Chemical Education Today

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Chemistry in the City: Columbia Sketches

by Leonard Fine

Four Sketches

Fifty years ago the American Chemical Society (ACS)

convened its 126th national meeting in the City of New York.
At the same time and place, Columbia Universitythe fifth
oldest in Americacelebrated its bicentennial. The Journal
of Chemical Education (JCE) marked both events with
sketches of four remarkable chemists: Charles Frederick
Chandler, Marston Taylor Bogert, Henry Clapp Sherman,
and John Maurice Nelson (1). Each practiced chemistry in
the house that Chandler built for them as Columbia moved
to its third and current campus on Morningside Heights in
upper Manhattan. Historic Havemeyer Hall, one of six origi-
nal buildings designed by Charles Follen McKim, is still the
centerpiece of the chemistry complex. McKim was the found-
ing partner of the fabled fin de siecle architectural firm of
McKim, Mead, and White. His design of the campus trans-
formed Columbia into one of the citys landmark monuments
of the American Renaissance (Figure 1).
Today, as a century ago, the interior of this imposing
burnt-red brick and limestone-trimmed building is distin-
guished by its central lecture hall with its 40-foot domed ceil-
ing and skylight, 330 tiered seats, brass-railed gallery and
40-foot oak demonstration table. The east end of Havemeyer
no longer is home to the Chandler Museum, although ele-
ments of the collection are displayed at several locations
throughout the building, offering visitors to the department
sketches in the history of chemistry. Included in the collec-
tion and on display are samples and equipment from Priestley
and Pasteur; there is a collection of historic light bulbs dat-
ing from Edison, and dyes prepared by Perkin and Baeyer;
there is a battery collection of considerable historical interest.
Charles Frederick Chandler was educated at Harvards
Lawrence Scientific School and went to Europe (Gttingen)
as was typical of mid-nineteenth century Americans seeking
a Ph.D. (Whler). Coming to Columbia in 1864 from Union
College where he had gotten his first job as instructor and
janitorinstructors werent paid, janitors wereChandler
expanded chemistry in pharmacy and in medicine, and in
engineering and pure science. Over 30 years he developed
an American version of the European model for training and
educating chemists. He twice served as president of the ACS
and won the Perkin Medal. His essential legacy was the young
faculty he appointed.
With only a bachelors degree and virtually self-taught
in chemistry, Marston Taylor Bogert became Columbias first
professor of organic chemistry. A born-and-bred New Yorker,
over a long chemical lifetime, Bogert published more than
500 papers, the titles of which would not raise an eyebrow
today if discovered in any current volume of the Journal of
the American Chemical Society (JACS) or The Journal of Or-
ganic Chemistry (JOC). He professionalized the ACS and in-
ternationalized American chemistry.
Figure 1. Strikingly captured by Canadian artist Bonnie Folkins in
this 1993 watercolor portrait, the architectural features of
Havemeyer Hall are typical of the McKim design for the campus.
Henry Clapp Sherman, who came from Virginia to study
chemistry at Columbia, began his professional life as an ana-
lytical chemist yet is remembered for his lifelong work in food
chemistry and nutrition, anticipating the discovery of vita-
mins, hormones, and the essential role of amino acids. Among
his students was Nobel Laureate Edward Kendall.
Nebraska-born John Maurice Nelson studied with
Ostwald, made significant contributions to electrochemistry
and experimental physical chemistry, and eventually returned
to Columbia, completing a Ph.D. with Marston Bogert in
organic chemistry. Included in his early studies were the ef-
fects of neutral salts on hydrogen ion activity, and the salt
effectthe discovery that the addition of sodium chloride
increases hydrogen ion activity. Nelson counted among his
students Nobel Laureate John Northrup, who proved the pro-
tein nature of proteolytic enzymes.
Four More Sketches
With the ACS returning to New York now fifty years
later for its 226th national meeting and Columbias 250th
anniversary, we again mark both events with four more
sketches of remarkable chemists. Louis Hammett opened the
field of physical organic chemistry; Nobel Laureate Harold
Urey was one of the most influential scientists of his time
for his discovery of deuterium; the name Victor LaMer is syn-
onymous with colloid chemistry; and intimately tied to theory
and practice in chemistry as few others in the 20th century
is Irving Langmuir. The ties that bind these four together
and make them of special interest are the overlap of their re-
search and the intertwining of their lives. All four are recog-
nized by a wide community of scholars as good citizens of

