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}(
^ANNUAL SURVEY OF
AMERICAN CHEMISTRY
VOLUME X
1935
EDITED BY
CLARENCE J. WEST
DIRECTOR, RESEARCH INFORMATION SERVICE
NATIONAL RESEARCH COUNCIL
W. E. Bachmann
Lawrence W. Bass
Gustavus J. Esselen
Merrell R. Fenske
R. E. Gibson
Raleigh Gilchrist
P. H. Groggins
Herbert S. Harned
K. F. Herzfeld
Guido E. Hilbert
Wilbert J'. Huff
CONTRIBUTORS
Eric R. Jette
Webster N. Jones
M. S. Kharasch
Harry F. Lewis
Lloyd Logan
Pauline Beery Mack
C. M. Marberg
Benton B. Owen
L. H. Reyerson
F. O. Rice
R. C. Roark
Walter M. Scott
Caroline C. Sherman
Henry C. Sherman
Frank T. Sisco
Lyndon Small
G. Frederick Smith
Sherlock Swann, Jr.
E. Bright Wilson, Jr.
F. Y. Wiselogle
Don M. Yost
Published for
THE NATIONAL RESEARCH COUNCIL
BY
REINHOLD PUBLISHING CORPORATION
330 West 42nd Street, New York, N. Y.
1936
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QPl
Copyright, 1936, by
NATIONAL ACADEMY OF SCIENCES
Printed in the United States of America by
iHTESNATIONiO. TSXTBOOK PkESS
SCRANTON, Pa.
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FOREWORD
With this volume, the Annual Survey completes the first decade of
its existence, the ten volumes covering the period 1925 to 1935, inclu-
sive. During this time an endeavor has been made to cover, as com-
pletely as possible, the progress made in American Chemistry, and to
indicate, by implication if not by actual statements, the trends in the
various fields of pure and applied chemistry in the United States.
The favorable reception of the Survey leads us to believe that we have
accomplished these objectives as well as may be expected in a volume
of this size.
Any measure of success, however, is due entirely to the cordial and
unselfish cooperation of the many authors who have, in the various
volumes, given of their time, knowledge and experience in the prepa-
ration of their respective Chapters and it is a pleasure to acknowledge
this cooperation and to thank them for their contributions. Each chap-
ter represents many hours of thoughtful reading before a word can be
written, to say nothing of the time required to coordinate the hundreds
of papers into a unified whole.
Of the twenty- five chapters this year, twelve may be considered to
be devoted to industrial topics. This number is the same as last year,
although the subjects covered are quite different.
The Editor wishes to express his thanks to the Editorial Board
(F. W. Willard, P. H. Emmett and R. S. McBride) for the tjiought
given to the preparation of the Table of Contents and the selection of
authors; also, to Miss Callie Hull, for her assistance in checking the
thousands of references found in the present volume and in the reading
of the proof, and to Miss Marion E. Jackson, for the preparation of
the Author Index.
Clarence J. West
Washington, D. C,
May 18, 1936.
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CHAPTER
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
IX.
X.
XI.
XII.
XIII.
XIV.
XV.
XVI.
XVII.
XVIII.
XIX.
XX.
XXI.
XXII.
XXIII.
XXIV.
XXV.
Table of Contents
PAGE
Theories of Solution — Herbert S, Horned and Benton B.
Owen 7
The Kinetics of Homogeneous Gas Reactions — F. O.
Rice and K. h\ Herzfeld 33
Molecular Structure — E. Bright Wilson, Jr 45
Thermodynamics and Thermochemistry — R. E. Gibson . 59
Contact Catalysis — L. H. Reyerson 78
Inorganic Chemistry, 1933-1935— Don M, Yost .... 90
Analytical Chemistry, 1934 and 1935 — G. Frederick Smith 102
Applications of X-Rays in Metallurgy — Eric R. Jette . 117
Ferrous Metallurgy — Frank T. Sisco 124
The Platinum Metals — Raleigh Gilchrist 138
Electro-organic Chemistry — Sherlock Swann, Jr. , . . 152
Aliphatic Compounds — M. S. Kharasch and C. M. Marberg 163
Carbocyclic Compounds — W. E, Bachmann and F, Y. Wise-
logle 184
Heterocyclic Compounds — Guido E. Hilbert 205
Alkaloids — Lyndon Small 218
Food Chemistry — Caroline C, Sherman and Henry C. Sher-
man 229
Insecticides and Fungicides — R. C. Roark 253
Gaseous Fuels, 1934 and 1935 — Lloyd Logan and Wilbcrt
J. Huff 280
Petroleum Chemi^stry and Technology — Merrell R, Fenske 325
Detergents and Detergency — Pauline Beery Mack ... 341
Cellulose and Paper — Harry F. Lewis • . 359
Synthetic Plastics — Gust aims J. Esselen and Walter M.
Scott 378
RvBBER— Webster N. Jones 398
Unit Processes in Organic Synthesis — Edited by P. H,
Groggins 419
Chemical Economics (1931-1935) — Lawrence W. Bass . . 440
Author Index 459
Subject Index 483
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Chapter I.
Theories of Solution.
Herbert S. Harned and Benton B. Owen,
Yale University,
General. Two contributions to the general theory of chemical
statics and dynamics published during the year 1935 should receive
the closest attention of those interested in the interpretation of
the properties of condensed phases. The first is a general develop-
ment of the statistical mechanics of fluid mixtures by Kirkwood ®^
by a method which possesses both power and simplicity. The
second is a general theory of reaction velocity by Eyring,23 in
which the nature of the intermediate activation complex in chem-
ical reaction is interpreted.
Kirkwood's treatment of the statistical mechanics of gas mix-
tures and solutions is based upon a principle clearly stated by
Onsager that the parameters necessary to express the potential of
intermolecular forces have the same status as the parameters of
external force, and may be manipulated in the same manner. This
principle is not restricted to any kind of intermolecular force.
Indeed, it is possible to introduce arbitrary parameters for the
potential of intermolecular force by means of which the coupling
between molecules may be varied in any convenient manner.
Upon this very general basis Kirkwood has obtained expres-
sions for the chemical potentials of the components of fluid mix-
tures in terms of comparatively simple integrals of the configura-
tion spaces of molecular pairs. These integrals have been studied
comprehensively, the equation of state of a real gas mixture
discussed, and a molecular pair distribution function for dense
fluids computed. The value of obtaining a powerful theoretical
approach to the statistics of condensed systems cannot be over-
estimated, and this is probably the best method of treatment yet
suggested.
Eyring's theory of reaction velocity is based upon the consider-
ation that the forces between atoms are due to the motion and
distribution of electrons and therefore must be computed by
quantum mechanics. If these forces have been computed, it can
be assumed that the nuclei of the atoms in this force field move
according to classical mechanics. Thus, if the forces are known,
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8 ANNUAL SURVEY OF AMERICAN CHEMISTRY
it becomes possible to compute reaction velocities according to
the classical methods of statistical mechanics, such as those devel-
oped by Herzfeld, Tolman, Fowler, and Pelzer and Wigner.
A group of atoms may arrange theitiselves in an infinite number
of ways. If the energy of such a system for the lowest quantum
state of electrons be plotted against the distance between nuclei,
a potential surface is obtained which determines the motion of
the nuclei. Low places on such surfaces correspond to com-
pounds, and these are the more stable, the higher the pass over
which the atoms must move in order to get to another stable
state. A reaction corresponds to the passage of the system from
one to another of these low regions of potential, and it is certain
that this process shall take place by way of the lowest pass. The
"activated state" is the highest point along this lowest pass.
According to this definition, the activated complex is described
by a saddle point with positive curvature in all degrees of freedom
except the one which corresponds to crossing the barrier. These
barriers are flat near the top. According to this picture of the
activated state, it appears that the activated complex is repre-
sented by a configuration of atoms corresponding to a stable com-
pound, except in the mode which corresponds to decomposition,
and this mode, because of the small curvature of the barrier, may
be treated as a single translational degree of freedom by the classi-
cal mechanics. This idea is the most important innovation of
Eyring's theory. Upon this basis, the calculation of the concen-
tration of the "activated complex," and subsequently the reaction
velocity constants for reactions of different types, can be achieved
by straightforward statistics and will not be described here.
Reaction Velocities in Liquid Systems. The theory of reaction
rates developed by Eyring leads to the following equation for the
velocity constant, ^,
kT
k'^KK"" — (1)
h
where k is a transmission coefficient, K- a dissociation constant between
kT
the activated complex and the reactants, and — a universal frequency,
h
since k is Boltzmann's constant and h is Planck's constant, k is of the
order of unity, except in cases where the reaction is one of adsorption
on a solid surface, in which k can be identified with the accommodation
coefficient. Wynne- Jones and Eyring ^^^ have applied this theory to
reaction velocities in condensed phases. They have shown that Bron-
sted's equation is a special case of the theory. Their views of the
critical complex agree closely with the original interpretation of Bron-
sted, since they come to the conclusions that the intermediate complex
is of extremely short life {r^ 10-^^ sees.), and that the activity coeffi-
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THEORIES OF SOLUTION 9
cient factor is essentially thermodynamic in character, or that the
activity coefficient of the activated complex is a thermodynamic quantity.
This differs from the conclusion of La Mer who regarded this quantity
as possessing kinetic and not thermodynamic significance.
It is important to note that equation (1) possesses characteristics
similar to those derived by different methods by other investiga-
tors.''^^' ^^3, 114 Since K~ is an equilibrium constant, equation (1) may
be written
_ AF± kT _Atf± A-Sfi kT
^'=K^ HT =K^ HT g" R (2)
~ h h
where A F^, A H^y and A S^ are free energies, energies, and entropies
of activation. We note in particular that the appearance of an equi-
librium constant in equation (1) brings out the importance of a free
energy of activation in the expression for the reaction rate, a conclu-
sion previously reached by an entirely different procedure by La Mer."^®
Eyring's theory of absolute rates has been discussed by Rodebush,^^^'
and by Kassel,®® and contrasted with the theory of Rice and Gershino-
witz by these authors.^^^' ^^^ A . similar theory has also been devel-
oped by Evans and Polanyi.* Wynne- Jones and Eyring have applied
the theory to some cases of monomolecular and bimolecular reactions,
and to acid and base catalysis in solution.
La Mer and Kamner s^' ^^ and La Mer and Miller ^^ have studied
the temperature dependence of the entropy and energy of activation.
They employed the equation
logi^ = j5 , (3)
2.ZRT
where k is the velocity constant, E^^^^ is the energy of activation, and
B is associated with the entropy of activation. La Mer and Kamner ®®
studied the effect of electrolytes on E„cf ^^^ ^- ^7 combining Bron-
sted's i;eaction velocity equation and Debye's limiting law for activity
coefficients, they obtained the limiting laws for the variation of B and
Fact with ion concentration in the forms,
Eaci/23 RT = E\ci/23 RT+ OJl saSb Vm (4)
B = B^ + 1.52 SASBVli (5)
Thus, the square root of the B varies three times as rapidly as E^ct with
ionic strength of the solution. La Mer and Kamner ^^ computed B
and Eact for the reaction between bromoacetate and thiosulfate ions,
and found that these quantities vary with temperature. They^^ also
studied the influence of non-electrolytes upon the velocity constant of
this reaction. They found that the constant B varies almost linearly
♦Evans, M. G., and Polanyi, M., Trans. Faraday Soc, 35: 875 (1935).
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10 ANNUAL SURVEY OF AMERICAN CHEMISTRY
with the reciprocal of the dielectric coSstant. La Mer and Miller^
have made an extended study of the effect of temperature upon the
velocity of dealdolization of diacetone alcohol catalysed by hydroxyl
ion. They found that the energy of activation is a function of the
temperature. All these results bear out the contention that both the
energy and entropy of activation are important in interpreting the
kinetics of chemical reactions in solution.
If at constant composition, the velocity constant is taken to be a
function of the dielectric constant and the temperature, Svirbely and
Warner ^^^ ^^ve shown that
d log k dD
(E)n=(E*)d + 2,3RT^ — (6)
dD dT
where (E)^^ and (E*)jy are critical increments (free energies ot
activation) in a solvent of fixed composition, and in a medium of fixed
dielectric constant, D, respectively. E, not £*, should be considered
true critical increments. Svirbely and Warner used this idea, com-
bined with the Bronsted equation, and Scatchard's equation for medium
effects on reaction velocities, to derive equations for the influence of
dielectric constant and ionic strength on critical increments. The
predictions are in good agreement with observed results of the reac-
tion between ammonium and cyanate ions over a considerable tem-
perature range, and in water-methyl alcohol mixtures at dielectric
constants of 63.5 and 5 5.0. Part of the experimental resuhs used in
this computation were obtained by Warner and Warrick.^^s
Sturtevant^^^ has extended Christiansen's treatment of the theory
of bimolecular ionic reactions by taking into account the possibility
of orientation effects. He obtains a solution for the case in which one
of the ions is assumed to be a problate spheroid. The result shows
that electrostatic orientation effects in reactions between the ions are
negligible in dilute solution, and that deviations from Bronsted's equa-
tion must be attributed to other causes.
The velocities of the reactions of sodium bromomalonate andl)romo-
succinate and the thiosulfate ion have been determined by Bedford,
Austin and Webb ^ at different temperatures. The results are not in
accord with Bronsted's theory. The discrepancy was attributed to
orientation effects.
Straup and Cohn ^^o have measured the rates of reaction of the thio-
sulfate ion with the uncharged molecule of ethyl iodide and bromo-
acetate ions in aqueous solutions containing urea, ethyl iodide, and
amino acids. The rates of reaction with the uncharged molecule are
increased by alcohol, and to a small extent by urea, and decreased by
ions and amino acids. The rate of reaction with ions is increased
by the presence of ions and urea, but decreased slightly by alcohol.
The effect of change of media upon these reaction velocities is not
due entirely to the change in dielectric constant. In the presence of
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THEORIES OF SOLUTION 11
the amino acids the results may be accurately computed by the velocity
equations of Kirkwood, which the latter developed by the Bronsted-
Christiansen method from his theoretical treatment of activity coeffi-
cients of amino acids.
Further study of the decompostion of nitramide in acid and acid-salt
mixtures has been carried out by Marlies and La Mer.^®. The tech-
nique, both of preparation of the nitramide and measurement of its
decomposition, has been improved to the extent that the accuracy is
about 1 percent. A negative primary salt effect was found and was
attributed to the influence of the salts on the catalytic activity of the
base, water. The evidence indicates a small acid catalysis which had
not been observed by earlier investigators of this reaction. The
mechanism of the reaction has been discussed, and a mechanism for
the acid catalysis proposed. If a catalysis by the hydroxide ion be
assumed, then the catalytic constant for this ion is about 2,000 times
that of any other ion yet studied. A lower velocity is obtained in
heavy water than in ordinary water.
The velocity of inversion of sucrose catalyzed by strong acid solu-
tions has been investigated by Krieble.''^^ The velocity constants are
not functions of either the activity or concentration of the hydrogen
ion. The suggestion was made that both the hydrogen ion and hydro-
chloric acid molecule, or both ions, act as catalysts. On this basis,
the velocity constants for hydrochloric and hydrobromic acid as cata-
lysts may be expressed as a function of the activities. Krieble and
Reinhart*^^ have determined the activity coefficient of hydrochloric acid
at high concentrations in water and sucrose solutions. A definite
relationship between the velocity constant of inversion of cane sugar
and these activities was noted. The velocity constant of cane sugar
hydrolysis, catalyzed by acids and by invertase, has been investigated
by the dilatometric method by Hitchcock and Dougan.^^ The values
obtained for the acid hydrolysis agreed closely with those determined
polarimetrically. The effects of sucrose concentration and />H upon
the velocity of the invertase reaction, determined dilatometrically, were
in agreement with those evaluated polarimetrically. The total con-
traction per mole of sugar, when hydrolysis was complete, varied with
the concentration of the catalyst and sucrose. It was concluded that
the dilatometric method may be employed with confidence for the
investigation of cane sugar hydrolysis in acid solutions, and for the
study of invertase action.
The primary salt effect and temperature coefficient for the velocity
of hydrolysis of diethylacetal has been studied extensively by Riesch
and Kilpatrick.115 fjie energy of activation was found to be inde-
pendent of the salt concentration within the experimental error. It
was found that the logarithm of the velocity constant did not vary
linearly with the salt concentration, although at high concentrations a
linear relationship was approached.
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12 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The kinetics of the fourth order reaction,
BrOr+ 5 Br-+ 6H^ = 3 Br, + 3 H^O,
has been extensively investigated by Bray and Liebhafsky.® The elec-
trolyte was mainly perchloric acid in the presence of some sodium
bromide and sodium perchlorate. Comparison of the results with those
of Young and Bray for the velocity of the reaction,,
BrOr+ 3 H,0, = 3 Oa + Br-+ 3 H^O,
was made. No evidence of specific salt effects was noticed at ionic
strengths less than 0.5. The ionization constant of the bisulfate ion,
determined from the kinetic data in sulfuric acid and sulfate solutions,
was found to be in agreement with the value obtained from conductance
and electromotive force measurements.
Infra red absorption was employed by Plyler and Barr m to measure
the reaction rate of acetic anhydride and water. The error in the
determination of the velocity constant is of the order of 10 per cent.
The use of the Rayleigh interferometer for the determination of reac-
tion velocities in solution has been discussed by Luten.^^
Hammett ^^ has brought out several relationships between reaction
rates and dissociation constants for reactions of the type,
AB + C >A + BC.
As an example, we cite the reaction,
RCOOCH, + N(CH3)3 ^ RCOO- + NCCH,)^
in which case the logarithm of the velocity constant was shown to vary
approximately linearly with the logarithm of the ionization constant
of the acid of the ester. A similar correlation was found for the
reaction,
C.H5COOR + OH- ^QHoO- + RCOOH,
in which case the variation of the logarithm of the velocity constant
was linear with the logarithm of the ionization constant of RCOOH.
Acid and base catalyses for a number of reactions may be treated suc-
cessfully in a similar manner. Hammett ^^ has also obtained an inter-
esting correlation between a specially defined acidity function, mea-
sured in terms of reaction with a series of indicators, and the velocity
constants of some reactions catalyzed by strong acids, such as the
inversion of cane sugar, the hydrolysis of ethyl acetate, etc.
A number of possibilities for employing isotopes for the purpose of
determining mechanisms of reactions which take place in solution, have
been pointed out by Wynne- Jones.^^* Applications of these ideas to the
neutralization of nitroethane, the mutarotation of glucose, the inversion
of sucrose, and the decomposition of nitramide have been discussed.
Thermodynamics of Solutions. Electromotive Force and Thermo-
dynamic Properties of Electrolytes. A very accurate evaluation of the
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THEORIES OF SOLUTION 13
activity coefficient of sodium chloride at 25°, through the concentra-
tion range of 0.005 to 0.1 molal, has been carried out by Brown and
Maclnnes ^^ from measurements of the cells,
Ag I AgCl I NaCl (cO I NaCl (c.) | AgCl | Ag.
The accuracy of their measurements was of the order of 0.01 mv. By
combining these results with the transference numbers obtained by
Longsworth, and the equation of the Debye and Hiickel theory con-
taining the mean distance of approach, the activity coefficient of sodium
chloride was computed.
Keston^"^ has shown that a very reproducible silver-silver bromide
electrode can be made from an intimate mixture of 90 percent silver
oxide and 10 percent silver bromate made in the form of a paste,
which was held on a helix of platinum wire and then heated to 650°.
The cells,
H^ I HBr (m) | AgBr | Ag,
were measured from 0.001 M to 0.02 M at 25°. The electromotive
forces were found reproducible .to within ±0.1 mv., and the results
were found to fit the Debye and Hiickel equation very closely, if an
apparent ionic diameter of 4.5 Angstroms was employed. Owen ^^^
by measuring the cells,
H3 I HBO, (m,), NaBO, (m,), KX (w,) | AgX | Ag,
in which X was CI or I, was able to obtain the standard potential of
the silver-silver iodide electrode, relative to the silver-silver chloride
electrode, from 5° to 40°. Since the standard potential of the latter
is known, he was able to compute the standard potential of the silver-
silver iodide electrode through this temperature range. Silver-silver
iodide electrodes made electrolytically and by fusion gave identical
electromotive forces.
Hamer,^3 ^nd Harned and Hamer ^®' ^^ have completed a very com-
prehensive study of the thermodynamics of sulfuric acid in aqueous
solutions, the standard electrode potentials of the cells, and reversible
electromotive forces of the cells related to the lead accumulator. The
standard potential of the cells,
H, I H,S04 (m) I PbSO, I PbOa | Pt%
was determined at 5° temperature intervals from 0° to 60°, and at
concentrations from 0.0005 to 7 M. Two methods of extrapolation were
contrasted, and the one which employed the Debye and Hiickel theory
and the dissociation constant of the bisulfate ion, was considered the
better. From these data, and the electromotive forces of the cells,
H, I H3SO. (m) I Hg.SO, I Hg,
from 0° to 60° and from 0.05 to 17.5 M, Harned and Hamer computed
the activity coefficient, relative partial molal heat content, and specific
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14 ANNUAL SURVEY OF AMERICAN CHEMISTRY
heat of sulfuric acid in aqueous solution. Since the cell reaction of
the first of these cells involves two molecules of water, and the second
involves no water, it was possible to compute the activity of water, or
the vapor pressure, from the cell measurements. Results obtained by
this procedure were in good agreement with the best vapor pressure
data at 25°. At 0° the activity coefficient of the acid computed from
the electromotive force measurements were in excellent agreement with
the freezing point measurements of Randall and Scott. The relative
partial heat content at 25°, computed from these results, agrees very
closely with the direct measurements of this quantity made by Lange,
Monheim and Robinson in the region of concentration of 0.0005 to
0.05 M, Values of the relative partial molal heat content and specific
heat from 0° to 60° and from to 17.5 M were computed.
By combining the electromotive forces of the above cells with those of
the cell, Pb (2-phase amalgam) | PbS04 | Na2S04 | Hg2S04 | Hg+,
and the cell, Pb | PbS04 | Pb++ | PbS04 | Pb (2-phase amalgam),*
obtained by Gerke, Harned and Hamer ^^ computed the standard poten-
tials of the electrodes reversible to the sulfate ion, and those related to
the electrodes of the lead accumulator. They also obtained the rever-
sible electromotive forces of the cell,
Pb I PbSO, I H,SO, (m) I PbSO, I PbO, | Pt*,
from 0° to 60°, and from 0.05 to 7 M sulfuric acid.
SchoU, Hutchison, and Chandlee^22 j^^ve measured the cell with
hydrogen and mercurous sulfate-mercury electrodes in alcohol solutions
containing sulfuric acid. From their results, the standard potential
of the cell, and the activity coefficient of the acid from 0.003 to 0.7 M
have been computed.
The "salt error" and standard potential of the quinhydrone electrode
have been the subject of a careful investigation of Hovorka and
Dearing.^^ The "salt error" (for fourteen electrolytes) was found to
vary nearly linearly with the concentration of solute. La Mer and
Armbruster^^ designed a small quinhydrone-silver chloride cell of
2-4 cc. capacity, and found that its electromotive force could be repro-
duced with an accuracy comparable to that obtainable with a larger
cell.
Electromotive forces of the cells.
Ha I HCl (w), in X % CH,OH-HaO | AgCl | Ag,
have been measured from 0° to 40° at 5° intervals, and at hydrochloric
acid concentrations from 0.005 to 0.1 M, by Harned and Thomas.^
Two solvent mixtures were employed, containing 10 percent and 20
percent by weight of methyl alcohol, respectively. The standard poten-
tials of the cell were computed.
By employing suitable cells without liquid junction, Harned and
Mannweiler^2 have determined the ionic activity coefficient and dis-
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THEORIES OF SOLUTION 15
sociation of water in sodium chloride solutions. Values of these quan-
tities were obtained over a salt concentration range from 0.02 to 3 M,
and at temperatures from 0° to 60°. Also, values of the ionic activity
coefficient of water in seven chloride and bromide solutions at 25°
were compiled from the best available data. It was found that at a
given temperature and salt concentration, the logarithm of the ionic
concentration product varies nearly linearly with the sum of the recip-
rocal of the ionic radii obtained from crystallographic data. This
shows that greater dissociation of water molecules takes place in the
presence of ions of smaller radii.
The thermodynamic properties of mixtures of hydrochloric acid in
uniunivalent chloride solutions, and hydrobromic acid in bromide solu-
tions, have been subjected to an analysis by Harned.^® The results
were contrasted with the recent computations of Akerlof and Thomas ;
and it was shown that the two empirical rules suggested by these
writers were not valid in the more dilute solutions. In concentrated
solutions, the contentions of these authors are more nearly valid, but
not strictly so. The results were also discussed in relation to Bron-
sted's original theory of specific ionic interaction. The deviations
from this theory which occur at concentrations from 0.1 to ZM were
pointed out. The extended theory of specific interaction as developed
by Scatchard and Prentiss may account for these deviations.
Kolthoff and Tomsicek '^^ have determined the standard potential of
the ferrocyanide-ferricyanide electrode, and its change of the potential
in some salt solutions. The variations of the potential with ionic
strength in the dilute systems is greater than that predicted by the
Debye and Htickel theory.
Valuable contributions to the knowledge of the oxidation potentials
of argentous-argentic salts in acid solution have been made by A. A.
Noyes, Hoard and Pitzer,^*^^ ^ ^ Noyes, Pitzer and Dunn,i<>^ and
A. A. Noyes and Kossiakoff.^<^3 Although these studies have no direct
bearing on the theories of solutions, they are of interest as a contribu-
tion to the study of standard electromotive forces and are mentioned
in this connection. The oxidation potential of the alkaline permanga-
nate-manganese dioxide electrode has been determined by Andrews and
Brown.3
Garner, Green, and Yost ^o have measured the electromotive forces
of the cells: Zn (amal., Ng) | ZnClg . 6NH3(^) | NH4CI (in liquid
NHgCw)) I CdCl2.6NH3(^) | Cd (amal, Ng). By combining these
results with those of cells previously measured by Elliott and Yost,
the standard potentials at 25° of the half cells whose reactions are^
Tl(^) -h CI- = TlCl(^) -h E-, Zn(s) -\- 2C1- -f- 6NH3(0 = ZnCl^
.6NH3(^) -h 2E-, and Cd(^) -f- 2C1--|-6NH3(0 = CdCl2.6NH3(^>
-f-2E-, have been determined provisionally in liquid ammonia solu-
tions. Provisional values of the activity coefficient of ammonium
chloride in liquid ammonia from 1 to 24.4 (Af ) (sat.) have also been
obtained.
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16 ANNUAL SURVEY OF AMERICAN CHEMISTRY
McBain and Barker »<> computed the activity coefficients of different
soap solutions at 90°. The results may be interpreted upon the
assumption that, in a given solution, the anion is a polyvalent micelle
with its charges spaced far apart. The behavior corresponds to that
of a half-weak uniunivalent electrolyte. McBain and Betz ^^ esti-
mated the degree of dissociation of straight chain sulfonic acids in
aqueous solution from measurements of cells with a liquid junction
containing a hydrogen electrode. McBain ^^ has compared the degrees
of dissociation obtained in this manner with those derived from con-
ductivity and freezing point measurements.
Formal thermodynamic equations for the osmotic and activity coeffi-
cients of undissociated, partially dissociated, and completely disso-
ciated solutes, have been stated by van Rysselberghe.^^^ j^ another
contribution, ^^3 this author computed the osmotic and activity coeffi-
cients of acetic acid at 0° corresponding to each of these descriptions.
The free energies of reactions involving potassium lead sulfate, lead
sulfate, lead iodide, potassium, sodium and lithium ions have been
determined at 25°, and at various ion strengths, by Randall and
Shaw.112 The mean activity coefficients of the ions in the equilibrium
solutions are about the same as those of barium chloride. One of the
solid phases was found to be PbS04 . K2SO4.
A thermodynamic treatment of the theory of electrode potentials has
been developed by Gross and Halpem.^^ By considering the electrode
processes as proceeding first in the liquid and then in the gas phase,
these authors obtained an expression for the normal potential in terms
of partly known thermodynamic quantities.
Martin and Newton®^ derived an equation for the electromotive
force of a cell with a moving liquid junction. A cell was constructed
which contained two silver-silver chloride electrodes in solutions of
two different chlorides. A sharp boundary was formed by passing
an outside current through the cell. When the electrical flow was
interrupted, measurements of the potential were made. The results
were not in accord with the equation.
Activity Coefficients from Vapor Pressure. Robinson^^"^' ^^^ has
determined the activity coefficients of the alkali bromides, iodides,
nitrates, acetates, and /)-toluenesulfonates at 25° by measuring the con-
centrations of these solutions isotonic with known concentrations of
potassium chloride solutions. The activity coefficients of bromides and
iodides computed from these data are in good accord with electromotive
force and freezing point data. Those of the nitrates agree with values
computed from freezing point measurements. Dynamic vapor pressure
measurements of aqueous solutions of calcium and aluminum nitrates
at 25° have been made by Pearce and Blackman.i^^^ Larsen and Hunt®*
have measured the vapor pressure of solutions of ammonium nitrate,
iodide, bromide, and chloride in liquid ammonia solutions. Extrapo-
lation of the results to zero concentration was difficult. The measure-
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THEORIES OF SOLUTION 17
ments gave a quantity ^ y, and plausible vaJues of k' wer^ estimated,
from which approximate values of y may be obtained. The results
indicate considerable ionic association.
Wynne- Jones ^^5 has determined the composition of the vapor over
known compositions of the mixture H2O and D2O. The mixtures
approximate very closely ideal solutions.
The total and partial vapor pressures of mixtures of ethyl alcohol
and cyclohexanol at 25° have been measured by Washburn and Han-
dorf,^^*^ and the activity coefficients of the components of the mixtures
have been evaluated. The deviations from ideal behavior have been
interpreted on the basis of the differences in polarity and internal
pressure of the components.
Solubility . Hildebrand^^ reported a series of experimental tests of
his general equation for the calculation of solubility from the properties
of the pure solvent and solute. To make the tests as general and vigor-
ous as possible, he selected solutes which would lead to unusually large
deviations from ideality, and both polar and non-polar solvents were
used. In view of the approximations involved in the derivation of the
equation, the agreement with experiment is remarkable. It was shown
that departures from spherical symmetry in the molecules, and the
presence of dipole moments do not necessarily vitiate the calculations.
Indeed, even the liquid-liquid system W-C32H66 — Snl4 can be treated
with reasonable success. Guggenheim * has criticized the application
of Hildebrand's equation, based upon the assumption of perfectly ran-
dom distribution, to solutions deviating so widely from ideality as to
be only partially miscible. He proposed a general statistical treatment
of his own, but it predicts more serious consequences for departures
from random distribution than those observed. Furthermore, Scatchard
and Hamer,i20 \^ ^n extensive investigation of liquid-liquid systems,
found Guggenheim's treatment less satisfactory than their simpler
theoretical deductions.
Several important papers appeared on the thermodynamics of solid
solutions. Seltz ^^4 developed methods for determining the forms of
the liquidus and solidus curves for binary systems, showing complete
solid miscibility,. where the deviations from Raoult's law are known
for the liquid and solid solutions. Scatchard and Hamer ^21 applied
equations for the chemical potentials to such systems, and developed
general relations which they employed in a successful analysis of the
experimental data on the Ag-Pd, and Au-Pt systems. Seltz ^25 devel-
oped equations for calculating the solidus and liquidus surfaces, with
tie lines, for ternary systems composed of perfect liquid and solid solu-
tions. Thompson '^^^ made a study of the solubility of lead in mercury
throughout the temperature range 20° to 70°.
Several studies of the solubility of gases under high pressure have
been reported. Wiebe and Gaddy ^^^ measured the solubility of a 3 : 1
♦Guggenheim, E. A.. Proc. Roy. Soc. (London). A148: 304 (1935).
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18 ANNUAL SURVEY OF AMERICAN CHEMISTRY
mixture of Ha and Na at 25° and of He at 0, 25, 50, and 75°.i*» The
pressure range extended to 1,000 atmospheres. The solubility of He
passes through a minimum at about 30°. The solubilities of helium
and argon in numerous salt solutions at 25° were determined by
Akerlof.^ The data could be described by the ordinary "salting out"
relation, \ogS = \ogSo—km, in which Sq and S are the solubilities
in pure water and in m-molal salt solution. The salting out constants, k,
were found to have the same order of magnitude as those of other non-
electrolytes. This conclusion was based upon an extensive summary
of salting out studies for gaseous, liquid, and simple solid non-electro-
lytes appearing in the literature. The salting out coefi&cients of a
complicated compoimd such as hemoglobin ^^ is considerably higher
than those considered here. The peculiar specific nature of the salting
out constants was emphasized, however, and it was pointed out that
the magnitudes of these constants do not arrange themselves in the
order of the activity coefi&cients, or mean atomic radii of the electro-
lytes present.
Akerlof and Turck^ determined the solubilities of a number of
strong, highly soluble salts in methanol-water mixtures, and in hydro-
gen peroxide-water mixtures at 25°. The results in the methanol-
water solutions showed a steady decrease in the logarithm of the solu-
bility with mole fraction of methanol. The distribution of the plots of
these variables was parallelled by plots of the data for similar salt-
organic sol vent- water systems available in the literature. It was
pointed out, as a rough approximation, that the ratio of the slopes of
these plots (for small organic solvent concentration) for a given pair
of salts was independent of the organic solvent; and for a given pair
of organic solvents, the ratio was independent of the salt. In the latter
case, the numerical value of the ratio is of the order of magnitude of
the ratio of the corresponding slopes for the dielectric polarization
curves of the solvent mixtures.
In hydrogen peroxide-water mixtures the solubility relationships of
the various salts were highly specific. Sodium chloride and nitrate
were salted-out, and potassium chloride and nitrate and sodium fluoride
were salted-in by hydrogen peroxide, and the effects were very pro-
nounced. In the case of sodium chloride and nitrate (and also lead
jiitrate) this effect is contrary to what might be expected from consider-
ation of the very high dielectric constants of pure hydrogen peroxide-
water mixtures. This interesting situation is further complicated by
the distribution experiments of Gorin,^^ from which it was shown
that all of the above salts behaved similarly in salting-in hydrogen
peroxide. In one respect, however, Gorin's results also point to a
peculiarity of sodium salts, since it was found that with the exception
of sodium ions the order of the salting-in effects of the ions on hydrogen
peroxide followed the same order as the salting-out effect on other non-
electrolytes in general. The salting-out of allyl alcohol from water
solution by a wide variety of salts was investigated by Ginnings and
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THEORIES OF SOLUTION 19
Dees.33 They expressed their results satisfactorily by means of equa-
tions of the form,
in which a, h, and c are empirical constants, and x and y are the per-
centages, by weight, of salt and alcohol, respectively. The salting-out
of butyl alcohol by various amino acids was found ^i to decrease with
increasing length of the hydrocarbon chain and to decrease with
increasing concentration of the amino acid.
Brown and Maclnnes ^^ described an elect rometric titration method
by which they determined the solubility of silver chloride in a dilute
potassium nitrate solution. They included a theoretical discussion of
the liquid junction and volume corrections, and of their novel method
of carrying out the computations. By virtue of the high sensitivity
of the method, they were able to observe a small but unmistakable
decrease in solubility with time (about 0.06 percent per hour).
Several papers appeared on solubilities in non-aqueous solutions ot
electrolytes. Swearingen and Florence ^^^ measured the solubility of
sodium bromide in acetone solutions of lithium and calcium perchlo-
rates. The activity coefficient of sodium bromide was found to be con-
siderably lower than required by the Debye-Hiickel theory, although the
concentrations involved were probably too high to expect good agree-
ment. A similar result was obtained by Davidson and Griswold ^^ for
zinc acetate in glacial acetic acid solution of sodium and ammonium
acetates. In this case, however, it was possible to show, by comparison
with barium acetate under the same circumstances, that a part of the
observed departure could be attributed to the amphoteric nature of
zinc acetate.
The solubilities of various amino acids have been reported in water,^^**
and in alcohol-water mixtures.^^^ McMeekin, Cohn, and Weare®*^
made an extensive study of the solubility of amino acid derivatives for
comparison with previously reported values for the corresponding free
acids. It was found that the ratio of the solubility in alcohol to that
in water is increased approximately threefold for each terminal CH2
group in the molecule. This rule applies both to amino acids and to
their derivatives. On the other hand, a CH2 group situated between
strongly polar groups, as in aspartic acid and asparagine, does not
measurably affect the solubility ratio. The solubilities of the amino
acid derivatives increased with alcohol content of the mixtures, which
is contrary to the salt-like behavior of the free acids. An estimate of
the effect of zwitterionic structure upon solubility ratio was obtained
by a comparison of the data for hydantoic acid with asparagine, and
with glutamine. The values obtained are in excellent agreement. In
a review of the chemistry of proteins and amino acids, Cohn ^^ has
emphasized the importance of such comparisons in the study of the
spatial relationships in amino acid molecules. Cohn's review includes
extensive discussions of dimensions, dielectric properties, and salting-
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20 ANNUAL SURVEY OF AMERICAN CHEMISTRY
out effects of amino acids, and goes into considerable detail concerning
applications of the equations of Scatchard and Kirkwood.
Joseph ®3 reported an interesting potentiometric investigation of the
mutual interaction of amino acids and salts. The measurements were
made with amalgam double cells of the type,
Ag-AgCl I MCl^mg) I HgMx I MCl^mg), Amino acid^^^j | AgCl-Ag,
in which M represents Na, Tl, or Zn. The influence of amino acids
upon the salts is such that log (Ys/Ys^) increases linearly with W2 at
high salt concentrations, and that the slope is independent of W3.
Accordingly, the corresponding function log (y2/Y2°) increases linearly
with W3, and the slope is independent of t/12. These slopes are in agree-
ment with salting-out coefficients derived from solubility measure-
ments. It was pointed out that in aqueous solutions the salting-out
effects are significant even at low concentrations, because both the
salting-out and electrostatic forces appear to be approximately propor-
tional to the first power of the concentration. The interaction observed
between glycine and zinc chloride was shown to be closely parallelled
by the results of freezing point on glycine with other (2-1) valence
type salts.
Calorimetric Measurements. An extensive calorimetric study of
amino acids was reported by Zittle and Schmidt.^^*^ They measured
heats of dilutions for solutions of eighteen amino acids, and found much
larger differences than would be anticipated from considerations of
molecular structure. Thus the variation of the relative apparent molal
heat contents of c^-arginine and J-lycine with concentration are large,
but of opposite sign. Heats of solution were calculated and compared
with values derived from solubility data. The heat capacities of
glycine, JZ-alanine, and JZ- valine were found to be always positive, and
their variation with concentration linear in m. This supports the
theoretical predictions of Scatchard and Kirkwood. Partial molal vol-
umes were also positive, but varied only slightly with concentration.
Edsall ^^ showed qualitatively how the formation of zwitterions
might influence apparent molal heat capacities. The heat capacities of
aqueous solutions of various hydrazonium salts and their heats of solu-
tion were measured by Cobb and Gilbert.^^' ^2
Gucker and Rubin ^^ calculated the apparent isochoric heat capacities,
^(^2)* for six (1-1) electrolytes, and found that their variation with
\/c was approximately linear, but exhibited the same degree of individ-
uality as the corresponding isopiestic quantities, 0(Cp2). Since the
absence of the expansion term simplifies the theoretical interpretation
in the isochoric system, the persistence of marked individuality at low
concentrations is particularly striking. The difference between the
isopiestic and isochoric apparent molal heat capacities varied little with
concentration, and was of the order of 3 to 11 cals. depending upon the
salt. The values of ^(C^2) are the more negative.
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THEORIES OF SOLUTION 21
In continuing his interesting series of papers on the non-comparative
criteria of the purity of organic compounds, Skau^^*^ discussed some
of the limitations of the application of specific heat data to the deter-
mination of purity.
Ionization Constants. The use of ultraviolet spectrophotometry in
the determination of ionization constants was investigated by Flexser,
Hammett and Dingwall.^^ The validity of the method was indicated by
measurements on benzoic acid, aniline, and 2,4-dinitrophenol, and it
was then applied to a series of very weak bases in sulfuric acid
solutions.
Wooten and Hammett ^^^ measured the difference in the relative
ionization constants (referred to benzoic acid) of 33 carboxylic and
phenolic acids in water, and in butyl alcohol. In general, their results
were more readily interpreted according to a paper by Schwarzenbach
and Egli than by the familiar Born equation, but the data on ortho-
or a -substituted acids were not satisfactorily accounted for in either
case. Jukes and Schmidt ^* determined the apparent ionization con-
stants of ten fatty acids in ethanol- water mixtures at 20°.
La Mer and Korman ^^ found that the acidic ionization constant of
deuteroquinone is 3.84 times as great as that for hydroquinone. This
is in accord with known behavior of weak acids, and has been inter-
preted by Halpern^2 {^ terms of the difference in zero-point energy
of the proton or deuteron when attached to a water molecule, or to an
acid radical.
Kolthoff and Tomsicek '^^ evaluated the fourth ionization constant
of ferrocyanic acid (^^"4 = 5.6 X 10"^ at 25°). The method used was
unusual, and was based upon the effect of hydrogen ions upon the
potential of the ferro-ferricyanide electrode.
The classical dissociation constant of benzoic acid at 25° was deter-
mined by Riesch and Kilpatrick ^^^ in nine aqueous uniunivalent salt
solutions. From these results and available values of the salting-out
coefficient for molecular benzoic acid, the corresponding mean activity
coefficients of the ionized acid were calculated. A concordant redeter-
mination of the thermodynamic ionization constant of boric acid^^®
at various temperatures has been reported. The thermodynamic ioni-
zation constants of carbonic acid were determined by Maclnnes and
Belcher®® at 38° by means of the glass electrode. The values,
A:i = 4.91x10-'' and K2 = 62S xlO-^\ were obtained, but the value of
Ki(=4.82x lO-*^), determined conductometrically,^26 jg recommended
for adoption.
The apparent ionization constants of some dihalogenated tyrosine
compounds were determined at 25° and 40° by Winnek and Schmidt.®^
The solubility method was employed. Tomiyama ^^^ reported values
for canal ine and canavanine.
Greenstein and Joseph ^^ determined the apparent ionization con-
stants of a-aminotricarballylic acid and glycyl-a-aminotricarballylic
acid electrometrically at 25°. They estimated the thermodynamic con-
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22 ANNUAL SURVEY OF AMERICAN CHEMISTRY
stants. Kumler and Daniels ^^ determined the apparent dissociation
constants of ^ascorbic acid in water, and of diethyl dihydroxymaleate
in water, and alcohol-water solutions.
The thermodynamic ionization constant of acetic acid was deter-
mined in 10 percent and 20 percent methanol solutions by Hamed
and Embree.*^ They employed cells of the type,
Hg I HAC(mj), NaAC(«2), NaCl(«3) | AgCl, Ag,
and carried out the measurements at 0, 10, 20, 25, 30, and 40°. This
is apparently the first time that cells without liquid junctions have
been employed in an extensive study of a weak acid in solvents other
than water. The temperature variation of the ionization constants
could be expressed by the empirical equation,
\ogK = \ogKns - 5 X 10-» (f- 0)',
in which is the temperature of the maximum value K^. In this case
the equation expressed the data to better than 1.5 percent, and this
is the order of the concordance usually obtained for acids in water.
The well-known dangers inherent in the use of such an empirical
equation for the estimation of derived quantities (ACp, for the ioniza-
tion process, for example) has been emphasized by Walde.^^* The
effect of the alcohol upon the strength of the acid could be expressed
by the linear dependence of log K upon \/D as a first approximation.
Goodhue and Hixon^^ determined the apparent ionization constants
of five bases and five acids in pure ethanol by the use of the hydrogen
and Hg-Hgl2 electrodes. Agreement with conductance values reported
by Goldschmidt was satisfactory in view of the magnitude of the liquid
junction potentials. It was shown that the results were in harmony
with Bronsted's generalized interpretation of acids and bases.
Concerning subjects closely connected with the determination of
ionization constants, we might mention papers dealing with />H deter-
mination. Kilpatrick^^ reviewed the colorimetric method and Atkin
and Thompson* outlined a variety of methods. Kolthoff^® discussed
the mechanism of the ionization of acids and bases, and its statistical
interpretation at "absurdly" low concentrations. The effect of ionic
strength upon protein ionization was investigated by Smith ^^s ^ho
found that the />H of the apparent isoelectric point of Qgg albumin
varied linearly with both the ionic strength, and the concentration of
the albumin itself. These relationships were employed to determine
the "true" isoelectric point at zero ionic strength and protein con-
centration.
Compressibility. Gibson ^o published an important paper on the
concentration-compressibility relationships in solutions of electrolytes.
His conclusions were based on measurements of the compressions to
1,000 bars of solutions of sixteen salts, and acetic acid over the whole
concentration range at 25°. It was shown that the apparent com-
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THEORIES OF SOLUTION 23
pression of the salts varied linearly with the square root of the volume
concentration within the experimental error. By means of a pjot of
the bulk compressions of solutions of twenty-four salts against the
"modified ionic strengfth" [lc(v+£f+-f-v_£r_2), note that the valence of
the cation is raised to the first power only] it was found possible
empirically to estimate th^ bulk compression of any solution, with an
error less than =•= 10 percent from a knowledge of the concentration
and the nature of the solute. On the assumption of Tammann's
hypothesis, that water in aqueous solutions behaves like water under
a pressure greater than the external pressure, the "eflfective pressure"
which a salt exerts upon the solvent could be calculated from the data.
In all cases this "effective pressure" was directly proportional to the
product of the volume concentrations of salt and water. The linear
relationship between the concentration, and the apparent molal com-
pression of solutions of acetic acid is similar to that of solutions of
strong electrolytes. Gucker has previously observed similar behavior
in sugar solutions. In a later paper Gibson ^i reported the results
of his measurements of the compressions and specific volumes of
aqueous solutions of methanol and resorcinol at 25°. The apparent
compression of resorcinol varied linearily with the square root of the
concentration, but the apparent volumes of resorcinol and the apparent
volumes and compressions of methanol were definitely not linear in \/c.
Although the square root relation is predictable for strong electroljrtes
by differentation of the Debye-Htickel equation, the behavior of cer-
tain non-electrolytes reported above shows that important forces besides
those of interionic attraction are involved.
Scott and Bridger ^^3 observed pronounced departures from the usual
square root relationship between concentration and apparent molal
volumes, or apparent molal compressibilities, in concentrated solutions
of lithium chloride and bromide. Distinct discontinuities in the curves
of these variables were obtained, and several of these were reported
for the first time. The authors suggested that the results are more
readily interpreted in terms of variation in distribution of solute ions
than in the number of layers of water molecules involved in hydration
of the ions. Bridgman and Dow ^ determined the compressibilities of
aqueous solutions of glycine, a-aminobutyric acid, and c-aminocaproic
acid at 25 and 75°. Their results presented some very interesting
anomalies. The apparent molal volumes are neither linear in \/c, as
required by Debye-Htickel theory for ordinary ions, or linear in c, as
required by Scatchard and Kirkwood's equations for zwitterions. The
initial slopes of the curves obtained by plotting apparent molal volumes
against pressure are all negative. This requires that the apparent
molal compressibilities of the amino acids are positive. This is con-
trary to the behavior of all other electrolytes, and also to the behavior
of urea, which, in common with the amino acids, increases the dielectric
constant of aqueous solutions.
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24 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Conductance and Transference. Although the conductance of
aquepus solutions of strong electrolytes has received scant attention
this year, a very interesting study of conductance in water-deuterium
mixtures has been made. Baker and La Mer^ found that the con-
ductance of 0.01 N potassium chloride in H2O — D2O mixtures is very
nearly linear in the mole fraction of deutetium oxide, and more than
90 percent of the decrease in conductance can be accounted for by the
viscosities of the mixtures. In the case of 0.01 N hydrochloric acid,
the decrease in conductance exhibited a pronoimced departure from
linearity, with a well-defined maximum departure (6.5 percent of A)
in the 1 to 1 mixture. According to the generally accepted view, the
high conductance of the H-ion is attributed to a series of proton
exchanges, which in H2O — D2O mixtures may take the following
forms :
H3O + H3O* ^ n,0' -f- H,0 ( 1 )
D,0 + 0,0^ ?=± D,0^ + D,0 (2)
HDO + H,DO* ^ H,DO^ + HDO (3)
HDO + HD,0^ ^ HD,0^ + HDO (4)
HDO + H,DO^ ?=± HD,0^ + H,0 (5)
HDO H- HD^O^ ?=± H,D0* + D,0 (6)
H3O + D3O* ?=± H^DO^ + D,0 (7)
D,0 + H,0^ ?=± HD3O* + H3O (8)
The exchanges represented in equations 1 to 4 are symmetrical, and are
accompanied by no change in energy, but the remaining exchanges
can only occur with absorption or evolution of heat to the surrounding
medium. The necessity for this interchange of energy will tend to
decrease the frequency with which the latter types of exchanges take
place. Since in 50 percent deuterium oxide we have the maximum
probability that an acid ion will be in the immediate neighborhood of
water molecules to which it cannot readily transfer its proton, we
should expect a lower conductance than that calculated according to the
additivity law (linear variation with D2O). This effect had been
qualitatively predicted by Halpern.
Concerning conductance in media of low dielectric constants, and
the general question of the association of ions in solution, Fuoss ^6 and
Kraus '^^ have contributed reviews of their most recent work.
Together ^s they examined the conditions under which ion pairs might
associate into quadrupoles :
2AB ?=± A3B, ; k, = [AB] VA3B,
The numerical value of k^^ was calculated for tri-isoamylammonium
picrate in benzene solutions from freezing point data. Considering
the quadrupole as an ellipsoid (of axis a and \a) containing a point
dipole of strength u at its center, and parallel to the major axis, they
derived the equation,
2000 \3/ Dkt y/.
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THEORIES OF SOLUTION 25
where y = \i^/k^a^DkT, From the value of k^ derived for the above
salt, this leads to the physically reasonable value, Aa = 5.54x10"^ cm.
Cox, Kraus and Fuoss ^^ determined the conductance of several
tetrabutylammonium salts in anisole (D = 4.29), ethylene bromide
(D = 4.76), and ethylene chloride (D= 10.23) at 25°. Their results
can be qualitatively interpreted in terms of association into ion pairs
and triple ions in accordance with earlier papers by Fuoss and Kraus,
and the a-parameters (distances between charges) derived from their
equations are of the order of 5 or 6 Angstrom units. This paper is of
considerable technical interest in that, at concentrations between 10'^
and 10"^ N, the conductances were reproducible to 0.1 to 0.2 percent,
and allowed a very accurate determination of the influence of adsorption
of electrolyte upon the electrodes. The amount of adsorbed electrolyte
(tetrabutylammonium picrate in ethylene chloride) was, within the
experimental error, independent of the concentration, and corresponded
to a monomolecular layer on the surface of the electrodes.
Jones and Christian ®^ made a careful study of galvanic polarization
by alternating current in conductance cells, and found it independent
of electrode separation and current density, and not very sensitive to
temperature, or the nature of the electrolyte. It was, however, greatly
influenced by the composition of the electrodes. Polarization capaci-
tance decreases with increasing frequencies, and polarization resistance
is inversely proportional to the square root of the frequency. This
latter relation was proposed by Jones and Bollinger ^® as a means of
testing the quality and sufficiency of electrode platinization, and of cal-
culating the true resistance, free from polarization effects.
Fuoss 27 tabulated values of the function, F(2), for the rapid cal-
culation of the degree of ionization of binary electrolytes from conduc-
tivity measurements. The equation is
A
*"" A°F(5)*
The conductance concentration curves obtained by McBain and
Betz ®2 with simple straight chain sulfonic acids exhibit several inflec-
tions, with pronounced minima at about N/20. The possibility of
association of like ions to form ionic micelles was considered. Freez-
ing point data were also brought to bear on this question.^^
The conductance of saturated solutions of some slightly soluble sub-
stances have been determined by Johnson and Hulett,^® and the values
obtained were proposed for the convenient determination of cell con-
stants. They also studied sodium and potassium chlorides at 0° and
25°. Campbell and Cook ^^ made a conductometric investigation of
the precipitation of strontium sulfate from its supersaturated solutions.
Conductivities of aqueous solution of glycine, JZ-valine and Z-aspara-
gine were determined by Mehl and Schmidt,^®^ and these and other
data on amino acids were compared with theoretical predictions. The
agreement is only approximate. Bent and Dorfman ^ interpreted their
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26 ANNUAL SURVEY OF AMERICAN CHEMISTRY
conductance data on sodium triphenylboron and disodium tri-a-naph-
thylboron in ether as showing that the sodium atoms in the latter salt
ionize simultaneously by virtue of a rearrangement of valence electrons
in the molecule.
From new measurements of the conductance of potassium bicarbonate
and carbonic acid solutions at 25°, and of the relative conductances of
saturated carbon dioxide solutions, and of potassium bicarbonate, potas-
sium chloride, and hydrochloric acid (0.001 N) at other temperatures,
Shedlovsky and Maclnnes ^^e calculated the first ionization constant of
carbonic acid from to 38°. Their values are considered more reliable
than those' previously determined electrometrically.
Greenberg and Larson ^^ measured the conductivities of solutions of
casein, edestin, and gelatine in anhydrous lactic, acetic, and formic
acids. In the first two solvents, the conductivities were very low, but
in formic acid solutions, the conductance of the proteins were compar-
able to those of alkali formates, indicating the formation of well
defined, ionizable salts with formic acid. Some Hittorf numbers were
also determined.
McBain and Foster®^ reported new measurements of surface con-
ductivity exhibited by potassium chloride solutions in contact with glass
surfaces, and by films of fatty acids at the air-water interface. Several
interpretations are discussed. Urban, White and Strassner^^^ devel-
oped equations, based on the Stern double layer, for calculating specific
surface conductivities, and the thickness of the diffuse (Gouy) layer.
The authors' experimental measurements of specific surface conduc-
tivity in potassium chloride solutions are in accord with their equations,
but not with Gou/s theory. The numerical magnitude of their values
is less than that of data obtained by McBain and co-workers. Urban,
Feldman, and White ^^^ showed that specific surface conductivity mea-
sured with alternating current is higher than with direct current.
Longsworth ^^ continued his careful moving boundary measurements
to include five more 1-1 electrolytes, and calcium chloride and soditmi
sulfate. At the lowest concentrations studied (0.01 AT) the results for
the uns)mimetrical salts did not approach the theoretical limiting tan-
gents, for which the slope should be about \/2 times greater than that
observed for calcium chloride, and of opposite sign from that found
for sodium sulfate. Among the 1-1 electrolytes, only potassium nitrate
exhibited a persistent departure (more positive) from the theoretical
slope, and in this respect parallelled the previously reported behavior
of silver nitrate. No quantitative explanation of these "anomalous"
results has yet been advanced, but it is usually assumed that they are
due to ionic association. A summary of the moving boundary data
from the same laboratory shows that all of the other 1-1 electrolytes
studied approach the theoretical slopes at high dilution, and their regu-
lar departures at higher concentrations conform to the semi-empirical
equation previously proposed by Longsworth. Owen '^^ found that the
characteristic arbitrary parameter of this equation could be approxi-
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THEORIES OF SOLUTION 27
mated in terms of the limiting slope. This leads to a more general,
though less accurate, equation by which it is possible to estimate cer-
tain transference numbers in dilute solutions from limiting ionic con-
ductances alone. The assumption, that the "normal" behavior of the
free ions, of potassium and silver nitrates is represented by such a
general equation, might lead to some semi-quantitative explanation of
the departure of these salts from the theoretical slopes.
Longsworth ^^ determined the mobility of the hydrogen ion con-
stituent in aqueous mixtures of hydrochloric acid and calcium chloride
at a constant total concentration of 0.1 N. The observed decrease in
hydrogen ion mobility is only 44.1 percent of the value predicted theo-
retically. Such a discrepancy is not unexpected at 0.1 N, but it is
surprising that this figure is almost identical to that previously obtained
(44.2 percent) in hydrochloric acid-potassium chloride mixtures at
the same concentration.
Hamer ** completed a very comprehensive electromotive force study
of the transference number of the hydrogen ion in aqueous sulfuric
acid solution. The concentration range varied from 0.05 to 17 molal,
and the values at concentration were estimated by extrapolation.
Measurements were made at 0, 10, 15, 25, 35, 45 and 60°.
Diffusion. Two valuable contributions have appeared from the
Rockefeller Institute for Medical Research on the theory of dif-
fusion in cell models. Longsworth ^'^ has extended his theory * to
the case of the simultaneous diffusion of two electrolytes and
water. A solution of the equations has been obtained for the
steady state. A general solution which would include the time
curve has not been obtained. Favorable comparison has been
obtained between the theory and the experiments on ion distribu-
tion in living cells performed by Osterhout, Kamerling, and Stan-
ley. Teorell ^^^ has deduced equations for an interesting case.
Electrolytes are on both sides of the membrane, and one of them
is assumed to diffuse. The concentration and electrical potential
gradients set up by this diffusion cause a redistribution of all the
ions. By employing the method of treatment of Nernst and
Planck, equations for the steady state were developed. It was
shown that very marked differences in concentrations of the ions
on the two sides of membrane were to be expected, and the sugges-
tion was made that such considerations may explain some of the
large concentration differences occurring in biological systems.
Eversole and Doughty 22 have deduced equations for the diffu-
sion coeflScient of both charged and uncharged particles as a
function of the distance of penetration into a medium, such as a
gel. Concentration-distance curves for this undisturbed diffusion
are given. Preliminary colorimetric measurements of the diffusion
of cupric chloride into gels indicate that the equations are useful.
McBain and Dawson ®* employed a diffusion cell with a sintered
♦Longworth, L. G., /. Gen. Physiol., 17: 211 (1933).
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28 ANNUAL SURVEY OF AMERICAN CHEMISTRY
glass membrane to measure the differential and integral diffusion
coefficients of potassium chloride at 25°, and at concentrations from
0.1 to 2N, This method is rapid and simple, and the results indicate
that it is among the most precise for the determination of diffusion data.
Viscosity. The theoretical predictions of the interionic attrac-
tion theory applied to viscosity have been subjected to a careful
experimental test by Jones and Fornwalt.^^ They measured the
relative viscosities of solutions of potassium chloride, bromide, and
iodide, and ammonium chloride at 25° in absolute methanol down
to concentrations as low as 25 to 50xlO-^iV. It was found that the
general equation of Onsager and Fuoss,
r\ = \+ Ac^ + Bc + Dc log c,
represents the data up to 0.35 AT, with an average deviation less than
=^0.01 percent. A comparison of the experimental and theoretical
values of the limiting slope. A, brought out discrepancies of about the
order of the differences obtained by curve- fitting over the entire con-
centration range, or at high dilution only. In the latter case the
logarithmic term was not included. Although the propriety of testing
the theory quantitatively by the inclusion of data at concentrations out-
side of the "high dilution" range may be open to question, it seems
quite proper to interpret the agreement obtained as indicative of the
essential validity of the theory.
The viscosities and densities of concentrated solutions of pure
sodium and potassium carbonates and hydroxides, and of their
mixtures, have been reported.^^
Surface Tension. Jones and Ray ^^ published an important note
on an experimental study of the surface tensions of very dilute
salt solutions. They found that the relative surface tensions of
the electrolyte solutions studied (potassium chloride, cesium
nitrate, and potassium sulfate), were slightly less than unity at high
dilution (C < 0.006 A^ for potassium chloride), and increasingly greater
than unity at higher concentrations. This initial decrease in surface
tension is contrary to the theoretical predictions of Wagner and of
Onsager and Samaras. Measurements on 0.0005 to 0.005 molar sugar
solutions with the same apparatus showed only an increase in surface
tension.
Surface tension measurements have been applied to a kinetic
study of ester hydrolysis,**^ and a simple device described for carry-
ing out measurements upon very small samples.^^^ Washburn and
Berry ^^^ applied the capillary rise surface tension method to the
estimation of the dimensions of the sodium palmitate molecule.
Their results are of the same order of magnitude as similar quanti-
ties measured by the Langmuir film method. Cassel ^^ pointed
out objections to the theory underlying the calculations of these
authors.
Some important physical properties of methanol-chloroform
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THEORIES OF SOLUTION 29
mixtures were measured by Conrad and Hall.^^ Although the
vapor pressure and viscosity of these mixtures are quite abnormal,
the surface tension, compressibility, density, and index of refrac-
tion were found to be ideal functions of the composition.
Dielectric Constants. Greenstein, Wyman, and Cohn 3» investi-
gated the dielectric constants of solutions of the tetrapoles
diaminodithiodicaproic acid and lysylglutamic acid. The increase
in dielectric constant with concentration is linear, and especially
large in the case of lysylglutamic acid. The data were interpreted
in terms of a twisting of the hydrocarbon chains due to electro-
static forces between the charged amino and carboxyl groups.
Measurements of this sort can be expected to shed some light
upon the very obscure question of the spatial configuration of
proteins.
Because of their solubility in solvents of either high or low
dielectric constants, and their ability to retain their zwitterion
structure in nearly all solvents, the betaines and a closely related
substance, A^-dimethylanthranilic acid, offer interesting possibilities for
dielectric investigations. Edsall and Wyman ^^ made a very extensive
study of the dielectric constants (and apparent molal volumes) of
dilute solutions of o-, w-, and />-benzbetaine, pyridinebetaine, betaine,
and A/'-dimethylanthranilic acid and its methyl ester. The solvents
employed were water, ethanol, and benzene, and various water-ethanol
and ethanol-benzene mixtures selected to give a representative range
in dielectric constants. Because of the relative rigidity of the benzene
ring in the benzbetaines (compared to straight chain amino acids) it
was possible to estimate polarizations with some certainty from models
based on x-ray and electron diffraction data. The authors' calcula-
tions indicated that the volume polarizations derived from Wyman's
equation, p= (D—l)/3, are about 20 percent higher, but closely
proportional to the true values. The dielectric data were expressed
numerically as S from the limiting linear relation, D = Do + Sc. In
solvents of low D, it was found that S-values for the betaines are much
lower than in water. Reasons were advanced for interpreting this fact
in terms of molecular deformation rather than association. The dipole
moment of iV-dimethylanthranilic acid in benzene is about three times
as great as that of its methyl ester, indicating that the acid retains its
zwitterion structure even in benzene. Electrostriction of the solvent
due to the betaines decreases with increasing dielectric constant of the
solvent, and the magnitude of the observed effects is in accord with
theory.
Kumler '^^ pointed out that the current designation of association as
the cause of the variation of molecular polarization (P2) of polar liquids
(in non-polar solvents) with concentration can be only partially cor-
rect. He showed that a large part of the variation is accounted for
by the form of the Debye equation, which sets the limit, /)2 = molal
volume, if D is increased without limit.
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30 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Wilson and Wenzke ^^^ measured the electric moments of a number
of acetylenic acids. The values for propiolic, tetrolic, and phenylpro-
piolic acids are about 25 percent higher than those of acetic, propionic,
and phenylacetic acids. Since the presence of the triple bonds is also
accompanied by about a hundred-fold increase in ionization constant,
the hydrogen of the carboxyl group undoubtedly becomes more positive
in character in the presence of the triple bond.
Svirbely, Ablard and Warner ^^i measured the densities and dielec-
tric constants of solutions of c?-pinene, c?-limonene, methyl benzoate and
ethyl benzoate in benzene. Because these properties were not linear
with mole fraction of solute at high dilution, the molar polarization
at infinite dilutions were obtained by graphical extrapolation. The
values so obtained were subsequently checked by Otto,^®^ who per-
formed the extrapolation according to Hedestrand's formula. Otto
also determined the moments for solutions of various alkyl esters and
derivatives of boric acid in benzene and dioxane. Approximate equality
of the values in the two solvents indicated absence of association and
compound formation. Otto and Wenzke ^^"^ measured the dielectric
constants of solutions of phenylethylene and some of its simple deriva-
tives in benzene at 25°. Phenylethylene was found to possess a small
electric moment opposite in direction to that of toluene.
Svirbely and Warner ^**3 discovered an empirical relation between
electric moment and directive influence for substitutions in the ben-
zene ring. They showed that if the electric moment of a mono-substi-
tuted benzene derivative is greater than /^ 2.07 X 10"^® e.s.u., the next
substituted group will be directed to the we/a-position, but if the
moment is less than r^ 2.07 X 10-^^ e.s.u., the next group will be
directed to the ortho- and /jara-positions. Changes in the directive
influence with concentration, solvent, temperature, etc., are anticipated
by alteration in electric moment with these variables.
The electric moments of a number of acetylenic halides and alcohols
were determined by Toussaint and Wenzke.^^^ The moments of the
halides were influenced by the position of the triple bond. Otto^^
measured the dielectric constants of solutions of several dialkoxyalkanes
in benzene at 25°. The independence of the calculated electric
moments of the nature of the alkyl group was submitted as evidence
of constancy in the valence angle between the two alkoxy groups,
Williams ^^^' ^^^ reviewed the chemical applications of recent dielec-
tric constant theory and measurements, and included an extensive
bibliography.
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Chapter 11.
The Kinetics of Homogeneous Gas
Reactions,
F. O. Rice and K. F. Herzfeld,
The Johns Hopkins University.
Organic Decompositions. A number of studies have appeared
this year which indicate the importance of molecular fragments in
many forms of chemical reactions. The mechanism of the methane
decomposition is still under consideration and Kassel^s has
affirmed his belief in the primary decomposition into CH2-fH2, as
opposed to the primary reaction CH4— >CH3H-H proposed by
Rice and Dooley.* Belchetz and Rideal,^ from experiments on the
decomposition of methane on carbon filaments, agree with the
former mechanism of dissociation into methylene radicals and
hydrogen. The reaction of deuterium atoms produced by excited
mercury has recently been studied*^® and shown to proceed at tem-
peratures as low as 40° C, indicating a value of very approximately
5 calories for the reaction D + CH4, in contrast with the value of
17 calories obtained by Geib and Harteck.t The exchange reac-
tion 3® between deuterium and methane occurs readily on catalytic
surfaces above 184° C. Preliminary results on the rate of com-
bination of deuterium and ethylene have been reported,^® and the
conclusion has been reached that both the heterogeneous and the
homogeneous reaction can be studied if the conditions are care-
fully controlled, without interference by the exchange reaction.
Kistiakowsky 2« has continued his studies of thermal cis-trans isom-
erizations. Since free radicals are known to react easily with double
bonds, it seems extremely desirable to investigate whether or not radi-
cals play a role in such changes.
Littmann 35 has studied the thermal decomposition of some
unsaturated bicyclic compounds, and has shown that the C-C bond
next to the double bond is stronger than normal, whereas the
next' C-C bond is weaker than normal.
The thermal decomposition of nitrogen chloride has been studied *^^
between 150° and 250° C; it is homogeneous, follows a bimolecular
law, and has an activation energy of 24 calories.
•Rice, F. O., and Dooley, M. D., /. Am. Chem. Soc, 56: 2747 (1934).
tGcib, K. H., and Harteck, P., Z. phys. Chem., 170A: 1 (1934).
33 '
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34 ANNUAL SURVEY OF AMERICAN CHEMISTRY
O. K. Rice and Sickinan^^ report the induced decompositions of
propionic aldehyde and isobutane by azomethane. Several percent of
azomethane cause decomposition of only part of the propionic aldehyde,
so that this cannot be a "degenerate explosion" as suggested by
Semenov.* The same authors find that, at 300° C, ethylene is rapidly
polymerized by small quantities of azomethane, the rate being pro-
portional to the square root of the azomethane pressure and to the
three-halves power of the ethylene pressure.^^
The photolysis of azomethane was studied ;i* the quantum yield was
found to approach unity as its upper limit and to be independent of
temperature up to 226° C, so that no reaction chain occurs in this tem-
perature interval. The photochemical decomposition products formed
at 30° C. and the thermal decomposition products at 300° C. seem to
be the same.^^ Mercury vapor has no effect on the rate.
Glyoxal^^ decomposes at a measurable rate in the range 410 to
450° C; the reaction is homogeneous and first order; however,
the reaction cannot follow any simple scheme, such as C2H2O2
— > CO-fHCHO— >2CO + H2, because carbon and tar are formed
during the course of the decomposition, as well as a large amount
of condensible products.
At least half of the process of the thermal decomposition of
alkyl halides can be attributed to a unimolecular dissociation; in
the case of methyl iodide, the recombination reaction is more
important than inter-radical reactions.^^
The decomposition of ethyl nitrite ^^ seems to be a curious exam-
ple of a primary dissociation into a molecule and a radical, fol-
lowed by reaction of this with the substrate. No chain reaction
should occur, because of decomposition of the radical CH3CHONO
into the two molecules, namely, acetaldehyde and nitric oxide.
Steacie and Shaw have shown ^® that propyl nitrite decomposes
in a similar manner to its two lower homologs.
Sickman and O. K. Rice have studied ^^ the thermal decomposi-
tion of propylamine in the pressure range between a few tenths
of a mm. to over 100 mm. The reaction is probably a chain, but
it was not found possible to give a satisfactory explanation of its
course.
West 81 has decomposed methyl iodide, acetone, propionic alde-
hyde and benzene photochemically in the presence of a 1 : 1 ortho-
para hydrogen mixture. The results indicated the production of
radicals by methyl iodide and acetone, but not by propionic alde-
hyde and benzene. This is strong evidence in support of Norrish's
views * on the photochemical dissociations of aldehydes and
ketones.
H. A. Taylor and coworkers '^^' "^"^ find that the decompositions
of diethyl- and triethylamines probably involve the formation and
♦Semenov, N. N., Z. phys. Chem., 28B: 62 (1935).
* Norrish, R. G. W., Trans. Faraday Soc, 30: 107 (1934).
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THE KINETICS OF HOMOGENEOUS GAS REACTIONS 35
subsequent decomposition of substituted hydrazines but the exact
mechanism is not clear.
The decomposition of nitromethane '^^ proved to be an extremely
complex reaction, in which nitrosomethane and its isomer, formald-
oxime, are intermediate products.
Mead and Burk ^"^ studied the thermal decomposition of benzene
in a flowing system and report that it is a heterogeneous bimo-
lecular reaction, whereas Pease and Morton t had previously
reported the decomposition as homogeneous and first order.
F. O. Rice and Polly *^ made a preliminary study of the decom-
position of mercury diheptyl and conclude that the heptyl radical
decomposes, at least to some extent, into cyclohexane plus methyl
radicals.
Egloff and Wilson ^^ have reviewed the thermal reactions of
paraffins, olefins, acetylenes, and cycloparaffins.
Lang and Morgan 2» have studied the pyrolysis of propane in
the presence of water vapor and conclude that their -experimental
results are best explained on the basis of Nefs hypothesis. A
similar study on pentane ^^ showed that the results could be
explained by a primary decomposition into radicals, followed by
a chain.
Halogenations. The photochlorination of gaseous ethylene has
been studied '^^ and found to have many of the characteristics of a
chain reaction; probably chlorine or the complex CI3 or both are
intermediaries. One curious result observed was that the chlori-
nation of ethylene in an ethylene-hydrogen mixture proceeds with-
out formation of appreciable quantities of hydrogen chloride.
Willard and Daniels ^^ have studied the effect of oxygen in the
photobromination of tetrachloroethylene and have proposed a
mechanism for the reaction.
The thermal reaction between formaldehyde and chlorine has
been discussed 27, 28, 65 ^nd certain similarities with the photo-
chemical reaction pointed out, such as the possible formation of
formyl chloride as an intermediate.
Yuster and Reyerson ^^ have studied the homogeneous chlori-
nation of propane and found that the reaction exhibits all the
peculiarities of the chain type. The photochlorination of liquid
pentane is a chain.^i
Oxidations. The hydrogen-oxygen reaction * has been made
the subject of several detailed and critical discussions especially
by Kassel and Storch,^* who studied the thermal reaction of oxy-
gen with both hydrogen and deuterium. Smith and Kistiakowsky ®3
have studied the photochemical hydrogen-oxygen reaction and
Lind and Schiflett ^^ have studied the rate of combination of oxygen
and deuterium under the influence of alpha-rays. Cook and Bates ^
t Pease, R. N., and Morton, J. M., /. Am. Chem. Sac, 55: 3190 (1933).
* See Kassel, "Annual Survey of American Chemistry," VIII: 27 (1933).
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36 ANNUAL SURVEY OF AMERICAN CHEMISTRY
have examined the reaction of hydrogen and deuterium atoms with
molecular oxygen, by studying the photo-oxidation of hydrogen
and deuterium iodides.
Rodebush and Spealman ^'^ suggest that recombination of hydro-
gen atoms in presence of hydrogen chloride is due to the reaction
H-l-HCl— > H2H-C1, followed by a rapid reaction between chlorine
and hydrogen atoms to reform hydrogen chloride.
The rate of oxidation of carbon monoxide catalysed by nitrogen
dioxide appears to be determined at low concentrations of the
catalyst by a chain mechanism and at higher concentrations by
the trimolecular oxidation of nitric oxide.^
The oxidation of gaseous glyoxal has been studied®*^ and appears
to proceed through the intermediate formation of an activated
peracid.
The oxidation of 2-butene gives ^^ mainly acetaldehyde and
butadiene and not methyl ethyl ketone, as might be expected on
the basis of the hydroxylation theory.* A mechanism of the reac-
tion is proposed. Small amounts of oxygen have been found to
accelerate greatly the reaction of ethylene-hydrogen mixtures; the
effect is probably to accelerate the hydrogenation, rather than the
polymerization, of the ethylene.'*'^
Pease *^ has studied the slow oxidation of propane in a reaction
tube coated with potassium chloride. This largely eliminated
peroxide formation, the primary products being methanol, formal-
dehyde, carbon monoxide, and water. The results could be for-
mulated by using a radical chain mechanism t in which the
methoxyl and propyl radicals are the chain carriers. When the
oxidation of propane is conducted in bulbs not coated with potas-
sium chloride, there is a long induction period.'*^
Chapman ^ has studied the oxidation of chloroform, using chlo-
rine as a photosensitizer; the products are phosgene and hydrogen
chloride; the reaction is clearly a chain but enough data have not
yet been accumulated to determine completely the mechanism.
Both the thermal and photochemical oxidations produce an inter-
mediate peroxide, which yields initially chlorine and finally hydro-
gen chloride and phosgene.^
Polymerizations. H. A. Taylor and Van Hook "^^ have studied
the polymerization and hydrogenation of acetylene and conclude
that in each reaction the principal process is bimolecular. On the
other hand, Jungers and H. S. Taylor 21 conclude that the mercury
photosensitized polymerization of acetylene is a process involving
short chains. The rates of polymerization of acetylene and deu-
tero-acetylene are equal within the limits of experimental error.^*
O. K. Rice and Sickman ^^ have found that ethylene is rapidly
♦ Bone, W. A., and Wheeler, R. V., /. Chem. Soc, 85: 1637 (1904).
t Rice, F. O., and Rice, K., "The Aliphatic Free Radicals," Baltimore, The Johns-
Hopkins Press, 1935, 204 p.
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THE KINETICS OF HOMOGENEOUS GAS REACTIONS 37
polymerized by small quantities of azomethane at about 300® C.
Storch ^* concludes that the ethylene polymerization is not a sim-
ple bimolecular reaction; traces of impurities exert such a marked
effect that it was not found possible to obtain reproducible results
even with "pure" ethylene.
Atomic Reactions. The question as to the nature of the pri-
mary process in chemical reactions is still very much to the fore,
and was discussed in considerable detail at a symposium on reac-
tion kinetics held during the New York meeting of the American
Chemical Society. Kistiakowsky ^5 reviewed the present theory of
truly unimolecular reactions, presented the experimental facts, and
finally gave a list of decompositions and isomerizations which go
homogeneously in the gas phase without chains. F. O. Rice *^
reviewed the subject of organic decompositions from the stand-
point of free radical formations and the initiation of chains.
Jackson 20 has proposed various mechanisms to account for the
formation of carbon dioxide and hydrogen peroxide when carbon
monoxide reacts with the products of a water vapor discharge
tube.
Lewis and von Elbe^^ i^^ve collected data that include the
reaction energies of a number of the simpler elementary reactions.
Morris and Pease *^ agree with the accepted Christiansen-Herzfeld-
Polanyi mechanism for the HBr formation and take as heats of
activation Br-fHg, 17.7 Kcal; H-|-HBr, 1 Kcal; and H-j-Brg,
1 Kcal. For the photochemical formation of HCl, they take, with
Bodenstein, Cl2 + /tv = 2Cl, Cl-f Hg = HCl-hH(6 Kcal); H-I-CI2
= HCl + CI (2-3 Kcal); H + HCl = Hg-fCKS Kcal); H-|-02 = H02
in three-body collisions or H-l-HCl on a surface is assumed as the
chain-breaking mechanism. Finallv, H-fHI = H2-|-I (1 Kcal);
H-hl2 = HI-|-I (0 Kcal), I-|-H2 = HI-hH (33 Kcal).
Spealman and Rodebush ^* have studied the reactions of nitrous
and nitric oxides with both atomic oxygen and atomic nitrogen.
Oldenberg*^ has made a study of the free hydroxyl radical and
agrees with Urey and Lavin * that it can be pumped out over con-
siderable distances from a water-vapor discharge tube.
Bond Energies. Deitz ® has discussed the bond energies of
hydrocarbons and Serber ^^ has calculated the energies of a num-
ber of hydrocarbon molecules and compared the calculated and
observed values.
Rossini ^^ has estimated the heat of formation of neopentane
from the heats of formation of the two isomers of butane.
Lasereff^^ has suggested the very high value of 123 calories for
the carbon-carbon bond but this conclusion has been questioned
by Gershinowitz,^^ who prefers the older figure pi 77 calories.
Nilsen ^^ calculates the electron affinity of certain radicals con-
taining aromatic rings. Starting out with the benzyl ion, he cal-
♦ Urcy, H. C, and Lavin, G. I., J. Am. Chem. Soc, 51: 3290 (1929).
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38 ANNUAL SURVEY OF AMERICAN CHEMISTRY
culates the "exchange" energy between the eight non-bonding
electrons (6 from the ring, one from the CH2 group, one as nega-
tive charge) and subtracts the energy for seven electrons (the
uncharged radical). Electron aflSnities of more complicated cases
(e.g., triphenylmethyl) are then found by the use of a formula of
Pauling and Wheland, permitting their calculation from the val-
ues of the constituents. The comparison with experiment shows
the theoretical values to be too high.
Nilsen then draws more qualitative conclusions about the ability
to form ions and emphasizes the much stronger tendency of radi-
cals containing a double bond besides a benzene ring to form ions,
as compared with the same tendency without the double bond;
for example, the cinnamyl radical has seven possible structures
giving resonance, while the hydrocinnamyl radical has only two
(two arrangements of double bonds in the ring). Hylleraas ^*
strongly attacks Nilsen's method of calculation.
Pauling and Wheland ** agree with this criticism and emphasize
that the main contribution to the electron affinity should come
from the changed coulomb attraction, the difference in exchange
energy being very small.
Sherman, Sun, and Eyring^i discuss the addition of hydrogen
to benzene. The first method, which assumes that, in the activated
state, the electrons involved in the double bonds and those in the
H2 resonate between fourteen different combinations, gives a heat
of reaction of -|-8S Kcal. (absorbed by the addition), while the
experimental value is slightly negative. The heat of activation is
found to be 96 Kcal. Better agreement results if one assumes
with Pauling and his coworkers a directed valance, namely inter-
action of only the four neighboring electrons, two from H2 and
two from the disappearing double bond. If one takes the energy
of the CH bond as 120 Kcal., the heat of reaction is found to be
— 11 Kcal, that of activation 78. Similarly, these heats are calcu-
lated for the adsorption of CqHq ( — 5 and 3 Kcal.) and H2 (—4.6
and 24 Kcal.). The authors point out that the usual bond energy
of CH is much smaller than 120 Kcal., the value for the free C-H
radical, due to the repulsion of the other atoms in the molecule
which weakens the bond.
Explosions. The explosion of azomethane ^ seems to follow the
simple Semenov theory,* in which the rate of generation of heat by
the reaction is faster than the rate of removal of heat. The explosion
of ethyl azide* also appears to be a pure thermal one; however, the
decomposition of ethyl azide may occur through a chain with the
imposed condition that the chains cannot branch. The induction times
in the cases of such explosions as azomethane and ethyl azide have
been studied ^^ and it has been found possible to calculate rough
values for the heats of decomposition of the substances.
•Semenov, N., Z. Physik, 48: 571 (1928); Z. physik. Chetn., 2B: 161 (1929).
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THE KINETICS OF HOMOGENEOUS GAS REACTIONS 39
Storch ^3 has shown that the low pressure explosion limit of methane-
oxygen mixtures is very sensitive to the nature of the surface of the
containing vessel.
Scorah^® discusses the thermod)mamic theory of detonation and
Lewis and von Elbe^^ calculate explosion pressures in hydrogen-
oxygen mixtures. Explosions in presence of the inert gas, helium, per-
mits the heat of dissociation of water into H and OH to be calculated.
Theoretical. About twenty years ago, Trautz took the "con-
stant" factor A in front of the exponential in the expression of the
reaction velocity, k=:A exp ( . ), to be the number of collisions
( 1^)'
for bimolecular reactions and pointed out that A for unimolecular reac-
tions is always of the same order of magnitude. Approximate theories
were given for this fact, but further experiments showed a variation
between 10^^ and 10^^. An approach to this problem was made by
Rodebush * and O. K. Rice and Gershinowitz.t The latter have pur-
sued the subject in papers discussed later on. Eyring and his coworkers
have taken the matter up from a systematic viewpoint that permits
clear understanding. Whenever ^2 there exists a heat of activation,
there must exist a system, the "activated complex," having at least this
energfy, which is sufficient for reaction. If one considers the energy
surface which gives the total mutual potential energy of all the reac-
tion participants as function of the coordinates, there must be a flat
saddle dividing the regions before and after the reaction. If one is
able to calculate the concentration, n', of the activated complex, then
the numbers passing the saddle, i.e., reacting, are given by this concen-
/kT \i
tration, n', times the velocity across the saddle, namely, ( • ) . The
\2TTm/
variation of A is therefore mainly a variation of n'; n' is calculated
statistically. The statistical weight of a state is proportional to the
phase volume allotted to it, which, for high temperatures, is for trans-
lation under standard conditions oc 3.5 X lO-*^ (distance between mole-
cules) for rotation oc lO-*^ (circumference of a molecule), for a
molecular vibration oc 10-^ cm (amplitude). Therefore n' (and A)
will be greater, the more translations or rotations compared with vibra-
tions the activated state has. The ratio of the phase integral of the
activated complex to that of the initial substances gives the relative
concentration of the former. In the case of unimolecular decomposi-
tions, one leaves out in the phase integral of the activated complex the
bond that breaks, considering it as having been already changed into
translation. The contribution it gives, together with the velocity fac-
tor, results in a factor kT/h,
After the discussion of some general cases, namely, A-f-BC— > A— B
♦Rodebush, W. H., /. Chem. Phys., 1: 440 (1933).
tRice, O. K., and Gershinowitz, H., /. Chem. Phys., 2: 853 (1934); Gershinowitz, H.,
and Rice, O. K., ibid., 2: 273 (1934).
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40 ANNUAL SURVEY OF AMERICAN CHEMISTRY
~C -» AB-hC A + BC-fD -> A B C D -> AB + CD in the first paper,
the next task is the actual calculation of the activated complex in
specific cases. This can be done either by calculating the energy sur-
face theoretically or by taking the properties of the activated complex
from similar molecules.
As examples of the case where the properties of the activated com-
plex are reconstructed from those of similar molecules, the reactions
2NO -h O2 -» 2NO2 and 2N0 -h CI2 -» 2N0C1 are considered^^ In the
former, the activated complex N2O4 is taken to have the form O ^O
I I
N N
II II
O O
and to have, besides three translations and a fourth along the
breaking bond, three external and one internal rotations and
ten vibrations, compared with nine translations, six rotations
and three vibrations of the 3 molecules NO, NO, O2. Of these fre-
quencies, seven are taken from the known frequencies of N2O4 and
three are considered too high to be of importance in the range of tem-
peratures used. The result for A is a decrease with temperature, due
to the strong temperature increase of the phase integral of the 15 trans-
lations plus rotations of the original molecules, while the correspond-
ing vibrations of the activated complex are largely suppressed by the
quantum theory. It turns out that if c, the activation energy at r = 0,
is put zero, the value of A so calculated represents the measurements
well, both in their absolute value and the dependence on T. In the
second reaction, the activated complex is taken to be of similar form
as in the preceding case, but as no stable molecule, (NOC^g, is known,
the frequencies have to be estimated. In this case the assumption of
an activation energy of 4780 cal. represents the facts well.
The next problem '^^ is the decomposition of nitrous oxide into
N2-I-O. Here the energy surface can be calculated theoretically, as
the potential energy curve of nitric oxide as function of the N — O
distance is known. However, the O atom would leave the N2O mole-
cule in the d-state (i.e., with a resultant orbital quantum number 2)
if it dissociated without change of the electron structure. Further-
more, this state is so highly excited, that much more energy would
be necessary. The 0-ground state has one orbital quantum (/>-state),
but can not be bound to N2. The potential curves for the attraction
N2 — O {d) and repulsion N2 — O (/>) intersect, and at this place a
transition between the two states is possible. The height of this inter-
section gives an activation energy of 52 kcal, compared with the experi-
mental value of 53. The small probability of the transition between
the two curves, which belong to two different systems of levels (triplet
and singlet), introduces a new factor, small compared with one, into
the reaction velocity. It can be determined only by division of the
experimental reaction velocity through the theoretical one and turns
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THE KINETICS OF HOMOGENEOUS GAS REACTIONS 41
out to be 2 X 10"*. Theoretically, it depends on an interaction energy,
probably between the spins. This must be about 5 cal./mole, a reason-
able amount, to give the above transition probability. Other cases of
change of electron level multiplicity are discussed.
A new problem ^3 turns up in the recombination of atoms without
hump in the curve of mutual potential energy. Such an activation
energy, i.e., such a hump, arises however, from a consideration of the
rotation of the activated complex. For a given quantum number of
rotation n, the energy of rotation is /"^n^, where I, the moment
8tt2
of inertia, is proportional to the square of the dimensions. On approach,
the rise of the attractive (negative) potential energy plus the rise of
the positive energy of rotation gives a maximum at a distance, which
depends on n. Upon averaging over the different states, the authors
find that hump at 500° K. if the atoms are 4-5 A apart.
They first investigate the reaction H2-|-H-»3H. The simplest
case is one where all three atoms lie in a straight line. The potential
surface for this case had been calculated before.
The activated complex has two degrees of freedom of rotation and
two of transversal vibrations. The motion in the line of the three
atoms is such that the main contribution comes from cases where the
two hydrogen atoms of the molecule are not in their normal position,
but farther apart, so that their mutual potential energy is a 45 kcal.
They are to be hit by an atom of kinetic energy, such that the total
energy is higher than the dissociation energy phis the small activation
energy coming from the rotation. As soon as the incoming atom has
approached to a distance equal to that of the two other atoms, its
kinetic energy is redistributed, part of it going over into the vibration.
If enough goes over, dissociation occurs, but in about % of the collis-
sions with sufficient energy the redistribution is not sufficient for the
reaction to occur. Next the case of the third atom arriving normal
to the axis of H2 is investigated and found to give a smaller contribu-
tion than the one first discussed. The theoretical result for the inverse
reaction (recombination of 2 H with H as third body) is found so to
be oc 3 X 10^5^ while the experiment gives 1-2 X 10^^. Helium as third
body is then discussed and it is pointed out that the efficiency as third
body is connected with reactivity.
In a lecture ^^ at the Symposium at the American Chemical Society
meeting in New York, Eyring gives a review of the historical develop-
ment and of his own theory and then applies it to reactions in con-
ifer
densed systems. As the velocity is determined, apart from the factor — ,
hm
by the equilibrium concentration of the activated complex, one can put
the concentration-ratio of the activated complex and the original sub-
stances in solution equal to that in the gas times the ratio of the solu-
bility of the activated complex to that of the original substances. If,
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42 ANNUAL SURVEY OF AMERICAN CHEMISTRY
in a monomolecular decomposition, the original molecule and the
activated complex are very similar, their solubility will be equal and
the reaction velocity equal in gas and solution. In other cases, the
solubility of the activated complex is estimated from that of a similar,
stable molecule or calculated backward from measured velocities.
Kassell 22 raises the objection that during the short life of the acti-
vated complex no full quantization might take place. While this objec-
tion seems justified, it seems that the important shortlived bonds have
usually so low frequencies that classical formulas are sufficient and
then the degree of quantization does not matter. Rodebush ^^ draws
attention to the historical development.
O. K. Rice and Gershinowitz,^^ ^^o have the great merit of having
started the detailed application of statistics to this problem, continue
the development of their method, which does not include the consider-
ation of the activated complex at first. They first calculate the prob-
ability of a given quantum state. Then they classify the degrees of
freedom into those which are not affected by the reaction and those
that are. Of the first, all quantum states are assumed to be able to
react. Therefore one has to sum up over these, whereby the phase
integral over these quantum states drops out of the reaction constant.
The assumption which the authors think most probable is that, for a
dissociation, one quantum state of the vibration along the bond that is
to be broken is available and all states in the other degrees of freedom.
Conversely for the association, all the quantum states in the fragments
are available except of those rotations that will not be possible after
reunion. Of these degrees of freedom, only those quantum states can
react, which, taken together, have an entropy equal to that of the vibra-
tion to be formed. A reaction following these prescriptions is said to
occur with complete orientation. This theory is applied to the following
cases. Decomposition of alkyl iodides : theory ^ = 1.5 X 10^^ ; experi-
mental values for various alkyls, 3.9x10^2. 1.8x1013, 2.8xl0i3.
Decomposition of alkyl nitrites: theory 2.4x10^3. experimental values,
0.9x10^3; 7.0x1013. Tertiary butyl alcohols: 1.2 xlO^^; experi-
mental value, 4.8 X 10^^. In addition, tertiary amyl alcohol is treated.
Then the mechanisms for the isomerization of cyclopropane and the
decomposition of CICOOCCI3 are discussed and found to be in good
agreement with the hypothesis. In contrast, the decomposition of cer-
tain esters shows much lower values, which is explained by the for-
mation of an activated complex with less internal free rotations than
the original molecule. In the decomposition of azoisopropane, the
hypothesis gives again the right magnitude, but for azomethane, the
rate is 10^ times too high, which is explained by saying that no orien-
tation is necessary for the methyl group. The authors point out that
their formulas for exact orientation are identical with Eyring's, pro-
vided that the activated complex is in every respect, except the vibra-
tion along the breaking bond, identical with the decomposing mole-
cule. They have been very successful in selecting the right assumptions.
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THE KINETICS OF HOMOGENEOUS GAS REACTIONS 43
but a further theoretical discussion seems desirable to the reviewer.
As Rice and Gershinowitz define the heat of activation not as that
at r = but as the average value at T, it varies with temperature, a
variation connected with that of the factor A in front of the exponen-
tial. They show now ^^ that the new formula discussed above leads
to the same consequences as Kassel's theory for the dependence of the
rate of unimolecular reaction on the energy the molecule has above
the minimum activation.
O. K. Rice 5^ investigates the problem of inelastic collisions between
two atoms, i.e., such collisions that the electron structure is changed.
He considers the two atoms as an unstable molecule, and the two states
of the atomic electron system as two different electron states of the
molecule, both of which are repulsive. The transition probability
between these two repulsive states at the place where the two energy-
atomic distance curves intersect gives then the probability of excitation:
The discussion of the general mathematical features show that the
problem is not yet solved.
References.
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44 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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Chapter III.
Molecular Structure.
E. Bright Wilson, Jr.,
Harvard University,
This section covers most of the material formerly grouped under
the title "Subatomics." With the tremendous growth of nuclear
physics, to which the name subatomics properly belongs, it was
felt necessary to change the title of this section. Crystal struc-
ture, although it is of course of great importance in the study of
molecular structure, is too large a field to be included.
Electron Diffraction by Gas Molecules. The structures of chlo-
rine monoxide, oxygen fluoride, dimethyl ether, 1,4-dioxane,
methyl chloride, methylene chloride, and chloroform,^ germanium
tetrachloride,^ 4,4'-diiododiphenyl ether, phosphorous (P4), and
arsenic (As4),^ sulfur dioxide, carbon disulfide, and carbonyl sul-
fide,^ nickel carbonyl,^ phosgene, vinyl chloride, 1,1-dichloroethy-
lene, m-dichloroethylene, ^rawj-dichloroethylene, trichloroethylene,
tetrachloroethylene, thiophosgene, a-methylhydroxylamine, and nitro-
methane ^ have been obtained by electron diffraction studies during the
past year.
Several methods of interpreting the experimental photographs
are used by the two groups of American workers. One method is
to compare the calculated intensity of scattering based on an
assumed model with the experimental values obtained from densi-
tometer curves by the use of plate calibrations.^ The difficulties
of this method are the extent of the calculations necessary, the
calibration requirement, and the fact that no true maxima occur
on the curves, so that they are difficult to compare. The latter
defect may be remedied by multiplying each curve by a certain
factor which changes the slight prominences of the curves into
true maxima. The simplest method of interpretation * is based
on the assumption that the visual maxima (psychological)
observed on the photographs can be identified with the maxima
of a very much simplified form of the theoretical function. There
is a certain amount of evidence that this much easier method
yields reasonably accurate results. Recently a quite different
approach has been developed,^ in which no preliminary model
needs to be postulated. Instead, visual ring diameters and esti-
• Pauling, L., and Brockway, L. O., /. Chem. Phys., 2: 867 (1934).
45
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46 ANNUAL SURVEY OF AMERICAN CHEMISTRY
mated ring intensities are taken from the photograph and used to
calculate a radial distribution curve, based on a simplified approxima-
tion to a treatment developed earlier for crystal and liquid studies.
The maxima in this curve give the prominent internuclear distances
in the molecule to a claimed accuracy of a few percent.
There is not sufficient space to discuss the many interesting
conclusions which have been drawn from these structure determi-
nations. One such discussion,*^ however, has been published which
treats chiefly the effect of resonance on bond distances, resonance
between a single and a double bond yielding a distance inter-
mediate between the single and double bond distances but more
nearly the double bond value.
The Raman Effect. There has been strong emphasis on deu-
terium derivatives in the experiments on the Raman effect carried
out during the year, Raman spectra of H2, HD and 02,^** C2D2,^^
CH3D,i« CDCl3,22 CeDgSi and (CH3)3CCH2Di8 having been
obtained. Of these only the three forms of the hydrogen molecule
were examined in the gas phase with sufficient resolving power to
show the rotational lines. The vibrational lines of all these mole-
cules, when used with the known vibration lines of the ordinary
light molecules, have given valuable assistance in the problem of
assigning each observed line to a definite mode of vibration of
the molecule, or to combinations or overtones thereof. In addi-
tion, more information concerning the form of the molecular
potential energy function can be obtained if the data for the iso-
topic molecules are available. ' Both of these types of information
are important in thermal calculations, the former because the
degeneracy of each level is needed, the latter because inactive fre-
quencies must often be calculated.
H2O in the gas phase was studied again,^^ with the detection of
but one line. There still remains a discrepancy between the Raman
frequency observed and that calculated from the infrared data.
Two trichloroethanes have been studied in the liquid phase,^* as
well as eight compounds related to tetramethylmethane.^^ Oxalic
acid has been measured ^^ both in the crystalline form and in solu-
tion in water and alcohol. 1,3-Cyclohexadiene has been observed.^*^
The Raman effects of sulfuric acid,® orthophosphoric acid,!^ and
magnesium sulfate,^^ all in water solutions, have been published.
In the last of these no shift of the strong line with concentration
was found, while with the others a slight and gradual shift was
observed. Zinc chloride and bromide were observed as fused
salts.i»
Infrared Absorption Spectra. The experimental results in infra-
red spectroscopy will be taken up in the order of the complexity
of the molecules involved. The rotational fine structure of the
low frequency fundamental of DCN when compared with the simi-
lar band of HCN leads to interatomic distances of 1.06 A and
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MOLECULAR STRUCTURE 47
1.15 A for the H-C and C-N distances, respectively.^s The data
available also sufficed for a calculation of the four vibrational
force constants, enabling the missing fundamental of DCN to be
estimated as 1896.7 cm-i. New vibration-rotation bands for car-
bonyl sulfide have made possible an evaluation of the ten constants
in the expression for the vibrational energy as a function of the
quantum numbers (including quadratic or anharmonic terms in
Vi, V2, and V3).33
The problem of the water molecule is not yet completely solved,
although a great deal is known of its spectrum and structure. A
re-examination of the pure rotation spectrum of ^12^^^ g^^ve
results in quite good agreement with Mecke's term values obtained
from the photographic infrared, although the latter are not suffi-
cient to account for all the lines. D2O has been studied,^^ also
HDO, so that now eight of the nine fundamental frequencies for
the three species of water are known. The fine structure of cer-
tain of the D2O and HDO bands was also obtained. The theory
of the asymmetric top needs to be further refined if it is to fit all
the data accurately, but it seems clear that the water molecule is
an isosceles triangle with angle of roughly 105° and 0-H dis-
tance of about 0.95 A. A very thorough study ^'^ of the fine struc-
ture of the infrared band at 10,100 A of the similar molecule H2S
yields an angle of about 92° and a H-S distance of 1.345 A. The
method used was to compute the theoretical line frequencies from
an assumed model, derive equations for the effect of small changes
in the molecular constants, and then to solve these equations by
least squares, using the observed, data. A rough correction for
centrifugal expansion was included.
The vibrational assignments for acetylene, for which a great
deal of data exists, are not absolutely unambiguous as yet, although
a new band at 7989 A has been reported.^^
The structure of ammonia is believed to be a flat, symmetrical
pyramid with altitude of about 0.4 A and base of about 1.59 A on
a side. These figures have been obtained from a study of NH3
and ND3 in the infrared. The pure rotation spectra of these two
species has been mapped from 40 u to 170 \i?^ The low frequency
fundamental for each of the four possible species is double,^^ as
required by theory for a molecule capable of inversion (turning
inside out). Most of the observed bands of ammonia, especially
in the photographic region,^** 36 have not bejen analyzed and
classified with certainty, probably in part because they are com-
plicated by the interaction of rotation and vibration '^^ and by
inversion.*^^
An important series of papers ^^» ^^' ^^ on the methane-type mole-
cules, methane, silane, and germane, shows that the fine structure
of the fundamental bands is much more complicated than previous
measurements (on methane) with lower dispersion had indicated.
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48 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Whether this is due to absorption by excited molecules, or to the
breaking down of the degeneracy of the energy levels by the dis-
tortion of the tetrahedron during vibration, is as yet unknown.
The six fundamental frequencies of CH3D have been found and
resolved.^® One of the parallel vibrations yields a particularly
clear band from which one of the moments of inertia and hence
the molecular dimensions can be obtained. The C-H distance is
1.093 A. This molecule, being the simplest symmetric top not
complicated by inversion, deserves extensive study.
The low frequency fundamental bands (essentially a CH3 against
X vibraton) for CH3CI, CHaBr, and CH3I have been found and
resolved into P, Q, and R branches but only for CH3CI partially
into lines.2^
With the preparation and study of CgDe, the benzene problem
has been greatly clarified. The infrared spectrum has been
obtained,^^ and the Raman results are mentioned elsewhere.
Whereas, formerly, certain European investigators believed the
spectroscopic results incompatible with the conventional plane
hexagon structure, there now remains little doubt of its correct-
ness. The assignment of all the active fundamental frequencies to
the theoretical modes of vibration is fairly certain and a set of
approximate force constants for the bonds is available.* Further
evidence for the plane structure is provided by a search 2» of the
far infrared which yielded no fundamental bands, such as would be
expected to appear for the models of lower symmetry.
Work in solutions ^^ and pure liquids ^^ indicates empirically
that the CN group in cyanides and nitriles has a characteristic
absorption region at about 4.4 \i with perhaps another at 7 u. A
large number of natural substances, as well as the liquids carbon
tetrachloride, ethylene chloride, ethylbenzene, o-dichlorobenzene,
ethyl acetate, propyl bromide, butyl bromide and pentachloroethane,
have been measured in the infrared from 1 to 15 ii.*^ An extensive
study ^^ of the absorption of a large number of organic compounds
in carbon tetrachloride solution in the region 6000 to 7400 cm-^ has
yielded considerable information regarding the characteristic
absorption bands associated with .the OH, NH, and CH groups.
The results have been applied to the problem of chelation,^^* since
it is found that these characteristic absorptions are greatly reduced
by chelation.
A paper^2 dealing with both the experimental results for the
absorption of crystalline MgO and the theory of the absorption of
crystals in general shows that there are many secondary absorp-
tion maxima for cubic crystals instead of just one as previously
believed. This is explained on the basis of anharmonic forces
between the atoms, which break down the simple selection rules.
The absorption of solid HCH^ in the 3.7 u region shows a fine
• Kohlrausch, K. W. F., Z. physik, Chem., 30B: 305 (1935).
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MOLECULAR STRUCTURE 49
structure, probably not completely resolved, differing from that of
gaseous HCl.
The optical dispersion of gaseous HCl between 1 and 10 u has
been measured *^ with results indicating that the effective charge
for the vibrator-rotator is (l.OOdzO.05) X 10-i<> e. s. u., which is too
small to explain the discrepancy between the polarization obtained
from the index of refraction extrapolated to infinite wavelength
and that from the temperature invariant part of the dielectric
constant.
Ultraviolet Absorption Spectra. A good many papers giving
experimental data have appeared during the year. One series gives
the results for the far ultraviolet for 02,^^ C2H2, C2H4, C2He,'*®
CHaBr, CHaCl,^^ CHsI,^^ CeHg, QDc^i C2H5CI, CgHsBr, CaHsI,^^
H2O, and H2S.^^ In some of these it was possible to fit the results
into a Rydberg series and thus find the ionization potential. Acetone,*^
cis- and /ranj-dichloroethylene,^^ NHs,^^ and NDs^^ j^^yg likewise
been studied in the ultraviolet. A summary ^® of vibration fre-
quencies in excited states indicates that the strong frequencies all
correspond to symmetrical vibrations. The SO2 spectrum has been
examined and an assignment of vibrational quantum numbers
given.*'^' ^^
In this brief survey it has been necessary to omit many papers
dealing with diatomic spectra, of most interest to physicists (except
for thermodynamic results), and other papers in which the ultraviolet
spectra of very complicated molecules were used as an empirical tool.
Theory of Molecular Vibrations and Rotations. The past year
has been characterized by an increasing realization that the intui-
tive application of the equations for the rotational energy levels
of a rigid top to the data for real molecules has not been based on
any sound theoretical treatment. In a sequence of papers ®^» ^"^
such a treatment was given, to a certain order of approximation,
resulting in the conclusion that the ordinary formulas are approxi-
mately applicable if, and only if, the coupling of the angular
momenta of rotation and vibration is taken into account. This
latter effect has been known for some years but has not been
sufficiently emphasized until quite lately. A detailed study of the
coupling of the angular momenta in methane and ammonia has
been made,^^» "^^ with a comparison of theory and experiment which
is generally favorable but which shows some discrepancies.
There is still lacking a complete mathematical treatment of poly-
atomic molecules comparable to that which exists for diatomic
molecules, even assuming harmonic binding, but it is now recog-
nized that the problem is not as simple as formerly believed. A
group theory discussion ®3 has been given which indicates that the
splitting of fine-structure lines observed for certain symmetrical
molecules *^' ^^ may possibly be due to some of the neglected terms
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so ANNUAL SURVEY OF AMERICAN CHEMISTRY
in the mathematical treatment. This discussion was based on an
earlier group theory treatment ^2 of the permutation symmetry of
polyatomic molecules which yielded a complete and general method
of calculating the statistical weights of the rotational states, for-
merly obtained for molecules such as methane only by very difficult
arguments.
A number of papers on molecular vibrations have appeared.
Mechanical models ''**• "^^ have been built and observed in an effort
to interpret the spectra of benzene and some of its derivatives,
with results for benzene in qualitative harmony with the earlier
analytical treatment. The use of mechanical models to solve the
secular equation of the molecular vibration problem is a very clever
device of great promise, which, however, has not so far been very
successful. The method suffers from several defects, the chief of
which is the lack of flexibility since the springs representing the
bonds must be taken out and replaced in order to change the force
constants.
An analytical treatment '^^ has been made of ammonia-type mole-
cules, in which the most general quadratic potential function has
been used. With the advent of deuterium compounds sufficient
data are available in a few cases to utilize the general quadratic
potential, with the result that the deficiencies of the simple valence-
type or central-force type approximations are becoming increas-
ingly apparent. Nevertheless, by using a two constant valence
force treatment (the general function has six constants) a success-
ful prediction ^® of the fundamental frequencies of ND3 was made,
using the known data on NH3. The same paper also discusses
PH3 and ASH3. In all analytical treatments made recently the
full symmetry of the molecule has been used to factor the secular
equation, usually by employing coordinates having the same sym-
metry as the normal coordinates. These coordinates may be
obtained either intuitively or from group theory. A normal vibra-
tion treatment ^^ of acetylene with one heavy hydrogen atom has
been given and applied to the data.
A more accurate potential function for the inversion of the
ammonia molecule was used to correlate the vibrational energy
levels (belonging to the overtones of the symmetrical bending fre-
quency) of NH3 and ND3.''* The dynamical problem of the
energy levels of vibration and internal rotation for a four-carbon
chain (such as in butane) having only valence forces has been
approximately solved.''^
The relation between the force constant and the interatomic dis-
tance has been refined ^^ and extended to polyatomic molecules.®*
The potential energy function for diatomic molecules has been
discussed in connection with known data.^® Two papers dealing
with the intensities of vibration-rotation bands of diatomic mole-
cules have appeared.^''' ^^
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MOLECULAR STRUCTURE 51
The energy levels of a polyatomic molecule rotating in a crystal
have been mathematically consideredJ^
Dipole Moments. A great many molecules have been subjected
to dipole moment studies during the year. Of these, water,^^
deuteroammonia,^^ trimethylene chloride and 1,1,2,2-tetrachloro-
ethane,^^ heptyl bromide, and butyl chloride ^^ were measured as
vapors, thus yielding dipole moments presumably more accurate
than those from solution. The moment of water was found to be
1.831=t0.006x 10-18 e. s. u. The difficulty previously encountered of
non-linear polarization vs. pressure curves was traced to adsorbed
films on the insulation and largely eliminated. The moment of
deuteroammonia was found to be 0.03 X 10-^^ units higher than the
value 1.466x10-18 redetermined for ordinary ammonia, possibly
because the anharmonic character of the potential function gov-
erning the symmetrical bending vibration and the lower zero point
energy of deuteroammonia cause the average value of the apex
angle of the pyramid to be slightly smaller for deuteroammonia.
A very complete theoretical treatment of the temperature change
of electric moment for molecules in which restricted "free** rota-
tion occurs has been given,®^ including a calculation of the statis-
tical weight function more rigorous than any previously published.
This work was applied to the data for 1,2-dichloroethane and used
to obtain the potential energy restricting free rotation, in the form
of a two-term Fourier expansion.
The number of compounds investigated in solution is too large
to list here but the papers involved are all included in the bibli-
ography. It is becoming evident that measurements in solution
do not often give the same value as measurements in the gas phase,
the moments being ordinarily lower in the former case. Attempts
to correct for the effect of the solvent by using empirical formulas
involving the dielectric constant of the solvent sometimes, but not
always, give good results. Important conclusions drawn from
solution measurements are : the mercuric halides ^5 have an appre-
ciable moment, indicating that the molecule is not linear; the
dielectric constant of solid nitromethane ^'^ is normal, suggesting
that the molecule is not rotating in the solid; the presence of a
triple bond raises the electric moment of the carboxyl group ;i^3
a triple bond also increases the moments of alcohols ;i<^i and the
carbon valence angle is constant in compounds with two oxygens
and either two hydrogens or an amyl and a methyl group attached
to the same carbon.®**
The anomalous dispersion of the large molecule lecithin in vis-
cous mineral oils 8® has been studied with results not amenable
to a simple treatment. The dielectric constant increments and
apparent molal volumes have been determined for various betaines
and AT-dimethylanthranilic acid.®*^ Discussion of the results in terms
of zwitterion theory was given. An extended study of the dielectric
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52 ANNUAL SURVEY OF AMERICAN CHEMISTRY
and thermal changes in solid camphor at transition points has been
published,^^' ^^^ together with a discussion based on the idea of rota-
tion of molecules and groups in a crystal.
A rule ^^ has been suggested for determining whether a substituent
on a benzene ring will be meta or ortho-para directing ; namely, "if the
electric moment of a mono- substituted benzene derivative is greater
than about 2.07 units, the next substituted group will be directed to the
meta position, if less than 2.07 to the ortho and para positions."
Magnetism. Several papers concerning para- and diamagnetism
are of importance in connection with valence theory. One ^^®
shows that the observed variations of the paramagnetism of salts
of transition group elements can be explained equally well by the
ideas of covalent bond formation, strong ionic fields, or by the
use of molecular orbitals. Therefore, except that, empirically,
covalent bond formation seems to have the strongest effect in
quenching electron spin magnetic moment, the magnetic data do
not distinguish between covalent and ionic bonds. Furthermore,
predictions of structure [such as square Ni(CN)4— ] can be made •
by any of these methods. The theory is applied quantitatively in
another paper ^^'^ to the data for K3Fe(CN)6 with results for die
magnitudes, anisotropy and temperature dependence of suscepti-
bility in good agreement with experiment. A computation "^^^ of
the effect of the crystalline field on the susceptibility of samarium
and europium ions enables the experimental data to be correlated
with the theory. Measurements have been published ^^® of the
paramagnetic susceptibilities at several temperatures of a number
of compounds of iron group elements and the results are com-
pared with the theory wherever possible, with generally good
agreement. Similar measurements for certain palladium com-
pounds are given in another publication.^^ These latter were all
found to be diamagnetic.
One draws the conclusion from these papers that the theory of
the paramagnetism of solid compounds of transition group ele-
ments has been developed to a fairly satisfactory stage. The prin-
cipal contribution to the susceptibility comes from the unpaired
electrons but the orbital moment, though largely quenched, may
contribute appreciably in certain cases. Measurements of mag-
netic properties may yield important information regarding the
structure of the crystal in the immediate neighborhood of the mag-
netic atom.
Measurements on the diamagnetic susceptibility of the first five
primary alkyl acetates and of methanol,^!^ ^11 as liquids, and of
solid lithium hydride ^^ have been published. In the first set, the
susceptibility varies very little with temperature and Pascal's addi-
tivity law holds quite well. In lithium hydride the observed sus-
ceptibility is much less than that calculated by any of the rough-
methods for computing ionic susceptibilities. The author suggests
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MOLECULAR STRUCTURE 53
that the soHd may possess a paramagnetism independent of tem-
perature which decreases the apparent diamagnetism.
Quantum Mechanics of Valence. There are still three rather
distinct approaches to the quantum-mechanical treatment of valence:
(a) The only quantitatively reliable method is the use of the variation
method with very complicated series-type variation functions, a
procedure which has so far been applied only to the very simplest
molecules, such as H2 and Li2. The excellent quantitative results
of such calculations are of great value but the enormous labor
required has so far prevented their use for more complicated cases.
During the year He2%^^^ Li 2* ^^^ and certain excited states of H2^^^
have been so treated.
In an endeavor to obtain approximate results for much more com-
plicated molecules, the method of atomic orbitals {h) and the method
of molecular orbitals (c) are in vogue. The approximations intro-
duced are of such an uncertain nature that both of these methods
require empirical justification. Several papers have appeared giv-
ing various improved methods of handling the technical formalisms
of the first of these procedures. These papers show the relation
between the Van Vleck vector method and the bond eigenfunction
method,^^^ the method of expressing bond eigenfunctions in terms
of a linearly independent set of functions,^^^ the relation of the
method of spin valence to that of Slater,^^^ and a procedure for
finding the number of structures Oi each degree of excitation for
certain types of complicated molecules.^^^ These are all highly
technical papers with no bearing on the fundamental questions.
A treatment ^^^ of hydrocarbon molecules, in which atomic orbi-
tals, electron-pairing, and empirically determined integrals have
been used, results in calculated energies agreeing to within a few
tenths of a volt with the experimental values. The author con-
cludes from his calculations that the principle of bond activity has
no theoretical basis and does not hold, for example, in benzene.
A consequence of this is that empirical resonance energies are of
doubtful meaning, since they are based on bond additivity.
A long series of papers 121-130 q^ ^^g use of the molecular orbital
method to assign quantum numbers to the excited electronic states
of polyatomic molecules has appeared. The ground states are also
studied and ionization potentials, electroaffinity, and dipole
moments discussed. A quantum-mechanical treatment ^^^ of the
orientating power of substituents on the benzene ring was published,
in which the electroaffinity of the substituent, resonance, and the
polarizing influence of the reacting group were all considered in a
rough semi-quantitative manner. A group theory discussion i^*^
of the molecular and atomic orbital methods sheds considerable
light on the relation between these two approaches.
Two reviews of the problem of valence were produced during
the year. One ^^^ is a survey of the classical background of elec-
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54 ANNUAL SURVEY OF AMERICAN CHEMISTRY
tronic theories, leading up to a discussion of the Lewis theory,
while the other ^^s Js a more mathematical discussion, dealing with
the quantum-mechanical methods listed above. The latter will be
found useful by any one wishing to learn the present day status
of the problem, but it requires some quantum-mechanical back-
ground.
The quantum-mechanical treatment of solids, especially metals,
received considerable attention during the year. Lithium,^2o ^Qp.
per,^^^ and diamond ^^^ were treated by an approximate method
in which solutions of the wave equation for each atom are obtained
(using a Hartree field) obeying certain boundary conditions at
the center of each face of a polyhedron surrounding the nucleus,
these polyhedra fitting together to form the whole crystal. Lithium
was also treated in a more accurate manner,i34 starting with Fock's
equations (which include interchange) and proceeding to a higher
approximation. The energy and interatomic distance so calcu-
lated agree well with experiment. The Thomas-Fermi statistical
method was adapted to crystals ^^6 ^nd modified to include inter-
change. The results are not accurate enough to give any stable
interatomic distance but might serve as a starting point for the
more exact treatments. The possibility that a solid metallic
modification of hydrogen might exist under high pressures has
been investigated theoretically ,^*3 with the conclusion that such a
form probably is not realizable with available pressures.
Even the more approximate calculations of this sort on the solid
state yield very interesting qualitative information, such as the
nature of the difference between metals and non-metals, and
promise results of great value in the future.
The Allison Magneto-Optic Effect. The status of the so-called
magneto-optic method of analysis discovered by Allison over five
years ago remains, to the outside observer, in an extremely
unsatisfactory condition. If this effect is genuine, it ranks among
the most important discoveries of its time, both for its possibilities
of practical usefulness in a large number of directions and for its
theoretical implications. If the effect is a result of experimental
or psychological error, then there is indeed a very large body of
data to be explained away. To the best of my knowledge there are
six successful installations of this apparatus, in Auburn, Emory,
St. Louis, Berkeley, Ames, and Urbana. The men who have oper-
ated these have made many tests, such as the analysis of difficult
unknowns, which have convinced them of the reality of the effect.
Nevertheless, a considerable number of observers have attempted
to reproduce the experiment without success and some of these
have expressed the opinion, based on their own experiences, that
the minima of light intensity found are entirely psychological in
nature.
If the effect is genuine, then it seems to be true that in its
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MOLECULAR STRUCTURE 55
present form it requires a very skilled operator. Furthermore, the
conditions under which minima are observed do not seem to have
been properly studied. Finally, practically no progress toward an
explanation of the phenomenon has been made and little work
seems to be in progress regarding this all-important problem. As
a personal opinion, it would seem that a very great responsibility
rests upon those who have succeeded in making this apparatus
work; namely, to develop the equipment so that other investiga-
tors can reproduce the phenomenon and, perhaps by a publication
of the results of tests of a really large number of unknowns, put
an end to the doubts which exist concerning the reality of the
method.
Miscellaneous Topics. An interesting paper ^^^ on the entropy
of ice and other crystals having some randomness of atomic
arrangement leads to certain conclusions regarding the positions
of the hydrogen atoms in the lattice, including the idea that there
exists a large number of possible configurations. A classical
mechanical treatment ^^^ of the rotational entropy of molecules
with freely rotating parts leads to formulas applicable to a number
of cases. An extension of the methods for calculating thermo-
dynamic quantities for polyatomic molecules from spectroscopic
data has been made to the case in which degenerate frequencies
occur.151
A new calculation ^^^ of the energy of the lowest state of the
lithium ^tom, using a variation function which includes the dis-
tance between the electrons (Hylleraas type), gives a total energy
in much better agreement with experiment than former computa-
tions but an ionization potential only slightly better (the old value
having been quite accurate).
A thorough theoretical treatment of the van der Waals inter-
action of two hydrogen atoms has appeared.^^^
The polarizability of the hydrogen molecule has been com-
puted,^52 using Wang's and Rosen's wave functions.
A rough wave mechanical treatment of the Mills-Nixon effect
(the apparent stabilization of one of the Kekule structures of
benzene by certain substitutions) has been given.^^s
The Kerr constants for gaseous O2, N2, and NH3 have been
measured.^*^
Two papers dealing with the absorption spectra of crystals at low
temperatures have appeared, the first '^^'^ on the Zeeman effect
with K2Cr(S04)2 . I2H2O and the other ^54 on the spectrum of
EU2(S04)3.8H20.
References.
Electron diffraction by gas molecules,
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19. Salstrom, E. J., and Harris, L., 7. Chem Phys., 3: 241 (1935).
20. Teal, G. K., and MacWood, G. E., 7. Chem. Phys., 3: 760 (1935).
21. Wood, R. W., 7. Chem. Phys., 3: 444 (1935).
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22a. Wright, N., and Lee, W. C, Nature, 136: 300 (1935).
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Infrared spectra.
24. Adel, A., Phys. Rev., 48: 103 (1935).
25. Barker, E. F., and Migeotte, M., Phys. Rev.^ 47: 702 (1935).
26. Barker, E. F., and Plyler, E. K., 7. Chem. Phys., 3: 367 (1935).
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29. Barnes, R. B., Benedict, W. S., and Lewis, C. M., Phys. Rev., 47: 129 (1935).
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31. Barnes, R. B., and Brattain, R. R., 7. Chem. Phys., 3: 446 (1935).
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34. Bell, F. K., 7. Am. Chem. Soc, 57: 1023 (1935).
35. Bradley, C. A., Jr., and McKellar, A., Phys. Rev., 47: 914 (1935).
36. Chao, S-H^ Phys. Rev., 48: 569 (1935).
37. Cross, P. C., Phys. Rev., 47: 7 (1935).
38. Ginsburg, N., and Barker, E. F., 7. Chem. Phys., 3: 668 (1935). •
39. (Jordy, W., and Williams, D.. 7. Chem. Phys., 3: 664 (1935).
39a. Hilbert. G. E., Wulf, O. R., Hendricks, S. B., and Liddel. U., Nature, 135: 147
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40. Nielsen, A. H., and Nielsen, H. H., Phys. Rev., 48: 864 (1935).
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42. Shearin, P. E., Phys. Rev., 48: 299 (1935).
43. Stair, R., and Coblentz, W. W., 7. Research Natl. Bur. Standards, 15: 295 (1935).
44. Steward, W. B., and Nielsen, H. H., Phys. Rev., 47: 828 (1935).
45. Steward, W. B., and Nielsen, H. H., Phys. Rev., 48: 861 (1935).
46. Wulf, O. R., and Liddel, U., 7. Am. Chem. Soc, 57: 1464 (1935)
Ultraviolet absorption spectra.
47. Clements, J. H., Phys. Rev., 47: 220 (1935).
48. Clements, J. H.. Phys. Rev., 47: 224 (1935).
49. Duncan, A. B. F., 7. Chem. Phys., 3: 131 (1935).
50. Duncan. A. B. F., 7. Chem. Phys., 3: 384 (1935)
51. Duncan, A. B. F., Phys. Rev., 47: 822 (1935).
52. Duncan, A. B. F., Phys. Rev., 47: 886 (1935).
53. Mahncke, H. E., and Noyes, W. A., Jr., 7. Chem, Phys., 3: 536 (1935).
54. Melvin, E. H., and Wulf, O. R., 7. Chem. Phys., 3: 755 (1935).
55. Price, W. C, J. Chem. Phys., 3: 256 (1935).
56. Price, W. C., 7. Chem. Phys., 3: 365 (1935).
57. Price, W. C, Phys. Rev., 47: 419 (1935).
58. Price, W. C, Phys. Rev., 47: 444 (1935).
59. Price, W. C, Phvs, Rev., 47: 510 (1935).
60. 'Price, W. C, and C>)llins, G.. Phys. Rev., 48: 714 (1935).
61. Price, W. C, and Wood, R. W., 7. Chem. Phys., 3: 439 (1935).
Theory of molecular rotations and vibrations,
63. Badger, R. M., Phys. Rev., 48: 284 (1935).
64. Badger, R. M.. 7. Chem. Phys.. 3: 710 (1935).
65. Colby, W. F., Phys. Rev., 47: 388 (1935).
66. Dennison, D. M., and Johnston, M., Phys. Rev., 47: 93 (1935).
67. Eckart. C., Phys. Rev., 47: 552 (1935).
68. Hirschfelder, J. O., and Wigner, E., Proc Natl. Acad. Sci., 21: 113 (1935).
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MOLECULAR STRUCTURE 57
69. Howard, J. B., /. Chem Phys., 3: 207 (193S).
70. Huggins, M. L., /. Chem. Phys., 3: 473 (1935).
71. Johnston, M., and Dennison, D. M., Phys. Rev., 48: 868 (1935).
72. Kassel, L. S., /. Chem. Phys., 3: 326 (1935).
73. Kemble, E. C, /. Chem. Phys., 3: 316 (1935).
74. Manning, M. F., /. Chem. Phys., 3: 136 (1935).
75. Murray, J. W., Deitz, V., and Andrews, D. H., /. Chem. Phys., 3: 180 (1935).
76. Nielsen, H. H., /. Chem. Phys., 3: 189 (1935).
77. Rosenthal, J. E., Proc. Natl. Acad. Set., 21: 281 (1935).
78. Rosenthal, J. E., Phys. Rev., 47: 235^ (1935).
79. Teets. D. E., and Andrews, D. H., /. Chem. Phys., 3: 175 <1935).
80. Van Vleck, J. H., Phys. Rev., 47: 487 (1935).
81. Wilson, E. B., Jr., /. Chem. Phys., 3: 59 (1935).
82. Wilson, E. B., Jr., /. Chem. Phys., 3: 276 (1935).
83. Wilson, E. B., Jr., /. Chem. Phys., 3: 818 (1935).
Dipole moments,
84. Altar, W., /. Chem. Phys., 3: 460 (1935).
85. Curran, W. J., and Wenzke, H. H., /. Am. Chem. Soc, ST: 2162 (1935).
86. Bruyne, J. M. A. de. and Smyth, C. P., /. Am. Chem. Soc., 57: 1203 (1935).
87. Edsall, J. T., and Wyman, J., Jr., /. Am. Chem, Soc, 57: 1964 (1935).
88. Ferguson, A. L., Case, L. O., and Evans, G. H., 7. Chem. Phys., 3: 285 (1935).
89. Greenstein, J. P., Wyman, J., Jr., and Cohn, E. J., /. Am. Chem. Soc, 57: 637
(1935).
90. Otto, M. M., J. Am. Chem. Soc, 57: 693 (1935).
91. Otto, M. M., J. Am. Chem. Soc, 57: 1147 (1935).
92. Otto, M. M., J. Am. Chem. Soc, 57: 1476 (1935).
93. Otto, M. M., and Wenzke, H. H., /. Am. Chem. Soc, 57: 294 (1935).
94. Pearce, J. N., and Berhenke, L. F., J. Phys. Chem., 39: 1005 (1935).
95. Smyth, C. P., and McAlpine, K. B., /. Chem. Phys., 3: 347 (1935).
96. Smyth, C. P., and McAlpine, K. B., J. Am. Chem. Soc, 57: 979 (1935).
97. Smyth, C. P., and Walls, W. S., /. Chem. Phys., 3: 557 (1935).
98. Stranathan, J. D., Phys. Rev., AS: 538 (1935).
99. Svirbely, W. J., Ablard, J. E., and Warner, J. C, 7. Am. Chem. Soc, 57: 652
(1935).
100. Svirbely, W. J., and Warner, J. C, 7. Am. Chem. Soc, 57: 655 (1935).
101. Toussaint, T. A., and Wenzke, H. H., 7. Am. Chem. Soc, 57: 668 (1935).
102. White, A. H., and Morgan, S. O., 7. Am. Chem. Soc, 57: 2078 (1935).
103. Wilson, C. J., and Wenzke, H. H., 7. Am. Chem. Soc, 57: 1365 (1935).
104. Yager, W. A., and Morgan, S. O., 7. Am. Chem Soc, 57: 2071 (1935).
Magnetism.
105. Frank, A., Phys. Rev., 48: 765 (1935).
106. Freed, S., and Thode, H. G., 7. Chem. Phys., 3: 212 (1935).
107. Howard, J. B., 7. Chem. Phys.. 3: 813 (1935).
108. Janes, R. B., Phys. Rev., 48: 78 (1935).
109. Janes. R. B., 7. Am. Chem. Soc, 57: 47l (1935).
110. Van Vleck, J. H., 7. Chem. Phys., 3: 807 (1935).
111. Walden, G. H., Hammett, L. P., and Gaines, A., Jr., 7. Chem. Phys., 3: 364 (1935).
112. Witmer, E. E., Phys. Rev.. 48: 380 (1935)
113. Woodbridge, D. B., Phys. Rev., 48: 673 (1935).
Quantum mechanics of valence.
114. Bear, R. S., and Eyring, H., 7. Chem. Phys., 3: 98 (1935).
115. Eyring, H., and Gershinowitz, H., 7. Chem. Ph^s., 3: 224 (1935).
116. James, H. M., 7. Chem. Phys., 3: 9 (1935).
117. James, H. M., and Coolidge, A. S., 7. Chem. Phys., 3: 129 (1935).
118. Kimball, G. E., 7. Chem. Phys.. 3: 560 (1935).
119. Krutter, H. M., Phvs. Rev., 48: 664 (1935).
120. MUlman, J., Phys. Rev., 47: 286 (1935).
121. Mulliken, R. S., Phys. Rev., 47: 413 (1935).
122. Mulliken, R. S., 7. Chem. Phys., 3: 375 (1935).
123. Mulliken. R. S., 7. Chem. Phys., 3: 506 (1935).
124. Mulliken, R. S., 7. Chem. Phys., 3: 514 (1935).
125. MulUken, R. S., 7. Chem. Phys., 3: 517 (1935).
126. Mulliken, R. S., 7. Chem. Phvs., 3: 564 (1935).
127. Mulliken, R. S., 7. Chem. Phys., 3: 573 (1935).
128. Mulliken, R. S., 7. Chem. Phys., 3: 586 (1935).
129. Mulliken, R. S., 7. Chem. Phys., 635 (1935).
130. Mulliken, R. S., 7. Chem. Phys., 3: 720 (1935).
131. Noyes, W. A., Chem. Rev., 17: 1 (1935).
132. Pauling, L., and Wheland, G. W., 7. Chem. Phys., 3: 315 (1935).
133. Present, R. D., 7. Chem. Phys., 3: 122 (1935).
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58 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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138. Van Vleck, J. H., and Sherman, A., Rev. Modem Pkys,, 7: 167 (1935).
139. Weinbaum, S., /. Chem. Phys., 3: 547 (1935).
140. Wheland, G. W., 7. Chem. Phys., 3: 230 (1935).
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143. Wigner, E., and Huntington, H. B., /. Chem. Phys., 3: 764 (1935).
The Allison magneto-optic effect,
144. BaU, T. R., Phys. Rev.^ 47: 548 (1935).
145. FarweU, H. W., and Hawkes, J. B., Phys. Rev., 47: 78 (1935).
146. Hughes, G., and Goslin, R., Phys. Rev., All 317 (1935).
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148. MacPherson. H. G., Phys. Rev., 47: 310 (1935).
Miscellaneous topics,
149. BreaiKilc. W. M., Phys, Rev., 4B: 237 (1935).
150. Eidinofi. M. L.. and Aaton, J. G., J. Chem. Phys., 3: 379 (1935).
151. Gordon, A. R., 7. Chi'm. Phys,, 3: 259 (1935).
152. HiTscbfelder, J. O., 7. Chem. Phys., 3: 555 (1935).
153. James, H. M., and CooHdf-e, A, S., Phys. Rev., 47: 700 (1935).
154. Meehan, E. J,. 7. Cht^m. Phys.. 3: 621 (1935).
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Chapter IV.
Thermodynamics and Thermochemistry.
R. E. Gibson,
Geophysical Laboratory, Carnegie Institution of Washington,
Most of the articles containing the contributions to Chemical
Thermodynamics and Thermochemistry published from American
laboratories during the calendar year 1935 are listed by authors at
the end of this chapter in such a way that the reader may have
some idea of the nature of their contents. It will be seen that the
output of work has been copious and so the space allotted is ade-
quate only for very brief accounts of some of these papers. No
attempt has been made to give a critical evaluation of the various
publications and any apparent selection of topics has been dictated
solely by the interests of the author.
Classical thermodynamics furnishes an invaluable system into
which the facts of at least one-half of physical chemistry may be
neatly fitted. The theory has long been complete, so that the
advances in the subject go mainly along experimental lines. The
sections of this chapter are, therefore, essentially classifications
based on different types of experimental attack on physicochemical
problems. Several papers have been published, however, on theo-
retical matters. Families of thermodynamic equations fpr poly-
component homogeneous systems have been systematically studied
and the group theory applied.^ In this way the number of thermo-
dynamic relations readily available has been greatly increased.
Van Rysselberghe contributed several articles on technical points
in the development of the subject,^^, 13, u including an attempt to
develop a thermodynamics of irreversible changes. The temper-
ature conditions for thermal equilibrium in a general gravitational
field have been worked out by Tolman.^^ Several papers were
written on the thermodynamics of explosions.^* '^» ®' ^® Lewis and
von Elbe^ discussed the calculation and measurement of flame
temperatures and decided against the presence of latent energy
(highly excited molecules) in exploding gases. They*^ also used
the thermodynamic functions computed from molecular constants
to calculate theoretical explosion pressures for hydrogen and oxy-
gen mixtures, with or without admixture of inert gases, and
advanced hypotheses to account for the differences between the
observed and calculated pressures. They noticed intense audible
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60 ANNUAL SURVEY OF AMERICAN CHEMISTRY
vibrations during the explosions of lean mixtures, an effect which
they explained by the time lag in the heat capacities of nitrogen
and oxygen.
Bridgman ^ surveyed high pressure phenomena from a theo-
retical standpoint and also published a book on the thermody-
namics of the electrical phenomena in metals.* The thermo-
dynamics of magnetization incidental to low temperature measure-
ment was outlined by Giauque and MacDougall.^* Perhaps one
of the most interesting contributions of the year was that of
Bridgman 2 on the combined effects of high hydrostatic pressure
and shearing stress on solids. A film of solid was compressed
between a steel anvil and the circular face of a cylindrical piston.
The anvil was rotated with respect to the piston, thereby applying
a shear to the solid. While the paper is essentially experimental,
it supplies excellent food for theory. The explosive decomposi-
tion of alums, silver nitrate, manganese dioxide, lead dioxide,
celluloid and many other substances under these conditions, the
curious transformations of organic substances, such as wood,
rubber, bromothymol blue which becomes insoluble, open up an
entirely new field in the chemistry of solids. These results are
incidental, most of the paper being devoted to the polymorphism
of elements under these conditions, and the changes produced in
the tensile strength and other interesting properties.
The borderline field between thermodynamics and molecular
mechanics has continued to yield results of advantage to both sub-
jects. As a discussion of the details of these researches belongs
in other chapters, only results will be given here. The heat capac-
ity, entropy, free energy and dissociation constants of oxygen, cal-
culated from molecular mechanics, have been revised to take
account of the ^A electronic state — the correction becomes impor-
tant above 3000° K.23 Values of the heat capacity of oxygen
determined from ozone explosions, corrected for temperature gra-
dients, agree well with these theoretically determined figures.^^ A
very extensive compilation of the thermodynamic functions, includ-
ing the dissociation constants, of gases (with full reference to
sources) was published by Lewis and von Elbe.2« New data for
gases include the free energy of nitrous oxide, sulfur dioxide,
hydrocyanic acid, and acetylene,^!. 22 Gordon having extended his
method to include tetratomic collinear molecules; the thermo-
dynamic functions of sulfur dioxide, carbon disulfide, and carbon
oxysulfide, calculated from molecular constants, determined by
electron diffraction, Raman and infra-red spectra; the free energy
of formation of carbon disulfide and carbon oxysulfide and thermo-
dynamic data for reactions involving hydrogen, sulfur, carbon, and
oxygen ; ^"^^ ^8 the thermodynamic functions from infra-red band
spectra for hydrogen sulfide and its energy of dissociation into
normal atoms ;^^ the heat capacities of methane, methyl chloride.
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THERMODYNAMICS AND THERMOCHEMISTRY 61
methylene chloride, chloroform, and carbon tetrachloride over the
range from to 500° C, computed within 3 percent from Raman
spectra data.^s The entropy of nitrous oxide at its b.p. and at
298.1° K. and 1 atm. was computed from band spectra data^^ and
compared with calorimetric data. The observed entropy is 1.14
units less than the calculated, a result which indicates that in the
solid at low temperatures there is some lack of discrimination
between the ends of the NNO molecule. Complete lack of dis-
crimination between the ends would give a discrepancy of 1.38 E.U.
Ahlberg and Freed^^ give theoretical reasons for the assump-
tion that the difference between the molal heat capacities of
Gd2(S04)3 . 8H2O and Sm2(S04)3 . 8H2O measures the electronic
heat capacity of the latter salt. They have measured these heat
capacities accurately from 17 to 295° K. i^, 4i ^nd find good agree-
ment between the experimental heat capacity differences and the
calculated electronic heat capacity of Sm+++.
Significant information concerning the structures of crystals in
which the possibility of randomness exists is obtainable from ther-
mally measured entropies. The structure of ice has been made
more definite in this way.^'^ The lattice energies of alkali hydro-
sulfides were computed and found to be nearly the same as those
of the corresponding bromides.^^ The results of Simon and Swain *
on the heat capacities of argon adsorbed on carbon were discussed
with a view to throwing light on the mechanism of the binding
of the adatoms.5
Fuoss and Kraus ^^' 20 have continued their work on the com-
putation of thermodynamic properties of solutions from molecular
hypotheses, in particular the hypothesis of ion association, and
Kirkwood^^ has made a significant contribution to the subject of
solution thermodynamics by a discussion of the statistical mechan-
ics of fluid mixtures.
Temperature. Details of the apparatus and method for cool-
ing a system below 1° K. by the adiabatic demagnetization of
Gd2(S04)3 .8H2O and for measuring the temperature were pub-
lished from Giauque's laboratory ^3, 34 during the year. A temper-
ature scale from 12 to 273° K., in terms of a copper-constantan
thermocouple, was determined by the helium thermometer and
checked with the Leiden scale by hydrogen and oxygen vapor
pressures. The results include a table of E.M.F.'s. and tempera-
tures from 12 to 90° K.^^ Four constant power series with the
linear term omitted express the E.M.F.'s of these couples as a func-
tion of temperature from 2 to 90° K.^^ Observations of the varia-
tion with temperature of the refractive index of vitreous silica
(determined by an interferometer method) were extended to
— 200° C. The results were applied to the caHbration of vitreous
♦ Simon, F., and Swain, R. C, Z. physik. Chem., B28: 189 (193S).
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62 ANNUAL SURVEY OF AMERICAN CHEMISTRY
silica refraction thermometers to —200° C. Data for these ther-
mometers over the range —200 to 1000° C. are now available.^^
A long paper on the methods of testing thermocouples and mate-
rials ^'^ and another on chromel-alumel thermocouples ^6 were pub-
lished from the National Bureau of Standards. High-temperature
work included an article on the emissivities at 0.66 u of cobalt,
thorium, rhenium, and molybdenum between 1300 and 2200° K.,^
a sonic method for measuring the temperature in arcs,^^' 3®» ^® and
an exact discussion of the hot-wire method of measuring flame
temperatures.^
Thermal Measurements. This section deals with those thermo-
d)mamic quantities which have been determined from thermal meas-
urements ; the results are arranged according to the t3rpes of compotmds
or reactions studied.
The heat capacities of solids up to high temperatures may be well
represented*^ by an equation of the type Cp = a-^hT-^CT-K A com-
bustible impurity present in tank oxygen, in amounts which vary with
the pressure in the tank, may introduce an error into thermochemical
measurements.^^ A new method is proposed for measuring the heats
of evaporation of pure liquids by measuring the temperatures at two
points in a vertical column of the liquid.**^ The heat capacity, heat of
fusion, heat of evaporation and entropy of nitrous oxide up to its boil-
ing point have been measured.** Heat capacities of strontium and
barium oxides (55-300° K.),*2 of the two forms of tricalcium phos-
phate (15-200° K.),«» and of Gd2(S04)3.8H20 (16-300° K.)*i have
been measured and the corresponding entropies computed. From
experimental determinations of heats of solution in N sodium hydroxide
and from vapor pressure measurements, Yost and Sherbourne'^^ deter-
mined the heat of formation and free energy of formation of arsenous
fluoride.
During the year much work was done on the thermal properties of
hydrocarbons and petroleum products. Gaucher*® examined all the
available data on the heat capacities of hydrocarbons and petroleum
products and gave an equation expressing C^ as a function only of the
specific gravity, the boiling point and the temperature. It fits the data
within 2 percent. Rossini ®^ extended his very accurate work on heats
of combustion at 25° to include isobutane (Aii/'= —686.31 ±0.13 kilo
cal per mole) and, by observing the regularities in heats of combustion
of methane, mono-, di- and trimethylmethane, he estimated the heat of
combustion and thence the heat of formation of tetramethylmethane
(neopentane).®^ The adiabatic expansion principle combined with
thermal expansions was used in the determination of Cp for butane
and propane under temperatures and pressures where the systems were
all liquid.^*^ Measurements of C^ for the two-phase systems were made
in an adiabatic calorimeter by observation of direct input of electrical
energy.^'' Enthalpy-pressure-temperature diagrams (200-800° F. and
up to 1000 Ib./sq. in.) for pentane and benzene vapors have been made
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THERMODYNAMICS AND THERMOCHEMISTRY 63
and compared.^® By the air flow evaporation method the heats of
evaporation at 40° of 8 selected gasolenes were measured.^^ Pearce
and Tanner ^3 determined the heat capacity and energy of formation
of naphthalene. Realizing the acute need for accurate thermochemical
data for compounds of high molecular weight and recognizing the
limitations in precision imposed on the heats of combustion of these
compounds, Kistiakowsky ^^ and his associates built a calorimeter for
measuring the heats of catalytic hydrogenations and other reactions
in the gas phase at temperatures not exceeding 150° C. Their pre-
cision was of the order of one per mille. With this apparatus ^"^ they
determined at 355° K. the heats of hydrogenation of the following
olefinic hydrocarbons: propylene, 1-butene, 2-butene {trans) y 2-butene
(cw), isobutene and ethylene. The heats for ethylene are also given
at 298, 273, and 0° K. They observe that their results do not sup-
port the idea of constant bond energies but that the deviations from
constant energies of bonding are in the same direction as Rossini found
for the normal alcohols, increasing instability of the lower homologs.
The biologically important sulfur compounds, Z-cysteine, /-cystine,
3-thiolactic acid, and 3, p'-dithiodi lactic acid have been studied thermo-
chemically with a new calorimeter. The heats of combustion at con-
stant pressure at 25°,^^ ^nd the heat capacities ^^ from 90 to 298° K.
were measured; from these data the entropies and standard free ener-
gies of formation were calculated. From the same laboratory''<^» '^^
the same kind of data and results for seven purine and pyrimidine
derivatives were published. These results also throw light on the
hypothesis of constant bond energies and indicate that, in the crystals
at least, the bond energies are functions of the position of the bonds
in the molecule.
Investigations of systems involving rubber hydrocarbon were pub-
lished from the National Bureau of Standards. The heat of reac-
tion ^^» ^2 of purified rubber with sulfur was measured at 175° C. and
brought to 25° by observation of the heat content changes of the
reactants over that range of temperature. The heat capacities ^^ of
crystalline and amorphous rubber hydrocarbon from 15 to 320° K. and
its heat of fusion were measured and the entropies and the free energy
of formation of the hydrocarbon computed.
In a study of the influence of impurities on physical properties, Skau
measured the heats of fusion of an assortment of organic compounds.^®
The molecular heats of adsorption^* of alkyl chlorides on charcoal
change little from 25 to 50° ; they increase with the size of the mole-
cule, but are less with branched chains than with normal chains. Lamb
and Ohl ^^ used an ice calorimeter to measure heats of adsorption of a
number of gases and vapors on chabasite, thomsonite, and brucite.
The heats vary only slightly with the amount adsorbed and are
considerably greater than those for the same gases adsorbed on
charcoal. The heats of solution of some hydrazonium salts ^^' *^^
and the heat capacities of the solutions were measured.'*^» *^^
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64 ANNUAL SURVEY OF AMERICAN CHEMISTRY
EdsalH® published data on the apparent molal heat capacities of
aqueous solutions of amino acids.
Volume-Pressure-Temperature-Concentration Relations. The
activity coefficients (fugacity/pressure) of 24 gases have been
shown to be functions only of the reduced temperature, (T/T^), and
the reduced pressure, (P/P^),^^ over an extremely wide range of P
and T, For helium, hydrogen, and neon (^^ + 8) and (7^ + 8) are
used instead of P^ and Tq. This relation permits the prediction of
activity coefficients for other gases with good approximation. It has
also been applied ^^^ in the calculation of the effect of pressure and tem-
perature on gaseous equilibria, and of the integral Joule-Thomson
effect, and hence the change in enthalpy with pressure at constant tem-
perature for many gases. The relation is not exact but does give
results of very useful accuracy. Measurements of P-V-T relations at
temperatures between 152 and 174° C. and from 1 to 8 atmospheres,
on gaseous solutions of ethanol and water, indicate that the highest
deviations from ideality are only 2 percent even at the highest pres-
sures.^^ The critical constants of ethane '^^ and propane '^^ and P-V-T
data for ethane '^^ from 25 to 250° and up to 200 atmospheres have
been determined with high precision. These data are well repre-
sented by the Beattie-Bridgeman equation, which even allows a
long extrapolation to the critical point. Booth and his associates '^'^
determined the critical constants of seven fluoride gases and exam-
ined critical phenomena in the system BF3-A.'^^ These latter
experiments have yielded very interesting results, retrograde con-
densation and a retrograde immiscibility at low temperatures and
high pressures being observed.
Studies of the Joule-Thomson effect in gases include experi-
mental determinations for nitrogen from —150 to 300° and from
1 to 200 atmospheres,^^ a correction by Deming and Deming^^
to previous calculations for this gas, and calculations ^^ of the
coefficient for nitrogen, methane, and their mixtures by the Beattie-
Bridgeman equation over the range 200-400° K. and 1 to 100 atmos-
pheres.
At room temperature and pressure a number of measurements
of volume-concentration relations in liquid solutions were made,
including the partial molal volumes of calcium and aluminum
nitrates over the whole concentration range at 25° ;^^^ the apparent
volumes of lithium chloride and bromide in aqueous solutions
which, when plotted against concentration, give curves showing
an incredible number of breaks ;^^i the specific volumes of solutions
of the chlorides of lanthanum, cerium, praseodymium, and neo-
dymium;^^ the apparent volumes of betaines in water, alcohol, and
benzene and in alcohol- water and alcohol-benzene mixtures ;85 and
the apparent volumes of two zwitterionic substances giving tetra-
poles in water.^^
The compressibilities, fluidities, vapor pressures and surface ten-
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THERMODYNAMICS AND THERMOCHEMISTRY 65
sions of chloroform-methanol mixtures were measured and com-
pared.s2 jn the light of further measurements it was found that
the modified Tait equation expressing the volume of an aqueous
salt solution as a function of the pressure extrapolates very well,
and the constant characteristic of the solution, viz., the effective
pressure, is a linear function of the product of the concentrations
of salt and water.^^ Gucker and Rubin ^^ used the results of such
extrapolations to compute the apparent molal isochoric heat capac-
ities of six 1-1 electrolytes. Other measurements of compressions
were made on aqueous solutions of lithium chloride and bromide,^^^
methanol, resorcinol,®^ and three amino acids,^^ and on fractions
of light midcontinent petroleum.^* In these last two papers data
are given to high pressures at different temperatures. The specific
volume of pentane has been measured from 70 to 220° F. and up
to 3000 Ib./sq. in.^^ Wiebe and Tremearne ^^^ measured the vol-
umes of liquid ammonia-hydrogen mixtures at 100° from 100 to 800
atmospheres, computed the partial volumes and discussed their
thermodynamic significance. Bridgman "^^ extended his measure-
ments of the compressions and thermal expansions of lithium,
sodium and potassium up to 20,000 kg/cm^. Interesting details of
technique are given in this paper. He also found that impurities
have very little effect on the compressibility of zinc,^^ and deter-
mined the compressibilities of a large number.of intermetallic com-
pounds.*^®* A careful study of the specific volume, thermal expan-
sion and compressibility (10 to 85° and up to 800 atmospheres) of
rubber-sulfur compounds was made by A. H. Scott.^^^^ The nega-
tive cubic coefficient of thermal expansion of solid silver iodide
has been confirmed by careful experiment.®* Expansion coeffi-
cients were also reported for single crystals of mercury,®^ 44 soda-
alumina-silica glasses,®'^ sodium tungstate,'^^ and antimony.®^
Homogeneous Equilibria, (a) In gaseous systems. Lewis and
von Elbe ^o published an extensive compilation of dissociation equi-
libria in gases. They have also obtained the energies of the reac-
tions H20 = H + 0H and OH = H-f O.*^ The general equation for
the activities of gases, already mentioned, enabled Newton and
Dodge ^1® to compute with useful approximation equilibrium con-
stants of homogeneous gas reactions at higher pressures. Eastman
and Ruben ^^^ have substantiated the work of Emmett and Schultz
on the disturbing nature of the Soret effect on certain observations
of equilibria in gas systems. The reaction, C2H4 -|- H2 = C2H6, on
which many equilibrium-constant measurements, all agreeing quite
well, have been made, presents a problem which is troubling several
sets of investigators. Statistical calculations, based on apparently
irreproachable thermal data, do not give equilibrium constants
which agree with those observed. Smith and Vaughan ^^2 made
an American contribution to the problem, showing that the con-
stants which they calculate are consistently one-half those observed
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66 ANNUAL SURVEY OF AMERICAN CHEMISTRY
and they suspect the entropy of free rotation of ethane. By mea-
suring the concentration of iodine photometrically, Cuthbertson
and Kistiakowsky ^^'^ determined the equilibrium constant of the
decomposition of ethylene iodide between 50 and 125° C. and cal-
culated the heat of dissociation. Equilibrium constants have been
measured for the transformation of cis- to fraw^-dichloroethylene
up to 975° by a flow method ^^^ and of the hydrogenation of pyri-
dine to piperidine ^^^ around 160°. In both cases heat and free
energy changes were computed. Calculations of the free energy
of formation of benzoic acid from benzene and carbon dioxide
at 522° K. lead to an equilibrium constant of the order lO"*^. That
benzoic acid actually is produced by such a reaction is laid to
combination with the zinc catalyst.^^^ Nies and Yost^^^ obtained
some thermodynamic constants for iodine trichloride by deter-
mining the equilibrium constants, Pici^ci2» ^^er the system IClgCj),
ICl(Z), IClC^r), ClaCflr) at 25 and 35° and Barton and Yost^o* found
that sulfur monochloride vapor did not decompose significantly at one
atmosphere until the temperature reached 300°. The dissociation at
lower pressures was studied between 160 and 800°.
(&) Liquid Systems. Chemical potential-concentration relations in
zinc amalgams become ideal if the assumption is made that in the
amalgam Zn2 and Zua are in equilibrium with Zn.^^o xhe first ioniza-
tion constant of carbonic acid has been measured at 38° both by an
E.M.F. method ^21 ^nd by a conductance method.^^* The results are,
respectively, 4.9 xlO""' and 4.82 xlO-^. From Harned's laboratory
there are reported measurements of the ionization constant of water
in sodium chloride solutions ^^^ and the ionization constant of acetic
acid in methanol-water mixtures.^^^ In the latter case log K varies
as the reciprocal of the dielectric constant of the solvent. Ionization
constants for HSO4-, calculated from kinetic data, agree well with those
computed from conductance measurements.^^^ The apparent dissocia-
tion constants of multivalent amino acids and peptides were determined
in water solutions.^^^ Walde ^^5 examined the significance of the
first and second temperature derivatives of the logarithms of the ioni-
zation constants of weak electrolytes and found that log K cannot be a
quadratic function of the temperature. The classical dissociation con-
stant of benzoic acid in aqueous salt solutions varies greatly with the
nature of the salt.^22 Other papers report the fourth ionization con-
stant of ferrocyanic acid,^^® the f erro-f err i cyanide equilibrium data,^^^
and a study of the equilibrium, Fe+++ -f Ag ^ Fe++ + Ag+ in aqueous
solution. ^23
Heterogeneous Equilibria. The heading of this section covers
a multitude of topics and it seems convenient to split the descrip-
tions into three classes: (1) systems of one component, including
polymorphism and vapor pressures; (2) systems of two compo-
nents, including most of the work on solutions; (3) systems of
more than two components, under which sub-heading such things
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THERMODYNAMICS AND THERMOCHEMISTRY 67
as distribution coefficients and "salting out" effects naturally fall.
All work on the thermodynamics of systems of isotopes and some
of the E.M.F. measurements will be discussed in separate sections.
Equilibria in Systems of One Component, The outstanding advance
in the thermodynamics of pure substances during the year was Bridg-
man's extension ^2« of his observations on phase changes under pres-
sure up to 50,000 kilograms per sq. cm., at least three times any former
maximum working pressure. The vessel in which such pressures were
generated was shaped like a truncated cone and, as the pressure inside
was raised, this conical bomb was forced into a strong external sleeve
so that a supporting pressure was applied to the outer wall. The
pistons were made of a cemented alloy of tungsten and cobalt, car-
boloy. With this apparatus new modifications of bismuth, mercury,
thallium, tellurium, gallium, and iodine were found and their stability
was examined. Above 20,000 kg./cm.^ potassium chloride, bromide,
and iodide invert, assuming possibly the cesium chloride type of struc-
ture. Goranson and Kracek ^^2, iss studied the effect of pressures up
to 1000 bars on the inversions and melting of sodium tungstate. The
related thermodynamic quantities were calculated and the density of
the solid was found to be 5.13, 20 percent higher than that given
in the literature. Alumina inverts rapidly at 1300° when heated in
vacuo; the temperature of the rapid inversion rises in atmospheres
of hydrogen, air, and argon. ^^^ The importance of polymorphism and
the frequency of its occurrence in organic compounds is steadily being
realized; dimorphism (monotropy) was found in amyl bromide ^^^ and
the solid-solid transitions in fl?-camphor, fl?Z-camphor, fl?-camphoric anhy-
dride, borneol, isoborneol, and bornyl chloride were studied intensively
by examination of the effect of temperature on a wide variety of their
physical properties. ^3®- '^^'^ Vapor pressures of the following substances
were measured : solid and liquid nitrous oxide '** up to the boiling point,
ethane '^^ at and 25° C, seven normally gaseous fluorides of group
IV, "^"^ and barium by an effusion method.^^* Germann and Knight ^^^
published a book on vapor pressure- temperature charts. If methane
and ethane are omitted, the boiling points of the normal paraffins may
be expressed by the relation log lo T^C^K.) = 1.07575 + 0.949128 logw
— 0.101 log2 m, where m is the molecular weight of the paraffin. ^^o
Equilibria in Systems of Two Components. If / is any quantity that
din/ ^H
may be appropriately used in the well-known type of equation — — = — -
(e.g., equilibrium constant, velocity constant, vapor pressure, etc.), Aus-
tin ^38 jias shown that, when A/J is either constant or varies linearly with
f /T'\rt'
T, a plausible approximation on integration gives — = ( — j , where
T' is any fixed standard temperature, e.g., melting point of pure sol-
vent in a binary system. A similar approximation for equilibrium
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68 ANNUAL SURVEY OF AMERICAN CHEMISTRY
constants was published by Douglas and Crockford.^^* With the
help of this simplified equation, Austin calculated solubilities in
certain simple eutectic systems and equilibria in binary systems
involving solid solutions. He pointed out that simple conse-
quences of the equation are the Ramsay-Young and Duhring rules.
Simple semi-theoretical equations, expressing the chemical poten-
tial changes on mixing in binary systems in terms of the mole frac-
tion, the volume fraction, and two parameters representing the
departures from ideality, were evaluated by Scatchard and
Hamer ^^^ from the mutual solubilities of several partially miscible
substances and, hence, data on the liquid-vapor equilibria in the
same systems were calculated, the results agreeing well with experi-
ment. They also applied the same equations ^^^ to equilibria involv-
ing the solid and liquid solutions of silver-palladium and gold-
platinum. Another paper giving a method for using data from
one type of equilibrium in a given binary system to predict other
equilibria in the same system is by Seltz.^®^ He considers systems
with complete liquid and solid miscibility and by a graphical method
predicts the types of liquidus and solidus curves that correspond
to different types of departures from Raoult's law in the solid and
liquid solutions. The equation of Hildebrand and Wood* for
calculating solubilities from a knowledge of the properties of the
pure components was tested by experiments o.n solutions of iodine,
stannic iodide, sulfur and phosphorus. The results indicated that
the equation was even more satisfactory than could have been
expected from the approximations involved.^'*'^ The temperature-
solubility curves of helium in water between and 75° at pressures
up to 1000 atmospheres ^'^^ show minima in the neighborhood of 30°.
Measurements ^"^^ also show that at 25° and up to 1000 atmos-
pheres the solubility of a 3-1 hydrogen-nitrogen mixture in water
may be calculated within a few percent from the solubilities of the
pure constituents. Other measurements on liquid-gas equilibria
(vapor pressures) were made on the following systems: calcium
and aluminum nitrates in water at 25° over the whole range of
concentration;^^* 10 and 20 percent solutions of methanol in water
from to 40°;2ii glycol-water, equations given for dependence of
vapor pressure on temperature;^®^ methane-crystal oil mixtures up
to 50 percent methane, 70-220° F. and up to 150 atmospheres i^^^
solutions of the halides and nitrate of ammonium in liquid ammo-
nia at 25°, from which data activities and deviations from Raoult's
law were computed ;i^^ ethanol-cyclohexane at 25°, positive depar-
ture from Raoult's law all the way;^'^^ pyridine-acetic acid (boiling
points at one atmosphere);^®® and butanol-butyl acetate and
butanol-acetone, in which systems the boiling points at one atmos-
phere were determined. Butanol and butyl acetate form an azeo-
tropic mixture boiling at 116.50°.^*^ Descriptions of apparatus for
♦Hildebrand, J. H., and Wood, S. E., /. Chem. Phys., U 817 (1933).
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THERMODYNAMICS AND THERMOCHEMISTRY 69
the accurate determination of boiling points under reduced pres-
sure,^®^ and molecular weights by the ebullioscopic method ^^^ were
published from the National Bureau of Standards.
An extremely interesting paper on solid-liquid-gas equilibria is
that by Booth and Willson ^^^ on melting curves in the system
boron trifluoride-argon. The curves indicate that six compounds
ranging from A.BF3 to A.I6BF3 are formed. Electronic consider-
tions show that such compounds are possible. The dissociation
pressures of these compounds are high, indicating considerable
instability. The maxima and minina on the curves range between
— 127 and —133° C. At pressures above 35 atmospheres retro-
grade immiscibility was observed in this system.
In the course of an extensive program on the purification of organic
compounds, Skau examined the systems (a) benzamide-m-nitrophenol,
(6) acenaphthene-m-dinitrobenzene, (c) 3-naphthylamine-w-dinitro-
benzene,^®^ and {d) acetanilide-propionanilide.^^^ System (&) is prac-
tically ideal but a compound is formed ; a new compound was discovered
in system {d). The following systems depart almost insignificantly
from ideality: />-dichlorobenzene-diphenyl, />-dichlorobenzene-naphtha-
lene, and />-dichlorobenzene-triphenylmethane.^^2 Ethylene dichloride
forms a solid addition compound with ether (1-3, m.p. 170° K.) but
not with benzene. ^*^
During 1935 determinations were made of the solubilities of
ammonium oxalate in water (0 to 100°, the monohydrate stable), ^*^
silver chloride in water,^^^^ mannose and other sugars in alcohols,^*^^
lead iodide in lead oxide,^*^^ and lead in mercury (20-70°, results
expressed by empirical equations). ^^^ From room temperature to
575° solid solutions ranging in composition from FeS to FeSi.14
appear from thermal analysis to exist in six forms, although such
analysis does not show definitely whether the system remains
homogeneous. The characters of the inversions from one form to
another are modified by change in the sulfur content.^'*^^ Draper ^'^^
investigated the mineralizing action of HCl on the system MgO-
Fe203. Further studies on hydrated alumina were reported.^^^
In a series of papers some aspects of the equilibria in the system
Na20-B203 were described 1*2-145 xhe preparation of crystalline
B2O3 by dehydration of H3BO3 in vacuo was announced; melting
points of different compounds of Na20 and B2O3 and of K2O and B2O3
were given, together with the vapor pressures of B2O3, Na20 . B2O3
and Na20 . 2B2O3, determined by a dynamic method between 1150
and 1400° C.
