Lewis and Randall (1923)

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Thermodynamics and the Free Energy of Chemical Substances by G.N. Lewis and M. Randall, published by McGraw-Hill Book Company Inc. and printed in the USA. This copy is a first edition from 1923.

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Click on the image to view the entire book on The Internet Archive


Lewis and Randall were among the first to apply the thermodynamic principles developed by Josiah Willard Gibbs (1839-1903) to chemical processes, and are credited with establishing chemical thermodynamics as a modern, practical science.

This book adopted the use of the term ‘free energy’ to refer to the zeta function (U-TS+PV) introduced by Gibbs rather than the “freie Energie” function (U-TS) introduced by Helmholtz in his 1882 paper “Die Thermodynamik chemischer Vorgänge” (On the Thermodynamics of Chemical Processes).

The authors cited ‘confusion in the literature’ for this move, which had the effect of associating the free energy concept with Gibbs (who never used the term) and removing it from Helmholtz (who actually coined the term). This historical unfairness has been corrected since Lewis and Randall’s day, with U-TS now known as the Helmholtz Free Energy and U-TS+PV known as the Gibbs Free Energy.

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Extract of an article by William B. Jensen, Dept. of Chemistry, University of Cincinatti, published in 2000 by Britannica Online

Lewis’ major area of research was the field of chemical thermodynamics. In 1899 there was still a large gap between thermodynamic theory and practice. On the one hand, there was a complete theory of chemical equilibria developed 24 years earlier by the American physicist Josiah Willard Gibbs, which showed that chemical equilibrium was determined by the free energies of the reacting substances, and, on the other, there was a vast collection of data on the enthalpies of formation and reaction of chemical substances as measured by such chemists as Julius Thomsen and Marcellin Berthelot earlier in the century, as well as a series of empirical laws dealing with the behavior of ideal gases and dilute solutions which formed the substance of the newer physical chemistry championed by such European chemists as Wilhelm Ostwald, Svante Arrhenius, Jacobus van’t Hoff, and Walther Nernst. Lewis set himself the task of closing this gap. This required that he either directly measure the missing free-energy values for chemical substances or supplement the existing enthalpy data with entropy values, which would allow their calculation. It was also necessary to find some way of extending the empirical laws to include the behavior of real gases and concentrated solutions.

In pursuit of the first of these goals, Lewis initiated a vigorous experimental program designed to measure the missing free-energy and entropy values and, in pursuit of the second, he successively introduced the concepts of fugacity (1901), activity (1907) and ionic strength (1921). These efforts culminated in 1923 in the publication of the book, Thermodynamics and the Free Energy of Chemical Substances, written in collaboration with his personal assistant, Merle Randall. A revised second edition of this book was published in 1961, 15 years after Lewis’ death.

Link: https://chemistry.as.miami.edu/_assets/pdf/murthy-group/gn-lewis-jensen.pdf

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