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Figure 2. The questionable activity of rainmaking got a boost when Langmuir and
others began dry ice and silver iodide nucleation experiments in the 1940s and
1950s. Left: A 20-mile long racetrack pattern produced by dropping crushed dry ice
from an airplane; right: Langmuir standing in the background (left) with GE colleagues
and laboratory cloud-seeding experiment.
chemistry and great teachers. At the heart of our interest is
their tie of Columbia and the City of New York.
Irving Langmuir (18811957)
Few scientists, whether in academic, industrial, or gov-
ernment laboratories, have careers as remarkable as that of Irv-
ing Langmuir, Nobel Laureate in Chemistry for 1932. Born
in Brooklyn, New York, Langmuir received his early training
and education in the School of Mines, which was then home
to chemistry and chemical engineering at Columbia. He
graduated just a century ago with the Class of 1903, study-
ing with Charles Frederick Chandler. Langmuir followed
Chandlers footsteps to Gttingen half a century later where
he earned M.S. and Ph.D. degrees with Walther Nernst.
Nernst was interested in illumination (as was Edison)
and held patents on a glower, which he licensed for hand-
some fees to European electrical-giant Siemens. One of sev-
eral topics he suggested young Langmuir might work on was
the formation of NO in air in the vicinity of a Nernst glower.
The idea was that the incandescent filament would catalyze
the reaction between nitrogen and oxygen and the equilib-
rium position might prove to be related to the temperature
of the glowing filament. That turned out not to be the case
and Langmuir went on to write a thesis on the gas phase dis-
sociation of carbon dioxide in the vicinity of a glowing plati-
num filament. Returning to America, he taught for a while
at the fledgling Stevens Institute (New Jersey) before begin-
ning a 40-year career with General Electric and a lifelong as-
sociation with Columbia where he often lectured, consulted,
and collaborated in research and teaching (2).
Langmuir joined General Electric in July of 1909. By
then, Edisons light bulb, not Nernsts glower, had proved to
be the invention of choice, leaving Nernst with personal
wealth but pushing Siemens to the sidelines. Now came the
need for rapid commercial development. Early Edison/GE
incandescent bulbs were vacuum lamps and better vacuums
made better, longer-lived bulbs. Langmuir took the opposite
tack and studied what gases could be added to the bulb. His
first successful experiments with hydrogen over tungsten at
JChemEd.chem.wisc.edu Vol. 80 No. 8 August 2003 Journal of Chemical Education
Chemical Education Today
Photos: GE CR&D Labs
high temperatures and low pressures led to de-
tailed investigations of atomic hydrogen, the
effects of water vapor in incandescent lamps,
and the cleanup mechanism for nitrogen,
oxygen, and other gases. They led to the in-
ert gas-filled lamp: nitrogen then, argon now.
Based on observations of the heating effects
that accompany the recombination of atomic
hydrogen on metal surfaces, Langmuir in-
vented the atomic hydrogen welding torch
where copious amounts of H produced be-
tween tungsten electrodes recombined on a
metal surface.
Langmuir helped us imagine electrons
(3) and gave us the means to count them be-
fore just about anyone else, thereby opening
the field of surface science for which he was
recognized with the Nobel Prize, the first to
be awarded to a scientist from an industrial
research laboratory. His name will be forever linked (with
Katherine Blodgett) to the study of liquid films; a scientific
journal carries the name LANGMUIR; and there is an ACS
annual Award in Chemical Physics in his name. He was an
academician in industry with a small army of Ph.D. students
at any one time working on the problems that filled the pages
of 54 research notebooks. Widely acknowledged as a great
lecturer, his style is said to have been fast-paced, emphatic,
and filled with the intensity of his topic.
His theory of electron-pair bonds gained wide acceptance
for the originality of ideas put forward simultaneously by
Gilbert Newton Lewis giving some authority to the notion
that perhaps the more important person is the popularizer,
not the discoverer, of the idea. As a chemist, Langmuir con-
sidered molecules as complex entities with variously distrib-
uted chemical forces acting over short ranges. Coupled to
Lewis cubic structure for atoms, Langmuir postulated an
octet theory. No longer were Bohrs electrons centrally lo-
cated; rather they were distributed throughout, but station-
ary in their region; that is, describing a restricted orbit within
a region.
Irving Langmuirs imagination stretched his experiments
to environmental issues long before that was popular. He col-
laborated on inventions to prepare smokes, gels, and sols; he
was interested in soaps, bubbles, and foams; and he studied
wind and ocean currents and temperatures, anticipating theo-
ries of global warming currently popular today. Stretching
his imagination, Langmuir seeded clouds to cause precipita-
tion (Figure 2). Langmuir was concerned with the structure
of scientific theories, the psychology of science, and patho-
logical science. He loved to debunk mythology and pseudo-
science (4).
Louis Hammett (18941987)
While an undergraduate at Harvard, this native New
Englander managed to impress Kohler and Conant and
wangle a fellowship to work for a year in the middle of WW I
with Staudinger in Switzerland. He returned from Europe
and put his practical experience with chemistry to work on
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Photo: Columbia University, Chandler Collection

