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HERBERT SPENCER HARNED
December 2, ~ 888 July 29, ~ 969
BY JULIAN M. STURTEVANT
HERBERT SPENCER HARNED started graduate work in
chemistry at the University of Pennsylvania shortly
after the introduction into this country of the theoretical and
mathematical approach to chemical problems emboclied in
physical chemistry. His doctoral research was in preparative
inorganic chemistry under the direction of Edgar F. Smith,
but before he started this work, he spent a brief period in the
laboratory of Joel H. Hildebrand. This apprenticeship with
Hildebrand appears to have played a major role in steering
his interests away from classical chemistry, toward the newer
physics-oriented discipline.
Hildebrand, after obtaining his Ph.D. at Pennsylvania in
1906, hack studied with Walther Nernst in Berlin, and after
returning to Philaclelphia, had instituted a program of re-
search and instruction in physical chemistry. In Hildebrand's
laboratory, Harned worked on a titrunetric method for the
determination of magnesia in limestone, and a joint publica-
tion, Harned's first, resulted from this work in 1912. This
research involved the use of the hydrogen electrocle, with
measurements of potential to an accuracy of only ~O-2 volt.
Harned was confident that measurements with this electrode
could be carried to much better levels of accuracy, and an
important part of his later scientific work consisted in show-
215
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216
B I OG RA P H I C A L M E M O I RS
ing that the hydrogen electrode could be utilized in a wide
variety of electrochemical cells having potentials stable and
reproducible to i0-4, or even 10-5 volt. This drive toward
experimental perfection and accuracy characterized Har-
ned's long-continucc} studies of electrolytic solutions. His pri-
vately states] aim was to obtain thermodynamic data that
could stanc! unchallenged! for decades, and he certainly
achieved this aim in abundant measure.
Herbie, as he was always known to his countless friends,
was born on December 2, IS8S, in Camden, New Jersey, the
son of Augusta Anna Traube! Harned and Thomas Biggs
Harned. Herbie was the youngest child in the family, with a
sister, Anna, ten years older than he, ant] a brother, Thomas,
· · .
SIX years 11S SenlOr.
Herbie's mother and father, as well as other Harneds, had
been very close to the poet Walt Whitman. Herbie's mother
was hostess at the Whitman dinners which were held every
Sunciay night in the Harned home. She was the one who held
the Whitman coterie together, ant] the hostess who sat next
to the poet at his seventieth birthday party. Although Herbie
was only four when Whitman cried, and one of his few
remembrances of Whitman was his being frightened by the
poet's beard, he was always very proud of his parents' inti-
macy with the poet. Herbie's lifelong interest in literature was
doubtless in large part clue to the influence of parents and
relatives who were intimate with literary figures such as
Whitman.
When Herbie was five years old, the family moved to
Germantown, an outlying section of Philadelphia. His father
established a successful law business in downtown Philadel-
phia. The Germantown household was a lively place, with a
succession of dinner parties and dances. Although Herbie, as
the youngest member of the family, was for many years only
a spectator of these events, the constant presence of guests,
OCR for page 217
HERBERT SPENCER HARNED
217
many of them distinguished individuals, made a deep im-
· ·
presslon on elm.
Herbie was a boy of slight build, but under the tutelage of
his brother Tom he developed early a knack for sports
requiring sharp eyes and good coordination to the point
where he became a match for boys of larger physique, espe-
cially in tennis and cricket. The family lived close to the
Germantown Cricket Club, where excellent instruction ant!
facilities in a wide variety of sports were available. Among
Herbie's playmates in Germantown were several boys, includ-
ing William Tilden, who later became outstanding athletes.
Herbie was fond of telling how he defeater! Bill Tilden at
tennis when he was fourteen years oIcI, and Bill was eleven.
At about this time, Herbie began to show a real talent for
cricket, ant! he devoted much time to the sport until he was
twenty-six. He played on various teams, in prep school and in
college, and on f~rst-cIass amateur teams organizer! at the
Germantown Cricket Club. He playecl against numerous
American teams, as well as against outstanding English,
Canadian, Australian, and Bermudan teams, both in this
country ant] abroad. Once in a match in Bermuda, he batted
an entire inning, making ~ ~ 3 runs not out, his greatest
achievement in the sport. Herbie felt that cricket taught him
a great clear that carried over into his professional life. It
emphasized fair play and good sportsmanship; it showed him
that by hare! practice with careful attention to form, he couIc!
overcome the disadvantage of his relatively small stature;
and it required playing not only on the team, but also for the
team.
