, and
Physics of the Globe ; — Section 2. Botany ; — Section 3. Zoology
and Physiology ; — Section 4. Medicine and Surgery. Class III.,
Section 1. Philosophy and Jurisprudence ; — Section 2. Philol-
ogy and Archaeology ; — Section 3. Political Economy and
History ; — Section 4. Literature and the Fine Arts.

2. Fellows, resident in the State of Massachusetts, only, may
vote at the meetings of the Academy.* Each Eesident Fellow
shall pay an admission fee of ten dollars and such annual assess-
ment, not exceeding ten dollars, as shall be voted by the Academy
at each Annual Meeting.

* The number of Resident Fellows is limited by the Charter to 200.
VOL. XXX. (n. s. xxii.) 39

610 STATUTES OF THE AMERICAN ACADEMY

3. bellows residing out of the State of Massachusetts shall be
known and distinguished as Associate Pellows. They shall not
be liable to the payment of any fees or annual dues, but on remov-
ing within the State shall be admitted to the privileges,* and be
subject to the obligations, of Resident Fellows. The number of
Associate Fellows shall not exceed owe hundred, of whom there
shall not be more than forty in either of the three Classes of the
Academy.

4. The number of Foreign Honorary Members shall not
exceed seventy-five ; and they shall be chosen from among per-
sons most eminent in foreign countries for their discoveries and
attainments in either of the three departments of knowledge
above enumerated. And there shall not be more than thirty
Foreign Members in either of these departments.

CHAPTER II.

Of Officers.

1. There shall be a President, three Vice-Presidents, one for
each Class, a Corresponding Secretary, a Recording Secretary, a
Treasurer, and a Librarian, which officers shall be annually elected,
by ballot, at the Annual Meeting, on the second Wednesday in
May.

2. At the same time, and in the same manner, nine Councillors
shall be elected, three from each Class of the Academy, but the
same Fellows shall not be eligible on more than three successive
years. These nine Councillors, with the President, the three
Vice-Presidents, the two Secretaries, the Treasurer, and the
Librarian, shall constitute the Council. It shall be the duty of
this Council to exercise a discreet supervision over all nomina-
tions and elections. With the consent of the Fellow interested,
they shall have power to make transfers between the several
Sections of the same Class, reporting their action to the
Academy.

3. If any office shall become vacant during the year, the
vacancy shall be filled by a new election, and at the next stated
meeting, or at a meeting called for this purpose.

* Associate Fellows may attend, but cannot vote, at meetiugs of the Academy.
See Chapter I. 2.

OP ARTS AND SCIENCES. 611

CHAPTEE III.

Of Nominations of Officers.

1. At the stated meeting in March, the President sliall appoint
from the next retiring Councillors a Nominating Committee of
three Fellows, one for each class.

2. It shall be the duty of this Nominating Committee to
prepare a list of candidates for the offices of President,
Vice-Presidents, Corresponding Secretar}^, Recording Secretary,
Treasurer, Librarian, Councillors, and the Standing Committees
which are chosen by ballot ; and to cause this list to be sent by
mail to all the Resident Fellows of the Academy not later than
four weeks before the Annual Meeting.

3. Independent nominations for any office, signed by at least
five Resident Fellows and received by the Recording Secretary
not less than ten days before the Annual Meeting, shall be in-
serted in the call for the Annual JMeeting, which shall then be
issued not later than one week before that meeting.

4. The Recording Secretary shall prepare for use, in voting
at the Annual Meeting, a ballot containing the names of all
persons nominated for office under the conditions given above.

5. When an office is to be filled at any other time than at the
Annual Meeting, the President shall appoint a Nominating Com-
mittee, in accordance with the provisions of Section 1, which shall
announce its nomination in the manner prescribed in Section 2
at least two weeks before the time of election. Independent
nominations, signed by at least five Resident Fellows and received
by the Recording Secretary not later than one week before the
meeting for election, shall be inserted in the call for that
meeting.

•"O"

CHAPTER IV.

Of the President.

1. It shall be the duty of the President, and, in his absence,
of the senior Vice-President present, or next officer in order as
above enumerated, to preside at the meetings of the Academy ;
to summon extraordinary meetings, upon any urgent occasion ;
and to execute or see to the execution of the Statutes of the

612 STATUTES OF THE AMERICAN ACADEMY

Academy. Length of continuous membership in the Academy
shall determine the seniority of the Vice-Presidents.