improving paints and var- tracted to colloids by the popular course Arthur Thomas
nishes for the canvassing of taught graduate students at Columbia. More likely it was the
aircraft. In 1922 he wrote a lectures Irving Langmuir gave at Columbia in 1916 and that
Ph.D. thesis with Hal Bean culminated in his famous papers of 1917 on surface action.
at Columbia before embark- Later, on LaMers return from Copenhagen, Peter Debye took
ing on a New York career up residence in the United States (Cornell), making it pos-
that lasted half a century. sible to establish a life-long professional collaboration.
Hammett shares credit As was generally true of their generation, LaMers career
with Christopher Ingold and was punctuated by an interlude of applied research. At the
Arthur Lapworth for estab- time, little was known about nucleation phenomena, particu-
lishing the field of physical lates in smokes, and the properties of aerosols. LaMers labo-
organic chemistry, with the ratory produced a stream of classified research ranging across
lions share belonging to the field of colloid science from light-scattering methods for
Hammett (Figure 3). He determining particle size and sol and dust removal problems
earned that when he wrote Figure 3. Louis Plack Hammett in by sedimentation and filtration techniques to the principle
the first edition of Physical 1963, the year he received the of foreign nucleation for generating monodisperse aerosols.
Organic Chemistry (5). The National Medal of Science. In 1931, experiments that led to the discovery of deu-
thematic devices that defined terium allowed LaMer to begin pioneering investigations of
this new discipline changed what was largely a synthesis-based the characteristic properties of heavy water. His investigations
organic chemistry into a principles-and-ideas-driven physical of acidbase equilibria in heavy water were the first of its kind.
organic chemistry. The consequences of this new dimension In collaboration with Hammett and his students, LaMer in-
were enormous. To validate the point, consider the acidity vestigated acidbase equilibria in poorly ionizing solvents
function that Hammett created and the concept of such as benzene. Questioning the then-prevailing idea that
superacidity that followed. That sulfuric acid is a stronger acid activation energies were independent of temperature, he and
in benzene (than in aqueous solution) eventually led George his students demonstrated otherwise for reactions involving
Olah to the 1995 Nobel Prize for demonstrating catalytic ef- ions in solution; in turn, these studies strengthened the fragile
fects of superacids. And then there is the famous equation foundations of transition-state theory.
named for Hammett and used by all studying mechanistic The importance of colloid chemistry in the environment
organic chemistry and stereochemistry. did not escape LaMers attention. He and his students made
All his life, Louis Hammett was a concerned citizen of contributions to the problem of limiting water evaporation
scientific and human rights, speaking out on the issues of by the use of monomolecular films and commercial scale re-
his daybasic versus applied research; the need for public covery of potable water from brackish waters. His studies of
understanding of science; the militaryindustrial establish- surface tension are still considered important work.
ment, government relationships and the responsibility of sci- LaMer founded the Journal of Colloid Science and wrote
entists; stimulating creativity; and taking direct responsibility many theoretical papers on the physics and chemistry of col-
for filling the pipeline with the next generation of young sci- loids. As is true even for Einstein (whose most heavily cited
entists (6). In 1954, he looked backward and wrote for JCE papers are on peptization phenomena, making of cements
of four generations of leadership in chemistry within his own and homogenized milk, and refrigeration), among LaMers
department (1); looking forward, he spoke of the need to most often cited papers are those with practical implications.
mentor young faculty, post-doctoral fellows, and graduate He taught one of the core courses in the graduate chemistry
students. curriculum that reflected the current state-of-the-art as well
as the history of the field. LaMer left a legacy at Columbia
Victor LaMer (18951966) in experimental physical chemistry that sustains to this day
The namesake of the ACS Award in Colloid or Surface (Figure 4).
Chemistry given each year since 1954, this Kansan came to
Columbia with a bachelors degree from Kansas State Uni- Harold Clayton Urey (18931981)
versity in 1915 and received his Ph.D. with Arthur Thomas Figure 5 shows Harold Urey (right) in November of 1931
in 1921. He was a post-doctoral student at Cambridge for with Ph.D. student Donald MacGillavry in the grating room
two years in Europes premier colloid science research cen- at Columbia observing an electric discharge through hydro-
terthe first American to be invited. From there, he went gen gas concentrated in deuterium. This spectroscopic experi-
to Copenhagen to work with Brnsted in the critical year of ment proved the existence of deuterium for which Urey won
1923 when the famous DebyeHckel paper appeared, set- the 1934 Nobel Prize in Chemistry, and the ACS Gibbs
ting the theory of complete dissociation on a firm founda- Medal. Early in 1931 he had conceived and worked out a
tion. He was predestined for the career in physical chemistry method for concentration of the heavy hydrogen isotope by
and colloid science that unfolded (7). distillation of liquid hydrogen. At the time, although suspected
At the beginning of the age of specialization, how LaMer by Aston and others, not only was there no evidence for the
chose colloid chemistry suggests something more than just existence of the isotopes but many believed the theories of
latent interest or innate aptitude. One can assume he was at- Prout, suggesting atomic weights to be whole number mul-