Equilibria in Systems of More Than Two Components. Seltz ^^^
worked out the equations for the solidus and liquidus surfaces and
the tie lines for solid-liquid equilibria in a ternary system where
both the solid and liquid solutions are ideal. He points out that
whereas the system copper-nickel is practically ideal, the system
copper-nickel-gold is by no means ideal. Binary and ternary sys-
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70 ANNUAL SURVEY OF AMERICAN CHEMISTRY
terns with biphenyl, bibenzyl and naphthalene approximate closely
to ideal behavior.^®^ Distribution coefficients of acetic acid between
isopropyl ether and water,^^® of amino acids between butanol and
water at 25° ^^^ and of hydrogen peroxide ^^'^ between aqueous salt
solutions and isoamyl alcohol or a mixture of acetophenone and car-
bon tetrachloride were determined. In the last case activity coeffi-
cients of hydrogen peroxide in the salt solutions were computed
and lyotropic series observed. All the salts except sulfuric acid
"salted in" the hydrogen peroxide.i^'^ Derivatives of amino acids
which do not give zwitterions were prepared and their solubilities
in water and alcohol studied.^^^ xhe solubilities of nine salts in
mixtures of methanol and water and of hydrogen peroxide and
water were determined at 25°.^'^'' From the same laboratory were
published data on the solubilities of helium and argon in many salt
solutions.^*^^ The solubility of sodium bromide in acetone is
increased by the presence of lithium or calcium perchlorate much
more than the simple interionic attraction theory predicts.^oi An
important and interesting paper by Schroeder, Gabriel, and Part-
ridge ^^'^ gives an account of the solubility curve of sodium sulfate
between 150 and 350° C. and of the influence of sodium hydroxide
and sodium chloride on this solubility. Below 300° C. addition of
either of these substances decreases the solubility of sodium sulfate
but above 300° it causes an increase, which in the case of sodium
hydroxide is quite large and increases rapidly with the amount
added. The following ternary systems involving water were studied
over limited temperature ranges: Fe203-S03-H20 (continuous
solid solutions and many compounds, no congruent points) ;^''^
Na2S04-Al2(S04)3-H20 (0, 30 and 42°, alum found at the two
higher temperatures) ; ^^^ cadmium acetate-acetic acid-water at
25° (complex addition compounds) ;i8i CaS04-(NH4)2S04-H20
between 25 and 100°;i8» Na2S04-NaBr03-H20 (10, 25, 30 and
450 ). 196 NH4CI-NH4NO8-H2O (0.4, 25 and 50°, no complex salt,
solid solution nor hydrate) ;^^^ lithium phthalate-phthalic acid-H20
(0, 25 and 50°, compound formation) ; 200 allyl alcohol-salts-
H20;^®^ benzene-isopropyl alcohol-water (25°, ternary solubility
diagram, distribution ratio, viscosity and refractive indices) ;^®3
isoamyl alcohol-propyl alcohol-water (25°, solubilities, densities,
and refractive indices). ^^^ Three very important contributions to
the knowledge of equilibria at high temperatures were published
during the year: the system MgO-FeO-Si02 by Bowen and
Schairer;!*^® an exhaustive thermal, optical, and x-ray study of the
system Fe304-Fe208-02;^®® and an investigation of the system
CaO-K2O-Al2O3.i80 Hydrothermal synthesis of clay minerals ^^s
and the phase changes occurring when kaolinite and dickite were
heated were reported by Insley and Ewell.^^^
Electromotive Force Measurements. As usual, much has been
published on electromotive force measurements. Although some
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THERMODYNAMICS AND THERMOCHEMISTRY 71
of this work had for its primary object the securing of thermo-
dynamic data, much of it was directed towards theoretical studies
on solutions and is more appropriately treated under that topic.
Gros§ and Halpern ^ot propounded a theory expressing normal
electrode potentials in terms of one set of thermodynamic quanti-
ties characteristic of the solid phase only and another set charac-
teristic of the solution. An investigation of the thermodynamics
of the lead accumulator from to 60° and over a wide range
of acid concentration was made by Harned and Hamer. The
results include determinations of the molal electrode potentials
of the cells,208. 209 H2 I H2S04(w) I PbS04 j PbOa | Pt, and
H2 I H2S04(w) I HgS04 I Hg, under these conditions, computations
of those thermodynamic properties which may be calculated from
the chemical potential and its temperature derivatives, and quad-
ratic equations 210 expressing the E.M.F. of lead accumulators over
ranges of temperature and concentration. By fusion of AgO with
AgBrOg, etc., on platinum wire, silver-silver halide electrodes yield-
ing reproducible results in very dilute solutions were made and
they were used in HBr solutions to 0.0001 molal^is and in the
determination 221 of the normal potential of the silver-silver iodide
electrode from 5 to 40°. Cann and Mueller 205 determined the
normal potential of the silver-silver chromate electrode and AF°
for the reaction Ag2Cr04 ^ 2Ag+ + Cr04-". Mercury-mercuric oxide-
saturated barium hydroxide and calcium hydroxide electrodes
were found to be easy to prepare, reproducible and constant.222
Harned 212 measured the E.M.F. of cells H2 | HCl(O.Ol),
NaCl(w) I AgCl I Ag from to 60°, computed results for other
halide mixtures, and found further support for the linear variation
of log Y with molality at constant total ionic strength. He cast
doubt on the validity of the empirical rules of Akerlof and Thomas,
and extended Bronsted's theory of specific ionic interaction. The
activity coefficients of sodium chloride in aqueous solutions were
determined accurately from observations on cells with transfer-
ence.204 A considerable discrepancy was noticed between the
observed and calculated E.M.F. of cells with a moving boundary
between two electrolytes with a common ion; the cause was dis-
cussed.2i® Work has been continued on cells with solvents other
than water: activities of sulfuric acid were determined in ethanol
solutions with hydrogen and mercurous sulfate electrodes; 223 the
molal electrode potentials of the silver-silver chloride electrode
in 10 and 20 percent methanol-water solutions were determined
from to 40°, with the idea of examining the effect of the dielectric
constant of the medium ;2ii from measurements on cells of the type
Zn (amalgam) | ZnCl2 . 6NH3(^) | NH4CI in NH3 | CdCla . 6NH3(^)
I Cd (amalgam), the thermodynamic constants, AF°, A/J°, 5° at
25°, were calculated for the ammino cadmium chlorides and cadmium
chloride. Provisional values for known potentials in terms of a stand-
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72 ANNUAL SURVEY OF AMERICAN CHEMISTRY
ard hydrogen half cell in liquid ammonia were also given.206 La Mer
and Armbruster described a micro cell for use in heavy water investi-
gations.215 Some thermodynamic properties of solutions of straight
chain sulfonic acids have been determined bv a variety of experimental
methods.217-220
The Thermodynamics of Isotopes and their Compounds. Assum-
ing that the recombination of the gaseous atoms at the electrode
is the rate-determining process in electrolyses where gases are
produced, Halpern and Gross ^29 derived a formula for the sepa-
ration coefficients of hydrogen and deuterium in terms of their
thermodynamic constants and their frequencies of thermal oscilla-
tion at the electrode. The formula limits the separation coefficient
to approximately 11 to 13, which agrees with that found in the
experiments of Brown and Daggett.227 The differences between
the vapor pressures ^27, i28 Qf ^-h^ 20.4° K. equilibrium mixture of
deuterium (0.978 orthodeuterium) and of normal deuterium, AP(^-n),
were measured from 15 to 20.4° K. and hence the difference between
the vapor pressures of ortho and para deuterium was calculated and
compared with values for ortho and para hydrogen. ^P(e-n) for
deuterium is small compared with AP(e-n) for hydrogen, but the ratios
of these differences to the vapor pressures of the corresponding normal
liquids are about the same. Heats of evaporation were computed and
it was found that, in the absence of a catalyst, the vapor pressures of
liquid normal deuterium changed less than one mm. of Hg in 200
hours whereas the vapor pressure of liquid normal hydrogen changed
by one mm. in four hours. The results were discussed theoretically.
By a distillation method,236 the ratios of the vapor pressures of
HgOi^ and HDOi«, and of HgOie and HgOis were measured
between 11.25 and 46.35° C. The vapor pressure of HDO^^ is very
nearly the geometric mean of the vapor pressures of water and
deuterium oxide. Over the temperature range considered, the
vapor pressure of H20^® is between 1.014 and 1.008 times that of
H20^8. Hydrogen isotopes may be separated by the distillation
of water, but the separation of oxygen isotopes by this method
will be very difficult. From measurements of liquid-vapor equi-
libria, it was concluded that H2O-D2O solutions are practically
ideal.237 Tables of the molar volumes of water and deuterium
oxide from -20 to 95° C. and up to 12,000 kg./cm.2, and the
transition parameters for the liquid and solid modifications between
-60 and 20° C, up to 9000 kg./cm.2 were published by Bridg-
man.226 Unstable modifications, Ice IV, of both deuterium oxide
and water were found in the field of stability of Ice V. In general,
the molar volumes of deuterium oxide are always higher than
those of water at the same pressure and temperature, and the equi-
librium curves of deuterium oxide are always at higher tempera-
tures. The broad differences in thermodynamic behavior may be
ascribed to the greater zero point energy of water, but an expla-
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THERMODYNAMICS AND THERMOCHEMISTRY 73
nation of a detailed comparison of the results calls for some other
considerations. The differences in zero point energy of protons
and deuterons when attached to the anion or neutral water mole-
cule lead to the conclusion that the ratio of the dissociation con-
stants of acids in light and heavy water increases as the strength
of the acid decreases.^^o Measurements with a quinhydrone elec-
trode with hydrogen chloride in water and deuterium oxide gave
the free energy of the reaction: 2DCI (0.01m) +QH2 = 2HC1 (0.01 w)
+QD2(QH2 = quinhydrone) and showed that the dissociation constant
of QH2 in water is 3.84 times that of QD2 in deuterium oxide.^^i The
absorption spectra and vapor pressures of hydrogen iodide and deu-
terium iodide 224 and hydrogen bromide and deuterium bromide ^25
have been compared over a range of temperature for both solids and
liquids. The vapor pressure of deuterium iodide is slightly greater
than that of hydrogen iodide; indeed, the log of the vapor pressure
of liquid deuterium iodide may be obtained by adding 0.01 to the cal-
culated value of the log of the vapor pressure by hydrogen iodide. The
vapor pressures of solid and liquid hydrogen and deuterium bromides
are practically identical. It is interesting to note that the Trouton
AH
constants, , for a number of isotopic compounds are not the same
for the hydrogen as for the corresponding deuterium compound.
(The Hildebrand correction is insignificant.) In general, the iso-
topic change produces the greatest difference in the values of the
constants for those substances which deviate most from Trouton's
rule, e.g., water and ammonia.225
From spectroscopic data, Urey and Greiff234 calculated equi-
librium constants and enrichment factors for several exchange
reactions involving isotopes of the lighter elements. A theo-
retical limit, which has been reached in some cases, is set to the
precision of atomic weight determinations. Reactions for practical
separations are suggested. The reaction CH3COCH3 H- DOH
^CH3COCH2D-f-HOH was studied between 35 and 80° C. in the
presence of potassium carbonate. It is pseudo unimolecular with
a high temperature coefficient of velocity and almost zero heat of
reaction. The limiting equilibrium constant is 2.1 when corrected
for the very disturbing formation of higher deuteroacetones.228
Equilibrium constants for the reaction C2H2-i-HDO = C2HD
+ H2O are as follows: 0.365 at 0°, 0.45 at 25° and 0.51 at 100° .232
Most of the thermodynamic and other properties of deuterium
determined before 1935 are summarized in a very exhaustive review
article by Urey and Teal.235
Miscellaneous. A symposium on chemical thermodynamics was
held at the San Francisco meeting of the American Chemical
Society. Several papers on heat transfer and heat interchange
largely from the industrial point of view were published during
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74 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the year.230. 240, 243 The applications of thermodynamics to air con-
ditioning 238 and to the problem of the swelling of wood ^41 have
also been discussed.
Repesxnces.
General.
1. Allen, A. O., and Rice, O. K., /. Am. Chem. Soc, 57: 310 (1935).
2. Bridgman, P. W., Phys. Rev., 48: 825 (1935).
3. Bridgman, P. W., Rev. Modern Phys., 7: 1 (1935).
4. Bridgman, P. W., "The Thermodynamics of Electrical Phenomena in Metals," The
Macmillan Co., New York, 1934. 200 p.
5. Cassel, H. M., /. Am. Chem. Soc, 57: 2724 (1935).
6. Koenig, F. O., /. Chem. Phys., 3: 29 (1935).
7. Lewis, B., and von Elbe, G., /. Chem. Phys., 3: 63 (1935).
8. Lewis, B., and von EHbe, G., Phil. Mag., 20: 44 (1935).
9. Rossini, F. D., /. Wash. Acad. Set., 25: 399 (1935).
10. Scorah, R. L., /. Chem. Phys., 3: 425 (1935).
11. Tolman, R. C, Proc. Natl. Acad. Set., 21: 321 (1935).
12. Van Rysselberghe, P., Chem. Rev., 16: 29 (1935).
13. Van Rysselberghe, P., Chem. Rev., 16: 37 (1935).
14. Van Rysselberghe, P., /. Phys. Chem., 39: 403 (1935).
Thermodynamics and Molecular Mechanics.
15. Ahlberg, J. E., and Freed, S., /. Am. Chem. Soc, 57: 431 (1935).
16. Cross, Paul C, /. Chem. Phys., 3: 168 (1935).
17. Cross, Paul C, /. Chem. Phys., 3: 825 (1935).
18. Cross, P. C, and Brockway, L. O., /. Chem. Phys., 3: 821 (1935).
19. Fuoss, R. M., Chem. Rev., 17: 27 (1935).
20. Fuoss, R. M., and Kraus, C. A., J. Am. Chem. Soc, 57: 1 (1935).
21. Gordon, A. R., /. Chem. Phys., 3: 259 (1935).
22. (Gordon, A. R., /. Chem. Phys., 3: 336 (1935).
23. Johnston. H. L., and Walker, M. K., /. Am. Chem. Soc, 57: 682 (1935).
24. Kassel, L. S., /. Chem. Phys., 3: 115 (1935).
25. Kirkwood, J. G., /. Chem. Phys., 3: 300 (1935).
26. Lewis, B., and von Elbe, G., /. Am. Chem. Soc, 57: 612, 2737 (1935).
27. Pauling, L., /. Am. Chem. Soc, 57: 2680 (1935).
28. Void, R. D., /. Am. Chem. Soc, 57: 1192 (1935).
29. West, C. D., /. Phys. Chem., 39: 493 (1935).
Temperature.
30. Ahlberg, J. E., and Lundberg, W. O., /. Am. Chem. Soc, 57: 2722 (1935).
31. Aston, J. G., Willihnganz, E., and Messerly, G. H., /. Am. Chem. Soc, 57: 1642
(1935).
32. Austin, J. B., and Pierce, R. H. H.. Jr., Physics. 6: 43 (193"?).
33. Giauque, W. F., and MacDougall, D. P., Phys. Rev., 47: 885 (1935).
34. Giauque, W. F., and MacDougall, D. P.. /. Am. Chem. Soc, 57: 1175 (1935).
35. Poritsky, H., and Suits, C. G., Physics, 6: 196 (1935).
36. Roeser, W. F., Dahl, A. I., and Gowens, G. J., J. Research Natl. Bur. Standards,
14: 239 (1935).
37. Roeser, W. F., and Wensel, H. T., 7. Research Natl. Bur. Standards, 14: 247 (1935).
38. Suits, C. G., Physics, 6: 190 (1935).
39. Suits, C. G., Physics, 6: 315 (1935).
40. Whitney, L. V., Phys. Rev., 48: 458 (1935).
Thermal Measurements.
41. Ahlberg, J. E., and Clark, C. W., /. Am. Chem. Soc, 57: 437 (1935).
42. Anderson, C. T., /. Am. Chem. Soc, 57: 429 (1935).
43. Bekkedahl, N., and Matheson, H., /. Research Natl. Bur. Standards. 15: 503 (1935).
44. Blue, R. W., and Giauque, W. F., 7. Am. Chem. Soc, 57: 991 (1935).
45. Chipman, J., and Fontana, M. G., 7. Am. Chem. Soc. 57: 48 (1935).
46. Cobb, A. W., and Gilbert, E. C, 7. Am. Chem. Soc, 57: 35 (1935).
47. Collins, S. C, 7. Am. Chem. Soc, 57: 330 (1935).
48. Edsall, J. T., 7. Am. Chem. Soc, 57: 1506 (1935).
49. Gaucher, L. P., Ind. Eng. Chem., 21 1 57 (1935).
50. Gilbert, E. C, and Cobb, A. W., 7. Am. Chem. Soc, 57: 39 (1935).
51. Gilbert, E. C. and Bushnell. V. C, 7. Am. Chem. Soc. 57: 2611 (1935).
52. Huffman, H. M., and Ellis, E. L., 7. Am. Chem. Soc, 57: 41 (1935).
53. Huffman, H. M., and Ellis. E. L., 7. Am. Chem. Soc, 57: 46 (1935).
54. Jessup, R. S., 7. Research Natl. Bur. Standards, 15: 227 (1935).
55. Keffler, L. J. P., 7. Phys. Chem., 39: 277 (1935).
56. Kistiakowsl^, G. B., Romeyn. H.. Jr., Ruhoff, J. R., Smith, H. A., and Vaughan.
W. E., 7. Am. Chem. Soc, 57: 65 (1935).
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THERMODYNAMICS AND THERMOCHEMISTRY 75
57. Kistiakowsky, G. B., Ruhoff, J. R., Smith, H. A., and Vaughan, W. E., /. Am.
Chem. Soc, 57: 876 (1935).
58. Lamb, A. B., and Ohl, E. N., /. Am. Chem. Soc, 57: 2154 (1935).
59. Lewis, B., and von Elbe, G., /. Am. Chem. Soc, 57: 1399 (1935).
60. Lindsay, J. D., and Brown, G. G., Ind. Eng. Chem., 27: 817 (1935).
61. McPherson, A. T., and Bekkedahl, N., /. Research Natl. Bur. Standards, 14: 601
(1935).
62. McPherson, A. T., and Bekkedahl, N., Ind. Eng. Chem., 27: 597 (1935).
63. Pearcc, J. N., and Tanner, W. B., Proc Iowa Acad. Sci., 41: 123 (1934).
64. Pearce, J. N., and Reed, G. H., /. Phys. Chem., 39: 293 (1935).
t>5. Rossini, F. D., J. Chem. Phys., 3: 438 (1935).
66. Rossini, F. D., /. Research Natl. Bur. Standards, 15: 357 (1935).
67. Sage, B. H., and Lacey, W. N., Ind. Eng. Chem., 27: 1484 (1935).
68. Skau, E. L., /. Am. Chem. Soc, 57: 243 (1935).
69. Southard, J. C, and Milner, R. T., /. Am. Chem. Soc, 57: 983 (1935).
70. Stiehler, R. D., and Huffman, H. M., /. Am. Chem. Soc, 57: 1734 (1935).
71. Stiehler, R. D., and Huffman, H. M., /. Am. Chem. Soc, 57: 1741 (1935).
72. Yost, D. M., and Sherborne, J. E., /. Am. Chem. Soc, 57: 700 (1935).
P-V-T-X Relations.
73. Austin, J. B., and Pierce, R. H. H., Jr., /. Chem. Phys., 3: 683 (1935).
74. Beattie, J. A., Hadlock, C., and Poffenberger, N., J. Chem. Phys., 3: 93 (1935).
75. Beattie, J. A., Poffenberger, N., and Hadlock, C, /. Chem. Phys., 3: 96 (1935).
76. Birch, F., and Law, R. R., Bull. Geol. Soc. Am., 46: 1219 (1935).
77. Booth, H. S., and Swinehart, C. F., /. Am. Chem. Soc, 57: 1337 (1935).
78. Booth, H. S., and Willson, K. S., /. Am. Chem. Soc, 57: 2280 (1935).
79. Bridgman, P. W., Proc Am. Acad. Arts Sci., 70: 71 (1935); summarized in Proc.
Natl. Acad. Sci., 21: 109 (1935).
79a. Bridgman, P. W., Proc Am. Acad. Arts Set.. 70: 285 (1935).
80. Bridgman, P. W., Phys. Rev., 47: 393 (1935).
81. Bridgman, P. W., and Dow, R. B., /. Chem. Phys., 3: 35 (1935).
82 Conrad, R. M., and Hall, J. L., /. Am. Chem. Soc, 57: 863 (1935).
83. Deming, W. E., and Deming, L. S., Phys. Rev.. 48: 448 (1935).
84. Dow, R. B., and Fenske, M. R., Ind. Eng. Chem., 27: 165 (1935).
85. Edsall, J. T., and Wyman, J., Jr., /. Am. Chem. Soc, 57: 1964 (1935).
86. Essex, H., and Kelly, W. R., /. Am. Chem. Soc, 57: 815 (1935).
87. Faick, C. A., Youn?, J. €., Hubbard, D., and Finn, A. N., /. Research Natl. Bur.
Standards, 14: 133 (1935).
88. Gibson, R. E., /. Am. Chem. Soc, 57: 284 (1935).
89. Gibson, R. E., /. Am. Chem. Soc, 57: 1551 (1935).
90. Greenstein, J. P., Wyman, J., Jr., and Cohn, E. J., /. Am. Chem. Soc. 57: 637 (1935).
91. Gucker, F. T., Jr., and Rubin, T. R., /. Am. Chem. Soc. 57: 78 (1935).
92. Hidnert, P., /. Research Natl. Bur. Standards, 14: 523 (1935).
93. Hill, D. M., Phys. Rev., 48: 620 (1935).
94. Jones, G., and Jelen, F. C, /. Am. Chem. Soc, 57: 2532 (1935).
95. Mason, C. M., and Leland, H. L., /. Am. Chem. Soc, 57: 1507 (1935).
96. Newton, R. H., Ind. Eng. Chem.. 27: 302 (1935).
97. Pearce, J. N., and Hanson, A. C, /. Phys. Chem., 39: 679 (1935).
98. Perry, J. H., and Herrmann, C. V., /. Phvs. Chem., 39: 1189 (1935).
99. Roebuck, J. R., and Osterberg, H., Phys. Rev., 48: 450 (1935).
100. Sage, B. H., Lacey, W. N., and Schaafsma, J. G., Ind. Eng. Chem., 27: 48 (1935).
101. Scott, A. F., and Bridger, G. L., /. Phys. Chem., 39: 1031 (1935).
102. Scott, A. H., /. Research Natl. Bur. Standards, 14: 99 (1935).
103. Wiebe, R., and Tremearne, T. H., /. Am. Chem. Soc, 57: 2601 (1935).
Homogeneous Equilibria — Gases.
104. Barton, R. €., and Yost, D. M., /. Am. Chem. Soc, 57: 307 (1935).
105. Bonner, W. D., and Kinney, C- R., /. Am. Chem. Soc, 57: 2402 (1935).
106. Burrows, G. H., and King, L. A., Jr., /. Am. Chem. Soc. 57: 1789 (1935).
107. Cuthbertson, G. R., and Kistiakowsky, G. B., J. Chem. Phys., 3: 631 (1935).
108. Eastman, E. D., and Ruben, S., /. Am. Chem. Soc, 57: 97 (1935).
109. Maroney, W., /. Am. Chem. Soc, 57: 2397 (1935).
110. Newton, R. H., and Dodge, B. F., Ind. Eng. Chem.. 27: 577 (1935).
111. Nies, N. P., and Yost, D. M., /. Am. Chem. Soc, 57: 306 (1935).
112. Smith, H. A., and Vaughan, W. E., /. Chem. Phys., 3: 341 (1935).
Homogeneous Equilibria — Liquids, etc
113. Bray, W. C, and Liebhafsky, H. A., 7. Am. Chem. Soc, 57: 51 (1935).
114. Douglas, T. B., and Crockford. H. D., /. Am. Chem. Soc, 57: 97 (1935).
lis. Greenstein, J. P., and Joseph, N. R., J. Biol. Chem., 110: 619 (1935).
116. Hamed H. S., and Embree, N. D.. 7. Am. Chem. Soc, 57: 1669 (1935).
117. Hamed, H. S., and Mannweiler, G. E., 7. Am. Chem. Soc, 57: 1873 (1935).
118. Kolthoff, I. M., and Tomsicek, W. J., 7. Phys. Chem., 39: 945 (1935).
119. Kolthoff, I. M., and Tomsicek, W. J., 7. Phys. Chem., 39: 955 (1935).
120. Liebhafsky. H. A., 7. Am. Chem. Soc, 57: 2657 (1935).
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76 ANNUAL SURVEY OF AMERICAN CHEMISTRY
121. Maclnnes, D. A., and Belcher, D., /. Am. Chetn, Soc, 57: 1683 (1935).
122. Riesch, L. C, and Kilpatrick, M., /. Phys. Chem., 39: 891 (1935).
123. Schumb, W. C, and Sweetser, S. B., /. Am. Chem. Soc, 57: 871 (1935).
124. Shedlovsky, T., and Maclnnes, D. A., /. Am. Chem. Soc, 57: 1705 (1935).
125. Walde, A. W., /. Phys. Chem., »: 477 (1935).
Heterogeneous Equilibria (1)
126. Bridgman, P. W., Phys. Rev., 48: 893 (1935).
127. Brickwedde, F. G., Scott, R. B., and Taylor, H. S., J. Chem. Phys., 3: 653 (1935).
128. Brickwedde, F. G., Scott, R. B., and Taylor, H. S., /. Research Natl. Bur. Standards,
15: 463 (1935).
129. Cox, E. R., Ind. Eng. Chem., 27: 1423 (1935).
130. Gallup, J., /. Am. Ceram. Soc, 18: 144 (1935).
131. Germann, F. E. E., and Knight, O. S., "Line Coordinate Charts for Vapor
Pressure-Temperature Data."
132. Goranson, R. W., and Kracek, F. C, /. Chem. Phys., 3: 87 (1935).
133. Goranson, R. W., and Kracek, F. C, /. Chem. Phys., 3: 546 (1935).
134. Rudberg, E., and Lempert, J., /. Chem. Phys., 3: 627 (1935).
135. Skau, E. L., and McCullough, R., /. Am. Chem. Soc, 57: 2439 (1935).
136. White, A. H.. and Morgan, S. O., J. Am. Chem. Soc, 57: 2078 (1935).
137. Yager, W. A., and Morgan, S. O., /. Am. Chem. Soc, 57: 2071 (1935).
Heterogeneous Equilibria (2)
138. Austin, J. B., /. Am. Chem. Soc, 57: 2428 (1935).
139. Booth, H. S., and Willson, K. S., /. Am. Chem. Soc, 57: 2273 (1935).
140. Brown, A. S., and Maclnnes, D. A., J. Am. Chem. Soc, 57: 459 (1935).
141. Brunjes. A. S., and Furnas, C. C, Ind. Eng. Chem., 27: 396 (1935).
142. Cole S. S., and Taylor, N. W., /. Am. Ceram. Soc. 18: 55 (1935).
143. Cole, S. S., Scholes, S. R., and Amber, C. R., /. Am. Ceram. Soc, 18: 58 (1935).
144. Cole, S. S., Taylor, N. W., and Scholes, S. R., /. Am. Ceram. Soc, 18: 79 (1935).
145. Cole, S. S., and Taylor, N. W., /. Am. Ceram. Soc, 18: 82 (1935).
146. Draper, R. B., Am. J. Set., [5] 30: 106 (1935).
147. Hildebrand, J. H., /. Am. Chem. Soc, 57: 866 (1935).
148. Hill, A. E., and Distler, E. F., /. Am. Chem. Soc, 57: 2203 (1935).
149. Huettig, H., Jr., and Smyth, C. P., /. Am. Chem. Soc. 57: 1523 (1935).
150. Larsen, W. E., and Hunt, H., /. Phys. Chem., 39: 877 (1935).
151. Mair, B. J., /. Research Natl. Bur. Standards, 14: 345 (1935).
152. Morris, R. E., and Cook, W. A., /. Am. Chem. Soc. 57: 2403 (1935).
153. Parks, G. S., Warren, G. E., and Greene, E. S., /. Am. Chem. Soc. 57: 616 (1935).
154. Pearce, J. N., and Blackman, L. E., /. Am. Chem. Soc. 57: 24 (1935).
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156. Roberts, H. S., .7. Am. Chem. Soc. 57: 1034 (1935).
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168. Thompson, H. E., Jr., /. Phvs. Chem., 39: 655 (1935).
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THERMODYNAMICS AND THERMOCHEMISTRY 77
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193. Olsen, A. L., and Washburn, E. R., /. Am. Chem. Soc, 57: 303 (1935).
194. Prutton, C. F., Brosheer, J. C, and Maron, S. H., /. Am. Chem. Soc, 57: 1656 (1935).
195. Randall, M., and Shaw.D. L., /. Am. Chem. Soc, 57: 427 (1935).
196. Ricci, J. E., /. Am. Chem. Soc, 57: 805 (1935).
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201. Swearingen, L. E., and, Florence, R. T., J. Phys. Chem., 39: 701 (1935).
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Electromotive Force Measurements.
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204. Brown, A. S., and Maclnnes, D. A., /. Am. Chem. Soc, 57: 1356 (1935).
205. Cann, J. Y., and Mueller, G. B., /. Am. Chem. Soc, 57: 2525 (1935).
206. Garner, C. S., Green, E. W., and Yost, D. M., /. Am. Chem. Soc, 57: 2055 (1935).
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Isotopes.
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Chapter V.
Contact Catalysis.
L. H. Reyerson,
The University of Minnesota.
The past year has been one of progress in the attack on the
problems of the Mechanism of Contact Catalysis. Coupled with
this work there have been marked advances in the theoretical as
well as the experimental side of the kinetics of homogeneous gas
reactions. The many studies on the kinetics of reactions, in which
the wall of the reaction vessel acts either as a catalyst or an
inhibitor, have their important bearing on the subject here dis-
cussed. However, since the subject of kinetics is fully taken up
elsewhere in this volume only rarely will such work be considered
in this Chapter.
Deuterium continues to be a valuable tool in the elucidation of
the mechanism of catalytic reactions. Studies of the ortho-para
hydrogen conversion on various catalyst surfaces have made addi-
tional contributions to our knowledge of the mechanism of contact
catalysis. An important contribution not only to the subject of
catalysis but also to the whole field of chemistry has been made by
Kistiakowsky ^i. 32 ^nd his coworkers. These investigators made
remarkably careful and accurate determinations of the heats of
reaction resulting from the catalytic hydrogenation of ethylene
and other simple olefinic hydrocarbons. By using a flow system
they were able to eliminate the problem presented by the adsorption
of the gases by the catalyst. The heats of reaction differ some-
what from the present values which are obtained from heats of
combustion. Such differences are likely to raise many questions
in theoretical chemistry. The results so far reported do not bear
out the theory of constant bonding energies.
Again it seems best to divide the work into two general groups.
Accordingly, the work which primarily concerns the "Mechanism
of Contact Catalysis" will be considered first and this will be
followed by a consideration of "Catalytic Reactions." The terms "acti-
vated adsorption" and "chemosorption" will again be used as equivalent
expressions. It is to be regretted that important foreign contributions
as well as many interesting points and suggestions by American inves-
tigators have had to be omitted from this survey.
78
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CONTACT CATALYSIS 79
Mechanism of Contact Catalysis
Use of the rate equation in studying a number of heterogeneous
reactions has led to an apparent relationship of A = Coe^^, where A
is the activity constant of the reaction, E, the energy of activation and
Co and c are constants. In a theoretical consideration of problems of
activity and activation energy in heterogeneous gas reactions, Storch ^'^
found that changes in the frequency of energy transfer between the
adsorbed gas and the surface was an important factor in determining
the above relationship. Frequency of the energy exchange in the
adsorbed phase may be reduced markedly when multiple adsorption
occurs and hence be a function of the spacing of catalyst atoms. It was
shown that the above relationship could not be due entirely to a prob-
ability distribution of the active centers. In hydrogenations it did not
seem necessary to postulate a hydrogen atom leakage through an energy
barrier.
The use of deuterium continued to lead to further insight into the
mechanism of surface action. Morikawa, Benedict and Taylor ^o
studied the exchange between deuterium and methane on the surface
of reduced nickel catalysts in the temperature range up to 305°. At
the upper temperature, equilibrium on the heavy methane side was estab-
lished in twenty hours. At 218° the equilibrium was reached in fifty
hours. At 110° no exchange was detected in ninety hours. Exchange
was found to occur at as low a temperature as 170°, which was taken as
evidence for the activated adsorption of methane at this temperature.
This is at least 200° lower than the temperature at which the usual
methods of adsorption reveal any activated adsorption of methane on
nickel. These same authors ^^ used deuterium to study the activation
of specific bonds in complex molecules. Deuterium or hydrogen was
adsorbed under such conditions that it was present in an activated form.
It was possible to determine the conditions under which exchange of
deuterium with ethane occurred without any appreciable amount of
ethane having reacted with the deuterium (or hydrogen) to form two
molecules of methane. At 138° exchange proceeded quantitatively,
while the production of methane set in at 150° and was sensibly complete
at 200°. Since the exchange reaction involved only the C-H bond,
while methane production involved the C-C bond, the different condi-
tions of reaction, temperature, and catalyst, were obtained for the
activated adsorption of ethane molecules producing either a C-H or a
C-C bond split. This work will no doubt have important consequences
in the study of the catalytic behavior of saturated hydrocarbons and the
activation of specific chemical bonds in the more complex molecules.
Further studies have been conducted on the catalytic exchange
reaction between water and deuterium. Taylor and Diamond ^^ found
a rapid exchange between deuterium gas and the water retained by
such catalytic materials as chromic oxide, zinc oxide, zinc chromite,
alumina, and platinized asbestos. The reverse action between hydrogen
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80 ANNUAL SURVEY OF AMERICAN CHEMISTRY
and heavy water on the surface was demonstrated. The mechanism of
the reaction was considered to be due to the activated adsorption of
hydrogen (or deuterium) on the chromic oxide, zinc oxide, and zinc
chromite, while the water was adsorbed in an activated state by the
alumina. The existence of this exchange is important, since it may
cause unintentional replacement of deuterium by hydrogen in reaction
mixtures. At room temperature Taylor and Jungers^^ obtained an
exchange between ammonia gas and deuterium over an iron synthetic
ammonia catalyst. Activated adsorption of both ammonia and deuterium
must take place in order for the exchange to occur; since at higher
temperatures these reactions would proceed rapidly, they cannot be
the rate-determining steps in the ammonia synthesis. The activated
adsorption of nitrogen probably is the rate-determining step. Such
studies as these indicate the delicacy of isotopic chemistry in revealing
the nature of the association between surface adsorbent and adsorbate.
In this latter case activated adsorption of ammonia is shown to exist
at temperatures where the usual methods could not distinguish between
van der Waal's and activated adsorption.
Additional studies on the effectiveness of catalysts in ortho-para
hydrogen conversion have given further information on the nature of
the catalyst surface and the types of adsorption. Emmett and Hark-
ness,^^ using iron, nickel, and platinum as catalysts, observed the effect
of the previous treatments of the catalysts on the ortho-para conversion
at —190°. A catalyst outgassed at 450° and cooled to —190° in
helium gas was ten to twenty times as effective as a catalyst cooled
in hydrogen gas. The iron catalyst could be run indefinitely at — 190°
with no poisoning effect due to adsorbed hydrogen, while the nickel
catalyst lost activity at this temperature. Nitrogen added to the
iron catalyst reduced its activity when used at 100° and 450°. Adding
nitrogen at — 190° to the iron catalyst which had been cooled in hydro-
gen reduced its activity seventy percent. The adsorbed nitrogen could
be rather well removed by warming in hydrogen to room temperature.
The platinized asbestos lost activity at 130° on being exposed to hydro-
gen at atmospheric pressure. The poisoning of these catalysts by the
various gases was attributed to their activated adsorption. These
results support strongly the concept that activated adsorption is a sur-
face phenomenon. In this investigation, as well as in their study of
the adsorption of hydrogen by iron synthetic ammonia catalysts, Emmett
and Harkness^^ obtained additional evidence for the existence of at
least two kinds of activated adsorption of hydrogren. The first type
occurred at a convenient rate at —90° and a1)ove, while the second
kind was found at 100° and above. Both types were largely surface
adsorptions rather than activated diffusion. The ortho-para and the
para-ortho conversion of hydrogen was also used by Taylor and Dia-
mond *® to determine the effectiveness of sixteen different paramagnetic
and diamagnetic surfaces. Paramagnetic gadolinium and neod)miium
oxides caused rapid conversion, while diamagnetic lanthanum oxide had
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CONTACT CATALYSIS 81
an effectiveness that was several orders lower. For comparable sur-
faces paramagnetic substances showed greater effectiveness than dia-
magnetic surfaces for similar van der Waal's adsorptions. Paramag-
netic surface atoms must exist on diamagnetic bulk copper and silver
in order to explain their catalytic effect or else residual activated adsorp-
tion may be present. High temperature activated adsorption was found
to be effective in the para-ortho conversion at higher than liquid air
temperatures. A new high temperature conversion was found on an
alumina surface which seemed to indicate a possible exchange
mechanism with the water adsorbed in an activated state.
Evidence, supporting the concept that hydrogen may be adsorbed
in different ways by the same metal surface, depending upon the tem-
perature, was obtained by Rowley and Evans ^^ in their measurements
of the accommodation coefficient of hydrogen on iron. If the surface
of the metal remained unchanged, the accommodation coefficient should
fall with falling temperature. These investigators found, instead, a
greater rise in the coefficient than they had previously observed in the
case of platinum and tungsten wires. They attributed this to a greater
adsorption of hydrogen and offered the explanation that above 500° K.
the surface of the iron was uniformly covered by activated hydrogen
(probably atomic). Below 500° K. a second type of more loosely bound
gas was present on the surface and below 350° K. a molecular type of
adsorption predominated. When special techniques were used to remove
the adsorbed hydrogen, the values of the coefficient always dropped.
Cashman and Huxford'^ studied the photoelectric properties of mag-
nesium in the presence of traces of hydrogen and oxygen. Chemi-
sorbed layers of hydrogen and oxygen were considered to produce
single layers of MgH and MgO on the surface. These layers produced
shifts in the photoelectric threshold of magnesium. A second shift in
this threshold was found when more hydrogen was added; this was
attributed to induced dipoles in weakly adsorbed hydrogen molecules.
Additional oxygen desensitized the magnesium, probably as a result of
the formation of a thicker magnesium oxide coating. Mixed hydrogen
and oxygen, present in traces, markedly sensitized magnesium and this
was thought to be due to the formation of a single layer of MgOH.
Copper catalysts, poisoned to varying degrees by oxygen, were used
by Russell and Ghering^* in the hydrogenation of ethylene at 0° for
the purpose of studying the nature of the copper surface. The surfaces
showed extreme sensitivity to variations in the method of preparation.
Copper poisoned at 0° by oxygen showed a slow removal of the
oxygen at 20° by the hydrogen-ethylene mixture but no removal was
observed at 0°. Catalytic activity toward the hydrogenation of ethylene
disappeared completely when the surface was only 40 percent saturated
with oxygen. Calorimetric measurements were obtained for the heat
of adsorption of oxygen by these catalysts. These results indicated
that the direct sorption of oxygen was largely non-preferential, so that
the heats of adsorption gave no indication of the catalytic behavior of
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82 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the surface. However, successive removal of small amounts of the
adsorbed oxygen by reduction with hydrogen showed that the leas'
active part of the surface was released first. Nitrous oxide was also
used as a poison and interesting results were obtained in this case. The
decomposition of the nitrous oxide on the copper surface proceeded
with no increase in pressure up to a temperature of 75°. Thus, the
oxygen of the nitrous oxide was adsorbed while the nitrogen was given
off. Decomposition occurred at as low a temperature as —78°. Con-
siderable oxygen was taken up from the nitrous oxide before any
poisoning resulted. The catalyst could be completely poisoned for the
jiitrous oxide decomposition by the adsorption of oxygen and still be
catalytically active enough to cause some hydrogenation of ethylene.
A more active surface thus was needed for the decomposition of nitrous
oxide than for the hydrogenation of ethylene. The evidence in the main
supported the point of view that the investigators were dealing with a
non-uniform surface of copper. A large part of the surface was not
catalytically active. The most active portion of the surface was prob-
ably inactive in the hydrogenation of ethylene at 0°, due to the
adsorption of ethylene itself as a poison. According to Griffin ^^ a
supported copper catalyst which had been poisoned by a trace of car-
bon monoxide showed an increased capacity to adsorb hydrogen at all
pressures up to one atmosphere. A larger amount of carbon monoxide*
caused a low pressure increase in the adsorption of hydrogen but a
decrease at higher pressures. The traces of carbon monoxide seemed
to be adsorbed on the most active centers and aided in binding more
hydrogen, while the larger amounts were adsorbed on the less active
centers to the exclusion of equivalent amounts of hydrogen. In spite of
these recent contributions to the problem, the mechanism, or perhaps
one should say the mechanisms, of the different types of activated
adsorption still remains in doubt.
Adsorption of Gases. Several papers have appeared concerning
the adsorption of gases by solids which are related to catalysis either
directly or indirectly. Cunningham® has extended the Langmuir
theory by considering that a gas molecule need only come within a
certain range of attraction of the surface to be adsorbed. The
theory leads to the conclusion that surfaces may have several kinds
of elementary spaces and gives a method for determining their
number. For the examples used the mathematical treatment is in
good agreement. Herzfeld 23 considered the speed of condensation
and sublimation from the surfaces of solids. The formula for the
equilibrium pressure was found to be changed in the case of the
condensation and sublimation of atoms if the electron weight in
the gaseous state is different from the solid state. For true metals
the speed of sublimation is probably increased, while for non-metals
a reflection coefficient exists. The equilibrium pressure for mole-
cules comes out to be higher than for atoms because in sublimation
there is a transition from limited oscillation of the axes to free
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CONTACT CATALYSIS 83
rotation which tends to increase the speed of sublimation. Lamb
and Ohl^* measured the heats of adsorption of a number of gases
and vapors on dehydrated chabasite, thomsonite, and brucite.
Molar heats of adsorption of those substances copiously adsorbed
were found to be somewhat larger than those previously observed
for charcoal and silica gel but, like them, they varied only slightly
with the amount adsorbed. These crystalline substances seemed
to exert more intense adsorptive and compressive forces on the
gases and vapors studied than does charcoal. Polanyi's potential
theory was applied to the van der Waals' adsorption of argon and
nitrogen on iron synthetic ammonia catalysts at liquid air tempera-
tures by Emmett and Brunauer.^* The results fitted the Polanyi
theory very well. The early part of the potential curves represented
the building of monomolecular layers, the straight line section
indicated the formation of multimolecular layers, while the high
pressure part pointed to condensation of the gas in capillaries of
the adsorbent. Thus Polanyi's theory is not limited to multimolec-
ular layers of adsorbate but in this case, at least, it applies to
monomolecular layers and capillary condensation as well. Brunauer
and Emmett ^ determined the van der Waals' adsorption of such
gases as nitrogen, oxygen, and argon by iron synthetic ammonia
catalysts for the purpose of estimating the surface area of these
catalysts. By extrapolating the linear portion of the isotherms
back to zero pressure and assuming close packing, they calculated
the mean value of the surface area to be 17.6 square meters for a
46 gram sample, if the molecular diameters are taken from the densi-
ties of the solidified gases, and 20.6 square meters if the diameters
are obtained from the densities of the liquefied gases.
Rather unusual results were found by Beebe and his coworkers 2
when they measured the adsorption of hydrogen and deuterium on
copper at pressures from zero to two mm. At —78° the rate of
adsorption of deuterium was less than for hydrogen but equal
amounts of the two isotopes were adsorbed at equilibrium. It
was concluded that activated adsorption occurred at this tempera-
ture. In the temperature interval to 125°, the rates at which the
two isotopes are adsorbed underwent an inversion, deuterium being
more rapidly adsorbed at the higher temperature. Direct calori-
metric measurements of the differential heats of adsorption of
the two isotopes showed them to be identical within the limits of
experimental error. The early rate of adsorption at —78° was auto-
catalytic.
Surface Properties and the Preparation of Catalysts. Copley and
Phipps ^ directed a constant molecular beam of potassium iodide
against a heated tungsten filament and studied the positive ion
current obtained. The tungsten filament was first oxygen coated
and later stripped of this gas by flashing at high temperatures.
In the region of a stable oxygen layer the positive ion current was
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84 ANNUAL SURVEY OF AMERICAN CHEMISTRY
constant and higher than after the wire was flashed. The current
decreased with increasing temperature. This behavior was the
same as found when a beam of potassium atoms was used, which
indicated that the ionization process was the same in both cases.
Preliminary dissociation of the adsorbed salt into atoms must first
occur. Positive ions were found by Kunsman and Nelson ^3 to be
emitted from an iron potassium catalyst for ammonia synthesis
after the catalyst had become inactive as a clean up agent, indicat-
ing that metal surfaces emitting positive ions were not necessarily
good catalysts.
A new method was worked out by DuMond and Youtz,^^
whereby gold atoms could be successively laid down in step-wise
layers of twenty atoms thick. They then measured the selective
x-ray reflection from these stratified metal films whose thickness
was 10,000 A. Diffraction maxima, whose intensity falls off
exponently with the time, were obtained from this grating. The
half life of the surface was from two to three days. If this tech-
nique could be applied to the study of the surface of metal catalysts,
it might provide a means of studying intimately the diffusion of
atoms in the solid state.
A new way to prepare finely divided metals was developed by
Insley,24 who carefully distilled the mercury from amalgams of
these metals. Copper, iron, cobalt, and nickel, prepared in this
way, were neither as good adsorbents for hydrogen, ethylene, or
ethane, nor were they as good catalysts in the hydrogenation of
ethylene as the same metals obtained in a fine state of division by
reduction of the oxides. The results indicated a small amount of
van der Waal's adsorption of hydrogen by the nickel prepared from
the nickel amalgam and a somewhat larger activated adsorption.
However, it was not proved that the last traces of mercury were
completely eliminated by the process and any such traces might
well act as poisons. Baldeschwieler and Mikeska ^ were able to
prove that the poisons and impurities on spent platinum catalysts
must be eliminated before the material could be made into an effec-
tive platinum oxide catalyst once more. Recommended procedures
were not successful in doing this and modifications were worked
out. Conversion to chloroplatinic acid and precipitation by ammo-
nium chloride under controlled conditions enabled them to prepare
a catalyst of high activity. The effectiveness of various zinc oxide-
chromium oxide catalysts in the methanol synthesis was made the
basis of a study by Molstad and Dodge.^^ Short time tests indi-
cated the best ratio to be Znjg Cr25 but it was found that catalysts
of higher chromium content increased in activity with use coupled
with operation at temperatures above maximum activity. The com-
position of the catalyst, having maximum activity, was finally
located at ZnsoCrsQ. This catalyst was rugged, produced nearly
pure methanol, and appeared to be uninjured by long use. Such
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CONTACT CATALYSIS 85
complete studies as this show how futile it is to decide on the
composition and behavior of a catalyst before full information is
available.
Heterogeneous Reaction Kinetics. In order to evaluate more
satisfactorily the kinetics of reactions of the type A(^) = B(j) +C(^),
Benton and Cunningham ^ studied the rate of thermal decomposi-
tion of light sensitive silver oxalate, on which nuclei had been
previously produced by irradiation. Exposure to light, especially
to AX<520mu, greatly increased the rate of the subsequent thermal
reaction. Oxygen present during exposure resulted in marked
initial poisoning as compared to exposure in nitrogen and carbon
dioxide. Long exposure to light resulted in slight decomposition
of the oxalate. Exposure to light produced a greater effect in the
lower decomposition temperature range than it did in the higher
range. The increased yield over unexposed samples was roughly
proportional to the number of quanta absorbed for short exposures
but long exposures were relatively less effective. The theoretical
treatment, based on simple assumptions regarding nuclei formation
and their subsequent growth, was found to be in reasonably good
agreement with the early stages of decomposition. Activation
energy of nucleation was found to be about 64 K. cal., while that
for growth of nuclei was 8.5 K. cal.
The decomposition of deuteroammonia on tungsten wires at
about 950° K. was observed to be approximately of zero order by
Jungers and Taylor ^^ in the pressure range of 3.5 cm. to 15 cm.
The surface area was nearly saturated but the zero order decom-
position was slower than for ammonia under the same conditions.
The temperature coefficient of decomposition was the same for
the two ammonias. Zero point energy differences are able to
account for the differences in the decomposition velocities. Pease
and Wheeler ^^ used a copper catalyst and measured the rate of
hydrogenation of ethylene by hydrogen and deuterium at 0°. The
results indicated a ratio of rates of H2/D2 = 1.59. At higher tem-
peratures this ratio fell but the possibility of exchange was not
excluded. The exchange reaction between benzene and heavy
water was found by Bowman, Benedict and Taylor * to proceed
slowly over a nickel catalyst at 200° in a closed system. Finally,
all of the hydrogen atoms of benzene were found to be replaced
by deuterium resulting in the formation of benzene dg.
A smooth platinum wire was used by Dixon and Vance ^^ in
their study of the reaction between hydrogen and nitrous oxide
at 260 to 471°. The reaction was nearly independent of the hydro-
gen pressure and approximately proportional to the nitrous oxide
pressure, indicating that reaction occurred when nitrous oxide
molecules with an activation energy of 23,100 cal. collided with
surfaces which were practically covered with hydrogen. Jackson ^o
placed tungsten or platinum as a catalyst in the gas vStream, coming from
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86 ANNUAL SURVEY OF AMERICAN CHEMISTRY
an electrical discharge through water vapor, to remove atomic hydro-
gen. This gas stream with 80 percent of the atomic hydrogen
removed was about 90 percent as effective in the oxidation of
carbon monoxide. Possible chain reactions, involving OH radicals
or hydrogen peroxide, were suggested as mechanisms for this
reaction. In the slow oxidation of propane, Pease ^^ had to use a
glass tube poisoned by potassium chloride, because the reaction
was strongly inhibited by the glass surface. Heisig and Wilson ^2
found that the action of bromine on butadiene was a surface reac-
tion, occurring rapidly on glass surfaces as catalysts. Adsorption
of the product on the glass slows down the action to a constant
rate.
Catalytic Reactions.
Hydrogenation. Carbon dioxide was hydrogenated to formic
acid over Raney nickel catalysts at 80° or less in the presence of
amines as reported by Farlow and Adkins.^*^ Sheet brass was
effective as a catalyst at 250°. Formates were formed but, if the
reaction was carried out at much above 100°, the formate of the
amine was dehydrated to the substituted formamide. Using
platinic oxide as a catalyst, Glattfeld and Schimpff ^® observed that
the delta-lactones of aldonic acids were reduced to the correspond-
ing sugars. Gamma-lactones were also reduced but the sugar yields
were usually lower, due to the further reduction to the correspond-
ing sugar alcohols. Both platinic oxide and Raney nickel were
used by Lutz and Palmer ^^ in the hydrogenation of 1,4-diketones.
/ranj-Dibenzoylethylene may imder different conditions give both
mono and dimolecular products, while other 1,4-diketones, includ-
ing m-dibenzoylethylene and the halogen derivatives, imderwent
largely monomolecular reduction. The formation of furous and
cyclic dimolecular products suggested that in these cases catalytic
hydrogenation involved conjugate addition. Stevinson and Ham-
ilton,*^ using Raney nickel, were able to catalytically reduce nitro-
arylarsonic acids to amino-arylarsonic acids without affecting the
arsono groujJ. Raney nickel catalysts were also found by Van
Duzee and Adkins ^^ to be effective in the hydrogenation and
hydrogenolysis of a series of ethers. Hydrogenolysis occurred in
some cases at temperatures lower than necessary for hydrogenation.
Oxidation. The rate of burning or the disappearance of a carbon
film from glass surfaces or from glass coated with chlorides of the
alkalies, chlorides and hydroxides of the alkaline earth metals or
the sulfates of sodium and potassium, was made the basis of a study
by Day, Robey, and Dauben.^^^ The salts markedly speeded up the
disappearance of the carbon film at temperatures of 515 to 575°.
The salt surfaces probably acted as catalysts in the decomposition
of surface complexes of the type C^Oy. This was previously sug-
gested by Taylor and Neville for the effect of salts on the reaction
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CONTACT CATALYSIS 87
of steam upon carbon. By an improved technique Milas and
Walsh 37 oxidized furane, furfural, furfural alcohol, and furoic acid
over such catalysts as vanadium pentoxide, bismuth vanadate, and
a ten percent molybdenum oxide, ninety percent vanadium pent-
oxide. Maleic acid was found to be the chief solid product. Walker
and Christensen ^* accomplished the quantitative oxidation of
methane by passing it twice over mixed oxides of cobalt and copper
on unglazed porcelain at a rate of 20 to 25 cc. per minute over 3.5 g.
of catalyst at 550°, provided the ratio of oxygen to methane was
at least three to one.
Miscellaneous Reactions. Several interesting investigations
have appeared which involve alkylation and polymerization. Direct
alkylation of aromatic hydrocarbons was achieved by Malishev,^^
who used phosphorus pentoxide, mixed with cresol peptized lamp-
black, as a dispersion catalyst in the hydrocarbons. At tempera-
tures of 200° to 250° under pressures up to 40 atmospheres, ethylene
added to benzene to form mono- and hexaethylbenzene, isobuty-
lene added to benzene to form ^^rf-butylbenzene, propylene added to
toluene (at 150°) to form />-c)rmene and naphthalene was ethylated by
ethylene. Grosse and Ipatieff ^i obtained what was termed destruc-
tive alkylation when a paraffin hydrocarbon in the presence of
AIQ3 or ZrCl4 at 50-75° split into a lower hydrocarbon and an
olefin which immediately reacted with an aromatic hydrocarbon to
alkylate it. Ipatieff and Grosse ^7 further found that different
classes of hydrocarbons, i. e., paraffins, naphthenes, aromatics and
olefins, reacted with ease among themselves in the presence of
catalysts. The halides of a number of the elements proved to be
effective but boron fluoride in the presence of finely divided nickel
and either water or anhydrous hydrogen fluoride was studied most
completely in the cases of reactions between paraffins and olefins.
The paraffins so far alkylated gave higher weight molecules through
addition of one, two or more molecules of olefin — and they all
contained a tertiary carbon atom. Together with his coworkers,
Ipatieff 25, 26, 28 has followed the polymerization of gaseous olefins
under high pressure in the presence of phosphoric acid. Ethylene
yielded a mixture of paraffinic, olefinic, napthenic and aromatic
hydrocarbons. Propylene polymerized to a mixture of mono-olefins
and isomeric butylenes at atmospheric pressure and relatively low
temperature formed liquid polymers which proved to be mono-
olefins.
Using copper-silica gel and copper chloride-silica gel catalysts,
Reyerson and Yuster*^ followed the chlorination of propane over
a temperature range from about 50 to 275°. In the presence of the
catalysts the heat of activation was about half of that for the homo-
geneous reaction and the extent of chlorination was greater at a
given temperature. A new type of hysteresis was observed when
the partial pressure of chlorine was half an atmosphere or over.
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88 ANNUAL SURVEY OF AMERICAN CHEMISTRY
When, and only when, the reaction was carried to a temperature
such that there was a 100 percent chlorination was the hysteresis
effect found. If the temperature of the catalyst chamber was
lowered as much as 60 to 80°, the chlorination persisted at 100 per-
cent, instead of dropping as it had in the homogeneous reaction.
This catalytic hysteresis made it possible to study the pyrolysis of
the propyl chlorides which was found to take place. A coupling
reaction was also shown to be present. Anhydrous zinc chloride
was the catalyst used by Underwood and Baril ^2 j^ their study
of the decomposition of esters and acids. The methyl, ethyl,
propyl, and butyl esters of monobasic aliphatic acids were not
affected but esters of higher alcohols, i. e., amyl and above, decom-
posed over this catalyst into an unsaturated hydrocarbon and the
monobasic acid. Aliphatic monobasic acids themselves were not
affected. Esters of aromatic acids decomposed into an unsaturated
hydrocarbon and the aromatic acid which, in turn, gave carbon
dioxide and the aromatic hydrocarbon if the acid were monobasic.
Cases were found where halogenated aliphatic acids decomposed,
yielding carbon monoxide as one of the products.
Ebert ^^ attempted to find a catalyst which would enable him to
produce acetaldehyde from carbon monoxide and methane. A
nickel catalyst proved to be the best to catalyse the decomposition
of acetaldehyde into carbon monoxide and methane. Equilibrium
was thought to have been reached in this decomposition but
attempts to approach the equilibrium from the other side were
not successful. A number of catalysts were tried out by Graeber
and Cryder ^^ in the dehydration of formic acid. At 280 to 360° a
thoria-silica gel catalyst proved to be the most efficient as to yield
and purity of carbon monoxide. The method offers a good way to
prepare pure carbon monoxide from formic acid, in place of the
liquid phase dehydration used at present. Singh and Krase*^
sought to develop a catalytic vapor phase synthesis of acetic acid
from methanol and carbon monoxide under pressure. Active car-
bon impregnated with phosphoric acid was found to be an effective
catalyst for this reaction but its life was limited. The influence of
fuel and water gas conversion catalysts formed the basis of an
investigation by Brewer and Reyerson ^ on the rate of production
of hydrogen from lignite char at 600 to 800°. Catalysts were found
which produced higher yields of water gas, with a corresponding
increase in hydrogen as compared with untreated char.
References.
1. Baldeschwieler, E. L., and Mikeska, L. A^ /. Am. Chem. Soc, 57: 977 (1935).
2. Beebe, R. A., Low, G. W., Jr., Wildner, E. L., and Goldwasser, S., /. Am. Chem.
Soc, 57: 2527 (1935).
3. Benton, A. F., and Cunningham, G. L., /. Am. Chem. Soc, 57: 2227 (1935).
4. Bowman, P. I., Benedict, W. S., and Taylor, H. S., /. Am. Chem. Soc, 57: 960
(1935).
5. Brewer, R. E., and Reyerson, L. H., Ind. Eng. Chem., 27: 1047 (1935).
6. Brunauer, S., and Emmett, P. H., /. Am. Chem. Soc, 57: 1754 (1935).
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CONTACT CATALYSIS 89
7. Cashman, R. J., and Huxford, W. S., Phys. Rev., 48: 734 (1935).
8. Copley, M. J., and Phipps, T. E., /. Chem. Phys., 3: 594 (1935).
9. Cunningham, G. E., /. Phys. Chem., »: 69 (1935).
10. Day, J. E., Robey, R. F., and Dauben, H. J., /. Am. Chem. Soc, 57: 2725 (1935).
11. Dixon, J. K., and Vance, J. E., /. Am. Chem. Soc, 57: 818 (1935).
12. DuMond, J. W., and Youtz, J. P., Phys. Rev., 48: 703 (1935).
13. EJbert, M. S., /. Phys. Chem., 39: 421 (1935).
14. Emmett, P. H., and Brunauer, S., /. Am. Chem. Soc, 57: 2732 (1935).
15. Emmett, P. H., and Harkness, R. W., /. Am. Chem. Soc, 57: 1624 (1935).
16. Emmett, P. H., and Harkness R. W., /. Am. Chem. Soc, 57: 1631 (1935).
17. Farlow, M. W., and Adkins, H., /. Am. Chem. Soc, 57: 2222 (1935)
18. Glattfeld, J. W. E., and Schirapff, G. W., /. Am. Chem. Soc, 57: 2204 (1935).
19. Graeber, E. G., and Cryder, D. S., Ind. Eng. Chem., 27: 828 (1935).
20. Griffin, C. W., /. Am. Chem. Soc, 57: 1206 (1935).
21. Grosse, A. V., and Ipatieff, V. N., /. Am. Chem. Soc, 57: 2415 (1935).
22. Heisig, G. B., and Wilson, J. L., /. Am. Chem. Soc, 57: 859 (1935).
23. Herzfeld, K. F., /. Chem. Phys., 3: 319 (1935).
24. Insley, E. G., /. Phys. Chem., 39: 623 (1935).
25. Ipatieff, V. N., Ind. Eng. Chem., 27: 1067 (1935).
26. Ipatieff, V. N., and Corson, B. B., Ind. Eng. Chem., 27: 1069 (1935).
27. Ipatieff, V. N., and Grosse, A. V., /. Am. Chem. Soc, 57: 1616 (1935).
28. Ipatieff, V. N., and Pines, H., Ind. Eng. Chem., 27: 1364 (1935).
29. Jackson, W. F., /. Am. Chem. Soc, 57: 82 (1935).
30. Jungers, J. C, and Taylor, H. S., /. Am. Chem Soc, 57: 679 (1935).
31. Kistiakowsky, G. B., Romeyn, H., Jr., Ruhoff, J. R., Smith, H. A., and Vaughan,
W. E., /. Am. Chem. Soc, 57: 65 (1935).
32. Kistiakowsky, G. B., Ruhoff, J. R., Smith, H. A., and Vaughan, W. E., /. Am.
Chem. Soc, 57: 876 (1935).
33. Kunsman, C. H., and Nelson, R. A., /. Chem. Phys., 3: 754 (1935).
34. Lamb, A. B., and Ohl, E. N., /. Am. Chem. Soc, 57: 2154 (1935).
35. Lutz, R. E., and Palmer, F. S., /. Am. Chem. Soc, 57: 1957 (1935).
36. Malishev, B. W., /. Am. Chem. Soc, 57: 883 (1935).
Z7, Milas, N. A., and Walsh, W. L., /. Am. Chem. Soc, 57: 1389 (1935).
38. Molstad, M. C, and Dodge, B. F., Ind. Eng. Chem., 27: 134 (1935).
39. Morikawa, K., Benedict, W. S., and Taylor, H. S., /. Am. Chem. Soc, 57: 592
(1935).
40. Pease, R. N., /. Am. Chem. Soc, 57: 2296 (1935).
41. Pease, R. N., and Wheeler, A., /. Am. Chem. Soc, 57: 1144 (1935).
42. Reyerson, L. H., and Yuster, S., /. Phys. Chem., 39: 1111 (1935).
43. Rowley, H. H., and Evans, W. V., /. Am. Chem. Soc, 57: 2059 (1935).
44. Russell, W. W., and Ghering, L. G., /. Am. Chem. Soc, 57: 2544 (1935).
45. Singh, A. D., and Krase, N. W., Ind. Eng. Chem., 27: 909 (1935).
46. Stevinson, M. R., and Hamilton, C. S., /. Am. Chem. Soc, 57: 1298 (1935).
47. Storch, H. H., /. Am. Chem. Soc, 57: 1395 (1935).
48. Taylor, H. S., and Diamond, H., /. Am. Chem. Soc, 1256 (1935).
49. Taylor, H. S., and Diamond, H., /. Am. Chem. Soc, 57: 1251 (1935).
50. Taylor, H. S., and Jungers, J. C, /. Am. Chem. Soc, 57: 660 (1935).
51. Taylor, H. S., Morikawa, K., and Benedict, W. S., /. Am. Chem. Soc, 57: 2735
(1935).
52. Underwood, H. W., Jr., and Baril, O. L., /. Am. Chem. Soc, 57: 2729 (1935).
53. Van Duzee, E. M., and Adkins, H., /. Am. Chem. Soc, 57: 147 (1935).
54. Walker, I. F., and Christensen, B. E., Ind. Eng. Chem., Anal. Ed., 7: 9 (1935).
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Chapter VL
Inorganic Chemistry, 1933-1935.
Don M. Yost,
California Institute of Technology,
In his review for 1929-1932 H. I. Schlesinger rightly remarked that
the field of pure inorganic chemistry has become considerably circum-
scribed in recent years. This is not because of lack of interest or of
things to do, but rather because other subdivisions of chemistry have
arisen which are concerned with specialized aspects of inorganic chem-
istry. Thus the original all-inclusive domain has become separated
into a number of smaller kingdoms. In this case the subdivision is not
regrettable, providing, of course, the broader aspects of chemistry are
recalled with sufficient frequency.
From time to time it is pertinent to enquire whether all investiga-
tions carried out by chemists as scientists are worth while. We have
no good criteria for a judgment. It might be said that when an investi-
gation merely illustrates a principle which is well understood, then it
is of doubtful value. To be sure, new results or new phenomena may
be uncovered in routine investigations, and an effort should be made
in the selection of the problems to make more probable these eventuali-
ties; however, one has sometimes the fear that such possibilities are
remote. The distinction between data that have permanent value and
are of practical importance, and results which merely add unnecessary
confirmation to an accepted theory, should, of course, be made. There
is the possibility too that a less pretentious result of the present may
become important in the future; great wines do not come from hand-
some grapes. This possibility must not be overemphasized, however.
It may well be considered the duty of the inorganic chemist to keep
the more fundamental goals before the specialized groups, when we
know what they are.
The present review must, of necessity, confine itself to inorganic
chemistry as distinguished from physical chemistry, thermodynamics,
molecular structure, and other specialized subdivisions. This leaves
such topics as the discovery and description of new elements and new
compounds as the field to be surveyed. It must be emphasized, how-
ever, that more often than not the most interesting and useful results
arise in the course of studies in the specialized fields.
New Elements. The remarkable discovery of Curie and Joliot,*
• Curie, I., and Joliot, F., Compt. rend., IW: 254 (1934).
90
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INORGANIC CHEMISTRY, 1933^1935 91
Crane and Lauritsen,^ and Fermi and his associates,^ that it is
now possible to bring about the transmutation of most of the
known elements, has been of special interest to chemists. Of his-
torical importance is the fact that that which the original chemists
tried to attain is now possible. In most cases the transmutations
have led to elements already known, but when uranium is bom-
barded with neutrons, at least one, and possibly three new elements
result, namely, 93, 94, and 95. The first experiments by Fermi and
his associates, showing the existence of the new elements, were not
regarded as conclusive by some chemists. The subsequent experi-
ments made by Grosse and Agruss ^ on the chemistry of 91 (prot-
actinium) have clarified the doubtful points considerably and
have led to experiments establishing the existence of the new ele-
ments. In this connection Grosse^ has discussed the probable
chemical properties of 93 and 94 from the point of view of the
periodic law and Bohr's theory of atomic structure. In order to
establish which element is formed in a transmutation process, purely
chemical experiments are made in which the unknown element is
mixed with another, assumed to be isotopic with it. This pro-
cedure was used by Livingston and McMillan* to show that nitro-
gen is changed to oxygen by deuteron bombardment, and by Yost,
Ridenour and Shinohara^ to establish that boron and carbon are
converted into carbon and nitrogen, respectively, by deuteron
bombardment. Further details on the physical side of transmuta-
tion will be found in the chapters on radioactivity and atomic
structure.
The fact that the elements formed by neutron, proton, deuteron,
and alpha particle bombardment are frequently radioactive may be
employed to follow a given substance through various chemical
reactions. Thus, Grosse and Agruss^ have studied the exchange
of bromine between bromide ion and bromine in solution of tri-
bromide. They show also that the rate of evaporation of bromine
from tribromide solutions at 100° is more rapid than the rate of
bromine hydrolysis. It seems likely that the future will see further
applications of the radio elements both in inorganic chemistry and
in biology.
The Noble Gases. Chemists have made many attempts to cause
the noble gases to combine with other elements. These efforts have,
until recently, resulted in failures. The most important recent
research in this field has been that of Booth and Willson,*^ who
showed that argon and boron trifluoride, at low temperatures, com-
bine to form the compounds, A.BFg, A.ZBFg, A.3 BFg, A.6 BFg,
A.8 BF3, and A.16 BF3. In addition to this, the same authors® have
made a study of the critical phenomena of A-BFg mixtures. An
attempt to make xenon combine with chlorine and fluorine by
tFermi, E., et al., Ric. sclent., 2: 280 (1934).
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92 ANNUAL SURVEY OF AMERICAN CHEMISTRY
sending an electrical discharge through mixtures of these gases
was made by Yost and Kaye,® but no compounds were detected.
The Halogens. The most outstanding result obtained in this
field is that of Cady^® who prepared the compound NO3F by the
action of fluorine on dilute solutions of nitric acid. The sub-
stance is gaseous at room temperatures (b.p. —42°) and it explodes
on heating. Yost and Beerbower^^ found that the same substance
can be easily prepared by passing fluorine over solid potassium
nitrate. They also found that at low temperatures and in the
solid state NO3F is dangerously explosive. It is disconcerting to
note that foreign chemists have already designated it as a possible
war gas. Cady^^ h^s investigated and clarified the reaction between
fluorine and aqueous solutions of acids and alkalis and finds that
little if any ozone is formed, but that OF2, O2 and peroxides are
formed. The nature of the reaction products depends somewhat
on the acidity or alkalinity of the solutions. By treating alkaline
solutions with fluorine, Dennis and Rochow^^ found highly oxidiz-
ing substances which they suggested were salts of oxyacids of
fluorine; Cady ^* considers that their results are due to the presence
of oxyacidic salts of chlorine. Cady^^ has studied the system
KF-HF and has given the most desirable mixtures to be used in
electrolytic fluorine generators. A modified cell for preparing
fluorine is described by Dennis and Rochow.^^ Ebert and Rodow-
skas ^'^ have prepared AgF2, a powerful oxidizing agent. Eyring
and Kassell ^^ have shown that H2 and F2 do not react at room
temperatures except in the presence of a catalyst, or when an
initiating reaction takes place.
Ewart and Rodebush ^® have found that active nitrogen, formed
in an electric discharge, reacts with HCl, HBr, and HI to form the
ammonium salts. A phase rule study of the system Pbl2-KI by
van Klooster and Stearns 20 showed that KPbIg exists. In the
system Pb^PbO the compounds Pbl2 . PbO, Pbl2.2PbO, and
possibly Pbl2 . 4PbO are formed.^® Willard and Thompson 21 have
shown that under various conditions lead periodate precipitates
have the formula Pb3H4(I04)2. On heating this at 275°, Pb3(I05)2
results. Nichols and Willits 22 have made an extensive study of
the compound formed when ammonia and Nessler*s solution react
and find it to be NH2Hg2l3. It is very insoluble and the fine col-
loidal precipitate is negatively charged. KPbl3 . 2H2O is the only
double salt found in the system 23 KI-Pbl2-H20 at 0° and 25°.
Ricci 24 has found that the double salts 2NaI03 . 3NaBr . I5H2O
and 2NaIO3.3NaBr.l0H2O are formed in the system NalOg-NaBr-
H2O at 5°, 25°, and 50°. Cartledge and Goldheim 25 have made an
extensive study of the complex ions and compounds formed in
aqueous solutions of HgCl2 and K2C2O4. They found that HgCl2,
HgCl2(C204)2=, HgCl3-, Hg2Cl4, and PIg2Cl5- were present in equi-
librium in the solutions studied.
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INORGANIC CHEMISTRY, 1933-1935 93
Dobbins and Colehour^^ have found that solutions of perrhenic
acid, HRe04, are best prepared by oxidizing Re or Re02 with 30
percent H2O2 and then evaporating the resulting solution until
viscous.
The Elements of the Sixth Group. The many compounds of sul-
fur have been the subject of a large number of investigations in
the past. With the introduction of improved methods of experi-
mentation, a number of interesting investigations are now possible
that formerly were too time-consuming or otherwise difficult.
Shumb and Hamblet^^ have carried out a very thoroughgoing
investigation of the reactions of SOCI2 and S2CI2 with lead oxalate
and formate. They find that lead oxalate reacts quantitatively
with SOCI2 to give SO2, CO2, CO, and PbCl2. When S2CI2 reacts
with lead oxalate, S, SO2, CO2, and CO are the products. The
reaction with lead formate is not simple. McCleary and Fernelius^s
have studied the oxidation reactions between oxygen and the alkali
polysulfides, selenides, and tellurides in liquid ammonia solutions.
Mixtures of the ite and ate salts are, in general, formed. It is
gratifying to note that attention is being given to the interesting
reactions that take place in liquid ammonia solutions. Barton and
Yost^^ carried out vapor density and dissociation experiments on
sulfur monochloride, S2CI2, in the temperature range 200° to 800°,
in order to determine the nature and extent of dissociation.
Although the results were best explained by assuming S2 and CI2
to be the dissociation products, the calculated heats of reaction
were not in agreement with existing thermal data.
The anhydride of selenic acid has been prepared by Kramer
and Meloche.3® They caused selenium to react with oxygen in the
negative region of a glow discharge. Anyone who has worked with
telluric acid will be pleased to learn that it may be readily prepared
by refluxing a mixture of tellurium dioxide, sulfuric acid, and 30
percent hydrogen peroxide. This method was found satisfactory
by Gilbertson.3i Claussen and Yost ^^ found a new volatile
fluoride of tellurium when they passed fluorine over tellurium. The
exact formula was not determined, but it was established that
each molecule contained two atoms of tellurium and had the
possible formula Te2Fe.
Oxygen compounds are, in general, best considered under other
compounds. The existence and separation of the oxygen isotope,
O^®, as a problem of interest in itself, has attracted considerable
attention and rightly so, since more exact knowledge of nuclear
and even molecular structure is to be obtained by working with
the pure isotopes. Green^^ found some concentration of O^®
resulted on the electrolysis of water. By extended electrolysis of
an old commercial electrolyte. Hall and Johnston ^^ established the
separation factor to be 1.008, and found the concentration of O^^
to be 4 p.p.m. (parts per million).
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94 ANNUAL SURVEY OF AMERICAN CHEMISTRY
A modified and relatively safe method of preparing liquid ozone
has been described by Byrns.^^ The ozone generator itself is
operated at liquid air temperatures. '
Further interesting and important results on the properties of
the sulfur group elements have come from x-ray and electron
diffraction studies. These results are to be looked for in the
chapters dealing with these subjects.
The metals of the sixth group have not received a great amount
of attention recently. Of interest is the study made by Windsor
and Blanchard^^ of the properties of Cr(CO)e. They established
the formula by vapor density measurements and, in addition, meas-
ured its vapor pressure as a function of the temperature. Ehret
and Greenstone^'^ have studied the decomposition products of Cr04-
. 3 NHg ; at 120° the substance decomposes in a lively fashion to
give CrOa . NH3, which is not a peroxy compound. Schlesinger
and Hammond^® have determined the formulas and dissociation
pressures of a series of complex ammonia compounds of chromous
chloride. The formulas of these complex salts are given by CrCV
nNHg, where n has the values 6, 5, 3, and 2. Of considerable interest
is the effect of chlorine on these substances. The ammonia groups
are oxidized first, and the chromous chromium is not affected until
all of the ammonia has been converted to nitrogen and hydrogen
chloride. Fricke and Brownscombe^^ have found that the dichro-
mates in sulfuric acid solution are reduced to chromic salts when
irradiated with x-rays. The effect is due to the hydrogen peroxide
formed by the action of the x-rays on the aqueous solution.
The magneto-optic method of chemical investigation has not
yet been made sufficiently objective to be generally accepted as
reliable. This writer has talked with people who have observed the
effect and believe it to be real. He knows others who have tried and
failed. If someone would only make it as nearly completely objec-
tive as possible, a number of purely chemical questions of
importance could be settled with ease. Ball and Crane,*® for
example, have used the method to show that the dichromates are
reduced, to a small extent, to pentavalent chromium. The method
might find application in the study of chemical kinetics, in which
intermediates are assumed to exist in small amounts.
Sears and Lohse *^ have shown that the products of the reaction
between chlorine and intimate mixtures of tungstic acid and carbon
are the volatile oxychlorides. The carbon is not consumed but
acts as a catalyst only.
The Elements of the Fifth Group. The trinitrides have, since
their discovery, been of great interest to inorganic chemists. This
is perhaps due to the large number of reactions that they undergo
and to the question of their structure. All will doubtless agree that
Edward C. Franklin has been preeminent in this field. He has
recently *2 discussed the nature of the trinitrides from the point of
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INORGANIC CHEMISTRY, 1933-1935 95
view of their reactions, and concludes that they are salts of ammono
nitric acid. That is, the trinitrides are the ammonia system analogs
of the nitrates. The reaction KNO3+3 KNH2 = KN3+3 KOH
H-NHs illustrates the general idea. Another American chemist who
has made many worthy contributions in this field is A. W.
Browne ^^' **• *^. He and his associates have prepared and investi-
gated the physical and chemical properties of ammonium trinitride,
hydrazine trinitride, and azido dithiocarbonic acid. The last com-
pound is an acid of about the same strength as sulfuric acid. It
was also found that ammonium trinitride could be sublimed from
mixtures of sodium trinitride and ammonium nitrate or sulfate.*®
Howard and Browne *'^' ^^ have discovered that when small tungsten
filaments (0.05 mm.) are heated to 3000° under liquid ammonia,
hydrazine is formed to the extent of some 0.25 percent. They
determined the yield as a function of current consumption, tem-
perature, and other factors. Nichols *^ determined the gaseous
products resulting from the reaction between solutions of silver
salts and hydroxylamine. An accurate determination of the normal
density of ammonia was made by Dietrichson, Bircher, and
O'Brien.^® The results are not useful for an atomic weight
determination due to uncertainties in the values of the gas law
constants.
The action of antimony trifluoride, with antimony pentachloride
as a catalyst, on phosphorus trichloride has yielded, in the hands
of Booth and Bozorth,^^ the new gaseous compounds PF2CI and
PFCI2. They find that the same gases are formed when gaseous
mixtures of phosphorus trichloride and trifluoride are heated to
200°. Pauling ^2 jj^s given a penetrating discussion of the proper
formula for antimonic acid and concludes that HSb(OH)e best
expresses the known properties. From the results of cell measure-
ments, Carpenter 53 has concluded that pentavalent vanadium in
acid solution is present as the ion VO2*. Coryell and Yost^* had
assumed the ion to be V(OH)4+ as a result of similar measurements.
It is quite possible that Carpenter's conclusion is the correct one.
Grosse and Agruss 5^' ^^ have made an important advance in hav-
ing prepared 0.1 gram of protactinium, element 91. They have
determined some of its chemical properties and the nature of the
compounds Pa205 and PaCls- The chemical properties were made
use of in clarifying the question of the existence of elements 93 and
94, as noted above under New Elements.
The Elements of the Fourth Group. The compounds of carbon
come properly under organic chemistry, this classification being one
purely of convenience. But because the reactions involved illustrate
a type that is important at present in inorganic synthesis, the com-
pounds obtained by Booth, Burchfield, Bixby, and McKelvey ^"^ are
here noted. They treated C2F3CI3, C2F2CI4, and CFCI5 with zinc
in alcoholic solution and found that C2F3CI, C2F2CI2, and C2FCI3,
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96 ANNUAL SURVEY OF AMERICAN CHEMISTRY
respectively, were formed, two chlorine atoms being removed in
each case. They attempted to convert C2CI4 to C2F4 by treating
the former with silver fluoride, but without success. Contrary to
the statements encountered in some books, they found that carbon
tetrachloride with silver fluoride does not give carbon tetrafluoride
but a mixture of gases consisting principally of C2CI2F2.
More attention has been devoted recently to the compounds of
silicon. Johnson and associates,^®, 59 applying a method used by
Kraus, have shown that the silicon hydrides can be efficiently pre-
pared by treating magnesium silicide with a liquid ammonia solu-
tion of ammonium bromide. They report yields of 70 to 80 percent.
Booth and Stillwell ^^' ®^ have prepared and have determined the
physical properties of the compounds SiHClg and SiHFg. The
first compound results from the reaction between silicon and
hydrogen chloride, and the second compound is prepared from
the first by treating it with antimony trifluoride and a catalyst,
antimony pentachloride. Schumb and Bickford^^ have measured
the boiling and freezing points of SiHBrs. Booth and Swinehart ^
obtained the new compound, SiFCla, together with the correspond-
ing substances containing two, three, and four atoms of fluorine,
when they treated silicon tetrachloride with antimony trifluoride.
Antimony pentachloride was used to catalyze the reactions.
An interesting study of the reaction between titanium tetra-
chloride and hydrogen at elevated temperatures was made by
Schumb and Sundstrom.^* Titanium trichloride is one product of
the reaction and at about 475° this decomposes appreciably into
the di- and tetrachlorides. Both the tri- and dichlorides were found
to form ammonia complexes. The TiCl2 . 4 NH3 decom.poses at
300° to give a nitride of titanium. Roseman and Thornton ^^ have
developed a method for preparing iron-free titanous solutions.
Liquid ammonia as a solvent has found many applications in the
field of organic synthesis and is being used more and more in
inorganic preparations. Kraus and Carney ®^ have applied it in the
preparation of germanium hydride. They treated magnesium ger-
manide with liquid ammonia solutions of ammonium bromide. The
germanium hydride reacts quantitatively with sodium in liquid
ammonia to give NaGeHs. Dennis and Work ^'^ have found that
monochlorogermane in liquid ammonia reacts to give germane and
(GeH)x, while dichlorogermane gives germanium. Germanium
tetraiodide reacts with liquid ammonia with the formation of
Ge(NH)2i®® Germanium nitride, Ge3N2, was obtained by Johnson
and Ridgley ^^ from the reaction between ammonia and germanium
diiodide. The first product is an imide, and the nitride is formed
by heating the imide at 250-300° for several hours. The recovery of
germanium from germanite (a sulfide ore) has been very much
simplified by the process discovered by Johnson, Foster, and
Kraus.*^® The germanite is first heated at 800° in a stream of
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INORGANIC CHEMISTRY, 1933-1935 97
nitrogen, and arsenous sulfide and sulfur are driven off. The
residue is then treated with ammonia at 825°, which effects the
reduction and volatilization of the germanium as GeS. About 99
percent of the germanium in the ore can be recovered. Dennis and
Staneslow "^^ have determined types of salts and their crystal forms
that have GeFe= as the acidic constituent.
The effect of potassium on zirconium tetrabromide "^^ Jn liquid
ammonia and the action of some organic liquids on thorium tetra-
bromide '^^ have been investigated.
Elements of the Third Group. The Rare Earths. The hydrides
of boron have interested both experimental and theoretical chem-
ists for some time. The kind of bond in diborane, especially, has
given the theoretical people no end of- trouble to explain. The
results of the researches of Professor Schlesinger and his asso-
ciates have been of importance in this field. Recently he has
studied the reaction between diborane and boron trimethyP* and
has found the compounds B2H5CH3 to B2H2(CH3)4. The
reactions of these compounds with water indicate that to each
boron is attached a hydrogen which is differently banded than the
others, an important result. Burg and Schlesinger "^^ have also
made a study of B5H11 and its method of preparation. It results
on allowing diborane to stand for long periods of time at room
temperature, or, more effectively, by passing diborane through a
tube heated to 100-120°. These authors '^^ have prepared dimeth-
oxyborine, (CH30)2BH, by means of the reaction between methyl
alcohol and diborane. Burg^^ has prepared chlorodiborane by
subjecting a mixture of hydrogen and boron trichloride to an
electrical discharge. He also describes an improved method of
fractional condensation. Sowa, Kroeger, and Nieuwland '^'^ have
discovered a new hydroxyfluoboric acid to which they give the
F
structural formula H(HO-B-OH). Schumb and Hartford "^^ have
F
prepared BASO4.
A careful determination of the physical properties and prepara-
tion of gallium trichloride and gallium was made by Craig and
Drake.''^^ Gallium melts at 29.755°, and the pure metal does not
supercool. The extraction of gallium from germanite has been
simplified by Foster, Johnson and Kraus.^^
Indium trimethyl has been prepared and its properties determined
by Dennis, Work, Rochow and Chamot.^^ They heated indium with
mercury dimethyl at 100°. The indium trimethyl, a colorless solid,
is rapidly oxidized by oxygen. Seward ^2 prepared and measured
the decomposition pressures of some hydrated normal and oxy
sulfates of indium. Both indium and scandium were found in a
zinc-free pegmatite ore by Romeyn.^^ Thallium triethyl was
studied by Rochow and Dennis.®*
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98 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The program of researches on the rare earths initiated by B. S.
Hopkins has been continued. He and his co-workers have investi-
gated the relative basicity of the rare earths and find that it
increases with decrease in atomic number.^^ The rare earth oxides
were found to react with dry ammonium chloride to give the
anhydrous chlorides.®* Of greater interest are the amalgams that
Hopkins and his associates have prepared. By the electrolysis of
concentrated alcoholic solutions of the chlorides with a mercury
cathode,®*^ and by the action of sodium amalgams on these solu-
tions,88 amalgams of the rare earth metals were obtained. In some
cases it was possible to distill off the mercury and obtain the rare
earth metals themselves. A novel method for the separation of
europium from the other rare earths has been discovered by
McCoy.®^ It consists in reducing EUCI3 solutions in a Jones
reductor (zinc) to EUCI2 and allowing the reduced solution to
run into a solution of magnesium sulfate. Europous sulfate pre-
cipitates out. An iodometric method of analysis for europium is
also outlined. Yagoda ^® has pointed out the advantages of a con-
ventional periodic classification of the rare earths for use in pre-
dicting their chemical properties.
The Elements of the First and Eighth Groups. Since the dis-
covery of the hydrogen isotope, deuterium, by Urey in 1932, there
have appeared a large number of articles dealing with this important
substance. The majority of these papers deal with the physical
properties of deuterium, such as the spectra of its compounds and
its application in transmutation experiments. On the purely
chemical side may be mentioned its occurrence, preparation, proper-
ties, and effects in reactions. Deuterium is present in all natural
water. Gilfillan ®2 reports, as a result of density measurements, that
sea-water contains more deuterium than does tap-water. Using
the electrolytic method discovered by Washburn, G. N. Lewis ^^
prepared D2O containing less than 0.01% H. Harkins and Doede^*
have also described an electrolytic method for separating D2O
from water. By electrolyzing D2O (i. e., alkaline solutions in it),
Selwood and associates'^ have concentrated a third isotope of
hydrogen, tritrium (H^). They report it to be present to the extent
of 7 p.p.m. in water. Selwood and Frost®® made determinations
of the physical properties of D2O, as did also Taylor and Selwood.'*^
The latter authors give 3.82° as the freezing point of their highest
density samples. Lewis '^ has observed a rapid interchange of H
with D when NHg is dissolved in D2O.
The methods of x-ray crystal structure analysis were applied
by Thomas and Wood ®' to the salts formed when mixtures of KF
and NaCl are heated. They concluded that KCl and NaF were
among the reaction products. Kraus and Parmenter ^<^ have
examined the compounds formed when potassium in liquid
ammonia combines with oxygen. They prepared K2O3 and K2O4
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INORGANIC CHEMISTRY, 1933^1935 99
and established the existence of the hydrates K2O2 . H2O, K2O2-
.2H2O, and K2O3.H2O.
A very careful and complete investigation of the oxidation
states of silver in nitric acid solutions was made by A. A. Noyes
and his co-workers.^^^ Saturated solutions of silver nitrate were
oxidized with ozone and the dark colored solutions that resulted
were analyzed and shown to contain bivalent silver. Measure-
ments of electrode potentials and the rates of formation and
decomposition gave added confirmation to the analytical results.
It is necessary to assume the existence of trivalent silver in con-
nection with the reaction mechanisms, and the black precipitate
obtained on diluting the dark colored acid solutions probably
consists of a trivalent oxide, but in solution the bulk of the silver
is certainly bivalent. It is gratifying to have this question
settled.
New ways for the preparation of nickel carbonyl have been
developed by Windsor and Blanchard.^^^ The method consists in
shaking a suspension of nickel sulfide in an alkaline solution
with carbon monoxide. The optimum yield is obtained from a
suspension obtained from 1 f.w. (formula weight) NaOH, 0.1 f.w.
Na2S, and 0.5 f.w. NiS04, all in one liter. More interesting still is
the substance CoNO(CO)3^^3 obtained by shaking an alkaline sus-
pension of nickel cyanide with carbon monoxide and nitric oxide.
In another communication Blanchard and Windsor ^^^ discuss the
structures of the carbonyls. They conclude that, since Ni(CO)4
does not form compounds analogous to KCo(CO)4, the cobalt
carbonyl group has the nickel carbonyl electronic structure, the
extra electron being furnished by the potassium.
The chemistry of the platinum metals has not received the
attention it deserves. The one paper that contains matters of
chemical interest in addition to physical chemical data is that of
Kirschman and Crowell.^®^ They studied the reaction between
osmium tetroxide and hydrobromic acid at 100°. At low con-
centrations of .OSO4 and acid and high concentrations of bromine,
reduction to the septavalent form is indicated. A measurable
equilibrium is attained. At higher acid concentrations tetravalent
osmium is formed.
The system FeS04-MnS04-H20 has been investigated by
White.^^® Lange and Krueger ^^"^ have prepared a copper ammoni-
sulfate dihydrate.
In two theoretical papers W. A. Noyes ^^^ gives consideration
to the electronic structure of inorganic complexes, and the types
of reactions from the point of view of current electronic theories.
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100 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Repekences.
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(1933).
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38. Schlesinger, H. I., and Hammond, E. S., /. Am. Chem. Soc. 55: 3971 (1933).
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40. Ball, T. R., and Crane, K. D., /. Am. Chem. Soc, 55: 4860 (1933).
41. Sears, G. W., and Lohse, F., /. Am. Chem. Soc. 57: 794 (1935).
42. Franklin, E. C, /. Am. Chem. Soc, 56: 568 (1934).
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49. Nichols, M. L., /. Am. Chem. Soc, 56: 841 (1934).
50. Dietrichson. G., Bircher, L. J., and O'Brien, J. J., /. Am. Chem. Soc, 55: 1 (1933).
51. Booth, H. S., and Bozorth, A. R., /. Am. Chem. Soc, 55: 3890 (1933).
52. Pauling, L., /. Am. Chem. Soc. 55: 1895, 3052 (1933).
53. Carpenter, J. E., /. Am. Chem. Soc, 56: 1847 (1934).
54. Coryell, C. D., and Yost, D. M., 7. Am. Clxem. Soc, 55: 1909 (1933).
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58. Johnson, W. C, and Hogness, T. R., /. Am. Chem. Soc. 56: 1252 (1934).
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63. Booth, H. S., and Swinehart, C. F., /. Am. Chem. Soc, 57: 1333, 1337 (1935).
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INORGANIC CHEMISTRY, 1933-1935 101
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74. Schlesinger, H. I., and Walker. A. O., /. Am. Chem. Soc, 57: 621 (1935).
75. Burg, A. B., and Schlesinger, H. I., /. Am. Chem. Soc, 55: 4009 (1933).
76. Burg, A. B., and Schlesinger, H. I., /. Am. Chem. Soc, 55: 4020 (1933).
77. Sowa, F. J., Kroeger, J. W., and Nieuwland, J. A., /. Am. Chem. Soc, 57: 454 (1935).
78. Schurab, W. C, and Hartford, W. H., /. Am. Chem. Soc, 56: 2646 (1934).
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80. Foster, L. W., Johnson, W. C, and Kraus, C. A., /. Am. Chem. Soc, 57: 1832 (1935).
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84. Rochow, E. G., and Dennis, L. M., /. Am. Chem. Soc, 57: 486 (1935).
85. Sherwood, G. R., and Hopkins, B. S., /. Am. Chem. Soc, 55: 3117 (1933).
86. Reed, J. B., Hopkins, B. S., and Audrieth, L. F., /. Am. Chem. Soc, ST: 1159 (1935).
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91. Burg, A. B., /. Am. Chem. Soc, 56: 499 (1934).
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95. Sdwood, P. W.. Taylor, H. S., Lozier, W. W., and Bleakney, W. C, /. Am. Chem.
Soc, 57: 780 (1935).
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98. Lewis, G. N., /. Am. Chem. Soc, 55: 3502 (1933).
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Chapter VII.
Analytical Chemistry, 1934 and 1935.
G. Frederick Smith,
Chemistry Department, University of Illinois.
General Trends of Progress. A review of the progress and
advancements in research and development in analytical chemistry
during 1934 and 1935 brings the conclusion that the period has
been one of gratifying, and in some fields, unusual progress.
Trends in progress have been towards unity of purpose and
coordination of efforts. The contributions of new developments
have met the demands of changes in the required method of attack
to best suit the conditions. Such research has been prolific in
leading to extended fields of application. Progress has been made
possible by the analyst drawing upon many related scientific fields
to reach the goal. Instrumental methods of analysis applied to all
fields have made notable advances. The determination of small
amounts of important elements in the presence of large amounts
of foreign material is one of the problems particularly well met.
The development of a new series of oxidation-reduction indicators
with practical applications of note has been accomplished. The
determination of small amounts of fluorine in water and of selenium
in soils and plants or foods has demanded a concerted effort
The theory of the mechanism of the processes of precipitation has
received an inspiring treatment and the complexity of the sup-
posedly simple precipitation process has been clearly brought out.
The application of the photronic process to studies in colorimetry
and nephelometry have been numerous. New developments in the
application of organic reagents as applied to colorimetry and to
gravimetric precipitation processes are important. The study of
comparative results in the determination of />H using indicator
methods, the hydrogen, glass, and oxide electrodes, has resulted
in the glass electrode gaining in preference for a number of rea-
sons. Electrometric schemes of analysis have been well repre-
sented with conductimetric and electrodeposition methods not so
prominent. American contributions following the development
of the Heyrovsky polarigraphic method of analysis were conspicu-
ously absent. The complete scheme of analysis to be used in the
quantitative separation and determination of the noble metals has
102
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ANALYTICAL CHEMISTRY, 1934 and 1935 103
been described. Spectroscopic methods of analysis have offered
contributions. The use of organic solvents has not been stressed
to any considerable extent. « Contributions in the field of alkali
metal analyses have been quite unimportant. An interesting study
is that of the catalytic reactions of silver as explained by the
formation of argentic silver nitrate.
While it is not within the scope of this review to include the
subject of physical testing of industrial materials, it is to be noted
that during 1934 and 1935 published reports involving procedures
of industrial physical testing have been numerous and of high
quality. This, it would appear, indicates a beneficial influence
being exerted by the prominence with which physico-chemical
methods have, and are being, adapted to analytical chemical pro-
cedures. Mention of the important determination of electrode
potentials has been omitted, notwithstanding its importance to
instrumental methods of analysis, since it is strictly speaking
physical chemistry in nature. Qualitative analysis, organic analysis,
industrial gas analyses, microanalysis and atomic weight investiga-
tions are not included in this review. The attempt is made to
emphasize the development only of the general trends in progress.
The art of analytical chemistry is not in general to be recognized
in the work of the accumulation of a large group of isolated
processes. Rather the emphasis should be placed on schemes which
are prolific and capable of systematized application to new develop-
ments, or which lead to a broadened insight of the theoretical
backgrounds of known type reactions. It is by this emphasis that
the trained research analyst may gain in prestige and the develop-
ments in the field will receive greatest impetus.
Indicators. A symposium on the subject of indicators is reported
in Chemical Reviews. The historical aspects were presented by Brock-
man,^ a system of indicators for use in determining the acidities of
concentrated acid media was reviewed by Hammet ^ and the
analytical applications of radioactive indicators was reviewed by
Rosenblum.3 The rather limited application of adsorption indi-
cators was described by Kolthoff^ with discussion of the mechanism
of their action. The subject of the colorimetric determination of
hydrogen ion concentration was taken up by Kilpatrick.^ The
study of the development of new indicators for oxidimetry was
reviewed by Walden and Edmonds ^ and the greatly improved
synthesis of the ideal oxidimetric indicator base c?-phenanthroline
was described by Smith and Getz.''
Probably the most valuable group of adsorption indicator studies,
both the radioactive type of Paneth and the adsorption type of
Fajans to which these types have been applied, was that of Kolthoff,
Fisher and Rosenblum ^ and Kolthoff and Rosenblum.® Applying
the radioactive indicator Thorium B, and the adsorption indicator
wool violet (4 BN), to the very exhaustive study of the mechanism
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104 ANNUAL SURVEY OF AMERICAN CHEMISTRY
of the processes involved in the precipitation of lead sulfate, has
given rise to a most instructive series of conclusions. The results
of this study indicate that the fresh* precipitates of lead sulfate,
though apparently well-formed microscopic particles, are in reality
spongy masses of exceedingly minute amicroscopic crystals. The
total surface of the precipitate is determined colorimetrically by
measuring the adsorption of wool violet from dilute solutions of
this dye in contact with the surface of the particles. The large size
of its molecule prevents its adsorption by the sub-surface lead sul-
fate to which it is attached on the surface by expulsion of sulfate
ions. The total surface exposed by the particles of lead sulfate is
measured by the radioactivity of the isotopic Th B in both the
precipitate and solution surrounding it. The surprising feature of
this series of studies consists in the disclosure that the aging of
precipitated lead sulfate results in the rapid diminution of external
surface, produced, not by a rearrangement within the spongy
mass of the particles themselves (the natural assumption originally
made), but through the process of solution and reprecipitation.
The investigation, as yet incomplete, has included a study of the
ideal conditions for the precipitation of lead sulfate and the mechan-
ism of the change in specific surface upon heat treatment of the
freshly precipitated particles out of contact with the mother liquor.
If the disclosures of this series of investigations can be safely
applied by analogy to the case of other elements, for which we have
no radioactive isotopes of sufficiently low half life, the mechanism
of the general process of precipitation is disclosed in a most
enlightening degree.
This type of study has been extended, including studies made
possible through the use of artifical radioactive elements by Grosse
and Agruss.^® The extent of interchange of bromine in the
inactive state with the bromine of activated sodium bromide was
determined. The activation of sodium bromide was accomplished
through bombardment by neutrons from the action of radon in
contact with beryllium. The extent of the interchange of inactive
for active bromine was measured by a Geiger-Miiller counter,
helium filled, and a thyratron operated watch. Except for the
inability to use the electroscope in measuring activity, this method
of attack holds great promise.
Although it is not correctly placed at this point, another study
concerning the mechanism of crystal formation was that of Camp-
bell and Cook.^^ The quite definitely established principle that
microscopic crystals are more soluble than larger crystal magnitudes
is doubted as shown by the study of strontium sulfate solubility
equilibria. The effects are said to be those of super-saturation
rather than augmented solubility. In this connection also, the
correct composition of the precipitate obtained by the use of
Nessler's reagent has been established by Nichols and Willits.^^
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ANALYTICAL CHEMISTRY, 1934 and 1935 105
The study of the mechanism of precipitation was further extended
by the complete investigation of Walden and Cohen,^^ who made
an x-ray study of the composition of precipitated barium sulfate.
The contamination of the precipitate formed in the presence of
nitrate ion was shown to result from solid solution formation
rather than isomorphism, occlusion, or adsorption; long wave-
length x-rays, using a calcium metal target, served in the determina-
tion of lattice parameters, with an accuracy of 0.01 percent.
New indicators for oxidimetry were studied by Hammett, Walden
and Edmonds. ^^ o-Phenanthroline and its nitro and amino
derivatives were discussed. The indicator properties show them
to be inferior to the plain indicator but prove that substitution in
the organic molecule materially alters the potential of change of
the ferrous complex. />-Nitro- and aminodiphenylamines as well as
2,4-diaminodiphenylamine were also prepared and studied. A study
of the oxidation potentials of the phenanthroline-ferrous complex
with variation in acidity was applied to the differential determina-
tion of iron and vanadium in ferro-vanadium, using eerie sulfate
as oxidant. This study was made by the same authors.^^ They also
studied the use of a silver reductor in the titration of iron in pres-
ence of vanadium^®; this is valuable in the reduction of iron in the
presence of titanium; molybdenum interferes. The method of
Walden and coworkers ^^ was further investigated by Willard and
Young,^'' using KMn04 in place of Ce(S04)2. The use of lower
acid concentrations are thus possible and the determination of
Cr and V in steel is improved.
Diphenylbenzidinesulfonic acid has been prepared by Sarver and
Fischer^^ and its use shows a smaller end point correction and
tungsten does not interfere. A method for preparing diphenyl-
benzidine with 50 percent yields was described by Sarver and
Johnson.^® A system of hypobromite titrations using H. T. H.
(low chloride) calcium hypochlorite was proposed by Kolthoff and
Stenger ^o and its application to the determination of ammonia
made, using a series of indicators previously described, of which
Bordeaux was found best. A group of new indicators for dichro-
mate titrations was described by Strada and Oesper ^i and benzoyl
auramine G has been proposed as an indicator in Kjeldahl determi-
nations by Scanlan and Reid.22 Dichlorofluorescein as adsorption
indicator was applied by Bambach and Rider.^s A portable radium
detector was described by Curtiss.^^
Colorimetry and Nephelometry. Photronic colorimeters of
various types were described by Wilcox,25 Russell and Latham,2«
Muller,27 Zinzadze^s and Yoe and Crumpler.^^ A photronic tur-
bidimeter was described by Bartholomew and Raby,^^ a photronic
nephelometer by Greene ^i and by Furman and Low.32 The sim-
plicity of these instruments and the multiplicity of their applica-
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106 ANNUAL SURVEY OF AMERICAN CHEMISTRY
tions indicate that colorimetric and nephelometric determinations
in which they are used are becoming rapidly standardized.
A procedure for the preparation of uniform nephlometric sus-
pensions, with description of the simple apparatus employed, was
described by Scott and Hurley ^^ and results given for silver
chloride nephelometry. A thorough study of the preparation of
permanent standards for use in the colorimetric determination of
silica by the molybdate process was made by Swank and Mellon.^*
Potassium dichromate buffered with Na2B407 . 10 H2O is recom-
mended to the A.P.H.A. for recognition as an official method.
A spectrophotometric study of ferric chloride in relation to the
influence of free HCl and the conformity with Beer's law was
reported by Mellon and Kasline.^** The best range was found to be
0.02 to 0.5 molar in FeClg and 0.005 to 5 molar in HCl. The study
was again made of the starch-iodine method for the' colorimetric
determination of iodine by Woodward.^® Correction factors are
given for the determination of 0.05-0.7 mg. of iodine per liter.
The most important error is that due to dissociation of the starch-
iodine compound. A statistical study of the uniformity of Lovibond
red and yellow glasses was made by Walker ^7 and by Gibson and
Haupt.38
The most interesting contributions to the colorimetric research
reports were those dealing with the determination of micro-
quantities of lead in the presence of large amounts of vegetable and
biological products. In these cases the various colorimetric modi-
fications in the use of dithizone as color reagent have been employed.
The titrimetric extraction method was used by Wilkins, Wil-
loughby, Kraemer and Smith.^^ The sample (15 grams of blood or
other biological materials) is decomposed, using a mixture of
HNO3, H2SO4 and HCIO4. A preliminary lead double extraction
with technical dithizone in chloroform removes all the lead. The
lead dithizone compound is oxidized to lead nitrate and the lead
is then determined, using purified dithizone added in small portions
until extraction is complete. Large amounts of iron do not inter-
fere. Bi, Tl, and Sn++ interfere. An accuracy of 0.001 mg. Pb is
attainable by this process. The process was extended by these
authors ^^ to include the separation of bismuth by dithizone at a
/>H of 2 followed by the regular 3» procedure for lead determination.
A very complete study of the same determination was made in the
case of spray residues by Winter, Robinson and Lamb.^^ Their
method is also applicable to biological materials and includes lead
determination in amounts from 0.005-0.04 mg. The semi-micro-
determinations of lead was carried out by Randall and Sarquis.*^
They combined the method of electrodeposition as Pb02 with the
colorimetric PbS determination of undeposited lead. Amounts
between 2.5-15 mg. lead were determined with fair accuracy.
A novel new method for the determination of microquantities of
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ANALYTICAL CHEMISTRY, 1934 and 1935 107
bromites was devised by Stenger and Kolthoff.*^ Hypochlorite
was used to oxidize bromide to bromine which in turn oxidized
phenol red to phenol blue. The bromide present was then deter-
mined colorimetrically. Chlorides do not interfere and iodides may
be removed by use of nitrite. Manganese in sea water was deter-
mined by the only successful colorimetric method found by Thomp-
son and Wilson,*^ namely, the periodate method. It has also been
shown by Hough ^^ that titanium interferes with the colorimetric
persulfate oxidation to permanganate and the periodate method
must be substituted. The colorimetric determination of molyb-
denum was described by Hurd and Reynolds *® and by Stanfield.*''
The former use cyclohexanol in place of ether to extract Mo-
(CNS)3, while the latter use butyl acetate.
The determination of fluorine is represented by a group of papers.
The work of Kolthoff and Stansby ^^ uses the purpurin test in the
range of 0.5-15 mg. and find the limit of detection at 0.005 mg. fluo-
rine. The accuracy of their method is 2 percent and Co(N03)2-
. 6H2O + K2Cr207 are used as color standards. Smith and
Dutcher *^ use the quinalizarin reagent and advocate the use of
HCIO4 to distill out the fluorine in the presence of interfering
elements. The same reagent was used by Sanchis ^^ and a com-
parison of various methods was made by Smith.^^ The study of
toxic quantities of fluorine leads to the determination that 0.9-1.0
p.p.m. and greater concentrations of lead cause mottled teeth.
The microdetermination of fluorine in chloro-fluorides which are
volatile has been made by Hubbard and Henne.^^ j^ is a com-
bustion method, passing the volatile fluorine-chlorine compound
over Si02 at 900° C. and absorbing the products in NaOH. The
fluorine is determined with cerous nitrate and the chlorine by the
Volhard process; 1.10 mg. of fluorine can thus be determined.
The determination of selenium in biological materials was
described by Dudley and Byers.^^ The method is colorimetric
after reduction with bisulfite and accounts for 0.02-27 p.p.m. of
selenium. A clinical procedure is given. The determination of
selenium in soils, plants and tissues is described by Robinson,
Dudley, Williams and Byers.^* The colorimetric determination
following HBr distillation is employed. The determination of
selenium in the Colorado River waters was also described by Wil-
liams and Byers.^^ A colorimetric determination of silver used
to sterilize swimming pool water is given by Schoonover.^^ This
method uses the color reagent />-dimethylaminobenzalrhodamine
and determines 1-40 p.p.m. There are a comparatively large num-
ber of interferences. The determination of copper in milk is
described by Conn, Johnson, Trebler, and Karpenko,^'' using
sodium diethyldithiocarbamate in basic solution after ashing and
extraction of CuS from the ash. The spectrophotometric deter-
mination of ammonia after nesslerization is employed in the deter-
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108 ANNUAL SURVEY OF AMERICAN CHEMISTRY
mination of amino-nitrogen in plant tissue as described by Pucher,
Vickery, and Leavenworth .^^ The separation of amino-nitrogen
is made after distillation in presence of MgO. Total nitrogen is
determined on a separate sample and the amide nitrogen obtained
by difference.
Numerous other colorimetric procedures have been described,
which space does not permit considering individually.
Electrometric Methods. A device utilizing a radio tube circuit
and amplification system to operate a buret cut-off for an auto-
matically terminated oxidation-reduction titration has been
described by Shenk and Fenwick.^® A bimetallic (W-Pt) elec-
trode system and arrangement to use only the power line voltage
and one dry cell is applied. The titrations of ferrous iron with
dichromate and the reverse titration, as well as the titration of zinc
with ferrocyanide, are applied with results satisfactory to the
ordinary degree of accuracy. The apparatus is said to be particu-
larly serviceable in the case of large groups of routine analytical
determinations.
The ferrous-ferric electrode potentials has been reinvestigated
by Schumb and Sweetser ^^ and by Bray and Hershey.^^ The val-
ues obtained were in fair accord but approximately 25 mv. higher
than previous determinations. Many other studies of electrode
potentials of direct interest in analysis have been investigated,
which cannot be reviewed in a report of this length. One of the
most interesting and valuable of such studies is that of Furman
and Low,^2 namely, the use of the concentration cell in the deter-
mination of minute quantities of chloride in the presence of large
amounts of ordinary reagents. The silver chloride electrode is
used and to the unknown salt solution a known amount of chlo-
ride is added. The two cells, one, of the sample to which no
chloride is added, and the other, with the chloride added, are
connected. The junction potential is negligible and the correc-
tion for solubility of the electrodes was determined experimentally.
The equation for the calculation is derived, £ = 0.0591 log
[2(;r+0.01)/(^ + V-^-+(4Po/f))], where Po is the solubility prod-
uct of AgCl in water and / is the activity coefficient of AgCl when the
solubility is P. The method is comparable in accuracy with the neph-
elometric procedure and foreign salts do not cause difficulty. Traces
of chloride as small as 3.5 X 10"^ g. of chloride per liter were measured
accurately. It would appear that this method can be extended in its
application.
A direct reading />H meter for glass, quinhydrone and H2 electrodes
has been described by Hemingway, ^^ which employs a ballistic galva-
nometer and voltage amplifier and having an accuracy of ±0.02 />H
units. A glass electrode potentiometer system was developed by
Burton, Matheson and Acree ®* and a test of various determina-
tions shows the glass electrode to agree with the isohydric indicator
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ANALYTICAL CHEMISTRY, 1934 and 1935 109
method. Reliability tests of glass electrodes, including asymmetry
tests, H2 electrode function and D.C. resistance, have been made
by Laug.^5 A study of the choice of catalyst for the H2 electrode
was made by Lorch.^^ Bright Pt or Ir deposits are recommended
for low acidities and unbuffered solutions. Metallized glass quin-
hydrone electrodes are described by Newberry.^"^ A modification
of the Partridge vacuum tube potentiometer apparatus is described
by Burton, Matheson and Acree.^®
The application of the glass electrode to unbuffered solutions is
discussed in a very complete paper by Ellis and Kiehl ^ and to
dairy practice by Parks and Barnes.*^^ The determination of the
second ionization reaction of H2Cr04, using the glass electrode,
was described by Neuss and Rieman.*^^ A simple cell for glass
electrode work as appHed to the determination of the pH of leather
extracts was described by Highberger and Thayer; "^2 ^he glass
electrode is the most satisfactory in determination of the />H of
leather extracts as shown by Wallace,'^^' '^^ as also is the opinion
of the committee on the determination of acid in leather ;^^ it has
been recommended to discontinue the Procter and Searle method.
The determination of the degree of olation in chrome tanned
leathers using a conductimetric titration by Theis and Serfass ^^
was an important application of this type procedure ; an electronic
bridge balance indicator assembly for conductimetric titrations
using a single amplification tube was described by Garman and
Kinney.'^''
The electrodeposition of indium from a cyanide solution in the
presence of c?-glucose to give silver white deposits was described
by Gray,*^® although the subject was not treated analytically.
The salt error and its influence upon quinhydrone electrode mea-
surements was discussed by Hovorka and Dearing.*^^ Several sub-
stitutes for the H2, glass and quinhydrone electrodes have been
described. A new type of antimony electrode, an oxide and sulfide
electrode, was studied by Ball, Schmidt and Bergstresser.^^ No
advantage over the ordinary antimony electrode was claimed. A
benzaldehyde electrode as a substitute for the quinhydrone elec-
trode in the />H range 7-13.64 was described by Herndon and
Webb;^^ it has an accuracy of 0.2 />H unit but is irreversible in
nature. The germanium-germanium dioxide electrode was described
by Nichols and Cooper ^2 and not found to be constant and repro-
ducible. The same authors ^^ found some application for the elec-
trode in spite of its non-reproducibility. A type of silver chloride
electrode suitable for use in dilute solutions was described by
Brown.^* It gave results reproducible to ±0.02 volts. A novel
method for the preparation of silver-silver bromide electrodes was
described by Keston;^^ both of these methods of preparing the
electrodes should be of great value in the use of these electrodes
in concentration cell work.
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110 ANNUAL SURVEY OF AMERICAN CHEMISTRY
In the field of applied potentiometric determinations, some
highly serviceable methods have been described. Willard and
Young ®^ describe the determination of small amounts of trivalent
chromium in the presence of large amounts of chromic acid. The
method uses Ce(S04)2 to oxidize chromium and nitrite to quanti-
tatively titrate the excess. The method is accurate and the study
of the influence of manganese has been made. The potentiometric
determination of copper after precipitation as CuCNS, using the
iodate oxidation in strong HCl solution process, was made by Hope
and Ross.®*^ Zinc and iron do not interfere. A mercury electrode
potentiometric determination of thiocyanate was described by
Kolthoff and Lingane.^^ An important contribution to the volu-
metric reduction process, using chromous sulfate, was described by
Crowell and Baumback ®® and was applied to the determination of
osmium with very accurate results. The bismuthate method for
manganese was studied by Park,^^ using arsenate and a W-Pt
bimetallic electrode system. A potentiometric precipitation reac-
tion was studied by Hanson, Sweetser and Feldman.®^ The arse-
nates are precipitated using AgNOg in a 50 percent alcohol-water
solution. The volumetric determination of iron in vegetable and
chrome-tanned leather was described by Smith and Sullivan,^^
using titanous chloride and visual end point determination. Other
potentiometric determinations have been applied, which space does
not permit mentioning.
Spectrographic Determinations. The method of Nitchie was
applied by Park and Lewis ^^ for the determination of lead in
copper. The copper is first precipitated from a 50 g. sample by
co-precipitation with CaCOs as Pb3(P04)2. The range covered
was 0.0007-0.006 percent of lead. The spectrographic determina-
tion of lead in biological materials was studied by Cholak,®* using
the logarithmic sector procedure comparing lines of bismuth and
of lead. The determination of bismuth, antimony, tin and molyb-
denum in copper was studied by Park,^^ using graphite electrodes
and the Nitchie process. The elements were concentrated by
co-precipitation with Mn02, two precipitations being required.
The spectral determination of fluorine in water, using graphite
electrodes impregnated with calcium chloride, was carried out by
Petrey.^® The quantitative analysis of solutions by spectrographic
study was made by Duffenbach, Wiley and Owens.®'' In this
work the uncondensed spark between silver electrodes was applied
to the determination of sodium, potassium, magnesium and calcium
in samples of urine. The effect of one element upon the deter-
mination of the other was described. A spectrographic micro-
determination of zinc is preliminarily described by Rogers,®^ using
selenium as an internal standard. A spectrophotometric determi-
nation of copper as the ammonium complex was made by Mehlig.^
The application of ultraviolet spectrophotometry as applied to the
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ANALYTICAL CHEMISTRY, 1934 and 1935 HI
determination of the strength of very weak bases was studied by
Flexser, Hammett and Dingwall.^^ A very complete paper on this
new subject was presented. The logarithmic sector procedure with
internal standards in the spectroscopic analysis of solutions was
studied by Erode and Steed.^o^ The pairs Co(Mn), Pb(Ni),
W(Mn), Mo(Cr), Be(Bi), and Be(Mn) were studied. The range
of determination is widest for cobalt, medium for lead, and small
for chromium. The accuracy found was 12 percent down to 0.01-
0.001 percent. The application of the spectrograph to the determi-
nation of carbon in steel was studied by Emery and Booth ^^^ and
found unsatisfactory. The spectrophotometric determination of
manganese in steel was studied by Mehlig^^^ but no advantage
was found over the bismuthate method.
Separation and Determination of the Noble Metals. A fascinat-
ing study of the separation and determination of the six platinum
metals and their gravimetric determination was made by Gilchrist
and Wickers ^^* and represents a vast amount of research and its
applications. The methods are also discussed by Gilchrist.^®^ The
separation of gold from tellurium is reported by Lenher, Smith and
Knowles.^^® The gold is separated from the tellurium by preferen-
tial reduction using NaN02 or FeS04, at a />H of 1. In this con-
nection the unique and dehcate process for the detection of certain
rare metals by colored absorption on Hg2Cl2 was reported by Pier-
son.^^"^ The tests are extremely delicate and simple.
Standards of Reference in Volumetric Analysis. After many
years of observance of the McBride method for the use of sodium
oxalate as a volumetric reducing standard, particularly in the
evaluation of KMn04 solutions, this method has been found by
Fowler and Bright ^^^ to give slightly low results. A new and
corrective procedure is described. Potassium dichromate as a
standard oxidimetric material was studied by Willard and Young,^^
using insufficient K2Cr207 to oxidize AS2O3, with determination
of excess AS2O3 using Ce(S04)2 in the presence of osmic acid and
o-phenanthroline-ferrous complex as indicator. Foulk and Pappen-
hagen ^^® have compared a simple method for the purification of
silver with the atomic weight method of purification and have
used this easily prepared silver as a standard in the evaluation of
hydrochloric acid. Potassium ferro- and ferricyanides have been
studied as reagents for standardizing titanous solutions by Smith
and Getz.^^^ K3Fe(CN)e is particularly suited to the standard-
ization of 0.01 N titanous solutions, because of the high equivalent
weight. Potassium thiocyanate has been studied as a primary
standard by Kolthoff and Lingane.^^2 j^ is shown that it is suit-
able for ordinary accuracy in the Volhard procedure, which is
accurate because of a compensation of errors. Potassium ferro-
cyanide is recommended as reference in case of KMn04 for weak
solutions by DeBeer and Hjort.^^^ Preparation of pure Ti02 as
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112 ANNUAL SURVEY OF AMERICAN CHEMISTRY
standard for volumetric comparison with titanous solutions was
described by Plechner and Jarmus.^^* A new standard in acidimetry
is furoic acid, studied by Kellog and Kellog ^^^ and an additional
study of anhydrous sodium carbonate was made by Waldbauer,
McCann and Tuleen.^^^ They contend that sodium carbonate
may be heated to 375-450° C. without dissociation, which is far
beyond acoepted values. Finally, a comparative study of drying
properties of a large group of drying agents has been made by
Bower,^^*^ which has proven of great value in properly classifying
such materials.
Miscellaneous Procedures. A series of studies dealing with the
role of silver salts in catalysis was reported by A. A. Noyes and
collaborators. This topic is of great importance in analysis, since
the oxidation potential involved is extremely high. The study of the
preparation of argentic nitrate by the reaction of ozone upon nitric
acid solutions of silver nitrate was described by Noyes, Hoard and
Pitzer.ii® The presence of divalent silver as Ag(N03)2 and the
comparative absence of the trivalent salt, Ag(N03)3, was proven
by Noyes, Pitzer, and Dunn,^^*^ while the oxidation potential of
argentic nitrate in acid solution was shown to be approximately
1.94, which compares favorably with the highest of known values
for other reactants as classified in this work. Nitric acid solutions
of argentic nitrate are more stable than either perchloric or sulfuric
acid solutions. The latter work was by Noyes and Kossiakoff.^^o
Fluorescence analysis was employed by Damon ^^i for the
determination of minute impurities of oxygen in gas mixtures.
The usual blue ultraviolet fluorescence of acetone vapor is green
in the presence of oxygen and the duration of the green color can
be made the basis of a quantitative determination of oxygen. The
technique, which is simple, is described and the results show that
alkaline pyrogallol and yellow phosphorus for the absorption of
oxygen are not nearly as sensitive. Oxygen can be determined in
Ng, Ha, CO, CO2, CI2, C2H4, CH4 and (CgHrOzO. The method
would appear to have interesting possible extensions in analytical
procedures.
The always troublesome separation of iron, aluminum and
chromium from cobalt, nickel, zinc and manganese, for which
process so many different methods of attack have been devised, is
apparently better solved by the new method of Kolthoff, Stenger
and Moskovitz.^22 Their precipitant is sodium benzoate and the
separation is better than by use of the basic acetate method.
Co-precipitation is reduced to the minimum while phosphate is not
all removed. The precipitation of iron, aluminum, and chromium
takes place in acetic acid solution.
A determination of small amounts of zinc in steel and iron was
developed by Bright.^23 Three methods are compared. The
separation of europium from other rare earths, depending upon its
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ANALYTICAL CHEMISTRY, 1934 and 1935 113
reduction with zinc to the divalent form and precipitation under
carbon dioxide as sulfate with magnesium sulfate, was described
by McCoy.^24 ^he method serves for both purification and
analysis. A separation of zinc from cobalt based upon a method
using acrolein to prevent post-precipitation of cobalt was described
by Caldwell and Moyer.^^s The use of 8-hydroxyquinoline in the
separation of aluminum from beryllium and magnesium was
reported by Knowles ^^e and also in the separation of beryllium
from aluminum, iron, titanium, and zirconium.
A modified persulfate-arsenite method for manganese in steel
was described by Sandell, Kolthoff, and Lingane.^27 jhe oxidation
of the manganese, using persulfate and silver, is followed by titra-
tion with arsenite containing nitrite to avoid the usual troublesome
gray end point obtained in the absence of nitrite. Small amounts
of chromium, vanadium, nickel, and molybdenum ^do not interfere.
The Volhard chlorine determination has been cleverly modified by
Caldwell and Moyer ^^s jn such a manner that, using a protective
coating of nitrobenzene on the silver chloride precipitate, it need
not be filtered before titration of excess AgNOg by KCNS.
The vacuum induction furnace method for the determination
of oxygen and nitrogen in steel was improved by Chipman and
Fontana.^29 ^^^ features of the apparatus assembly are
described and oxygen from alumina is included in the analysis. A
rapid method for the determination of sulfur in ferro-magnetic
alloys was described by Clarke, Wooten and Pottenger.^^o The
method depends upon ignition in hydrogen with evolution of H2S.
The method is accurate to ±0.001 percent.
The application of aeration to Kjeldahl nitrogen distillation is
advocated by Meldrum, Melampy and Myers.^^i Fifteen minutes
are required for the operation and inconveniences of boiling and
bumping are eliminated, while the change in apparatus required
is small.
The determination of tellurium in lead, which is recently in
demand because of its increased use as an adulterant in lead cable
sheath and tank linings as well as lead pipe, was worked out by
Brown.^^2 xhe method is undesirably long and will undoubtedly
be much improved by additional work.
Methods of Analysis Involving the Use of Perchloric Acid to
Destroy Organic Matter. A number of the developments previously
mentioned have employed perchloric acid for various reasons. This
reagent has rapidly become almost indispensable for use in the
destruction of organic matter to be followed by determination of
inorganic matter in the residue from large samples of various
products. The digestion of biological materials prior to the determi-
nation of calcium and phosphorus was described by Gerritz ^^^
and, by the same author,i34 \q^ ^^e determination of phosphorus
in urine. The destruction of organic matter in plant products using
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114 ANNUAL SURVEY OF AMERICAN CHEMISTRY
perchloric and nitric acids to be followed by the determination of
calcium, magnesium, potassium, and phosphorus was studied by
Gieseking, Snider, and Getz.^^^ The determination of iron in
milk, blood, eggs, and feces, following the perchloric and sulfuric
acid oxidation of organic matter after perchloric acid oxidation,
was described by Leavell and Ellis.^^® Besides many other methods
in which perchloric acid is employed, the greatly facilitated
determination of chromium in leather was described by Smith and
Sullivan.^^''
Conclusions. The necessarily restricted extension of available
space for this summary of the progress of analytical chemistry in
the United States in 1934-35 has caused a great number of worthy
developments to go unmentioned which might well have been in-
cluded. Many gas analytical procedures had to be omitted. Micro
methods, in spite of their increasing number, were in general
omitted. The attempt was made to classify and emphasize pro-
cedures having a unity of purpose. Those which lead to the solu-
tion of the more difficult of analytical problems as taught by past
experience are most desirable of improvement. The review stamps
at least one point as established, namely, that progress has been
made in no uncertain degree and a standard of quality of a gratify-
ing nature has been realized.
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Chapter VIII.
Applications of X-Rays in Metallurgy.
Eric R. Jette,
School of Mines, Columbia University,
X-ray techniques have a well-recognized position in metallurgy.
In preparation for a formal symposium to be held in 1936, the
American Society for Testing Materials conducted a preliminary
survey of the field at a meeting in June, 1935, at which over forty
short papers were presented; these, however, have not been pub-
lished.
The purpose of this chapter is to review the applications of
x-rays in metallurgy during the past year. Because of the wide
range of interest, such a review cannot confine itself strictly to
metallurgy. Mention will, therefore, be made of theoretical and
related material which is of special interest in the metallurgical
field. Articles dealing with structural data and electron diffraction
phenomena are not included but it should be mentioned that the
electron diffraction technique is rapidly becoming important in
the study of corrosion of metal surfaces.
General. Two important books have appeared during this year.
"Xrrays in Theory and Experiment" by Compton and Allison,^
while not dealing with the details of crystal structure analysis nor
with the methods ordinarily applied in metallurgical problems,
gives the fundamental background for the entire subject. Wyck-
off's supplement to the second edition of his "Structure of Crys-
tals" ^ gives a complete bibliography of x-ray structure work from
1930 to 1934 and critically reviews many of the newer structures.
Progress is being made by theoretical physicists in the under-
standing of the metallic state by applications of quantum and wave
mechanics."^ The temperature function of x-ray reflection in the
neighborhood of the melting point of a crystal has been discussed
briefly.^
Further advances have been made in the precise determination
of lattice constants. An important contribution to this subject
was made by Cohen,^ who has devised a mathematical method of
calculating lattice constants from powder diffraction data, so as
to eliminate all errors, excepting those in the wave-length used
in the computation. It applies particularly to symmetrical cameras
117
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J 18 ANNUAL SURVEY OF AMERICAN CHEMISTRY
of the Debye, Sachs, or focusing types, and examples are given
of applications to cubic. Hexagonal, and orthothombic structures.
The particular advantage of this method is that it eliminates the
systematic error, which in many cases far exceeds the accidental
errors in measuring the diffraction angles. Jette and Foote ® have
given a detailed discussion of the inherent errors of symmetrical
focussing cameras and their elimination by Cohen's method of
computation. They emphasize that the precision attainable in
lattice-constant measurements today has reached the point where
the investigator must pay particular attention to the mode of
preparation of materials for x-ray work. There are seldom deviations
of as much as one part in ten thousand, between precision measure-
ments of different investigators, using properly prepared materials
of the same purity. Precise measurements of lattice constants for
fourteen metallic elements are included in this article. Other appli-
cations of Cohen's method are given.^^, 17 Short reviews of prog-
ress in diffraction methods ^ and the general application of x-rays ^
have been given.
Equipment and Cameras. A convenient and easily-constructed
gas tube with interchangeable anti-cathodes is described by Walden
and Cohen.^"^ Buerger ^^ gives designs of cathode assemblies for
both Hadding and Shearer type gas tubes. Parratt ^^ describes a
method of evaporating metal films for use as x-ray targets. In
this way targets of metallic elements, which are difficult to handle
mechanically or to obtain by electrodeposition, for example, titan-
ium, may be obtained. The use of alloy targets to obtain a larger
number of diffraction lines within the limited range of angles
covered by back-reflection focussing cameras, in order to increase
the precision, has been described.^ The targets used were binary
alloys of approximately fifty atomic percent of each metal. An
electric arc furnace has been used for casting molybdenum buttons
in brass for use as targets in x-ray tubes.^® Metallic calcium has
been successfully used as a target.^*^ A new needle valve for x-ray
tubes ^3 and the use of oil-diffusion pumps for gas tubes ® have
also been described.
For measuring the diffraction angles, a simple photometric
device has been given ^ and the Geiger-Miiller counter has been
adapted for experiments where molybdenum K-radiation ^* is
used.
Several modifications of back-reflection focussing cameras have
been described, all of them providing for moving the speci-
men.^' ^'^' ^5 One of them ^ permits temperature control of the
camera and the use of an inert gas atmosphere. Another ^"^ pro-
vides for either evacuation or filling of the camera with any desired
gas. Norton ^^ reviews a simplified technique for lattice parameter
measurements with modified Sachs and focussing types of cameras.
Goss ^2 describes an equipment for studying metals at high tem-
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APPLICATION OF X-RAYS IN METALLURGY 119
peratures, while Frevel ^^ gives a technique for x-ray studies of
substances under high pressures.
Solid Solution and Precipitation Hardening. The determination
of solubility limits by means of x-ray methods continues to be an
important application of these methods. It may be remarked that
the development of cameras and methods capable of high precision
was required before such determinations could be carried out in a
satisfactory manner. The methods which have proved most useful
have been based upon large angle reflections in focussing cameras
of either the Phragmen or symmetrical types and in the Sachs type.
The extreme importance of proper annealing and quenching tech-
niques of the sample actually exposed to the x-ray beam is now
generally recognized.
Mooradian and Norton 25 have made an interesting study of the
influence of lattice distortion on diffusion in metals. Their rather
limited set of experiments showed that lattice distortion disap-
peared before diffusion began. The discussion of this subject by
Mehl and Barrett immediately following the article should be
mentioned.
DuMond and Youtz^o attempted to make a grating for the
determination of the absolute wave length of x-rays, by evaporating
alternate layers of gold and copper on glass plates. They made
the interesting observation that the diffraction maxima from such
a grating decreased in intensity wit^ time, which could be accounted
for only by diffusion of copper and gold atoms into their neigh-
boring layers. They suggest that this is a possible way of study-
ing diffusion in the solid state.
Norton 2« has determined the solubility of copper in iron by
x-ray methods and followed the changes in lattice parameters
during aging. Jette and Fetz^s determined the solubility of tin
in nickel. Walters and Wells ^9 used x-ray methods to assist in the
determination of the solubility of iron in manganese. These
methods were also used ^8 in an attempt to determine the solubility
of iron in zinc. This solubility was so small that results by this
method were scarcely to be expected. Die casting alloys consisting
mainly of zinc and aluminum are subject to certain slow dimensional
changes after solidification. The nature of the change involved
has been studied by Fuller and Wilcox.^i. 22 j^ the first article,
they showed that the decomposition of the beta-phase cannot be
the sole cause for the shrinkage phenomenon. In the second paper
it is proved that the shrinkage is due to the change in the com-
position of the alpha-phase, and that the extent of the shrinkage
can be calculated from x-ray data.
Phillips and his co-workers ^® have continued their work on
quenching stresses and also studied the precipitation reactions in
Al-Mg and Cu-Al alloys. After confirming their earlier results
on the existence of these stresses in quenched, massive material
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120 ANNUAL SURVEY OF AMERICAN CHEMISTRY
(as compared to powders), they have calculated the stresses from
lattice constant measurements by the method proposed by Barrett.
They also studied precipitation rates by means of changes in lattice
constants.
H. A. Smith 27 has studied isothermal diffusion reactions in
austenite by several methods, including changes of lattice parameter
with time, and the widths of the diffraction lines. He showed that
the reaction curves determined by different methods generally do
not agree. There has been considerable discussion as to whether
the change in the lattice parameter would indicate the initial stages
of precipitation from a solid solution. Opinions from various
sources and mention of work as yet not published in detail have
been given in E. J. Kennedy, Jr.'s column in Mining and Metallurgy?^
The present opinion seems to be that microscopic examination is
better for this purpose. This is quite reasonable, in the light of
the nature of the phenomenon and the quantity to be measured, but
Phillips, et al^^ find that when precipitation takes place in strained
metal, when the atoms can diffuse more readily, the lattice constant
changes throughout the entire solid-solution matrix.
Constitutional Diagrams and Phase Identification. Van Horn ^s
has presented the x-ray evidence about the various constituents of
steel. X-ray methods have been used in conjunction with the
more classical methods of physical metallurgy in setting up the
constitutional diagrams of the sjjstems, Fe-Mn,29 Mo-C,^^ Co-Mo,^*^
In-Ag,30 Fe-Cr,3^ and for the copper corner of the ternary systems
Cu-Sn-Be.35 McKeehan ^^ has discussed the structure of MgZn and
MgZns. X-ray methods were also used to a minor extent in study-
ing the polymorphism of the FeS-S solid solutions.33 The oxide
films formed during the wear of steels have been identified by
x-ray methods as Fe203 and Fe304.^^
Orientation of Crystals (Grains) in Metals, Preferred Orientation
and Grain Distortion. The determination of the orientation of a
single crystal of a metal, when the crystal is thick, or imbedded in a
mass of other crystals, has been a matter of considerable difficulty;
this is now largely removed by Greninger's development of the
back-reflection Laue method.^^' ^^ He has applied this to the
study of single crystals of copper."*^ Goetz and Dodd ^ have
determined the direction of growth of bismuth and selenium crys-
tals formed by condensation in vacuo. Mehl and Smith ^^ have found
that ferrite and pearlite assume a discreet number of determinate
orientations which bear a direct relationship to the orientation of the
original austenite. Barrett, Kaiser and Mehl ^9 have reported work
on the Widmanstatten figures in copper-silver alloys and find that
previous theories for the mechanism of formation of such figures failed
to explain their results. Post ^^ has developed the experimental method
of Davey and his co-workers for the determination of preferred orienta-
tions into a more rigid analytical procedure. It is applicable par-
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APPLICATION OF X-RAYS IN METALLURGY 121
ticularly to cubic metals. When applied to the earlier work of Davey
on rolled silver, the anal3^ical method yields somewhat different results.
In the discussion of an article by Phillips and Dunkle,^® Mehl reports
the results of x-ray determinations on preferred orientations in some
low-carbon steels. Goss ^^ has studied preferred orientation in electrical
strip steels of 3 to 3.5 percent silicon, in connection with the magnetic
properties, using these studies to devise a method of preparing a strip
steel of good magnetic properties. Bozorth ^® has studied some of the
samples prepared by Goss but does not agree with the latter's determina-
tion of the orientation.
Mehl and Gensamer^*^ show that the formation of Liider's lines
and of strain figures in annealed low-carbon steels is accompanied by
a distortion which can be readily demonstrated by the peripheral widen-
ing of x-ray diffraction spots. Nusbaum and Goss ^^ have studied grain
distortion in metals during heat treatment by means of the radial
asterism in Laue photograms. They find that the degree of cold
work, the chemical composition, and the time and temperature of
treatment are important in determining the presence or absence of
"distorted" grain growth. Clark and Beckwith^^ give a method for
detecting and evaluating residual distortion in crystals.
Radiographic Inspection of Metals. The use of x-rays for inspec-
tion of metals, particularly castings and welded sections, is increas-
ing. More and more powerful tubes are being constructed which
permit the application of these methods to materially greater
thickness. Lippert,^^ for example, has reported in his column a
new 400,000 volt installation which is used to inspect manganese
steel sections five inches or more in thickness. There is also an
increasing understanding of the necessity for proper x-ray tech-
nique and extensive correlation with other methods of examination
to secure conclusive results.
Isenburger ^^ has given a very useful set of x-ray exposure
charts for steel. Moses ^^ has given some results of using diffrac-
tion methods to study the existence of strains or preferred orienta-
tions in the immediate vicinity of fusion welds. A number of obser-
vations on castings and welds are reported,^^-^^ ^srhich give a fair
indication of the important position of this type of inspection in
present-day industry. Occasional reports of this type may appear
so widely scattered through engineering and other technical litera-
ture, that the bibliography of this section is probably not complete.
Miscellaneous. A number of articles on diverse subjects of
possible interest to metallurgists have been reported. In a study
of the solid phase reactions between certain carbonates and refrac-
tories, x-rays have been used to identify artificial mullite.®'^ The
diffraction of x-rays by liquid Na-K alloys in a magnetic field has
been studied.^^ Waldo ^^ gives a very complete tabulation of
intensities and inter-planar spacings of 38 copper minerals for
identification purposes. The conversion of quartz to cristoballite
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122 ANNUAL SURVEY OF AMERICAN CHEMISTRY
in the presence of sodium silicate has been investigated.^* Weiser
and Milligan ^^ report a new modification of ferric oxide mono-
hydrate, which is of possible interest in connection with the rust-
ing of iron. Clark, Lincoln and Sterrett ^^ studied the orientation
of polar molecules on metal surfaces with relation to wear and
lubrication. Jesse®® describes a simplified apparatus for quanti-
tative chemical analysis by x-rays generated in a cathode-ray tube.
References.
1. Clark, G. L., Elec. Eng., 54: 3 (1935).
2. Cohen, M. U., Rev. Set. Instruments, 6: 68 (1935).
3. Compton, A. H., and Allison, S. K., X-Rays in Theory and Experiment, New York,
Van Nostrand, 1935. 828 p.
4. Isenburgcr, H. R., Instruments, 8: 302 (1935).
5. Jacobs, R. B., and Goetz, A., Phys. Rev., 47: 94 (1935).
6. Jette, E. R., and Foote, F., /. Chem. Phys., 3: 605 (1935).
7. Slater, J. C, and Knitter, H. M., Phys. Rev., 47: 559 (1935).
8. Wyckoff, R. W. G., The Structure of Crystals, Supplement for 1930-1934, New
York, Reinhold Pub. Co., 1935. 256 p.
Equipment and Cameras.
9. Bearden, J. A., Rev. Set. Instruments, 6: 276 (1935).
10. Buerger, M. J., Rev. Set. Instruments, 6: 385 (1935).
11. Frevel, L. K., Rev. Set. Instruments, 6: 214 (1935).
12. (Joss, N. P., Metal Progress, 28, No. 4: 163 (1935).
13. Kersten, H., Rev. Set. Instruments, 6: 175 (1935).
14. LeGalley, D. P., Rev. Set. Instruments, 6: 279 (1935).
15. Norton, J. T., Metals and Alloys, 6: 342 (1935).
16. Parratt, L. G., Rev. Set. Instruments, 6: 372 (1935).
17. Walden, G. H., Jr., and Cohen, M. U., 7. Am. Chem. Soe., 57: 2591 (1935).
18. Trimble, F. H., Rev. Set. Instruments, 6: 216 (1935).
Solid Solution and Preeipitation Hardening.
19. Brick, R. M., Phillips, A., and Smith, A. J., Trans. Am. Inst. Mining Met. Engrs.,
Inst. Meials Div., 117: 102 (1935).
20. DuMond, J. W. M., and Youtz, J. P., Phys. Rev., 48: 703 (1935).
21. Fuller, M. L., and Wilcox, R. L., Trans. Am. Inst. Mining Met. Engrs., Inst. Metals
Div., 117: 338 (1935).
22. Fuller, M. L., and Wilcox, R. L., Metals Teehnology, 2: (Tech. Paper 657) (1935).
23. Jette, E. R., and Fetz, E., Metallwirtsehaft, 14: 165 (1935).
24. Kennedy, E. J., Jr., Mining and Met., 16: 228, 268, 306, 340, 512 (1935).
25. Mooradian, V. G., and Norton, J. T., Trans. Am. Inst. Mining Met. Engrs., Inst.
Metals Div., 117: 89 (1935).
26. Norton, J. T., Trans. Am. Inst. Mining Met. Engrs., Iron & Steel Div., 116:
386 (1935).
27. Smith, H. A., Trans. Am. Inst. Mining Met. Engrs., Iron & Steel Div., 116:
342 (1935).
28. Truesdale, E. C, Wilcox, R. L., and Rodda, J. L., Metals Teehnology. 2: (Tech.
Paper 651) (1935).
29. Walters, F, M., Jr., and Wells C, Trans. Am. Soc. Metals, 23: 727 (1935).
Constitutional Diagrams and Phase Identification.
30. Frevel, L. K., and Ott, E., 7. Am. Chem. Soe., 57: 228 (1935).
31. Krivobok, V. N., Trans. Am. Soe. Metals, 23: 1 (1935).
32. McKeehan, L. W., Z. Krist., 91: 501 (1935).
33. Roberts, H. S., 7. Am. Chem. Soc., 57: 1034 (1935).
34. Rosenberg, S. J., and Jordan, L., Trans. Am. Soc. Metals, 23: 577 (1935).
35. Rowland, E. S., and Upthegrove, C, Trans. Am. Inst. Mining Met. Engrs., Inst.
Metals Div., 117: 190 (1935).
36. Sykes, W. P., Van Horn, K. R., and Tucker, C. M., Trans. Am. Inst. Mining
Met. Engrs., Inst. Metals Div., 117: 173 (1935).
37. Sykes, W. P., and Graff, H. F., Trans. Am. Soc. Metals, 23: 249 (1935).
38. Van Horn, K. R., Metal Progress, 28, No. 2: 22 (1935).
Orientation of Crystals (Grains) in Metals; Preferred Orientation and Grain Distortion.
39. Barrett, C. S., Kaiser, H. F., and Mehl, R. F., Trans. Am. Inst. Mining Met.
Engrs., Inst. Metals Div., 117: 39 (1935).
40. Bozorth, R. M., Trans. Am. Soc. Metals, 23: 1107 (1935).
41. Clark, G. L., and Beckwith, M. M., Z. Krist., 90: 392 (1935).
42. Goetz, A., and Dodd, L. E.. Phys. Rev., 48: 165 (1935).
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APPLICATION OF X-RAYS IN METALLURGY 123
43. Goss, N. P., Trans. Am. Soc. Metals. 23: 511 (1935).
44. Greninger, A. B., Trans. Am. Inst. Mining Met. Engrs., Inst, Metals Div., 117:
6; (1935).
45. Greninger, A. B., Z. Krist., 91: 424 (1935).
46. Greninger, A. B., Trans, Am. Inst. Mining Met. Engrs., Inst, Metals Div,, 117:
75 (1935),
47. Mehl, R. F., and Gensamer, M., Metals &• Alloys, 6: 158 (1935).
48. Mehl, R. F., and Smith, D. W., Trans. Am. Lnst. Mining Met. Engrs., Iron & SPeel
Div., 116: 330 (1935).
49. Nusbaum, C, and Goss, N. P., Trans. Am. Soc. Metals, 23: 621 (1935).
50. Phfllips, A., and Dunkle, H. H., Trans. Am. Soc. Metals, 23: 398 (1935).
51. Post, C. B., Z. Krist., 90: 330 (1935).
Radiographic Inspection of Metals.
52. Isenburger, H. R., Trans. Am. Soc. Metals, 23: 614 (1935).
53. Lippert, T. W., Iron Age, 135, No. 5: 25 (1935).
54. Moses, A. J., /. Am. Welding Soc, 14, No. 4: 5 (1935).
55. Adrain, M. B., /. Am. Welding Soc, 14, No. 8: 12 (1935).
56. Chapman, E. C, /. Am. Welding Soc, 14, No. 11: 2 (1935).
57. Hobrock, R. H., Metals & Alloys, 6: 19 (1935).
58. Hobrock, R. H., Metals & Alloys, 6: 41 (1935).
59. Hopkins, R. K., Trans. Am, Inst. Mining Met. Engrs., Inst. Metals Div., 117: 387
(1335).
60. Isenburger, H. R., Welding Engr., 20, No. 6: 26 (1935).
61. Ward, N. F^ /. Am. Welding Soc, 14, No. 12: 11 (1935).
62. Ziegler, F. K., Metal Progress,' 27, No. 6: 44 (1935).
Miscellaneous
63. Qark, G. L., Lincoln, B. H., and Sterrett, R. R., Proc Am. Petroleum Inst., Vol,
16, Section 3, Preprint, Nov. 13 (1935).
64. Cole, S. S., /. Am. Ceram. Soc, 18: 149 (1935).
65. Heaps, C. W., Phys. Rev., 48: 491 (1935).
66. Jesse, W. P., Rev. Sci. Instruments, 6: 47 (1935).
67. Taylor, N. W., and Williams, F. J., Bull. Geol. Soc. Am., 46: 1121 (1935).
68. Waldo, A. W., Am. Mineralogist, 20: 575 (1935).
69. Weiscr, H. B., and Milligan, W. O., /. Am. Chem. Soc, 57: 238 (1935).
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Chapter IX.
Ferrous Metallurgy.
Frank T. Sisco,
Alloys of Iron Research, The Engineering Foundation, New York,
In the past two years, there has been no diminution in the
quantity or quality of research in ferrous metallurgy as reported
in the transactions of the technical societies and in the metallurgical
journals. In fact, both have increased'; so many important papers
have been published that it was difficult to choose those which
represent best the recent progress. Moreover, it was necessary to
omit reference to nearly all of the many papers — some of them very
important from the practical viewpoint — which deal with the
development of new steels for specific applications or the discovery
of new uses for well-known materials.
Pig Iron and Steel Manufacture. Recent changes in the design
and operation of the blast furnace have been of minor importance.
Interest in beneficiation, not only of the ore but also of the blast,
continues unabated. Oxygen enrichment of the blast, as a practical
method of increasing thermal efficiency or speeding up chemical
reactions, has not yet reached the experimental stage; so far, the
progress in this field — if it can be called progress — has been con-
fined to a discussion of whether or not blast beneficiation is eco-
nomically feasible.
There have been a number of important contributions in the
past two years to the physical chemistry of steel making. The
fundamental work by the Metallurgical Advisory Board to the
U. S. Bureau of Mines and Carnegie Institute of Technology, under
the supervision of C. H. Herty, Jr., was closed with the publication,
in book form, of Bulletins 64 to 69.^ The first four of these report
results concerning the effect of deoxidation on structure, age
hardenability, and properties; Bulletin 68 is on iron oxide control
in the basic open-hearth furnace; the last paper is a summary of
knowledge of the various slag systems. The work by the Metal-
lurgical Advisory Board over the past seven years has been of
outstanding importance to the steel makers of this country; its
influence should be felt for many years to come.
A symposium 2 on slag control was held late in 1934 by the
Iron and Steel Division of the American Institute of Mining and
Metallurgical Engineers. Papers were read on slag control in the
124
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FERROUS METALLURGY 125
blast furnace (Sweetser), on the manufacture of rimming steel
(Reinartz), low-carbon steel (Norris), high-carbon basic open-
hearth steel (Reagan), rail steel (Washburn and Miller), alloy
forging steel (Feild and Good), acid open-hearth steel (Foley), and
basic electric steel (Walther). Kinzel concluded the symposium
with a discussion of the physical testing of slag. The symposium
attracted a large attendance and elicited an animated discussion.
The 1935 Howe Memorial Lecture to the Iron and Steel Division
by E. C. Smith was also on slags ^ and included a broad survey of
their constitution and the identification of the various constitu-
ents by petrographic methods. Other important papers on steel
making were those by Arganbright ^ on the manufacture of basic
open-hearth steel for cold-heading wire, Fleming^ on the manu-
facture of rimming steels, Tranter ^ on ladle and teeming practice,
and Nelson '^ on the effect of mold design on rate of solidification
and soundness of ingots.
Dean, Barrett, and Pierson ^ summarized the properties of sponge
iron — which has been attracting considerable attention lately —
and showed that wrought iron made from this material has a
cellular structure which is inherited from the sponge iron. An
important contribution to the literature of steel making was the
paper by Henning^ on Bessemer steel, for which the author
received the 1935 Robert W. Hunt Award by the American Institute
of Mining and Metallurgical Engineers. The Bessemer process
has received little or no attention metallurgically for many years.
Chipman's paper ^® on the thermodynamics of deoxidation received
the Howe medal as the most important contribution to the 15th
annual meeting of the American Society for Metals. Chipman
presented evidence to show that oxygen is present in liquid steel as
dissolved oxide, probably FeO. Carbon exists in liquid iron and
in austenite mainly as FcgC. The deoxidizing power of the various
deoxidizers was computed; in the order of increasing power at
1600° C. these are : Cr, Mn, Si, Ti, V, Zr, Al, Mg, and Ca.
Inclusions and Gas. As is characteristic of past years, most of
the work on inclusions and gas has been on methods. Hoyt and
Scheil ^^ recommended the use of reflected polarized light in the
study of inclusions, and Urban and Chipman ^^ described the inclu-
sions formed by deoxidizing liquid iron which had been previously
saturated with oxygen. The inclusions were removed by a new
technique and studied with the ore microscope. In a second paper,^3
these investigators identified and studied the constitution of inclu-
sions in iron, melted in vacuum and in air, to which iron sulfide
or titanium or zirconium had been added.
Progress to date at the National Bureau of Standards in the study
of methods for the determination of oxygen was reported by
Thompson.^^ Brower, Larsen, and Shenk ^^ eliminated errors
in the Ledebur method, so that they now believe that oxygen
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126 ANNUAL SURVEY OF AMERICAN CHEMISTRY
values thus determined are definite and reproducible; but "the
precise significance is still open to question, as indeed is true of all
methods of oxygen determination so far developed." Hamilton,^^
on the contrary, in a paper on the determination of oxygen in alloy
steels and its effect upon tube drawing, expressed the belief that
oxygen may be determined by the vacuum-fusion method with an
accuracy of 0.0005 percent, when proper precautions in sampling
are taken.
Yensen and Herty ^'^ proposed a terminology and classification
of non-metallic elements and gases in metal, which, it is hoped, will
be the basis of an internationally adopted classification, or at least
a starting point for discussions which will assist in eliminating
some of the present confusion in nomenclature and classification.
In addition to the paper by Hamilton mentioned above, there are
a few reports on the effect of inclusions on structure and properties.
Reagan ^® determined the segregation of silicates in bottom-cast
ingots, and Mahin and Lee ^^ the influence of non-metallics upon
the precipitation of primary cementite in hypereutectoid steel. In
■ two important investigations, Yensen and Ziegler 20, 21 determined
the effect of carbon and oxygen on magnetic properties of iron.
The results were expressed in a ternary diagram. The latter paper ^i
received the 16th Howe Medal award of the American Society for
Metals.
High-purity Iron and Iron-carbon Alloys. The research of the
world on the manufacture and properties of high-purity iron was
correlated and critically reviewed in the sixth Alloys of Iron
Research monograph, "The Metal — Iron".22 Holmquist^s deter-
mined the effects of stress on the transformation temperatures of
iron, and Austin and Pierce,^* by thermal expansion data on high-
purity iron determined by a vacuum interferometer, were able to
fix the A3 temperature at approximately 910° C, which is in good
agreement with the temperature chosen in "The Metal — Iron".22
There were a number of important papers on different phases of
the iron-carbon system. Mehl and associates ^5 Reported further
studies upon the Widmanstatten structure of high-purity iron and
iron-rich alloys of iron with nitrogen and phosphorus. Schwartz ^^
secured corroboration experimentally that in an iron-carbon alloy
containing 0.03 percent silicon the reaction FcsC ?:± 3 Fe -|- C pro-
ceeds to the right at all temperatures from 630° C. to above the
eutectic. Further light upon the important but still unsolved
question of the stability of FcgC at low temperatures was supplied
by Kinzel and Moore,^^ who found graphite in a 0.15 percent carbon
steel which had been subjected to long heating somewhat below
the eutectoid temperature ; this indicates that cementite is unstable
even below the Ai transformation. In an investigation of ferro-
magnetism, Zavarine 28 found that the recovery of magnetism dur-
ing quenching does not take place at a single temperature but
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FERROUS METALLURGY 127
over a temperature range. Other investigations which should be
mentioned are those of Austin ^9 on the dependence of the rate of
transformation of austenite on temperature, and of Knight and
Muller-Stock ^o on the transformation of austenite to martensite in
which the martensite needles formed spontaneously.
There has been a marked re-awakening in interest in the struc-
ture of iron-carbon alloys, especially in the transitional structures
which result from thermal treatment. One whole issue of "Metal
Progress" ^^ was devoted to a discussion of troostite and sorbite
and to a consideration of the proper nomenclature for the struc-
tures now called by these terms but which are formed under differ-
ent thermal treatments. Lucas ^^ reported the results of a metallo-
graphic examination of nodular troostite, and Mehl and Smith ^^
determined by x-ray methods the orientation of ferrite in pearlite
with respect to the original austenite. In a paper on the application
of thermomagnetic methods to metallographic research, Ellinger
and Sanford^^ showed that martensite is relatively unstable but
can be stabilized by reheating or by aging.
Constitution of Binary and Complex Alloys of Iron. Since the
work of Smith and Palmer on copper steels in 1933 (This Survey,
Vol. VIII: 213), the interest in copper as an alloy with iron has
become widespread. The fourth Alloys of Iron Research mono-
graph 3^ was published in 1934 and gave a comprehensive critical
summary of the constitution of iron-copper alloys and the effect
of copper on the structure and properties of carbon steel, alloy
steel, and cast iron. Norton 3« redetermined the solubility of
copper in iron as 1.4 percent at 850° C. This decreases to 0.35 per-
cent copper at 650° C. and is constant below this temperature.
Norton also investigated lattice changes in aging.
The important research at Carnegie Institute of Technology on
the constitution of iron-manganese and iron-manganese-carbon
alloys, by Walters and his associates, which was mentioned in pre-
vious issues of the "Annual Survey" (Vol. VI : 200; Vol. VIII : 212)
was completed with the publication of two papers.^^ One of the
papers contained the iron-manganese diagram and the other the
7 percent manganese section of the ternary iron-manganese-carbon
diagram.
Among the other papers on the constitution of iron alloys which
should be mentioned are those of Ziegler,^^ who found that no
appreciable diffusion resulting in a change of composition takes
place in iron-silicon alloys during heat treatment, and of Schowalter,
Delammater, and Schwartz,^® who attempted to locate the meta-
stable eutectoid point in Fe-C-Si alloys containing 1 percent silicon.
An alloy with 100 percent pearlite has 0.92 percent carbon.
Chipman and Murphy ^<^ determined the solubility of nitrogen
in iron as 0.04 percent at 1600° C. The temperature coefl&cient of
solubility is small, about 1.5x10"^ percent per degree. Work on
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128 ANNUAL SURVEY OF AMERICAN CHEMISTRY
iron-chromium alloys was reported by Hicks,^^ who studied the
diffusion of chromium into iron, and by Austin and Pierce,*^ ^j^q
determined the linear thermal expansion and studied transforma-
tion phenomena in low-carbon iron-chromium alloys containing
3 to 10.5 percent chromium.
Properties of Carbon and Alloy Steels. Normal-temperature
properties of carbon steels were studied by Rosenberg and Jordan,^^
who investigated the influence of oxide films on wear, Phillips and
Dunkle,^^ who determined directional properties of rolled and
annealed low-carbon steels, especially ductility as shown by the
cupping test, Polushkin,^^ who studied the effect of cold work on
structure and properties of tubes drawn by three processes,
Harvey,*^ who determined the effect of cold working on the proper-
ties of cold-headed bolts and who gave a heat treatment which
would remove the effect of cold work in the head without materially
affecting the properties of the cold-worked stem, and Cook,*"^ who
studied the relation between chemical composition and transverse
fissures in rails.
Papers on the properties of low-alloy steels were numerous.
Armstrong ^® gave a comparison of the mechanical properties of 25
low-alloy cast steels after 9 different heat treatments, and Gritchett*^
summarized the mechanical properties and corrosion resistance of
low-chromium steel castings containing up to 7 percent chromium.
As noted in a previous section, the properties of steels and cast
irons containing copper have been reviewed and correlated in the
monograph "The Alloys of Iron and Copper".^^ Epstein and
Lorig^^ found that copper steels can be carburized successfully
if the copper is 2.8 percent or below. A new copper alloy steel for
sheet, containing 0.50 to 1.00 percent manganese, 0.50 to 1.50 per-
cent copper, 0.50 to 0.80 percent nickel, 0.20 percent molybdenum,
and 0.12 to 0.30 percent carbon, for which higher strengths are
claimed, was announced by Miller.^^
Phosphorus, long looked upon as a harmful impurity in steel,
has been recently used as an alloying element. Progress in the
development of the phosphorus-bearing steels was reported in a
correlated abstract by Gillett.^^ ^ recent development in silicon
steel for electric sheet was published by Goss,^^ who described the
material as a fine-grained strip, the properties of which approach
the properties of a single crystal.
The nitriding process is still of interest. Norton ^^ presented data
to indicate that the aluminum in nitrided steels is precipitated
as aluminum nitride. This compound in finely dispersed form is
the primary cause of the high hardness. Strauss and Mahin ^^
reported the development of a new nitriding steel free from alumi-
num. The material contains about 2.5 percent chromium and small
amounts of molybdenum and vanadium.
There were two important papers on fatigue, both from the
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FERROUS METALLURGY 129
National Bureau of Standards. Shelton and Swanger ^^ described
a special long-span rotating-beam machine for determining fatigue
properties of wire. The fatigue limits of cold-drawn wire with
the original surface unmachined and unpolished were found to be
40, 60, and 82 percent of the fatigue limits of highly polished speci-
mens of the same materials. McAdam and Clyne ^"^ reported the
results of a large number of tests on ferrous and non-ferrous
materials to show the effect of mechanically and chemically formed
(corrosion-fatigue) notches.
Three papers on corrosion will be mentioned. Speller,^^ i^ the
1934 Howe -Memorial Lecture to the Iron and Steel Division,
American Institute of Mining and Metallurgical Engineers, gave a
broad survey of the corrosion problem. Knight and Benner^^
compared the corrosion resistance of wrought iron, made by hand
puddling, mechanical puddling, and the Aston process, in salt
water, dilute acids, and air. Denison and Hobbs ^^ made a report
on the corrosion of steel in acid soils. This is a part of the com-
prehensive research on soil corrosion which has been going on
for several years at the National Bureau of Standards.
Effect of Temperature. There were fewer investigations than
usual on the properties of carbon and alloy steel at subnormal and
elevated temperatures. Papers on properties at subnormal tem-
peratures were given by Hiemke and Schulte,^^ who gave data on
the impact resistance of 1.25 percent manganese plate steel at low
temperatures, and by Campbell,^^ ^^q found that the addition of
nickel in small amounts tends to improve the low-temperature
impact values. The amount of nickel depends on the carbon con-
tent and varies from 2 to 3.5 percent. Proper heat treatment is
very important.
Another investigation of low-temperature properties was made
by Heindlhofer,*^® who determined the relation between the abrupt
change in impact strength at low temperatures and the plasticity
of high-purity iron.
There were several important papers on creep. McVetty ^^ gave
an interpretation of creep tests ; Wilson and Thomassen ^^ found a
secondary maximum in the creep strength of manganese-molyb-
denum steels at 480° C, which is paralleled by a precipitation-
hardening effect detectable by x-ray examination; White and
Clark ^^ compared single-step long-time creep values with Hat-
field's time-yield value and found that the latter is of importance
as a qualitative test for classifying a series of steels of a given
type at a given temperature but does not yield quantitative results
in agreement with long-time creep values.
Cross and Johnson ^^ determined creep properties of steel tubes
containing 5 percent chromium and 0.5 percent molybdenum, and
Sale^*^ reported compression tests of structural steel at elevated
temperatures. An investigation on the elevated-temperature
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130 ANNUAL SURVEY OF AMERICAN CHEMISTRY
properties of 0.10 and 0.45 percent carbon steels with and without
silicon, chromium, and molybdenum by White, Clark, and Wilson ^^
indicated that these properties are dependent chiefly on the initial
heat treatment and upon the alloying elements and may be inde-
pendent of the carbon content. A report by Shelton®^ included
thermal conductivity at elevated temperatures of ingot iron,
wrought iron, cast iron, and carbon and alloy steels.
Corrosion- and Heat-resistant Steels. The unflagging interest in
this class of materials is evidenced by the large number of reports
of investigation and also by the appearance, in less than two years,
of a second and enlarged edition of "The Book of Stainless Steels".'^^
In addition to the use of titanium as an inhibitor of intergranular
corrosion, Becket and Franks '^^ recommended the use of colum-
bium. When this element, to the extent of ten times the carbon
percentage, was added to the 18 percent chromium 8 percent nickel
(18-8) alloy, no intergranular embrittlement was noted below 650°
C. Wells and Findley ''^ investigated the corrosion resistance of
18-8 wire containing 0.15 to 0.20 percent carbon and discussed the
advantages and disadvantages of this higher carbon content. The
heat treatment of the wire at 815° C. for various lengths of time
was investigated as a means of stabilizing this higher carbon
material against intergranular corrosion, but it was found to be
not. so effective as the addition of titanium.
An investigation with wide implications reported by Franks ''^
shows that it is practicable to add nitrogen to low-carbon high-
chromium steels to limit the grain size and improve stength and
ductility without unduly increasing brittleness. Other investiga-
tions of stainless steels include those reported by Sommer,'^^ yf\yo
studied the relation between plastic deformation in deep drawing
and tensile properties, Grimshaw,*^^ who recommended the addi-
tion of 4 to 6 percent manganese and 3 percent copper to retain the
austenitic structure even after severe cold working, and Newell,'^''
who correlated the structure, after the addition of a number of
elements, with the ductility at elevated temperatures. An interest-
ing study of oxide inclusions in stainless steel and ferrochromium,
giving methods for differentiating between the two oxide phases
present, was reported by Baeyertz.'^^
One of the recent outstanding improvements in heat-resisting
alloys was revealed in a paper by Hoyt and Scheil,''® who have
developed an alloy containing 55 percent iron, 37.5 percent chro-
mium, and 7.5 percent aluminum for use in resistor electric furnaces.
