William Lash Miller (1866-1940) - American Chemical Society

Chapter 12

William Lash Miller (1866-1940)

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W . A. E. McBryde Department of Chemistry, University of Waterloo, Waterloo, Ontario N 2 L 3G1, Canada Physical chemistry was still in its infancy when Miller earned his second German Ph.D. under Ostwald in 1892. His first Ph.D. in 1890 had been in organic chemistry. His thesis work at Leipzig incorporated a validation of the theoretical ideas of Willard Gibbs by demonstrating that the electrode potentials of several fusible metals at their melting points were the same whether the metals were solid or liquid. Miller went on to become one of the leading exponents of Gibbs' chemical thermodynamics in North America; and electrochemistry — theoretical and applied — under his leadership became a major research interest at the University of Toronto throughout and even beyond his own lifetime. In his heyday he was undoubtedly the Canadian chemist best known in the United States, and held high office in many chemical and scientific societies in that country as well as in Canada. This paper will examine parts of his career especially pertinent to pure and applied electrochemistry. The Department of Chemistry at the University of Toronto is housed in a handsome building known as the Lash Miller Chemical Laboratories, opened just twenty-five years ago. The person after whom this edifice was named is William Lash Miller, the fourth professor or headof-department of chemistry to serve during the first 95 years in which that university — originally known as King's College, Toronto — was in operation. It would be no exaggeration to state that for a time Miller was the most distinguished, the most colorful, and the best-known chemist in Canada. The occasion of this great North American Chemical Congress in Toronto is a suitable time in which to illuminate some aspects of his career; and this particular symposium affords an opportunity to dwell on one part of that career — his achievements in electrochemistry.

0097-6156/89/0390-0165$06.00/0 © 1989 American Chemical Society

Stock and Orna; Electrochemistry, Past and Present ACS Symposium Series; American Chemical Society: Washington, DC, 1989.

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Academic Career Miller might be described as a quintessential Canadian of his time. His great-great grandfather settled as a loyalist in Niagara, British North America, in the early 1780s. His descendants gradually moved inland into what became Canada West, and ultimately Ontario; several of them made careers in law. Lash Miller's grandfather served as a lawyer in Dundas, and then as a judge in Galt; his father was a prominent Toronto lawyer. When young Miller entered the University of Toronto in 1883 he may well have had in mind following his forebears' vocation. He arrived from high school with honors in classics, and continued the study of classics for two more years. However, in his first year he also received instruction in chemistry from William H. Pike, who had come as Toronto's second professor of chemistry from Merton College, Oxford, and whose credentials included a Ph.D. from Göttingen. Pike's lectures appear to have taken Miller's fancy, for in succeeding years his academic program veered to the sciences and his academic standing rose significantly. In his graduating year Miller stood at the top of his class in Natural Science, and he received a gold medal from the chemistry department. Pike was an enthusiastic advocate of the merits of chemical education in Germany at that time, and he encouraged Miller to undertake further studies in that country. Following the prevailing practice Miller spent some time in each of three universities: with Hofmann in Berlin, with Victor Meyer in Göttingen, and with Claisen in Munich. He submitted a dissertation at Munich on certain derivatives of acetone oxalic esters, thereby earning a Ph.D. in 1890. That summer he went to Leipzig, where he worked in Ostwald's laboratory; subsequently he spent the summer of 1892 also with Ostwald, and incorporated the work he did there into a second dissertation for a second Ph.D. From Ostwald, Miller quickly gained insight into the still comparatively young subject of physical chemistry, and especially into the language and method of Gibbsian thermodynamics. No other aspect of chemistry was ever to be so closely linked with Miller's name as this last-mentioned one. The investigation described in his second thesis was a demonstration that the emf of an electrochemical cell containing a fusible metal electrode (mercury, tin, or lead) was independent of whether the metal was in the liquid or solid state. Given the equality of the chemical potential in either phase of the electrode substance, the importance of the Gibbs free energy in fixing the electrode potential was confirmed. This was Miller's first exploit in electrochemistry, a topic with which he and many of his students became closely identified. University of Toronto. Miller was appointed a Fellow in chemistry at the University of Toronto in the autumn of 1890, Demonstrator the following year, and Lecturer in 1894. In 1898 Pike was afflicted by a severe throat ailment and was given a year's leave of absence; in the following year he submitted his resignation. However, no action was taken to fill the chair until 1900, and consequently Miller was in charge of the chemistry department for two years, Pike having returned to England. Then occurred one of those strange obliquities of judgment of which examples litter the pages of history. The vacant professorship was advertised and attracted a number of excellent