Herbie's father became seriously ill in 1910, and never
fully recovered his health, with the result that the family
circumstances became very straightened. It is a good inclica-
tion of the calibre of this man that although he was going
heavily into debt to keep his family together, he nevertheless
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218
BIOGRAPHICAL MEMOIRS
donated his very valuable collection of"Whitmania" to the
Library of Congress. In 1914, Herbie's mother, to whom
Herbie was most cleeply attached, diect of cancer. The home
in Germantown ant! other properties were sold to retire
debts, and the family moved to an apartment in German-
town. Since Herbie's elcler brother had gone to Chicago, the
responsibility of maintaining the family fell primarily on
Herbie. It was this responsibility, according to his own ac-
count, that stimulates! him to adopt a very serious and deter-
mined approach to his preparation for a professional life.
In the fall of 1915, Herbie met Dorothy Foltz of Chestnut
Hill. A year later they became engaged, and they were mar-
riec! on September 8, 1917. Dorothy, who survives Herbie,
prover! to be the ideal wife for a young man deeply involved
in establishing a scientific career, with the long hours of
extra-familial activity involved in that pursuit. Herbie's
father, by then nearly seventy, lived with the young couple,
and a close relationship soon developer! between him and his
daughter-in-law.
Herbie became a captain in the Chemical Warfare Service
in June 1918. After two months at the cws establishment at
the American University in Washington, during which he
wrote a long report on phosgene, he was sent to France. A
period of field training was followed by duty at the central
research laboratory of the American Expeditionary Force
near Paris. A number of lasting friendships were made with
chemists stationed there. A study of the kinetics of adsorption
of gases on charcoal which Harned started at this laboratory
was completed after his return to the States. This was a pio-
neering effort in this field ant! has been frequently cited.
Herbie's father died in September 1921. A very close
father-son relation had cleveloped, most particularly since
Herbie's return from France, and this was another keenly felt
tragecly.
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HERBER r SPENCER HARNED
219
To return now to Harned's educational and professional
careers, it is evident that he received much preschool training
at home. He has particularly singlecl out as of incalculable
value to him the instruction his mother gave him in arithme-
tic before he went to school at the age of nearly seven. His
success in learning arithmetic gave him confidence in un-
clerstancling any kinc! of school work. After three years at a
small school run by two Misses Knight, he was sent to the
Penn Charter School, an excellent Quaker preparatory
school in Philadelphia, where his course was strictly classical,
with no hint of science. He has stated that his teachers there
were all excellent, and that after his strict training there, he
found his college courses to be quite easy.
In 1905 Herbie entered the University of Pennsylvania,
where in his freshman year, although he continuer! with his
classical studies including Greek ant! Latin, he had his first
contact with science. He took the course in chemistry and was
immensely impressed by the accuracy of the measurements
which fixed the composition of air and water to the extent
that he decided to pursue a career in science. By the time he
became an upperclassman, his two major interests were
chemistry and literature, the latter from an entirely nonpro-
fessional point of view.
Harned graduated from college in 1909, and, as noted
above, stayed on at Pennsylvania for graduate work in chem-
istry. Three of his teachers in graduate school he has singled
out as having had an especially great influence on him. Two
of these, Edgar F. Smith an(l Joe! H. HildebrancI, have al-
rea(ly been mentioned. The third was a philosopher, Edgar
Singer. His course on the history of modern philosophy was
considered by Harned to be the best seminar course he ever
had, and lee! him to take several adclitional courses with
Singer. His experience in these courses gave him a viewpoint
which significantly motivated his later professional career:
OCR for page 220
220
BIOGRAPHICAL MEMOIRS
search for the most fundamental quantity you can find and
then measure it with the highest accuracy you can achieve.
Some years later he discoverer! this quantity, the chemical
potential, in the work of [osiah Willard Gibbs, and the major
portion of his research career involvecl the accurate measure-
ment of this quantity.
In summarizing his studies in philosophy, Harned wrote
that after being tossed this way and that by the conflicting
views of nineteenth century philosophical thought, there was
only one mode of thought and action to which he could
subscribe. This was the quantitative method of science, as
exemplified in the work of Copernicus, Galileo, Kepler and
Newton. There was beautifully illustrates! here the impor-
tance not only of fundamental laws and theories, but also of
accurate observations and measurements.
