Nonequilibrium thermodynamics formalism for Marcus theory of heterogeneous and self-exchange electron-transfer rate constants.
The cross-exchange electron-transfer rate constant expression of Marcus is derived from the Flux-force formalism of non-equilibrium thermodynamics. The relationship governing the Onsager's phenomenological coefficients for cross-exchange and self-exchange electron-transfer processes is deduced. Onsager's phenomenological coefficient pertaining to the Butler-Volmer equation is derived and estimated from the experimental exchange current densities. The correlation between the heterogeneous and the homogeneous electron-transfer rate constants derived by Marcus is analyzed in terms of the corresponding phenomenological coefficients.
Sethi
Richa
R
Department of Chemistry, Indian Institute of Technology, Madras, Chennai-600036, India.
Sangaranarayanan
M V
MV