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candidates (including one who later won a Nobel prize, and two others who were subsequently knighted and became Fellows of the Royal Society). Miller was in the running with Pike's strong endorsement. In the event, the position was awarded to one W.R. Lang, a recentlyappointed lecturer at the University of Glasgow, Miller's junior by three years, and with a very modest record of research accomplishment. It was a bitter snub for Miller, who had served ten years as a staff member in the department, and who was by this time gaining recognition as a productive scholar. He very nearly left Toronto and, indeed, went so far as to lease a house in Ithaca, N.Y. for a year (although he never occupied it) on the promise of an appointment at Cornell University. In the end he decided to stay on and fight. His situation was made at least more palatable by his immediate appointment as Associate Professor (then a relatively rare title at Toronto) of Physical Chemistry. Relations between Lang and Miller at no stage ever became cordial, but Miller's title, which was changed to Professor of Physical Chemistry in 1908, gained for him a measure of independence, especially in budgetary and research matters. Tensions, which were acute during the first year or two of Lang's professorship, gradually eased, especially through the intervention of W.H. Ellis — the Professor of Applied Chemistry in the School of Practical Science (which later became the Faculty of Applied Science and Engineering in the University of Toronto). Ellis had been assistant to Henry Croft, the first professor of chemistry in the university; he was an older man of sterling qualities, and appears to have served as an effective peace-maker among the chemists. He also appears to have facilitated the creation of a sub-department of electrochemistry in the university, and its installation in a new Chemistry and Mining Building built in 1905. (This housed the Department of Applied Chemistry, while the Department of Chemistry occupied the Chemical Laboratory across the street.) An account of activities in that unit will be given presently. but first it will be appropriate to complete an outline of Miller's academic career at Toronto. When the first World War broke out in 1914, Professor Lang, who had had a long record of service with militia unit in Britain and then in Canada, enlisted for active duty. On this account Miller inherited much of the day-to-day running of the chemistry department, consulting with Lang as necessary on important matters. After the war Lang was appointed to a professorship of Military Studies in the University of Toronto, and Miller finally became head of the department in 1921. He served in that capacity until 1937, retiring at age 70 with the title Professor Emeritus. He died a few days before his 74th birthday. Electrochemistry and Thermodynamics. Miller's researches were varied, and not always easy to identify because he frequently omitted his own name as an author of papers describing work done by his students. Given the particular emphasis of this symposium we shall give prominence in this account to electrochemical investigations conducted under his supervision or at his instigation. As early as 1903 he began with T.R. Rosebrugh (a professor of Electrical Engineering) the evaluation of certain functions



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of e-x required for the quantitative study of diffusion and similar phenomena. Later (1910) the same two men published an important mathematical treatment of diffusion and chemical action at electrodes. This collaboration is suggestive of the interdisciplinary character of the sub-department of electrochemistry to which reference has already been made. Undergraduate instruction in electrochemistry was given to chemistry and chemical engineering students together for decades, and graduates of either department engaged in postgraduate research in the unit. Papers published from the electrochemical laboratory bear titles suggestive of a wide range of interests and activities. As well as the topics already mentioned, work of a fundamental character is suggested by the numerical evaluation of infinite series and integrals which arise in certain problems of linear heat flow, electrochemical diffusion, etc. (1931), or the theory of the direct method of determining transport numbers (1908). There were studies of electrodeposition from aqueous solutions, including polarization and concentration changes at electrodes (1924). There were papers dealing with more practical matters, such as the formation of a badly-conducting film on copper anodes working in cyanide solutions (1915), or electrodeposition of copper or nickel on aluminum (1922). There were papers dealing with electrical conductivity of various refractories (1922, 1925), multiple electrode systems and throw in electroplating baths (1923), current-voltage relationships in carbon arcs (1923-24), and so on. It was quite an active school of research. Two of Miller's students in this field remained as staff members: J.T. Burt-Gerrans and A.R. Gordon. The latter earned an enviable reputation for the excellence of researches done in his laboratory on conductivity, transference numbers, diffusion coefficients, and other thermodynamic properties of solutions. Lest the preceding information create the impression that Miller's researches were restricted solely to electrochemistry, it may be appropriate to mention briefly the considerable amount of other work in which he and his students were engaged over the years. This included quantitative studies of the kinetics of a number of familiar reactions in solution, and several investigations of vapor pressures of binary systems as a basis for evaluating partial free energies in solution. This latter work was extensively continued in the department by John B. Ferguson, a former student who was appointed to the teaching staff in 1921. And, finally, some allusion must be made to Miller's search, throughout a period of more than twenty years, for the identity of the nutrient substances essential for the growth and reproduction of micro-organisms. This almost obsessive undertaking to determine the nature of Wildier's 'bios' became the quest for Miller's personal scientific 'holy grail'. In retrospect, it must be acknowledged to have yielded very little of consequence. It was an attempt too far in advance of the sorts of separative and analytical techniques that are commonplace today to have permitted a successful outcome, and represented an investment of time and effort too costly in proportion to the meagre and probably now inconsequential results that it yielded. Miller's fascination with Gibbsian thermodynamics, to which reference was made previously, was a cornerstone not only for his own approach to chemistry but also for much of the teaching in the