Harnecl obtained his Ph.D. in 1913. In that same year,
Hildebrand left Pennsylvania to join the faculty at the Uni-
versity of California at Berkeley, and Harned was macle an
instructor and head of the Physical Chemistry Division at
Pennsylvania. As was more frequently the case in those clays
than now, he was saddled with an extremely heavy load of
undergraduate ant! graduate teaching. There were approxi-
mately forty students in his undergracluate course in physical
chemistry, and since the laboratory only accommodated ten
students, he hac! to clivicle the group into four sections, each
of which spent many hours a week in the laboratory. All of
this, combined with graduate lectures, constituted a tough
assignment, carrier! with far 1~.~s heln from teaching assistants
than is customary tociay.
r
_O ~
It is a clear measure of the strength of Harne(l's dedica-
tion to research that within two years, despite these formida-
ble teaching~duties, and working entirely on his own, he was
able to publish a pioneering twenty-two page paper on the
precise (+ ]0-4 volt) utilization of the hydrogen and calome!
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HERBERT SPENCER HARNED
221
electrodes in the determination of the activities of hydrogen
and hydroxide ions in neutral salt solutions. This paper, in
which he showed without any doubt that the law of mass
action was not applicable for calculating ionic equilibria in
solutions of strong electrolytes, attracted much attention and
spurred visits by chemists from other universities to his labo-
ratory. All of this served to bolster his self confidence at the
threshold of his career, and to confirm his belief that he had
initiated an important program of research.
It was evident to Harned that a definitive interpretation
of the results obtained in this first work was hampered by the
presence of small but unknown liquid junction potentials. In
the following year, 1916, he published his first paper on
electrolyte activities determined using cells without liquid
junction, and he continued using such cells, in a steadily
expanding diversity of applications, over the next forty-odd
years.
Harned wished to avoid too narrow a specialization at this
period in his career. His papers on conductimetric titrations
~19~7 and 19~ 8) constituted the first utilizations in this coun-
try of a conductance bridge in chemical analyses. Also in
1918, just before entering the army, he published his first
paper in the field of reaction kinetics in solution. He re-
turned briefly to reaction kinetics several times in later years,
but as one may infer from remarks he made, not as fre-
quently as he would have liked.
Harned's remaining years at Pennsylvania became in-
creasingly productive, and by the time he left there to go to
Yale University in the fall of 192S, he had published thirty-
four papers. After a long period of working alone, he finally
began to have collaborators, both graduate students and peo-
ple of more advanced standing. In 1924 Gosta AkerIof came
from Sweden to his laboratory on the recommendation of
Svante Arrhenius. He remained in close association with
OCR for page 222
222
BIOGRAPHICAL MEMOIRS
Harned for more than twenty years at Pennsylvania and Yale,
although he worked essentially indepenclently after receiving
his Ph.D. In 1927 Robert A. Robinson came as a Common-
wealth Fellow from Birmingham, EnglancI. He and Harned
maintained throughout the rest of Harnect's career a close
relation that culminated in the joint publication of a mono-
graph on multicomponent electrolyte solutions in 1968.
During these years, he made systematic measurements of
the activity coefficients of strong acids and bases, in both
dilute ant! concentrated solutions, in the presence of neutral
salts. He discovered useful regularities in these systems, one
of which has come to be known as Harnecl's rule. This states
that in solutions of constant total ionic strength, the loga-
rithm of the activity coefficient of one solute is clirectly pro-
portional to the concentration of the other. This was to be a
matter of continuing interest to him, and three of his last
papers, published between 1959 anc! 1963, are concerned
with the effect of temperature on such systems. It should be
added that Harned was well aware that this rule is not uni-
versal, and that caution must be exercised in its application.
In this period he initiated his work on the thermodynam-
ics of electrolytes in mixed solvents with a stucly of hydro-
chioric acid in water-ethanol mixtures. This work was greatly
extended in later years, culminating in a series of papers,
publisher! from 1936 to 1939, concerning hydrochloric acic!
in water-dioxan mixtures containing as much as 82 weight
percent dioxan Dielectric constant about 10 at 25°~.
Harnecl has written that he regarcled the year 1927-28,
his last year at Pennsylvania, as the most fruitful one in his
scientific life. A graduate student, John M. Harris, ikerIof,
Robinson, and he worked jointly on four separate topics: the
use of amalgam electrodes in studying the thermodynamics
of solutions of electrolytes; the thermodynamics of solutions
of mixtures of electrolytes at high concentrations; the first
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HERBERT SPENCER HARNED
. . .
223
application of cells without liquid junction to determine the
Ionization constants of weak electrolytes; and the investiga-
tion of neutral salt effects in homogeneous catalysis. During
this year, ideas anct methods were developed which were later
widely employed not only in his laboratory, but in many
others arounc! the world.
Although his research was going very well, HarnecI
deciclect to accept an offer from Yale. He felt that this move
would significantly expand his research opportunities. There
was available in the Sterling Chemistry Laboratory, then only
five years old, what seemec! like almost unlimited space for
his laboratories; he was assured of initial financial support in
his research which quite surpassed that to which he was ac-
customecl; and it seemed probable that he could expect to
have a good group of graduate students as colleagues.