2. The President, or, in his absence, the next officer as above
enumerated, is empowered to draw upon the Treasurer for such
sums of money as the Academy shall direct. Bills presented on
account of the Library, or the Publications of the Academy, must
be previously approved by the respective committees on these
departments.

3. The President, or, in hi-s absence, the next officer as above
enumerated, shall nominate members to serve on the different
committees of the Academy which are not chosen by ballot.

4. Any deed or writing to which the common seal is to be
affixed shall be signed and sealed by the President, when thereto
authorized by the Academy.

CHAPTER V.

Of Standing Committees.

1. At the Annual Meeting there shall be chosen the following
Standing Committees, to serve for the year ensuing, viz. : —

2. The Committee of Finance, to consist of the President,
Treasurer, and one Fellow chosen by ballot, who shall have
charge of the investment and management of the funds and trusts
of the Academy. The general appropriations for the expendi-
tures of the Academy shall be moved by this Committee at the
Annual Meeting, and all special appropriations from the general
and publication funds shall be referred to or proposed by this
Committee.

3. The Eumford Committee, of seven Fellows, to be chosen
by ballot, who shall consider and report on all applications and
claims for the Rumford Premium, also on all appropriations from
the income of the Kumford Fund, and generally see to the due
and proper execution of this trust.

4. The C. M. Warren Committee, of seven Fellows, to be
chosen by ballot, who shall consider and report on all applica-
tions for appropriations from the income of the C. M. Warren
Fund, and generally see to the due and proper execution of this
trust.

5. The Committee of Publication, of three Fellows, to whom
all memoirs submitted to the Academy shall be referred, and to

OF ARTS AND SCIENCES. 613

whom the priuting of memoirs accepted for publication shall be
intrusted.

6. The Committee on the Library, of three Fellows, who
shall examine the Library, and make an annual report on its
condition and management.

7. An Auditing Committee, of two Fellows, for auditing the
accounts of the Treasurer.

CHAPTER VI.

Of the Seceetaries.

1. The Corresponding Secretary shall conduct the correspond-
ence of the Academy, recording or making an entry of all letters
written in its name, and preserving on file all letters which are
received ; and at each meeting he shall present the letters which
have been addressed to the Academy since the last meeting.
With the advice and consent of the President, he may effect
exchanges with other scientific associations, and also distribute
copies of the publications of the Academy among the Associate
Fellows and Foreign Honorary Members, as shall be deemed
expedient ; making a report of his proceedings at the Annual
Meeting. Under the direction of the Council- for ISTomination,
he shall keep a list of the Fellows, Associate Fellows, and Foreign
Honorary Members, arranged in their Classes and in Sections in
respect to the special sciences in which they are severally profi-
cient; and he shall act as secretary to the Council.

2. The Recording Secretary shall have charge of the Charter
and Statute-book, journals, and all literary papers belonging to
the Academy. He shall record the proceedings of the Academy
at its meetings; and after each meeting is duly opened, he shall
read the record of the preceding meeting. He shall notify the
meetings of the Academy, and apprise committees of their ap-
pointment. He shall post up in the Hall a list of the persons
nominated for election into the Academy ; and when any indi-
vidual is chosen, he shall insert in the record the names of the
Fellows by whom he was nominated.

3. The two Secretaries, with the Chairman of the Committee
of Publication, shall have authority to publish such of the pro-
ceedings of the Academy as as may seem to them calculated to
promote the interests of science.

614 STATUTES OF THE AMERICAN ACADEMY

CHAPTEE VII.

Of the Teeasuree.

1. The Treasurer shall give such security for the trust reposed
in him as the Academy shall require.

2. He shall receive officially all moneys due or payable, and
all bequests or donations made to the Academy, and by order of
the President or presiding officer shall pay such sums as the
Academy may direct. He shall keep an account of all receipts
and expenditures ; shall submit his accounts to the Auditing
Committee ; and shall report the same at the expiration of his
term of office.

3. The Treasurer shall keep a separate account of the income
and appropriation of the Rumford Fund, and report the same
annually.

4. All moneys which there shall not be present occasion to
expend shall be invested by the Treasurer, under the direction of
the Pinance Committee, on such securities as the Academy shall
direct.

CHAPTEPt VIII.
Of the Librarian and Library.

