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Research Papers

What is a Chemical Equilibrium State?*

[+] Author and Article Information
Gian Paolo Beretta

Universitá di Brescia,
Brescia, Italy,
Massachusetts Institute of Technology,
Cambridge, MA 02139

Elias P. Gyftopoulos

Massachusetts Institute of Technology,
Cambridge, MA 02139

*Proceedings of the International Symposium Ecos'92 on Efficiency, Costs, Optimization and Simulation of Energy Systems, Zaragoza, Spain, June 15–18,1992, edited by A. Valero and G. Tsatsaronis, ASME book I00331, pp. 1–6 (1992). Reprinted with permission.

J. Energy Resour. Technol 137(2), 021008 (Mar 01, 2015) (4 pages) Paper No: 08-GyftopoulosBeretta-Pr; doi: 10.1115/1.4026384 History: Online November 18, 2014

We review the chemical equilibrium equations, and conclude that both their derivation and their meaning are problematic. We find that these equations can be established for a suitably defined simple system without chemical reactions.

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References

Guggenheim, E. A., 1967, Thermodynamics, Fifth, Revised Edition, North-Holland, Amsterdam, pp. 35–38.
Denbigh, K., 1966, The Principles of Chemical Equilibrium, Second Edition, Cambridge University Press, London, pp. 139–140.
Modell, M., and Reid, R. C., 1974, Thermodynamics and Its Applications, Prentice Hall, Englewood Cliffs, New Jersey, pp. 389–391.
Gyftopoulos, E. P. and Beretta, G. P., 1991, Thermodynamics: Foundations and Applications, Macmillan, New York.
Gyftopoulos, E. P., and Beretta, G. P., op.cit., Chapter 30.
Gyftopoulos, E. P., and Beretta, G. P., op.cit., Chapter 17.
Slater, J. C., 1965, Quantum Theory of Molecules and Solids, Vol. 2, McGraw-Hill, New York.
Hatsopoulos, G. N., and Gyftopoulos, E. P., 1979, Thermionic Energy Conversion, Vol.2, MIT Press, Cambridge, Massachusetts, pp. 82–100, and pp. 168–182.
Gyftopoulos, E. P., and Beretta, G. P., op.cit., Section 10.3.
Gyftopoulos, E. P., and Beretta, G. P., op.cit., Chapter 13.
All the results can be readily extended also to systems with other parameters in addition to volume, such as, for example, the location in a uniform gravity field, and the intensity of a uniform electrostatic or magnetostatic field.

Figures

Grahic Jump Location
Fig. 1

Energy versus entropy diagram of the states of simple system A with given values of V,na and ν. Curve (1) represents the states Aε1 and coincides with the curve of the stable equilibrium states of surrogate system B for the given value V of the volume and fixed values n1=na+ε1 ν of the amounts of constituents, that is, a fixed ε1. Curve (2) represents the states Aε2 and coincides with the curve of the stable equilibrium states of surrogate system B for the given value V of the volume and fixed values no n2=na+ε2 ν of the amounts of constituents, that is, a fixed ε2. Curve (3) represents the chemical equilibrium states of system A for the given values of V, na, and ν.

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