The Influence of Reagent Association on the Kinetics of Liquid-Phase Chemical Reactions

The influence of the association of reagents on the kinetics of liquid-phase chemical reactions was studied using several simple kinetic schemes (first- and second-order reactions and radical chain reactions with initiation, chain propagation, and chain termination steps). Analytic equations relating the observed (effective) rate constants to the rate constants of elementary reaction events, equilibrium constant between monomers and dimers, and reagent and solvent concentrations were obtained. These relations were shown to be nonlinear and independent of the kinetic law of the reaction. The temperature dependence of the effective rate constant was found to be described by a dependence more complex than the Arrhenius equation.