1. It shall be the duty of the Librarian to take charge of the
books, to keep a correct catalogue of same, and to provide for
the delivery of books from the Library. He shall also have the
custody of the publications of the Academy.

2. The Librarian, in conjunction with the Committee on the
Library, shall have authority to expend, as they may deem ex-
pedient, such sums as may be appropriated, either from the Eum-
ford or the General Fund of the Academy, for the purchase of
books, and for defraying other necessary expenses connected with
the Library. They shall have authority to propose rules and
regulations concerning the circulation, return, and safe-keeping of
books ; and to appoint such agents for these purposes as they
may think necessary.

3. To all books in the Library procured from the income of
the Rumford Fund, the Librarian shall cause a stamp or label to
be affixed, expressing the fact that they were so procured.

OP ARTS AND SCIENCES. 615

4. Every person who takes a book from the Library shall give
a receipt for the same to the Librarian or his assistant.

5. Every book shall be returned in good order, regard being
had to the necessary wear of the book with good nsage. And if
any book shall be lost or injured, the person to whom it stands
charged shall replace it by a new volume or set, if it belongs
to a set, or pay the current price of the volume or set to the
Librarian ; and thereupon the remainder of the set, if the volume
belonged to a set, shall be delivered to the person so paying for
the same.

6. All books shall be returned to the Library for examination
at least one week before the Annual Meeting,

CHAPTEE IX.

Of Meetings.

1. There shall be annually four stated meetings of the Acad-
emy ; namely, on the second Wednesday in May (the Annual
Meeting), on the second Wednesday in October, on the second
Wednesday in January, and on the second Wednesday in March.
At these meetings only, or at meetings adjourned from these
and regularly notified, shall appropriations of money be made,
or alterations of the statutes or standing votes of the Academy
be effected,

2. Fifteen Fellows shall constitute a quorum for the transac-
tion of business at a stated meeting. Seven Fellows shall be
sufficient to constitute a meeting for scientific communications
and discussioiis.

3. The Recording Secretary shall notify the meetings of the
Academy to each Fellow residing in Boston and the vicinity ; and
he may cause the meetings to be advertised, whenever. he deems
such further notice to be needful.

616 STATUTES OF THE AMERICAN ACADEMY

CHAPTER X.

Of THE Election of Fellows and Honorary Members.

1. Elections shall be made by ballot, and only at stated
meetings.

2. Candidates for election as Resident Fellows must be pro-
posed by two or more Resident Fellows, m a recommendation
signed by them, specifying the Section to which the nomination
is made, Avhich recommendation shall be transmitted to the
Corresponding Secretary, and by him referred to the .Council for
Nomination. No person recommended shall be reported by the
Council as a candidate for election, unless he shall have received
a written approval, signed at a meeting of the Council by at least
seven of its members. All nominations thus approved shall be
read to the Academy at a stated meeting, and shall then stand on
the nomination list during the interval between two stated meet-
ings, and until the balloting. No person shall be elected a Resident
Fellow, unless he shall have been resident in this Commonwealth
one year next preceding his election. "If any person elected a
Resident Fellow shall neglect for one year to pay his admission
fee, his election shall be void ; and if any Resident Fellow shall
neglect to pay his annual assessments for two years, provided
that his attention shall have been called to this article, he shall be
deemed to have abandoned his Fellowship ; but it shall be in the
power of the Treasurer, with the consent of the Council, to dis-
pense (sub silentlo) with the payment both of the admission fee
and of the assessments, whenever in any special instance he shall
think it advisable so to do.

3. The nomination of Associate Fellows shall take place in
the manner prescribed in reference to Resident Fellows ; and
after such nomination shall have been publicly read at a stated
meeting previous to that when the balloting takes place, it shall be
referred to the Council for Nomination ; and a written approval,
authorized and signed at a meeting of said Council by at least
seven of its members, shall be requisite to entitle the candidate
to be balloted for. The Council may in like manner originate
nominations of Associate Fellows, which must be read at a stated
meeting previous to the election, and be exposed on the nomina-
tion list during the interval.

OF ARTS AND SCIENCES. 617

4. Foreign Honorary Members shall be chosen only after a
nomination made at a meeting of the Council, signed at the time
by at least seven of its members, and read at a stated meeting
previous to that on which the balloting takes place.

5. Three fourths of the ballots cast must be affirmative, and
the number of affirmative ballots must amount to eleven to effect
an election of Fellows or foreign Honorary Members.