Immecliately on arrival at Yale, Harned, in harmonious
cooperation with the other physical chemists on the staff,
carried through revision of the graduate program in physical
chemistry. He was determined that the orientation of this
program should be exclusively toward pure research, with a
firm basis in the mathematical and theoretical aspects of the
subject. He eliminates! everything in the nature of conven-
tional undergraduate courses from the graduate program.
Harned's arrival at Yale coinciclec! with the start of a vigor-
ous university-wide expansion in plant and program. He has
written very approvingly of what the president, James Row-
land Angell, and the graduate dean, Wilbur Cross, accom-
plishecl for the university, particularly in bringing about a
remarkable upgrading of the graduate school.
r shall take the liberty of inserting here some personal
comments. ~ went to Yale as a graduate student in chemistry
in 1927, and joined the staff in 1931. I therefore had fre-
quent contact with Herbie until his retirement in 1957. There
is no doubt that, despite the general growth of the University
OCR for page 224
224
BIOGRAPHICAL MEMOIRS
referred to above, his own initially promising situation at Yale
began to deteriorate a few years after he arriver! there as a
result of decreasing financial and administrative support for
his own research program and for physical chemistry in gen-
eral. The Chemistry Department entered a period of decline
relative to chemistry departments at other institutions and to
other science departments at Yale. Fortunately, a goodly
stream of graduate students continued in physical chemistry,
most of whom worked with Harned. It is greatly to his credit
that despite the cliff~culties inherent in the situation, he re-
mainec! a very productive scientist.
This period of relative quiescence of the Chemistry
Department was enlivener! by a few very important events.
The first of these Harned consiclerect to be the single most
important thing he accomplished at Yale. In 1931 he received
a letter from Lars Onsager stating that clue to financial exi-
gencies, he was losing his post at Brown University. Within
hours Harned hac! arranged the offer of a Sterling Fellow-
ship to Onsager which, most fortunately for Yale, was ac-
ceptecI. Needless to say, this fellowship was soon converted to
a permanent position on the faculty.
In 1945, largely through Harnecl's efforts, Raymond M.
Fuoss was persuaded to leave the central research laboratory
at General Electric to join the Yale faculty. His aciclition to the
staff made certain the preeminence of Yale in the physical
chemistry of electrolytes.
In 1951, after the retirement of Arthur I. Hill as chair-
man of the Chemistry Department, the university was most
fortunate in persuading John G. Kirkwood to come from the
California Institute of Technology to serve as chairman.
There ensued a period of very healthy clevelopment of chem-
istry at Yale which markocIly improved the atmosphere for
Harned's last few years before retirement.
Shortly after setting up his laboratories at Yale, Harned,
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HERBERT SPENCER HARNED
235
With N. D. Embree. The temperature variation of ionization con-
stants in aqueous solutions. I. Am. Chem. Soc., 56:105~53.
1935
Thermodynamic properties of uniunivalent halide mixtures in
aqueous solution. I. Am. Chem. Soc., 57:186~73.
With H. C. Thomas. Molal electrode potential of the silver-silver
chloride electrode in methanol-water mixtures. I. Am. Chem.
Soc.,57:1666~8.
With W. I. Hamer. The thermodynamics of aqueous sulphuric acid
solutions from electromotive force measurements. I. Am.
Chem. Soc., 57:27-33.
With W. I. Hamer. Molal electrode potentials and the reversible
electromotive forces of the lead accumulator from 0° to 60°. l.
Am. Chem. Soc., 57:33-35.
With G. E. Mannweiler. The thermodynamics of ionized water in
sodium chloride solutions. I. Am. Chem. Soc., 57:1873-76.
With N. D. Embree. Ionization constant of acetic acid in methyl
alcohol-water mixtures from 0° to 40°. I. Am. Chem. Soc.,
57:1669-70.
1936
With H. C. Thomas. The thermodynamics of hydrochloric acid in
methanol-water mixtures from electromotive force measure-
ments. I. Am. Chem. Soc., 58:761~6.
With A. S. Keston and D. G. Donelson. The thermodynamics of
hydrobromic acid in aqueous solutions from electromotive force
measurements. I. Am. Chem. Soc., 58:989-94.
With J. O. Morrison. Thermodynamics of hydrochloric acid in
dioxane-water mixtures from electromotive force measure-
ments. I. Am. Chem. Soc., 58:1908-11.
With G. L. Kazanjian. The ionization constant of acetic acid in
dioxane-water mixtures. J. Am. Chem. Soc., 58:1912-15.
With M. E. Fitzgerald. The thermodynamics of cadmium chloride
in aqueous solution from electromotive force measurements. l.