The alloy has many times the life of the standard nickel-chromium
resistance alloys; moreover it can be used at higher temperatures,
up to 1300° C. or even above.
Scaling tests were made by Kosting,^^^ who determined the
deterioration of chromium-tungsten steel in ammonia gases, and
by Rickett and Wood,^^ who studied the action of oxygen and
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FERROUS METALLURGY 131
hydrogen sulfide on iron-chromium alloys containing up to 28
percent chromium. The effect of alloy composition and kind
of atmosphere was determined; it was found that hydrogen sulfide
causes much more pronounced scaling than oxygen.
Heat Treatment and Aging. A few of the papers already men-
tioned under "high-purity iron and iron-carbon alloys" might with
justification be also mentioned under heat treatment and aging;
especially the reports of Zavarine,28 Austin,^^ Knight and Miiller-
Stock,30 and Ellinger and Sanford.^*
Reports which also deal with constitutional changes but which
are more important as discussions of the theory of heat treatment
are those by Nielsen and Dowdell ^^ on the relation of stress to the
transformation of austenite to martensite, and by Upton ^^ on the
habits and laws of decomposition of supercooled solutions with
special reference to austenite.
Scott, who for some time has been investigating quenching rates,
presented two papers. In the first,"*^'' he studied the application of
the laws of heat conductivity to the cooling rate of steel cylinders
in quenching. The thermal constants for certain steels and for
important quenching media were evaluated. In the second paper,®^
Scott showed that there were three stages of heat transfer in
quenching, of which the manifestations are: (a) a vapor blanket
which momentarily retards cooling, (b) the carrying away of the
heat by the vapor, and (c) cooling by convection. Other papers on
heat treatment were those of Hughes and Dowdell ^^ on the effect of
quenching steel in hot lead on the mechanical properties, and a coni-
parison of the properties of steel treated in this way with the properties
of similar steels after quenching and tempering, and of Nusbaum and
Goss ^"^ on grain distortion in metals during heat treatment as deter-
mined by the x-ray. McMullan ^^ reported the properties of the case
and core of a large number of carburized and heat-treated carbon and
alloy steels, which showed the effect of grain size. Two papers on
furnaces should be mentioned. Mawhinney^^ discussed heat transfer
in fuel-fired furnaces, and Weinland^^ presented a graphical method
of calculating heat loss through furnace walls.
Heat treating in controlled atmospheres, which has lately become
of outstanding commercial importance in the annealing of sheet,
received much attention. One of the most important of the sev-
eral papers is the correlated abstract and critical summary of
advances in this field which was published serially in "Metals and
Alloys," ®^ Results of annealing in mixed gas atmospheres were
reported by Marshall ^^ and of gaseous carburizing by Austin,^^
who showed to what extent decarburizing and recarburizing might
take place if the composition of the furnace atmosphere changed.
Data on the amount of scaling in a low-carbon steel at 900 to
1150° C, depending upon the furnace atmosphere, were presented
by Siebert and Upthegrove.®^
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132 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The subject of age hardening, as was to be expected, was covered
by a large number of papers. The present status of this phenom-
enon and its theoretical aspects were discussed by Harrington.®^
Ellinger and Sanford^® investigated the constitutional changes
taking place in an 0.80 percent carbon steel aged at room tempera-
ture and 100° C, using thermomagnetic analysis (cf.^*), and Ken-
yon and Burns ^'^ presented methods for testing low-carbon sheets
for blue brittleness and for stability against changes in aging.
Two conflicting views on the role of oxygen in aging were pre-
sented. Burns ®* claims that carbon is the cause of aging in nitro-
gen-free steels and nitrogen is responsible in nitrogen-bearing
steels; oxygen apparently plays no significant part in either.
Davenport and Bain ®® recognize two types of aging, one of which
is caused by carbon, while the other, called strain aging, is caused
by an iron-oxygen compound in the slip bands of cold-worked
grains, which was rejected from material supersaturated with oxy-
gen. Sauveur ^^ studied the aging of cold-worked or quenched
carbon steels in the light of the precipitation theory. Nitrogen and
oxygen greatly increase the tendency of the material to age. The
amount of aging depends upon the amount of free ferrite. To
reduce or eliminate aging, Sauveur suggests that the material be
quenched to form martensite and that the martensite be tempered
to the hardness desired.
Aging in 4 to 6 percent chromium steel was investigated by Wil-
ten and Dixon,^®^ who found that the brittleness after long expo-
sure at 480° C. is similar to that resulting from duralumin-type
aging. In the 9th Campbell Memorial Lecture to the American
Society for Metals, Krivobok ^^^ gave data on the effect of temper-
ature on iron-chromium and iron-chromium-carbon alloys. The
hardening of these materials after aging is caused by nitrogen.
Grain Size. One of the outstanding technical meetings of the
past two years was the symposium on grain size held late in 1933
by the American Society for Metals and published in the 1934
Transactions, Twelve papers were presented. The symposium was
arranged so that the papers would, so far as possible, cover broadly
the field of ferrous metallurgy.
The control of grain size in the manufacture of basic open-hearth
steel was discussed by Epstein, Nead, and Washburn,i<>3 and the
relation between the grain size and the machinability and other
properties of Bessemer screw stock by Graham.^^ Papers giving
data on the relation between grain size and the following properties
were presented: hardness and toughness of automobile steels,^^*^
structure and properties of medium-carbon (1040) steel,^^^® forging
properties and machinability,^^^'^ tensile strength, impact resistance
and creep strength at high temperatures,^®^ sheet for deep draw-
ingr^ioo impact properties,^!® and magnetic properties of 5 percent
silicon steel.!!! The P-F (penetration-fracture test) characteristic
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FERROUS METALLURGY 133
of steel was discussed by Shepherd.1^2 This test affords a simple
and rapid means of distinguishing between high-carbon steels of
the same chemical composition. The penetration in units of
^ inch of hardening by quenching under standard conditions plus
the grain size number from a fracture test gives a numerical value
which can be used to grade the steel.
The relation between grain size of the austenite and the prior
heat treatment was discussed by Grossmann ^^^ and the relation
between grain size and hardenability and normality of steels by
Davenport and Bain,^^* also at the symposium. Other papers on
grain size which should be mentioned are those pf Herty ^^^ on the
effect of deoxidation on grain size, hardenability, aging, and impact
resistance at low temperature, and of Sefing and Trigger ^^^ on
the relation between grain size and cracking or distortion in
quenching medium-carbon steels. In the 10th Campbell Memorial
Lecture to the American Society for Metals, McQuaid ^^"^ sum-
marized progress to date in controlling grain size in commercial
steels, and the relation between the aluminum addition to the
molten metal and the resulting grain size, hardenability, and pearl-
ite divorce.
Tool Steels. A report by Digges and Jordan,^^^ which might
have been classified under grain size, contained data on the effect
of the original structure of carbon tool steel on the austenite grain
size and the critical cooling rate and hardening temperature.
Properties of tool steel were investigated by Luerssen and
Greene,^^®' ^^o ^ho developed a torsion impact test which showed
peaks of maximum toughness with low tempering temperatures.
The location of these peaks could be varied by varying the heat
treatment.
Three papers on high-speed steel will be mentioned. Garratt ^^i
described a new steel containing about 1.5 to 2.0 percent tungsten,
8 percent molybdenum, about 3.75 percent chromium, and 1 per-
cent vanadium. This is apparentlj'^ the newest development in
molybdenum high-speed steel, a class of material which has been
attracting considerable attention lately. Phillips and Weldon ^22
mvestigated the effect of furnace atmosphere on the grain size of
molybdenum high-speed steel. Liedholm ^23 reported a study of
retained austenite and its decomposition in cobalt high-speed steel.
One paper was published ^^4 on the manufacture, heat treatment,
properties, and uses of 2 percent carbon 12 percent chromium tool
steel with and without vanadium or vanadium and molybdenum.
Cast Steel and Cast Iron. In a symposium ^25 q^ the porosity of
steel castings Sims gave data on proper mold and pouring practice
to reduce porosity, Batty discussed molds and cores, and Wood-
ward the mechanism of porosity.
Of the large number of papers on cast iron only a few, most of
which are on alloy iron, will be mentioned. Saeger and Ash ^^6
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134 ANNUAL SURVEY OF AMERICAN CHEMISTRY
reported the results of the research going on at the National Bureau
of Standards on the properties of gray iron as affected by casting
practice, and Morken ^27 ^nd Eddy ^^s gave data on heat treatments
which result in improved strength, ductility, and resistance to shock
and fatigue. Toiiceda ^^o described a fluidity test for cast iron,
and Dahle ^^^ gave data on the impact resistance of plain and
molybdenum cast irons at elevated temperatures. In a study of
unalloyed malleable iron, Sauveur and Anthony ^^^ found that by
varying the annealing practice malleable iron could be produced
which had a ferritic, pearlitic, or sorbitic matrix.
As may be judged from the number of papers published recently,
the use of copper as an alloy in cast iron is increasing. Eddy ^^^
reviewed the effect of copper on the structure and properties.
Smith and Palmer ^^3 found that copper accelerates graphitization,
reducing the annealing time about 50 percent. Moreover, copper
induces precipitation hardening. Lorig and Smith ^34 found that
as much as 3 percent copper is soluble in white iron, and that
from 0.70 to 1.50 percent improves the fatigue strength of the
resulting malleable. Less than 0.50 percent has no effect. Pre-
cipitation hardening may be induced if the copper exceeds 0.70
percent.
Other reports on alloy cast iron are those of Vanick,^^^ who gave
properties and uses of cast iron to which nickel, copper, and molyb-
denum had been added, of Wood,^^^ who reported thermal expan-
sion characteristics of some nickel cast irons, including specimens
containing nickel and copper in the monel ratio (70-30), and of
Pennington and Jennings,^^'^ who studied the effect of tungsten
and manganese on the graphitizing rate of white cast iron. Both
of these elements promote carbide stability; the time for graphitiz-
ing reaches a maximum with 3 percent manganese; the effect of
tungsten depends upon the manganese content.
Phillips ^3^ gave data on the heat and corrosion resistance of irons
containing 20 to 35 percent chromium. The castings were made
with ferrochromium containing nitrogen to control the grain size.
Phillips also described the melting practice and structure and gave
typical mechanical properties. The use of zirconium as a deoxi-
dizing agent and as a graphitizing accelerator was recommended
by Hall.^3® Nitrided cast iron has recently come into use for auto-
motive parts, such as cylinder liners, cams, and the like, which
should have high resistance to wear. The base iron usually con-
tains chromium, aluminum, molybdenum, and occasionally vana-
dium. The properties and structure of this material have been
described by Colwell ^^^ and by Homerberg and Edlund.^*^
Miscellaneous. A recent Alloys of Iron Research monograph ^^^
was prepared to explain the fundamentals of thermodynamics and
the construction of binary, ternary, and higher phase diagrams to
chemists, metallurgists, and others to whom the original work of
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FERROUS METALLURGY 135
Gibbs and some of the diagrams now appearing in the regular
Alloys of Iron Research monographs and other publications are
incomprehensible.
Two papers on non-destructive inspection should be mentioned.
Isenburger ^^^ published x-ray exposure charts for steel, and Nor-
ton and Ziegler ^^* investigated the sensitivity of gamma-ray radi-
ography. They found the sensitivity nearly constant for sections
of 2.5 to 6 inches of iron or steel.
In a very interesting and provocative paper, entitled "A Chem-
ical Engineer Views the Steel Industry," Ramseyer^^^ gave the
metallurgists and steel makers of this country his opinion of the
inefficiency of their industry. While much of Ramseyer's trenchant
criticism is undoubtedly justified, the very high cost of large-scale
research at steel-making temperatures makes the investigation of
most of his suggestions a matter for the distant future. Whether
we agree with him about our inefficiency and the need for such
drastic changes in practice, the viewpoint expressed was refreshing.
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FERROUS METALLURGY 137
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(1934).
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117. McQuaid, H. W., Trans. Am. Soc. Metals, 23: 797 (1935).
118. Digges, T. G., and Jordan, L., J. Research Natl. Bur. Standards, 15: 385 (1935).
119. Luerssen, G. V., and Greene, O. V., Trans. Am. Soc. Metals, 22: 311 (1934).
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129. Toiiceda, E., Metals & Alloys, 6: 130 (1935).
130. Dahle, F. B., Metals & Alloys, 5: 17 (1934).
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Chapter X.
The Platinum Metals.*
Raleigh Gilchrist,
Chemist, National Bureau of Standards.
Since the chapters prepared by Wichers ^» ^ in Volumes II and
III of the Annual Survey of American Chemistry, in which the
subject matter was restricted to the inorganic and analytical chem-
istry of silver, gold, and the platinum metals, no account of the
platinum metals has appeared in this series of reviews. In the
present chapter, only the platinum metals are considered, and the
attempt has been made to include all of the published work of
American origin during the three-year period 1933-1931.
Economics. The annual chapter 3' * on platinum and allied met-
als, prepared by Davis for the Minerals Yearbook of the Bureau
of Mines, contains statistics on the production, purchase, market,
and price of domestic crude platinum; on the price and consump-
tion of refined platinum metals; on the stocks of platinum metals
in the hands of refiners in the United States and on the amounts
sold by them to consuming industries; on the imports of platinum
metals into the United States and the exports therefrom; as well
as on production in foreign countries and on world production.
Roush,^» ® during the same period, covered much the same sort of
statistics.
The average yearly price of platinum remained practically sta-
tionary during 1932 and 1933, at $32.00 and $3075 a troy ounce,
respectively. Improved activity in the industries using platinum
and restriction on the use of gold for industrial purposes are
reflected in the sales of platinum metals by refiners in the United
States in 1933, which amounted to 107,821 ounces, an increase of
29 percent over 1932.
Chemistry. Analytical and Inorganic, With the publication of two
papers by Gilchrist '^' ^ and of two by Gilchrist and Wichers,^» ^®
the development of an analytical procedure by which the six plati-
num metals can be separated from one another quantitatively, in
the absence of other elements, and determined gravifeietrically, has
been completed. The order in which the separations are made is :
♦•Publication approved by the Director of the National Bureau of Standards of the
U. S. Department of Commerce.
138
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THE PLATINUM METALS 139
osmium, ruthenium, platinum, palladium, rhodium, iridium. In
turn osmium, and ruthenium are isolated by distilling their respec-
tive tetroxides. Palladium, rhodium, and iridium are separated
jointly from platinum by precipitating them hydrolytically as
hydrated dioxides. Palladium is separated from rhodium and
iridium by precipitating it with dimethylglyoxime. Rhodium is
separated from iridium by reducing it to metal with titanous chlo-
ride. Titanium, introduced as reagent, is separated from iridium by
precipitating it with cupferron.
The distinctive features of the method, by which it differs from
traditional methods, consist in the conditions under which ruthe-
nium is separated ; the reagent solution used to absorb the liberated
tetroxides of osmium and ruthenium; the application of controlled
hydrolytic precipitation to the separation of platinum from pal-
ladium, rhodium, and iridium, either singly or jointly; the recovery
of osmium, of ruthenium, and of iridium by hydrolytic precipita-
tion ; the separation of rhodium from iridium by titanous chloride ;
and in the avoidance of the use of potassium chloride, ammonium
chloride, pyrosulfate fusions, and of extraction of metallic mix-
tures with acids.
A valuable contribution to the analytical chemistry of the plati-
num metals was made by Whitmore and Schneider,^^ who studied,
with the aid of the microscope, the reactions of the six platinum
metals (and also gold) with 33 different reagents, and developed
for them a scheme of microscopical qualitative analysis.
Ogburn and Brastow ^^ published a method for the separation
of palladium from the other platinum metals by reduction with
ethylene. They reported the error in the determination to be
0.75 percent. Hopkins ^^ outlined a procedure for the assay of
black sands, while Byers ^*' ^^ studied the effect produced by the
metals of the platinum group on the surface of beads obtained by
cupellation. Pierson ^^ described tests for the estimation of small
amounts of palladium and platinum, which involve reduction to
metal by mercurous chloride and comparison with known quanti-
ties reduced in a similar manner. Haigh and Hall ^"^ described a
procedure for the recovery of platinum used in potash determina-
tions, which consists in precipitation of the platinum by zinc.
A new value for the atomic weight of osmium, 191.5, based upon
the determination of the average osmium content of ammo-
nium chloroosmate, (NH4)20sCl6, and of ammonium bromoosmate,
(NH4)20sBr6, by Gilchrist,^^ was adopted by the Committee on
Atomic Weights ^^ of the International Union of Chemistry in
1934. This is the first change in the atomic weight of osmium
since the value 190.9 was determined by Seubert 20. 21 j^ 1391^ only
one investigation having been undertaken in the interim, namely
that of Seybold.22
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140 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Kirschman and Crowell ^3 studied the reaction between osmium
tetroxide and hydrobromic acid in a closed tube at 100° C. More
recently, Crowell and Baumbach ^4 described a method for the
potentiometric determination of osmium in potassium chloro- and
bromoosmate, using chromous sulfate, with a reported error of less
than 0.2 percent. Brunot,^^ from a medical point of view, investi-
gated the toxic effect of osmium tetroxide on white rabbits. The
animals showed evidence of acute irritation shortly after exposure
began, soon became semi-comatose, and died somewhat later. The
lungs were found to be particularly affected and death was attrib-
uted to purulent broncho-pneumonia.
Wichers 2«» 27 described the preparation of the pure iridium and
of the pure rhodium which were used in the recent determination
of the freezing points of these metals at the National Bureau of
Standards. His descriptions concerning the refining of these two
metals supersede those given in a previous publication-^^
A mixture of hydrazoic acid, HN3, and hydrochloric acid, in
water solution, was found by Franklin 29 to show properties of aqua
regia to the extent that the solution dissolved platinum. Urmston
and Badger ^o studied the photochemical reaction between bromine
and finely divided platinum with light of wave-length shorter than
5000 A and that longer than 5300 A, as well as the thermal reaction
from to 25° C.
Adsorption and Diffusion of Gases. Sears and Becker ^i reported,
in abstract form, that as the amount of platinum adsorbed on a
tungsten surface increases, the thermionic activity decreases rap-
idly up to one layer, and then more slowly until at about ten layers
it approaches platinum activity. McKinney ^2 measured the adsorp-
tion of carbon dioxide and of carbon monoxide on palladium oxide
over the temperature range —78 to 218° C. and found that adsorp-
tion of carbon dioxide is of the reversible physical type, whereas
carbon monoxide shows physical adsorption at —78° and activated
adsorption at higher temperatures, the apparent maximum for the
latter at 350 mm. being at about 100° C. The isothermal absorption
of hydrogen by palladium was studied by Krause and Kahlenberg ^
at temperatures ranging from to 138° C.
Ferguson and Dubpernell,^* in a study on overvoltage, published
a paper on the mechanism of the transfer of electrolytic hydrogen
and oxygen through thin sheets of platinum and palladium. Ham,^^
in one paper, reported the results of experiments on the diffusion
of hydrogen through platinum, which checked those of Borelius
and Lindblom,^^ and in another 9*^ those on diffusion through pal-
ladium. Harris, Jost, and Pearse^* found that there was a ten-
fold increase in the concentration of the heavier isotope, in a
single step, when hydrogen was diffused through palladium under
a 100-fold decrease in pressure, and concluded that the diffusion is
an atomic process, and that there is an activation factor favorable
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THE PLATINUM METALS 141
to the lighter isotope. Fink, Urey, and Lake,^® from preliminary
experiments, reported that with a palladium tube as cathode, frac-
tionation of the two isotopes of hydrogen occurred, protium, the
lighter isotope, diffusing through more readily.
In a paper concerning the shunt action of the electrolyte, when
measuring the resistance of immersed and hydrogen-charged pal-
ladium wires, Smith *^ raises several objections to an expla-
nation given by Knorr and Schwartz.*^ Somewhat later, Smith
and Derge *2 investigated the role played by intergranular
fissures in the occlusion and evolution of hydrogen by palladium
and confirmed the conclusion, previously formed, that diffusion
of hydrogen occurs primarily along slip-plane fissures, and
only secondarily through the undistorted lattice. In a second
paper. Smith and Derge ^^ published an account of a study on the
occlusion and diffusion of hydrogen in palladium and particularly
of metallographic effects of gaseous hydrogen. Herzfeld and
Goeppert-Mayer,^* on the basis that hydrogen dissolved in palla-
dium is apparently partially dissociated into protons and electrons,
applied the concepts of the Debye-Hiickel theory of electrolytic
solutions, and by using Fermi statistics of the electrons, made a
first-order calculation for the energy and conductivity.
Catalysis. Owing to the catalytic properties possessed by the metals
of the platinum group, various investigators employed them in this
capacity. Shepherd and Branham ^^ used platinum in a critical
study of the determination of ethane by combustion in excess oxy-
gen, while Kobe and Arveson *^ studied the oxidation of hydrogen
and of carbon monoxide over platinized silica gel, and later Kobe
and Brookbank^*^ used the same catalyst in experiments on the
oxidation of methane hydrocarbons.
Heath and Walton *8 investigated the effect of salts on the cata-
lytic decomposition of hydrogen peroxide by colloidal platinum.
Hammett and Lorch ^^ determined the activation of hydrogen
by bright electroplated platinum and iridium by measuring the
polarization of electrodes carrying these catalysts, and in a subse-
quent article, Lorch ^^ discussed the choice of catalysts of the
hydrogen electrode and described the preparation of such elec-
trodes plated with platinum black, bright platinum, and bright
indium. Kahlenberg, Johnson, and Downes ^^ stated that a small
portion of the hydrogen released from cathodically hydrogenated
palladium reduces sulfur above 65° C.
McKinney and Morfit ^^ have stated that platinum oxide is
reduced by carbon monoxide at 0° C, and that the reaction is auto-
catalytic and has an induction period. In a subsequent paper,
McKinney ^3 reported that well-dried platinum oxide (Pt02) is
reduced by carbon monoxide at 25° C. with an induction period of
two hours, which period is shortened to thirty minutes at 40° C.
He found, however, that if the platinum oxide is not dried at
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142 ANNUAL SURVEY OF AMERICAN CHEMISTRY
110° C, or if moist carbon monoxide is used, reduction occurs at
0° C. with a short induction period.
Wiig ^* found that hydrogen and oxygen at low pressures reacted
in the ratio of 2 : 1 by volume on platinum as a catalyst, when care
was taken to eliminate any possibility of a change in concentration
of the gaseous mixture due to differential diffusion.
Hartung and Crossley ^^ employed a catalyst consisting of pal-
ladium on charcoal to reduce quickly and easily propiophenone to
propylbenzene. The substitution of hydroxyl or methoxyl groups
in propiophenone was found to influence the rate but not the
extent of the reduction. A similarly prepared platinum catalyst
proved to be inactive. In his studies on reduction of compounds
in the morphine series, Small ^^-^^ and his co-workers used plati-
num oxide and also palladium as catalysts.
Andrews and Lowy ^^ used a platinum catalyst in the reduction
of azo-type compounds. Thomson ®^ found that the acid oxidation
products of olefins are the impurities which offset the poisoning
effect of iron on platinum catalysts used in the reduction of ole-
fins. Bjerrum and Michaelis ®^ say that nitric oxide oxidizes leuco
dyes in the presence of a little colloidal palladium.
Baldeschwieler and Mikeska ^2 described the preparation of plati-
num oxide catalyst from spent material, using essentially the
method, of purification given by Wichers ^^ for the preparation of
pure platinum.
In a study of the reaction between nitrous oxide and hydrogen
on platinum, Dixon and Vance ®^ found that between 260 and
471° C. the rate is proportional to the partial pressure of nitrous
oxide and nearly independent of that of hydrogen. The apparent
energy of activation is 23,100 calories. Emmett and Harkness ®®
noted the poisoning effect of activated adsorption of hydrogen on
the para-ortho conversion of hydrogen at — 190° C. over platinum,
and consider this effect as constituting very strong evidence that
the activated adsorption of hydrogen by platinum is in part at least
a surface phenomenon.
Electrochemistry. Thews and Harbison ^^ described the electra-
lytic plating of platinum on noble and on base metals, in connec-
tion with which they disctissed technical details, endorsed the use
of Pt(NH3)2(N02)2, and stated that platinum plating lasts longer
than that of gold or silver. Experiments on the plating of rhcrdium
from various types of baths were reported by Fink and Lam-
bros ®'^'®^ who concluded that the most satisfactory results were
obtained with a bath containing 4 g. of rhodium per liter, 80 g. of
sulfuric acid per liter, and 3 percent of ammonium sulfate, at 50° C.
with a current density of 8 amperes per square decimeter.
McClain and Tartar®^ studied the effect of an electric field on
the potential at a platinum-solution interface, while Steiner and
Kahlenberg "^^ measured the electric potential of platinum in nitric
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THE PLATINUM METALS 143
acid. The electrode potentials of platinized platinum and of
smooth platinum in mildly alkaline sugar solutions were measured
by Ort and RoepkeJ^
Jones and Christian ^2 measured the resistance and capacitance
due to galvanic polarization with alternating current, using smooth
platinum and platinized platinum electrodes. In another paper,
Jones and Bollinger ^^ discussed the various criteria as to quality
and sufficiency of platinization in the measurement of the con-
ductance of electrolytes.
Stareck and Taft*^* investigated the systems Pt/AgNOg/Pt,
Pt/KAg(CN)2/Pt, and Pt/KCN/Pt with the aid of a modified
Haring cell, while Bancroft and Magoffin,*^^ using platinum elec-
trodes, made a study of energy levels in a number of common
reactions.
Using a platinum anode, and various metals as cathode, Topley
and Eyring"^^ studied the electrolytic separation of the hydrogen
isotopes and discussed the mechanism of the cathode process.
Physics. General Physical Properties. Platinum-rhodium alloys
containing approximately 10, 20, 40, 60, and 80 percent of rhodium
were prepared by Acken,*^*^ who determined for each of these alloys
the melting point, hardness, density, electrical resistivity, tempera-
ture coefficient of resistance, and the thermal electromotive force
against platinum, while Wise and Eash "^^ reported the results of
investigations dealing with the tensile strength and annealing
characteristics of platinum, palladium, and a number of their com-
mercial alloys. Bridgman '^^ measured, at pressures up to 12,000
atmospheres, compressibilities and pressure coefficients for rhodium
at 30 and at 75° C, and for ruthenium at 0, 30, 75, and 95° C. Drier
and Walker 8<> found, by means of x-rays, that the gold-rhodium
system consists of two solid solutions and that the solubility of
rhodium in gold is between 4 and 8 atomic percent, whereas the
solubility of gold in rhodium is between 1.1 and 2.5 atomic percent.
They did not detect, however, any solubility of silver in rhodium
or of rhodium in silver.
Using the Gouy method, Janes ^^ measured the magnetic suscep-
tibilities of a number of bi-, ter-, and quadrivalent palladium salts
and found them to be diamagnetic.
Lawrence, Livingston, and Lewises bombarded various targets,
including platinum, with deutons having energies ranging from
600,000 to 1,330,000 volts. In addition to the emission of a-par-
ticles, high-range protons were observed in large numbers. The
emission of protons became unobservable when the deuton energy
was below 800,000 volts. A technic for evaporating platinum from
a crucible, heated in a vacuum, by bombardment with electrons at
4000 volts produced from a tungsten filament, was described by
0*Bryan.88
In an extensive paper^^ devoted to the equilibrium relationships
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144 ANNUAL SURVEY OF AMERICAN CHEMISTRY
of Fe304, Fe203, and oxygen, mention is made of the effect of cru-
cibles of platinum and of rhodium on charges of magnetite, of
volatilization of platinum and rhodium in oxygen, and of the con-
sequent effect on thermocouples. In a general summary of the
phenomenon of precipitation-hardening, Merica ®^' ®® included a
discussion of hardenable gold alloys containing silver, copper, plati-
num, and palladium. In a discussion of the use of frangible disks
in pressure-vessel protection, Bonyun ®'^' ^^ stated that platinum is a
superior rupture-disk material.
Crystal Structure, Dickinson ®® published a paper on the crystal
structure of tetramminepalladous chloride, [Pd(NH3)4]Cl2 . H2O,
and West®<> reported an investigation on chloropentamminerhodium
chloride, [Rh(NH3)5Cl]Cl2, concluding that the crystal structure of
the isomorphous orthorhombic pentammines, [R(NH3)5X]Y2, where
R is Cr, Co, Rh, or Ir, and X and Y are halogens, is a distortion of
the cubic structure of the hexammines, [R(NH3)e]Y2.
Pauling and Huggins ^^ reported the interatomic distances in
crystals containing electron-pair bonds and listed the following
compounds of the platinum metals: RUS2, RuSe2, RuTe2, PdTe2,
PtS2, PtSe2, PtTe2, OSS2, OsSe2, OsTe2, PdAs2, PdSb2, PtPg,
PtAs2, PtSb2, Rb2PdBr6, K2PtCl6, (NH4)2PtCl6, and [N(CH3)4]2-
PtCle.
Isotopes, Bartlett®2 has discussed the prediction of isotopes and
included reference to palladium, rhodium, ruthenium, iridium, and
platinum.
Dempster ®3. 94, 95 has reported the isotopic constitution of plati-
num, rhodium, palladium, and iridium. For platinum, he found
isotopes of masses 192, 194, 195, 196, and 198 on analysis of the
platinum ions from a high frequency spark, using a new spectro-
graph. Rhodium was reported to have an average atomic weight
of 102.92±0.03, with only a single isotope. Palladium was found to
consist of six isotopes of masses 102, 104, 105, 106, 108. and 110.
the four middle ones being about equally strong while the one at
110 was weaker and the one at 102 faintest of all. U'sing electrodes
made of platinum-iridium alloy, Dempster found for iridium two
isotopes, 191 and 193, the latter being definitely the stronger.
Together with thallium and rhenium, this instance, according to
Dempster, forms the third exception to the rule that the lighter
of a pair of isotopes of an odd-numbered element is the more
abundant.
Spectra. In the field of spectral analysis, Hansen and Stoddard®^
published a paper on a relation between the probability of excita-
tion of line and continuous x-ray spectra of palladium. Allison ^'^
determined the line-widths of Koj and Ka2 for 14 elements from
Fe to Ag, including ruthenium, rhodium, and palladium, with a
double crystal spectrometer, and Williams,®^ with Allison's appa-
ratus, measured the full widths at half-maximum of the La^, Lp^,
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THE PLATINUM METALS 145
L32, and Lyi lines of platinum and iridium. Williams ®^ also mea-
sured the relative intensities and transition possibilities of the
/!L-series lines of ruthenium, rhodium, and palladium by the ioniza-
tion-chamber method, and Ross,^®^ using a double crystal spec-
trometer, studied the K-absorption discontinuity for these three
metals. The radiated frequency and ionization potential of palla-
dium were investigated by Kruger and Schoupp.^^^ Purdom and
Cork,^^2 t)y means of a ruled grating, measured the x-ray emission
wave-lengths in the M-series of 13 elements of higher atomic num-
ber than 71, including osmium, iridium, and platinum, and found
that the results were consistently 0.32 percent higher than those
found by the crystal method.
Richtmyer and Kaufman ^^^ examined for satellites the x-ray
lines, Lai and La2, of elements from Ta to U, including osmium,
iridium, and platinum. Two satellites were found, La*^ extending
from Au to U and La^ from Os to Bi. They also found that L(32
had two satellites, one extending from Ta to U, the other having
a slightly greater range. In a subsequent paper, Hirsh and Richt-
myer ^^* attacked the problem of the origin of x-ray satellites by
a study of their relative intensities under both cathode and fluo-
rescent excitation. Among the elements studied were ruthenium,
rhodium, and palladium. Kaufman ^<^^' ^^^ reported the measure-
ment of many weak lines in the L-spectra of iridium, platinum, and
of osmium, and stated that many were diagram lines due to quad-
ripole radiation and that others were satellites of L(32. Wilhelmy,^^*^
with a double crystal spectrometer, obtained quadripole lines in the
K-series of ruthenium. Goble,^^^ in a paper mainly mathematical,
discussed the four-vector problem and its application to energies
and intensities in platinum-like spectra.
With the aid of a mechanical interval recorder, Albertson ^^®
found a number of energy levels of Os I, and in a subsequent
paper ^^^ classified over 1050 osmium lines (of the arc spectrum)
as transitions between 137 terms of Os I.
Temperature Scales and Thermocouples. The ratio of brightness of
black bodies immersed in freezing iridium and freezing gold was deter-
mined directly, by Henning and Wensel,^^ in terms of the previously
measured ratio of platinum to gold. With the freezing point of plati-
num previously established as 1,773±1° C, that of iridium was found
to be 2,454 it 3° C. In a subsequent paper, Roeser and Wensel,^^ in a
similar manner, determined the freezing point of rhodium as 1,966
±3° C.
Southard and Milner ^^^ measured the resistance of platinum
and of platinum-10 percent rhodium alloy between 14° and 90° K.,
with an estimated error of about ±0.02°. They constructed a
reference table of R/Ro for platinum between 14° and 109° K.,
giving values for each degree in this interval.
The thermal electromotive forces and the thermoelectric powers
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146 ANNUAL SURVEY OF AMERICAN CHEMISTRY
of a series of platinum-rhodium alloys against pure platinum from
0° to 1200° C. were determined by Caldwell,^^^ ^j^q ^Iso made com-
parisons between these values and those of several other investi-
gators, the maximum difference found being of the order of
300uv. Roeser and Wensel ^^^ prepared reference tables for use
with platinum to platinum- 10 percent rhodium and with platinum
to platinum-13 percent rhodium thermocouples. Through an inter-
change of platinum-platinum rhodium thermocouples and of speci-
mens of silver between the National Physical Laboratory, the
Physikalisch-Technische Reichsanstalt, and the National Bureau
of Standards, an international comparison ^^*» ^^^ of temperature
scales between 660 and 1063° C. was made, with an agreement to
0.1°. Roeser, Dahl, and Go wens ^^^ prepared tables giving the
thermal electromotive force of chromel P against alumel, chromel
P agfainst platinum, and alumel against platinum at various tem-
peratures in the range —310 to 2500° F. In establishing tempera-
ture scales for Cb, Th, Rh, and Mo, spectral emissivities were mea-
sured at A. = 0.667u by Whitney,^^*^ who found, for rhodium, 0.242
between 1300 and 2000° K.
Roeser and Wensel ^^^ described various methods used for test-
ing thermocouples and thermocouple materials, in particular the
methods developed and used at the National Bureau of Standards,
as well as precautions which must be observed to obtain various
degrees of accuracy. Bradley,^^^ in articles primarily for the prac-
tical man, gave information to users of thermocouples, while
Brenner,i2o j^ a paper devoted to recent developments in platinum
thermocouples, discussed the essential requirements, constancy of
calibration and life, and mechanical strength of platinum-platinum
rhodium thermocouples of high quality.
Industry. In an article of a popular nature, Wise^^i related
the march of platinum in industry, while in another paper Wise
and Eash ^^2 discoursed on the role of the platinum metals in dental
alloys, treating particularly of the influence of platinum and pal-
ladium, as well as of heat treatment, upon the microstructure and
constitution of these alloys. Harder ^^3 likewise, in a review, discussed
the use of platinum and palladium in dentistry and in dental alloys.
In a brief article. Carter ^23a discussed the hardening of platinum
by means of iridium, osmium, and ruthenium. Hess,^24 j^ a popular
article, included a brief description of the occurrence, distribution,
and use of platinum. In a paper devoted to the geologfy of the
beach placers of the Oregon Coast, brief reference is made by
Pardee ^^^ to the occurrence of platinum, which is thought to
have been carried from the interior, the original source, however,
being not definitely known.
In a paper covering a survey of testing in the precious metal
field, Wright ^^6 discussed the industrial, household, and personal
uses of the platinum metals. Hoke ^^7 published the second edition
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THE PLATINUM METALS 147
of a booklet, designed for the layman, on testing precious metals,
which was reviewed by Wichers.^^s
Harbison ^^9, i30 stated, in a paper devoted to the plating of
metals by palladium, that for satisfactory results the palladium
should be plated on silver, copper, or a copper alloy, and that if
it is to be plated on iron, zinc, or tin a coating of copper or of
silver should first be applied.
From a critical study of precious metal catalysts for the oxida-
tion of ammonia to oxides of nitrogen, Handforth and Tilley ^^^
concluded that platinum-rhodium alloys containing from five to
ten percent of rhodium are the most advantageous and economical
of any catalysts of this class thus far proposed.
A description of the silver refinery of the Raritan Copper Works
at Perth Aniboy, N. J., and of the recovery of platinum and pal-
ladium therein was given by Mosher.^32
Patents. Wise ^^^^ ^^^ was granted two patents on alloys containing
25 to 98 percent of palladium, 1 to 50 of copper, and 1 or more percent
of silver, suitable for dental uses, electrical conductors, etc., and
assigned them to the International Nickel Company, Inc. A foreign
patent on palladium alloys was later taken out by the International
Nickel Company. ^35 Aderer ^^6, 137 likewise obtained patents on
alloys for dental purposes, one for alloys containing 30 to 40 parts of
gold, 35 to 50 of palladium, 10 to 23 of silver, 4 to 20 of copper,
and 2 to 6 of zinc, the other for those containing 30 to 40 parts of
gold, 35 to 50 of palladium, 18 to 30 of copper, and 2 to 6 of zinc.
Holbrook ^^^ assigned to the H. A. Wilson Company his patent
rights to alloys, suitable for electrical contacts or sparking points,
containing 50 to 90 percent of osmium and 50 to 10 percent of
rhodium. Taylor ^^^* ^^^ patented alloys suitable for dental work
and jewelry formed of 25 to 65 percent of gold, 10 to 33 of silver,
2 to 25 of palladium, 10 to 25 of copper, and 0.5 to 5.0 percent of
indium, and assigned the patents to Spyco Smelting and Refining
Company. His second patent related to similar alloys which
also contained 0.5 to 10 percent of platinum. Baker and Company,
Inc.^*^ was granted a foreign patent on alloys for jewelry, etc.,
containing 40 to 45 percent of palladium, 5 to 10 of platinum, 45 of
silver, and 5 percent of nickel. Capillon and Carter ^^2, 143, 144
received three patents, assigned to Baker and Company, Inc., on
alloys suitable for watch cases, electrical contacts, dentures, etc.
The first patent covered alloys formed of palladium and platinum,
35 to 70 percent (of which amount 5 to 10 percent is platinum), and
the remainder silver. The second patent related to similar
alloys formed with nickel instead of with silver, and the third on
the use of both silver and a nickel group metal with palladium
and platinum.
Bart ^^^' ^*^' ^^"^ took out one domestic and two foreign patents,
assigned to the Precious Metals Developing Company, Inc., relat-
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148 ANNUAL SURVEY OF AMERICAN CHEMISTRY
ing to the prevention of tarnishing of silver articles, such as table-
ware, prize cups, etc., by electroplating them with palladium and
with rhodium. Baker and Company, Inc.^^^ obtained a foreign
patent for the electrolytic deposition of rhodium from a phosphate
solution containing sulfuric acid. A similar domestic patent was
also taken out by Zimmermann and Zschiegner ^^^ and assigned
to Baker and Company, Inc. In another foreign patent. Baker
and Company, Inc.^^<* covered an electrolyte for rhodium plating
made by heating an aqueous solution or suspension of a double
nitrite of rhodium, such as (NH4)3Rh(N02)6- Shields ^^i ^as
granted a patent on an electrolyte comprising an aqueous solution
of a soluble rhodium salt, such as the sulfate or chloride, a soluble
aluminum salt, such as potassium aluminum sulfate or aluminum
chloride, and a free inorganic acid, such as sulfuric or hydro-
chloric acid. Wise ^^2, 133 likewise was granted patents on elec-
trolytes, assigning them to the International Nickel Company, Inc.,
which covered, in one instance, a bath containing a soluble com-
plex nitrite of a platinum group metal and to be operated within
a range, 4:1 to 6:1, of nitrite to platinum metal, and in another
instance, a bath containing an amminocyanide of platinum, pal-
ladium, or rhodium.
Ernst ^^* obtained a patent, assigned to E. I. duPont de Nemours
and Company, Inc., for a process of decorating ceramic surfaces
with a palladium-gold alloy.
Ridler ^^^* ^®®' ^^'^ was granted three patents, assigned to the
Grasselli Chemical Company, on the regeneration of spent platinum
catalysts, used in the oxidation of sulfur dioxide, by means of allyl
alcohol, formaldehyde, oxalic, acetic, and formic acids.
Tilley and Whitehead ^^^ of E. I. duPont de Nemours and Com-
pany, Inc., were given a patent on a catalyst for the oxidation of
ammonia, formed of alloys of platinum and rhodium having a
solid surface of platinum, while Hickey,^^^ assigning his rights to
J. Bishop and Company, patented an alloy of platinum, rhodium,
and cobalt to be used in the form of gauze as a catalyst for the
oxidation of ammonia.
Rodrian ^^^ obtained a patent on a process for the recovery of
gold and platinum from ores. Wise and Vines ^^^ were granted
a foreign patent, assigned to the International Nickel Company,
Inc., for the metallurgical recovery of precious metals from
nickel-copper mattes.
Woodward ^^2 assigned to Kastenhuber and Lehrfeld his patent
rights to an apparatus, used in the manufacture of pen points,
for shattering molten platinum alloys into drops by the action of
a revolving disk.
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THE PLATINUM METALS 149
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THE PLATINUM METALS 151
135. International Nickel Co.. Inc., German Pat. 593,466 (Feb. 26, 1934).
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137. Aderer, J., U. S. Par, 1,965,093 (July 3, 1934).
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141. Baker and Co., Inc., French Pat. 777,839 (Mar. 1, 1935).
142. C:apillon, E. A., and Carter, F. E., I'. S. Pat. 1,999,864 (Apr. 30, 1935).
143. Capillon, E. A., and Carter, F. K., IT. S. Pat. 1,999,865 (Apr. 30, 1935).
144. Capillon, E. A., and Carter, F. E„ IT. s. Pat. 1,999,866 (Apr. 30, 1935).
145. Bart, B., U. S. Pat. 1,947. ISO (Feb. 13, 1934).
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158. Ti^ey, J. N., and Whiteliead, H., U. S. Pat. 2,004,141 (June 11, 1935).
159. Hickty. O. M., U. S. Pat. 2.018.760 fOct. 29, 1935).
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Chapter XL
Electro-organic Chemistry.
Sherlock Swann, Jr.,
Chemical Engineering Division, Engineering Experiment
Station, University of Illinois.
The most notable advances in electro-organic chemistry during
the past several years have been made in the development of new
electrolytes for oxidation and reduction of organic compounds, in
research on the electrolysis of organo-metallic compounds, and on
the electrodeposition of metals from non-aqueous solutions and
from organic electrolytes.
Some of the more important phases of electro-organic chemistry
before 1932 have been reviewed by Brockman.^ This chapter will,
therefore, include material published after this review.
Electrolysis of Aliphatic Acids (Kolbe Synthesis). Wallis and
Adams^ have shown that the 3,4-dimethylhexane formed in the
electrolyses of both d- and ^potassium methylethylacetate is optically
inactive.
The electrolysis of aliphatic acids of the ammonia system has
been studied for the first time by Fulton and Bergstrom.^ They
found that potassium acetamidine in liquid ammonia yielded ethane
in a manner similar to its formation from potassium acetate in
aqueous or alcoholic solutions. Higher homologous amidines
yielded mixtures of methane and ethane, due to deep-seated decom-
position. It is interesting to note that high current densities are
necessary for a successful Kolbe synthesis in liquid ammonia just
as in aqueous solution.
Petersen's preparation of tetracontadiene by the electrolysis of
potassium oleate was repeated by Dover and Helmers*^ They were
unable to obtain the completely pure product described by Petersen.
Electrolytic Oxidation. Rasch and Lowy^ have carried out the
electrolytic oxidation of anthraquinone to hydroxyanthraquinones
at a platinum gauze anode in a concentrated sulfuric acid electrolyte.
Leucobases of triphenylmethane dyes have been oxidized to the
color-bases electrolytically by G. H. White, Jr., with Lowy.* Both
acid and alkali soluble materials have been studied. A platinum
gauze anode was used. Contact between the anode and the depolar-
izer was made by pressing a paste consisting of leucobase and car-
bon into the anode. The compounds used were the leuco-bases of
152
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ELECTRO-ORGANIC CHEMISTRY 153
Malachite Green, Brilliant Green, Guinea Green, and Brilliant
Blue. The colors obtained by the electrolytic oxidation of Malachite
Green, Brilliant Green, and Guinea Green compare favorably with
those resulting from the customary lead dioxide oxidation.
The electrolytic oxidation of naphthalene to a-naphthoquinone
has been studied by E. G. White with Lowy*^ in acid solution.
The anode was made up by the method described in the preceding
paragraph.
McKee and Brockman^ found it impossible to oxidize benzene or
toluene to phenols in the aromatic sulfonate electrolytes which
were so successful in the reduction of nitro to azo compounds
(described under the section on reductions).
McKee and Heard ^ have made further studies of electrolytic
oxidations in sulfonate solutions. They have been able to oxidize
benzyl alcohol and benzaldehyde to benzoic acid in good yields.
An interesting observation made by the investigators was that these
oxidations could be catalyzed by copper and manganese oxides and
by nickel and cobalt hydroxides but not by cerium hydroxide. The
best results were obtained with nickel hydroxide.
In a subsequent paper ^^ the authors have studied the oxidation
of a wide variety of organic compounds. Hydroquinone was oxi-
dized to quinhydrone. The linseed fatty acids showed an oxygen
absorption efficiency of 92 percent. There is some evidence that
hydroxylation of the double bonds takes place during this oxida-
tion. Benzoin was oxidized to benzoic acid in good yield. Toluene,
naphthalene, anthracene, and borneol underwent no oxidation.
It was found that nickel anodes could be used without corrosion
in alkaline solutions of the sulfonates. This makes it possible to
carry out oxidations at a comparatively low oxygen overvoltage and
thus avoid oxidizing the depolarizer to carbon dioxide and water.
Since no organic solvent is necessary for blending the depolarizer
with the electrolyte the efficiency of oxidation in these solvents is
enhanced due to the fact that all of the oxygen may be absorbed
by the depolarizer. Under neutral or alkaline conditions the sul-
fonates are unattacked by anodic oxygen.
A patent has been granted to Youtz ^^ for the electrolytic
hydroxylation of ethylene to ethyleneglycol in caustic soda solution.
Reactions of Organic Compounds with Products of Electrolysis.
Isbell, Frush and Bates ^^ have continued their work on the oxi-
dation of dextrose to calcium gluconate. The oxidation is brought
about by bromine liberated at the anode in the electrolysis of cal-
cium bromide. The method has been found very satisfactory for
the production of large quantities of calcium gluconate. Helwig ^^
has been granted a patent for the electrolytic separation of aldoses
from ketoses, in which the aldoses are oxidized in a similar manner.
Magnesium xylonate ^*' ^^ has been prepared from xylose in the
manner described above, except that magnesium ion was substi-
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154 ANNUAL SURVEY OF AMERICAN CHEMISTRY
tuted for calcium ion. The yields are excellent. Cook and Major ^®
have succeeded in preparing calcium S-ketogluconate from glucose
by the electrolytic method.
Hockett ^"^ has prepared strontium xylonate in excellent yield by
the electrochemical oxidation of xylose.
McKee and Heard ^^ have attempted the electrolytic halogenation
of toluene in sodium xylenesulfonate solution. They found that
both the toluene and the solvent were halogenated simultaneously.
The electrochemical nitration of naphthalene has been studied
by Calhane and Wilson ^^ and optimum conditions determined for
the formation of nitronaphthalene.
Kirk and Bradt ^® have carried out a research on the electro-
chemical nitration of toluene for the first time. Both nitration and
oxidation took place It was found that certain metal salts catalyzed
the nitration.
Electrolytic Reduction of Nitro and Nitroso Compounds. A
number of patents have been taken out on the electrolytic reduc-
tion of nitro compounds. Jewett ^o. 21 has been granted two patents
covering apparatus for this type of reduction.
Cupery22 has found that nitro compounds may be successfully
reduced to amines if the oxygen of the air is kept out of the cathode
compartment by hydrogen chloride gas.
Fieser and Martin 23 have used the method of Gattermann suc-
cessfully for the electrolytic preparation of 4-amino-5-hydroxy-,
4-amino-7-hydroxy- and l-methyl-4-nitro-7-hydroxy-benzothiazoles
from the corresponding nitro compounds.
The same authors have also carried out the reduction of 5(8)-
nitroisoquinoline 24 to 5(8)-amino-8(5)-hydroxyisoquinoline by the
same procedure.
Brigham and Lukens25 have made a thorough study of the
electroljrtic reduction of nitrobenzene to />-amidophenol.
Kerns 26 has determined the optimum conditions for the elec-
trolytic preparation of azoxybenzene from nitrobenzene.
McKee and Brockman ^ have discovered that concentrated
aqueous solutions of the sodium and potassium salts of aromatic
sulfonic acids will dissolve large quantities of organic compounds
and may, therefore, be used as electrolytes for reductions, obviating
the use of a blending agent for putting the organic depolarizer into
solution.
In this medium the authors have carried out the reduction of
many aromatic nitro compounds to the azo stage in excellent yield;
the sulfonate bath becomes mildly alkaline as electrolysis pro-
ceeds. A phosphor bronze cathode was found superior to copper
or nickel. McKee and Gerastopolou 27 have extended this work
to include reductions to hydrazo compounds and amines in acid
solution. The reductions to hydrazo compounds were particularly
successful both in laboratory size and large size equipment.
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ELECTRO-ORGANIC CHEMISTRY 155
Alles 28 found that the electrolytic method was superior to others
for the reduction of certain phenylnitropropylenes to rf/-3-phenyliso-
propylamines.
Cook and France ^^ have succeeded in preparing A/^-amidoisoindoline
in excellent yield by the electrolytic re?luction of iV-nitrosoisoindoline.
Electrolytic Reduction of Carbonyl Compounds. Swann^o has
determined the optimum conditions for the electrolytic reduction
of methylpropyl ketone to pentane at a cadmium cathode in
aqueous sulfuric acid. Swann and Feldman ^i have studied the
effect of other common metal cathodes under the same experi-
mental conditions. Cadmium, zinc, lead, and mercury cathodes
caused the highest yields of hydrocarbon. Swann, Deditius, and
Pyhrr ^2 have compared the behavior of sulfuric-glacial acetic acid
to aqueous sulfuric acid as an electrolyte in this reduction. They
showed that the yields of pentane at different common metal
cathodes corresponded more closely with the hydrogen overvoltage
of the cathode in glacial acetic acid than in aqueous solution. The
yields in the two media differed markedly but were of the same
order of magnitude.
Very small amounts of iron were found by Swann ^3 to lower
the yield of benzopinacol resulting from the electrolytic reduc-
tion of benzophenone at an aluminum cathode in acid solution.
The electrolytic reduction of benzophenone in glacial acetic acid
has been studied by Swann.^* It was found that benzopinacol is
the main product in both aqueous and glacial acetic-sulfuric acid
solution, but that it undergoes rearrangement to the pinacolone in
the acetic acid electrolyte An iron cathode gives the best results.
Even though the hydrogen overvoltages in glacial acetic acid
solution are much higher than in water, reduction does not go to
completion.
The electrolytic reduction of acetophenone in acid solution
has been studied at all the common metal cathodes by Swann and
Nelson.3^ The main products are acetophenone pinacol, bis-
(a-methyl) -benzyl ether, and a resin of unknown constitution.
The best yield of pinacol occurred at a lead cathode.
Kyrides ^^ has used the electrolytic method for the preparation
of 3-methylpentane-2,4-diol from 3-methylpentane-4-ol-2-one.
Creighton ^'^ has improved his process for the electrolytic reduc-
tion of sugars to alcohols in alkaline solution by changing the
mercury cathode formerly used to amalgamated lead. This process
is now operating industrially.
Kyrides and Bertsch ^^ have carried out the electrolytic reduction
of maleic to succinic acid at a lead cathode in a benzenesulfonic
acid electrolyte in high yield.
Muskat and Knapp ^^ have shown that vinylacrylic acid, when
reduced in a sodium chloride electrolyte, undergoes 1,4 addition of
hydrogen to give A^-pentenic acid.
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156 ANNUAL SURVEY OF AMERICAN CHEMISTRY
McKee and Brockman ^ obtained high yields of benzoin by the
electrolytic reduction of benzil in sulfonate solvents.
Cook and France ^o have studied the electrolytic reduction of
phthalimide, phthalimidine, methylphthalimide and methylphthali-
midine at several of the common metal cathodes of high hydrogen
overvoltage. The best yields of isoindolines were obtained at lead
and cadmium cathodes.
Craig,^^ using the method of Tafel and Stem for the electrolytic
reduction of succinimides together with a method for the continuous
extraction of the cathol)rte by chloroform, has succeeded in obtaining
high yields of A^-methyl-a-pyrrolidone from iV-methylsuccinimide.
Electrolytic Reduction of Miscellaneous Nitrogen Compounds.
Cook and France ^^ have studied the electrolytic reduction of o-, m-,
and />-tolyldiazonium chlorides to the corresponding hydrazines. Satis-
factory yields were obtained only at a mercury cathode. The highest
yield was obtained with the ortho-compovaid, while the /»ara-compound
yielded the least hydrazine.
Wenker ^^ has reported some excellent yields of benzylamines in the
electrol)^ic reduction of imido ethers.
Small and Lutz^^ have prepared dihydrodesoxycodeine-B in nearly
quantitative yields by the electroljrtic reduction of desoxycodeine-C.
They have also used the electrolytic method to reduce pseudocodeine to
dihydropseudocodeine-B.**
Morris and Small *^ have used the electrolytic method in alkaloid
researches to reduce S-ethylthiococide-A to dihydro-S-ethylthiocodide-A
and dihydrodesoxycodeine. The electroljrtic method was unsuccessful
in the reduction of a- and 3-ethylthiocodides.
Electrolytic Dehalogenation. Hood and Imes ^® have shown that
the maximum current efficiency in the electrolytic reduction of
chloroacetic acid to acetic acid occurs at a lead cathode.
Electrolysis of Organometallic Compounds. Overcash and
Mathers ^^ have found that dimethylaniline gives the best results
as a solvent in the electrodeposition of magnesium from Grignard com-
pounds. Evans and Lee^^ have studied the anode products in the
electrolysis of Grignard compounds in ether. They found that ethyl-
magnesium halides yielded ethane and ethylene and that propyl com-
pounds yielded propane and propylene. Traces of hydrogen were always
found. A mixture of ethyl and phenyl Grignard compounds yielded
only ethane. In concentrated solution methylmagnesium halides yielded
ethane as the main product. In more dilute solutions methane and
olefins appeared. The authors suggest a mechanism for these reactions.
Evans, F. H. Lee, and C. H. Lee*^ have determined the discharge
potentials of anions in the electrolysis of Grignard compounds in ether.
The anions listed in order of descending potential are : phenyl-, methyl-,
propyl-, butyl-, ethyl-, isobutyl-, isopropyl-, tert-hntyl-, and allyl-.
Adams ^^ compares the above results to those of Derick^^ on the
ionization constants of aliphatic acids and points out that the effect of
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ELECTRO-ORGANIC CHEMISTRY 157
substituting methyl groups in the a-position has the same effect on the
decomposition potentials of the Grignard reagents as on the logarithms
of the ionization constants of organic acids.
Keyes, Phipps, and Klabunde ^^ have patented the method for
electrodepositing aluminum from tetra-alkyl ammonium bromide-alu-
minum bromide solution.
A patent has been taken out by Keyes and Swann ^^ on the electro-
deposition of aluminum from Grignard tj'^pe compounds in ether. Blue
and Mathers ^^ have found that aluminum can be electroplated success-
fully from solutions prepared by allowing aluminum-Grignard com-
pounds to react with aromatic hydrocarbons in the presence of aluminum
bromide. The bath conducts current without the addition of any solvent.
Foster and Hooper ^^ have electrolysed sodium triphenyl germanide
in liquid ammonia. The anode products are hexaphenyldigermane,
triphenylgermane, and nitrogen. At a platinum anode the quantity of
nitrogen corresponds roughly to the amount of triphenylgermane pro-
duced; at mercury it is markedly smaller.
The Electrodeposition of Metals from Non-Aqueous Solutions
and from Organic Compounds in Aqueous Solution. Stillwell and
Audrieth ^® have electrodeposited arsenic, antimony, and bismuth
from their chlorides in glacial acetic acid. It was found that,
under the experimental conditions used, the electrodeposited arsenic
was always amorphous, while the bismuth was crystalline. Depend-
ing on conditions of temperature and concentration, antimony was
deposited in the metastable or in the crystalline form. The
authors point out that the solvent must be considered as an addi-
tional important factor among the conditions which affect the
structure of electrodeposited antimony.
Blue and Mathers ^"^ have succeeded in electrodepositing alumi-
num as an alloy with iron from a solution of their chlorides in
formamide. Aluminum would not deposit in a pure state under
these conditions. The electrodeposition of other metals was studied
from both chloride and sulfocyanate solutions in formamide, but
the results were in general inferior to those obtained in aqueous
solution.
Meints, Hopkins, and Audrieth^® have continued their work on
the electrolytic preparation of rare earth amalgams in non-aqueous
solvents. In this paper they describe the electrodeposition of
lanthanum from the chloride in ethyl alcohol. Jukkola with
Audrieth and Hopkins ^^ has extended this work to include neo-
dymium, cerium, samarium, and yttrium. Experimental details of
the electrolytic preparation of rare earth alloys are given in a
paper by Hopkins and Audrieth.®^
Fink and Young,®^ in a paper on the electrodeposition of cad-
mium-zinc alloys, point out that the function of an addition agent
is not necessarily confined to preventing the growth of large crystals
but may also affect the proportion of the metal ion being deposited
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158 ANNUAL SURVEY OF AMERICAN CHEMISTRY
by forming a complex with it. They found that the only success-
ful addition agents in their work were organic nitrogen compounds.
Since it is known that cadmium forms complexes with such com-
pounds and the corresponding zinc complexes are not found in
the literature, the authors assumed that the cadmium formed com-
plexes, while the zinc did not, with the effect that the proportion
of zinc increased in the alloy plate in the presence of these addition
agents.
Calbeck ^^ has been granted a patent on an electrolytic cell suit-
able for the deposition of sponge lead and lead peroxide from lead
acetate solution.
Electrothermal Processes in Organic Chemistry. Dow^ has
patented a process for the production of carbon disulfide by passing
sulfur vapor over charcoal which has been heated to reaction tem-
perature by an electric current passing through the charcoal and
conducting carbon.
Acetylene and other products have been produced by Nutting
and Rowley ^^ in the thermal decomposition of a hydrocarbon oil
by an electric arc.
The electric arc has been used by Jakosky®*^ in the production
of carbon black by the thermal dissociation of hydrocarbon liquids.
Williams ®® has been granted a patent for converting benzene to
biphenyl in an electric furnace.
Strosacker and Schwegler^^ have taken out a patent on the
preparation of tetrachloroethylene and hexachloroethane by allow-
ing carbon tetrachloride to come into contact with electrically
heated carbon.
Miscellaneous Industrial Applications of Electro-Organic Chem-
istry. Cellulose has been bleached by passing it near an anode in
a sodium chloride solution by Seavey, Phillips, and Olsen.^®
The anode process for the electrodeposition of rubber is dis-
cussed by Beal ^^ and by Hirsch.*^® The following topics are taken
up: electrodeposition on metals, electrodeposition on permeable
materials, anode ionic deposition, the processing of deposits, and
commercial applications.
Watson '^^ has described a successful method for decreasing salts
in whey protein (lactalbumin) by electrodialysis. Lima '^^ has been
granted a patent on the purification of sugar-containing liquids.
The method consists in electrolysis between aluminum electrodes.
The aluminum is attacked and forms salts with the acids of the
liquor. These may be removed by charcoal treatment. Hazzid^^
has isolated the sulfuric acid ester of galactan in an impure state
by the electrodialysis of its sodium salt.
Roberts '^^ has patented a process for breaking emulsions by
subjecting them to repeated action of magnetism at different fre-
quencies. Hanson '^^ and van Loenen '^^ have taken out patents on
the electrical dehydration of petroleum emulsions. In order to
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ELECTRO-ORGANIC CHEMISTRY 159
improve the efficiency of dehydration of emulsions natural gas
is forced into the emulsion under pressure by EddyJ*^ A patent
has been granted to Harlow '^^ for the electrostatic removal of pitch
from gases such as coal gas or producer gas.
A method for preparing catalysts for hydrogenating hydrocarbon
oils has been patented by Weber J^ The hydrocarbon material is
mixed with sodium chloride or a caustic alkali solution and elec-
trolysed between electrodes of iron, chromium, or tungsten. The
electrodes are attacked and the products formed act as hydro-
genating catalysts.
Electrical Discharge Through Organic Compounds. Jaeger ^^
has been granted a patent for the decarboxylation of organic dibasic
acids to monobasic acids by electronic discharge at high tem-
peratures.
Hillis ®^ has patented a process for synthesizing liquid hydro-
carbons from gaseous aliphatic hydrocarbons by subjecting the
gases first to cathode and x-rays and then subjecting them to a
mercury vapor arc discharge under pressure in the presence of
powdered nickel. The latter acts as a dehydrogenating catalyst.
Thornton and Burg with Schlesinger ^2 have found that dichloro-
difluoromethane, while very stable to heat treatment, undergoes
decomposition in the high tension electrical discharge to a variety
of products.
Voltaic Cells with Organic Electrolytes. Bent and Gilfillan ^3
have measured for the first time the electromotive force of galvanic
cells containing alkali metal derivatives of triphenylmethyl as the
electrolyte in ether. They found that, when potassium amalgams
are used for both electrodes, the cells give potentials which might
be expected for normal salts, while if one electrode is pure potassium
the potentials are erratic. The erratic behavior of the latter cell
is due to some change in the electrolyte which takes place in the
presence of potassium.
Organic Dielectrics. The behavior of dielectrics as insulators is
engaging the attention of a number of investigators. Race ^^ has
found that the longer the time of heating a mineral insulating oil
with air, the greater the increase in conductivity when the oil is
heated to high temperature. He also found that oxidation increases
the high frequency dielectric losses but does not affect the fre-
quency at which the maximum loss in each sample occurs.
The conductivities of synthetic resins and varieties of wood as
a function of the temperature have been determined by Clark and
Williams.®^
A symposium on dielectrics was held by the Electrochemical
Society in 1934. The papers on organic dielectrics follow. The
first paper was by Barringer,^^ who discussed the relation between
chemical and physical structure and dielectric behavior from a prac-
tical point of view. Whitehead ^'^ pointed out that dielectric loss
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160 ANNUAL SURVEY OF AMERICAN CHEMISTRY
in insulating liquids is to a great extent due to conduction. Some
general properties of liquid organic dielectrics were discussed by
Karapetoff.^® Clark 8» described new synthetic liquid dielectrics.
Pentachlorodiphenyl, a liquid with a pour point of 10° C, is
superior in many ways to hydrocarbon insulating oils in its stability
to heat and oxidation. This compound when mixed with the proper
proportion of trichlorobenzene has excellent properties as a trans-
former oil. The pour point is lowered to —18° C. with accompany-
ing drop in viscosity. A voltage-time study of the failure of rubber
compound insulation has been made by Mason.®^ Alkyd-resins as
dielectrics have been discussed by Kienle and Race.®^ Finally,
Morgan ^^ has studied the dielectric behavior of halowax and paper,
and glycerine.
The dielectric constant of cellophane has been studied by
Stoops; ^3 it has been found to be nearly twice that of cellulose
acetate.
Clark ^* has found that chemical changes resulting in an increased
power factor and decreased dielectric strength result from heating
cellulose insulation to temperatures higher than 100° C.
White ^^ has pointed out that the maximum dielectric loss factor
in a polar substance increases with decreasing temperature while
in a heterogeneous mixture the maximum decreases with decreas-
ing temperature.
The progress in dielectric research for 1934-1935 has been
reviewed by Whitehead.^®
Oxidation-Reduction Potentials of Organic Compounds.
Research in the field of oxidation-reduction potentials is always
adequately covered in the chapters on analytical, organic, and bio-
chemistry and will, therefore, not be discussed here.
Organic Depolarizers. Hunter and Stone ^"^ have measured the
potentials of several depolarizers against different cathodes. They
found that the order of sequence of the potentials at a series of
cathodes was the same regardless of the depolarizer, but that the
magnitude of the potential changed with different depolarizers.
The order of sequence of the potentials is related to the work
function of the cathode, while the magnitude of the potential at
any given cathode is related to the electron affinity of the depola-
rizer.
References.
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4. Dover. M. V., and Hclmers, C. J., Ind. Eng. Chem., 27: 455 (1935).
5. Rasch, C. H., and Lowy, A., Trans. Electrochem. Soc, 62: 167 (1932).
6. White, G. H., Jr., with Lowy, A., Trans. Electrochem. Soc, 61: 305 (1932).
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10. McKee, R. H., and Heard, J. R.. Jr., Trans. Electrochem. Soc, 65: 327 (1934).
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30. Swann, S., Jr., Trans. Electrochem. Soc, 62: 177 (1932).
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53. Keyes, D. B., and Swann, S., Jr., U. S. Pat. 1,939,397 (Dec. 12, 1933).
54. Blue, R. D., and Mathers, F. C, Trans. Electrochem. Soc. 65: 339 (1934).
55. Foster, L. S., and Hooper, G. S., /. Am. Chem. Soc, 57: 76 (1935).
56. Stillwell, C. W., and Audrieth, L. F., 7. Am. Chem. Soc, 54: 472 (1932).
57. Blue, R. D., and Mathers, F. C, Trans. Electrochem. Soc, 63: 231 (1933).
58. Meints, R. E., Hoj^ins, B. S., and Audrieth, L. F., Z. anorg. allgem. Chem., 211:
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Chapter XIL
Aliphatic Compounds.
M. S. Kharasch and C. M. Marberg,
The University of Chicago.
For the sake of simplicity of presentation, the subject matter
published during the year is discussed under separate topics. A
discussion of the results by the reviewers, while eminently desir-
able, was made impossible by the number of topics and lack of
space. It is hoped, however, that the arrangement used and some
of our comments will give the reader an adequate idea of the
trends of research in the chemistry of aliphatic compounds.
Deuterium Compounds. By far the most interesting work with
deuterium involves the isotopic exchanges, particularly those
carried out at ordinary temperatures. We may as well begin our
review with the polemical papers ; an indication that the analytical
methods have not yet reached a high degree of precision, or are not
sufficiently standardized. Thus, in last year's Journal of the American
Chemical Society, it was reported that an isotopic interchange takes
place between heavy water and acetylene in alkaline solution.^ This
year that claim is contested. No interchange is reported even under
conditions more drastic than those previously described.^ The senior
author of the first publication, however, reaffirms his previous posi-
tion, and records preliminary data on equilibrium studies at different
temperatures and pressures. A mass spectrograph analysis of the
acetylene produced under one set of equilibrium conditions indicated
ten percent of C2HD in the gas mixture.^ There is little doubt now
that the hydroxyl hydrogen atoms of carbohydrates can be replaced
by deuterium merely by dissolving the substances in different con-
centrations of D2O.* Ten carbohydrates were studied and in each
case the exchange number coincides with the number of hydroxyl
groups in the molecule. A more complete study of the kinetics and
equilibrium of the isotopic exchange was made in the case of acetone.*^
Alkali was used as the catalyst, and under those conditions the exchange
is reversible:
CH, . CO . CH, + DOH ?=± CH, . CO . CH,D + HOH.
It is of interest in this connection to recall that treatment of benzene
with D2SO4 (90 percent) at room temperature resulted in an exchange
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164 ANNUAL SURVEY OF AMERICAN CHEMISTRY
of H for D, and that some substituted benzenes exchanged nuclear H
for D more readily.^
A few preliminary papers on heterogeneous catalysis in the exchange
of deuterium and the hydrogen in methane have appeared. Con-
siderable formation of mixtures of deuteriomethanes* is observed by
exposing methane and deuterium to the action of excited mercury'' at
temperatures from 40° to 300°, as well as under the influence of a
reduced nickel catalyst at 184-305°.^
Acetylene and deuterioacetylene (acetylene-d2) polymerize at equal
rates under the influence of Rn a-rays,® but differ considerably in the
mercury photosensitized polymerization.^^ The rate of polymerization is
30 percent greater with acetylene than with deuterioacetylene, over a
considerable pressure range.
In the homogeneous reaction at 524° and 560°, hydrogen and
deuterium combine with ethylene at the same rate,^^ while hetero-
geneous catalysis rates with Cu indicated a rate ratio, H2/D2, of 1.59.
The preparation of pure deuteriochloroform is described.^^ xhe
properties closely resemble those of ordinary chloroform.
Saturated Aliphatic Hydrocarbons and Alkyl Halides. A great
deal of work was done in this field by both organic and physical
chemists. Unfortunately, neither a consolidation of the old posi-
tions nor a distinct advance has been made. No new facts, but a
few improvements in methods of preparation and a few more (pre-
sumably) exact measurements of properties and interactions of
molecules, are recorded. The general picture, however, appears
about as "blurred" as before.
Perhaps the most interesting reaction described is the interaction
of paraffin and olefin hydrocarbons in the presence of the halides
of Al, B, Be, Ti, Zr, Hf, Th, Cb, and Ta as catalysts, and under
otherwise mild conditions.^^ The alkylation of benzenoid hydro-
carbons by paraffin hydrocarbons in the presence of a catalyst is
of interest. Thus, it is stated that 2,2,4-trimethylpentane reacts
with benzene in the presence of aluminum chloride and zirconium
chloride as catalysts to yield a mixture of isobutane and di-^^r^-
butylbenzenes.^^
The hydrolysis of secondary and tertiary aliphatic halides has
been studied. Two papers deal with the action of inorganic bases
on isobutyl bromide and on tertiary amyl halides (chloride and
bromide). The effects of bases (KOH, NaOH, AgOH, and water)
on isobutyl bromide were studied under varying conditions of
temperature and concentration. Olefin yields of 10.8-65.5 percent
were obtained, depending upon the temperature and concentration
of alkali, while the rate of reaction is greater in more dilute solu-
tion.^^ The same factors influence the amount of olefin formation
in the case of the tertiary amyl halides and the percentage of olefin
* For the infrared absorption spectra of methyl deuteride see N. Ginsburg and E. F.
Barker, /. Chem. Phys., 3: 668 (1935).
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ALIPHATIC COMPOUNDS 165
formation is dependent upon the nature of the base.^^ The hydrol-
ysis of secondary and tertiary alkyl halides is unimolecular and
independent of reagent anions. A mechanism of hydrolysis is
postulated.^''
The thermal decomposition of pentane mixed with steam was
investigated at temperatures of 600-800°. Cleavage of the mole-
cule took place, yielding all possible isomers, saturated and unsatu-
rated. The variation of conditions that affects the yield of ethane,
ethylene, and hydrogen is discussed.^^ The isomerization of hep-
tane with aluminum chloride is claimed to yield about one percent
of hexane and four percent of 2-methylhexane, and no other
isomers.^®
Adequate synthetic methods for the preparation of hexadecane,^^
hexadecyl iodide,^! l,5-dibromopentane,22 and dodecyl bromide ^3
are described. The use of alkyl bromides and sodium sulfite
(Strecker reaction) has been extended to the preparation of sul-
fonic acids of octane, decane, dodecane, tetradecane, hexadecane,
and octadecane.2*
A procedure for the classification of hydrocarbons is described.^^
It is based upon miscibility with nitromethane, aniline, and benzyl
alcohol; bromate-bromide titration; and upon the usual constants
(melting point, boiling point, and density). A tabulation of the
number of calculated isomers of the simple aliphatic compounds
has appeared.2^
A discussion of the mathematical papers dealing with the elec-
tronic structure of polyatomic molecules and energies of hydro-
carbon molecules is out of place in this review. Brief mention is
made of this work in case it is not treated in some more appro-
priate chapter. The energies of a number of hydrocarbon mole-
cules have been calculated by the Heitler-London-Pauling-Slater
method. In spite of the agreement of calculated and experimen-
tally determined values, the validity of the additivity rule is ques-
tioned.2''
The ionization potentials of ethane, ethylene, and acetylene are
interpreted in terms of the electron configuration. Of consider-
able interest is the treatment by the author of "reduced" inter-
atomic distances. These are studied as a measure of overlapping
of orbitals of different atoms.^s Spectroscopic data have also been
used in the calculation of the heat capacity of methane and the
four chloromethanes. It is claimed that these figures are more
reliable than the thermal data.^^ A new type of "stereoisomerism,"
in which the two ethyl groups of butane rotate around the central
C-to-C bond, is discussed in a mathematical paper.^o
The mechanism of the oxidation of a few hydrocarbons with
oxygen has been studied. In the case of methane the limiting pres-
sure of low pressure explosion mixtures depends upon the sur-
faces used.3^ An induction period in the oxidation of propane has
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166 ANNUAL SURVEY OF AMERICAN CHEMISTRY
been demonstrated, and a study made of the effect of surfaces on
the reaction.82 Thg oxidation of propane by oxygen is assumed
to be a chain reaction, with the free radicals, propyl (C3H7) and
methoxyl (CH3O), as the chain carriers. The primary products
of oxidation are: formaldehyde, methanol, carbon monoxide, and
water.83 The intermediate peroxide formation in the oxidation of
chloroform by oxygen of air is postulated. The peroxide presum-
ably decomposes to yield phosgene and hydrogen chloride.^^ A
study on the oxidation of iodoform solutions has been reported.^^
The question of methylene versus methyl radicals in the decom-
position of methane is again in the foreground. The validity of
the conclusion drawn from the removal of tellurium mirrors is
questioned, and the view is again put forward that the kinetics of
the decomposition are inconsistent and incompatible with any
mechanism involving methyl radicals, but in good agreement with
the methylene mechanism.^^
A number of papers, photochemical and others, deal with the
halogenation of aliphatic compounds, and the effect of different
radiations on the decomposition of organic halides.
The chlorination of propane in the homogeneous reaction has
been shown to be of the chain type (induction period, inhibitory
oxygen effect, reduction of rate by packing, and explosions). ^^
The chlorination over catalysts was also studied.^® The formation
of 1,2-dichloropropane was shown to be due to the addition of
chlorine to propylene, formed by pyrolysis of propyl chloride. In
the photochlorination of pentane in the liquid phase, with light at
3650 A, the reaction is proportional to the first power of chlorine
concentration.^® The quantum efficiency is 192 ± 14 at 25°.
Carbon tetrachloride is stable to light of 2537 A. In the presence
of oxygen, however, the reaction is assumed to take the follow-
ing course :*^ 2CCl4-f- O2 -» 2COCI2+2CI2. The chlorine-sensitized
photochemical oxidation of chloroform leads to phosgene and
hydrogen chloride. The quantum efficiency is about 100 moles
of chloroform oxidized per einstein of radiation absorbed.*^
The photobromination of tetrachloroethylene is accelerated by
small amounts of oxygen. With large amounts of oxygen as in the
case of chloroform, the halogen-sensitized oxidation begins to play
an important role, with a consequent drop in the rate of bromi-
natidn.* Mixtures of liquid chloroform and liquid bromine react
when illuminated with light of 2650 A in the presence of oxygen,
but not otherwise.*^ The effect of wave-lengths of 4358, 5461, 5770,
and 5790 A on the iodine-sensitized decomposition of ethylene
iodide in solution at 76.6° gave ^^ rate constants of 1 : 0.931 : 0.861.
The absorption spectra of cis- and frawj-dichloroethylenes have been
•It is unfortunate that the accelerating eflfect of HBr on the addition of bromine
to ethylenic compounds is not taken into account or discussed by these authors.
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ALIPHATIC COMPOUNDS 167
photographed from the visible to 750 A.*^ The Raman spectra of 1,14-
and 1,1,2-trichloroethane have been compared.*^
Physical Constants. The heat of combustion of gaseous isobutane
at constant pressure is 686.31 ±0.13 Kg.Cal.,*^ and that for tetramethyl-
methane (neopentane) is estimated as 840.4±1.0 Kg.Cal.^'^ The com-
pressibility of gaseous ethane has been determined and an equation of
state has been formulated in agreement with the data.*® The critical
constants for propane have been determined.*® The specific heat data
of a number of pure liquid hydrocarbons have been collected.^^ An
empirical equation connecting the logarithms of the boiling points and
molecular weights has been developed for normal paraffin hydrocarbons
(with the exceptions of methane and ethane) :^^
logio Tb V K.)= 1.07575 + 0.949128 log^ow -0.101 log,o*w.
The dipole moments of heptyl bromide and butyl chloride in the
vapor state have been determined.**^
Patents, Numerous patents on the replacement of chlorine by
fluorine in halogenated organic compounds were granted. The most
interesting patent ^^ deals with the preparation of CI2CF2 from CCI4,
HF, and SbQs. Another fairly large number of patents deals with
the preparation of alkyl halides, such as ethyl chloride ^^ and tert-hntyX
chloride ^^ by conventional chemical methods.
Very little of any theoretical interest is contained in many patents
directed toward chlorination, purification, and separation of hydro-
carbons, and hence they are omitted.
Olefins. A description of the apparatus ^^ and the heats of hydro-
genation of a few simple olefins has appeared in two papers entitled
"Heats of Organic Reactions." The heats of hydrogenation at 355° K.
of propylene, butene-1, butene-2 {trans and cis)y and isobutene are
30.115, 30.341, 20.621, 28.570, and 28.289 cal./mole, respectively.67
Small amounts of oxygen in ethylene-hydrogen mixtures greatly
increase initial reaction rates in the homogeneous reaction at 538°. '^^
The determination of ethylene bonds in the case of simple alkenes can
be effected most conveniently by a bromate-bromide titration. In cases
of cycloalkadienes the method fails when titrations are made in air.^® A
total asymmetric synthesis by addition of bromine to trinitrostilbene
(in a beam of right circularly polarized light of 3600-4500 A) is
claimed.^^ In view of the small rotations observed, duplication of this
work by other investigators, and extension in directions suggested by
the original investigators, will be awaited with interest. A chain
mechanism for the addition of halogens to ethylenic linkages is sug-
gested :®^
Br -
1. Br-+RCH = CHR >RC-CH
H R
H . Br Br
2. RC-CH + BrBr ^RC-CH + Br"
Br R H R
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168 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The author extends this view to the addition of halogen acids, in spite
of the fact that there is ample literature evidence to the contrary.
Nitric acid adds to Me2-CCHMe and iso-C4H8 to form the tertiary
esters. It does not add to C2H4, H2C = C(C6H5)2, I-G4H8, or cyclo-
hexene. The mechanism of the addition is discussed, and the conclu-
sions drawn are applied in the interpretation of the mechanism of
nitration in the aromatic series.^^
Under pressure, ethylene, but not propylene, combines with solid
cuprous chloride to give CuCl . C2H4. The dissociation pressure of the
compound has been measured at different temperatures.®^
A study has been made of the effect of radicals in molecules of the
II
type — C — C — COOH upon treatment with bases. With the proper
Br Br
choice of substituents, decarboxylation takes place and the bromo olefin
(in 70 percent yield) is readily obtained.®* Reactions of bromo and
dibromo olefins with a number of reagents (EtOH, EtONa, EtSNa,
etc.) are recorded.®^
An interesting competitive study between ethylene and hydrogen for
chlorine has been made. Either in the dark, or when illtuninated,
ethylene reacts with chlorine preferentially.®^
The action of oxygen on 2-butene at high temperatures (375-490°)
yields mainly acetaldehyde and butadine, and small amounts of other
products.®'^ A mechanism involving the intermediate formation of a
peroxide is put forward to explain the results. It is of interest in this
connection that, when amylene is treated with hydrogen peroxide in
the presence of FeS04, Me2C0, CO2, HCOOH, and AcOH are
formed.®^
A large number of unsaturated compounds and unsaturated alcohols
were prepared by the condensation of allyl bromide and crotonaldehyde,
respectively, with Grignard reagents. These were then converted into
alkadienes and alkynes.®® The formation of tetratriacontadiene by
electrolysis of potassium oleate in dilute alcohol has been confirmed. "^^
The preparation of crotyl and methylvinylcarbinyl bromides has been
reported. "^^ The direct addition of organic acids to vinylacetylene yields
esters, which polymerize very readily.'^^ Further condensations with
these esters are described. "^^
The rate of mercuration of ethylenes has been found to depend on a
bimolecular reaction.*^* The effect of surfaces on the addition of bro-
mine to butadiene indicates that, after an initial period, the l,4-.dibromo-
butane, by forming a unimolecular layer on the glass, becomes the
active catalyst.''^
Boron trifluoride is an effective catalyst in the condensation of propyl-
ene and aromatic hydrocarbons. Of interest is the claim that with
this catalyst /)-isopropylbenzene is obtained, while aluminum chloride
gives the m-derivative.*^® Other investigators claim that at high pres-
sure, H3PO4 and H2SO4 are excellent catalysts for this reaction.'^''
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ALIPHATIC COMPOUNDS 169
Patents. A few interesting patents have appeared. These are briefly
mentioned here: the preparation of dichlorobutadiene ;'^s oxidation of
olefins to oxides;*^® preparation of styrene from ethylbenzene ;^*^ and
the selective halogenation of tertiary olefins.^^
Acetylenes. The following references, already quoted, belong in
part to this discussion.^^' 28, 69
4-Methoxy-2-butyne and 2-octyne react with methyl alcohol in
the presence of BF3 as a catalyst to give 2,2,4-trimethoxy butane
and 3,3-dimethoxyoctane, respectively.^^ Some a-unsaturated ethers,
RC(OR') : CH2 are readily obtained by distillation of the 2,2-dimeth-
oxyalkanes with /)-MeC6H4S03H.^3
Another paper of the series "Acetylene Polymers and their Deriva-
tives" deals with the polymerization of oxyprenes and their synthesis
from vinylacetylene.^* A physicochemical study of the high-tempera-
ture polymerization and hydrogenation of acetylene has appeared. ^^
Some accurate physical constants of dimethylacetylene have been
obtained.®^ The dielectric constants of a large number of acetylenic
acids (as well as substituted aromatic acids) have been measured in
dioxane, and the electric moments computed.^'' The position of the
triple bond in acetylenic halides influences the electric moment, which
is least with chloro compounds and greatest with iodo compounds. The .
moments of a large number of acetylenic alcohols have been reported.®^
Patents. It is claimed that organic liquids containing highly reactive
acetylenic compounds (or polymers) can be dehydrated with the aid
of calcium carbide.^® The addition of alcohols to mono- and divinyl-
acetylenes presumably takes place when these components are heated in
the presence of sodium alcoholate.®^ Mercury sulfonate and benzene-
disulfonic acid are supposed to accelerate the addition of acetic acid to
acetylene.®^
Pyrolysis. Qualitative experiments on the decomposition of
methane, propane, and butane on carbon and platinum filaments indi-
cate that the primary decomposition of methane gives methylene and
hydrogen (c/.^^). The energy of activation for the decomposition on
carbon is about 95 K. cal./mole.^^ j^ the case of propane and butane
the primary dissociation is into hydrogen and the olefin. Propylene
then pyrolyzes into methylene and a lower olefin, while butylene may
undergo further dehydrogenation to butadiene. ^^ The attempt is made
to correlate the pyrolysis of ethane, or rather, the equilibrium constant
of the ethane-ethylene-hydrogen equilibrium with the data of the heat
of hydrogenation of ethylene; a cause for the discrepancy is sug-
gested.®*
At 600° the thermal decomposition of pentane proceeds according
to the following equations :
CsH^ > C,H4 + QH, + CH, ( 1 )
C5H,, ^ C3H, + QH« (or QH, + H,) (2)
C5H„ ^QHs + CH^ (3)
CsH^ > C3H8 + C.H4 (4)
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170 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The effects of external factors on the yields of the different products
are discussed.®*^ Summaries of data on the pyrolysis of hydrocarbons
from the standpoint of thermodynamics and chemical kinetics have
appeared.®^' ^'^
The thermal decomposition at, low pressure of propyl-,®® diethyl-,®*
and triethylamines ^^ is reported. Intermediate formation of tetra-
substituted symmetrical hydrazines is postulated in the case of the last
two amines. The hydrazines then undergo further decomposition into
nitrogen and hydrocarbons.
In the presence of an inert gas, but not otherwise, ethyl nitrite vapors
remove metallic mirrors when passed through a furnace at low pres-
sure. ^^^ The thermal decomposition of propyl nitrite is formulated as
a homogeneous first-order reaction:
C,H,NO > NO -f i QH.CHO + i C,H,OH.
It is suggested that the same decomposition takes place in the case of
other nitrites. An estimate of the value (strength) of the O-N-bond
is made.^*^2 The initial thermal decomposition of nitromethane into
nitrosomethane and oxygen is postulated.^^^
The decomposition of acetaldehyde at equilibrium conditions by dif-
ferent catalysts (Ni proved to be best) into carbon monoxide and
methane has been studied. The synthesis from the fragments, how-
ever, was not effected.^*^^ <
Peroxide Effect. The effect of oxygen in promoting the reaction
in an ethylene-hydrogen mixture has already been discussed.^® In the
presence of peroxides hydrogen bromide adds to methylacetylene to
give a quantitative yield of 1,2-dibromopropane, while in the presence
of antioxidants the 2,2-dibromopropane is formed exclusively.^®^ It
has been shown that peroxides, and not the solvent, direct the addition
of hydrogen bromide to allylacetic acid, and that, in the few cases care-
fully studied, peroxides apparently have no effect on the direction of
addition in molecules which do not contain a terminal double bond,
or where the double bond is adjacent to a carboxyl group.^®^
Pol)mierization. The following articles on polymerization have
already been discussed.®' ^®' ®^
That unsaturated compounds polymerize under the action of heat
and pressure, particularly in the presence of peroxides, has been known
for some time. It would appear that the polymerization is a chain
reaction, which, in the case of ethylene, is initiated by the presence of
free methyl radicals.^®*^ A well-planned and painstaking attempt at
elucidation of the kinetics of ethylene pol3mierization was unsuc-
cessful.^®®
All of the other work on the polymerization of ethylene, propylene,
and butylene deals with conditions ^®® and catalysts which produce
large quantities of liquid products. The use of phosphoric acid as a
catalyst in high-pressure polymerization has given some interesting
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ALIPHATIC COMPOUNDS 171
•
results, and some of the resulting compounds have been identified.^^^ A
review of the work on the polymerization of isoprene has appeared.^^^
The work on polymerization and ring-formation is being continued;
the 24th to 27th papers ^^^a i^ ^^j^^ series made their appearance this
year. A new class of linear polymers is described . . (CH2-0-R-0)x. .
These were obtained by the action of alkyl formals on glycols above
tetramethylene. The behavior of these linear polymers to further poly-
merization and to depolymerization is described.^^^ xhe other two
papers deal with the optimum conditions for depolymerization of linear
esters, ^^^ and the formation of meta and para rings in the condensation
of resorcinol and hydroquinone diacetates with glycols of the series
(CH2),(OH)2."*
4-Cyano-l,3-butadiene has been prepared and found to polymerize to
a rubber-like product twenty times faster than isoprene.^^^ a-Dialkyl-
aminomethyl-3-vinylacetylenes are prepared from the amine, para-
formaldehyde, and CH2 : CHC : CH. When treated with 38 percent
HCl containing CuCl, the corresponding a-dialkylaminomethyl chloro-
prenes are obtained. These substances polymerize very slowly.^^®
The pol3mierization of styrene is more sensitive to traces of oxygen
than that of heptaldehyde or citral.^^*^ Mention should be made of a
paper on the relation between solvation, solubility and viscosity of
polystyrenes.^^®
Heating to a high temperature in an open vessel of cyanamide (free
from appreciable amounts of ammonia) gives about 98 percent of the
polymerized molecule (dicyanodiamide).^^®
Patents, Numerous patents have appeared on the polymerization of
the simple olefins by heat and pressure ^^o and with catalysts at rela-
tively low temperatures ( 100-250° ) .^^i The interest in the pol3mieriza-
tion of vinyl compounds to resins has apparently not subsided as yet \^^^
the preparation of useful products by polymerization of methylacrylo-
nitrile,^23 ureaformaldehyde,i24 urea, ammonium thiocyanate and
urea,^^^ of diolefins (butadiene), ^26 jg claimed. Aldol pol3mierizes best
in the presence of minute amounts of a 30 percent solution of sodium
hydroxide. The amount must be so small that the mixture is just
alkaline to phenolphthalein.^27
Alcohols. A 14 percent yield of methanol is obtained from car-
bon monoxide and hydrogen, in the presence of a catalyst (75 atomic
percent Zn and 25 atomic percent Cr in the form of their oxides) at
375° and at a pressure of 178 atmospheres.^28 xhe reduction of
aromatic aldehydes by formaldehyde in the presence of alkali leads
to excellent yields of some aromatic alcohols (anisyl, piperonyl, and
veratryl alcohols ).^29 ^ number of primary alcohols of the type
S,yCH . CH2 . OH have been synthesized; R and R' are straight chain
aliphatic radicals.^^^ A large number of high molecular weight
a,3-ketoalcohols, up to stearoin, have been prepared. ^^i Detailed pre-
parative methods are given for oleyl alcohol (9-octadecene-l-ol),^32
dibutylcarbinol,^33 ^nd trichloroethyl alcohol.^*^
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172 ANNUAL SURVEY OF AMERICAN CHEMISTRY
•
A number of papers dealing with specific anal)i:ical tests for alcohols
have appeared. It is suggested that methyl alcohol be determined in
the presence of large quantities of ethyl alcohol by conversion of the
mixture into the alkyl iodides, and combination of the low-boiling
fractions with trimethylamine.^^^ Isopropyl alcohol is best recognized
by oxidation to acetone with CrOs and H2SO4, and identification of
the latter substance. ^^^ A method has been devised for the analysis
of solvents from the butyl-acetonic fermentation of com mash, contain-
ing butanol, acetone, and ethanol in aqueous solution.^^'^ Some ana-
lytical properties of commercial sulfated alcohols useful in the differen-
tiation of these substances from soaps and sulfonated fatty acids are
described. 138 A rapid, and what is claimed to be precise, method for
the determination of primary and secondary hydroxyl. groups in
organic compoimds, based on the use of acetyl chloride and pyridine,
has been reported.^^®
Two papers have appeared on the effect of substituents and of sol-
vents on the reactivity of acyl and alkyl halides with ethyl alcohol.^^^
The rate of combination was used as a criterion of reactivity. The
solvent was shown to have a sigpiificant influence on the rate.^^^ It
is impossible to summarize these data except to indicate that the differ-
ential effects of solvents upon the reactivities of acyl and alkyl chlo-
rides are erratic. Rather disconcerting is the claim that previous
observations and calculations regarding the rate of interaction of
diphenylchloromethane and alcohol are in error. The data were pre-
viously treated upon the assumption that the reaction is reversible;
further investigation has yielded no evidence of reversibility.^^
A study of the vapor pressure-boiling point-composition relations of
glycol-water mixtures has shown that they follow Raoult's law rather
closely.1^3 Large positive deviations from this law were observed,
however, in the case of the vapor pressures of binary solutions of ethyl
alcohol and cyclohexane.^^* The vapor pressure curves over the range
10-760 mm., the densities, and the indices of refraction have been deter-
mined for the following glycols: ethylene, 1,2-propyIene, 1,3-propylene,
1,3-butylene, and 2,3-butylene.i^^
An analysis of the x-ray diffraction pattern of methyl alcohol has
been made. Of interest to the organic chemist is the suggestion that
methyl alcohol shows short-lived hydrogen binding (dipole binding)
between oxygen atoms of neighboring molecules.^^^
Within certain limits, tert-h\\Xy\ alcohol was found to be a satisfac-
tory solvent for molecular-weight determinations by the freezing-point
method.i4«a
Aldehydes and Ketones. The effects of constitution and of
reagents on the equilibria of enol-keto tautomers is still attracting a
great deal of attention, as evidenced by publications in this country and
abroad. The HNO3 acid-catalyzed enolization (in the two possible
manners) in compounds of the type rf-C2H5(CH3) . CH . COR, where
R is methyl, ethyl, cyclohexyl or benzyl has been studied in glacial
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ALIPHATIC COMPOUNDS 173
acetic acid solution. As a check on the method, the rate of racemiza-
tion of ^/-methylethylacetophenone was compared with the rate of iodi-
nation. The two were found to agree very well.^^*^ The velocity con-
stants of alkaline chlorinations of ketones in solutions more alkaline
than 0.3 M NaOH, were found to be linear functions of the hydroxyl
concentration and the rate of reaction increases in the order : pinacolone,
acetone, acetophenone. An interpretation of the results is suggested.^^^
A third paper of a series on the Michael condensation deals with the
addition of simple ketones to a,3-unsaturated ketones. The data are
interpreted upon the basis that an increase in substitution about an
active CH2 group greatly lowers its reactivity and that the ethyl group
is less effective in that respect than the methyl.^*® The acidity of
brominated ketones (such as MeC0CH2Br) is attributed to the coordi-
nation of the CO group with the (OH) from water. The mechanism
of bromination of a number of ketones and aliphatic acids is dis-
cussed. ^^^ It has been shown that the unusual product obtained in the
condensation of methylchloroform with phenol in the presence of sodium
hydroxide, was not the ketone diphenylacetal or phenyl orthoacetate,
but rather the diphenyl ether of ethyleneglycol. As in similar cases,
it has been shown that this unusual product arises from an impurity
in the starting material — in this case ethylene chloride.^^^ Evidence is
adduced that the bisulfite addition compounds of formaldehyde are salts
of a-hydroxy sulfonic acids. It is suggested that other aldehyde and
keto bisulfites have similar structures. ^'^^
Pyridine is used as the reagent to displace the equilibrium in oxime
formation and thus allow the reaction to proceed to completion. The
procedure has been tested for about thirty aldehydes. ^^^ The effects
of hydrogen-ion concentration and of buffer media on the rate of hydra-
zone formation have been studied. Phosphate buffers were shown to
be about ten times as effective as the acetate in catalyzing the formation
of phenylhydrazones.^^^ The effect of salts on the hydrolysis of diethyl-
acetal, catalyzed by strong acids in water solution, has been studied.
From the temperature coefficient of the reaction, the heats of activation
were determined and found to be independent of the electrolyte con-
centration. ^^^ The rate of diacetone alcohol deal dolizat ion by sodium
hydroxide has been studied at various temperatures. Conclusions are
drawn with regard to the validity of the collision theory and the entropy
of activation for reactions in solution. ^^^ The condensation of a num-
ber of common aldehydes and ketones with nitroaminoguanidine to
yield the corresponding nitroguanylhydrazones is reported. ^^"^
Several papers deal with the physical constants of organic aldehydes
and ketones. The ionization potential of acetone vapor was found to
be 10.1 volts, in good agreement with that calculated from spectroscopic
data.^^^ In the far ultraviolet, acetone shows discrete bands above
1300 A, and only continuous absorption between 1300 and 850 A. A
Rydberg series, converging to an ionization potential of 10.2 volts,
was found.^^^ The far ultraviolet absorption spectrum of formalde-
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174^ ANNUAL SURVEY OF AMERICAN CHEMISTRY
hyde has been investigated and a value of 10.83 volts is suggested for
the first ionization potential of the C= O bond, and about 164 Cal./mole
for the strength of the bond.^®^ A very important paper discusses the
electron configurations of the normal states for several aldehydes and
ketones, and the low excited states of formaldehyde.^®^
Patents, The vapor-phase catalytic reactions appear to be the most
favored means recorded in the patent literature for the preparation of
ketones and aldehydes. Dipropyl ketone is made from butyl alcohol ;^®2
acetone from ethyl alcohol ;^®^ glyoxal from acetylene and oxygen in
the presence of NO ;^®^ acetaldehyde from ethyl alcohol and a dehydro-
genating catalyst (reduced copper together with 1-5 percent chromium
in an inert carrier) ;^^^ and ketones by dehydrogenation of secondary
alcohols.^®® The preparation of acetone from acetylene and steam is
claimed. ^^"^ Another interesting claim is made, pertaining to the prepa-
ration of acetaldehyde and formaldehyde. These substances are presum-
ably formed in substantial amounts when CH4 and CO2 are subjected
to the action of an electric discharge, the frequency of the A.C. not
exceeding 1000 cycles.^®^
Other miscellaneous patents of interest deal with the azeotropic dry-
ing of alcohols and ketones,^®® the preparation of ketobutyl derivatives
and their uses,^*^*^ separation of isomeric pentanones,^*^^ concentration
of aqueous solutions of formaldehyde,^'^^ ^nd the preparation of alkoxy
acetaldehydes and alkoxyacetic acids.^'^^
Carboxylic Acids. A most interesting paper deals with the opti-
cal resolution of an allenic acid.^*^^ The resolution was accomplished
by means of the brucine salt of its glycolic ester, and rotations of [a]D
= 4-29.5° and —28.4° were obtained for the active glycolic esters
of the acid
C.H«\ /QHs
C=C=C
HOOC/ \QoH,
The effect upon optical rotation of the number of CH2 groups inter-
vening between the asymmetric carbon atom and a substituent carboxyl
group has been investigated in an extensive series of compounds.^*^^*
The results are correlated in terms of config^rational relationships of
the acids.
The hydrogenation of carbon dioxide in the presence of a variety
of amines yields formic acid or formamides.^*^^ Acetic acid formation
in the vapor phase from methanol and carbon monoxide has been
studied.^*^® Because of side- reactions, and the short life of the phos-
phoric acid catalyst, the process is unsatisfactory. Formic acid has
been dehydrogenated in the presence of aluminum oxide and phosphate,
silica gel, alone, and with phosphorus, thorium, and thallium oxides.^'^'^
Under suitable conditions, at about 300°, 90 percent decomposition
occurs.
A method for the preparation of formic acid of high concentration
has been described.^*^^ The statement that />-bromophenacyl formate
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ALIPHATIC COMPOUNDS 175
is a solid derivative of formic acid, melting at 140°, is reaffirmed.^''®
It has been reported that the presence of acetic acid permits the direct
acidometric titration of /)-hydroxybenzoic acid, using bromthymol blue
as indicator.^8^ The hydrogen electrode (Pd and Pt) has been used
for the determination of the dissociation constants of a series of acids
and amines in ethanol.^®^ The relative strengths of a large series of
carboxylic and phenolic acids, in butyl alcohol, have been investi-
gated.^^2
The rates of oxidation of formate and oxalate ions by halogens in the
dark is in agreement with the empirical expression: Rate = a ^(«^^/3i?r)^
where e is the natural log base, E is the oxidation reduction potential
of the system, and n, F, R, and T are the conventional electrochemical
symbols. ^^3' ^®*
Pyruvic acid condenses with veratric aldehyde in alkaline solution
to give a 50 percent yield of 3,4-dimethoxybenzalpyruvic acid.^®^
Numerous derivatives of this acid are also described.
Phenylketene is formed in the dehalogenation of 3-bromophenyl-
pyruvic acid by means of aqueous AgOH. Under suitable conditions
a 94 percent yield of phenylacetic acid has been obtained.^®® The
extension of the method to the preparation of other ketenes is suggested.
The dimensions of the sodium palmitate molecule have been
reported ^s'^ to be 23 by 6.2 by 3.7 cm. X lO"®.
A method for the determination of thionyl chloride in the presence
of its decomposition products was worked out;^®^ it is based upon the
reactions of thionyl chloride, and its thermal decomposition products,
with oxalates and formates.
Patents, Catalytic reactions for the preparation of organic acids
still hold their preeminence in the patent field. ^^^ Other patents on
acids issued during the year are of little theoretical interest.
Ethers. Butan-2-ol is partly polymerized to 3,4-dimethyl-2-
hexene, and partly transformed into di-^^c-butyl ether by 75 percent
sulfuric acid at 80° under pressure.^®^ Variable yields of aliphatic
ethers (3-32 percent) are obtained in the interaction of sodium alk-
oxides with alkyl halides. The bromides are most suitable for this
purpose. In addition to ethers, amines and olefins are formed in this
reaction.^®^ Methods for the preparation of higher 2-alkyl ethers of
l,3-dibromopropane,^®2 dialkyl ethers of 2,2-bis-(hydroxpyhenyl)-pro-
pane,^®^ and a-unsaturated ethers have been described. The ct-unsatu-
rated ethers were made by the distillation of 2,2-dimethoxyalkanes with
/>-toluenesulfonic acid.^®^ The electric moments of a number of dialk-
oxyalkanes have been determined. ^^^ It is claimed that the valence
angle (O) is constant in
H\ /0\ Me\ /0\
C ^ and C e.
H/ \0/ Am/ \0/
Under certain conditions antimony pentafluoride interacts with tri-
chlorodimethyl ether to yield difluorochlorodimethyl ether and trifluoro-
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176 ANNUAL SURVEY OF AMERICAN CHEMISTRY
dimethyl ether. ^^^ The catalytic chlorination of dioxane has been
studied, i^*^
Patents, In spite of the variety of terminology employed (hydra-
tion, hydrating, absorption reactions, etc.) it is the old method of
preparation of alcohols from olefins in the presence of acid that con-
stitutes the basic idea disclosed in numerous patents granted in this
country.^®^ The direct oxidation of hydrocarbons to alcohol and alco-
hols, aldehydes, and acids is claimed in others.^®® New catalysts for
the methanol synthesis are claimed.^*^^ New ethers, particularly mixed
tertiary, and improved preparatory methods for known ethers, are
claimed.2<>i The reviewers have failed to find a "really new idea" in
any of the patents. That some of them are definite improvements in
the art is not disputed; most of them, however, are "pure invention."
Esters. The "acetoacetic ester condensation" has been used to
explain the intramolecular condensation of ethyl a-ethyl-a'-carbethoxy-
adipate to 2-ethyl-2,5-dicarbethoxycyclopentanone.202 Two comprehen-
sive papers deal with the mechanisms of reactions of acetoacetic ester,
the enolates, and structurally related compounds. In the first paper,
carbon and oxygen alkylation is discussed,203 and in the second the
reactions of sodium enolates toward acyl chlorides.^^^^ The papers do
not lend themselves to a brief review, but are strongly recommended
to all interested in tautomerism. The cyclizatiori of certain ethylene-
dimalonic esters by sodium ethoxide to cyclopentanone derivatives has
been studied and a reaction mechanism is suggested.205
A study has been made of the extent of replacement of one alkyl
group by another in the alcoholysis of various acetates. The relative
replacing values of fourteen alkyl groups referred to methyl have been
calculated.206 it is claimed that the mechanism of alkaline hydrolysis
of ethyl carbonate consists of a reaction of the second order followed by
one of the first order. The velocity constants of the two reactions were
determined and the temperature coefficients computed.^o'^ -
Methods are given for the preparation 6f 2,3-dihydroxypropyl-
malonic ester, its propyl homolog,208 the glycol esters of dibasic kcids ^^
(the di-3-hydroxyethyl esters), and a synthetic fat (trinonodecylin).^!^
Patents. An earnest effort was made by the reviewers to classify the
patents on esters, but in spite of many hours of effort the task at the
end appeared as hopeless as at the beginning and hence they are
omitted.
Nitrogen Compounds. The thermal decompositions of amines,
nitro compounds, and nitrites have already been discussed.®^-^^^ The
explosion of gaseous diazomethane has been noted at temperatures
slightly above those used in measuring the rate of its quiet decom-
position. An explanation based upon the Semenoff theory of explo-
sions is advanced.211 This theory also explains in a reasonably satis-
factory way the explosion of ethyl azide.^^^
The dipole moments of nitromethane and chloropicrin were calcu-
lated. From a study of the dielectric constant of nitromethane in the
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ALIPHATIC COMPOUNDS \77
liquid and solid states, the conclusion is drawn that it does not show
any molecular rotation in the solid state.^i^ The infrared absorption
spectra of a number of aliphatic and aromatic nitriles are characterized
by a well-defined absorption band at 4.4 for the alkyl and at 4.5 for
the aryl nitriles.^i*
Rearrangement of diazo-(3,(3,(3,-triphenylethane into triphenylethylene
(as the main product) has been effected. A concise discussion of the
bearing of these results upon the theory of the mechanism of primary
amine nitrite decomposition, and some molecular rearrangements is pre-
sented.215 A 26 percent yield of ethylene imine is claimed by the
dehydration upon heating of ethanolamine hydrosulfate.^!® The prepa-
ration, and some of the properties, of allylnitrosourethane and vinyl-
diazomethane have been recorded.^^^
Improved methods have been reported for the preparation of nitroso-
methylurea,2i8 diazomethane,^!^ and acetonecyanohydrin.220 The series
of normal aliphatic thiocyanates has been completed up to fourteen
carbon atoms.221 Four new amidines were prepared by the applica-
tion of the usual amidine synthesis.222 The preparation of nitroso-
guanidines by reduction of nitroguanidines is of interest. Either cata-
lytic hydrogenation 223 or zinc and ammonium chloride 224 j^ay be
employed.
Satisfactory yields of amides containing more than seven carbon
atoms are said to result from the interaction of the acids and urea at
180-250°. 225 Several normal fatty acid amides of ethylenediamine
have been prepared. The appearance of many under the polarizing
microscope is described.226
The effect of structure and configuration upon the course of the
reaction of acylated ketoximes with alkali has been investigated. Two
types of reaction have been found to take place, one a hydrolytic split,
and the other a second-order Beckmann cleavage.227 The reaction of
ethyl nitrite with certain isopropyl and cyclohexyl ketones has been
invest igated.228 The vesicant properties of chlorinated ethylamines have
been pointed out.229
Patents. Improved methods for preparation of carbonate salts are
claimed.230 Claims are made for the preparation of amines from the
alcohols (or phenol) and ammonia with the aid of catalysts in the
vapor phase.231 Glycerol is claimed as a solvent in the condensation
of secondary amines with alkyl halides.232 The successful demethy-
lation of trimethylamine to dimethylamine is claimed.233 The prepa-
ration of amino alcohols is still attracting attention ;23* their prepara-
tion by the hydrogenation of monosaccharides in the presence of
ammonia and a catalyst is claimed. ^^s Numerous amidines have been
patented.236
Amino Acids. An adaptation of the Knoevenagel reaction has
led to preparation of some 3-amino acids.237 Note also the prepara-
tion of glutamic acid hydrochloride from zein (obtained from gluten
press cake). 238 The first of a series of papers on multivalent amino
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178 ANNUAL SURVEY OF AMERICAN CHEMISTRY
acids and peptides has appeared. The paper deals with the synthesis
of certain quadrivalent amino acids and their derivatives. Conven-
tional methods were employed in the preparation of these substances.^^o
The formol titration of amino acids has been studied by two investi-
gators. Both authors reach the conclusion that each amino group
reacts with one (or two) moles of formaldehyde, at />H 8-10. The
titration constants for arginine, histidine and lysine are given in one
paper,24o and those of glycine, alanine and proline in the other.^^i It
has been shown that amino acids are sufficiently basic in glacial acetic
acid to permit titration with 0.1 N HC104.2^
Several physicochemical papers on amino acids and peptides have
appeared. These deal with the compressibility of solutions of amino
acids,243 molal heat capacities,^** the dielectric constants and electro-
strictions of the solvent in solutions of tetrapoles,^*^ apparent disso-
ciation constants,^*^ heats of solution, heats of dilution and specific
heats of aqueous solution,^*^ solubilities of derivatives of amino acids
in alcohol-water mixtures,^*^ and the distribution coefficients of amin6
acids between water and butyl alcohol.^*® A discusssion of any of
these papers here is inadvisable in view of the comprehensive and
detailed summary of recent physicochemical studies on amino acids and
proteins.^^^
Sulfur Compounds. A number of alkyl sulfonic acids have been
S)mthesized. The butyl compound was prepared by oxidation of the
mercaptan with HNO3.251 An improvement of the silver nitrate
method of determining mercaptans in hydrocarbon solvents has been
described.262
The reaction of sulfur dioxide and olefins in the presence of per-
oxides has been carefully studied. Propylene was found to give a
polypropylenesulfone. A structure for the compound is suggested.^^^
In the third paper of the series the reactions with higher olefins are
studied and some limitations of the reaction are indicated. The cleav-
age of the polysulfones with alkali was carefully studied.^^* Compound
formation between a number of aliphatic and aromatic amines and
sulfur dioxide is recorded. The 1 : 1 ratio of SO2 to amine predomi-
nates in the systems studied, although 1 : 2 and 2 : 1 ratios were also
obtained.255 The heats of combustion of 1 -cysteine, 1 -cystine, B-thio-
lactic acid and 3-3-dithiolactic acid are recorded,^^^ as well as their
heat capacities, entropies, and free energies.^^'^
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2,006,157 (June 25. 1935) ; Peski, A. J. van, U. S. Pat. 1,999,621 (AprU 30, 1935) ;
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ALIPHATIC COMPOUNDS 183
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Chapter XIIL
Carbocyclic Compounds.
W. E. Bach MANN and F. Y. Wiselogle,
University of Michigan.
As a result of the interest in carcinogenic, oestrogenic and other
biologically active substances, considerable work has appeared on
the synthesis of derivatives of phenanthrene and other condensed
ring systems, sufficient to justify the inclusion of a section entitled
"Polycyclic Compounds." Other fields in which activity continues
to be manifested include free radicals, the Grignard reaction, molec-
ular structure, mechanism of reaction and stereoisomerism.
Alicyclic Compounds. Bis-2,2'-(l,3-diphenylindenol-3) (I) has
been synthesized by Eck and Marvel ^ and by Koelsch and Richter ^
by two different methods ; the product proved to be different from that
of Dufraisse and Badoche but the difference may be one of stereo-
CeHe
i
C«Hi OH HO CHs
V V
OeHs CftHs
(n)
CHa — CH2
CH, C
CH,-CH,
CH-
i
CH
(HI)
-CH-CO
CH CH-do
isomerism. Treatment of the corresponding dichloride with silver did
not give the expected rubrene, (II), but 40 percent sodium amalgam
appears to give an alkali derivative from which the rubrene may be
obtained. The maleic anhydride addition products of all types of ful-
venes (III) dissociate in solution at room temperature ;3 the rate of
dissociation is greater than the rate of hydrolysis but the addition prod-
ucts may be stabilized by stepwise hydrogenation, the semicyclic double
184
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CARBOCYCLIC COMPOUNDS
185
bond being the last attacked. A polyene (probably IV) has been pre-
pared from a-ionone by Milas and McAlevy which has properties
Me Me
V
H^C CH-CH = CH-C(Me) = CH-CH = CH-C(Me) = CH-CH8
H,C C-CH,
H
(IV)
resembling those of vitamin A> Intermediate ketones in the synthesis
of perhydrovitamin A have been synthesized by condensing acetylene
with 3-ionone and with tetrahydroionone using potassium /^r^-amylate
as a condensing agent.^ Some bromine derivatives of indene and indane
have been prepared and their structures have been established.®
Compounds Containing Active Methylene Groups. The action
of acetyl and benzoyl chlorides on the sodium derivative of acetoacetic
ester gives the C-acyl esters directly; the intermediate 0-acyl deriva-
tives postulated by Claisen are not formed.*^ Further confirmation for
the mechanism of the malonic ester condensation proposed by McElvain
has been obtained.^' ^ Esters of the type (V) are cyclized by sodium
ethylate through the intermediate aldol (VI) to cyclopentanone deriva-
tives (VII) with elimination of ethyl carbonate. Because of the
R
CH2-C(COOEt)2
CH,-Cj
k
;cooEt)2
(V)
R
CH,-C-COOEt
\c(OH)OEt
iH2-(5(COOEt)2
(VI)
i
R
CHi-C-COOEt
Nc=o
H2-C-C00Et
(vn)
absence of an a-hydrogen in the intermediate, the reaction involving
elimination of a molecule of alcohol cannot take place. The ccmdensa-
tion of benzoylformanilide, CeHsCOCONHCeHs, with malonitrile,
cyanoacetamide, ethyl cyanoacetate,^® acetone, ethyl phenylacetate and
diethyl malonate ^^ has been investigated. In the Michael condensation
of simple ketones with a,3-unsaturated ketones, increase in substitution
about an active methylene group greatly lowers its reactivity. ^^ a,a-Di-
haloacetophenones containing two ortho groups are acidic, dissolving
in alkalies and being regenerated from their salts on acidification.^^
Compounds Containing Conjugated Systems. The addition of
Grignard reagents to compounds containing conjugated systems has
been the subject of a number of investigations. The properties and
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186 ANNUAL SURVEY OF AMERICAN CHEMISTRY
reactions of the ketosulfone, CeHgCOCH = CHSOgCeHg, are quite sim-
ilar to those of dibenzoylethylene ;^* with phenylmagnesium bromide the
principle reaction is 1,4 addition to the conjugated system C= C— C = O,
although some 1,2 addition to the carbonyl group takes place. a,3-Un-
saturated sulfoxides, C6H5 — CH = CHSOC7H7, are cleaved by Grig-
nard reagents, a behavior entirely different from that of the sulfones.^^
While ethyl- and phenylmagnesium bromides add 100 percent to the
1,4 positions in benzalpropiophenone, methylmagnesium iodide gives a
75 percent yield of an indene which appears to be derived from a pri-
mary 1,2 addition.^® 2,3- Dimethyl- 1,4-naphthoquinone, which reacts
more like duroquinone than anthraquinone, gives with phenylmagnesium
bromide (a) a reduction product, (b) 1,2 or 1,4 coupling or both.^''
Phenyl- and ethylmagnesium bromides add 1,6 to methyleneanthrone ;^8
methylmagnesium iodide and fuchsone give />-hydroxy- 1,1,1 -triphenyl-
ethane.^® These are the only established cases of 1,6 addition of a
Grignard reagent to a conjugated system of multiple linkages. Benzal-
anthrone takes on methyl- or phenylmagnesium bromide in the 1,2 posi-
tions, giving a very sensitive dihydroanthranol.^^ Anthraphenone
undergoes 1,6 dimolecular reduction with phenylmagnesiimi bromide
but 9,10-dihydroanthraphenone undergoes normal 1,2 addition.^o These
meso-unsaturated anthracene ketones offer striking analogies to
a,3-unsaturated ketones. Phenylmagnesium bromide and the ketene,
Et(EtOOC)C = C=0, or its cyclic dimer, give 3-keto esters, indicat-
ing probably 1,2 addition to the ketene carbonyl group.21
Addition of certain mercaptans to the ethylenic linkage of a,P-unsatu-
rated ketones takes place readily without catalysts ;22 thus, benzalaceto-
phenone takes on />-tolyl- and benzylmercaptans and forms compoimds
of the type C6H5CH(SR)CH2COC6H5. Similar addition to corre-
sponding esters takes place if piperidine is present. The mesitylene
group has no conspicuous effect on the general reactions of compounds
of the type CgHnCH = CHCOCgHn ; corresponding derivatives of tri-
phenylbenzene react less readily but it is difficult to determine to what
extent the difference is attributable to space relations.^^ Mesitylben-
zylglyoxal C6H5CH = C(OH)COC6H2(CH3)3 is entirely enolic m the
solid state but ketonizes to the extent of 10-20 percent in solution; the
diortho groups offer steric hindrance to all addition reactions to the
carbonyl groups except reduction.^* Treatment of glycosidic ethers of
the type C6H5C = C(OR)COC(OR)C6H5 with acid or alkali splits
^ O '
off the glycosidic alkyl group and gives open chain monoalkyl deriva-
tives of benzoylformoin such as CeHjCCOH) =C(OR)COCOC6H5.2«
Fuson, Weinstock and Ullyot have found that benzoins can be readily
synthesized from a-ketoaldehydes and aromatic hydrocarbons by the
action of aluminum chloride: RCOCHO-hR'H-»RCOCH(OH)R'.2«
In benzene solution mesitylglyoxal and the corresponding benzoin
undergo auto-oxidation and reduction to mesityl phenyl diketone and
l,2-di-(2,4,6-trimethylbenzoyl) -ethylene glycol. CiHnCOCHCOH)-
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CARBOCYCLIC COMPOUNDS 187
CeHg + 2C9HnCOCHO -» CgHnCOCOCeHg +C9HnCOCH(OH)-
CH(OH)COC9Hii. Various reactions of compounds containing con-
jugated systems have been reviewed.^^
Free Radicals. H. Bent and co-workers have been making a
careful study of the electron afiSnity of free radicals ;28-83 ^U free radi-
cals studied appear to have about the same electron affinity. Dissociation
may be explained by assuming that the ethane C-C bond is abnormally
weak or that the radicals are stabilized because of a large resonance
energy ; dissociation appears to be a combination of the two and weaken-
ing of the bond may be due to steric hindrance. From results of a
quantitative absorption spectra study Anderson has obtained confirma-
tion that triphenylmethyl in ether and sulfur dioxide exists in a quino-
noid modification.^* In dilute solutions in sulfur dioxide there appears
to be not only complete dissociation of the ethane but also quantitative
formation of the triphenylmethyl cation; in concentrated solutions the
color of the free radical may be ascribed to non-ionized triphenylmethyl
rather than to the anion.
Marvel and co-workers have s)mthesized a series of hexa-/>-alkyl-
phenylethanes 3^ and di-/>-alkylphenyldibiphenyleneethanes;^® the eth-
anes are readily oxidized by air to crystalline peroxides; the color of
the radicals increases with the weight of the alkyl groups. Free radi-
cals containing the phenanthrene group and the corresponding per-
oxides have been prepared.^"^ Treatment of triphenylchloromethane
with silver hyponitrite gives immediate evolution of nitrogen and a
variety of products are formed; the intermediate formation of the
(C6H5)3CO— radical is postulated.^^ Triphenylboron adds sodium
and is considered to be a free radical.^® Tri-a-naphthylboron adds two
sodium atoms, the second atom being held very much ICvSs firmly than
the first; conductance experiments reveal, however, that both sodium
atoms ionize simultaneously.^^ The two electrons furnished by the
two sodium atoms are localized in the ion on a carbon atom in a
quinonoid ring.
Grignard Reaction. Porter has found that complete racemiza-
tion takes place in the preparation of the Grignard reagent from an
optically active halide.^® The decomposition voltage of a molar solu-
tion of phenylmagnesium bromide is 2.17 volts, which is considerably
higher than the decomposition potentials of simple alkylmagnesium bro-
mides.*® The study of the relative rates of formation of Grignard
reagents has been continued ; there is no essential diflference in the rates
of formation of o-, m-, and />-tolylmagnesium bromides, but 3-naphthyl
bromide reacts less readily than o-naphthyl bromide, which in turn is
less reactive than bromobenzene.*^ Yields of Grignard reagents and
organolithium compounds have been compared *2 and the effect of sol-
vent and temperature on the equilibrium: 2CeH5MgBr^ (C6H5)2Mg
-|-MgBr2 has been studied. *3 Directions for the preparation of an
effective activated magnesium catalyst are given.**
a-Bromoacetomesitylene is largely reduced by magnesium, acetome-
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188 ANNUAL SURVEY OF AMERICAN CHEMISTRY
sitylene being obtained in 45 percent yield along with 10 percent of the
coupling product, l,2-di-(2,4,6-trimethylbenzoyl)-ethane.^5 x^g study
of the reaction between Grignard reagents and o-bromoketones is being
continued;** the first step probably consists in formation of a complex
addition product, which may rearrange into a normal addition product
or decompose to give metathetical products, depending upon space rela-
tions and relative affinities. The reaction of phenylmagnesium bromide
with dibenzylmalonitrile and other malonitriles has been studied;
dibenzylmalonitrile adds one equivalent of Grignard reagent to yield a
compound which decomposes into phenyl cyanide and (C6H5CH2)2C-
= C = NMgBr>'^ o-Naphthoic acid can be conveniently prepared from
a-naphthylmagnesium bromide and excess diethyl carbonate, steric hin-
drance preventing immediate formation of the ketone or carbinol.*^
The Grignard reagent has been applied to the s)^thesis of anthracene,
dihydroanthracene, acenaphthene, fluorene and phenanthrene deriva-
tives.*® The Grignard reagent does not add to imsaturated linkages
of hydrocarbons at temperatures as high as 300°.^®
Methods of Identification. Aromatic hydrocarbons can be iden-
tified by condensing them with phthalic anhydride to o-aroylbenzoic
acids which can be dehydrated to the corresponding quinones.^^ Alde-
hydes and ketones can be identified by condensing them with nitro-
aminoguanidine ; hydrolysis with 20 percent hydrochloric acid regener-
ates the aldehyde or ketone.^^ Phenols can be condensed with 2,4-di-
nitrochlorobenzene giving highly crystalline stable solids suitable for
identification.^^ A number of 3-nitrobenzohydrazones and 2,4-dinitro-
phenylhydrazones have been prepared for the identification of carbonyl
compounds.^* A large number of aromatic acids have been coupled
with benzylamine and a-phenylethylamine to give derivatives which
may serve for identification.^^ Acetyl chloride possesses advantages
over acetic anhydride for the quantitative determination of hydroxyl
groups; the method is applicable to aromatic alcohols and phenols.^®
Bryant and Smith have discovered that addition of pyridine displaces
the equilibrium between aldehyde or ketone and hydroxylamine in the
direction of oxime formation, which is an important contribution to the
preparation of oximes ;^'^ by this method, with the modification of leav-
ing out water entirely, the reviewer has prepared oximes which failed
to form in aqueous-alcoholic solutions without the addition of pyri-
dine. Contrary to previous reports, /)-bromophenacyl formate can be
prepared.^^
Quantitative light absorption curves in the infra-red region are given
for a number of organic compounds containing the NH, NH2 and OH
groups;^® it is suggested that these curves should prove suitable for
identification of the particular groups and to determine any coupling
eflfects.
Molecular Rearrangements. Stoughton has studied the Fries
rearrangement of esters of a-naphthol and the lower fatty acids; the
main product was 2-acyl-l-naphthol in 50-60 percent yields.®** 4-Acetyl-
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CARBOCYCLIC COMPOUNDS 189
1-naphthol gave the same products when treated with aluminum chlo-
ride as a-naphthol acetate ; in view of this result it is impossible to state
whether the reaction is intra- or m^f»rmolecular. o-Isobutylphenol
derivatives are conveniently prepared by rearrangement of methylallyl
phenol ethers followed by catalytic reduction; furans are also obtained
in the rearrangements. ^^ Alkenyl ethers of pyrogallol rearrange to
alkenylpyrogallols at 200°. ^^ Condensation of g-phenylethyl alcohol
with phenol gave />-( a -phenylethyl) -phenol; dehydration of the alcohol
probably precedes addition of the phenol.^
Nine diaryldihydrophenanthrenediols (VIII) have been rearranged
by Bachmann and Chu; in all cases the group R migrated and diaryl-
phenanthrones (IX) were formed exclusively.®* According to Kohler
R-C-C-R R-C-C=0
i I I
HO OH R
(vm) (IX)
and Bickel 3-oxanols of the type (X) may either undergo cleavage or
a molecular rearrangement; cleavage depends on replacement of the
CJIsCH(OH)CH-C(C6H5), <r- C6H5CH-CHC(OH)(C«H5)2
O
-> CHsCHaCHO + (C.H6),C0
hydrogen of the hydroxyl group by a metal.®^ The Grignard reagent
from phenyl-/^rf-butyl-/^r^-butylethynylbromomethane gives allene
derivatives, (CH3)3CC(X) =C=C(C6H5)C(CH3)3, where X repre-
sents the group introduced by the reaction.®®
A number of rearrangements of nitrogen compounds have been
observed. Hellerman and Garner found that diazo-3,B,(3-triphenyl-
ethane (C6H5)3CCHN2 is readily converted to triphenylethylene by a
variety of reagents ; acetic and benzoic acids, however, decompose solu-
tions of the diazo compound in a unique way, giving benzyldiphenyl-
methyl acetate (or benzoate).®"^ That the Curtius rearrangement of
a-bromoacid azides can lead to the formation of carbonyl compounds
as pointed out by von Braun has been confirmed.®® o-Nitrophenyl-
sulfanilide (XII) was rearranged by heating in the presence of excess
of aniline to give a 70 percent yield of (?-nitrophenyl-/>'-aminophenyl
sulfide (XIII) ;®® heating in alcoholic sodium hydroxide solution gave
o-mercapto-o'-nitrodiphenylamine (XI) 'P^ thus, the sulfanilide may,
o-0,NC.H4NHCeH4SH-o < o-CNQH.SNHCeH. >
(XI) (Xn) o-0,NCeH,SCeH,NH,./»
(xm)
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190 ANNUAL SURVEY OF AMERICAN CHEMISTRY
depending on conditions, undergo both ortho and para tjrpes of
rearrangements.
Molecular Structure. Gomberg and Gordon ''^ have shown that
the colored compounds formed in the reaction between triarylmethyl-
thioglycoUic acids, R3CSCH2COOH, and metal halides (or perchloric
acid) are not, as has been postulated by Wallis, merely addition com-
pounds of the thio compound with the halochromizing agent, but are
double salts of the triarylmethyl halide and the metal halide, R3CCI-
. MeG„ ; the primary reaction consists in a cleavage of the C-S linkage
by the metal halide, forming a triarylmethyl halide, the latter then com-
bining with a molecule of the salt. The color and salt-like character
of the compounds are entirely expressed by the quinocarbonium salt
structure ( RgC = C6H4 < H ) +X-.
Physical methods have been applied to a considerable extent to deter-
mine the structures of compounds. The structure (R2C = 0H)+-
OSO3H' is postulated to account for the colors associated with aliphatic
and aromatic ketones in sulfuric acid ; in xanthone and fluorenone there
appears to be stabilization of a quinonoid structure, since new absorp-
tion bands are acquired. '^^ piper and Erode "^^ have found that, with
sufficient separation, the two chromophores in a disazo dye act inde-
pendently of each other ; conjugated or closely linked /)ora-coupled dyes
show marked deviations from theoretical additive absorption effects.
The infra-red absorption spectra of phenylacetonitrile, benzonitrile, and
a-naphthonitrile have been examined.*^* Absorption spectra curves for
the sugar phenylosazones confirm the classical formula proposed by
Fischer. "^^ The general agreement of the mechanical and Raman spec-
tra for benzene is now interpreted as consistent only with the oscilla-
ting Kekule formula.*^^ The only acceptable structure for naphthalene
is the symmetrical Erlenmeyer structure with immobile bonds ;''^ this
also strongly substantiates the Kekule structure for benzene. The fine
structure of naphthacene and condensed quinones has been discussed.*^^
From experimental values of the interatomic distances between
carbon atoms (C = C, 1.38 A; benzene, 1.39 A; graphite, 1.42 A;
C — C, 1.54 A), Pauling and co-workers "^^ have plotted a function show-
ing the dependence of interatomic distances on bond character for single
bond-double bond resonance; a small amount of double bond character
causes a large decrease in interatomic distance below the single bond
value. X-ray investigations support the views that the I- 1 bond in
diphenyliodonium iodide is ionic.^^ Dipole moment measurements indi-
cate that AT-dimethylanthranilic acid exists largely as the "z witter ion,"
even in benzene solution.®^ Electric moments have been determined
for four /^-substituted phenylethylenes.®^
The compound, boranilide, reported by Chaudhuri, is probably a
double salt of aniline and zinc chloride. ^^ The ketene, diphenylacetal,
reported by Higinelli, and the phenyl orthoacetate, reported by Heiber,
appear to be the diphenyl ether of ethylene glycol.®*
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CARBOCYCLIC COMPOUNDS 191
Organo-Metallic Compounds. Blicke and Monroe ^^ have pre-
pared tetraphenylarsonium bromide, (CeH5)4AsBr, from triphenyl-
arsine oxide and phenylmagnesium bromide ; the corresponding chloride
is very soluble in water and the solution is a strong electrol)rte. The
reactions of phenyl- and diphenylarsine have been further studied.^^ A
series of arsenated phenoxyethanols have been prepared by condensing
propylene chlorohydrin with 4-hydroxyphenylarsonic acid.®"^ Twenty-
one different types of mercury derivatives have been synthesized and
tested for bacteriological properties.®^ />-Cymene was directly mercu-
ated to give a mixture of monomercurated compounds.®^ The direct
mercuration of six polymethylbenzenes has been studied ;®® nitrous
anhydride, nitrogen dioxide and nitrosyl chloride give nitroso com-
pounds as primary products with these organomercury derivatives.®^
A carboxylic acid group in the five position has no labilizing effect on
the activity of the chlorine atom in 2-chlorophenylarsonic acid;®^ the
stibono group is less effective than the arsono group in rendering the
halogen labile.®^
Simons ®* cleaved tetraarylgermanes by hydrogen bromide to triaryl-
germanium bromide and hydrocarbon ; the order of decreasing activity
to cleavage is />-tolyl, w-tolyl, phenyl, benzyl. The electrolysis of
sodium triphenylgermanide in liquid ammonia, using a mercury cathode,
gave sodium amalgam and varying amounts of hexaphenyldigermane
and triphenylgermane.®^
Oxidation. Fieser and Fieser are continuing their studies on
the oxidation-reduction potentials of a- and 3-naphthoquinones ; the
effect of substitution is considerably less in the benzenoid nucleus than
in the quinonoid nucleus with para quinones; groups which lower the
potential of the parent quinone facilitate substitution in the benzene
ring and vice versa,^^ Substitution of two or more methyl groups in
the nucleus of the benzene ring of acetophenone appears to render
the nucleus more susceptible to the action of hypohalite solution ; unsub-
stituted derivatives in general are not halogenated, merely undergoing
cleavage.®"^ Tertiary hydrocarbons of the type C6H5CH(CH3)R, in
which R is methyl, propyl or butyl, on oxidation with gaseous oxygen
lose the larger group, acetophenone being formed in each case ; as with
secondary hydrocarbons, the reaction is not inhibited by water.®® The
oxidation of 5-bromo- and 5-nitropseudocumene has been investigated.®®
Evidence for the existence of semiquinones in the oxidation of hydro-
quinones has been summarized.^®®
Polycyclic Compounds. Fieser and co-workers have been par-
ticularly active in the investigation of polycyclic compounds. The
carcinogenic hydrocarbon, 20-methylcholanthrene can be obtained in
5.4 percent yield from cholic acid, the most abimdant bile acid;^®^
the structure of this hydrocarbon, determined by Cook and Hasle-
wood, has been confirmed by synthesis, an isomer also being
obtained. ^®2' i®^ Fieser and Seligman have synthesized cholanthrene
(XIV), 15;16-benz-dehydrocholanthrenei®* and 16,20-dimethylcholan-
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192 ANNUAL SURVEY OF AMERICAN CHEMISTRY
11
16
J-J
7
Al T
VV vx/
Cholanthrene 1, 2-Cyclopenteno-
OV)
phenanthrene (XV)
1, 2-Benzopyrene Dehydroandro-
(XVI) sterone (XVII)
threne ;^^5 l',9-methylene-l , 2, 5, 6-dibenzanthracene,^^^ 1, 2-benzpyrene
(XVI), 4'- methyl - 1 ', 2'- dihy dro - 1 ,2 - benzpy rene, 4'- methyl - 1 ,2-benz-
pyrene ^^"^ and 4'-hydroxy-l, 2-benzpyrene ^^^ have also been prepared.
The 2,3-(naphtho-2',3')-acenaphthene of Cook and co-workers has
been obtained from 3-o-toluoylacenaphthene by the Elbs reaction. ^^^
In view of the physiological importance of compoimds containing the
phenanthrene skeleton, the chemistry of phenanthrene is being inten-
sively investigated. Bachmann^^^ has synthesized 1,2-cyclopenteno-
phenanthrene (XV) from phenanthrene and has developed a method
for synthesizing 1 -substituted phenanthrenes. A series of amino alco-
hols from l,2,3,4,S,6,7,8-octahydrophenanthrene of the type C14H17C-
(OH)--CH(R)NR'2 has been prepared by van de Kamp and Moset-
tig.^^^ Amino alcohols derived from 1,2,3,4-tetrahydrophenanthrene,
in which the hydroxy 1 and amino groups are directly attached to the
nucleus, have been synthesized. ^^^ Phenanthrene derivatives may be
prepared by the addition of dienes to maleic anhydride derivatives, fol-
lowed by decarboxylation and dehydrogenation '}^^* ^^* thus, from
3,4-dihydronaphthalene-l,2-dicarboxylic acid anhydride and 2,3-di-
methylbutadiene 2,3-dimethylphenanthrene may be obtained. The anhy-
dride of dihydrophenanthrene-o-dicarboxylic acid may be readily pre-
pared by the Bougault reaction; condensation of Y-(l-naphthyl) -butyric
ester with oxalic ester, followed by treatment with 80 percent sulfuric
(CHO2CHI 7 ^ ..
(XIX)
acid, yields the anhydride of 3,4-dihydrophenanthrene-l,2-dicarboxylic
acid (XVIII) ; this compound and phenanthrene- 1,2-dicarboxylic acid
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CARBOCYCLIC COMPOUNDS 193
anhydride possess oestrogenic activity. ^^^ Dicyclohexenyl-1,1' has been
condensed with maleic anhydride and acrolein to give some hydro-
genated phenanthrene derivatives.^^^ Sulfonation of retene (XIX)
gives the 6-sulfonic acid, from which several derivatives were pre-
pared.^ ^"^ Phenanthrene and anthracene are preferentially hydroge-
nated in the 9,10-positions if a copper-chromium-barium oxide catalyst
is used.^^^ The Grignard reaction has been applied to the synthesis
of some o-toluoylphenanthrenes ;^i® 1-, 2- and 3-benzoylphenanthrenes
are obtained through the Friedel and Crafts reaction from phenan-
threne and benzoyl chloride ;^^ the acetyl group enters the 2-position of
dihydrophenanthrene to the extent of 90 percent. ^^^
The preparation of glycocholic acid from cholic acid in 40-60 percent
yield has been reported^^o Molecular compounds of desoxycholic acid
and certain polycyclic hydrocarbons have been prepared; since the
sodium salts of these complexes are soluble in water, this provides a
way of obtaining aqueous solutions of carcinogenic compounds.^^^
Improvements in the synthesis of androsterone have been made ^^2 and
a method for converting the cw-hydroxyl group to the ^ran^-form has
been developed. ^^3 fhe preparation of dehydroandrosterone (XVII)
and its oxidation and reduction products have been described. ^24, 125
Miller and Bachman ^^c, 127 h^ve begun a systematic study of fluorene ;
the structures of several monobromofluorenes, -9-fluorenols and -fluore-
nones have been established. Sobotka has reviewed the chemistry of
the bile acids ;^28 Elderfield has done the same for the closely related
cardiac glycosides.^^o
Polymerization. The polymerization of styrene in the presence
and substantial absence of oxygen has been studied; highly purified
styrene polymerizes to relatively few large molecules and such a result
is explicable if the reaction is catalytic and the catalyst remains
attached during the growth.^^^ Aromatic mercaptals undergo a con-
densation reaction with formaldehyde in the presence of acetic and
hydrochloric acids to give crystalline products of high molecular
weight.^3^ 3-Cyclohexylpropene and 3-methylcyclohexene give polysul-
fones by the addition of sulfur dioxide.^^^
Pyrolysis. No significant amount of ketene dimer is produced
in the pyrolysis of acetylphthalimide.^^^ The C-C bonds which are
once removed from the unsaturation rather than adjacent to it undergo
a ^
pyrolytic rupture; for a type C = C — C — C, a represents strength and
3 weakness.^^^ Instantaneous decomposition of eleven substituted ben-
zalchlorimines has been studied by Hauser, Gillaspie, and LeMaistre ;^35
the reaction RCH = NC1 -> RCN-f-HCl predominates to the extent of
90 percent at higher temperatures. The thermal decomposition of ben-
zene is a heterogeneous bimolecular reaction, with an apparent activa-
tion energy of 50,000 cal.^^e Allyl-/>-phenetidine decomposes slowly at
270° to give /)-phenetidine, propylene and resinous products ; the initial
step appears to be cleavage of the C-N bond.^^*^
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194 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Reactions. For this review the investigations of reactions have
been classified roughly according to whether they deal with addition
reactions, condensation reactions, mechanism of reaction, rate reactions
or reactions not falling into these divisions. Ammonia adds to the
double bond of benzylidenemalonic ester to yield 3-amino derivatives.^^^
Methylamine, ethylamine, and dimethylamine readily add to dibipheny-
leneethylene, giving the corresponding alkylaminodibiphenyleneethanes ;
thus, the properties of the double bond in certain hydrocarbons can
approach liiose of the unsaturated linkage in the grouping — CH = CH-
— CO — .^3® Trihalomethyl-o- and -/>-chlorophenylcarbinols are formed
by addition of chloroform and bromoform to o- and />-chlorobenzalde-
hyde.^*®' ^*^ By addition of hydrazoic acid to a- and 3-naphthoqui-
nones quantitative yields of the 2-amino- and 4-aminonaphthoquinones
are obtained. ^*2 Sulfur dioxide forms loose chemical compounds with
aromatic and aliphatic amines.^*^ It has been reported that biphenyl
forms only a tetraozonide, the non-addition of two more molecules of
ozone being attributed to steric hindrance. That this is not the factor
involved has been shown in the addition of ozone to 1-phenylcyclo-
hexene-1 and dicyclohexeny 1-1,1'.^**
The condensation of propylene with benzene ^^^ and with m- and
/>-hydroxybenzoic acids, ^*® and the reaction between naphthenes and
olefins in the presence of aluminum chloride and boron fluoride have
been investigated.^**^ Finely dispersed phosphorus pentoxide is suit-
able for condensing olefins with aromatic hydrocarbons; benzene and
ethylene under pressure gave products from which mono- and hexa-
ethylbenzenes were isolated.^*^ Naphthalene gave principally mono-
and diethylnaphthalenes. Sodium phenate and amyl bromide can be
condensed to amyl phenyl ether in liquid ammonia under pressure.^*^
The preparation of chlorobenzophenones by the Friedel and Crafts reac-
tion from benzoic acid and chlorobenzene has been studied.^^® Grosse
and Ipatieff have found that paraffins will react with aromatic hydro-
carbons in the presence of aluminum chloride; 2,2,4-trimethylpentane
and benzene gave isobutane and a mixture of mono- and di-f^rf-butyl-
benzene.^^^ In the Friedel-Crafts reaction between benzoyl chloride
and toluene, using mixed catalysts, the formation of a bimetallic com-
plex, RCOR' . AICI3 . FeCls, is postulated, since less than one mole of
product is formed for each mole of total metal chlorides present.^*^^
Calloway ^^^ has prepared an extensive review, with over 500 refer-
ences, of the Friedel-Crafts reaction.
The mechanisms of a number of reactions have been investigated and
in many cases elucidated. Kharasch ^^* has reached the conclusion
that the Cannizzaro reaction is catalyzed primarily by peroxides ; with
peroxide-free aldehydes in absence of oxygen no Cannizzaro reaction
took place. MichaeP^^ objects to Wieland's mechanism for the addi-
tion of nitric acid as HO— and — NO2 to a double bond, followed by
splitting off of water, and suggests an earlier view that aromatic
nitration proceeds in the first phase by aldolization : C6HeH-HON02
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CARBOCYCLIC COMPOUNDS
195
->C6H6NO(OH)2-»C6H5N02 + H20. From studies made on the
rate of hydrolysis of ald-chlorimines to nitriles, evidence has been
obtained in support of the mechanism that a proton is removed first,
followed by the chlorine ion with a completed electron octet.^^® Both
a- and 3-aldoxime acetates undergo fundamentally the same type of
R-C-H
NOH
R-C-H
lie
RCN
predominates NOOCCHs occurs to
from O-lOO** syn (o) small extent
R-C-H R-C-H
II < ^11
HON predominates H,CCOON
at 0** anti (P)
> RCN
predominates
above 30**
reaction with alkali, forming oximes by hydrolysis and nitrile by
elimination of acetic acid.^^'^ The relative yields of nitriles and oximes
formed in the reactions of carbethoxy-a-benzaldoximes are also a func-
tion of temperature. ^^^ Chemical evidence supports the view that, in
the formation of amides by the action of ammonia on anhydrides or by
hydrolysis of acid imides, the primary reaction is addition to the car-
b+NH,
H+NaOH
CONH,
COOH
COONa
CONH,
bonyl group, since different amides are obtained in the two reactions
when an unsymmetrical anhydride or imide is employed.^^^ The pro-
duction of sulfides by interaction of sulfur and aromatic amines appears
to involve the intermediate formation of a sulfanilide type of compound,
followed by rearrangement; the reaction takes place only when a
labile hydrogen is present :i«o 2C6H5NH2 + S -» CeHgNHSHNCeHg
—> H2NC6H4SCeH4NH2. That the haloform reaction actually involves
stepwise halogenation, followed by cleavage, has been demonstrated by
Fuson and co-workers ^^^ through the isolation of the mono-, di- and
tribromo derivatives in the bromination of 2,4,6-tribromo-3-acetylben-
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196 ANNUAL SURVEY OF AMERICAN CHEMISTRY
zoic acid. Hypoiodite reacts with certain hindered methyl ketones to
give mono- and diiodomethyl ketones but not triiodo derivatives. ^^^
The haloform reaction has been reviewed by Fuson and BulL^®* The
mechanism proposed by Lifschitz ^^^ for the fading of the compound
produced by illumination of the leucocyanide of malachite green is
inadequate. In the preparation of fuchsine by the formaldehyde proc-
ess, scission of the diphenylmethane molecule must occur and this sup-
plies only one of the benzene nuclei and the central carbon atom of the
triphenylmethane.^^^ Further evidence has been obtained that treat-
ment of an unsaturated compound with mercuric acetate in methanol
solution results in addition of the intermediate CHaOHgOOCCHs
to the ethylene linkage.^®^ Alkylation of phenols using zinc chloride
or boron fluoride is not a direct exchange reaction but is preceded by
dehydration of the alcohol and addition of phenol to the unsaturated
hydrocarbon.®^' ^^"^
Bachmann ^®^ has cleaved unsymmetrical ketones by means of potas-
sium hydroxide and measured the relative rates of the two competing
reactions : RgCOOH -h RiH <- RiRgCO + KOH -^ RiCOOH + RgH ;
the resistance to cleavage is a function of the groups. The rates of the
chloroform reaction for acetone, acetophenone, and pinacolone have
been determined ; the increase in reaction velocity with increase in alka-
linity is assumed to be due to the ionization of the enolic form.^®^
Norris and co-workers i70-i73 have been investigating the relative rates
of ester ification of substituted benzoyl chlorides with alcohols and of
etherification of benzyl chlorides; temperature and solvent effects have
also been studied. o-Aminophenol, cysteine, and potassium sulfite
inhibit the absorption of oxygen by alkaline solutions of catechol;
pyrogallol and hydroquinone catalyze the oxidation; the reaction prob-
ably has a chain mechanism.^*^*
The reaction between perthionic acid, C2H2N2S3, and various
amines,^*^^ the properties of 3,4-dimethoxybenzalpyruvic acid and
3,4-dimethoxycinnamic acid,!''^® and the reaction between mercury di-
aryls and diarylselenium dihalides have been the subjects of investiga-
tion, i*^*^ Anhydrous zinc chloride catalyzes the pyrolytic decomposition
of esters of aromatic acids, giving an unsaturated hydrocarbon and the
acid, which in turn may lose carbon dioxide or, if dibasic, form an
anhydride.i'^s Dehalogenation of 3-bromophenylpyruvic acid in aque-
ous solution gives phenylacetic acid: CeHgCHBrCOCOOH — HBr
- CO2 -> (CeHgCH = C = O) + H2O -> C6H5CH2COOH ; the inter-
mediate formation of phenylketene is postulated. ^"^^
Reduction. Lutz and co-workers 180-I82 have made a thorough
study of the reduction of dibenzoylethylene ; soluble reducing agents
lead to monomolecular products ; catalytic reduction and reduction by
zinc and acetic acid give open chain and cyclic dimolecular products.
It is probable that a conjugate reaction occurs with cyclization taking
place through intermediate enolic groups, since the possibility is
excluded that the ethylene linkage alone is involved.
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CARBOCYCLIC COMPOUNDS 197
Adkins and co-workers have continued their studies on catalytic
hydrogenation ; the order of increasing resistance to C— O cleavage by
hydrogenation is benzyl alkyl ethers, diaryl ethers, aryl alkyl ethers,
dialkyl ethers.^^^ Reduction of imido ethers in acid solution by sodium
amalgam yields aldehydes; electrolytic reduction leads to primary
amines.^^* Nitrobenzene undergoes a reduction-chlorination reaction
with isopropyl or isobutyl bromide and aluminum chloride, giving a
mixture of o- and />-chloroaniline.^s^ The reduction of nitrobenzene with
dextrose in alkaline solution has been studied to determine the relative
yields of azoxybenzene, azobenzene and aniline under varied condi-
tions.is® A general method for the catalytic reduction of nitroaryl-
arsonic acids to the aminoarylarsonic acids has been developed. ^^"^
Hypophosphorus acid is a better reagent than alcohol for converting
diazotized amines to hydrocarbons. ^^^ Treatment of l,l-diaryl-2-acyl-
ethylenes with benzene and aluminum chloride involves both replace-
ment of the aryl groups and hydrogenation :^^^ Ar2C = CHC0R
+ 2CoH64-2H -^ (C6H5)2CHCH2COR+2ArH.
Ring Closure. Bogert and co-workers^^o have obtained further
evidence that, in the cyclodehydration of aralkyl alcohols, cyclization or
polymerization is preceded by olefin formation. Kohler and Blan-
chard^s prepared a number of highly phenylated compounds from
.yym-triphenylbenzene ; triphenylbenzoic acid, (CoHr,)3C6H2COOH, is
easily condensed to diphenyl fluorenone (XX); triphenvlbenzohydrol,
(C6H5)3C6H2CH(OH)C6H5, yields 1,3,9-triphenyl fluorene (XXI);
and hexaphenylbenzohydrol, ( CeHr, ) 3CeH2CH ( OH ) — CeH2 ( CcHs ) 3,
gives l,3-diphenyl-9-triphenylphenylfluorene (XXII).
CeH-s Cells H Cells (CeHB)3CeH.2 H CeliB
CeHs I J I JCeH-B I J I ICeH.5
(XX) (XXI) (xxn)
Stereoisomerism. Adams and co-workers are continuing their
investigations of the biphenyl derivatives. A compound (XXIII) with
hydrogens in the 2- and 6-positions has been resolved.^®^ The ratio of
the half-life periods of the optically active 2-nitro-6-carboxy-2'-alkoxy-
H2N
H,C<^
Br
NH2
~^CH,
CeHs CbHb
HOOC-CH2OOC CoHt
(xxm)
(XXIV)
biphenyls is OCH3/OC2H5/OC3H7 = 1/5/7 regardless of the solvent
or temperature. ^®2 Introduction of groups into 2-nitro-6-carboxy-2'-
methoxybiphenyl stabilizes it toward racemization in the order nitro>
bromo> chloro> methoxy> methyl; this result coincides with the
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198 ANNUAL SURVEY OF AMERICAN CHEMISTRY
order of increase of the dipole moments of the substituents ; the more
negative the group the greater is the stabilizing action.^^^
Kohler, Walker and Tishler^®* have resolved an allenic acid
(XXIV) into two optically active stereoisomers. As)anmetric s)m-
theses in circularly polarized light have been achieved in the addition
of chlorine ^^^ and bromine ^®® to trinitrostilbene ; the products lose
their activity on standing. Condensation of 2-bromofluorene with
rf-2-octyl nitrate in the presence of potassium ethoxide gave an optically
active potassium salt of 9-nitro-2-bromofluorene. Thus a partially
asymmetric synthesis has resulted from optically active reagents.^®*^
The two racemic a -cyano-a -methyl- 3-phenylglutaric acids have been
resolved. ^^^ The two methods of preparing 9,10-diaryldihydrophenan-
threnediols, (1) by addition of Grignard reagent to phenanthrene-
quinone and (2) by reduction of 2,2'-diacylbiphenyls, give difiFerent
pinacols; this difference is probably due to stereoisomerism.^ The
CIS- and ^row^-2-chlorocyclohexanols have been prepared.^®® The rate
of isomerization of cw-methyl cinnamate has been studied ; a mechanism
for the cis-trans isomerism, involving excitation of the electrons form-
ing the double bond, is proposed.^^ Acyl derivatives of ketoximines
having an hydroxyl, carbonyl, or carboxyl group alpha to the C = N
linkage undergo hydrolysis if the oximino group is syn to the alpha
standing group and a second order Beckman cleavage (to aldehyde and
nitrile) if the oximino group is anti,^^^ Salts of rf-camphor-10-sul-
fonic acid and primary amines exhibit slow mutarotation in anhydrous
solvents. This mutarotation is believed due to the establishment of an
equilibrium between the rf-salt and the l-anil.^^' ^^^
Substitution and Orientation. Svirbely and Warner ^04 have
found that the directing influence of groups appears to be related to the
dipole moments; if the moment of a mono-substituted benzene deriva-
tive is greater than 2.07D, a second group will be directed meta; if
less than this value, the entering group will go to the o- and /^-positions.
Nitration of /^r^-butylbenzene with mixed acid g^ves 77 percent para
and 23 percent ortho products.^os That direct iodination of vanillin
gives the 5-iodo derivative has been established.^^ The nitration of
polymethylbenzenes has been studied.^o^, 208 Sulfonic acid groups on
the benzene ring of phenol are stable toward halogenation, even in the
presence of acid, if the reaction is carried out in an inert anhydrous
solvent.200 The relative reactivities of the acidic hydrogen in substi-
tuted benzoic acids have been compared ;^'^® for ortho groups the order
of increased labilizing action is CH3O, CH3, H, CI, Br, NO2. The
dissociation constants of all of the mono- and di-chlorophenols have
now been measured in 50 percent methanol solution ; the values increase
in proportion to the number of substituents and to the proximity of the
substituents to the hydroxyl group.^^o Pauling and Wheland ^n have
extended the quantum mechanical treatment of Huckel to obtain the
charge distribution in aromatic molecules undergoing substitution
reactions.
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CARBOCYCLIC COMPOUNDS
199
Syntheses. Davidson and Bogert^ia have discovered that aro-
matic alcohols can be prepared from the aldehydes in excellent yields
by the "crossed" Cannizzaro reaction, using formaldehyde as the
oxygen-acceptor : RCHO -f- CHgO + H2O -» RCH2OH + HCOOH.
The Diels- Alder reaction has been adapted to the synthesis of anthra-
quinones: aroyl-acrylic acids are condensed with butadiene or 2,3-di-
O
i
\CH H,C=C-CH,
I + T
COOH
/V/
-CH,
-CH,
HOOC
methylbutadiene and the addition product is dehydrogenated and
cyclized.213 The procedure of Staudinger and Freudenberger, employ-
ing the action of hydrogen sulfide and hydrogen chloride on the 0x0-
ketone, has been applied to the synthesis of some new thioketones.^^*
The phosphates and alkyl ethers of o- and />-hydroxybiphenyl ^is and
several dialkyl ethers of 2,2-bis- (4-hydroxyphenyl) -propane 216 have
been prepared. The optimum conditions for obtaining the best yields
of diphenyl sulfide and thianthrene from benzene, sulfur and aluminum
chloride have been worked out.^^''^ Methods for the preparation of
chloroacetocatechol,^^® of w-chlorofluorobenzene and 2,4,6-trichloro-
fluorobenzene 2i» have been described. Benzotrifluoride and deriva-
tive6,220 some derivatives of />-fluorophenylsulfinic acid,22i and the
indium salts of some organic acids have been prepared.222 cD-Mono-,
-di-, and -tribenzylacetophenone have been prepared by a sodamide
synthesis.223 Mottern's synthesis of vanillin reported in last year's
Survey has been questioned. ^24
A large number of nitrogen containing compounds have been pre-
pared. Several compounds related to ephedrine have been synthe-
sized.^' 225, 226 A niunber of compounds related to novocaine have
been prepared; various dye intermediates were coupled with diazotized
novocaine 227 and some dialkylaminoethoxyethyl-/>-aminobenzoates228
and 3-alkoxy-ethyl esters of />-aminobenzoic acid were synthesized.220
Cyclohexylthiocyanate,230 urethanes derived from phenyl-a-naphthyl-
amine,23i p. and w-ethoxybenzylureas,232 menthyl- and bornylurea,^^^
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200 ANNUAL SURVEY OF AMERICAN CHEMISTRY
arylacetic acids and 3-arylethyIamines from aldehydes,234 A^-substituted
sulfon-w- and /^-toluidides^^as iV^iV'-diphenylbenzidinej^ss a,a-bisbenz-
oylaminopropionic acid,^^^ AT-acyl-o-benzenesulfonaminophenylbenzene-
sulfonates,238 acyl derivatives of o-anisidiney^^^ some new benzene sul-
finamides and sulfonamides,^'*^ and some new amidine hydrochlorides ^^^
have been prepared. Optimum conditions for the practical preparation
of {7-benzenesulfonylaminophenol and {7-benzenesulfonylaminophenyl
benzene sulfonate have been worked out.242
Checked directions for the preparation of the following carbocyclic
compounds are given in "Organic Syntheses," Vol. XV : 2,6-dibromo-4-
nitrophenol, 2,6-dibromoquinone-4-chloroimide, 5,5-dimethyl- 1 ,3-cyclo-
hexanedione, 2,4-dinitroaniline, 3,4-dimethoxyphenylacetic acid, /?-iodo-
phenol, {7-nitrophenylsulfur chloride, orthanilic acid, phenylarsonic acid,
phenylbenzoyldiazomethane, y-phenylbutyric acid, phenylglyoxal, 2,4,6-
trihydroxyacetophenone, a-ketotetrahydronaphthalene and 3,4-dimeth-
oxybenzonitrile.24^
(XXV)
(XXVI)
Tautomerism. Treatment of 1,2-dihydroxynaphthalene with
benzophenone dichloride yields an equilibrium mixture of 4-diphenyl-
methyl-l,2-naphthoquinone (XXV) and 2-hydroxy-l,4-naphthofuch-
CeHfi OH
OH
(XXVn) (XXVIH)
02N<( )^NH-N=<(^^^^^^=0
NO2
(XXIX)
O2N/ S— NH-N=<^ N=0
^ ^0. H-^ ^H
HC-CH2-CH
(XXX)
CH = CT
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CARBOCYCLIC COMPOUNDS 201
sone (XXVI) instead of the expected diphenylmethylene ether; these
fuchsones are quinonoid in structure but not quinone-like in properties
other than color.^^* There is some evidence that (XXVII) and
(XXVIII) exist in equilibrium in solution.^^ Cyclopentadiene adds to
2,4-dinitrobenzeneazophenol to give the addition product (XXX) ; it is
believed that inner salt formation may stabilize the quinonoid structure
(XXIX). 245 The yield of addition product increases with the acidity
of the medium. The mesityl group decreases the speed of the eno-
lization, >C = C(OH) -R^ri >CH-CO-R, to such an extent that
the ketone 1,1- dipheny 1 - 2 - benzoy 1-2- ( 2,4,6-tr imethylbenzoyl ) -ethane,
(CoH5)2CH-CH(COC6H5)COC6H2(CH3)3, and its enol exist in
stable forms in solution.^^^
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CARBOCYCLIC COMPOUNDS 203
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133. Hurd, C. D., Dull, M. F., and Williams, J. W., 7 Am. Chem. Soc, 57: 774 (1935).
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138. Scudi, J. v., 7. Am. Chem. Soc, 57: 1279 (1935).
139. Pinck, L. A., and HUbert, G. E., 7. Am. Chem. Soc, 57: 2398 (1935).
140. Howard, J. W., and Castles, I., 7. Am. Chem. Soc, 57: 376 (1935).
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146. Croxall, W. J., Sowa, F. J., and Nieuwland, J. A., 7. Am. Chem. Soc, 57: 1549
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147. Ipatieff, V. N., Komarewsky, V. I., and Grosse, A. V., 7. Am. Chem. Soc, 57: 1722
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148. Malishev, B. W., 7. Am. Chem. Soc, 57: 883 (1935).
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150. Newton, H. P., and Groggins, P. H., Ind. Eng. Chem., 27: 1397 (1935).
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168. Bachmann, W. E., 7. Am. Chem. Soc, 57: 737 (1935).
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204 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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186. Opolonick, N., Ind. Eng. Chem., 27: 1045 (1935).
187. Stevinson, M. R., and Hamilton, C. S., /. Am. Chem. Soc, 57: 1298 (1935).
188. Raiford, L. C, and Oberst, F. W., Am. J. Pharm., 107: 242 (1935).
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190. Roblin, R. O., Jr., Davidson, D., and Bogert, M. T., J. Am. Chem. Soc. 57: 151
(1935).
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197. Thurston, J. T., and Shriner, R. L., /. Am. Chem. Soc, 57: 2163 (1935).
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199. Bartlett, P. D., /. Am. Chem. Soc, 57: 224 (1935).
200. Kistiakowsky, G. B., and Smith, W. R., /. Am. Chem. Soc. 57: 269 (1935).
201. Barnes, R. P., and Blatt, A. H., 7. Am. Chem. Soc, 57: 1330 (1935).
202. Schreiber, R. S., and Shriner, R, L., 7. Am. Chem. Soc, 57: 1306 (1935).
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204. Svirbely, W. J., and Warner, J. C, 7. Am. Chem. Soc, 57: 655 (1935).
205. Craig, D., 7. Am. Chem. Soc, 57: 195 (1935).
206. Raiford. L. C, and Wells, E. H.. 7. Am. Chem. Soc, 57: 2500 (1935).
207. Smith, L. I., and Harris, S. A., 7. Am. Chem. Soc. 57: 1289 (1935).
208. Smith, L. I., and Tenenbaum, D., 7. Am. Chem. Soc, 57: 1293 (1935).
209. Huston, R. C, and Neeley, A. H., 7. Am. Chem. Soc. 57: 2176 (1935).
210. Murray, J. W., and Gordon, N. E., 7. Am. Chem. Soc, 57: 110 (1935).
211. Wheland, G. W., and Pauling, L., 7. Am. Chem. Soc. 57: 2086 (1935).
212. Davidson, D., and Bogert, M. T., 7. Am. Chem. Soc. 57: 905 (1935).
213. Fieser, L. F., and Fieser, M., 7. Am. Chem. Soc, 57: 1679 (1935).
214. Bost, R. W., and Cosby, B. O., 7. Am. Chem. Soc. 57: 1404 (1935).
215. Vernon, C. C, Struss, E. F., O'Neill, M. A., and Ford, M. A., 7. Am. Chem. Soc,
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218. Hoberman, H. D., 7. Am. Chem. Soc, 57: 1382 (1935).
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(1935).
220. Bco^h. H. S., Elsey, H. M., and Burchfield, P. E., 7. Am. Chem. Soc, 57: 2066
(1935).