6. Each Section of the Academy is empowered to present lists
of persons deemed best qualified to fill vacancies occurring in the
number of Foreign Honorary Members or Associate Fellows
allotted to it ; and such lists, after being read at a stated meeting,
shall be referred to the Council for Nomination.

7. If, in the opinion of a majority of the entire Council, any
Fellow — Kesident or Associate — shall have rendered himself
unworthy of a place in the Academy, the Council shall recommend
to the Academy the termination of his Fellowship ; and provided
that a majority of two thirds of the Fellows at a stated meeting,
consisting of not less than fifty Fellows, shall adopt this recomr
mendation, his name shall be stricken off the roll of Fellows.

CHAPTER XI.

Of Amendments of the Statutes.

1. All proposed alterations of the Statutes, or additions to
them, shall be referred to a committee, and, on their report at a
subsequent meeting, shall require for enactment a majority of
two thirds of the members present, and at least eighteen affirma-
tive votes.

2. Standing Votes may be passed, amended, or rescinded, at
any stated meeting, by a majority of two thirds of the members
present. They may be suspended by a unanimous vote.

CHAPTER XII.

Of Literaky Performances.

1. The Academy will not express its judgment on literary or
scientific memoirs or performances submitted to it, or included in
its publications.

618 STATUTES OF THE AMERICAN ACADEMY

STANDING VOTES.

1. Communications of which notice had been given to the
Secretary shall take precedence of those not so notified.

2. Resident Fellows who have paid all fees and dues charge-
able to them are entitled to receive one copy of each volume or
article printed by the Academy, on application to the Librarian
personally or by written order, within two years from the date
of publication. And the current issues of the Proceedings shall
be supplied, when ready for publication, free of charge, to all the
Fellows and members of the Academy who desire to receive them.

3. The Committee of Publication shall fix from time to time
the price at which the publications of the Academy may be sold.
But members may be supplied at half this price with volumes
which they are not entitled to receive free, and which are needed
to complete their sets.

4. Two hundred extra copies of each paper accepted for publi-
cation in the Memoirs or Proceedings of the Academy shall be
placed at the disposal of the author, free of charge.

5. Resident Fellows may borrow and have out from the
Library six volumes at any one time, and may retain the same
for three months, and no longer.

6. Upon special application, and for adequate reasons assigned,
the Librarian may permit a la/"ger number of volumes, not exceed-
ing twelve, to be drawn froni the Library for a limited period.

7. Works published in numbers, when unbound, shall not be
taken from the Hall of the Academy, except by special leave of
the Librarian.

8. Books, publications, or apparatus shall be procured from the
income of the Rumford Fund only on the certificate of the Rum-
ford Committee that they, in their opinion, will best facilitate
and encourage the making of discoveries and improvements which
may merit the Ruraford Premium.

9. The Annual Meeting and the other stated meetings shall be
holden at eight o'clock, P. M.

10. A meeting for receiving and discussing scientific commu-
nications may be held on the second Wednesday of each month
not appointed for stated meetings, excepting July, August, and
September.

OF ARTS AND SCIENCES. 619

RUMFORD PREMIUM.

In conformity with the terms of the gift of Benjamin, Count
Rum ford, granting a certain fund to the American Academy of
Arts and Sciences, and with a decree of the Supreme Judicial
Court for carrying into effect the general charitable intent and
purpose of Count Eumford, as expressed in his letter of gift, the
Academy is empowered to make from the income of said fund, as
it now exists, at any Annual Meeting, an award of a gold and
silver medal, being together of the intrinsic value of three
hundred dollars, as a premium to the author of any important
discovery or useful improvement in light or in heat, which shall
have been made and published by printing, or in any way made
known to the public, in any part of the continent of America, or
any of the American islands ; preference being always given to
such discoveries as shall, in the opinion of the Academy, tend
most to promote the good of mankind ; and to add to such
medals, as a further premium for such discovery and improve-
ment, if the Academy see lit so to do, a sum of money not
exceeding three hundred dollars.

INDEX.