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Toronto chemistry department. Miller himself taught this in each of three years to the students specializing in chemistry. He did not lecture, but rather conducted seminars based on Socratic inquiry — probing, cajoling, bullying, always making his point by relentless logic. He taught direct from Gibbs, and there is the story told dramatically by Wilder Bancroft of the time when Miller personally bought up the publisher's entire residual stock of Gibbs' volume on thermodynamics to ensure continuity of supply for his students. He retained Gibbs' Greek symbols for the thermodynamic functions in all his teaching and writing; of these, only the use of μ has survived to the present day. Miller's first major independent application of Gibbs' theories came with his published explanation of the unexpected observation, made by one of his students, that the addition of salt to aqueous alcohol raised the partial vapor pressure of the alcohol. He was able to explain by thermodynamic reasoning how this phenomenon came about in a paper published in 1897, "On the Second Differential Coefficient of Gibbs' Function T" (1). This title provides a clue to a seldom-realized difference between Miller's treatment of the thermodynamics of binary systems and that developed by G. N. Lewis, which ultimately came to be adopted worldwide. In Miller's system, of which an account was published in 1925 (2), the critical quantity from which partial free energies of components were calculated was the symmetrical second derivative of the Gibbs free energy of the system, symbolically represented by μ12. This method had a certain mathematical elegance, and was perhaps easier to grasp than that based on a standard state and an activity coefficient, as devised by Lewis, but the latter proved to be the more practically useful (3) . Professional Service In surveying Miller's career certain things stand out as highlights, and warrant mention as we summarize his achievements. He was in his time undoubtedly the Canadian chemist best known in the United States. He had encountered and acquired some mastery of the new sub-discip line of physical chemistry at a time when this was not yet well understood or developed in North America. He was fortunate in having found a close friend and personal ally in his fellow student at Leipzig, Wilder Bancroft, who provided Miller with scope for selfdevelopment as a key editor of the former's new Journal of Physical Chemistry. He was endowed with a brilliant mind and boundless energy and enthusiasm, and these qualities earned for him a high level of respect and many honors. He took an active and often leading role in scientific assoc iations. He was a charter member and later chairman of the Canadian Section of the Society of Chemical Industry, the first professional association for chemists in Canada, formed in 1902. Early in this century he was persuaded to join the American Chemical Society, and it is of some interest that he served as secretary of the local com mittee for the 36th Annual Meeting of that body, held in Toronto in 1907. Later he served on the Executive Committee of the Division of Physical and Inorganic Chemistry, and in 1926 was made the first Canadian honorary member of that society. He was an active parti cipant in the American Electrochemical Society, and served as its



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President in 1912; at that body's meeting in Toronto in 1929 he was made an honorary member. He was a member of the Washington Academy of Science, and of the American Association for the Advancement of Science, serving as Vice-President of the latter in 1921. Three years later he was Vice-President of the British Association for the Advancement of Science. Later, in 1934, he served as President of the Royal Society of Canada. In 1923 he was chosen as "one of the seven greatest chemists of the world", who were invited to give addresses on the occasion of the opening of the new Sterling Chemistry Laboratory at Yale University. His address was later published as Reference 2 of this paper. Even when allowance is made for the hyperbole in which such occasions are invested, the inclusion of Miller in this group was no trifling accolade. In 1935, two years before his retirement, he was invested with a national honor as a Commander of the Order of the British Empire (C.B.E.) Miller was a fascinating person, and he acquired both disciples and detractors. A forthcoming history of the Chemistry Department at the University of Toronto, written by the author of this paper, will provide an opportunity for a more complete account of his life, his strengths and his weaknesses. Literature Cited 1. 2. 3.

Miller, W. L. J. Phys. Chem. 1897, 2, 633-642. Miller, W. L. Chem. Rev. 1925, 1, 293-344. LeRoy, D. J. In Dictionary of Scientific Biography; Gillespie, C. C , Ed.; Scribner's: New York, 1974; Vol. 9, pp. 393-95.

RECEIVED August 9, 1988


William Lash Miller (1866-1940) - American Chemical Society

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