Chemistry in the City: Columbia Sketches - Journal of Chemical

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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 University—the fifth oldest in America—celebrated 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 original buildings designed by Charles Follen McKim, is still the centerpiece of the chemistry complex. McKim was the founding partner of the fabled fin de siecle architectural firm of McKim, Mead, and White. His design of the campus transformed Columbia into one of the city’s 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 distinguished by its central lecture hall with its 40-foot domed ceiling 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 elements 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 collection and on display are samples and equipment from Priestley and Pasteur; there is a collection of historic light bulbs dating from Edison, and dyes prepared by Perkin and Baeyer; there is a battery collection of considerable historical interest. Charles Frederick Chandler was educated at Harvard’s Lawrence Scientific School and went to Europe (Göttingen) as was typical of mid-nineteenth century Americans seeking a Ph.D. (Wöhler). Coming to Columbia in 1864 from Union College where he had gotten his first job as instructor and janitor—instructors weren’t paid, janitors were—Chandler 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 bachelor’s degree and virtually self-taught in chemistry, Marston Taylor Bogert became Columbia’s 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 Organic Chemistry (JOC). He professionalized the ACS and internationalized American chemistry. 850

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 analytical chemist yet is remembered for his lifelong work in food chemistry and nutrition, anticipating the discovery of vitamins, 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 effects of neutral salts on hydrogen ion activity, and the salt effect—the discovery that the addition of sodium chloride increases hydrogen ion activity. Nelson counted among his students Nobel Laureate John Northrup, who proved the protein nature of proteolytic enzymes. Four More Sketches With the ACS returning to New York now fifty years later for its 226th national meeting and Columbia’s 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 synonymous 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 research and the intertwining of their lives. All four are recognized by a wide community of scholars as good citizens of

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


Photos: GE CR&D Labs

high temperatures and low pressures led to detailed 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 inert 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 invented the atomic hydrogen welding torch where copious amounts of H produced between tungsten electrodes recombined on a metal surface. Langmuir helped us imagine electrons 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 (3) and gave us the means to count them be1950s. Left: A 20-mile long racetrack pattern produced by dropping crushed dry ice fore just about anyone else, thereby opening from an airplane; right: Langmuir standing in the background (left) with GE colleagues the field of surface science for which he was and laboratory cloud-seeding experiment. 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 chemistry and great teachers. At the heart of our interest is Katherine Blodgett) to the study of liquid films; a scientific their tie of Columbia and the City of New York. journal carries the name LANGMUIR; and there is an ACS Irving Langmuir (1881–1957) annual Award in Chemical Physics in his name. He was an academician in industry with a small army of Ph.D. students Few scientists, whether in academic, industrial, or govat any one time working on the problems that filled the pages ernment laboratories, have careers as remarkable as that of Irvof 54 research notebooks. Widely acknowledged as a great ing Langmuir, Nobel Laureate in Chemistry for 1932. Born lecturer, his style is said to have been fast-paced, emphatic, in Brooklyn, New York, Langmuir received his early training and filled with the intensity of his topic. and education in the School of Mines, which was then home His theory of electron-pair bonds gained wide acceptance to chemistry and chemical engineering at Columbia. He for the originality of ideas put forward simultaneously by graduated just a century ago with the Class of 1903, studyGilbert Newton Lewis giving some authority to the notion ing with Charles Frederick Chandler. Langmuir followed that perhaps the more important person is the popularizer, Chandler’s footsteps to Göttingen half a century later where not the discoverer, of the idea. As a chemist, Langmuir conhe earned M.S. and Ph.D. degrees with Walther Nernst. sidered molecules as complex entities with variously distribNernst was interested in illumination (as was Edison) uted chemical forces acting over short ranges. Coupled to and held patents on a “glower”, which he licensed for handLewis’ “cubic” structure for atoms, Langmuir postulated an some fees to European electrical-giant Siemens. One of sev“octet” theory. No longer were Bohr’s electrons centrally loeral topics he suggested young Langmuir might work on was cated; rather they were distributed throughout, but stationthe formation of NO in air in the vicinity of a Nernst glower. ary in their region; that is, describing a restricted orbit within The idea was that the incandescent filament would catalyze a region. the reaction between nitrogen and oxygen and the equilibIrving Langmuir’s imagination stretched his experiments rium position might prove to be related to the temperature to environmental issues long before that was popular. He colof the glowing filament. That turned out not to be the case laborated on inventions to prepare smokes, gels, and sols; he and Langmuir went on to write a thesis on the gas phase diswas interested in soaps, bubbles, and foams; and he studied sociation of carbon dioxide in the vicinity of a glowing platiwind and ocean currents and temperatures, anticipating theonum filament. Returning to America, he taught for a while ries of global warming currently popular today. Stretching at the fledgling Stevens Institute (New Jersey) before beginhis imagination, Langmuir seeded clouds to cause precipitaning a 40-year career with General Electric and a lifelong astion (Figure 2). Langmuir was concerned with the structure sociation with Columbia where he often lectured, consulted, of scientific theories, the psychology of science, and pathoand collaborated in research and teaching (2). logical science. He loved to debunk mythology and pseudoLangmuir joined General Electric in July of 1909. By science (4). then, Edison’s light bulb, not Nernst’s glower, had proved to be the invention of choice, leaving Nernst with personal Louis Hammett (1894–1987) wealth but pushing Siemens to the sidelines. Now came the need for rapid commercial development. Early Edison/GE While an undergraduate at Harvard, this native New incandescent bulbs were vacuum lamps and better vacuums Englander managed to impress Kohler and Conant and made better, longer-lived bulbs. Langmuir took the opposite wangle a fellowship to work for a year in the middle of WW I tack and studied what gases could be added to the bulb. His with Staudinger in Switzerland. He returned from Europe first successful experiments with hydrogen over tungsten at and put his practical experience with chemistry to work on JChemEd.chem.wisc.edu • Vol. 80 No. 8 August 2003 • Journal of Chemical Education

