Journal
JOURNAL OF CHEMICAL EDUCATION
Volume 89, Issue 9, Pages 1159-1167Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ed1007712
Keywords
Upper-Division Undergraduate; Biochemistry; Physical Chemistry; Inorganic Chemistry; Aqueous Solution Chemistry; Bioinorganic Chemistry; Biophysical Chemistry; Catalysis; Electrochemistry; Enzymes; Kinetics; Oxidation/Reduction; Thermodynamics
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Although it is generally true that thermodynamics do not influence kinetics, this is NOT the case for electron transfer reactions in solution. Marcus Theory explains why this is so, using straightforward physical chemical principles such as transition state theory, Arrhenius' Law, and the Franck-Condon Principle. Here the background and applications of Marcus Theory are presented, with special emphasis given to biological redox reactions. Interesting conclusions that arise from the theory are also discussed. These include the nonlinear contribution of reorganization energy (lambda) to the activation free energy (Delta G(double dagger)), as well as the existence of a defined normal range of reaction cell potential (Delta E degrees): Only if Delta E degrees is within this range does a reaction of lower lambda have a lower Delta G(double dagger); outside of this range, the lower-lambda reaction will have the higher Delta G(double dagger).
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