221. Hann. R. M., 7. Am. Chem. Soc. 57: 2166 (1935).
222. Ekeley, J. B., and Johnson, W. W., 7. Am. Chem. Soc, 57: 773 (1935).
223. Hill, G. A., and Confrancesco, A. J., 7. Am. Chem. Soc, 57: 2426 (1935).
224. Barch, W. E., 7. Am. Chem. Soc, 57: 2330 (1935).
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230. Allen, P., Jr., 7. Am. Chem. Soc. 57: 198 (1935).
231. Boese, A. B., Jr., and Major, R. T.. 7. Am. Chem. Soc, 57: 175 (1935).
232. Wertheim, E., 7. Am. Chem. Soc, 57: 545 (1935).
233. Bateman, R. L., and Day, A. R., 7. Am. Chem. Soc, 57: 2496 (1935).
234. Julian, P. L., and Sturgis, B. M., 7. Am. Chem. Soc, 57: 1126 (1935).
235. Young, G. H., 7. Am. Chem. Soc, 57: 773 (1935).
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Chapter XIV.
Heterocyclic Compounds.
GUIDO E. HiLBERT,
Bureau of Chemistry and Soils, U. S, Department of Agriculture.
Perhaps the most interesting development in this field was that deal-
ing with the structure of vitamin Bi by Williams, Clarke and collab-
orators. The gross structure of this physiologically important material
has apparently been determined and it seems probable that the few
remaining uncertain details will soon be solved and a synthesis accom-
plished. Much of the synthetic work in the field of heterocycles has
been stimulated by the aim of preparing products that are either
physiologically active or of commercial value. Several very significant
contributions have been made on the theoretical side. An attempt
has been made by Fieser and Martin ^ to establish the relationship
between various kinds of data and the aromaticities of difiFerent types of
heterocycles. Franklin and Bergstrom^ have endeavored to correlate
the properties of pentacyclic compounds containing one, two, three,
and four nitrogen atoms in the ring with those of the well known
nitrogen system of compounds and Fuson ^ has offered an explanation
of the reactivities of groups located on the a- and y-positions of pyridine
and related compounds. It is interesting to note that quantum mechanics
is even invading the field of organic chemistry; for example, Pauling
and Wheland * have presented a quantum mechanical discussion of
orientation of substituents in some of the more common heterocycles.
Furans and Oxygen Ring Compounds. Syntheses of furans from
aliphatic compounds have, in general, followed the well known scheme
of cyclizing 1,4-diketones in the presence of acid.^' ^* '^' ® Zinc bromide
has a pronounced catalytic effect in the formation of 2,3,S-triphenyl-
furan by the zinc-glacial acetic acid reduction of either dibenzoylphenyl-
bromoethylene or dibenzoylphenylethylene.® One example of the con-
version of a l-bromo-2-hydroxy-4-keto compound to a furan derivative
has been reported.^® Of interest in the synthesis of furans is the
isomerization of methylallylphenols to give the dimethyldihydrobenzo-
furans ; addition of mercuric salts in these reactions produces the mer-
curated dimethyldihydrobenzofurans.^^
For the past few years most of the work on the reactions of the
furans has been carried out by Oilman and coworkers and has dealt
with the fundamental study of orientation. 2-Furfural and isopropyl
chloride in the presence of aluminum chloride form 4-isopropyl-2-
205
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206 ANNUAL SURVEY OF AMERICAN CHEMISTRY
furfural, the structure of which was rigorously determined. This is
apparently the first instance reported in which substitution occurs in
the 3-position of a furan when an a-position is available. ^^ This reaction
is all the more remarkable, since n-, iso, and tert-hutyl chlorides give
with 2-furfural, 5-/^rf-butyl-2-furfural. Another anomalous result was
obtained in the study of the alkylation of ethyl 5-bromo-2-furoate, which
with the butyl as well as the amyl, hexyl and octadecyl halides gives
ethyl 4-f£'r/-butyl-5-bromo-2-furoate.i2 jhe Friedel-Crafts reaction of
2-nitrofuran and propionyl chloride produces 5-chloro-2-furyl ethyl
ketone.^3 It has been demonstrated that the pivotally significant "3,5-
dibromo-2-furoic acid" of Hill and Sanger is actually 4,5-dibromo-2-
furoic acid.i*
Furan and a number of its derivatives have been oxidized catalytically,
giving as the chief solid product maleic acid.^^
For the first time arsenical s containing the furan nucleus have been
prepared. Arsenic trichloride with 2-chloromercurifuran under various
conditions gives furyldichloro-, difurylchloro-, and trifurylarsine.^® On
chlorination three separate reactions take place: (1) the oxidation of
trivalent arsenic, (2) the saturation of the furan nucleus and (3) the
scission of the carbon-arsenic bond. A number of other stubstituted
furan arsenical s were prepared and their behavior towards mercuric
chloride studied in order to determine their relative aromaticities.^''^
Tertiary tetrahydrofurylcarbinols are best prepared by the action of
the appropriate Grignard reagent upon ethyl tetrahydrofuroate ; dehy-
dration of these alcohols takes place readily when they are heated with
magnesium sulfate.^®
Considerable work has been done on dibenzofuran owing, in part at
least, to its relationship to morphine. Nitration of dibenzofuran takes
place predominantly in the 3-position and, to a limited extent, in the 2-
position.^® However, on dimetalation the 4,6-positions are substituted
and, in the 4-methyl and 4-methoxy derivatives, the 6-position is
attacked. 2<> The relative ease of nuclear substitution reactions of
dibenzofuran can be correlated with the hydrogen chloride scission of
the 2-, 3-, and 4-dibenzofuryltriphenyl-leads. Pyrolysis of resorcinol
over tungstic oxide gives 3- and not 1-hydroxydibenzofuran.^®
In order to study their physiological action, a number of amino
derivatives and amino alcohols of dibenzofuran were prepared.^i. 22 Pq^
a similar reason, the benzofuroquinolines were also investigated.^^
Orientation studies of 1,2,3,4-tetrahydrobenzofurans show that metala-
tion and nitration involve the same relative positions as observed with
dibenzofuran and that sulfonation and acetylation take place in the 7-
position rather than in the 8-position. Some earlier reported hexa-
hydrodibenzofurans have now been shown to be substituted tetrahydro-
dibenzofurans, the substituents being in the 7- and not in the 8-posi-
tion.24
2,4,6-Triarylpyrylium acid sulfates are formed from methyl aryl
ketones in the presence of sulfuric acid and potassium pyrosulfate.
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HETEROCYCLIC COMPOUNDS 207
Curiously, one methyl group is lost in the formation of the pyrylium
derivatives from three molecules of the ketone.^^
The important physico-organic studies on free radicals by Bent and
coworkers show that the electron affinities of aryl xanthyl radicals differ
little from those of other organic free radicals previously studied.^^. 27
Absorption spectra of xanthone and dibenzodioxin have been deter-
mined.28 Some physical properties of two enantiotropic forms of
rotenone have been reported.^^
Catalytic chlorination of dioxane has been studied and a practical
method for the preparation of 2,3-dichlorodioxane developed.^^ This,
with a number of Grignard reagents, gives /)-dioxene. To the unsatu-
rated linkage of />-dioxene can be added halogens, hydrogen chloride, and
phenylmagnesium bromide.^^
Further light has been thrown by Spanagel and Carothers ^^ on
the interesting problem concerning the closure of rings through the w-
and />-positions of the benzene nucleus. Esterification of m- and p-
C6H4(OCH2COOH)2 with glycols of the series HO(CH2)nOH, and
subsequent depolymerization of the resulting polyesters, yield m- and p-
oxygen-containing rings.
Sulfur-Containing Rings. Nitration of bromothiophene yields a
bromonitrothiophene, that is believed to be the 2,S-derivative.33
Fieser and Kennelly ^^ have developed methods for preparing quinones
having a thiophene ring in place of the benzene ring of o- and />-
naphthoquinones. Higher reduction potentials of these quinones indi-
cate a lower degree of aromaticity for the thiophene as compared with
benzene. Chlorosulfonic acid acts upon retylthioglycollic acid to
form 6-retylthioindigodisulfonic acid and the thioindoxyl, ketodihydro-
6-retothiophene. The latter readily condenses with aldehydes and is
also easily oxidized to the corresponding amorphous thioindigo.^^
Varying the aluminum chloride content in a semi-quantitative study
of the reaction between sulfur and benzene markedly affects the yield
of thianthrene.3^
A cyclic disulfone is formed by the action of normal alkali on poly-
propylenesulfone 3"^ and a ring containing two sulfur atoms and six
carbon atoms is considered to be formed by the condensation of formalde-
hyde with />-thiocresol.3®
Pyrroles, Indoles and Carbazoles. Quantitative absorption of
light in the infra-red region of the spectrum by a number of pyrroles,
indoles and carbazoles has been measured by Wulf and Liddel;^® this
absorption is characteristic of the NH group. Ultra-violet absorption
spectra for tryptophane and indole have been determined and found
to resemble each other.*^
Interesting examples of ring closure yielding pyrrolones and male-^
inanils have been encountered by Lindwall and coworkers, when con-
densation products of benzoylformanilide with such compounds as-
acetophenone,^^ diethyl malonate*^ and ethyl cyanoacetate ^^ are-
treated with acid. The equilibrium between proline and formaldehyde
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208 ANNUAL SURVEY OF AMERICAN CHEMISTRY
has been studied^* and potentiometric titration curves for proline and
tryptophane have been described.*^
A new method for the preparation of porphyrins, which consists of
interacting pyrrole and aldehydes, has been described by Rothemund.
The reaction between formaldehyde and pyrrole is believed to give
porphin, the parent ring system of the porphyrins.^^ Pyrroporphyrin,
a chlorophyll decomposition product, has been isolated from beef bile;
spectroscopic examination indicates that traces of coproporphyrin are
also present.**^ Absorption spectra of oxidized and reduced hemin
and hemochromogens have been described ^^ and the relative rates of
absorption of carbon monoxide by reduced hemin and pyridine hemo-
chromogen have been determined.^^
Diazoesters act upon indole to give 3-substituted as well as a small
amount of 1,3-disubstituted derivatives. Jackson and Manske ^^ have
found this reaction to be a convenient one for the synthesis of a wide
diversity of indole compounds and have utilized it to develop a practical
synthesis of indolyl-3-acetic acid.
The fundamental studies of Julian and coworkers in the indole series
have been directed towards the syntheses of physostigmine ^^* ^^' ^^ {see
Chapter XV on "Alkaloids") and oxytryptophane, which is considered
to be the first product formed in the intermediary metabolism of trypto-
phane. Although the latter goal has not yet been attained, they have
succeeded in preparing the closely related dimethyl derivative (I) by
CH3
I
C-CH2CHCOOH
I
NH2
A=o
CH3
(I)
the following series of reactions. 1,3-Dimethyloxindole was condensed
with bromoacetal, the product hydrolyzed and the aldehyde converted
by means of the Strecker synthesis into the amino acid. Attempts to
carry out the same reaction with oxindole failed, because of difficulties
met with in the initial condensation with bromoacetal. A number of
other possible routes for the synthesis of oxytryptophane were
explored.^^ Also, of considerable significance in the study of the metab-
olism of tryptophane is the work of Gordon and Jackson.^ They pre-
pared amino-ZV-methyl-, Bz-3-methyl-, and Pr-2-methyl-tryptophane
and found that only the first is capable of stimulating growth in rats
subsisting on a diet deficient in tryptophane. This is suggestive that
the iV-methyl amino acids may be metabolized and utilized in place of
the natural amino acids.
3-Naphthisatin ^^ has been combined with acetophenone, acetone, and
nitromethane in order to correlate its condensation reactions with those
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HETEROCYCLIC COMPOUNDS 209
of isatin.^"^ Aldols were obtained that dissociate in solution when
heated and that suffer dehydration when subjected to acid.
Improvements in the Fries-Rosenmund rearrangement of iV-acetyl to
3-acetylcarbazole have been made; 1-acetylcarbazole is a by-product in
this reaction.^s
Pyridines and Quinolines. Byrant and Smith have utilized
pyridine (1) to displace the oxime synthesis equilibrium in the direc-
tion of completion (for the determination of aldehydes and
ketones), ^^ (2) for the rapid determination of primary and secondary
hydroxyl groups by means of acetyl chloride ^^ and (3) for the
determination of water in organic liquids.^^
Pyridyl and quinolyl acrylic acid dibromides have been prepared by
Alberts and Bachman^^ ^nd their dehalogenation with bases studied.
Rather curiously the original acrylic acids were found to be the principal
products of the reaction. Pyridylchloroethylene with alkali gives 3-
pyridylacetylene. The malonic ester grouping has been introduced
in the 2-position of pyridine with the aim of using it as an intermediate
for the preparation of pyridyl substituted barbituric acids.®^ Volume
XV of "Organic Syntheses" contains directions for the preparation of
1 -methyl-2-py ridone.^^
The interesting rearrangement of indoles into quinolines has received
additional study; condensation products of isatin and malonic acid
derivatives ®^ and of 3-naphthisatin and ketones ^^ on acid treatment
give quinolones. The oxido-reduction systems from quinoline- and
isoquinoline-5,8-hydroquinone have been studied potentiometrically.^
5-Benzyl-8-hydroxyquinoline has been prepared by a modified SJcraup's
reaction for bactericidal tests ^"^ and improvements have been made in
the Skraup sjoithesis of o-phenanthroline, the ferrous complex of which
is an excellent oxidation-reduction indicator.^^ l-(2-Quinolyl)-4-allyl
thiosemicarbazide is a sensitive precipitant for cadmium ion.^^
Bromination of a number of aminovaleric acid derivatives results in
ring closure to give dibrominated a-piperidone derivatives."^^
The equilibrium between pyridine, hydrogen, and piperidine has
been measured and the heat of reaction and accompanying free energy
change calculated. "^^ Catalytic hydrogenation of several nicotinyl acyl
methanes results in the formation of a variety of products in which the
pyridine ring is reduced and the 1,3-diketone moiety hydrogenolyzed.'^^
Reduction of carbon dioxide in the presence of piperidine gives N-
formylpiperidine.'^^ The relative reactivities of nine different 2- and
2,6-disubstituted piperidines towards butyl bromide have been deter-
mined."^* Several piperidine and isoquinoline derivatives of tetra-
hydrophenanthrene have been synthesized.'^^
Imidazoles, Pyrimidines and Purines. Much of the synthetic
work carried out in this group has been motivated by the possibility that
the compounds prepared might possess pharmacological activity. Higher
members of the alkyl glyoxalidines have been prepared by an improved
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210 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Hofmann s)rnthesisJ^ 3-Diethylaminoethoxy derivatives of several
pyrimidines (and quinazoline) were synthesized by treating the sodium
salt of the amino alcohol with the chloropyrimidinesJ^ Many S^S'-
disubstituted barbituric acids have been prepared by an improved pro-
cedureJ® New types of barbituric acids contain 3-picolyl "^^ and acet-
anilido®^ groups in the 5-position. Of theoretical interest is the
preparation of S,5'-diphenylbarbituric acid by condensing benzene and
alloxan in sulfuric acid.^^ Some thiobarbituric acids have been foimd
to be powerful hypnotics.^^
A new practical synthesis of carnosine, 3-alanyl-Z-histidine, has been
developed by Sifferd and du Vigneaud.®^ Carbobenzoxy-3-alanine is
converted to the acid azide which is condensed with the methyl ester of
Z-histidine to give carbobenzoxycarnosine. Saponification and removal
of the carbobenzoxy group by catalytic hydrogenation resulted in the
formation of carnosine. Cystine cyamidene (II) has been prepared
from a, a'-diguanido-di-(3-thiopropionic acid) and, like analogous
disulfides, is very labile in alkali.^^
HN C=0
HN = C
HN-
CH-CHtS-
(H)
Addition products obtained from aromatic amidines and glyoxal,
when treated with an aromatic aldehyde and alkali, give compounds
that are considered to be diphenylhydroxypyrimidines (or benzoyl-
phenylglyoxalines ) .^5
Cytosine has been synthesized by the ammonolysis of l,2-dihydro-2-
keto-4-ethoxypyrimidine, which is obtained by the alkaline treatment of
2,4-diethoxypyrimidine.^ Various' substituted ethylmercaptopyrimi-
dines, when treated with chlorine in water, are converted to the sulf ones ;
these on acid hydrolysis yield the corresponding oxypyrimidines.®^
Of considerable importance is the recent work of Levene and Tipson.
Trityl and tosyl derivatives of thymidine have been prepared and from
their behavior it has been deduced that the sugar is a furanoside. This
information offers an explanation for the differences in the behavior of
the ribo- and desoxyribonucleic acids. Structures have been assigned
to these acids which are in agreement with the facts.®® In the partial
synthesis of nucleotides, inosine is converted to the monoacetone inosine,
which, on phosphorylation and subsequent hydrolysis, yields hy^o-
xanthine-S-phosphoribofuranoside, which is claimed to be identical with
muscle inosinic acid.®®
A new method for the estimation of purines in tissues has been pro-
posed®^ and improvements in the micromethods for the determination
of uric acid, creatinine, and allantoin have been described.®^
Some properties of hepatoflavin ®2 and of imidazole flavianates ®^
have been studied and the titration constants of a number of imidazoles
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HETEROCYCLIC COMPOUNDS 211
have been determined.®* A systematic study of the equilibria between
formaldehyde and histidine or histamine has been developed.^^ Heats
of combustion,®^ heat capacities and entropies ^"^ of naturally occurring
purines have been reported. Of considerable practical importance is
the description of the preparation of the pure purines.
Quinazolines, Piperazines and other Nitrogen Ring Systems. In
order to study their physiological effects, quinazoline derivatives have
been synthesized ®8 that are structurally related to some of the angostura
alkaloids. 2-Veratryl-6,7-dimethoxyquinazoline, which is structurally
related to papaverine, has also been prepared.®® This work also
includes some fundamental information on the chemistry of quinazoline.
2,4-Dichloroquinazoline behaves like a typical imino-chloride and reacts
with ammonia or methylamine to give the corresponding diamino-
quinazolines.^®®
On the basis of acylation, nitrosation and reduction studies and of a
new synthesis, Spielman ^®^ has assigned to Troger's base, which is pre-
pared from />-toluidine and formaldehyde, the tetrahydroquinazoline
structure (III). Subsequently Wagner ^®2 determined the probable
mechanism involved in its formation.
i\r^'-Disubstituted piperazines are obtained by condensing piperazine
or iV-phenylpiperazine with derivatives of monochloroacetic acid,^®^' ^®*
with ethylene oxide ^®^ (for the preparation of procaine analogs), and
with aldehydes, in the presence ^®^ or absence ^®'^ of reducing agents.
Piperazine adds to the ethylenic linkage of maleic or fumaric esters to
give piperazino-l,4-bis-(alkyl succinates).^®®
In very dilute solution y-bromopropyldimethylamine reacts intra-
molecularly to form the cyclic dimethyltrimethyleneammonium bromide,
which rearranges slowly to give a linear polymer. The impure diethyl
analog behaves similarly, although rearranging less readily. Under
the same conditions cyclic salts with alkyl groups higher than ethyl do
not change into polymeric products.^®®
A quinoxaline derivatives^® was formed by the condensation of a
monomethyl ether of benzoylformoin with o-phenylenediamine and a
pyrazoline derivative ^^^ by the action of diazomethane on a 1,4-
naphthoquinone.
Methods have been investigated and developed for preparing Zm-bis-
triazoloquinone and quinones of the benzo- ^^^ and naphthotriazole
series.ss^ Some of these products were studied potentiometrically and
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212 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the bearing of the results on the fine structure of the triazole ring
discussed.
An interpretation of the reversible oxidation-reduction exhibited by
certain phenazines has been presented,^^* and the mechanism of the
chemiluminescence of 3-aminophthalhydrazide investigated. ^^^
Miscellaneous Nitrogen, Oxygen, and Sulfur-Containing Rings.
Certain carbocyanine dyes containing the chain =CHC(CH3) =CH —
can now be prepared by the new method of heating, in a basic medium,
a quaternary salt of a heterocyclic ammonium base containing a reactive
methyl group.^^^ Improvements have been made in the old methods
for making these dyes ^^^ and the 2'-cyanines,ii8 and many new types
containing the oxazole, thiazole, selenazole and pyridine rings were
S)^thesized. Optical and photographic properties of many of these
new dyes are recorded.^^*
Phenylated benzoxazoles ^^o were prepared from o- and />-hydroxy-
diphenyls and converted into azo dyes. These dyes were examined
spectroscopically and a study made of their tinctorial properties.^^i
Nitrostilbenes or their components are converted by alcoholic ammonia
into isoxazoline oxides, which are considered to be intermediates in
the formation ©f triphenylisoxazol derivatives by the Knoevenagel
reaction.^22 iV-Acyl-Z-aminoethanols yield A^-oxazolines under condi-
tions favoring dehydration and A^-thiazolines when heated with phos-
phorus pentasulfide.^23
Anils are intermediate products in the formation of benzothiazoles
from either o-aminothiophenol, its zinc salt or the disulfide. ^^4 Con-
densation products of the indirubin type are obtained by the interaction
of 2-methylbenzothiazoles with isatin or certain of its derivatives.
Isatin a-chlorides give either a- or ^-condensations, depending upon
the experimental conditions. As dyes, these products proved to be of
little value.^2^ Fluorinated thiazoles ^^6 and aryl substituted thiazoli-
dones ^^7 have been synthesized. Alkylation of any of the latter pro-
duces two isomeric products, the structures of which were determined.
Dithiazanes are formed when methylene dihalides react with thiourea,
monoarylthioureas and l,5-diaryldithiobiurets.^28 Perthiocyanic acid
reacts with a number of o-substituted aromatic amines to give fused side
rings.129 A practical method for the preparation of rhodamine has
been reported. ^^^
Sultams of the camphor series are prepared by dehydration of certain
i\r-phenylaminocamphanesulfonic acids.^^^
Vitamin Bi. Intense activity and* competition and considerable
progress have marked the study of the structure of vitamin Bi by the
group of collaborators, namely, Williams, Clarke, Buchman, Winter-
steiner, Gurin, Ruehle, Waterman, and Keresztesy at Columbia Uni-
versity. Analyses of the purified crystalline hydrochloride, which has
been made available in comparatively large amounts ^^^ agree best,
when calculated as the base, with the formula Ci2HieN40S,^33 in
agreement with the formula adopted earlier by Windaus, Tschesche,
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HETEROCYCLIC COMPOUNDS
213
and Ruhkopf.^34 The absorption of vitamin Bi in the ultra-violet region
of the spectrum, has been described by a number of groups of workers
but the results differed, usually in detail. Ultra-violet absorption of the
purified hydrochloride in either aqueous or alcoholic solution is now
reported ^^s to occur as two bands, one at 235 ji and the other at 267 \i.
Evidence for the presence of an amino and an aliphatic hydroxyl
group is obtained by heating the vitamin with hydrochloric acid; the
amino group is hydrolyzed and the —OH is replaced by non-ionic
chlorine.^3^
C^H^^NaS
-NH,
-OH
C^H^^NaS
-OH
-CI
In the degradative studies ingenious use was made of the observation
that sulfurous acid as a preservative against bacterial decay of rice
polish extracts resulted in a rapid loss of their antineuritic activity.
Careful examination of this curious reaction yielded fruitful results.
When vitamin Bi is subjected to the action of sulfurous acid at />H S a
rapid scission into two fragments, one acidic (IV) and the other basic
(V) is effected. ^^^ The basic product (V), which is an oil, was
C«H,.N,OS + H,SO,-
► C,H,N,SO, + CeH.NOS
(IV) (V)
converted into a number of crystalline salts and on treatment with p-
nitrobenzoyl chloride yields a /^-nitrobenzoate, which still exhibits basic
properties. This is considered to be evidence for the presence of an
— OH group and of a tertiary nitrogen atom in (V). Additional
evidence in favor of this view was secured by converting (V) into an
organic chloro compound by heating with hydrochloric acid [CgHgNSO
-^CgHgNSCl (VII)] and into a methiodide, which, with alkali, does
not regenerate an ether soluble base. Oxidation of (V) with nitric
acid gives a sulfur-containing acid (VI) [(C4H4NS)-C2H40H
-»(C4H4NS)-COOH (VI)], which proved to be identical with the
acid obtained by Windaus, et al,^^'^ by direct nitric acid oxidation of
vitamin Bj. From a consideration of this information, together with
the optical inactivity of (V) and the absence of iodoform when subjected
to alkali and iodine, it was inferred that (V) is a tertiary heterocyclic
base with a 3-hydroxyethyl side chain.^^^ The behavior of the vitamin
and the basic cleavage product (V) toward alkali plumbite, toward
bromine and toward nitric acid suggests that they are derivatives of
thiazole;^^^ absorption spectra also support this deduction.^*^ The
nitric acid product (VI), therefore, was expected to be a thiazole-
carboxylic acid, and work in the characterization of this was facilitated,
as its properties agreed closely with those of the known 4-methylthiazole-
5-carboxylic acid. Comparison of the methyl ester of this thiazole with
the methyl ester of (VI) showed them to be identical.^^® Tomlinson
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214 ANNUAL SURVEY OF AMERICAN CHEMISTRY
has also reported that the s)rnthetic thiazolecarboxylic acid is identical
with (VI).^^^ In view of this result the basic cleavage product (V) of
the vitamin was expected to be 4-methyl-5-3-hydroxyethylthiazole
(VIII), and this was rigorously established by the syntheses of (VII)
and (VIII) and the comparison of their properties with those obtained
from the natural products.^^®
CH,
<io
CHCl
CH2<
HJ^
+
\.
CH,
C N-
CH
\
CH,
C ^N
CH
/
rCHjOCH,
CH,<
-S
CH
CHjCl
CHjCHjOCiB,
(vn)
CH.
c — s
CHjCHaOH
(vni)
Although there can be no question as to the structure of the thiazole
portion of the vitamin, there remains some doubt as to the constitution
of the other fragment. In addition to the thiazole, sulfite treatment of
the vitamin gives a practically quantitative yield of a crystalline "amino
sulfonic acid" (IV) and this on hydrolysis with concentrated hydro-
chloric acid liberates ammonia and gives an "oxysulfonic acid." Since
the chemical characteristics are similar to those of cyclic amidines and
the absorption spectra in particular resemble those of 4-amino-
pyrimidines (in contrast to those of 2-aminopyrimidines) (IV) is con-
sidered to be a 4-aminopyrimidine.^^3 The following tentative structure
for vitamin Bi hydrochloride which is consistent with all of the above
data has been proposed by Williams.^^^ Inspection of this formula
t=CCHaCHaOH
.HCl
shows the presence of quaternary nitrogen and evidence in favor
of this has been obtained by titrative^*^ as well as by comparative
chemical studies.^^® However, evidence in regard to the presence of
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HETEROCYCLIC COMPOUNDS 215
an ethyl group (or two methyls) or the position to which it and the
thiazole group are attached is lacking. Windaus, et al}^^ favor a
structure which differs from that of Williams only by having methyl
groups attached to the (2) and (6) positions in place of the ethyl group
in the (6) position, since they believe such a structure accounts more
easily for the formation of a nitric acid oxidation product, C7H11N3O5
(ethyl ester), which has not yet been characterized.
Attempts to s)rnthesize the "pyrimidine" portion of vitamin Bi have
also been made. Robinson and Tomlinson ^^^ and Buchman ^*2 inde-
pendently have S3mthesized 4,S-diamino-6-ethylpyrimidine. Johnson
and Litzinger^^^ have described some of the properties of uracil-S-
methylamine, which they believe will be of interest in the development
of the chemistry of vitamin Bj.
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HETEROCYCLIC COMPOUNDS 217
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Chapter XV.
Alkaloids.
Lyndon Small,
University of Virginia
There has been in recent years a marked and gratifying development
of interest in the field of natural products among American chemists.
This is reflected in the increasing number of publications dealing with
the isolation, structure, and S3mthesis of alkaloids, and with the relation-
ship between structure and physiological action. The present review
covers advances in the chemistry of the plant alkaloids in the period
1933-1935, with additional references to such pharmacological studies
as are pertinent to the alkaloid groups discussed.
Ergot Alkaloids. The discovery of a new ergot alkaloid of
exceptionally high oxytocic power is undoubtedly one of the outstanding
recent contributions of chemistry to medicine, and it is regrettable that
the issue of priority has become so prominent. The observation of
Chassar Moir ^ in 1932 that the water-soluble fraction of certain ergots
possessed unexpected physiological action on oral administration appears
to have furnished the stimulus 2 that has led to the isolation of the
crystalline base, C19H23O2N3, known (in alphabetical order) as ergo-
basine,^' * ergometrine,*^' ^' ^ ergostetrine or x-alkaloid,^-^^ ^nd ergoto-
cin, €21^.27^3^ S'^^'^^ The descriptions of the alkaloid published by
the several investigators agree remarkably well, and the concensus of
opinion is that the four above-named bases are identical.^. 4» ^* 7' 12, 20
The physical properties (melting point, optical rotatory power) of the
new alkaloid appear to be changed by intensive purification ^2 or by pro-
longed standing of the base in methanol solution, but the change, if a
structural one, does not greatly affect the physiological action.21 In
contrast to most other ergot alkaloids, the base yields no ammonia on
alkaline hydrolysis. The fragments isolated are lysergic acid, and a
dextrorotatory aminopropanol, thought to be derived from rf-alanine,
whence it appears that the new alkaloid is probably a hydroxyisopropyl-
amide of lysergic acid.20 It is related to an isomeric new ergot alka-
loid, ergometrinine, of which it is a transformation product. This rela-
tionship recalls the isomeric interconvertible pairs ergotamine —
ergotaminine and ergotoxine — ergotinine.22
The most notable advances in our knowledge of the structure of the
ergot bases have come from the study of the products of hydrolysis.
Ergotinine, C35H39O5N5, yields on alkaline hydrolysis ammonia,
lysergic acid (C16H16O2N2), isobutyrylformic acid, and what appears
218
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ALKALOIDS 219
to be a peptide fraction, which can be further hydrolyzed to proline and
nearly inactive phenylalanine.^^. 24 Isobutyrylformic acid, as the amide,
was obtained many years ago from destructive distillation of ergotin-
ine,25 and it is now certain that the degradation product previously
known as ergine, CieHijONg, is the amide of lysergic acid.^^' 27 jn
acid hydrolysis of ergotinine, on the other hand, Jacobs and Craig find
that the lysergic acid portion of the molecule is destroyed, and the
identifiable fragments are /-phenylalanine, (/-proline methyl ester (after
esterification), and a peptide of proline and phenylalanine.^^* ^s
Reductive hydrolysis of ergotinine, with sodium in amyl or butyl
alcohol, has been very productive. In addition to dihydrolysergic acid,
C16H18O2N2, the isomeric a and 3-dihydrolysergols, CieH2oON2, are
formed (provisional formula II), probably by reduction of the lysergic
acid carboxyl group. With these is found proline methyl ester and a
series of bases, designated as Bases II, IV, V, and VI.^® Base II,
C14H20N2, is suggested to be a piperazine resulting from reduction of
prolylphenylalanine anhydride ; Base IV is probably a substituted piper-
azine, C10H18N2, from reduction of proline anhydride; Base V,
C5H11ON, is a hydroxyamine and may be formed by reduction of
proline or its ester to a-pyrrolidyl carbinol ; Base VI is a phenylpropanol-
amine, perhaps derived from phenylalanine and probably represents the
portion of the ergotinine molecule that yields benzoic or /)-nitrobenzoic
acid in nitric acid oxidations. Ergotinine and, therefore, ergotoxine
appear to be built up of lysergic acid or its amide, ergine, with proline,
phenylalanine, and isobutyrylformic acid.^^. so, 31
Reductive hydrolysis of lysergic acid methyl ester gives dihydro-
lysergic acid and the epimeric dihydrolysergols, but none of the above-
mentioned bases, whence it may be inferred that these bases are derived
from the extra-lysergic acid portions of the ergotinine molecule.^^ The
degradation fraction, lysergic acid, characteristic of all the ergot alka-
loids thus far examined by Jacobs and Craig, appears to be a 4-carboline
type, carrying a carboxyl, AT-methyl, and propylene group, for which
formula (I) has been advanced tentatively.^^ The nature of the tri-
carboxylic acid C14H9O8N, and of the acid Ci3H808N2, arising from
nitric acid oxidation of ergotinine and lysergic acid, respectively, is still
unknown.30' ^3 The provisional structure suggested for lysergic acid,
H,
1 H
/\ /Y-^OOH f\ /\,
H CH
H CH
CH,OH
N-CH,
:3H CH
CH, CH,
(I) Lysergic acid (11) Epimeric dihydrolysergols
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220 ANNUAL SURVEY OF AMERICAN CHEMISTRY
3-propenyl-4-methyl-3,4-dihydro-4-carboHne-5-carboxylic acid, has
already led to the synthesis of similar compounds, e. g., of 3,4,5,6,-
tetrahydro-4-carboline-5-carboxylic acid and its derivatives, from con-
densation of trjrptophane and formaldehyde or other aldehydes.^* Ergo-
clavine, on alkaline hydrolysis, yields ammonia, lysergic acid, isobutyryl-
formic acid, and leucine, while on acid hydrolysis fractions are obtained,
which may consist of racemized leucine and hydroxyproline.^s
With the recognition of the new ergot alkaloid as the most important
oxytocic principle of ergot, the question of assay and standardization
arises ^^' ^^ and may affect the value of some of the recent publications
on ergot assay.^^-^^ The ergot base ergothioneine, long known to be
present in the blood of the pig, has now been found in urine."** The
effect of ergotamine tartrate on cerebral circulation has been studied.*^
Physostigmine. A complete synthesis of physostigmine *®
(eserine), based on preliminary syntheses of dZ-desoxyeseroline *'^' *^
and dZ-eserethole *® has been accomplished by Julian and Pikl. N-
Methylphenetedine was condensed with a-bromopropionyl bromide, and
the resulting analide converted to l,3-dimethyl-5-hydroxyindole by
heating with aluminum chloride. After ethylation, this product was
condensed with chloroacetonitrile and reduced at the nitrile group to
the primary amine, l,3-dimethyl-3-B-aminoethyl-5-ethoxyoxindole. The
amino group was methylated by Decker's method, and the methylamino
compound then resolved with rf-camphorsulfonic and rf-tartaric acids.
The levo form, reduced with sodium and alcohol, gave Z-eserethole,
identical with that derived from physostigmine. By dealkylation to
Z-eseroline and treatment with methyl isocyanate, Z-physostigmine was
obtained.*^ Antagonistic action of physostigmine with barbiturates and
with nicotine has been studied.^^
Vasicine. In an attack on the structural problem of vasicine
(peganine), the 4-hydroxy-3-allyl-3,4-dihydroquinazoline formula sug-
gested by Spath and Nikawitz ^^ was first shown to be incorrect by
synthesis of 3-allyl-3,4-dihydroquinazoline, which proved to be different
from desoxyvasicine.^2 xhe correct desoxyvasicine formula was demon-
strated to be 2,3-trimethylene-3,4-dihydroquinazoline by synthesis,^^
establishing the vasicine skeleton. The 4-keto derivatives of vasicine
and of desoxjrvasicine were prepared by oxidation, and 4-ketodesoxy-
vasicine synthesized for structural proof. Oxidized desoxyvasicine
yielded with lead tetraacetate a hydroxy derivative identical with
oxidized vasicine, a fact indicating that the vasicine hydroxyl group is
on the methylene group attached to the 2-carbon atom.^* This conclu-
sion is confirmed by the complete vasicine synthesis of Spath.^^
Nicotine Types. Investigations concerned with the existence of
a toxifore grouping in nicotine have led to improved methods for the
synthesis of nornicotine and nicotine.^^ a-Substituted-iV-methylpyr-
rolidines can be prepared in good yields by the application of suitable
reduction methods to the corresponding a-substituted-iV-methylpyrro-
lines.^"^' ^® The toxicity of a number of these compounds for goldfish
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ALKALOIDS 221
and in insect sprays has been compared ; the most negative a-substituents
cause the greatest increase in toxicity. a-Nicotihe [a-(a-pyrridyl)-
iV-methylpyrrolidine] and a-nornicotine were likewise synthesized for
these toxicity studies.^®' ^^ The observation that partial detoxication of
nicotine occurs during ultraviolet irradiation has been confirmed, but
over-radiation restores the toxicity. No reasonable amount of irradia-
tion will detoxify nicotine.®^' ^^ Attempts to dehydrogenate nicotine with
sulfur in boiling toluene resulted in the formation of thioditiicotyrine,
together with a small amount of nicotyri'ne.^^ Anabasine (3-pyridyl-
a-piperidine) has been found in Nicotiana glauca R. Grab, in amounts
up to one percent ^^ and the wild plant may serve as a good source of
this valuable insecticide. The physical constants of very pure anabasine
have been carefully measured,®^ and several investigations have been
conducted on the pharmacological action and toxicity of anabasine and
nicotine.®®-*^^
Cinchona Alkaloids. In the cinchona group an interesting search
is being made at the Mellon Institute for derivatives of cinchona alka-
loids which may be less toxic and more effective than optochin in the
treatment of pneumonia. A large number of compounds have been
prepared and examined for pneumococcidal value. Isoquinine and
hydroxyethylhydrocupreine are less toxic than optochin, and are mod-
erately effective.''^ Ethylapoquinine has given some favorable results,'^^
indicating that the apoquinine series may be important. The a- and
|3-apocupreines have been prepared by treatment of quinine with hydro-
chloric and sulfuric acids; they show a fairly high pneumococcidal
effect in vitro, and a protective power in mice similar to that of opto-
chin, together with low toxicity. "^^ A conversion of several cinchona
alkaloids to the corresponding cinchona ketones by the action of sodium
amide has been reported.''* The form and optical properties of the
crystals of a large number of cinchonine salts,''^ and the solubilities
of cinchonine derivatives '^^ have been studied. Quinine sulfate is
found to crystallize with eight molecules of water, but this form is
unstable and gradually breaks down to the dihydrate. No evidence is
found for the existence of the previously-reported heptahydrate.'^'^'^^
The frequent adulteration of illicit narcotics with cinchonine and strych-
nine has necessitated the development of methods for the separation
and identification of these two alkaloids in such mixtures.^*^' ^^
Opium Alkaloids. The research units engaged with the problem
of addiction to the drugs of the morphine group have reported some
progress on the study of the relationship between constitution and
physiological action.^^ gy the application of special hydrogenation
technique to the morphine and codeine isomers of the pseudocodeine
type, the dihydro derivatives of 3- and Y-isomorphines,^^, 84 Qf pseudo-
and allopseudocodeines,®^' ^^ and of pseudocodeine methyl ether ^7
have been made available for pharmacological study. The comparison
of sixteen closely related drugs is thus possible, for observation of the
pharmacodynamic result of methylation of the phenolic hydroxyl^ of
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222 ANNUAL SURVEY OF AMERICAN CHEMISTRY
saturation of the alicyclic double bond, and of changes in position or
configuration of the alcoholic hydroxyl. The effect of these changes
on blood pressure,^®' ®® on respiration,®^- ^^ on intestinal action,®2-95 as
well as on toxicity, analgesia, and general depressant action has been
measured.^-®® The general similarity of the two drugs codeine and
allopseudocodeine, and of the pair isocodeine and pseudocodeine in
respect to physiological action leads to the conclusion that in the first-
named pair of positional isomers, the alcoholic hydroxyl probably has
the same configuration and in the last-named pair, the opposite con-
figuration.
Extensive studies have been carried out to ascertain the part played
by the alcohol hydroxyl group in the picture of morphine physio-
logical action. To this end, compounds were prepared in which the
alcoholic group of morphine and codeine, or the isomers and their
dihydro derivatives, was covered by a methyl ®® or acetyl group, con-
verted to a carbonyl group,^^^ or replaced entirely by hydrogen.^^^-^^
The inevitable conclusion reached from the investigation of a consider-
able series of such derivatives is that the alcoholic hydroxyl group as
present in the morphine series exerts an inhibiting influence with
respect to most physiological effects. With its replacement or conver-
sion to another chemical type, marked increase in toxicity, general
depression, and especially analgesia is seen, combined with a decrease
in emetic effect. The maximum narcotic effect is realized in drugs
having the free phenolic hydroxyl and a masked or eliminated alco-
holic hydroxyl, as desoxycodeine-C, dihydrodesoxymorphine-D, hetero-
codeine, dihydroheterocodeine, a-acetylmorphine, and dihydromorphi-
none.^^^-^^^ Information concerning the relative importance of groups
located at 6- and 8-positions in the morphine molecule, with elimination
of the influence of asymmetry at these points has been obtained through
the study of the isomeric pairs, dihydrocodeinone (Dicodid) and
dihydropseudocodeinone, dihydromorphinone (Dilaudid) and dihydro-
isomorphinone. Comparison of the physiological action of these sub-
stances leads to the conclusion that a functional group located on C-6
is in some respects about ten times as effective as the same group on
(;;_3ioo The presence 'of the tertiary nitrogen atom of morphine and
codeine seems to be essential for the typical morphine effects. Trans-
formation to the quaternary ammonium salts results in a marked dimi-
nution in pharmacological action, and in the appearance of the well-
known curare-like action of quaternary ammonium compounds.^^^
While an extensive discussion of non-alkaloidal material can not be
included in this review, attention should be drawn to the fact that
several of the phenanthrene derivatives synthesized by Mosettig and his
co-workers show a surprising similarity in effect to some of the mor-
phine derivatives.®^. ii3 it should be especially noted that the physio-
logical effectiveness characteristic of groups in the 3- and 6-positions
of the morphine molecule is likewise observed in the phenanthrene
series, and the changes in physiological action resulting from modifi-
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.ALKALOIDS 223
cation of such groups in the morphine series are roughly paralleled in
the phenanthrene derivatives.
The researches on the preparation of morphine substitutes have long
since reached the stage where the development of reliable clinical meth-
ods for determining the degree of tolerance and addiction in man is
imperative. This phase of the work is being conducted by the United
States Public Health Service. In this connection the addiction liability of
codeine, isocodeine, pseudocodeine, and Dilaudid has been studied; all
of these drugs are foimd to be definitely habit-forming in man.^^*"^^^
Gross and Pierce conclude from the effects of morphine on the
oxygen consumption of brain tissue that morphine administered subcu-
taneously stimulates rather than depresses brain tnetabolism.^^'^ Numer-
ous investigations have been carried out on excretion,^^®, 119 toler-
ance, ^20, 121 and the effect of morphine on circulation, intestinal activity,
and acidosis,^22-i25 ^nd the effect of Dilaudid on the intestine has like-
wise been rather extensively studied.^^*- 126-129
Reduction of pseudocodeine electrolytically or with sodium in alco-
hol, yields the phenolic isomers dihydropseudocodeine-B and -C, respec-
tively. These isomers differ only in the location of the alicyclic
unsaturation, and can be degraded to the corresponding isomeric meth-
ine bases.13^ The mechanism advanced to account for the appearance
of these isomers led to the search for analogous isomers in the sup-
posedly homogeneous reduction product from desoxycodeine-C and
a-chlorocodide, namely, dihydrodesoxycodeine-A. It could be demon-
strated that this substance consists of a mixture of dihydrodesoxyco-
deines -B and -C, differing likewise only in the location of the unsatu-
rated linkage, and crystallizing together in practically constant pro-
portion, ^^i
The alkylthiocodides are formed by mercaptolysis of the halogeno-
codides, a process parallel to the hydrolysis of these compounds.
a-Ethylthiocodide undergoes an internal rearrangement to the phenolic
3-ethylthiocodide, a reaction demonstrably analogous to the rearrange-
ment of codeine methyl ether to thebainone methyl enolate. 3-Ethyl-
thiocodide and thebainone methyl enolate both undergo hydrolysis to
the true thebainone. The so-called y-ethylthiocodide is in reality only
an oxide of 3-ethylthiocodide, and 8-ethylthiocodide is an ethylthio
analog of pseudocodeine methyl ether. 1^2 jjig metathebainone ques-
tion has been studied with the object of obtaining positive evidence for
the Schopf formula. The series of metathebainone reduction products
obtained supports the 9,14-position postulated for the ethanamine side
chain, the synthesis of a tetrahydrodesoxymetacodeine different from
tetrahydrodesoxycodeine being particularly convincing.^^a
The structure of pseudomorphine is one of the problems of morphine
chemistry that still awaits final solution, and upon which investigation
is still in progress. As a step in this direction, the oxidation of phe-
nolic bases of the morphine series was undertaken, a-, 3-, Y-Isomor-
phines, dihydro-y-isomorphine, dihydromorphine, heterocodeine, and
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224 ANNUAL SURVEY OF AMERICAN CHEMISTRY
dihydrodesoxymorphine-D yield dimolecular oxidation products simi-
lar to pseudomorphine. The point of union of the two nuclei still
awaits demonstration. ^34 jt jg quite certain that any of the morphine
substitutes used in medical practice having the free (or easily freed)
phenolic hydroxyl group, as Dilaudid or heroin, will give dimolecular
products of similar properties, so that specific tests for morphine rely-
ing on pseudomorphine formation can be used only with caution. Tests
for pseudomorphine, preparative methods, and pharmacological data
have been published. ^^5, i36 The need for large quantities of mor-
phenol or methylmorphenol for the study of the physiological action
of simple substitution products (especially amino alcohols) has led to
the development of a greatly improved technique for the degradation
of morphine, of which the unique feature is the decomposition of a- or
3-methylmorphimethines in the presence of sodium cyclohexanolate.^^'^
A large number of salts of codeine with benzoic acid and its derivatives
have been prepared and described, and may be added to the already
very numerous known salts of this important alkaloid.^^® A similar
series of benzoates of strychnine has likewise been published.^39 Codeine
phosphate, crystallized from water, consists entirely of the sesqui-
hydrate.i*o
The opium alkaloids, narceine and narcotine, have been reinvesti-
gated, especially with the view of verifying the identity of opium nar-
ceine with that prepared from narcotine quaternary alkylates. The
results obtained confirm this identity, and indicate that the generally
accepted substituted desoxybenzoin formula for narceine is correct.^*^
A study of the hydrolysis, alcoholysis, and ammonolysis of narcotine
and hydrastine alkyl salts has led to the proposal of a new mechanism
to explain these reactions. The mechanism advanced, which involves
formation of a highly unstable intermediate resulting from opening of
two rings in the quaternary ammonium salt, is supported by the fact
that the reaction between narcotine methyl salts and HA reagents
always produces salts of narceine derivatives.^^^ ^^w contributions to
the pharmacology of narcotine ^^^ and hydrastine and related alka-
loids ^** have appeared.
Several assay procedures have been reported for opium ;i*5-i47 the
International Committee method appears to be less satisfactory in sev-
eral respects than the Group Committee method recommended for adop-
tion in U. S. P. XI. Analytical procedures for the detection of very
small amounts of morphine and heroin have been worked out, especially
for these drugs in saliva ("race horse doping") and in the notorious
"Red Pills" which have lately appeared in the illicit narcotic mar-
Miscellaneous Alkaloids. A new synthesis of racemic pseudo-
ephedrine, based on the a, 3-dibromoether synthesis of Boord, has been
developed, and provides a good method for the preparation of an
extended series of substituted ephedrine derivatives. i"^ An investiga-
tion of the crystalline forms of ephedrine shows it to exist in an anhy-
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ALKALOIDS 225
drous form of m. p. 38.1°, and as a hemihydrate of m. p. 40°. The two
forms give a eutectic mixture melting at 32.1°.^^^ The effect of ephe-
drine on coronary circulation i*"*^ and on spinal reflexes of monkeys ^^®
has been described.
Additional evidence for the cuscohygrine formula is found in the
fact that synthetic ethyl- l-methyl-2-pyrrolidine acetate is identical with
ethylhomohygrinate. This, together with the observation that cusco-
hygrine does not react with benzaldehyde and gives no iodoform test,^^*^
seems to confirm the ^3fm-bis-(l-methylpyrrolidyl) acetone cuscohy-
grine formula of Liebermann and Cybulski.
A number of esters of yohimbic acid, the hydrolysis product from
yohimbine, have been described, in particular, esters with ethylene-
glycol, trimethyleneglycol, glycerol, ethyl enechlorohydr in, trimethylene
chlorohydrin, and cetyl and benzyl alcohols.^^^* ^^^ Weinberg ^^^ has
studied the pressor action of yohimbine and quebrachine.
In the caffeine series a variety of new 8-ethers have been prepared
from 8-chloro- and 8-bromocaffeine.^^i Several of these were con-
verted by the method of Biltz to the corresponding trimethyl-9-substi-
tuted uric acids.^^^ Utilizing the acid anhydride method of Boehringer
Sons, 8-alkylcaffeines were prepared by replacing the 8-hydrogen with
alkoxyl and heating with the acid anhydride containing the desired alkyl
residue. ^^3
Assay procedures, which can be only mentioned here, have been pub-
lished for cinchona,^^* hyoscyamus,^^**'^^"^ Ma Huang,^^® Washington
belladonna,^^^ and for strychnine alkaloids in strychnine sulfate.^*^^
Among analytical methods may be cited those for cocaine in the pres-
ence of procaine,^^^' ^^^ for strychnine and brucine as hydroferrocyan-
ides or dichromates,^^^' ^^^ for the aconite alkaloids,^"^^' ^'^^ and for
ephedrine,^"^"^ as well as general analytical procedures and reagents
applicable to whole groups of alkaloids.^"^**-^^^ See also under the
opium alkaloids.
New Alkaloids. From Lupimis Corymbosis Heller a new alkaloid,
hexalupine, C15H20ON2, has been isolated. Lnpinus Palmeri S. Wats,
yields lupinine and the new bases tetralupine, CioHjgON, and penta-
lupine, Ci6H3oON2.-^^^ The toxic principle of Crotolaria spectabilis
Roth has been identified as an alkaloid, monocrotaline, to which the
formula Ci6H260eN is tentatively assigned.^^"^ The Chinese drug han-
fang-chi, probably from Cocculiis japonicus (Hoffman and Schultes),
a diuretic and cathartic, contains about two percent of alkaloids, the
main constituent being C38H420eN2, probably identical with tetran-
dine.^^^ The tonic and antipyretic drug chin-shih-hu, a mixture of
several Dendrobimn species contains (Szechuan variety) chiefly den-
drobine, CieH2502N, an alkaloid having a slight antipyretic and
depressor action.^^^* ^^^ The pharmacological action of peimine and
peiminine, first isolated in 1932 from the drug Pei Mu, has been inves-
tigated.^®^ From Ceanothus velutinns bark a new alkaloid, C23H26O4N2,
has been obtained.^^^ Coptis occidentalis Salisbury (Western Golden-
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226 ANNUAL SURVEY OF AMERICAN CHEMISTRY
thread) is found to contain about the same amounts of coptine and
berberine as Coptis trifolia, and is a more abundant source of these
alkaloids.^^3 Investigation of Datura innoxia Miller shows it to con-
tain only /-scopolamine.^®* From wu chii 3^11 (Evodia rutaecarpa),
in addition to the known alkaloids rutaecarpine and evodiamine, the
new base wuchuyine, C13H13O2N, has been isolated. The indifferent
compound evodin, for which Keimatsu found C18H22O6, appears to
have the formula C26H3o08.^®^
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97. Simon, A K., and Eddy, N. B., Am. 7. Psychol, 47: 597 (1935).
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119. Plant, O. H., and Slaughter. D., 7. Pharmacol. 54: 157 (1935).
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124. Gmber, C. M., and Brundage, J. T.. 7. Pharmacol, 53: 120 (1935).
125. Rakieten, N., Himwich, H. E., and DuBois, D., 7. Pharmacol, 52: 437 (1934).
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126. Gruber, C. M., and Brundage, J. T., 7. Pharmacol., 53: 445 (1935).
127. Gruber, C. M., Brundage, J. T., DeNote, A., and Heligman, R., /. Pharmacol., 55:
430 (1935).
128. Mitchell, J. B., Jr.. and Hamed, B. K., /. Pharmacol., 53: 331 (1935).
129. Walton, R. P., and Lacey, C. F., /. Pharmacol., 54: 53 (1935).
130. Lutz, R. E., and Small, L., /. Am. Chem. Soc, 56: 1741 (1934).
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134. Small, L., and Faris, B. F., /. Am. Chem. Soc, 56: 1930 (1934).
135. Fulton, C. C, Am. J. Pharm., 105: 503, 511 (1933).
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138. Poe, C. F., and Strong, J. G., 7. Am. Chem. Soc, 51: 380 (1935).
139. Poe, C. F., andi Suchy, J. F., 7. Am. Chem. Soc, 56: 1640 (1934).
140. Wales, H., 7. Am. Pharm. Assoc, 23: 879 (1934).
141. Addinall, C- R., and Major, R. T., 7. Am. Chem. Soc, 55: 1202 (1933).
142. Addinall, C. R., and Major, R. T., 7. Am. Chem. Soc, 55: 2153 (1933).
143. Cooper, N., and Hatcher, R. A., 7. Pharmacol., 51: 411 (1934).
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Pharm., 105: 458 (1933).
146. Bliss, A. R., Rosin, J.. Grantham, R. I., and Blome, W. H., Am. 7. Pharm., 107:
193 (1935).
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152. Munch, J. C., 7. Am. Pharm. Assoc, 24: 557 (1935).
153. Bossert, R. G., and Brode, W. R., 7. Am. Chem. Soc, 56: 165 (1934).
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155. Stoland, O. O., and Ginsberg, A. M., 7. Pharmacol., 49: 345 (1933).
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Chapter XVI.
Food Chemistry.
Caroline C. Sherman and Henry C. Sherman,
Department of Chemistry, Cohmtbia University.
Arrangement of this Review. We here take up, first, the indi-
vidual chemical entities important in foods; second, chemical investi-
tions of food commodities; and, finally, investigations of certain rela-
tions of food to health and longevity, in some of which the experimental
variables have been individual elements and in others have been natural
articles of food.
Carbohydrates and their Enzymes. Continuing their well-
known investigations, Taylor ^' ^ has contributed further to the chem-
istry of starch ; Caldwell 3' * to the chemistry of the amalyses ; and
Nelson^ to that of the invertases (sucrases). Kertesz ^'"^ has stud-
ied the relations of viscosity and water concentration to invertase action.
Spoehr and Milner ^ have entered a practically new area of research
in their studies of the starches of leaves, the first results of which have
appeared toward the end of the year under review. Bendana and
Lewis ® find inulin to be utilized, by the growing rat, as a supplemen-
tary source of energy; but distinctly inferior to sucrose or fructose as
a sole dietary carbohydrate. 3-Lactose has been officially "accepted"
by the American Medical Association ;^^ and Cajori ^^ has determined
a number of the properties of intestinal lactase.
The nutritive value of lactose in man has been studied, from the
viewpoints both of the normal chemistry of nutrition and of medicine,
by Koehler, Rapp, and Hill.^^
In comparisons of the nutritional responses to different sugars, the
year has brought interesting reports. Feyder,^^ experimenting with
rats, found that sucrose has a significantly greater fattening effect than
dextrose; and Whittier, Cary, and Ellis ^* (who employed both rats
and pigs) found that lactose was less fattening than sucrose and more
favorable both to growth and longevity. Carruthers and Lee ^^ find
maltose to be the main product of the action of muscle amylase upon
glycogen. Olmsted, Curtis, and Timm ^^ have studied the feeding of
pentosans and cellulose (fiber) to man.
Fats, Lipoids, and Lipases. Hughes and Wimmer ^'^ find no
increase in the amount of soluble, volatile fatty acids present as glycer-
ides in the thoracic lymph during the digestion of fats which contain
such acids, indicating that the utilization of these acids as food follows
229
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230 ANNUAL SURVEY OF AMERICAN CHEMISTRY
a different path from that of the insoluble fatty acids. Lepkovsky,
Ouer, and Evans ^® found that, when lard was saponified and its dis-
tilled fatty acids esterified with glycerol to form "synthetic" lard, this
was as satisfactory for the normal growth of rats as the original lard,
whether fed as 25 or 60 percent of the diet. When the free fatty acids
were fed alone or merely mixed with glycerol the results were good at
the 25 percent, but somewhat inferior at the 60 percent level. The
methyl and ethyl esters were satisfactory substitutes for the glycerides
at the lower but not at the higher level.
Using the rat as experimental animal, Olcott, Anderson, and Men-
del ^® have studied the influence of cereal diets upon the composition
of the body fat.
Ward, Lockwood, May, and Herrick 20 have described the production
of fat from glucose by molds, and especially the large-scale cultivation
of PeniciUium javanicum for this purpose.
Hileman and Courtney ^i have studied the seasonal variations in
lipase content of milk.
Mattill and Olcott 22 have continued their investigation of antioxi-
dants and the autooxidation of fats. Weber and King^s have studied
the specificity and inhibition characteristics of liver esterase and of
pancreatic lipase. Sure, Kik, and Buchanan ^^ find that a deficiency
of vitamin B or of the vitamin B complex markedly reduces the lipase
and esterase activity of pancreas extracts. Falk and McGuire^^ find
patterns of relative hydrolyzing actions upon ten esters which are
different for the lung tissues of normal and of rachitic rats, whereas
no corresponding differences were found in kidney or liver tissues.
Boyd 26 finds that in man the taking of food under normal conditions
does not cause great variations in the concentration of plasma lipids.
Schoenheimer and Rittenberg have prepared stearic acid 6-7-9- 10d4
from linoleic acid and deuterium,^^ described methods of following its
fate in the body,^^ and shown that the fatty acid radicals thus tagged
with heavy hydrogen were largely carried to the fat depots before
undergoing catabolism.^^ Similarly, coprostanone 4-5d2 has been pre-
pared and studied as an intermediate in sterol metabolism.^®
Sinclair has continued his studies of the phospholipids and found rela-
tively constant ratios of solid to liquid fatty acids, regardless of the
degree of unsaturation of the mixed acids, this depending upon the
relative proportions of the different unsaturated fatty acids present.^^
He also finds further evidence of the selection and retention of imsatu-
rated fatty acids by the phospholipids of animal tissues ;32 ^nd of
the existence in the body of at least two classes of phospholipids: (1)
those essential to the structure of the cell, and (2) those fimctioning
as intermediates in the metabolism of fat. The former tend to con-
tain the more highly unsaturated, the latter the less highly unsaturated,
fatty acids.^^
Amino Acids, Food Proteins and Proteases. The "unknown
essential amino acid" of Rose and his coworkers is now 8*'^*^'^®
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FOOD CHEMISTRY 231
reported to be an a-amino-3-hydroxybutyric acid; the second
"unknown essential" referred to in previous work was found to be
isoleucine. CitruUine and hydroxyglutamic acid are definitely shown
to be non-essential, since satisfactory growth has been secured on
highly purified diets devoid of both of these amino acids.
The observation of Boyd and Mover ^"^ that more diazotized
arsanilic acid couples with proteins than can be accounted for by the
histidine and tyrosine present, remains unexplained; the isolation
(McMeekin ^8) from hydrolyzed protein of a blood pressure depressing
material, which gives a positive diazo reaction, but is apparently not
histamine or histidine, may have some bearing on this question.
The use of potassium trioxalatochromiate, [Cr(C204)3K3], as a
specific precipitant for glycine,^® and of rhodanilic acid, [Cr(CNS)4-
(C6H5NH2)2H], for proline,*^ has enabled Bergmann*^ to speculate
concerning the structure of gelatin. Patton *^ reports new data on the
glycine contents of a large number of proteins, as determined by the
colorimetric method which he has developed.
The sulfur-containing amino acids continue to be the subject of
extensive researches in many laboratories, both from the viewpoint
of their structural significance in proteins generally and in specific
substances of special biological interest, and in their rather unique
interrelationships as indispensable dietary factors. Evidence for the
existence in proteins of at least two other forms of sulfur than cystine
and methionine has been discussed by Blumenthal and Clarke *2 ; one
of these yields sulfate on treatment with bromine water, and sulfide
with alkaline plumbite, while the other yields sulfate on boiling with
nitric acid, but fails to respond to plumbite.
A number of sulfur-containing compounds of interest have been
synthesized by du Vigneaud and his associates; crystalline cystinyldi-
glycine and benzylcysteinylglycine have been obtained and their identity
with the products isolated from glutathione has been proved *3;
homocysteine has been crystallized and converted into the corresponding
thiolactone ** ; a new synthesis for homocystine, not involving costly
methionine as starting material, has been described*^; and this sub-
stance has been resolved into the optically active isomers and their
configurational relationship to naturally occurring methionine estab-
lished.46
The next higher homologs of homocystine and methionine, pento-
cystine and homomethionine, respectively, are entirely ineffective in
replacing cystine for growth,**^ as are also dithioethylamine,*® and the
hydantoins and phenylhydantoins of cystine and cysteic acid.*^ Diben-
zoylcystine appeared to show some value for growth on a cystine-defi-
cient diet.*^ Although rf-cystine appears wholly ineffective in replacing
/-cystine in nutrition. Dyer and du Vigneaud ^^ found that both d- and
/-homocystine supported growth in rats on a cystine-deficient diet; and
Stekol ^"^ observed that Z- and ^/-methionine were equally well retained
in adult and growing dogs.
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232 ANNUAL SURVEY OF AMERICAN CHEMISTRY
White and Jackson ^^ found that the feeding of bromobenzene to
rats in addition to an otherwise growth-promoting diet results in
growth cessation analogous to that on a cystine-deficient diet ; additional
supplements of cystine or methionine, but not of taurine or sodium sul-
fate, permit resumption of growth. The rat is shown to detoxicate
bromobenzene with the formation of /)-bromophenylmercapturic acid.
Medes ^^ presents contributory evidence for the theory that cystine sulf-
oxide may be an intermediate in the metabolism of cystine. Brand,
Cahill, and their associates ^*' ^^' ^^ have studied the effect of various
amino acids on the cystine excretion of a cystinuric. A normal cystine
content of the hair and nails of cystinurics was reported by Lewis and
Frayser ^"^ ; Hess ^® found an abnormally low cystine value in the
nails of arthritic individuals.
Gordon and Jackson ^^ report that amino- A^'-methyltryptophane can
support growth in rats on a tryptophane-deficient diet, while Bz-3-
methyltryptophane and Pr-2-methyltryptophane are without appreciable
effect.
Butts, Dimn, and Hallman ®^ observed both a glycogenic and a
ketolytic action following administration to rats of (/-alanine, e/Z-alanine,
and glycine, the effectiveness of the amino acids in both respects decreas-
ing in the order named.
Borsook and Jeffreys ^^ have adapted the Warburg technique to the
study of the intermediary metabolism of mixtures of natural amino
acids by surviving slices of rat liver, kidney, diaphragm, spleen, and
small intestine; space does not permit mention of their interesting
and significant findings.
With the discovery that phenylalanine and proline are constituents of
crystalline insulin, ^^ Jensen and his coworkers have accounted for
practically all of the molecule, without obtaining any indication of a
prosthetic group which might explain the unique physiological activity
of this protein. After treatment of the hormone with phenylisocyanate
or with a-naphthylisocyanate, only five percent of the potency remains,
although the sulfur and cystine values are unchanged.®^ xhe inactiva-
tion by sulfhydryl compounds and by metallic derivatives has also been
studied.^^
Kunitz and Northrop ^* report the isolation from pancreas of a new
crystalline zymogen, chymotrypsinogcn, changed by crystalline trypsin
(but not by enterokinase) to an active proteolytic enzyme, chymotrypsifiy
which has also been crystallized and which differs somewhat in its
enzymatic behavior from crystalline trypsin. Both of these new products
seem to be pure proteins, in which the activity is a property of the
protein molecule.
Contrary to the old theory that long chain peptides are the major
products of the action of pepsin on proteins, Calvery ^^> ^® has confirmed
his earlier observation that the enzyme (in 8 to 40 days) can hydrolyze
about one-third of the peptide linkages in crystalline ^gg albumin, and
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FOOD CHEMISTRY 233
he has shown that free amino acids and dipeptides are among the split
products.
Methods for the preparation and assay of trypsinogen and enterokinase
are discussed by Bates and Koch,^^ who conclude that enterokinase
behaves as a catalyst in activating trypsinogen. Cohn and White,^^ in
studying the hydrolysis by pepsin and by trypsin of heat-treated and
raw egg white, obtained indications that the latter contained an anti-
tryptic agent. Sure, et al.^^' "^^ report a technique for the estimation
of the tryptic-ereptic activity of pancreatic and intestinal extracts of
the rat; and note that this activity is unimpaired in deficiency of
vitamin B or of the vitamin B complex.
The chemical and configurational requirements for the substrate in
dipeptidase action have been defined by Bergmann, et al.,'^^ who dis-
cuss in detail a theory for the mechanism of dipeptidase action. Natural
papain has been shown to contain two proteolytic systems, a proteinase
and a new polypeptidase, the former being reversibly inactivated by
oxidation, the latter irreversibly inactivated. "^2 ^he substrate require-
ments of the polypeptidase, which have been studied in detail with a
large number of synthetic peptides, differentiate this enzyme from the
already known dipeptidase, aminopolypeptidase, and carboxypoly-
peptidase.'^^' "^^
Tyrosinase has been studied by Graubard and Nelson,*^^* "^^ who define
a new unit of activity and present evidence that the same enzyme
catalyzes the oxidation of both mono- and di-hydric phenols. The
activafion of arginase by metals has been studied by Hellerman and
Perkins,"^"^ who have also observed hydrolysis of arginine in the absence
of arginase by crystalline urease with suitable metallic ions.
Quantitative aspects of the nutritive efficiency of proteins and of the
protein requirement in nutrition. While space does not permit of its
full discussion here, mention should be made of the extended work of
Smuts "^^ (under the direction of, and prepared for publication by,
H. H. Mitchell at the University of Illinois) upon the relation between
the basal energy metabolism and the endogenous nitrogen metabolism,
with particular reference to the estimation of the maintenance require-
ment for protein. In the same laboratory, the metabolic nitrogen of
the feces of the rat, swine, and man has been investigated by Schneider "^^
from the viewpoint of dividing it into a "digestive fraction," which
varies directly with the quantity of food consumed, and the true
"endogenous nitrogen," which is independent of the food consumed.
Mason and Palmer ^^ report comparative experiments upon the nutri-
tional efficiency of casein, gelatin, and zein for maintenance in adult
rats. "The percentage retention (of nitrogen) calculated by McCol-
lum's method averaged 74 for casein, 23 for gelatin, and 57 for zein.
The percentage retention increased as less protein was ingested,
even though it was never fed above the endogenous level." The original
article must be consulted for full interpretation. In a carefully con-
trolled series of experiments, Forbes and his coworkers ^^ observed a
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234 ANNUAL SURVEY OF AMERICAN CHEMISTRY
progressively increasing efficiency of utilization of food energy for
growth in rats as the percentage of protein (casein) in the diet was
increased from 10 to 25 percent. Daggs and Tomboulian ^^ find those
proteins especially favorable to support lactation which furnish richly
the constituents of glutathione. Csonka®^ has investigated the pro-
teins of yeast and reports that "The cystine, tryptophane, histidine, and
lysine content of yeast protein places it in a favorable position among
those considered of good quality."
Hematopoietic substances. Substances of protein or polypeptide
nature, whose special significance is related to hemoglobin and
erythrocyte formation, are reviewed in connection with iron.
Mineral Elements. Variations in the intake of each of the com-
mon mineral elements during a prolonged series of balance experiments
have been studied by Bassett and Van Alstine.®* When the diet was
kept constant in terms of the kinds and amounts of the articles of food
used, the variations in intake from period to period were, in many
cases, significantly larger than the variations in a series of analyses
of the same sample, indicating that in metabolism balance experiments
food should actually be analyzed for each balance period.
Calcium and phosphorus, Daniels and coworkers®*^ have reported
experiments from which they conclude that the calcium needs of normal
children of preschool age can be met by foods furnishing 45 to 50 mg.
of calcium per kilogram of body weight, or 7 to 9 mg. per centimeter
of height, provided sufficient vitamin D is allowed; and that the phos-
phorus needs can be met with 60 to 70 mg. per kilogram, or 9 to 11
mg. per centimeter. Sherman and. Campbell ^^ have published the
results of an extended series of experiments upon the effects of increas-
ing the calcium content of a diet which had already been shown ade-
quate in that it maintained normal growth, health, reproduction, and
lactation through successive generations of rats. The enrichment
of the calcium content from 0.2 percent to 0.35 percent of the dry food
resulted in more efficient utilization of the food (whether calculated on
the basis of its energy value or protein content), earlier maturity, and
higher adult vitality, showing that the optimal intake is considerably
higher than the "need."
Kohman and Sanborn®"^ have reported preliminary indications that
oxalates in foods act both to diminish the absorption of calcium from
the digestive tract and to increase the body's loss of calcium in the
urine. Simultaneously, Fincke and Sherman ^^ investigated the
quantitative nutritional availability of the calcium of milk, kale, and
spinach. The calcium of milk was excellently utilized, and that of
kale showed almost as high a percentage availability, while the cal-
cium of spinach was utilized to only a very small extent, if at all. The
unavailability of the calcium of spinach was not due to fiber, and was
shown experimentally to be at least chiefly due to the oxalic acid or
oxalates present.
Clinical cases of calcium deficiency in infancy and in childhood
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FOOD CHEMISTRY 235
have been reported by Nesbit®®; and Newburgh®^ has emphasized
the dependence of normal skeletal development upon the supply of
calcium and phosphorus available to the fetus through the mother;
while Campbell, Bessey, and Sherman ^^ have shown how a low intake
of food calcium, not recognizable as a deficiency in the first genera-
tion, may result in the deterioration and dying out of the family if
continued too long.
Iron and hematopoietic substances, Vahlteich, Funnell, MacLeod,
and Rose ^^ find the iron of tgg yolk and of bran, prepared for human
consumption by steaming and toasting, to be equally effective for
the maintenance of iron equilibrium in the human adult. These experi-
ments also add to our knowledge of the quantities of iron needed in
normal human nutrition. The data for one subject (a woman of 56
kilograms body weight) indicated a need of 6.0 mg. iron per day, or
0.11 mg. per kilogram. The other subject, weighing 71 kilograms, had
a larger proportion of body fat and appeared to need only 6.1 mg., or
0.09 mg. per kilogram, per day. The iron requirement of the normal
human adult has also been studied by Farrar and Goldhamer®^. ^nd
the iron metabolism of preschool children, by Ascham.®*
Orten, Smith, and Mendel,®^ in experiments with rats whose diet was
relatively poor in mineral elements, found that an increase of the cal-
cium allowance exerted a markedly favorable effect upon the iron
economy and normal blood formation. Ellis and Bessey ®^ have studied
the effects of different diets upon the hemoglobin concentration of the
blood in rats at one month and at one year of age.
Whipple and coworkers ^^ have studied further the relative efficiencies
of heart, kidney, liver, and spleen preparations in blood regeneration.
They conclude that several factors, rather than a single hematopoietic
factor, are concerned with regeneration after blood loss; and that this
process should be distinguished sharply from that of recovery from
pernicious anemia. In the same laboratory,®^ \^ ^^s found possible, by
adjustments and alternations of feeding and fasting periods, to vary the
"metabolic path" taken by the nutrients and metabolites, with resulting
differences in efficiency of hemoglobin formation, striking conservation
of metabolized material being sometimes effected. Whipple ®® has also
summarized both the most recent and the previous work of his laboratory
upon hemoglobin regeneration as influenced by diet and other factors.
Dakin and West ^^^ have discussed the chemical nature of a hema-
topoietic substance isolated from liver, which has the properties of a
hexosamine-peptide. Subbarrow, Jacobson, and Fiske ^^^ have briefly
reported the separation of two crystalline substances from liver, both
of which are reticulocytogenic in guinea pigs and one of which is
effective in the cure of experimental blacktongue in dogs.
Iodine, Holmes and Remington ^^^ find from 3,000 to 13,000 parts
per billion of iodine in cod liver oil; and estimate that 10 cc. of cod
liver oil, the daily amount recommended by the U. S. Pharmacopoeia,
furnishes by itself about enough iodine to meet the daily needs of
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236 ANNUAL SURVEY OF AMERICAN CHEMISTRY
normal nutrition. Coulson ^^^ finds 290 parts per billion of iodine in
the meat of the conch, for which he j^ives the analysis (on the fresh
basis) : moisture 74.6, protein 18.6, fat 0.3, ash 1.7, calcium 0.089,
phosphorus 0.112, magnesium 0.246, and sulfur 0.315 percent.
Holley, Pickett, and Brown ^^^ have studied the causes of variation
in the iodine contents of vegetables.
Other mineral elements, McCollum and his coworkers ^^^' ^^^ have
continued their investigation of jnagnesium as a nutritionally essential
element ; and Duncan, Huffman, and Robinson ^^'^ have observed the
development of tetany associated with low blood magnesium in calves
reared on a milk diet.
Daniels and Everson ^^^ have found a dietary deficiency in manganese
to be responsible for the congenital debility of the young of mothers
reared on milk modified with copper and iron.
Zinc was found by Stirn, Elvehjem and Hart '^^^ to be indispensable
to the normal nutrition of the rat.
The effects of diets deficient in mineral elements generally have been
investigated further by Clarke and Smith,^^^ and by Swanson, Timson,
and Frazier.m
Fluorine toxicosis has been studied extensively by workers at the
University of Wisconsin 112-114 ^^d by Smith and Lantz.^i^
Franke and his associates ii<5-i20 continue their investigation of
poisoning by natural plant foodstuffs with an abnormally high selenium
content.
Vitamin A and Its Precursors. Mackinneyi^i has studied the
carotenes of the leaves of 59 species of plants and found that 3-carotene
is the major fraction in all these cases, while in 40 of the 59 cases
a-carotene was found in proportions ranging from traces to 35 percent
of the total carotene present. "Phylogenetic considerations have been
applied with fair success in predicting that leaves of closely related
plants or groups of plants will not differ materially in their carotene
complexes." Strain ^22 has made a further study of the carotenes from
different sources and of the properties of a- and 3-carotene.
Treichler, Grimes, and Fraps ^^^ have studied the relation of the
color and carotene content of butter fat to its vitamin A value, especially
in the case of cows kept on rations consisting largely of white and
yellow corn (maize), respectively. In both cases, transfer from pasture
to the grain ration resulted in gradual decline both of the carotene con-
tent and of the vitamin A value of the milk fat, but to a less extent
with yellow corn than with white corn. Their bulletin should be read
in full by those interested in the subject.
Guilbert and Hart ^^^ have continued their studies of the vitamin A
requirement of cattle and the storage of this vitamin and its precursor
in the different parts of the body.
Vitamin B Complex. Following the preliminary report of Wil-
liams ^25 suggesting the structure for vitamin B hydrochloride much
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FOOD CHEMISTRY 237
confirmatory evidence has appeared. ^26-133 (s^g Chapter XIV for
discussion.)
Some clinical- observations with crystalline vitamin Bj have been
reported by Vorhaus, Williams, and Waterman,i34 ^^^o found strikingly
beneficial results in a large number of cases of neuritis of various origin
and in the small number of cases of "unexplained gastrointestinal
hypotonia with anorexia" which they studied. These authors con-
cluded that "there is evidence to suggest frequent deficiency of vitamin
Bi in the human dietary." Further studies, the details of which are
not available, have indicated a beneficial effect of large doses of
the vitamin in some cases of deranged carbohydrate metabolism.^^*' ^^^
Waterman and Ammerman ^^^ found that the administration to young
rats on the Chase- Sherman diet of graduated doses of the crystalline
vitamin up to 160 gamma per day (80 to 160 times that necessary for
maintenance of life) resulted in progressive increases in the growth
rate until "the growth at the higher levels of B dosage approaches the
best obtainable with rich mixed diets (Yale)." There was thus no
indication of requirement of a second heat-labile B factor; "A more
probable explanation is that large amounts of B exercise a growth
acceleration sometimes confused with that due to B4." Adult pigeons,^^*^
depleted of vitamin B on a diet of autoclaved whole wheat for three
weeks, showed progressive increases in weight with supplements of
10 to 80 gamma per day of crystalline vitamin, but even with 160
gamma (40 times the amount required to cure polyneuritis) the "normal**
weight (i. e., the weight before depletion) was not attained, although
amounts of raw whole wheat containing not more than 50 to 60 gamma
of vitamin Bj restored the birds to normal weight. "The results
reported furnish additional evidence that there is a B complex factor
other than B (B^) needed for the complete nutrition of pigeons."
Members of Williams' group have also reported studies on the
injection method of measuring the vitamin B values of purified
preparations.^^®
The relative concentrations of vitamin B found by Brodie and Mac-
Leod ^^^ in tissues from young adult rats reared on an "adequate" diet
were roughly as follows : liver 10, heart 10, kidney 5, brain 3, and muscle
1. Spleen, lung, and blood showed only traces of the vitamin. The stores
in some organs could be significantly increased by fortifying the diet
with brewers* yeast. After animals had been maintained for four to
five weeks on a depletion diet, the presence of vitamin B could not be
demonstrated in any organ except the brain. In accordance with this
work, Griffith ^^^ found that the body stores of vitamin B were readily
depleted when rats were fed a B-deficient diet ; on the other hand, even
after 100 days on a G-deficient diet, the tissues still contained much
vitamin G. Evans and Lepkovsky ^^^ noted a definite sparing effect
of high-fat diets on the vitamin B content of the liver, muscle, and
brain of rats reared on a diet deficient in vitamin B. A marked deple-
tion of the absolute amount of the vitamin present in the liver was
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238 ANNUAL SURVEY OF AMERICAN CHEMISTRY
noted under conditions in which but little loss occurred from the
muscles, indicating that "the liver seems to be the site of the greatest
initial withdrawal of vitamin B."
Using the chick as test animal, Keenan, Kline, Elvehjem, and Hart ^^
find that the thermolability of vitamin B4 is similar to that of vitamin
Bi; and that under some conditions of dry heat to which vitamin Bi
is relatively stable, vitamin B2 may be inactivated.
Bisbey and Sherman ^*^ have studied the extractabilities and sta-
bilities of vitamins B (Bj) and G (lactoflavin) in the forms in which
these occur naturally as in milk. An effective method for the complete
extraction of all of the vitamin B complex from yeast has been
described by Itter, Orent, and McCollum.^** These workers ^^^ have
also reported a simplified procedure for preparing lactoflavin, and a
study of its growth effect. Stare ^^® has described the preparation of
hepatoflavin, and has foimd with this, as others have foimd with lacto-
flavin, that flavin is a growth-essential, but does not possess the entire
growth-promoting or antidermatitic fimction of the heat-stable part
of the vitamin B complex.
Lepkovsky, Popper, and Evans '^^'^ have described the preparation
of crystalline flavin (vitamin G) which, under their experimental con-
ditions, promoted the growth of chicks; but which, in the hands of
Lepkovsky and Jukes,^*^ did not prevent the appearance of the so-called
pellagra-like syndrome in chicks as also reported by Elvehjem and
Koehn.i*^ In view of the experiments of Booher,^^^ as well as of
several investigators abroad, it should not be inferred that promotion of
growth and protection from skin troubles are functions of separate
vitamins, but rather that of these two vitamins (G; and H, Bq or Y)
both are needed for permanently good skin condition as well as for
growth.
A possible role of the sulfhydryl group in the syndrome usually
viewed as vitamin G-deficiency was emphasized by Itter, Orent, and
McCollum,^^^ who found that certain sulfhydryl compounds cured
the alopecia and tended to prevent a decline in weight in animals on a
vitamin G-deficient diet; whereas, under the same conditions, lacto-
flavin failed to cause growth of hair but induced a definite gain in
body weight.
Spies and Dowling ^^^ report the experimental production of anemia
in dogs by means of a blacktongue-producing diet consisting of: corn-
meal, 400 gm. ; cowpeas, 50 g^m. ; purified casein, 95 g^m. ; cottonseed
oil, 30 cc. ; cod liver oil, 15 cc. ; and salt mixture, 22 gm. They con-
clude that "in view of our present inadequate information concerning
the nature of the chemical substance or substances involved, it seems
unwise to assume that the dermatitis, stomatitis, anemia, neuritis, and
dementia of pellagra in human beings ; and the dermatitis, blacktongue,
diarrhea, anemia, and neurological involvement developed in dogs
restricted to an unbalanced diet are all produced by the lack of the
same specific chemical substance."
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FOOD CHEMISTRY 239
According to Elvehjem, Sherman, and Arnold,^^^ pork muscle, heart
muscle, and kidney are "fairly rich" in vitamin B, whereas beef muscle,
mutton muscle, brain, and lung are "very low." Sebrell, Wheeler, and
Hunt ^^* find rabbit meat, lean pork shoulder, and canned chicken to
be good, peaches fair, prunes and canned beets poor sources of the
pellagra-preventing substance. Morgan and coworkers ^^^' ^^^ have
compared the quantitative distribution of vitamins B and G in wheat
products and some other foods, and have found no significant loss of
vitamin B in the baking of bread. Poe and Gambill ^^'^ foimd an
average of 0.21 unit of vitamin G value per cc. of home-canned tomato
juice.
Vitamin C. The American Medical Association ^^^ ^^s an-
nounced that, "By reason of its rules against therapeutically sug-
gestive names, the Council could not recognize the name 'Ascorbic
Acid,' although this term has been used in the literature The
Council adopted the term 'Cevitamic Acid' as a non-proprietary
designation for the crystalline vitamin C introduced as Ascorbic
Acid The Council feels strongly that investigators in naming
newly discovered medicinal substances should bear in mind the
fundamentally sound objections to the use of therapeutically
suggestive names."
Guerrant, Rasmussen, and Dutcher ^^^ have found that titration
against a standard solution of 2,6-dichlorophenol indophenol yields
results in satisfactory agreement with feeding experiments in the
examination of grapefruit, lemon, orange, or fresh pineapple juice ;
but that "some juices contain interfering substances that react with
the dye, thus complicating the titration results and leading to
erroneous conclusions."
Dann and Cowgill ^^^ have reported results which indicate that the
vitamin C requirement of the guinea pig is directly proportional to the
body weight, and is almost exactly 1 cc. of lemon juice per 100 grams.
"There is no evidence from these data that the young, rapidly growing
guinea pig requires a proportionately greater amount of this dietary
factor than the adult." They also conclude that: "The role of the
metabolic rate, which in the case of vitamin B has been found to be
of equal importance to body weight as a determinant of the require-
ment of various species for the vitamin, appears insignificantly small
so far as vitamin C is concerned." These findings have a twofold
significance for food chemistry in that, ( 1 ) they show the importance
of vitamin C in practical food values for adults, and (2) they correct
a very prevalent overestimate of the vitamin C value of lemon juice
in terms of nutritional need. Goettsch ^^^ has compared the effects
of pure vitahiin C with those of orange juice in clinical scurvy of
infants.
King and Menten ^^^ find that a liberal intake of vitamin C is favor-
able to stamina and ability to resist injury from diphtheria toxin.
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240 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Bogart and Hughes ^^^ have investigated anew the development of
vitamin C in the sprouting of grain (in this case oats).
Vitamin D. The trend of recent work is strongly to complicate
the consideration of vitamin D. Most students of the subject now
recognize the existence of at least three vitamins D; while Bills, at
the Johns Hopkins Conference on the Chemistry of the Vitamins
(July, 1935), spoke of the probability of at least ^\q.
Study of the species differences in the relative response to vitamin D
from various sources, which earlier demonstrated the non-identity of
the antirachitic factor in irradiated ergosterol with that in fish liver
oils, and suggested the existence of at least two forms of the vitamin
in the latter source, has now afforded abundant confirmation is^-iee of
the finding of Waddell that the provitamin D in crude cholesterol
is not ergosterol, and, indeed, it now appears probable that the light-
activatable substance in animal tissues is not ergosterol ^^^ ; on the
other hand, plants of both higher and lower botanical orders contain
a provitamin D which, like ergosterol, gives rise to an antirachitic
factor relatively much less effective in the chick than in the rat.^^®
Carrying the vitamins D which are relatively less effective in the
chick than in the rat are irradiated ergosterol, irradiated plant
materials ^^^ (cottonseed oil, wheat middlings, alfalfa leaf meal, dried
mycelium, yeast), and milk produced by cows fed irradiated yeast. ^®^"^^^
Containing the forms of vitamin D which are of relatively high effective-
ness for the chick are cod liver oil, irradiated crude cholesterol,^^^"^^^
irradiated animal products in general ^^^ (hog brains, butter fat, lard),
irradiated milk,^^^' ^^^ irradiated purified cholesterol in which activata-
bility has been produced by heating,^^^' ^^^ and apparently the
cholesterilene sulfonic acid of Yoder.^*^^
Clinical studies of the year lend increasing confidence to the assump-
tion that antirachitic effectiveness as determined on the rat is a reliable
measure of the potency in infantile rickets. Equal antirachitic effective-
ness (rat unit for rat unit) in the human infant has been found for
the various forms of "vitamin JD milks" : irradiated (fresh and
evaporated), "fortified" (by the addition of cod liver oil concentrate),
and "metabolized" (produced by cows receiving irradiated yeast ).^^^'
171-174 However, Compere, Porter, and Roberts ^'^^ still find that 1.1
to 3.3 times as many rat units in the form of irradiated yeast as in the
form of cod liver oil must be administered for comparable degrees of
healing in human rickets.
The methods of increasing the vitamin D potency of dairy products
have been discussed critically by Krauss and Bethke.^*^^ Guerrant and
coworkers ^"^"^ and Russell and Taylor ^'^^ have investigated further the
relationship between the vitamin D intake of the hen and the antirachitic
potency of the eggs produced. The Committee on Foods of the Ameri-
can Medical Association has disapproved fortification of "foods other
than dietary staples" and of miscellaneous accessories with vitamin D.
Bills and his coworkers ^"^^ reported a taxonomic study of the dis-
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FOOD CHEMISTRY 241
tribution of vitamins A and D in 100 species of fish, representing
seventeen zoological orders. They found that three-quarters of the
liver oils which they investigated were more potent than cod liver oil.
Vitamin D, however defined, appears a somewhat less controlling
factor in rickets than has commonly been assumed during the preceding
decade. In a paper on the phytin phosphorus of the corn component of a
rachitogenic diet, Harris and Bunker ^®^ report the development of
diets "which were devoid of extractable vitamin D, low in total phos-
phorus, and with Ca:P ratios as exaggerated as 8:1 (and which)
failed to induce rickets" in rats. Healing of rachitic lesions in young
rats transferred to a diet of normal phosphorus content but containing
only traces of calcium and vitamin D has been reported by Jones and
Cohn.^^^ Huffman and Duncan ^^^ observed that rickets in calves on a
diet inadequate in vitamin D may be checked by the addition of
magnesium salts, although in the complete absence of vitamin D these
salts are ineffective. Further observations on the alleged rachitogenic
factor in cereals have been reported by Harris and Bunker ^^^ and by
Lachat and Palmer.^^^
Evidence as to the effectiveness of vitamin D, or any of the five (?)
vitamins D, in promoting retention, as distinguished from mohilization,
of calcium and phosphorus in nutrition continues to be indecisive.
Coons and Coons ^®* find only slight and irregular effects under con-
ditions of pregnancy with calcium and phosphorus need such as would
seem to have been well suited to permit the vitamin to show what-
ever favorable effect it may have upon the economy of these elements
in metabolism. Swanson and lob ^^^ report that feeding vitamin D
in the form of cod liver oil to the mother rat increased the calcium
content of the offspring 10 percent, and their phosphorus content 12
percent. Slightly smaller increases resulted from the feeding of
viosterol (commercial irradiated ergosterol), even though the dosage
in antirachitic units was much more liberal.
Wallis, Palmer, and GuUickson ^^^ find that under certain conditions
vitamin D is specifically needed by calves, and when given acts to
improve the retentions of calcium and phosphorus as demonstrated by
the balance of intake and output of these elements.
An extension of the studies on the interrelationship of the para-
thyroid hormone and vitamin D has led Morgan and Samisch ^^'^ and
also Jones ^^® to the conclusion that vitamin D does not act exclusively
through the parathyroid mechanism.
Vitamin E. According to press dispatches, Evans ^^® has isolated
vitamin E in crystalline form in sufficient quantities for identification.
Olcott 1^^ has investigated further the chemical behavior of vitamin E ;
and Barnum ^^^ has studied the vitamin E content of eggs as related
to the diet and to hatchability.
Indications of Other Factors. Leucopenia and anemia, resulting
in the monkey from a vitamin deficiency or deficiencies the exact
nature of which is still under investigation, have been reported by
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242 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Day, Langston, and Shukers.i**^ Dried brewers' yeast prevented
this deficiency disease. Almquist and Stokstad ^^^ report pre-
liminary investigations of the apparent dietary origin of a hemor-
rhagic disease of chicks.
Meats, Fish and Shellfish. Pittman and coworkers i^*' ^^^ have
reported the second and third parts of their experimental investi-
gation of the utilization of meat (here beef muscle, heart, and
liver) by human subjects. Further studies upon the nutritive value
of beef heart, kidney, roimd, and liver after heating and after alcohol
extraction have been reported by Seegers and Mattill.^^® Williams
and coworkers ^^'^ continue their experiments upon the cooking
of meats with acid to bring more of the calcium of meat-bone into
the service of human nutrition.
Devaney and MunselH®^ find between 0.4 and 0.5 International
unit of vitamin D per gram of beef or hog liver; slightly less than
0.2 unit in lamb liver; and only about 0.1 unit in calf liver. Oysters
have been found by Whipple ^®® to be "an excellent food source of
vitamin B (Bj), a relatively good one of vitamin A, and a very
modest source of vitamin D." Devaney and Putney 200 find canned
salmon a good source of vitamin D, and a variable source of
vitamin A, of which one sample showed 30 times as much as
another. The chemical and physical properties of haddock-liver
oil, and its yitamin values, have been investigated by Pottinger
and coworkers.201
Fowler and Bazin202 have published the maxima, minima, and
averages of their analyses of meats and fish for moisture, protein,
fat and ash.
Coulson, Remington, and Lynch ^os find that the naturally occurring
arsenic in the shrimp is in a form which, when the shrimp is eaten
and digested, is rapidly eliminated through the kidneys and apparently
without toxic effect.
Rupp204 has investigated the effect of />H on the formation of
ferrous sulfide from the viewpoint of preventing discoloration of canned
meats. The chemistry of the deterioration of fish, and its prevention
by carbon dioxide, have been studied by Stansby and Griffiths.^^"^
Eggs. Bailey 2o« has introduced a new method for the deter-
mination of the foaming power of ^^g white and for testing the
stability of the foam. Unfrozen whites and whites thawed after short
periods of frozen storage showed little if any difference in this property.
Thick white, however, had a higher foaming power than thin white;
and the stability of the foam was found to be influenced by various
treatments. The addition of olive oil decreased foaming power to a
greater extent than did the addition of the same amount of fat in the
form of tgg yolk. The same author ^07 also shows the practicability
of refractometric estimation of the total solids of eggs (white and yolk)
and of egg-yolk magma. Sell, Olsen and Kremers^^^ have studied
lecithoprotein as the emulsifying ingredient of tgg yolk and with
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FOOD CHEMISTRY 243
reference to mayonnaise. Preliminary results of an investigation
of the gelation of tgg sols in the presence of electrolytes have been
reported by Woodruff, Pickens, and Smith.^o^
The transmission of light through tgg shell as a factor in the
candling of eggs has been studied by Givens, Almquist, and Stokstad.210
The nutritive value of the tgg in child feeding has been investigated
experimentally by Rose and Borgeson.^n Devaney, Titus, and
Nestler 212 find that feeding of vitamin D does not influence transfer of
vitamin A to the ^gg) but considerable increases of vitamin A intake
led to marked increases in the vitamin A values of the eggs produced.
Koenig, Kramer, and Payne ^13 have studied the vitamin A values of
eggs as related to the laying-record of the hen. Yoimg hens, nearing
the end of their first four months of ^gg production, yielded eggs with
yolks of similar value, about 25 units per gram; while near the end of
a year of laying, those of low production laid eggs whose yolks showed
33 units, and those of high production, about 20 units. Pale eggs
produced on a ration devoid of carotene and xanthophyll but containing
cod liver oil had 25 units per gram of vitamin A value in the yolk.
Milk. Homogenization has been found by Trout, Halloran, and
Gould 2^* to increase the titrable acidity of raw, but not of pasteurized,
milk. Also the process seemed to increase the viscosity of raw milk
and to decrease that of pasteurized milk, though causing no important
change in the specific gravity. The stability of the protein of milk
toward alcohol was decreased by the homogenization, as was also the
curd tension. Lasby and Palmer ^is have reinvestigated the effect of
pasteurization and find no change in the calcium and phosphorus con-
tents of milk, and no significant difference between raw and pasteur-
ized milk as to the retention of these elements and the support of normal
development of the bones. The nitrogen also was of equal nutritive
value in raw and pasterized milk.
The phospholipids of milk have been found by Perlman^io to be
more thermostable than previously supposed. He reports ^17 that they
are concentrated proportionately to the fat in cream up to a fat content
of about 55-58 percent, beyond which the proportion of phosphatide
diminishes.
Development of color in heated lactose solutions and evaporated milk
has been studied by Webb.^is
In the experiments of Jack and Bechdel,^!^ the injection *of thyroxine
seemed to increase the yield but not to influence the composition of
milk.
Butter and Buttermilk. Templeton and Sommer 220 report that
the addition of citric acid or sodium citrate to either cream or the starter
or both tended to produce a butter of superior flavor and aroma.
Michaelian and Hammer 221 find that acetylmethylcarbinol and biacetyl
are formed in the butter-making process, and have studied the condi-
tions influencing their production. Whittier and Trimble 222 have
investigated the differences in lactic acid content among butters. The
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244 ANNUAL SURVEY OF AMERICAN CHEMISTRY
nature of the fatty materials in buttermilk has been further investigated
by Bird, Breazeale, and Sands.223
Cheese and Whey. Goss, Nielsen, and Mortensen^s* have
developed, at the Iowa Agricultural Experiment Station at Ames, a
process for the manufacture and curing of a Roquefort-type cheese
to which they have given the name Iowa Blue. Lane and Hammer 225
have investigated the effects of pasteurizing the milk used in cheese-
making upon the transformations which occur in the nitrogenous con-
stituents of Cheddar cheese. Heiman^se finds that much the larger
part of the vitamin G of milk passes into the whey in cheese-making,
the whey solids showing about 50 percent higher vitamin G value
than the solids of skimmed milk.
Grain Products, Baking and Brewing. Alsberg 227 has reinvesti-
gated the variations in quality and baking value of wheat flours, with
special reference to the influence of their starches. The diastatic
activity of wheat as influenced by various factors has been studied by
Swanson228j that of flour by Steller, Markley and Bailey 229 j and
the catalase activity of wheat flour by Blish and Bode.230 Bailey and
Sherwood 231 have investigated the interlocking significances of the
actions of amylases and of yeast in the breadmaking process.
Bayfield 232 has continued the study of the relations of the kinds and
amounts of the proteins in wheats to the bread-making qualities of their
flours. The effects of mixing and fermentation upon the protein
structure and colloidal properties of dough, and the problem of free
and bound water in bread doughs have been discussed by Skovholt
and Bailey 233 J and the peptization of wheat-flour proteins under the
influence of organic acids by Mangels and Martin.234 Balls and
Hale 235 have investigated the phenomena of proteolysis in flours.
The pigments of wheat have been studied extensively by Markley
and Bailey,236 and the bleaching of flour by Munsey.237
Hooft and de Leeuw238 find acetylmethylcarbinol, formed as a by-
product of the action of yeast upon sugar, in bread, where they believe
it to be an important factor in flavor.
The distribution of nitrogen in the maize kernel at different stages
of maturity has been reported by Zeleny.239
Bailey, Capen, and LeClerc 2*0 have reported their extended investi-
gation of the composition and characteristics of soybeans, soybean flour,
and soybean bread.
A notable symposium on developments in brewing processes and their
control includes the papers of Schwartz,24i of Michaelis,242 and of
Siebel and Singruen.243
Fruits and Vegetables and their Products. Haas and Klotz 244 have
studied the solids, individual mineral elements, and />H of citrus fruits
from the viewpoint of the influence of maturity and of the determina-
tion of physiological gradients between the calyx and stylar halves of
the fruit ; and Haas and Bliss 245 have made a similarly thorough inves-
tigation of the composition of Deglet Noor dates in relation to water
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FOOD CHEMISTRY 245
injury. The composition of the developing asparagus shoot was
studied by Culpepper and Moon^^e jn relation to its use as food and
its properties as material for canning. Total nitrogen showed its high-
est concentration at the tip, while the concentration of sugar was highest
at the base and diminished toward the tip at all stages of growth.
Adams and Chatfield^^? have published a new classification of fruits
and vegetables according to their carbohydrate content.
Coleman and Ruprecht ^48 found no marked or constant influence of
soil type upon the mineral composition of vegetables; and concluded
also that fertilizers containing nitrogen, phosphates, and potassium
salts, when used in amounts necessary for optimal crop production,
exert very little influence upon the composition of the vegetables grown
with them. Haas^^o has reported upon the differences in chemical
composition of the juices of oranges grown upon differently fertilized
soil. Mitchell ^^o has studied the relationships and variations of com-
position and color in commercial tomato juice. The Federal require-
ment for drained solids in canned tomatoes has been increased to 50
percent.251 Pitman ^52 finds the oil content to be the best criterion
of maturity in olives.
Balls and Hale^^a have investigated the role of peroxidase in the
darkening of the cut surfaces of apples, which is prevented by gluta-
thione or cysteine salts. The respiratory activities and other chemical
changes of apples in storage have been studied by Harding.254 Advances
in the technology of the production of apple juices, concentrates, and
syrups are reported by Poore.^ss Baker and Kneeland ^56 have inves-
tigated conditions for the extraction of pectin and control of the proc-
ess by the determination of viscosity; they^si have also studied the
influence of diastatic preparations upon the properties of apple pectin.
Fellers and coworkers ^58 have continued their investigation of cran-
berries. Joslyn and Marsh ^^o have found that the browning of orange
juice can be prevented by the addition of small amounts of sulfites or
other antioxidants, or by canning the juice in tin.
Rittinger, Dembo, and Torrey^^o report favorably upon the use of
soybean "milk" in feeding children. A soybean product containing
lecithin and associated phosphatides with oil, and intended as an emul-
sifying agent for use in foods, has been "accepted" by the American
Medical Association.^^! Horvath262 shows the presence of at least
two phosphatides in the soybean ; and Jamieson and McKinney 203 find
that, in general, soybeans of the western states are richer in phospha-
tides than those of the eastern states. Horvath 264 has contributed fur-
ther to the chemical technology of the soybean industry.
Culp and Copenhaver 265 have studied the losses of iron, copper, and
manganese from vegetables cooked by different methods.
Morgan 266 has reported her studies upon the influence of the cus-
tomary dipping in lye, of air- and sun-drying, and of sulfuring, upon
the vitamin values of fruits. Sulfuring, while conserving the vitamin C
value, proved destructive of vitamin B (Bj). With Hunt and Squier,267
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246 ANNUAL SURVEY OF AMERICAN CHEMISTRY
she has determined the vitamin B and G values of prunes; dried Cali-
fornia (French) prune flesh showed at least 2.66 units of vitamin G per
gram, a value comparable with that which they obtained for wheat
germ, whereas the wheat germ showed about ten-fold higher concentra-
tion of vitamin B than did the prune flesh. Morgan and her associates
have also reported the vitamin values of figs,^^^ and of grapes and
raisins.^^^
Grapefruit was found by Roehm^^o to be an excellent source of
vitamin G, though not of vitamin B. Both the leaf and the flower of
broccoli were rich in vitamin G, though they contained only the moder-
ate amounts of vitamin B which are found in green foods generally.
Batchelder and coworkers ^'^i find the blackberry to have a vitamin A
value comparable with those of bananas, cantaloupes, and dates; and
to be a relatively less potent, but not insignificant, source of vitamin C.
Magistad ^'72 reports that the flesh of the pineapple > owes its yellow
color to both carotene and xanthophyll, the carotene predominating.
The concentration of carotene ranged between 0.15 and 0.25 mg. per
100 grams of the pineapple flesh.
MacLeod and coworkers 2^3 studying the vitamin A values of five
varieties of sweet potato found the Triumph and Southern Queen to
show 2 and 4 imits per gram, respectively, while the Yellow Jersey,
Nancy Hall, and Puerto Rico varieties (all more highly pigmented)
showed about 30 to 40 imits per gram. Apparently the development of
the provitamin A continued after the harvesting of the roots, as the
vitamin A values were higher in the roots taken from storage than in
those of the same variety freshly dug.
Fellers, Clague, and Isham ^74 have compared the values of commer-
cially canned and laboratory-prepared tomato juices as antiscorbutics.
This work is deemed to show "that although individual samples of
commercially or home-canned tomato juices vary considerably in vita-
min C content, all may be considered satisfactory antiscorbutics."
Somers and Sweetman ^75 report relatively large differences in the anti-
scorbutic values of commercial tomato juice cocktails.
Kleiner and Tauber^ie fi^d (by the oxidation-reduction titration
method) much less vitamin C in dandelions than in other common
greens.
A symposium on the chemistry and technology of wine, published in
November, contains papers on: vinification in California wineries ;2'^''^
manufacture of champagne and sparkling Burgundy ;2'^8 metals in
wineries ;2'^^ efifect of filter aids and filter materials on the composition
of wine ;^^^ voltatile acids of wine ;28i rate of precipitation of cream of
tartar from wine;282 and pasteurization of New York State wines.^^s
Joslyn and Marshes* have also reported the effects of cold and freez-
ing storage on the rate and extent of removal of cream of tartar from
wine and on other changes in its composition.
Commercial Sweets. During the year, Home 285 has given us a
comprehensive and expert review of the sugar industries of the United
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FOOD CHEMISTRY 247
States with their current developments. However, a few additional
reports may be noted briefly. The distribution of impurities in the
crystals of white sugar has been studied by Keane, Ambler, and Byall.^se
They found over 50 percent of the ash, sulfates, chlorides, sodium, potas-
sium, and nitrogen to be located in the outer 5 percent of the crystal ;
whereas, calcium, sulfites, and color were more uniformly distributed
throughout the crystals. Sugar from which the outer layer of the crys-
tal had been dissolved off was found superior for the making of barley
candies.
The hygroscopicity of sugars and sugar mixtures has been studied by
Dittmar 287 from the point of view of preventing bacterial deterioration
of sugars in storage. The bacterial causation of ropiness in maple
syrup has been investigated by Fabian and Buskirk.^ss
Other Studies of Food in Relation to Growth, Health, and Length
of Life. Fellers289 records a large number of quantitative deter-
minations of vitamins C and D in foods which are commonly used in the
feeding of children and concludes "that the modern choice of foods for
infants and young children, from a vitamin viewpoint, is well founded" ;
while on the other hand the experiments of McCay, Crowell, and May-
nard^^o with a diet very rich in protein and vitamins has been much
quoted in support of the general idea that with such a diet growth may
be "forced" beyond the rate which is optimal for later health and for
length of life. A group of rats whose growth was retarded by restric-
tion of food intake lived longer than a parallel group which had been
allowed to eat the same diet ad libitum. Retardation of growth in this
way seemed to retard sexual development also ;2^i but as the animals were
not mated, these experiments yielded no information as to the influence
of the food restriction upon reproduction or upon the offspring.
Sherman and Campbell 292, 86 ^^ve continued their study of the rela-
tion of food to length of life, in experiments having a quite different
point of departure and continued through successive generations.
Starting with a dietary which (like the food of the majority of people)
was nutritionally adequate but not optimal, it was found that an increase
in the proportion of milk resulted in a better and also more uniform
nutritional response.2®2 The improvement was partly but not entirely
due to increased intake of calcium.^^ The investigation is being con-
tinued. Mendel and HubbelP^s find that the rate of growth of the
rats of the breeding colony of the Connecticut Agricultural Experiment
Station has been increasing for 25 years and that "the improved growth
rate has been accompanied by superior reproductive performance."
Hitherto we have been accustomed to hear that heredity furnishes the
plan for the growth and development of each individual, while the fac-
tors of environment (largely the chemical factors of the nutritional
intake) determine to what extent the potentialities of the plan are
actually realized. Now, Todd 2^4 recasts the statement with the intro-
duction of a highly significant modification. He writes: "The adult
physical pattern is the outcome of growth along lines determined by
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248 ANNUAL SURVEY OF AMERICAN CHEMISTRY
heredity but enhanced, dwarfed, warped, or mutilated in its expression
by the influence of environment in the adventures of life." The recog-
nition that our control of environment can enhance the potentialities
conferred by heredity is highly important. And while Todd speaks only
of the physical pattern, the American Medical Association has been told
in its Presidential address ^os that science promises to those who will
take advantage of the newer chemistry of nutrition, "greater vigor,
increased longevity, and a higher level of cultural development."
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243. Sicbcl, F. P., Jr., and Singrucn, E., Ind. Eng. Chem., 27: 1042 (1935).
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266. Morgan, A. F., Am. J. Pub. Health, 25: 328 (1935).
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268. Morgan, A. F., Field, A., Kimmel, L., and Nichols, P. F., /. Nutrition, 9: 383 (1935V
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270. Roehm, G. H., /. Home Econ., 27: 663 (1935).
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Research, 50: 181 (1935).
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Chapter XVIL
Insecticides and Fungicides.
R. C. ROARK,
Division of Insecticide Investigations, Bureau of Entomology and
Plant Quarantine, United States Department of Agriculture,
During 1934 and 1935 organic insecticides received increased atten-
tion. New uses that were found for the rotenone-bearing plants, derris
and cube, greatly stimulated their importation. In 1934 about 1,000,000
pounds of derris root and 500,000 pounds of cube root were imported
into the United States, whereas a few years ago neither was commer-
cially available. Dusts made by diluting these finely ground roots to a
rotenone content of from 0.5 to 1 percent are the most effective insecti-
cides known for combating cabbage worms and the Mexican bean beetle,
and leave no poisonous residues.
Chemists have been active in developing synthetic organic compounds
as insecticides and fungicides. Phenothiazine is a striking example of
this class. It is even more toxic than rotenone to mosquito larvae,
killing them in a concentration of 1 part in 1,000,000. It has attracted
much attention recently because of the promising results it has given
against the codling moth. Phenothiazine is not toxic to warm-blooded
animals when taken by mouth. Insecticide workers are now encour-
aged to believe that satisfactory substitutes for the poisonous arsenic,
lead, and fluorine insecticides may be found among synthetic organic
compotmds.
Arsenicals. Richardson ^ei tested arsenious oxide and acid lead
arsenate in standard bran-molasses bait as poisons for the differen-
tial grasshopper. The median lethal dose of arsenious oxide is
about 0.11 mg. per gram of body weight; that of acid lead arsenate
is 2 to 4 mg. per gram. Whitehead ^^^ reported that bran poisoned
with arsenic for grasshopper bait had no effect on quail or chickens.
Gross and Nelson ^^7 described an apparatus for the determination of
arsenic evolved from tobacco during smoking. To produce an insecti-
cide, Thordarson 3^^ mixes neutral waste sulfite liquor and a solution
containing arsenic and an alkali hydroxide and adds a soluble non-
alkali metal salt to produce a precipitate. Dearborn ®^ prepared homo-
logs of Paris green in which formic, propionic, butyric, monochloro-
acetic, and trichloroacetic acids were substituted for acetic acid. Analy-
sis indicated that these homologs, like Paris green, are definite com-
pounds of copper meta-arsenite and the copper salt of the corresponding
253
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254 ANNUAL SURVEY OF AMERICAN CHEMISTRY
acid and that the ratio of the two constituents is very close to 3 : 1 in
all cases. Munday^ss produced a larvicide by agitating Paris green
with a solution of sodium amyl xanthate, filtering, drying the powder,
and sifting it. Latimer ^®^ makes arsenic acid by the action of iodine
and nitric acid on arsenious acid, and Boiler 22 oxidizes arsenious acid
by air in the presence of an iodide and activated carbon. Wagner and
Mowe^27 produce sodium pyroarsenate from arsenious oxide, sodium
nitrate, and sodium carbonate. Tucker ^23 reported that standard, or
acid, lead arsenates bum foliage severely in the coastal fog belts of
California, an effect that may be due to the reaction of the acid lead
arsenate with sodium chloride carried from the ocean by winds, form-
ing a basic chloroarsenate and releasing 35 percent of the original
arsenic. A basic lead arsenate may be used in these regions without
foliage injury. Various agents for increasing and maintaining lead
arsenate deposits for codling moth control are discussed by Marshall,
Edie, and Priest,203 and the distribution of arsenic on the foliage of
trees sprayed with arsenicals is discussed by Farley.®*^ Kadow and
Anderson i'^^ found that. the addition of zinc sulfate to lead arsenate-
lime sprays for peach trees prevented arsenic injury, and Poole ^50
found that zinc sulfate and powdered sulfur are both effective in reduc-
ing the arsenical injury of peach trees treated with lead arsenate.
Young 3^^ found that three or more thorough applications of herring
oil-lea^l arsenate combination sprays reduced the carbon dioxide intake
of apple leaves, and Hough ^^^ reported that severe foliage injury by
lead arsenate occurred on trees sprayed heavily and frequently with oil
during the previous season. The decrease in natural control of white-
fly and scale insects by fungi on orange trees caused by the use of
arsenical and copper insecticides was studied by Hill, Yothers, and
Miller, 155 and the use of arsenical sprays reduced the percentage of
parasitization by Ascogaster carpocapsae on codling moth larvae by
more than one-half, according to Cox and Daniel.^^
Hedenburg ^^'^ manufactures zinc arsenate from zinc oxide, sodium
hydroxide, and arsenic acid, and produces lead arsenate from litharge
and arsenic acid in kerosene.^*® Dickson '^^ has patented an insecticide
comprising lead arsenate and ferric arsenate and also ''^ an insecticide
consisting of 85 parts of lead arsenate, 5 parts of lead cyanide, and
10 parts of Bordeaux mixture containing J^ copper.
The preparation of a new chloroarsenate of calcium, (CaCl)2-
HASO4 . 2H2O, was reported by Smith.^^® Pearce, Norton, and Chap-
man ^^^ described a new method for determining the relative safeness
to foliage of calcium arsenates, which is based on the observation that
if water-soluble arsenic is determined after neutralization or removal
of the free lime normally occurring in commercial preparations, values
are obtained which may be used as an index to injury. Hagood^^
patented a method of preparing stabilized calcium arsenate insecticides
containing a fluorine compound, and Fales ^® patented a plant-protecting
agent containing calcium arsenate, basic copper sulfate, and nicotine.
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INSECTICIDES AND FUNGICIDES 255
Howard and Davidson ^^^ made six samples of calcium arsenate safe
for use on bean foliage by treatment in an autoclave under 150 pounds
steam pressure (366° F.) for two hours and subsequent drying at
131° F. for 48 hours. Marshall 202 reported that in an arid area the
injury to foliage by calcium arsenate is eliminated by the use of a metal
sulfate as a buffer; for example, 1 pound of zinc sulfate peritahydrate
and 2 pounds of hydrated lime are added to 3 pounds of calcium
arsenate per 100 gallons. Chapman ^^ reported that calcium arsenate
is perhaps equal to lead arsenate in toxicity to the apple maggot but is
inferior against the codling moth in New York. Webster ^32 reported
that encouraging results have been obtained where calcium arsenate has
been used with metallic sulfates and hydrated lime to check injury to
foliage. Acid washes were effective in reducing the calcium arsenate
deposit on apples. Webster ^^^ studied the arsenic deposit produced and
the degree of codling moth control obtained by the use of lead arsenate,
manganese arsenate, and calcium arsenate combinations with fish oil,
calcium arsenate-mineral oil, and calcium arsenate soap.
Antimony. Burdette^*^ reported that, when a spray containing
an invert sugar syrup and 1.5 to 2 poimds of tartar emetic per 50 gal-
lons was used on corn in the field, from 85 to 90 percent of the com
ear worm moths fed on the syrup but the toxic action was not suffi-
ciently rapid to prevent &gg laying before the moths died.
Copper. Collaborative studies on methods for the determination
of copper and lead oxide in insecticides were reported by Graham. ^22
de Ong 240 found it possible to carry minute amounts of copper into the
tissue of leaves and twigs by the use of copper resinate dissolved in a
specially prepared pine-tar oil, and later 242 reported that analysis of
twigs 30 days after spraying with oil-soluble copper showed 60 percent
of the copper originally applied on the surface and 21 percent in the
tissue itself. No copper was foimd in the tissue of Bordeaux-sprayed
twigs. Hildebrand and Phillips "^^^ found that, while copper sulfate is
poisonous to bees, it is also a repellent and it is impossible to predict
the damage to bees which might result from the application of copper
sulfate to open fruit blossoms. Wilson ^43 reported that the efficiency
of Bordeaux mixture in controlling cucumber diseases was improved
by the addition of one percent oil emulsion. Bordeaux mixture alone
injured the plants. The best results were obtained with mixtures
(sprays or dusts) of copper phosphate, copper sulfate, basic copper
sulfate, basic copper chloride, or a copper ammonium silicate with cal-
cium or manganese arsenate. Several patents on copper fungicides
were issued. Green ^^6 patented copper silicate with lime, Sessions ^88
a complex copper ammonium silicate, and Goldsworthy ^^^ copper phos-
phate with lime and also ^^o cupric oxide with lime. Roberts and asso-
ciates 274 reported good fungicidal results from the application of a
copper phosphate-bentonite-lime spray, and Groves ^^^ reported control
of apple scab with copper phosphate. A process for making a solution
of copper and zinc sulfates, which comprises dissolving brass in dilute
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256 ANNUAL SURVEY OF AMERICAN CHEMISTRY
sulfuric acid under pressure in the presence of compressed air, was pat-
ented by Corson,^^ who also ^^ patented a process for producing copper
sulfate by the action of sulfur dioxide and oxygen on copper in the
presence of water. A process for impregnating the soil with an insol-
uble copper salt to combat termites was patented by Chandler.*^
Cadmium. Migrdichian 221 patented a seed disinfectant compris-
ing cadmium cyanide, cadmium diisopropyl dithiophosphate, cadmium
cyanamide, cadmium xanthate, and cadmium phenyl cyanamide.
Migrdichian and Horsfall 222 patented a seed disinfectant comprising a
toxic metal salt of an aromatic hydrocarbon-substituted cyanamide, the
toxic metal being selected from the group : lead, zinc, mercury, cad-
mium, bismuth, and iron.
Zinc. Kadow^"^*^ reported that zinc sulfate-lime sprays were
ineffective against peach scab, brown rot, and bacterial spot disease.
Added to lead arsenate-lime sprays, zinc sulfate prevented rapid con-
version of the lime into calcium carbonate and also prevented an
increase in the concentration of water-soluble arsenic. Liipfert ^^^ pat-
ented a bactericide and fungicide composition comprising basic zinc
sulfate intermixed with free calcium hydroxide in the form of a powder
adapted to be dusted on plants and trees. Mills 225 patented aqueous
solutions of zinc 2,4,5-triclilorophenolate as fungicides.
Mercury. Zimmerman and Crocker ^^^ reported that certain
varieties of plants are injured by vapors from mercury or mercury
compounds in the soil. There was evidence that mercury compounds
in the soil are reduced to metallic mercury. Muncie and Frutchey232
classified 25 fungicides tested for control of stinking smut caused by
Tilletia levis on wheat in the following three groups: (a) certain
organic mercurials, a mercury-copper carbonate mixture, two percent
ethyl mercuric chloride, and copper carbonate, which were very effec-
tive; (b) mainly mercury-copper combinations, not yet sufficiently
tested, which are promising; (c) calomel and other compounds, com-
pletely ineffective. Kharasch ^^^ patented a disinfectant in dust form
for the control of seed and plant diseases, comprising an alkyl mercuric
acetate and a dry diluting agent. Riker, Iranoff, and Kilmer 2«5
reported that mercuric chloride (1:1000) and cadmium chloride
(1: 100) are effective in killing all surface bacteria on nursery apple
trees without visible evidence of root injury. Young 356 found that
organic mercury dusts and formaldehyde controlled oat smut and the
former exhibited stimulating effects on early-sown seeds. Dust con-
taining ethyl mercuric chloride or phosphate improved the stand of
cotton, although actual yield increases were few. A mercury ammo-
nium silicate gel prepared by the action of a solution of mercuric chlo-
ride on a mixture of ammonium hydroxide and sodium silicate was used
by White ^^^ as a treatment for gladiolus corms.
Fluorine Compounds. Sodium fluoride, pyrethrum, borax, and
derris comprise the materials employed in roach powders, and the
merits of various mixtures are discussed.^ Fluoride-pyrethrum mix-
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INSECTICIDES AND FUNGICIDES 257
tures have come to be looked upon as the standard roach powder. Per-
sing 247 reported that to increase the deposit and subsequent adherence
of cryolite or barium fluosilicate when used with oil emulsions as fruit
sprays, they should be wetted with the oil before being placed in the
tank. The fluorine compounds, particularly natural cryolite, were found
by Dobroscky ''^•i to be effective in the control of the tobacco flea
beetle, the eggplant flea beetle, and the Mexican bean beetle. Dietz
and Zeisert '^^ found barium fluosilicate dusts to control black and mar-
gined blister beetles and to be safe to a comparatively wide range of
plants. Basinger and Boyce ^^ controlled the orange worm by dusting
the trees in June- August with a mixture of barium fluosilicate, cryolite,
fiber talc, and refined mineral oil or by spraying with cryolite.
DeLong'^^ concludes from a review of the literature that synthetic
cryolite is superior to natural cryolite.
Sulfur. McGregor 209, 210 reported that the effectiveness of sul-
fur dusts against the citrus thrips is related to the percentage of sulfur
that passes a 325-mesh sieve. Finely ground sulfur is effective against
the smutty fungus of citrus. Tower and Dye322 patented a parasiti-
cidal composition consisting of 100-mesh powdered sulfur coated with
a substantially water-insoluble green dye and dye carrier to render it
inconspicuous on foliage. The preparation of a colloidal bentonite-
sulfur, much more toxic than mechanical mixtures, is described by
McDaniel.207 Davis and Young ^^ found flowers of sulfur the best
form to use for fumigation in a mushroom house ; the distribution of the
sulfur dioxide gas produced was studied. They ^'^ also determined the
optimum gas concentration and time of exposure for various conditions
of temperature and humidity for sulfur fumigation of mushroom houses,
and described ^^ the construction of an outside sulfur burner for mush-
room-house fumigation. Henderson ^^^ found calcium sulfide alone,
of all ftmgicides tested, to give results approaching commercial control
of downy mildew of tobacco. The composition, properties, and uses of
sulfur spray materials are discussed by Groves, ^^9 ^nd the factors affect-
ing the fungicidal value of lime-sulfur solutions and elemental sulfur
by Peterson.249 MacDaniels and Burrell ^^® presented data confirm-
ing the view that sulfur applied as a dust or lime-sulfur spray, either
before or shortly after pollination, reduces the set of apple fruit. The
method of Kiihl ^^'^-^ is applied by Small ^95 to the determination of the
amount of sulfur adhering to the foliage of trees treated with sulfur
fungicides. Hurt ^^"^ patented a method for the preparation of an insec-
ticide and fungicide comprising adding sulfonated water-gas creosote
oil to a solution of calcium polysulfides. Christmann and Jayne^^
claim an insecticide comprising powdered sulfur, a wetting agent, and a
deflocculating agent.
Selenium. Ries2«4 reported that a proprietary insecticide con-
taining selenium compounds showed promising results against eggs and
active forms of a new mite (Neotetranychus huxi) on boxwood. Gnad-
inger ^^* patented insecticides containing sodium, potassium, potassium-
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258 ANNUAL SURVEY OF AMERICAN CHEMISTRY
ammonium, and sodium-ammonium selenosul fides, and also ^^^ an insec-
ticide containing ammonium selenosul fide and a process for making this
substance.
Miscellaneous Inorganic Compounds. McCallan and Wil-
coxon^oe presented data on the toxicity to certain fungi and spores
of compounds of the elements arranged in terms of the periodic system.
The toxicity increases toward the center of the periodic table and is
less at the two ends ; toxicity within a group increases with molecular
weight. Compounds of positive elements show nearly the same toxicity
regardless of the compound used, but hydrides of negative elements are
all toxic, while highly oxidized forms are only slightly so. Compounds
of silver and osmium are the most toxic. Other elements besides mer-
cury and copper that can be used as fungicides are cerium, cadmiimi,
lead, thallium, chromium, and arsenic. Karns ^"^^ patented a prepa-
ration for freeing plants of parasites, which consists of a mixture of an
iodine compound (e.g., iodides of sodium, potassium, calcium, barium,
etc.) and an oxidizing agent, which under atmospheric influence
undergo reaction, slowly releasing free iodine. Hamilton ^^^ patented
a jelly-like ant-killing mixture containing a thallium compound, sugar,
water, agar, and honey. Exposing apples to a solution of sodium
hpyochlorite in the rinse water after the washing process is recom-
mended by Baker and Heald ^^ for the prevention of blue-mold decay.
Spray Residue Removal. The United States Department of Agri-
culture requires that fruits shall not bear more than 0.01 grain of
arsenious oxide (AS2O3), 0.018 grain of lead (Pb), and 0.01 grain of
fluorine (F) per pound when offered for interstate shipment. Much
activity was manifested in 1934 and 1935 in devising analytical methods
for determining, and methods and apparatus for washing off, spray
residues on fruits. Wichmann, et. al.^^^ described six methods for the
determination of small quantities of lead, particularly in insecticidal
spray residues, and Frear and Haley ®^ proposed a method for the rapid
determination of lead residues on apples, which is based on the use of
the photronic cell. The solvent action on lead arsenate of a number
of inorganic and organic acids, acids plus salts, salts, alkaline solutions,
alkaline solutions plus salts, and wetting agents with and without acid
was studied by Carter.** Addition of mineral oil to acid wash solutions
reduces the danger of fruit injury at high temperatures and increases
the efficiency of residue removal, according to Smith.^^^ Beaumont
and Haller ^^ discussed the effectiveness of seven wetting agents in
removing lead residues from apples. Horsfall and Jayne^^*^ reported
that wool grease, thinned with petroleum naphtha, may be used to con-
trol excess foaming when Vatsol is used with certain washing com-
pounds in commercial washing machines where agitation is present.
The effect of the spray program adopted on the amount of lead residue
on apples and its removal is discussed by Haller, Beaumont, Murray,
and Cassil.^''^^ Haller, Smith, and RyalP^^ described the optimum
conditions for removal of spray residues by hydrochloric acid and by
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INSECTICIDES AND FUNGICIDES 259
sodium silicate. The removal of arsenic residues by hydrochloric acid
from apples receiving various spray schedules is discussed by McLean
and Weber ^n Bordeaux residues on fruits and vegetables are removed
by dilute acetic acid. Wakeland ^^^ summarized numerous data on the
lead and arsenic contents of washed apples in relation to the spray pro-
gram. Haller, Beaumont, Gross, and Rusk ^37 gave general recom-
mendations for washing apples with hydrochloric acid, with salt and a
wetting agent if necessary, to remove lead arsenate. Fluke, Dunn, and
Ritcher^^ reported that sodium silicate aids in the removal of lead
arsenate spray residues from apples by three methods which differ from
the usual tank washing : ( 1 ) By incorporation of the silicate in the last
regular lead arsenate spray; (2) by applying a spray of silicate of
soda, followed by clear water, to the fruit just before picking; and
(3) by dipping the picked fruit first in an unheated bath of sodium
silicate and then in an unheated water bath. Carter *^' *^ reported that
sodium chloride, sodium bicarbonate, and monosodium phosphate each
decreases the solubility of cryolite in water at 20° C. Boric acid, alu-
minum salts, and ferric salts increase the solubility of cryolite in 1.5
percent hydrochloric acid or water. The results of recent experiments
on the removal of lead, arsenic, and fluorine residues from apples with
various washes are discussed by Smith, et. al. ^^^' ^^^ Ryall ^79 reported
that a double washing process using sodium silicate or sodium carbo-
nate, followed by hydrochloric acid, is more effective than either solu-
tion alone for the removal of fluorine residues. Mineral oil added to
acid increases its effectiveness. Sodium chloride decreases the solvent
action on fluorine, while ferric chloride and aluminum sulfate show
promise for increasing the solvent action of hydrochloric acid. Fruit
sprayed throughout the season with cryolite has not been consistently
cleaned below the tolerance for fluorine by any method so far devised.
McLean and Weber 212 patented a process for washing to remove spray
residue with a solution containing 1 to 2 percent hydrochloric acid, 0.5
to 1 percent of a sulfonated aromatic hydrocarbon, and not over 0.5
percent of a substance to prevent foaming. A general view of the
arsenic and lead spray residue situation throughout the country during
1933 was presented by White.^^^ Henry ^^o- ^^^ patented processes for
the removal of residual poisons from fruits and vegetables which com-
prised subjecting them to a dilute solution of hydrochloric acid or
an alkali, with subsequent removal of the alkali by washing in water.
Wetters, Spreaders, and Adhesives. Hensill and Hoskins 1^2
proposed definitions for wetting agent, spreader, sticker, and emulsify-
ing agent. Cupples®^ reported a study of the wetting and spreading
properties of sodium hydroxide-oleic acid mixtures. Ginsburg^^®
found several new sulfated fatty alcohols (10 to 18 carbon straight
chain) and their sodium salts, sulfated fatty acids, and sulfated phenol
compotmds to have promising properties as spreaders. Cory and Lang-
ford ^^ studied a number of sulfated alcohols to ascertain their value
as toxic agents for insects, as emulsifying agents for oils and other
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260 ANNUAL SURVEY OF AMERICAN CHEMISTRY
insecticides, as dispersing and carrying reagents for insecticides that
deteriorate in alkaline solution, as wetting agents for alkaline and acid
sprays, and as an aid in removal of the arsenical and lead residues on
sprayed fruit. Bousquet^* patented a contact insecticide comprising
an aqueous preparation containing technical soybean lecithin as the
essential active ingredient and sulfonated fish oil as a dispersing agent.
Eddy^* described two formulas for the preparation of a spreader for
nicotine consisting of pine tar oil, in one formula plus water, potassium
hydroxide, ethyleneglycol monoethyl ether, oleic acid, and in the other
formula plus phenol and isoamyl alcohol. Littooy and Lindstaedt ^^^
patented a spreader for insecticidal use comprising a thorough mixture
of lime, soybean flour, and skimmed-milk powder. Green ^^8 patented
a flocculated bentonite, characterized by failure to swell or disperse in
water, for use as an adjuvant for horticultural sprays. The prepara-
tion of a bentonite- Bordeaux mixture is described. Bamhill ^^ patented
a pest-annihilating dusting composition comprising a toxic ingredient
(sulfur, cupric sulfate, hydrocyanic acid, Paris green, nicotine, etc.)
and oil sorption foots (clay, fuller's earth, or bentonite that has been
used to refine oils). Merrill 21* patented a process for the production
of an insecticide by mixing a finely divided water-insoluble toxic com-
poimd (e.g., arsenious oxide, Paris green, London purple, or barium
carbonate) in molten asphalt and emulsifying with a slurry of clay
and water. Fulton®^ patented an insecticidal spray non-injurious to
foliage comprising a finely divided gas black in colloidal suspension in
a neutral aqueous liquid containing an emulsifying agent, e.g., soap.
Yothers and Miller ^^^ found blood albumin to be an effective adhe-
sive for sulfur dusts. Forbes ®^ patented an insecticidal and fungicidal
dusting powder comprising a hygroscopic mixture of desiccated milk
and molasses and an active agent. Dills and Menusan^^ reported a
study of the relative toxicity to insects of a number of fatty acids and
their soaps. Fleming and Baker ^® reported laboratory tests with con-
tact insecticides against Japanese beetles which showed that sodium
soaps are more effective than potassium soaps, and soaps containing
excess alkali are more effective than neutral soaps or soaps containing
free oleic acid. The effectiveness of the neutral potassium soaps of the
saturated fatty acids increases with the molecular weight. Eddy^
described a preparation of soybean oil and meal suitable for emulsifying
mineral oils for spraying. Flint and Salzberg^^ patented certain
amino alcohol salts of organic acids (e.g., methylglucamine stearate)
for use as emulsifying agents for insecticides.
Oils and Emulsions. Cressman and Dawsey ^2 reported spraying
experiments with mineral oil emulsions which showed that oil deposit
and insecticidal efficiency vary inversely with the concentration of soap
emulsifier in the aqueous phase and directly with the concentration of
oil in the emulsions. Rohrbaugh ^75 reported a study of the penetration
and accumulation of petroleum spray oils in the leaves, twigs, and fruit
of citrus trees. Yotmg^^^ described with the aid of drawings the
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INSECTICIDES AND FUNGICIDES 261
microscopic and macroscopic phenomena observed during the freezing
and melting of Cresoap emulsions of six commercial petroleum oils.
jje354 also demonstrated a general parallelism between the tolerance
of fimgi and of apple leaves to petroleum oils having less than 11 per-
cent of sulfonatable matter. A technic for predicting oil injury in
apple is based on this phenomenon. Martin 204 discussed the employ-
ment and study of petroleum oil as a spray insecticide. The sulfonic
acids produced during acid refinement include gamma-acids whose cal-
cium salts are water-soluble and are promising spray materials, and
beta-acids, the acids and the sodium salts of which are relatively oil-
soluble and of possible use as emulsifiers. Carter ^'^ reported the suc-
cessful use of Diesel fuel oils as insecticides when adequately emulsified
and dispersed in water. Cleveland ^2 found a new type of summer
spray oils which exhibits distinctive physical properties in regard to
spreading, oil deposit, thickness of film, and retardation of rate of pene-
tration into fruit and leaf tissue, as compared with the usual type of
cream emulsion or tank-mix oils, and are superior to the latter for
codling moth control. Ebeling^^ made a comparative study of results
obtained in control of red scale on lemon by treatment with three low-
concentration oil sprays at intervals and with a single more concen-
trated spray. The former method gave very promising results. Farrar
and Kelley ®® fotmd that dormant oil sprays applied over 5- and 10-year
periods to relatively young apple trees did not affect tree growth mea-
surably under orchard conditions. Knight ^^^ reported that both gly-
ceryl oleate and aluminum naphthenate improve the viscosity and per-
sistence of petroleum oils and increase the insecticidal effectiveness
against the codling moth and pear psylla. Freeborn, Regan, and
Berry ^"^ studied the effect of petroleum-oil sprays in increasing the
body temperature of dairy cows. Woglum and LaFollette ^^^ reported
that soluble oils promise to displace pasty emulsions and tank-mix in
citrus spraying. Young ^^^ found that decane caused ring-spot of apple
leaves and killed juvenile apple leaves and dormant apple buds. Fifty
percent of decane in a" spray oil apparently did not increase the toxicity
of the oil to apple leaves. Decane killed the treated parts of potato
leaves and passed into the stems. It passed from onion leaves to the
roots. Decane is present in petroleum oils, but in its pure form is too
toxic to represent petroleum spray oils in experimental work. Stanley,
Marcovitch, and Andes ^^^ reported that the control of the San Jose
scale and peach leaf curl is in direct proportion to the amount of creo-
sote oil (wood oil) in the spray. Mixtures of creosote oil and oil
emulsion for control of these pests produce a synergistic effect. Parker,
Shotwell, and Morton ^^s reported that grasshopper baits containing a
low-grade lubricating oil gave higher kills than non-oil baits containing
m61asses and water. Newcomer 2S7 has reviewed recent work on oil
sprays as insecticides. Adams'^ patented a composition capable of
forming a stable emulsion and intended as an antiparasitic spray for
plants and trees, which consisted of oil-soluble mineral oil stdfonates,
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262 ANNUAL SURVEY OF AMERICAN CHEMISTRY
soda resin soap, water, alcohol, straw oil, and creosote. Grant ^^4
patented an insecticidal composition comprising an oil-wax gel. Home
and Hopkins ^^^ patented a process for rendering a shale-oil distillate
miscible with water. Volck^^* patented a method of applying para-
siticidal oil to infested plants, which consisted in embracing the oil
in finely divided dried cane sugar and then dusting the resultant
powdery material upon the plant. Volck ^^o also patented a parasiticidal
spray comprising an emulsion of a non-volatile oil, water, and an
ammonia soap of a fatty acid. Johnson ^"^^ patented a spray for use
against mealy bugs on pineapples, consisting of an emulsion of water,
iron sulfate, clay, and refined mineral oil. de Ong and Smith 2*3
patented a process in which pine oil is oxidized by bubbling air through
it and then neutralized, yielding a product safe to spray on plants and
soluble in petroleum.
Tar Distillates. Hartzell, Harman, and Reed ^^^ found the use of
mixtures of tar distillates and lubricating-oil emulsions objectionable
because they appear more toxic to weak trees than either oil alone. They
stressed the desirability of standardization of spray oils. Hartzell ^**
and Hurt^^® discussed the physical and chemical properties and uses
of tar-distillate sprays.
Synthetic Organic Insecticides and Fungicides. Oserkowsky ^44
reported that exposure to saturated vapors of naphthalene or its mono-
chloro or monobromo derivatives, trioxymethylene, benzene, toluene,
xylene, nitrobenzene and o-, m-, and />-dichlorobenzene killed the
mycelium of Sclerotium rolfsii. Substitution of a nitro radical in the
benzene ring resulted in greater toxicity than the substitution of amino,
bromine, or two chlorine atoms in the para position. Substitution
of bromine for chlorine in chloropicrin increased the toxicity. Gins-
burg and Granett ^^^ tested 74 organic compounds against silk moth
larvae, and found pentachlorophenol, cinchonine, nicotine tannate, and
diphenylguanidine to be highly toxic and methoxyquinoline, diphenyl-
guanidine, isoquinoline, and o-nitroanisol to be distinctly repellent.
Many patents have been issued covering the use as insecticides of a
wide variety of organic compounds. Products patented include o-phenyl-
phenol, by Britton and Mills ^i; c?-phenylphenol emulsified in water
with coconut oil soap, by Schaffer and Tilley ^s^ ; a mixture of phenyl-
phenols, by Britton ^o ; a mixture of a- and 3-naphthols, by Britton and
Stearns ^^ ; a mixture of phenol naphthenates in a petroleum hydrocarbon
oil, by Teichmann ^^"^ ; chlorobenzene, by Seydel ^s^ ; o-dichlorobenzene
in solid solution in rubber, by Gardner ^^^ ; an oil emulsion containing
triamylamine, by Sharpies 2»i; the reaction product of a mono- or
diamylamine with a dihalogenopentane, by Wilson ^^4. compounds of
hexamethylenetetramine with chromium, copper, or lead, by De
Rewal '^^ ; and certain diazoamino compounds, by Markush.2<>i Britton ^
patented a method for the preparation of sodium />-phenylphenate. Salz-
berg and Meigs ^^^ patented a parasiticide comprising an organic
fluorine compound selected from the class consisting of fluoronaph-
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INSECTICIDES AND FUNGICIDES 263
thalenes, fluorodiphenyls, fluoroanilides, fluorophenols, fluoroacetic acid,
and phenylfluoroform. Esters of benzoic and salicylic acids have been
patented ; for example, a mineral-oil solution of an alkyl benzoate ( 1 to 6
carbon alkyl groups), which may be combined with the oil-soluble prin-
ciples of pyrethrum flowers, by Adams ® ; certain 5-alkylsalicylic acids
as fungicides (e. g., 2-hydroxy-5-^^c-amylbenzoic acid and 2-hydroxy-5-
^^c-hexylbenzoic acid), by Bruson and Stein 3*; and aralkyl esters of
salicylic acid as insect repellents, by Cleveland.^^ Merrill ^is has pat-
ented a diethyleneglycol monoalkyl ether ester of meta-arsenious acid
suitable for use as an insecticide and wood preservative. Knight and
associates ^^^■^^'^ have. patented mixtures of mineral oil with various
products, such as partially esterified glyceryl oleate and aluminum
naphthenate, an oil-soluble ester of a fatty acid derived from an organic
oil, and a polyhydroxy alcohol partly esterified with a high-molecular
weight fatty acid. These mixtures are emulsified in water and sprayed
on plants. Sibley 2»3 patented an insecticide comprising an alkali or
alkaline-earth salt of a sulfuric acid derivative of the reaction product
of a monohydric aliphatic alcohol containing less than 17 carbon atoms
and a hydroxy-substituted diaryl containing 12 to 20 carbon atoms.
Burwell ^^ patented an insecticidal, bactericidal, and fungicidal com-
position comprising, in liquid dispersion, a mixture of alkali salts of
saturated aliphatic monocarboxylic hydroxylated ketonically-constituted
acid oxidation products of 4- to 15-carbon petroleum hydrocarbons,
accompanied by non-acidic, unsaponifiable, generally ketonic, oxidized
compounds of petroleum hydrocarbons. Sharma ^^o patented a process
in which fruit is coated with a waxy material containing a chloramine
to retard decay from mold spores.
The organic sulfur compounds have been found to contain
many insecticides and fungicides. Campbell, Sullivan, Smith, and
Haller*2 reported that, of 68 synthetic organic compounds, most of
which contained sulfur, 24 were found to equal or exceed nicotine in
effectiveness against culicine mosquito larvae. Diphenylene oxide and
diphenylene sulfide were the most effective. Of seven thioethers tested,
phenylacetimido-thio-/)-tolyl ether hydrochloride was the most toxic.
Roark and Busbey^^z issued a comprehensive bibliography, with brief
abstracts, of the literature relating to the use of organic sulfur com-
pounds (exclusive of mothproofing materials) as insecticides. Hartzell
and Wilcoxon ^^^ reported that, of various organic thiocyanogen com-
pounds examined as insecticides, the most satisfactory was y-thiocyano-
propyl phenyl ether, which acted as a paralytic agent and was non-
injurious to plants. Later Wilcoxon and Hartzell ^41 reported that,
of five organic thiocyanates tested as insecticides, only trimethylene
dithiocyanate was equal to or better than y-thiocyanopropylphenyl ether.
Yeager, Hager, and Straley^^s found that 10 aliphatic thiocyanates
tested tended to inhibit the contraction rate of the isolated heart
preparation of the oriental roach. The thiocyanates produce increased
heart dilation by causing an increased tonus of the alary muscles.
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264 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Bousquet, Salzberg, and Dietz^s reported a study of the relation
between molecular weight and toxicity to insects of the thiocyanates of
the higher fatty alcohols. Patents have been issued to Lee^®^ for a
process of making sec- and tert- alkylthiocyanates, to Salzberg and
Bousquet 280 q^ the use of lauryl thiocyanate against lower forms of
life, to Alvord ^^ for the use of thiazoles as a bacteride and fimg^icide,
to Tisdale and Williams ^^i for sodium dimethyl dithiocarbamate, and
to Remy200 for fuller's earth impregnated with readily vaporizable
organic disulfides recoverable from petroleum. Neiswander ^34
reported that a proprietary aliphatic thiocyanate was successfully used
for the control of greenhouse mealybugs. Wilcoxon and McCallan ^^^
showed that the organic thiocyanates and the alkyl and acyl resorcinols
are highly toxic to fungi. The thiazoles, catechol, and pyrocatechuic
acid are less effective. Tests on control of tomato-leaf mold indicated
that, while trimethylene dithiocyanate was equal to Bordeaux mixture
and sulfur dust, none of these gave control of the disease. Salzberg
and Bousquet ^si patented a parasiticide comprising a compound of the
formula R-(CNX) in which R = an aliphatic hydrocarbon radical" of at
least 6 carbon atoms, X = sulfur, selenium, or tellurium, and the group
CNX stands for the radicals thiocyano, isothiocyano, selenocyano, iso-
selenocyano, tellurocyano, and isotellurocyano (e. g., lauryl, cetyl,
stearyl, and octyl thiocyanates). Bolton ^3 patented an insecticide com-
prising an organic substance containing in its molecule a 5-membered
ring composed of 3 carbon, 1 sulfur, and 1 nitrogen atom, 1 of said
carbon atoms carrying a salt-forming group. Smith, Munger, and
Siegler^^^ reported that phenothiazine shows promise as a substitute
for lead arsenate in codling moth control.
Cyanides. Peters ^48 described a new apparatus for measuring
hydrogen cyanide concentration in tree fumigation, which draws the
sample through a known volume of five percent potassium bicarbonate
solution, after which the hydrocyanic acid is determined by titration
with standard iodine solution. The results of studies on 'the effect of
temperature and relative humidity on fumigation with hydrocyanic
acid against red scale were reported by Quayle,^^^ Quayle and Rohr-
baugh 258 and Moore.228 Pratt, Swain, and Eldred 254 found that of a
large number of organic and inorganic gases tested as auxiliaries
methylthiocyanate was the only one which increased the toxicity of
hydrocyanic acid to scale insects, but this combination caused severe
foliage injury. Haas ^^^ made a study of the chemical composition of
citrus scale insects in relation to the part of the tree infested and also
in relation to the resistance of the scale to cyanide fumigation. Quayle and
Ebeling257 reported that red scale resistant to hydrocyanic acid fumi-
gation is controlled well by fumigating twice or by spraying with heavy
oil to loosen the scales and then fumigating. Swain and Buckner^is
reported that the use of a form to hold the fumigating tent away
from the citrus tree definitely increased the effectiveness of control of
scale on the periphery of the tree, because the concentration of hydro-
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INSECTICIDES AND FUNGICIDES 265
cyanic acid is lower near the tent wall than near the center of the tree.
Haas and Quayle ^^^ reported that, to avoid injury, fumigation with
hydrocyanic acid should be delayed after copper treatment of citrus
trees. Citrus trees showing damage from fumigation year after year
contained relatively large amounts of copper. Bliss and Broadbent^i
made a statistical study of stupefaction time and mortality as criteria
for the measurement of the action of hydrocyanic acid upon Drosophila
melanogaster Meigen. Young, Wagner, and Cotton ^^^ reported that,
for general purposes, a dosage of 8 ounces of hydrocyanic acid per
10,000 pounds of flour for a 3-hour exposure is effective against all
stages of the flour beetle. This dosage is based on the use of low pressure
(about 2 inches of mercury) and with flour temperatures of 70° F. or
higher. Cupples ^ listed, with brief abstracts, all references appearing
in the 1930 abstract journals concerning cyanide compounds used as
insecticides.
Several patents covering the manufacture and application of cyanide
compounds as fumigants were issued. Pranke^si produces sodium
cyanide from sodium calcium cyanide by treating the latter with liquid
anhydrous ammonia. Carlisle and Dangelmajer ^^ prepare hydrated
calcium cyanide from unslaked lime and hydrocyanic acid. Macallum ^^^
prepares cyanide from formamide and sodium carbonate. Gilbert ^^^
produces alkali metal cyanide and calcium carbide from calcium cyana-
mide and alkali metal. Pranke ^52 produces cyanide by reaction of a melt
of calcium carbide, sodium chloride, and carbon with nitrogen. Marvin
and Walker ^^^ produce hydrocyanic acid containing 0.05 to 0.5 percent
of sulfur dioxide by the action of an acid on a mixture of sodium
cyanide and a metal sulfite. Pranke ^53 claims a process for the prepara-
tion of calcium sodium cyanide, CaNa2(CN)4. Dimning,^** and Magill,
Dimning and Ressler 200 patented a process for the generation of hydro-
cyanic acid ; Harris ^^^ prepares hydrocyanic acid from carbon,
ammonia, hydrocarbon, and oxygen. Buchanan and Winner ^^ patented
a process in which a crude cyanide compound containing a cyanide
unstable in aqueous solution is treated with water vapor under reduced
pressure and hydrocyanic acid is recovered. Houghton ^^^ prepares a
sealed package containing a mixture of carbon tetrachloride and acetone
having hydrocyanic acid and cyanogen chloride absorbed therein.
Cooper 57 patented a fumigant comprising a mass containing a water-
decomposable cyanide and a hygroscopic soluble salt of an alkali-earth
metal. O' Daniel ^38 claims a method of fumigating grain with calcium
cyanide.
Ethylene Oxide. Horsfall ^^s reported that ethylene oxide affects
the stage or portion of the bean weevil that is undergoing the greatest
cellular activity. It is thought that the factors favoring an increased
intake of oxygen also favor the intake of ethylene oxide. Britton,
Nutting, and Petrie ^^ patented a method for the preparation of ethylene
oxide from chlorohydrin, and Baer,^^ ^ method of fumigation with
carbon dioxide and ethylene oxide. Young and Busbey^^i published
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266 ANNUAL SURVEY OF AMERICAN CHEMISTRY
a list of 189 references relating to the use of ethylene oxide for pest
control.
Chloropicrin. Godfrey i^*^' ^^^ and associates found that adequate
confinement of chloropicrin in the soil by means of an impervious cover
is indispensable for nematode control. In the greenhouse, kraft paper,
sized with casein glue and sealed down at the edges, was efficient, as
was paper covered with cellulose acetate. Barnes and Fisher ^^ studied
the stimulating effect of chloropicrin, ethylene dichloride-carbon tetra-
chloride, carbon disulfide, and calcium cyanide on fig insects by determin-
ing the number of insects caused to leave the fruit before death occurred.
Ramage25» makes chloropicrin by chlorinating nitromethane in an
acid solution. Johnson ^"^^ reviewed the advantages of chloropicrin for
fumigation, and Roark 267 ^nd Roark and Busbey ^73 prepared bibliogra-
phies of chloropicrin containing a total of 614 references.
Miscellaneous Fumigants. Shepard and Lindgren 292 found car-
bon disulfide to be more toxic than ethylene dichloride or propylene
dichloride to the rice weevil, while for the confused flour beetle the
relation is reversed, carbon disulfide being less toxic. It is therefore
impossible to generalize regarding the relative toxicity of various
fumigants. The respiratory response of adult Orthoptera to carbon
dioxide, carbon disulfide, nicotine vapors, and hydrocyanic acid was
studied by McGovran.^^s Zimmerman ^^'^ determined the lowest con-
centration of gas necessary to cause anesthesia in centipedes, katydids,
and rose chafers for propylene, butylene, ethylene, acetylene, carbon
monoxide, and carbon dioxide. The anesthetic effect of these on plants
and of carbon monoxide on Mimosa pudica was also studied. Jones ^'^^
reported that the toxicity of a given concentration of carbon dioxide to
the confused flour beetle may be markedly increased by the addition of
small quantities of methyl formate. Klotz ^^^ found concentrations of
nitrogen trichloride gas as low as 4 to 6 mg. per cu. ft. for 30 minutes
to be lethal to several fungi and their spores. 1,2,3,4-Tetrahydr6-
naphthalene showed promise as a fumigant against the webbing clothes
moth, according to Colman.^^ Methods claimed to be more accurate
than those now in use for the determination of naphthalene in insecti-
cides are described by Miller.223
Attractants and Repellents. Metzger, van der Meulen, and
Mell 219 found that plant extracts with a fruity odor were much more
seriously infested with the Japanese beetle than those without such an
odor. Metzger 218 found that phenylethyl alcohol increased appreciably
the attraction of the geraniol-eugenol bait used in traps to capture the
Japanese beetle. Eyer ®^ reported that isobutylphenyl acetate and com-
mercial rum ether, which are among the esters formed in fermenting
sugar and vinegar baits, were the most consistent in their attraction of
the codling moth in southern New Mexico. Frost ^^ tested 40 chemicals
for their efficiency in attracting the oriental fruit moth. Linalool,
safrol, propyl acetate, amyl acetate, anethol, fennel seed oil, terpinyl
acetate, and furfural were promising. Safrol is the most satisfactory
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INSECTICIDES AND FUNGICIDES 267
material to be added to five percent syrup solution to attract the moths.
Hoskins and Craig ^^^ studied the olfactory response of blowflies
(Lucilia sericata) to various concentrations of secondary amyl mer-
captan and of methallyl thiocyanate. Price ^55 repelled codling moths
from fruit trees by spraying with a mixture of naphthalene and oil
emulsion. Dove and Parman '^'^ recommended treatment with benzene
to kill screw worm larvae in wounds, and pine tar oil as a repellent to the
flies. Herrick^^^ reported that />-dichlorobenzene, naphthalene, and
cedar oils are repellent to clothes moths, but according to Abbott and
Billings ^ these are useless for that purpose, de Ong ^^i found that a
coating of calcium carbonate protects stored rice against weevil injury.
Flint, Farrar, and McCauley ^^ reported that chinch bugs are strongly
repelled by the odors from crude naphthalene or creosote, and Flint,
Dungan, and Bigger ®2 presented recommended specifications for creo-
sote for chinch bug barriers. Moore ^27 discussed the effectiveness of a
number of esters as repellents for the house fly. The best materials
were a very slightly vo^tile unsaturated cyclic ester, such as the dialkyl
phthalates, and the pyrethrins. A formula for a commercial fly spray
has been developed.
Nicotine. Richardson, Glover, and Ellisor ^62 found that pyridine,
piperidine, and nicotine in vapor form can pass directly through cuticula
of insects. Kitchel and Hoskins ^^^ determined the toxic dose of nicotine
vapor to the cockroach to be 0.005 mg* per gram of body weight. The
addition of a little carbon dioxide increases the toxic effect of nicotine.
Smith 303 reported that it is possible to kill codling moths in trees with
nicotine vapors produced by atomizing a solution of 95 percent nicotine
in kerosene, gasoline, or petroleum ether, but the method is not eco-
nomically practical. Smith and Persing304 later reported that it is
possible to kill codling moths in an orchard by the use of 15 to 30 cc.
of 50 percent nicotine per tree, applied when the atmosphere is calm.
Thomas ^^^ found that nicotine fumigants, dusts, or sprays gave satis-
factory control of springtails attacking mushrooms. The effect of
sodium and potassium chlorides and bicarbonates on the paralytic
activity of nicotine solutions for cockroaches was studied by Levine and
Richardson. 1^2 Steiner ^u^ reported that nearly all soaps with nicotine
sulfate gave a high immediate kill of the white apple leafhopper, but
the residual kill varied with the kind and amount of soap. A correlation
existed between high residual kill and the amount of nicotine recovered
from the foliage. O'Kane, Westgate, and Glover ^39 determined that
the action of nicotine on mosquito larvae is not proportional to its con-
centration alone, but is indirectly associated with absorption phenomena.
Richardson 263 found the deposit left by a nicotine sulfate-molasses
spray to be the most effective of eight nicotine-spray residues tested for
the control of the gladiolus thrips. Eddy®3 made a study of pine tar
and pine tar oil in water-soluble form in the hope of finding chemical
activators or accelerators for nicotine. The Bureau of Entomology
and Plant Quarantine ^ has issued directions for the preparation of
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268 ANNUAL SURVEY OF AMERICAN CHEMISTRY
insecticidal spray solutions from tobacco. Smith 2»7 studied the base
exchange reactions of bentonite with salts of nicotine and other org^anic
bases. Nicotine forms a definite compound with bentonite. Swingle ^^^
tested six substances containing nicotine in relatively insoluble and non-
volatile form and water-soluble nicotine bitartrate against lepidopterous
larvae. Nicotine silicate proved the most toxic of the fixed-nicotine
preparations, surprisingly so because of its extreme insolubility. Drig-
gers '^^ reported that bentonite-sulfur fixes and sticks the nicotine of
nicotine tannate and nicotine sulfate to apple foliage more firmly than
when the nicotine compounds are used alone, thus increasing the
effectiveness as a control for the codling moth.
The following nicotine products were patented : nicotine 2,4-dinitro-
6-methyl (or phenyl or cyclohexyl) phenolate, by Mills ^24; and
nicotine alginate and nicotine abietate, by Lindstaedt.^®*' ^®^ Mew-
borne 220 patented the preparation of an insecticidal product from
tobacco, and Inman ^^^ a product resulting from the reaction of a-nicotine
with a sulfonated partially oxidized petroleum#hydrocarbon.
Anabasine. Smith 2»8 isolated anabasine from the root and leaves
of Nicotiana glauca, a plant growing in Arizona. Nelson 236 prepared
a sample of anabasine of high purity and determined some of its physical
constants. Ginsburg, Schmitt and Granett^^^ found that anabasine
sulfate equals or exceeds nicotine sulfate in toxicity to a number of
aphids, whereas it is much less toxic than nicotine sulfate as a stomach
poison for silk moth larvae and grasshoppers. Garman ^^2 reported that
sprays of anabasine sulfate gave satisfactory kills of the white apple
leafhopper.
Pyrethrum. In California pyrethrum insecticide manufacturers
are requested to give on their labels the percentage of pyrethrins
and of inert ingredients.^ Seil 287 described a method for the estima-
tion of pyrethrins. Gnadinger and Corl ^^^ reported that pyrethrum
samples showed a higher pyrethrin content when assayed by the Seil
acid method than by the Gnadinger-Corl copper- reduction method.
Haller and Acree ^^^ described a new method for the determination of
pyrethrin II, which is based on the fact that it is the pyrethrolone
methyl ester of chrysanthemum dicarboxylic acid and therefore yields
methyl iodide when boiled with hydriodic acid. The methyl iodide is
determined by the volumetric method of Viebock and Schwappach as
modified by Clark. Tattersfield ^i^ discussed methods of estimating the
active principles of pyrethrum and results of cultural investigations.
Experiments by the United States Department of Agriculture indicate
that the cotton stripper can be altered to harvest pyrethrum satis-
factorily.2 Bake ^* reported that lead and solder react very rapidly
with extracts of pyrethrum, decomposing the pyrethrins. These pietals
should not be present in containers used for storage. Hoyer and
Weed ^^* found that pyrocatechin, a so-called stabilizer or antioxidant
for pyrethrum, protects the active principles of pyrethrum dissolved
in kerosene only to a negligible degree. The deterioration of the active
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INSECTICIDES AND FUNGICIDES 269
principle of properly stored pyrethrum extracts is negligible for at
least nine months. Voorhees^^e patented a process for making oil-
soluble pyrethrum extracts stable against light by adding an amino-
anthraquinone compound. Roney and Thomas ^"^"^ reported that
pyrethrum-sulfur mixtures controlled the belted cucumber beetle and
the bean leafhopper slightly better than did sulfur alone, but the margin
of difference does not justify the extra cost. The percentages of control
obtained with various pyrethrum-sulfur mixtures do not correspond
to their pyrethrin content. Nelson ^35 developed a cattle spray com-
prising a medium viscosity, neutral petroleum oil, pyrethrum extract, and
diethyl phthalate, the last-named as a fly repellent. Searls and Snyder 28«
found that 2 percent of an oil extract of pyrethrum adjusted to 2.1
percent pyrethrins was an efficient control of body lice on rats when
applied by atomization, and destroyed about 81 percent of the mites
present.
Pyrethrum products have been patented as follows : A process for the
purification of pyrethrum extract, by Sankowsky, Grant, and Grant, -283
a mixture of pyrethrum extract and dibutyl phthalate in mineral oil,
by Adams ;^ a mixture of pyrethrum extract and a furoic acid ester in
mineral oil, by Adams and McNulty;® and a mixture of pyrethrum
extract, a thiocyanate, and methylprotocatechuic aldehyde, by White.334
Rotenone-bearing Plants. Haller and LaForge ^^^ obtained crys-
talline deguelin in the optically inactive form only from a deguelin
concentrate from derris root, but after catalytic hydrogenation some
crystals of active dihydrodeguelin were obtained. LaForge and
Haller ^^^ prepared and studied four isomeric isorotenolones. Jones ^'^^
described the preparation of lonchocarpic acid, a new compound, m.p.
199° C., from the root of a species of Lonchocarpus. Gross and Smith ^^8
developed a colorimetric method for the determination of rotenone in
the absence of isorotenone, deguelin, or dihydrorotenone, which utilizes
the red color produced when an acetone solution of rotenone is treated
with alcoholic potash and then, after an interval, with nitric acid solu-
tion containing sodium nitrite.
Gersdorff studied the toxicity to goldfish of optically active and opti-
cally inactive dihydrodeguelin,^^^ and of acetyldihydrorotenone, acetyl-
rotenolone, acetyldihydrorotenolone, and dihydrorotenolone.^^^ By a
consideration of the type of concentration-survival time curve obtained,
he was led to propose ^^* the minimum ct product (i.e., concentration
Xtime) as a criterion for comparing toxicities, and using this criterion
in a comparison ^^^ of rotenone and seven of its derivatives, he demon-
strated a quantitative correlation between changes in structure and
changes in toxicity. Tischler 320 made studies on the respiratory proc-
ess of insects together with other physiological studies, which strongly
indicate that derris acts primarily by deranging the respiratory function
in such a way that oxygen utilization by the various tissue cells is
greatly inhibited. Fleming and Baker ®^ reported that rotenone is
inferior to, and dihydrorotenone dust is about equal to, acid lead
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270 ANNUAL SURVEY OF AMERICAN CHEMISTRY
arsenate in effectiveness against the Japanese beetle. Ginsburg^^®
found that residues from derris root, completely extracted with acetone,
possess practically no toxicity to aphids, but are both toxic and repel-
lent to caterpillars. The residue from derris root, extracted first with
acetone and then with water, does not seem to possess direct toxicity
to caterpillars, but acts as a deterrent to feeding. Granett ^^s reported
that ethyl alcohol was the only solvent which removed practically all
the insecticidal substances from derris root. All other marcs tested
exerted a deterrent effect on silkworms. Water-soluble organic solvents
tend to extract more total solids from the root and also more of the
active ingredients than do water- insoluble ones.
White ^^'^ reported that derris dusts, home-mixed or commercial, con-
taining from 0.5 to 1.0 percent of rotenone, gave the most satisfactory
results of any of the insecticides (derris, pyrethrum, Paris green, cal-
cium arsenate, and natural and synthetic cryolite) tested for cabbage
worm control. Several non-alkaline diluents, including finely ground
tobacco dust, finely pulverized clay, talc, diatomaceous earth, infusorial
earth, and sulfur, proved satisfactory. Good control was obtained with
a spray consisting of a derris root powder, containing 0.02 to 0.05 per-
cent rotenone, suspended in water. Under some conditions a non-
alkaline spreader or sticker was necessary. Sprays made by diluting
pyrethrum or pyrethrum-derris extracts gave fairly satisfactory results.
Huckett and Hervey ^^^ reported that the zebra caterpillar and the cab-
bage aphid were not satisfactorily controlled with derris or cube dusts.
Derris and cube sprays and dusts have shown promise against thrips
on cauliflower and against the Mexican bean beetle, but neither was
satisfactory against the corn ear worm. Walker and Anderson ^30
found that derris dust containing 0.5 percent rotenone gave satisfactory
control of the cabbage looper and the larvae of the diamond back moth,
the striped cucumber beetle, and adult squash bugs. Results against
harlequin bugs were erratic. The Mexican bean beetle was satisfac-
torily controlled by a derris dust containing 0.75 percent rotenone.
