J . Phys. Chem. 1989, 93, 2091-2092 In summary, it can be supported that the theory developed in this paper sheds new light on the hydrogen intercalation reaction within transition-metal oxide mediated by metal particles and that it yields a number of interesting thermodynamic parameters characterizing this important class of reactions.
2091
Acknowledgment. J.J.F. thanks Drs. P. Levitz, D. Tinet, and H. Vandamme for interesting discussions. This work was supported by the University of Wisconsin-Milwaukee, in particular by a postdoctoral fellowship awarded to J.-F.L. by the Laboratory of Surface Studies and by the Graduate School. Registry No. H2,1333-74-0;Pt, 7440-06-4.
(23) Tinet, D.; Fripiat, J. J. J . Chim. Phys. 1979, 76, 867.
Thermodynamics of Chemical Systems Far from Equilibrium John ROSS* Department of Chemistry, Stanford University, Stanford, California 94305
and Leopoldo S. Garcia-Colin Department of Physics, UAM-Iztapalapa, APDO Postal 55-534, Mexico, D.F. 09340 (Received: June 23, 1988; In Final Form: September 1 , 1988)
A critique is presented of some recent work in this and other journals on the relation of thermodynamics to the mass action law of kinetics. For most chemical reactions, the thermodynamic variables change on the same time scale as the progress variable and there is no need for an “extended thermodynamics”.
The formulation of thermodynamics of systems far from equilibrium is in the process of development. In this work we focus on chemical reactions and a series of articlesi4 concerned with the relation of thermodynamics to the mass action law, time scales in such systems, and the possible need of a so-called *extended thermodynamics”. Some approaches and statements in these articles require, we believe, correction. Consider a single reaction step with progress variable [ and affinity
where u1is the stoichiometric coefficient of species 1 in the reaction (>0 for products,
