摘要:

AbstractTwo very general methods for dealing with chemical relaxation in solution near equilibrium are developed in detail along parallel lines; in the first of these the normal modes of relaxation are obtained as linear combinations of a set of basic reactions whereas in the second the normal coordinates are obtained as linear combinations of the deviations of the solute concentrations from those at equilibrium. The general procedures described in the literature, differing both in their basic assumptions (some being based on the theory of irreversible thermodynamics, others on kinetic considerations) and also in the concentration units adopted and the normalization procedures used, form special cases of the above two general methods and are considered from this point of view. The two general methods are compared critically and shown to be complementary since each has its own special advantages and disadvantages. In particular, the significance of the normal modes of relaxation corresponding to infinite relaxation times are shown to be entirely different in the two cases; in the first method these modes are “reactionless” and have little significance whereas the “improper” normal modes obtained by the second method show how the concentrations of the various solutes can be changed without disturbing the chemical equilibrium of the

ISSN:0021-2148    

DOI:10.1002/ijch.197300043

出版商:WILEY‐VCH Verlag    

年代:1973

数据来源: WILEY

摘要:

AbstractSolution reactions which occur in pre‐equilibrium excited states, i.e. before the system has reached the lowest thermalized excited state are discussed. Two examples, the photodissociation ofβ‐naphtholate into a solvated electron plus radical and the acid dissociation of excitedβ‐naphthol are dealt with in some detail. It is proposed that in these two cases at least the reactions might take place in a, so called, solvent Franck Condon state, i.e. a state in which the solvent has not yet attained the appropriate excited state orie

ISSN:0021-2148    

DOI:10.1002/ijch.197300044

出版商:WILEY‐VCH Verlag    

年代:1973

数据来源: WILEY