Derris dust was not successful against the corn ear worm, the potato
flea beetle late in the season, or aphids. Walker and Anderson ^^9
reported that, of eight carriers for derris root dusts, talc gave the best
control, closely followed by gypsum and a clay. Roney and Thomas ^^e
reported that a dust containing 10 percent of derris, or 0.5 percent rote-
none, and 90 percent of 300-mesh conditioned sulfur was more effective
and economical than any other dust or combination used for controlling
cabbage worms. Campbell, Sullivan, and Jones *^ found kerosene
pyrethrum extracts to be more effective in paralyzing flies, and derris
extracts more effective in killing them. They also reported*^ that
rotenone is not the only toxic constituent of kerosene extracts of derris
and cube root, but that it is an important one. Lacroix ^^^ found both
pyrethrum and derris to be highly toxic to the tobacco flea beetle, but
the toxicity of these substances is lost in a few days after application
to the tobacco plants. Ginsburg and Granett ^^^ reported that the
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INSECTICIDES AND FUNGICIDES 271
toxicity of derris root to aphids does not always bear a directly pro-
portional relationship to its rotenone content, especially in samples con-
taining large amounts of rotenone. Derris and cube roots are practi-
cally equal in toxicity to aphids, provided they contain approximately
the same amounts of rotenone and total extractives. The combination
of derris with lead arsenate, lime, or sulfur compounds caused derris
to lose toxicity. Ginsburg, Schmitt, and Granett ^^^ found that water-
soluble organic solvents, such as acetone and 'alcohol, are able to extract
practically all the water-soluble and water-insoluble ingredients of
derris root toxic to sucking insects. Anderson ^^ reported that derris
products give good results against the tobacco flea beetle on a small
scale but in field tests do not afford permanent protection. Howard,
Brannon, and Mason ^^^ reported the results of tests with derris against
the Mexican bean beetle. Very good control was obtained with sprays
at dosages of 1.5, 2, and 2.5 pounds of derris of 4.4 percent rotenone
content in 50 gallons of water. At these dosages there is little or no
saving of derris as compared with dust mixtures, but the better control
and increased residual effect obtained with the water suspension make
its use as a spray preferable. Water suspensions of the ground derris
root are superior to the extracts of either derris or pyrethrum or a
combination of the two. Roark 2^8, 270, 271 reviewed patents and litera-
ture relating to derris and cube, and Whittaker ^^^ reviewed the devel-
opment of rotenone as an insecticide.
Jones ^"^2 patented a process for making a chemical compound of
rotenone and carbon tetrachloride consisting substantially in extracting
the roots of plants of the genus Derris, Lonchocarpus, or Spatholobus
with warm carbon tetrachloride and crystallizing. The following mix-
tures were patented: derris root with a sulfonated petroleum product,
by James ;^^® rotenone with pyrethrins, by Fulton ;i^^ and rotenone with
a highly halogenated hydrocarbon in petroleum oil, by Buc.^^ Bousquet
and Tisdale^^ patented a contact insecticide comprising a water emul-
sion of 3,3-dichlorodiethyl ether, and an insecticide of the group con-
sisting of water- insoluble dithiocarbamates, water-insoluble thiuram
sulfides, and the toxic ingredients of derris root. Haller and Schaffer ^^^
patented a process for preparing dihydrorotenone by hydrogenating a
rotenone-bearing plant extract dissolved in an organic solvent in the
presence of a specially prepared nickel catalyst. Mills and Fayer-
weather226 patented l,2-dihydroxy-4-/^r/-butylbenzene and 1,2-dihy-
droxy-4-/^r/-amylbenzene for use as stabilizers for insecticides such as
pyrethrum and rotenone.
Little 1®^ described ecological studies and experimental cultivation of
Cracca virginiana in Texas. This plant can be made to yield as many
pounds of roots per acre as derris. It can be grown on marginal land and
produced for a few cents a pound. It is a nitrogen fixer, and its stems
and leaves have some value as hay. Marked variations occur in the
plants, indicating different varieties, or perhaps species. Physiological
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272 ANNUAL SURVEY OF AMERICAN CHEMISTRY
tests are being conducted on these plants, to eliminate the poor and
grow only the best, with encouraging results.
Jones, Campbell, and Sullivan ^^^ compared the toxicity to house
flies of extracts of samples of derris root, cube root, haiari stem, and
Cracca virginiana root with the values obtained on these samples by
certain chemical determinations. The amounts of rotenone present in
the samples were too low to account for all the toxicity. In more than
half the samples the figures by the Gross-Smith test, considered as
representing the sum of rotenone and deguelin, agreed with the toxicity
value, but in the other samples they were lower. Total-extractive val-
ues were higher than toxicity, and values based on the methoxyl con-
tent of the extract, although somewhat closer, were also too high. When
an approximate value for toxicarol was subtracted from the methoxyl
figures, the results agreed more closely with the toxicity figures than
did the results of other determinations. However, it is impossible, on
the basis of the present results, to recommend unreservedly any one
of these chemical determinations as a measure of the insecticidal effec-
tiveness of rotenone-bearing plants. Further work is needed on this
subject, particularly on the individual constituents present in such plant
materials. Jones, Campbell, and Sullivan ^'^^ made chemical and insec-
ticidal tests on 32 samples of Cracca, mostly C virginiana, collected in
different parts of the United States. The relative effectiveness of
kerosene and acetone extracts against house flies was tested. The two
extracts were similar in effectiveness, and the acetone extract was well
correlated with the degree of blue or blue-green color given by the
Durham test. The insecticidal results were not well correlated with
other chemical determinations. The most effective samples of C znr-
giniana root came from Texas. A sample of C latidens root from
Florida and one of C. lindheimeri root from Texas and seeds of the
latter were highly effective. In spite of its lower content of toxic
materials, it is believed that Cracca might be developed to an extent
permitting competition with derris and cube. Roark^^s prepared a
resume of the information available up to April, 1934, on devil's shoe-
string {Cracca virginiana).
Croton Bean. Spies 3^^' ^ot found croton resin more toxic than
rotenone to goldfish. Free hydroxyl groups rather than unsaturation
are responsible for this toxicity and also for the vesicant action of the
resin. Drake and Spies '^^ studied the fatty acids obtained by saponifi-
cation of croton resin, and Spies and Drake ^^^ isolated rf-ribose from
the croton bean.
Tree Bands. Davis ^^ reported that bands treated with a-naph-
thylamine were somewhat more effective than those treated with mix-
tures of tallow oil and 3-naphthol in trapping codling moth larvae.
Worthley^*^ reported that corrugated strawboard bands treated with
3-naphthol in lubricating oil appear preferable to untreated burlap
bands for trapping codling moth larvae.
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INSECTICIDES AND FUNGICIDES 273
Wood Preservatives. Sweeney ^^^ patented a process for ren-
dering moldproof a synthetic lumber prepared from cornstalks by treat-
ment with copper sulfate solution before pressing and drying or by
spraying with copper sulfate solution.^!* Conn^* patented a process
for protecting cellulose material comprising treatment of the degummed
material with an aqueous solution of tannic acid and tartar emetic, dye-
ing with a bactericidal dye such as crystal violet, thioflavine-S, or
malachite green, thereafter treating with an aqueous solution of potas-
sium bichromate, copper sulfate, and acetic acid, and finally applying
a cover treatment of tar. Another process of preserving fibrous cellu-
lose materials, patented by Conn,^^ comprises treating the degummed
material with a solution of tannic acid, then with tartar emetic, and
finally with potassium bichromate. A protective reagent for cellulose
material (Conn^^) comprises tar and an oil-soluble residue resulting
from the reaction of a-naphthylamine with acetaldol. Bowen^^. 28
fastens creosote-saturated felt pads on top of wooden piles to preserve
them. Derby and Cislak*^^ introduce sulfur dioxide into wood and
thereafter impregnate the wood with creosote oil to preserve it. Hart-
man and Whitmore ^^^ patented a composition to protect wood from
fungi and insects comprising a water solution of a metal salt, a fluoride
(e.g., sodium fluoride), an ammonium salt, and a material to hold
metal salts in solution (e.g., hydrochloric acid). Andrews and Finlay-
son ^2 protect fabrics from decay organisms by incorporating in the
fabric a galvanic couple (e.g., Zn-Cu) which, when immersed in an
electrolyte, produces soluble, poisonous compounds. Siever 2»4 impreg-
nates cellulosic material with a mixture of creosote, acetone, and mer-
curic chloride. Other products patented as wood preservatives include
a mixture of a petroleum hydrocarbon, an arsenic ester, and mercury
naphthenate, by Merrill ;2i<^ a mixture of creosote and an acid-treated,
cracked pressure residuum, by Goodwin, Rearick, and Ferguson ;^2i
a mixture of turpentine and oil of tar for tree injection, by Yates ;^*'^
and a mixture of kerosene, benzene, o-dichlorobenzene or naphtha con-
taining about five percent a-naphthylamine, by Calcott and Foreman.^®
Morrell ^so has patented a process for converting relatively high boil-
ing coal-tar acids into lower boiling products which are suitable for
use as wood preservatives and animal dip. Arsenical wood preserva-
tives have been patented as follows: a mixture of diphenylamine and
arsenic trichloride with an organic oil, by Walker ;^^^ and a mixture
of a petroleum hydrocarbon, asphalt, arsenic ester, and mercury naph-
thenate, by MerrilL^i*^
Mothproofing. The following mothproofing compositions were
patented: petroleum naphtha containing 3-chloro-4-hydroxydiphenyl
and a bonding agent of crude paraffin wax and stearic acid anilide to
prevent crystallization, by Spokes ;^^^ a solution in an organic solvent
of a compound of the formula CeHs— (jr— C— jr')„— CeHs, in which
X and x^ represent hydrogen or alkyl groups, by Moore ;22» brucine
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274 ANNUAL SURVEY OF AMERICAN CHEMISTRY
anilide in a dry solvent, by Ritter;2«« and a blue fabric impregnated
with sodium arsenite, by Mucha.^^i
Weed Killers. Kiesselbach, Stewart, and Gross ^^^ reported that
bindweeds are controlled in fields by treatment with sodium chlorate.
The following products have been patented for use as herbicides: a
solution of arsenious acid and concentrated sulfuric acid, by Rose ;278 a
mixture of four parts calcium chlorate and one part calcium chloride,
by Heath ;i*^ ammonium thiocyanate, by Sauchelli '^^^ and a mixture of
kerosene, heavy petroleum oil, and furfural, by Melhus.^is The use of
ammonium thiocyanate for soil sterilization for the eradication of
potato wart disease was studied by Bell.^o
Refekences.
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INSECTICIDES AND FUNGICIDES 275
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348. Yeager, J. F., Hager, A., and Straley, J. M., Ann. Entomological Soc Am., 28:
256 (1935).
349. Yothers, W. W., and Miller, R. L., Citrus Ind., 16, No. 2; 22 (1935).
350. Young, G. W., Proc Am. Soc Hort. Sci., 32: 101 (1934).
351. Young, H. D., and Busbey, R. L. References , to the Use of Ethylene Oxide for
Pest Control. U. S. Dept. Agr., Bur. Ent. and Plant Quar. Multigraphed.
1935. 16 p.
352. Young, H. D., Wagner, G. B., and Cotton, R. T., /. Econ. Entomol., 28: 1049 (1935).
353. Young, P. A., Plant Physiol., 9:795 (1934).
354. Young, P. A., Phytopathology, 24: 266 (1934).
355. Young, P. A., Am. J. Bot., 22: 629 (1935).
356. Young, V. A., Phytopathology, 24: 840 (1934).
357. Zimmerman, P. W., Contributions from Boyce Thompson Inst., 7: 147 (193S).
358. Zimmerman, P. W., and Crocker, W., Contributions from Boyce Thompson Inst.,
6: 167 (1934).
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Chapter XVIII.
Gaseous Fuels. 1934 and 1935.
Lloyd Logan,
Associate Professor of Gas Engineering,
and
WiLBERT J. Huff,
Professor of Gas Engineering, The Johns Hopkins University.
Although, judged by the respective revenues reported for the
two branches of the gas industry, the economic value of the manu-
factured gas distributed to customers still appears to exceed some-
what that of the natural gas so distributed, statistics ^ indicate that
the total marketed production of natural gas, amounting in 1933 to
over one and one-half trillion cubic feet, represented on the basis
of volume over four-fifths, and on the basis of heating value, per-
haps seven-eights of the national production of gas of sufficiently
high heating value for use as city gas. On the basis of energy,
natural gas represented about 8.3 percent of the total national pro-
duction of energy from all sources, exceeding that of anthracite
and approaching, on the basis of the low thermal efficiency
assumed, the fuel equivalent of the entire national supply of water
power.
Of the enormous total recorded production of natural gas, by far
the greater amount was consumed near the source, in large part
for uses commanding but low unit prices, only about 347 billions,
or about 22 percent, having been transported across state boiylers.
Based on reports of the Bureau of Mines,^ the consumption of
natural gas accounted for in 1933 was divided thus: domestic, 18
percent; commercial, 6 percent; industrial (including gas used in
the field, in carbon black plants, electric public utility power plants,
Portland cement plants and the like), 76 percent. The heating
value of the gas listed under "field use" alone represents about
three times that of the manufactured gas distributed to consumers
by the gas industry. The total amount of gas wasted is unknown.
It is stated that the waste of gas in the Texas Panhandle alone
reached a billion cubic feet per day towards the end of 1933, repre-
senting a heating value more than twice that of the average total
daily sales of manufactured gas to consumers by utilities.
280
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GASEOUS FUELS. 1934 AND 1935 281
In the same year, an amount of gas approximately equal to the
recorded production of natural gas was treated for natural gaso-
line, yielding 1,420,000,000 gallons. Sales of propane, butane, pen-
tane, and propane-butane mixtures reached nearly 39,000,000 gal-
lons, a relatively small fraction, however, of the potential supply.
Carbon black production amounted to over 269 million pounds.^
For 1933, of the total gas sales by utilities to consumers, 1,171,-
909,000,000 cubic feet, that distributed by natural gas companies
comprised about 71.4 percent by volume and that distributed by
manufactured gas companies, 28.6 percent, natural gas purchased
and distributed by such companies representing about 3.5 percent
of the total.2 Thus, on a volume basis nearly three-fourths of the
gas distributed to customers by utilities in the United States is
natural gas ; on an energy basis, natural gas constitutes over five-
sixths of the total energy in the gas thus distributed. The revenues
from manufactured gas continued, however, somewhat greater than
those from natural gas distributed to customers, if returns from
sales near the source for carbon black manufacture and the like
are excluded.
Turning to the gas produced and purchased for distribution to
consumers by the manufactured gas industry, we find for the same
year 2 a total of approximately 367 billion cubic feet, of which water
gas constituted 41.7 percent; coke oven gas produced by utilities
14.0 percent; coke oven gas purchased, 23.6 percent; retort coal
gas, 8.0 percent; natural gas purchased, 9.2 percent; reformed oil
refinery gas, 1.2 percent; oil gas, 1.0 percent; and reformed natural
gas and butane-air gas each less than 1 percent.
There were used in 1933 in the manufacture of gas by utilities a
total of 10,500,000 tons of solid fuels and 521,108,000 gallons of oil.
Of the solid fuels used in the production of coke oven and coal gas
in 1933, exclusive of that purchased from the coke and steel com-
panies, 7,042,000 tons were carbonized and 786,000 tons were used
for bench and producer fuel. Of the total of solid generator fuel
of 1,743,000 tons, coke constituted 1,298,000 tons, or 74.5 percent;
bituminous coal 399,000 tons, or 22.9 percent; and anthracite but
2.6 percent.
Statistical summaries from 1929 to, but not including, 1935 ^
show that both the natural and the manufactured gas industries
have rounded the depth of the depression and are now on the rise.
The lowest total sales of natural gas, exclusive of that used in field
operations, manufacture of carbon black, by distributing compa-
nies in gas operations, or mixed with manufactured gas, occurred
in 1932, amounting to about 808 billion cubic feet; the highest,
960 billion cubic feet in 1934, represents an increase of about 19
percent over this low. In the manufactured gas industry the total
gas sold showed a low in 1933, amounting to 334 billion cubic feet.
The high of 1930, 396 billion, was about 18 percent above this, and
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282 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the recovery in 1934, giving a total of about 347 billion, represents
an increase of about 4 percent from the 1933 low. The revenues
from both forms of gas passed through a low in 1933. For natural
gas, the gain in revenue for 1934 over 1933 was about 6 percent;
for manufactured gas the percentage gain in revenue was much
smaller, amounting to only about 0.7 percent. Of the major
manufactured gases, water gas production, which had been declin-
ing consistently prior to a low in 1933 when the production was
about 153 billion cubic feet, rose 2.4 percent to nearly 157 billion in
1934. The output of coke oven gas made by utility companies was
rising prior to 1932, when it declined, but not to the 1929 level. In
1933 and 1934 the production rose again, gaining nearly 5 percent
in 1933 over 1932, .and about '4 percent in 1934 over 1933. Retort
coal gas output has been falling rather consistently since 1929, but
showed a recovery of 1.6 percent from the 1933 low to a 1934 pro-
duction of over 30 billion cubic feet. The production of oil gas,
amounting to about one percent of the total gas manufactured in
1933, fell continuously, the decline from the year 1933 to the year
1934 being 12 percent, and was about the same amount for the year
1933 compared to 1932. Although the production of reformed nat-
ural gas, reported for the first time in 1933, contributed less than
one-third of one percent of the total production of manufactured
gas in that year, its jump in output of 110 percent in 1934 is of
interest. Eutane-air gas production, likewise amounting to a frac-
tion of a percent of the total, continued to grow, that in 1934
amounting to about 28 percent over that of 1933.
The decreased production of manufactured gas has been in a
considerable measure compensated for by the natural gas pur-
chased, which has been steadily rising since 1929. In 1932 the
amount of natural gas purchased increased to over 420 percent of
that purchased in the preceding year. In 1933 the natural gas pur-
chased was 24 percent over 1932 and in 1934 it was about 21 percent
over 1933. The volume purchased during 1934 was over 41 billion
cubic feet.
At the time of writing, the summaries for 1935 are not available,
but trends for the total gas industry compiled through September 3
indicate that the revenues for 1935 will be higher than for 1934 but
well below the 1929 level. The total sales of natural gas are, how-
ever, greater than for 1929, and the revenues from natural gas are
comparable with those of 1929 for a similar period.
The foregoing statistics have a direct bearing upon the scientific
developments relating to the industry, for with increased business
the need of and support for such development increases. The rise
in certain operations, as, for example, the reforming of natural gas,
follows certain fundamental investigations and in turn promotes
other studies of an allied nature.
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GASEOUS FUELS. 1934 AND 1935 283
Production and Operation Studies
Manufactured Gas. Water Gas; Reformed Gas. The increasing
use of natural gas is reflected in the technical studies of the indus-
try, especially with respect to the manufacture of high B.t.u. gases
with local equipment as substitutes for natural gas during peak
load periods and emergencies such as line breaks. A thorough and
timely survey of standby processes has been made by Willien,^ who
compares such processes with respect to the starting-up time, gas
making capacity, force of operators required, and interchange-
ability of the resulting gas with the gas ordinarily distributed.
Among the processes considered by Willien as substitutes for nat-
ural gas and manufactured gases are (a) the refractory screen oil
gas process, (h) the Pacific Coast oil gas process, and (c) various
modifications of the standard water gas process including, respec-
tively, conventional operation with cracking of oil in the carburet-
ter, cracking of oil in an atmosphere of steam, cracking of oil in the
carburetter together with some cracking of oil through the gener-
ator fire either with or without the admixture of cracked butane,
and finally by cracking butane in the carburetter, admixing the gas
formed with blue gas.
The question of the rate of flame propagation of such substitute
gases is, of course, an important one. Willien ^ cites the results
of Ferguson, showing the presence of acetylene in high B.t.u. water
gas made at high temperatures, amounting to as high as one-fourth
of the illuminants, and the conclusion of the latter that the occur-
rence of the yellow tips in one appliance and flash back in another
is due to the presence of acetylene and its high rate of flame propa-
gation.
Willien,® in summarizing the status of standby gas processes,
states that, for each kind of gas, some type of substitute gas has
been developed or proposed and indicates that the Pacific Coast
oil gas process appears to be adaptable in many cases. Johnson
and Hemminger*^ have discussed the load conditions and the eco-
nomics of the standby gas supply for systems distributing natural
gas. Plant experiments on the utilization of a heavy oil, rather
than gas oil, in the production of a high B.t.u. standby gas have
been reported by Beard.^ The operating practice of a standby
plant of the refractory screen type has been described by Wehrle.^
Wiedenbeck ^^ has reviewed the operating experiences in the
production of reformed natural gas at the Chicago By-Product
Coke Company, particularly with respect to handling of lampblack
and gummy mixtures of tar and carbon. A report by Workman ^^
on the use of high B.t.u. gas for standby purposes covers plant
tests of the Laclede Gas Light Company, St. Louis, the Peoples
Gas Light and Coke Company, Chicago, the Public Service Com-
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284 ANNUAL SURVEY OF AMERICAN CHEMISTRY
pany of Colorado, and the Memphis Power and Light Company,
together with a bibliography of oil gas processes by Willien.
Several reports on the reforming of natural gas are presented by
the 1935 Gas Production Committee of the American Gas Associa-
tion.i2 One plant reports that the formation of lampblack appeared
wholly within the control of the operator and is a function of the
relation of steam and natural gas through the generator. A mix-
ture of blue gas and reformed natural gas of 400 B.t.u. per cubic
foot and 0.38 specific gravity causes only a scum on the surface of
the scrubber sumps and slightly fouls the purifiers. By increasing
the steam slightly beyond what is usually termed normal, the lamp-
black can be eliminated completely at the expense of an increased
density of the resultant gas. If the rate of flow of natural gas is
increased, lampblack is produced in proportion and the density is
lowered more than necessary, with a resultant increase in the cost.
Studies of the determination of lampblack, fly ash, and tar in
reformed natural gas have also been made by the committee.
Further plant studies of the reforming of natural gas in water
gas sets have been presented by Young ^^ with especial reference to
the formation and removal of the lampblack formed. It was found
that when lampblack was formed in the water gas set, deposits of
a mixture of lampblack and very viscous tar not removable by
steaming were formed in the relief holder and tubular condensers.
Recirculation of hot water gas tar thinned with primary conden-
sate from the light oil plant resulted in preventing stoppages in
the tubular condensers. Experiments are described on the use of
water and hot tar in the removal of lampblack from gas entering
the relief holder. The substitution of a coke having a fusion point
of 2300° F., for one having a fusion point of 2725° F., resulted in
the almost complete elimination of lampblack and fly ash.
Experimental work directed toward the commercial recovery of
carbon black produced in the reforming of natural gas in a water
gas set without the use of steam is described by Willien.^* Mul-
cahy,^^ in giving operating data on the production of reformed
natural gas at Terre Haute, Indiana, describes the removal of lamp-
black by means of shavings boxes.
Perry ^® has patented the process of reforming refinery gases
employing the combustion of a portion of the gas by means of pure
oxygen introduced into the center of the gas stream to effect crack-
ing of the remainder. Garner, Miller, and Leyden ^"^ treat natural
gas by burning a portion of it, premixed with air up to the theoret-
ical amount required for combustion, in a reaction zone maintained
at about 800° C., through which the remainder of the gas is passed
for the purpose of cracking it. The process is so carried out as to
give a mixture of reformed gas and products of combustion of the
desired heating value.
The use of refinery oil gas is discussed by Schaaf,^^ and by Work-
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GASEOUS FUELS. 1934 AND 1935 285
man,i^ operating results using other fuels than coke in a water gas
plant by Jebb,^^ the use of steam during a blowrun by Willien,^!
and the use of a special oil of 19.5 A.P.I, gravity containing a large
amount of wax by Eck.^ia
Operating practice in the production of blue gas and its admix-
ture with natural gas is discussed by Roberts.22 Robison ^3
describes the use of natural gas instead of, or simultaneously with,
gas oil for carburetting blue water gas.
For economic reasons, the production of carburetted water gas
from heavy oils still holds an important place among the indus-
try's developments, as attested by a number of articles and patents.
There has been a trend toward an increase in the proportion of oil
used in the generator and the reforming of the oil through the fire
to lower the specific gravity of the gas. The problem of handling
heavy oil tar emulsions is apparently one besetting a large number
of companies. Dashiell 2* has summarized the reasons for this situ-
ation, pointing out that most of the heavy fuel oils are residues
from the distillation of asphaltic crude oils, that there is a tendency
in most plants towards undercracking of at least some of the oil,
that the tars produced are extremely viscous with resulting
increased stability of the emulsions, and the reforming of the oil
vapors through the fuel bed increases the viscosity of the tar
because of the increased free carbon.
The character of the tar from water gas sets employing bitumi-
nous coal for the manufacture of uncarburetted blue gas in a
water gas set has been improved by the introduction of water into
the carburetter through oil sprays to maintain the temperature of
the blue gas at about 1000° F. through the carburetter and super-
heater.25 Parke ^6 has described the alterations in plant and
operation resulting from the changeover from the use of gas oil to
heavy oil. The same writer has also compiled various experiences
and expedients developed to cope with tar and emulsion problems.^''
The continued interest in the use of heavy oils in water gas
manufacture is indicated by the number of patents directed toward
the use of such fuel in gas production. For example, in a process
proposed by Terzian,^^ oil is vaporized, a portion of the product
passing through an incandescent fuel bed to produce a reformed
hydrocarbon gas, the other portion being cracked less completely,
thus producing a mixed water gas and reformed oil gas. Another
patent of Terzian^^ relates to the manufacture of a mixture of
water gas and oil gas of low specific gravity, in which a portion
of the water gas generated is burned and the heat stored to serve
for vaporizing an increased quantity of oil, the oil vapors being
reformed by passage through the fuel bed in the generator. Hall ^^
proposes to increase the proportion of reformed oil gas in a mixed
water gas and reformed oil gas. Attention to the problem of secur-
ing Water gas tar of satisfactory character is shown in the patent
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286 ANNUAL SURVEY OF AMERICAN CHEMISTRY
of Evans,3i who proposes separate removal of the high free-carbon
tar from the reformed gas made from heavy oil and of the tar of
low free-carbon content from the unreformed carburetted water
gas. Terzian ^2 aims, in reforming natural gas or refinery oil gas,
to insure the liberation of carbon taking place within the fuel bed,
rather than in the gas space, thus producing a low gravity gas free
from carbon black.
Interest in the use of heavy oil is further shown by the patents of
Merritt and Koons ^^ and of Nordmeyer and Stone,^* on processes
involving the use of oil in the generator and the use of a reverse
air blast. Nordmeyer,^^ in a process employing the reversed air
blast, specifies the passage of the major portion of the latter
through the upper portion only of the fuel bed and its withdrawal
circumferentially of the generator. Perry and Hall ^® have devised
a process for the production of low gravity carburetted water gas
employing a marginal blast. Perry ^^ proposes a method of oper-
ating in which high-carbon oil is introduced on the top of the
generator fuel bed and low-carbon oil in the carburetter during the
uprun, the*greater part of the high-carbon oil being introduced
during the first half of the run and the greater part of the low-
carbon oil during the latter part of the run.
NageP^ proposes a flash system of carburetting a lean hot gas.
MorrelP® has patented a process in which motor fuel is produced
from coal and heavy oil in a flash distillation system involving par-
tial condensation of vapors and of distillate products. A heavy oil
is gasified as an emulsion in a patent of Ditto.*® Blast furnace gas
and the like are enriched, after heating, by means of atomized
liquid fuel, followed by further heating before combustion with
preheated air in a process of Mathesius.*^
A process for the simultaneous production of a carburetted water
gas and motor fuel is proposed by Sachs.*^
Arnold ^^ has suggested a process for coking heavy oils involving
the addition of coke fines to the initial supply of heavy oil.
An experimental investigation by Elliott with Huff ** has shown
that sodium carbonate exerts a marked influence on the gasifica-
tion of heavy oil in the presence of steam at temperatures encoun-
tered in water gas practice. Experiments were made on a labora-
tory scale with Bunker C oil cracked in the presence of steam at
temperatures between 1300° and 1600° F., employing for compari-
son refractory surfaces of magnesite blocks both untreated and
impregnated with 5 percent of sodium carbonate by weight. The
use of sodium carbonate resulted in a decrease in the carbon depos-
ited, a large acceleration in the steam-carbon reactions, a marked
improvement in the thermal yield, and a decrease in the hydrogen
sulfide formed per gallon of oil.
The production of high-hydrogen water gas from younger coal
cokes has been the subject of an extensive experimental study by
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GASEOUS FUELS. 1934 AND 1935 2^7
Brewer and Reyerson,*^ dealing with the steam-carbon reactions,
the effect of carbon dioxide upon cokes, and the effects of catalysts
added to the fuel and of water gas conversion catalysts.
The removal of carbon monoxide from city gas is the subject of
a patent by Perry and Fulweiler.^^ The passage of blue gas with
steam through a reacting mass of ankerite, a native carbonate of
calcium, magnesium, iron and manganese, for the elimination of
carbon monoxide has been patented by Bossner and Marischka.**^
Kunberger ^^ has proposed the production of a low gravity water
gas in a process involving the alternate reduction of iron oxide by
blast gases and reoxidation of the iron by means of steam, with
accompanying production of hydrogen.
That attention continues to be given to the possibility of employ-
ing pulverized fuel in the water gas process is indicated in the
patents of Heller,*^ Duke,^® and Air Reduction Company .^^ In the
last-named patent, blue water gas is produced by supplying pow-
dered coal or oil, together with oxygen, to a heated reaction cham-
ber to which superheated steam, with or without a further fuel
supply, is subsequently delivered.
Structural and operative features of water gas equipment are
embodied in a number of patents.^2
A number of departures from conventional forms of the water
gas process appear Jn the patents of Hillhouse ^^ on the continuous
production of water gas, the continuous system of Lucke ^* involv-
ing the passage of metal balls through the fuel bed, and the con-
tinuous production of carburetted water gas,^^ employing producer
gas, produced simultaneously, to supply the heat required for the
process.
A new automatic control for water gas plants, as well as other
cyclic operations, a portable blue gas set unit, a scroll tar separator,
and further developments of the refractory screen process for gas
of high heating value have been described.^^
Coal Gas, and Coke, In a review of the progress in coal carboni-
zation, gas-making, and by-product recovery in the 25 years pre-
vious to 1934, Porter ^"^ has pointed out that in 1934 the percentage
of the total coal production carbonized was about the same as
30 years before — namely, 16.0 to 16.5 percent; that there has been
no progress in the displacement of raw coal for steam generation
by products of carbonization; and that the considerable increase
in the use of coke and coal gas in domestic heating has been nearly
counterbalanced by the decreased demand in the metallurgical
industry arising from increased fuel efficiencies. The technical
progress in the coking of coal has been marked, as evidenced by the
increased output per unit cost due to the use of higher and longer
ovens and of silica refractories, better design of flues, improved
control of pressure inside the oven, underfiring with producer gas
and blast furnace gas, steaming of the hot coke in the oven for a
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288 ANNUAL SURVEY OF AMERICAN CHEMISTRY
short period, admixing fine coke or dust with the coal charge with
consequent increased coke strength and lessened cost, and the
development of dry quenching, and of vertical chamber ovens with
gravity discharge.
Reference is made by Porter ^"^ to semi-commercial developments
of the processes of Wisner and of Warner,^^ operating in the low
temperature range.
Lavine,*^® in a comprehensive review of the properties character-
istic of low-rank coals (lignite and sub-bituminous), outlines work
on the destructive distillation and coking, as well as the dehydra-
tion, of such coals.
Recent developments in coal utilization for 1932-1933 are reviewed
by Fieldner,®® who refers to progress in this country and abroad in
high temperature carbonization and the recovery of by-products,
and the status of low temperature carbonization, hydrogenation
and liquefaction of coal, hydrogenation of tar, and the synthesis of
chemical products. Fieldner points out that the continued com-
petition of cheap petroleum and natural gas has prevented applica-
tion of new methods of coal processing, such as low temperature
carbonization, because of the lack of adequate market for the liquid
and gaseous by-products; that the technical process for hydro-
genating and liquefying coal is now available and may be put to
use when and if a failing petroleum supply reqyires the production
of oil from coal, but that the process is too costly for use under
present conditions ; that a number of important chemical products,
such as ammonia, methanol, higher alcohols, solvents, etc., are now
being made from gases obtained from coal, but that even if all the
ammonia and methanol consumed in the United States were made
from coal, it would require only 0.15 percent of the 1930 production
of bituminous coal.
Fieldner ®i reviews progress for 1933 in the preparation of coal,
including coal washing, crushing, froth flotation of fine coal sludges,
and briquetting, combustion of solid fuels, the use of automatic
house heating furnaces adapted for use with summer air condition-
ing, the use of colloidal fuel, coal dust engines, high temperature
and low temperature carbonization, and by-product recovery.
Three low temperature carbonization plants are cited as having
been in operation during 1933 and 1934. Of considerable interest
is the use of a modification of the Wisner process in a plant at
Champion, Pennsylvania, having a capacity of 95 tons a day. In
this process partial oxidation is employed to destroy the excess
plasticity of high volatile, strongly coking coals. Oxidation of the
coal is effected on rectangular multiple hearths. The carbonization
is then completed in a rotor six feet in inside diameter by eighty-
four feet long, the product being so-called coal balls. No by-prod-
ucts other than tar and gas are produced. A plant of the Lurgi
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GASEOUS FUELS. 1934 AND 1935 289
type is reported in operation in North Dakota and one of the
Hayes type has been operated intermittently in West Virginia.
During the past year, the very comprehensive work on the gas,
coke, and by-product making properties of American coals carried
on at the United States Bureau of Mines in cooperation with the
American Gas Association during the past few years has been sum-
marized by Fieldner and Davis.^^ These tests, carried out on sam-
ples of coal ranging from 75 to 180 pounds in a metal retort, cover
carbonization of 30 coals at 500, 600, 700, 800, 900, 1000, and 1100° C.
and the yields and properties of the various products. These tests
also include the study of one coal, both washed and unwashed.
Unusually complete data are given, including, in addition to the
usual proximate and ultimate analyses, ash fusion and calorimeter
tests, analyses for sulfur forms, carbon dioxide, and fusain. Sol-
vent extractions, rational analyses, and petrographic examinations,
as well as determinations of the softening and plastic properties,
agglutinating index, friability, and slacking properties were carried
out. In addition, three standard assay tests — the Fischer, Fuel
Research Board (Great Britain), and U. S. Steel Corporation — were
employed. Commercial plant yields, available for eleven of the
coals tested, showed good agreement of plant and test data.
Fieldner and Davis ®^ have applied standardized laboratory meth-
ods for the determination of reactivity, electrical resistivity, hygro-
scopicity, ignition temperature and minimum air blast to repre-
sentative cokes, made in large laboratory scale apparatus at car-
bonizing temperatures of 500 to 1100° C, from coals covering the
entire range of coking rank. They present data to show that the
coke becomes less reactive, less easily ignited, requires more air
to sustain combustion, becomes less hygroscopic, and conducts
electricity more readily as the carbonizing temperature is raised;
that the reactivity as determined by the ignition temperature and
minimum air required to sustain combustion is virtually a straight
line function of the carbonizing temperature over the whole range;
that cokes made at 500 and 600° C. conduct electricity hardly at
all, but that between 600 and 700° C. there is a rapid increase in
conductivity, with a tendency at carbonizing temperatures of 1000
and 1100° C. to approach a constant high value comparable with
that of graphite.
Reynolds ®* points out that cokes made at low temperatures are
considerably more hygroscopic than those made at ordinary by-
product coke oven temperatures, being usually greatest for cokes
made at 600 to 700° C.
The effects of the rate of heating and of the maximum tempera-
ture in the pyrolysis of a coking coal upon the yields and character-
istics of the principal products are reported by Warren.^^ f^e yields
of tar increase with increase in the rate of heating at the expense
of the yield of gas and coke, the increase being proportional tQ
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290 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the ratio of the rates of heating. The conclusion is drawn that the
mechanism of coking involves competition between distillation and
decomposition processes, and that differences in the values of their
temperature coefficients are responsible for the increase in tar yield
as the rate of heating is increased. Davis and Auvil ®® have studied
the effect of varying the free space over the charge upon the
yields, of gases and tars in the high temperature carbonization of
coal in a series of experiments in the Bureau of Mines- American
Gas Association type of retort, with free spaces corresponding to
3.9, 11.6, and 23.1 percent of the retort volume of 3.82 cubic feet.
With increased free space, the yield of light oil at 900° C. increased
27 percent for an increased time of exposure of from 1.3 to 9
seconds, the benzene yield practically doubling and the paraffins
disappearing. The gas yield was also increased. The neutral oils,
aromatic liquids and tar acids in the tar decreased and the pitch
and aromatic solids increased.
The effect of tempering coals of various ranks to moisture con-
tents up to 14 percent, in carbonization at 800° C, was studied by
Sherman, Blanchard, and Demorest.®''
A comprehensive critical review of the chemical structure of
coal has been made by Lowry,^® who considers the molecular
structure of coal as resulting from condensation and polymeriza-
tion of polynuclear six-membered carbon ring compounds, and
that this structure becomes more and more condensed in succeed-
ing ranks of coal — peat, lignite, bituminous coal, and anthracite.
The condensation of aromatic nuclei appears to be the main reaction
in the solid residue during pyrolysis of coal and does not end
until graphite is formed. Lowry regards solvent extaction,
vacuum distillation, and low-temperature carbonization as repre-
senting increasing severity of thermal treatment of coal and yielding
progressively simpler products. A comparison of a single coal
by all of these methods is stated as an objective of the Coal
Research Laboratory of the Carnegie Institute of Technology
which should shed light on the mechanism of the thermal decom-
position of coal.
A study of the primary decomposition and distillation of a coal in vacuo
of the order of 10~^mm., using as a new research tool in this field
a so-called molecular still in which the purpose is to ensure
that the molecules from the coal surface neither collide with other
molecules nor encounter a hot surface before being condensed
on a cooler surface, has been carried out at the Coal Research
Laboratory of the Carnegie Institute of Technology by Juettner
and Howard.®^ Using this means for avoiding secondary decom-
position of initial products, these workers have made a compari-
son of the condensates and gaseous products from high vacuum
distillation of 20-40 mesh coal and of coal ground to a particle size
of about 0.001 mm., with those from distillations at the same
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GASEOUS FUELS. 1934 AND 1935 291
temperature in a Fischer retort. The yields of phenols and of
neutral ether-insoluble substances was studied. The conclusion is
reached that, in the coal used, the simpler phenolic substances
are produced from the neutral ether-insoluble substances.
The Pittsburgh Experiment Station of the Bureau of Mines has
continued its studies of the gas-, coke-, and by-product-making
properties of American coals.'^^ Splint-coal bands from the Elk-
horn bed in western Kentucky gave a higher yield and a stronger
coke than was obtained from bright coal bands in the same seam.
The yield and quality of gas from the two types of coal were
nearly the same.
The expansion of coking coals is discussed by Altieri'^^ who
described a new type of coal expansion tester designed to permit
simulating conditions affecting the expansion of the coal during
carbonization in coke ovens.
Seyler^2 ^^s reported that the addition of 8 percent of 20-100
mesh inerts to high volatile unwashed Klondyke coal prior to
carbonization improved the physical properties of the coke, the
best results being obtained with 6 percent of coke dust.
Meredith ^^ has made a comparative study of materials used
or proposed for the dustproofing of domestic coke.
A study of the gases liberated from Virginia coals at various
temperatures is described by Fish and Porter.'^^a
Further data on the correlation of small and large scale car-
bonization tests are given by Selvig and Ode.''*
The hydrogenation of coal is treated by Wright and Gauger,''^
together with the effect of partial hydrogenation on coking proper-
ties, and other topics in this field.
A number of patents on coal carbonization processes and equip-
ment, assigned chiefly to the larger builders of coke ovens, have
appeared. Among these are those of Still,''® characterized by the
withdrawal of the products of distillation from the interior of the
coal charge, thus minimizing the secondary cracking reactions to
give increased yields of benzol, an improved quality of tar, and
reduced formation of naphthalene. Other patents have been
granted on coke ovens ^'' and accessories,^^ and special types of
destructive distillation apparatus.''^
The heating of regenerative coke-oven batteries by means of
atomized tar oils or petroleum oils, using preheated air, is speci-
fied by Richardson.s*^
Various modifications of conventional types of carbonization
processes have been proposed or carried out. Keillor ^^ describes
the operation of a plant at Vancouver in which coal gas is made in
a given retort for the first twelve hours, water gas for the next four
hours, and carburetted water gas for the last four hours. Miller ®2
proposes a combined high- and low-temperature carbonization
process producing a blended tar product, wherein the gases from
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292 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the high temperature coking of coal are brought in direct contact
with coal to effect low temperature carbonization. Rose and
Hill 83 have patented the use of a mixture of coal with naphthalene
which is heated in a retort to the carbonizing temperature of the
coal but below the critical temperature of the naphthalene,
naphthalene and tar being separated from the coke after the
carbonization. Bunce ®* describes the coking by means of hot
gases of agglomerates of coke breeze and bituminous coal. Rose
and Hill 85 have patented the treatment of coal and tar together
in thin layers in the presence of steam, in which substantially all
the tar oils are vaporized leaving a homogeneous mass of undecom-
posed coal and pitch suitable for gas manufacture. The passage
of oil refinery gas through coal undergoing carbonization with
resultant cracking is patented by Odell.^® The coking of pitch and
coal in a by-product coke oven battery is provided for by Tiddy ^7
through the use of heat resistant metal linings in those ovens
used for coking pitch. Other patents cover the production of coke
and gas from oil in a retort,^^ the gasification of powdered fuel in
an externally heated oven with production of rich gas and water
gas,8» and the continuous production of coal gas in a vertical
retort with zones of gradually increasing temperature.^
Wisner^i specifies the partial oxidation of finely divided coal by
preheating it to about 175 to 235° C. to prepare it for coking.
Another patent by Wisner^^ relates to the rotating heating drum
equipment and associated cooler for production of carbonized coal
balls.
The production of low-boiling liquid hydrocarbons by heating
bituminous coal, peat, or lignite with an alkaline acetate has been
patented by Michot-Dupont.®^
Kemmer^^ describes apparatus for the utilization of the waste
heat of coke-oven plants or gas works for refrigeration for gas puri-
fication. Suggestions for the improvement of the operation and
maintenance of coal gas retort benches are given by Niles.^^
Gas Producers. Weiss and White ®® have extended the work of
White and Fox on the influence of sodium carbonate on the pro-
ducer gas reaction and its possible use in the manufacture of water
gas. This work involved studies of the reaction of graphite, treated
with sodium carbonate, with air and with steam, employing slower
cooling than in the earlier case in order to permit reversal of the
reaction Na2C03-|-2 C = 2 Na-h3 CO, to which the observed effects
are attributed. This reversal was almost quantitative in the region
where the furnace cooled from 900 to 750° C. Although as little
as 0.1 percent of sodium carbonate was effective in greatly increas-
ing carbon monoxide production at 900° C, one percent of soda
was ineffective with foundry coke, apparently because of the reac-
tion of the soda with the ash to form silicates. Admixture of 5
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GASEOUS FUELS. 1934 AND 1935 29Z
880° C. than could be obtained from the untreated coke at 1090° C.
percent of soda with the coke was effective, giving a richer gas at
Attention is called by NageP^ to improvements in the liquefac-
tion and distillation of air and the availability of large capacity
units for the production of oxygen and cites German costs for
oxygen of 80 percent and of 95 percent purity.
By-Products. Porter ^^ has reviewed changes affecting coke
oven by-product recovery, especially the decline in revenue from
ammonia resulting from the competition of synthetic ammonia,
the recovery of sulfur from gas by the Koppers Thylox process
and the possible use of such sulfur in the production of sulfuric
acid for the manufacture of ammonium sulfate, and recent develop-
ments in the uses of tar products, in phenol recovery, and in the
distillation of the coke oven tar by the sensible heat of the coke
oven gas.
Tar, Dashiell,^® in reviewing developments in heavy oil tar and
emulsion handling, states that the use of heavy oil brings about a
tar dehydration problem more acute than gas oil and that a tar
dehydrating plant is a necessary adjunct to every water gas plant,
whether it uses heavy oil or gas oil of the types available in large
quantities, that is, asphaltic base oils. Such dehydration may be
carried out (1) by heating in high, open tanks to 195° F., as
described by Parke,^^^ with subsequent treatment in stills, (2)
by treatment in stills equipped for decantation, (3) by heating in
closed tanks at up to 75 pounds pressure, and (4) by the use of
centrifugal force. Operating and maintenance costs are given.
Zane ^^^ has described commercial apparatus for continuous dis-
tillation. Parke ^^^ discusses pressure flash dehydration and
dehydration by spraying or pumping through restricted orifices.
Zane ^^^ also describes automatic tar dehydration by heating under
pressure and flashing into a column.
Morgan and Stolzenbach ^^^ have investigated the mechanism of
tar emulsions and state that the emulsifying agent is primarily a
hydrocarbon substance which appears in the emulsion as a mem-
brane surrounding the water droplets and preventing their coales-
cence, that the toughness of this membrane determines the stability
of the emulsion, and that the effect of the membrane may be
increased by the presence of free carbon.
Numerous patents have been issued in the field of tar technology,
especially as to recovery from gases,^^^ tar distillation,^^® tar
acids ^^"^ and pitch.^^®
Delorey ^^® reports an increase from 60 percent to 127 percent
of rating obtained by the use of coal tar for boiler firing in place
of slack coal.
Patents issued in the by-product field cover carbon dioxide
recovery,^^® acetylene removal,^^^ benzene recovery,!^^ ammonia
recovery,^^^ phenol recovery,^^* light oil absorption,^^^ naphthalene
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294 ANNUAL SURVEY OF AMERICAN CHEMISTRY
and anthracene,^^® and hydrogenation of carbonaceous mate-
rials.i", 118
Overall transfer coefficients for the absorption of amnfonia and
sulfur dioxide into a water spray, and the absorption of benzene
vapor from air into an oil spray have been determined by Hixson
and Scott.^^^ This work also develops equations correlating the
effects of variable fluid flows for use in spray tower design.
Purification of Gas. The developments in gas purification have
related principally to improvements in liquid purification, the con-
trol of oxide box purification to minimize the escape of nitric oxide,
and improvements in plant practice in the operation of oxide boxes.
The chemistry of the Thylox gas purification process has been
studied by Gollmar.^^o Sodium or ammonium thioarsenate is the
active agent in this process. The solution is regenerated by blowing
with air. The principal reactions are believed to be
Na4As2S502 + H2S = Na4As2SeO -|- H2O (in absorption)
Na4As2S60H-0 = Na4As2S502H-S (in actification)
Unless the />H value of the solution is maintained at 6,7 or higher, the
arsenic tends to revert to its lower valence and probably a mixture
of arsenous sulfide and sulfur is precipitated. Sodium thiosulfate
slowly forms from a little of the sulfur in suspension. The hydrogen
cyanide in the gas is converted to sodium sulfocyanate. Carbon
dioxide has practically no effect because of the low alkalinity of
the solution. The toxicity of the solution, usually containing less
than one percent equivalent AS2O3, was studied but no evidence
was found of arsenic poisoning.
Continued attention to the use of ammonia in liquid gas purifi-
cation is indicated in the patents of Hansen,^2i Qf Davies,^22 ^nd
of Eymann.123 fhe use of arsenic,^24 Qf non-aqueous solvents in
conjunction with alkaline solutions,^25 Qf phenolates and the like,^*
of diethylenetriamine,^27 ^nd other liquid purification processes are
described in various patents.^^s xhe removal of carbon disulfide
by a liquid process is the subject of a patent by Hansen and
Eymann.^29
The purification of natural gas containing small amounts of
hydrogen sulfide in an iron oxide plant is described by Allyne.^^*^
Brewer ^^^ has modified the method of Seil, Heiligman, and Clark
for testing the activity of purifying material, by passing a part of
the foul gas stream around the absorption solution, thus permitting
the passage of a test gas containing 400 grains of hydrogen sulfide
per 100 cubic feet to the glass absorption tower. With the gas
quality and rate of flow constant, the amount of gas purified is a
direct function of activity. This modified method showed that
certain samples having the same capacity varied greatly in activity.
The use of granulated blast furnace slag for dry box purification
is discussed by Presbrey.^^^ Purifying materials for use in oxide
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GASEOUS FUELS, 1934 AND 1935 29S
boxes have been patented by Seil ^^3 and by Smyly.^34 Broche ^^^
specifies the operation of oxide boxes in a two stage process involv-
ing the use of a somewhat elevated temperature and the controlled
admission of oxygen containing gases in the second stage. Mur-
phy 136 has reported that the addition of four to six grains of
ammonia per 100 cubic feet of coke oven gas maintains the />H
value of the drain water from the boxes between 7 and 8 and results
in a greater activity of the oxide, complete removal of the hydrogen
cyanide, and increase in the sulfur content of the spent oxide to
as high as 56 percent.
Seil, Heiligman, and Crabill ^^t find that the nitrogen oxide is
held in relatively stable combination with fouled iron oxide sponge
until after revivification and that the nitric oxide can be eliminated
by blowing the sponge with air and steam at a relatively high tem-
perature before re-use. Fulweiler ^^^ has described a patented
method ^^^ of oxide box operation designed to prevent gum forma-
tion in gas distribution systems.
Seil, Heiligman, and Crabill i*^ describe a procedure for con-
ducting the Kunberger test on iron oxide for gas purification.
Other patents in the gas purification field refer to the use of
sodium chloride solutions containing lime ^^^ and to the separation
of sulfur from the sulfur dioxide of flue gases.^^^ Further patents
on the purification of gas at 'elevated temperatures have appeared.^^^
Gas Storage. The most radical development in gas holder con-
struction appears to be that of a centrally guided waterless
holder.^** In connection with the operation of waterless gas
holders, some attention has been devoted to possible substitutes
for water gas tar as a sealant. For example, the use of a viscous
solution of waste sulfite material from the digestion of wood by
the sulfite process is proposed by Laue ^^^ and that of various
specified viscous aqueous solutions by Sperr.^^® Gruse ^^'^ pro-
poses a heavy tar distillate from the tar produced in cracking a
low-boiling petroleum distillate.
Unremitting attention has been given by the gas industry to the
safety features of the operation and maintenance of gas holders.
Theoretical and practical considerations in purging holders have
been outlined by Tomkins.^^^ Alrich ^^^ has discussed the mainte-
nance of the M.A.N, holder with particular reference to the char-
acteristics- of the sealing fluid. Gas holder corrosion problems are
summarized and discussed by Munyan,^^® who emphasizes the
importance of periodical internal and external inspection as a
safety measure. Inspection and maintenance of gas holders are
covered in the Rules and Regulations of the New York State
Department of Public Service.i^i Experience in the removal of
sediment from the tank of a five-lift gas holder is described by
Knowlton.162
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296 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Operation of a large gas holder in connection with a compressor
station is described by Geiger.^^a
Dunn ^^^ has indicated the conditions making an underground
reservoir suitable for natural gas storage, namely, that it has con-
sistently produced gas according to Boyle's law, properly applied,
and has not ceased producing.
Purging. The subject of purging gas plants, mains, and storage
equipment has been given the closest attention by the gas industry.
Specific instructions are given by the American Gas Association ^^^
for the purging of purifiers, and other gas works apparatus, includ-
ing oil tanks, complete water gas plants, coal gas plants, gas mains,
and works connections. Competent supervision, positive isolation
of the container during the purging operation, an adequate supply
of inert gas for purging, and reliable means for determining when
the contents of the container are substantially free from gas or
vapors are stressed. Definite directions for the production of inert
gas are given.
Tomkins ^^® has given a very complete discussion of the purging
of apparatus with an inert gas, together with the explosive limits
of different gases with air and maximum permissible oxygen and
air contents of safe mixtures with inert gases. Carbon dioxide is
indicated to be the most effective inert gas, and methods of pro-
ducing it for this service are discussed.
Natural Gas. Comprehensive statistical studies of natural gas
production have been presented by Swanson ^^'^ and by Swanson
and Struth.i^^ Comparative natural gas production and consump-
tion statistics for 1929-33 and for 1912, 1922, and 1930-32 are given
by Hopkins and Backus.^^^' ^^^ Further statistical data on natural
gas are included in a review by Knapp.^^^ Advances in the tech-
nology of natural and refifiery gases, including the removal of
hydrogen sulfide, gas transmission problems, natural gasoline plants,
liquefied gas, carbon black, and gas cracking are outlined by Bur-
rell i«2 and Burrell and Turner.i«3
In presenting a review of technical developments in petroleum
and natural gas production. Fowler ^^^ emphasizes the importance
of the oil-gas-energy relationships, refers to conservation measures,
including proration and unit operation, and reviews recent engineer-
ing research problems. These include methods of obtaining and
interpreting subsurface pressures and temperatures in wells, solu-
bility of gas in oil and the phenomena attending the liberation of
natural gas under conditions approximating those of the reservoir,
and the flow of oil, gas, and oil-gas mixtures through porous media,
with particular reference to the problem of well spacing. Cattell
and Fowler,^®^ in a well-documented review, have discussed the
recent work on fluid-energy relationships of petroleum and natural
gas, and point out the value of such studies in the equitable alloca-
tion of production, the estimation of capacities of wells to produce
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GASEOUS FUELS. 1934 AND 1935 297
oil and gas, estimation of reserves, control of movement of gas, oil,
and water within a structure, and similar problems.
Engineering factors in the conservation of natural gas are con-
sidered in a report of the Federal Oil Conservation Board.^^® Fur-
ther discussions of the waste of natural gas ^^'^ and of conservation
measures ^*»^ have appeared. Among recent studies referring to
production are those relating to subsurface pressures and tempera-
tures in flowing wells in the East Texas field,^®® solubility and
liberation of natural gas from oil,^*^^ the energy liberated in isother-
mal expansion by gas-saturated oil sampled in high pressure bombs
from within oil wells,^'^^ and the measurement of the permeability
of porous media.^^2
Recent patents on chemical and other methods for treating gas
and oil wells to maintain or increase production include those of
Grebe and Stoesser,^'^^ Pitzer and Huffaker,^^^ Boundy and
Pierce,i75 Mills,i76 and Heath and Fry.i^T
A number of articles on the chemical treatment of wells,^*^®* ^'^®' "^^
drilling fluids,^®^' ^^^ ^nd the like have appeared.
Important contributions to the knowledge of phase equilibria in
hydrocarbon systems have been made by Sage and Lacey ^^^ and
co-workers, who discuss both simple and complex systems in the
range of pressures up to 200 atmospheres and of temperatures from
20 to 100° C. Data are presented which permit the prediction of
the density, composition, and relative mass of each phase present
when a mixture of any total composition is brought to equilibrium
at any set of temperature and pressure conditions within the range
studied. Particular attention is paid to the methane-propane sys-
tem 1®^ through the temperature and pressure ranges commonly
found in underground petroleum formations, solubility of a dry
natural gas ^®^ in crude oil, the solubility of propane in two different
oils,^^® the pressure-volume-temperature relations and thermal
properties of propane,^®*^ and the thermodynamic properties of
pentane.^^^
The rates of solution of methane ^^^ and of propane ^^^ in qui-
escent liquid hydrocarbons have been studied experimentally by
Hill and Lacey.
The economic aspects of gas-solubility experiments have been
discussed by Morris.^®^ Lacey ^^^ has likewise referred to the
bearing of such studies on the practical problems of pressure
maintenance in petroleum production.
Other papers dealing with the energy relations of natural gas
and oil are those of Umpleby,^^^ relating to the efficient utilization
of reservoir energy, of Moore and Shilthuis ^®* on the calculation
of pressure drops in flowing wells, and of Hurst ^^^ on unsteady flow
of fluids in oil reservoirs.
Conservation measures are reviewed by Lewis ^®® and by Wal-
lace,^®'^ who outlines practice in the protection of wells from
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298 ANNUAL SURVEY OF AMERICAN CHEMISTRY
underground wastage and flooding. Eckert ^®® describes practice
in deep drilling in the Tioga and Potter County fields of Penn-
sylvania.
Neyman and Pilat ^®® report that the heat of solution of natural
gas associated with petroleum oils is of a very small order com-
pared with the heat of compression, to which the thermal effects
are practically confined.
The viscosity of natural gas has been determined for a number
of natural gases of widely different chemical compositions by Ber-
wald and Johnson,200 through the use of the relationship between
the friction factor and the Reynolds number for the flow of gas
through pipes.
There has recently been reported the formation in natural gas
transmission lines of solid compounds resembling snow or ice in
appearance, which are attributed to the formation of hydrates
with methane, ethane, propane, and isobutane in the presence of
water at elevated pressures and temperatures. Hammerschmidt ^^^
has studied the conditions for formation of these compounds, as
well as their melting points.
Considerable study has been devoted to the occurrence of gas
in coal beds. Selden 202 has reviewed critically the factors involved,
as well as theories as to the origin of the methane and carbon
dioxide in such gas. Ranney^oa has patented a method for the
recovery of mine gas and urges such recovery as commercially
feasible. Lawall and Morris ^o* have studied the occurrence of gas
in Pocahontas No. 4 bed in southern West Virginia and have
measured gas pressures and flows in holes bored into the coal.
Burke and Parry 205 have developed mathematically the laws of
flow governing the movement of gas in coal seams and discuss
the origin of such gas.
The production and sales of natural gasoline and of liquefied
petroleum gases are reviewed by Shea.2<>« The huge potential
supply of liquefied gases has led to a number of studies of means
for their utilization. OberfelPOT has reviewed progress in this
direction with respect to their use as industrial fuels, in gas manu-
facture, and for domestic use. Gould ^^^ has made an economic
study of this field. The use of propane and butane in the gas
industry is reviewed by Friend.^^ The advantages of these fuels
over fuel oiPio for various purposes and of propane as a sub-
stitute for acetylene in the steel industry are presented by Jamison
and Bateman.211 Hunt 212 has described the use of propane in
metal cutting and salvaging operations.
Experiences in substituting butane-air gas for 550 B.t.u. oil gas ^18
and a description of a recent butane-air gas plant ^^^ have been
given. A detailed description of typical butane-air gas plant equip-
ment is given by Perrine.^i^
Patents on various processes and apparatus for generating gas
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GASEOUS FUELS, 1934 AND 1935 299
by carbureting air with liquid fuels have been issued.^i® De
Florez^iT has patented a fuel for engines of lighter-than-air craft
consisting of mixtures of hydrogen and butane and hydrogen and
propane, respectively.
Pyrolysis of Hydrocarbon Gases. In addition to the reforming
of natural gas and oil refinery gases in the production of low
gravity gas for city use, considerable attention has been directed
towards the chemical utilization of these gases.
In a review of the literature on the pyrolysis of saturated hydro-
carbons with special attention to the primary decomposition
reactions, Frey ^is points out that the paraffin hydrocarbons decom-
pose chiefly into simpler olefins and paraffins and that high cracking
temperatures favor the concomitant formation of complementary
olefins and hydrogen. Two reaction mechanisms have been pro-
posed. Surface catalysis dehydrogenates paraffins to the cor-
responding olefins or degrades them to carbon, methane, and hydro-
gen, converts cyclohexanes into the corresponding aromatics, and
rearranges the other cycloparaffins. Storch 2i9 reviews critically
data on the pyrolysis of methane, ethane, ethylene, gasoline, and
petroleum to yield acetylene and has formulated mathematical
expressions relating to the decomposition of methane. He has
also discussed possible industrial processes utilizing the thermal
decomposition of methane or ethylene diluted with 75 to 90
percent hydrogen or carbon dioxide. A survey is made of the
recent developments in pyrolysis of unsaturated hydrocarbons by
Hurd,22o who proposes a mechanism correlating the fact that
unsiaturated hydrocarbons pyrolyze characteristically into (1)
simpler products, (2) isomers which include branched chain hydro-
carbons from straight chain members, (3) dehydrogenated mem-
bers, and (4) polymers. The importance of the contact time and
the influence of metal tubes are discussed.
The physical factors governing cracking operations are
reviewed by Brown, Lewis, and Weber,22i who outline methods,
based on the pressure-volume-temperature relations of hydrocar-
bons, for computing the conditions existing at equilibrium, with
special attention to the extrapolation of these methods, and their
application to cracking plant problems. Paul and Marek222 give
velocity constants for propane, butane, and isobutane. Ipatieff,
Corson, and Egloff 223 discuss a catalytic process for the polymeri-
zation of high olefin cracking still gases in the production of
gasoline and mention a commercial plant which is in operation,
producing more than five gallons of gasoline per 1000 cubic feet
of cracking still gas.
The thermal decomposition of pentane is discussed by Morgan
and Munday.224 Lang and Morgan 225 have studied in great detail
the pyrolysis of propane at low partial pressures. The results of
their investigations show that a bimolecular primary decomposi-
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300 ANNUAL SURVEY OF AMERICAN CHEMISTRY
tion occurs to a certain extent, that in the range of temperatures
employed temperature has no effect upon the proportions of
primary products obtained from propane, and that the proportion
of propylene to ethylene in the unsaturated hydrocarbons obtained
by commercial pyrolysis of propane may be increased at higher
pressures. A critical study was made of the proposed mechanism
of hydrocarbon pyrolysis, which is explained on the basis of Nef s
dissociation hypothesis.
Among the patents in the field of pyrolysis of hydrocarbon gases
are those of Sullivan and Ruthruff,22« whereby saturated hydro-
carbon gases are cracked, the methane and non-hydrocarbon gases
eliminated by the selective absorption in oil of the hydrocarbons
higher than methane, which are then polymerized at elevated tem-
peratures and pressures to give a gasoline of high anti-knock
properties. Another patent of Sullivan and Ruthruff227 covers
the polymerization of light olefins in a continuous system in the
presence of naphtha, gas oil, or the like, at temperatures above
650° F. and pressures above 500 pounds per square inch to give
gasoline of high knock rating. Wilson 228 j^^s specified a process for
the polymerization of unsaturated hydrocarbons at elevated tem-
peratures and pressures. The production of liquid aromatic hydro-
carbons from cracking still or coke oven gases by polymerization
in a pipe coil, with immediate introduction of cooling oils into the
heated gas to check conversion, followed by the rectification and
condensation of the products is claimed by Egloff.22» In another
patent Egloff 230 proposes to crack natural gas or refinery gas, fol-
lowing the primary cracking operation with a secondary cracking
at increased pressure and temperature in the presence of steam
and hydrogen preactivated by an electric discharge. Plummer23i
proposes to combine the processes of polymerization of unsatu-
rated hydrocarbon gases and the cracking of petroleum in a single
process. Other processes are those of Wagner,232 Egloff,233
Dunstan and Wheeler 234 ^nd Youker 235 for the polymerization of
natural gas or oil-cracking gases.
A process for the production of light oils, wherein natural gas
or oil still gases are so cracked as to give the optimum yield of
aromatic hydrocarbons, and the resulting tars and residual gases
then hydrogenated catalytically, is specified by Smith and Rall.23«
Odell 237 specifies a process in which gases containing unstable ole-
fins are converted into stable hydrocarbons, employing firebrick
with or without aluminum phosphate, aluminum oxide, iron oxide,
or thorium oxide as catalysts.
The production of a gas rich in hydrogen by the catalytic con-
version of hydrocarbons with steam is patented by Russell and
Hanks.238 A catalyst for this purpose is specified by Davis and
Franceway.23»
Among the patents for producing gas primarily for use in
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GASEOUS FUELS. J 934 AND 1935 301
internal combustion engines are those of Reichhelm,24o Lacas-
sagne,24i and deGrey.242 Apparatus for generating fuel gases from
liquid fuels and air are patented by Jagmin ^43 and by Cordes.^^^
Garner 245 ^^s pointed out a number of possibilities and accom-
plishments in the chemical utilization of natural gas, including
the use of an improved carbon black process which also yields
hydrogen, the production of unsaturated hydrocarbons, the manu-
facture of formaldehyde from methane, the chlorination of hydro-
carbon gases, the use of liquid butane as a solvent, and the
recovery of bromine from brines from gas wells. Ellis 245a j^^s
reviewed the chemical utilization of cracking gas, including a
bibliography of 175 references.
Laboratory and plant data on the direct oxidation under high
pressures of methane, ethane, propane, butanes, pentanes, and
heptanes have been reported by Wiezevich and Frolich.246 xhe
products obtained may be separated into fractions having narrow
boiling ranges. Oxidation of methane at relatively high tempera-
ture results in the production of some methanol. Higher hydro-
carbons undergo a carbon-carbon scission during oxidation, with
the formation of lower derivatives in high yields. By recirculating
intermediate derivatives, acids are produced. Increase in pres-
sure tends to lower the temperature at which oxidation takes place
and to retard the decomposition of intermediate products. The
authors include a bibliography of 93 references.
Recent patents on the partial oxidation of hydrocarbons under
pressure for the production of alcohols and alehydes include those
of Walker.24'^ Other patents refer to the production of acety-
lene,248 of benzene,^^^ and of hydrogen-nitrogen mixtures,^^© and
to the removal of small amounts of oxygen from natural gas by a
combustion method.^si
The extensive investigations of Johnson and Berwald on the
transmission of natural gas have recently been summarized.252
Formulas for the flow of gas at high pressure in parallel lines have
been included in this and other papers.253 Problems in the design
of natural gas transmission systems have been discussed by Mer-
riam.254 Van der Pyl,255 in reviewing recent advances in the flow of
fluids, has discussed the flow of natural gas at high Reynolds
numbers.
A study of the values of discharge coefficients of square-edged
orifices has been presented by Bean.256
Problems in the Distribution of Gas. Because of the large invest-
ment involved in the construction of distribution systems, the fixed
charges on which constitute a great part of the cost of gas service,
the problems of minimizing the investment costs and increasing
the life of the system have received deserved attention. Of equal
importance has been the problem of ensuring unfailing continuity
of service. Many of these studies relate to problems of design and
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302 ANNUAL SURVEY OF AMERICAN CHEMISTRY
construction which cannot be included here. Others, however,
relating to the protection of the distribution system and to means
for ensuring continuity of service involve problems of chemical
interest.
The protection from corrosion of the enormous investment in
underground pipe systems has been the subject of continued
attention. Ewing^ST reports on a four months' field trip during
the summer of 1935 to consult with gas engineers throughout the
country and to remove and examine the third set of coated pipes
which were buried in 1929 in the American Gas Association field
coating tests, outlines the experience and practice of various com-
panies with respect to pipe coatings, and offers suggestions for the
logical attack on soil corrosion problems. Ewing^ss ^^s also
reported in some detail laboratory studies of the performance of
pipe coatings in which periodic determinations of the electrical
conductance of the coatings were made while they were exposed
to the action of salt water and of soil which was alternately wet
and dry. Among the important factors in estimating the protective
value of pipe coatings are moisture penetration and the mechanical
effect of the soil. These tests were designed to parallel field tests
but with the end in view of developing a more rapid method.
Although much work is being carried out on protective pipe
coatings. Turner ^so expresses skepticism as to the value of coatings
in congested areas and points out the great care necessary to pre-
vent bare spots in precoated pipe used in such locations. He
states that, after a few years underground, the resistance of the
coating may be reduced to zero and in many cases, particularly
where stray current electrolysis prevails, the use of a coating
invites rather than prevents corrosion, because of the restriction
of the action to small areas where a break in the coating occurs.
The problem of electrolysis has received considerable attention.
Ewing,26o in a detailed report of the American Gas Association
sub-committee on pipe coatings and corrosion, describes methods
for making preliminary surveys and for determining where drain-
age stations should be located, where cathodic protection is
employed, as well as for determining the effectiveness of the pro-
tection at any time after the installation is in operation. Bridge ^^^
has reviewed the cathodic protection of pipe lines and states that
it has been demonstrated that a negative potential of 0.2 volt (net)
pipe to soil will effectively prevent corrosion. Smith 2«2 ^as given
an exposition in simple terms of cathodic protection of pipe lines
and urges its more general adoption because of its simplicity and
effectiveness. Schneider ^63 has investigated the economics of
such protection. Allyne^^^ has reported on experimental work
showing the practicability of intermittent electric drainage for
pipe line protection. Kuhn ^65 has likewise surveyed cathodic pro-
tection of pipe lines from soil corrosion.
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GASEOUS FUELS, 1934 AND 1935 303
Scott and Ewing 2«6 have studied the relative importance of the
factors influencing the density of the pattern in the so-called pattern
test for pipe coatings which depends upon the precipitation of
ferrous (ferric) ion by ferricyanide or ferrocyanide ion on a suitable
paper, which is then immersed in developing solution. The blue
stains produced record the discontinuities in the pipe. An improved
procedure adaptable to field conditions is specified. Ewing 2«7 has
summarized work on pipe corrosion carried out during 1934.
Abbott 2«8 has also discussed the present status of work of this t)rpe.
Although the emphasis has generally been placed on external
corrosion, the problem of internal corrosion is receiving increasing
attention, especially in connection with the transmission of natural
gas. Allyne 2«» points out that in California this type of corrosion
is very serious, resulting from the action of hydrogen sulfide and
oxygen in the presence of condensed moisture. Removal of hydro-
gen sulfide and oxygen by chemical methods is considered imprac-
ticable and dehumidification the only feasible solution. Schmidt
and Bacon ^70 have collected considerable information regarding the
causes and effects of internal corrosion in natural gas transmission
lines. The consensus of opinion appears to be that the most eco-
nomical method of prevention now available is that of dehydration
of the entering gas.
Brennan 27i has formulated a mathematical correlation of corro-
sion with the age and soil index for steel mains.
The corrosive effect of hydrogen sulfide on steel has been recog-
nized as responsible for large economic losses, according to work
of the Bureau of Mines.272
Although the increased use of mechanical joints for gas mains
has tended to eliminate the hazards of broken mains, the bolts and
nuts necessary for the joints are far more subject to corrosion and
failure than the pipe itself. Perry ^78 has recognized the impor-
tance of increasing the life of the bolts and nuts and has presented
the results of an investigation directed toward this end.
During recent years, the use of automatically controlled gas
appliances has increased rapidly, requiring the use of thermostats,
safety pilots, and time controls. The corrosion-resisting properties
of the metals employed in these appliances are of the greatest
importance in their successful operation. Ward and Fulweiler274
have made a study of the corrosion resistance of copper base alloys
used in the manufacture of safety pilots and the like, when exposed
to city gas containing organic sulfur at ordinary and slightly ele-
vated temperatures (up to 275° F.), in the effort to find a corrosion-
resisting alloy more readily machinable than aluminum. Alloys
containing less than 63 percent copper and in sheet or rod form
are almost perfectly resistant to corrosion resulting from the pres-
ence of organic sulfur and are further improved by the addition of
one to two percent of either lead or aluminum. It was noted that
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304 ANNUAL SURVEY OF AMERICAN CHEMISTRY
tubes of similar alloys, unless polished internally, were distinctly
less resistant and the authors recommend that, pending the devel-
opment of a commercially practicable method for cleaning the inside
surface of tubing, aluminum tubing be used for installations where
the tubing does not come in contact with alkaline insulation mate-
rial, and that either tin plated tubing or a bimetallic tubing with
aluminum on the inside and copper or brass on the outside be used
where the tubing comes in contact with such material.
A discussion of the corrosion and oxidation of metals employed
for gas appliance tubing, together with a bibliography, is given by
Wright.275
The problems peculiar to high pressure storage and distribution
in connection with gas supply to outlying districts have been stud-
ied by Larson.275a
The importance of ensuring continuous operation of automatic
gas appliances and pilot lights has justified continued attention to
the problem of eliminating the gums found to contribute, along
with dust, to shortcomings in this respect.
In concluding the most recent of a series of papers describing an
extensive investigation of the subject. Ward, Jordan, and Ful-
weiler 276 emphasize the importance of vapor-phase gum as a cause
of pilot outages and malfunctioning of automatic gas appliances
and attribute the formation of such gum to the action of oxides of
nitrogen, largely nitrogen peroxide, on any of a number of organic
compounds present in manufactured gas. The oxides of nitrogen,
arising primarily in any type of manufactured gas from products
of combustion, are present chiefly as nitric oxide, which is slowly
oxidized to nitrogen peroxide, which then reacts rapidly to form
gum. Vapor phase gum, existing dispersed in the gas in the form
of a very large number of electrically charged particles of submicro-
scopic size, coalesce until a size of 1 to 1.5 u is reached. Above this
size they no longer remain so dispersed. The authors recommend
the reduction of the concentration of nitrogen oxides to below
0.0003 grain per 100 cubic feet, equivalent to five parts per billion
by volume, to ensure freedom from formation of vapor-phase gums
and announce the development of a process involving a modified
oxide box operation for ensuring the removal of nitrogen oxides
by contact with sulfided iron oxide.^^^ Further papers on this sub-
ject are those of Fulweiler ^78 and that of McElroy with Brady 27»
on the continuous addition of nitric oxide to city gas for use in
accelerated tests of pilots.
Powell 280 has discussed the principles underlying the selective
absorption of liquid phase gum-formers and naphthalene by oil
scrubbing.
In a study of the effect of fogging oil on gum deposits, Mathias ^si
reports laboratory and plant tests on the use of a fogging oil con-
taining an inhibitor in order to prevent gum formation.
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GASEOUS FUELS. 1934 AND 1935 305
Patents have appeared relating to removal of gum-forming con-
stituents from gas by solvents 282 and by an electric discharge,283
the prevention of gum formation 284 ^y the addition of inhibitors
to the gas or to meter oil, and the humidification of the gas in the
mains to inhibit gum formation .^ss xhe use of an aftercooler and
a Blaw-Knox gas cleaner to prevent deposits believed due to liquid
phase gum-formers has been discussed by Tenney.286
Shnidman 287 has made a timely study of the problem of dust in
gas, which appears to be more important at present in the trans-
mission of natural gas than that of manufactured gas.
Experiments on the resistance to dust stoppage of various pilot
orifices are reported by Corfield.288
Investigations of combustibles in manholes in Boston, Massa-
chusetts, covering the findings of over 12,000 tests in Boston Edison
manholes and over 3,000 manholes of the New England Telephone
and Telegraph Company are reported by Jones.28» Knowlton,^^^
points out that notable progress has been made in eliminating
explosion hazards and toxic conditions as a result of the coopera-
tive effort of telephone, electric, and gas companies, and the U. S.
Bureau of Mines. Statistics regarding carbon monoxide poisoning
from various sources are cited by Briggs.^^^ In a study of factors
affecting the lethal action on experimental animals of mixtures of
city gas with air, Smith, McMillan, and Mack found that the sur-
vival time was less in young adult rats than in old animals, and in
male than in female rats, and that pregnancy and the use of a meta-
bolic stimulant (a-dinitrophenol) greatly reduced the lethal inter-
val.2®2 Barker 2»3 gives a case history of carbon monoxide poison-
ing from a smoking oil stove. Studies of the "normal" carbon
monoxide content of the blood, supported by tests of the blood of
dwellers of both city and rural districts have been made by Gettler
and Mattice.2^^ The average proportion of the hemoglobin com-
bined with carbon monoxide was, for 18 persons in New York City
under minimal conditions of exposure, 1.0 to 1.5 percent; for 12
institutional cases in a rural locality, less than 1.0 percent; for
12 street cleaners, about 3 percent; and for two taxi drivers from
8 to 19 percent.
A test is reported by Corfield 2»5 jn which exposure to an atmos-
phere containing 24-29 percent of natural gas with the oxygen con-
tent reduced to 14-16 percent for a period of one hour and 15 min-
utes in a tightly closed room resulted in no injury to any of five
men acting as subjects. Diffusion characteristics in gas leaks and
the possibility of explosive mixture formation were also studied.
Klar 2»^ has reviewed the leather characteristics and defects of
meter diaphragms, giving consideration to the value of various oils
and diaphragm dressings. Some of the engineering aspects of dia-
phragm meters have been treated by MacLean.^^^ Several articles
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306 ANNUAL SURVEY OF AMERICAN CHEMISTRY
have been published concerning meter repair shop practice,^^^ and
factors and trends in meter maintenance.^^®
A patent has been granted to Fulweiler and Jordan 3oo fQj. ^
material for gas meter diaphragms, consisting of leather stuffed
with soap composed of aluminum and saponified coconut oil, which
is insoluble in benzene and other hydrocarbons normally present in
gas drip and also insoluble in water.
The effect of humidity on meter proofs has been discussed by
Corfield,8<^i and in a report of the Pacific Coast Gas Association.^*^^
Bean describes ^^ a convenient procedure for testing laboratory
wet meters.
Zoll 3^* has been granted a patent for an apparatus for determin-
ing the amount of "corrected gas" in a stream of raw gas such as
producer or water gas.
Among the general reviews of developments in gas distribution
are those of Battin ^os and of Larson.^^^
Utilization. The principal developments in the industrial utiliza-
tion of gas have related to the design and construction of equip-
ment for giving the proper gaseous atmospheres in which to carry
out a wide variety of metallurgical operations. Equipment installed
in industrial plants for the cracking, washing, and refrigeration of
natural or manufactured gas has resulted in important new uses of
gas where the effect of the atmosphere, whether oxidizing or reduc-
ing,, is of importance. Considerable progress has been made in the
use of controlled atmospheres in carburizing and other heat treat-
ing furnaces. A new development ^^'^ is the use of so-called radiant
tubes of alloy steel in which combustion takes place over a con-
siderable length. Tubes of this kind have found considerable use
in steel mills in the large annealing boxes for treating sheets and
plates.
A continuation of the integration of the industrial uses of gas
in the production lines of manufacturing processes has been
observed. Typical examples of such applications, together with
numerous references to the improvement of forging, hardening,
and carburizing, to the bright annealing of copper tubing and of
other non-ferrous metals, the melting of brass and soft metals,
various low temperature baking and drying operations, melting of
glass, vitreous enameling, the preparation of food products, indus-
trial steam applications, and the like may be found by reference
to the extensive annotated bibliographies appearing from time to
time in the American Gas Association Monthly .^os
Relatively little theoretical work appears to have been accom-
plished with respect to such subjects as the transmission of heat
by radiation in furnaces, notwithstanding the fundamental impor-
tance of accurate knowledge of the temperature distribution in
furnace design. Substantially all attempts to formulate equations
covering the rate of heat transfer by radiation are based on the
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GASEOUS FUELS, 1934 AND 1935 307
wholly empirical Hudson-Orrok equation developed in connection
with boiler furnace design. There seems little evidence that the
highly mathematical treatments suggested by various investigators
for the prediction of the distribution of radiant heat in furnaces
have found any important engineering application, chiefly because
pf their complexity. There is little doubt that progress in furnace
design has been greatly retarded by the lack of simplified design
procedures. Hottel and Mangelsdorf ^^^ have presented data
covering the absorption and emission of radiation from non-
luminous gases and indicates very considerable changes in the
magnitudes of these effects from those given in earlier publica-
tions.
Radiation from luminous and non-luminous natural gas flames
has been studied experimentally by Sherman.^^®
Cowan 311 has discussed the development of heating, annealing,
and other heat treating processes in controlled atmospheres with
special reference to the use of diffusion combustion, in which the
strata of air and gas travel parallel to each other throughout the
furnace chamber without substantial turbulence, with the object
of preventing oxidation by blanketing the metal undergoing treat-
ment with a stream of raw gas. The use of methanol to prevent
the formation of oxide films in the bright annealing of brass and
the use of various hydrocarbon gases or hydrogen-liberating gases
for the same purpose is mentioned. Segeler^^^ has reviewed the
recent work on special industrial furnace atmospheres, in which he
refers to the necessity for consideration of the oxidizing effect of
flight amounts of oxygen and water vapor, methods for the detec-
tion of traces of oxygen, the desirability of oxidizing or reducing
atmospheres in various processes, the factors influencing scaling or
decarburization effects, the methods for obtaining the desired
furnace atmospheres, and a list of specific recommendations
regarding the type of atmosphere and methods for attaining the
correct gas composition for various industrial heating operations.
Murphy and Jominy ^13 have studied the influence of atmosphere
and temperature on the behavior of steel with respect to scaling
in forging furnaces and find that in a reducing atmosphere a higher
temperature may be used. The scaling of steel increases with
increasing time of exposure and temperature and is aggravated
by the presence of small amounts of sulfur dioxide in the furnace
gases.
Jominy 81* has studied the effect of pure gases including steam,
carbon dioxide, air, nitrogen, hydrogen, and various synthetic mix-
tures of pure gases, the effect of pressure and that of rate of flow,
temperature and period of exposure, of reducing and oxidizing
atmospheres and the like on the surface decarburization of steel
at heat treating temperatures.
Progress in the heat treatment of ferrous metals including
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308 ANNUAL SURVEY OF AMERICAN CHEMISTRY
annealing, normalizing, bright annealing, carburization, and forging
in connection with continuous furnaces in the automotive industry
is reviewed by Clark.^is Manier ^^^ has reported on the use of gas
in the treatment of non-ferrous metals with special reference to
the use of controlled atmospheres employing in certain cases gas
preparation units for the cracking of gas to provide the desired
conditions.
Gehrig 3^^ has discussed the application of gas-fired, radiant
tubes to porcelain enameling. The results of experiments on 58
porcelain glazes employing direct gas firing in an oxidizing furnace
atmosphere are reported by Watts.^^s It was found that both
white and colored glazes can be direct-fired without damage either
to body or glaze but that flashing or direct impingement of the
flame against the glaze surface must be avoided. Direct firing
results in a material reduction in firing time. Young ^i® has
described the bright annealing of non-ferrous metals and points
out ^2^ the favorable opportunities for load building offered by the
application of city gas for the production of special atmospheres
in industrial furnaces.
Gillett^^i has made a valuable comprehensive review of con-
trolled atmospheres in steel treating, covering the difficulties to be
avoided by the use of controlled atmospheres, the effects of scaling,
the properties of gases available for such use, reactions of gases
with iron and carbon, various equilibrium data, cost and action of
available gases, types of controlled atmosphere furnaces, correla-
tion of experiments and experiences on scaling and its avoidance,
decarburization, carburization, and bright annealing, the use o£
city gas for carburizing, and the like. A bibliography of 86 refer-
ences is included. In a summary of this subject, Gillett ^^^ empha-
sizes the necessity of further research and points out unsolved
problems in this field.
Among the various research projects pursued by the Committee
on Industrial Gas Research ^23 q{ the American Gas Association,
are the studies of the effect of operating temperatures and of fur-
nace pressures on the combustion of industrial gas, the develop-
ment of individually heated and controlled deck bake ovens, the
application of heat to ceramic firing, to sheet steel enamelling,
ceramic decoration, and the development of gas operated house
cooling and air conditioning equipment for both large comfort and
industrial applications and smaller unit air conditioners.
Progress in the application of gas to summer air conditioning for
comfort employing the silica gel method, as well as in the use of
lithium chloride solutions for the dehydration of air, has been
reported.324 Among industrial uses of gas for air conditioning may
be mentioned that in the printing industry, described by Fonda.^^©
A detailed discussion of silica gel and its uses is given by Lednum.326
The possibilities of improving the character of the gas load by
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GASEOUS FUELS, 1934 AND 1935 309
the development of air conditioning by gas are discussed by
Parker.327
King 328 i^as outlined the principal consideration in the conser-
vation of heat in gas-heated buildings. A bibliography of 148
recent articles on house heating and cooling appears in a report of
the House Heating and Cooling Committee of the American Gas
Association. 329
Methods of calculating gas heating have been presented by
Kuenhold,^^^ together with data on conditioned air heating. A
graphical method for determining flue losses from industrial gas
furnaces is outlined by Smith.^^i Data on the heat content of
gases from to 1900° C. have been given by Taylor.^^^
The importance of gas fuel in modern power generation has
been pointed out by German ^^^ and by Philo.^^^ A renewed
interest in gas engines, after a long period in which their use was
limited chiefly to blast-furnace gas plants and in oil and gas fields,
has been noted. A tabulation, giving data on 33 new engine plants,
the largest being of 6600 h. p. total capacity, is given by Tanger-
man.33^ The development of automatic gas engines for refrigera-
tion and pumping purposes is receiving attention.^^®
A revival of interest in gas lighting, with especial reference to
flood lighting and indoor industrial lighting, has taken place in the
past few years and a number of notices of successful installations
employing high pressure street lighting have appeared.^^*^
Among papers relating to the design of domestic gas burners is
that of Conner 338 ^nd of Leonard and Howe,33» who have estab-
lished performance curves for a single port burner and a multi-
port burner and suggest that it should be possible to interpret the
form of such curves in terms of ignition velocity data. Mattocks 3*o
has discussed the factors affecting the design and application of
industrial gas burners. Appliance testing and laboratory operation
are described by Conner.^^i The function and design of draft
hoods 342 and the operating characteristics of domestic gas pressure
regulators 343 have been discussed by Smith and the venting of
flues by Clow.344
Attention is given to the design and performance of safety pilots
by Leighton,345 to the resistance of range pilots to drafts by Smith,34«
and to the capacity of domestic flues and vents by Wills.34'^
Combustion. Morgan and Stolzenbach 348 have established
experimentally that the ratio of the volume of carbon monoxide to
that of hydrogen in products of combustion of carbonaceous fuels
containing sufficient hydrogen is constant at 2.9 when the fuels are
burned under such conditions that the free hydrogen in the incom-
pletely burned products does not exceed 3 percent, thus confirming
the conclusion of Minter,34» who contended that, contrary to
rather common opinion, hydrogen does not burn at high tempera-
tures at a greater rate than carbon monoxide. Hamilton 35o has
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310 ANNUAL SURVEY OF AMERICAN CHEMISTRY
described a device for exhaust gas analysis based on the constancy
of the carbon monoxide .-hydrogen ratio in automobile exhaust
gases.
A study has been made of the combustion rate of carbon by Tu,
Davis, and Hottel.^^^ A quantitative formulation of the rate of
combustion of carbon in air is given, based on the concept of a
surface covered by a relatively stagnant film through which oxygen
and combustion products must diffuse countercurrently.
The effect of ash on combustion characteristics of carbons has
been studied by Oshima and Fukuda,^^^ ^j^o present data on the
effect of natural ash and of added salts in carbonaceous materials
upon their ignitibility and combustion velocity.
The soap-bubble or constant pressure method as applied to the
explosive oxidation of carbon monoxide has been described by
Fiock and Roeder.^*^^ Results for this system of gases are reported
over a wide range of mixture ratios. In an earlier report ^^* tjhe
authors point out that water appears to be an essential factor in
attaining equilibrium in this reaction.
The combustion of carburetted water gas in luminous flames has
been studied by Altpeter and Kowalke.^^^ The criterion of com-
pleteness of combustion was the carbon monoxide content of the
flame. Combustion rates at which carbon monoxide was reduced
to 0.2 percent varied from 208 cubic feet per hour for a ratio of
furnace volume: furnace area (V/A) = 16 to 132 cubic feet for
(V/A)=4,
A review of various experimental determinations of the mecha-
nism and rate of combustion of solid carbon by gaseous oxygen, a
discussion of previous mathematical analyses of the process, and
an account of some measurements at low pressures are given by
Mayers,^*^® who concludes that much more experimental work will
be necessary before a complete formulation of the rates or mecha-
nism of the reaction can be made.
In another paper, Mayers ^^^ discusses the mechanism of com-
bustion in both pulverized coal and in grate firing, together with
the characteristics of coals determining the attainable rating.
A marked catalysis of the oxidation of carbon, employing as
catalysts lithium, sodium, potassium, strontium, and barium chlo-
rides, and sodium and potassium sulfates, is reported by Day,
Robey, and Dauben.^^®
Lewis and von Elbe ^^^ have calculated the theoretical explosion
pressures for oxygen-hydrogen mixtures by means of thermody-
namic functions of gases derived from band spectra and offer
explanations for the difference between observed and calculated
values in the cases of dried oxygen-hydrogen mixtures and in those
containing excess oxygen or nitrogen.
Water vapor, in amounts above five mm. vapor pressure, has
been found by Jones and Seaman 3«o ^q j^ise the ignition tempera-
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GASEOUS FUELS, 1934 AND 1935 311
tures of methane-air mixtures slightly. The maximum increase,
for a saturated mixture containing above 4 percent methane, was
found to be 11° C.
A study by Pease ^®^ of the mechanism of the slow oxidation of
propane at lower temperatures and oxygen concentrations than
heretofore employed indicates that methanol, formaldehyde, carbon
monoxide, and water are the primary products. Results are inter-
preted in terms of the radical-chain theory of Rice, on the assump-
tion that methoxyl (CHgO) and propyl (C3H7) are the chain
carriers.
Benton and Bellies have made a study of the kinetics of the
oxidation of carbon monoxide with a reduced silver catalyst in the
range of 80-140° C, together with the adsorptions of the three
gases involved.
According to McKinney,^^^ platinum oxide is a catalyst for the
combustion of carbon monoxide at 80° C. and is not reduced as
long as oxygen is in excess.
The activation energies of the reaction + H2 = H20 have been
studied by Bear and Eyring.^^*
Composition and Analysis. Among the papers relating to gas-
works control and industrial problems are those of Willien,^^^ of
Glover 3^^* and of Bermann,^^^ the last including a number of
nomographic charts. Jones and Kennedy ^^^ have investigated the
values below which the oxygen must be maintained to prevent
explosions of combustible gases and vapors and have given critical
oxygen values for the paraffin hydrocarbons up to and including
hexane and for ethylene, propylene, hydrogen, and carbon monox-
ide using carbon dioxide and nitrogen, respectively, as the inert
diluents. The effect of elevation of temperatures for the range
below 40° C. was studied.
Yeaw and Shnidman^^s have studied experimentally the dew
point of flue products from the combustion of manufactured gas
and find that the true dew points are higher than those calculated
from the water estimated to be present according to the chemical
equations involved in the combustion by an increasing amount as
the excess air in the gases decreases, thig result being attributable
to the presence of a trace of sulfur trioxide in the flue products.
Scott,^^^ in a review of methods of fuel calculations, has outlined
the computation of the ultimate analysis of coal from B.t.u. con-
tent of fuel, percentage ash, and the composition of the flue gas.
Other papers relating to the stoichiometry of fuels include those of
Paul and Gleason^"^^ relating to engine exhaust gas analyses and
their interpretation and application in the determination of air-
fuel ratios and engine economy.
Anthes and Fahey^*^^ recommend the determination of such
combustion data for gaseous fuels as the air requirements for com-
bustion for a given gas or the volume of flue products by calcula-
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312 ANNUAL SURVEY OF AMERICAN CHEMISTRY
tions based on the results of an explosion test of the gas in an
Elliott apparatus and a determination of the heating value in a
Junkers calorimeter with the measurement of condensate and
analyses of calorimeter flue gas samples.
Charts have been presented by Nutting ^72 fQj. reduction to stand-
ard conditions of gas saturated with water vapor.
Gas Analysis. The developments in gas analysis have related
chiefly to the use of physical methods, such as thermal conductivity
through the increased use of micro-analytical methods, the devel-
opment of automatic gas analysis apparatus, and the use of low-
temperature methods. The use of the conventional absorption
methods has been given attention by Kobe and Williams,^*^^ who dis-
cuss the merits of various confining liquids with respect to the solu-
bility of carbon dioxide. They conclude that a solution containing
20 percent of sodium sulfate by weight and 5 percent by volume of
sulfuric acid is the most satisfactory. Mulcahy ^'^^ has discussed the
application of exact gas analysis to gas plant problems, pointing out
the variety of types of gas encountered because of the recent changes
in the industry. Various possible sources of error and methods for
their correction are given.
A new modification of the circular manifold type of gas analysis
apparatus employing the Huff pumping pipette is described by
Jones.^^**
Gas absorption apparatus has been described by Dillon.376
Further work on the micro-analysis of gases, using solid reagents,
has been carried out by Blacet and MacDonald,^'^'^ who have
extended their earlier methods to include a new method for the
determination of hydrogen and carbon monoxide, and to include
hydrogen chloride and ammonia as gases determinable by the use
of reagents already available.
The analysis of combustibles in flue gas has been discussed in
detail by Evans and Davenport,^'^^ who have developed a gas
analysis apparatus employing slow combustion and several novel
details. An improved slow combustion pipette has been developed
by Porter and Cryder-^*^® Walker and Christensen ^^^ recommend
the determination of methane by catalytic oxidation over cobalt
oxide. A comparison of the Elliott and Hempel explosion appara-
tus, employing measured volumes of gas and air, has been made
by Anthes and Fahey,^^^ who conclude that the accuracy of the
Elliott apparatus for use in routine gas plant practice may be made
considerably higher than ordinarily assumed.
Branham and Shepherdess have made a critical study of the
determination of ethane by explosion, employing pure oxygen,
commercial oxygen, and air.
The sampling and analysis of entrained matter in gases, especially
as a test of the efficiency of Cottrell precipitators, is discussed by
Varga and Newton.^ss A new dew point apparatus for the deter-
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GASEOUS FUELS, 1934 AND 1935 313
mination of water vapor in natural gas which permits the test to
be carried out in line under flow conditions, is described by Wood-
ruff.3®^ The determination of water and hydrogen sulfide in gas
mixtures is discussed by Fraas and Partridge.^^^
Littlefield, Yant, and Berger 386 have described a hydrogen sulfide
detector based on the color change reaction on the surface of gran-
ules coated with activated aluminum oxide with silver cyanide or
lead acetate and placed in a glass tube through which the atmos-
phere to be examined is aspirated by a rubber bulb or hand pump.
Further use of the thermal conductivity principle for the analysis
of gas is disclosed in the papers of Smith ^^'^ and of Anderson ^^s
for the continuous determination of the helium content of natural
gas.
Other apparatus employing electrical resistance effects are dis-
closed in the patents of Stein 38» and of Jacobson.^®^ Schmidt ^^^
proposes to determine the oxygen content of flue gases and the like
by carrying out combustion in the presence of an excess of flowing
hydrogen and determining the temperature rise imparted to a
separately metered stream of cooling fluid. Howe ^^^ proposes a
method for determining oxygen in gas involving measurement of
the temperature rise resulting from the catalytic reaction of the
oxygen and combustible gas. An analysis apparatus for the deter-
mination of carbon dioxide in flue gas is patented by Brown and
Harrison.3®3
A simplified design of carbon monoxide alarm and ventilation control
is described by Houghten and Thiessen.^^^
An improved automatic analyzer for carbon monoxide in air in which
the necessary removal of water vapor is accomplished by the use of
silica gel or activated alumina is described by Frevert and Francis.^®^
A simple carbon monoxide testing device has been described by Dun-
ham.306
The increased interest in the utilization of cracking still gases and
natural gas condensates has resulted in the direction of further attention
to the low temperature analysis of hydrocarbon gases. Among the con-
tributions in this field may be mentioned the method of Happel and
Robertson ^^'^ for the analysis of dry refinery gases below pentane by
simple batch distillation employing a master graph whereby the composi-
tion of a refinery gas may be determined by an ordinary simple distilla-
tion of the condensed gas. Tropsch and Mattox 3»8 describe a low tem-
perature fractional condensation method for determining the gasoline
content of refinery gases. Lang ^^^ has employed a combination of the
Podbielniak distillation column and the Shepherd apparatus in the analy-
sis of complex gas mixtures encountered in the pyrolysis of propane. A
method for determining ethylene, propene, and butene is outlined by
Tropsch and Mattox ^^^ which depends on the fractional solution of
propene and butene in 87 percent sulfuric acid, the density of the mixture
of propene and butene serving to give the ratio of the two hydrocarbons.
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314 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The ethylene is determined by absorption in concentrated sulfuric acid
activated with nickel and silver sulfates.
Podbielniak ^^^' ^^^ has described a fluid-reacting apparatus espe-
cially adapted for fractionation in which gravity has been replaced
by centrifugal force, and in which a consequent remarkable increase
in efficiency of fractionation is said to be obtained in the fractiona-
tion analysis of petroleum.
Fulweiler^^3 has reviewed the analytical method for the deter-
mination of nitric oxide in city gas and summarized work carried
out during the past five years. An apparatus has been developed
for the automatic detection of nitric oxide in city gas.
Various Analytical and Test Methods. Kemp, Collins, and Kuhn *^
have shown that by refinements in the apparatus and its use, the effu-
sion method for determining the specific gravity of gases may be greatly
improved.
Considerable material of interest in connection with the analysis
of gas making materials and by-products of gas manufacture is
contained in the work of Fieldner and Davis,^^^ Selvig and Ode,*^
of Kirner^®*^ on the microdetermination of carbon, hydrogen, and
oxygen, of Merkus and White ^^^* on the evaluation of gas oils,
and of others.^®^
A method for determining moisture in coal is described by
Wood.-^o®
Berry ^1® has analyzed the accuracy of humidity computations
and points out that since very small errors in wet-and-dry bulb
temperatures produce relatively large errors in determinations of
humidity, there is no gain, in the absence of highly precise wet-and-
dry bulb temperature measurements, in using the equations of
Carrier or of Ferrel as compared with the much simpler equation
of Apjohn, proposed about a century ago, and that, indeed, the use
of the Apjohn equation, together with steam tables and the equa-
tion of state of air, may be more convenient for the occasional
worker than that of established humidity charts. Ebaugh,^ii in
agreement with the analysis of Berry, presents an air density chart,
based on the Apjohn equation.
Among the papers presented before the Division of Gas and Fuel
Chemistry at the 1935 New York and San Francisco meetings of
the American Chemical Society are a number relating to ana-
lytical methods as yet appearing only in abstract form,^^^ including
those of W. A. Millikan, H. A. Cole and A. V. Ritchie on the deter-
mination of gaseous olefins or hydrogen by catalytic hydrogenation,
of W. H. Fulweiler and C. W. Jordan on the development of prac-
tical methods for determining small quantities of nitric oxide in
different types of gas, of E. S. Hertzog on the determination of
arsenic in coal, of W. T. Reid on the effect of iron on ash fusion
temperatures, of W. R. Kirner on the direct simultaneous micro-
determination of carbon, hydrogen, and oxygen in coal and its
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GASEOUS FUELS, 1934 AND 1925 315
products, of C. C. Furnas on a new method for the determination
of the reactivity of solid carbon, and of D. T. Bonney with W. J.
Huff on the determination of hydrogen by liquid reagents, in which
a new and active reagent consisting of colloidal palladium and of
an organic acceptor which readily undergoes reduction and reoxi-
dation is announced.
An investigation of the accuracy of the Junkers calorimeter, occa-
sioned by errors occurring under conditions of high temperatures
and low humidities, has been made by Richford,^^^ who presents
new charts and graphs for calorimeter corrections particularly
applicable to high B.t.u. natural gas.
As a part of the 1935 Production Committee Report of the Pacific
Coast Gas Association, White ^^^ has offered a scheme for a rapid
systematic qualitative analysis for metallic ions employing the
microscopic identification of crystal forms, as well as certain non-
microscopic identifications. The procedure is detailed and the
crystal forms obtained illustrated by photomicrographs.
Trials have been made of the photoelectric cell for the measure-
ment of the haze density of combustion gases,^^^ such as water gas
blast gas.
Chemical Engineering Processes. Among the papers of interest
in connection with the chemical engineering phases of the produc-
tion of gaseous fuels are those of Brown and co-workers,^^^ of
Carey, Griswold, McAdams, and Lewis ^^"^ on plate efficiencies in
the rectification of binary mixtures, and of Holbrook and Baker
on the entrainment in bubble cap distillation towers.*^®
The course of liquor flow in packed towers has been studied by
Chilton, Vernon, and Baker."*!®
Of considerable interest are the efforts of Colburn ^20 ^nd of
Chilton and Colburn ^21 to correlate data on convective heat trans-
fer, fluid friction, and absorption in such a manner as to permit
the prediction of one from the other.
The practical usefulness of the Reynolds number in the calcula-
tion of the flow of fluids has been extended through the classifi-
cation of pipe roughness and the establishment of friction factors
for such classes of roughness by Pigott ^^2 and Kemler.^23
The protection of gas plant equipment against corrosion has
been given some attention. Thus, Korany and Bliss ^^4 report on
a tubular condenser in which the corrosion was reduced by 98.8
percent, by the use of the Kirkaldy system in which the system is
made cathodic through the use of 5 amperes d.c. per 1000 cubic
feet of cooling surface, the anodes consisting of stout iron bars
arranged near the side walls.
Colburn and Hougen ^^5 have outlined a method for the compu-
tation of condenser surfaces and call attention to possible improve-
ments in operations through the use of higher gas and water
velocities.
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316 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Other papers of interest relating to unit processes are those on
the diffusion of vapors through gas films by Sherwood and Gilli-
land,^^ on the film concept in petroleum refining by Monrad,^^?
and of Fenske, Tongberg, and Quiggle^^s q^ packing materials
for fractionating towers.
Van der Pyl2o5 ^as outlined recent developments in the flow of
fluids. Huff and Logan,^29 i^ reviewing the status of gas engi-
neering flow formulas, present a method for determining the flow
of gas applying the Reynolds number in a form convenient for
computation and include an alignment chart illustrating the
method.
A review of solution cycles, including such processes as those of
Koenemann for generating high pressure steam by the use of
exhaust steam, has been given by Sellew.^^®
The writers are indebted to the several members of the Department
of Gas Engineering who aided in assembling the material used in the
preparation of this chapter.
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55. Subkow, P., U. S. Pat. 1,972,833 (Sept. 4, 1934).
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57. Porter, H. C, Ind. Eng. Chem., 26: 150 (1934).
58. Warner, A. W., patents pending.
59. Lavine, I., Ind. Eng. Chem., 26: 154 (1934).
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of Coal to the Reactivity, Electrical Conductivity and Hygroscopicity of Coke.
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64. Reynolds, D. A., Ind. Eng. Chem., 26: 732 (1934).
65. Warren, W. B., Ind. Eng. Chem., 27: 72 (1935).
66. Davis, J. D., and Auvil, H. S., Ind. Eng. Chem., 27: 459 (1935).
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73. Meredith, H. J.. Am. Gas Assoc, Proc, 1934: 916.
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74. Selvig, W. A., and Ode, W. H., Ind. Eng. Chem., Anal. Ed., 7: 88 (1935).
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(Dec. 19, 1933).
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(Oct. 16, 1934); van Ackeren, J., U. S. Pat. 1,980,018 (Nov. 6, 1934); Leithauser,
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8, 1935).
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U. S. Pat. 1,944,192 (Jan. 23, 1934); Odell, W. W., U. S. Pat. 1,983,943 (Dec.
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80. Richardson, R. F., U. S. Pat. 1,935,298 (Nov. 14, 1933).
81. Keillor, J., Gas Age-Rec. 76: 139 (1935).
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318 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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87. Tiddy, W., U. S. Pat. 1,940,893 (Dec. 26, 1933).
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89. Herzberg, F., U. S. Pat. 1,939,498 (Dec. 12, 1933).
90. Kropiwnicki, E., U. S. Pat. 1,964,639 (Tune 26, 1934).
91. Wisner, C. B., U. S. Pat. 1,993,198 (Mar. 5, 1935).
92. Wisner, C. B., U. S. Pat. 1,993,199 (Mar. 5, 1935).
93. Michot-Dupont, G. F., U. S. Pat. 1,981,614 (Nov. 20, 1934).
94. Kemraer, H., U. S. Pat. 1,932,076 (Oct. 24, 1933).
95. Niles, G. H., Am. Gas J., 141, No. 5: 15, 110 (1934).
96. Weiss, C. B.. and White, A. H., Ind. Eng. Chem., 26: 83 (1934).
97. Nagel, T., Am. Gas J., 143. No. 6: 22 (1935); Mining and Met., 16: 215 (1935).
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(Oct. 9, 1934); 2,005,102 (June 18, 19,^5); 2.016,751 (Oct. 8. 15J5) ; Weiss, J. M.,
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15, 1934); Stupp, C. G., U. S. Pat, ],^SBA50 (May IS. 19.^4); Zavertnik, J., Jr..
U. S. Pat. 1,972,468 (Sept. 4, 1934); Witti^nberir. L., U. S. Pat. l,976.90fi (Oct.
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I. H., U. S. Pat. 1,984,731 (Dec. ]». 19.14); DLckson, J. V. E., V. S. PaL
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2,011,633 (Aug. 20, 1935); Miller, S. P., U. S. Pat. 2,002,704 (May 28, 1935);
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109. Delorey, C. W., Gas Ind., 52: 506; Gas Age-Rec, 76: 33 (1935).
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U. S. Pat. 1,992,486 (Feb. 26, 1935).
111. Pyzel, D.. U. S. Pat. 1,985,548 (Dec. 25, 1934).
112. SchSneborn, H., U. S. Pat. 1,980,009 (Nov. 6, 1934) ; Hofsasz, M., U. S. Pat. 1,997,144
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(Aug. 28, 1934); Shoeld, M., U. S. Pats. 1,980,006 (Nov. 6, 1934); 2,003,560 (June
4, 1935); Jacobson, D. L., U. S. Pat. 1,983,375 (Dec. 4, 1934).
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(Mar. 12, 1935).
119. Hixson, A. W.. and Scott, C. E., Ind. Eng. Chem., 27: 307 (1935).
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122. Davies, C, Jr., U. S. Pat. 1,942,050 (Jan. 2, 1934).
123. EVmann, C, U. S. Pat. 1,957,253 (May 1, 1934).
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GASEOUS FUELS, 1934 AND 1935 319
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1,942,054 (Jan. 2, 1934).
126. Shoeld, M., U. S. Pats. 1,971,798 (Aug. 28, 1934); 2,002,357 (May 21, 1935).
127. Perkins, G. A., U. S. Pat. 1,951,992 (Mar. 20, 1934).
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1,995,545 (Mar. 26, 1935); Fitz, W., U. S. Pat. 1.947,467 (Feb. 20, 1934); The
Girdlcr Corp., Fr. Pat. 762,364 (Apr. 10, 1934); Forbes, A. L., Jr., and Byrne,
C. O., U. S. Pat 2,014,250 (Sept. 10, 1935).
129. Hansen, C. J., and Eymann, K., U. S. Pat. 1,964,572 (June 26, 1934).
130. AUyne, A. B., Western Gas, 10, No. 10: 14, 44 (1934).
131. Brewer, J. E., Am. Gas Assoc, Proc, 1933: 894.
132. Prcsbrey, R. L., Gas Age-Rec, 73: 531 (1934).
133. Seil, G. E., Fr. Pat. 776,903^ (Feb. 7, 1935).
134. Smyly, A. L., U. S. Pat. 1,934,242 (Nov. 7, 1933).
135. Broche, H., U. S. Pat. 2,007,741 (July 9, 1935).
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142. Ahlqvist, H., U. S. Pat. 1,955,722 (Apr. 24, 1934).
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146. Sperr, F. W., Jr., U. S. Pat. 1,961,254 (June 5, 1934).
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148. Tomkins, S. S., Am. Gas J., 141, No. 6: 16 (1934); Am. Gas Assoc, Proc, 1934: 799,
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151. Am. Gas J., 142. No. 6: 18 (1935).
152. Knowlton, L. E., Gas Age-Rec, 75: 216 (1935).
153. Geiger, C. W., Gas Age-Rec, 74: 233 (1934).
154. Dunn, J. H., Gas Age-Rec, 75: 525 (1935).
155. Report, Committee for Purging and Placing Gas Piping and Gas Apparatus into
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157. Swanson, B. B., Bur. Mines Minerals Yearbook, 1932-1933: 517.
158. Swanson, E. B., and Struth, H. J., Bur. Mines Minerals Yearbook, 1934: 723.
159. Hopkins, G. R., and Backus, H., Bur. Mines Minerals Yearbook, Statistical
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160. Bur. Mines Minerals Yearbook, Statistical Appendix, 1932-3: 103.
161. Knapp, A., Mineral Ind., 42: 418 (1933).
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166. Report V of Federal Oil Conservation Board to the President of the United
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167. Gas Age-Rec, 75: 134 (1935).
168. Davis, R. E Gas Age-Rec, 75: 565 (1935).
169. Reistle, C. E., Jr., and Hayes, E. P., Bur. Mines, Rept. of Investigations, 3211
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170. Lindsly, B. E., Bur. Mines, Tech. Paper, 554 (1933).
171. Lindsly, B. E., Bur. Mines, Rept. of Investigations, 3212 (1933).
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177. Heath, S. B., and Frey, Wm., U. S. Pat. 2.011.579 (Aug. 20, 1935).
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320 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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190. Hill, E. S., and Lacey, W. N.. Ind. Eng. Chem., 26: 1327 (1934).
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192. Lacey, W. N., Oil and Gas J.. Nov. 17; 1932, p. 49; OU Weekly, Jan. 9, 1933, p. 19.
193. Umpleby, J. B., OU Weekly, Mar. 5, 1934, p. 22.
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195. Hurst, W., Physics, 5: 20 (1934).
196. Lewis, J. O., Oil and Gas J., Aug. 10, 1933, p. 11.
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198. Eckert, F. E., Gas Age-Rec., U: 9 (1934).
199. Neyman, E., and Pilat, S., Oil and Gas J., 33, No. 49: 13 (1935).
200. Berwald, W. B., and Johnson. T. W., Bur. Mirites, Tech Paper, 555 (1933). 34 p.
201. Hammerschmidt, E. G., Ind. Eng. Chem., 26: 851 (1934).
202. Selden, R. F., Bur. Mines, Rept. of Investigations, 3233 (1934)*. 64 p.
203. Ranney, L., U. S. Pat. 1,992,323 (Feb. 26, 1935); Gas Age-Rec, 75: 585 (1935).
204. Lawall, C. E., and Morris, L. M., Trans. Am. Inst. Mining Met. Engrs., 108: 11
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205. Burke, S. P., and Parry, V. F., Am. Inst. Mining Met. Engrs., Tech. Pub., 607
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207. Oberfell, G. G., Gas Age-Rec, 73: 179 (1934); 75: 131 (1935).
208. Gould, M. D., Gas Ape-Rec, 75: 335 (1935).
209. Friend, W. Z., Am. Gas J., 140. No. 5: 69 (1934).
210. Jamison, E. A., and Bateman, W. H., Iron Steel Eng., 12: 209 (1935).
211. Jamison, E. A., and Bateman, W. H., Iron Steel Eng., 11: 344 (1934).
212. Hunt, A. E., Natural Gas, 16, No. 5: 80 (1935).
213. York, D. E., Western Gas, 10, No. 9: 40 (1934).
214. Avcra, A. U., Ga^ Age-Rec, 76: 471 (1935).
215. Perrine, R. O., Gas Age-Rec, 76: 541 (1935).
216. Hermsdorf, W. H., U. S. Pats. 1,945,550 (Feb. 6, 1934); 1,994,247 (Mar. 12. 1935).
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222. Paul, R. E., and Marek, L. F., Ind. Eng. Chem., 26: 454 (1934).
223. Ipatieff, V. N., Corson, B. B., and Egloflf, G., Ind. Eng. Chem., 27: 1077 (1935).
224. Morgan, J. J., and Munday, J. C, Ind. Eng. Chem., 27: 1082 (1935).
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226. Sullivan, F. W., Jr., and Ruthruff. R. F., Canadian Pat. 340,080 (Mar. 13, 1934).
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GASEOUS FUELS. 1934 AND 1935 321
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254. Merriam. C. W., Jr., Trans. A. S. M. E. (Pet. Mech. Eng. Paper No. 9, 65-73)
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257. Ewing, S., Observations on Soil Corrosion Mitigation in the Gas Industry. Pre-
print, Tech. Section, Am. Gas Assoc., 1935.
258. Ewing, S., Am. Gas Assoc. Monthly, 16: 98 (1934).
259. Turner, C. F., Am. Gas J., 142, No. 5: 37 (1935) ; Natural Gas, 16, No. 7: 10 (1935).
260. Ewing, S.. Gas Age-Rec, 75: 179 (1935).
261. Bridge, A. F., Western Gas, Nov., 1934, p. 12.
262. Smith. W. T., Gas Age-Rec, 76: 331 (1935).
263. Schneider, W. R., Gas Age-Rec, 73: 11 (1934).
264. Allyne. A. B., Gas Age-Rec, 74: 335 (1934).
265. Kuhn, R. J., Gas Age-Rec, 75: 337 (1935).
266. Ewing, S., and Scott, G. N., Am. Gas Assoc Monthly, 16: 136 (1934).
267. Ewing, S., Am. Gas J., 142, No. 1: 29 (1935).
268. Abbott, A. H., Am. Gas J., 140, No. 1: 9 (1934).
269. Allyne. A. B., Gas Age-Rec, 72: 463 (1933).
270. Schmidt, E. F., and Bacon, T. S., Gas Age-Rec, 74: 531 (1934).
271. Brennan, J. F., Gas Age-Rec, 75: 359 (1935).
272. Gas Age-Rec, 73: 108 (1934).
273. Perry, J. A., Am. Gas J., 142, No. 1: 22 (1935).
274. Ward, A. L., and Fulweiler, W. H., Am. Gas. J., 143, No. 5: 42 (1935). Corrosion
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275. Wright, F. R., Am. Gas Assoc Monthly, 17: 35 (1935).
275a. Larson, E., Am. Gas J., 142, No. 1: 17 (1935).
276. Jordan, C. W., Ward, A. L., and Fulweiler, W. H., Ind. Eng. Chem. 26: 947, 1028
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277. Ward, A. L., and Jordan, C. W., U. S. Pat. 1,976,704 (Oct. 9, 1934).
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279. McElroy, W. D., with Brady, E. J., Am. Gas Assoc Monthly, 16: 64, 103 (1934).
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281. Mathias, H. R., Gas Age-Rec, 76: 151 (1935); Am. Gas J., 142, No. 6: 24 (1935).
282. Jacobson, D. L., and Shively, W. L., U. S. Pat. 1,932,525 (Oct. 31, 1933), Powell,
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286. Tenney, R. F., Gas Age-Rec, 75: 255 (1935).
287. Shnidman, L., Gas Age-Rec, 73: 563 (1935).
288. Corfield, G.. Gas Age-Rec, 73: 485 (1934).
289. Jones, G. W., Campbell, John, and GJoodwin, F. M., Bur. Mines, Repts. of Investi-
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290. Knowlton, H. S., Telephony, Apr. 20, 1935, p. 34.
291. Briggs, G. M., Nat. Safety Netvs, Oct., 1934, p. 35.
292. Smith, E., McMillan, E., and Mack, L., 7. Ind. Hygiene, 17: 18 (1935).
293. Barker, L. F., /. Ind. Hvgiene, pp. 238-42, July, 1933.
294. Gettler, A. O., and Mattice, M. R., 7. Am. Med. Assoc, 100: 92 (1933).
295. Corfield, G., Proc Pac Coast Gas Assoc, 26: 51 (1935).
296. Klar, R. L., Am. Gas J., 140, No. 1: 31 (1934).
297. MacLean, A. D., Gas Age-Rec. 76: 320 (1935).
298. (Sodsoe, J. A., Am Gas J., 141, No. 5: 21 (1934); 142, No. 1: 12 (1935).
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305. Battin, H. W., Gas Age-Rec, 74: 443 (1934).
306. Larson, E., Rept. of Distribution Committeee, Am. Gas Assoc., (1935).
307. Rutledge, F. J., Progress in Industrial Gas Utilization. Report of committee on
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308. Am. Gas Assoc Monthly, 16: 60, 212, 365 (1934).
309. Hottel, H. C, and Mangelsdorf, H. G., Trans. Am. Inst. Chem. Engrs., 31: 517 (1935).
310. Sherman, R. A., Trans. A. S. M. E., 56: 177 (March, 1934).
311. Cowan, R. J., Am. Gax Assoc. Monthly, 16: 46 (1934).
312. Segcler, G. E., Am. Gas J., 143, No. 6: 9 (1935).
313. Murphy. D. W., and Jominy, W. E., Univ. Michigan, Engineering Research Bull.,
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322 ANNUAL SURVEY OF AMERICAN CHEMISTRY
314. Jominy, W. E., Univ. Michigan, Engineering Research Bull. No. 18. 1931. 51 p.
315. Clark, H. A., Am. Gas Assoc. Monthly, 17: 230 (1935).
316. Manier, R. L., Am. Gas Assoc. Monthly, 17: 295 (1935).
317. Gehrig, E. J., Am. Gas Assoc. Monthly, 17: 466 (1935).
318. Watts, A. P., Am. Gas Assoc. Monfhly,' 16: 8 (1934).
319. Young, W. W., Gas Age-Rec, 75: 409 (1935).
320. Young, W. W., Gas Age-Rec, 73: 56 (1934).
321. Gillett, H. W., Metals and Alloys, 6: 195, 235, 293, 323 (1935).
322. Gillett, H. W., Trans. Am. Inst. Chem. Engrs., 31: 706 (1935).
323. Rutledge, F. J., Am. Gas Assoc. Proc, 1934: 144.
324. Interim Bulletin No. 12, Commercial Section, Am. Gas Assoc.
325. Fonda, B. P., Am. Gas Assoc. Monthly, 17: 46 (1935); Heating, Piping and Air
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326. Lednum, J. M., Am. Gas Assoc. Proc, 1934: 664.
327. Parker, G. M., Natural Gas, 16, No. 7: 13 (1935).
328. King, T., Am. Gas Assoc Proc, 1934: 513.
329. Nash, C. A., Am. Gas Assoc. Proc, 1934: 496.
330. Kuenhold, O. J., Am. Gas. J., 139, No. 9: (1933); 140. No. 3: 9 (1934).
331. Smith, H. W., Jr., Am. Gas Assoc Monthly, 16: 194 (1934).
332. Taylor, G. B., Ind. Eng. Chem., 26 1 470 (1934).
333. German, W. W., Am. Gas. Assoc. Monthly, 17: 276 (1935).
334. Philo, E. G., Western Gas, Jan., 1934, p. 30.
335. Tangerman, E. J., Power, 78: 16 (1934).
336. Natural Gas, 16, No. 5: 86 (1935).
337. Blinks, W. M., Am. Gas Assoc, Proc, 1934: 454.
338. Conner, R. M., Am. Gas Assoc. Monthly, 16: 41-5 (1934).
339. Leonard, A. S., and Howe, E. D., Proc. Pacific Coast Gas Assoc, 26: 98 (1935).
340. Mattocks, E. O., Am. Gas Assoc Monthly, 16: 188 (1934).
341. Conner, R. M., Am. Gas Assoc. Monthly, 16: 76 (1934).
342. Smith, H. W., Jr., Am. Gas J., 140, No. 6: 7 (1934).
343. Smith, H. W., Jr., Am. Gas Assoc Monthly, 16: 226 (1934).
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345. Leighton J. A., Am. Gas J., 142, No. 4: 17; No. 5: 42 (1935).
346. Smith, H. W., Jr., Am. Gas Assoc Monthly, 16: 297 (1934).
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349. Minter, C. C, /. Soc Chem. Ind., 48: 35T (1929).
350. Hamilton, W. F., Traru. Am. Inst. Chem. Engrs., 29: 292 (1933).
351. Tu, C. M., Davis, H., and Hottel, H. C, Ind. Eng. Chem. 26: 749 (1934); Davis,
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352. Oshima, Y., and Fukuda, Y., Ind. Eng. Chem., 27: 212 (1935).
353. Fiock, E. F., and Roeder, C. H., Natl. Advisory Comm. Aeronautics, Report
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354. Fiock, E. F., and King, H. K., Natl. Advisory Comm. Aeronautics, Report No.
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355. Altpeter, A. J., and Kowalke, O. L., Gas Age-Rec, 76: 109 (1935).
356. Mayers, M. A., Chem. Rev.. 14: 31 (1934).
357. Mayers, M. A., Am. Inst. Mining Engrs., Tech. Pub. No. 575. 1934. 17 p.
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360. Jones, G. W., and Seaman, H., Ind. Eng. Chem.. 26: 71 (1934).
361. Pease, R. N., /. Am. Chem. Soc, 57: 22% (1935).
362. Benton, A. F., and Bell, R. T., /. Am. Chem. Soc, 56: 501 (1934).
363. McKinney, P. V., /. Am. Chem. Soc, 56: 2577 (1934).
364. Bear, R. S., and Eyring, H., /. Am. Chem. Soc, 56: 2020 (1934).
365. Willien, L. J., Gas Analyses in the Study of Water Gas Operations. Preprint,
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365a. Glover. F. B., Gas Age-Rec, 7A: 453 (1934).
366. Bermann, M., Gas Age-Rec, 72: 211 (1933).
367. Jones, G. W., and Kennedy, R. E.. Ind. Eng. Chem.. 27: 1344 (1935).
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373. Kobe, K. A., and Williams, J. S., Ind. Eng. Chem., Anal. Ed., 7: 37 (1935).
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376. Dillon, R. T., Ind. Eng. Chem., 26: 111 (1934).
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378. Evans, R. N., and Davenport, J. E., Ind. Eng. Chem., Anal. Ed.. 7: 174 (1935).
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GASEOUS FUELS, 1934 AND 1935 323
382. Branham, J. R., and Shepherd, M., /. Research Natl. Bur. Standards, 13: 377 (1934).
383. Newton, R. H., and Varga, F. V., Ind. Eng. Chem., Anal. Ed., 7: 240 (1935).
384. Woodruff, L. E., Western Gas, 11, no. 2: 22 (1935); Oil & Gas J., 33, no. 27: 39
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385. Fraas, F., and Partridge, E. P., Ind. Eng. Chem., Anal. Ed., 7: 198 (1935).
386. Littlefield, J. B., Yant, W. P., and Berger, L. B., Bur. Mines, Kept. Investiga-
tions 3276 (1935). 13 p.
387. Smith, A. S., Am. Gas J., 141, no. 3: 24 (1934); Bur. Mines, Rept. Investigations
3250 (1934). 11 p.
388. Anderson, C. C, Bur. Mines, Inf. Circular No. 6796. 1934. 11 p.
389. Stein, J. A., U. S. Pat. 1,940,513 (Dec. 19, 1933).
390. Jacobson. M. G., U. S. Pat. 2,010,995 (Aug. 13, 1935).
391. Schmidt, E. X., U. S. Pat. 2,001,114 (May 14, 1935).
392. Howe, A. H. D., U. S. Pat. 2,005,036 (June 18, 1935).
393. Brown, R. P., and Harrison, T. R., U. S. Pat. 2,000,119 (May 7, 1935).
394. Houghten, F. C, and Thiessen, L., Heating, Piping and Air Conditioning, 7: 149
(1935).
395. Frevert, H. W., and Francis, E. H., Ind. Eng. Chem., Anal. Ed., 6: 226 (1934).
396. Dunham, A. R., Gas Age-Rec. 74: 145 (1934).
397. Happel, J., and Robertson, D. W., Ind. Eng. Chem., Anal. Ed., 6: 323 (1934).
398. Tropsch, H., and Mattox, W. J., Ind. Eng. Chem., Anal. Ed., 6: 405 (1934).
399. Lang, J. W., Ind. Eng. Chem., Anal. Ed. 7: 150 (1935).
400. Tropsch, H., and Mattox, W. J., Ind. Eng. Chem., Anal. Ed., 6: 404 (1934).
401. Podbielniak, W. J., A new basic principle in the design of fractionating, absorbing,
and other countercurrent fluid-reacting equipment. Meeting of the Am. Chem.
Soc. Petroleum Division, New York, Apr. 22-23, 1935.
402. Podbielniak, W. J., U. S. Pats. 2,009,814 (July 30, 1935); 1,967,258 (July 24, 1934).
403. Fulweiler, W. H., Gas Age-Rec, 75: 586 (1935); Am. Gas J., 142, no. 6: 27 ri93S^.
404. Kemp, L. C, Jr., Collins, J. F., Jr., and Kuhn, W. E., Ind. Eng. Chem., Anal. Ed.,
7: 338 (1935).
405. Fieldner, A. C, and Davis, J. D., Gas, Coke and By-Product Making* Properties of
American Coals. U. S. Bur. Mines, Monograph 5, 1935. 64 p.
406. Selvig, W. A., and Ode, W. H., Ind. Eng. Chem., Anal. Ed., 7: 88 (1935).
407. Kirner, W. R., Ind. Eng. Chem., Anal. Ed., 6: 358 (1934); 7: 363, 366 (1935).
407a. Merkus, P. J., and White, A. H., Am. Gas Assoc, Preprint, 1934.
408. Russell, W. W., and Marks, M. E., Ind. Rng. Chem., Anal. Ed., 6: 381 (1934).
Adams, J. E., Ind. Eng. Ch^m., Anal. Ed., 6: 277 (1934). Niederl, J. B., and
Roth, R. T., Ind. Eng. Chem., Anal. Ed., 6: 272 (1934).
409. Wood, W. H., Combustion, 7, no. 2: 16 (1935).
410. Berry, C. H., Combustion, 6, no. 2: 15; no. 3: 24; no. 4: 21 (1935).
411. Ebaugh, N. C, Combustion, 6, no. 6: 22 (1935).
412. Abstracts of papers. Division of Gas and Fuel Chemistry, W. J. Huff, Chairman,
Am. Chem. Soc., New York meeting, April 22-26, 1935, and San Francisco
meeting, Aug. 19-23, 1935.
413. Richford, M. A., Proc Pac Coast Gas Assoc, 1934: 101.
414. White. C. E., Proc Pac Coast Gas Assoc, 26: 90 (1935).
415. Gas Age-Rec, 73: 292 (1935).
416. Brown, G. G., and Souders, M., Jr., Trans. Am. Inst. Chem. Engrs.. 30: 438 (1934);
Brown, G. G., Souders, M., Jr., and Hesler, W. W., Ibid., 30: 457 (1934); Brown,
G. G., Soude-s, M., Jr., Nyland, H. V., and Ragatz, E. G., Ibid., 30: 477 (1934).
417. Carey, J. S., Griswold, J., McAdams, W. H., and Lewis, W. K., Trans. Am. Inst.
Chem. Engrs., 30: 504 (1934).
418. Holbrook, G. E., and Baker, E. M., Trans. Am. Inst. Chem. Engrs., 30: 520 (1934).
419. Chilton, T. H., Vernon, H. C, and Baker, T., Trans. Am. Inst. Chem. Engrs., 31:
296 (1935).
420. Colburn, A. P., Trans. Am. Inst. Chem. Eng.. 29: 174 (1933).
421. Chilton, T. H., and Colburn, A. P., Ind. Eng. Chem., 26: 1183 (1934); 27: 255 (1935).
422. Pigott, R. J. S., Mech. Eng., 55: 497 (1933).
423. Kemler, E., Heating, Piping and Air Conditioning, 5: 252, 298 (1933).
424. Korany, J. A., and Bliss, E. M., Gas Age-Rec, 75: 33 (1935).
425. Colburn, A. P.. and Hougen, O. A., Ind. Eng. Chem.. 26: 1178 (1934).
426. Sherwood, T. K., and Gilliland, E. R.. Ind. Eng. Chem., 26: 1093 (1934)
427. Monrpd, C. C, Ind. Eng. Chem., 26: 1087 (1934).
428. Fenske, M. R., Tongberg, C. O., and Quiggle, D., Ind. Eng. Chem., 26: 1169 (1934)
429. Huff, W. J., and Logan, L., Preprint, Am. Gas Assoc. (1935).
430. Sellew, W. H., Trans. Am. Inst. Chem. Engrs., 30: 546 (1934).
BOOKS
Among the recently published books of interest in the field of f^aseous fuels are:
Morgan, J. J.. "American Gas Practice, Vol. II, 2nd ed. Maplewood. N. J.. The
Author, 1935. 1040 p.
Pacific Coast Gas Association, Gas Engineers* Handbook Committee. "Gas Engineers*
Handbook.** San Francisco. The Association, 1934. 1017 p.
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324 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Lunge, George, "Technical Gas Analysis"; revised and rewritten by H. R. Ambler,
New York, Van Nostrand, 1934. 416 p.
Ley, Henry A. (editor), "Geology of Natural Gas." Tulsa, Okla., Assoc, of Petroleum
Geologists, 1935. 1227 p.
Finley, G. H. (editor), "The Handbook of Butane-Propane Gases." 2nd. ed. Los
Angeles, Western Gas (>)., 1935. 375 p.
Callen, A. S., and Ulmann, A., Jr., "^Principles of Combustion." Scranton, Inter-
national Textbook Co., 1933. 50, 45 and 71 p.
Wadleigh, F. R.. "List of Books and CHher Sources of Information Regarding Coal
and Coal Products.'* Washington, The Author. 1935. 63 p.
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Chapter XIX.
Petroleum Chemistry and Technology.
Merrell R. Fenske,
The Pennsylvania Stale College.
General and Economic Developments. Petroleum still con-
tinues to be big business. The annual gasoline bill is estimated at 2.5
billion dollars and the oil bill at 250 million dollars.^ Gasoline con-
sumption is about 16.5 billion gallons per year ^ and it is estimated that
two million dollars per day is paid by the American gasoline consumer
for taxes over and above the cost of the motor fuel. While Diesel fuels
are hardly known to the average consumer, 31 states already have a tax
on Diesel fuels ranging from 2 to 6.5 cents per gallon.^ It is also esti-
mated that there are some 925,000 more cars, trucks and busses on the
roads today than a year ago. This alone requires an additional 13
million barrels of gasoline.^ The use of fuel oil is also extending.
The new S. S. Normandie consumes a minimum of some 60,000 barrels
of fuel oil on a round trip from Europe to the United States.
During the year the oil business was confronted with various Euro-
pean nationalistic policies, as well as legislation and government control
problems at home. Despite all this there has been a general increased
development and construction throughout the industry, involving addi-
tional investments of many million dollars. A survey of the supply of
petroleum has been made and methods for increased conservation out-
lined.^ ConserA^ation is also being effected through better control of
evaporation losses.^
Production. There has been increased production activity
throughout all the oil-producing states. Geophysical prospecting meth-
ods have caused increased drilling operations, not only in new areas but
also deeper drilling is being resorted to in old areas.'^"^® Daily pro-
duction of crude oil in 1935 is estimated to be about 2.7 million barrels
per day higher than in 1934. Texas is the largest producer, with Cali-
fornia and Oklahoma next in order. The total crude oil produced in
the United States up to 1935 is 16.6 billion barrels, while crude pro-
duction for the first six months in 1935 was 473 million barrels.^^* ^^
During the first six months of 1935 there were 10,329 wells drilled;
71 percent of these were oil wells, 22 percent were dry wells, and 6 per-
cent were gas wells.^^ In California there were more wells drilled in
the first nine months of 1935 than in all of 1934. The Rodessa field in
Louisiana, opened this year, has an initial potential production esti-
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326 ANNUAL SURVEY OF AMERICAN CHEMISTRY
mated at 25,000 barrels per day ^^' ^^ while in the Michigan field, in
which there was increased activity, a peak production of 50,000 barrels
per day was reached. The output of the Michigan field for the first
nine months of 1935 is estimated at 11,190,000 barrels.^^ In Pennsyl-
vania there have been several large gas wells discovered, having an
estimated production of several million or more cubic feet of gas per
(lay. 17-19 The deepest oil well, in Upton County, Texas,20 is now at
12,786 feet and there are many wells producing at the 8000 to 10,000
foot level.21 Water flooding is being applied with greater care in the
East Texas ^2 and Mid Continent areas.^^ Oil sands, as well as lime-
stone formations, may respond to proper acid treatment, and under
favorable conditions the production of wells may increase one hundred
or more percent by treating wath hydrochloric acid.^"*
Corrosion and Construction Materials. Large quantities of
material are needed to replace those rendered useless by corrosion. In
underground pipe lines cathodic protection is stated to be practical, and
if power from a mechanical source is not available, the installation of
zinc anodes is recommended.^^ As a means for generating power for
this type of protection, wind mill electric current generators have been
placed along pipe lines.2^-28 Corrosion inside pipe lines from sour
crudes is also a problem. It may be reduced by removing either the
water or hydrogen sulfide or both from the crude, but at present there
is no economical method for hydrogen sulfide removal.^® In refining
equipment the use of alloy steels is steadily being extended.^^ Chro-
mium, nickel, and molybdenum steels are used in distillation and crack-
ing equipment.^i' ^2 ^t low temperatures, such as those encountered
in vaporizing propane, which is being used in lubricating oil manufac-
ture, ordinary steels have been found to have an unsatisfactory impact
resistance, so that unnecessary hazards are encountered. Certain solid
solution types of alloys as the austenitic chrome-nickel steels and copper
alloys seem more satisfactory for this purpose, and there are encourag-
ing possibilities in the manganese-silicon steels.^^ In producing oper-
ations alloy steels are used extensively.^"*
Low Molecular Weight Paraffins. There has been a consider-
able amount of new information reported on the normally gaseous
paraffins during the year. Natural gas has been fractionally distilled
in a commercial way to yield relatively pure fractions of methane,
ethane, propane, or butane. In producing ethane, the fractionating
column may be operated at a pressure as high as 1500 pounds per square
inch; temperatures as low as —100° F. are also obtainable by using
liquid propane as the cooling agent in the condenser. In one plant
capacities of the order of 2 million cubic feet per day are planned.33, 36
Uses for the readily liquefiable hydrocarbons, such as propane and
butane, are increasing. These gases are used for cooking, water heat-
ing, and refrigeration in homes, camps and towns not served by natural
or manufactured gas. They are also being used for motor fuels, and
industrially in glass making, steel treating, pottery manufacture, oxy-
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PETROLEUM CHEMISTRY AND TECHNOLOGY 327
propane cutting of iron and steel, lubricating oil manufacture, and for
heating orchards and greenhouses. It is reported that these gases,
used in special heaters in greenhouses, give a phenomenal growth to
plants, because the combustion products, carbon dioxide and water
vapor, saturate the atmosphere and stimulate a rapid gro^yth of vege-
tation.^"^' 3^
A summary has been made of the thermal reactions or pyrolysis of
the gaseous paraffin, olefin, acetylene, and cycloparaffin hydrocarbons. ^^
The thermal decomposition of methane, ethane, propane, butane, and
the corresponding olefins have been studied from the viewpoint of
maximum olefin and liquid fuel production. Propane was studied in
detail and the removal of hydrogen from the gas mixture by selective
oxidation is reported.^^ Acetylene has been obtained by pyrolyzing
methane, ethane, propane, butane, and isobutane at temperatures of
1100 to 1400° C.41 Under optimum conditions in KA2S steel tubes, it
was possible to convert 74 percent and 82 percent by volume, respec-
tively, of ethane and propane into olefins.'*^ Propane and butane were
pyrolyzed at 725 pounds per square inch and 550 to 575° F., yielding
a gas containing lower molecular weight paraffin and olefin hydro-
carbons, as well as a liquid product. By subsequently polymerizing
the olefins to liquids it was thought that upwards of 10 gallons of liquid
fuel per 1000 cubic feet of commercial butane might be produced. ^^
The primary decomposition products of propane in the presence of
water vapor may be accounted for by three reactions : ( 1 ) dehydration,
(2) demethanation, and (3) a bimolecular decomposition into propyl-
ene, ethane, and methane. Water vapor is substantially an inert gas
up to 700° F.^^ The primary decomposition of pentane appears to be
a first order reaction at 600° C. Increase of dilution with steam
decreases the amount of ethane and increases the amount of ethylene
and hydrogen formed.'*^
The chlorination of propane, butane, isobutane, pentane, and iso-
pentane was studied ; it was found that carbon skeleton rearrangements
do not occur during either photochemical or thermal chlorination, if
pyrolysis temperatures are avoided. Every possible monochloride deriv-
able without such rearrangement is always formed. This generaliza-
tion also applies to the polychlorides so far as studied.**^ Further work
has given a method for calculating from the structural formula of any
paraffin hydrocarbon, the percent of its various isomeric monochlorides
obtainable by noncataljrtic chlorination at temperatures from —65 to
600° C.47
The nitration of paraffin hydrocarbons with less than six carbon
atoms has been accomplished in the vapor phase. Hydrocarbon vapors
were passed through concentrated nitric acid at 108° C. and the result-
ing mixture of about 2 : 1 molal ratio of hydrocarbon to nitric acid, was
passed through a tube at temperatures from 150 to 420° C. Possible
uses for these nitro compounds are: (1) primary compounds for Diesel
fuels, (2) raw materials for synthesizing such products as aldehydes.
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328 ANNUAL SURVEY OF AMERICAN CHEMISTRY
ketones, amines, nitro-alcohols, nitro-olefins, amino-alcohols, and fatty
acids; (3) refining solvents for lubricating oils, and (4) lacquer sol-
vents.*®
The formation of alicyclic hydrocarbons from free radicals was stud-
ied by decomposing diheptyl mercury at about 350° C. Cyclohexane
and some unidentified cyclic products were obtained. It appears that
the cyclohexane was produced by direct decomposition of the heptyl
radical rather than through some polymerization process of ethylene.*®
Low Molecular Weight Unsaturated Hydrocarbons. It is esti-
mated that some three hundred billion cubic feet of gas are produced
yearly by cracking processes. This gas contains a considerable quantity
of olefin hydrocarbons. Utilization of the gas is, in general, develop-
ing along two lines; (1) chemical utilization, as evidenced by the
placing in operation of the ten million dollar plant of the Carbide and
Carbon Chemicals Co. at Whiting, Indiana, using these gases as raw
materials, and (2) polymerization into hydrocarbon fuels by the refin-
ers themselves. The industrial significance of this latter development
will be outlined under motor fuels. Other than the cracked gas itself
the cheapest raw material for producing olefins is gas oil. New data
are available on cracking this material primarily for olefin production
at temperatures higher than those used in gasoline production. The
effect of pressure in promoting the absorption of ethylene in sulfuric
acid is reported, and the formation of ethyl ether by reaction of diethyl
sulfate and ethyl alcohol has been reviewed. ^^ The reactions of the
simpler acetylenic hydrocarbons, such as monovinylacetylene and its
polymers, which lead to the preparation of synthetic rubber, have been
reported.^^ Cheap acetylene is one of the principle factors in cheap
synthetic rubber, or DuPrene, and methods for producing it have been
studied. Acetylene is formed by pyrolyzing ethylene, propylene and
1-butene at temperatures of 1100 to 1400° C. with fractions of a second
time of contact. Under these conditions over half the decomposition
may take place to yield acetylene.^^
The polymerization of olefins has been studied rather extensively.
The kinetics of ethylene polymerization were studied particularly for
the purpose of obtaining more information on the effect of minute
traces of oxygen on the rate of polymerization, the temperature coeffi-
cient of the reaction, and the character of the primary products formed.^^
Under optimum conditions the polymerization of pure ethylene and
propylene may give yields of liquid polymer amounting from 70 to 80
percent from ethylene, and from 60 to 65 percent from propylene.
Polymerization of these two hydrocarbons was studied over the pres-
sure range 500 to 3000 pounds per square inch and at temperatures
from 650 to 850° F. Octane numbers of the liquid polymer are also
reported. ^2 Polymerization of olefins in the presence of 90 percent
phosphoric acid gives a mixture of paraffinic, olefinic, naphthenic and
aromatic hydrocarbons. The high pressure cataljrtic polymerization of
ethylene gives isobutane, the percent increasing with increasing tem-
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PETROLEUM CHEMISTRY AND TECHNOLOGY 329
perature of polymerization. From 250 to 330° C. it varies from 2.5 to
18.8 percent by weight of the ethylene that reacted.^* The mechanism
of olefin polymerization by catalysts such as boron fluoride, aluminum
and zinc chlorides, phosphoric acid, alumina, and silica gel has been
discussed.55 Propylene polymerized by liquid phosphoric acid at 135
to 200° C. and 1 to 15 atmospheres pressure yields a mixture of mono-
olefins. A mechanism for the reaction is suggested, involving the
formation of intermediate esters.^® Isomeric butylenes are similarly
polymerized by phosphoric acid, isobutylene polymerizing the most
readily and a-butylene the least. The presence of isobutylene has been
found to accelerate the polymerization of the n-butylenes.^'^ Polymer-
ization of propylene by aluminum silicate catalysts at atmospheric pres-
sure and 350° C. yields a mixture of five-, six-, seven-, eight-, and nine-
carbon hydrocarbons, with olefins predominating. Pentenes are the
lowest boiling product of the polymerization and consist principally of
trimethylethylene. The dipropylenes formed are 2-methyl-2-pentene,
and tetramethylethylene ; 2-methylpentane is also formed.^^
Condensation reactions involving olefins have also been reported
during the past year. Olefins and paraffins have been found to react in
the presence of boron fluoride gas, finely divided nickel, and a small
amount of water. The reaction consists of the alkylation of the paraffin
to higher molecular weight paraffins through the addition of one, two,
or more olefin molecules. The paraffins alkylated so far contained a
tertiary carbon atom. Attempts to alkylate n-paraffins, such as pen-
tane, propane, and methane with boron fluoride, were not successful.
»- Paraffins, with the possible exception of methane and ethane, can be
alkylated in the presence of aluminum or zirconium halides.^^ Naph-
thenic hydrocarbons and olefins have been condensed. Cyclohexane,
methylcyclohexane, and methylisopropylcyclohexane have been alky-
lated by ethylene in the presence of aluminum chloride. Boron fluoride
catalyzes the alkylation of methylcyclopentane and methylcyclohexane
with ethylene.^^ The direct alkylation of aromatic hydrocarbons is
reported by periodically introducing ethylene at 250° C. under pressure
into a stirred mixture of 10 mols. of benzene, 50 grams of phosphorus
pentoxide, 24 grams of lampblack and 10 grams of cresol, to form
mono- and hexaethylbenzenes. In a similar way, benzene and isobuty-
lene, toluene and propylene, and naphthalene and ethylene were alky-
lated.®^ Using 85 percent phosphoric acid, the direct alkylation of
benzene, naphthalene, and tetrahydronaphthalene with ethylene at
300° C. was obtained; similarly alkylation of naphthalene and fluorene
by propylene occurred at 200° C.®^ ^he mono-, di-, tri-, and tetraiso-
propyl derivatives of benzene were prepared by condensing propylene
with benzene, employing boron fluoride. Aluminum chloride promotes
the formation of 7w-diisopropylbenzene, while boron fluoride gives the
/>-diisopropylbenzene.®3 The addition of sulfur dioxide to methylpro-
pene, 1-pentene, 2-pentene, 1-nonene, 3-cyclohexylpropene, and 3-meth-
ylcyclohexene yields polysulfones. These are neutral products and the
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330 ANNUAL SURVEY OF AMERICAN CHEMISTRY
first five of them have alcohol groups at the ends of the chains. The
molecular weights of these polysulfones are in the range of 100,000
to 200,000.«4
The limits of inflammability of ethykne in air and in oxygen were
determined as volume percent and found to be for air, lower limit 2.75
percent, and upper limit 28.6 percent; for ethylene in oxygen, lower
limit 2.9 percent and upper limit 79.9 percent.^^
Physical Data. The properties of methane in hydrocarbon oils
have been studied,®^ as well as the viscosity of methane and propane
solutions in hydrocarbon oils at various pressures and temperatures.^*^
The physical constants of propane have been summarized ^® and specific
heat data for propane and butane in the range of 60 to 220° F. are
reported.^^ The heat of combustion of isobutane, forming gaseous car-
bon dioxide and liquid water at 25° C. and one atmosphere pressure,
was found to be 686.3±0.13 kilocalories per mole. It was calculated
that at 25° C. the internal energy of isobutane is less than that of butane
by 1.63±0.15 kilocalories per mole."^^ A temperature-entropy diagram,
specific gravity as a function of pressure and temperature, and pressure-
fugacity ratios are now available for pentane.*^^ The effect of pressure
on the isothermal change in heat content for pentane was calculated
and found to agree with experimentally determined values. The effect
of pressure on the heat content (enthalpy) of benzene has been experi-
mentally determined and used for the construction of an enthalpy-
pressure-temperature chart.'^2 The properties *of 1-octadecene, octa-
decane, di-w-tolyethane,'^^ and tetratriacontadiene (C34H6e) have been
measured.*^* Variations in hydrocarbon structure have been correlated
with spontaneous ignition temperatures. It has been found that, for
the same number of carbon atoms, the spontaneous ignition temperature
falls roughly in the order, aromatics, alkylated aromatics, naphthenes,
alkylated naphthenes, straight chain paraffins, branched chain paraffins,
and unsaturated aliphatics.*^^ Molecular weights by the cryoscopic
method are reported for various Mid Continent cracked gas oils and
pressure still charging stocks. Molecular weights have been correlated
with boiling point, viscosity, and density to enable an estimation of the
molecular weight of any given cracked stock to be made.*^^ High tem-
perature viscosities of liquid petroleum fractions have been measured
over the range 100 to 800° F., and from atmospheric to 500 pounds per
square inch.'^'^
Internal Combustion Engine Fuels. Tests on a large number of
cars in the New England and Eastern states showed that from 5 to
6 percent of the passenger compartments contained dangerous pro-
portions of carbon monoxide. A person breathing air containing
8 parts of carbon monoxide per 10,000 of air would probably experience
headache, impaired judgment and decreased mental alertness in about
1 hour, collapse in about 1.5 hours, and death in about 2 hours if
not removed from the poisoned atmosphere. "^^ This is important in
view of the increased use of automotive power. Busses are steadily
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PETROLEUM CHEMISTRY AND TECHNOLOGY 331
replacing street cars, because motor bus transportation synchronizes
with all other forms of motor traffic present today on streets and high-
waysJ^ The use of Diesel-electric drives on railroads is also increasing.
Regarding air-fuel ratio in automotive engines, the maximum thermal
efficiency is found at about 16 to 1, the highest mean effective pressure
or torque at 12.5 to 1, and the maximum economy at about 14 to 1.
Experiments have shown that 6.4 percent more gasoline is used with
S.A.E. 60 oil than with S.A.E. 30 oil, and 3 percent more for S.A.E. 30
than for 10-W, in consequence of higher friction.^^ Furthermore, com-
pilation of results obtained on 213 automobiles and trucks and 184
busses used by the Milwaukee Electric Railway and Light Company
shows that gasoline consumption of vehicles reasonably well maintained,
does not depend on the age of the vehicles or the miles from overhaul
or piston ring change, is influenced greatly by carburetor conditions,
proper jets, proper float level, choke operation and freedom from
leaks; increases greatly as the number of starts and stops increases,
depends on loads carried, is influenced by average daily mileage,
is influenced by temperature and weather conditions, is adversely
affected by very fast schedules, and is affected adversely if the gasoline
is too volatile.^^ The ten, fifty, and ninety percent distillation points
on the gasoline distillation curve are now lower than for any previous
year, 82 ^cad there have been several studies made on gasoline
volatility.83-85
Propane and butane have been used alone as motor fuels. There
are two advantages claimed, namely, high octane number — 125 for
propane and 93 for butane — and high volatility, ensuring good dis-
tribution to the cylinders. A compression ratio of 10 to 1 is reported
possible with propane, and 7 to 1 with butane, if the engine is of suffi-
ciently rugged construction. However, the power produced, as well
as the fuel consumption in terms of B.t.u., are found to be nearly the
same as when gasoline is burned. This is explained by the cooling
effect of the liquid gasoline vaporizing in the cylinder. From the
standpoint of supply, availability, cost of distribution, and price, the
general replacement of gasoline as an automotive fuel with liquefied
petroleum gases is not economical. However, use will likely be found
in large high powered stationary engines, in rail cars and trains, and
in switching, tunnel, and construction engines.®®"^^.
There has been marked activity throughout the petroleum industry
to make commercially available a high octane number fuel, i. e., one
of the order of 100 octane number. The demand for such a fuel comes
practically entirely from the aviation field, where fuel costs are
reckoned on the basis of cost per ton mile of pay load rather than
cost per gallon. It has been pointed out that if a fuel of extremely high
anti knock were available, the cost per ton mile may be lower even if
the cost of the gasoline were doubled. The result is that a technical
grade of isooctane or 2,2,4-trimethylpentane, has been made available
and a considerable quantity has been ordered by the U. S. Army for
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332 ANNUAL SURVEY OF AMERICAN CHEMISTRY
experiments on increase in engine power without a corresponding rise
in weight. Gasoline of such high anti knock quality permits further
increases in the supercharging of aircraft engines, thus increasing
overall performance, the ease and safety of take-offs, and a quicker
pick-up in emergencies. It further permits increases in compression
ratio with a resultant decrease in fuel consumption. This is of par-
ticular importance for military long distance bombers, and for com-
mercial transports where long non-stop flights are made. Now that
the successful non-passenger flights of the Pan American clipper ship
to Hawaii, Midway, and Wake Islands and the Philippines have been
realized, there is considerable need for higher octane number fuels
that would permit even relatively small decreases in fuel consumption,
for on these long trans-Pacific flights this would permit a substantial
increase in the passenger load. It was hoped that the gasoline resulting
from polymerizing the olefins in cracked gases would be this unusually
high octane number fuel. While polymer gasoline has a knock rating
of 80 octane number or better, it does not as yet appear that it will be
the much sought for 100 octane number fuel. Furthermore, while the
addition of lead tetraethyl to isooctane affords even additional significant
increases in the highest useful compression ratio and consequently in
power and output, the polymer gasoline appears to have the character-
istic of not responding very well to lead tetraethyl additions. That is,
octane number does not rise nearly so fast as in the case of isooctane
upon the addition of lead tetraethyl.^®-^^
It is estimated that if, throughout the United States, the olefins
present in cracked gases were polymerized, there would be available
an additional 30 million barrels of polymer gasoline, or about 7 percent
more gasoline than is now being produced.^^ There are already plants
in operation having capacities of the order of one thousand barrels
of polymer gasoline per day. In general, the polymerization of these
olefins occurs in one of two ways : ( 1 ) at relatively low temperatures
in the presence of catalysts, or (2) at elevated pressures and tempera-
tures in the absence of catalysts. In the catalytic method, the opera-
tion is reported as taking place at about 400° F. at pressures of 175 to
200 pounds per sq. in. in the presence of a phosphoric acid type catalyst.
Yields of from 2.5 to 10 gallons of an 80 octane number gasoline per
1000 cubic feet of gas are reported.^^' ^^ In one type of non-catalytic
polymerization, operating conditions are about 1000° F., and 800 to
1000 pounds per sq. in.^^' ^'^ while in another operation the temperatures
are higher, namely 1150 to 1300° F., and the pressures 50 to 75 pounds
per sq. in. It is reported that under these latter conditions complete
rearrangement of the molecules occurs, giving cyclic as well as
aromatic hydrocarbons such as benzene, toluene, xylene, and naph-
thalene.93. 98, 99
The use of alcohol for addition to gasoline has continued to be dis-
cussed. It is claimed that the farmers consume some 23 percent of
the gasoline in the United States and that the addition of 10 percent
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PETROLEUM CHEMISTRY AND TECHNOLOGY 333
alcohol would create a market for 1.6 billion gallons of alcohol a year.
This procedure is reported to be unsound in this country at present,
for it is claimed that the fuel consumption of a 10 percent alcohol blend
is about five percent higher than straight gasoline, and the consumer
would likely pay more for this fuel.^^"^^^
The addition agents for gasoline at present consist of one or more
of the following types of materials: (1) halogenated hydrocarbons
reported to minimize carbon troubles in engines,^^^ (2) antioxidants or
gum inhibitors, (3) top cylinder lubricants, (4) color stabilizers such
as the aliphatic amines of less than 5 carbon atoms,^^^ and (5) lead
tetraethyl as an anti knock addition agent. Iron pentacarbonyl has
the ability to suppress knock. It is reported that 3 cc. per gallon can
raise the octane number from 58 to 96, but that the compoimd is so
unstable to both light and air that it is nowhere in commercial use.
A long literature and patent bibliography is available for iron car-
bonyl.106
Diesel fuel standards are desired which will include ignition quality,
viscosity, gravity, distillation characteristics, cleanliness, Conradson
carbon, ash, sulfur and corrosion acids, flash point, and pour point.^^^
Gasoline Preparation and Manufacture. In connection with the
American Petroleum Institute Project No. 6 at the National Bureau of
Standards, it is reported that in the 55 to 145° C. fraction of a Mid
Continent gasoline there have now been isolated: (1) the normal
paraffins, hexane, heptane, and octane; (2) the 2-methyl derivatives of
these normal paraffins; (3) the hexane isomers, 2,3-dimethylbutane and
3-methylpentane ; (4) methylcyclopentane and methylcyclohexane ; (5)
the aromatics, benzene, toluene, ethylbenzene, and the three xylenes.
The hydrocarbons now isolated account for about two thirds of the
entire volume boiling between 55 and 145° C. The paraffins, naph-
thenes, and aromatics boiling in this range are present in about the
proportion 6:3:1. In the fraction boiling between 145 and 180° C,
nonane was present to the extent of 15.5 percent, decane 12.5 percent,
mesitylene 0.3 percent, pseudocumene, 3.0 percent, hemimellitene 0.9
percent. It is very likely that this fraction will yield far less than the
total of 80 compounds reported in the literature as boiling within these
limits.^^®' ^^^ The separation of aromatic and olefin hydrocarbons from
paraffins and naphthenes by means of adsorption on silica gel is
reported. 1^^ A procedure has been outlined for the classification of
hydrocarbons depending upon grouping according to physical constants,
as well as on standardized chemical reactions. m
In the natural gasoline field, there are over 1,000 plants in operation
in the United States producing about 10 million gallons of natural
gasoline per day. About 200 of these plants are in Oklahoma, and
about 130 plants are in each of the following states: Texas, Pennsyl-
vania, and California.112. lis j^ view of the importance of natural
gasoline to the overall volatility of motor fuels in general, an index
for fuel volatility has been proposed in which the variables of engine
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334 ANNUAL SURVEY OF AMERICAN CHEMISTRY
performance, atmospheric temperature, starting, and fuel efficiency ai*e
considered.^i*
The effectiveness of lead tetraethyl in different hydrocarbons has been
studied. Quantitative measurements were made of the specific anti
knock effect of lead tetraethyl in 62 different hydrocarbons, by finding
the increase in critical compression ratio, in a single-cylinder-variable-
compression engine, made possible by the addition of one cc. per gallon
of lead tetraethyl. On this basis there are variations of as much as
twenty-fold in the effectiveness of lead tetraethyl in suppressing knock
in different hydrocarbons. ^^^ It has also been found that the various
sulfur compounds in gasoline affect the lead susceptibility of the gaso-
lines. ^^^ For the removal of sulfur compounds from gasoline, treatment
with solutions of copper salts has been found to be economical. ^^"^
Increasing amounts of valuable data on distillation equipment desig^n
are available.^^^'^^o ^ single distillation tower now produces five
products from crude oil at the rate of 17,000 barrels per day.^^i Factors
affecting entrainment in bubble cap columns have been studied ^22 ^nd
an outline of the primary distillation applications in the petroleum
industry has been made, together with design data for gas recovery
and stabilization systems, and gasoline and lubricating oil manu-
facture.^23
Cracking operations are now on a highly developed scale. Single units
combining the processes of cracking, skimming, reforming, and stabili-
zation are in operation resulting in greatly reduced manufacturing
costs.124 The largest combined distillation and cracking unit is the new
plant at Texas City, Texas, of the Pan American Petroleum Corporation.
The daily charging capacity is 35,000 barrels of crude oil. Long time
cracking runs of 98 and 123 days have been reported.^^s, 126 jhe various
factors in cracking such as time, temperature, pressure, and conversion
per pass through the apparatus have been studied. ^^7 Experimental
cracking apparatus has been worked out for giving data applicable
to plant design, such as yields of gas, gasoline, coke and polymers as a
function of time, temperature, and pressure. Specific volume data
are also available as a function of time, temperature, and pressure. As
a result of these data a new basis has been found for the design of
cracking plants.^^s ^ correlation of plant cracking data has been
obtained that satisfactorily gives the octane number obtainable in
reforming naphtha in terms of the octane number of the charge
and the amount of cracking to which it has been subjected.^20
Antioxidants and gum inhibitors are now used extensively to prevent
gasoline deterioration and eliminate the necessity for acid refining.
These products are daily applied to more than five million gallons of
gasolines, resulting in annual savings of millions of dollars. The critical
oxidation potential of inhibitors has been studied with regard to the
induction period afforded cracked gasolines.^^^ It has been found
that gum formed by oxidized gasolines is high in peroxides, aldehydes,
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PETROLEUM CHEMISTRY AND TECHNOLOGY 335
and acids. It appears that peroxides are the substances primarily
responsible for gums.^^^
Standardized tests for gasoline color stability have been reported,^^^,
133 as well as a potentiometric method for the determination of mer-
captans.134 Improvements in the A.S.T.M. lamp method for sulfur
have also been suggested. ^^s
Lubricating Oil Preparation and Manufacture. Improvements
in lubricating oil preparation have been principally in solvent extrac-
tion processes, and in addition agents such as pour point depressors,
oiliness or lubricity carriers, extreme pressure materials, anti-oxidants,
and viscosity index improvers. A new addition compound for lubricat-
ing oils, methyl a,c(-dichlorostearate, is being used.^^e
Solvent extraction of lubricating oils consists essentially of a suit-
able mixer or tower wherein oil and solvent are contacted as two liquid
phases, distillation equipment to separate solvent from these phases
for reuse, i. e., a solvent recovery system, the further processing of
the insoluble oil, or raffinate, to make finished lubricating oil, and the
disposal of the dissolved oil or extract. At present the following sol-
vents are in industrial use in refining lubricating oils : sulfur dioxide,
nitrobenzene, benzene-acetone-toluene mixtures,^^! ethylene dichloride
and benzene, dichloroethyl ether,i38 propane and cresylic acid,i39 fur_
fural,^^^ phenol,^^! propane ^^2, 143 and aniline, i^^' ^^^ ^ graphical
method, employing triangular coordinates for representing equilibrium
in complex oil-solvents systems, has been developed as a basis for the
solvent refining of oils. Calculations using data obtained in nitro-
benzene extraction are given.^^^ The decolorization of lubricating oils
by percolation through earths has been studied.^^*^
A means for characterizing petroleum fractions is reported, employing
empirically developed charts and the factors of specific gravity, boiling
point, viscosity, aniline point, viscosity index, and hydrogen content.