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Victor LaMer (1895–1966) The namesake of the ACS Award in Colloid or Surface Chemistry given each year since 1954, this Kansan came to Columbia with a bachelors degree from Kansas State University in 1915 and received his Ph.D. with Arthur Thomas in 1921. He was a post-doctoral student at Cambridge for two years in Europe’s premier colloid science research center—the first American to be invited. From there, he went to Copenhagen to work with Brønsted in the critical year of 1923 when the famous Debye–Hückel paper appeared, setting the theory of complete dissociation on a firm foundation. He was predestined for the career in physical chemistry and colloid science that unfolded (7). At the beginning of the age of specialization, how LaMer chose colloid chemistry suggests something more than just latent interest or innate aptitude. One can assume he was at852

Photo: Columbia University, Chandler Collection

improving paints and varnishes for the canvassing of aircraft. In 1922 he wrote a Ph.D. thesis with Hal Bean at Columbia before embarking on a New York career that lasted half a century. Hammett shares credit with Christopher Ingold and Arthur Lapworth for establishing the field of physical organic chemistry, with the lion’s share belonging to Hammett (Figure 3). He earned that when he wrote Figure 3. Louis Plack Hammett in the first edition of Physical 1963, the year he received the Organic Chemistry (5). The National Medal of Science. thematic devices that defined this new discipline changed what was largely a synthesis-based organic chemistry into a principles-and-ideas-driven physical organic chemistry. The consequences of this new dimension were enormous. To validate the point, consider the acidity function that Hammett created and the concept of superacidity that followed. That sulfuric acid is a stronger acid in benzene (than in aqueous solution) eventually led George Olah to the 1995 Nobel Prize for demonstrating catalytic effects of superacids. And then there is the famous equation named for Hammett and used by all studying mechanistic organic chemistry and stereochemistry. All his life, Louis Hammett was a concerned citizen of scientific and human rights, speaking out on the issues of his day—basic versus applied research; the need for public understanding of science; the military–industrial establishment, government relationships and the responsibility of scientists; stimulating creativity; and taking direct responsibility for filling the pipeline with the next generation of young scientists (6). In 1954, he looked backward and wrote for JCE of four generations of leadership in chemistry within his own department (1); looking forward, he spoke of the need to mentor young faculty, post-doctoral fellows, and graduate students.

