Orthonormal chemical reactions and chemical relaxation. Part 3.—Reactions in solution under various thermodynamic conditions

Abstract

The method described previously 2 for obtaining the relaxation times, normal coordinates and normal modes of relaxation of a non-ideal chemical system at constant temperature and pressure is extended to relaxation under adiabatic conditions and/or at constant volume; in each case the normal modes of relaxation are obtained as an orthonormal set satisfying orthonormality conditions similar to those pertaining to constant temperature and pressure. First-order perturbation theory is used for evaluating the various corrections required when the simple dilute-solution theory 1 is used at concentrations which are too high for the theory to be strictly applicable.