Acanthomyces, Thaxter, 468.
Acetals derived from Substituted

Quinones, 409.
Acetylchloride, action on Etliyliso-

cyanide, 156.
Acid Clilorides, action on Nitropar-

affine Salts, 147.
Alcoholic Potash, action on a Ben-

zylhydroxylamine, 192.
Alkyliodides, action of Silver Dini-

troethane on, 14'2.
Ammon-Cupriammonium Acetobro-

mide, 460.
Ammonia, behavior of formylchlo-

ridoxime towards, 174.
behavior of Cyanisonitrosoa-

cethydroxamic acid tovpards,

176.
Aniline, behavior of Formylchlori-

doxime towards, 172.
action on Dichlordiphenoxy-

quinone, 425.
Antimony, Double Haloid Salts of,

•9.
Arceuthobium, 121.
Argentic, ratio to Strontic Bromide,

388.
Ascidian Egg, on the cell lineage of

the, 200.
Aster lepidopodus, 117.
Auramin Pyrophosphates, 267.
Auramin- pyrophospho-Molybdates,

270.
Auro-pyrophospho-Molybdates, 269.

B.

Basic Mercuric Carbondioxidoxime,
138.

Batteries, the Properties of, formed
of Cells joined up in Multi-
ple Arc, 194,

Bellis orthopoda, 117.
Benzoylformic Methylamide, 151.
Benzoylformic methylamide-phe-

nylhydrazouhydrate, 152.
Benzoylformic-phenylhydrazone
from benzoylformic-me-
thylamide, 153.
Benzylhydroxylamine, action of
Chloroformic and Alcoholic
Potash on a, 192.
Biographical Notices, list of, 553.
William Holmes Chambei's

Bartlett, 570.
Charles Edouard Brown-Se-

quard, 589.
Hermann Ludwig Ferdinand

von Helmholtz, 592.
Oliver Wendell Holmes, 555.
Edward Jackson Lowell, 562.
Ezekiel Gilman Robinson, 572.
Gaston, Marquis de Saporta,

598.
AVilliam Dwight Whitney, 579.
Robert Charles Winthrop, 566.
Bivalent Carbon, 151.
Bravoa densiflora, 122.
Bromanil, action of Sodic Phenyl-

ate on, 451.
Bromdinitrophenylbrommalonic
Ester, 407.
properties of, 408.

c.

Cacalia globosa, 119.

Calcium, Double Haloid Salts of, 9.

Carbyloxime, Fulminic Acid identi-
cal with, 160.

Carbyloxim-esters, 189.

Caustic Potash, behavior of Cyaniso-
nitrosoacethydroxamic Acid
towards concentrated, 178.

Ceratomyce mirabilis Thaxter, 480
confusus, 481.

622

INDEX.

Cerico-Molybdates, 278.
Centhophili, The North American,
11.

table of the genera of, 20.
Ceuthophilus, Scudder, 23.

table of the species of, 24.

agassizii, 81.

alpinus, 78.

arizonensis, 52.

bicolor, 72.

blatchleyi, 57.

brevipes, 49.

bruneri, 79.

csecus, 60.

calif ornianus, 93.

celatus, 48.

corticicola, 41.

crassus, 85.

devius, 99.

discolor, 88.

divergens, 76.

ensifer, 32.

fusiformis, 62.

gracilipes, 35.

grandis, 38.

henshawi, 97.

heros, 54.

inquinatus, 87.

lapidicola, 50.

latebricola, 37.

latens, 64.

latibuli, 44.

latipes, 95.

maculatus, 68.

meridionalis, 66.

mexicanus, 82.

neglectus, 67.

neomexicanus, 100.

nigricans, 61.

nodulosus, 73.

occultus, 77.

pacificus, 96.

pallescens, 83.

pallidus, 90.

palmeri, 40.

pinguis, 86.

sallei, 63.

scabripes, 102.

seclusus, 45.

secretus, 39.

spinosus, 58.

stygius, 33.

sylvestris, 84.

tenebrarum, 70.

terrestris, 46.

testaceus, 92.

Ceuthophilus uhleri, 56.
utahensis, 102.
uniformis, 53.
valgus, 74.
varicator, 42.
variegatus, 31.
viuculatus, 91.
Chloranil, action of Sodic Alcohol-
ates on, 409.
action of Potassic Phenylate
on, 423.
Chlorocarbonic Ether, action on

Ethylisocyanide, 158.
Chloroform, action on a Benzylhy-

droxylamine, 192.
Coefficient of Self-induction, a Heat
Method for measuring the,
247.
Communications, —

Wilder D. Bancroft, 324.
Francis Gano Benedict, 9.
W. E. Castle, 200.