852 Journal of Chemical Education Vol. 80 No. 8 August 2003 JChemEd.chem.wisc.edu


Photo: Columbia University, Chandler Collection
Figure 4. Victor Kuhn LaMer at the electrical bench in his Havemeyer
laboratory in 1938. Besides his essential work on colloids, he pro-
duced experimental and theoretical studies on thermodynamics and
the kinetics of electrolyte solutions.
tiples of hydrogen, the lightest element. Some believed the
isotopes, if present, would be inseparable for their identical
extranuclear electron configurations.
The fractional distillation was done in collaboration with
Ferdinand G. Brickwedde at the National Bureau of Stan-
dards (now NIST) in Washington, DC where 4000 mL of
liquid hydrogen was distilled down to 1 mL (8, 9). High reso-
lution hydrogen atom visible spectra were taken on a 21-foot
spectrograph. The lines gave an abundance ratio of 4500:1
for the isotopes, in reasonable agreement with the known
abundance of 0.02%. The critical spectrum clinching the dis-
covery was taken on Thanksgiving Day, 1931. The letter to
the editor of Physical Review posted next day narrowly estab-
lished the priority of the discovery, which led to the 1934
Nobel Prize, two years after Irving Langmuirs Nobel Prize.
In one of the ironies of modern science, Ureys principal com-
petitor for the deuterium discovery was none other than his
Berkeley mentor, Gilbert Newton Lewis.
Born in Walkerton, Indiana, this grandson of pioneers
was educated in rural America, beginning in a one-room
schoolhouse before entering what is today the University of
Montana (Missoula) and graduating in Zoology in 1917. In
1921, he studied thermodynamics at the University of Cali-
fornia at Berkeley with Lewis and followed that with a post-
doctoral year with Niels Bohr in Copenhagen studying
quantum theory and spectroscopy. While in Copenhagen he
crossed paths with Victor LaMer working with Brnsted. Re-
turning to the United States, Urey was first appointed assis-
tant, then associate, professor at Johns Hopkins where he
collaborated with F. O. Rice, among others. He was a pio-
neer in the application of quantum mechanics to molecules
and published research on the entropy of diatomic molecules
and the absorption spectra of simple polyatomic molecules.
With A. E. Ruark in 1930, Urey published a widely read
monograph on atoms, molecules, and quanta. He was 36
years old.
In the decade following the discovery of the hydrogen
isotope of mass 2, Urey systematically found practical ways
JChemEd.chem.wisc.edu Vol. 80 No. 8 August 2003 Journal of Chemical Education
Chemical Education Today
Photo: Columbia University, Chandler Collection
Figure 5. This photographic record of an historical moment was
recorded by Roger Herriott, a graduate student at the time with
John Nelson, and later Professor of Biochemistry at Johns Hopkins
Univerity in the School of Hygiene and Public Health.
to concentrate isotopes, and used these isotopes to probe
chemical reactions. With Bureau of Standards colleagues, he
obtained heavy water in bulk by electrolysis. He worked with
LaMer on mechanisms of reactions in aqueous electrolyte
solutions. With Ph.D. student Mildred Cohn he began to
explore 18O exchange reactions between water and organic
compounds; she later joined the faculty at the University of
Pennsylvania Medical School and pioneered the biological use
of oxygen isotope tracers. His student T. Ivan Taylor explored
isotope effects in surface reactions, and later joined the Co-
lumbia chemistry faculty. Urey was founding editor of the
Journal of Chemical Physics. He used his Nobel Prize money
for support of his own research and the research of two col-
leagues in the department.
After the war, in an apparent rift with Hammett, he
moved from Columbia to the University of Chicago. In the
late 1940s Urey invented the paleotemperature methods that
are now universally used to analyze climate warming and cool-
ing cycles. These involve measuring the 16O/18O ratio in car-
