E.A. Guggenheim (1933)

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Modern Thermodynamics by the methods of Willard Gibbs by E.A. Guggenheim, published by Methuen & Co. and printed in Great Britain. This copy, which once graced the library shelves of Christ’s College Cambridge, is a first edition from 1933.

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

This is one of the two books – Lewis and Randall’s Thermodynamics and the Free Energy of Chemical Substances (1923) was the other – which are credited with establishing chemical thermodynamics as a modern, practical science.

That said, the two books are about as far apart as you can get, in this writer’s opinion. Thermodynamics and the Free Energy of Chemical Substances was essentially a vehicle for Lewis’ own ideas about how the equations for perfect gases and ideal solutions could be made to apply to imperfect gases and non-ideal solutions through the use of conceptual contrivances called fugacity and activity. Lewis’ desire to make his mark on the subject is also apparent in the introduction of his phrase ‘escaping tendency’ to replace the name Gibbs gave to his most powerful idea, the chemical potential μ. This, together with the extraordinary fact that the book stops short of stating Gibbs’ famous phase rule formula, gives the impression that Lewis was – knowingly or unknowingly – diminishing the lofty presence of Gibbs while at the same time elevating his own.

Guggenheim’s book takes the opposite approach, as is immediately apparent from the cover title’s reference to ‘the methods of Willard Gibbs’. Chapter One: Introduction and Fundamental Laws not only spells out Gibbs’ Phase Rule but every other Gibbsian contribution to the subject in compendious detail.

Guggenheim was a gifted mathematician and this no doubt helped him to recognize that Gibbs’ achievements did not necessarily benefit from Lewis’ attempts to improve them. It is pointed out at the end of the chapter on non-ideal solutions that since the activity is simply proportional to the product of the mole fraction and activity coefficient, its introduction merely replaces one term with another with no gain in physical meaning.

Although Guggenheim describes fugacity as “a useful conception” in this 1933 book, by 1950 he had reconsidered his view of it, writing in the monograph Thermodynamics: An advanced treatment for chemists and physicists: “The simplification attained by the introduction of the fugacity is one of appearance or elegance, but leads to nothing quantitative unless we express the fugacity in terms of the pressure and we are then back where we started.”

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