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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.

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Figures

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

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