tracted to colloids by the popular course Arthur Thomas taught graduate students at Columbia. More likely it was the lectures Irving Langmuir gave at Columbia in 1916 and that culminated in his famous papers of 1917 on surface action. Later, on LaMer’s return from Copenhagen, Peter Debye took up residence in the United States (Cornell), making it possible to establish a life-long professional collaboration. As was generally true of their generation, LaMer’s career was punctuated by an interlude of applied research. At the time, little was known about nucleation phenomena, particulates in smokes, and the properties of aerosols. LaMer’s laboratory produced a stream of classified research ranging across the field of colloid science from light-scattering methods for determining particle size and sol and dust removal problems by sedimentation and filtration techniques to the principle of foreign nucleation for generating monodisperse aerosols. In 1931, experiments that led to the discovery of deuterium allowed LaMer to begin pioneering investigations of the characteristic properties of heavy water. His investigations of acid–base equilibria in heavy water were the first of its kind. In collaboration with Hammett and his students, LaMer investigated acid–base equilibria in poorly ionizing solvents such as benzene. Questioning the then-prevailing idea that activation energies were independent of temperature, he and his students demonstrated otherwise for reactions involving ions in solution; in turn, these studies strengthened the fragile foundations of transition-state theory. The importance of colloid chemistry in the environment did not escape LaMer’s attention. He and his students made contributions to the problem of limiting water evaporation by the use of monomolecular films and commercial scale recovery of potable water from brackish waters. His studies of surface tension are still considered important work. LaMer founded the Journal of Colloid Science and wrote many theoretical papers on the physics and chemistry of colloids. As is true even for Einstein (whose most heavily cited papers are on peptization phenomena, making of cements and homogenized milk, and refrigeration), among LaMer’s most often cited papers are those with practical implications. He taught one of the core courses in the graduate chemistry curriculum that reflected the current state-of-the-art as well as the history of the field. LaMer left a legacy at Columbia in experimental physical chemistry that sustains to this day (Figure 4).

Harold Clayton Urey (1893–1981) Figure 5 shows Harold Urey (right) in November of 1931 with Ph.D. student Donald MacGillavry in the “grating room” at Columbia observing an electric discharge through hydrogen gas concentrated in deuterium. This spectroscopic experiment proved the existence of deuterium for which Urey won the 1934 Nobel Prize in Chemistry, and the ACS Gibbs Medal. Early in 1931 he had conceived and worked out a method for concentration of the heavy hydrogen isotope by distillation of liquid hydrogen. At the time, although suspected by Aston and others, not only was there no evidence for the existence of the isotopes but many believed the theories of Prout, suggesting atomic weights to be whole number mul-





Figure 4. Victor Kuhn LaMer at the electrical bench in his Havemeyer laboratory in 1938. Besides his essential work on colloids, he produced experimental and theoretical studies on thermodynamics and the kinetics of electrolyte solutions.

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.

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 Standards (now NIST) in Washington, DC where 4000 mL of liquid hydrogen was distilled down to 1 mL (8, 9). High resolution 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 discovery was taken on Thanksgiving Day, 1931. The letter to the editor of Physical Review posted next day narrowly established the priority of the discovery, which led to the 1934 Nobel Prize, two years after Irving Langmuir’s Nobel Prize. In one of the ironies of modern science, Urey’s principal competitor 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 California at Berkeley with Lewis and followed that with a postdoctoral year with Niels Bohr in Copenhagen studying quantum theory and spectroscopy. While in Copenhagen he crossed paths with Victor LaMer working with Brønsted. Returning to the United States, Urey was first appointed assistant, then associate, professor at Johns Hopkins where he collaborated with F. O. Rice, among others. He was a pioneer 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

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 Columbia 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 colleagues 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 cooling cycles. These involve measuring the 16O/18O ratio in carbonate 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 condensation 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 initiating rigorous study of “cosmochemistry”, a term he himself coined. In 1953, he and Ph.D. student Stanley Miller performed an experiment not sufficiently honored in this anniversary year because of another, more famous, experiment. The Urey–Miller experiment demonstrated the synthesis of amino acids via electrical discharge in gases thought to be present in the Earth’s original reducing atmosphere. The other (of course) is the Watson–Crick 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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Report Literature Cited and Reading List 1. Hammett, Louis P. J. Chem. Educ. 1955, 32, 498–517. A lengthy historical statement describing the character and careers 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, 868–934. 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, 36–48. Although he never published his investigations 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. Hammett’s classic monograph was reprinted many times, in several editions and in a dozen languages.

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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, Hammett’s remarks 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 Memoirs, Vol. XLV; National Academy of Sciences Press: Washington, DC, 1975. Appearing in this same volume are biographies of Irving Langmuir (by Suits and Martin) and Marston Taylor 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, 164–165. 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 deuterium collaboration with Urey.

Leonard Fine is in the Department of Chemistry, Columbia University, Havemeyer Hall, New York, NY 10027; [email protected].


Chemistry in the City: Columbia Sketches - Journal of Chemical

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