Am. Chem. Soc., 58:262~29.
The general properties of a perfect electrochemical apparatus. In:
Commentary on the Scientif c Writings of f. Willard Gibbs, ed. F. G.
Donnan II and Arthur Haas, pp. 709-35. New Haven, Conn.:
Yale Univ. Press.
OCR for page 236
236
BIOGRAPHICAL MEMOIRS
1937
With i. O. Morrison. A cell for the measurement of the thermody-
namic properties of hydrochloric acid in dioxane-water mix-
tures. Am. l. Sci., 33:161-73.
Relative partial molal heat content of zinc sulphate in aqueous
solution. I. Am. Chem. Soc., 59:360~1.
With M. A. Cook. The thermodynamics of aqueous potassium hy-
droxicle solutions from electromotive force measurements. I.
Am. Chem. Soc., 59:49~500.
With I. G. Donelson. The thermodynamics of ionized water in
lithium bromide solutions. l. Am. Chem. Soc.., 59:1280-84.
With M. A. Cook. The thermodynamics of aqueous potassium chlo-
ricle solutions from electromotive force measurements. I. Am.
Chem. Soc., 59: 1290-92.
With F. C. Hickey. The ionization of acetic acid in aqueous sodium
chloride solutions from 0° to 40°. I. Am. Chem. Soc.,
59: 1284~8.
With F. C. Hickey. The hydrolysis of the acetate ion in sodium
chloride solutions. I. Am. Chem. Soc., 59:1289-90.
With M. A. Cook. The activity and osmotic coefficients of some
hydroxide-chloride mixtures in aqueous solution. I. Am. Chem.
Soc., 59:1890-95.
With M. A. Cook. The ionic activity coefficient product and ioniza-
tion of water in uniunivalent halide solutions. A summary. I.
Am. Chem. Soc., 59:230~5.
With F. C. Hickey. Salt action on the ionization of acetic acid and on
the hydrolysis of the acetate ion. I. Am. Chem. Soc.,59:2303~.
With G. C. Crawford. The thermodynamics of aqueous sodium
bromide solutions from electromotive force measurements. I.
Am. Chem. Soc., 59:1903-5.
With C. G. Geary. The ionic activity coefficient product and ioniza-
tion of water in barium chloride solutions from 0° to 50°. J. Am.
Chem. Soc., 59:2032-35.
1938
With C. Calmon. The thermodynamics of hydrochloric acid in
dioxane-water mixtures from electromotive force measure-
ments. II. Densities. I. Am. Chem. Soc., 60:33~35.
OCR for page 237
HERBERT SPENCER HARNED 237
The thermodynamics of hydrochloric acid in dioxane-water mix-
tures from electromotive force measurements. III. Extrapola-
tions according to the Gronwall-LaMer extension of the Debye
and Huckel theory. I. Am. Chem. Soc., 60:33~39.
With l. G. Donelson. The thermodynamics of hydrochloric acid in
dioxane-water mixtures from electromotive force measure-
ments. IV. Properties of the 20% dioxane-water mixtures. I.
Am. Chem. Soc., 60:339-41.
With I. G. Donelson. The thermodynamics of hydrochloric acid in
dioxane-water mixtures from electromotive force measure-
ments. V. 45% Dioxane-water mixtures. I. Am. Chem Soc., 60:
212~30.
With C. Calmon. The thermodynamics of hydrochloric acid in
dioxane-water mixtures from electromotive force measure-
ments. VI. Extrapolation in 70% dioxane mixtures and stan-
dard potentials. I. Am. Chem. Soc., 60:2130-33.
With I. G. Donelson and C. Calmon. The thermodynamics of hy-
drochloric acid in dioxane-water mixtures from electromotive
force measurements. VII. Properties of the 70% mixtures. I.
Am. Chem. Soc., 60:2131-35.
Ions in solution. Present status of the thermodynamics of electro-
lytic solutions. I. Comparison of thermodynamic properties of
electrolytes determined by various methods. II. Weak electro-
lytes. III. Electrolytes in nonaqueous solvent-water mixtures.
IV. Calculation of the solubility of highly soluble salts in salt
solutions by the method of ~kerlof. I. Franklin Inst.,
225:623-59.
With G. Akerlof. Electromotive forces. Oxidation-reduction poten-
tials (1931-61. Annual Tables of Constants, no. 9. N.Y.: McGraw-
Hill.
1939
With M. A. Cook. The thermodynamics of aqueous sodium chlo-
ride from 0° to 40° from electromotive force measurements. J.
Am. Chem. Soc., 61:495-97.
