Gilbert N. Lewis : biography

Thermodynamics

Most of Lewis’ lasting interests originated during his Harvard years. The most important was thermodynamics, a subject in which Richards was very active at that time. Although most of the important thermodynamic relations were known by 1895, they were seen as isolated equations, and had not yet been rationalized as a logical system, from which, given one relation, the rest could be derived. Moreover, these relations were inexact, applying only to ideal chemical systems. These were two outstanding problems of theoretical thermodynamics. In two long and ambitious theoretical papers in 1900 and 1901, Lewis tried to provide a solution. Lewis introduced the thermodynamic concept of activity and coined the term "fugacity".(1908) "The osmotic pressure of concentrated solutions, and the laws of the perfect solution," J. Am. Chem. Soc. 30: 668-683. His new idea of fugacity, or "escaping tendency", was a function with the dimensions of pressure which expressed the tendency of a substance to pass from one chemical phase to another. Lewis believed that fugacity was the fundamental principle from which a system of real thermodynamic relations could be derived. This hope was not realized, though fugacity did find a lasting place in the description of real gases.

Lewis’ early papers also reveal an unusually advanced awareness of J. W. Gibbs’s and P. Duhem’s ideas of free energy and thermodynamic potential. These ideas were well known to physicists and mathematicians, but not to most practical chemists, who regarded them as abstruse and inapplicable to chemical systems. Most chemists relied on the familiar thermodynamics of heat (enthalpy) of Berthelot, Ostwald, and Van’t Hoff, and the calorimetric school. Heat of reaction is not, of course, a measure of the tendency of chemical changes to occur, and Lewis realized that only free energy and entropy could provide an exact chemical thermodynamics. He derived free energy from fugacity; he tried, without success, to obtain an exact expression for the entropy function, which in 1901 had not been defined at low temperatures. Richards too tried and failed, and not until Nernst succeeded in 1907 was it possible to calculate entropies unambiguously. Although Lewis’ fugacity-based system did not last, his early interest in free energy and entropy proved most fruitful, and much of his career was devoted to making these useful concepts accessible to practical chemists.

At Harvard, Lewis also wrote a theoretical paper on the thermodynamics of blackbody radiation in which he postulated that light has a pressure. He later revealed that he had been discouraged from pursuing this idea by his older, more conservative colleagues, who were unaware that W. Wien and others were successfully pursuing the same line of thought. Lewis’ paper remained unpublished; but his interest in radiation and quantum theory, and (later) in relativity, sprang from this early, aborted effort. From the start of his career, Lewis regarded himself as both chemist and physicist.

Valence theory

Lewis’ [[cubical atoms (as drawn in 1902)]]

About 1902 Lewis started to use unpublished drawings of cubical atoms in his lecture notes, in which the corners of the cube represented possible electron positions. Lewis later cited these notes in his classic 1916 paper on chemical bonding, as being the first expression of his ideas.

A third major interest that originated during Lewis’ Harvard years was his valence theory. In 1902, while trying to explain the laws of valence to his students, Lewis conceived the idea that atoms were built up of a concentric series of cubes with electrons at each corner. This “cubic atom” explained the cycle of eight elements in the periodic table and was in accord with the widely accepted belief that chemical bonds were formed by transfer of electrons to give each atom a complete set of eight. This electrochemical theory of valence found its most elaborate expression in the work of Richard Abegg in 1904, but Lewis’ version of this theory was the only one to be embodied in a concrete atomic model. Again Lewis’ theory did not interest his Harvard mentors, who, like most American chemists of that time, had no taste for such speculation. Lewis did not publish his theory of the cubic atom, but in 1916 it became an important part of his theory of the shared electron pair bond.