B. M. Duggar, 396.
Wolcott Gibbs, 251.

C. Loring Jackson and H. S.
Grindley, 409.

C. Loring Jackson and C. A.

Soch, 401.
F. A. Laws and H. E. Warren,

490.
Charles F. Mabery, 1.
J. U. Nef, 124, 151.
B. O. Peirce, 194, 390.
Theodore William Richards,

369.
T. W. Richards and A. H.

Whitridge, 458.
B. L. Robinson and M. L. Fer-

nald, 114.
Samuel H. Scudder, 17.
P. G. Spalding and II. B. Shaw,

247.
Charles E. St. John, 218.
Roland Thaxter, 467.
A. W. Weysse, 283.
Morrill Wyman, 482.
Cooke, Josiah Parsons, death of,

508.
Commemorative meeting, 512.

Addresses by, —
Charles Loring Jackson, 513.
Henry Barker Hill, 523.
Augustus Lowell, 526.
Francis Humphreys Storer,

528.
Charles William Eliot, 530.

INDEX.

623

Council, Report of, 553, 599.
Crossosoma parviflora, 114.
Cupriaumionium Double Salts, 458.
Cupriauiinonium Formilrhloiide,
45S.
Lactobromide, 4G4.
Lactochloride, 465.
Propionobromide, 462.
Cyauisonitrosoacetainide, Desoxy-
pulminuric Acid identical
with, 180.
synthesis of, 183.
Cyanisonitrosoacethydroxamic acid,
174.
behavior towai'ds ammonia,

176.
behavior towards water, 177.
behavior towards concentrated

caustic potash, 178.
behavior towards concentrated

hydrogen chloride, 178.
constitution of, 179.

D.

Daihinia, Haldeman, 108.
table of the species, 108.
brevipes, IDS.
gigantea, 109.
Dalea Lumholtzii, 115.
Desoxypulminuric Acid, identical
with Cyanisonitrosoaceta-
mide, ISO.
Dibenzoate of Dichlordiethoxyhy-
droquinone, 443.
properties of the, 443.
Dibromdimethoxyquinone Dime-

thylheraiacetal, 452.
Dichlordiethoxyhydroquinone Di-
benzoate, properties of the
oxide of, 441.
reduction of the oxide of, 442.
Dichlordiethoxyquinone Dibenzoyl-
diethylacetal, 437.
properties of, 438.
saponification of, 440.
Dichlordiethoxyquinone Diethylace-

taldicarbonic Ester, 445.
Dihclordiethoxyquinone Diethyl-
hemiacetal, 432.
properties of, 433.
Dichlordietlioxyquinoue Tetraethyl-
acetal, 435.
properties of, 436.

Dicblordimethoxyquinone Diben-
zoyldimethylacetal, 444.
saponification of, 445.
Dicblordimethoxyquinone Dimethyl-
heraiacetal, 428.
other methods of preparing,
430.
Dicblordimethoxyquinone Diethyl-

hemiacetal, 434.
Dichlordiphenoxydroquinone, prop-
erties of, 424.
action of Aniline on, 425.
action of Sodium Malonic Ester

on, 425.
action of Sodic Methylate on,

428.
action of Sodic Ethylate on,

432.
action of Potassic Phenylate on,
446.
Dichlorquinonedimalonic Ester, So-
dium Salt of, 427.
Dichomyces princeps, 479.
Diethoxydiphenoxyquinone, 449.
Diethoxyquinonedimalonic Ester,

427.
Dimethoxydiphenoxyquinone, 450.

properties of, 450.
Dinitroethane. preparation of, 142.
Diphenoxyanilic Acid, properties of,

448.
Diplomyces, 468.

Actobianus, 469.

E.

Electrical Resistances of certain
Poor Conductors, On the, 390.
Encelia oblonga, 118.
J]riodendron acuminatum, 114.
Esenbeckia Hartmanii, 115.
Ethoxyformamidine, formation of,

191.
Ethylisocyanchloride, or Ethylimi-

docarbonylchloride, 156.
Ethyl Isocyanide, 151.
Ethylisocyanide, molecular rear-
rangement of, to Propioni-
trile, 154.
action of sulphur on, 155.
action of hydrogen sulphide on,

155.
action of acetylchloride on,

156.
action of phosgene on, 158,

624

INDEX.

Ethylisocyanide, action of chloro-

carbouic ether on, 158.
Ethyluitrolic Acid Benzoate, 143.
Eucantharomyces, 480.
atrani, 480.

r.

