Thermodynamics and the Free Energy

In 1923. Lewis published a classic book (later reprinted by Dover Publications) titled Valence and the Structure of Atoms and Molecules. Here, in Lewis s characteristically lucid style, we find many of the basic principles of covalent bonding discussed in this chapter. Included are electron-dot structures, the octet rule, and the concept of electronegativity. Here too is the Lewis definition of acids and bases (Chapter 15). That same year, Lewis published with Merle Randall a text called Thermodynamics and the Free Energy of Chemical Substances. Today, a revised edition of that text is still used in graduate courses in chemistry. 

G. N. Lewis and M Randall. "Thermodynamics and the Free Energy of Chemical Substances", First Edition, McGraw-Hill Book Company. New York. 1923, p. 448. 

Lew Lewis, G.N., Randall, M. Thermodynamics and the Free Energy of Chemical Substances, New York McGraw Hill, 1923. 

Lewis, G. N. and M. Randall, Thermodynamics and the Free Energy of Substances, 1923. Pourbaix, M., Atlas d equilibres Mectrochimiques, Gauthier-Villars, Paris, 1963 English translation Atlas of Electrochemical Equilibria in Aqueous Solutions, Pergamon Press, Oxford, 1966. 

C. H. P. Lupis, Chemical Thermodynamics of Materials. New York North-Holland, 1983. K. S. Pitzer, Thermodynamics. New York McGraw-Hill, 1995. (Based on G. N. Lewis and M. Randall, Thermodynamics and the free energy of chemical substances. New York McGraw-Hill, 1923. 

The concept of substance activity was derived by Gilbert N. Lewis in 1907 from the laws of equilibrium thermodynamics and is described in detail in the text entitled Thermodynamics and the Free Energy of Chemical Substances by Lewis and Randell (1923). In a homogeneous mixture, each component has a chemical potential (jjl), which describes how much the free energy changes per mole of substance added to the system. The chemical potential of water (pw) in a solution is given by... 

Lewis and Randall s Thermodynamics and the Free Energy of Chemical Substances used a notation different from Continental notation, necessitating a standardization in notation by a committee set up jointly by the Faraday Society, the Chemical Society, and the Physical Society. See Slater, Introduction, v. 

The fascination of a growing science lies in the work of the pioneers at the very borderland of the unknown, but to reach this frontier one must pass over well travelled roads of these one of the safest and surest is the broad highway of thermodynamics. (Lewis, G.N., Randall, M. (1923). Thermodynamics and the Free Energy of Chemical Substances, New York McGraw-Hill.)... 

Gibbs epochal paper of 1873-76 represents a watershed in the history of thermodynamics. The following seven decades of physical chemistry research were largely devoted to working out the rich consequences of that work, which served as the master blueprint for the classic edifice of thermodynamics. As described by G. N. Lewis and M. Randall in the near-mystical opening words of their Preface to Thermodynamics and the Free Energy of Chemical Substances (McGraw-Hill, New York, 1923) ... 

The free energies in (18) are illustrated in Fig. 10. It can be seen that GA is that part of AG ° available for driving the actual reaction. The importance of this relation is that it allows AGXX Y to be calculated from the properties of the X and Y systems. In thermodynamics, from a list of n standard electrode potentials for half cells, one can calculate j (m — 1) different equilibrium constants. Equation (18) allows one to do the same for the %n(n— 1) rate constants for the cross reactions, providing that the thermodynamics and the free energies of activation for the symmetrical reactions are known. Using the... 

G. N. Lewis (above) conceived the octet rule while lecturing to a class of general chemistry students in 1902. He was also one of the two authors of a now classic work on thermodynamic, Lewis and Randall, Thermodynamics and the Free Energy of Chemical Substances (1923). (right) This is his original sketch. From G. N. Lewis, Valence, Dover Publications, Inc., New York, 1966. 

Lewis and Randall, J. Am. Chem. Soc., 43, 1112 (1C21) Thermodynamics and the Free Energy of Sub nces/ 1023, Chaps. XXII to XXVIII Glasstone, Text-book of Physical Chemistry, 1940, Chap. IX. 

Lewis and Randall, Thermodynamics and the Free Energies of Chemical Substances," New York, McGraw-Hill Book Co., 1923, p. 574. 

In this section we describe two methods for determining partial molal quantities for two-component systems from experimental data. In both cases the experimental data necessary are the behavior of the extensive property G or, equivalently, the intensive property as a function of the mole fraction of one of the components. (More details can be found in the book Gilbert Newton Lewis and Merle Randall, Thermodynamics and the Free Energy of Chemical Substances, pp. 36-41, McGraw-Hill Book Company, Inc., New York, 1923.)... 

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