NONEQUILIBRIUM EFFECTS ON FORWARD AND REVERSE RATE COEFFICIENTS OF REVERSIBLE-REACTIONS IN SOLUTIONS - A STOCHASTIC APPROACH

The kinetics of irreversible and reversible reactions in solution is studied by applying a stochastic approach in the sense of Teramoto and Shigesada. For sufficiently low reactant concentrations the random processes attributed to the reactions reduce to Markovian ones, i.e. rate equations follow as deterministic approximation form a master equation and rate coefficients from its transition rates. The forward and reverse rate constants for the reactions A + B half-arrow-pointing-right-half-arrow-pointing-left- C, A + B half-arrow-pointing-right-half-arrow-pointing-left C + B and A + B half-arrow-pointing-right-half-arrow-pointing-left C + D derived in this way have the involved structure well-known from other papers. Our treatment does not confirm the objections to former results recently rised by Lee and Karplus [1].