Fellows, Associate, elected, —

Walter Gould Davis, 504.

Hermann Eduard von Hoist,
504.

William R. Livermore, 551.

James McCosh, 512.
Fellows, Associate, deceased, —

James Edward Oliver, 551.

E. G. Robinson, 508.

W. D. Whitney, 508.
Fellows, Associate, List of, 605.
Fellows, Resident, elected, —

Samuel Fessenden Clarke, 547.

William Thomas Councilman,
547.

Charles Benedict Davenport,
547.

Robert Tracy Jackson, 547.

John Sterling Kiiigsley, 548.

George Howard Parker, 548.

John Eliot Wolff, 547.

William McMichael Woodward,
548.
Fellows, Resident, deceased,

Oliver Wendell Holmes, 508.

Edward J. Lowell, 508.

Robert C. Winthrop, 512.
Fellows, Resident, List of, 601.
Ficus Jaliscana, 122.
Foreign Honorary Members elected,

Sir Henry Bessemer, 550.

Ingram Bywater, 504.

Sven Love'n, 550.

Sir Frederick Pollock, 550.

Sir John Robert Seeley, 505.
Foreign Honorary Members, de-
ceased, —

Arthur Cayley, 540.

Baron von Helmholtz, 508.

Ferdinand Marie de Lesseps,
513.

Jean Charles Galissard de Ma-
rignac, 503.

Sir Henry C. Rawlinson, 549.

Marquis de Saporta, 549.

Sir John R. Seeley, 549.

Foreign Honorary Members, list of,

607.
Formylchloridoxirae, 160.

formation of, from sodic ful-
minate, 1G2.
preparation of, from silver ful-
minate, 164.
properties of, 164.
behavior towards silver nitrate,

166.
behavior towards aniline, 172.
behavior towards ammonia,
174.
Franseria nivea, 117.
Fulminic Acid identical with Car-
byloxime, 160.
esters of, 189.

G.

Galium Wrightii, 116.
Gammarotettix, Brunner, 111.
bilobatus. 111.

H.

Hadenoecus, Scudder, 22.
cavernarum, 22.
puteanus, 22.
Heimatomyces distortus, 477.
spinigerus, 478.
uncigerus, 478.
Hospitals, Experiments and Obser-
vations on the Summer Ven-
tilation and Cooling of, 482.
Hydrogen Chloride, Concentrated,
behavior of Cyanisonitrosoa-
cethydroxamic Acid towards,
178.
Hydrogen Sulphide, action on Ethyl-
isocyanide, 155.
Hysteresis, Experiments on the Re-
lation to Temperature of,
490.

Ilex rubra, 115.

Inorganic Acids, Researches on the

Complex, 251.
Isuretine, preparation of, 173.
Phenylisuretine from, 174.

INDEX.

625

L.

Laboulbeniacese, Xotes on, 467.
Laboulbenia Aspidoglossse, 473.

confusa, 476.

cornuta, 476.

decipiens, 473.

Hageni, 470.

Kunkelii, 471.

macrotheca, 474.

melanotheca, 472.

Oberthuri, 477.

palraella, 471,

pilosella, 467.

rigida, 475.

terniinalis, 475.
Leptosyne Arizonica, 118.
Lycium retusum, 120.

M.

Magnesium, Double Haloid Salts
of, 9.

Mangano-araraonic Pyrophospho-
jVIolybdates, 263.

Mangano-sodic Pyrophospho-Molyb-
date, 262.

Mangano-sodic Pyrophospho-Tung-
states, 265.

Marsilia mollis, 123.

Maurandia geniculata, 120.

Mercury Fulminate, Synthesis of,
135.

Methyl Isocyanide, 151.

Mimulus dentilobus, 120.

Molybdico-Tungstates, 271.

Monochlordiphenoxyquinone, prop-
erties of, 453.

N.

Nitroparaffine Salts, On the Consti-
tution of the, 124.
decomposition of primary and
secondary, by means of acids,
125.
action of acid chlorides on, 147.

Nitroeth ane-mercuric-chloride, de-
composition of, by means of
acids, 131.

North American Ceuthophili, 17.

0.

Officers elected, 505.

VOL. XXX. (n. S. XXII.)

P.

