Research Papers: Energy Storage/Systems

Principle of Detailed Balance and the Second Law of Thermodynamics in Chemical Kinetics

[+] Author and Article Information
Mohammad Janbozorgi

Aerospace and Mechanical
Engineering Department,
University of Southern California,
Los Angeles, CA 9008
e-mail: mjanbozorgi@gmail.com

Hameed Metghalchi

Mechanical and Industrial
Engineering Department,
Northeastern University,
Boston, MA 02115

1Corresponding author.

Contributed by the Advanced Energy Systems Division of ASME for publication in the Journal of Energy Resources Technology. Manuscript received December 11, 2012; final manuscript received April 5, 2013; published online June 24, 2013. Assoc. Editor: Mansour Zenouzi.

J. Energy Resour. Technol 135(4), 041901 (Jun 24, 2013) (4 pages) Paper No: JERT-12-1287; doi: 10.1115/1.4024221 History: Received December 11, 2012; Revised April 05, 2013

The principle of detailed balance is shown to be a sufficient condition for the second law of thermodynamics in thermally equilibrated elementary chemical reactions. For an elementary reaction, the principle of detailed balance relates the forward and the reverse rate constants through the reaction equilibrium constant. It is shown that, in addition to the long known thermodynamic inconsistency at chemical equilibrium state, departure from this principle introduces an extra source/sink of entropy in the entropy balance for an elementary chemical reaction. The departure results in the wrong final chemical equilibrium state and, depending on the choice of the reverse rate constants, may lead to negative entropy productions during kinetic transients.

Copyright © 2013 by ASME
Your Session has timed out. Please sign back in to continue.


Huynh, L. K., Carstensen, H. H., and Dean, A. M., 2010, “Detailed Modeling of Low–Temperature Propane Oxidation: 1. The Role of the Propyl + O2 Reaction,” J. Phys. Chem. A, 114(24), pp. 6594–6607. [CrossRef] [PubMed]
“Lawrence Livermore National Laboratories,” https://www-pls.llnl.gov
Keck, J. C., 1990, “Rate-Controlled Constrained-Equilibrium Theory of Chemical Reactions in Complex Systems,” Prog. Energy Combust. Sci., 16(2), pp. 125–154. [CrossRef]
Slattery, J. C., Cizmas, P. G. A., Karpetis, A. N., and Chambers, S. B., 2011, “Role of Differential Entropy Inequality in Chemically Reacting Flows,” Chem. Eng. Sci., 66, pp. 5236–5243. [CrossRef]
Fay, J. A., 1965, Molecular Thermodynamics, Addison-Wesley, Reading, MA.
DeGroot, S. R., and Mazur, P., 1962, Non-Equilibrium Thermodynamics, North-Holland, Amsterdam.
Sun, Z. F., and Carrington, C. G., 1991, “Application of Nonequilibrium Thermodynamics in Second Law Analysis,” ASME J. Energy Resour. Technol., 113(1), pp. 33–39. [CrossRef]
Petzold, L., 1982, “Differential/Algebraic Equations are Not Ode's,” SIAM (Soc. Ind. Appl. Math.) J. Sci. Stat. Comput., 3(3), pp. 367–384. [CrossRef]
Kee, R. J., Rupley, F. M., and Miller, J. A., 1989, “CHEMKIN-II: A FORTRAN Chemical Kinetics Package for the Analysis of Gas–Phase Chemical Kinetics,” Technical Report No. SAND89-8009B.
Gyftopolous, E. P., and Beretta, G. P., 2005, Thermodynamics, Foundations and Applications, Dover Publications, New York, Reading, MA.
Gordon, S., and McBride, B., 1994, Computer Program for Calculation of Complex Chemical Equilibrium Compositions and Applications, NASA sp-273, NASA Glenn Research Center.
Reynolds, W. C., 1986, “The Element Potential Method for Chemical Equilibrium Analysis: Implementation in the Interactive Program,” Stanjan, Stanford University, Report No. ME270 7.
Bishnu, P. S., Hamiroune, D., and Metghalchi, M., 2001, “Development of Constrained-Equilibrium Codes and Their Applications in Nonequilibrium Thermodynamics,” ASME J. Energy Resour. Technol., 3(123), pp. 214–220. [CrossRef]


Grahic Jump Location
Fig. 1

Comparison of predictions of the rate of entropy production under PDB and the original reverse rate constants

Grahic Jump Location
Fig. 2

Rate of entropy production when Arev = 1 × 1020 in HO2 + H = H2 + O2



Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In