These determinations enable the predictions of other properties with
fair approximation for engineering use.^^^ Another correlation of
viscosity, gravity, and S.A.E. classification has been made.^^^
Performance and Testing of Lubricants. It is stated that oil
consumption can be controlled by using the minimum practical clear-
ance between pistons and cylinder walls, by providing large oil return
capacity in oil return rings, piston oil holes, and passages, by designing
pistons so they are round when hot, by replacing rings when they are
badly worn or when the oil return grooves are clogged, by using
expanders in back of piston rings in worn cylinders, by maintaining
correct main bearing clearances, and by preventing excessive crank-case
temperatures.^^ The effect of viscosity and volatility on oil consump-
tion, and of cylinder carbon on knock has also been reported.^^^ Dur-
ing the year there have been several laboratory testing machines
described for testing the ordinary as well as the extreme pressure
characteristics of oils.^^^* ^^^ Improvements have been made in
apparatus for accurately determining the kinematic viscosities of oils
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336 ANNUAL SURVEY OF AMERICAN CHEMISTRY
at various temperatures,!^^ ^nd conversion tables have been formulated
on the basis of experimental data giving the relationship between
kinematic viscosity and Saybolt Universal Seconds.^^^ A boiling point-
gravity constant is proposed as an index of lubricating oil character-
istics.i^^ Improved viscosity index tables are available for calculation
in terms of kinematic viscosity as well as Saybolt Seconds.^^®
Bearing corrosion has placed additional problems on the refiner of
lubricating oils. It has been found that excessive oil temperatures
with oils which have been made to resist oxidation, and which are
considered to be of the highest quality, appear to corrode the new bear-
ing metals, such as cadmium-nickel, cadmium-copper, or copper-lead
alloys. It is believed that this is due principally to excessively high oil
temperatures, and that these temperatures should be kept below 250°
jr 157, 158 ii has also been found that different types of extreme-pressure
lubricants should not be mixed in automobiles. Most extreme-pressure
lubricants contain one or more of the following elements in one com-
bination or another: lead, sodium, aluminum, chlorine, and sulfur.
In addition other materials may possibly be used such as castor oil,
lard oil, and glycerin. Lead may therefore react under proper condi-
tions with sulfur or chlorine to give insoluble sulfides or chlorides,
and these are no part whatever of extreme-pressure lubricants. In
other ways, mixing of different extreme-pressure lubricants may cause
foaming, thickening, sludge, or other undesirable results.^^^
Improvements in greases have been in the direction of avoiding
acidity and consequent bearing corrosion, avoiding hydrolysis of
greases, and decomposition due to a change in the degree of dispersion
of the soaps.!^^' ^^^ Laboratory service testing methods of automotive
lubricating greases have been outlined, and the best methods for
correlation with actual service performance tests have been studied.^^^
The fine structures of lubricating greases have been examined by a dark
field microscope technique, and the suggestion has been made that a
useful classification of greases would result, depending on the length
of the soap fibers, where the fiber length varies from 0.001 mm. to
0.080 mm.i63
Miscellaneous Developments. A system to evaluate the suscepti-
bility of asphalts to temperature change has been used similar to the
viscosity index system for lubricating oils. Asphalts from heavy Mexi-
can crude have been used as the basis for the 100 index material, while
petroleum tar from cracking served as the basis for the zero index.
Results using this method on various straight reduced asphalts have
been tabulated. ^^^ The oxidation of the constituents of asphalts has
also been studied. It is believed that through oxidation unstable com-
pounds form, from which carbon dioxide and water are eliminated,
leaving residues that polymerize.^^^
Spray oils apparently injure foliage because of the unsaturates^
hydrocarbons they may contain. Oils containing over 10 percent of
unsaturated hydrocarbons may contain injurious quantities of asphalt-
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PETROLEUM CHEMISTRY AND TECHNOLOGY 337
ogenic acids formed from the unsaturated hydrocarbons by oxygen in
the presence of light. ^^^
The field of petroleum solvents is increasing. A study has been
made of the industrial solvents in use. The list contains petroleimi
solvents, ketones, polyethers, esters, ether-alcohols, alcohols, chlorinated
compounds, naval stores solvents and furane derivatives.^®*^ A modified
and improved Kauri butanol test for the solvent power of hydrocarbon
solvents has been reported.^®^
The oiling of coal for dust proofing and preventing spontaneous com-
bustion is reported. The oil specifications suggested are 100 to 225
Saybolt viscosity at 100° F., with a flash point of 305 to 370° F. The
oil is sprayed onto the coal and it may also be emulsified with water.
It is stated that in the ordinary method of water- wetting coal, the
consumer loses in two ways: (1) by substituted weight and (2)
by a loss in heat units required to vaporize the water.^®^ There is also
a need for standardization in fuel oil burners for household heating.
Several billion barrels of fuel oil are consumed per year and it is
becoming desirable to standardize on one or two grades instead of the
many types now existing.^*^^
Over 300 million pounds of carbon black are now made yearly.
The yield from natural gas is about 1.4 pounds per thousand cubic
feet of gas. Over half the production goes into rubber manufacture;
the remainder goes into inks, paints, and other miscellaneous uses.^*^^
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Chapter XX.
Detergents and Detergency.
Pauline Beery Mack,
The Pennsylvania State College.
The term detergent is derived from the Latin verb detergere, which
means "to wipe away, or wash away, or cleanse." Agents used for
this purpose in daily life and in industry are so numerous that it is
difficult to classify them, and the present chapter will be devoted to a
few of the more common types only. These will be classed in the
following groups: soaps, and similar detergents, soap builders, dis-
persing compounds for hard waters, enzymes, and bleaches.
This presentation includes chiefly the development of detergents dur-
ing the past few years, with emphasis on the progress made during
1935. Methods of measuring detergency efficiencies and theories con-
cerning the action of the more common detergents will be included
also. The chapter will be confined to the work of American investi-
gators, except in cases in which foreign work needs to be cited in
order to make American contributions understandable.
For many years, the term soap has been used almost exclusively for
the sodium and potassium salts of the higher fatty acids. The more
recent introduction of detergents which serve the same general pur-
pose as these older soaps causes the literature to be somewhat confused
as to whether or not the newer soap-like detergents will be classed as
soaps. In the laundry and drycleaning industries, in which both of these
classes of substances are now used, there seems to be a tendency to
refer to the older sodium and potassium fatty acid salts as "soaps,"
and the newer introductions as "detergents." This presents a problem
in nomenclature which is in need of clarification.
An extensive bibliography on launderability has been published by
Gugelman,^ which should prove helpful to everyone in the field. This
covers the period from 1910 through 1934.
An interesting history of the soap industry through 1925 was written
by Ittner,2' 3 ^rho recently extended the review to include the last ten
years. He points out that there have been no revolutionary changes
in soap manufacture during the past few years, although progress has
been steady. Improvements have been made in methods of alkali
manufacture and of oil and soap production, in effecting a more com-
plete saponification reaction, and in glycerol recovery. Unusual atten-
tion has been given to the physical form of soaps, to increase their
solubility and convenience in use.
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342 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The New Detergents. There are many references in the litera-
ture to the new detergents which are being substituted in part for the
older types of soap. These detergents were introduced to eliminate
one of the chief shortcomings of ordinary soap — namely, its tendency
to form curdy precipitates in hard waters. The chief difficulty with
soaps of the older type is that they are salts of strong bases and weak
acids, and hence are unstable in strong acids. Moreover, at ordinary
temperature, they form precipitates in hard water by ordinary meta-
thesis of the alkali soaps with any calcium and magnesium compounds
which may be present, as follows: 2RC02Na-|-MgS04— » Na2S04
-\- (RC02)2Mg. At higher temperatures (because the carboxylic acids
are weak), these salts hydrolyze more completely as follows :
(RC02)2MgH-2 H2O -» Mg(OH)2H-2 RCO2H.
In order to take advantage of the desirable qualities of the ordinary
soaps, while eliminating or reducing their shortcomings, various types
of new detergents have been prepared. They comprise two main
classes of compounds: (1) Acid sulfates of long-chain alcohols; and
(2) condensation products of ordinary fatty acids or their derivatives
with substances containing a strong acid group.
The first class of detergents is exemplified by compounds of the type
of sodium lauryl sulfate, frequently abbreviated as SLS. The second
type is illustrated by the Igepons, in which the carboxyl group is
"blocked" by condensation with a hydroxy- or an amino-sulfuric acid.
The advantages of the introduction of a strongly acid group, such as
the ( — SO3H) group of the sulfonic acids, or the ( — OSO3H) group
of the substituted sulfuric acids, depend upon the fact that the sodium
salts of compounds containing these groups are more stable in acids
than are the salts of weak acids, such as stearic acid and the other
members of the fatty acids which are the basis of ordinary soaps.
Moreover, the calcium and magnesium salts of sulfated, sulfonated, and
similar compounds are more readily soluble than calcium and mag-
nesium soaps.
Sulfonated and Sulfated Compounds as Detergents. The sul-
fonated oils are numerous, and include both straight-chain and aromatic
compounds. They have a wide application as wetting agents, because
they penetrate textile fibers, and are stable in acid solutions. Hence
they can be used in dyeing operations in acid solutions, in which soaps
are unstable. Most of them form relatively soluble magnesium and cal-
cium salts, and are stable in acid solutions, but they do not meet all
of the other requirements for a detergent, in that they are low in dirt
removal. Recently there has been introduced a group of sulfated
compounds which are good detergents, and which have the other
desirable properties of the sulfonated oils. These are now marketed by
a number of American firms under various trade names.
Sulfated Alcohols, The sulfated alcohols are sulfuric esters of the
straight-chain fatty alcohols, containing from 8 to 19 carbon atoms in
the chain, and sometimes more. These are produced by a hydrogena-
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DETERGENTS AND DETERGENCY 343
tion process, in which high temperatures and pressures cause the
hydrogen to react with the carboxyl group in the fatty acid molecule;
this reaction reduces the fatty acid either to the alcohol ( — CH2OH), or
to the hydrocarbon ( — CH3) group, according to the temperature,
pressure, and other conditions which are maintained during the reaction.
This process differs from the older hydrogenation methods, in which
relatively low temperatures and pressures were maintained, and. in
which hydrogen was applied only at the double bond, with no change
in other parts of the molecule.
The sulfated alcohols have certain characteristics in common, although
they differ from each other in certain properties according to the length
of the carbon chains. The lower members of this group of compounds,
which are called hymolal salts, are good detergents, while those of
the longer chains are poor detergents but good wetting agents.
The following formulas represent the principal components of three
representative sulfated alcohols:
(1) Sodium lauryl sulfate: CH3(CH2)ioCH20S03Na.
(2) Sodium octadecyl sulfate : CH3(CH2)i6CH20S03Na.
(3) Sodium oleyl sulfate: CH3(CH2)7CH: CH(CH2)7CH20S03-
Na.
The first of these is made by hydrogenating coconut or palm kernel
oils, which are then fractionally distilled. The sodium salts of these
and of similar alcohols are marketed as detergents in this country under
such trade names as gardinol WA, Gardinol LS, gardinol CA, Orvus,
and Dreft. These products yield insoluble calcium and magnesium salts
below 100° F. This is not a serious handicap, however, since these
salts are soluble at the temperatures most frequently used in washing.
The second of the sodium alcohol soaps, for which formulas are given
above, has some value as a detergent, but is chiefly useful as a wetting
agent. It is made by the high pressure-high temperature hydrogena-
tion of sperm, tallow, or vegetable oils, and can be used satisfactorily
only in water solutions above 130° F., because its calcium and mag-
nesium salts are insoluble below this point. The third of the salts is
made from sperm oil. Products of this range of molecular construction
serve chiefly as wetting and finishing agents in textile and allied
industries.
The early work on sulfated alcohols was done by many people in
different places. Among these should be mentioned H. Berth of the Ger-
man firm of H. T. Bohme, A. G., who was the first to point out that the
carboxyl group in detergents must be eliminated or blocked, for reasons
already mentioned. Killeffer "^ presented the following brief discussion
of the early history of the high temperature-high pressure hydrogena-
tion reactions to which reference has previously been made : "In 1931
Adkins and Folkers ^ published two papers describing, respectively, the
preparation of a hydrogenation catalyst, and the use of this catalyst in
the direct hydrogenation of aliphatic acids to the corresponding alcohols
having the same number of carbon atoms. Shortly thereafter, Schrauth,
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344 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Schenck, and Stickdorn,®' ^^ Deutsche Hydrierwerke, A. G., published a
paper describing their method of accomplishing the same result and
referring to patent applications previously made by them in Germany
in 1928. Normann ^^ also published a paper on the process, pointing out
the possibility of control of the product (alcohol or ester) by controlling
the temperatures. In 1932, a patent was issued in the United States
to Lazier ^^ describing a similar method of hydrogenation with the rather
specific idea of hydrogenating to secure esters simultaneously with the
alcohols. Between 1928 and 1931 the commercial development of
these fatty alcohol derivatives proceeded abroad and numerous patents
were issued to cover them. . . ."
The literature in this country on the sulfated alcohols has become
voluminous, and therefore only a few recent contributions will be men-
tioned. The place of sulfonated and sulfated alcohols in the detergency
and textile processing industries was discussed by Harvey ^^ at the
1935 meeting of the American Association of Textile Chemists and
Colorists. The analytical properties of the commercial sulfated alcohols
have been investigated and reported by Biffen and Snell.^^ Sunder-
land 1^ discussed the manufacture, properties and applications of these
products in a series of recent articles. Richardson ^® gave some details
concerning the manufacture of sulfated alcohols, and stated that in the
United States the E. I. du Pont de Nemours and Company and The
Proctor and Gamble Company hold licenses from Bohme and Hydrier-
werke in Germany for the manufacture and sale of the sulfonated and
sulfated alcohols covered by the patents of the latter firms.
Igepons. A second group of important new detergents includes
the Igepons. These are best known in two forms — Igepon A, and
Igepon T. The former is made by producing the sodium salt of a
compound formed when isethionic acid combines with oleic acid or its
derivatives. It has been found to be a good detergent, neutral in
reaction, stable in acids of moderate concentration, but decomposed by
strong acids, or on long contact even with weak acids. The term
Igepon was coined from the first initials of the German combine which
introduced these products — ^the I. G. Farbenindustrie Akt.-Ges. — ^the
"A" being the first letter of the German word for the acid used in
making it — namely, isethionic (German, aethionic) acid.
The lack of stability of Igepon A in alkalies or in strong acids led
to the production of Igepon T, the '*T'* indicating that tauric acid was
used in making it. The two Igepons are similar in properties except
for the fact that Igepon T is more stable in acid and alkaline solutions.
The formulas of these two substances are the following:
Igepon A: CH3(CH2)7CH:CH(CHo)7COOCH2CH2S03Na .
Igepon T: CH3(CH2)7CH: CH(CH2)7CON(CH3)CH2CH2S03Na
These formulas illustrate the commonly used term "blocking the
carboxyl group." In the first instance the hydrogen of the carboxyl
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DETERGENTS AND DETERGENCY 345
group is replaced by a group which itself contains a polar solubilizing
group, while in the second case, the ( — OH) of the carboxyl group
is similarly replaced.
Sweet ^"^ discussed the compounds and uses of the Igepons. Lederer ^^
described the results of tests on these compounds, which include solu-
bility in water and organic compounds, density of aqueous solutions,
viscosity, surface and interfacial tensions, foam number, and foam con-
sistency. Niisslein i®' ^o, 21 described the performance of the Igepons
in actual use, and gave a history of their development. In this country,
the Igepons are marketed by various firms : Syntex is a trade name for
Igepon T sold by Colgate Palmolive Peet, and various Igepons are dis-
tributed by General Dyestuffs.
Miscellaneous New Detergents. A wide variety of new deter-
gents is being proposed or sold in the United States and abroad, all of
which are having some influence on practices in the field of detergency.
Naphthenic compounds, prepared from the naphthenes recovered from
certain petroleums, have been studied and used, chiefly in Russia 22 and
Japan.^'"^ Sulfonated naphthalene compounds ^^ are marketed as soap
substitutes because of their wetting, dissolving, and dispersing proper-
ties. A discussion of sulfonated hydrocarbons as detergents is given
in Chapter 46 of the recent book by Ellis entitled **The Chemistry of
Petroleum Derivatives" (New York, The Chemical Catalogfue Com-
pany, 1934). Nekal BX, the sodium salt of a naphthalene sulfonic acid
with side chains, is an agent of this type. Other products marketed
under the trade names **Nekal," "Alkanol," and "Neomerpin N" are sub-
stances of similar kind, the latter of which is the free acid instead of
the sodium salt. Other agents which assist in soil removal because of
their wetting and emulsifying properties have been prepared from
related hydrogenated products, such as tetralin.
In some of the new detergents which have been proposed, or actually
placed on the market, phosphates or halides have been inserted either
as substitutes for the sulfate group, or to increase the polarity of the
compound, or for both purposes. Thus, the H. T. Bohme A. G.,^^ in
Germany, has patented a wide variety of esters of pyrophosphoric acid
with the higher aliphatic alcohols, in which the phosphate groups have
replaced the sulfate groups.
The Carbide and Carbon Chemicals Corporation,^^ in America, has
patented a cleansing, wetting, impregnating, and emulsifying agent
made from methyl isobutyl ketone and ethylhexaldehyde, having this
formula ( CH3 ) 2CHCH2COCH2CHOHCH ( C2H5 ) C4H9. Baldwin
and Davidson,2'^ in England have patented a group of ethers produced
by the reaction of an alcohol, such as cetyl, dodecyl, or oleyl, with an
aliphatic or aralkyl halide, such as benzyl chloride, in the presence of
aluminum powder and magnesia or chalk. When heated, and when
treated with chlorosulfonic acid, the compounds formed are sulfonated
products with good detergent properties.
Calcott and Clarkson ^s have patented a series of detergents of the gen-
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346 ANNUAL SURVEY OF AMERICAN CHEMISTRY
eral formula: C„(OH)„_iH„^2NRiR,2 where n is five or six, R^ is an
aliphatic radical having an open chain of at least eight carbon atoms,
and R2 is a hydrogen atom or an aliphatic radical. These compoimds
are obtained by a process which comprises the reaction of an aliphatic
halide having an open chain of at least eight carbon atoms with an amine
of the general formula CnHn+2(OH)n_iNXY, related to a 5- or 6-carbon
sugar. An example of such a compound formed from glucose and lauryl
alcohol would have the formula Ci2H25NHCH2(CHOH)4CH20H.
Aliphatic sulfonamides,^^ sulfonated dicarboxylic acids,30 pine oil
preparations, and terpineol sulfate are among the other detergents
which have recently been proposed or introduced. Such compounds as
phenylphenol sulfate, under such trade names as Aresket, Aresklene,
and Areskap, also have been developed.
Chemical Tests of Detergents. Space does not permit a complete
review of all of the chemical tests for various ingredients in soaps and
detergents proposed or used in this country before the close of 1935.
Mention should be made, however, of the fact that Hart,^! acting as
Chairman of the Sub-Committee on Sulfonated Oils of the American
Association of Textile Chemists and Colorists, reported on tests for
sulfonated and sulfated oils during 1935, which indicates that there is
increasing interest in reagents of these types in this country.
Practical Tests for Detergency. Chemical analysis of a deter-
gent is an insufficient method of evaluating its cleansing properties. An
actual washing test is necessary, either in addition to, or instead of,
chemical tests. These involve the use of standard soiled and standard
white fabrics which possess homogeniety of initial light reflectancy, and
which come to have the same final light reflectancy after the same
washing treatment. In 1927, the Subcommittee of the American Oil
Chemists Society ^^ made a report on its work on practical washing
tests. In this report, a standard soiled fabric was proposed which con-
sisted of a piece of cotton sheeting which was desized and treated with
a soiling mixture of lubricating oil, edible tallow, and lampblack. A
method of evaluating the results was proposed, and a machine suitable
for making washing tests was described. The method recommended
by this Committee evidently was not widely accepted, since we find
many investigations with different types of soiled pieces, and different
methods of evaluating and reporting results. Thus, Chapin ^^ used a
cotton fabric soiled with an ointment of lampblack and vaseline, lard,
or medicinal oil He employed a special instrument and evaluated his
results by the use of a colorimeter used as a reflectometer.
Rhodes and Brainard ^^ measured the detergency of soaps of various
concentrations directly under practical laundry conditions. Hill ^^
made a study of the comparative performances of various possible con-
stituents of a soiling mixture, and adopted a preparation containing
Oildag, olive oil, tallow, and mineral oil. He stated that this contained
the chief constituents of general soil, with the exception of albuminous
matter. He omitted the latter because it would have made necessary a
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DETERGENTS AND DETERGENCY 347
relatively low maximum temperature during the experimental pro-
cedure. He found that weighing the soiled piece before and after
laundering did not give a satisfactory measure of soil removal, and he
therefore adopted a photometric method. He used a small agitator t)^e
of washing machine in his tests.
Vail 3^ stated that the trend in soiling tests was in favor of simple
pigments. He described two possible methods of making soiled fabric
— one in which umber in a water suspension was applied to a white
fabric by passing the fabric back and forth through a clothes wringer,
and the other by applying umber in a water suspension in a launder-o-
meter.
Morgan ^^ described a standard soiled fabric made by the application
to desized white cotton of 3 grams of Russian tallow, 10 grams of
Nujol, and 2 grams of lampblack, suspended in 2000 c.c. of carbon
tetrachloride. Tests were made in a miniature washwheel with results
which showed the sensitivity of this fabric. Carter and Stericker ^7 used
carbon black, burnt umber, and raw umber or ferric oxide as an inert
soil in testing the comparative soil-removal values of various soaps
and soap builders.
Oesterling and Mack^® have worked for a number of years on the
efficiencies of the standard soiled fabrics described in the literature, and
have developed as a result a fabric which now has considerable use in
laundry research. This fabric is desized with an amylolytic enzyme,
and is soiled in a standard manner with carbon black of definite particle
size, motor oil of definite specifications and melted Crisco in a bath
of Stoddard solvent. The fabric is treated with the soiling substances
in a Stoddard solvent bath, and is rinsed in a Stoddard solvent solution
containing Crisco and motor oil of the same concentration as in the
soiling bath. The fabric is then dried, washed with soap and water,
and rinsed in a definite manner after which it is again dried. Test
specimens from each square yard of fabric are examined by means of a
light reflectancy spectrophotometer, and only those pieces are retained
which have a definite percentage initial light reflectancy with a toler-
ance of =•= 1 percent. In addition, test samples from each square yard
are given a standard washing test, and only those soiled pieces are
retained which show a specified increase in light reflectancy as a result
of the treatment. The authors have found that results with this test
piece are duplicated within narrow limits of error (provided that tests
are based on a 50- wash procedure) that the piece is sensitive to slight
changes in the washing formula, and that results with the test piece
are in accord with practical results in a commercial laundry.
Factors Involved in Detergency. A satisfactory detergent must
perform a number of functions, of which the following are important:
(1) it must wet the fabric or surface to be washed; (2) it must wet
the various types of soil which are to be removed from the surface,
such as inert soil and oily substances; and (3) it must form a stable
emulsion of these soils so as to prevent their re-deposition on the sur-
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348 ANNUAL SURVEY OF AMERICAN CHEMISTRY
face from which they have been removed. Fall ^o presented a critical
resume of the conditions suggested by different investigators as enter-
ing into detergent action, and employed various ones of these on differ-
ent types of soap and soap builders.
Surface and Interfacial Tensions. The tensiometer of duNoiiy ^®»
^1' ^2 i^as been used by various American investigators to determine the
surface and interfacial tensions of detergents. In most studies of this
type, the instrument is calibrated against analytical v^eights, and the
calibration is tested by determining the surface tensions of water and
benzene, using the ring corrections of Harkins and Jordan.^^ Cupples *^
in 1935 published the results of a very thorough investigation on the
use of the duNoiiy tensiometer to find the wetting and spreading proper-
ties of aqueous solutions. Although he was interested primarily in
dipping and spraying solutions, he used sodium oleate and oleic acid-
sodium hydroxide mixtures in a series of experiments which should be
of interest to the scientist who is determining spreading coefficients of
detergents.
The falling drop method continues to be used as a measure of inter-
facial tension. One of the most recent American works in which this
method is described is that of Snell,^^ in which the interfacial tensions
were determined by falling drops of water in oil, and by rising drops
of oil in water.
Adhesion Tension Studies. Ostcrhof and Bartell ^® made an
attempt to correlate the views expressed by different investigators and
writers on the wetting of solids by liquids. They classified wetting into
three types — namely, adhesional, spreading, and immersional wetting.
They suggested that adhesion tension be adopted as a term to designate
degree of wetting, and suggested that apparent differences in conclu-
sions of investigators could be harmonized if the nomenclature in the
field were clarified. Bartell and Walton '*^ gave various tests for
determining the degree of wetting of solids by liquids. They found
that data on settling properties for certain powders dispersed through
liquids agreed with adhesion tensions as determined by the pressure
displacement method. It is possible that the methods developed by
Bartell could be applied in determining the wetting of soils and of
fibers.
Miscellaneous Measurements. The viscosity of soap solutions is
measured in some laboratories, as an indication of the particle size of
the soaps. Viscosity may also play an important part in the stability
of the emulsions formed from oily material in the soil and the soap
or detergent.
A sinking time test for wetting agents was introduced by Draves and
Clarkson,^^ in" which the time required for a standard skein of cotton to
sink in a solution of the reagent was recorded under a specified set of
conditions. The effect of variations of temperature, />H, and other
conditions on the sinking time were studied by the authors of the test,
and the relationship between sinking time and surface tension was
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DETERGENTS AND DETERGENCY 349
investigated. The relationship between sinking time and concentration
of the agent was found to be logarithmic. Although it is not entirely
clear what property or properties the method measures, it is apparently
a convenient empirical criterion which has become widely used.
Lenher and Smith, on the other hand,^^ pointed out that the Draves
sinking time method does not measure the penetration of the fiber by
the solution, and proposed an absorption test for determining the effi-
ciency of a penetrating agent.
The de flocculating power of soaps is associated with the formation
of sorption complexes and suspensions by a combination of soil par-
ticles with the detergent. This determines whether or not soil, after
removal from a surface, will be kept in a stable suspension, or whether
it will floccculate and be redeposited on the surface. McBain, Har-
bome, and King ^^ developed and standardized a method for the rapid,
direct measurement of the amount of finely-divided carbon which
various soap solutions carry through filter paper. The work of these
authors showed that a slight variation in conditions resulted in
changes in deflocculating power of the detergent under examination.
Chapin ^^' ^2, 53 proposed and used a graphite test for investigating the
fundamental principles of deflocculation in relation to detergency.
Fall 3^ used manganese dioxide in studies on deflocculation, and others
have used umber and rouge.
Theories Concerning the Action of Detergents. McBain and his
co-workers have published extensively in the field of detergency from
1911 to the present time. McBain and Taylor ^^ studied the solubility
of detergents in water, their colloidal behavior,, and their degree of
hydrolysis. McBain and Martin ^^ determined the dissociation product
and other fundamental properties of alkalies and soaps. McBain ^®
drew a number of conclusions from previous work on the constitution
and hydrolysis of soap solutions, the composition of soap curd, the
osmotic properties and viscosities of soap solutions, and the mechanism
of soap behavior toward soil. He further showed the comparative
behavior of sodium and potassium soaps at 18° and 90° C, and the
influence on properties of the position in the homologous series occu-
pied by the fatty acid radicals in soaps.
McBain and Salmon ^'^ determined the molecular weights of sodium,
potassium, and ammonium soaps, and concluded that the metallic ion
was the only crystalloid constituent of a soap, the negative radical
being an ionic micelle, made up of normal soap and acid soap. They
reported, also, that the addition of electrolytes to soap solutions caused
dehydration and a reduction of the proportion of the ionic micelle.
Further evidence favoring the theory of the ionic micelle is given by
McBain,^^ and by McBain and Bowden.^^ The last two authors
reported the results of studies on migration in soap solutions, trans-
port numbers, and ultrafiltration.
McBain ^^ reported results on measurements of electromotive force
in soap solutions, ultrafiltration, osmotic pressure, and change in freez-
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350 ANNUAL SURVEY OF AMERICAN CHEMISTRY
ing and boiling points in solution, which showed that the hydroxyl ion
exerts only a very minor influence on the action of soap solutions, and
that the activity of soaps can therefore not be attributed to hydrolysis.
The results of their tests were believed to confirm further the ionic
micelle theory.
McBain ^^ used the hydrogen electrode to study the rate of saponifi-
cation of soaps; McBain and McBain ®2 studied the scattering effect
of pure sodium oleate sols and gels ; McBain, Lazarus, and Fitter ^
determined the effect of temperature upon equilibrium in soap solu-
tions ; McBain and Liu ®'* determined the rate of diffusion of potassium
laurate by means of the Northrop diffusion cell ; McBain and Field ®^
studied the system potassium laurate-Iauric acid over a wide range of
temperatures and by several different methods ; McBain and Field ®®
found two definite crystalline compounds in the system sodium palmi-
tate-palmitic acid — ^namely, Na . HF and 2NaF . HP, and also deter-
mined the transition temperatures and the eutectic point; McBain and
Stewart ^''^ similarly investigated the system potassium oleate-oleic acid.
McBain ®^ determined the diffusion behavior of soaps in relation to
osmotic pressures and other properties.
McBain and Watts ^^ observed the viscosities of soap solutions and
explained the results in terms of two kinds of cohesion within the
solution. McBain and McBain '^^ developed a formula for the con-
centration gradient of a neutral molecule or a primary colloid at the
isoelectric point. McBain, Kawakami, and Lucas '^^ studied the ultra-
filtration of potassium laurate solutions with special reference to hydra-
tion. They found that, when electroljrtes were used as reference sub-
stances, a Donnan equilibrium was superimposed upon the filtration
effect. They found also that, for high concentrations of ions, the hydra-
tion is 12 moles of water for one of potassium laurate.
McBain and Field '''^ mapped out phase rule diagrams for three-
component systems of potassium laurate-Iauric acid-water, and studied
the equilibrium conditions of the system. McBain, Bull, and Staddon '^^
demonstrated the presence of bound water in the soap curd, and deter-
mined the amounts of water present in the hydrates of sodium palmitate
and other soaps. McBain '^^ included soap in a discussion of the char-
acteristic factors of the colloidal state.
Lawrence '^^ presented evidence which seemed to show that the
behavior of soap is due to two effects in the molecule : ( 1 ) the carboxyl
group with its attraction for water, and (2) the hydrocarbon group
with its insolubility in water. Lawrence '^^ gave further evidence which
seemed to show that ordinary soap films do not have a colloidal struc-
ture, but consist of a pair of surface layers of adsorbed, molecularly
dispersed soap, enclosing between them a true soap solution. He stated
that the formation of a stable soap film required (1) the lowering of
the surface tension of water to one third its normal value by the for-
mation of an oriented, adsorbed layer of soap, and (2) the formation
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DETERGENTS AND DETERGENCY 351
of such a layer which has an effective, lateral, cohesive strength greater
than the disruptive force of the residual surface tension. In a later
paper, Lawrence '^'^ reviewed the properties of soap micelles.
Johnson '^^ considered the mechanism of detergent action from the
points of view of wetting, deflocculation, emulsification, and solution,
and compared some common detergents on these bases.
Spychalski '^^ gave confirmation to the idea of a crystalline micelle
by spinning various sodium salts of fatty acids into threads under ten-
sion, and examining the threads by means of x-rays. The x-ray dia-
grams indicated that the micelles have a crystalline structure which is
not disrupted even by intensive drying, and that the water in the
hydrate filled only the interstices of the fiber. He calculated the space
lattice of the micelles, and concluded that the micelles have the form
of rectangular prisms with the longest edge parallel to the fiber axis.
Bertsch ^^ found that, when sodium oleate is dissolved in water, the
( — COONa) groups of the surface layer are oriented toward the
interior, while the rest of the hydrocarbon chain is directed toward
the exterior.
Bartell and Hershberger ^^ studied the degree of wetting of a solid
by a liquid, and related this and other properties to the polarity of the
solid.
Tate ^^ found that detergency in salts of fatty acids is limited to
a narrow range of molecular weight of the hydrocarbon chain. If the
alkali group constitutes too great or too insignificant a proportion of
the molecular weight of the compound, the relation of the water- solu-
bility and -insolubility of the two parts of the molecule is not satisfac-
tory, or in other words, the compound does not possess the desired
degree of polarity. ^
Soap Builders. There are four chieitypes of alkaline builders,
or alkaline reagents used to improve the detergency of soaps in water
washing. These are carbonates, silicates, phosphates, and caustic soda.
To these might be added a less common fifth type — namely, sodium
aluminum silicate. The carbonates used are soda ash, sodium bicar-
bonate, and sodium sesquicarbonate. The silicates include water glass,
sodium metasilicate, and sodium sesqui silicate (or orthosilicate), the
last of which was recently introduced. It contains 36.9 percent sodium
oxide, 23.8 percent silicon dioxide, and 39.3 percent water, as compared
with 29.2 percent sodium oxide, 28.3 percent silicon dioxide, and 42.4
percent water in metasilicate. The advantages of sesquisilicate are its
increased alkalinity and its ready solubility.
Experimental results on the detergent properties of the alkaline
builders differ from one investigation to another, because methods, of
test are not standardized, and because conclusions have been based on
widely different tests without definite knowledge of the significance of
each. The comparative detergency efficiencies of various builders have
recently been investigated in washing tests by Snell,^^' ^^ Rayner,^^
Carter and Stericker,^^ and Morgan.^^' ^^ The deflocculating proper-
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352 ANNUAL SURVEY OF AMERICAN CHEMISTRY
ties of various alkaline builders have been studied by Carter,^^ Baker,^^
and Snell.^^ Vail ^^ discussed the various silicates with relation to
their detergency at a meeting of the American Institute of Chemical
Engineers, in New Orleans, 1930. Rhodes and Bascom ^^ investigated
the detergency of alkaline builders quantitatively, both alone and com-
bined with soaps.
Sodium Hexaphosphate in Hard Water. The recent introduc-
tion of sodium hexametaphosphate (NaP03)6 has placed ordinary soap
on a parity with the fatty alcohol sulfates and the Igepons for use in
hard water, since this compound ties up calcium and magnesium in
complex ions and prevents them from forming insoluble calcium and
magnesium soaps. Gilmore ^^ described the method of making sodium
hexametaphosphate (known in the textile industry as '*Calgon") by
heating monosodium phosphate (NaH2P04) to form (Na2P207).
Further heating at a low temperature converts the latter to sodium
metaphosphate (NaPOg). Upon heating this to redness, it polymerizes
into the hexametaphosphate. The />H value of this compound is about
5.5 in dilute solution. The present trend in the use of this reagent is
as an adjuvant in every type of cleaning which is conducted in hard
water. The applications of sodium hexametaphosphate as an assistant
in the textile industry is described by Bell.®^
Enzymes as Detergents. Enzymes have had some use in gen-
eral laundry procedure in Germany ^® for a number of years. In the
old detachable collar days in this country, amylolytic enzymes were
employed in some laundries to remove starch and simplify laundering.
At present, however, the use of enzymes in laundering and drycleaning
is restricted to the employment of proteolytic enzymes for the removal
of blood and other albuminous stains in hand stain removal processes.
Keeney and Mack ^^ condracted laboratory and practical tests in which
standard soiled fabrics coated with starch and with albuminous stains
were treated with amylolytic and proteolytic enzymes, alone and
together, in one of the baths of a recommended laundry procedure.
Amyloljrtic enzymes were found to improve detergency efficiencies in
the case of starched fabrics, and proteolytic enzymes assisted in remov-
ing soil by digesting albuminous stains, provided that conditions of
concentration, /)H, and temperature were suitable for the enzyme in
question.
Powers ^^ gave the optimal conditions for the action of certain
enzymes, and discussed methods of measuring enzyme activity.
Nopitsch^® investigated the effect of enzymes on the strength of
cotton fabrics and concluded that there was no evidence of cellulose
destruction throughout his work. Keeney and Mack^^ extended his
investigations to include a larger number of enzymes under a wide
variety of conditions of time, temperature, /)H, and concentration, and
found no case in which the loss in breaking strength of a cotton fabric
was greater when enzymes were present than when they were absent,
all other conditions of the test being similar.
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DETERGENTS AND DETERGENCY 353
Bleaching Agents. Bleaching agents, principally sodium hypo-
chlorite and similar reagents, have long been used in American laundry
practice. Contrary to the popular belief, they are of no value in gen-
eral soil removal, although they are effective in the removal of vari-
ous stains, and to some extent in the maintenance of the whiteness of
white fabrics. The destructive action which sodium hypochlorite
exerts on textile fibers has eliminated its use with protein fibers, and
has made its application to the cellulose fibers one which calls for
extreme care.
The shortcoming of the chlorine bleaches just mentioned has opened
up two important lines of research in this field: (1) investigations of
the ideal conditions for using the chlorine bleaches; and (2) searches
for chlorine bleach substitutes.
A study of the strength losses in cotton fabrics under a wide variety
of conditions was made at the Massachusetts Institute of Technology.^^*^
The influence of chlorine bleaches on the whiteness and breaking
strength of fabrics was studied at the American Institute of Launder-
ing.^^^ Oesterling and Mack^^ have found that the />H of a bleach
bath has a great influence on the degree of degradation of cellulose, the
breakdown being very small at high />H values, and very great when the
/>H is low. They found that chlorine bleach baths made in a large
variety of ways, either from sodium or calcium salts, were similar in
their effect on the breaking strength of fabric, if the chlorine concen-
tration, the />H, and other conditions were the same. They found fur-
ther that moderately low temperatures (110 to 140° F.) and low con-
centrations of chlorine were as effective (in stain removal and white-
ness retention), as higher temperatures, while causing only small losses
in fabric strength. They also found that increase in breaking strength
losses of a fabric showed a numerical relationship to copper number
of the fabric, which indicates that the loss in strength is due in con-
siderable measure to chemical breakdown within the fiber.
Among the substitutes for chlorine bleaches which have been pro-
posed, or actually introduced into practice in this country, are sodium
hydrosulfate, hydrogen peroxide, and various borates. Keeney and
Mack ^'^ found that sodium hydrosulfate produced insignificant losses in
the strength of cotton under a considerable variety of conditions, but
was unsatisfactory as a laundry bleaching agent because of its yellowing
effect upon fabrics. Oesterling, Mack, Krawiec, and Ebert, in unpub-
lished work done at The Pennsylvania State College, have investigated
hydrogen peroxide as a laundry bleach through a wide range of con-
ditions, and have found that it is more effective in stain removal and
whiteness retention than chlorine bleaches of similar concentration,
and that it causes a smaller degree of breakdown in cotton than is
caused by the other type of bleach. It may also be used, with proper
precautions, on wool and silk fabrics, and on certain dyes. Its use
requires care, however, and there is a definite concentration, tempera-
ture, pliy and time range within which it is most satisfactory. Various
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354 ANNUAL SURVEY OF AMERICAN CHEMISTRY
borates and perborates have been investigated as bleaching agents
abroad,i®2 which have a limited application in laundry and drycleaning
practice in this country. Bleaches of the borate and perborate type are
being studied at present in various American laboratories to determine
their possible utility for large-scale laundry use.
Discussion. A survey of the literature in the field of detergents
and detergency shows that a vast amount of valuable data has been
accumulated by American investigators working in this field during
the past few years. It is frequently difficult to relate the data of one
investigator with that of another, however, because of the following
facts: (1) there is no uniformly accepted standard procedure for the
practical measurement of detergency; (2) methods of making chemical
and physical tests on detergents have not been standardized; and (3)
there is no agreement among investigators as to the significance of
chemical and physical tests after they have been made. Too frequently,
an investigator assumes that one or two measurements give all of the
information necessary about a certain detergent. The factors involved
are not simple, however, and several t)rpes of chemical and physical
tests must be made and interpreted in order to explain the behavior of
a detergent in practical tests.
The chemical and physical tests on detergents which have been
emphasized in the literature include the following: surface, interfacial,
and adhesion tension; emulsion number and foam number, or height
of suds ; deflocculation ; penetration, sinking time of fibrous material in
a solution of the detergent; lubrication, and absorption; viscosity of
solutions of the detergent; solubility and solubilizing effect of the
detergent; />H; and chemical stability.
Surface tension has been used by some investigators as a measure of
the activity of the detergent. Actually, a low surface tension is merely
indicative of strong surface or capillary active substances, and does not
necessarily denote that the substance has other properties required in a
detergent. Adhesion tension seems to be directly related to surface
tension, while interfacial tension depends upon the polarity as well as
the type of groups in the molecule of the detergent. The emulsifica-
tion of oil by a detergent depends upon a low interfacial tension, while
the foam number depends upon the surface tension, the type of micelle,
and other factors. The balance between the surface tension of oil, the
surface of the solution of the detergent, and the interfacial tension
between the two determines the spreading coefficient, and shows
whether one liquid will spread over or wet another.
Good detergents apparently have the property of dispersing and
suspending particles of soil, and they form films of sufficient viscosity
to produce stable emulsions. The viscosity of a solution of a deter-
gent also features in the ease of preparation and convenience of
handling soap solutions. Lubrication, penetration, and absorption of
detergents appear to play a part in the displacement of soil in fibers,
and the production of a clean fabric with certain desirable properties
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DETERGENTS AND DETERGENCY 355
as to finish. At the same time, absorption is important in its relation
to the rate at which the detergent is removed from the bath. Such
factors as /^H and chemical stability are important also.
The evaluation of the properties just discussed, either singly or in
combination, must depend upon parallel washing tests in which soil
removal from fabrics and whiteness retention are determined.
The author wishes to thank Lawrence P. Hall for invaluable assis-
tance in the writing of this chapter, and Mary D. Caulk for helpful
assistance with the bibliography.
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UNITED STATES PATENTS
1934
1,942,812. Organic products from 7,18-stearic glycol. F. Guenther and K. Saftien.
January 9.
1,943,253. Toilet soap powder. Wm. H. Alton. January 9.
1,943,519. Washing composition. P. S. Denning. January 16.
1,944,300. Wetting agent. K. Ott, W. Hentrich, and H. Keppler. January 23.
1,944,848. Silicate flakes. A. W. Scheidt. January 23.
1,946,079-80. Wetting agent. Alkylolamine soaps. J. G. Kern and C. J. Sala. February 6.
1,946,272. Cleaning composition. R. H. Brownlee. February 6.
1,947.650. Derivatives of higher fatty acids containiner nitrogen. K. Keller. February 20.
1,947,673. Wetting agent. H. Bertsch. February 20.
1,947,994. Apparatus for handling dissolving soaps. C. M. Larson. February 20.
1,950,287. Water-soluble capillary-active substances. L. Becker and R. Muller. March 6.
1,951.469. Wetting agent. H. Bertsch. March 20.
1.951,511. Making soap. M. H. Ittner. March 20.
1,951,696. Alkali metal sahs of fatty acids. M. Hofsasz. March 20.
1,951,784-5. Wetting agents. H. Bertsch. March 20.
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DETERGENTS AND DETERGENCY 357
1,952,008. Emulsifying, detergent and wetting agent. H. A. Bruson. March 20.
1,953,745. Aliphatic alcohols. C. L. Campbell. April 3.
1,957,674. Washing, cleaning, emulsifying agent. W. Schrauth. May 8.
1,957,918. Sulfur soap. T. Tanaka. May 8.
1,958,860. Wetting agent. O. A. Pickett. May 15.
1,959,590. Fatty acid esters of carbohydrates. E. J. Lorand. May 22.
1,959,930. Hydroxyalkyl ethers of polyhydric alcohols. O. Schmidt and E. Meyer. May 22.
1,962,299. Detergent suitable for laundry purposes. E. F. Drew. June 12.
1.964.006. Fabric cleaning composition. E. C. Pailler. June 26.
1.964.654. Wetting agent. H. Ulrich and P. Koerding. June 26.
1,966,187. Sulfonic acids. E. Schirm. July 10.
1,966,383. Cleansing agent, silicate and hypochlorite. H. G. Elledge and A. Hirsch.
July 10.
1.967.655. Alkoxyalkyl esters of organic carboxylic and sulfonic acids. H. Bertsch.
July 24.
1.967.656. Wetting agents. H. Bertsch. July 24.
1,968,526. Powdered soap of low moisture content. B. Clayton, W. B. Kerrick, and H.
M. Stadt. July 31.
1,968,628. Powdered soap. Wm. H. Alton. July 31.
1,968,793. Sulfuric ester of higher alcohols. H. Bertsch. July 31.
1,968,794-6. Sulfonated alcohols. H. Bertsch. July 31.
1,968,797. Sulfonated alcohols. H. Bertsch. July 31.
1,969,612. Capillary active agents. W. J. Kaiser and A. Kirstahler. August 7.
1,970,578. Textile assistants. Polymethylene. C. Schoeller and M. Wittwer. August 21.
1,971,375. Soft soap. L. F. Hoyt. August 28.
1,971,566. Powdered soap. W. A. Hutton. August 28.
1.971.742. Primary alcohols. H. Bertsch. August 28.
1.971.743. Reducing organic compounds. H. Bertsch. August 28.
1,972,032. Neutral Na pyrophosphate. A. Reimann. August 28.
1,972,458. Dry soap powder. Mechanic's soap. L. H. Phillips. September 4.
1.974.007. Wetting agent. H. Bertsch. September 18.
1,975,946. Detergent. Silicate and phosphate mixture. H. K. Ihrig and A. S. Butler-
worth. October 9.
1,976,886. Wetting agents. H. Lier. October 16.
1,980,342. Wetting agents. R. Kern. November 13.
1.983.414. Sulfo- acids of high molecular weight. K. Lindner. November 13.
1,980,543. Wetting agent. E. Lurie. November 13.
1.980.691. Sodium ammonium carbonate. R. B. MacMullin. November 13.
1,981,792. Sulfonated fatty acid esters of monoethanolamine. J. W. Orelup. Novem-
ber 20.
1,981,901. Alkali metal salt of elaidyl sulfuric ester. H. M. Bunbury and A. W. Bald-
win. November 27.
1.984.713. Wetting and detergent agents. H. J. Weiland, C. O. Henke and G. Etzel.
December 18.
1.984.714. Wetting agents, etc. H. J. Weiland, C. O. Henke and M. A. Prahl. Decem-
ber 18.
1,985,747. Ether-like wetting, dispersing, emulsifying and washing compounds. A. Stein-
dorff, K. Daimler and K. Platz. December 25.
1935
1,985,987. Spray drying soap. T. E. Hall. January 1.
1,986,286. Laundering fabrics. S. M. RatzkoflF. January 1.
1,986,808. Wetting agent. R. Greenbalgh. January 8.
1,987,526. High molecular aliphatic sulfides. E. Elbel and A. Kirstahler. January 8.
1.987.558. Producing alcohols. A. Hintermaier. January 8.
1.987.559. Boron tricarboxylate. A. Hintermaier. January 8.
1,989,312. Laundering. A. B. Gerber. January 29.
1,989,759. Chlorinated alkaline silicate. P. Logue and Wm. N. Pritchard, Jr. February 5.
1,989,765. Sodium metasilicate detergent. H. V. Moss and F. D. Snell. February 5.
1,992,160. Wetting, emulsifying and washing agent. C. A. Thomas. February 19.
1.992.692. Detergent and application thereof. L. H. Englund. February 26.
1,993,375. Sulfonated poducts. M. Luther and A. v. Friedolsheim. March 5.
1.993.415. Sulfonated polymerized terpene product suitable for use as a wetting agent.
A. L. Rummelsburg and B. H. Little. March 5.
1,993,431. Solid salts of higher alkyl sulfuric acids. H. Bertsch. March 5.
1,994,467. Detergents and emulsifying agents. R. B. Flint and P. L. Salzberg. March 19.
1,994,927. Wetting, penetrating and cleansing substances. R. L. Sibley. March 19.
1,997,474. Soap cake reinforced with buoyant center. J. S. Stone. April 9.
1,999,184. Soap powder. C. Ellis. April 30.
1,999,315. Wetting, dispersing and detergent agents. A. W. Baldwin and A. Davidson.
April 30.
1,999,628. Detergent compositions. P. Friesenhahn. April 30.
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358 ANNUAL SURVEY OF AMERICAN CHEMISTRY
2,000,994. Wetting-out and emulsifying agents. W. Schrauth. May 14.
2,001,275. Ethers of hydroabietyl alcohol. C. O. Henke and M. A. Prahl. May 14.
2,002,613. Cleansing, wetting, emulsifying and dye-stabilizing products. L. Orthner
and H. Kep|>ler. May 28.
2,003,471. Sulfonated terpene products. A. L. Rummelsburg. June 4.
2,004,670. Perborate soap powder. C. W. Moore and H. Ballantyne. June 11.
2,004,874. Superfatted soap. W. A. Lazier. June 11.
2,005,160. "High percentage" transparent toilet soap. W. Pape. June 18.
2,006,309. Hydroxy sulfonated fatty acid esters. C. C. Clark. June 25.
2,006,557. Stable wetting and penetrating emulsions. S. Lenher and C. T. Mentzer, Jr.
July 2.
2,007,974. Soap composition containing pine oil. C. E. Kaltenbach. July Id.
2,008,649. Aliphatic polyamides (wetting, cleansing and dispersing agents). H. Ulrich
and J. Nuesslein. July 16.
2,009,413. Liquid cleaning composition. F. H. Relyea. July 30.
2,009,796. Composition for wetting, emulsifying, etc. B. R. Harris. July 30.
2,010,661. Forming suds from soap. G. French. August 6.
2,012,073. Salts of o-ether alkylthiosulfuric acids. E. Schirm. August 20.
2,013,300. Detergents for textile materials. C. Dunbar. September 3.
2,014,007. Fabric-cleansing and -dyeing compositions. E. C. Pailler. September 10.
2,014,502. Emulsifying, cleansing and wetting agents. K. Marx, K. Brodersen and M.
Quaedvlieg. September 17.
2,014,782. Inorganic acid esters of higher glycols. W. Schrauth and R. Heuter. Sep-
tember 17.
2,015,912. Lathering and dispersing compositions. F. Sommer. October 1.
2,016,109. Wetting and dispersing agents. F. Guenther. October 1.
2,016^265. Detergent suitable for cleaning oily surfaces. W. T. Doherty. October 1.
2,016,289. Rice-hull composition suitable for cleaning and scouring. H. T. McGill.
October 8.
2,016,956. Amino derivatives suitable for use as detergents. Wm. S. Calcott and R. G.
Clarkson. October 8.
2,019,775. Soap. B. Clayton and R. E. Burns. November 5.
2,020,385. Compositions for use as wetting agents. Wm. Todd. November 12.
2,020,453. "Assistants" as wetting agents. H. Beller and H. Schuette. November 12.
2,022,766. Emulsifying agents containing fatty acid esters of polyglycerols. B. R. Har-
ris. December 3.
2,025,984. Esters of hydroxy carboxylic acids (wetting and detergent agents). B. R.
Harris. December 31.
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Chapter XXI.
Cellulose and Paper.
Harry F. Lewis,
Institute of Paper Chemistry, Lawrence College,
Appleton, Wisconsin
•
The very considerable increase in interest and research activity
in the fields of cellulose and paper, noted by this reviewer in the intro-
duction to Chapter VIII of the 1933 Annual Survey, has continued
throughout the past two years. Technical papers and patents have so
increased in number that only the barest discussion is possible of the
various literature references cited, while the patent literature must
of necessity be entirely omitted. A recent TAPPI publication ^ con-
tains 71 pages of U. S. patents granted in 1934 in the fields of cellulose
and paper and lists only the titles, names of patentee, and necessary
dates and description. The year 1935 has been even more prolific.
Two historical surveys should be included in this review. The first,
by Johnson,^ refers to the development of the pulpr and paper industry
in the United States. The second, that of Esselen,^ deals with the
rayon industry. A compilation of current researches on pulp and
paper making in nineteen laboratories has been prepared by West.*
Shaw ® summarizes the research work being carried out with the
experimental paper machine at the Bureau of Standards.
The scope of technical control in pulp and paper manufacture is
indicated by Kidder,® Phelps,*^ and Minor.^ Heritage® discusses the
fundamental relationship between research and operation from the
standpoint of the product manufactured, and management, research, and
operation.
A new laboratory has been established at the University of Michigan
with facilities for pulp and paper testing. Additional laboratory and
semi-plant construction is in process at The Institute of Paper Chem-
istry, whereby laboratory facilities will be about doubled.
Reference should be made to the symposium on the nature of cellulose
held under the auspices of the Cellulose Division of the American
Chemical Society at the spring meeting in New York in 1935. Review
papers were prepared by authorities in the various fields to cover
the chemical and physical properties of cellulose, x-ray structure and
molecular weight determinations, the micro-structure of cellulose
fibers, and the formation of cellulose in membranes.
359
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360 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Wood. The source of the future pulpwood supplies in the
United States is a matter of general interest. Curran ^^ has made a
survey of the situation and discusses the possible use of Engelmann
spruce, ponderosa pine, redwood, and the western cedars in the remote
areas of the country. Hunger ^^ and Davis ^^ describe the wood stands
of the Pacific Northwest. The latter refers particularly to standing
hemlock, spruce, noble fir, and three species of the white fir. The
above reference by Curran shows the trend away from spruce, which
in 1899 furnished 76 percent of the pulp and in 1932 but 37 percent,
toward hemlock, southern yellow pine, balsam fir, and jack pine.
Improvement in yield and quality of pulp wood by controlled
hybridization of forest trees in the poplar breeding project of the
Oxford Paper Company is described by Schreiner.^^ These new hybrid
poplars are decidedly better than the native poplars for they grow
more rapidly, are more easily propagated and are more resistant to
disease. Many will produce wood with a longer average fiber length
and somewhat higher density than the native poplar used in Maine
for the preparation of soda pulp.
The work of the Forest Products Laboratory in the evaluation of
additional pulp woods has been continued so as to include the short
leaf pine (Pinus echinata), cajeput, white mangrove, Australian pine,
and Cunningham pine. Bray and Paul ^^ report that chemical analyses
of the pulp obtained from the first wood showed no outstanding evi-
dence adverse to the production of good quality pulps of average yields
by the kraft process. Curran, Schwartz, and Bray,^-^ in discussing the
kraft cooking of Fl©rida-grown species of the last four, point out that
the pulps are short fibered and inferior to pulps from the common
pulpwood species.
Stamm ^^ has continued his investigations of the colloidal char-
acteristics of wood. Measurements have been made of the equilibrium
permeabilities of softwoods to air at different relative vapor pressure.
On the basis of these, a new means has been developed for determining
the distributions of size of openings in a porous membrane. He and
Seborg ^"^ have measured the adsorption compression of water on Sitka
spruce and white spruce heartwood sawdust, cotton linters, alpha cellu-
lose, a normal sulfite pulp, and the same pulp in a "highly hydrated"
condition in benzene. The evidence indicates that this force is of the
order of several thousand atmospheres. A means of minimizing wood
shrinkage and swelling in wood, involving the impregnation of green
or dry wood with a water insoluble oil or molten wax or resin has been
based by Stamm and Hansen ^^ upon the primary replacement of
water in the wood with Cellosolve and the subsequent replacement of
the Cellosolve by waxes or resins at temperatures above their melting
point. The process serves as a combined seasoning and anti-shrink
impregnation treatment for refractory species.
Stamm ^^' ^o has likewise measured the effect of inorganic salts on
the swelling and shrinking of wood, as well as other factors affecting
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CELLULOSE AND PAPER 361
dimension changes such as result from variations in moisture content.
Stamm and Loughborough 21 have applied thermodynamic methods to
the calculation of equilibrium moisture content, relative pressure curves
and isotherms, fiber saturation points, temperature curves, differential
heats and free energy changes of swelling, isosteres, and entropy
changes with swelling for Sitka spruce.
Buckman, Schmitz, and Gortner^s have studied certain factors
influencing the movement of liquids in wood. These include: (a)
the relative effectiveness of the maximum and average pore diameter
of the openings in the pit membranes for woods at different moisture
contents, {h) the influence of pressure on the rate of flow of water
through wood, and (c) the movement of organic liquids and salt solu-
tions through wood. The diffusion of neutral molecules such as urea,
glycerol, and lactose from aqueous solutions with samples of wood
of known capillary dimensions has been investigated by Cady and
Williams.22 Measurements have been made with heart and sapwood
in transverse radial and semi-tangential sections.
The series of articles on the chemistry of woods has been continued
from the laboratory of the New York State College of Forestry.
Peterson, Maughan, and Wise^^ have investigated the water-soluble
polysaccharide from the European larch (Larx decidua Null) and
establish its identity with the carbohydrates from the two American
species; namely, an arabogalacton containing 11.63 percent anhydro-
arabinose and 81.95 percent anhydrogalacton. Its separation as an ash-
free chemically homogeneous material was effected by electrodialysis.
Herty and Rasch.^^ have prepared rayon from southern pine pulp
and have found that with the exception of the higher ash content,
it compares favorably with rayon made from commercial rayon pulps.
Brannock, Bunger, and Doud^s check these observations in the main.
Cellulose. A large number of significant articles relating to the
physical characteristics of cellulose and cellulose fibers have appeared.
Stoops 2*^ has measured the dielectric constant and power factor data on
dried glycerol-free Cellophane for a wide range of temperature and
frequency. The dielectric constant for Cellophane is found to be
nearly twice that of cellulose acetate. An explanation of this based
on a variation in chemical structure is advanced. Sanders and Cam-
eron 28 find the x-ray unit cell of the cellulose in cotton stalks and
cusp to be the same as that in linters, and spruce, pine, and poplar
wood. They trace differences in the physical properties of products
from cellulose of different origins to the micellae in the fibroid structure.
The sorption of water by cellulose as an index of the fine structure
of the gel has been considered by Sheppard and Newsome.^^ Alpha-
pulp has higher sorption than cotton cellulose, approaching mercerized
cellulose. Sorption is unaffected by heating (hydration), which effect
depends upon an increase in external surface or dispersity. Bancroft
and Calkin ^^ believe that the reaction of caustic soda and cellulose is
entirely described by adsorption rather than by compound formation.
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362 ANNUAL SURVEY OF AMERICAN CHEMISTRY
The adsorption of organic liquids by cellulose products has been
investigated by Wiertelak and Garbaczowna,^! who have been inter-
ested in the extent to which the adsorption of organic liquids will
interfere with the standard analysis of wood and cellulose products.
They jfind ready adsorption of alcohols, pyridine, and benzene-alcohol
mixtures, which liquids are not removed from the fiber by heating at
105° C. Neither benzene nor gasoline is adsorbed.
The sorption of dyes by cellulose has been considered by Clark and
Southard 32 and by Friedman and Kuykendall.^^ Such work throws
light both on the mechanism of commercial dyeing and also on the
fine structure of fibers. The latter paper describes particularly the
effect of />H variations on the absorption. Lenher and Smith 34 show
that electrolyte-free substantive dyes in water solutions are only slightly
absorbed by cotton of low ash content, that the addition of an elec-
trolyte induces adsorption, and that a maximum particle size exists
above which dyes are not readily adsorbed by cotton. The particle size
and the salt sensitivity of the* dyes are the controlling factors in their
dyeing characteristics. '
Rowland ^s presents a critical survey of recent work on selected topics
concerning the colloidal behavior of cellulose as related to the technical
problems of paper making.
Two papers of interest bearing on the formation of carbohydrates or
cellulose membranes are those of Sponsler 3« and Farr.^^ Sponsler has
followed under the microscope the rate at which cell wall material is
developed as a new cross wall is formed in the growth of green algae.
The material is of carbohydrate origin. Farr traces the cell membrane
formation in young cotton fibers to the existence of cellulosic elliptical
particles covered with thin layers of pectic materials. These may be
freed from the pectins by treatment with hydrochloric acid (sp. gr. 1.19). .
They can neither be regarded as micellae nor as macromolecules.
Three other papers concerning the work of Farr and Eckerson ^s, 39
and Farr and Sisson ^^ give additional material on this subject.
Important studies on the molecular weights of cellulose and cellulose
derivatives have been reported by Kraemer and Lansing.^i Com-
parisons are presented for molecular weight determinations by osmotic
pressure and viscosity measurements, end group determinations, and
ultracentrifugal analysis. The authors describe the latter method as
being the most reliable. The influence of solvation on molecular associa-
tion and molecular weight values for cellulose are discussed. These
range between 60,000 and 180,000.
Kurth and Ritter ^^ have removed the easily hydrolyzable fraction
from the holocellulose of spruce and maple wood by treatment with one
percent sulfuric acid. This gives a fraction which, under the older
methods of analyses, has always been mixed with other wood con-
stituents. It is composed of constituents containing methoxyl, carboxyl,
acetyl, and formyl groups and hydrolyzing to mannose, glucose, galac-
tose, arabinose, and xylose. Salley^^ ^as studied the effect of ferric
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CELLULOSE AND PAPER 363
salts and alkali in carrying on an oxidation of mannitol in aqueous
solution. The factors increasing the rate of auto-oxidation are con-
centration, temperature, and light. In the latter case, the increase in
rate is directly proportional to the light absorbed. Oxidation inhibitors
have no effect on this system. A comparison is drawn to the well-
known behavior of cellulose.
The utilization of bagasse as a source of cellulose has been considered.
Lathrop and Munroe^^ show how the sugar cane may be preserved
during storage by piling the bales in such a manner that the heat of
carbohydrate fermentation is used to raise the temperature of the
interior bales to a pasteurizing temperature. Payne ^^ pulps bagasse by
digesting with two percent nitric acid at 90-100° C. for one hour,
followed by two alkaline treatments. The method is said to be applicable
to large scale production.
A quantitative method for the separation of cellulose acetate, silk,
regenerated cellulose rayons, cotton, and wool has been developed by
Mease and Jessup.**^ After desizing the acetate silk is removed with
acetone, and silk and regenerated cellulose rayon are removed with
calcium thiocyanate solution of 1.20 and 1.36 sp. gr., respectively.
Cotton and wool are determined by the solution of cotton in aluminum
chloride with heat or the solution of the wool in the potassium hydroxide
solution. The method is accurate for each fiber present to within two
percent of the weight of the specimen analyzed.
The physical properties of a series of the cellulose triesters of
homologous fatty acids from the acetates to the stearates, as measured
by Sheppard and Newsome,^*^ show that the cellulose character is pro-
gressively submerged as the length of the side chain is increased. The
structure of the solids is interpreted from x-ray data and by spreading
and wetting experiments. Kirkpatrick *® has made a fire-resistant
cellulose acetate sheet by incorporating 20 percent or more of triphenyl
phosphate or a mixture of triphenyl phosphate and methyl phthalyl ethyl
glycollate. The latter improves flexibility at the expense of fire resis-
tance. Noncombustible fillers may also be incorporated in the latter.
White ^^ describes how to avoid difficulties in the production and appli-
cation of cellulose acetates for the various uses.
A double dyeing method for estimating the increase in specific sur-
face of beaten nitrocellulose has been devised by Phillips,^^ and has
been confirmed by microscopic analysis. This permits a differentiation
impossible by the settling test. Gloor ^^ lists the properties of low
viscosity nitrocellulose of varied nitrogen content. He states that the
film properties of these low viscosity types result from the degradation
of cellulose residues and vary with the nitrogen content, viscosity,
formulation, and plasticizer. McBain, Grant, and Smith ^^ have meas-
ured the viscosity of nitrocellulose in over 100 solvents and solvent
mixtures. They emphasize that the chief factor in the apparent viscosity
of nitrocotton solutions is structural viscosity due to colloidal aggre-
gates of easily varied degree of ramification and dismemberment. Time
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364 ANNUAL SURVEY OF AMERICAN CHEMISTRY
experiments at 55° C. extended to three years have yielded solutions
approaching the viscosity of the pure solvent within a few percent —
an enormous drop in viscosity. In some cases these low viscosities may
again increase and even set to a jell. Four new methods for determining
degree of solvent power are briefly indicated.
Lignin. Phillips ^^ has presented a 51 page survey of the chem-
istry of lignin with 304 literature references. Phillips and Goss ^^
have investigated the lignin isolated from barley straw. Two fractions
are found, one with the formula C40H48O15 ; the other, C40H42O16. The
chemical characteristics of maple and spruce lignin, isolated by various
methods, are described by Harris, Sherrard, and Mitchell.^^ Cold sul-
furic acid lignin is free of carbohydrates and contains all the methoxyl
not accounted for in the carbohydrates of the wood.* Hydrochloric acid
lignin has lost methoxyl and contains carbohydrates. Cuprammonium
lignin also contains carbohydrates. The number of hydroxy! and unsatu-
rated groups from hard and soft wood lignin is different. Results from
chlorination and methylation show that lignin is little changed during
isolation by the sulfuric acid method. There is some evidence that
lignin in wood is combined with carbohydrates. The reason for the
difficulty in the use of Douglas fir for sulfite pulp has been ascribed by
Bailey^® as being due to a difference in the structure of the lignins.
Bailey believes that Douglas fir lignin consists of four rather than three
polymerized coniferyl aldehyde residues in terms of the Klason lignin
structure, and because of this the wood is more difficult to delignify
than spruce. Ammonia lignin has been oxidized by alkaline halogen
solutions. Alkaline iodine oxidation proceeds quantitatively and forms a
compound containing carboxyl groups and iodine^®*; iodoform is also
isolated as one of the products of reaction. Alkaline bromine solutions
yield carbon tetrabromid^. The authors postulate the presence of a
secondary group of the type CH3CH— (OH) in the lignin molecule.
A number of papers relating to the microbiological decomposition of
lignin have appeared. Levine, Nelson, Anderson, and Jacobs ^^
attempted without success to develop a specific lignin-digesting anaerobic
flora. Alkaline lignin when added to an actively digesting sludge pro-
duces no gas, and, when used in conjunction with fermenting corn stalk
flour or packing house sludge, inhibits the gasification of the latter
materials. This is not due to toxic action of the lignin on the bacterial
flora, but to chemical combination with the production of complexes
resistant to microbial decomposition. Boruff and Buswell '""'^ have
investigated the anaerobic fermentation of lignin in cornstalks and
the lignin isolated by four methods, and show that appreciable quantities
ferment to carbon dioxide and methane in the natural state, while
isolated lignin ferments very slowly and incompletely. Waksman and
Smith ^^ deal with the problem of the transformation of the methoxyl
groups of lignin in the decomposition of plant residues. The relation
of this to humus formation in oils, peats, and composts is discussed.
Mitchell and Ritter ®^ have analyzed three fossil woods mined from
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CELLULOSE AND PAPER 365
the Miocene auriferous gravels of California, and find that a marked
decrease has occurred in the extraneous and carbohydrate content of
the wood, while the lignin contents are abnormally high. On the basis
of the original wood, the lignin has decreased less than any other con-
stituents. Decomposition of the cellulose appears to be due to hydrolysis
rather than fungus attacks.
Groundwood. Curran, Schafer, and Pew^^ find that much of
the color in western hemlock groundwood is due to reddish inclusions
present in the ray cells. These inclusions resemble chemically the
material extracted by alkali from the bark and are therefore probably
tannin or tannin derivatives. The fine-fibered portion contains more
coloring matter than the coarse-fibered portion. Bisulfite and hydro-
sulfite improve this color, while certain oxidizing agents in alkaline
solution, especially hydrogen peroxide, are effective bleaching agents
but of doubtful economic value. Lowen and Benson ^^ have prepared
plastics from groundwood pulp, utilizing the pentosans for the produc-
tion of a resinous adhesive to serve as a binder in place of extraneous
adhesives. The products are of excellent appearance and are suitable
for various purposes. They are slightly brittle and not very resistant
to boiling water.
Cooking Process. Aronovsky and Gortner have continued
their series of articles on the cooking process. In Part V ^^ they describe
the use of sodium sulfite and aspen sawdust, in Part VI ^* sodium sul-
fide, and in Part VII ®^ sodium hydroxide and trisodium phosphate.
They consider all these chemicals to be strong pulping agents.
In Part VIII ^^ they tell of the formation of volatile acids when aspen
sawdust is cooked with sodium carbonate for two hours at 170° C.
The production of volatile acids is attributed to saponification. Aronov-
sky ^"^ has summarized these previous reports, especially from the
standpoint of the main components of the residual woods and liquors.
A continuous pulp cooking system has been described by Braun and
Lundberg.^8 The object has been the development of a continuous
cooking, washing, and bleaching system with separate units for each
step. No plants have yet utilized the process.
Sulfite Process. A number of papers have appeared which
describe work on some phase of the sulfite process. The commercial
installation and operation of a new spray type sulfur burner is
referred to by Kress, Swanson, Porter, and Smith.^^ The formation
and dissociation of sulfur trioxide in sulfur burner gases from the
above spray burner has been measured by Browning and Kress.*^^ The
variables covered include temperature, the composition of the gas, and
catalytic effects of various materials of construction. Frank and
Beuschlein "^^ have investigated the equilibrium relations in the system
calcium oxide-sulfur dioxide-water under conditions similar to the raw
acid coming from the absorption towers. Beuschlein and Conrad '^^
have applied the film concept to the operation of sulfite acid towers
and describe the role played by the several fluid films which control
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366 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the rate of sulfur dioxide absorption. Pressure-composition curves are
presented for the system described above.
McGovern and Chidester '^^ present data to show the effect of chip
length upon the time of penetration and pulping of western hemlock
heartwood, the chips ranging from % inch to 1^ inches. Time of
penetration increased in a parabolic manner with increasing chip
length. The optimum strength values were reached in pulps from
chips % io yi inch long, but no significant variation in rate of pulping
was noted. Hrubesky and Chidester '^^ have measured the rate of pene-
tration of calcium bisulfite liquor in western hemlock chips and the time
required to burn the chips under varying conditions. Benson, Erwin,
Hendrickson, and Tershin '^^ pulped Douglas fir by an ammonia base
liquor with and without a pre-treatment with 5 percent ammonia at
temperatures below 70° C. Young Douglas fir and pre-treated Douglas
fir approach spruce and hemlock. Old Douglas fir pulps are distinctly
lower in quality.
Sulfite waste liquor studies have appeared in a considerable num-
ber. Warrick and Holderby '^^ describe recent waste liquor develop-
ments, emphasizing especially the Howard and Paulson processes.
Howard '^'^ al§o has written of his process, in which the waste liquor
is fractionally precipitated with lime, whereby three-fourths of the
pollution loading is removed, while Wells '^^ has described the Paulson
process. Phillips, Goss, Brown, and Reid*^® treat the dry residue of
sulfite waste liquor with ammonia at high temperatures and have investi-
gated the fertilizer value of this ammoniated material containing up to
10.5 percent N. It has some value but is not the equal of either dried
blood or a mixture of sodium nitrate and ammonium sulfate as a source
for mixed fertilizer. O'Dell and Greenlaw ^^ show that under properly
controlled conditions, ponding and aeration will greatly reduce the
biochemical oxygen demand of waste sulfite liquor, thus eliminating
part of its pollutional effect. Pollock and Partansky ^^ describe a
simple and inexpensive method for the determination of sulfur in sulfite
waste liquor and other organic compounds. Leitz, Sivertz, and Kobe ^^
have measured the />H of sulfite waste liquor with the glass electrode and
find a pH of 9.6 to be optimum for the precipitation of organic material
with ammonia. Winiecki ^^ describes the use of "Raylek B" as a road
binder and dust palliative. "Raylek B" is produced by concentrating
waste liquor. The process leaves the material with an acidity about a
fourth as much as vinegar. The material has been satisfactory as a
patching material and is now under test as a binder for permanent road
construction. Kobe and Centenero^^ show that the amount of com-
bustible sulfur in sulfite waste liquor is much below the total sulfur con-
tent. Methods for removing sulfur dioxide from the stack gas are
also discussed.
Billington, Chidester, and Cur ran ^^ have outlined a method for the
conversion of sodium sulfide in the ash obtained from burning waste
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CELLULOSE AND PAPER 367
soda-base sulfite liquor to sodium carbonate which is re-used in the
preparation of fresh cooking liquor.
Alkaline Pulping. An investigation by Holzer ^e of the coloring
matter in pine kraft pulps reveals that this material appears to be
related to the phlobotannins. Analysis shows organic sulfur and
further evidence leads to the conclusion that the material is probably
a sulfur derivative of the phlobotannins. Organic sulfur content in
kraft pulp is dependent upon the sulfidity of the cooking liquor; in
bleached and unbleached pulps the color varies with the sulfur content.
Kress and Mclntyre ^'^ have followed the distribution of sulfur during
the kraft cooking process. In carrying out the work, it was necessary
. for them first to evaluate the methods used in the estimation of sulfide.
Kress and Harrison ^^ find that pulps made from kraft cooks using
improperly settled white liquor have poor strength and color, due
possibly to the presence of mechanically entrained calcium carbonate.
Pillow and Bray ^® have pulped compression wood by the kraft proc-
ess and find, in contrast to normal wood, a lower yield of crude pulp
with poorer physical and chemical characteristics and an increase in
bleach requirements. Gordon and Creitz ®® remove the mercaptans
and alkyl sulfides from the non-condensible gases present in the kraft
relief gases by spraying a solution of hypochlorite into the gases. The
aqueous layer of the condensate as well as the condensate from the
evaporation of the black liquor are similarly treated. The odor is not
entirely removed and the author states it to be unpractical to destroy
all the mercaptans by the alkaline treatment.
Pulp Properties. Lary and Davis ^^ have determined the effect
of a variation in />H between 4 and 9 upon the freeness of chemical
and groundwood pulps. With the chemical pulps, the drainage time
increases as the />H is increased from />H 4 to a maximum in the range
/)H5-6 ; it then decreases to reach a minimum at />H 9. The effects
are of considerable magnitude in the case of samples given the most
refining. With groundwood the effect is quite different; above />H6
the values are erratic, below this the drainage time increases 60 per-
cent in going from />H 4 to />H 4.4.
McGregor ^2 ^^s studied the relation between the physical charac-
teristics of pulp and their chemical components, using two rag pulps,
an alpha pulp, and a Mitscherlich sulfite. These he degraded by vari-
ous means to definite viscosities and then ran strength tests and chem-
ical analyses. There appears to be a definite relation between viscos-
ity and fold quality within the various types of pulp. In general the
relation between the properties of the pulps and the degrading influence
depends upon the type of degradation.
Beating and Hydration. Lewis and Gilbertson®^ find that the
temperature effect in the beating of rag stock is a matter of some
importance on the strength of hand sheets prepared from the stock.
The physical characteristics such as fold, tear, tensile, and Mullen are
much lower for stocks beaten hot than for stocks beaten at lower tem-
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368 ANNUAL SURVEY OF AMERICAN CHEMISTRY
peratures, while the chemical constants bear no relation either to time
or temperature of beating. The effect of beating on fiber structure ,is
described by Weil,^* who indicated the purpose of beating as two fold,
first to bruise the various membranes and damage them in such a way
that the first and subsequent layers of fibrils are loosened without
harming the length of the fiber, and second, to form a fiber debris and
structureless slime or gel which serves to cement the fibers in the
dried sheet of paper.
Bleaching. Henderson ^^ describes the art of bleaching in theory
and in practice, dealing particularly with the basic chemistry of the
reaction between chlorine and lignin. Recent developments in the
bleaching of chemical wood pulps are surveyed by Rue.^® A method
for the determination of available chlorine in hypochlorite solutions
by direct titration with sodium thiosulfate is outlined by Willson.^^
Sizing. Little work of fundamental interest in sizing has
appeared in the literature of the United States during the past two
years. Dreshfield^^ has discussed the agents and methods which may
be used to make paper repellant to different liquids. Various rosin
sizing methods in commercial use have been described, Montgomery
and Batchelor ^^ taking up the Delthirna process ; Kennedy,^^^^ the
Bewoid, and Sinclair ^^^ and Neitzke,^^^ t^^ Bennett size making proc-
cess. Descriptive papers have been published by DeCew ^^'^ and
Stevens.^^^ Sutermeister ^^^ has completed a very excellent review
of the literature of sizing, going back to 1900 and referring to the more
important works prior to that date. Krimmel ^^^ points out the losses
in the manufacture of rosin size milk with a number of hot processes
and gives a practical method for measuring these losses.
Permanence. Work has been continued in the laboratories of
the Bureau of Standards and of the Brown Company on problems
relating to the permanence of papers. Richter ^^"^ describes experi-
mental work carried on in which papers have been exposed to natural
sunlight for periods of time. He finds that losses in tear, tensile
strength, and Mullen are minor as compared with the loss in fold. He
suggests special sizing agents for use in papers so as to enable them to
withstand the action of sunlight more successfully. While the fold-
ing strength of a paper is enhanced by tub sizing with glue, this incre-
ment in fold is largely lost when the papers are exposed to sunlight.
He has likewise exposed papers for an extended period in a circulating
air current maintained at 38° C. He reports that the physical changes
correlate well with the corresponding changes taking place with the
same types of paper subjected to the 100°, 72 hour test. He notes that
severe chemical oxidation of an unbeaten cellulose fiber is reflected in
a marked sacrifice in the stability of the paper produced.
Rasch and Scribner ^^^ report on a series of 33 papers tested for
chemical purity and strength after four years of normal aging. The
folding endurance during this time has undergone marked change.
The papers are placed in about the same order of stability by normal
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CELLULOSE AND PAPER 369
aging as by the accelerated aging test. Scribner ^^^ further reports on
an investigation relating to the preservation of old newspapers. For
retarding decay he recommends the use of Japanese tissue paper or
transparent cellulose acetate sheeting. Weber, Shaw, and Back ^^^
find that the ordinary fumigants, such as hydrocyanic acid gas, carbon
bisulfide, etc., have no significant deleterious effect on the life of tjie
paper and conclude that these can be used safely for killing insect life
in records of permanent value.
Zimmerman, Weber, and Kimberly ^^^ report that the life of written
records depends upon the stability of the ink as well as upon the paper.
Iron gallotannate prepared according to the government formula for
standard writing ink greatly accelerates the deterioration of papers in
the heat test. They recommend an ink made with ammonium-ammonium
oxyierrigallate.
Shaw, Bicking, and O'Leary ^^^ have carried on a study of the
relation of some of the properties of cotton rags to the strength and
stability of experimental papers made from those rags. The results
demonstrate that stable paper can be made from new rags and confirm
the belief that high acidity from excess use of alum in rosin sizing has
a marked deteriorating effect upon paper. They recommend a />H of
5.0 Blaisdell and Minor ^^^ have done some work on the permanence
of poor grades of paper, such as those made from cheap wood pulps.
Of special interest is their conclusion that a marked change of copper
number with oven or light aging may be considered as indicative of a
definite loss of absorbency with natural aging.
Of significance is the description by Farquhar ^^^ of the special edi-
tion of 25 copies of scientific works being printed by the University of
California Press on a permanent 100 percent rag paper. These copies
are being distributed to a selected list of repositories throughout the
world.
Paper. High opacity papers continue to receive attention.
Belcher,^^^ Cyr,^i® and Steele ^^'^ discuss the advantages resultant from
the use of zinc pigments. Smith ^^^ brings out the fact that the zinc
pigments slow up the rate of growth of organisms causing slime and
discoloration. Willets 119-122 reports on the use of titanium oxide as
a pigment and in the last reference takes up in a comprehensive
manner the factors favoring retention in the sheet. Sutermeister 1^3
concludes that the formula for satin white is probably 3 CaO • AI2O3-
• 3 CaS04 • 31 H2O.
The use of rubber latex in paper is reviewed by Townsend i^^ and
by Birchard.125 A method for the de- inking of paper involving the
use of sodium silicate and fatty acids is outlined by Snyder and Mac-
laren.12® For the removal of color from broke, Binns 1^7 recommends
the use of zinc hydrosulfite and outlines the conditions for its use. As
a softener and plasticizer in paper, Leete i^s has used sugar combina-
tions. The application of nitro-cellulose emulsions to paper is described
by Hollabaugh.i2» Rancidity-retarding wrappers may be prepared by
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370 ANNUAL SURVEY OF AMERICAN CHEMISTRY
incorporating colored materials which absorb blue and ultra-violet
light, according to Morgan.^^^
Piper 131 describes a method for removal of oil from oil-impregnated
papers for testing purposes.
Bailey 132 presents a number of photomicrographs of thin paper
sections ; these demonstrate the characteristics of the fiber to fiber bond.
The significant sheet properties for use in developing paper specifica-
tions are listed by Baird.i33 The basic principles of sheet formation
as they relate to the head box and slice have been considered by
Bearce,i34 while Rubin ^^o takes up the factors governing sheet forma-
tion on the Fourdrinier wire. Doughty ^36 outlines the effect of
mechanical treatment of fibers on sheet structure. Fundamental infor-
mation on the drying of paper is presented by McCready ^37, 138 ^nd
by Adams. 130
Anderson i*^ discusses the possibility of manufacturing newsprint
from southern pine under commercial operating conditions. The
southern fibers apparently do not felt as well as the northern spruce
fibers nor are their surface characteristics as good. Lee i*i reviews
the work of Herty and his associates on the pulping of southern pine.
Stamm i^^ and Baker i*3 consider the advantages to be gained by
the use of white water in various mills and on various types of
machines under differing conditions. Chase i*^ states that the acidity
in paper may be measured by determining the H-ion concentration of
the tray water and outlines a method for determining this />H. Minor
and Blaisdell i*** criticize Chase's paper and present data which would
indicate that there is no direct relation between the />H of white water
and that of the distilled water extract of the finished paper, except
under special conditions open to variations for each mill and each
t)rpe of paper. DeCew i*^ has determined the adverse effects of gases
in the manufacture of paper.
Weber and Snyder,!^*^ jj^ ^^e laboratories of the Bureau of Standards,
have published much data on the relation of lithographic papers to
variations in atmospheric humidity and temperature. They find
that the moisture content of these papers is influenced by relative
humidity, temperature, and the history of conditioning. Humidity
changes are the most important. The usual sizing materials have
little influence on the moisture content response of paper to changing
relative humidity, except with respect to the rate. The relation of
sheet properties to register in offset lithography has been discussed by
Weber.i^^ Trial printings of three groups of special papers made in
different mills from different pulps lead to certain conclusions in regard
to the use of chemical wood papers from multi-color offset printing.
These conclusions may be summarized by saying that desirable paper
should have low machine direction coefficient of linear expansion. This
is lowest when the greatest number of fibers are parallel to the machine
direction and the hydration at a minimum which can be controlled in
the mechanical treatment of the fibers.
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CELLULOSE AND PAPER 371
Wehmhoff ^*^ discusses the work of the Ink Resistance TAPPI Sub-
committee regarding methods for evaluating the printing quality of
paper. The committee recommends the adoption of density, oil pene-
tration, oil absorption, and printing smoothness as tentative TAPPI
standard tests.
Pulp Testing. Morgan ^^^ has compared the action of a number
of milling equipments such as have been proposed for strength testing of
pulp. Simmonds and Baird ^^^ have determined some of the variables
in processing pulp in a pebble mill, in a rubber surfaced ball mill, and
in a beater. A detailed comparative study of five diflFerent sheet
machines for pulp evaluation is presented by Doughty and Currah.^^2
Williams ^^^ describes a new, rapid pulp and paper testing outfit, and
Green ^^^ outlines the defects in the design of the sheet-forming device
specified by the TAl^PI tentative standard T205m and compares this
instrument to his own standard sheet mold.
Kress and Brainerd ^^^ have fractionated a series of chemical an,d
mechanical pulps and the isolated fractions have been tested for
chemical and physical properties. They conclude that chemical and
physical properties grow poorer in successively shorter fractions of
unbeaten chemical pulps, while the strength of mechanical pulps
increases with decreasing fiber lengths. They have also investigated
the effect of beating on the nature of the fractions from chemical
pulps. The conclusions were that in the case of bleached pulps the
resistance of pulps to cutting action appears to be related to the purity
of the pulps.
Physical Testing of Paper. The advent of the N. R. A. and the
subsequent establishment of the Paper Industry Authority with its
Central Grading Committee resulted in a very considerable activity
in the field of physical testing of paper. The subject of specifications
and tests and their application to grading has been considered in
papers by Mahler,i56-i58 Strange,i50-i«i Heritage,i62 Carruth,i63
Krimmel,i«4 Briggs,i65 Annis,i66 Stuart,i67. les Plumstead,i69
Wriston,i70 Boyce,"i Bullock,i72 and Addoms."^
The adoption of optical methods for evaluating paper characteristics
in code grading has stimulated a large amount of work, and a number
of papers relating to optical methods for testing paper are worthy of
note in a survey such as this one. Lewis,^*^** i'^^ Michaelson,^*^^ Davis,^*^*^
Hunter,^*^^ and Judd ^'^^ describe various methods for measuring the
brightness and whiteness of paper. By means of one of these instru-
ments, the General Electric Reflectometer, Laughlin and Kress ^^^
have studied the effect of variables encountered in the manufacture of
paper on the brightness of the sheet. They conclude from mill studies
that the paper machine itself presents no difficulty in regard to bright-
ness control. Variations produced by tub sizing and calendering are
likewise practically negligible. The control of brightness appears to
be dependent largely upon the uniformity of raw materials and upon
the filler content.
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372 ANNUAL SURVEY OP AMERICAN CHEMISTRY
The question of the measurement of gloss likewise has received con-
siderable attention and Hunter ^^i' ^^2 and Kress and Morgan ^^^ write
regarding new instruments for measuring the gloss of paper. The
instrument which has been described by the latter, the Oxford Gloss-
meter, possesses distinct advantages over the polarization glarimeter
since it is very little effected by color, brightness, and t)q)e of coating.
The subject of the measurement of opacity has likewise been gone
into rather thoroughly by Judd.^^*"^^^ Dodge and Tarvin ^^"^ show that
the printing quality of newsprint is primarily a function of smoothness,
absorptiveness, and opacity. Instruments are described for measuring
these characteristics. Davis, Roehr, and Malmstrom ^^^ have described
a photoelectric formation tester and Williams ^^^ a finish and formation
tester. A number of papers have also appeared relating to the more
common types of physical testing of paper. Monnberg ^^^ considers
critically the probable error and accuracy of testing. Carson ^^^ writes
of the maintenance, calibration, and use of paper testing instruments,
and in a second paper 1^2 describes the whole problem of the scope of
paper testing.
New or revised TAPPI methods have appeared, including a tentative
revision of method T402m,^®3 "conditioning paper for testing," a tenta-
tive revision of T400m,i®* "sampling paper for testing," and a tentative
revision of T410m,i^^ "basis weight of paper." TAPPI committee
reports include that of the sub-committee on physical tests of paper as
presented by Clark ^^^ and Scribner's report ^^"^ for the paper testing
committee.
Reports have also appeared on the measurement of other character-
istics of paper such as the water resistance of paper and fiber board
by Carson,^^^ a sizing test by Cobb and Lowe,^®^ air permeability by
Carson,200, 201 tj^^ moisture vapor transmission by Tressler and Evers ^^^
and Charch and Scroggie,203 water absorbency by Reese and Youtz,^^
and oil and varnish penetration by Albert.^^s
Methods for studying the stiffness, rigidity, and softness of paper
are described by Minor and Minor 206 and Clark.^o^ a Gurley stiffness
tester has also been described.^os
Several papers on the manufacture and properties of fiber board
have appeared. Arnold 20» has applied the distillation method for the
determination of moisture and consistency in the manufacture of insulat-
ing board. Arnold and Cleaves ^^^ have added zinc chloride to insulat-
ing board in order to retard attack by mold and insects. A method
for counting the plies in solid fiber board has been developed by
Baechler.211 Whittemore, Overman, and Wingfield2i2 describe an
electrical conductivity method for following the drying of board in the
hot press. Jahn ^13 outlines tests carried out on fiber board.
Chemical Testing of Paper. A number of critical papers on the
various methods for the chemical testing of pulp and paper have
appeared. Bump^i^ ^as determined the effect of variation in the
alkaline solution and the time of treatment on the alpha-cellulose deter-
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CELLULOSE AND PAPER 373
mination. The effect of the removal of extraneous materials by the pre-
treatment of wood on the lignin determination has been investigated by
Ritter and Barbour.^is Hendrickson and Benson 216 have used the
determination of lignin as a method for measuring the degree of
cooking.
The TAPPI Non-Fibrous Materials Testing Committee 2i7 has»
approved a method for the analysis of rosin. The proposed revision of
the official TAPPI method for the determination of the amount of
coating of mineral coated paper has been described, as approved by
the TAPPI Paper Testing Committee.^i* That same Committee has
also proposed a tentative standard testing method for the determination
of acid-soluble iron in paper.2i» 'pi^^ analysis of paper for titanium
pigment is outlined by Jarmus and Willetts.220 Methods for the
determination of bleach demand are described by John and Poppe 221
and by Seborg.222 'pj^e determination of the bleach requirement of
pulp by means of its permanganate number is outlined by Wiles.223
Hughes and Acree 224 describe the quantitative estimation of furfural
with bromine, which has an application in the determination of pento-
sans in pulp and paper.
Fiber Identification of Structure. Graff writes in detail on the
estimation of fibers in pulp or paper. He 227 goes into the nature of
the factors involved in the accuracy of fiber analysis. Other papers 22J>.
226 take up new stains for fiber evaluation, which stains apply in the
differentiation of a number of the new types of fibers now appearing in
paper. Kantrowitz and Simmons 228 discuss the relative merits of the
commonly used methods for the determination of bleached and unbleached
fibers in pulp and paper. Calkin 229 calls attention to the importance
of using standard dyes in stains for the differentiation of fibers. Harrar
and Lodewick 230-232 present a detailed series of papers relating to the
identification and microscopy of woods and wood fibers such as are
used in the manufacture of pulp.
Changes in the structure of wood fibers during cooking and bleaching
are described by Carpenter and Lewis.233 The article has been supple-
mented by a number of cinephotomicrographs in which the swelling
analysis has been used to demonstrate the changes which take place in
the structure of fibers as the result of degradation.
Ritter 234-230 j^^s continued his work on the microscopic structure of
cellulose fibers. In addition to presenting a review of existing material
on this subject, he has outlined new evidence on the behavior of fiibers
during the processing of pulp previous to its manufacture into paper
and the relation between this behavior and the inter-fibrillar material.
Measurements on the internal and external swelling of wood fibers
show that a substantial part of the swelling is internal.
Sisson.237 has continued his x-ray study of the crystallite orientation
in cellulose fibers. He explains his latest results with natural fibers on
the assumption that a definite discontinuity of crystal structure exists in
the concentric layers of cellulose in the cell wall.
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374 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Slime and White Water Problems. The production of parch-
ment-like membranes from pulp and paper mill slimes deposited upon
a sheet-forming substratum and treated with glycerol and mineral oil
is described by Sanborn.234 The slime particles appear to have highly
adhesive properties and suggest a probable application as binding and
cementing agents. The same author ^39 ^as described factors which are
involved in slime control in the mill. Holderby and Warrick ^^o have
made a pollutional waste survey of Wisconsin pulp and paper mills and
have compared these findings to those of previous years. They find
that average fiber losses materially increased during 1934.
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89. 'Pillow, M. Y., and Bray, M. W., Paper Mill, 58, No. 51: 15 (1935) ; Paper Trade J.,
101, No. 26: 31 (1935).
90. Gordon, W. O., and Creitz, E. E., Ind. Eng. Chem., 26: 565 (1934).
91. Lary, E. C, and Davis, D. S., Paper Ind., 17, No. 4: 249 (1935).
92. McGregor, G. H., Pacific Pulp and Paper Ind., 9, No. 10: 9; No. 11: 17; No. 12: 20
(1935).
93. Lewis, H. F., and Gilbertson, L. A., Paper Trade J., 100, No. 15: 37 (1935).
94. Weil, C, Paper Ind., 16, No. 12: 842 (1935).
95. Henderson, C. T., Paper Trade J., 98, No. 26: 59 (1934).
96. Rue, J. D., Paper Trade J., 101, No. 18: 87 (1935).
97. Willson, V. A., Ind. Eng. Chem., Anal. Ed., 7: 44 (1935).
98. Dreshfield, A. C, Paper Trade J., 98, No. 5: 23 (1934).
99. Montgomery, A. E., and Batchelor, T. G., Paper Trade J:, 100, No. 1: 25 (1935);
Paper Mill, 57, No. 52: 8 (1934).
100. Kennedy, G. F., Paper Mill, 57, No. 50: 8 (1934); Paper Trade J., 99, No. 26: 31
(1934).
101. Sinclair, H., Paper Trade J., 99, No. 26: 27 (1934).
102. Neitzke, O. F., Paper Trade J., 100, No. 17: 39 (1935).
103. DeCew, J. A., Paper Trade J., 100, No. 11: 44 (1935).
104. Stevens, R. H., Paper Ind., 16: 249 (1934).
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376 ANNUAL SURVEY OF AMERICAN CHEMISTRY
105. Sutcrmeister, E., Paper Trade /., W, No. 4: 18; No. 21: 26; No. 22: 20 (1933); 58,
No. 1: 25 (1934).
106. Krimmel, M., Paper Trade J., 101, No. 1: 44 (1935).
107. Richter, G. A., Ind. Eng. Chem.. 26: 1154 (1934).
108. Rasch, R. H., and Scribner, B. W., Bur. Standards J. Research, 11: 727 (1933).
109. Scribner, B. W., Paper Trade /., 99, No. 14: 31 (1934).
110. Weber, C. G., Shaw, M. B., and Back, E. A., /. Research Natl. Bur. Standards,
15: 271 (1935).
111. Zimmerman, E. W., Weber, C. G., and Kimberly, A. E., /. Research Natl. Bur.
Standards, 14: 463 (1935).
112. Shaw, M. B., Bicking, G. W., and O'Leary, M. J., /. Research Natl. Bur. Standards,
14: 649 (1935).
113. Blaisdell, C. A., and Minor, J. E., Paper Ind., 15: 512 (1933).
114. Farquhar, S. T., Paper Trade J., 98, No. 11: 22 (1934).
115. Belcher, V. A., Paper Trade /., 98, No. 11: 37 (1934).
116. Cyr, H. M., Paper Ind., 16, No. 4: 257 (1934).
117. Steele, F. A., Paper Trade /., 99, No. 12: 105 (1934).
118. Smith, O. A., Paper Trade J., 99, No. 19: 41 (1934).
119. Willets, W. R., Paper Trade /., 100, No. 1: 26 (1935).
120. Willets, W. R., Paper Mill, 58, No. 45: 15 (1935).
121. Willets, W. R., Paper Trade J., 98, No. 6: 37 (1934).
122. Willets, W. R., Paper Trade J., 101, No. 13: 81 (1935).
123. Sutcrmeister E., Paper Ind., 15: 6% (1934).
124. Townsend, H. B., Paper Mill, 57, No. 50: 5 (1934); Paper Trade J., 99, No. 25: 37
(1934).
125. Birchard, W. H., Paper Ind., 15: 561 (1934).
126. Snyder, F. H., and Maclaren, S. F. M., Paper Trade J., 98, No. 17: 46 (1934).
127. Binns, F. W., Paper MUl, 57, No. 49: 3 (1934); Paper Trade J., 99, No. 25: 32 (1934).
128. Leete, J. F., Paper Mill, 58, No. 28: 21 (1935).
129. Hollabaugh, C. B., Paper Trade /., 101, No. 25: 39 (1935).
130. Morgan, W. L., Ind. Eng. Chem., Ill 1287 (1935).
131. Piper, J. D., Ind. Eng. Chem., Anal. Ed., 6: 380 (1934).
132. Bailey, A. J., Paper Trade J., 101, No. 3: 40 (1935).
133. Baird, P. K., Paper Trade J., 98 No. 2: 40 (1934).
134. Bearce, G. D., Paper Trade J., 100, No. 3: 40 (1935).
135. Rubin, M. M., Paper Trade J., 101, No. 6: 39 (1935).
136. Doughty, R. H., Paper Trade J., 101, No. 16: 31 (1935).
137. McCready, D. W., Paper Trade J., 101, No. 13: 63 (1935).
138. McCready, D. W., Paper Trade J., 101, No. 13: 66 (1935).
139. Adams, F. W., Paper Trade J., 98, No. 1: 38 (1934).
140. Anderson, L. C, Paper Trade J., 98, No. 9: 31 (1934).
141. Lee, J. A., Chem. Met. Eng., 41, No. 8: 429 (1934).
142. Stamm, F. C, Paper Trade J., 98, No. 15: 39 (1?34).
143. Baker, C. M., Paper Mill, 57, No. 3: 4 (1934).
144. DeCew, J. A., Paper Trade J., 100, No. 5: 31 (1935).
145. Cniase, G. C, Paper Trade /., 98, No. 22: 42 (1934).
146. Minor, J. E„ and Blaisdell, C. A., Paper Ind., 16: 401 (1934).
147. Weber, C. G., and Snyder, L. W., Bur. Standards J. Research, 12: 53 (1934).
148. Weber, C. G., /. Research Natl. Bur. Standards, 13: 609 (1934).
149. Wehmhoff, B. L., Paper Trade J., l(K), No. 6: 41 (1935).
150. Morgan, H. W., Paper Trade J., 98, No. 15: 44 (1934).
151. Simmonds, F. A., and Baird, P. K., Paper Trade J., 98, No. 20: 33 (1934).
152. Doughty, R. H., and Curran, C. E., Paper Trade J., 97, No. 25: 38 (1933).
153. Williams, F. M., Paper Mill, 58, No. 34: 19 (1935).
154. Green, A. B., Paper Ind., 17, No. 3: 164 (1935).
155. Kress, O., and Brainerd, F. W., Paper Trade J., 98, No. 13: 35 (1934).
156. Mahler, E., Paper Mill, 57, No. 8: 32 (1934).
157. Mahler, E., Paper Mill, 57, No. 42: 1 (1934).
158. Mahler, E., Paper Mill, 58, No. 47: 6 (1935).
159. Strange, J. G., Paper Trade J., 99, No. 21: 35 (1934) ; Paper Mill, 57, No. 48: 6 (1934).
160. Strange, J., Pac. Pulp Paper Ind., 9, No. 11: 9 (1935).
161. Strange, J. G., Paper Mill, 58, No. 52: 15 (1935); Paper Trade J., 101, No. 26: 21
(1935).
162. Heritage, C. C, Paper Trade J., 98, No. 17: 51 (1934).
163. Ca-ruth, H. P., Paper Mill, 57, No. 8: 28 (1934).
164. Krimmel, M., Paper Trade J., 98, No. 16: 33 (1934).
165. Briggs, L. J., Paper Trade J., 98, No. 16: 38 (1934).
166. Annis, H. M., Paper Trade J., 100, No. 10: 43 (1935).
167. Stuart, N. H., Paper Trade J., 98, No. 16: 41 (1934).
168. Stuart, N. II., Paper Trade J., 98, No. 17: 48 (1934).
169. Plumstead, J. E., Paper Trade /., 98, No. 5: 43 (1934).
170. Wriston, H. M., Paper Mill, 57, No. 8: 60 (1934).
171. Boyce, C. W., Paper Mill, 57, No. 8: 24 (1934).
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CELLULOSE AND PAPER 177
172. Bullock, W. B., Paper Mill, 57, No. 10: 6 (1934).
173. Addoms, C, Paper Mill, 57, No. 8: 18 (1934).
174. Lewis, L. C, Paper Mill, 57, No. 25: 20 (1934); Paper Trade /., 98, No. 26: 71
(1934).
175. Lewis, L. C, Pa/»^r Trad^ /., 101, No. 6: 36 (1935).
176. Michaelson, J. L., Gen. Elec. Rev., 38, No. 4: 194 (1935).
177. Davis, M. N., Paper Trade /., 101, No. 1: 36 (1935).
178. Hunter, R. S., Paper Trade J., 100, No. 26: 37 (1935).
179. Judd, D. B., Paper Trade J., 100, No. 21: 40 (1935).
180. Laughlin, E. R., and Kress, O., Paper Trade J., 100, No. 8: 110 (1935).
181. Hunter, R. S., Paper Trade J., 99, No. 7: 38 (1934).
182. Hunter, R. S., Rayon and Melliand Tevtile Monthly, 15: 283 (1934).
183. Kress, O., and Morgan, H. W., Paper Trade /., 100, No. 26: 41 (1935).
184. Judd, D. B., Bur. Standards J. Research, 12: 345 (1934).
185. Judd, D. B., /. Research Natl. Bur. Standards, 13: 281 (1934).
186. Judd, D. B., Paper Trade /., 101, No. 5: 40 (1935).
187. Dodge, W. G., and Tarvin, C. E., Paper Trade J., 100, No. 5: 38 (1935).
188. Davis, M. N., Roehr, W. W., and Malmstrom, H. E., Paper Trade /., 101, No. 4:
31 (1935).
189. WUliams, F. M., Paper Trade J., 98. No. 15: 41 (1934).
190. Monnberg, R., Paper Trade J., 98, No. 12: 41 (1934).
191. Carson, F. T., Paper Ind., 16: 621 (1934).
192. Carson, F. T., Paper Trade J., 101, No. 8: 31 (1935).
193. TAPPI, Paper Trade J., 99, No. 21: 38 (1934).
194. TAPPI, Paper Trade J., 99, No. 21: 41 (1934).
195. TAPPI. Paper Trade J., 99, No. 21: 42 (1934).
196. Clark, J. d'A., Paper Trade /., 98, No. 14: 44 (1934).
197. Scribner, B. W., Paper Trade J.. 98- No. 12: 47; No. 13: 39 (1934).
198. Carson, F. T., Paper Trade /., 98, No. 21: 36 (1934).
199. Cobb, R. M., and Lowe, D. V., Paper Trade J.. 98, No. 12: 43 (1934).
200. Carson, F. T., Bur. Standards J. Research, 12, No. 5- Sff7 (1934).
201. Carson, F. T., Bur. Standards J. Research, 12, No. 5: 567 (1934).
202. Tressler, D. K., and Evers, C. F., Paper Trade J., 101, No. 10: 33 (1935).
203. Charch, W. H., and Scroggie, A. G., Paper Trade /., 101, No. 14: 31 (1935).
204. Reese, S. W., and Youtz, M. A.. Paper Trade /.. 100, No. 7: 33 (1935).
205. Albert, G. A., Paper Trade J.. 101, No. 11: 31 (1935).
206. Minor, C. A., and Minor, J. E., Paper Ind., 17: 35 (1935).
207. Clark, J. d'A., Paper Trade /., 100, No. 13: 41 (1935).
208. Gurley, R. D., Paper Trade /., 99, No. 25: 43 (1934).
209. Arnold, L. K., Paper Trade J., 98, No. 1: 40 (1934).
210. Arnold, L. K., and Cleaves, D. L., Paper Trade /., 98, No. 24: 31 (1934).
211. Baechler, R. H., Fibre Containers. 20, No. 6: 31 n^3S).
212. Whittemore, E. R., Overman, C. B., and Wingfield, B., Ind. Eng. Chem., 27: 831
(1935).
213. Jahn, E. C, Paper Trade J., 101, No. 12: 34 (1935).
214. Bump, C. K., Ind. Eng. Chem., Anal. Ed., 6: 223 (1934).
2a5. Ritter, G. J., and Barbour, J. H., Ind. Eng. Chem., Anal. Ed., 7: 238 (1935).
216. Hend-ickson, J., and Benson, H. K., Pac. Pulp Paper Ind., 8, No. 3: 10 (1934).
217. TAPPI, Paper Trade J., 98, No. 13: 33 (1934).
218. TAPPI, Paper Trade J., 98, No. 1: 37 (1934).
219. TAPPI, Pat>er Trade J.. 98, No. 3: 37 (1934).
220. Jarmus, J. M., and Willets, W. R., Paper Trade /., 98, No. 1: 41 (1934).
221. John, H., and Poppe, F. W., Paper Trade /., 99, No. 9: 36 (1934).
222. Seborg, C. O., Paper Trade J., 98, No. 8: 109 (1934).
223. Wiles, R. H., Paper Trade /.. 98. No. 11: 34 (1934).
224. Hughes, E. E., and Acree, S. F., Ind. Eng. Chem., Anal. Ed., 6: 123 (1934).
225. Graff, J. H., Paper Mill, 57. No. 25: 22 (1934); Pat>er Trade J., 99, No. 1: 31 (1934).
226. Graff, J. H., Paper Trade J., 100, No. 16: 45 (1935).
227. Graflf, J. H., Paper Trade J., 101, No. 2: 36 (1935).
228. Kantrowitz, M. S., and Simmons, R. H., Paper Trade J., 98, No. 10: 46 (1934).
229. Calkin, J. B., Paper Trade J., 100, No. 3: 35 (1935).
230. Harrar, E. S., and Lodewick, J. E., Paper Ind., 15, No. 11: 630 (1934).
231. Ha-rar, E. S., and Lodewick, J. E., Paper Ind., 16, No. 2: 103 (1934).
232. Harra-, E. S., and Lodewick, J. E., Paper Ind., 16, No. 5: 327 (1934).
233. C'lrpenter, C. H., and Lewis, H. F., Paper Trade J., 99, No. 3: 37 (1934).
234. Ritter, G. J., Paper Ind., 16, No. 3: 178 (1934).
235. Ritter, G. J., Rayon & Melliand Textile Monthly, 16: 522, 606 (1935).
236. Ritter, G. J., Paper Trade J.. 101, No. 18: 92 (1935).
237. Sisson, W. A., Ind. Eng. Chem.. 27: 51 (1935).
238. Sanborn, J. R., Ind. Ena. Chem., 26: 532 (1934).
239 Sanborn, J. R., Paper Mill, 57, No. 49: 9 (1934).
240* Holderby, J. M., and Warrick, L. F., Paper Trade J., 101, No. 3: 19 (1935).
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Chapter XXII.
Synthetic Plastics.
GUSTAVUS J. ESSELEN AND WALTER M. ScOTT,
Gustavus J. Esselen, Inc.,
Boston, Mass,
In view of the fact that the last review of Synthetic Plastics
appeared in Volume 7 for the year 1932, this present survey includes
the years 1933, 1934, and 1935. The material selected for discussion
in this chapter includes all synthetic compounds of a plastic or
semi-plastic nature with the exception of the cellulose esters and
ethers. These compounds are commonly designated by the term
"Synthetic Resins."
Two excellent reviews ^' ^ of the chemistry of these resins have
been published during the period in question, and this subject has
been exhaustively covered in two volumes published by Ellis ^ in
1935. Nevertheless, the actual progress in the chemistry of syn-
thetic plastics has been reflected to a much greater extent in the
patent literature than in any of the scientific journals. Therefore,
it is from the former source that most of the information recorded
in this chapter was derived.
The synthetic production of resinous materials is practically
always accomplished by either of two general classes of chemical
interactions; namely, polymerization and condensation. It is under
these headings that the developments during the past three years
will be discussed. Sometimes both types of reaction are involved
as when an already ploymerized substance condenses with some
other material.
Polymerization
The term "polymerization," as it is used in this review, compre-
hends those processes in the course of which a more or less con-
siderable number of similar molecules unite to form larger com-
plexes. The degree of polymerization is influenced by the nature
of the unsaturated linkages and the substituent groups adjacent to
these linkages, by heat, by light, by pressure, and by the presence
or absence of a great variety or catalysts. All of these factors will
be discussed in connection with the various groups listed below.
Compounds With a Triple Bond ( — C = C — ). Acetylene
(CH : CH) is capable of polymerization under certain conditions
378
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SYNTHETIC PLASTICS 379
with the formation of products with a definite resinous character.
There is a certain amount of danger inherent in this reaction,
because of the possibility of forming compounds of an explosive
nature. Calcott and Downing^ have discovered that the formation
of explosive compounds during the polymerization of acetylene
was inhibited by performing the reaction in an inert medium, such
as nitrogen. A catalyst ^ for producing polymers from acetylene
has been formed from materials including a cuprous salt, such as
cuprous chloride, and an ammonium salt, such as ammonium chlo-
ride, together with a non-aqueous solvent for the cuprous salt, such
as ethyleneglycol. In a study of the efficiency of carbon dioxide as
a radiochemical catalyst for the polymerization of acetylene,^ it
was determined that only 30 percent of carbon dioxide ionization
was used in promoting the reaction.
Methylacetylene (CH • CCH3) has been polymerized to a white
solid by exposure to ultra-violet light.*^
The polymerization of vinylacetylene (CH2:CHC : CH) has
been investigated by members of the Du Pont organization.^"^^ It
was shown that vinylacetylene can undergo at least three distinct
types of polymerization as follows :
Type Catalyst Resultant Polymer
A Quprous Acetylene
chloride tetramer (CH, : CHC i C-CH : CHCH : CH,)
B None Cyclobutene
derivative (CH ; CCH-CHC • CH)
I I
C Acids Styrene (CeH^CHrCH,)
It was inferred that the higher polymers had polycyclobutene-
cyclobutane structures. Divinylacetylene has been partially hydro-
genated in the presence of a nickel catalyst and the resulting prod-
uct was polymerized by heating in the presence of benzoyl peroxide
to obtain a product of good stability to light.
Halogen derivatives of vinylacetylene were also polymerized.^^, 13
2-Iodo-l-vinylacetylene (CH2:CHC • CI) formed a hard resin-like
mass which deflagrated when struck, emitting iodine vapor and
clouds of heavy brown smoke. The polymerization of l-halo-2
vinylacetylenes could be accelerated by ultra-violet light, benzoyl
peroxide, or ozonides. Chloro-, bromo-, and iodo-polymers have
been prepared. The chloro derivative formed the least explosive
polymer.
Porous materials such as cloth, paper, or wood have been impreg-
nated with derivatives of vinylacetylene and the material was then
subjected to superatmospheric pressure to cause polymerization of
the occluded compound.^^ Other products suitable for the impreg-
nation of paper, as well as for the manufacture of safety glass.
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380 ANNUAL SURVEY OF AMERICAN CHEMISTRY
have been obtained by the polymerization of vinylethinylcarbinol
[CHg: CH(CH i C)CHOH] in the presence of suitable catalysts.^^
Compounds With a Single Double Bond (-CH = CH-). Poly-
mers of vinyl esters, such as the chloride and acetate, have become
important factors in the synthetic resin industry and have conse-
quently been the subject of considerable study. The mechanism of
the polymerization was first investigated by Staudinger in 1927 and,
according to the review published by Allen, Meharg, and Schmidt 2
in 1934, the following structure is quite generally ascribed to the
polymers (R denoting the chloride or acetate radical) :
R H R H R H
-C-C-C-C-C-C-,
H H H H H H
Morrison and Shaw ^^' ^"^ have investigated the catalysts and con-
ditions influencing the formation of vinyl acetate and ethylidene
diacetate from the direct combination of acetylene and acetic acid.
The progress of the photopolymerization of vinyl acetate has been
followed by a determination of the iodine number with Wijs solu-
tion.18 Vinyl chloride and vinyl acetate have been conjointly poly-
merized ^^ with the aid of various catalysts, notably peroxides. In
one case 20 acetyl benzoyl peroxide has been directly formed in the
reaction mixture by passing dry air or oxygen through a mixture
of benzene and acetic anhydride. In addition to the peroxides, a
catalyst-assisting material,^! such as lead, tin, or aluminum, has
been used. A polymerized mixture of vinyl chloride and vinyl ace-
tate has been made more resistant to the influence of heat and
exposure 22 by including in the reaction a small proportion of hexa-
methylenetetramine. Polymerized mixtures of vinyl chloride and
vinyl acetate have been fractionated ^3 by treating them with
selected solvents in which the desired fractions were insoluble.
The polymerized mixture has been obtained in the form of a mold-
ing powder 2* by dissolving it in acetone, treating the solution with
ammonia of at least 5 percent concentration with rapid agitation,
and then precipitating a powder by adding hydrochloric acid.
The polymerization of vinyl esters and similar unsaturated com-
pounds has been accomplished under the influence of extremely
high pressures, such as 2000 to 12,000 atmospheres.25 The fusi-
bility and solubility of the polymerized esters has been diminished ^^
by precipitating them from solution in the presence of an aqueous
solution of alkali, whose strength was not sufficient to cause appre-
ciable hydrolysis of the resin. Low viscosity vinyl polymers have
been obtained 2"^ by polymerizing the acetate and the chloride in
the presence of an acid whose deleterious action is counteracted as
much as desired by the addition of ethylene oxide. The character-
istics of the vinyl ester polymers have been further modified by the
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SYNTHETIC PLASTICS 381
presence of rubber,^^ rosin or a rosin ester,^® ester gum and drying
oils such as linseed oil or China-wood oil.^^' ^i
Various applications of the polymerized vinyl acetate and chlo-
ride have been proposed. A solution of polyvinyl acetate in ethyl
lactate has been used as a varnish for new and old paintings.^^
Vinyl resins have been used for phonograph records,33. 34 fQj. ^g^.
tures,35 for protective coatings,3«. 37 ^nd for the impregnation of
paper 38 and fabrics.3^
Vinyl compounds other than the acetate and chloride have also
been studied. A substantially chlorine-free resin has been obtained
by reacting vinyl chloroacetate with an alkali metal salt of an
alcohol, phenol, or carboxylic acid and polymerizing the resultant
product.^^ Divinyl ether has been polymerized to a highly viscous,
resinous material by heating it at 70 to 150° C. for 20 to 24 hours.^i
A product suitable for use in lacquers and in molded products has
been obtained by heating vinylnaphthalene to below its decompo-
sition point (i.e., about 300° C.).*2
Styrene (vinylbenzene) is capable of polymerization with the
formation of hard glass-like resins. These resins have found
numerous applications in industry. Houtz and Adkins ^3 have fol-
lowed the course of the polymerization of styrene by determina-
tions of the viscosity of the solution, and the weight and specific
viscosity of the resultant polystyrene. The polystyrene chains
of greatest length, as measured by the specific viscosity, were
formed in an atmosphere of nitrogen at 110° C. Certain per-
oxides (especially diisobutylene ozonide) were much more active
catalysts than ozone. Crude styrene has been polymerized by heat-
ing it in the presence of benzoyl peroxide formed in situ from
ozone and benzene.^^ Styrene will even polymerize in the absence
of ozone but at a diminished rate.^^ Polystyrene, after precipita-
tion and drying, retained its capacity to add more styrene with the
formation of chains of greater length. Polymerized styrene ^^ has
been found particularly suitable for making acoustic diaphragms
such as those of telephone transmitters and microphones.
Those resins obtained by the polymerization of indene and of
cumarone have been known for many years. The structure of poly-
indene has been represented as follows:^
H
The structure of polycumarone is similar with an — O— replacing
the — CH2— group.
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382 ANNUAL SURVEY OF AMERICAN CHEMISTRY
A recent patent ^'' stated that cumarone may be polymerized,
with the aid of a catalyst such as sulfuric acid, in the presence of a
liquid diluent, such as a petroleum fraction which is inert to the
polymerizing reaction and is a solvent for the resulting resin but a
non-solvent for the catalyst. In the formation of resins of the
cumarone-indene type, polymerization of the initial materials has
been effected in the presence of an absorbent earth, such as fuller's
earth, and an acid ferric sulfate.'*^
Acrylic acid (CH2:CHCOOH) and its derivative^ have been
transformed by polymerization into very interesting resins, many
of them of a hard, colorless, glass-like nature. However, most of
the recent investigations along this line have been carried out in
countries other than the United States. One recent United States
investigation ^® has revealed that a bubble-free polymer of an
acrylic or alkacrylic acid may be obtained by heating.it until the
temperature of at least some portion of the mass approaches the
temperature of bubble formation, then cooling until the reaction
is substantially stopped and again heating. and cooling alternately.
Compositions for the production of sound-records ^^ have been pro-
duced from thermoplastic resins obtained by the polymerization of
acrylic acid, alkacrylic acid or their esters, nitriles, or amides.
Polymerization products of esters of ethylenedicarboxylic acids,
such as fumaric, maleic, citraconic, and mesaconic acids,^^ have
been used conjointly with polymerized vinyl esters or styrene.
Compounds With Conjugated Double Bonds. The polymers of
unsaturated organic compounds of this class are distinguished by
the fact that they are more rubbery than resinous. The most
important member of this group is Chloroprene, chemically desig-
nated as 2-chloro-l,3-butadiene (CH2:CC1CH:CH2), whose poljrmer,
Duprene, has been developed by E. I. du Pont de Nemours & Com-
pany as a substitute for rubber. The basic patents on the prepara-
tion and polymerization of the chlorobutadienes were issued in
March, 1934.^2
The structure of polychloroprene has been represented as fol-
lows:^
CI CI CI
C-C:C-C-C-C:C-C-C-C:C-C
Ha H H, H, H H, H, H H,
Williams and Walker ^^ have studied the effect of oxygen and
water on the polymerization of Chloroprene. They concluded that
oxygen increased the rate of polymerization of Chloroprene, but
that it was not necessary for either the polymerization to a-poly-
chloroprene or for the conversion of a to u-polychloroprene during
vulcanization. The rapid polymerization in emulsions was due to
the nature of the polar interfaces and to their distance apart rather
than to the increased surface of accelerating action of the dispers-
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SYNTHETIC PLASTICS 383
ing agent. In the commercial application of the Chloroprene plas-
tic polymer,^^ the scorching of this polymer has been guarded
against by mixing it with a plastic, elastic reaction product of an
aromatic compound, such as benzene, with ethylene chloride.
In the polymerization of the related compound, 2-methyl-l,3-
butadiene (CH2:C(CH3)CH :CH2), commonly known as isoprene,
an insoluble polymer was largely formed when the aluminum chlo-
ride catalyst was in the solid state. When the aluminum chloride
was put in solution as a complex in the isoprene, a soluble polymer
was largely formed.^^ The homogeneous thermal polymerization
of isoprene has been investigated in the temperature range of 286.5
to 371° C. at pressures ranging from 212 to 739 mm.^®
The chlorine derivatives of butadiene have been the subject of
exhaustive studies.^"^ The polymerization of 2,3-dichloro-l,3-buta-
diene was inhibited by hydroquinone and accelerated by air or ben-
zoyl peroxide. The polymer was an opaque, tough, hard mass,
non-plastic and lacking in extensibility. l,2,3-Trichloro-l,3-buta-
diene polymerized very slowly to form a dark-colored, rather soft
and friable mass. The speed of spontaneous polymerization of the
chlorobutadienes was graded as follows: 2,3-» 2-1:^ 1,2,3- > 1-^
1,2,3,4-chloro. Only the second member of the series (Chloro-
prene) yielded a definitely rubber-like polymer.
The preparation and polymerization of other butadiene deriva-
tives has been reported by Coffman ^^ and Dykstra.^^ Among
those studied were 4-cyano-l,3-butadiene and the oxyprenes, 2-eth-
oxy-l,3-butadiene and 2-butoxy-l,3-butadiene. As substitutes for
rubber the polymers of these oxyprenes were inferior to poly-
chloroprene.
The polymerization of unsaturated organic compounds with con-
jugated double bonds has been studied by Starkweather ^^ at pres-
sures ranging from 2000-9000 atmospheres and temperatures rang-
ing from 20 to 74° C. At about 6000 atmospheres an increase of
1000 atmospheres doubled the rate of polymerization. The rate
was increased by substituent groups in the 3- or 2-position in the
order alkyl, phenyl, chlorine, bromine, iodine. In the a- or 1-
position, halogens were less effective and alkyl groups were
inhibitory.
Werntz ^^ has investigated the addition of organic carboxylic
acids to vinylacetylene. Acetic acid reacted with vinylacetylene in
the presence of a catalyst, such as a mercury salt or boron fluoride,
to give l,3-butadienyl-2-acetate. The corresponding formate,
chloroacetate and butyrate were similarly formed. These esters
were polymerized under normal conditions or under high pressure
or in emulsions, with the formation of a rubber-like material.
Unlike Chloroprene, the acetate, when polymerized under the influ-
ence of peroxide catalysts, yielded resinous products.
A product which was suitable for coating compositions has been
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384 ANNUAL SURVEY OF AMERICAN CHEMISTRY
produced by heating furylethylene in the presence of a catalyst
such as benzoyl peroxide and discontinuing the heating before the
polymer became insoluble in toluene.^^
Mixtures of Olefins and Diolefins. The polymerization of mix-
tures of unsaturated hydrocarbons obtained from cracked petro-
leum distillates was first reported by Thomas and Carmody in
1932.^' ®* The resins obtained in this manner offered possibilities
for use in varnishes and were of particular commercial interest
because of their low cost.
These mixtures of unsaturated hydrocarbons have been poly-
merized by heating at 25 to 35° C. in the presence of aluminum
chloride as a catalyst,^^ and also in conjunction with an alkyl ben-
zene, if so desired.^^ Unsaturated components of cracked petro-
leum distillates boiling below 230° C. have been polymerized to
products boiling at 300° C. or higher and oils of lower boiling point
were then separated from the polymers.^"^ Compounds transparent
to light in a layer thickness of 2 inches and having drying properties
equal to vegetable oils have been prepared by fractionating unre-
fined vapor-phase cracked gasoline and polymerizing the lighter
condensable fraction having a boiling point not over 112° C.^^ An
oil such as a crude coal-tar naphtha has been heated with lead
oxide, then distilled and treated with a polymerizing agent, such as
sulfuric acid, to obtain light-colored varnish resins.^^ Resinous
material has been formed from petroleum sludge by heating the
sludge and treating it with sodium chlorate or other similar agent J*^
Unsaturated Linkages With Elements Other Than Carbon.
Lactide (CH3CH<^^q>CHCH3) has been polymerized by heat-
ing it at temperatures ranging from 250° C. to a temperature
approaching that at which decomposition of the polymerized prod-
uct began to occur. The polymerized product was further heated
within this temperature range and at a pressure below 100 mm. of
mercury, in order to remove monomeric lactide by distillation."^!
It has been reported that bromoalkyldimethylamines polymerize
readily to give products which are hygroscopic and vary in physical
state from resinous gums through glass-like products to amor-
phous solids.'^^
Condensation.
The term "condensation," as used in this review, distinguishes
those polymerization processes, usually involving two or more com-
pounds, in which there is a separation of some substance, such as
water, as a by-product of the reaction. Within the wide limits of
this definition, condensation includes those processes ordinarily
described as esterification, etherification, lactone and anhydride
formation, oximation, etc. As in the case of straight polymeriza-
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SYNTHETIC PLASTICS 385
tion, condensation is promoted by a great variety of catalysts, as
is indicated in connection with the various groups listed below.
Phenol With Formaldehyde. The mechanism of the phenol-
formaldehyde condensation has been the subject of considerable
study ever since Baekeland developed this reaction on a commer-
cial scale. In the excellent review of this work by Allen, Meharg,
and Schmidt,^ the great variety of reactions possible between
phenol and formaldehyde either in neutral, acid, or alkaline solu-
tions, and either with phenol or formaldehyde in excess, are repre-
sented by the following equations:
(a) Alkaline reaction = phenol alcohol
OH OH
-6'
l+CHaO^ ^' |CH,OH
(b) Alkaline or acid reaction = Novolak
OH OH OH
CH,OH_^ _^ +H.0
(c) Alkaline reaction = Resol (Bakelite A)
OH OH OH OH
CHaOH
+H,0
{d) xResol-fyResol = Resit (Bakelite C)+ water
{e) xNovolak -f y formaldehyde = Resit + water
If the reactions represented by equations (a) and (b) are con-
sidered as a unit, one molecule of phenol has reacted with 0.5 mole-
cule of formaldehyde. As the ratio approaches 1 to 1 the chains
which constitute the Novolak become longer, resulting in a resin of
higher melting point, of lesser solubility in caustic or alcohol, and
finally of complete infusibility and insolubility as the 1 to 1 limit
is reached.
In the limited space of this review it is possible to give only a
brief summary of the developments in the phenol-formaldehyde
resins during the years 1933, 1934, and 1935. The initial condensa-
tion of phenol with formaldehyde has been performed in the pres-
ence of strong alkaline catalysts, such as sodium hydroxide and
potassium carbonate, and the reaction mixture has then been
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386 ANNUAL SURVEY OF AMERICAN CHEMISTRY
neutralized by such acids as sulfuric, hydrochloric/^ lactic,*^^ tar-
taric,''^^ or succinic/® In certain cases the entire condensation has
been carried out in an alkaline medium, e. g., in the presence of
aniline,"» '^^ ammonia,*^^ hexamethylenetetramine,®^ triethanol-
amine, or trisodium phosphate.^^ The condensation has been halted
at the desired stage by running the condensate directly into water
to form a suspension ®2 or by the addition of a relatively cold sol-
vent, whose boiling point is above 100° C, such as butyl alcohol
or amyl acetate.^® The condensation products have been freed
from uncombined phenol by distillation at a temperature of 140°
C. or higher in the presence of high-boiling non-resinous organic
fluxing compounds such as glycerol, ethyleneglycol, or phthalic
esters.^3 Transparent phenol-formaldehyde resins have been
formed by adding to the condensation a decolorizing agent con-
sisting of a mixture of acetic acid, camphor, glycerol, and hydro-
chloric acid. 8^ The condensate has been hardened while it was
still liquid and hot by adding a slight excess of oxalic or phos-
phoric acid.^^ Products of high brilliancy have been obtained by
the addition to the partially condensed mixture of about 0.5 percent
of an oxidizing agent, such as ammonium chromate or potassium
permanganate.^®
The phenol-formaldehyde condensates have been modified for
coating purposes by including in the condensation certain oils
such as linseed oil^"^' ®^ wood oil,^^ or tung oil,^^ as well as certain
natural resins, such as rosin ®i or the glycerol ester of a
natural resin acid.^^ ^ resin which may be hardened by heating has
been formed from phenol, formaldehyde, and an alkyl ester of citric
acid which served as a plastifier.^^ Oil-soluble synthetic resins have
resulted from the condensation of phenol and formaldehyde with
bis-(4-hydroxyaryl) dialkylmethane ketone.®^ Tests have been
described in which a part of the linseed oil in typical house paints
was replaced with tung oil-phenolic resin varnishes. After over 2
years exposure the indications were that weathering would result
in chalking rather than checking or cracking.^^ It has been deter-
mined that the hardness and speed of drying of phenolic-resin var-
nishes were proportional to the melting point of the resin.^® Var-
nishes must be free from the initial condensation products of phenol
and formaldehyde.^*^ For varnishes, the non-heat-hardening type
of phenolic resin has been found superior to the heat-hardening
type, in that the former is susceptible to better control during
cooking and to less yellowing.®^
The adaptation of phenol-formaldehyde condensation products to
molding compositions has received considerable attention in the
period covered by this review. The phenolic resins have found
continued use as binders in the production of toothed gears,®®* ^^
threaded caps,^^^ and large plant equipment where resistance to
acid was desired.^^^ fhe resinous binder has been incorporated
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SYNTHETIC PLASTICS 387
with fillers, such as asbestos, mica,^^^' ^^* wood flour,i<>5, loe and
fabrics of various kinds. A molding composition has been formed
by including barium phenoxide in the reaction mixture and then
incorporating a filler in the condensate.^^*^ Bakelite resinoid has
been used as a mounting medium for small metallographic speci-
mens and metal powders.^^® The molded Bakelite products have
been of considerable interest for electrical insulation. Fibrous
material, such as paper, has been impregnated with the resinous
condensate to form a product suitable for electric insulation.^^*®
The electrical conductivity, dielectric strength, direct-current resist-
ance and power factor of various types of Bakelite materials have
been determined. It has been shown that all three tests were
required to describe completely the electrical properties of these
resins.iiO' ^^^
Phenolic Mixtures with Formaldehyde. In many cases it has
been found expedient to substitute in place of the purified phenol,
certain cruder mixtures containing phenol as one constituent. For-
maldehyde has been condensed with "phenol oir',^^^ crude cresylic
acid,^^^' ^^* and with a low-temperature coal tar distillate either
in an acid,^^^ or alkaline solution.^^^"^2o j^ one modification of this
process, an intermediate phenol-formaldehyde resin was treated
with the addition of an alkaline solution of the high-boiling tar acid
components of a low-temperature coal tar together with at least a
molecular equivalent of formaldehyde.^21
Resinous compositions substantially not penetrable by short-
wave rays, such as x-rays or radium rays, have been prepared by
the condensation of an aldehyde with a phenolic compound of lead,
uranium, thallium, or thorium.^22
Homologues of Phenol with Formaldehyde. Formaldehyde has
been condensed with a dihydroxybenzophenone to form a synthetic
resin compatible with cellulose esters ^^3 and with m- and />-cresols
in the presence of a coal tar acid containing a substantial amount
of xylenol.^24 ^ xylenol-formaldehyde-magnesium oxide resin has
been formed by heating and by vacuum drying. This resin softened
but did not flow on a hot plate at atmospheric pressure, whereas
it flowed freely and set to a hard mass when hot-pressed at about
165° C.^26 Resorcinol-formaldehyde resins have been found suit-
able for sound records. They may be plasticized with rape-seed
oiP26 Qr modified by adding to the condensation cresol in
which />-nitraniline is dissolved.^27 They have also been emulsi-
fied by the use of beeswax in the presence of an alkaline salt such
as borax.^28
Oil-soluble resins have been prepared by condensing formalde-
hyde with thymol,^^® p-teri-hvLtyl- or amylphenol,^3o ^-crotyl- or
allylphenol,^^^ />-cyclohexylphenol,^32 q_ qj- ^-hydroxybiphenyl,^^^
xylenol ^^* or a neutral alkyl ether of xylenol.^^^ The condensates
were readily soluble in tung oil and permitted the preparation of
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388 ANNUAL SURVEY OF AMERICAN CHEMISTRY
varnishes which dried rapidly to films highly resistant to moisture,
alkalies, and sunlight.
Phenol with Aldehydes, Ketones and Carbohydrates. Phenol has
been condensed with paraldehyde in the presence of an acid
catalyst ^^^ and with furfural in the presence of an alkaline con-
densing agent.^37.139 Condensation products suitable for use with
nitrocellulose lacquers have been produced by heating phenol with
benzoyl-(7-benzoic acid in the presence of sulfuric acid.^*^ Phenol has
been condensed with ketones such as acetone ^^^ or a-chloracetone ^^^
to form products compatible with cellulose derivatives. Phenol has
been reacted with formaldehyde and a ketone, such as acetone or
cyclohexanone, in the presence of an alkaline catalyst to form an
elastic resin which was readily hardened by heat and was not
darkened when heated at 180° CM^
A water-soluble synthetic resin has been produced by con-
densing phenol and formaldehyde with an alkaline solution of
sucrose and terminating the reaction before the product became
insoluble.^** A primary carbohydrate-phenol resin has been heated
to about 230° C. with the addition of glycerol to form a product
which was substantially infusible.^*^ A coating composition com-
prised a carbohydrate-phenol reaction product and a metal oxide
or hydroxide in a volatile solvent together with a reactive hardening
agent such as hexamethylenetetramine.^*^
Urea and Thiourea with Formaldehyde. The condensation
products of urea and formaldehyde have been very important as
plastics but have not been extensively used in varnishes or lacquers.
They are particularly distinguished by their hardness, transparency,
and absence of color, and for this reason have been widely heralded
as substitutes for glass.
The structure of the urea-formaldehyde polymer has been
represented as follows: 2
NH, NH, NH,
o=c c=o c=o
I H3 I H. I H.
-N-C-N-C-N-C-
The condensation of formaldehyde with urea, like the condensa-
tion with phenol, has usually been carried out in several stages.
In general the urea was first caused to react with not more than
1.4 mols. of formaldehyde at a temperature of not over 70° C.
and additions of formaldehyde were then made with continued
heating until the final proportion was about 1.1 to 1.3 mols. of urea
for every 2 mols. of formaldehyde.^*^-^®^ An excess of formaldehyde
might be used in the beginning and then removed by passing air
or steam through the solution before completing the polymeriza-
tion.15* The formation of cloudiness has been prevented by adding
salts, such as sodium chloride.^^^
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SYNTHETIC PLASTICS 389
The urea-formaldehyde condensation has been carried out in
the presence of phthalic anhydride,^^^ acetaldehyde,^^'^ zinc chlo-
ride,^^^ silica gel,^^^ hydrogen sulfide,^^^ ferrous sulfide,^^^
thiourea,^^2 phenol,^^^ or a substantially anhydrous alcohol con-
taining an inert dehydrating agent.^^^ Superatmospheric pressure
has been used to facilitate the condensation.^^^' i^® An intermediate
condensation product has been preserved in the jelly stage by the
addition of a colloidal retarder such as gum tragacanth ^^"^ or
gum acacia.^^®
Molding compositions have been obtained by mixing the urea-
aldehyde condensation product with water,^^^ resorcinol,^*^^ a
natural resin,^''^ sulfite fiber,^'^^ ^nd nitrocellulose.^''^ The con-
densate has been rendered substantially insoluble by heating with
an acid, such as salicylic acid.^''* Urea has been mixed in the dry
state with a solid polymeric aldehyde (such as paraformaldehyde)
and a filler to give a mixture which could be condensed and hardened
at the same time by hot-molding.^''^' ^''^ A powder suitable for
molded articles was obtained by reacting formaldehyde with
ammonium thiocyanate or unaltered dicyandiamide and urea or
thiourea.^''''' ^''^ Alternatively, the resinous condensation product
of formaldehyde and thiourea has been contacted with an excess
of water to precipitate a fine powder suitable for molding.^''®
Solutions suitable for use as a varnish or lacquer have been pre-
pared by dissolving a permanently fusible resin from thiourea and
formaldehyde, together with a hardening agent, such as para-
formaldehyde, in a mutual solvent, such as ethyl lactate or ethylene-
glycol.^^^ Water solutions of a thiourea-formaldehyde condensate
have been stabilized with ammonia and carbon dioxide to render
them suitable for coating various materials.^^^
Other Amines with Formaldehyde. Resins which are compatible
with cellulose derivatives have been formed by condensing form-
aldehyde with toluenesulfonamide i«2-i84 qj. ^j^j^ ammonium thio-
cyanate.^^5 Products of a resinous character suitable for rust-
proofing coatings on metals have been obtained by reacting para-
formaldehyde with a phosphorus amide.^^® Formaldehyde has also
been condensed with a primary aromatic amine, such as aniline or
naphthylamine ^®'' and with dicyandiamide and a protein material,
such as casein.i^s
Polyhydric Alcohols with Polybasic Acids. According to Kienle's
theory of flexible resin formation,^^® long-chain molecules (heat-
nonconvertible) attached through primary valence linkages to heat-
convertible resin molecules (such as glyceryl-phthalate) should
yield flexible heat-convertible resins. Such resins were prepared
by heating together a dihydric alcohol-dibasic acid polyester as
the heat-nonconvertible, flexibilizing phase and glyceryl triphthalate
as the heat-convertible phase. Since the flexibility of the product
depended largely on the mole ratio of the phases, it thus became
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390 ANNUAL SURVEY OF AMERICAN CHEMISTRY
possible to produce resins of definite and controlled flexibility by
intentional formulation.^®^-^®^
In commercial practice the glycerol-phthalic anhydride con-
densation has been modified by the presence of natural glycerides
or the fatty acids obtained by hydrolysis of such glycerides. The
following oils have formed a source of supply for this purpose:
China-wood oil,^®^ linseed oil,^^**^^^ tung oil,^^^^"^®^ rubber-seed
oil,20« castor oil,207. 208 and corn oil.^o® Other modifying agents
have been recommended, sugh as borneol,2io butanol,2ii. 219
rosin,2i2 shellac,^!^ oleic acid,2i*» 216 ^ ketene,2i« glycerol gluta-
matCj^i"^ zinc or calcium oxide,2i8 and partially esterified glycerides
made by treating a drying oil in the presence of water with a
hydrolyzing enzyme.220 A fusible alkyd resin has been rendered
infusible by heating it with acetic anhydride or acetyl chloride.221
Phthalic acid has been condensed with compounds other than
glycerol to produce resinous products, e. g., maleic acid,222, 223 oleic
acid with triethanolamine,224 and lactic acid in combination with
ethyleneglycol.225 Glycerol has been condensed with compounds
other than phthalic anhydride, e.g., bromomaleic anhydride with
the monoisopropyl ester of monochlorosuccinic acid,226 bromo-
maleic anhydride with acrylic acid,227 and citric acid.228
Alkyd resins have been extensively used for varnishes, either
straight, phenol-modified and oil-extended or natural-resin modi-
gg(j 229-285 They have been used for lacquers in combination with
nitrocellulose 236-238 and with cellulose acetate.^so The question of
suitable solvents for these resins has received consideration.^*® High-
boiling solvents, such as diethyl oxalate and ethyl lactate, have been
recommended for some purposes.^*^ Solutions of alkyds in mix-
tures of xylene and naphtha have been reduced in viscosity by the
addition of small amounts of butyl alcohol.2*2 The tolerance of
toluene solutions for denatured alcohol, ethyl acetate and mineral
spirits has been determined. In general the most tolerance was
shown for ethyl acetate and the least for alcohol.2*3 An oil-modified
alkyd resin has been used with a highly volatile solvent to pro-
duce a wrinkle-finish coating.^** Hart and Gardner ^^s have noted
the tendency of white and light-tinted paints using alkyd vehicles
to chalk.
Alkyd resins have also been used for molded products,24^"2**'
both alone and in combination with urea-aldehyde resins,^*^ casein-
formaldehyde,250 and rubber.^si They have formed the basis of
solventless cements whose hardening was accelerated by dehydra-
tion catalysts, such as zinc oxide.2o2
Kienle and Race ^53 have studied the electrical, chemical, and
physical properties of alkyd resins. They pointed out that alkyd
resins might be hard, rigid, soft, balsam-like, flexible, or rubbery.
During the formation of unmodified alkyd resins, there occurred a
progressive increase in electrical resistance with time, the tempera-
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SYNTHETIC PLASTICS 391
ture being kept constant. The observed electrical characteristics
of alkyd resins were best explained by the theory of conduction
in the solvating component of a gel structure.
Other Condensations with Separation of Water. Resinous plas-
tics have been formed by the condensation of aldehydes with guani-
dine and its homologues,^^* sulfonamides,265 benzidine,256 polyvinyl
alcohol,257, 258 cracked hydrocarbon oil distillates,^^^ and hardwood
tar distillates ;2«o also by the condensation of allyl alcohol with
cresol in the presence of zinc chloride,^^^ of furfural with urea in
the presence of China-wood oil,^^^ of phenol and o-cresol with
hexamethylenetetramine,2^3 and of alkylolamines with themselves
in the presence of an alumina catalyst.^^* Carbohydrates and pro-
teins have entered into resinous condensations: as for example,
sucrose or glucose with formaldehyde,283 pectose with formalde-
hyde or a ketone,28^ dextrose with maleic anhydride,285 casein,
gelatin, or albumin with glycerol,^^^ and corn gluten with for-
maldehyde and phenol.287
Condensations Involving Sulfur or its Compounds. Resinous
plastics have also been formed by the interaction of divinylacetylene
with sulfuryl chloride (SO2CI2) 2«5 and sulfur chloride (SaCla),^^^
of phenol with sulfur chloride,^^'^ of cracked hydrocarbon distillates
with sulfur,2«8 of aldehydes or ketones with a mercaptan,^^® of
ethylene dichloride with soluble polysulfides,^''^"^'^^ ^nd of aldehydes
of furfural with polysulfides.273, 274
Miscellaneous Condensations. Other plastic forming condensa-
tions have included methylene dichloride with sodium phenate,^''^
ethylene dichloride with benzenoid hydrocarbons,276 a-terpinene or
terpinolene with maleic anhydride,^'^'' pinene with maleic anhy-
dride,^'^®' ^^o cineol with maleic anhydride,28o pinene with toluene,^^^
and trichloroethylene with itself in the presence of aluminum
chloride.282 Abietic acid has formed the basis of synthetic resins
which were also suitable for use as plasticizers.288-291
Rubber Derivatives
The story of recent developments in synthetic plastics would not
be complete without mention of the modified-rubber compounds.
A chlorinated rubber, marketed under the name of Tornesit, has
proved to be a valuable base for coating compositions.2»2 Chlor-
inated rubber is a light yellow solid which has a specific gravity of
1 5 293 The best solvents for chlorinated rubber are the aromatic
hydrocarbons.^^* Suitable plasticizers are the soft alkyds, chlo-
rinated naphthalene, methyl or benzyl abietate, and some synthetic
oils.
A new molding resin, called Plioform, has been formed by cer-
tain adaptations of the reaction between rubber and the chlorotin
acids.2»6 This resin is tough, odorless and tasteless, resistant to
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392 ANNUAL SURVEY OF AMERICAN CHEMISTRY
alkalies, most acids, and moisture, and is thermoplastic. It is
soluble in gasoline or benzene but insoluble in acetone. It is also
available in sheet form.
Summary
During the period covered by this survey there have been several
comprehensive reviews 296-304 ^hich emphasize the important place
which synthetic plastics have established for themselves in modern
industry, and which point out the probable trends of these develop-
ments in the near future.
Synthetic Plastics for Coatings. The varnish industry has, in
the past few years, undergone a radical change with the introduc-
tion of the newer types of phenolic and alkyd resins which are
not only oil-soluble but also exert a beneficial influence on the
resulting oil-resin coatings. Thus, there have been developed a
series of quick-drying varnishes in which the objectionable processes
of the drying of siccative oils have been substantially eliminated
by uniting the drying element in the structure of the synthetic
resin molecule.
Ellis 1 summarizes the present trend of the coating industry as
being towards the development of an ideal resinous substance
which shall be soluble in cheap solvents, quick-drying, light-
colored, flexible, even at low temperatures and highly resistant to
heat, water, light, acids, and alkalies. Change to an insoluble
form shortly after application is desirable. There should be little
or no progressive change upon aging.
Synthetic Plastics for Molded Articles. Breskin298 states that
among the present-day molded plastics are a number of applica-
tions so common that few think of them as novelties any longer.
Heat resistance makes them ideal for radiator knobs. Electrical
resistance makes them ideal for switches, plugs, insulators, and
other electrical fixtures. Resistance to wear has brought them into
favor for door knobs, bell pushes, and various articles of fur-
niture. Their decorative qualities and workability are making
them increasingly popular as a building material, particularly in
laminated sheets for interior decorative effects.
Molded plastics have also been used for phonograph records, for
dentures and for the construction of plant and laboratory apparatus
which is distinguished by its acid resistance. Synthetic plastics
of the clear, colorless type have been proposed as a substitute for
glass for a number of purposes and some appear to have possi-
bilities as the intermediate films in laminated safety glass.
Other Applications for Synthetic Plastics. Improvements in
grinding wheels have been made by using phenolic resinoids as the
binder for the abrasive. Paper has been impregnated with a
phenol resinoid and used instead of glue in the production of wood
veneers. A flexible waterproof cloth, called Revolite, has been
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SYNTHETIC PLASTICS 393
manufactured by calendering the fabric with a phenolic resinoid.
This fabric has been used for surgical tape, raincoats, shower
curtains, etc. Special anti-crease fabrics impregnated with the
colorless urea resins are coming into increasing prominence.
Phenolic resinoids have proved quite valuable in floor-covering
compositions of the type of linoleum, and as binders in various
brake linings.
References.
1. Ellis, C, Ind. Eng. Chem., 25: 125 (1933).
2. Allen, I., Jr., Meharg, V. E., and Schmidt, J. H., Ind, Eng. Chem., 26: 663 (1934).
3. Ellis, C, "The Chemistry of Synthetic Resins," N. Y., Reinhold Publishing Corp.,
1935. 2 V.
4. Calcott, W. S., and Downing, F. B., U. S. Pat. 1,924,979 (Aug. 29, 1933).
5. Downing, F. B., Carter, A. S., and Hutton, D., U. S. Pat. 1,926,039 (Sept. 12, 1933).
6. Rosenblum, C, /. Phys. Chem,, 37: 53 (1933)
7. Lind, S. C, and Livingston, R., /. Am. Chem. Soc, 55: 1036 (1933).
8. Carter, A. S., and Downing, F. B., U. S. Pat. 1,896,162 (Feb. 7, 1933).
9. Dykstra, H. B., J. Am. Chem. Soc, 56: 1625 (1934).
10. Calcott, W. S., and Downing, F. B., U. S. Pat. 1,950,429 (Mar. 13, 1934).
11. Calcott, W. S., Carter, A. S., and Downing, F. B., U. S. Pat. 1,959,343 (May 22,
1934).
12. Vaughan, T. H., and Nieuwland, J. A., /. Chem. Soc, 1933: 741.
13. Jacobson, R. A., U. S. Pat. 1,967,864 (July 24, 1934).
14. Calcott, W. S., Carter, A. S.. and Downing, F. B., U. S. Pat. 1,950,430 (Mar. 13,
1934).
15. Carothers, W. H., Berchet, G. J., and Jacobson, R. A., U. S. Pat. 1,963,074 (June
19, 1934). > J^
16. Morrison, G. O., and Shaw, T. P. G., Chem. Met. Eng., 40: 293 (1933).
17. Morrison, G. O., and Shaw, T. P. G., Trans. Electrochem. Soc, 63: 425 (1933).
18. Jeu, K. K., and Alyea, H. N., /. Am. Chem. Soc, 55: 575 (1933).
19. Reid, E. W., U. S. Pat. 1,935,577 (Nov. 14, 1933).
20. Shriver, L. C, U. S. Pat. 1,938,870 (Dec. 12, 1933).
21. Young, C. O., and Douglas, S. D., U. S. Pat. 2,011,132 (Aug. 13, 1935).
22. Young, C. O., and Douglas, S. D., U. S. Pat. 2,013.941 (Sept. 10, 1935).
23. Young, C. O., and Douglas, S. D., U. S. Pat. 1,990,685 (Feb. 12, 1935).
24. Smith, C. N., U. S. Pat. 1,992,638 (Feb. 26, 1935).
25. Bridgman, P. W., and Conant, J. B., U. S. Pat. 1,952,116 (Mar. 27, 1934).
26. Robertson, F., U. S. Pat. 1,921,326 (Aug. 8, 1933).
27. Wemtz, J. H., U. S. Pat. 1,988,529 Qan. 22, 1935).
28. Reed, M. C, U. S. Pat. 1,989,246 (Jan. 29, 1935).
29. Barrett, H. J., U. S. Pat. 1,942,531 (Jan. 9, 1934).
30. Lawson, W. E., and Sandbom. L. T., U. S. Pat. 1,975.959 (Oct. 9, 1934).
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286. Sly, C, U. S. Pat. 2,009,029 (July 23, 1935).
287. Berlin, H., U. S. Pat. 1,988,475 (Jan. 22, 1935).
288. Hercules Powder Co., Melliand Textile Monthly, 4: 135 (1932).
289. LaLande, W. A., Jr., Ind. Eng. Chem., 26: 678 (1934).
290. Peterson, E. G., U. S. Pat. 1,978,598 (Oct. 30, 1934).
291. Seymour, G. W., and White, B. B., U. S. Pat. 2,004,297 (June 11, 1935).
292. Koch, W., U. S. Pat. 1,957,786 (May 8, 1934).
293. Wiggam, D. R., Koch, W., and Mayfield, E., Ind. Eng. Chem., News Ed., 12:
179 (1934).
294. Krumbhaar, W., Official Digest Fed. Paint & Varnish Production Clubs, 133:
33 (1934).
295. Thies, H. R., and Cliflford, A. M., Ind. Eng. Chem., 26: 123 (1934).
296. Baekeland, L. H., Ind. Eng. Chem., 27: 538 (1935).
297. Ellis, C, Ind. Eng. Chem., 26: 37 (1934).
298. Breskin, C. A., Ind. Eng. Chem., 27: 1140 (1935).
299. Chase, H., Elec. Mfg., 14, No. 1: 23 (1934).
300. Martin, R. C, Metal Cleaning & Finishing, 5: 203 (1933).
301. Stoppel, E. A., Official Digest Fed. Paint & Varnish Production Clubs, No. 126:
189 (1933).
302. Worstall, R. A., Paint, Oil & Chem. Rev., 96, No. 12: 20 (1934).
303. Chase, H., Am. Machinist, Til 241 (1933).
304. Hunt, J. K., and Lansing, W. D., Ind. Eng. Chem., 21 1 26 (1935).
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Chapter XXIII.
Rubber.
Webster N. Jones,
Carnegie Institute of Technology,
Chemistry has continued to play a major role in the advance-
ment of the rubber industry. Although there have been no spec-
tacular discoveries during the year 1935, hundreds of investigators
have been actively applying their chemical knowledge to solve the
intricate problems of this major industry.
The executives of the large rubber companies, several of whom
served their apprenticeships in the chemical laboratory,^ appreciate
the potentialities of chemical research as evidenced by their gener-
ous support of research work and the resulting publications. The
government laboratories have also contributed some very impor-
tant papers. Many suppliers to the rubber industry are maintain-
ing very productive research laboratories and have contributed
freely to the literature. One of the suppliers, E. I. du Pont de
Nemours & Company, was given the award for chemical engineer-
ing achievement for bringing to fruition during the past two
years the successful industrial development of synthetic rubber,
"DuPrene."2
A noteworthy general paper, "Rubber Industry at the Cross-
roads," was contributed by Geer,^ who was largely responsible for
the awakening of the rubber industry to the value of research.
Geer feels that there are two courses open: "either to keep on
along present lines or to branch out upon a broad, intense program
of fundamental research. Executives must face now the law of
diminishing returns in research conducted along present lines. If
an ample appropriation were made for a cooperative research
laboratory and continued over a period of ten years, the entire
scope, quality, and utility of the rubber industry might be revo-
lutionized."
Crude Rubber. By a method of total reflection, McPherson and
Cummings * have determined the refractive index values of rubber
in different forms. The average (N. D. 25) values of Hevea crude
rubber and purified rubber were approximately the same, regard-
less of differences in the non-rubber components, nor were the
values altered by mastication. The "n" value of crude rubber was
not altered by the addition of rubber-insoluble fillers, whereas solu-
398
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RUBBER 399
ble substances changed the "n" value in proportion to their own
"n" values and their proportional weight of the rubber. The "n"
value offers a method for determining the solubility of a substance
in rubber. Sulfur in rubber increased the niy^^ of crude rubber by
0.0016 for each percent and phenyl-3-naphthylamine by 0.0015 for
each percent. The combination of a given proportion of sulfur
with rubber increased the "n" value more than the solution of the
same proportion of sulfur in the rubber, and therefore, when rub-
ber is vulcanized, there is a progressive increase in its "n" value.
A formula for finding "n" is given, and the changes in the slope
of the curve, plotted with "n" values as a function of the tempera-
ture, are discussed.
Forms of rubber as indicated by temperature-volume relation-
ship have been investigated by Bekkedahl.^ Temperature-volume
measurements were made from —85 to +85° C. on rubber hydro-
carbon and three soft rubber-sulfur compounds. Measurements
of linear expansion were taken on one specimen of rubber hydro-
carbon from —190 to 0° C. These measurements indicate that
unvulcanized rubber may exist in at least four forms : amorphous I,
crystalline I, crystalline II, and amorphous II. Vulcanized rubber, in
the unstretched state, exhibited only the amorphous I and the amor-
phous II forms. The results of this investigation afford a basis for
correlating and interpreting data obtained by the author and other
investigators on the heat capacity, electrical properties, and behavior
of rubber on stretching.
A method was previously described for purifying the hydro-
carbon in Hevea latex and separating it into two fractions by
extraction with ethyl ether. The present paper of Smith and
Saylor ^ deals with the insoluble (the gel) fraction, of which about
25 percent of the total hydrocarbon is composed. Presumably the
gel is insoluble in ether, because of a complex structure and high
molecular weight. When traces of oxygen are present, it becomes
soluble in suitable organic liquids. The dissolved gel was crystal-
lized from a dilute solution at low temperatures and the crystals
were examined. The refractive indices, £=1.535 at —5° C. and
J^= 1.583 at —5° C, are very close to the values previously found
for crystals of ether-soluble hydrocarbon. Melting temperatures
( — 5 to -f-14° C.) depend upon the history of the sample and indi-
cate that the crystals are solid solutions, probably of many closely
related components. As witnessed by micromanipulation below their
melting temperature, the gel crystals contrast sharply in elasticity with
the crystals of sol rubber. The former appear to be elastic, the latter
are plastic. Also, after the loss of birefringence indicates that the
crystals are melted, the gel is more resistant to deformation than the
sol. Crystals of ether-soluble rubber have been vulcanized below their
melting point by means of sulfur chloride. The shape of the crystal^
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400 ANNUAL SURVEY OF AMERICAN CHEMISTRY
remains unchanged, but birefringence disappears, and their resistance to
deformation is increased.
Bekkedahl and Matheson*^ have determined the heat capacity,
entropy, and free energy of rubber hydrocarbon. Measurements of
heat capacity were made on rubber hydrocarbon in its different forms
from 14 to 320° K. At 14° K. the heat capacity was found to be
0.064 j/g/° C. for both the metastable amorphous and the crystalline
forms. With increase in temperature, the heat capacity increases gradu-
ally up to a transition temperature at about 199° K. At 199° K. both
forms undergo a transition of the second order, the heat capacity rising
sharply. For the amorphous form above this transition, the heat
capacity rises gradually without discontinuity to the highest temperature
of the measurements. The crystalline form undergoes fusion at 284° K.,
the heat of fusion being 16.7j/g. At 298.1° K. the heat capacity of the
rubber is 1.880 ± 0.002 j/g/° C. The entropy of rubber at 298.1° K. is
1.881=*= 0.01 Oj/g/° C. The free energy of formation of rubber from
carbon (graphite) and gaseous hydrogen is 1.35 ='=0.1 Ok j/g.
Jessup and Cummings^ have investigated heats of combustion of
rubber and of rubber-sulfur compounds. Measurements with a bomb
calorimeter have been made of the heats of combustion of samples of
rubber purified by various methods, and of compounds of rubber and
sulfur containing up to 32 percent sulfur. The average value for the
heat of combustion of ether-soluble rubber in gaseous oxygen to form
gaseous carbon dioxide and liquid water at a temperature of 30° C. and
a constant pressure of 1 atmosphere is 45,207 international joules per
gram. The values obtained foy the heats of combustion of compounds
of rubber and sulfur may be represented by the equation 0^=^5200
— 37823w, where Q^ is the heat of combustion in joules and m is the
mass of sulfur per gram of compound. From these data, and the data of
Eckman and Rossini on the heat of combustion of sulfur, the heat of
combination of rubber with rhombic sulfur has been calculated to be
1,881 international joules per gram of sulfur and is independent of the
percent of sulfur in the compound.
Gehman^ studied the Raman spectrum of a solution of rubber in
carbon bisulfide and carbon tetrachloride. Concentrations of rubber
from 10 to 40 percent by volume were used. Raman lines were
exhibited by a 4358A mercury line. Three most intense Raman fre-
quencies for rubber are 1672, 1460, and 1382 cm.-^ The Raman spec-
trum data appear to confirm the generally accepted views regarding the
chain structure of rubber, although a cyclic structure is not definitely
excluded, since cyclic terpenes have a spectrum of this nature.
Midgley and co-workers ^^ have shown that natural rubber contains
oxygen, while synthetic rubber is oxygen-free. The oxygen appears
to be of an hydroxylic type, and its quantity corresponds to about one
hydroxyl group for each 1,000 isoprene units of the rubber molecule.
A mechanism of reaction has been proposed to interpret the quantitative
data obtained.
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RUBBER 401
Bridgman ^^ applied a pressure of 50,000 kg/cm^ to a specimen of
crude rubber. The sample became a hard, translucent material, not
imlike horn in appearance. The change was permanent. Sackett^^
studied the deleterious effect of manganese salts in plantation rubber.
He studied also the consumer's crude rubber requirements.^^ Ingman-
son and Mueller ^^ developed a process of treating gutta percha which
comprises cold leaching of the resins from the gutta hydrocarbon by
petroleum naphtha, heating to 100° C. to expel the naphtha, and allow-
ing albane to precipitate out at room temperature.
Plasticizers. One of the first production operations in the manu-
facture of a rubber article is the milling of the crude rubber. The mill
rooms are large consumers of power and labor. Testing machines
have been devised to measure the plasticity of milled rubber and are
used to maintain imiformity. Technologists have been attempting for
years to discover plasticizers which will lessen the time of milling
without affecting the workability of green stock and the quality of the
finished product.
Williams and Smith ^^ have investigated the use of hydrazine and
its derivatives as rubber plasticizers. They advance the theory that
hydrazine may react chemically to assist in the destruction of a
carbon-carbon bond in the rubber molecule, it may react chemically
without the rupture of a carbon bond in such a manner that the at-
traction between molecules of rubber is decreased, or it may act in
a purely physical manner to decrease the intermolecular forces in
the rubber.
Tuley ^^ claims a method for breaking down crude rubber by adding
an oxide of lead and then milling at a temperature sufficient to reduce
its viscosity. He also proposes the breaking down of crude rubber
prior to compoimding by adding a relatively stable aryl peroxide in
an amount sufficient to reduce the viscosity of the rubber.^*^
Gibbons ^^ has devised a means of improving physical properties
of rubber by plasticizing a body of solid rubber by adding, at the
beginning of its breakdown, a substance which furnishes upon hydroly-
sis a sufficient concentration of hydrogen ions to decompose the alkali
proteinates and alkali soaps.
King and King ^^ have developed a thermo-plasticizing composition
made of a hydrocarbon solvent, non-volatile at vulcanizing temperature,
and an oil-soluble sulfonated product as activator. This composition
acts on unmasticated rubber to enable it to be readily plasticized.
They ^o also claim that, by the addition of a small amount of non-liquid
softener, unworked raw rubber becomes more readily plasticized and
is made ready for compounding without preliminary mastication and
with a saving in time and power required. Hyman^i claims as a
rubber plasticizer the high pressure liquid phase polymerization product
obtained from cracking gasoline at 450 to 750° F.
Vulcanization and Structure of Vulcanized Rubber. Thibodeau
and McPherson 22 have studied the photoelastic properties of soft, vul-
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402 ANNUAL SURVEY OF AMERICAN CHEMISTRY
canized rubber. A study was made of double-refraction under tensile
stress of transparent, vulcanized rubber at about 25° C. by means of
a Babinet compensator, using light of wave length, 5461 A. The rela-
tive retardation per unit thickness and the stress-optical coefficient
were found to be related to the stress by equations of the form D^ = aT
-f&T^ H-cT3, and C = a-hbT-hcT^, where D^ is the retardation coeffi-
cient, C the stress-optical coefficient, T the stress, and a, b, and c are
constants for any given rubber compound. Formulas for the compounds
investigated, in parts by weight, were given. The parameters a, b, and
c were functions of the type of compound. The values of a, b, and c
were given under the different conditions.
Nutting, Squires, and Smithes discuss the effect of cure on some
physical properties of a high-sulfur rubber mix. A mixture of smoked
sheet 100 and sulfur 50 was vulcanized isothermally through the range
from soft rubber to ebonite, and the sulfur coefficients of vulcanization,
tensile strengths, ultimate elongations, and densities were determined
as vulcanization progressed. A table and graphs show these properties
as functions of the time of vulcanization.
Smith and Holt^* have studied the vulcanization and stress-strain
behavior of sol, gel, and total rubber hydrocarbon. The stress-strain
properties in three different types of vulcanization were fotmd to be
similar for each type "of cure. Vulcanized rubbers prepared from the
insoluble rubber hydrocarbons were less extensible, and those pre-
pared from the soluble rubber hydrocarbon more extensible, than those
prepared from the total rubber hydrocarbon.
Garvey,25 as the result of experiments, concludes that the main
vulcanizing effect of sulfur chloride is a catalytic reaction rather than
an addition to the hydrocarbon.
Williams 26 concludes that vulcanization appears to consist of a
chemical reaction that is accompanied by changes of a colloidal nature.
The experiments which were described lead to the conclusion that vul-
canization is the result of several actions which take place to a varying
extent under different conditions.
Somerville^^ vulcanizes rubber by introducing a catalytic anti-
oxidant to prevent oxidation by atmospheric oxidation to which the
compound may be exposed, an organic oxygen absorber to eliminate
any oxygen initially present in the compound, and an organic base to
activate the organic absorber.