Perityle Lloydii, 118.
Phacelia rupicola, 119.
Phenoquiuone, experiments on, 455.
Phenylisuretiue, from Isuretiue, 174.
Philibertia cynanchoides, 119.
Phosgene, action on Ethylisocy-

anide, 158.
Phospho-Tungstate, new, 280.
Phrixocnemis, 102.

table of the species, 103.
bellicosus, 106.
truculentus, 103.
validus, 105.
Picrylbrommalonic Ester, 405.

properties of, 406.
Picrylmalouic Ester, 402, 404.

properties of, 405.
Pinus Lumholtzii, 122.
Platino-molybdate of Ammonium,

256.
Platino-molybdate of Potassium,

258.
Platino-Tungstates, 251.
Potassic Phenylate, action on Chlor-
amil, 423.
action on Dichlordiphenoxyqui-

noue, 446.
action on Trichlorquinone, 453.
Potassium Salt, secondary, 176.
Proceedings of Meetings, 503.
Propionitrile, molecular rearrange-
ment of Ethylisocyanide to,
154.
Pyrophospho-Molybdates, second

series of, 261.
Pyrophospho-Tungstates, second se-
ries of, 261.
Pyruvic - ethylamide - phenylhydra-
zone, 156.

Q.

Quinone, action of Sodic Ethylate
on, 454.

Quinones, Acetals derived from sub-
stituted, 409.

E.

Rhachomyces, 468.
speluncalis, 468.

40

626

INDEX.

S.

Salvia rubropunctata, 121.
Sedum Lumholtzii, 116.
Selenoso-Molybdates, 275.
Selenoso-Tuugstates, 276.
Sicyos collinus, 116.
Silico-Molybdates, 274.
Silver, ratio to Strontio Bromide,

384.
Silver Dinitroethane, action of Alky-

liodides on, 142.
Silver Fulminate, preparation of
Formylchloridoxime from,
164.
synthesis of, 166.
Silver Nitrate, behavior of Formyl-
chloridoxime towards, 166.
Silver Salt, primary, 176.
Sodic Alcoholates, action on Cblor-

anil, 409.
Sodic Ethylate, action on Dichlordi-
phenoxyquinone, 432.
action on Quinone, 454.
Sodicferrofulminate, 186.
Sodic Fulminate, formation of For-
mylchloridoxime, 162.
Sodic Methylate, action on Dichlor-
dijihenoxyquinone, 428.
action on Tetraphenoxyquinone,
450.
Sodic Nitroethane, decomposition

of, by acids, 128.
Sodic Nitromethane, decomposition

of, by means of acids, 132.
Sodic Nitropropane, decomposition

of secondary, by acids, 134.
Sodic Phenylate, action on Brom-

anil, 451.
Sodic Platino-tungstate, 253.
Sodium Malonic Ester, action on
Dichlordiphenoxyquinone, 425.
Sodium Picrylmalonic Ester, 402.
Sphaleromyces occidentalis, 469.
Spiranthes velata, 122.
Statutes and Standing Votes, 609.

amendments of, 508.
Strontic Bromide, the analysis of,
369.
properties of, 373.
ratio of Silver to, 384.
ratio of Argentic Bromide to,
388.
Strontium, Revision of the Atomic
Weight of, 370.

Sulphur, action on Ethylisocyanide,
155.

Sulphur in Volatile Organic Com-
pounds, On the Determina-
tion of, 1.

Sus Scrofa domesticus, On the Blas-
todermic Vesicle of, 283.

Telluroso-Molybdates and Tung-
states, 277.
Temperature, Experiments on the
Relation of Hysteresis to, 490.
Ternary Mixtures, 324.
Tetraphenoxyhydroquinone, 448.

properties of, 449.
Tetraphenoxyquinone, 446.
saponification of, 447.
action of Sodic Methylate on,
450.
Trichlorquinone, action of Potassic

Phenylate on, 453.
Trinitrophenylbrommalonic Ester,

405.
Tiinitrophenylmalonic Ester, 401.
Tropidischia, Scudder, 18.
xanthostoma, 19.

u.

Udeopsylla, Scudder, 109.

table of the species, 109.

nigra, 109.

robusta, 110.
Uranoso-Tungstates, 272.
Uredo Polypodii, variability in the
Spores of, 396.

V.

Volatile Organic Compounds, On
the Determination of Sulphur
in, 1.

W.

Water, behavior of Cyanisonitrosoa-
cethydroxamic acid towards,
177.

Wave Lengths of Electricity on Iroa
Wires, 218.

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