With F. Walker and C. Calmon. The thermodynamics of hydro-
chloric acid in dioxane-water mixtures from electromotive force
measurements. VIII. Extrapolations in 82% dioxane mixtures
and standard potentials. I. Am. Chem. Soc., 61:44-47.
OCR for page 238
238
BIOGRAPHICAL MEMOIRS
With F. Walker. The thermodynamics of hydrochloric acid in
dioxane-water mixtures from electromotive force measure-
ments. IX. Properties of the 82% mixtures. l. Am. Chem. Soc.,
61 :4~9.
With B. B. Owen, l. O. Morrison, F. Walker, I. G. Donelson, and C.
Calmon. The thermodynamics of hydrochloric acid in dioxane-
water mixtures from electromotive force measurements. X.
Summary and critique. I. Am. Chem. Soc., 61:49-54.
With C. Calmon. The properties of electrolytes in mixtures of water
and organic solvents. I. Hydrochloric acid in ethanol- and
isopropanol-water mixtures of high dielectric constant. J. Am.
Chem. Soc., 61:1491-94.
With B. B. Owen. Determinations of the ionization and thermody-
namic properties of weak electrolytes by means of cells without
liquid junctions. Chem. Rev., 25:3145.
Experimental studies of the ionization of acetic acid. J. Phys.
Chem., 43:275~0.
With L. D. Fallon. The properties of electrolytes in mixtures of
water and organic solvents. II. Ionization constant of water in
20%,45% and 70% dioxane-water mixtures. l. Am. Chem. Soc.,
61 :237~77.
With L. D. Fallon. The properties of electrolytes in mixtures of
water and organic solvents. III. Ionization constant of acetic
acid in an 82% dioxane-water mixture. I. Am. Chem. Soc., 61:
2377-79.
With E. C. Dreby. The properties of electrolytes in mixtures of
water and organic solvents. IV. Transference numbers of hy-
drochloric acid in water and dioxane-water mixtures from 0° to
50°. J. Am. Chem. Soc., 61: 3113-20.
With L. D. Fallon. The second ionization constant of oxalic acid
from O°to50°. }.Am. Chem.Soc., 61: 3111-13.
1940
With R. A. Robinson. Temperature variation of the ionization con-
stants of weak electrolytes. Trans. Faraday Soc., 36: 973-78.
1941
With T. E. Dedell. The ionization constant of propionic acid in
dioxane-water mixtures. J. Am. Chem. Soc., 63: 330~12.
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HERBERT SPENCER HARNED
239
With R. S. Done. The ionization constant of formic acid in dioxane-
water mixtures. I. Am. Chem. Soc., 63: 257~82.
With R. A. Robinson. The activity coefficient of hydriodic acid at
25° from isopiestic vapour-pressure measurements. Trans.
Faraday Soc., 37: 302-7.
With A. M. Ross. The acid hydrolysis of methyl acetate in dioxane-
water mixtures. I. Am. Chem. Soc., 63: 199~99.
With S. R. Scholes. The ionization constant of HCO3 from 0° to 50°.
J. Am. Chem. Soc., 63: 1706-9.
With R. A. Robinson. Some aspects of the thermodynamics of
strong electrolytes from electromotive force and vapor pressure
measurements. Chem. Rev., 28: 41~77.
1943
With C. M. Birdsall. The acidic ionization constant of glycine in
dioxane-water solutions. l. Am. Chem. Soc., 65: 5~57.
With R. Davis. The ionization constant of carbonic acid in water and
the solubility of carbon dioxide in water and aqueous salt solu-
tions from 0° to 50°. I. Am. Chem. Soc., 65: 2030-37.
With C. M. Birdsall. The basic ionization constant of glycine in
dioxane-water solutions. I. Am. Chem. Soc., 65: 1117-19.
With B. B. Owen. The Physical Chemistry of Electrolytic Solution. N.Y.:
Reinhold Publishing. 612 pp.
1945
With F. T. Bonner. The first ionization of carbonic acid in aqueous
solutions of sodium chloride.3. Am. Chem. Soc., 67: 102~31.
With D. M. French. A conductance method for the determination
of the diffusion coefficients of electrolytes. Ann. N.Y. Acad.
Sci., 46: 267-81.
1946
With F. H. M. Nestler. The standard potential of the cell,
H2|HCl~m)|AgCl-Ag, in 50% glycerol-water solution from 0° to
90°. I. Am. Chem. Soc., 68: 665-66.
With F. H. M. Nestler. The ionization constant of acetic acid in fifty
percent glycerol-water solution from 0° to 90°. l. Am. Chem.
Soc., 68: 966-67.