Accelerators. Since the discovery of the use of organic acceler-
ators in the vulcanization of rubber by George Oenslager in 1906, this
field of investigation has been explored by many chemists. Each year
the patent literature discloses new and more complicated organic
compounds.
Aldehyde Amines, Cadwell^s claims that the products obtained
from treating a preformed heptaldehyde and an aniline condensation
product with a strong mineral acid gave a new class of compounds
suitable for the vulcanization of rubber. Powers ^^ produced a high
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RUBBER 403
boiling viscous liquid or resinous solid accelerator by the reaction of
an aldehyde, a primary aromatic amine, and carbon disulfide with the
elimination of water. SebrelP^ used the product resulting from the
reaction of acetaldol with aniline and the further reaction of this
material with formaldehyde. Messer^^ investigated the reaction
product of formaldehyde, a 2-mercai)to-aryl-thiazole of the benzene
series, and a primary aromatic amine of the benzene and naphthalene
series.
Mercaptohenzothiazole, Sebrell and Clifford ^2 claim di-(aryl-
thiazyl) monosulfide and an accelerating amine. Sebrell vulcanizes
rubber in the presence of a mercaptothiazole in combination with a
compound selected from the group consisting of ammonia, amines
having a primary amine group, aliphatic amines, and alkyl aryl
secondary amines.^^ Sebrell ^^ has also patented a method of prepar-
ing mercaptan-amine derivatives, and Teppema ^^ evolved a process of
preparing carbamyl disulfides. Teppema ^^ also uses thiazyl com-
pounds of the group consisting of the nitrophenyl nitrobenzothiazyl
sulfides and the nitrophenyl halo-benzothiazyl sulfides.
Williams 3*^ vulcanizes with an accelerator of the type mercapto-
henzothiazole, diphenylguanidine, tetramethylthiuram monosulfide, and
butyraldehyde-aniline, and an activator consisting of the zinc, lead,
mercury, or cadmium salt of propionic acid. Semon and Ford^® have
patented a process for the manufacture of mercapto aryl thiazoles,
which comprises heating a mixture of mononuclear arylamine and car-
bon disulfide with an organic oxidizing agent. Coleman ^^ suggests
the use of iV-nitrosoarylaminomethyl arylenethiazyl sulfide for the
vulcanization of rubber. Coleman *^ also claims a chemical compound
which is the product of reaction of a mercaptohenzothiazole, formalde-
hyde, and a primary aromatic amine. Harman *^ studied the vulcaniza-
tion of rubber, using an accelerator comprising the reaction product
of an organic base and a mercaptoarylthiazole in the presence of a
primary amine acid phthalate. Tuley*^ vulcanizes with mercapto-
henzothiazole and an amino derivative of carbamic acid, adapted to
decompose at vulcanizing temperatures to yield ammonia and an ali-
phatic amine.
Evans *^ prepares an accelerator by reacting a furoyl halide and a
mercaptoarylthiazole in an aqueous medium containing a small amount
of an inert organic solvent. Dunbrook and Zimmerman** describe a
new method of preparing 2-mercaptobenzothiazole in one step from
o-nitrochlorobenzene.
Thiuram. Cramer *5 prepares thiuram disulfides by a method which
comprises oxidizing the sodium salt of a cyclic dithiocarbamate with
ammonium persulfate. Northam *^ claims an accelerator consisting of
thiuram polysulfide derived from a secondary amine, and thiuram
monosulfide derived also from a secondary amine. Semon *^ accelerates
vulcanization by heating rubber in the presence of a tetraaryl substituted
thiuram sulfide.
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404 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Miscellaneous. Christensen *^ discusses a method of vulcanizing
rubber by heating with sulfur in the presence of an accelerator com-
posed of the reaction product of acetic acid and the product formed by
reacting methylenedipiperidine and carbon disulfide. Coleman^®
accelerates the vulcanization of rubber by use of a vulcanizing agent
and zinc oxide with />,/>'-diaminodiphenylmethane as the accelerator.
Sibley ^® discusses a process for retarding the vulcanization of rubber,
which comprises heating a mixture of rubber, sulfur, and an acceler-
ator comprising the crotonaldehyde derivative of the reaction product
of mercaptobenzothiazole and hexamethylenetetramine in the pres-
ence of 2,4-dinitrophenol as a retarder of the accelerating action.
Reed ^^ claims accelerators of the general formula
Y<CH:=CHi>N-R-OH.
where R is an aromatic nucleus, Y is CH2, O, S or AT-aryl.
Lubs and Williams ^2 vulcanized rubber by adding, before vulcani-
zation, the products obtained by hydrogenating carbazole until at least
part of the hydrogenated carbazole is soluble in 10 percent acetic
acid. Meuser and Leaper^^ reacted a ketone and an aromatic amine,
containing only secondary amino groups, at 100° C, using a hydrogen
halide as catalyst. Sibley^* has patented a process of preparing
diphenyl derivatives — ^the sulfuric acid derivatives of the reaction
products of a monohydric alcohol and a nuclear hydroxy substituted
diphenyl and their alkali metal and alkaline earth salts. Clifford ^^^
prepares dithiazyl disulfides by a process which comprises oxidizing a
thiazyl mercaptan with hydrogen peroxide in the presence of an
inorganic acid. Gracia^^ prepares dithiazyl disulfides by heating an
aqueous alkaline solution of mercaptobenzothiazole and mixing there-
with an aqueous solution of hydrogen peroxide and an amoimt of sul-
furic acid sufficient to neutralize said alkaline solution of mercapto-
benzothiazole.
Age Resisters. The first age resister appeared on the market in
1921. Since that date the study of age resisters has been a fruitful
field of research. Each year new organic compounds are added to the
already long list of materials that are used to prolong the life of rubber
compounds.
Tener and Holt^*^ have studied the effect of antioxidants on the
natural and the accelerated aging of rubber. Five different tjrpes of
vulcanizates, in each of which were incorporated five common anti-
oxidants, were ( 1 ) kept in darkness at room temperature for 7-8 years ;
(2) exposed outdoors for 16-20 months; (3) heated in air at 70° C
for 32-42 hours; (4) heated in air at 90° C. for 4-7 days; and (5)
heated in oxygen at 60° C. under 300 lbs. per sq. in. pressure for 18-33
hours. Changes in tensile strength are shown in graphs. Two numeri-
cal criteria are suggested for expressing the effectiveness of anti-
oxidants, a "time" index (the increased time during which a vul-
canizate will remain serviceable) and a "tensile" index to show the
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RUBBER 405
improvement in the integrated tensile strength over a definite period of
aging effected by the antioxidant. Sommerville ^^ presented a very
interesting paper on the effect of oxygen absorbers in rubber to prevent
cracking. Pyrogallol-ethanolamine and pyrogallol-quinolethanolamine
combinations were used. Semon^® has patented the condensation
product of an unsaturated aliphatic ketone with a primary aromatic
amine ; the reaction product of a ketone with not more than two oxygen
atoms with (1) an aromatic amine containing both primary and
secondary amino groups ; (2) an aromatic amine derived from benzene
or an alkyl or alkoxy substituted benzene and containing only one
primary amino group. Semon^® also claims the use of symmetrical
diphenyl substituted naphthylenediamine as an antioxidant. He has
devised a method for preserving rubber by adding, before vulcanization,
a plastic mass resulting from the cooling of a solution of a diarylamine
in a molten neutral wax;®^ he prepared antioxidant by condensing an
aromatic mono-amine with a ketone to produce an intermediate amine,
and further reacting the intermediate amine with an aromatic mono-
amine at a temperature at least 50° C. higher than that at which the
intermediate amine is produced. ^^ Sloan ^^ retarded deterioration of
rubber by treating with a poly-aryl carbinol containing one or two
amino groups. He has also patented an antioxidant of the formula
A — R — X — R'— A', where A and A' represent amino groups, X an
aliphatic nucleus, and R and R' represent aromatic nuclei attached to
different carbon atoms of X.^* Craig ^^ uses an antioxidant consisting
of diary lamines having at least one aliphatic hydrocarbon group which
contains at least two carbon atoms substituted in the aromatic nucleus.
Clifford ®® preserves rubber by treating with an aryl naphthylamine
having at least one hydroxyl group substituted on an aromatic nucleus.
Sibley ^^ preserves rubber with the reaction product of one mole of
acetone-anil and one atomic weight of sulfur. He also claims the use
of an age resister consisting of products of one of these reactions : ( 1 )
dihydroxydiphenylmethane and an amine ; (2) 2,4-tetrahydroxydiphenyl-
methane and o-toluidine or 13-naphthylamine ; (3) 2,3-tetrahydroxy-
diphenylmethane and a-naphthylamine.^^ Calcott and Douglass ^^ claim
the use of a mono-hydroxy-diaryl methane as an age resister. Wolfe '^^
uses the addition product of a mono-hydroxydiphenyl and an amine of
the group consisting of primary aliphatic mono- and diamines, primary
aromatic monoamines of the benzene and naphthalene series, benzyl-
amine, cyclohexylarnine and hexamethylenetetramine. Scott "^^ pre-
serves rubber by treating it with a sulfur derivative of a diaryl amine, a
phenyl radical of said diaryl amine containing a nuclear alkoxy sub-
stituent only. Howland "^^ preserves rubber by the use of the reaction
product of an alkali metal upon a ketone-aromatic amine condensation
product.
Control and Testing. Havenhill and MacBride "^^ have devised
a new laboratory machine for evaluating "breakdown" characteristics
of rubber compounds. The new apparatus measures the flexing force
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406 ANNUAL SURVEY OF AMERICAN CHEMISTRY
and also indicates the time of initial failure before destruction. The
specimen is rotated between oflF-center plates, and samples may be com-
pared under constant load or constant deflection. Unexpectedly the
flexing force increases, i. e., the rubber stiffens on continued flexing,
which indicates a structural change. The effects of volume loading,
type of pigment, and other changes of ingredients are shown. Tests
showed excellent correlation with service results, both for tire and
carcass mixtures.
Holt '^^ describes a study of the compression cutting test, also referred
to as the shear test, for rubber. The test consists of compressing a
sample of rubber to failure between a flat plate or anvil and a cutting
tool and recording the relation between the thickness of the sample
and the load up to failure. Data are presented on (1) different tools
used for the test; (2) conditions affecting the results; and (3) a com-
parison of the compression cutting tests with other common tests.
Advantages and disadvantages of the compression cutting test are
discussed. The conclusion is reached that it is a valuable supplement
to, rather than a substitute for, the tensile test.
McPherson and Bekkedahl ^^ have developed a simpler method for
determining the heats of reaction of rubber-sulfur. The description of
the calorimeter methods and results is given and a comparison with
the results of previous investigations is made.
Barnett and Mathews "^^ show that good correlation exists between
pendulum tests on rubber compounded with various types of zinc
oxide and flexing life as measured by the Firestone flexometer. The
effect of particle size of zinc oxide on the results obtained in both tests
has been investigated and the optimum size found to vary greatly with
changes in pigment loading.
Rainier and Gerke "^^ have devised a new laboratory test for calculat-
ing the resistance to fatigue cracking of tire tread stocks. Data are
given which show that ozone cracking and fatigue cracking are additive,
that the rate of growth of cracks is a function of the maximum strain,
that endurance limits may exist, and that the addition of antioxidants
decreases the rate of growth of cracks and raises the endurance limit.
Scott "^^ has determined the specific volume, compressibility, and
volume thermal expansivity of rubber-sulfur mixtures containing from
3 to 31 percent sulfur at 10-85° C. at pressures up to 800 bars (790
atmospheres). The effect of the pressure on the specific volume was a
function of the sulfur content and the temperature. The apparatus and
technique are described and illustrated in detail.
McPherson and Bekkedahl "^^ have studied the heats of reaction of
rubber with sulfur to form vulcanized compounds having empirical
formulas lying between CsHg and CsHgS.
Scott ^^ determined the effect of pressure on the dielectric constant,
power factor, and conductivity of rubber-sulfur compounds. The effect
of pressure on the three properties varied with the sulfur content.
Wiegand and Snyder ^^ claim that the rubber pendulum furnishes
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RUBBER 407
a convenient method of visualizing and, to some extent, measuring the
thermodynamical implications of the Joule effect ; the extent and conse-
quences of fatigue; the conditions for and degree of reversibility; and
the way in which these properties vary with the state of strain, with
temperature, and with other conditions. Clark ^^ described the progress
in x-ray research with rubber.
Sager ^^ determined the permeability to hydrogen of a number of
synthetic film-forming materials spread on closely woven cotton fabric.
Of the films studied, those in which the molecule is rich in hydroxyl
groups show very low permeabilities to hydrogen.
Walton and Osterhof ^* encountered numerous difficulties in attempt-
ing to rate rubber carbon blacks by means of heat of wetting meas-
urements.
Fisher and Schubert ^^ analyzed four samples of hard rubber for
carbon and hydrogen content. Sulfur apparently adds to the rubber
hydrocarbon until saturation is complete before any substitution takes
place, provided proper vulcanizing conditions are maintained. It is
pointed out that the carbon-hydrogen ratio is one of the best indica-
tions of substitution by sulfur.
Kraemer and Lansing^® have used the Svedberg ultracentrifuge to
determine the molecular weights of ether-soluble sol rubbers and of
polychloroprenes. The molecular weights as determined in the ultra-
centrifuge are several times as great as Staudinger's viscosity values.
Ward and Gehman®^ have determined the rubber content of latex
optically in an extinction cell by the use of a green filter.
Cole ^s has studied the effect of binary mixtures of zinc oxide, channel
black, and clay on the physical properties of rubber. Hardman and
Barbehenn^^ report that the long-used method of fixing the free
sulfur in the acetone extract of vulcanized rubber by means of copper
gauze gives the true free sulfur in vulcanizates containing acetone-
soluble organic sulfur compounds or other interfering substances.
De Vries ^^ has shown that the density of latex is not a linear function
of the percentage rubber by weight. Because of De Vries' work,
Rhodes ^^ has reexamined the data on the density of rubber in latex and
has corrected the value from 0.902 to 0.9064.
Dillon and Torrance ^^ used an extrusion plastometer in the pressure
measurements exerted by rubber on the walls of the die of a tubing
machine; the results obtained were employed in correlating the plasto-
meter with a tubing machine.
Humphrey ^^ has devised a new method of determining guanidine in
uncured rubber stocks.
Abbott and Sloman^* describe a traveling test track capable of
movement and of being dusted for the testing of tires.
Compounding Ingredients. Schoenfeld^^ has investigated the
surface chemistry of carbon black and its effect on the vulcanization of
rubber. There are so many different theories to explain the retarding
effect of channel carbon blacks on vulcanization that a systematic study
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408 ANNUAL SURVEY OF AMERICAN CHEMISTRY
was carried out to ascertain to what extent (1) physical adsorption,
where the adsorbed substances are recoverable, (2) activated adsorp-
tion, with probable formation of molecular complexes and only par-
tial recovery, and (3) solution of the adsorbed substances by the carbon
black are responsible for the retardation. Blacks treated in various
ways to alter their adsorptive power showed no relation between their
adsorptive power and their influence on the rate of vulcanization.
Channel black heated with sulfur and extracted with acetone gave a
sulfur-bearing black (2.61 percent sulfur), which was used in rubber
mixtures compensated and not compensated for sulfur; the sulfur in
such a black is inert, but it alters the surface properties and thus
increases the rate of vulcanization. Study of the impurities in gas
blacks by means of blacks treated in various ways and added to mix-
tures accelerated with basic and acidic accelerators showed, among
other inert components, an acid molecular complex of carbon and oxy-
gen which is removable only at very high temperatures, and which
retards the rate of vulcanization in a way similar to organic acid
retarders. Extraction of black with concentrated ammonia, evapora-
tion in vacuoy washing with ethyl alcohol, and evaporation in vacuo
gave a mixture of unidentified organic acids, one of which behaved
like mellitic acid. These acid components are the determinant factor
in the retarding effect of blacks on vulcanization.
Park and Morris ^^ have studied the effect of stearic acid and other
so-called dispersing agents on the dispersion of channel gas black.
Experiments show that channel gas black disperses with difficulty in
rubber in which the acetone-soluble components are reduced to 0.5 per-
cent or less. The addition of stearic acid to such extracted rubber
facilitates the dispersion, which is a direct proof that stearic acid is
a dispersing agent for gas black in rubber. Because of these facts,
acetone-extracted rubber may be used as the basis of a method for
testing the effect of various agents on the dispersion of gas black in
rubber. In this way, various substances were found to improve the
dispersion of gas black, others were without influence, and still others
were antagonistic to the dispersion. The dispersing power of a given
agent for gas black in rubber bears no relation to the deflocculating
action of the agent on the same black in a paste with dipentene.
Wiegand^*^ has shown that glycerine improves the curing behavior
of tread mixings accelerated with mercapto and softened with pine tar.
The effect of direct addition of glycerine, without reduction of tar, was
quite marked, whereas similar direct addition of higher aliphatic alco-
hols was without specific effect. A pre-cooked mixture of one part
glycerine with three parts of medium pine tar improved the rate of
cure, modulus, and tensile strength of a mercapto tread stock contain-
ing 50 percent of carbon black, as compared with a control using
straight pine tar. The above conclusions, since they do not include
aging results nor road tests for abrasion resistance, must be accepted
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RUBBER 409
as preliminary, but seem to warrant a further study of glycerine in
tread compounding.
Smith ^® presents a historical review of the uses of coal tar products
in rubber. He describes the use of cumar as a rubber ingredient.
Jack^® discusses the use of wood flour as a compounding agent in
rubber.
Spear 1^^ claims the production of a carbon black by the thermal
decomposition of a mixture of a hydrocarbon gas with twice its volume
of diluent gas, followed by passing the mixture over high temperature
surfaces. The solid carbon particles are separated from gaseous decom-
position products. Spear ^<>i also claims a carbon black identified by
the following physical characteristics (1) apparent density 0.37; and
(2) maximum loading value in rubber when compounded therein as a
reinforcing agent in excess of 100 but not substantially in excess of
150.
Wiegand ^^^ claims a process for the manufacture of carbon black,
which consists of burning a hydrocarbon gas in a restricted supply of
oxygen, causing the flame to impinge upon a cooler collecting surface,
and subjecting the deposited carbon black to controlled oxidation by
an oxidizing atmosphere between 300 and 1000° C. to produce a carbon
black of improved color and workability. Wiegand ^<>3 ^Iso claims a
carbon black of high color intensity and a high degree of workability.
Richardson ^^* has developed a process for producing hydrogen and
carbon black, which consists of mixing hydrocarbon gas and steam and
heating to effect thermal decomposition. The relative amounts of car-
bon black to gases are controlled by relative volumes of steam and
hydrocarbon.
Odell ^^5 claims a fine particle size carbon black formed by thermal
decomposition of a gas, which consists of pure carbon nuclei with the
vapor of a metallic catalyst on the surface.
Park 1^^ has patented a pigment comprising a dried froth formed by
co-precipitating a mixture of barium sulfate and ferric oxide, using
pine tar, pine oil, cresylic acid, w-, c?-, or />-cresol as foaming agent.
Coolidge and Holt ^^'^ claim that a pigment is rendered non-caking by
the addition of from 0.25 to 1.0 percent of a protective agent dispersed
in a liquid medium, said agent being taken from the group consisting
of rubber, rubber latex, balata, and gutta percha, whereby a film is
deposited on individual pigment particles when the mass is dried.
Gray and Kemp ^^^ have patented a vulcanizable insulating com-
pound for coating electrical conductors at 160° F. and 400 feet per
minute. The compound contains rubber, plasticizer, softener, and
ultra accelerator.
Cowdery ^^® has advanced a composition comprising rubber com-
pounded with coal tar free from crystalline material. Cowdery ^^^ also
claims the use of an oil resin containing one to five parts of heat polym-
erized cumarone resin and five parts of coal tar oil boiling at 170° C.
as a compounding ingredient. Bergeim ^^^ proposes the use of a com-
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410 ANNUAL SURVEY OF AMERICAN CHEMISTRY
position comprising rubber and a coal tar distillate, the distillate boiling
above 200° C. under atmospheric pressure. Frolich ^^^ uggs a rubber
composition containing an asphaltene powder derived from cracked
petroleum tar, free from hydrocarbon oils and resins.
Minor 113 proposes the addition of triethanolamine which has
absorbed an equal volume of carbon dioxide gas to a rubber compound
as an agent for fhe preparation of sponge rubber.
Kiernan ^^^ uses a leuco compound of a vat dye, which has been pre-
pared by the action of a reducing carbohydrate, to color unvulcanized
rubber. Croakman ^^^ uses the leuco compound of a dye with latex,
followed by oxidation, to obtain a colored, vulcanized rubber. He also
mixes the leuco compound of a dye with solid, unvulcanized rubber,
followed b.y oxidation, to obtain a colored, vulcanized product.ii®
Damon ^^^ claims to have improved carbon black, intensifying the
color by continuously agitating a charge and subjecting it to a slow
oxidation at a temperature below that at which calcining takes place
but high enough to increase the stable oxygen content of the carbon
black. Bolton and Hayden^i^ have developed a process for preparing
a rubber composition containing carbon black and an open chain ali-
phatic alcohol of at least eight carbon atoms.
Rubber Technology. Davies ^^^ discusses the discoloration and
transparency in vulcanized rubber. Discolor ization originates from
various causes, including natural components of the latex, putrefaction
of protein, contamination with iron, smoke and dust, the natural brown
color of the rubber-sulfur compound, and impurities in nominally color-
less or white compounding ingredients. This discoloration makes the
production of colorless transparent vulcanized rubber and white vul-
canized rubber impossible without excessive loading.
Keenan ^^o gives a short discussion of the uses of aluminimi in the
rubber industry. It is used for molds because it heats evenly, requires
little cleaning, is immune from attack by sulfur, sulfur compounds,
rubber solvents, and ammonia, is strong, hard, light, cheap, and inert,
and gives a very smooth surface, dimensional accuracy, and good
detail.
Peterson ^^i discusses new uses of rubber. He mentions the use
of sponge rubber as an expansion joint for highways. The rubber lasts
15 to 20 years. Townsend 122 discusses the application of latex in the
preparation of paper fibers. Madge ^23 makes rubber thread by forcing
an aqueous dispersion of rubber through a nozzle into a coagulant, the
nozzle being cool enough to freeze the dispersion. Minor ^24 manu-
factures sponge rubber by adding an inert gas under pressure to the
latex and vulcanizing, the water escaping as steam, which condenses.
Gilbert and Malm i^s impregnated a cable conductor with material
formed from a composition of matter comprising at least semi-fluid
depolymerized natural rubber mixed with an antioxidant not soluble
in water.
Muller 126 proposes a degummed or artificial silk fiber treated with
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RUBBER 411
a solution of the reaction product of rubber with chlorostannic acid.
Bodle ^27 makes a decorated rubber article by electrodeposition of the
rubber in the cavities of an engraved anode plate, transferring the
deposited rubber to an unvulcanized rubber surface by adhesive contact
therewith, and vulcanizing.
Hoover ^28 explains how the excessive wastes in the pickling of steel
may be eliminated by the use of a new type of rubber-lined acid tank.
Cements and Adhesives. Contributions to cements and adhe-
sives have appeared in the patent literature from the laboratories of
the consumer industries.
Kronquest and Robison ^^^ have patented a coating dough for pro-
ducing a coating material, comprising a mixture of 100 parts of rubber
solution containing 30 parts rubber, 15 parts adhesive ester gum,
3 parts liquid petrolatum, and approximately 100 parts of zinc oxide.
Williams and Smith ^^o reduce the viscosity of rubber solutions by
the addition of a small amount of unsymmetrical substituted hydrazine.
Kronquest and Robison ^^^ have patented a liquid coating material
for sealing the seams of cans — 3. mixture of rubber, zinc oxide, an
adhesive ester gum, a plasticizer, sulfur, an accelerator, an antioxidant
in a volatile solvent for the rubber and the gum. Kronquest and
Robison ^^^ have also patented a coating material of milled rubber
(30 parts rubber and 80 parts zinc oxide), an adhesive gum, and a
plasticizer.
Robinson ^^^ claims a composition for lining can. ends which consists
of a solid body material, a solution of latex, and fortified ammonium
alginate. B oilman and Ornes ^^^ claim a liquid adhesive adapted to
vulcanize firmly and secure durably a plastic rubber composition to
leather-like surfaces.
Reclaiming. Reclaimed rubber has played an important role in
stabilizing the price of crude rubber. The principle use of reclaim
rubber is in mechanical goods. As the price of crude rubber advances,
the use of reclaim will increase, and more attention will probably be
devoted to research in this important field.
Lane ^^^ reclaims rubber by heating fiber-containing vulcanized scrap
with a small amount of caustic alkali. Busenburg ^^^ claims a method
which comprises shredding scrap rubberized fibrous material, removing
the major portion of the rubber from the shredded material, partially
decomposing the remaining shredded essentially fibrous material by
treatment for at least eight hours with steam at superatmospheric
pressure, and physically disintegrating the treated material to produce
a relatively free flowing earth-like product.
CampbelP^'^ has devulcanized scrap rubber by introducing an oil,
including benzene, toluene, xylene, and a heavy solvent, into a digestor
with a desulfurizing agent. Upon application of heat and pressure in
the presence of moisture, the rubber swells and softens, thereby allow-
ing the desulfurizing agent to react.
Fairley ^^^ has patented a process of treating vulcanized rubber which
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412 ANNUAL SURVEY OF AMERICAN CHEMISTRY
comprises subjecting vulcanized rubber to destructive distillation up to
400° C, continuing the distillation until a dry residue is obtained, con-
densing all resultant vapors, and collecting the mixture of vapors as a
single distillate. Davies ^^® has patented a method of treating rubber
to produce depolymerization which comprises subjecting the rubber to
the action of caustic soda and a hypochlorite.
Hard Rubber. Kemp and Malm ^^^ give a resume of the litera-
ture on hard rubber, including vulcanization, chemical and physical
properties, compounding, and mechanical and electrical properties.
Edland^^^ makes hard rubber products by vulcanizing rubber mix-
tures with a percentage of sulfur sufficient to form hard rubber and
with the addition of a sufficient amount of selenium to accelerate the
vulcanization but not exceeding about 14 percent of the sulfur.
Latex and Rubber Dispersions. Latex and rubber dispersions
are playing an increasingly important role in the rubber industry. A
book "Latex in Industry" has been written by R. J. Noble and published
by "Rubber Age."
Cotton ^*2 gave a review and discussion dealing with latex as a
colloid system, surface phenomena, stabilization, coagulation, concen-
tration, compounding, filler dispersions, viscosity, surface tensions, the
influence of humidity, "setting," heat sensitizing, drying ornamental
surfaces, and vulcanization. McGavack^^^ discussed the use of latex
as wire insulation and described latex purification, water absorption,
advantages of latex insulation, and the electrical properties of the
product.
McGavack and Teflft ^^^ have prepared a water-resistant rubber for
electrical insulation, containing creamed latex with wax dispersed in it
and an ammonium soap of the wax. Tefft ^*^ uses a latex containing up
to 0.5 parts of a water-soluble alkylated cellulose per 100 parts of latex
solids for creaming. McGavack ^^^ patented a process for increasing
the rate of creaming of latex by subjecting a mixture of creaming agent
and latex to a violent shearing stress for a brief period of time, then
allowing the serum and rubber-rich portions to separate by gravity.
McGavack ^^"^ also thickens latex with a small amount of hydrophilic
colloid, introducing additional amounts of said hydrophilic colloid into
at least a portion of the serum, and mixing the thus-treated serum with
the cream portion.
Madge ^^^ claims a golf ball thread deposited directly from latex,
having smooth faces and rounded edges.
Noble ^^^ claims a process which comprises adding to rubber latex
a water-soluble stabilizer, flocculating the latex with a chemical that
insolubilizes the stabilizer, dewatering the rubber floes partially, then
adding water and a chemical that restore the insolubilized stabilizer,
thereby causing the mass to revert to latex. Noble ^^^ has also pre-
pared granulated rubber from rubber latex by adding an insolubilizable
hydrophilic stabilizer to the latex, flocculating the latex with an agent
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RUBBER 413
that insolubilizes the stabilizer, separating the floes, dewatering and
granulating the cake.
Leguillon ^^^ makes a decorated rubber article by using two distinct
types of plastics, a body stock, and a surface-decorating stock. The
body stock is roughly formed to desired pattern and then the decorating
stock with a lower plasticity is poured on and the whole vulcanized
in a mold under pressure. Leguillon ^^^ also decorates rubber articles
by applying to a body of rubber a multitude of bodies of decorating
stocks of at least two different light reflectivities. This forms a surface
with a multitude of diffusion planes. Leguillon ^^^ makes multicolored
rubber articles by producing a localized deposit of rubber in the cavities
of an open cavity engraved mold.
Szegvari ^^* makes rubber articles by a method which comprises
applying to a base surface a coagulant whose thickness varies over
the surface and thereafter applying a coagulable dispersion of rubber
and drying the coagulated rubber.
Linscott ^^^ has patented a stable concentrated latex composition
capable of producing a dried rubber film substantially free of water-
soluble ingredients, comprising a creamed latex containing a soap of
a voltatile base and a soap forming acid, and a volatile resin solvent
which is a non-solvent of rubber.
Williams and Dales ^^^ stabilize artificial and natural latex by adding
sulfonated abietane or sulfonated abietene and sulfonated abietine.
Hazell ^^^ manufactures a rubber fabric by applying a coating of
rubber from an aqueous dispersion to a fabric and applying another
coating of rubber which is less basic (alkaline) than the first. Win-
chester^^® prepares rubber goods directly from latex by applying a
dehydrating agent to a form, alternately dipping the form in a bath
of latex and removing it to the air, and drying the whole when the
desired thickness is reached. Dehydrating agents used are bentonite,
wilkenite, and ardmorite.
Partridge ^^® prepares an artificial rubber dispersion by dispersing
the aqueous medium in the rubber and then inverting the phases of the
dispersion by adding a soluble peptizing agent capable of furnishing
polyvalent negative ions. Levin ^^^ produces a cellulose-rubber mix-
ture by mixing a solution of viscose with an aqueous suspension of
rubber, adding a chloride of an alkaline earth metal, heating, and recov-
ering the solid components.
Willson 1^1 claims a coagulant composition, comprising a latex coagu-
lant, a volatile organic solvent, and a substance which improves wet-
ting of the form and also of the residue. Cake ^^2 preserves latex with
a mixture of phenol, soap, ammonia, and alkali metal hydroxide.
Chapman and associates ^^^ control the speed and degree of thicken-
ing of a latex dispersion by addition of a salt of hydrofluosilicic acid.
Messer ^^ claims a lactex composition containing a vulcanizing agent
and a water-soluble dithiocarbamate. Erdahl ^^^ uses a composition of
matter comprising alginic acid and rubber latex. Grupe and Kienle ^^®
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414 ANNUAL SURVEY OF AMERICAN CHEMISTRY
claim a plastic composition comprising a mixture of vulcanized rubber
or rubber latex and an alkyl resin.
Synthetic Rubber and Rubber-Like Products. Brous and
Semon ^^^ present some of the properties and uses of a new plastic,
"Koroseal." The generic term "Koroseal" refers to a particular class
of compositions with properties varying from those of hard rubber to
those of a jellied rubber cement embodying modified, substantially
insoluble polymers of vinyl halides. By a suitable choice of raw mate-
rials in proper proportions and of methods of processing, a variety
of useful rubber-like products can be prepared, the chemical and physi-
cal properties of which depend upon the above factors. The process-
ing, compounding, physical and chemical properties, and applications
are discussed. Koroseal is characterized by remarkable resistance to
various oils, mineral acids, alkalies, oxygen, and radiation.
Korolac is the solution of Koroseal and is recommended for covering
plating-racks.^^® It withstands alkalies, sulfuric acid, nitric acid,
hydrochloric acid, hydrofluoric acid, chromic acid, and water. Its film
is tough and elastic and easily repaired. Korogel is the jelly form of
Koroseal and is used for molds for plaster of Paris, Keene's cement,
Portland cement, Hydrocal, and other types of synthetic stone. It gives
fine detail and will not dry out. It can be remelted and re-used.
Special mention is given to a type of coating with a trade name of
Thiokol C-103.^®® It can be sprayed, spread, dipped, or brushed on.
It bonds solidly to most surfaces, and it does not age. It is highly
resistant to aromatic hydrocarbons and chlorinated solvents.
Thiokol D is an oil-proof synthetic rubber with a tensile strength
up to 1,700 lbs. per square inch.^*^^ It is flexible at —45° F. and resistant
to hot oil at 200° F.
Reed ^"^^ claims as a plastic composition and process of making the
same a homogeneous and amorphous composition, comprising rubber
together with a vinyl resin identical with a resin resulting from the
conjoint polymerization of two different vinyl esters.
Brooks ^"^2 has patented a process of making a rubber-like material
by separating mono- and diolefins of four to five carbon atoms from
a mixture of hydrocarbons. The diolefins are separated from the mono
by cuprous chloride and the former polymerized to form a rubber-like
material.
Nieuwland ^"^^ presented a general paper on the preparation, prop-
erties, and uses of DuPrene.
Carothers and Berchet ^"^^ claim a process which comprises reacting
1,2,3,4-tetrachlorobutane with an alkaline compound which will remove
hydrogen chloride from the said chlorobutane.
Collins ^^^ uses an aqueous dispersion of a halogen-2-butadiene-l,3
and protein in which the ratio of one to the other is never greater
than 9:1.
Gibbons and Smith i'^« produce a styrol from alkyl benzol by pyro-
genically dehydrogenating material containing sulfur, whereby the
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RUBBER 415
released hydrogen combines at least in part with the sulfur, and sepa-
rating the styrol from the reaction by-products.
Derivatives of Rubber. Calvert ^"^^ has patented a transparent
film composed of a rubber hydrohalide and a substance to retard photo-
chemical disintegration of the rubber hydrohalide.
Baymiller ^"^^ proposes the treatment of a rubber surface by subjecting
it to the action of a solvent for a suflficient time to cause slight flowing
of the surface and then to the action of a halide of an amphoteric
element.
Ford^*^^ prepares a derivative of rubber by heating a mixture of
rubber, a smaller proportion of an aldehyde, and a phenol in the pres-
ence of an aromatic sulfonic acid. McGavack^so jj^s produced chlo-
rinated rubber by introducing chlorine into the vulcanized latex.
Miscellaneous. Thies ^^^ proposes the use of a small amount of
furoic acid to prevent the scorching of rubber.
Fine ^82 has shown that the use of rubber cements as a constituent
of paints is made possible only by the reduction of viscosity. A number
of catalysts have been tried and formulas developed that yield ready-
mixed paints, as well as gloss paints with improved qualities. At pres-
ent the addition of rubber to enamels has not been as satisfactory as
in the case of paints.
Jacobs ^^^ has patented a paint consisting of a liquid composition com-
prising crude rubber, solvent naphtha, petroleum, turpentine, linseed
oil, China wood oil, kauri gum, ester gum, manganese borate, zinc sul-
fate, and red lead in such proportions as to make the composition suitable
for use as a paint
Fairley ^®* prepared a varnish gum by a method which comprises
subjecting vulcanized rubber to destructive distillation until a dry resi-
due is obtained, collecting the mixture of vapors as a single distillate,
heating said distillate in contact with nitric acid, and cooling the reac-
tion product. Fairley ^^^ also claims a flowable coating comprising a
drying oil, which is the total distillate obtained by distilling vulcanized
rubber to dryness, a resin, and a drier.
Holm ^®® has patented an artificial leather from a mixture of rubber,
fiber, and leather.
Werder ^^^ has patented a lubricant consisting of a heavy lubri-
cant, a volatile solvent, and a rubber cement.
Weller^®^ vulcanized rubber by interposing between the contacting
surfaces of the article and the mold the salt of a polybasic acid ester
of an alcohol having from 6 to 20 carbon atoms.
Seaman ^^^ developed a rubber solvent consisting of a liquid organic
sulfide selected from the class consisting of alkyl thioethers and poly-
sulfides.
Bonney and Egge^^® claim a protective coating composition con-
sisting of a homogeneous mixture of chlorinated rubber and that com-
ponent of oxidized drying oil which is separated from the unoxidized
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416 ANNUAL SURVEY OF AMERICAN CHEMISTRY
and non-hardening constituents and is capable of hardening without
further oxidation.
Lawson ^^^ isomerizes rubber with anhydrous fluoric acid.
Flint ^®2 claims a composition of matter comprising peracylated rub-
ber and a film forming material of the class consisting of cellulose
derivatives and resins, the peracyl group of said peracylated rubber
being derived from a non-basic acid.
Rodman ^^^ claims a rubber composition containing a pig^nent and
a dispersing agent selected from the group consisting of aliphatic dihy-
dric and aliphatic trihydric alcohols containing at least eight carbon
atoms.
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Chapter XXIV.
Unit Processes in Organic Synthesis.*
Edited by P. H. Groggins,
Bureau of Chemistry and Soils,
U. S. Department of Agriculture
Nitration. Practically all of the recent contributions to the
literature of nitration are concerned with the technical art and
relate to some modification or slight improvement in industrial
processes. As is to be expected, mixed acid (i. e., nitric-sulfuric
acid) was the principal nitrating agent employed.
Mixed Acid as a Nitrating Ag-ent, In the preparation of the
iso-tneric nitrochlorobenzefnes, an eutectic mixture (65 percent
para and 35 percent ortho) is obtained after the />-isomer is crystal-
lized out. When this mixture is submitted to dinitration with
mixed acid (67 percent H2SO4, 33 percent HNO3) at 60® C, the
o-isomer is preferentially nitrated to 2,4-dinitrochlorobenzene,
whereas, the />-isomer is largely unattacked.^ Beard and Lulek^
report the nitration of anthraquinone-2-carboxylic acid dissolved
in about 100 parts of concentrated sulfuric acid with mixed acid;
the same product can also be obtained by a similar treatment
of the keto acid before cyclization.^
In the preparation of 4-nitro-2-aminotoluene ^ and 4-nitro-2-
aminoanisole ^ from the corresponding amines, it has been found
advantageous to treat the diluted reaction mass with naphthalene-
sulfonic acids. A sulfonic acid salt of the amine is formed and
precipitated. The free bases are obtained by washing and hydro-
lyzing the sulfonates. Another method of separating nitroamines
has been proposed by Flett.® In the nitration of acetanilide, the
o-isomer is separated by diluting the reaction mass to a residual
H2SO4 acidity of 65 percent and permitting the sulfate of the
/>-isomer to separate as crystals. The use of adsorbent silicious
material, such as kieselguhr, to facilitate the separation of nitro-
benzene from the spent acid is reported by Simon.*^
Acetyl and benzoyl derivatives of 4,5,6-tribromoguaicol were
nitrated, with fuming nitric acid at room temperature.® The
products were 2-methoxy-3-nitro-4,S,6-tribromophenyl acetate and
♦ Compiled by the following authors of "Unit Processes in Organic Synthesis,"
McGraw-Hill Book Company, 1935: M. R. Fenske, P. H. Groggins, S. J. Lloyd, L. F.
Marek, H. P. Newton, A. J. Norton, E. E. Reid, A. F. Shepard, R. N. Shreve, W. A.
Simpson, A. J. Stirton, and H. E. Woodward.
419
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420 ANNUAL SURVEY OF AMERICAN CHEMISTRY
2-methoxy-3-nitro-4,5,6-tribromophenyl w-nitrobenzoate, respec-
tively. It is significant that no bromine was split off in these nitra-
tions and that, in the last case, both nuclei were nitrated.
Craig ® has studied the nitration of fer^butylbenzene with mixed
acid, a mixture of 77 percent para and 23 percent ortho and no
meta derivatives being obtained.
Michael and Carlson ^^ have made an excellent study of the
mechanism of the nitration process. With respect to the nitration
of ethylene with mixed acid, they conclude the acid mixture must
contain mixed anhydride, HOSO2ONO2, which should add readily
to ethylene to yield CH2(OS03H)CH2N02, from which the SO3H
group should be displaced by the more negative NO2 radical with
the formation of pyrosulfuric acid and the nitro nitric ester. Grog-
gins ^^ has presented tabulated data indicating that nitration gen-
erally occurs through the intervention of simple or mixed anhydrides
of nitric acid.
Amination by Reduction. During the past few years very little
of real importance has been added to our knowledge of amination
by reduction.
Metal-Acid Reductions, It was well known that, in the metal-acid
reduction, the acid could be substituted by any salts which, in the
presence of metals, are hydrolyzed in aqueous solutions, resulting
in the formation of hydrogen ions. Calvert ^^ has pointed out that
a solution of ammonium chloride and finely divided iron can be
used for the reduction of 2,4-dinitrodiphenylamine. It has also
been shown that comminuted, tinned, ferrous scrap can be employed
in reductions requiring iron.^^ Iron etched with hydrochloric
or other suitable acids can be utilized for the reduction of nitro-
biphenyl in benzene solution.^^ Zinc dust and a solution of zinc
acetate and copper sulfate has been recommended for the reduction
of nitroguanidine,^^ while zinc and HCl are suggested for the
reduction of either iV-(/>-nitro- or nitrosophenyl)-morpholine.^^
Sodium arsenite in alkaline solution is employed by Dahlen and
Carr ^"^ for the preparation of 3,3'-diaminoazoxybenzene.
Reduction by Hydro genation, Unsjonmetrically substituted ethyl-
enediamines ^^ may be prepared by reducing nitriles (which are
made by causing an aldehyde or ketone to react with a metal
cyanide in the presence of a mineral acid) with hydrogen under
pressure, and then causing the product to react with an amine.
/>-Nitro- or nitrosophenol in acetone can, likewise, be reduced by
hydrogen in the presence of a platinum catalyst.^® Wojcik and
Adkins ^o have reported on an extensive investigation relating to
the catalytic reduction of amides to amines. Machlis and Blanch-
ard^i have described the reduction of a-isonitroso-4-propionylbi-
phenyl with hydrogen at 35 pounds pressure in the presence of
palladiumized charcoal.
Diazotization. In recent years American chemists have shown a
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UNIT PROCESSES IN ORGANIC SYNTHESIS 421
moderate interest in the diazotization reaction, as shown by their
publications.
Snow 22 has extended our knowledge of the effect of temperature
and of substituting groups on the stability of diazonium com-
pounds by quantitative studies on a series of 32 such compounds.
He confirms the rule that negative groups increase the stability of
diazonium compounds, and shows that many amines may be
diazotised at higher temperatures than were formerly used. It
has been known that 2-aminofuranes are not easily diazotised.
Oilman and Wright ^3 suggest that 3-aminofuranes are more easily
diazotised because they are more basic. They describe the diazoti-
zation of 4-amino-5-acetylamino-2-furoic acid ethyl ester and some
monoazo compounds obtained from it.
The diazonium group may be replaced by the acetate group,
according to Haller and Schaeffer,^^ by reaction of diazonium boro-
fluorides with acetic acid or acetic anhydride. Smith and Haller ^5
report an exception to this reaction in the case of l-amino-3,4-
dimethoxybenzene, which gives 2-hydroxy-4,5-dimethoxyaceto-
phenone, probably by rearrangement of the acetate first formed.
Clark 26 shows that 4,6-dinitrobenzene-2,l-diazooxide is useful
as a detonating agent for initiating the explosion of dynamite and
other explosives. A method of obtaining this diazo compound in a
free flowing form which makes its use practical is disclosed by
Hancock and Pritchett;^^ the process consists of a gradual addition
of acid to a solution of a picramate and a nitrite.
A process for obtaining a stable dry preparation which on addi-
tion to water gives a solution of a diazonium salt is reported by
Kemmerich.28 The preparation consists of the reaction of an
amine, in the form of a condensation product with an aldehyde,
with a nitrite and an acid salt, such as sodium bisulfate.
A peculiar reaction of diazotised aminopentamethylbenzene was
observed by Smith and Paden.29 With pentamethylbenzene, it
reacted to give a colorless hydrocarbon, C22H30, not decamethyl-
biphenyl.
Halogenation. Reports and patents dealing with recent research
and advances in the field of halogenation are so numerous that no
detailed or adequate survey of the literature can be presented here.
Chlorination (Hydrocarbons). Sharp ^o describes the chlorina-
tion of propane with chlorine in presence of cupric or ferric
chloride under the influence of actinic rays. The liquid phase mono-
chlorination of pentane in the presence of poly chlorinated products
is also reported. Benzene in the liquid phase under 4 atmospheres
pressure at -- 15° C. gives a highly chlorinated product.^^
Acid and Alkyl Chlorides. The conversion of carboxylic acids to
acid chlorides is the subject of a number of patents. Thus, acid
anhydrides may be treated with chlorine in the presence of phos-
phorus or phosphorus trichloride or alternatively phosphorus tri-
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422 ANNUAL SURVEY OF AMERICAN CHEMISTRY
chloride in the presence of phosphorus oxychloride.** Phosphorus
pentachloride in benzene solution is similarly employed for 1,4- or
1,5-anthraquinonedicarboxylic acids.^^ Conover^s shows that
benzoyl chloride may be obtained from phthalic anhydride by
reacting with hydrogen chloride at 200° C. in the presence of a
decarboxylating agent, such as chromium chloride.
The preparation of alkyl halides from alcohols and olefins has
been the subject of widespread study. Daudt reports the prepara-
tion of alkyl halides by reacting ethanol with hydrogen chloride
in the presence of bismuth chlorides.^^ The halogenation may also
be carried out in the presence of zinc chloride.^*^ Olefins may
similarly be converted by hydrogen chloride in the presence of
sulfuric acid or a metal halide catalyst, such as antimony or bismuth
chloride.^® Tert-hutyl alcohol is converted to the alkyl halide by
hydrogen chloride in the presence of calcium chloride,*® while
copper is employed to increase the yield of ethyl bromide from
ethanoH^ when the reaction is carried out in aqueous sulfuric
acid. The presence of copper results in the production of sulfur
dioxide which reduces any bromine to bromide ion.
Lutz and Wilder ^^ have studied the action of phosphorus penta-
chloride and thionyl chloride on 2,5-diphenylfurans and unsaturated
1,4-diketones. Phosphorus pentachloride reacts to produce 2,5-
diphenylmono- and -dichlorofurans and also apparently adds to
dibenzoylhydroxyethylene to give diphenyl-4-chloro-3-butene-l,2-
dione. Thionyl chloride behaves similarly in some cases, but is not
so active. 1-Aminoanthraquinone dissolved in nitrobenzene is
chlorinated in the 4-position by the action of sulfuryl chloride *^ in
the presence of aluminum chloride. Bass and Burlew ^^ report the
preparation of a- and 3-chloropropionic acids by chlorination of the
acid with chlorine gas in the presence of the corresponding acid
chloride.
Bromination. Raiford and Milbery^^ have brominated the benzoic
esters of phenol and the cresols under different conditions and the
position of the bromine was determined. Sachs and Peck ^^ show
that in the bromination of anthraquinone with bromine, chlorine
under pressure can be employed to regenerate bromine in situ from
the hydrogen bromide that is liberated.
Fluorination, Due to the economic value or potential possibilities
of many fluorine compounds as refrigerants or in the manufacture
of dyestuffs, research in this comparatively new field has been both
intense and widespread.
With respect to the preparation of aromatic fluorine derivatives,
Aelony*^ reports an improved method of synthesizing w-fluoro-
benzotrifluoride. The fluorination of hexachlorobenzene is dis-
cussed by Bigelow and Pearson.^*^ The reaction of acyclic com-
pounds with hydrogen fluoride and a hydrocarbon halide containing
a halogen other than fluorine in the presence of ferric chloride
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UNIT PROCESSES IN ORGANIC SYNTHESIS 423
and activated carbon is recorded in one patent *® and the use of
antimony pentachloride and hydrogen fluoride in another.^® Instead
of antimony pentachloride, numerous other halides are suggested.^^
For the preparation of aliphatic fluorine derivatives, e. g.,
dichlorodifluoromethane from carbon tetrachloride, Henne ^^ sug-
gests the use of antimony trifluoride and the addition of chlorine
to the reaction zone. Henne and colleagues ^2, 53 further elaborate
on this process in subsequent patents, and the use of calcium
fluoride ^^ and antimony sulfate ^^ are also reported. Daudt and
his coworkers have also contributed largely to the advances in
this field and their contributions are recorded in numerous
patents.^®-^<*
Calcott and Benning^^ describe the preparation of fluoro-
chlorethanes by reacting tetrachloroethane with fluorine in an
inert liquid medium.
Deanesly^2 adds to our understanding of the halogenation
process by his investigation of the inhibitory influence of oxygen
in the chlorination of propane, butane, and pentane. In the addition
of chlorine to olefins, no inhibition by oxygen was observed, but
this may be due to the speed of the reaction.
Sulfonation. Recent contributions in the field of sulfonation
indicate clearly a better understanding of the fundamental prin-
ciples involved in this unit process. The use of cycle acids, the
employment of sulfur trioxide in comparatively inert solvents, and
the utilization of chlorosulfonic acid for the preferential sulfonation
of one of two isomers exemplify the progress in the art.
In the sulfonation of benzene Carswell®^ employs a heel from
a previous sulfonation and progressively adds definite proportions
of oleum and hydrocarbon so that the sulfuric acid concentration
in the sulfonator is at all times approximately 98 percent; sulfone
formation is inhibited and the process may be carried out con-
tinuously.
Gubelmann and Rintelman ®* report an improvement in the pro-
duction of the anthraquinone-2,6- and -2,7-disulfonic acids. The
disodium salt of />'-sulfobenzoyl-2-benzoic acid is cyclized to form
3-anthraquinonesulfonic acid by means of 1.5 parts of 25 percent
oleum in the presence of a small amount of vanadium oxide. Disul-
fonation is then effected by adding two parts of 60 percent oleum
and heating to 150° C. In this way a mixture of 2,6- and 2,7-anthra-
quinonedisulfonic acids is produced in a purer form than by the
usual process starting with anthraquinone. a-Isomers, oxidation
products, and unreacted anthraquinone are largely avoided.
Chlorosulfonic acid was used by Gilman, Smith, and Oatfield®^
for sulfonating dibenzofuran in their study of the orientation of
nuclear substituents. They found that sulfonation occurs in the
2-position and with great ease. An 89 percent yield was obtained.
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424 ANNUAL SURVEY OF AMERICAN CHEMISTRY
SO,H
+HC1
Chlorosulfonic acid, in 5 percent excess, was dropped into a
solution of the dibenzofuran in carbon tetrachloride at 25° C.
This is the first time that orientation of a dibenzofuransulfonic
acid has been definitely established.
An interesting and important use of chlorosulfonic acid is pro-
posed by Kyrides.^® The eutectic mixture obtained in the dichlo-
rination of benzene is treated at 25° C. with chlorosulfonic acid,
whereby the o-isomer reacts preferentially and the /^-isomer is left
unattacked.
The extended use of sulfur trioxide in inert solvents for direct
sulfonations has progressed as was to be expected. Tinker®^
employs it in tetrachloroethane for the sulfonation of 3-naphthyl-
amine, while Weiland and Prahl ^® employ the same agents for the
sulfonation of abietene. Temperatures of 0-25° C. are preferred.
The monosulfonation of biphenyl with concentrated sulfuric acid
in the presence of nitrobenzene was disclosed by Stoesser and
Marschner.^® The reaction is not carried to completion, the unat-
tacked biphenyl being separated. Biphenyl-4-sodium sulfonate is
then obtained as colorless plates by treating the sulfonic acid with
sodium sulfate.
Lauer and Langkammerer "^^^ investigated the action of sodium
bisulfite solution on resorcinol at the boiling temperature and
obtained the hitherto unreported sodium salt of phenol-m-sulfonic
acid. The reaction mixture, after boiling, was treated with caus-
tic soda and then hydrochloric acid. The sodium salt of phenol-wi-
sulfonic acid was then obtained from the evaporated and dried mix-
ture by extraction with alcohol.
Reed and Tarter '^'^ studied the action of aqueous sodium sulfite
on alkyl halides of higher molecular weights, by carrying out the
reaction in an autoclave at about 200°. Bromides were used in
their investigation, except in the preparation of sodium lauryl
sulfonate, in which case lauryl chloride was used. Octyl, decyl,
myristyl, cetyl, octadecyl, and lauryl sulfonates were prepared.
This investigation settles a point of argument concerning the
Strecker reaction and firmly establishes this reaction as a method
of obtaining alkyl sulfonates of higher molecular weight.
Hitch and Black '^^ describe a method of separation of 1-amino-
naphthalene-5-sulfonic acid, "Laurent's Acid", from 1-amino-
naphthalene-8-sulfonic acid, "Peri Acid". It is stated that the most
effective means of separating these acids is to treat an alkaline
solution of the two acids with sulfuric acid until the />H is adjusted
to between 4.0 and 4.6. This treatment results in the precipitation
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UNIT PROCESSES IN ORGANIC SYNTHESIS 425
of the 1,8-acid, which is filtered off. The filtrate is then made acid
to Congo, whereupon the 1,5-acid precipitates.
Adamson'^3 studied the purification of 1-nitroanthraquinone-
6-sulfonic acid from impurities present in large scale manufacture.
This acid is an intermediate in the production of l-nitro-6-chloro-
anthraquinone. It has been found that erratic results were obtained
in the conversion of the sulfonic acid to the chloro compound
unless the sulfonic acid was previously purified. It was found that
the nitroanthraquinonesulfonic acid could be removed from impuri-
ties with practically complete success by recovering the sulfonic
acid from a 40-45 percent sulfuric acid solution instead of the 70
percent residual acidity previously used. Sodium sulfate is used
to decrease the solubility of the sulfonic acid.
Amination by Ammonolysis. The progress in this field has been
characterized by improvements in the established art, rather than
the introduction of new principles. Because certain groups of com-
pounds require fairly specific treatment, this review is arranged
accordingly.
Aliphatic Halogen Compounds. Lauter '^^ has modified the process
of Curme and Lommen '^^ for the preparation of ethylene-
diamine from the corresponding dichloride. Instead of employing
aqueous ammonia alone, a prodigious quantity of such salts, e. g.,
cuprous chloride, capable of forming a ternary addition complex
with the reactant, is added. Upon hydrolysis of the complex, the
diamine is obtained.
Aromatic Halogen Compounds. Wuertz '^^ has extended the work
of Groggins and Stirton "^"^ with respect to the use of ammonium
salts and oxidants. Such compounds have been found useful in
the preparation of amines which are not readily susceptible to oxi-
dation. SucK. compounds inhibit the formation of hydroxy com-
pounds and facilitate completion of the reaction.
Treatment of Aliphatic Alcohols. The vapor phase conversion of
alcohols to amines has been the most active field of investigation.
Arnold '^^ thus prepares butylamine by passing the corresponding
alcohol over a porous gel impregnated with a dehydrating oxide.
Methylamine '^^ is similarly prepared by passing the reactants over
aluminum oxide ®^ or activated charcoal.^^
Bottoms 82 discovered that glycerol dichlorohydrin can be con-
verted to 1,3 diamino-2-propanol by treatment with aqueous
ammonia in the presence of sufficient alkali to form sodium chloride
with the replaced chlorine. Isomeric isopropanolamines have been
prepared by Wickert^^ by diffusing propylene oxide into aqueous
ammonia.
Treatment of Carbohydrates. Flint and Salzberg ^^-^^ have developed
procedures for the preparation of glucamines and related products
by reacting glucose with aqueous ammonia or alkylamines in the
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426 ANNUAL SURVEY OF AMERICAN CHEMISTRY
presence of a nickel catalyst and under a hydrogen pressure of
1500 pounds.
Calcott 8*^ has prepared secondary and tertiary amines by treating
-AT-glucyl-iV-methylamine with cetyl chloride at 150° C. in a copper
autoclave. Bruson ®® has discovered that amides can be prepared
from fatty acids by reacting in open vessels with urea at 180 to
250° C.
Oxidation. Considerable money and effort has been spent in
attempts to make use of two basically cheap chemical raw mate-
rials, i. e., air and the alphatic hydrocarbons of petroleum, for the
formation of more valuable oxygen-containing compounds. An
historical account of this work has been given by Marek and
Hahn.8» From the standpoint of the use of petroleum as a raw
material for chemical synthesis, Ellis ^ has given an account of the
work dealing with oxidation. Other reviews have appeared, many
of them associated with original work.
Wiezevich and Frolich ®^ have discussed their laboratory and
semi-commercial work on the direct oxidation of saturated hydro-
carbons at high pressures, the results of which showed the possi-
bilities for the formation of oxygenated compounds from methane,
ethane, propane, butanes, pentanes, and heptanes as raw materials.
Elevated pressures were found to lower materially the temperatures
necessary for reaction. An extensive bibliography is given.
The kinetics of oxidation has been studied further. Pease and
Munro ^^ report on the slow oxidation of propane, having investi-
gated liquid as well as gaseous products. The reaction was found
to be highly autoaccelerating, to be suppressed by inert foreign
gases and by glass packing, and to have no simple kinetic scheme.
Pease ^^ also found that slow oxidation of propane at low temper-
atures and low oxygen concentrations gave rise to formation of
methanol, formaldehyde, carbon monoxide, and water as the pri-
mary products.
Few details are available on the results obtained from oxidation
of petroleum fractions. Sheely and King ^* show that vapor phase
oxidation of kerosene leads to the production of a mixture of alde-
hydes and acids containing from 8 to 10 carbon atoms per mole.
BurwelP^ also has discussed the formation of fatty acids from
petroleum by low-temperature, liquid-phase oxidation, on the basis
of several years of practical work.
Frear^® studied the nature of methane-oxygen reaction by the
flow method. Studies have been reported on the oxidation of 2-
butene, in which the principle products were found to be acetalde-
hyde and butadiene, and less important products to be glyoxal,
olefin oxide, acids, and some peroxide.^*^ Oxidation of triisobutylene
has been studied from the standpoint of evaluating the structure of
the acids obtained.®^' ^®
Oxidizing agents other than oxygen itself form a large field and
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UNIT PROCESSES IN ORGANIC SYNTHESIS 427
receive considerable attention both industrially and experimentally.
It has been shown that activated carbon under certain conditions
can absorb oxidizing agents, such as halogens, nitric acid, potas-
sium permanganate, potassium dichromate, and ammonium persul-
fate, and in such condition can be effectively used in the chemical
treatment of liquids and gases.^^ Bancroft ^^^ has discussed the
use of oxides in general as oxidizing agents, and Fisher ^^^ des-
cribes the effect of selenium oxide in the oxidation of aromatic
side chains, such as the methyl of toluene.
The oxidation-reduction potential for stannous-stannic acid
system has been redetermined and the range of data extended.^^
Potassium permanganate was found to give rapid oxidation of the
benzene ring of arylboric acid resulting in the formation of phthalic
acid.^*^ The oxidation of acetylhydrazobenzene by sodium dichro-
mate in glacial acetic acid was studied by Ritter.^^^
The oxidation-reduction reaction of mixed perchloric and sul-
furic acids in quantitative analysis has been discussed by Smith.^^
Oxidation-reduction with hydrogen peroxide was studied by Ban-
croft and Murphy and discussed at length.i^*'^
The theories relating to autoxidation have long been under dis-
cussion and new data are continually being presented in support of
the various mechanisms. Thus, Milas ^^^ and Stephens ^^ come
to the support of their theories. Egerton ^^^ has also discussed
the mechanism of autoxidation and suggests possible mechanisms
of general types of oxidation on the basis of the active molecule
theory.
The results of an extensive investigation on the electrochemical
oxidation of various organic substances in concentrated aqueous
organic salt solutions have been reported.^^^ The electrochem-
ical oxidation of toluene in nitric and sulfuric acids has been
studied; 112 ^^at of xylose in the presence of alkaline earth bromides
and carbonates was studied by I shell and Frush.i^^
The oxidation of various organic compounds has been reported ;
thus, vapor phase oxidation of ethanol,ii* propionaldehyde,ii^
cinnamaldehyde,!!^ hydrazine,ii'^ mannitol,ii^ furan series,ii® autox-
idation of animal fats and inhibition,i20 autoxidation of catechol,!^!
oxidation of tertiary hydrocarbons with oxygen ^^2 and others.
The study of atmospheric oxidation was continued by Spoehr ^^3
in his work on the catalytic oxidation of trioses and related com-
pounds. The mechanism of carbohydrate oxidation was discussed
by Swan and Evans ^^4 as a continuation of the work on this
problem.
Hydrogenation. Domestic developments in hydrogenation have
been confined largely to new researches and primarily to new
laboratory preparations.
The heats of hydrogenation of some simple olefins, employing a
copper catalyst, have been studied at 82° C.^^s, i26 xj^g ^g^t of
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428 ANNUAL SURVEY OF AMERICAN CHEMISTRY
hydrogenation of pyridine to piperidene has been determined to
be 48,680 cal. per mole over the temperature range 150 to 170° C.
In addition, the equilibrium in the gas phase system pyridine,
hydrogen, and piperidine was studied at 150 and 170° C., using
a nickel catalyst. The free energy decrease for the hydrogenation
of pyridine at 150° C. was found to be +3835 cals. per mole, while
at 170° C. it was -f 1760 cals. per mole.^27 fhe influence of oxygen
on the hydrogenation of ethylene was studied. It was found that
small amounts of oxygen in ethylene-hydrogen mixtures greatly
increased the initial hydrogenation reaction rate for the homo-
geneous reaction at 538° C.^^
In the presence of a variety of amines, carbon dioxide and
hydrogen under pressures of 200 to 400 atmospheres and tempera-
tures of 80 to 250° C, with Raney nickel or brass catalysts, yielded
formates of the amines. It is believed that the amines only serve
to neutralize the formic acid formed by the direct hydrogenation
of the carbon dioxide; i. e., that the formic acid is produced
directly and not through the reduction of compounds formed
by the reaction of carbon dioxide and amines. At temperatures
above 100° C, the formates of the amines may be dehydrated to
the substituted formamides.^^®
The catalytic hydrogenation of nitroguanidine at low pressures
with platinum oxide or Raney nickel catalysts has been found to
result in satisfactory yields of nitrosoguanidine.^^o Using platinum
oxide catalysts and low pressure hydrogenation the S-lactones of
aldonic acids have been reduced in good yields to the correspond-
ing sugars. The y-lactones have also been reduced, but usually
gave lower yields of sugars, owing to the further reduction of the
sugars to the corresponding sugar alcohols. The sugar alcohols
have been obtained in yields of from 60 to 80 percent.^^^
Using a palladium catalyst and low pressure hydrogenation,
a-isomorphine was converted to dihydro-a-isomorphine. In the
case of 3-isomorphine with a platinum oxide catalyst, two moles
of hydrogen were added to yield tetrahydro-3-isomorphine, along
with the dihydro product.^^^ ^ platinum oxide catalyst and low
pressure hydrogen also reduced pseudocodeine methyl ether to
tetrahydropseudocodeine as the principal product; the methoxyl
group was not eliminated.^^^
The hydrogenation of cis- and /ran^-dibenzoylethylene was
studied, using a platinum catalyst and various solvents. In the
case of the ^raw^-compound both mono- and unexpected di-mole-
cular products were formed, while in the case of the cw-compound
the usual expected reduction of the ethylenic double bond took
place. Parallelisms between catalytic reductions with hydrogen
and reductions with zinc combinations indicated a common reac-
tion mechanism for these two reduction methods.^^*
Dialkyl, diaryl and aryl alkyl ethers were hydrogenated at 175-
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UNIT PROCESSES IN ORGANIC SYNTHESIS 429
200° C. and 150-250 atmospheres with about 5 weight percent of
Raney nickel catalyst. The reaction consisted of hydrogenolysis
or cleavage of the ether linkage, yielding a hydrocarbon and an
alcohol. Depending on the ease of breaking the ether linkage in
compounds having unsaturated structures, there may or may not
be hydrogenation of the unsaturated linkages along with the ether
linkages. The stability of various ethers toward hydrogenolysis is
compared.^'^
The electrochemical reduction of sugars to alcohols, e. g., glu-
cose to sorbitol and mannitol was accomplished by Creighton.^^e
Lead amalgamated with mercury serves as the cathode and also
keeps the catholyte in an alkaline condition. Sorbitol may also be
obtained by agitating a neutral solution of glucose under a hydro-
gen pressure of at least 20 atmospheres at 100-150° C. in the
presence of a partially reduced nickel chromate carried on a
siliceous materiaL^^*^
Alkylation. For convenience alkylated compounds are classi-
fied according to the linkage of the alkyl radical to the rest of the
molecule. The following classification is used in this survey:
alkyl bound to oxygen, to tri- and pentavalent nitrogen, and to
carbon or to a metal; when the binding is to the carbon of an
aromatic nucleus, it is termed nuclear alkylation.
Alkyl Bound to Oxygen. Stoughton, Baltzly, and Bass ^^^ report the
preparation of new alkyl phenols by the Fries migration of
phenolic esters and subsequent reduction. Catechol and hydro-
quinone were first condensed with acid chlorides of fatty acids
and then subjected to the aforementioned treatment. Tabulated
data are given for a number of new compounds. The simul-
taneous production of 4- and 2-tertiary alkyl phenols of the ben-
zene series is reported by Perkins, et alM^ The process com-
prises reacting a tert-a\kyl halide with a monohydric phenol, having
the 2- and 4-positions free, in the presence of aluminum chloride.
The similar preparation of /(?r/-butylphenol in the presence of
hydrated ferric chloride is described by Seymour.^^^ Buc^^^ sug-
gests the production of alkyl phenols by reacting an olefin, e. g.,
hexene or cyclohexene, with cresol in the presence of sulfuric
acid.
Alkyl Bound to Nitrogen. Zimmerli ^^^ proposes the following pro-
cedure for the preparation of alkyl amines. The condensation
product of molar proportions of /)-aminophenol and furfural is
treated with dimethyl sulfate in chlorobenzene at 60° C. for two
hours. The crystalline addition compound is dissolved and reacted
with a mixture of 95 percent sodium carbonate and 5 percent
sodium sulfite, whereby furfural is liberated and monomethyl-/?-
aminophenol is obtained. According to Carleton and Wood-
ward ^^^ mono- and diethylanilines are obtained by autoclaving at
180-185° C. 465 parts by weight of aniline, 208 parts of ethyl
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430 ANNUAL SURVEY OF AMERICAN CHEMISTRY
chloride and 250 parts of ethanol. The same investigators^*^
effect a similar synthesis by reacting ethanol, aniline and hydrogen
chloride under pressure at 180-185° C. Clarke and coworkers***^
produced tertiary amines from simple aliphatic amines by reacting
with methanol and formaldehyde; yields in excess of 80 percent
are reported.
Nuclear Alkylation. Thomas ^^^ produces higher alkyl derivatives
of aromatic compounds by partially chlorinating an alip'hatic
hydrocarbon of eight or more carbon atoms and then reacting
this mixture with an aromatic compound in the presence of a
Friedel and Crafts condensing agent. Another method for pro-
ducing alkylated aromatic compounds is suggested by Isham.**''
Propylene gas, for example, is led into a mixture of naphthalene
and naphthalenesulfonic acid at 120*^ C. until the desired absorp-
tion is effected. The propylated naphthalene separates as a clear
yellow layer when the reaction mass is treated with hot water.
Ipatieff and Komarewsky **® obtained ethylbenzene and biphenyl
in rather small yields by autoclaving benzene and dry hydrogen
chloride at 125° C. Destructive hydrogenation occurred, giving
ethane, which then alkylated the ring.
Alkyl Attached to Metal. Calcott and coworkers ^*® suggest that
the subsidence of pressure be used as a guide for controlling the
reaction between large amounts of lead mono-sodium alloy and
alkyl chloride. With respect to the preparation of tetraethyl
lead, a small proportion of the total ethyl chloride required is
first added to the surface of the alloy and then other portions
are added as the reaction pressure abates.
Esterification. The preparation of esters has, in all probability,
been the most active field of organic research in recent years.
The development of new and important esters of carbohydrates, the
expanded use of the higher fatty acids, and the economic introduc-
tion of many new acids and alcohols suitable for the production
of solvents and plastics have contributed to increase the technical
and patent literature on the subject of esterification. An adequate
discussion of all types of esters cannot be made here. Some, such
as the esters of cellulose, will be omitted entirely.
Phosphoric Acid Esters. Levene and Schormiiller ^^^ have studied
the phosphoric esters of hydroxyamino acids, e. g., 1-hydroxy-
prolinephosphoric acid. Tritolyl phosphates were prepared by
reacting cresol successively with either phosphorus pentachloride
or pentoxide.^^^ The production of mixed esters, by reacting
various phosphoric acids with a mixture of alcohols obtained by
the reduction of fatty oils, is described by Graves^^^
Tremendous progress has been made during the past few years
in the preparation of mineral acid esters of alcohols, e. g., by
reacting olefins obtained from refinery wastes with sulfuric acid.
Wilson 153 reports the procedure for the preparation of ethjrl
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UNIT PROCESSES IN ORGANIC SYNTHESIS 431
acetate, which consists in hydrolyzing the reaction product of
ethylene and sulfuric acid to decompose all the diethyl sulfate
present and then adding calcium acetate, while maintaining an
excess of free sulfuric acid or monoethyl sulfate. Similar processes
relating to the preparation of isopropyl and butyl esters are also
described.^^* Such esters may also be obtained by heating the
carboxylic acid with the olefin in the presence of sulfuric acid and
permitting the reaction mixture to stratify into a solvent phase
containing the ester and an acid phase.^*^*^ Another modification
consists in reacting olefins, having less than seven carbon atoms,
with lower fatty acids, above the boiling point of the ester and
in the presence of halides of zinc, aluminum, etc., or relatively
nonvolatile inorganic acids, such as sulfuric or phosphoric acids.^^®
Vail ^^"^ shows that similar esters can be produced by reacting an
olefinic hydrocarbon, e. g., propylene, carbon monoxide, and an
alcohol under pressure.
Mono- and dicarboxylic acids have been employed extensively
in the preparation of esters. Oxalic and malonic acids, esterified
with an excess of ethyleneglycol at 100° C, produce formic and
acetic esters, respectively.^^® When an alkylene diester, such as
ethyleneglycol diacetate, is treated with ethanol in the presence
of hydrogen chloride, ethyl acetate and ethylenechlorohydrin are
formed.^^® The esterification of dicarboxylic acids, such as adipic,
methyladipic, pimelic, sebacic, muconic, zeronic, etc., with ether-
alcohols is described by Izard.^^^» ^^^
Alcohols derived by the hydrogenation of oils i^2-i64 ^j^ay be
esterified by suitable acids to produce didodecyl adipate and
phthalate, tridodecyl citrate, dimyristyl succinate, etc., by reacting
in the presence of a water-removing agent or carrier, e. g., sul-
furic acid or benzene. Numerous esters of levulinic acid and
alcohols such as octyl, nonyl, cyclohexanol, etc., are described by
Lawson and Salzberg,^^^ while terpene esters of phthalic acid are
reported by Borglin.^^^
The esterification of polyhydric alcohols with anhydrides of
dicarboxylic acids in the presence of pyridine is described by Malm
and Fordyce '^^'^ and a study of the esterification of glycerol with
chloro- and trichloroacetic acids is reported by Helgeson and
Shaw.^^® It is also shown that glycerol or glycols may be esteri-
fied by a ketene in the presence of sulfuric acid.^^®
The preparation of vinyl esters of lower aliphatic carboxylic
acids is described by Perkins.^'^^* The conditions for the synthesis
of vinyl acetate from acetic anhydride and paraldehyde are given.
The preparation of aromatic esters has been studied by a num-
ber of investigators. Nitrobenzyl esters of organic acids have been
studied by Kelly and Segura.*''^ The formation of tolyl phthalates
from cresols and phthalic acid is described in one patent ^'^^ ^nd
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432 ANNUAL SURVEY OF AMERICAN CHEMISTRY
the preparation of benzyl esters of halogeno-o-benzoylbenzoic
acids in another.^'^^
The acetylation of sucrose has been reported by Cox and Fer-
guson ;^'^* sucrose is treated with acetic anhydride in the presence
of about a third part of sodium acetate which serves as a catalyst.
Hydrolysis. Some notable advances in technical hydrolytic
operations have been reported during the past year.
Downing and coworkers have investigated the preparation of
o-dihydroxybenzenes from the corresponding dihalogen derivatives.
It was found that the introduction of a reducing agent, such as
sodium formate,^''** to the reacting materials, C6H4CI2, NaOH
(31 percent), BaCl2, and CU2O, gave good yields of the phenolic
compound. The gradual introduction of aqueous sodium hydroxide
during the course of the runj^*^® so as to maintain the alkali con-
centration at about 2.9 normal, was found to be advantageous;
the feasibility of making the process continuous was also indi-
cated.^'''^ When a barium hydroxide concentration of 2.44 normal
is used and the charge is heated at 275° C. for 10 hours, a yield
of 69.7 percent of catechol was obtained.^''®
Britton ^''^ has discovered that when an 0- or />-monochlorinated
aromatic hydrocarbon, having the general formula R— C6H4— CI,
wherein R represents an aryl or alkyl group (e. g., chlorobiphenyl
or chlorotoluene), is treated at about 360° C. with 10 percent
sodium hydroxide, a substantial portion of the product is a
w-hydroxy derivative. o-Chlorotoluene under such conditions
yields 77 percent of cresols, consisting of 59 percent m- and 41
percent o-cresol. Moose ^^^ has shown that when a mixture of
monochlorobiphenyls, preferably the eutectic (25 percent 4-chloro-
and 75 percent 2-chloro-), m. p. 14° C, is similarly treated, the
product will contain from 35 to 50 percent of the w-hydroxy
derivative, the remainder being almost wholly 2-hydroxybiphenyl.
Britton and Stoesser ^®^ report on the conversion of a-bromo-
naphthalene to a-naphthol by reacting with 15 percent sodium
hydroxide at 225° C. When, however, a-chloronaphthalene is
treated in an iron autoclave with 10 percent sodium hydroxide at
360° C, the product contains both a- and (3-naphthols in about
equal proportions.^^^
Bannister 1^8 has demonstrated that a group of organic acids,
consisting of formic, acetic, oxalic, and succinic acids, can be
obtained from cellulose-containing materials by fusing such
materials with caustic soda at 200-260° under pressure. When
corn cobs are treated with about an equal quantity by weight of
caustic, a typical yield of acids based on the weight of corn cobs
(containing 7 percent moisture) is as follows : Acetic 25, oxalic
30, formic 15, and succinic 10 percent.
The production of indanthrones, particularly the technically
important Ar-dihydro-l,2,l',2'-anthraquinoneazines from 2-amino-
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UNIT PROCESSES IN ORGANIC SYNTHESIS 433
anthraquinone, has received considerable attention. In addition
to the usual caustic alkali and oxidant, Bishop and Perkins ^^*
recommend the incorporation of butyl alcohol and sodium phe-
nolate to the fusion mixture. Murch ^^^ suggests the addition of
alkali metal chlorates and nitrates with 2-aminoanthraquinone as
an aqueous slurry to the fused caustic alkali. Thompson ^^^ has
developed a procedure involving the treatment of 2-aminoanthra-
quinone with a caustic melt in the presence of sodium phenolate
and an alkali salt of a lower fatty acid. A procedure for the
separation of the azine from the fusion mass is reported by Peck
and Knowles.^^'^
The preparation of monohydroxy alcohols by the hydration of
olefins has been investigated by Larson.^^^ In the proposed proc-
ess the olefin and steam react in the presence of a volatile halide,
e. g., ammonium chloride, and activated charcoal.
The addition of a relatively small amount of soap is proposed
to prevent the formation of a hard scale of magnetic iron oxide
on the reactor walls in the hydrolysis of chlorobenzene.^^^
The Friedel and Crafts Reaction. Substantial progress has been
made during the past few years in our understanding and appli-
cation of the Friedel and Crafts reaction.
Groggins and his coworkers have carried out extensive investi-
gations in the preparation of ketones by condensing aromatic
compounds with carboxylic acids, their anhydrides, and acid
chlorides. Studies with Nagel and Stirton ^^® and subsequently
with Newton ^^^ showed that carboxylic acids, e. g., acetic and
benzoic, could be used instead of the acid chlorides or anhydrides.
In some of these investigations ^^^ \^ ^yas found that the addition
of powdered aluminum or iron exerted no marked deleterious
effect ^^^ and the use of iron alloy reactors was suggested.^^* It
was also found that both acyl groups of acid anhydrides could be
made to enter into reaction ^^^ when three or more moles of alumi-
num chloride are used, thus doubling the yield of ketones. A theory
regarding the mechanism of reaction in the condensation of car-
boxylic acids and their anhydrides is set forth.^®^
Oilman and his colleagues have continued their investigations
in the furane series. Studies with Calloway and Burtner ^^®
showed that furfural and isopropyl chloride gave 4-isopropyl-2-
furfural. Oilman and Burtner ^^'^ discuss certain anomalous reac-
tions, and in a further investigation with nitro compounds,^®^ it
was found that nitrofuran, propionyl chloride, and titanium tetra-
chloride gave 5-chloro-2-furyl ethyl ketone. Nitrobenzene, how-
ever, undergoes reduction and chlorination when treated with
isopropyl bromide and aluminum chloride to give o- and />-chloro-
anilines.
Machlis and Blanchard ^^^ report that 4-propiobiphenyl, and
not the 3-isomer as previously reported, results when biphenyl
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434 ANNUAL SURVEY OF AMERICAN CHEMISTRY
and propionyl chloride are permitted to react in the presence of
aluminum chloride. Silver and Lowy^^ have condensed biphenyl
with acetyl chloride and dichloroacetic anhydride to obtain p.f-
diacetylbiphenyl and chloromethyl /►-xenyl ketone, respectively.
With phosgene, a mixture of di-/>-xenyl ketone and />-xenil was
obtained and with thionyl chloride /►-xenyl-Zj-sulfinylbiphenyl was
the principal product.
Dougherty and Hammond^* have studied the reaction between
benzene and sulfur in the presence of aluminum chloride ; diphenyl
sulfide and thianthrene were formed, the percentage of the former
increasing with the ratio of aluminum chloride used.
Stoughton202 has reported on Fries' migrations with esters
of a-naphthol. The propionate under the influence of
aluminum chloride yields 54 percent of the 2-propionyl, 6 percent
of the 4-propionyl, and 2 percent of the 2,4-dipropionyl derivative.
Other esters give similar products. Sekera^^^ has found that
ferric and zinc chlorides can be used instead of aluminum chloride
to effect transformation of aryl esters of carboxylic acids into
hydroxyaryl ketones.
It has been shown that olefins and cyclic compounds can be
condensed in the presence of either BF3 or AICI3; C3H6 with ben-
zene yields mono- to tetra-isopropyl derivatives.^o^
In the preparation of alcohols, e. g., 3-phenylethyl alcohol from
ethylene oxide and benzene, Carpenter ^os discovered that the
introduction of air greatly improved the yields.
Polymerization. Theoretical. A number of valuable articles
have appeared which deal with newer polymerizations and their
reaction mechanisms. Theoretical studies of such important resin-
forming reactions as those between urea or phenol and formalde-
hyde continue to be neglected.
The polymerization of divinylacetylene by heat has been shown
by Cupery and Carothers^oe to involve the formation of cyclo-
butane derivatives, 1,2-divinylethynyl cyclobutane being the dimer
and bisvinylethynylcyclobutylacetylene the probable trimer.
Dykstra^OT has demonstrated a similar mechanism for the heat
polymerization of vinylacetylene.
Marvel and co-workers ^os, 209 have prepared polysulfones of
high molecular weight from olefins and sulfur dioxide in the
presence of oxidizing catalysts; these polysulfones appear to be
linear polymers terminated by hydroxyl groups. Other linear
polymers of interest are the polymeric formals of Hill and Car-
others 210 the polymeric decamethylene oxide of Hill,2ii and the
linear ammonium salts described by Gibbs and Marvel.212
Catalysts which seem destined to become of increasing import-
ance for polymerization reactions are phosphorous pentoxide 218-215
and boron trifluoride and its derivatives.^i^. 217 xhe accelera-
tion of polymerization by extreme pressure (6000 atmospheres)
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UNIT PROCESSES IN ORGANIC SYNTHESIS 435
was determined by Starkweather 218 for a large number of sub-
stances ; it was observed that the polymers thus formed differ little
from those obtained under more nearly normal conditions.
Thompson and Burk^^^ found that, in the substantial absence of
oxygen, citral and heptaldehyde do not polymerize, while styrene
continues to polymerize at a diminished rate, catalyst effects still
being predominant.
Applications. While no strictly new resin seems to have come into
general commercial use, new applications and improvements of
well known resins are of much interest.
Phenol-formaldehyde resin, in the form of the colloidal plywood
glue described by Sontag and Norton,220 fills the need of the ply-
wood industry for a waterproof and vermin proof bond. Trans-
lucent and transparent cast phenolic resins meet a demand for a
durable material of extreme beauty.221 Phenolic resin with a
mineral filler is well adapted to the fabrication of acid-proof chem-
ical equipment.222
Oil soluble resins of various types are finding wider use in
the varnish and paint industries 223, 224 ^o give films which are
more durable, faster drying, more stable in color, or more
resistant.
Improvements in molding technique have brought about
increased use of thermoplastic resins. Plasticized vinyl halide
resins 225 have formed the basis for thermoplastic molding materials
of a wide range of properties. Likewise, the technique of isomeriz-
ing rubber to tougher and less extensible products has been
improved, and a light colored thermoplastic material,226 similar in
properties to hard rubber, has been made from rubber by the use
of tin halides. Both the above resins have remarkable resistance
to ordinary chemical reagents.
References.
Nitration
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438 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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Esterification
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173. Canon, F. A., and Zimmerli, A., U. S. Pat. 1,998,489 (April 23, 1935).
174. Cox, G. J., and Ferguson, J. H., U. S. Pat. 2,013,034 (Sept. 3, 1935).
Hydrolysis
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176. Downing, F. B., and Clarkson, R. G., U. S. Pat. 1,970,363 (Aug. 14, 1934).
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179. Britton, E. C, U. S. Pat. 1,996,744 (Apr. 9, 1935).
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181. Britton, E. C, and Stoesser, W. C, U. S. Pat. 1,992,154 (Feb. 19, 1935).
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184. Bishop, O. M., and Perkins, M. A., U. S. Pat. 1,975,248 (Oct. 2, 1934).
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186. Thompson, M. S.. U. S. Pat. 1,997,610 (Apr. 16, 1935).
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188. Larson, A. T., U. S. Pat. 2,014,740 (Sept. 17, 1935).
189. Grebe, J. J., and Reilly, J. H., U. S. Pat. 1,986,194 (Jan. 1, 1935).
Friedel and Crafts Reaction
190. Groggins, P. H., Nagel, R. H., and Stirton, A. J., Ind. Eng. Chem., 26: 1317 (1934).
191. Newton, H. P., and Groggins, P. H., Ind. Bng. Chem., 27: 1397 (1935).
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195. Groggins, P. H., U. S. Pat. 1,991,743 (Feb. 19, 1935).
196. Gilman, H., Calloway, N. O., and Burtner, R. R., /. Am. Chem. Soc, 57: 906
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197. Gilman, H., and Burtner, R. R., /. Am. Chem. Soc, 57: 909 (1935).
198. Gilman, H., Burtner, R. R., Calloway, N. O., and Turck, J. A. V., Jr., /. Am. Chem.
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199. Machlis, S., and Blanchard, K. C, /. Am. Chem. Soc, 57: 176 (1935).
200. Silver, S. L., and Lowy, A., /. Am. Chem. Soc, 56: 2429 (1934).
201. Dougherty, G., and Hammond, P. D., /. Am. Chem. Soc, 57: 117 (1935).
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Polymerization
206. Cupery, M. E., and Carothers, W. H., /. Am. Chem. Soc, 56: 1167 (1934).
207. Dykstra, H. B., /. Am. Chem. Soc., 56: 1625 (1934).
208. Frederick, D. S., Cogan, H. D., and Marvel, C. S., /. Am. Chem. Soc, 56: 1875
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209. Hunt, M., and Marvel, C. S., /. Am. Chem. Soc, 57: 1691 (1935).
210. HUl, J. W., and Carothers, W. H., /. Am. Chem. Soc, 57: 925 (1935).
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212. Gibbs, C. F., and Marvel, C. S., /. Am. Chem. Soc, 57: 1137 (1935).
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218. Starkweather, H. W., /. Am. Chem. Soc, 56: 1870 (1934).
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Chapter XXV.
Chemical Economics.
(1931-1935)
Lawrence W. Bass,*
The Borden Company, New York City,
No marked increase in quantity or quality of publications on chemical
economics has occurred since the first review appeared in the "Annual
Survey" (Volume V, Chapter XL, 1931). Only two major events
have occurred to indicate a more general interest in the subject: the
American Chemical Industries Tercentenary in New York under the
chairmanship of A. W. Hixson in 1935, and the Silver Anniversary
of the American Institute of Chemical Engineers in Chicago in 1933.
During the Tercentenary celebration special chemical issues were pub-
lished by The Wall Street Journal ^ and the Boston Evening Tran-
script.^ Also, a general symposium on chemical economics was arranged
by R. P. Soule, and a plan was carried out to have a paper of economic
interest scheduled in each divisional program. At the time of the
Chemical Engineers' Anniversary, a symposium ^ was published on
economic and technological progress in the process industries during
the period 1908-33.
Although a sustained, marked expansion of interest in chemical eco-
nomics does not seem to be widespread, it must be emphasized that
the editors of the industrial journals are making every attempt to foster
the growth of this subject. A gradually increasing stream of chemical
thought is flowing into the torrent of financial and economic literature.
Some of the larger financial houses are employing chemically trained
men, and in some cases economists have entered the service of chemical
companies. The publication of "Chemical Economics"* by Haynes
should serve as a crystallizing force on chemico-economic concepts, and
the popular version of this work — "Men, Money and Molecules" ^ —
will undoubtedly transmit an interest in the business side of chemicals
to a numerous lay public.
Five major factors are responsible for the present unorganized con-
dition of chemical economics. First, the hybrid chemist-economist is
not easily developed; the chemist appears to be the more likely parent
stock. Second, the individual chemical industries are so diverse that
it is difficult to find a common economic ground. Third, the rate of
* Grateful acknowledgment is made of helpful suggestions and comments from R. T.
Baldwin, C. C. Concannon, T. W. Delahanty, W. A. Haraor, Williams Haynes, S. D.
Kirkpatrick, A. E. Marshall, D. 'P. Morgan, and W. N. Watson.
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CHEMICAL ECONOMICS 441
change in technology is much more rapid than in other industries that
have been subjected to extensive economic analysis. Fourth, there
is a real need for a chemical imagination less fanciful than that reflected
in the lay press; pseudo-economic reasoning can produce shapes that
are far distorted, without an added torque from chemical fiction.
Finally, there are at the present time few reliable statistics on which
a sound structure for the subject can be built; until such time as the
industry shall make adequate information available, efforts in this direc-
tion will be severely handicapped.
It is safe to prophesy, however, that eventually a rounded philosophy
of chemical economics will be evolved through mutual effort of the
chemist and the economist. It is the writer's hope that this survey of
the literature may stimulate that progress and mark a milestone on
the road.
Publications of a General Nature. The editors of our industrial
journals — Williams Haynes, H. E. Howe, S. D. Kirkpatrick, L. E.
Westman, and their associates — ^maintain a running fire of economic
comment on timely topics. Their annual review numbers, especially
in the case of Chemical and Metallurgical Engineering, are in a sense
textbooks of chemical economics.
Haynes, in "Chemical Economics," * devotes chapters to chemical
supply and demand; cost, value, and price; chemical distribution; car-
tels and consolidations; and American chemical mergers; in addition,
the historical background of the industry is covered in considerable
detail. In "The Development of American Industries," ^ brief eco-
nomic reviews are given of the following industries: pulp and paper,
textiles, rubber, leather, petroleum, glass, cement, chemicals, and paint,
varnish, and lacquer, as well as several metals. The broad scope of
"Twenty-Five Years of Chemical Engineering Progress" ^ has already
been mentioned. Weidlein and Hamor, in "Science in Action," '^ in
addition to reviewing the part that research has played in the develop-
ment of various industries, discuss the economic importance of research
in problems of waste utilization, engineering economics, industrial man-
agement, employment and banking, and in the creation of new industries.
In recent years studies by various state planning boards and uni-
versities have brought to the surface critical problems affecting indus-
trial structure, such as freight rates, raw materials, markets, power,
and water supply. Such activities have been particularly noteworthy
in mineral technology; the State Planning Reports of Illinois and
Colorado have advised closer study of the requirements of consumers
in order to improve marketing, and searches for new uses have been
begun in Michigan. Research on the development of new industries
has been advocated in many studies of this nature.®
Other subjects of a general nature which have been discussed include :
the relation of chemical industry to the state,^"^^ to the individual,^®* ^'^
to other industries,^® to other sciences,^^ to warfare,^**' 21 ^nd to the
tariff ;22» ^^ the chemical industry during the depression ;24-32 the chemi-
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442 ANNUAL SURVEY OF AMERICAN CHEMISTRY
cal industry and inflation ;38-3e and the chemical industry of the
future.87-40
Education in Chemical Economics. The desirability of training
in economics for engineering students is generally admitted by educa-
tors,**' *2 as shown by the following quotation from a report by the
Society for the Promotion of Engineering Education.*^ This point of
view is further emphasized by the Engineers' Council for Professional
Development.
"There seems to be rather general agreement that more than the
present emphasis on economics and its application in engineering should
be given; that sufficient time is now devoted to the subject of general
economics as taught by the Departments of Economics; and that it
would be desirable both to provide for specific instruction in engineering
economics, and to devote greater attention and emphasis to economic
phases of engineering problems in the engineering subjects themselves."
A survey of the curricula of institutions accredited by the American
Institute of Chemical Engineers indicates that these recommendations
are, in general, being followed. Practically all these schools list gen-
eral economics as a required course or as a preferred elective. Economic
aspects of chemical engineering problems are usually emphasized in
the engineering courses, and Tyler's monograph,** which unfortunately
has not been enlarged or revised since its publication ten years ago, has
been used as the basis of an organized course. Read*^ has included
a chapter on chemical economics in his textbook on industrial chemistry ;
Haynes' monograph* is being used as a text and as assigned supple-
mentary reading. "Economic Balance" has for a number of years been
included in the chemical engineering curriculimi at Massachusetts Insti-
tute of Technology, and, in one form or another, in many other insti-
tutions.
In chemical curricula, as distinguished from chemical engineering
curricula, much less emphasis is placed on economics. Some schools,
however, recommend the subject as an elective. It is to be hoped that
there will be an increasing trend in this direction.
Research in Chemical Economics. Professional economists still
practically ignore the chemical industry as a field for research. In most
cases in which data on chemicals have been studied, they have been
included as part of the manufacturing industries as a whole, and not
as a subject of interest in their own right. As an example of the gen-
eral situation, the thirty-second annual list*^ of doctoral dissertations
in political economy in progress in American universities and colleges,
which includes a total of 537 titles, contains none covering chemicals,
in the narrow sense of the word, one each on the steel, tire, and drug
industries, and two on the ceramic industry.
The chemist, on the other hand, appears to be gradually becoming
more and more interested in the economics of his industry. We can
look forward with confidence to an increasing number of researches by
chemical economists entering the profession from the chemical side.
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CHEMICAL ECONOMICS 443
Economic History. Many of the references cited in other sec-
tions are concerned to a considerable extent with the economic history of
chemical manufactures. For example, "Twenty-five Years of Chemi-
cal Engineering Progress" ^ includes historical discussions of the more
important process industries during the period 1908-33 and a statistical
review of the entire group by Weidlein and Bass. Haynes *» ^ and
Weidlein and Hamor '^ likewise include much valuable historical mate-
rial on industrial development in their treatises.
Browne*'^ has traced the early history of the chemical industry in
New York. Haynes and Bass *® have recorded in chronological form
the outstanding economic and technical developments in the industry
during the last three centuries. Histories of individual chemical com-
panies have been published in Chemical Industrie sj^"^ Industrial and
Engineering Chemistry, ^^ and Fortune,^^
Sources of Statistics.^^ xhe most important sources of statistical
data on the chemical industry are included in the following list.
General. Miscellaneous publications and releases from the Chemical
Division, Bureau of Foreign and Domestic Commerce (activities have
been described in detail by Concannon and Delahanty).^^ Tariff Infor-
mation Surveys issued by the Tariff Commission in 1921 and 1929.
Production and Sales. Census of Manufactures (biennial), including
mimeographed preliminary sheets and printed finals on divisions of
the industry. Minerals Yearbook (annual). Census of Dyes and
Other Synthetic Organic Chemicals (annual), U. S. Tariff Commis-
sion; the 1934 issue contains for the first time reports on "inorganic
chemicals used in the production of coal tar products." Sulphuric Acid
and Superphosphate (monthly). Bureau of the Census. Production of
Methanol (monthly), ibid. Statistics on Industrial and Beverage Alco-
hol (annual) ; Statistics of Industrial Alcohol (monthly) ; Bureau of
Internal Revenue.
Hours and Wages. Trend of Employment, Department of Labor. Sur-
vey of Current Business, Department of Commerce. Federal Reserve
Bulletin (monthly). Reports of the Chemical Alliance.
Prices. Wholesale Prices, Department of Labor. Survey of Current
Business, Department of Commerce. Federal Reserve Bulletin. OU,
Paint and Drug Reporter. Chemical Industries.
Distribution. Census of Manufactures and Minerals Yearbook con-
tain some meager data. (With the 1935 Census of Manufactures sche-
dule is appended a Census of Distribution schedule which specifically
covers a few chemical groups: agricultural insecticides, alkaloids, etc.)
Printed reports. Tariff Commission, under section 315, Tariff Act of
1922, and section 336, Tariff Act of 1930; for the products covered, the
data are very complete. Census of Wholesale Distribution, 1929,
Bureau of the Census (very little on chemicals). Census of Ameri-
can Business, 1933, Bureau of the Census. Tariff Commission press
•release on salt. World Trade Notes, Chemical Division, Bureau of
Foreign and Domestic Commerce.
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444 ANNUAL SURVEY OF AMERICAN CHEMISTRY
Consumption, Census of Manufactures. Annual review and statis-
tical issues of Chemical & Metallurgical Engineering present detailed
data for a number of heavy chemicals. Minerals Yearbook contains
some consumption statistics. Sulphuric Acid (monthly), Bureau of
the Census. National Fertilizer Association; data for acid, phos-
phate, nitrogen, and potash.
Exports and Imports, Foreign Commerce and Navigation of the
U. S. (annual), Department of Commerce. Monthly Simimary of
Foreign Commerce of the U. S., preliminary, Department of Com-
merce. Advance official data mimeographed sheets (monthly),
Chemical Division, Department of Commerce. U. S. Foreign Trade
Statistics (monthly), Bureau of Foreign and Domestic Commerce
(shows imports only). (The utility of United States foreign trade
statistics, with suggestions for their improvement, has been discussed
in detail by Mears.)^*
Finance, No official publication has much information on finance as
applied specifically to the chemical industries. Survey of Current
Business contains considerable financial statistics. Federal Reserve
Bulletin is a fundamental source. Chemical Markets {Chemical Indus-
tries since Oct., 1933). Annual reports of individual chemical com-
panies.
Construction, Monthly summaries in Chemical & Metallurgical Engi-
neering, (Sources of information on construction and employment in
construction have been described in detail by Gill).*'
Foreign Countries. The larger countries collect official statistical
material in a similar manner. In many cases statistical yearbooks are
published. Canadian data collected by the Dominion Bureau of Sta-
tistics have been summarized by Losee and McLeod.^^ Periodic reviews
of the more important foreign countries from the point of view of
chemicals have been published by the Chemical Division, U. S. Bureau
of Foreign and Domestic Commerce.^''
Technological Research and Development. The ultimate source of
new economic developments in the chemical industries lies in the research
laboratories. As an example of the importance of sustained research, a
recent news release from the General Electric Company stated that,
during the five depression years 1930-1934, the ratio between business
attributable to "new" lines of products (i. e., lines not manufactured
more than ten years prior to the year under consideration) and total
business for all lines manufactured by that company, was, on the aver-
age, approximately 10 percent higher than for the ^yq prosperity years
1926-1930. The achievements that have come as a result of research
have been discussed in detail by Boyd,^® by Redman and Mory,^* and
by Weidlein and Hamor.'^
According to a compilation by West and HuU,^® there were 1575
industrial and consulting laboratories in the United States in 1933.
Holland and Spraragen ®^ found that the tendency to decrease research
expenditures during the depression, while not marked in 1931, increased
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CHEMICAL ECONOMICS 445
progressively during 1932 and 1933;* further, that the major emphasis
on research has been changed from attempts at lower production costs
to the development of new products, new uses, new processes, and the
improvement of existing products.
Informative surveys of current practice in research laboratory man-
agement have been conducted by Ross ^^ and by the Metropolitan Life
Insurance Company.®^ Additional discussions of various aspects of
research management have appeared on: laboratory information ser-
vice,^* financing,®^ expenses,®^ objectives,^*^ and personnel.^^
Special attention has been accorded the use of pilot or semi-works
plants as an effective development procedure.®^"^^
The research chemist should be particularly well-informed on patent
matters, because the literature available to him is excellent. It includes
monographs by Deller,'^^ Geier,''^^ Rhodes,*^^ Rivise,''^^ Rossman,''^^ and
Toulmin;'^'^ a section by E. J. Prindle in the "Chemical Engineers'
Handbook" ;''^8 the patent index by Worden;*^® the report on the patent
system by the Science Advisory Board ;S^ and a number of journal
articles.8^-^*
A survey has been made of the respective merits of exclusive and
non-exclusive licensing of patented inventions.^^ Weidlein and Bass ®®
have pointed out that a comparatively low monetary valuation is set
on patents and goodwill by chemical companies.
Three additional related subjects have been discussed: the chemical
expert,^*^ engineering contracts,^® and competition between university
research and consultants.^^
Raw Materials. Emeny 20 and Zimmerman ^^^ have provided val-
uable source books of information on raw materials, including those
used by the chemical industries. Weber and Alsberg's ^^^ monograph
on vegetable shortenings is not only a masterly treatment of this indus-
try, but also a model to be followed in similar studies of a technico-
economic nature. Several discussions of miscellaneous substances as
chemical raw materials have appeared: agricultural products,^^^ cel-
lulose,^^^ fish and animal oils,^^^ lead,^^^ chemical raw materials in
petroleum refining,!^®* '^^'^ phosphate rock,^^^ and vegetable oils.^^®
Special mention should be made of the 8 page supplement to the Jan-
uary, 1934, issue of Chemical & Metallurgical Engineering entitled
"New Data on Chemical Raw Materials for the Process Industries."
Much interest has recently been aroused in the possibility of closer
relationship between the chemical industry and agriculture, particularly
from the point of view of increased use of agricultural products as
raw materials for chemicals. Many ideas have been suggested by
Hale,^^^ but there has been considerable criticism of his views.^^^ In
1935 a conference was held in Dearborn, Mich., for the purpose of dis-
cussing means of effecting closer economic cooperation between agri-
culture, industry, and science.^^^ xhis conference eventuated in the
* Since this survey was completed, the tendency has, in general, been reversed.— L. W. B,
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446 ANNUAL SURVEY OF AMERICAN CHEMISTRY
organization of the Farm Chemurgic Council, which has begun activi-
ties along the lines indicated.
Chemical Technogeography. The location of factories of all types
has in the past, with few exceptions, been more a matter of chance
than of selection based upon careful study of the various factors
involved.^^3 Chemistry has an intimate connection with the problems
of highway transportation, which, especially within the past two decades,
has changed profoundly merchandising methods, operations, and even
plant locations. The advent of the pipe line has been of notable economic
significance, and its future developments may be even more striking.
In the last half-century the production and distribution of electricity
has become a major American industry, and the resulting increase in
mobility of energy has removed many restrictions on plant location and
layout and the design and control of machinery and processes.
An excellent summary of economic factors to be considered in chemi-
cal plant location has been prepared by Cuno as a chapter in the "Chemi-
cal Engineers' Handbook."'^®' i^*» ^^^ The twelve governing factors
discussed are: raw materials; fuel; power; water; labor; transporta-
tion; freight rates; markets; consumer, feeder, and competitive indus-
tries; climate; taxes and corporation fees; and state and mtmicipal
restrictions. A bibliography on plant location containing 272 refer-
ences has been prepared by Perry and Cimo.^^® The economic factors
governing the choice of locations for major chemical plants recently
built in the South have been reviewed by Kirkpatrick ^^^ and by
Haynes.^^® Other summaries of chemical activities in various geo-
graphic regions have been made for New England,^^® the Far West,^®»
>2i the South,i22. 123 and the South-west.i24
Chemical Engineering Economics. Tyler's monograph,** al-
though bearing the title "Chemical Engineering Economics," broadly
covers not only the engineering phases of chemical processes, but also
the entire field of chemical economics. The recent developments in
the more strictly engineering aspects have also been treated in sections
of reviews of chemical engineering progress which have become a
feature of recent volimies of the "Annual Survey." To avoid duplica-
tion, mention of work in this field, except as covered in other sections,
will be limited to pointing out the economic importance of such sub-
jects as feasibility of processes and products,^*^ plant design and equip-
ment choice,'^^' ^25. 126 economic balance, and amortization and deprecia-
tion.i2T. 128
Production. In a comprehensive survey of the nation's produc-
tive capacity, Nourse ^2» found that, on the average, our entire manu-
facturing industry was operating during 1925-29 at approximately 80
percent of practical capacity. He cites the coke industry as the best
illustration of slow displacement of obsolescent capacity by a more
efficient process; in 1930 only 29 percent of beehive capacity was
utilized, while in normal times 85 to 90 percent of by-product oveai
rated capacity was used. Surplus capacity in petroleum refining is
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CHEMICAL ECONOMICS
447
uncertain in amount, but there is no evidence of an increase in excess
capacity. In the period 1925-29 capacity was utilized in portland cement
manufacture to the extent of 80 percent, in the rayon industry close
to 100 percent, in steel production 93 percent, and in plate glass manu-
facture 85 percent.
Using data compiled by Mills ^^^ for a large group of individual
industries, Weidlein and Bass®* pointed out that, in nearly all the
14 process industries included in the list, there has been a notable
increase in physical volume of production ^^^^ ^^^ ^nd in physical vol-
ume of production per wage earner. There has been a marked decrease
in cost of materials per unit of product in the post-war period and a
similar change in the labor costs.
Alford and Hannum^^^ have shown that there may be startlingly
large variations in production per kilo-man-hour in establishments
devoted to the manufacture of the same products, as, for example, in
petroleum refining. Labor costs in the chemical industry have been
analyzed.134-136
Prices.^^'^ Warren and Pearson,^^® in a study of wholesale prices
of basic commodities in the United States for the period 1797-1932,
found a striking decline, compared with all commodities, in the prices
of the chemical-and-drug group (Table I).
Table I.
Index Numbers of Wholesale Prices
1910-1914=100
1
Si's
4
p2|
1
1
It
£:3
ii
53
1800
129
427
99
157
62
225
159
322
51
1813
162
848
104
172
77
291
334
419
63
1830
91
207
58
94
85
181
116
209
47
1850
84
154
71
84
67
116
95
147
61
1865
185
300
148
180
152
266
214
306
118
1880
100
120
80
96
113
128
92
166
81
1900
82
101
71
79
77
95
88
115
84
1918
191
225
208
185
195
244
207
160
179
1920
226
203
211
213
266
293
311
175
272
1930
126
110
124
141
155
143 .
149
108
163
1932
95
91
68
95
113
99
133
94
130
Using the prices during the period 1910-14 as a base, it is seen that,
until the close of the World War, chemicals and drugs were one of
the highest priced commodity groups. A marked decreasing trend in
the index numbers is clearly apparent, however, throughout the period
covered. The effect of war-time demand on chemical prices is illus-
trated in the figures for 1813, 1865, and 1918. Since 1918, prices for
chemicals have dropped sharply, and were lower in 1932 than the mdexes
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448 ANNUAL SURVEY OF AMERICAN CHEMISTRY
for any other group of manufactured commodities, or than the index
for all commodities; they were even lower than during the period
preceding the War. It should be noted that in spite of this sustained
trend toward lower prices, the chemical industry has maintained an
outstanding record of financial return.
The prices of chemicals are not likely to rise during the next ten
years as rapidly as the general commodity index, according to Cope-
land.34 Pricing has not been reduced to a scientific basis, but there
are various applicable analytical methods that are of great assis-
tance.^^®-^*^ National monetary adjustments are most likely to be effec-
tive in changing the prices of commodities that enter into international
trade or that are traded on commodity exchanges. ^^^ Laufer ^^^ ^^s
pointed out the important bearing on chemical prices of supplantive
competition, new synthetic developments, and the protectionist policies
of nations.
Fuel and Power. McBride,^^^ introducing a symposium on fuel
and power sources from the point of view of the chemical engineer, has
pointed out that the process industries paid for almost half the fuel
and energy used in American factories in 1929. This is a notable
increase over the proportion in 1909.^* McBride further states that
the consumption of coal, the most abundant and cheapest fuel, is gradu-
ally decreasing as a result of more efficient use and because of com-
petition from other fuels. Oil now furnishes over 25 percent of the
energy supply, while as recently as the World War it accounted for
only about 10 percent. In Table II is given an estimate of the probable
importance of various energy sources in the United States in 1940.
Table II. Energy Sources of American Industry
Average 1923-27 Estimated for 1940
B. t. u. Percentage B. t. u. 'Percentage
(Trillions) of Total (TrUlions) of Total
Anthracite coal 2,000 8 1,500 5
Bituminous coal 14,000 60 15,500 48
Petroleum 5,000 20 8,000 25
Natural gas 1,500 6 5,000 16
Water power 1,500 6 2,000 6
. 24,000 100 32,000 100
Many state planning boards have analyzed their power situations.
Minnesota, Missouri, Arkansas, Indiana, Wisconsin, Iowa, Colorado,
Texas, Washington, Maine, and Pennsylvania have studied their elec-
tric power resources quite broadly. The Maine State Planning Board
published a bulletin dealing with markets for power, such as electro-
metallurgy and fertilizer and chlorine manufacture. Similar studies
have been published for Missouri, Oregon, and the Pacific Northwest.
Merchandising Research.i^^ Commercial or merchandising re-
search has received a new impetus, which is especially noticeable in
the marketing of chemicals, through the use of the laboratory as an
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CHEMICAL ECONOMICS 449
adjunct to market analysis. Switz,!*^ referring to the standard recom-
mendation for diversification and development of new products so fre-
quently made to companies operating in a closed market, has commented
on the fact that this is an exceptionally easy course of action in the
chemical industry, because of the similarity in scientific, technical, and
merchandising problems of its different products. Competition in the
chemical industry may come from other processes for producing the
same commodity or from new materials striving for the same outlets,
that is, inter-commodity or inter-process competition.^**^ The technic
of conducting commercial researches on chemical products, which
usually requires the services of the laboratory as a weapon of offense
and defense, has been discussed in some detail.^*^-^^® Other related
subjects that have been treated are : chemical demand,^^^* ^^^ seasonal
variation,^^^ customer research,^^* and technical servicing.^^^
Distribution. Considerable attention has been devoted in recent
years, particularly by the Manufacturing Chemists' Association, to the
development and standardization of suitable containers.^^®'^^^ Ques-
tions of freight rates ^®® and other distribution agencies ^®^ are of great
importance in chemical marketing.
"For a hundred years," Haynes* points out, "the chemical indus-
trialists of the world have been striving to make greater profits by
paring down their raw material and plant costs, improving their yields,
and increasing their sales volume. Every success has been but another
incentive to greater sales effort. And additional sales effort has piled
up selling expenses. Old markets have been more intensively culti-
vated. New markets have been invaded. The sales area has been
widened, thus adding not only to direct sales cost but also to packing
and transportation charges. . . . Better transportation and the desire
of consumers to hold down their raw material inventories has meant
smaller chemical orders and more frequent shipments. Expert advice —
both practical technological help in operating problems and scientific
assistance in research — is a part of the regular service a chemical
seller is expected to render to his customers. Stimulated by a pro-
duction program of ever increasing volume, the chemical sales executive
is goaded by competition to extend his efforts beyond the limit of reason
and fair profit.
"In this way distribution costs have climbed a steep spiral, but a
situation so unsound economically is sure to be righted. It is quite
logical, therefore, to find that marketing functions and policies are radi-
cally changing. As a result, distribution problems are today a chief
concern of the industry."
The average plant cost of a chemical product may be estimated at
60 percent of the selling price.** ^®2 Freight equalization is said to
account for 31.8 percent of the total sales expense of heavy chemicals.
Haynes * classifies marketing functions under the following headings :
assembhng, storing, grading, dividing, transporting, packing, selling,
financing, and risking. "About 96 percent of our total production of
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450 ANNUAL SURVEY OF AMERICAN CHEMISTRY
chemicals is consumed in industry and agriculture; but this indirect
consimiption of chemicals is not, from the marketing point of view,
their most distinctive feature. Coal, iron and steel, copper, zinc and
lead, wood, rubber, wool, silk, cotton, all enjoy widespread industrial
markets; but none of them, as do chemicals, find their principal con-
suming field right within their own industry." The chemical industry
consumes about 70 percent of all its products, either within the plant
of their origin or as chemicals sold for use in further chemical processes.
The high intensity of competition in chemical marketing has been
pointed out in several articles. ^^-^^^ Technical aspects of sales policies,
such as the 10th prox. discount ^^^ and the uniform sales contract ^"^^
have been discussed. The role played by specification buying in the
marketing of chemicals is important.^'^^ xhe various aspects of selling
chemicals to the retail consumer have been analyzed.^'^^ The factors
that play a part in sales costs have been pointed out^*^* There exists
a problem of choosing between a sales policy based on marketing
by products or one based on marketing by industries.^*^^ Beneficial
effects on profits can be shown from an analysis of customers in their
bearing on profitability.^^*
Haynes * has discussed the reasons for the non-existence of a Chemi-
cal Commodity Exchange. According to Smith,^'''^ the requisites for
successful exchange trading are reasonable durability of commodities,
accurate measurability, adequate standardization, sufficient volimae, and
comparatively high price fluctuations (inelastic supply). Haynes
argues that while some chemicals may meet most or all of these require-
ments, chemicals in general as a class do not meet a single one; hence
the organization of a chemical exchange is not a practical possibility.
Weld^^® quotes the following figures, compiled by the Association
of National Advertisers, on the advertising expenditures of various
industries.
Table III. Average Advertising Expenditures of Various
Industries Expressed in Percentage of Sales
Drugs and toilet articles 19.6
Paints and varnishes 6.4
Chemical and allied manu-
factures 6.1
Electrical and radio 5.9
Jewelry and silverware 5.7
Food 5.6
Office equipment and supplies 5.3
Hardware 4.7
Travel and transportation... 4.6
Household equipment, other
than electric 4.5
Agricultural equipment and
supplies 4.1
Clothing 3.8
Furniture 37
Automotive 3.5
Leather and shoes 32
Textiles 3.0
Building materials 2.8
Paper and paper products 2.6
Metals, machinery, etc 2.5
Industrial 2J
Finance and insurance 1.1
The successful use of radio programs as an advertising meditmi for
fertilizers is described by Garrard.^*^®
Foreign Trade. Weidlein and Bass,®^ summarizing the statistics
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CHEMICAL ECONOMICS 451
on foreign trade in products of the process industries, find a noteworthy
increase in both exports and imports during the twenty years ending
in 1929. In general, however, the volume of exports or imports is small
compared with the production volume in this country for the same year,
the average for exports of all manufactured products being 8.1 percent
in 1929. Detailed reviews of our foreign trade in chemicals have been
prepared by Wilson ^^o and by the Chemical Division, Bureau of For-
eign and Domestic Commerce.^'^ Other aspects of foreign trade dis-
cussed include the tariff,^^. 23 measures of exports,^®^ the effect of the
chemical revolution, ^^2 and the South American export business.^®^
The importance of the trend toward autarchy, or national self-suf-
ficiency, has been discussed by Howard.^^*
Accounting. A chapter by Prochazka in the "Chemical Engi-
neers' Handbook" ^^ is devoted to accounting under the following head-
ings : general accounting, analyzing financial statements, fixed-property
accounting, cost accounting, process costs, material accounting, product
costs, cost estimating, and budgeting. Articles have appeared on cost
elements,^®*^» ^^® costs from the point of view of the chemist or chemical
engineer,^^*^' ^®® "availability" in process steam cost accounting prac-
tice,i8» depreciation,i2T. 128, 190-192 and budget control. i»3, 194
Personnel. Considerable attention has been given to the earn-
ings of chemical engineering graduates.^®^"^*® The safety of chemical
workers has aroused much consideration.2^"2<>* Women in chem-
istry,205 chemists' contracts,2<>« and the technic of applying for a posi-
tion ^o^ have been discussed.
During periods of economic stress the larger industrial centers are
confronted with difficult problems because of unemployment; this situ-
ation has focused attention on the problem of the relocation and
development of new industries.^^s There should be a study of seasonal
aspects of the chemical industries.^os Technological unemplo)mient
has been much discussed.2i0' 211
Financial Aspects. Moulton,2i2 in his comprehensive analysis of
capital formation, observes that, in the years since the World War, the
growth of capital in the chemical industry has shown the characteris-
tics of a new industry. While increase in capital in established lines
Table IV. Financing of New Industries in Millions of Dollars
1924 192S 1926 1927 1928 1929 1930
Aviation 1.9 ... 0.2 55.1 172.8 42
Chemical 15.1 562 35.0 26.1 86.5 237.7 57.8
Motion picture 12.2 91.1 100.8 141.2 77.9 50.3 172.7
Natural gas 3.0 15.5 39.3 100.5 107.5 51.9 59.7
Radio 17.7 9.5 3.8 49.6 29.8 61.3 4.7
of manufacturing was relatively slow during this period, certain new
lines of business, as shown in the following table, exhibited a rapid
expansion in the later years of the boom period.
An analysis 213 of the $4,101,000 of new financing in the chemical
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452 ANNUAL SURVEY OF AMERICAN CHEMISTRY
industry since the Securities and Exchange Commission's activities
began in October, 1934, discloses that $300,000 was used for plant and
equipment, $531,000 for increased working capital, and $3,175,000 for
refinancing.
Weidlein and Bass,®* analyzing the financial data compiled by
Epstein ^^^ on 2,046 manufacturing corporations during the period 1919-
1928, point out the following conclusions. The chemical industries
show a low bonded debt in comparison with capitalization. They also
show a capital ratio (ratio of capital invested to annual value of prod-
ucts) well above unity, confirming a similar observation made earlier
by De Long.^is The large sums received by chemical companies as
dividends from other companies are a striking feature of the analysis.
The industry has been discussed by several writers from the point of
view of general financial background and eamings.216-223 Th^ hold-
ings of chemical securities in the portfolios of investment trusts have
been analyzed.^^*
A comparison made by the National City Bank 225, 226 of figures for
1933 and 1934, from the annual reports of 18 of the larger chemical
companies, reveals an increase in total net profits for the group from
$50,754,000 to $64,165,000 or 26.4 percent. The total net worth of
these companies remained approximately constant for these years, and,
accordingly, the percentage return increased from 7.1 to 9.0.
Industrial Organization. During the early 1930's, there was con-
siderable discussion of European cartels and their operation in periods
of depression.*' *^^' 227-229 The organization of NRA and the introduc-
tion of the codes shifted interest to the American scene. The voices
of the chemical industry were, in general, raised against the codes,23<>-240
and following the adoption of the various governing codes,2*i-244 there
was much discussion of their effect, frequently of a sceptical nature.
The following interesting comment is made by Haynes^ in regard
to NRA: "When the NRA was launched General Johnson wanted
employers to pay 40 cents an hour for 40 hours a week. But workers
in chemical plants were already being paid 56j^ cents for 41 hours.
Today they receive 61.9 cents, or more than half again as much as the
NRA ideal ; and they work 39.4 hours a week."
Individual Products. In addition to publications of an economic
nature relating to the industry as a whole, a number of valuable papers
are concerned with some specific chemical or chemicals. Space does
not permit detailed discussion, but for convenience a selected bibliog-
raphy has been prepared. A large number of additional papers have
been published on some of these products in journals specializing in
their respective fields. Acetic acid and cellulose acetate,245. 246 jjco-
hol from wood waste,247 alkalies,248, 249 carbon black,250 carbon diox-
ide,25i foreign trade in copper,252 fertilizers,253 fuels,254 hydrogen,255
naval stores,256 nitrogen,257-260 petroleum,26i phosphoric acid, phos-
phates and phosphate rock,2«2-265 plastics,2®« potash,229. 267 power alco-
hol and motor fuels,2«8-27i pulp and paper,272 rubber tires,273 salt,274, 275
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CHEMICAL ECONOMICS 453
sugar,276. 277 sulfur,278 sulfuric acid,279. 280 synthetic yarn,28i tartaric
acid.282
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454 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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CHEMICAL ECONOMICS 455
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456 ANNUAL SURVEY OF AMERICAN CHEMISTRY
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200. Chem. Markets, 32: 504 (1933).
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CHEMICAL ECONOMICS 457
210. "A State Plan for Indiana," 1934, 1.
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213. Business Week, Tan. 11, 1936, ip. 29.
214. Epstein, R. C, in collaboration with Clark, F. M., "A Source-Book for the Study
of Industrial Profits," U. S. Department of Commerce, 1932.
215. De Long, C. R., Chem. Met. Eng., 32: 853 (1925).
216. Florance, H., Review of Reviews, 1935, May.
217. Haskell, B., Jr., Ind. Eng, Chem., 24: 953 (1932).
218. Hessd, F. A., Ind. Eng. Chem., 23: 573 (1931); Chem. Markets, 29: 155 (1931);
Chem. Industries, 37: 135 (1935).
219. Mantell, C. L., Chem. Markets, 31: 329 (1932); Trans. Electrochem. Soc, «:
15 (1932).
220. Morgan, D. P., Chemist, 9: 170 (1932).
221. Stansfield, A., Trans. Electrochem. Soc, 63: 259 (1933).
222. Smith, E. L., Ind. Eng. Chem., 26: 608 (1934).
223. Crum, W. L., /. Am. Statistical Assoc, 30: 35 (1935).
224. Hessel, F. A., Chem. Markets, 29: 369 (1931); Chem. Industries, 34: 308 (1934);
36: 316 (1935).
225. Bulletin, National City Bank, 1935: 39.
226. Robinson, L. R., /. Am. Statistical Assoc, 29: 39 (1934).
227. Haynes, W., Ind. Eng. Chem., 23: 588 (1931).
228. Marks, L. H.. Chem. Markets, 30: 229^ (1932).
229. Stocking, G. W., "Potash Industry." New York, Smith, 1931. 343 p.
230. Allen, E. M., Chem. Industries, 36: 536 (1935).
231. Battley, J. F., Chem. Markets, 35: 309 (1934).
232. Belknap, E., Chem. Markets, 30: 549 (1932).
233. Derby, H. L., Chem. Met. Eng., 40: 582 (1933).
234. Chem. Markets, 33: 115, 211, 233 (1933); Chem. Industries, 34: 415 (1934); 36: 117,
145 (1935).
235. Chem. Met. Eng., 40: 396 (1933).
236. Garvan, F. P., Chem. Industries. 35: 19 (1934).
237. Hay?ies, W., Chem. Industries, 34: 16 (1934).
238. Hettinger, A. J., Jr., Chem. Industries, 36: 430 (1935).
239. Marks, L. H., Chem. Markets, 33: 121 (1933).
240. Quiggle, E. B., Chem. Industries, 34: 13 (134).
241. Chem. Met, Eng., 40: 396 (1933); 41: 278 (1934); 42: 20 (1935).
242. "Code-Sponsoring Trade Associations," Market Research Series No. 4, Bureau of
Foreign and Domestic Commerce, 1935. •
243. Brand, C. J.. Chem. Industries, 36: 524 (1935).
244. Chem. Met. Eng., 41: 9 (1934); 42: 52 (1935).
245. Curtis, F. J., Chem. Met. Eng., 38: 38 (1931).
246. Partridge, E. L., Ind. Eng. Chem., 23: 482 (1931).
247. Hurter, A., Chem. Markets, 33: 503 (1933).
248. Chem. Met. Eng., 38: 32 (1931).
249. LeSueur, E. A., Trans. Electrochem. Soc, 63: 187 (1933).
250. Murphy, W. J., Chem. Markets, 32: 419 (1933).
251. Jones, C. L., Ind. Eng. Chem., 23: 519 (1931).
252. Pettingill, R. B., Am. Economic Rev., 25: 426 (1935).
253. Burdick, C. L., Chem. Met. Eng., 38: 24 (1931).
254. Fieldner, A. C, Ind. Eng. Chem., 71 1 983 (1935).
255. Chem. Met. Eng., 38: 40 (1931).
256. Chem. Markets, 29: 142 (1931).
257. Curtis, H. A., "Fixed Nitrogen." New York, Chemical Catalog Co., 1932. 517 p.
258. Haynes, W., Chem. Markets, 28: 148 (1931).
259. Kalish, J., Chem. Markets, 29: 582 (1931).
260. Tyler. C. Chem. Met. Eng., 38: 42 (1931).
261. HUl, J. B., Ind. Eng. Chem., 27: 519 (1935).
262. Curtis, H. A., Chem. Industries, 34: 507 (1934).
263. Kalish, J., Chem. Markets, 29: 461 (1931).
264. McBride, R. S., Chem. Met. Eng., 38: 28 (1931).
265. Waggaman, W. H., /. Chem. Education, 10: 391, 476 (1933).
266. Baekeland. L. H., Ind. Eng. Chem., 27: 538 (1935).
267. Stocking, G. W., Chem. Markets, 28: 247, 368, 482 (1931).
268. Bridgeman, O. C, and Querfeld, D., Ind. Eng. Chem., 25: 523 (1933).
269. Haynes, W., Chem. Markets, 32: 307 (1933).
270. Killeffer, D. H., Ind. Eng. Chem., News Ed., 11: 117 (1933).
271. "Motor Fuels in Foreign Commerce." Trade Information Bulletin 805, Bureau of
Foreign and Domestic Commerce.
272. Johnsen, B., Ind. Eng. Chem., 27: 514 (1935).
273. Davis, R. E., Proc Am. Statistical Assoc, 1931: 10
274. Crawford, E. T., Jr., Ind. Eng. Chem., 27: 1109, 1274, 1411 (1935).
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458 ANNUAL SURVEY OF AMERICAN CHEMISTRY
275. Lonn, E.. "Salt as a Factor in the Confederacy." New York, Neale, 1933. 324 p.
276. Home, W. D., Ind, Bng, Chem,, 27: 989 (1935).
277. James, C. L., Am. Economic Review, 21: 481 (1931).
278. Cunningham, W. A., /. Chem. EducaHon, 12: 120 (1935).
279. Chem. Met. Eng., 38: 35 (1931); 39: 42 (1932).
280. Fairlie, A. M., Ind. Eng. Chem., Ul 1280 (1934). "Sulfuric Acid Manufacture."
New York, Rcinhold Publishing Corp., 1936. 669 p.
281. Mullin, C. E.. Chem. Markets, 28: 363, 492 (1931); h: 211 (1933).
282. Chem. Markets, 29: 485 (1931).
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AUTHOR INDEX
Abbott, A. H.. 303, 321
Abbott, A. O., Jr., 407, 417
Abbott. W. S.. 267. 274
Ablard. J.E..30.32, 67
Acken, J. S., 143, 160
Acree. P.. Jr., 268. 276
Acree, S. P.. 108. 116. 373,
377
Adair, P. L., 226
Adams, E. G., 216
Adams, E. Q., 166, 161
Adams, E. W., 261, 363, 269.
274
Adams, P. H., 162. 160
Adams, P. W.. 370, 376
Adams, G.. 246. 262
Adams, J. E.. 323
Adams, L. V.. 396
Adams. M. H.. 248
Adams, R., 197, 202, 204,
216. 226
Adams, W. B., Jr., 101
Adamson. W. A., 426, 436
Addinal!. C. R., 228
Addleatof], J. A., 76
Addoms, C. 371, 377
Adel, A.. 56
Adelaon, D. E., 216
AdcrcT, Jm 147. 161
Adkfns. H . 86. 89. 181, 182,
107, 20a, 216, 343, 366, 381,
a93> 420. 436, 437
Adlw, H., 438
Addan, M. B.. 123
Aelony. D.* 422. 436
AfifTtiss, M. S.. 91. 96, 100,
104. 114
Ahlberg. C. R., 340
Ahlberg, J. E., 61. 74
Ahlqvist, H.. 319
Ahmann, C. P.. 228
Ahrens, B.. 227
Akerlof. G., 16. 18, 30. 71. 76
Alberding. C. H.. 339
Albert, G. A.. 372, 377
Albert, W. D., 76
Alberts. A. A.. 209. 216
Albertson. W., 146. 160
Albrecht. A. J., 216
Albright, J., 338
Albright. J. C, 339
Albrook, R. L.. 182
Alden, R. C, 338
Alford. L. P.. 447, 466
Allen. A. O.. 43. 44, 74. 182
Allen. A. S.. 318
Allen, E. M.. 463. 467
Allen. I.. Jr.. 380. 386, 393
Allen, P., Jr.. 182. 204
Allen. W. P.. 228
Anes. G. A.. 166. 161
Alexander, L. L.. 204
AUison. S. K.. 117, 122. 144.
160
AUyne. A. B., 294. 302. 303,
319, 321
Almquist. H. J.. 242. 243.
261
Alrich, H. W., 205. 3iy
Akherg, C, D.. 244, 251
Alsbcrg. C. L,, 445, 455
Altamura, M.. 181
Altar. W.. 67
Alticri. V. J., 201, 317
Alton, W.H., 356.357
Altpeter, A. J., 310>a22
Alvord. E. B.p 2ft4, 274
Alyea, H. N., 3&3
Amber, C, R., 76
Ambler. H. R., 324
Ambler, J. A.. 247, 262
Amflur. I., 43
Am merman, M.. 237* 250
Amrhein, F, J.. 32S
Amundsen, L. H., 204
Anablc. A.. 456
Andersen, H. P*, 202
Ajadereon, C. C, 313, 323
Anderson, C, T., 74
Anderson, D. Q., 364, 375
Andenson, G. K., 303
Anderson. H. W., 254. 27ti
Anderson, L, C, 77. 178, 187,
201, 202, 215, 370, 376
AndetEon. L- D., 270. 271.
274. 279
Anderson. T. P., 66
Anderson. W. E-, 230, 248
Andes,J. 0.. 2fll,278
Anding, C. E,, Jr,, 183
Andrews, D, B., 181, 201
Andrews, D. H., 57, 202
Andrews, J. C, 248
Andrews, K, C. 248
Andrews, L, H, 142, 149
Andrews, L. V.. 15, 30
Andrews, P. R., 273, 274
Annis, H. M.. 371. 376
Anthes, J. P., 311. 312, 322
Anthony, H. L., 134, 137
Apgar, P. A., 394
Archibald, P. M.. 182
Ardagh. E. G. R.. 181
Arganbright. A. B.. 126. 136
Armbruster. M. H.. 14, 31.
72,77
Armstrong, C. B., 216
Armstrong. M. R., 262
Armstrong. T. N., 128, 136
Amdt, P., 182
Arnold. A.. 239. 260
Arnold, H. R.. 182, 426, 436
Arnold. L. K.. 372. 377
Arnold, W. P., Jr., 286, 317
Aronovsky, S. 1., 366, 376
Arveson, E. J., 141, 149
Ascham, L., 236, 249
Asdell. S. A., 262
Ash, C. S., 262
Ash. E. J., 133. 137
Ashbum. H. v., 204
Asser. E., 394
Aston, J. G., 68, 74, 182
Atkin, W. R., 22, 30
Audrieth, L. P., 101, 167, 161
Austin, C. R., 131, 136
459
Austin, J. B., 68, 74, 76, 76,
126, 127, 128. 131. 136.
136
Austin. J. H., 216
Austin. R. J.. 10. 30
Auvil, H. S.. 290. 317
Avera. A. U.. 320
Avery. S.. 204
Babasinian, V. S.. 215
Bach man. G. B„ 179, 181.
193. 203, 2m, 200, 216
Bachmann. W. E,. Ift4, 189.
192. 10*S, 201. 202. 203
Back, E. A., 369. 379
Backtis. H,, 20fl, 310
Backus, H, S., 76. 338
Bacon, T, S., 303, 321
Badger, R. M., 56, 140, 149
Badoche, M,. 184
Baechler, R. H., 372, 377
Backfcliind, L. H.. 397, 457
Baer, J. M., 265, 274
Baeyerti. M., 130. I3fl
Bahlke, W. H,. 339
Bailey. A, J,. 364, 370, 376.
376
Baiiey, C, H,. 244, 251. 262
Bailey, L. H., 244, 252
Bail&y. M.I.. 242, 251
Bain, E. C. 132, 133. 136.
137
Bain. J. P., 216
Baird, P. K., 370, 371, 376
Bake. L. S., 26S. 274
Baker. G. L.. 352, 356
Baker, CM., 370, 376
Bak«r, E. M„ 315, 323
Baker. F. B„ 260, 260. 276
Baker. G. L., 243, 252
Biiktr. K. F„ 258. 274
Baker. T.. 315, 323
Baker, TV. B., 228
Dokti. /;. N.. 24, 30
Baldeschwieler. E. L.. 84. 88.
142, 149. 340
Baldwin. A. W., 346. 366. 367
Baldwin. R. T., 440
Ball, T. R., 68, 94, 100, 109.
116
Ballantyne. H.. 368
Balls. A. K.. 244, 246. 261.
262
Balon. P. A.. 100
Baltzly, R., 429, 437
Bambach, K., 106, 114
Bancroft, W. D., 77, 143, 160,
361, 374, 427, 437
Banks. A. S., 466
Bannister. S. H.. 182
Bannister. W. J.. 277. 432.
438
Barbehenn, H. E., 407. 417
Barbour. P. A.. 227
Barbour, J. H., 373, 377
Barch, W. E., 204
Barger. G., 226
Baril, O. L.. 88. 89. 203
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Google
460
AUTHOR INDEX
Barker. B. P.. 66, 164
Barker, L. P.. 305, 321
Barker, M. M.. 16, 32
Barkhash. A. P., 179
Barnard, D. P., 338
Barnes, C.R.. 109. 116
Barnes, D. P., 266. 274
Barnes. K. B.. 337
Barnes, R. B., 66
Barnes. R. P., 182, 201. 204
Bamett, C. E., 406. 417
Bamett. M. M.. 201
BamhiU, G. B.. 260. 274
Bamum, G. L.. 241, 251
Barr, E. S., 12, 32
Barrett, C. S., 120, 122
Barrett, E. P., 119, 120, 126.
136
Barrett, H. J., 393
Barringer, L. E., 159. 162
Barsky. G.. 396
Bart. B., 147, 151
BarteU. P. E.. 348. 351. 365.
356
Bartholomew, E. T.. 106. 114
Bartlett. J. H.. Jr.. 144. 150
Bartlett. P. D.. 181. 203, 204
Barton, R. C. 66. 75, 93, 100
Bartow. E.. 182
Bartunek, P. P., 56
Bartz, Q. R., 202, 215
Bascom. C. H.. 352, 356
Base, E. L., 338
Bashour, J. T., 215
Basinger, A. J., 267. 274
BaskerviUe. W. H.. 76
Basnre. C. A.. 463
Bass, A., 420, 437
BasB. L, W.. 440, 443, 445,
447, 450. 4.'i2. 455
Ba3s. S, L., 422, 436
Baasdtt. S. H., 234, 249
BatcheMer. E, L., 2^^, 252
Batchfilor, T. G., 308, 375
Bateman, R. U, 204
Batemati, W. H., 208, 320
Batts, F. X, 163. 160
Bates, J. R., 35. 43, 77, 178
Bates. R. W., 2^3, 24©
Battiii, H. W., 306. 321
Battley, J. R, 4.57
Bfttty.a, 1^.137
Bauer, A. D., 338
Bauor. E. L., 182
Bauer, U N,, 215
Baumaii, L., 202
Biiuialach, H. L., IIU, 115.
140. 149
Baxter, G, P., 149
Bayfield, E. G, 244, 251
Bayndller, J. W., 415, 418
Badn, E. V., 242. 251
Beai:h, J. Y., 65. 5fi, 58. 202
Bcal. C. L., 168, 161
Bcal, G. a. 227, 454
Bcala, M. C, 251
Bean, H.S., 301,306, 321
Bear, R. S., 57, 311, 322
Bearce, G. D., 370, 370
Beard, E.E,, 419, 435
Beard, W,, 453
Beard, W. K,, 2S3, 316
Beanden, J. A„ 122
Beattie, J, A., 75, 179
Beatty, J. D,,45e
Beaumont, J. H., 25S, 259.
276, 379
Beavena, E. A., 252
Bechdel. S. 1,. £43, ^51
Bcchtel. V. R.. 466
Becker. A. E., 338
Becker. T. A.. 140, 149
Bt-cker^ L., 356
Bccket, F, M., 130, 136
B^ckwirth, E. A., 338
Btckwith, M. M., 121, 122
Beiforrl, M. H., 10,30
Bcebe, R. A-h 83, 8S
Beerbow^T, A, 02, 100
Bchrend, A.. 227
Behrman, A, S., 4S7
Bfiiswcnger, G. A,, 318
BtkkedaTiJ, N. 74, 75, 390,
400,406, 416,417
BelthiJT. D,, 21, 32, 76
Bekher, V, A.. 360, 376
Bekhetz, L., 33, 43, ISO
Belfit, R, W, 385
Belknap, E., 457
Bell, E. B.,362.36a
Bdl F. K., 5«. 182. 202
Bell, R. H., 274
Bt'll, R, M.,.S6. 58
Bell, R. P., 178
Bell,R. T.,311, 322
Bdl, W. B., 453
BeUer, H., 358
Bcndaaa, A., 220, 248
Bender, R, 58
Bender, H.. 436
Bender, H.L,.3tH
Benedict, W. L., 339
Benedict, W, S., 43, 44. 56,
79, 85. 88, 89, 178
Benner, J. R., 12tJ, 136
Botintng, A. F„ 170, 423, 436
Beimon, H. K., 385. 366, 373.
375. 377
Bent. H. E.. 25. 30. 159, 161,
187, 201, 207, 215
Benton. A. P., 85. 88, 311,
322
Berchet, G. J.. 180, 393, 394,
414, 418
Bergeim, P. H.. 409. 417
Berger. L. B.. 313. 323
Bergmann, M.. 231. 233. 248.
249
Bergstresser. K. S.. 109. 115
Bergstrom, P. W., 152. 160.
205. 215
Berberike, L. P„ 57
Berlin, H., 307
Btrliner, J. J., 456
Bermanii, M., 311, 322
Bemheim, F., 227
Berry, C, H„ 314, 323
Berry. G. W., 17, 2S, 32. 181
Berry, L, J.. 261, 275
Bertsch, A,,351, 355
Bertsch, H., 356, 357
Bertsch , J. A., 155, 161
Berwald, W. B., 208. 301,
320, 321
Bessey, O. A., 235, 249
Bethke. R. M.. 240, 250. 251
Bettman, B., 437
Betz, M. D.. 16, 26, 32,
77
Beuschlein, W. L., 365, 375
Bhagwat. M. R.. 394
Bibbins. P. E., 226
Bichowsky, P. R., 77
Bickel, 0. L., 189. 202
Bickford, P. A.. 96. 100
Bicking. G. W.. 369. 376
Biddulph, G., 453
Biffen. P. M., 181, 344, 355
Bigclow, L. A., 422. 436
Bigfeflf, J. H., 267, 275
Bifiinelli, R, 190
Biifnell. L. G. E, 338
Billings, H. P., 305
BiiUnjfs, S. C, 267. 274
Biilington, P. S,, 366, 375
Bills, C. E., 240, 251
Biltz, H.. 225
Binna, F. W., 369. 376
Birch, ?,. 75
Birehard, W. H., 369. 376
Bircher, L R., 32E
Bircher. L. J., 05, 100
Bird, E. W.. 344. 251
Bird, J- C, 304
BiBbey, B., 238, 250
Bishop, O, M„ 433, 438
Bi swell, C, B„ 202
Eitterich, p., 395
Bixby, E. M., 05, 100
Bjernjin, J , 142, 149
Blacet, P. E.. 313, 322
Black, A., 249
Black, C. K., 424, 436
Blackman. L. E., 16. 32. 76
BlaisdeU. C. A., 369, 370*
376
Blanchard, A. A., 94, 99, 100,
101
Blanchard, J. R., 290, 317
Blanchard, K. C., 204, 420.
433, 436, 438
Blanchard, L. W., Jr.. 197
201
Blanchard, M. H.. 31
Blatt. A. H., 182. 201, 204,
216
Bkakney, W., 77
Bleakney, W. C. 101
Blickc. P. R, 101, 202
Blinks, W. M., 322
BlJsh, M. J.. 244, 251
Blias, A. R., 228
Bliss, C.l,. 265, 274
Bbss, D. E.p 244, 252
Bliss, E. M„ 316, 323
Block, R. J., 249
Blome, W. H., 228
Bluomfteld, G., 181
Blue, R, D.. 157, 161
Blue, R. W., 74
Blumtacrg, H- S., 337
Blumenthal, D.. 231, 248
Blunck, R H., 201
Boatner, C. 201
Bode, C. E.. 244. 251
Bodlti, V. H.. 4U, 418
Bgese, A. B., Jr., 204
Boas net. P.. 287, 317
Bofiflrt. R., 240, 250
Bogert, M. T., 180, 197, 199,
202, 204. 215, 216, 217
BogjicBs, D„ 226
BoRin, Q,39a
Boiler, E. R., 254, 274
BoUinger, D. M., 25. 31, 143,
150
Bolhnan,R. R.,411. 418
Bolton, E. K., 264, 274, 410,
417
Bone, W. A., 36
Bonner, W. D., 75
Bonney. D. T., 316
Bonney, R. D., 415, 418
Bontoux, E., 356
Bonyun. M. E., 144, 150
Booher, L. E., 238, 250
Booth, C. P.. 435
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AUTHOR INDEX
461
Booth. H. S.. 64, 69. 76, 76,
91, 96, 96. 100, HI, 116,
182, 204
Bordner, E. R., 66
Borelius. G., 140. 149
Borgeson, G. M., 243, 261
BorgUn, J. N., 438
Borsook. H.. 216. 232. 249
Boruflf, C. S., 364, 376
Bossert. R. G.. 228
Bost, R. W.. 202. 204
Botset. H. G.. 319
Bottoms. R. R.. 182. 426. 437
Boundy, R. H., 297. 319
Bousquet, E. W., 260. 264.
271. 274
Bovier, L. S.. 182
Bowden, R. C, 349, 366
Bowen, A. H., 396
Bowen, E. L., 273. 274
Bowen. N. L., 70, 76
Bower. J. H.. 112. 116
Bowers, C. N., 338
Bowker. R. E.. 116
Bowman. P. I., 85, SS
Boyce< A. M,, 257, 274
Bf^yce, C. W.. 371, 376
Boyd. E. M., 230,248
Boyd, T. A.* 3^9, 444 < 454
Bayd, W. C, 231. 248
Boiorth, A. R., 95, lOO
Bo^orth, R„ 121. 122
Bradley, a A., Jr.. 56
Bradley, R, S., 146. 150
Bradley, T. P., 396
Bradt, W. E., 154, 161, 437
Brady, E. J.^ 304, ^2\
Braeg, G. A,, 319
BfaTnard, S. W.. 346. 355
Brainerd, F. W.h371,3T6
Branch. G. E. K., 203. 437
Branchpn. L. E., 182, 215
Brand, C J., 457
Brand, E., 232, 24S, 249
Brandee, O. H., 100
Brandon, G. E., 318
BranJiam. X R-p 141. 149,
312.323
Brannotk, D. Y.. 374
Brannon, L. W.. 271. 276
Brastow, W. C, 139, 149
Brattain. R. R.. 56
Braun. 0. E., 366, 376
Braun, J. von, 189
Bray, M. W., 360. 367, 374,
376
Bray. U. B.. 339
Bray. W. C, 12. 31. 76, 108.
116
Breazeale, D. P.. 244.261
Breazeale, W. M., 58
Bredberg. L. E.. 337
Bren, B. C, 393, 39fl
BTEanan, J. F., 303, 321
Brenner. B-, 146, IfiO
BTeskin, C. A.. 392, 397, 439
Breuer, F. W.. 179
Brewer, L E.. 294, 319
Brewer, R, E„ 88. 287, 317
Brick. R. M., 122
Brickwedde. F. C 76
Bridge, A. P.. 302. 321
Brid^man. O, C.» 457
Bridger. G. L.. 23, 32, 75
Bridgman, P. W,. 23, 31, 60,
65. 67, 74» 75, 7<i, 77, 143,
150,182,393.401,416
Brifigs. G. M.,305.32t
Briggs,L, J.,371,37fl
Brigham, P. M.. 164. 161
Bright. H. A.. 111. 112. 116
Britton, E. C., 179. 262, 266,
274. 432. 438
Broadbent. B. M.. 266. 274
Broche. H.. 296. 319
Brock. P. P., 394
Brt)ckman, C. J.. 103, 114,
162. 163. 164. 156. 160
Brockway. L. O., 46. 66. 66,
74, 202
Erode, W. R.. Ill, 116. 190,
202. 228
Brodersen, K., 368
Brodie, J. B., 237, 260
BrSnsted, J. N., 8, 9. 10, 11,
16,22
Brookbank, E. B., 141, 149
Brooker, L. G. S., 216. 217
Brooks, B. T.. 179. 182, 337,
338, 414, 418, 466
Brosheer. J. C.. 77
Brous, S. L., 414, 418, 439
Brower, T. E., 126, 136
Brown, A. S., 13, 19, 31. 76.
77. 109. 116
Brown. B. E.. 366. 376
Brown. D. J.. 16. 30. 77
Brown, E. M., 262
Tii-^-n. E. V„215
Brown, P., 227
Brown. G, G.. T5. 299, 316,
320, 323, 338, 339
Brovm. R. P., 313, 323
Brown, W. G,, 72. 77
BxQwn, W. J., lU, U6
Brown. W. L., 236. 249
Browne, A. W., 95. lOO, 437
Brt}wne, C. A.. 443^ 463
Browning. B. L,. 365, 376
Brownle^H R. H,, 356
BrownmiUer, L. T.. 76
Brownscombe, E. R., 94, 100
Brubaker, M. M., 396
Brunauer, S.. 83. 88, 89
Brundage, J. T.. 227. 228
Bruner. W. M., 216
Brunjes. A. S.. 76
Brunot. F. R., 140. 149
Bruson. H. A.. 182. 263. 274,
367, 396, 426, 437
Bruyne, J. M. A. de, 67
Bryant, G. R., 339
Bryant, W. M. D., 181, 188,
202. 209. 216
Bug. H. E.. 271. 274. 429. 437
Buchanan, G. H., 266. 274
Buchanan, K. S., 230, 248,
249
Buchman, E. R., 212, 216,
217, 260
Buckman, S. J., 361, 374
Buckner. R. P., 264. 278
Buehler. 0. A., 202
Buell. A. E.. 339
Buerger. M. J.. 118, 122
Bulbrook, H. M.. 318
Bull. B. A., 196. 203
Bull. H. I.. 360. 366
Bullock. W. B.. 371. 377
Bump. C. K.. 372. 377
Bunbury, H. M.. 367
Bunce. E. H.. 292, 317
Bunger, H.. 374
Bunker. J. W. M.. 241, 260,
261
Burchfield, P. E., 96. 100.
182 204
Burckhardt. E., 226
Burdette, R. C.. 266. 274
Burdick. C. L.. 318. 466, 467
Burg, A. B., 97, 101, 169. 161
Burger. A.. 202, 216, 227
Burk, R. E., 36, 43, 180, 203.
393, 436, 439
Burke. S. P.. 182. 298. 320.
394
Burlew. W. L.. 422, 436
Burmeister. H.. 396
Burnett, R. E.. 179
Bums, J. L.. 137
Bums, R. E.. 358
Bums, R. S., J32, I3fl
Burrell, A, B,, 257, 277
Burrell. G. A., 296. 319
Burrows, G. H., 76, 216. 437
Burtner. R. R,. 204. 215, 433.
438
Burton. J. O.. 108. 116
Burwell. A. W.. 263, 274. 426,
437
Busbey, R. L.. 263. 266. 266.
278, 279
BusenLurff, IL B., 4ll, 418
BushnelU V. C, 74
Buskrjrk, JI. H., 247. 252
Bub well. A, M., 364. 376
Butler, C. L,, 227
Butler. W. H.. 305. 439
Butterworth, A. S., 357
Butts. J. S., 232. 249
Buti, L. W„ 215
Byall.S.. 247,252
Byers, H. Q-. 107. 115
Bsrers, J/L.. 139, 149
Byers. J. R.. 179
Byrne. C. O., 319
Byms, A, C, M. 100
Bywater, W. G.. 215
Cadwell, S. M., 402, 410
Cady. G. H.. 92, lOO
Cady.UC. 361,374
Cagle, W. C, 76
CahiU, G. F.p 232, £48, 249
CajoK, R A.. 229, 248
Cake, W. E., 413, 418
Calbeck, J. H*, 158, 161
Calcott, W. S., 179, 273. 274,
346. 355. 358. 379, 393.
396. 397, 405, 417. 423. 426.
439, 436, 437, 438
Ciildwtll. F. R„ 146. 150
CalJweU, J. R., 113, 116
Calf! well. M.L.,229,248
Calliane, D. F. 154, 101
Calingaert G.. 179
Calkin, J. B., 361, 373^ 374.
Callen, A. S., 324
Calloway, N. O.. 194. 203,
204. 216. 433. 438
Calvert. W. C. 416. 418. 420.
436
Calvery. H. O.. 232. 249
Cameron. P. K.. 76. 361, 374
Cameron. H. J.. 394
Campbell. A. N.. 26. 31. 104.
114
Campbell. C. H.. 411. 418
Campbell. C. L.. 367
Campbell. D. A.. 129. 136
Campbell. F. L.. 263. 270.
272. 274, 276
Campbell. H. C. 43. 44. 182
Campbell. H. L.. 234. 236.
247. 249. 262
Campbell. J.. 321
Digitized by
Google
462
AUTHOR INDEX
Campbell, J. M.. 339
Cann. J. Y., 71, 77
Cannon, M. R., 330
Canon, P. A., 438
Capen. R. G.. 244, 252
Capillon. B. A.. 147. 151
Caplan, S., 394
Caprio. A. P.. 395
Carey. J. S., 315, 323, 389
Carleton. P. W.. 429. 438
Carlin. J. C, 396
CarUsle. P. J.. 265. 274
Carlson. G. H., 179. 182. 201
203. 420. 435
Carmack. B. M.. 455
Carmody. W. H., 394
Camahan, P. L.. 203
Carney, B. S., 96, 100
Carothers, W. H.. 180. 207.
215. 393. 394, 414. 418. 434.
439
Carpenter, C. tL. 373, 377
Carpenter, D. C, J.S2, 215
Carpenter, 0. B., l81
Carpenter, J. JL. jJ^, 100
Carpenter. M S.. 4:J4. 439
Carr. J. I.. 420. 4;i5
Carruth. H. P., 371. 376
Carruthers, A-, 22S, 248
Cars, N., 182
Carson, P. T.. 372. 377
Carson. L.. 202
Carswell, T. S., 423, 436
Carter, A. S., 393, 396, 397
Carter, P.. 146, 150
Carter, P. B., 147. 151
Carter. H. E.. 248
Carter, J. D., 361, 352, 356
Carter. R. H.. 258, 259, 274,
278
Carter. W.. 261. 274
Cartland. G. P.. 226
Cartledge. G. H.. 92. 100
Carvlin, G. M.. 318
Cary, C. A., 229, 248
Case, L. O., 57, 182
Cashman. R. J., 81, 89
Caspe. S.. 182
Cassel, H. M., 28, 31, 74
Cassil, C. C, 268. 276
Castles. I.. 203
Caswell, R. G.. 456
Cattell. R. A.. 296. 319
Caulk. M. D.. 356
Centenero. A. D.. 366, 375
Chalmers, P. S.. 455
Chalmers, W.. 181
Chamberlain. J. C. 216
Chamot, E. M., 97, 101
Champlin, P. M., 262
Chandlee, G. C, 14, 32, 77
Chandler, A. C. 256. 274
Chao, S.-H., 56
Chap, J. J., 216
Chapin, R. M., 346, 349, 355,
356
Chapman, A. T., 36, 43, 179
Chapman, E. C, 123
Chapman, P. J., 254, 265.
274, 277
Chapman, W. H., 413, 418
Charch. W. H., 372, 377
Chase. G. C, 370. 376
Chase, H., 397
Chatfield, C. 245. 252
Chaudhuri. T. C. 190
Cheetham. H. C. 394
Chen, A. L.. 228
Chen, K. K.. 226. 228
Cheney, L. C, 215
Chorry. O, A., ^M. 3M
CKidcatcj'p G. H.» 366. 37fi
rtiittitn. T. Km ISO, 315, 323
Ch[pmaii, J., 74. 113, 116,
12.^. 127. 135.136
Chltwood. Hh C, 21fl
Chitwood. L M., 251
Cholflk, J.,110. 115
ChDu, T, 0., 228
Chow, B. P.. 181
ChriVt, R. S.< 181, 202
C;.:,.,.c...,^ji, B. E.. 87. 89,
312. 322
Christensen. B. V.. 228
Christensen. C. W.. 404. 416
Christensen. L. M.. 181
Christian. S. M.. 25. 31. 143.
150
Christiansen. W. G.. 10, 11.
228
Christmann. L. J., 257. 274
Chrystler, P. M., 396
Chu, E. J-H., 189, 202
Churchill, W. L., 456
Cislak, P. B., 273, 275
Claffue. J. A.. 246. 252
Clark, C. C. 358
Clark. C. L.. 129, 130. 136.
137
Clark. C. W.. 74
Clark. D.. 455
Clark. E. P.. 268
Clark. P. M., 160, 162. 397.
457
Clark, G. L.. 121. 122. 123.
362. 374. 407. 417
Clark. H. A.. 308. 322
Clark. J. D.. 159. 161. 394
Clark. J. d'A.. 372. 377
Clark. L. V.. 421. 436
Clark. T. H , L>94
Clarke, B. L„ 113, 115
Clarke, H. T., 205. 212, 217,
231. 248. 25a. 430, 438
Clarke. M.R, 236, 24S
Clarke. W. J.,393
Clarkson, R. G.. 3lfi, 348.
355. 358. 437, 43&
Claussen, W. H., 03, 100
Clayden, A. L,. 3^9
Clayton, B., 367. 35S
Cleaves, H. E.. 135
Clements, J. H.,66
Cleveland. C. R.. 261. 263,
274. 276
Clifcom, L. B., 216
Clifford, A. M.. 397, 403, 404.
405, 416, 417. 439
Clifford, P. A.. 279
Cline. E. L.. 394
Clow. M. T.. 309. 322
Clyne. R. W.. 129, 136
Cobb. A. W., 20, 31. 74
Cobb. R. M.. 372. 377
Coblentz. W. W.. 56
Cockerille, P. O.. 180
Coffman, D. D.. 180, 383, 394
Coffman, D. H., 393
Cogan, H. D., 439
Cohen, P. L., 227
Cohen. M. U., 105, 114, 117,
118 122
Cohn.'B. N. E.. 241, 251
Cohn. E. J.. 10. 19, 29, 31, 32.
57, 75, 76, 77, 183
Cohn. B. W.. 233. 249
Colbum. A. P., 315. 323
Colby, W. P.. 56
Cole, H. A., 314
Cole, O. D., 407. 417
Cole. S. S.. 76. 123
Cole. W.. 201
Colehour. J. K.. 93. 100
Coleman. C. 403. 404, 416.
417
Colemfln, G. H„ ISO, 438
Coleman. J. M.. 245, 252
Collett, A. R,,304
ColKofl. A. M.. 393. 4U. 418
Collins. G.. 5n
ColliiiB.J. C. 340
Colltns, J. P., Jt., 314, 323
CnllEns, R, G,,3:^fl
CoJliiifi, S. C. 74
Ci.ll man. W., 286, 275
Col well, A, T., 134. 137
Compere. E. L., 251
Cismpton, A. H., 117. 122
Conant^ J. B., 393
ConcanfiDti, C. C, 440, 454
Confrancesco, A. j.. 2(M
Conine. R. a. 33?. 338
Conn, L. W,, 107, 115
Conn, W.T,, 273, 275
Conner, R. M., 300. 322
Connor, R . ISI. 201, 21
Conover. C, 422, 436
Conrad, F. H.. 365, 375
Coni^d.R. M..29.31, 75
Cook, E.. 128. 136
Cook. E. J. R., 25. 31, 104,
U4
CcKjk. E. W., 154, 155. 156.
161
Cook, G. A., 35, 43
Cook. J. W\, 191. 192
Cook. W. A.. 76
Cooke, M. B., 339
Coolidge. A. S., 57. 58
CooUdge. C. 409. 417
Coon, E. M.. 56
Coons, C. M.. 241. 251
Coons. R. R.. 241. 251
Cooper, T. P.. 268. 278
Cooper. K. P.. 266. 276
Cooper. N., 228
Cooper. S. R., 109. 116
Cope. A. C. 181. 201. 202
Copeland. M. A., 455
Copeland, M. T.. 463
Copenhaver. J. £.. 246. 262
Copenhaver. J. W.. 201
Copley. M. J., 83. 89
Cordes. J. H., 301, 320
Corfield, G.. 306. 306, 321
Cork. J. M.. 146. 160
Corl. C. S.. 268. 276
Cornell. W. B.. 453
CorBon. B. B., S9, 180, 299.
320. 338, 439
Corson, H. P., 266, 275
Cortese, P.. 202
Cory. E. N.. 259, 376
Coryell. C. D., 95, 100
Cosby. B,0.. 204
Cothran. J. C, 100
Conoti,F. H..412.418
Cotton, R. T,. 265. 279
Cottrell, F. G.. 454
O^uch, J. P,, 228
Coull. J.. 76
Coulson, £. J., 236. 242, 249.
251
Courtney, E., 230. 248
Cowan. R. J., 307, 321
Cowden, D. J^ 466
Cowdery. A. B.. 409, 417
Digitized by
Google
AUTHOR INDEX
463
CowgUl, G. R., 239. 260
Cox, E. R.. 76, 179
Cox. G. J.. 432. 438
Cox. J. A.. 275
Cox, N. L.. 25. 31
Cox. R. P. B., 182, 201
Cox, W. M., Jr.. 180
Ciabill. A., 295, 319
Cnti«. D., 180, 204, 405, 417.
420.435
Craig, L. C. 156, 161, 219,
226,227
Craiit. R., 2fl7, 276
CroiR, W. E.. 202
Craig. W,M.. 97, 101
Cramer. H. L, 40^, 416
Crane. H. R.. Ill, 100
Crane. K. D., 94, 100
Crawford, E. T., Jr., 457
CrawfortJ^P, M.. ISl
Crawford. H. M.,201
CreiRhton. H. J., 155. 161.
429, 437
Creitz. E. E„ 367, 375
Cressman. A. W., 260. 275
Cretchcr, L. H., 227
Crist, R. H., 43
Critchctt, J. H., 128, 136
Croakman, E. G.. 410, 417
Crocker, W., 250, 279
Crockfortl, H. D,. m, 75
Croope, D. H., 430
Crosbie, H, H,, 220
Cross, H. C, 129. 13fl
Cnjss, P. C, 55, 66, 74
CroGsIey, F. a. U2, 140, 204
Crowd U M. F., 247. 2i'J2
Crtiwell, Vir. R.. 99, 101. 110.
lift, 140, 149
Cfomlh W. J., 203
Crum, W. L., 457
Crump, J. W., 395
Cnimpler, T. B., 105, 1J4
Cmmpton, J. R., 337
Cryder. D, S., SS, 89, 181,
312. 322
Csonka. P. A.. 234. 249
Gulp. P. B.. 245, 252
Culpepper, C. W., 245, 252
Cummings, A. D.. 398, 400.
416
Cunningham. G. B.. 82, 89
Cunningham, G. L.. 85, 88
Cunningham, W. A., 458
Cuno. C. W., 446, 455
Cupery, M. B., 154, 161. 434.
439
Cupples, H. L., 259, 265, 275.
348. 355
Curie, I., 90
Curie. M., 149
Curme, G. O, Jr., 425, 436
Curran, C. E,, 3fM), 365, 366,
371, 374, 375, 37 B
Curran, W. J., 57
Curtis. P. J.. 457
Curtis. G.. 229, 24S
Curtis. H. A.. 457
Curtiss. L. P., 105, 114
Cuthbcrtson.^ G. R., 66, 75
Cybulski, G., 225
Cyr, H. M.. 369, 376
Daft, P. S., 249
Daggett, A. P., 72, 77
Daggs, R. G., 234, 249
Dahl, A. I., 74, 146. 150
Dahle, P. B., 134, 137
Dahlen. M. A.. 420. 435
Daimler, K., 357
Dains, P. B., 203. 217
Dakin, H. D., 235, 249
Dale, H., 226
Dales, B., 413, 418
Damon, B. H., 410, 417
Damon, G. H., 112, 116
Dangelmajer. C, 265. 274
Daniel, D. M., 276
Daniels, A. L.. 234. 236, 249
Daniels. P.. 35, 44. 179
Daniels, R. S.. 394. 395
Daniels, T. C, 22. 31
Daniloff. B. N.. 136
Dann. M.. 239. 250
Darlington. C. J., 464
Dashiell, P. T.. 285. 293. 316.
318
Dauben. H. J.. 86, 89, 310,
322
Daudt, H. W.. 179. 423, 436
Davenport, B. S., 132, 133,
137
Davenport. J. E., ,112, 322
Davey, W. P., 120, 121
Davidson, A.. 345, a-W, 357
Davidson, A. W., 19, 31
Dftviffsnn, D., ISO, 199, 204
Dttvidaon, J. G., 393
Davidson, R. H., 255, 276
Daviea, B, L., 410, 417
Da\its. C, Jr., 294, 318
Davies, R, L„ 412. 418
Davis, A, C., 257, 275
Davis, C. W.. 13S, 149
Davis, D. S„ ,167, 375
Davis, G, H. D„300, 320
Dflvifi. H., 310, 322
Davis, H. M., 180
Davis, H. W., 138, 149
Davis, J. A., 217
Davis, J. D., 289, 290, 314,
317, 323
Da^is, J. J.. 272, 275
Davis, L. L., 330
Davis, M., 300, 374
D^ivis, M. E, 226, 227
YMcAs, M, N., 371, 372, 377
Ii , is, R. E., 319, 457
is, T. L„ 179. 204, 215
i - is, W. W., 340
D-vy, B. D., 22 «
Dawsey, L. H., 260, 275
Dawson, C. R., 27, 32
Day, A. R., 204, 437
Day, H. G.. 249
Day, J. B., 86, 89, 310, 322
Day, P. L., 242, 251
Day, R. B., 396
Dean, R. S., 125, 135
Deanesly, R. M., 180, 423,
436
Dearborn, P. B., 253, 275
Dearing, M. C, 180, 395
Dearing, W. C, 14, 31, 109,
115
Debbink, H. S., 338
DeBeer. B. J., Ill, 116
DeCew, J. A., 368, 370, 375,
376
Deditius, L. P.. 155. 161
Dees, M., 19, 31, 76
De Holczer, L. J., 394
Deitz, v., 37, 43, 57
DeKay, H. G., 228
Delahanty, T. W.. 440, 454
Delammater. W. W.. 127.
