Orthonormal chemical reactions and chemical relaxation. Part 2.—Reactions in non-ideal solutions

Abstract

A general method is described for obtaining the relaxation times, normal coordinates and normal modes of reaction of a non-ideal chemical system. The normal modes are obtained as a set of orthonormal reactions, though the orthonormality condition is more complicated than in dilute solution. Earlier results¹ for the properties of an orthonormal set of reactions (not necessarily the normal modes) in dilute solution hold with but slight modification in the non-ideal case. In particular, the affinity of the kth orthonormal reaction is independent of the extents of reaction of the remaining reactions and is given by –RTξ_k where ξ_k is the extent of the kth reaction, in mol/mol of solvent, measured from equilibrium.