bonate minerals, and in ice as a function of depth in Arctic
core samples. His idea is based upon isotopic temperature
effects in evaporation of sea water (and subsequent conden-
sation as rain and snow), and in the equilibrium between
water and carbonate ion. After 1950 his interests turned to
the chemistry of the planets, and he is credited with initiat-
ing rigorous study of cosmochemistry, a term he himself
coined. In 1953, he and Ph.D. student Stanley Miller per-
formed an experiment not sufficiently honored in this anni-
versary year because of another, more famous, experiment.
The UreyMiller experiment demonstrated the synthesis of
amino acids via electrical discharge in gases thought to be
present in the Earths original reducing atmosphere. The other
(of course) is the WatsonCrick note published in Nature on
their DNA model (4) and its implications.
Retiring to the Scripps Institute at age 65 in 1957,
Harold Urey helped build the University of California at San
Diego and went on to publish more than 100 scientific
papers.
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Literature Cited and Reading List
1. Hammett, Louis P. J. Chem. Educ. 1955, 32, 498517. A
lengthy historical statement describing the character and ca-
reers of Chandler, Bogert, Sherman, and Nelson put together
by Hammett from original sketches prepared by their students.
2. Rosenfeld, Albert The Quintessence of Irving Langmuir;
Pergamon: New York, 1966. Here is the quintessential
Langmuir biography.
3. Langmuir, Irving. The Arrangement of Electrons in Atoms and
Molecules. J. Am. Chem. Soc. 1919, 41, 868934. Langmuir
said of the theory presented in his paper that it is essentially
an extension of Lewis theory of the cubical atom. This is a
wonderful paper for gaining insight into how the theory of
atoms has evolved.
4. Langmuir, Irving. Pathological Science, Phys. Today 1989,
October, 3648. Although he never published his investiga-
tions into what he called pathological science, Langmuir gave
a colloquium on the subject that was transcribed and recorded
and then printed in this remarkable paper. Stimulated by
Langmuir, Nicholas Turro recently published Paradigms Lost
and Paradigms Found: Examples of Science Extraordinary and
Science Pathological and How to Tell the Difference. Angew.
Chem. Int. Ed. 2000, 39, No. 13.
5. Hammett, Louis P. Physical Organic Chemistry; McGraw-Hill:
New York, 1940. Hammetts classic monograph was reprinted
many times, in several editions and in a dozen languages.
854 Journal of Chemical Education Vol. 80 No. 8 August 2003 JChemEd.chem.wisc.edu
6. Hammett, Louis P. Rights and Responsibilities in the Search
for Knowledge. Chem. Eng. News 1955, 32, No 15, 1462
1466. Considered in the context of its time, Hammetts re-
marks reflect the breadth of his interests and offer a view of
the profession in post-WW II America.
7. Hammett, Louis P.; LaMer, Victor Kuhn. In Biographical Mem-
oirs, Vol. XLV; National Academy of Sciences Press: Washing-
ton, DC, 1975. Appearing in this same volume are biographies
of Irving Langmuir (by Suits and Martin) and Marston Tay-
lor Bogert (by Hammett). A NAS biography of Hammett (by
Westheimer) appeared in 1997.
8. Urey, H. C.; Brickwedde, F. G.; Murphy, G. M. A Hydrogen
Isotope of Mass 2. Phys. Rev. 1932, 39, 164165. In its own
way, this paper had an impact equivalent to the paper by
Watson and Crick that is being widely celebrated this year (A
Structure of Deoxyribose Nucleic Acid. Nature 1953, 171,
737).
9. Lide, David R. A Hydrogen Isotope of Mass 2. In A Century
of Excellence in Measurements, Standards, and Technology; CRC
Press: New York, 2002. Well worth reading (or acquiring), the
NIST centennial publication annotates a range of discoveries
that emerged from the Bureau of Standards, including the deu-
terium collaboration with Urey.
Leonard Fine is in the Department of Chemistry, Colum-
bia University, Havemeyer Hall, New York, NY 10027;
fine@chem.columbia.edu.