136
Deller. A. W.. 445. 454
De Long. C. R.. 452, 457
DeLong, D. M., 257, 275
Delorey, C. W., 293. 318
Dembo, L. H., 245. 252
Deming, L. S., 64, 75
Deming, W. B., 64, 75
Dcmorest, D. J., 290, 317
Dempster, A. J., 144, 150
Denig, P.,318
Denison, I. A., 129, 136
Dennine, P. S., 356
Dennis, L. M., 93, 06, 97
100, 101
Dennifion. D. M„ 5fl. 57
DeNfotft, A., 228
Dent, H, M., 394
De RewHl, F. J„ 262, 275
Derby. H.L., 453. 457
Derby, I. IL, 273, 275, 318
D«rEe, G. J„ 141,149
Denck, C, G„ 156, Ifll
Dettwyler, W., 438
Devaney. G. M , 242, 243, 251
DtamOTid, H., 79. SO, 89
Dickey, E.. 320
UEckey, J. B.. 179, 201
Dkkh&uSBf , E., 180
Dickinson, B. M.. 144, 150
Diclrinaon, J,. 339
Dickinsan, J. T., 339
Dickinson. R. G., 179
Dickson, J. V. E., 31S
Dicksnn, W, M,, 254,275
Diesel, N. P., ISI
Dietrichson, G.. 95, 100
Dietz, H. P., 257. 264. 274.
275
Dietz. v.. 20
Dietzler, A.J., 437
Digges, T. G., 133. 137
Dike, T. W., 395
Dille, J. M., 226
DiUon, J. H., 407, 417
DiUon, R. T., 312, 322
DiUs, L. B., 260, 275
DingwaU, A., 21, 31, 111. 116
Distler. B. P.. 76
Dittmar, J. H.. 247, 252
Ditto, M. W., 286, 317
Dixon, B. S., 132, 137
Dixon, J. K . ^5, S9, 142, 149
Dobbins, J. 1., 70. 93, 100
Dobroseky, I. D., 257, 276
Dodd. L. E.. 120, 132
Dodge, B. P., 65, 75. 84, 89,
ISO, 182
Dndgis, J. F., 319
Dodge, W. O., 372,377
Doebbeling, S. E,, 248
Doede, C, 98, 101
Dohert^H W, T., 358
Doaleavy, J. J., 216
Dooley. M, P.. 33
Doolittle, A. K,, 340
Dorfman, M. 25,30.201
Duroiii^h, G. L., 304
niMifJ^ K,, H6l,374
Dougan,R.B., 11,31
Dougherty, G., 204, 215, 434,
438
Doughty, E. W., 27, 31
Doughty, R. H., 370, 371, 376
Douglas. S. D., 180, 393
Douglas, T. B., 68, 75
Douglass, W. A., 405, 417
Dounce, A. L., 215
Dove, W. B., 267, 275
Dover, M. V., 152, 160, 179.
338
Digitized by
Google
464
AUTHOR INDEX
Dow, H. H., 168, 161
Dow, R. B., 23, 31, 75, 182
Dowdell. R. L.. 131. 136
Dowling. A. S.. 238, 260
Downes, A. W., 141, 149
Downing, P. B.. 379, 393, 432.
438
Downs, C. R.. 396. 466
Doyle, J. E.. 216
Drabkin, D. L., 216
Drake. B. H., 396
Drake, G. W., 97, 101
Drake, N. L.. 181, 272, 276,
278
Draper, R. B., 69, 76
Draves, C. Z., 348, 366
Dreshfield, A. C, 368, 376
Dresser, A. L.. 100
Drew, E. P.. 367
Dreyfus, C, 397
Dreyfus, H., 181, 182
Drier, R. W., 143, 160
Driggers. B. P., 268, 276
Dryer. G. G., 339
DuBois, D., 227
Dubpemell. G.. 140, 149
Dubrisay, R.. 179
Dudley, H. C. 107. 116
Dudley, H. W., 226
Duffendack, O. S., 110, 116
Dufraisse, C, 184
Duke, W. v., 287, 317
Dull, M. P., 203
DuMond, J. W., 84. 89
DuMond. J. W. M., 119, 122
Dunbar, C, 368
Dunbrook, R. P., 403, 416
Duncan, A. B. P., 66, 181
Duncan, C. W., 236, 241, 249.
261
Duncan. R. A.. 366
Dunegan, J. C, 278
Dungan, P. H., 267, 276
Dunham, A. R., 313, 323
DunUe. H. H.. 121. 123. 128,
136
Dunn, C. L., 15, 32, 101, 112,
116
Dunn, E. P., 269, 275
Dunn, T. H., 296, 319
Dunn, M. S., 216, 232, 249
Dunning, J. W., 266, 276, 277
Dunstan, A. E., 300, 320
duPont, L., 463
Durant, W. W., 396
Dutcher, H. A., 107, 115
Dutcher, R. A., 239, 260
Dye, H. W., 257, 279
Dyer, H. M., 231, 248
Dykstra, H. B., 180, 383, 393,
394, 396, 434, 439
Dymock, J. B., 182
Eash, J. T., 143, 146, 160
Eastman, E. D., 65, 76
Ebaugh, N. C. 314. 323
EbeHng, W., 261. 264, 275,
278
Ebers, E. S., 201, 216
Ebert, G., 180
Ebert, M. S., 88, 89, 92. 100,
180
Eck, J. C, 184, 201
Eck, L. J., 286, 316
Eckart, C, 56
Eckerson, S. H., 362, 374
Eckert, P. E.. 298, 320
Eckman, J. R., 400
Bdds, R., 202
Eddy. C. O.. 260, 267, 275
Eddy, C. T., 137
Eddy, H. C. 169, 161
Eddy, N. B., 227
Eddy, W. P.. 134, 137
Edie. P. M., 254, 277
Bdland. L. A., 412, 418
Edlund, D. L., 134. 137
Ediund, K. R., 182. 438
Edmonds, S. M., 103, 105.
114
Edmunds, C. W., 227
EdsaU, J. T.. 20, 29, 31. 57.
64. 74. 76, 182, 202
Edwards, B. S.. 394
Egerton, L., 427. 437
Egge, W. S., 415, 418
EgU. H., 21
Egloff, G., 36. 43, 180, 299,
300. 320. 337, 338, 339. 397
Ehret. W. P., 94. 100
Eidinoff, M. L., 68
Eilers. L. K.. 227
Eisenmann, K., 396
Eifimgpr, J. O.. 338
EMey. J. B.. 1B2, 204, 216
Elbe, G. von, 37, 39, 43, 59.
60, 65. 7-4, 75, 310. 322
ElbeL E., a57
Eldprfield, R. C.. 193, 203
Eidfcdn D. N,. 264, 278
Eldn, L C. 77
ElfedEE. H. C 357
EUingfr, G. A.* 127. 131, 132.
Etliot, P. A. < 337
Elliott . M. A, 286, 317
Elliott. N.MS
Hllia, C, tSO, 301, 320, 367.
37S. mi. in^, 394, 395, 396.
3U7< 426, 437* 465
ElliB, E. L., 74, 183
Ellfs, L, N., 236, 249
Ellis, N. R., 114, 116,229,248
EIU5. S. B., 10ft, 116
El[[.w, L. O., 267, 278
KiCms, E. H., 318
Elsey. H. M., 204
Elvehjem, C. A.. 216, 236.
238, 239, 249. 250
Ely, E. C. 77
Embree, N. D., 22, 31, 75
Emrnv, ■B..44,'>, 463
Efiitry, F. H-, 111, 116
Eniniett, P. H., 65, 80, 83,
88, S9, U2, 149
Emsch^lller, G., 179
Engpl. L. L., 202
Enfiland, A.. Jr., 31, 76, 183
English, H.,249
EnghiTifl, L. H„367
Enterliiie, H. M., 394
Epstein, R. C, 462, 454, 457
Epstein, S.. 128. 132. 136.
137
Erdahl, B. P., 413, 418
Erickson. J. L. E.. 201
Ernst, A. H., 148, 161
Erwin, R. P., 366, 376
Esselen, G. J.. 369, 374. 378,
455
Essex, H., 76
Etzel, G., 367
Evans, C. 228
Evans, E. A., Jr.. 249
Evans, G. H., 67
Evans, H. M., 230, 237, 238,
241. 248. 260. 251
Evans. M. D.. 228
Evans, M. G., 9
Evans. O. B.. 286. 316
Evans, R. N., 312, 322
Evans, S, M , 403, 41d
Evans, T., 182, 43S
Evans, T, W., 77
Evans, W, L., 427, 437
E\^ne, W. V„ SI, 89, 156,
1B1,201
E verb art, J. L., 394
Evera, C. P.. 372, 377
Ever&dle, W. G.. 27, 31
Eversoti, G. J., 238, 249
Ewart, R. H., 02, 100
Ewdl, R.H;.70.7e. 77
Ewing, S., 302, 303, 321
Ewinfi, A, J., 226
Eyer, J. R., 266, 276
Eym&nn, C, 294, 31S
Eymann, JC.,2&4*3ie
Eyre, J. V., ISO
Eyring, H., 7, 8, 9, 3 1, 32. 38,
39, 41, 42, 43, 44. 57, 92.
100. 143, 160,311,322
Pabian, P. W., 247. 252
Pahey, P.. 311, 312, 322
Pahey, J. E.,278
Paick. C. A., 76
Pairley, T. J., 411. 416. 418
Pairlie, M., 458
Pajans, K., 103
Pales, J. H.. 254, 275
Palk, K. G.. 230. 248
Pall, P. H., 348, 349, 355
Pancher, G. H., 337
Parquhar, S. T., 369, 376
Paris, B. P.. 149, 227, 228.
437
Parley, A. J., 254, 275
Farlow, M. W., 86, 89, 181.
216, 437
Parr, W. K., 362. 374
Parrar. G. E., Jr., 235, 249
Parrar. M. D., 261. 267. 275
Parrell. J. K., 179
Parrington, B. B.. 340
Parwell, H. W.. 58
Pasce. E. V.. 181. 203
Payerweather. B. L.. 271. 277
Pehlandt. P. R., 182
Pield. A. L.. 126. 135
Peinstein, H. L., 228
Peldman, H. B., 110. 115
Peldman, J., 165, 161
Peldman, S.. 26, 32
Pellets, C. R., 246, 246, 247,
252
Peng, C. T., 228
Penning, K.. 454
Penske, M. R.. 75. 316. 323,
326. 339
Penwick, P., 108, 116
Peraud, K.. 215
Perguson, A. L.. 57, 140,
149
Perguson, C. S., 395. 396
Perguson, H. P., 273, 276
Perguson, J. H.. 432, 438
Permi, E., 91
Pemelius, W. C, 93, 100
Pemholz, E.. 203
Petz. E.. 119. 122
Peyder. S., 229. 248
Pield, A., 262
Pield. M. C.. 360. 356
Pieldner, A. C. 288, 289. 314.
317. 323. 457
Digitized by
Google
AUTHOR INDEX
465
Picser, L. P., 154, 161. 191.
202. 203. 204, 205, 207,
215, 216
Pieser, M., 191, 202. 204
Pincke, M. L., 234. 249
Pindley, J. K., 130, 136
Pine. R. L., 415. 418
Pink. C. G., 141. 142. 149,
150. 157. 161
Pinlayson, A., 273. 274
Pinlayson, D., 181
Pinley. G. H., 324
Pinn. A. N.. 75
Piock, E. P., 310. 322
Pischer. B.. 190
Pischer. W. von, 103. 105,
114
Pish, P. H., 291, 317
Pisher, C. H., 201. 202, 427.
437
Pisher. C. K., 266, 274
Pisher, E. K., 339
Pisher, H. L., 407, 417
Piske, C. H., 235, 249
Piske, W. P., 465
Pitz. W.. 319
Fitagerald. T. B., 183, 203
FitiiSiinofifi. O., 338
ineodng. S, H..Jr,. 181
Plemingr, W, E., 260, 2flft, 275
Fleming, W. R,, 125, 135
Pletclier, H. H.. 2+S
Flett, L. H.p 419, 436
FleKsert L. A.. £ 1 , 31. 111,1 16
Flint. R. B., 260, 276. 357.
416.418.425,437
Flint, W. P., 2fi7. 275
Flock, B. J., 339
Flood, D.T., 17a
Florance^ H,* 457
Florence, R. T., 19, 32. 77
Florenz. M,, 3^
Floret, L. de, 299, 320
Fltievog, E. A., 76
FltikE.iC. U, 259, 275
Foley, F, B., 125, 136
FoIkpT^, K.. 343, 355
Fonda, B. P.,308, 3:?2
Pontana. M. G., 74, 113. 110
Foohesr. W. L., 435
Foote. F., 118, 122
Forbes. A. L., Jr., 319
Forbes, E. H.. 533, 249
Forbes, G. S., 43
Forbes* W, A,. 260,275
Ford. A. S., 307
Ford. O. M,.319
Ford, J. H.. 202
Ford. M, A., 204
FoTd, T. P., 403. 415. 416, 418
Fordyce. C. R.. 431, 438
Foreman, M, O., 273, 274
Fqnnan, M„24!)
Fornwalt, H. J., 28, 31
Forrest, H, O., 455
PorTfist, L. R., 318
Forsce, W. T., Jr.,216
Foster, A. L,. dm
Foster, J. P., 26, 32
Foster. L. S.. 157, 161, 202
FoBtftT, L. W., m. 07, 101
Foster, R.H.K., 227
Foulk, a W., Ill, 116
Fowler. A.. 8
Fowler. A. F,. 242, 251
Fowler. 11. C, 296, 319
Fowler. R.M., 111. 116
Pox. S. W.. 248
Foy. M.. 203
Praas, P., 313. 323
Prance, W. G.. 156, 156, 161
Pranceway, J. A., 300, 320
Prancis, E. H.. 313. 323
Pranck. H. H., 182
Prank, A., 57
Prank, A. R.. 182
Prank, H. C., 365. 375
Pranke. P. E.. 227
Pranke. K. W.. 236. 249. 250
PrankUn. E. C., 94. 100. 140.
149. 205. 215
Pranks. R.. 130, 136
Pranz. R. A., 215
Praps, G. S., 236, 250
Frayser, L.. 233. 349
Frazer, J. C. W.. 100
FrajJer, E,, 236, 240
Frear. D. B. Hh. 258, 275
Frcar, G. L., 426, 437
Frederick, D, S.. 430
Frederick, H.^ 260
Preeborti, S. B., 261, 275
Freed. S., 57. 61. 74
FrencK, G.. 358
FrcDch, H. E,, 179
French, H. B.. 248
Fretidenberg:, W., 17S
Freud en bereer, H., 199
Frevel. L. C, U9, 122
Frevcrt. H. W., 313, 323
Frey, F. E.. 180. 2f>9, 320
Piickfi, H., 04, lOO
FriedmsTi, L..362, 374
FriedolahEim* A. v.. 357
Friend. W, Z., 208, 320, 338
FrieniQTi, W. J.. 100
Pries, F. A,. 180
Fricscnhahn, P.. 357
Frietsche. A. C, 319
Frolich. P. K., 301, 320, 338,
410.417.426.437
Fiw-i, ii.. A., 98, 101
Frost, S. W., 266, 275
Prost, W. S., 100
Prush. H. L.. 153. 160. 161,
427. 437
Prutchey. C. W., 256, 277
Pruton, J. S., 249
Pry, E. G., 227
Pry, W., 297, 319
Pukuda, Y., 310, 322
Puller. M. L.. 119. 122
Pulmer. E. I.. 181
Pulton. C. C., 228
Pulton, K. H., 260, 275
Pulton, R. A., 152, 160
Pulton, S. C., 271, 275
Pulweiler, W. H.. 287, 295.
303, 304, 306, 314, 317, 319,
321 323
Punndl. E. H.. 235, 249
Purman, N. H.. 105. 108.
115
Pumas, C. C., 76, 315, 453
Puoss, R. M., 24, 25, 28, 31,
61,74
Puson, R. C., 180, 196, 201,
203, 204, 205, 215
Garbacz6wna, I., 362, 374
Gabler. G. C.. 337
Gabriel. A.. 70, 77
Gaddy. V. L., 17, 32, 76
Gaines, A., Jr., 57
GaUup, J., 76
Gambill, E. L., 239, 250
Gans, H. B., 182
Gant, V. A.. 227
Garboch, P., 180
Gardner, H. A., 262. 276.
390. 396
Gardner. J. H.. 204
Garman. P.. 268, 275
Garman, R. L., 109, 115
Gamer. C. S., 15. 31, 77
Gamer. J. B., 284. 301. 316.
320
Gamer. R. L.. 182, 189, 202
Garrard, H. L.. 450, 456
Garratt, P., 133, 137
Garrison, C. W., 319
Garvan, P. P., 457
Garvey. B. S.. Jr, 402. 416
Gaucher, L. P., 62. 74. 179
Gauerke, C. G,. 396
Gauger, A. W.. 291,317
Gay. H., 327
Geer. W. C. 398, 416
Gehman, S. D». 400. 407. 416,
417
Gehrig, E. J., 308. 323
GehnnanTi, G. H., 456
Gcib, K, H- 33
Geier, O. A„ 445, 454
Geiger. C. W., 296. 319
Geniefise. J* C. 337, 338
Gensamer, M,, 121. 123
Gerastopoloii. B. G.. 154, 161
Gerber, A. B.. 357
Gerke, R.H.,14. 406. 417
Gerlach. G, H,. 227
German, W. W., 309, 322
Gcrrmann. F, E, E,. 67. 76
GerriLz, H. W., 113. 116
Gerry. H. T.. 179
Gersdorflf. W, A-, 269, 275
Gershinowiti, H., 9. 32. 37,
30,42,43,44. 57
GcTSteriberger. H. J.. 250
Gettlef.A. O., 305, 321
GeU, a A., 103, 111, 114.
116, 216
Geyer. B. P.. 202
Ghering, L. G., 81, 89
Giauque, W. P.. 60, 61, 74
Gibbons, W. A., 180. 401.
414. 416. 418
Gibbs, C. P.. 216. 434. 439
Gibbs, E. L., 226
Gibbs, P. A., 226
Gibson, K. H., 106, 115
Gibson. R, E,, 22, 23, 31, 59,
75
GieaekinE, J. E., H4, 116
Gilbert. E, C, 20, 31. 74
Gilbert. H. N.. 265. 275
Gilbert. J. J., 410, 4l&
Gilbertson, L, A., 367. 375
Gilbertsorj, L. I., 93, 100
Gilchrist, R.. Ul, 116, 138,
139, 149
Gilfillan, E. S., Jr., 98. 101.
159. 161
Gill. C.. 444. 454
Gillaspie. A. G.. 193. 203
Gillespie, B., 77
Gillespie, H. B., 438
GUlett, H. W.. 128. 136. 308.
322
Gilliland, E. R., 316, 323
Gilman, H.. 201, 204. 205,
215, 421. 423, 433, 436, 438
Gihnore, B. H., 352, 356
Ginnings, P. M., 18, 31, 76
Ginsberg, A. M., 228
Ginsburg, J. M., 259, 262.
268, 270, 271, 275
Digitized by
Google
466
AUTHOR INDEX
GiDBburs. N.. 06. 164
Ointcr. R. L.. 319. 337
Gist. W. J., 201
Givens. f. W.. 243. 261
Glattfeld, J. W. E.. 86. 80.
437
Gleuvcs, I>. L„ J72, 377
GleaaoD, a. W., 311. 322
Glotklu-, G.p 56
Gloor, W. E.. 3tt3. 375
Glover, P. B., 311. 322
Gbver, I. G., 453
Glover. L. C. 267. 277
Glovef. L. H.* 267. 278
Gly^^art. C. SL, 228
Gnadinger, C. B., 257. 268,
275
Goblc.A.T..145, 160
Godfrey. G. H.. 266, 275
Godsoe. J. A.. 321
Goeppert-Mayer. M.. 141. 140
Goettsch, £.. 239. 250
Goetz. A.. 120. 122
Gold. H.. 227
Goldhamer. S. M.. 235. 240
Goldheim. S. L.. 92. 100
Goldschmidt. H.. 22
Goldachmidt. S.. 396
Goldsworthy. M. C. 255.
275. 278
Goldwasser. S.. 88
GoBmar, H. A.. 294. 318. 319
GomtK^fB. M„ 190< 203
Good. R, C 125, 135
Gooden. E, L,, 216
Goodhue. L. D., 22. 31, 181
Goodinfi. C. M.p 2(^, 215
Goodrich, F, X.228
Goodwin, P. M., 321
Gond^n. R. T.. 27?t. 376
Goransou, R. W., t57, 76
Gordon. A. R., 58. 60. 74
Gordon. N. B.. 204
Gordon, W. B., 190. 202
Gordon, W. G.. 208, 216. 232.
249
Gordon, W. O., 367, 375
Gordy, E. L., 453
Gordy, W.. 56
Goresline, H. E., 262
Gorin. M. H., 18, 31, 76
Gortner, R. A.. 361, 365, 374,
375,455
Goslin, R., 58
Goss, E. P., 244, 251
Goss. M. J.. 364. 366. 375
Goss, N. P., 118, 121, 122,
123, 128, 131. 136
Gottlieb. H. B.. 438
Gould. I. A., 243, 251
Gould, M. D.. 298. 320
Gould, R. G., Jr.. 201. 215
Goury. L. G.. 26
Gowens, G. J., 74, 146, 150
Grada, A. J., 404, 417
Graeber, B. G., 88. 89, 181
Graff, H. P., 122
Graflf. T. H., 373, 377
Graflf.M..248
Graflf. S.. 216
Graham, H. W., 132, 137
Graham. J. J. T.. 266, 276
Granett, P.. 262. 268. 270.
271. 275, 276
Granger, F. S.. 394
Grant. D. H.. 262. 269. 276,
278
Grant. E.. 269, 278
Grant. E. M.. 363. 376
Grant. M.. 202
Grantham. R. I.. 228
Graubard, M.. 233. 249
Graves, G. DeW., 396, 430.
438
Gray. A. N.. 409. 417
Gray. D.. 109. 116
Grebe, J. J.. 297, 319. 438
Green. A. A.. 31
Green. A. B.. 371. 376
Green. E. L., 256, 260, 276.
278
Green, E. W., 15, 31. 77
Greenberg, D. M., 26, 31
Greene. C. H.. 93. 100. 105,
114
GrcMnfi. E. S., 78, Iftl
GTeEne, O. V,, 133, 137
Grt*nhalffh, R. ^67
Gr^i^nUw, A. Z., 36Q, 375
Greensteiti, J. P.. 21, 29. 31.
57. 76. 182. 183. 216
Greertatonep A., 91, 100
Green wald, W. F., 396
Gregff, J, L., 136
GrtlW, L. J., 73. 77
Greig, J. W., 77, 160
Greninger* A., B,. 120, 123
Grawe, R., 217
GTty. J. A, de, 301, 320
Griffin. C. W., 82, 8fl
GnEfith.R, H.. 3ia
Grirlith. W. H.. 237. 250
Gnffith^. F. P.. 242, 251
Grimes, M. A., 236. 260
Griinsbaw. L. C. ISO, 136
Gristtold. E., 19, 31
Griswold. J., 316. 323
GriswoH. T„ jr.. 454
Groff, F.. 393, 3fl4, 3B8
Grogfdns, P. H,. 203, 419,
420, 425. 433. 435, 436. 438
Qmaholi, R.. 33»
Gross. C. R., 263, 259. 269^,
276, 27S
Gross, D. L., 274, 277
Gross, B. G., 223, 227
Gross, P. P., Jr., 100
Gross, P., 16, 31, 71, 77
Grosse, A. V., 87, 89, 91, 96.
100, 104, 114. 179, 194,
203, 338
Grossmann, M. A., 133, 137
Grosvenor, W. M., 456
Grove, A. B., 256, 267, 276
Gruber, C. M., 227, 228
Gruber, E. E., 202
Grupe, H. L., 396, 413, 418
Grupelli, L. D., 466
Gruse, W. A., 296, 319
Gubelmann, I., 423, 436
Gucker, P. T.. Jr., 20, 23, 31,
67,75
GuelUch, G. E., 136
Guerrant, N. B., 239, 240,
250, 261
Gugehnan, L. M., 341, 366
Guggenheim, E. A., 17
Guenther, P., 366, 368
Guilbert, H. R., 236, 260
Gullickson, T. W., 241, 261
Gumaer, P. W., 466
Gurin, S., 212, 217, 260
Gurley, R. D., 372, 377
Gustafson, H., 437
Haag. H. B.. 227. 228
Haas. A. R. G.. 244. 245, 262.
264. 266. 276
Hadlock, C. 75, 179
Httjier. A,, 263, 379
HaffQod, J..2S4. 276
HahT5, D. A.. 426. 437
Haigh. L. D., 139, 140
Haines. E. C„ iSl, 203
Haines. H, W.. 3^
Hale. W. J.. 445, 453, 456
Hale, W. S., 244, 245, 251,
262
H&lc^y, D. E.. 26S. 275
Halford, j.Q.. 77,173
Hall, A. L., 456
Hall, A, R,, 139,149
Hall, E. L., 286, 286, 316, 317
Hall, H., 251
Hall, J. L., 29. 31.75
Hall, L. P.. 356
Hall. R., 134, 137
Hall. T. B.. 357
Hall. W. H., 93. 100
Hallcr. H. L.. 26-1, 26S, 269,
271,374.276.277,421,436
Haller, M. H.. 258, 350, 274,
276
HallfTian. L. P.. 232, 249
Hallomn, C- P., 243, 251
Hfllpem, O.p 16, 21, 24, 31,
71,77
Halpin. J. G,, 249
Ham. P. W., 396
Ham, W, R.. 140. 149
Hainan, R, W., 260
HamUet. C, H., 93. 100. 181
Hamer, W. J-, 13, 14, 17, 37.
31.32.65.71,76,77
Hamm, W. H., 178
Hamilton, C. C, 25S, 276
Hamilton, C, S„ 86, 89, 202,
21)4. 215
Hamilton. N.. 126. 135
Hamilton. W. P.. 309, 322
Hammer. B. W., 243. 244. 251
Hammerschmidt. E. G.. 298.
320
Hanmiett. L. P.. 12, 21, 31,
32, 67, 103. 106. 111. 114,
116. 141. 149, 181
Hammond, E. S., 100
Hammond, J. P., 180
Hammond, P. D., 204, 216,
434.438
Hamor. W. A.. 440, 441, 443,
444, 453. 464, 466
Hancock, R. S^ 421, 436
Handforth, S. L., 147. 160
Handorf, B. H.. 17. 31. 32,
76, 181
Hanford, W. E., 204. 226
Hanks. W. V.. 300. 320
Hann. R. M., 204, 217
Hannum, J. E., 447. 465
Hansen. C. J.. 294. 318. 319
Hansen. L. A.. 360. 374
Hansen. V. A.. 436
Hansen. W. W.. 144. 160
Hansley. V. L.. 180
Hanson. A. C., 75
Hanson. G. B.. 158. 161
Hanson. L. I.. 201
Hanson. N. D.. 395
Hanson. W. E.. 110. 115
Happel. J.. 313, 323
Harbison, R. W.. 142. 147.
149. 160
Harbome. R. S.. 349. 366
Harder. O. E.. 146. 160
Harding. P. L.. 246. 252
Hardman. A. P.. 407, 417
Digitized by
Google
AUTHOR INDEX
467
Hargreaves, C. C, 226
Harkina. W. D.. 98, 101, 34a
355
Harkness, R. W., 80. 89, 142,
149
Harlow, E. V., 159, 161
Haroldson, A., 396
Haroldson, A. H., 394
Harman, M. W., 403, 416
Harman, S. W., 262, 276
Harned, B. K., 228
Harned, H. S., 7, 13, 14, 15,
22, 31, 66, 71, 75, 77
Harper, I. M., 260
Harper, W. W., 100
Harrar, E. S., 373, 377
Harrington, R. H., 132, 136
Harris, B. R., 358
Harris. C. R., 265, 276
Harris, E. E., 364, 375
Harris. L., 56, 140. 149. 203.
216
Harris. M., 279
Harris. M. M., 248
Harris. P. L., ISO
Harris. R. S.. 241, 250. 251
Harris. S. A., 204
Harrison, P., A55
Harrison, R. W.. 251
Harrison, T. R., 313, 323
Harrison, W. D.. 367. 375
Hart. E. B„ 236. 238. 249.
250
Hart, G.H., 236. 250
Hart. L. P., 390. 395
Hart, M. C. 202. 326
Hart. R.. 34fi, 355
Harteck, P., 33
Hartford. P. D.. 455
Hartford. W. H., 07. 101
Hartman, E. F., 273, 276
Hartman. W. W., 17(1
Hartting. W. H., 142, 149,
204
HartweU, J, L.. 203, 204, 216
Haftwlp. C. E„ 318
HartzeM, A.. 263, 276
Hartzell, P* Z.. 2fi2, 270
Harvey, C. L., J 28. i:i6
Harvey < N. D., Jr., 344, 355
Haflclie, R. L,* 181
Hasalwood, G. A. D., 191
HaflfcolL B., Ji-,, 457
Hass, H. B., 338
Hasselstrom, T., 202. 215
Hassidt W. Z., iftg, 161
Hatcher, R, A., 227, 228
Hatcher, R, L., 228
Hatcher* W. H., 44, 437
Hatfield. H. S., 454
Hathaway, M. L.. 250
Haupt* G, W., 10«, 115
Hauser, C. R., 193, 203
Havsnhill, R. S., 405. 417
Hawerlander, A., 397
Hawkcs, J. B., 58
Haydea, A. H., 228
Hayden, O. M., 410, 417
Hayes, E. P., ai9
Hayncfl, W., 440. 441, 442,
443, 445/ 449, 450, 452.
45a, 455, 456. 457
Hasell, E., 413. 418
Haaua. T.. 3&4
Haslet, S. E., 204
Heald. F. D., 258, 374
Healy, F. J., 339
Hup, M.k,252
HeajMi. C. W„ 123
Heard. J. R.. Jr.. 153. 154.
160. 437
Heath. M. A.. 141. 149
Heath. S. B.. 274. 276, 297,
319
Hebl, L. E., 339
Heck, A., 394, 396
Hedenburg, O. P., 254, 276
Heggie, R., 179, 204
Heiber, P., 190
Heidt, L. J., 43
Heiligman, H. A., 294, 295,
319
HeiUgman, R., 228
Heiman, V., 244, 251
Heindlhofer, K., 129, 136
Heisig, G. B., 86. 89, 180
Helgeson, J., 431, 438
Heller, M., 287, 317
Hellerman, L.. 182. 189. 202,
233 249
Hehners, C. J., 162, 160, 179.
338
Helwig. E. L., 153, 160
Hemingway, A., 108, 115
Hemminger, C. £., 283, 316
Henderson, C. T., 368, 375
Henderson, R. G., 257, 276
Henderson, V. £.. 228
Hendricks. S. B., 56
Hendrickson, J. R., 366, 373,
375, 377,
Hendrixson, P., 436
Henke, C. O., 357. 358
Henne, A. L., 107, 115, 179.
400, 416, 423, 436
Henning, C. C., 125, 135
Henning, P., 145, 149
Hennion, G. P., 180, 181, 203,
439
Henriques, V. deP., 252
Henry, A. M., 259, 276
Hensill, G. S., 259, 276
Hensely, W. A.. 338
Hentrich, W., 356
Herbert, W., 318
Hereng, A. J. A., 317
Hergert, W. D., 251
Heritage, C. C.. 369, 371, 374,
376
Herman, C. R., 44, 180
Hermsdorf, W. H., 320
Hemdon, T. C., 109. 115
Herrick, G. W., 267. 276
Herrick, H. T., 230, 248
Herrmann, C. V., 75
Hersh, R. E., 339
Hershberg, E. B., 202
Hershberger, A., 351, 356
Hershey, A.V., 108. 115
Herty, C. H., 361, 370, 374
Herty, C. H.. Jr., 124. 126,
133, 135, 137
Hertzog, E. S., 314
Hervey, G. E. R.. 270, 276
Herzbcrg, P., 318
Herzfeld, K. P., 8. 33, 82, 89,
141, 149
Hesler, W. W., 323, 339
Hess. P. L.. 146. 150
Hess. W. C.. 226. 232. 249
Hessel. P. A., 457
Hester, E. A., 228
Hetherington, H. C., 180
Hettinger, A. J., Jr., 457
Heuer, W., 180
Heuter, R., 358
Heyrovsk^, J., 102
Hibben, J. H., 56
.L.. 230, 248
r 76. 77, 183, 203,
Hibbert. H.. 393
Hickfiy. G. M., 148, tSl
Hicks. L. C, 128. 136
Hidnert, P., 75
Hiemlce. H. W., 129, 136
Hiffhbergcr, J. H., lOD, US
Highstone, W. H.. 227
Hilbert, G. E., 66, 203, 205,
216
Hildebrand, E. M.. 265, 276
HildirbTarsd, F. C, 248
HildEbrand, J. H,. 17, 31. 68,
.76
Hileniati, J.
Hill. A. E.,
346, 355
Hill, A. L, 216
Hill. D. M., 76
Hill. E„ 220. 248
Hill. E. S., 320
Hill. G, A., 204
Hill. H. B., 206
Hill, J. B,, 457
Hill. J, W., 180, 434, 439
Hill. S. B„ Jr., 254, 27fl
Hill, W-H., 292. 317. 318
Hillhouae, C. B., 287, 317
Hillis, D. M., 159, 161
Himnielfarb, D„ 182
Himmelsbach, C. K.. 227
Himwich. H. E., 227
Hintermaier. A.. 367
Hippie, J. A., Jr., 77
Hirsch, A.. 158, 161,357
Hifscbf elder, J. 0., 56, 58
Hirsh. F, R., Jr., 145, 160
Hitcli, E, F,. 424, 436
Hitchcock, D. I., 11, 31
Hitchcock, L. B., 31
Hixon. R. M., 32, 31, ISI. 376
Hijtwn. A. W., 294, 318,440
HJQit, A. M.. Ill, 116
Hoard, J. L,. 15, 32, 101,112,
Hobba. R. B., 129. 136
Hoberman, H. D.. 204
Hobrock, R. H.. 123
Hockctt, R, C, 164. 161
Hochwalt. C. A.. 396
Hodge, E, B., 338
H5neU H., S95, 396
H5m(^3chmid. O., 149
Hofsasa. M„ ISO, 318, 356
Hogan, R W,. 318
Hogness. T,R, lOO
Hok&, C. M., 148, 150
Holbrook, G, E.,315. 323
Holbrook, H, E„ 147, 151
Holdcrby J. M.» 366. 374,
375. 377
HoUabflUgh, C. B., 369. 370
Holland, M., 444. 464
Molley, k. T., 236. 249
Holm. B., 415, 418
Holm, M. M., 182
Holmes, A., 340
Holmes^ A. D., 236, 349
Holmes, a R., 317
Holmquiat, J, L., 126. 136
Hoit,L. a,436
Holt>H.S., 396. 40^,417
Holt, W. L., 402. 404, 406,
416. 417
Holton, A. B., 182
Holzer, W. P., 367, 376
Homerbcrg, V. O., 134, 137
Honda, K., 136
Hood, G. R., 166, 161
Hooft. P. v., 244, 262
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468
AUTHOR INDEX
Hopper, G. S.* Ifi7. 161, 202
Hoover, J. R.p4tl. 418
HopChH, B„76, 110.115
Hopkina, B. S.. as, 101, 157.
Ifll
HopWaa, C, P., &G3. 276
Hopkins, G. R.. 2t>a, 319
Hopkins, H. H„ 305. 396
Hopkiiia, P., 139, 149
HopkinB. R. K., 12a
Hoitah, A, J,. 250
Home, J. W., 262. 276
Home, W. D.. 246. 252, 468
Horafall, J. L., S.-Sfl. 258, 276,
277
Horafall, W. R , 265, 276
Horsley, G. F., 183
HorvBth. A. A,, 245, 252
Hdi-vitz, D., 227
Horwood, J. R, 44
Ho9k£na,H.,275
HoskiDs, W. M., 369. 267,
276
Hossack, A. B.. 456
Hottel, H. C, 307. 310, 321.
322
Hiiugtiii. O. A,, 115, 323
HotJgh, G. J., 107, 115
Hough, W. S.. 254. 276
Houghton, P. C, 313h 323
Kounhton, H. W,, 265, 276
Houpt, A. G., 437
Routz, R. C, 381, 393
Hovey, A. G., 396
Hovorka. F., 14. 31. 109, 115
Howftld, A. M,, 395
Howsr^, D. H.. Jr., 95, 100
Howard. F. A., 451, 456
Howard. G. C, ^06, 375
Howard. H. C. 390, 317
Howard. J. B., 57
Hoflrard. J. W., 203
Howard, N. P., 255, 271, 276
HoTt-c, A. H. D., 313, 323
Howe, E, £>.. 300, 322
Howe, H. E„ 441
Howes* H., 227
Howland, L. H>. 405, 417
HowBon, C. E., 394
Hoyer, D, G., 285, 276
Hort, L, P.. 355. 357
Hoyt. S. L., 125, 130, 135, 136
Hru beaky, C. E., 366, 375
Htibbard, D,, 75
Hubbard, D. M., 107, 115
HubbeU. H. B., 247. 252
Hubaer, W. H,» 339
Huckett. H, C, 270, 276
HuettiK. H„ Jr.H 76
HiJey. C. S., 437
Hnff, W, J., 280, 286, 315,
310,317,319,323
HuiTaker, N. M.. 297, 319
Huffman. C. F., 236. 241. 249,
251
Huffjoan. II, M., 74. 75, 183,
216
HwgginB. M, L., 57, 144, 150
Hugbes, E. D., 179
Hughes, E, E,. 373, 377
Hughes, G., 58
HtiBhes, J. S,, 240. 250
Hughes. K, H., 229. 248
Hughes, T. P., 131. 136
Hulett, G. A., 25,31
Hull. C. 444,454
Hull, G, P., Jr., 66, 170
Huraphrijy. B, J., 407, 417
Humphrey, I, W., 397
Hunt, A. E., 298, 320
Hunt. D,J.. 239, 250
Hunt, F, B„ 318
Hunt. H., 16, 32, 76
Hunt, tK, 397
HuTit, M,, 183, 215, 439
Hunt, M. J.. 245. 250, 253
Huut^r, J. E.. 251
Hunter, R, S., 371, 372, 377
Hunter. T. G., 339
Hunter, W. H,. 160, 162
Hunttf^gton, H. B., 5S
Huntington, R. U, 339
Hurd. C. D., 181, 182, 201,
202, 203. 299. 320
Hurd, L, C., 107, 115
Hurley, P. H., 106, 116
Hurst. D. A,. 395
HuTst, E., 456
Hurst. W., 207. 320
Hurt, R.H„ 257. 262, 276
HurtftT, A., 457
HuBcher. M. K. 179,436
Huston, R, a, 204, 228
Hutchison, A. W., 14, 32. 77
Hutton, D,. 393
Hutton, M.K., 240
Hutton, W. A., 357
Hmcford, TV. S.. 81, fi9
Huyset.H. W.. 182
Hylbrsiia, B. A„ 38, 43
Hyman. J.. 394, 401, 415
Ihrig, H. K., 367
Iliff, J. W., 396
Imboden, M., 251
Imes, H. C. 166, 161
Ingmanson, J. H., 416
Ingold, C. IL, 178
Ingram, T. R., 337
Inman, M. T., 268, 276
Insley, B. G., 84. 89
Insley, H., 70, 76, 77
lob, L. v., 241, 261
Ipatieflf, V. N., 87, 89, 179,
180, 194, 203, 299, 320,
338, 430, 438, 439
Iranoflf, S. S., 256, 278
Irey, K. M., 394, 396
Isbell, H. S., 163, 160, 161,
427, 437
Isenberg, S.. 100
Isenburger. H. R., 121, 122,
123, 136, 137
Isham, P. D., 246, 262
Isham, R. M., 430, 438
Itter, S., 238, 260
Ittner, M. H.. 341, 366, 356
Ives, H. E., 393
Ivy, A. C, 227
Izard, E. P.. 431, 438
rack, E. L., 243, 261
rack, H. C, 409, 417
rackson, C. A., 339
rackson, £. A., 339
Jackson, E. H., 394
rackson, R. W., 208, 216,
232, 248, 249
Jackson, W. P., 37. 43, 89
Jacobs, P. B., 364, 376
Jacobs, R. B., 122
Jacobs, S., 416, 418
Iacobs, W. A., 219, 226
acobsen, C. P., 228
acobson, B. M., 235. 249
acobson, D. L., 318, 321
acobson, M. G., 313, 323
Jacobson, R. A., 393, 395, 396
acoby^ A. L., 204
Jaeger, A. O., 159. 161
Jagmin, A., 301. 320
Jahti. E, a, 372. 377
Jakosky, J. J., 158, 161
James, C. L., 453
James, H. M,. 57, 58
tamea, J. H., 271, 376
Jamieaon, G. S., 245, 252
Jamison, E. A-. 298. 320
Janes. R. B., 57. 143, 150
Jan sen, E* P.. 216
JaUBSen, P„ 183
Jarabek. H, S., 135
Jarmug. J. M„112, 116,373,
377
Tarry, R. M., 318
Jaync, D. W.. Jr., 257. 258,
274, 276
Jebb, W. T., 286, 316
JeflFreys, C. E. P., 232, 249
Telen, P. C, 76
ennings, W. H., 134. 137
ensen, H., 232, 249
eppesen, M. A., 66, 58
esse, W. P., 122, 123
essup, D. A.. 363, 375
essup, R. S., 74, 400, 416
ette, E. R., 117, 118, 119.
122, 417
Jeu, K. K., 393
ewett, J. E., 164, 161
ohn, H., 373, 377
Johnsen, B., 369, 374, 457
Johnson. A.. 283, 316. 394
Johnson, A. H., 107. 115. 351,
366
Tohnson, C. C, 266, 276
ohnson, C. R., 26, 31
fohnson, E. R.. 129, 136
Johnson, J. H., 204
Johnson, M. O.. 262, 276
Johnson, N. J., 141, 149
Johnson, R., 203
Johnson, T. B., 202, 203. 215,
216, 217
Johnson, T. W., 298, 301,
320 321
Johnsin, W. C. 96, 97, 100,
101
Johnson. W. W.. 204. 396
Johnston, C. B., 227
Johnston. H. L.. 74, 93, 100
Johnston, J. M., 227
Johnston, M., 66, 57
Joliot, P., 90
Jominy, W. E., 307, 321, 322
Jones. B., 463
Jones, C. L., 457
Jones, G., 25, 28, 31, 75, 143,
150
Jones, G. W., 306. 310. 311,
321, 322, 338
Jones, H. A., 269, 270, 271,
272, 274, 276
Jones, H. LaB., 179. 436
Jones, H. W., 466
Tones, I. H., 318
rones, J. H., 241, 248, 251
rones, M. C. K., 312, 322
fones, R. M., 266, 276
[ones. R. N., 201
rones, W. N., 398, 454, 466
rordan. C. B., 228
rordan, C. W.. 304, 306, 314,
319, 321
Jordan. H. P., 348, 355
Jordan, L., 122, 128, 133,
136. 137
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AUTHOR INDEX
469
Joseph. L.. 204
Joseph. N. R.. 20. 21. 31, 75,
183
Joshua. W. P.. 182
Joslyn. M. A., 203, 245. 246,
262. 437
Jost. W.. 140. 149
Judd. D. B.. 371. 372, 377
Juettner, B., 290, 317
Jukes. T. H., 21, 31, 238, 250
Jukkola. E. E., 101, 157. 161
JuKan, P. L., 201, 204, 208.
216, 217. 220. 226
Jungers, J. C, 36, 43, 80, 85,
89, 178
Jurgensen, D. P., Jr., 77
Junst, A. E., 228
Juterbock, E. E., 44, 180
Kable, J.. 201
Kadow, K. J., 254, 256, 276
Kahlenberg. L.,.140, 141, 142,
149. 150
KahlenberK, 0- J., 240
Kaiser, H. P., 120» 122
KAfser, W, J., 357
Kalish, J., 458, 457
ICaltenbftch, C. E., 358
Kamerlingt S, E.i 21
Kaminskr* J*, 203
Kanim* O., 2D3
Kamner, M. E.^ 9, 31
Kampp J. van de, 193, 202
Kane, T,, 43S
Kaneko, G. K.. 203
Kantrowitz, M. S., 373, 377
Kaplan. J., 215
Karapfltoff, V., 160, 162
Karus, G* M., 25a, 276
Karpenko, V., 107, 116
Kamck, L. a, 317
Kaflline, C, T.* 106. 115
Kaaul, L, S., 9, 31, 33 , 35, 42,
43, 57* 74p B2, 100, 179
Kaufman, S,, 145. 150
Kawakami, Y., 350, 356
Kaye, A. L., 92. 100
Keane, J. C. 247, 252
Keats, J. L., 396
Xeenan, J. A., 238, 250
Keenan, R. A., 410.417
Kceoe/, P. E,^, 352, 363, 356
Keffler, L. J. I^., 74
Keillor, J, 291, 317
Keith, P. C. Jr., 338, 339, 455
Keller* K,, 356
Kellej^. G, A„ 77
KfeUey, V. \Sr..261,275
Kcllog, A. M,, 112, 116
KeUqg,H. B., 112. 116
Kelly, T. L., 431, 438
Kdly. W. R.. 75
Kelaey, G, W., 455
Ktflsey. V. V., 453
Kembte, E. C-* 67
Kemlfir, E., 316, 323
Kemmer, H., 292, 3lS
Kemmeiich, W. E„ 421. 436
K-"-!.i. \ R , 4^1*^. J 12. 417,
418
Kemp, L. C, Jr., 314, 323
Kennard, M. A., 228
Kennedy, E. J.. Jr., 120, 122
Kennedy, G. P.. 368, 375
Kennedy, R. E., 311, 322, 338
Kennelly, R. G., 207, 215
Kenney, J. R.. 227
Kenyon. R. L.,^132, 136, 137
Keppler, H.. 356, 358
Keresztesy, J. C, 212, 217,
250
Kern, J. G., 356
Kern, R., 357
Keras, C, 154, 161
Kerrick, W. B., 357
Kersten, H., 122
Kertesz, Z. I., 229, 248
Keston, A. S., 13, 31, 77, 109,
115
Kettering, C. P., 453
Keyes, D. B., 157. 161
Keyes. G. H., 217
Kharasch, M. S., 163, 180,
194, 203, 226. 256, 276
Kidder, W.K., 359, 374
Kiehl, S. J.. 109. 115
Kienle, R. H., 160, 162, 309.
395,396,413.418
Kieman. H. G., 410, 417
Kiesselbach, T. A., 274. 277
Kik. M. C, 230, 248. 249
KiUeffer. D. H., 255, 343,
394. 454, 457
Killian, D. B., 180. 181
Kilmer, P. B.. 256, 278
Kilpatrick. M., 76. 103, 114,
181
Kilpatrick, M., Jr., 11, 21, 22,
31.32
Kimball. G. E., 57
Kimberly, A. E.. 369, 376
Kimmel, L., 252
Kind, W., 356
King, A. M., 349, 355
King, C. G.. 230, 239, 248,
250
King, E.C. 401,416
King, H. K., 322
Kiryr, L. A., Jr„ 75, 216, 437
King. M.R„ 227
King. R. J., 401, 415
Kmg, '1\, 3f)9. 322
King, W. H.. 426, 437
KinnesT, C. R., 75, 202
Kinjiey, G. P.. 109. 115
Kan ad, A. B.. 125, 126. 135
Kirby. J. E.. 393
Kifby,R.H.. 301
Kiroher, C. E,. Jr., 320
Kirk, R. C.. 154, 161,437
Kirkpatrick, A., 363. 375
KirkpatricV, S. D., 416, 440,
441, 446, 453, 455
Kirkpfltrick, W. H.. 215
Kirkwood, J. G., 7, U, 20, 23,
31.74
Kimer, W. R., 314, 323
Kirschman, H. D., 99, 101,
140, 149
Kirstahler, A., 357
Kise, M. A., 216
Kistiakowsky, G. B., 33, 35,
37, 43. 44, 63. 66, 74, 75.
78, 89, 179, 204, 437
Kitchel, R. L., 267, 276
Klabunde, W., 157. 161
Klar, R. L., 305. 321
Kleiderer. E. C.. 226
Klein. H.. 249. 436
Klein, J. j., 456
Kleiner, I. S., 246, 252
Klemgard, E. N.. 340
KUne, O. L., 238, 250
Klooster, H. S. van, 92. 100
Klotz, L. J., 266, 276
Klotz, L. P., 244, 252
Klugh, B. G., 456
Knapp, A., 296, 319
Knapp. B, H.,15B. 161
Kneeland. R. X, 24S, 252
KnJght. H,, 261, 263, 376^ 277
Knight, H. G., 455
Knight, O, A., 127, 129. 131,
135. 136
Knight, O. S.. 67, 76
Knoeppcl, C. E.. 456
Koorr, C. A., 141, 140
Koote, 1 M., 317
Knott, E. M.. 240
Knowles. D. a, Jr„ 111. 116
Knowlca, E. C. 340
Knowles. R, 433. 43 &
Knowles/H. U., 113, 116
KnpwltQn, H. S., 305. 321
ICnowlton, U E.t 29h5, 319
Kny- Jones, P. G., ISl
Kobe, K. A,. 141, 149, 202,
312, 322, 366,375, 453
Koch. E. M., 250
Koch, P. a, 233, 240. 250
Kodh, W., 397
Koehkr, A. E., 229, 248
Koehn. C. J.,Jr., 338, 250
Kodaoh, C, P., 184, 201
Koenig, P. O., 74
KofiTtig, M. C, 243, 251
KoerdTriR, P.. 357
Kohler. :£., 251
KoMer. E. P.. 181. ISO, 197,
198. 201. 202, 204, 215
Kohitian. E. P., 234, 249
Kollmann, T., 395
Kolthoff, I. M., 15, 21, 22,
81, 75. 103, 105, 107, 110.
112.113,114,115.116.181,
228
Komarewsky, V. I., 203, 338,
430. 438
Koons. G. I.. 286, 316
Koppanyi, T., 226
Koppers, H.. 318
Korany, J. A., 315, 323
Korman. S., 21, 31, 77
Kossiahoff, A., 15, 32, 101,
112, 116
KGsting, P, R.. 130, 136
Kracek, P. C, 67, 76
Kraemer, E. O., 106, 115,
362. 374. 407, 417
Kraratr. E. N., 93. 100
Kramer. M. M,. 243, 251
Krastt, N. W., SS, SO, 181
Kraup, G. A., 24, 26, 31, 61.
74, 96, 97, 98, 100, 101
KrauE, W„ 396
Krause. W., 140. 149
Krauskopf, K. B.. 43
Krauss, W. E., 249, 250, 251
Kremers, R. E., 242, 251
Kfcsa. 0„ 366, 367, 371, 372,
375, 376, 377
Kriehle,V.K.. 11, 31,77
Krimmd, M.. 368. 371. 376
Kristensson, A., 182
KriTobok, V. N., 122, 132.
137
Kroeger, J, W., 07, 101, 430
Kronquest. A. L., 411,418
Kropiwmcki, E., 3lB
Krueger, G. v.. 101
BCrueger, H., 227
Kniger, P. G.. 145, 150
Krumbhaar, W., 396, 3ff7
Kruae, H. D., 249
Knitter, H. M., 67, 132
Kucera, J. J., 1S2, 215
K^h], F„ 257, 277
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Google
470
AUTHOR INDEX
Kuenbold, O. T., 30f>, 322
KJuBitsAl. W. E., ISO, 338
Ktiffaer, P.. ^2&
Kuhfip C. S., 2lfl
Kuhn, R. L. 302. 331
Ktilm, W. E., 3U, 323
Kwck. L. P., 216
Kuuiler, W, D., 32. 39, 31
Kuiiberge^ A. R. 287, 317
KuTierth, B. L- 251
Kunitz, M.. 233 p 3iO
Kunsman, C. H., B4, S9
Kunst. J>, 456
Kurath, P,, 395
Kurth, E. P., 3B2. 374
Kut!, W. M.. 397
KuykendaU, D, V, Jr„ 362,
374
Kyrides, L, R. 155. 161, 424.
4136. 43S
Lacassagne, P. C, 301. 320
Lacey, C. P., 228
Lacey. W. N., 75, 76, 297,
319, 820, 338
Lachat, L. L., 241, 261
Lacroix, D. S., 270. 277
Lacy, K. B., 182
Ladoo, R. B., 456
LaPollette, J. R., 261, 279
LaPorge, P. B., 269, 276, 277
Lahev, R. W., 456
Laird, B. R., 56
Lake, D. B., 141, 149
LaLande, W. A., Jr., 397
Lamb, A. B., 63, 75, 83, 89
Lamb, P. W., 106, 115
Lambros, G. C.. 142, 150
La Mer, V. K., 9, 10. 11, 14,
21, 24, 30, 31, 32. 72. 77.
181
Landecker. M.. 395
Landis. W. S.. 453
Lane. C. B.. 244, 251
Lane, G. P., 411, 418
Lang, J. W.. 35, 43, 299, 313,
320, 323, 338
Lange, B., 14
Lange, N. A., 216
Lange, W., 101
Langedijk. S. L.. 181. 182
Langford. G. S.. 259, 275
Langkammerer. C. M.. 181.
424. 436
Langley. W. D., 216
Langmuir. I., 28. 82
Langston. W. C. 242. 251
Langwell, H.. 180
Lansing. W. D.. 362. 374. 397,
407. 417
Lantz. B. M.. 236, 249
Larchar. A. W.. 437
Larsen. B. M.. 126, 135
Larsen, R. G., 201, 202
Larsen, W. E., 16, 32, 76
Larson, A. T., 181, 182, 438
Lsrson, C. E., 26» 31
Larson. C. M- 356
Larson, E.,304h 306, 321
Lary, E. C, 397. 375
LoBby, Hh A., 24[i, 251
La^ereflf, W., 37, 43
Latham, D. S., Jn5, 114
Lathrop. E, C. 3rJ3, 374
Latimer. J. N,. 254, 277
U«c, E.* 206. 319
Lat]«r, W. M, ISl, 204, 424,
436
Laufer, E. Bh, 448, 455
Laug, E. P.t 10&, 115
l^ugbliPnER,, 371.377
LaugblTn. K. C„ 437
Laiuie, L. L., ISl
Laiaritaen, C. C. 01, 100
Lauter. M. U, 435, 436
taiittr, W. M., 22S
Lavin, G* 1.^ 37
Lavifie, I,. 288, 317
Uw, H. R.. 76
La wall, a H., 298, 330
Lawrence, A. S. C, 350. 351,
356
Lawrence, B. O., 143, 160
Lawrence, W., 261
Lawson. W. B., 393. 416. 418.
431, 438
Lazarus, L. H.. 350, 356
Lazier, W. A.. 181. 182, 344,
356. 358
Lazzell, C. L., 204
Leahy, M. J., 319, 339
Leapcr. P. J.. 404. 417
LeaveU. G.. 114. 116
Leavenworth, C. S., 108, 116
Lebeau, P., 149
LeClerc, J. A.. 244. 262
Lederer, B. L.. 345, 356
Lednum. J. M.. 308, 322
Lee. C. P.. 251
Lee. C. H.. 156. 161. 201
Lee. E. P.. 126. 135
Lee, P. H., 156, 161, 201
Lee, H. H., 77
Lee, T., 182
Lee, J. A., 370. 376
Lee. W. C, 56
Lee. W. M.. 264, 277
Lee, W. Y., 229. 248
Leekley, R. M.. 182
Leeming, B. J., 179
Leete, J. P., 369, 376
Leeuw, P. j. G. de, 244, 252
LeGalley, D. P., 122
Legatski, T. W., 338
Legault. R. R.. 226
Leguillon. C. W., 413, 418
Lehman. M. R., 394
Leicester, H. M., 203
Leighton, J. A., 309, 322
Leithftuser, H., 317
Leitz. C. P., 366. 376
Leland. H. L.. 76
LeMaistre. J. W., 193. 203
Lempert. J.. 76
Lenher. S.. 180. 181. 349, 355.
358, 362, 374
Lenher, V., Ill, 116
Lennox, W. G., 226
Leonard, A. S.. 309. 322
Leong. Y. S., 455
Lepkovsky. S.. 230. 237, 238,
248, 250
LeRoi, E. J., 339
Leslie, R. T., 339
LeSueur, E. A., 467
Levene. P. A.. 179, 180. 210.
216. 430, 438
Levey, H. A., 466
Levin, M., 413, 418
Levine, M.. 364. 375
Levine, N. D.. 267. 277
Levy. M.. 182. 216
Lewis. B.. 37, 39. 43. 59, 60.
65, 74, 76, 310. 322
Lewis. C. M.. 66
Lewis, E. J., 110, 115
Lewis, G. N.. 98. 101. 143. 150
Lewis. H. B.. 229. 232. 248.
249
Lewis, H. P., 359, 367. 373,
376, 377
Lewis, T. O., 297, 320
Lewis, L. C. 371. 377
Lewis. W. K„ 299. 315. 319.
320. 323
Ley, H. A., 334
Loyden, G, B., 284, 316
Leyden, T. F. H„ 465
Li, C. C, 204
Liafig, P., £28
Liddel. U,. 56, 202, 207, 216
Lieber, E., 182* 437
Liebermann, C. T., 225
Liebhafsky. H- A., 12, 31. 75
Liedholm, C. A.. 133, 137
Lier. H., 357
Liipfert. W. X. 256, 277
Lima. A., Jr., 158, 161
Lincoln. B. H.. 122, 123, 339
Lini!, S. C, 35, 43, 178. 393
Lindblom, S., 140, 149
Liud^ren. D. L,. 266, 27S
LIndhe, H. B., 39fl
Undner, K., 357
Lindsay, J. D.. 75, 338
Limialy, B, E.. 320
Lindstaedt, F. P., 260, 268.
277
Lindwall, H. G., 201, 207,
216, 216
Linegar. C. R., 226
Lingane. J. J.. 110, 111. 113.
116. 116. 228
Linscott. C. B.. 413. 418
Lionne. B.. 395
Lippert. T. W.. 121. 123
LitteU. N.. 464
Little. A. D.. 454
Little. B. H.. 357
Little. V. A.. 271. 277
Littlefield. J. B.. 313. 323
Littmann. E. R.. 33. 43. 203.
307
Ltttooy, J. P., 260> 277
Litzinger. A.,216*217
Liti* T. H., 360, 356
Livingston. A. E,. 227. 228
Livingston, M. J., 339
Livingston, M. S., 91. 100.
143, 150
Livingaton, R.. 393
Llnyci, S. J., 416
LoekwcKjd, L. B., 230. 248
Loder, D. J., 201
Lode wick, J, E*, 373, 377
Loebell, H. O., 317
Loetscher* E. C. 396
Logan. L., 280, 316, 319. 323
Loguc, P., 357
Lohsc, P., 04* 100
Lommcn. F. W., 435, 436
Long. 2.. 251
Longsworth. L. G.. 13. 26. 27.
32
Loim. B.. 468
Loos. K.. 394
Lorand. B. J., 357
Lorch. A. E.. 109. 116. 141.
149
Lorig. C. H.. 128. 134. 136.
137
Loring. H. S.. 248
Losee. W. H.. 444. 454
Lothrop. W. C.. 202
Loughborough. W. K., 77.
361. 374
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Google
AUTHOR INDEX
471
Lougovoy, B. N., 396
Loughrey, J. H., 279
Love, L., Jr., 203, 216
Lovell. W. G., 339
Low. G. W., Jr., 88, 105, 108,
116
Lowe, D, v.. 372. 377
Lowe, W. G,. 215
LoweTi.L., 36fi, 375
Lowry, C. D., Jr. 339
Lowry, H. H., 290, 317
I-K>wy. A., 1*2. 149, 162, 163,
IGO. 434» 438
Loiier, W, W., 101
LubB* H. A.. 404. 417, 436
Lucas, P. P., 127, 136
Lucas, H.X, 43, 170, 437
Luras. H. P.*360. 356
Lucke, C. E., 2S7< 317
Luedclce. A. W., 394
Luerssen, G, V, 133, 137
Lui, S. C, 182
Lukcns, H. S., 154, 161
Lulek, R. H.M 10. 435,436
Lundberg, A, H.. 366, 376
Luiidbenr, W. O., 74
Lundquiat* J. T.. 437
Lunge, G.. 324
Lurie, E., 357
Luflby, 0. W„ 31»
Luteu, D. B., Jr., 12, 32
Lttthflr, M.,367
Luta* R, E., 86. 89. 149, 166,
161, 196. 203h 215, 227, 228,
432, 436, 437
Lynch. K. M„ 242, 251
Lynn, E. V., 223
Lyon, L, S., 455
Lyons,E. H„ Jr., 179
Lyona, Ui,, 230
Lytic. R. W., 394
Mabey, H. M,. 456
McAdam. D, J, Jr.. 129, 136
McAdama. W. H, 315, 323
McAlevy, A.. 1S5. 201,437
McAlpfne. K. B.. 57. 179
McBain, J. W., 16. 25, 26, 27,
32, 77, 349, 350, 355, 366,
363, 375
McBaiu, M. E. L., 350, 366
McBee, E, T.. 33*
McBerty, F. H., 435
McBride, R. S., 448, 463,
465, 456, 457
MacBride. W. B., 406, 417
McCflbe, W. L.,45Q
McCallati, B. E. A,, 258, 264,
277, 279
McCallum, A. D., 277
McCann, D. C., 112, 116
McCarthy. B. L., 136
McCarthy, B. Y., 339
McCauley, W. E., 267, 276
McCay. C. M., 247. 262
McClain, H. K., 142. 160
McCleary. R. L.. 93, 100
McClenahan. R. W.. 321
Mcaoskey. G. B.. 318
McQuer, W. B., 339
McClure. H. B.,393
McCollum, E. v.. 236, 238,
249.260
McCoy, H. N., 98, 101, 113,
116
McCoy, R. H., 248
McCready, D. W.. 370. 376
McCullough. R.. 76
McDaniel. A. S.. 267. 277
MacDaniels, L. H.. 267, 277
McDermott, P. A.. 396
McDonald. P. G.. 261
MacDonald, G. D.. 812, 322
McDonald, R. D., 44
MacDonald, R. T., 101
MacDougall, D. P., 60. 74
MacDowell, L. G.. 216
McElroy, W. D.. 304. 321
McElvain, S. M., 182, 186,
201. 216
McGavack, J.. 412, 416, 418
McGill, H. T., 368
McGovern, J. N., 366, 376
McGovran. E. R.. 266. 277
McGreal. M. E., 202
McGregor. E. A., 267, 277
McGregor. G. H., 367, 376
McGrew, P. C, 204
McGuire, G.. 230, 248
Machlis, S., 204, 420. 433.
436. 438
Macht, D. L. 227
Mcrihcnny, J. S.,31
McTntyre. J,. 337
Mclntyi^, r W.. 367. 376
Maclnnes, D. A.. 13, 19, 21,
26,31,32.76,77
Mnck, L., 305, 321
Mack. P. B., 341, 347, 362,
363
McKw. J., 340
McKee. H, H,. 153, 154, 166.
160. 161, 437
McKcehan, L W., 120. 122
MacKetcsn, H. G.. 456
McKellor. A,. 56
McKelvey, J. B., 95. 100
Macktnney, G., 238, 260
McKinney, P, V.. 140, 141,
149, 311, 322
McKinney. R. S, 246. 252
Madachlart, W. W. G., 227
Mflclaren. S. F. M., 369, 376
MacLean, A. O., 305, 331
McLean, H. Q, 269. 277
MacLeod. F. L., 237. 246,
2.50h 252
MacLeud. G.. 245. 249
McUod. H., 444. 454
McLester. J. S., 253
Mc Master. L.. 216
McMcrekin. T. L., 19, 32» 77,
183, 231, 248
McMillan, E., 91, 100, 306.
321
McMullan, O. W., 131, 136
MacMuUin, R. B., 182, 367
McNab, J. G., 180
McNab, M. C, 180
McNary, R. R., 179, 436
McNiece, T. M., 466
McNidty, G. M., 269, 274
McPherson. A. T.. 76. 398.
401, 406, 416, 417
MacPherson, H. G., 68
McOuaid, H. W., 133. 137
Maculla. A., 216
McVetty, P. G., 129, 136
McWaters, L. S., 203
Mac Wood, G. E., 66
Madden, J. T., 463
Madge, N. G., 410, 412, 418
Maju, P. L., 266, 277
Magistad, O. C, 246. 262
Magoffin, J. E., 77, 143, 160
Mahin, £. G., 126, 136
Mahin, W. E., 128, 136
Mahler, E., 371, 376
Mahler. P.. 456
Mahnclce, H, E., 56, 179
Mains, G. H., 395
Mair, B. J.. 76. 339
Major, R. T. 354. 161, 204.
228, 435
Malfshev, B. W.* 87, S9, 203.
338, 439
Malisoff, W. M.. 183
Mallory, Gh E*, 227, 228
Matei, a J., 181, 431, 433
Malm, P. S., 410. 412, 418
Malmstrom, H. E., 372. 377
Mangels. C. E., 244, 251
ManRelsdorf. H. G.. 307, 321
Manter, R. L., 308. 322
Manky, K. E,.339
Mannin;^, M^ F.. 67
Manning. P, D. V., 455
Mannweiler, G. E., 14, 31, 76
Man^ke, R. H., 208, £16
MantcU, C.L.,4S7
Martiovitch. S., 261, 27S
Marek, L, F., 299. 320. 419.
426. 437
Marischka. C, 287, 317
Marker, R. £., 181, 203
Markley, M. C, 244, 261, 262
Marks, B. M.. 396
Marks. L. H., 467
Marks, M. B., 323
Markush. E. A.. 262. 277
Marlies, C. A.. 11. 32
Maron. S. H., 76, 77
Maroney, W., 76
Marr, E. B., 216
Marschner. R. P.. 338. 424.
436
Marsh, G. L., 345, 240. 262
Marsh. J. S.^ 137
Marshall, A. S., 440
Marshall, A, L., 131, U6
Marshall. J.. 254, 265. 277
Martin. E, L., 154, 161. 202.
205, 215, 216
Martin. P. D., 16, 32, 77
Martin, H.. 20!. 277
Martin. H. E., 349, 356
Martin, J, L, Jr., 244, 251
Martin, L, P., 203
Martin, H, C, 307
Marvfel, C. S.. 183, 184, 187,
£01. 2m, 203. 215, 216,
338, S94, 434, 439
Marvin. C. J, 265, 277
Man, K , 358
Mason, C. M.. 75
Mason, C. W., 100
Mason, H. C, 271. 276
Mason, H. E., 160, 162
Mason. I. D.. 233. 249
Massengale, O. N., 261
Mathers, P. C, 166, 167, 161
Mathesius, W., 286, 317
Matheson. G. L.. 4. 418
Matheson. H., 74, 108, 115.
400, 416
Mathews, W. C, 406, 417
Mathias. H. R.. 304, 321
Matthews, E. D., 182
Mattice, M. R.. 306. 321
Mattill, H. A., 230. 242. 248.
261
Matttson. B. L., 179. 436
Mattocks. E. O., 309, 322
Mattox, W. J., 179, 313, 323.
396
Maughan. M., 361, 374
Mawhinney. M. H.. 131. 136
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472
AUTHOR INDEX
May, O. B., 230, 24 S
Mayberty. M. G., 182
Ma yew. M. A., 310, ^T2
May field. B,. 397
May^ard. L. A., 247, 2fi3
Mayrhofcr. R. 390
MaJtwcll, L, R., m
Mead, F. C, Jr.. 3*, i3. 203
Meani, B. G., 454
Mea«, R. T. SOD, 3TA
Meae<, a., 232, 24 »
MedHn, W'. V,;303
Meehan.E, T.^fiS
MehaTH, V. K.. 380. ^85, 393
Mehl. J. W.,26,32. 119,120,
122,123,126,127.135,136
MehligJ, P,, 110, a 1, 116
MeiffB, R M.. 262. 27S
MeiffB, J. v., 318. a^fl
Meincke, E. R., 182. 201
MHnt8.R. E.. 157, 101
Meitaner, E , 316, 228
Mekler. L. A.. 337
Melampy, R., 113, 116
Meldnim, W. B., 113, 116
Melhus, I. E., 274, 277
Mell, C. W., 266, 277
MeUon. M. G., 106, 116
Meloche, V. W., 93, 100, 216
Melsen, J. A. van. 181, 182
Mdvin, E, H., 56
Mendel, L. B„ 230. 235, 247.
248, 249. 252
Mentcn. M. U, 239. 250
Mentzer, C. T., Jr., 36S
Menuaan. H.. Jr., 260, 276
Meredith. H/ /.. 291. 317
Merica. P. D., 144, IBO
Merkel. G.,317
Mfcfkua. F. J., 314, 323
Mfirriam, C. W., Jr., aOl, 321
Merrin, D, R,. 2fiO. 263, 273,
Merritt,'M. H., 286. 316
Mcrtz, E. T., 248
Merwin, H. E., 77, 160
Messer. W. E.. 403, 413, 416,
418
Messerly. G. H.. 74
Metzger. P. W., 266, 277
Meulen, P. A. van der, 266,
277
Meuser, L.. 404, 417
Mcwborne, R. G., 268, 277
Meyer. C. E., 248
Meyer. E., 367
Meyer, J. D., 180
Meyer, R. J.. 149
Michael, A., 179, 182. 194,
201. 203. 420. 436
Michaelian, M. B., 243, 261
Michaelis, L., 142. 149, 202.
216. 244, 252
Michaelson, J. L., 371, 377
Michalske, A.. 318
Michot-Dupont, G. P., 293,
318
Midgley. T., Jr., 179, 400,
416, 436. 453
Migeotte, M., 56
Migrdichian, V.. 256, 277
Mikeska, L. A.. 84, 88, 142.
149
Mikeska, V. J.. 217
Mikumo, J., 355
Milas, N. A., 87, 89, 185. 201.
215, 427, 437
Milbery. J. £., 422. 436
Miller, A. P.. 125. 135
Miller, E. J., 115
Miller. H. C.. 319
MiUer. H. P., 193. 202. 203
Mfller. H. L.. 128, 136
Miller, K., 252
Miller. M. L., 9. 10. 32. 181
Miller. N. P.. 182
MUler. R. P.. 202. 215
MiUer. R. L.. 254, 260. 276,
279
Mtller, R. W.. 2S4, 316
Miller, S E., 204
Miller, S. P., 291, 317,318
Miller, W, E., 33S
Miller, W, U, 266, 277
Milligan, W. O.. 122, 123
MilUkan. W. A., 314
MIlJs, P. C.t447, 45fi
Mills, L. E., 256, 262, 208,
271, 274, 277
Mills. R. v., 297, 319
MillinaTJ, J., fi7
Milner, U. W„ 229. 24S, 437
Mtlner. R. T., 7fi, 145, 160
Minor. C A„ 372, 377
Minor, H. R., 410, 417,418
Minor, J. E.. 350, 369, 370,
372, 374, 376, 377
M inter, C. C, 309, 322
MHcbelK H. H., 248
Mitchell, J. B., Jr., 228
Mitohell, J, S., 245, 252
MitchelJ, R. U. 364, 375
Mithoff, R. C. 181
Moif, C, 2 IS. 226
Mollett, C E, 228
Molatad,M.C., 84,89. 180
Monheim. J.. 14
Monnberg. R., 372, 377
Monrad, C. C, 316, 323
Monroe, E., 191. 202
Montfort. G. H., 338
Montgomery. A. E.. 368.
375
MontiUon. G. H., 77
Moon. H. H.. 245. 252
Mooradian. V. G.. 119, 122
Moore. C. C.. Jr., 339
Moore, C. G., 396
Moore, C. W., 358
Moore. E. E. 228
Moore. G. V.. 438
Moore. M. L.. 202, 203
Moore, R. J., 439
Moore, R. W., 126, 135
Moore. T. V., 297. 320. 337
Moore. W.. 264, 267. 273,
277
Moose. J. E.. 432. 438
Morfit. E. P.. 141, 149
Morgan, A. P.. 239. 241, 245.
246, 250. 251. 252
Morgan, D. P., 440, 453, 457
Morgan, H. W., 371. 372. 376,
377
Morgan, J. J., 35, 43, 179.
180, 293. 299, 309, 318, 320.
322, 323, 338. 370, 376
Morgan, M. D., 340
Morgan, O. M., 347, 351, 355,
356
Morgan. S. O., 57. 76, 160,
162
Morikawa. K.. 43. 44. 79. 89.
178
Morken, C. H.. 134. 137
MorreU, C. E., 56
Morrell, J. C., 273, 277, 286.
317. 318. 337, 339
Morris, A. B., 297, 320
Morris, D. E.. 156. 161. 227,
228
M'.frEi^-j, J. <.. .. .j7, -4 si
Morna, L. M„ 298, 320
Morris. M. M., 252
Morris, R. Ck. 226
Morris, R. E.,43, 76. 179. 437
Morris, S. G., 248
M orris. V. M„ 40S. 417
Morrison, G. O., 380, 393
Morriflon, R, W., 22S
Mortenscn, M^, 244. 251
Morton, A. A.^ 227
Morton, P. A., 261. 277
Morton. J. M., 35
Mory. A. V. H., 444, 454
Mns«r, H. A., 160
Moses, A, J., 121, 123
Mosftttig, E,. 192, 202. 215,
216,227.228
Moaher, M, A., 147, 150
Moskovltz, B., 112, U6
Moaley. V, M., 66
Moas, H. v.. 357
Mos^, W. H.. 394, 395. 396
Mottem. H. H., 199
Moulton, H. G., 451. 457
Mover, P.. 231, 24S
Mowte, W, U. 254, 279
Mojer, H. v., 113,116
Mucha, P., 274, 277
Mudd, O. a,337
M^hlendyck, W„ 318
MuJler. A., 179
Mueller, G. B.. 71, 77
Mueller, G. S., 401, 416
Mflller, R., 356
Mailer, R, H., 105, 114
MiiHor- Stock, H.. 127. 131,
135
Mulcahy, B. P.. 284, 312, 316.
322
Muller, O. P.. 410, 418
Mulliken. R. S.. 57, 179. 181
Mulliken, S. P., 179, 339
Mullin, C. H., 458
Munch, J. C., 204, 228
Muncie, J. H.. 256, 277
Munday, J. C., 43, 179, 180,
254, 277, 299, 320, 338
Munger, P., 264. 278
Mxingcr, T. T., 360, 374
Munro. W. P., 43. 179. 426.
437
Munroe, T. B.. 363. 374
MunseU, H. E.. 242. 251
Munsey, V. E.. 244, 252
Munyan, £. A., 295, 319
Murch, W. M., 433, 438
Murphey, E. A.. 418
Murphv, D. W., 127. 136.
:H>T. \^2\
Murphy, E. J., 295. 319
Murphy, G. B., 338, 339
Murphv, N. P.. 427. 437
\' R. R., 251
Murphy, W. J., 457
Murray. C. W.. 258. 276. 278,
279
Murray, J. W.. 56. 57, 202,
204
Muskat. I. E., 155. 161
Muskat, M.. 319
Myers, W. A., 339
Myers, W. D., 113, 116
Nadeau, G. P., 182, 215
Naef, E. P.. 250
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AUTHOR INDEX
473
Nagd, R. H., 433. 438
Nagel, T,. 336, 293, 317, 318
NaimaTi, B., 217
Nash* A. W„ 339
Naah, C. A., 322, 304
NatelBon. S., 32, 393
Natlmn, W. S., ISI
Nea4. J. H., 133, 137
Nes], W, M., 228
NeaJy. V. L.,a37
JNTeeley, A. H.. 204
Ndswander. C. ll,,277
Nmt^lre. O. P.. 36S, 376
Nelson, E. ?., 339
Nelson. P. C, 269. 277
Nfflson, G. H., 155, 161, 364,
375
Nelson, J. M.. 229, 233, 248,
249
Nelaon, L. H., J26, 135
Nelson, O. A., 227, 253, 268,
276, 277
Nelson, R. A„ 84. 89
Nelson. T, H,, 337
Nclaon, W. L., 227
Nesbit, H. T., 235, 249
Nestler. R. B.. 243, 251
Neuss. J, D.. 109, 115
Neville, H. A., m
Newberry, E.. 109. 115
NewbDund, R.,300
Ncwbtirgl], L. H., 235, 249
Newcomer, E. J, 2fll, 277
Newell, H. D. 130. 136
Newman, M, S.. 202, 203
Newsome, P. T.. 361, 363,
374, 376
Newstrom, J. E., 202
Newton, H. P., 203, 419, 433,
438
Newton, R. P., J6, 32, 77
Newton. R. H., 66, 76, 312,
323
Neyman, E.. 203, 330
Nichols, K. W., 339
Nichols, M. I^.. 92, 95, 100,
104, 109, 114. 115
Nichob, P. R, 252
Nicholson, F., 202
Nicolet. B. H.. 201, 203, 204
Niaderl. J. B., 202. 323
Nielfien. H. H., 5«. 57
Nielsen. H, P„ 131. 136
Nielson. V., 244. 251
Niea, N. P.. 06, 75, 179
Nieuwland, J. A,, 97. 101,
ISO, 181 . 203. 338, 393, 414,
418, 439
Kikawita, E., 220, 226
Niles. G. H..202,31S
Nilsen,B., 37,38. 43
Noble, R* J., 412, 418
Noll. A,, 355
Noller, C. R,, 203, 204
NopitscJi, M., 352. 350
Nordmeytr, G. T.. 286, 310,
318
Normann, W., 344, 366
Norris, P. G.. 126, 136
Norris, J. P., 181, 196, 203
Norrish, R. G. W., 34
North, E. O., 228
Northam, A. J., 403, 416
Northrop, J. H., 232, 249
Norton, A. J., 394, 419, 436,
439, 466
Norton, J. T., 119, 122, 127.
128, 135. 136, 137
Norton, L. B„ 264, 277
Nourse. E. G., 446, 465
Novak, I. J., 394
Novotny, E. E., 394, 396, 396
Noyes, A. A., 16. 32, 99, 101.
112, 116
Noyes. W. A.. 67. 99. 101
Noyes, W. A., Jr., 66, 179, 181
Nasslein, T., 346. 366, 368
Nu6y, P. L. du, 348, 366
Nusbaum, C, 121, 123. 131.
136
Nutting, G. C. 68
Nutting. H. S., 168, 161, 179.
266, 274, 312, 322. 436
Nutting. R. D.. 402, 416
Nygaard, O., 317
Nyland. H. V., 323, 339
Oakley, M., 228
Oatfield. H. J, 423, 436
Oberfell, G. G., 298, 320. 338
Dberst, F. W,. 204
O'Briftn, J, J., 05, 100
O^Btyan. H. M., 143, 160
O'Cotinnr, C, T., 394
O Connor, R., 203
0*Daniel. E. V„ 265, 277
Ode. W. H.. 291. 314, 317,
323
O'DeU, M. J., 366. 376
Odell, W. W., 292, 300, 317,
318, 320. 409, 417
Oesper, R. E., 106. 114
Oesterling, J. P., 347, 366
Ogbum. S. C., Jr., 139, 149
Ogg, R. A., Jr., 179
Ohl, E. N., 63, 76, 83, 89
O'Kane, W. C., 267, 277
Olcott, H. S., 230, 241, 248,
261, 437
Oldenberg. O., 37,43
O'Leary, M. J., 369, 376
Olive, T. R., 466
Oliveira, J., 276
Olmsted. W. H., 229, 248
Olpin, H. C., 182
Olsen, A. G., 242, 261
Olsen, A. L., 77
Olsen, P., 158. 161
O'Neil, M. A., 204
Oneto, J. P., 202
Ong, E. R. de, 266, 262, 267,
277
Onaagor. L.. 7, 28
Opnloiiick, N., 204
Or^lup, J. W., 357
Orent. E. R^^ 238. 249, 260
Ornes. C. L., 411,418
Ort, J. M,. 143, 160
Ortefi, J. M.,235, 249
Qrthner, [..,358
Oserkuwsky, J.,2a2, 277
Oshima, Y. 310, 322
Osol, A, 228
Osterberp, H..75,407,417
n^UThof, H. J., 348, 366
^1 ■ ■ ■ ■■.^^. J. v., 27
Ott, K., 366
Otto, C, 317
Otto, M. M., 30, 32, 67. 181.
202
Ouer, R. A., 230, 248
Overcash. D. M., 166, 161
Overman, C. B., 372, 377
Owen, B. B., 7. 13, 26, 32, 77
Owens, J. S., 110, 116
Owens, R. M., 76, 100
Oxley, H. P.. 181
Paden. J. H.. 421, 436
Pailler. E. C. 367. 368
Painter. E. P.. 260
Palmer. E. W.. 127. 134. 137
Palmer, P. S.. 86, 89, 203, 216,
437
Palmer. L. S.. 233, 241. 243.
249, 261
Paneth, P., 103
Pantke, O., 394
Pape. W.. 368
Pappenhagen. L. A.. 111. 116
Pardee, J. T., 146, 160
Park, B., 110, 115
Park, C. R., 408, 409, 417
Parke, P. B., 286, 293, 316,
318
Parker. A. S.. 216
Parker. G. M.. 309, 322
Parker, J. R., 261, 277
Parker, P. T., 215
Parks. G. S., 76. 131
Parks. L. R,, 109, 115
Parnian, D. C, 267, 276
Parmeloe. A, E, 438
Parmelee, H. C, 450
Parmelee, H. M,. 179, 436
Pannenter. E. F., 98, 101
Parrntt, L. G., 113, 122
Parrish, C. L. 202, 338
Parry, V. P., 29S, 320
Partansky, A. M., 306. 376
Partrirljue, E. G.. 413, 418
Partridge. E, L.. 457
Partridge. E. P., 70, 77, 313.
323
Patrick, J. C, 397
Patterson, G. D., 395
Patterson, J, A,, Jr„ 437
Patterson. W, t., 204, 248
Patton, A. R., 231, 248
Paul, B.H„ 300, 374
Pitul, R. E., 299, 320
Paul, W. H. ,31 1,322
Pauling, U, 38. 43, 45, 56. 56,
S7. 5R. 74, 95, 100. 144h 160,
190, 198, 202, 204. 205, 215
Payne, T. H.. 363, 374
Payne, L. F.. 243, 251
Peartre, G. W.. 254, 277
Pcarce, J. H„ 16, 32, 57. 63,
75,70
Pearl. A. H.. 32
Pearse, R, W. B.. 140, 149
Pearson, F. A.. 447, 455
Pearson, T. R., 4J2. 436
PeaBE. R, N., 35, 36, 37. 43,
44.85,80,39.179,311,322.
426, 437
Pechin. G., 394
Peck. F,W., 422, 436, 438
Poderson. C. S., 2.52
Pelicr, H., B
Pence, L. H.. 202
Pennlman, W. B. D.. 182
PenmnRton, W. A.. 134,137
Pepper. B. B., 275
PerlSna, G. A.,319,431. 438
Perkins, M.A„ 433. 436,438
Perkins, M. E. 233,349
Perkins, R, P.. 429, 437
Perlniaii. J. L,,213, 251
Permar, H. H.. 227
Perrine, R. O., 298, 320
Perry, J. A.. 2S4, 286. 287.
303,316,317. 321
Perry, J. H„ 75. 446, 454. 455
PersinfT. C. O.. 257, 267, 277,
278
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Google
474
AUTHOR INDEX
Pfiki. A. J. van. 182
Pettrkin, A, G.» 440
Peters, A. P., 228
Pfet^Ts, G.. 2m. 211
Ptettra, W.p 35fl
Petefsen. J, 152
PetcriHjn, E. G., 397
Peterson. P. C.p36t. 374
Petem-n. P. 0.257,277
Peterson. R.. 410.417
Petiey, A. U'., IID, 110
Petrie, P. S.. 179, 265, 274,
436
Pettengill, R. B., 457
Pew, J. C, 365, 376
Pffiff, G. C.. 317
Phelpa, M. W., :i5ft, 374
Philltfs. A.. 12a, 121, 122,
123, 128, 135. 136. 137, 168,
161
Phillips, A. J. 3(53, 376
Phillips, E. P., 265, 376
Phil lips, G, P,H 134, 137
PhilJipa. L, H., 357
Phillips, M,, 364. 366, 376
PhiUips, P. H„ 249
Philo, E. G., 309, 322
FhippB. T, E-, 83, 80, 157, 161
Pickens, L., 243, 361
Pickett. O. A., 367
Pickett, T. A.* 236, 249
Pier, M., 31S
Pierce, D. E,, 454
Pierct, I, H., 223. 227
Pierce. T. E„ 297. 319
Pierce. L„ 278
Pierces R. H. H., Jr., 74, 76,
126, 128, 135, 136
Pierson, C, 126, 135
Piereon, G. G., Ill, 116, 139,
149
Pigott, R. J. S.. 316, 323
Pikl, J., 216, 220, 226
Pilat, S., 298, 320
Pillow, M. Y., 367, 376
Pines, H.. 89, 180. 338
Pinck, L. A., 180, 203
Piper, J. D., 190, 202, 370,
376
Pitman, G., 245, 252
Fitter, A. V., 350, 356
Pittman, M. S.. 242. 251
Pitzer. K. S.. 15, 32, 101, 112,
116
Pitzer, M. B., 297, 319
Pitzer, P. W., 319
Pizzolato. P., 203
Plant, J. H. G., 181
Plant, O. H., 227
Platz, K., 367
Platzer, N., 226
Plechner, W. W., 112, 116
Plummer, W. B., 300, 320
Plumstead, j. E., 371, 376
Plyler, E. K., 12, 32, 66
Podbielniak, W. J., 313, 314,
323
Poe. C. F,. 227, 228, 239, 250
Poffenberger. N„ 75, 179
Polanyi, M.. 9. 83
Pollak, P.. 305
Pollard. C, B.. 201, 216
Pollock. R. N.. 36li. 376
Polly. O. L., 35, 44. 338
Polushkin, E. P., 128, 136
Ponts. D. F.. 203
Poole, R. P., 254. 277
Poore, H. D-. 246, 252
Poppe, P. W.p 373, 377
Popper. Wy,Jr., 238, 350
Porter, C. W,. 187, 201
Porter, D. C, 365. 375
Porter, D. J., 312, 3£2
Porter, H. C, 2S7, 288, 293,
317, 318
Porter. H.D., 201
Porter, J. L., 291, 317
Porter, T. E.. 361
Poritsky, H., 74
Poanjak, E., 77. 150
Post, C, B., 120. 123
Pottensfer. C. H.. 113.116
Potter. H. ,201.204
Pottcf. V. R.. 249
Pottinscr. S, R„ 242^ 251
Pntts.W , 76. 181
Pound. A.W.. 437
Pound, J. R.^7
Pounder, D. W., 418
Powell, A. R., 304. 321
Powers, D. H., 352, 356, 402,
416
Prahl, M. A., 367, 368, 424.
436
Pranke. E. J., 266, 277, 278
Prater, A. N., 43, 179, 437
Pratt, P. S., 264, 278
Pratt, H. J., 228
Prener, S., 181
Prentiss, S. S., 16
Presbrey, R. L., 294, 319
Present, R. D., 67
Price, W. C, 66, 181
Price, W. K., 267, 278
Priest, A. E., 254, 277
Prill, E. A., 216
Prindle, E. J., 445
Pritchard, W. N., Jr., 357
Pritchett, L. C, 421, 436
Prochazka, G. A., Jr., 451.
466
Prutton, C. P., 76, 77, 397
Pucher, G. W., 108, 115
Pungs, W., 395
Purdom, E. G., 146, 150
Purkis, P. T., 418
Putney, L. K., 242, 261
Pyhrr, W. A., 166, 161
Pyott, W. T., 339
Pyzel, D.. 318
Pyzel, P. M., 320
guaedvlieg, M., 368
uayle, H. J., 264, 266, 276,
278
Querfeld, D., 457
Quiggle. D.. 316, 323
Quiggle, E. B.. 457
Quigley, J. P., 227
Rabald, E., 180
Raby, E. C, 105, 114
Race, H. H., 159, 160, 161,
162, 390, 396
Rafter, J. R., 101
Ragatz, E. G., 323
Raiford, L. C., 204, 422, 435.
436
Rainier, E. T., 406, 417
Rainsford. A. £., 203
Raisin, C. G., 178
Rakieten, N., 227
RaU, H. T.. 300, 320
Ramage, W. D., 266, 278
Ramseyer, C, P., 135, 137
Rand, W. M., 456
Randall, M., 14, 16.32,77,
106, 116
Rank, D. H., 56
Ranney, L., 298, 317, 320
Rapoport, M., 260
Rapp, I,, 229, 248
Rasch, C. H., 152, 160
Rasch, R. H., 361, 368, 374.
376
Rasmussen, R. A.. 239, 260
Rathemacher, C. P., 436
Ratzkoflf, S. M., 367
Ray, W. A., 28, 31
Rayner, A., 361, 366
Read. B. E.. 228
Read, W. T., 442, 453
Reagan, W. J.. 126, 126, 136
Rearick, J. S., 273, 276
Record, P. R., 260
Redman, L. V.. 394, 444, 454
Reed, D. W., 319
Reed, G. H., 75
Reed, J. B., 101
Reed, M. C., 393, 404. 414,
417, 418
Reed, R. M., 179, 424, 436
Reed, T. W., 262, 276
Reese, S. W., 372, 377
Regan, W. M., 261, 276
Reichhelm, G. L., 301, 320
Reid, E. E., 179, 180. 183.
216, 419
Reid, E. W., 180, 393
Reid. F. R., 366, 375
Reid, J. D., 105, 114
Reid, J! G., 227
Reid, W. T., 314
Reilly, J. H.. 438
Reimann, A., 357
Reimer, M., 181, 203
Reinartz, L. P., 125, 135
Reinhart, P. M., 11, 31, 77
Reistle, C. E., Jr., 319
Relyea, P. H., 368
Remington, R. E., 235, 242,
249, 251
Rcmv. T. P.. 264, 2/8
Rendel, T. B., 339
Renfrew, A. G., 227
Renoll, M. W.. 416
Ressler. I. L.. 266. 277
Revukas, A. J.. 181. 202
Reyerson, L. H.. 35, 44, 77,
78, 87. 88, 89. 178, 179,
287, 317
Reynolds, D, A., 289,317
Reynolds, P., 107. 115
Reynolds, H, H.. 438
Rhodes, E.. 407, 417
Rhodes, P. H.. 77, 346. 352,
365, 366. 44J\. 464
Rhodes, G. I. 337
Ricci,J.E., 77.92. 100
Rice, P. O., 33, 35, 37, 44,
180, 338
Rice, K., 36
Rice, O. K., 9, 32. 34. 36. 39.
42, 43, 44, 74, 180, 182
Richards, B. H. P., 394
Richards, L. W., 228
Richardson, A. S., 344, 355
Richardson, C. H., 253. 267.
277 278
Richa'rdson, H. H.. 267, 278
Richardson, R. P., 291, 317
Richardson, R. S., 409, 417
Richford, M. A., 316, 323
Richter. G. A., 368, 376
Richter. G. H., 216
Richter, H. J., 184, 201
Richtmyer, P. K.. 146. 150
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AUTHOR INDEX
475
Rickett, R. L., 130, 136
RiddeU, W. A., 317
Rideal. E. K.. 33, 43. 180
Ridenour. L., 91, 100
Rider, T. H., 106, 114
Ridgley, G. H., 06, 101
Ridler, E. S., 148, 161
Riegel. B., 248
Riegel, C, 227
Rieman, Wm., Ill, 109, 116
Ries, D. T., 267. 278
Riesch. L. C, 11, 21, 32, 76,
181
Rfker, A. J., 256, 278
Riley. C. H.. 228
Rmtelman, W. L., 423, 436
Ripper, K., 395
Ritcher. P, O., 2i5§. 275
Ritchie, A. v., 314
Rittenberg. D., 330, 248
Ritter. P. O., 181. 427, 437
Ritter, G. J., 362, 364, 372,
373. 375. 377
Ritter, R. M„ 374,278
Rittinger. F,, 245, 252
RivisE, C. W., 445, 454
Roark, H. C, 253, 263. 266,
271.272. 27S
Rol>erts. CH, M,. 158, 161
Robert*. H. S., 76, 122
Roberts, /. M-, 285. 3J6
Roberts, J. W., 255, 278
Robfertfl, L. J„ 251
Robertson, D: W.. 313, 323
Robertson, P., 393
Robey, R. R, 86, 80, 310,
322
Robinson, C^ S., 236. 249
Rabinaon, H, M.. 106, 115
RobinBoo, J, E., 411, 413
Robinson. L. R„ 457
Robinson, P., 306. 396
Robmsort. R.. 216. 2J7
Robinsijn. R. Ah, 14, 16,32
Robinsfjn, W. O., 107. 116
RobiuoTJ, C. D., 285, iS16
Robfson. S. C, 411, 418
Hohlin, R. O.. Tr.. 204
Robacbeit'Robbtns. F. S., 249
RochDw, E. G.. 92. 97* 100.
101
Rodda, J. L.. 122
Rodebush, W. H., 32, 36, 37,
39, 42, 44, 77, 92, 100
Rodman. E.. 416, 418
Rodowskas, E. L., 44, 92, 100,
180
Ro<^r[aii, R 148, 151
Roduta, F. L., 202, 437
Roebuck, j. R,. 75
Roeder, C. H., 31 ft. 322
Rj>fhline, O. C.. 43
Roehtti. G, H., 246. 2h2
Roehr, W. W., 372, 377
Roepke. M. H,. 14:i. 150
Roeser. W. F,, 74, 146, 146,
140, 150
Rogers, G., 226
Rogers. L, H,, 110, 116
Ragera, W. F,. 337
Rohlfa. H. C. 395
RohrUaugh. P, W., 260. 264,
Roka, K., 181
Rollefson, G. K., 43
Rollefson, R., 66
Romeyn. H., Jr., 74, 89, 97,
101, 179. 437
Roney. J. N., 269, 270. 278
Ronzio, A. R., 182, 204, 216
Roorbach, G. B., 466
Root, P. B., 396
Rose, C. R., 274, 278
Rose, H. J., 292, 317, 318
Rose, M. S., 236, 243. 249.
261
Rose, W. C, 230. 248
Rogeman. R., 06, 100
Rosenberg, S„ 437
Rosenberg, S. J., 122. 128, 136
Rosen hi um, C, 103. 114,393
RMcnbluni, 1., 394. 396
RosenthAl. J. E.. 57
Ros-n, j.,22S
Ross. M., 110, 115, 445, 464
Ross, P. A., 145, 160
Ross, R. P.. 76
Ross, W. E., 203
Ross, W. P., 249
Rossini, P. D., 37, 44, 62, 63,
. 74, 76, 179, 338, 339, 400
Rossman, J., 446, 464
Rost. O. F., 456
Roth^ R. T,. M23
Rothcmimd, P., 208, 216, 216
Rothrock. H. S., 181
Rotondjiro. F, A*, 228
Roush, G. A.. 138, 149
Rowe. L, P., 76
Rrjwe, L. Wh, 226
RoB^^land. B. W., 362, 374
Rowland. E. S.. 122
Rowley. II. H.. 81. 89, 168.
161
Roy, M. F., 201
Ruben. S., 65, 75
Rub erg, L, A., 204
Rubin* M. M., 370, 376
Rnbm.T,R.. 20, 31,65.76
Ruriberg, E., 76
Ruder, W. E., 137
Rut. J. D., 368. 376
Ruehle, A. E., 322, 217. 260
Ruhkopf, H.. 213. 217
Rtihoflf, J. R.. 74, 75, 39. 179.
180,437
Rummelsburg. A. L., 367. 368
Runyan, A., 394
Rupp, V. R.. 242, 261
Ruprecht, R. W., 246, 262
Rusk, H. W., 269, 276
Rusoflf, L. L., 228
Russell, R. P., 300, 320
Russell, W. C, 240, 261
Russell, W. W., 81, 89, 106,
1 14 323
Rutherford, P. C, 181
Ruthruflf, R. P., 180, 300,
320. 338
Rutledge, P. J., 321, 322
Ryall, A. L., 268, 269, 276,
278
Ryan, P., 316
Ryden, L. L., 183, 203, 338
Ryland, L. B., 339
Sabetta, V. J., 182
Sachs, A. P., 286, 317
Sachs, J. H., 422, 436
Sackett, G. A., 401. 416
Sadtler, R. E., 464
Saeger, C. M., Jr., 133, 137
Saffien. K., 366
Sage, B. H., 76. 76. 297. 319.
320. 338
Sager. T. P.. 407, 417
Sala. C. J.. 366
Sale, P. D.. 129, 136
Salky. D. J., 362, 374, 437
Salmon, C. S.. 349, 356
SfilstTom, E. J., 56
Salzberg, P. L., 260, 262, 264,
274, 275, 278, 367, 396, 426.
431,437,438
Samaras, N. N. T., 28
Samiach, Z., 241, 251
Samuclson. G. J., 77
Sanbom, J. R.,374. 377
Sanborn, N. H., 234,249
Sanchis, J. M„ 107. 116
Sandborn, L. T„ 393
Sandell, E. B., 113, 116
Sanders, B. S,. 227
SandtifB, J. P., 361, 374
Sanders, W. E., 137
Sanderson, J. McE.. 396
Sandin. R. B.. 182
Sands. G. C. 244. 261
Sandford. R. L.. 127. 131.
132, 136
Sanger, C. R., 206
Sankowsky. N. A.. 269, 278
Sarquis, M. S., 106, 116
Sarver, L. A., 106, 114. 204
Sattler, L., 181
SaucheUi, V., 274, 278
Saul, E. L.. 248
Sauveur, A., 132, 134, 137
Saylor, C. P., 399, 416
Saywell, L. G., 262
Scanlan. J. T., 105, 114, 203
Scfltchard, G.. 10, 15. 17. 20,
23,32.68,76
Sdiajif, A. H., 284,316
Scliaafsma. J. G,, 75, 78, 319,
320, 338
SchHeffcr, A., 317
Scbaefer. A, E., 179
Schaefer, J.. 317
Schafer, E. R., 365. 375
Schaffer. LM., 27S
Schaffer, P. S., 271, 276, 421,
436
Schaffner, M., 181, 203
Schairer, J. P., 70, 76
Schane, P., Jr., 137
Scheldt. A. W., 366
Scheil, M. A., 126, 130, 136,
136
Schenck, O., 344, 366
Schicktanz, S. T., 76
Schierholtz, O. J., 181
Schiflett, C. H., 36, 43, 178
Schimpflf, G. W., 86, 89, 437
Schirm, E., 367, 368
Schleich, H., 249
Schleicher, H. M., 394
Schlesinger, H. I., 90, 97. 100.
101. 169, 161
Schlingman, P. P., 396, 396
Schmidt, C. P., 227, 228
Schmidt, C. L., 183
Schmidt, C. L. A., 20, 21, 26.
31. 32. 76
Schmidt. E. P., 303, 321
Schmidt, E. X., 313, 323
Schmidt, P., 394, 396
Schmidt, J. H., 380, 385, 393.
396, 396
Schmidt, L.. 337
Schmidt, O., 367
Schmidt, W. B., 109, 116
Schmitt, T. B., 268, 271, 276
Schmitz, H., 361, 374
Schneider, B. H., 233, 249
Schneider. P., 249
Schneider, G., 397
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476
AUTHOR INDEX
Schndder, H., 130, 14(»
SchneHer, W. R.. 302, 321
Schock. E. D.^24&
SchMllftf. C.* 357
Sch^ntbi^tm, H,. 318
Schoenfdcl* F. K,, 407, 417
Schoenheimer, R., 230, 248
Schottiwatd, O. H,< 31D
Schofield, P. H. IfiO
Scbr>l«. S. R„7a
SchoU, A. W,. U, 32, 77
Schnonovier, I. C, 107, llS
Schormulkr, A,. 430. 438
Schownlter, A. E., 127, 136
Schmuth, W., 3fi6. 357, 368
SdhrrtbeT, R, S., 204*217
Schrciner, E. J.. 360, 374
Schrocder, W, C. 70, 77
Schubert, v., 407, 417
Schuettf , H., 358
Scholer, R., 182
Schulte, W. C, 1KB, 136
SchuHz, J. F., 65
Schtike, W. A., 339
Schumb, W. C, 76, S3, PO, 67.
100, 101, 108, 115, 181
Scliwarti, E.. 141, 140
Sehwarti, H, A., 126, 137,
135. 136
Schwartz. S. L., 360, 374
Schwarz, R., 244, 262
Schwarzenbach. G., 21
Schwegler, C. C, 168. 161
Scorah, L. V. D., 180
Scorah, R. L.. 39, 44, 74
Scott, A. P.. 14, 23, 32, 76.
106, 116
Scott, A. H., 66, 76, 406, 417
Scott, A. W., 216
Scott, C. B., 294. 318
Scott, G. N., 303, 321
Scott, G. S., 311, 322
Scott, H., 131, 136, 137
Scott, R. B., 76
Scott, W., 406, 417
Scott, W. B., 182
ScQtt, W. M.. 378, 45,^
Scoville, W. L,,a28
Scribncr, B. W.. 368, 369.
372, 376, 377
Seribner, G. K.h 3t*4
Scroggie, A. G., 372, 377
Scnitchfield, P. H.. 305
Scudj. J. v., 182, 201. 203,216
^aman. A,. 415. 418
Seaman, H., 3 HI. 322
Searls.E. M., 269, 278
Sears, G. W,,94, 100
Seats, R. W., 140, 140
Seavey, F. R., 158, 161
Seborg, CO,. 373, 377
Setaorg, R. M., 360, 374
Sebrqil, L. B„ 403,416
Sebrell, W. H., 239, 260
xScehnch, R, 394, 395
Seegera. W. H., 242, 261
Sefifig, F. G., 133, 137
Segelcr, G. E.. 307, 321
Secuffl, M., 431, 438
Sfiil, G. E,,2&4, 295,310
SeiU H, A„ 208, 278
SeitJ. F., 66, 57
Sekera. V. C..438
Selby, W. M„ 2^01
Sftldcn, R, P., 298, 320
Sdigman, A, M.. 191, 202
SelUH, M.,242,251
Scllew, W. H.. 316. 323
Scltz. H.. 17, 82, 68. 69, 76, 77
Selvig, W. A., 291, 314. 317.
323
Sclwood, P. W., 77, 98. 101
Scmenov, N. N., 34, 38
Semon. W. L., 349, 403, 405,
414. 416, 417. 418
Scrber, R., 37, 44, 67, 179
Serf^s,B. J.. 109.116
Sessions, A. C., 266, 278
Seubert, K., 139, 149
Scvals, N., 262
Seward, R. P., 97, 101
Seybold, P., 139, 149
Seydel, H., 262. 278
Seyler, H. W., 291, 317, 321
Seymour, G. W., 396, 397.
429. 437
Sharma, J. N., 263, 278
Sharp, W. E., 421, 436
Sharpies, P. T., 262, 278
Shaw, D. L., 16, 32, 77
Shaw, E. H., Jr., 182, 431.
438
Shaw. G. T., 44, 180
Shaw. J. A., 318
Shaw. M. B.. 369. 369. 374.
376
Shaw, T. P. G., 380, 393
Shea, G. B., 298, 319, 320
Shearin. P. E.. 66
Shedlovsky, T.. 26, 32, 76
Sheely, C. Q., 426, 437
Shelton, S. M., 129, 130, 136
Shenk, W. E., 108, 116, 126,
136
Shepard, A. P., 416, 419
Shepard, H. H., 266, 277
Shepherd. B. P.. 133. 137
Shepherd. M.. 141. 149. 312,
323
Sheppard, S. £.. 361, 363.
374, 376
Sherborne, J. E.. 62. 76, 338
Sherk, K. W., 437
Sherman, A., 38, 44, 68
Sherman, CO.. 229
Sherman, H. C., 229, 234, 236.
238, 247, 249, 260, 262
Sherman, R. A.. 290. 307, 317,
321
Sherman. W. C, 239, 260
Sherrard, E. C. 364, 376
Sherwood, G. R., 101
Sherwood, R. C. 244, 261
Sherwood, T. K., 316. 323
Shields. T. P., 148. 161
Shiffler. W. H.. 181. 182
Shilthuis, R. J., 297. 320
Shinkle. S. D., 397
Shinohara, K., 91, 100
Shive, R. A., 396
Shively, W. L.. 321
Shnidman, L., 311, 322
Shoeld. M., 318. 319
Shorland. P. B., 182, 438
Shotwell, R. L., 261, 277
Shoupp, W. E.. 146, 160
Shreve, R. W., 419
Shriner. R. L., 204, 217. 228
Shriver. L. C. 393
Shuey. R. C, 439
Shukers, C. P., 242, 261
Sibley, B. E., 339
Sibley, R. L., 263, 278, 367,
404, 406, 417
Sickman. D. H., 34. 36, 43,
44.180
Sidwell, A., lOt
Rkbel. F. P., Jr., 244, 262
Siebert, C. A.. 131,136
Stcgler, E. H., 264,278
SEcver. C. H.. 273, 278
Sifferd, R. H., 210,216
Si«naigo, F, K., 3:^9
Silker. R. E„ 436
Silver, S. L., 434, 433
Stmard, R. G., 203
Sinjmonds. F* A., 371. 376
Simmonfi, R. H., 373. 377
Simon. A. K.. 227
Simon, F., 61
Samon, K. C, 419, 435
Simons, J. K,. 191, 302
Simpson, W. A., 419
Sims, C, E., 133, 337
Sinclair, H,. 368. 375
Sinclair, R, G., 230, 248
Singer, A. W., 216
SjnKef,S, C, Jr., 339
Singh. A. D.. 88, 89, 181
Stngnien, E., 244. 252
Sisco, F. T., 124
Sissnn. W. A., 362, 373. 374.
377
Sivertz. V., 366, 376
Skau, E. L., 21, 32, 63, 69. 75.
76
Skinner. S. S., 318
Skovholt, O., 244, 261
Slanina, S. J. 180. 203. 338.
439
Slater, J. C., 67, 122
Slaughter, D.. 227
Sleator. W. W., 66
Sloan, A. W., 406. 417
Sloan. E. C. 393
Slrj.-nan, CM., 407, 417
Sljr, C, 307
SmaK. C. G., 257, 278
Small, L. F., H2, 149, 166,
161, 218. 227, 228, 437
Smidth, L., 395
Smith. A, A., 77
Smith, A, H„ 236, 236. 249
Smith, A. J., 122
Smith, A. S„ Sl3, 323
Smith, B. P,. 3ft6, 376
Smith, C. C, 401, 402, 411,
41G. 418
Smith, C. M., 216, 264, 269,
276. 278
Smith, C. N., 393
Smith, C. R., 227, 268, 278
Smith, C. S., 127, 134, 137
Smith, D. M., 181, 188, 202.
209, 216
Smith. D. P., 141, 149
Smith, D. W., 120. 123. 127.
136. 136
Smith, E., 268. 259. 276, 278,
306, 321
Smith, E. B.. 262. 277
Smith, E. C., 126. 135
Smith. E. J., 362, 374
Smith, E. L., 467
Smith. E. R. B.. 22. 32
Smith. E. W.. 216. 423.
436
Smith. P. A. U.. 226
Smith. P. L., 2nd. 106. 116
Smith. G. B. L.. 100. 181. 182.
202 437
Smith. G. P., 102. 103. 110.
Ill, 114, 116. 116. 216,
427. 437
Smith, G. W.. 409, 417
Digitized by
Google
AUTHOR INDEX
A77
Smith, H. A., 36, 44, 66, 74,
76, 89, 120, 122, 179. 180,
437
Smith, H. M., 300, 320
Smith, H. v., 107, 115
Smith, H. W., 364, 376, 402,
416
Smith, H. W., Jr., 309. 322
Smith, I. P., 454
Smith, J. C, 180
Smith, J. E., 349, 355
Smith, J. P.. 454
Smith, J. G., 450, 456
Smith. J. M., 243, 251
Smith. L. E., 263, 264, 274.
278, 363. 375, 421, 436
Smith. L. I., 201, 202, 204,
421, 436
Smith, L. T., 303
Smith, M. A., 27S, 330
Smith, M. C. 230, 240
Smith, O. Am 369, 376
Smith. O. H., ISO, 414, 41B
Smith, 0,M.. 10^7,115
Smith. R. H., 297, 278
Smith, S.. 226
Smith, S. B., 77
Smith. W. H., 390, 416
SmEth, W, R„ 4.% 204
Smith, W. T., a02, 321
Smuts, D. B., 233, 249
Smyly. A. L., 29.^319
Smyth. C. P., 57, 76, 179, 1^2
Snell, R D,. ISI, 344, :M8,
351, 352,3515. 356,357
Snicicr, H.J,. 114, 116
Smder, L. C.. 337
Snow, C. C. 421, 436
Snyder, P. H., 369, 376
Snyder. P. M., 269, 278
Snyder, T. W., 406. 417
Snyder, L. W., 370, 376
Sobin, B., 181, 203
Sobotka, H., 203
Sohl. W. E., 228
Somers, D. M., 246. 252
Somerville, A. A., 402, 405,
416. 417
Sommer, F., 358
Summer, H. H., 243, 251
Sommer, M. H,. 130, 136
Sonta^, L.. 394
Sontag, L. A„ 435.439
Sorenson, B, E.. 31)4. 395
Sor«. L. v., 339
Sosmart, R. a., 77, 150
Sotiders. M., Jr., 323, 339
Souk, R. P., 440
Sotithard, J. C. 75. 145, 150,
362,374
Sowa, P, J.. 97, 101, 180, 203,
3,^5 S. 439
Spahr, W. E., 453
Spanagel, E. W., 180. 207,
215
Spaulding, L. B., 216
Spealman. M. L.. 36, 37, 44
Spear, E. B., 409, 417
Spedding, P. H.. 68
SpeUer. P. N., 129, 136
Spence, R., 44
Sperr, P. W., Jr., 295, 318,
319
Spiegler, L.. 435
Spiehnan. M. A., 201, 211.
216
Spies, J. R., 272. 276, 278
Spies, T. D., 238, 250
Spoehr, H. A., 229, 248, 427,
437
Sponsler, O. L., 362, 374
Spokes, R. E., 273, 278
Sprague, J. M.. 216
Spraragen, W., 444, 454
Spychalski, R.. 351, 356
Squier, M., 245, 252
Squires, L., 319, 402, 416
Staddon, L. S., 350, 356
Stadt, H. M., 357
Stair, R., 56
Stamm, A. J., 77, 360, 361,
374
Stamm, P. C, 370, 376
Staneslow, B._J., 97, 101
Stanfield, K. E., 107, 115
Staniforth, L. 456
Stanley, H. M., 182
Stanley. W. M., 27
Stanley, W. W., 261. 278
Stansby, M. E., 107, 115, 242,
251
Stansfield, A., 457
Stanton, E. J., 227
Staples. M. L.. 181
Stare, P. J.. 238,250
Stareck, J. E., 143, 150
Starkweather, H. W., 383,
393, 394. 435, 439
Starling. L., 262
Staub, W. A., 453
Staud, C. J., 181, 203
Staudinger, H., 180, 199, 380
Stauffer, C. H., 181
Steacie, E. W. R., 44, 180, 437
Stearns, A, E,, 44
Steams, E. 1., 93. 100
Stearns, H. A.. 262, 274, 438
Stecher, J. L., 438
SteerJ, J, Q„ 111, 110
Steele, P. A., 309, 376
StMinbqck. R., 350
Stwre. F. W., 317
Stdn, J. A.. 3L^, 323
Stein, O., 263. 274
Stein dorff. A., 357
Sterner, H. M,. 267,278
Stetnct, J., 142, 150
Stekoh J. A.. 231. 248
Stellet, M. R„ 244, 251
Stenger. V. A., 105, 107, 112,
114. 115, lie
Steph&ns, H. N.. 202. 427, 437
Sterickfir, W., 351, 356
Stem, M, 156
Stcrrptt, R. R.. \22. 123
Stevens, A. N., 2;Jti
Stevens, R. H., 368, 375
Stevinson, M. R., 86, 89, 202,
204
Steward, W. B., 56
Stewart, A., 350, 356
Stewart. P. S., 396
Stewart, P. H., 274, 277
Stewart. T. D., 44, 179
Stewart, W. C. 436
Sticht, G. A., 227
Stickdom, K.. 344. 355
Stiehler, R. D., 75, 216
Still. C, 291, 317, 318
Stillwell, C. W.. 167. 161
Stillwell, W. D., 96. 100
Stine, C. M. A.. 453
Stim, P. E., 236, 249
Stirton, A. J., 419, 425, 433,
436, 438
Stocking, G. W., 457
Stoddard, K. B., 144, 150
Stoesser, S. M., 297. 319
Stoesser, W. C, 424, 432,
436, 438
Stokes, f., Jr., 250
Stokstad, E. L. R., 242. 243,
251
Stoland, O. O., 228
StoU, A.. 226
Stolzenbach. C. P., 293. 309.
318, 322
Stone, T. S., 357
Stone, L. P., 160, 162
Stone, T. W., 286. 316
Stoops, W. N., 160, 162. 361,
374
Stoppel. E. A., 397
Storch, H. H., 35, 37, 39, 43,
44, 79, 89, 179, 180, 299.
320, 338
Slivrmont, R. T, 182
StoLjyhton. R. W., 138, 202,
429. 43 <, 437, 438
Straley. J. M., 263. 279
Strakci, L. E,. 105, 114
Strain, H. H., J02. 238, 350
Strain, W. H.. 203
Stramathan, J, D-. 57
Strange, J. G., 371.376
SUitsancr. E. A.. 26, 32
Straup. D., IOh 32
Strauss, J„ 128. 136
Strong. J. 0„ 228
Strong. H. A.. 250
Stmsacker. C. J., 158, 161
Struas. E. F., 204
Strutb, H, J.. 296, 3!9
Stuart, E. H., 226
Stuart, N. H., 371, 376
Stupp, C. G.. 318
Sturgis, B. M.. 304.217
Sturm, W, A., 77
Sturtcvant, J, M.. 10, 3a
Subbarrow. V.. 235, 349
Subkow, P., 317
Suchy. J. P., 228
Sussenguth, O., 395
Suits, C. G.. 74
Sullivan, P. W., Jr., 180, 300.
320. 338
Sullivan, M. X.. 226
Sullivan, V. R., 110, 114, 115,
116
Sullivan, W. N.. 263. 270,
272, 274, 276
Summerbell, R. K., 215
Sun, C. E., 38, 43, 44
Sunderland, A. E., 344, 355
SundstrOm, R. P.. 96, 100
Sure, B., 230, 233, 248, 249
Suter, C. M., 201
Sutermeister, E., 368, 369.
376
Sutton, L. E., 56, 58
Svirbely, W. J., 10, 30, 32, 57,
198, 204
Swain, A. P., 264, 278
Swain, R. C, 61
Swallen, L. C, 181, 277, 396
Swan, D. R., 427, 437
Swanger, W. H., 129, 136.
149
Swank, H. W., 106, 115
Swann, S., Jr., 152, 155, 157,
161
Swanson, C. O.. 244, 251
Swanson, E. B.. 296, 319
Swanson, E. E., 226
Swanson, H. R., 339
Swanson, P. P.. 236. 249
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478
AUTHOR INDEX
Swanson, W. H., 365. 375
Swanaon, W. W., 241, 261
Swearingen, L. B.. 19, 32, 76,
77
Sweeney, O. R., 273, 278
Sweet, H. A., 346, 355
Sweetman, M. D.. 246, 252
Sweetser, R. H.. 125, 135
Sweetser, S. B., 76, 108, 110,
115
Swift. A. H., 454
Swift, R. W., 249
Swinehart, C. P.. 75. 96, 100
Swingle, M. C, 268, 278
Swisher, C. A., 227
Swisher, R. D., 77. 178
Switz, T. M., 449, 466
Swoap, O. P., 226
Sykes, W. P., 122
Symonds, J. E.. 393
Ssalkowsia, C. R., 227
Szegvari. A., 413, 418
Szeszich, L. von, 318
Tabem. D. L., 216, 228
Tafel. J., 156
Taft, R., 143, 150
Tamele, M. W., 339
Tammann, G., 23
Tanaka. T.. 367
Tangerman. B. J., 309, 322
Tanner, W. B.. 63. 75
Tarr, L. W., 439
Tartar, H. V., 142. 150, 179,
424, 436, 437
Tarvin, C. B., 372, 377
Tate, G. S.. 351, 356
Tattersfield, P., 268, 278
Tauber, H„ 246. 252
Tiiylur, B. S„456
Taylor. P, L., 202
Taylor, G. B., 30ft, 322
Taylrtr. G. G,. 76
Taylor. H. A., .^1, 35. 44, 180
Taylor. H, S., Se, 4:^, 76, 77,
7(», SOh 85, 84, SS, 89, 98,
101, 17a
Taylor, M., 349. 356
Taylor, M. W., 340, 251
Tsylor, N. O.. 147, 151
Taylor, J^. W., 76, 123
Taylor, T. I., 76
Taylor, T. C. 229. 348
Taylor, W.H.. 203,215
Ttal. G. K.. 56, 73. 77
Tcets, D. E., 57
Tefft, R. P., 412. 41S
Ttichmanti. C. P., 262, 278,
436
TdiDplctun, H, L., 343. 251
Tenqnhaum, D.. 20+
Tener, R. P,, #04. 417
Tennty. H. R. 305. 321
Teordl, T., 27, 32
Ttppenia. J., 403, 416
Tershin, J. A„ 36fl, 375
Terzian, H. G.. 2S5, 286. 316
Thayer, F. D . Jr., 109, 115
ThWer, S., 337
Theis. E. R.. 109, 115
Thews, B. R.. 142, 149
Thibodeau, W. B., 401, 416
Thiele, B. W., 338. 339
Thienes, C. H., 227
Thies, H. R., 397. 415. 418.
439
Thiessen. L.. 313, 323
Thode, H. G., 57
Thomas. B. H., 250
Thomas. C. A.. 267. 278. 357,
394. 397. 430. 438
Thomas. C. L., 338
Thomas, B. B., 98, 101, 181
Thomas, P. L., 269, 270, 278
Thomas, H. C, 14. 15. 31, 71.
77
Thomas. J. D.. 320
Thomas. J. E.. 227
Thomas. R. E., 396
Thomassen, L., 129, 136
Thompson, A. P., Jr.. 201
Thompson, C. D., 202, 394
Thompson, P. C, 22, 30
Thompson, H. B.. 180. 203.
393. 435. 439
Thompson. H. B.. Jr.. 17. 32.
76
Thompson. J. G.. 107. 116.
125. 135
Thompson, J. J.. 92. 100
Thompson. M. R.. 226
Thompson, M. S.. 433. 438
Thompson, T. B., 455
Thompson, T. G., 107, 115
Thompson, W. I., 319
Thomson, G., 142, 149
Thordarson, W., 253. 278
Thornton. N. V., 159, 161
Thornton. W. M. Jr.. 96.
100
Thorp. W. L.. 456
Thorssell. C. T., 182
Thum. B. B.. 136
Thuras. A. L., 393
Thurston. J. T., 204
Thurston. R. R.. 340
Tiddy. W., 292. 318
Tieszen, D. V.. 182. 204
Tilley. P. W.. 278
Tilley. J. N.. 147. 148. 150.
151
Timm. J. A.. 216
Timm. O. K.. 229, 248
Timmis, G. M., 226
Timson. G. H.. 236. 249
Tinker, J. M., 424, 435, 436
Tipson,R.S., 210,216
Tisdale, W. H., 264, 271, 274,
278
Tischler, N., 269, 278
Tishler, M.. 181, 198, 201,
204, 215
Titus, H. W., 243, 251
Tobin, B., 181. 203
Todd, T. W., 247, 248, 252
Todd, W., 358
Tolbert, L. A., 252
Tolle, C. D., 251
Tolman. R. C, 8. 44. 59. 74
Tomboulian, R. L.. 234. 249
Tomiyama. T.. 21. 32. 182.
215
Tomkins. S. S.. 295. 296. 319
Tomlinson. M. L., 213. 215.
217
Tomsicek. W. J.. 15. 21. 31.
75
Tongberg. C. C, 316, 323
Topfey. B., 143, 150
Torrance. P. M., 407, 417
Torrey, G. G., 245, 252
Totzek, P.. 317
Touceda. E.. 134, 137
Toulmin, H. A.. 445. 454
Toussaint, J. A.. 30, 32. 67,
180
Tower, M. L., 267, 279
Towne, C. C., 320
Townsend. H. B.. 369. 376,
410, 418
Tranter, G. D., 135, 135
TraveU, J., 22S
Travers, M. W.. 180
Trebler, H. A., 107. 1 16
Treichler, R. 23«, 250
Tremeame, T. H.h 65. 76
Tressler, D. K,. 252, 372. 377
Trigger, K. J.. 133, 137
Trimble, C. S.. 24^, 251
Trimble, P. H.. 122
Trimble, H. M., 76, 181. 338
Troeller. W. J,, 540
Tropsch. H., 179, 313, 323.
338
Tri^Lt, G. M,, 243. 251
TMK-5d;^]L-. E. C. 123
Trusty, A. W.. 339
Tschesche, R., 212, 217
Tu, a M,. 310, 322
Tucker, C. M., 122
Tucker. J. T. 455
Tucker. N. B.. 182
Tucker, R. P., 254, 279. 340
Tulcen. t. F., 112, 116
Tuley, W. R, 401. 403, 416
Turck. H, E.. IS. 30, 76
Turck.J. A.V..Jr.,204,215,
438
Turkington, V. H., 395, 439
Turner, C. P., 302, 321
Turner, L. B., 338
Turner, N. C., 296, 319
Turner, S. D., 339
Turrill, P. L..^455
Tuttle, M. H., 339
Tyler, C., 442, 446, 453, 457
Ullyot, G. B.. 201
Ulmann, A., Jr., 324
Ulrich, H., 367, 358
Umpleby, J. B., 297. 320
Underwood, H. G., 203, 217
Underwood, H. W., Jr., 88,
89. 202. 203
Unger. E. D.. 76
Upson, P. W., 76
Upthegrove, C., 122, 131, 136
Upton, G. B., 136
Urban, P., 26, 32
Urban, S. P., 125, 135
Urey, H. C, 37, 56. 73 . 77 . 98.
141. 149
Urmston. J.. 140. 149
VaKHeich, E. McC, 235. 249
Vat I, J. C, 347, 352. -i55, 356
Vflil.W.E.. 181.431.438
Valaer, P., Jr^^ 227. 228
vun Ackeren. J., 317
Van AUtinc, H. E„ 234, 249
Vnn dcr Pyl, L ., 30 1, 316, 32 1
Van Ijcvi-ntqr, F. M..338
Van Duiee, E. M., 86, 89
203. 437
Van Heuckeroth. A. W.. 396
van Hook. A.. 36. 44. 180
Van Horn. A. L.. 250
Van Horn. K. R.. 120. 122,
135
Van Klooster, H. S., 76
van Loenen, W. P., 158, 161
Van Rysselberghe, P.. 16, 32,
59. 74, 77
Van Vleck, J. H., 57, 58
Van Vorrhis, M. G., 340
Vance, J. E., 85, 89, 142, 149
Vander Wal, R. J., 215
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AUTHOR INDEX
479
Vanderbllt, B. M., 33&
Vanick, J. S., IM, IST
VHUuhan, W. E., 65, 74, 75,
m. 179, 180. 3134, 4^7
Vaughn, T. Hh. 181, 203, 393
Vcit<;h. F. P., Jr., ISl
VemoTi, C, C. 204
Veraon. H, C, 315, ^423
ViissekjVHky, V. V.. 44, 180
Vickcty, H. B., lOR, U5
Viffncatid, V, du, 210, 216,
231. 34g
Vilbratidt, F. C, 454. 455
Vilella. J. R., 13fl
Vinqcnt, J. E„ 181,203
Vmi?ii, R, P., 148, 151
Vittha,lp.. 181.204
Vivian. D. L., 183
Vo«t. C. L. 338
Vogt, E. R., 181,203
Volck, W. JI.. 2112. 279
Void, R. D.. 74. l7iJ
Volwiler, E. H., 210
Voorhees, V., 269, 279
Vopicka. E.. 216
Vorhaus. M. G., 237. 260
Vorhes, F. A., Jr., 279
Vosbureh, W. C, 76
Voskuyl, R. J., 100
Voss, A.. 180
Vries, O. de, 407, 417
W.idt^ell, J., 510
Wflde. W. H., \7\y
Wadlcigh, F. R., 324
WflgBUman. W, H., 457
Wfl^oer. C. 28
WaF^er, C. R.. ISO. 300, 320,
338. 330
IVaf^ner. E. C. 2H, 2ie
Wa^er, G. S., 265. 270
Wagner, G. H., 254. 279
Wahl, M. H., 77
Wakefield, H. P., 304
Wakeham. G., 227
WakelaDd, C 250, 270
Wftkeman, R. L., 179, 339
Waksuian. S. A,, 364. 375
Waldbauer, L., 112, 116
Wfildp, A. W., 22, 32, 66, 76.
375
Waldcn, G. B., 240
WaJdcn, G. H.. 57
Walden, G. H., Jr., 103, 105,
114, 11S< 122
Waldo, A. W., 131, 123
Wales. H-, 227. 22S
Walker, A. 0„ 101
Walker. C. K., lOfl, 115
Walker, H. G., 270, 274, 279
Walker, H. L., 143. 150
Walker, H , W., 273, 270, 382,
303, 3D4
Walker, I . F., 87, 89, 312, 322
Walker, J. C, 182, 301.320
Walker. J. T., lai. 198. 204
Walker, M., 205. 277
Walker. M. K., 74
Wallace. E. L, 109,116
Wallace, H. A., 297, 320
Wallace, L. W., 454
Wallenmeyci'. J. C,,251
Walling, C.T,. 201, 202
Wajlis. E. S.. 162, 160. 100,
203
Wallis, G. C., 241, 261
Walls, W. S., 67, 182
Walsh, J. P., 395
Walsh, W. L., 87, 89, 202, 215
Walter, L. A., 216
Walters, P. M.. Jr.. 119, 122,
127, 136
Walther, H. T., 126. 136
Walton, C. W., 407. 417
Walton, C. W., Jr.. 348, 365
Walton, J. H., 141, 149
Walton, R. P., 228
Wannack. C. O.. 320
Wantz, P. E., 216
Ward, A. L., 303. 304, 319,
321
Ward, A. M„ ISl
Ward. A. T., ,S96
Ward, C. E., 230, 24 S
Ward, J. S.. 407, 417
Ward, J. T., 33S, 330
Ward, K., Jr.. 182
Ward, N, R, 123
Ward low, R. H., 215
Warner, A. W.. 2SS, 317
Warner.J.C, 10,30,32,57,
77, 198, 204
Warren, G. E., 76, 181
Warren, G. P., 447, 466
Warren, H. W. H.. 396
Warren, L. E., 227
Warren, W. B., 289, 317
Warrick, E. L., 10. 32
Warrick, L. P., 366, 374, 376,
377
Washburn, E. R., 28, 31, 32,
76, 77, 181
Washburn, E. W.. 98
Washburn, T. S., 126, 132,
136, 137
Wasum, L. W.. 180, 396
Waterman, R. E., 212, 217,
237, 260
Watson, H. B., 181
Watson. K. M., 338, 339
Watson, P. D., 168, 161
Watson, W. N., 440, 466
Watt. L. A.. 466
Watts, A. R. 30a 322
Watts, O. O., 350. 356
Weare, J. H,, 19. 32, 77. 183
Webb, B. H., 243, 251
Webb, H. A., 109, 116
Webb, W. L., 10. 30
Weber, A. L., 259. 277
Weber, C. G.. 369, 370, 376
Weber, G. M., 445, 465
Weber, H. C., 169, 161, 299,
320
Weber, H. H. R., 230, 248
Weber, P., 338
Webster, R. L., 266, 279
Weed, A., 268, 276
Weger, M., 394
Wehmhoflf, B. L., 371, 376
Wehrle, G., 283, 316
Weidenbaum, B., 44, 179
Weidlein, E. R., 441, 443, 444,
446, 447, 460. 462, 463.
464. 466
Weigel, W. M., 465
WeU. C.. 368, 376
Weiland, H. J., 367, 424, 436
Weinbaum, S., 58
Weinberg, A. J., 225, 228
Weinland, C. E., 131, 136
Weinstock. H. H.. Jr., 201
Weisberg, L., 396
Weiser, H. B., 122, 123
Weiss, C. D.. 292, 318
Weiss, J. M., 318, 393, 397
Weiasbaua, S. Z., 438
Wcith. A. J,. 394
Weith, G. S., 390
Welch, A, D,, 228
Weld. L.D.H.. 450. 456
Wcldon, M. J., 133. 137
WeUer. S. L„ 416, 418
Wells. C. 119. 122, 130
Wells, R:H.*204
Wells, J, H., 321
Wells. S. D., 366, 375
Wells, W. H.. 130, 136
Wenker, H., 15fl, 161, 182,
203. 217
WenseL H. T.. 74, 145, 146,
149, 160
Wenzke. H. H., 30, 33, 67,
150, 202
Wenler, J. F„4J5, 418
Wemtz, J. H.. 180. 383, 393,
394
Wertheitn, E„ 204
West, C, D.. 74, 144, 150
West , C. J., 350, 374, 444, 464
West, C, K., 319
Wtut, D. H„ 101
West, R,, 236, 24 Q
West, W., 34,44
Wi!sUjott. B. B.. 338
WestRHte, W. A,. 267, 277
Westmnn, L. E,. 441, 453
Wetberill, J. P., 217
Wheeler, A,. 44, 85, 89, 179,
437
Wheeler. G. A.. 230, 250
Wheeler, R. V.. 36. 300. 320
\^T]eland. G. W., 38, 43, 67,
58. 198, 204. 205, 215
Whik^hart. J., 320
Wliipple, D,. 242, 251
Whipple, D. v., 250
Whipple, G. H,, 235. 249
White, A., 232. 233, 248 » 249,
White, A. E., 129, 130, 136,
137
White. A , H., 57, 76, 160, 162,
292,314,318,323,453,456
Whitt, A. McL., 90, 101
White, B. B*. 305, 397
White, C. B., 31ii, 323
White, E, G., 16:i, IflO
White, F. L., 216, 217
White. G.H., Jr., 152, 160
White. K. C. 363. 376
White. H. L., 26.32
White, J, D.. 339
White, R. C., 200, 278
White, R. P.. 266, 270
White, W. B., 259, 279
WTiite.W.H., 270,279
Whitehead. P. E„ 253, 279
Whitehead. H., 148. 161
Wh^(rV,.nirl r. B., 150, 160,
Whiteley, J. M., 338
Whitmore, P. C., 201, 203,
338, 437
Whitmore, W. P., 139, 149,
181, 202. 273. 276
Whitney. L. V., 74, 146, 160
Whitney, R., 463
Whittaker, R. M., 271, 279
Whittemore, E. R., 372, 377
Whittier. E. O., 229, 243,
248. 261
Wichers, E., Ill, 116, 138,
140, 142, 147, 149. 150
Wichmann, H. J.. 279
Wickcrt, J. N., 182, 425, 437
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480
AUTHOR INDEX
Wiebe, R,. 17, 32, 65, 75, 76
Wisdeabeck. k. U 283, 316
WlMKld, W. B . 406, 408,
400,417
Wiekud, H., ISK
Wiesi. J. L., 338
WicrteUk. J.. 362 H 374
Wietkr. K., ISI
Wieievich, P, J., 301, 320.
338, 42fl, 437
Wiggam. D. R., 3U7
Wjgncr. E, 8- Wl, 58
Wi^, B. O., H2. 149
Wikoft. H. L,,4Sfl
Wilcox* 1>. A., 450
Wikojt, L. v.. 105* 114
Wikon* R. L., ng, 122
WllcDX, W. D.,3^
WUcnjton, P,. 2^, 263, 264,
276, 277, 270
Wild. W,. 44
Wilder, P. N., 422, 436
Wilder, O. IT. M., 250
WiHner. E. L..SS
Wiles. R. H., 373. 377
Wiley* F.H.. U0< 116
wiiiidTn* c. J.. :m
Wilheliiiy,E,*H5. 150
WilldnB, E. S,, Jr,* 106. 115
Wiliard, H. H., 92, 100, 105,
110. Ill, 114. 115, 116
WillaTd,i.H35, 44, 179
Willets. W. R.. Zm, 373, 376,
WiUiitma, U., 5il
WUliams, D. B., 339
Williams, P. J., 123
WiUiams, P. M.. 371, 372,
?76, 377
Williams. G. D., 228
Williams, I., 264, 278, 382,
393, 394. 401. 402, 403,
404*411.413,416,417,418
WiUiams. J. C.,242, Jfll
Wimarns. J. H., 144, 145, 150
WUHama, J. S.. 312, 322
Williams. J. W., 30, 33. 159,
161^ 203, 361* 374, 394
Williams. K. T-. 107. 115
Williams* N.* 337
Williams, R. R., 205, 2J2, 214,
216.217,230,237,250
Williams* T. L.* 182
Williams, W. H.. 158,161
WilHcu. L, r., 283* 284. 285,
311, 316, 322
Willihnganz, E., 74
Willis. S. L., 456
Willits. C. O., 92, 100, 104,
114
Willoughby, C. E., 106. 115
Wills, P., 309, 322
Wills. W. H., 137
Willson, C. O., 339
Willson, E. A., 413, 418
Willson, K. S., 69, 75, 76. 91,
100
Willson, V. A„ 3fl&, 37fi
Wilson, C.C. 154* 161
Wilson, C. D.* 437
Wilson, C. J., 30, 32. fi7, 180
Wilson. C. L.. 17S
Wilson, E., 35, 43. ISO, 338
Wilson, E. B., Jr., 45, 57
Wilson, T., ISO
Wilson, J. B-* 181
Wilson, J. D., 255* 270
Wilson, J. E,. 129* 138
WUson, J. L,. 86, 80, ISO
Wilson. M. M„ 262* 278
Wilson, rx, 451* 453, 456
Wilsijp. P. J.. Jr.. 318
Wilacm, R. E., 30O, 320
Wilaoo. R, L.. 130, 136
Wilson* R. W., 339
Wil&m. T. L., 107, 115
Wilwn. W. C. 305
Wilson. W. S., 430* 438
Wdtftn, H. M.. 132, 137
Winchester. G. W,* 413, 418
Windaus. A., 213. 213, 217
Windsor, M. M,. M, 90. 100,
101
WinffCTt. W. B., 318
Winpfield, B,* 372. 377
Winifroki,B.T., 366,375
Wimmer,E. J.. 229.248
Winnek* P. S., 21. 31, 76
Winner, G. B., 265. 274
Winstein. S., 179
Winter. O. B., 106, 115
Winterstdner. 0„ 212, 217,
250
Wirth, C. 3rd., 339
Wirth, W. v.. 179
Wise, E. M.. 143, 146. 147,
148, 150. 151
Wise. L. E., 361. 374
Wiselogle. P. Y.. 184
Wisner. C. B.. 292. 318
Withrow. J. R.. 454
Witmer, E. E., 57
Wittenberg. L.. 318
Wittwer, M.. 357
Woglum, R. S.. 261. 279
Wohnsiedler. H. P.. 395
Wojcik. B. H., 420, 436
Wolfe, W. D., 405, 417
Wolff, W. A., 227
Womack, M.. 248
Wood. L. J., 98, 101
Wood, R. W., 56, 96, 101
Wood, S. E., 68
Wood, T. P.. 201
Wood. T. J., 134, 137
Wood. W. H.. 314. 323
Wood. W. P.. 130, 136
Woodbridge. D. B.. 57
Woodhouse. J. C, 181, 182
Woodruff, L. E., 313, 323
Woodruff, S., 243, 251
Woodstock, W. H., 395
Woodward, H. E., 419
Woodward, H. Q.. 106, 115
Woodward, T. D.. 429. 438
Woodward, J. E., 148, 151
Woodward. R. C. 133. 137
Woolgar, C. W., 339
WooUey, D. W., 182
Wooten, L. A., 21, 32, 113.
116. 181
Worden. E. C, 445. 454
Work. R. W., 97
Workman. D. M., 283, 284,
316
Worrall, D. E., 217. 228
WorstaU, R. A., 397
Worthley, H. N.. 272, 279
Wright. C. C. 291, 317
Wright. C. I., 227
Wright. P. R.. 304. 321
Wright. G. P., 180, 203. 421,
Wright, H. P.. 319. 337
Wright. J. G. E., 396
Wright, N.. 56
Wright, O. E.. 249
Wright, T. A.. 146, 150
Wriston. H, M.. 371, 376
Wuerti, A. J.. 425, 436
Wulf. O. H„ 56. 202, 207, 215
Wulff, R. G., 320
Wyckoff. R. D., 319
Wyckoff* R. W. G.. 117, 122
Wyirr, J. A.. 435
Wyman. E. T., 250
Wyman. J,* Jr.. 29. 31. 57,
75, 183, 2C12
Wynne- Jones, W. P. K.. 8. 9.
12, 17*32, 77
Yager, W. A. 67, 76
Yagoda, H., 08, 101
Yanick* N. S., 77
Yant, W. P.* 313. 323. 338
Yates, A.. 273. 270
Yeager, J. R* 2B3, 379
Yeaw. J. S., 311,322
Yeasen, T. D,. 126. 136
Voder, L. 260
Yoc. J. H.. 105, 114
Yohe, a. R., 181, 204
York, D. E.. 320
Yost, D. M,. 15. 31, 56, 62,
66, 75* 77* 90* 02, 93. 95,
100
Yothfirt* W, W.. 254. 260,
276. 279
Youker, M. A., 179. 300, 320.
436
Young. C. B. P.. 157, 161
Young. C. O.. 180. 181, 393
Young, G. H., 204
Young. G. W., 254, 279
Young, H. A., 12
Young, H. B.. 284. 316
Young. H. D.. 257. 265. 275.
279
Young. H. H., Jr.. 203
Young. H. R.. 396
Young, J. C, 75
Young, P.. 105. 110. 111. 114.
115, 116
Young, P. A.. 260. 261, 279
Young, R. C., 101
Young, R. v., 215
Young, V. A.. 256. 279
Young, W. G., 179
Young, W. W., 308, 322
Younger, K. R., 77
Youtz, J. P., 84, 89, 119. 122
Youtz, M. A., 153. 160. 372.
377
Yuen. K. C.. 227
Yuster. S.. 35, 44, 87. 89. 178,
179
Zachariasen, W. H., 181
Zahn, v., 339
Zane, A. H., 293, 318
Zavarine, I. N., 126, 131,
135
Zavertnik, J., Jr., 318
Zeisert, E. E., 257, 275
Zeleny, L.. 244. 252
Zervas, L.. 249
Zeigler. A.. 135. 137
Ziegler. P. K., 123
Ziegler, N. A., 126, 127, 135,
136
Zimmerli, A., 429, 438
Zimmerman, A., 456
Zimmerman, E. W., 369, 376,
445, 455
Zimmerman, P. W., 256, 266,
279
Zimmermann, P., 148, 151
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AUTHOR INDEX 481
Zimmermann, M. H., 403. Zittle, C. A., 20, 32. 183 Zschiegner. H. B., 148, 151
416 Zoellner. B. A.. 201 Zucker. M.. 396
Zinzade, C. 105. 114 Zoll, M. B.. 306. 321 Zuffanti. S., 202
Zinzow, W. A., 394 Zrike, E.. 216 Zwilgmeyet, P., 396
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SUBJECT INDEX
(This index is only a guide to the principal topics covered by the Survey.)
Absorption spectra
Infrared. 46
Ultraviolet, 49
Accounting in chemical industry, 451
Acetylenes. 169. 328
Polymerization, 36, 169. 379
Acids
Aliphatic, 174
Electrolysis, 152
Ionization constants, 21, 66
Acrylic resins, 382
Activity coefficients, 13, 64
Vapor pressure, computation from, 16
Adhesion tension in detergency, 348
Adhesives, rubber, 411
Adsorption, 82
Alcohol as motor fuel, 332
Alcohols, 171
Analytical tests, 172
Ring closure, 197
Sulfated, as detergents, 342
Aldehydes, 172
Identification. 188
Alicyclic compounds, 184
Alkaline pulpmg processes. 367
Alkaloids. 218
Alkyd resins. 390
Alkyl haUdes. 164
Alkylation. 429
Catalytic. 87
Allison effect, 54, 94
Alloys, x-ray studies. 129
Amalgam cells. 15
Amides, 177
Amination, 420, 425
Amines, decomposition, 34
Amino adds. 177
Calorimetric measurements. 20
Compressibility of solutions. 23
Food value, 230
Ionization constants, 21
Solubility. 19, 20
Ammonia
Gas, removal from, 294
Liquid, as solvent, 96
Structure. 47
Anabasine, 268
Analsrtical chemistry, 102
Apples, 245
Argon, compounds of, 91
Arsenicals, 253
Asparagus, 245
Asphalts, 336
Atomic reactions, 37
Attract ants, 266
Azomethane
Decomposition, 34
Explosion, 38
Bagasse, 363
Bakelite resins. 385
Beating of pulps. 367
Benzene
Structure. 48
Substitution rule. 198
Thermal decomposition. 35
Benzoxazoles, 212
Blackberries, 246
Blast furnace operation, 124
Bleaching agents, 353
Bleaching of pulps, 368
Bond energies, 37
Boron compounds, 97
Bread. 244
Brewing, 244
Broccou, 24Q
Bromination, 422
Butane motor fuel, 331 *
Butter. 243
Buttermilk. 243
Cadmium in seed disinfection, 256
Caffeine ethers, 225
Calcium. r61e in metabolism. 234
Calcium chloroarsenate, 254
Cameras, x-rays, 118
Cannizzaro reaction, 194
"Crossed", 199
Carbazoles, 207
Carbohydrates, nutritional value. 229
Carbon black, 407
Carbon fluorides, 95
Carbon monoxide, analysis, 313
Carbon steels, 128
Carbonyls, 99
Carcinogenic compounds, 191
Camosine, 210
Carotene, 236
Cast iron, 133
Cast steel, 133
Catalysis, 8
Platinum metals in, 141
Catalysts, surface properties of, 83
Cellulose, 359, 361
Esters, 363
Cements, rubber, 411
Cheese, 244
Chemical economics, 440
Education in, 442
Research in, 442
Sources of statistics, 443
Chemical engineering economics, 446
Chemical industry, financial aspects, 451
Chemical kinetics, r61e of entropy, 9
Chemicals
Distribution. 449
Foreign trade, 450
Chlorination, 421
Catalytic, 87
Kinetics of, 35
Chlorine bleaches, 353
Chloroform, oxidation of, 36
Chloropicrin, 266
Chloroprene, 382
Chromium compounds, 94
Cinchona alkaloids, 221
Citrus fruits, 244
Coal
Carbonization, 287
Chemical structure, 290
Decomposition products, 290
Dust proofing, 337
Properties, 288
Coal coke, 287
483
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Google
484
SUBJECT INDEX
Coal ^as. 287
Codeine iaomen, 221
Cokes, 280
Colorimeters, photronic, 105
Colorimetry, 105
Commodity prices, 447
Compressibility, 22, 64
Concentration cells, 13, 71
"Condensation" resins, 384
Conjugated systems, 185
Contact catalysis, mechanism, 79
Copper catalysts, 81
Copper insecticides, 255
Corrosion, 129
Bearing, 336
Gas systems, 302
Petroleum industry, 326
Cracca firginiana, 271
Cranberries, 245
Critical constants, 64
Croton resins, 272
Crystal formation, mechanism of, 104
Crystal structure
Metals and alloys, 120
Platinum metals, 144
Cuscohygrine, 225
Cyanides, fumigation with, 264
Cyamne dyes, 212
Cystine, 231
Cytoeine, 210
Dates, 244
Depolarizers, organic, 160
Derris, 269
Deteigency, factors of, 347
Detergents, 341
Tests, 346
Theory of action, 349
Deuterium, 98
Exchange reactions, 79
Deuterium compounds,
AUphatic. 163
Raman spectra, 46
Thermodynamics pf , 72
Diama^etism, 52
Diazotization, 420
Dibenzofuran, 206
Dielectric constants, 29
Velocity constants, relation of, 10
Dielectrics, organic, 159
Diels- Alder reaction, 199
Diffusion, 27
Metals, 120
Dimorphism, 67
Dipole moments, 51
Dithiazanes, 212
Duprene, 382, 414
Eggs, 242
Electric moments, 30, 51
Benzene substitution, relation to, 51
Electrical conductance, 24
Electrochemistry, organic, 152
Electrode potentials, 16, 71, 108
Electrodes
Antimony, 109
Perrocyanide-ferricyanide, 15
Glass, 108
Hydrogen, 109
Quinhydrone. 14, 109
Silver chloride, 109
Silver-silver bromide, 13
Silver-silver iodide, 13, 71
Electrolytes
Compressibility of solutions, 22
Thermodynamic properties, 12
Electrolysis of gas pipe systems, 302
Electrometric titrations, 108
Electromotive force, 12, 70
Electron diffraction, 45
Electroplating with platinum metals, 142
Electrothermal processes, oiganic, 158
Elements, transmutation, 90
Energy of activation, rftle in chemical ki-
netics, 9
Entrophy, rdle in chemical kinetics. 9
Enzymes, value as detergents, 352
Ergot alkaloids, 218
Easterification, 430
Esters, 176
Ethers, 175
Ethyl nitrite, decomposition, 34
Ethylene, polymerization, 36
Ethylene oxide, fumigation with. 265
Explosions
Theory of, 38
Thermodynamics, 59
Fabrics, cleaning tests, 346
Factories, location of, 446
Fats, metabolism of, 229
Pigs, 246
Pish. 242
Flour, 244
Fluorescence analysis, 112
Fluorination, 422
Fluorine
Analysis, 107
Compotmds, 91, 92, 95
Insectiddal values, 256
Poods, 229
Free radicals, 187
Friedel and Crafts reaction, 194, 433
Fries' migration, 434
Fruits, 244
Spray residues, removal of, 258
Fuels
Economics, 448
Gaseous, 280
Petroleum, 325
Fungicides, 253
Synthetic. 262
Furans. 205
Gallium compounds, 97
Galvanic polarization, 25
Gardinols, 343
Gas
Analysis, 312
Combustion of. 309
Composition, 311
Distribution of, 301
Heat treatment with. 308
Heating with, 307
Purification, 294
Utilization, 306
Gas appliances, 303
Gas burners, domestic, 309
Gas holders, 295
Gas mixtures, statistical mechanics of, 7
Gas plants, purging, 296
Gas producers, 292
Gas reactions, kinetics of. 33
Gas storage, 295
Gas systems, corrosion in, 302
Gas tars, 293
Gases
Adsorption, 82
Platinum metals, 140
Diffusion through platinum metals, 140
Electron diffraction, 46
Homogeneous equihbria, 65
SolubiUty, 17, 68
Gasoline, 330
Alcohol and, as fuel, 332
Antioxidants, 334
Distillation, 334
Manufacture, 333
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SUBJECT INDEX
485
Gasoline, natural, 333
Glycerol-phthalic anhydride resins, 390
Glycol, 172
Glyoxal, decomposition, 34
Grapefruit, 246
Grapes. 246
Grignard reaction, 187
Halogen compounds, 92
Halogenation, 421, 427
Heat capacities, 20, 60, 62
Heats of adsorption, 83
Heats of combtustion, 62
Heats of fusion, 62
Heats of hydrogenation, 63
Hematopoietic substances, 236
Heterogeneous reactions, kinetics of, 85
Holocellulose, 362
Hydration of pulps, 367
Hydrocarbons
Aliphatic, 164
Chlorination, 166, 327
Classification, 165
Electronic structure, 166
Identification, 188
Ionization potential, 165
Nitration, 327
Oxidation mechanisms, 165
Petroleum, 326
Photobromination, 166
Physical properties, 167, 330
Pyrolysis, 165, 169, 299, 327
Rubber, 399
Hydrogen, ortho-para conversion, 80
Hydrogen ion concentration, 22
Hydrogen ion meter, 108
Hydrogen isotopes, 72
Hydrogenation, catalytic, 86, 197
Hydrolysis, 432
Velocity of, 11
Ice, entropy, 65
Igepons. 342. 344
Imidazoles, 209
Indicators, 103
Indium compounds, 97
Indoles, 207
Infrared spectra, 46
Insecticides, 253
Spreaders, 259
Sjmthetic, 262
Interfactial tension in detergency, 348
Internal combustion engine fuels, 330
Inversion, velocity of, 11
Iodine, r61e in metabolism, 236
Ionic mobility, 27
Ionic reactions, bimolecular, theory, 10
Ionization constants, 21
Iridium, 139
Iron
High purity, 126
Metabolism, r61e in, 236
Iron-carbon alloys, 126
Iron-chromium alloys, 128
Iron-copper alloys, 127
Iron-manganese alloys, 127
Iron-silicon alloys, 127
Isomerization, kinetics of, 33
Isoprene, 383
Isotopes
Hydrogen, 72
Oxygen, 93
Platinum metals, 144
Reaction mechanisms, use in study of, 12
Thermodynamics of, 72
Joule-Thomson effect, 64
Ketones, 172
Cleavage, 196
Electroljrtic reduction, 166
Identification, 188
Oxidation-reduction potential, 191
Ketoximes, 177
Kolbe synthesis, 162
Korolas, 414
Koroseal, 414
Lactide resins, 384
Larvicides, 264
Latex. 412
Lead, microanalysis, 106
Lead arsenate, 263
Lead sulfate, precipitation studies, 104
Light oils. 300
Lignin, 364
Lime-sulfur sprays, 267
Lipases. 229
Lipoids. 230
Low temperature studies, 60. 61
Lubricants, testing. 336
Lubricating oils. 335
Lupine alkaloids, 225
Lysergic acid, 218
Magnesium, r61e in metabolism, 236
Magnetism, 62
Magneto-optic effect, 54, 94
Manganese, rfile in metabolism, 236
Martensite, 127
Meats, 242
Mechanical pulp, 366
Merchandizing research, 448
Mercury disinfectants, 266
Metallurgy
Ferrous, 124
X-ray studies, 117
Metals
Constitutional diagrams, 120
Crystal orientation in, 120
Electrodeposition from organic solutions,
167
Grain distortion in, 120
Inspection by x-rays, 121
Solubility relations, 120
Meter diaphragms, 306
Methane
Pyrolysis. 33
Structure, 47
Methanol, synthesis, 171
Methionine, 231
Milk, 243
Minerals, role in metabolism, 234
Molecular polarization, 29
Molecular rearrangements, 188
Molecular rotation, theory of, 49
Molecular structure, 46
Molecular vibrations, theory of, 49
Morphine
Isomers, 221
Physiological action, 222
Mothproofing, 273
Moving boundaries, 26
Naphthalenes, sulfonated, 346
Naphthenes as detergents. 346
Narceine. 224
Narcotine, 224
Natural gas, 296
Nephelometry, 106
Nicotine, 220, 267
Nitration, 419
Nitro compounds, electrolytic reduction, 164
Nitrocellulose, 363
Nitrogen chloride, thermal decomposition, 33
Nitrogen compounds, organic, 176
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486
SUBJECT INDEX
Nitroao compotmds, electrolytic reductton,
154
Nitrous oxide
Decomposition, 40
Oxidation, 40
Novolak. 386
Nucleotides, 210
Oil emulsions as insecticides, 260
Olefins. 167. 328
Condensation reactions. 329
Poljrmerization, 328
Opium
Alkaloids. 221
Assay. 224
Orange juice. 245
Organic matter, destruction in analysis, 113
Oi^no metallic compounds, 191
Electrolysis, 156
Osmium. 139
Atomic weight. 139
Osmotic coefficients, 16
Overvoltage, 140
Oxidation. 426
Catal3rtic. 86
Electrolytic. 152
Gaseous, kinetics of. 35
Oxidation potentials, 15
Oxidimetry, indicators for, 105
Oxime formation, 173
Oxygen isotopes. 93
P-V-r relations, 64
Palladium. 139
Papain, 233
Paper, 359
Fiber analysis, 373
Permanency, 368
Properties, 369
Testing, 371
Paramagnetism, 52
Paris green homologs, 253
Peroxide effect, 170
Petroleum. 325
Cracking. 334
Petroleimi solvents, 337
Petroleum spray oils, 260
Phenanthrene derivatives, 192
Phenol-formaldehyde resins, 385
Phenols, identification, 188
Phenothiazine, toxicity, 253
Phosphates as detergents, 345
Phosphorus, rdle in metabolism. 234
Photochlorination, kinetics of, 35
Photolysis, 35
Physostigmine, 208, 220
Pig iron, 124
Pineapples, 246
Piperazines, 211
Plastidzers, 401
Plastics, synthetic, 378
Uses. 392
Platinum metals, 99, 138
Analysis. 111. 138
Industrial uses. 146
Physical properties, 143
Plioform. 391
Polycumarone, 381
Polyindene. 381
Polymerization, 170, 193, 328, 378, 434
C5atalytic, 87
Kinetics of, 36
Polymorphism, 67
Porphjrrms, 208
Propane
Decomposition, 35
Oxidation, 36
Propane motor fuel. 331
Propylamine, decomposition, 34
Protactinium, 91, 95
Proteases, 230
Proteins, 230
Nutritive efficiency, 233
Prunes, 246
Pseudoephedrine, 224
Pseudomorpfaine, 223
Pulp testing, 371
Puzines, 209
Pyrethrum. 268
Pyridines. 209
Pyrimidines. 209
Pyrolysis, 169, 193, 299, 327
Pyrroles. 207
Quantum numbers, 53
Quinazolines, 211
Quinolines, 209
Radioactive elements as indicators, 103
Raisins, 246
Raman effect, 46
Rare earths. 98
Raw materials. 445
Reaction velocity
Liquid systems. 8
Theory of, 7
Reduction, electrolytic, 154
Refinery oil gas. 284
Reformed gas, 283
Repellents, 266
Research, technological. 444
Resit. 385
Rhodium, 139
Roach powders, 257
Rotation, energy of, 41
Rotenone, 269
Rubber, 398
Age resisters, 404
Compounding ingredients, 407
Dispersion of, 412
Hard. 412
Plastidzers, 401
Reclaimed, 411
Synthetic, 414
Technology, 410
Testing, 405
Vulcanization, 401
Accelerators, 402
Rubber articles, 412
Rubber derivatives, 391
Ruthenium, 139
Salt error, 14
Salting out effects, 18
Salts, solubility of, 18
Seed disinfectants, 256
Selenium
Analysis, 107
Poisoning by, 236
Insecticides, 257
Shellfish, 242
Silicon compounds, 96
Silver, oxidation states, 99
Sinking time test, 348
Sizing of paper, 368
Slime in pulp mills, 374
Soap builders, 351
Soap solutions
Activity coefficients, 16
Properties, 349
Viscosity, 348
Soaps, 341
Deflocculating power, 349
Molecular weight. 349
Sodium hexaphosphate in soaps, 352
Sodium lauryl suuate, 342
Solubility. 68
Gases, 17
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SUBJECT INDEX
487
Solubility
Limits, x-ray studies, 119
Non-aqueous solutions, 19
Solutions
Compressibility, 22
Heterogeneous equilibria, 67
Solid, thermodynamics of, 17
Theories of, 7
Thermodynamics of, 12, 61
Sorbite, 127
Soybean milk, 245
Spectro|rraphic analysis, 110
Sponge tron, 125
Spray residue removal, 268
Stainless steels, 130
Steel
Age hardening, 131
Analysis, 112
Corrosion-resistant, 130
Creep properties, 129
Grain size, 132
Heat treatment, 131
High speed, 133
Inclusions, 125
Inspection by x-rays, 121, 135
Manufacture, 124
Nitrided, 128
X-ray studies, 120
Stereoisomerism, 197
Styrene polymers, 381
Sugar industry, 246
Sugars, electrolytic oxidation, 153
Sulfite process, 365
Sulfite waste liquors, 366
Sulfonated oils, 342
Sulfonation, 423-
Sulfur
Compounds, 93
Organic, 178
Insectiddal value, 263
Insectiddal value, 257
Surface conductivity, 26
Surface tension, 28
Detergency, rftle in, 348
Sweet potato, 246
Tautomerism, 200
Tellurium compounds, 93
Temperature scales, 145
Thermochemistry, 69
Thermocouples, 61, 145
Thermod3mamics, 69
Thiazoles, 212
Thiokol. 414
Thiourea resins, 388
Titanium compounds, 96
Tomatoes, 246
Tool steels, 133
Tomesit, 391
Trinitrides, 94
Troostite, 127
Tyrosinase, 233
Ultraviolet spectra, 49
Urea resins, 388
Vapor phase gums, 304
Vapor pressure, 67
Activity coefficients from, 16
Vasicine, 220
Vegetables, 244
Vinyl ester polymers, 380
Vinylacetylene, 379
Viscosity, 28
Vitamin A, 236
Vitamin B, 236
Vitamin Bi, structure, 212
Vitamin C, 239
Vitamin D, 236
Vitamin E, 241
Vitamin G, 238
Valence, quantum mechanics of, 63
Volumetric analvsis. 111
Voltaic cells with organic electrolytes, 159
Vulcanization, 401
Accelerators, 402
Water, structure, 47
Water gas, 283
Carburetted, 285
Heavy oils in, 285
High-hydrogen, 286
Water gas tar, 285
Weed lallers, 274
Wetting agents for insecticides, 269
Whey, 244
White water (paper mills), 374
Wines, 246
Wood, properties of, 360
Wood preservatives, 273
X-ray photographs, interpretation of, 45
X-ray spectra, platinum metals, 144
X-ray studies, equipment for, 118
Zinc, rdle in metabolism, 236
Zinc arsenates, 254
Zinc fungicides, 256
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