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240
BIOGRAPHICAL MEMOIRS
1947
With R. L. Nuttall. The diffusion coefficient of potassium chloride
in dilute aqueous solution. l. Am. Chem. Soc., 69: 736 40.
Quantitative aspects of diffusion in electrolyte solutions. Chem.
Rev., 40: 461-522.
1949
With R. L. Nuttall. Diffusion coefficient of potassium chloride in
aqueous solution at 25°. Ann. N.Y. Acad. Sci., 51: 781-88.
With R. L. Nuttall. The differential diffusion coefficient of potas-
sium chloride in aqueous solutions. }. Am. Chem. Soc., 71:
1460 63.
With A. L. Levy. The differential diffusion coefficient of calcium
chloride in dilute aqueous solutions at 25°. }. Am. Chem. Soc.,
71: 2781-83.
1950
With C. A. Blake. The diffusion coefficient of potassium chloride
in water at 4°. }. Am. Chem. Soc., 72: 2265~6.
With B. B. Owen. The Physical Chemistry of Electrolytic Solutions, Ed ed.
Am. Chem. Soc. Monograph No. 95. N.Y.: Reinhold Publishing.
675 pp.
1951
With C. L. Hildreth, Jr. The differential diffusion coefficient of
lithium and sodium chlorides in dilute aqueous solution at 25°.
I. Am. Chem. Soc., 73: 65~52.
With R. M. Hudson. The differential diffusion coefficient of potas-
sium nitrate in dilute aqueous solutions at 25°. }. Am. Chem.
Soc., 73: 652-54.
With C. A. Blake. The diffusion coefficients of lithium and sodium
sulfates in dilute aqueous solution at 25°. }. Am. Chem. Soc., 73:
244~50.
With R. M. Hudson. The diffusion coefficient of zinc sulfate in
dilute aqueous solution at 25°. }. Am. Chem. Soc., 73:3781-83.
With C. L. Hildreth. The diffusion coefficient of silver nitrate in
dilute aqueous solution at 25°. J. Am. Chem. Soc., 73:3292-93.
OCR for page 241
HERBERT SPENCER HARNED
241
With C. A. Blake, Jr. The differential diffusion coefficient of lanth-
anum chloride in dilute aqueous solution at 25°. i. Am. Chem.
Soc., 73:4255-57.
Solutions of electrolytes. Annul Rev. Phys. Chem., 2:37-50.
With R. M. Hudson. The differential diffusion coefficient of potas-
sium ferrocyanide in dilute aqueous solutions at 25°. I. Am.
Chem. Soc., 73:5083~4.
With R. M. Hudson. The diffusion coefficient of magnesium sul-
fate in dilute aqueous solution. }. Am. Chem. Soc., 73:5880~82.
With C. A. Blake, Jr. The diffusion coefficient of cesium sulfate in
dilute aqueous solution at 25°. I. Am. Chem. Soc!, 73:5882~3.
With L. I. Costing. The application of the Onsager theory of ionic
mobilities to self-diffusion. I. Am. Chem. Soc., 73:159-61.
1953
With T. R. Paxton. The thermodynamics of ionized water in stron-
tium chloride solutions from electromotive-force measure-
ments. I. Phys. Chem., 57:531-35.
With M. Blander. The differential diffusion coefficient of ru-
bidium chloride in dilute aqueous solution at 25°. J. Am. Chem.
Soc., 75:2853-55.
With F. M. Polestra. The differential diffusion coefficient of stron-
tium chloride in dilute aqueous solution at 25°. I. Am. Chem.
Soc., 75:416~69.
Diffusion coefficients of electrolytes in dilute aqueous solutions.
Natl. Burl Stand. (U.S.), Circ. No. 524, 67-79.
1954
With D. S. Allen. Standard potentials of silver-silver chloride cells
in some ethanol- and isopropyl alcohol-water solutions at 25°. I.
Phys. Chem., 58:191-92.
With F. M. Polestra. Differential diffusion coefficients of magne-
sium and barium chlorides in dilute aqueous solutions at 25°. I.
Am. Chem. Soc., 76:206~65.
The diffusion coefficients of the alkali metal chlorides and potas-
sium and silver nitrates in dilute aqueous solutions at 25°. Proc.
Natl. Acad. Sci. USA, 40:551-56.
With M. Blander and C. L. Hildreth, fir. The diffusion coefficient
of cesium chloride in dilute aqueous solution at 25°. I. Am.
Chem. Soc., 76:4219-20.
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242
BIOGRAPHICAL MEMOIRS
Relative chemical potentials of electrolytes and the application of
their gradients. J. Phys. Chem., 58:683-86.
With R. Gary. Activity coefficient of hydrochloric acid in concen-
trated aqueous higher-valence type chloride solutions at 25°. I.
System hydrochloric acid-barium chloride. I. Am. Chem. Soc.,
76:592~27.
1955
With H. W. Parker. Diffusion coefficient of calcium chloride in
dilute and moderately dilute solutions at 25°. I. Am. Chem. Soc.,
77:265~6.
With H. W. Parker and M. Blander. The diffusion coefficients of
lithium and potassium perchlorates in dilute aqueous solutions
at 25°. I. Am. Chem. Soc., 77:2071-73.
With R. Gary. Activity coefficients of hydrochloric acid in concen-
trated aqueous higher-valance type chloride solutions at 25°. II.
System hydrochloric acid-strontium chloride. }. Am. Chem.
Soc., 77: 199~95.
With R. Gary. Activity coefficients of hydrochloric acid in concen-
trated aqueous higher-valance type chloride solutions at 25°.
III. System hydrochloric acid-aluminum chloride. I. Am. Chem.
Soc., 77:4695-97.
1956
With R. G. Bates and E. A. Guggenheim. Standard electrode
potential of the silver-silver chloride electrode. I. Chem. Phys.,
25:2, 361.
1957
Recent experimental studies of diffusion in liquid systems. Discuss.
Faraday Soc., no. 24:7-16.
1958
With A. B. Gancy. The activity coefficient of hydrochloric acid in
potassium chloride solutions. I. Phys. Chem., 62:627-29.
With J. A. Shropshire. The diffusion and activity coefficients of
sodium nitrate in dilute aqueous solutions at 25°. I. Am. Chem.
Soc., 80:261~19.
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HERBERT SPENCER HARNED
243
With I. A. Shropshire. The activity coefficients of alkali metal ni-
trates and perchlorates in dilute aqueous solutions at 25° from
diffusion coefficients. I. Am. Chem. Soc., 80:2967-68.
With I. A. Shropshire. The diffusion coefficient at 25° of potassium
chloride at low concentrations in 0.25 molar aqueous sucrose
solutions. I. Am. Chem. Soc., 80:5652-53.
With B. B. Owen. The Physical Chemistry of Electrolytic Solutions, ad ed.
Am. Chem. Soc. Monograph No.95. N.Y.: Reinhold Publishing.
803 pp.
1959
The thermodynamic properties of the system hydrochloric acid,
sodium chloride and water from 0° to 50°. I. Phys. Chem., 63:
1299-302.
With R. Gary. The activity coefficient of hydrochloric acid in cad-
mium chloride solutions at 5 M total ionic strength. I. Phys.
Chem., 63:2086.
With A. B. Gancy. The activity coefficient of hydrochloric acid in
thorium chloride solutions at 25°. I. Phys. Chem., 63:2079~0.
With M. Blander. Glass conductance cell for the measurement of
diffusion-coefficients. I. Phys. Chem., 63:207~79.
Concentration dependence of the four diffusion coefficients of the
system NaCl-KCl-H2O at 25°. In: Structure of Electrolytic Solutions,
ed. W. J. Hamer, pp. 152-59. N.Y.: John Wiley.
1960
The thermodynamic properties of the system: hydrochloric acid,
potassium chloride and water from 0° to 40°. I. Phys. Chem., 64:
112-14.
With J. A. Shropshire. Diffusion coefficient at 25° of potassium
chloride at low concentrations in 0.75 molar aqueous sucrose
solution. I. Am. Chem. Soc., 82:799~00.
With L. Pauling and R. B. Corey. Preparation of (Nb6Cl~2)Cl2.
7H2O. I. Am. Chem. Soc., 82:4815-18.
1961
The activity coefficient of hydrochloric acid in organic solvent-
water mixtures. U.S. At. Energy Comm. TlD-12097. 12 pp.
OCR for page 244
244
BIOGRAPHICAL MEMOIRS
Osmotic coefficients of hydrochloric acid, potassium and sodium
chlorides from 0° to 40° or 50°. U.S. At. Energy Comm.
TlD-12096. 7 pp.
1962
A rule for the calculation of the activity coefficients of salts in
organic solvent-water mixtures. I. Phys. Chem., 66:589~91.
1963
Thermodynamic properties of the system: hydrochloric acid, lith-
ium chloride, and water from 15° to 35°. I. Phys. Chem., 67~8~:
1739.
1968
With R. A. Robinson. Topic 15: equilibrium properties of electro-
lyte solutions. In: The International Encyclopedia of Physical Chem-
istry and Chemical Physics, vol. 2, Multicomponent Electrolyte Solu-
tions. N.Y.: Pergamon. 110 pp.
OCR for page 245
Representative terms from entire chapter:
chloride solutions
