THE DOUBLE-WELL CAGE EFFECT FOR A FERROCYANIDE DIMETHYLVIOLOGEN ION-PAIR IN VISCOUS MEDIA - KINETIC AND THERMODYNAMIC PROBINGS THROUGH THE CT TRANSITION BAND/
De. Khoshtariya et al., THE DOUBLE-WELL CAGE EFFECT FOR A FERROCYANIDE DIMETHYLVIOLOGEN ION-PAIR IN VISCOUS MEDIA - KINETIC AND THERMODYNAMIC PROBINGS THROUGH THE CT TRANSITION BAND/, Chemical physics letters, 284(1-2), 1998, pp. 121-127
The ion pair recombination kinetics following the electric field induc
ed predissociation, and the ion pair formation kinetics following dire
ct mixing, were studied by temperature jump and stopped-flow technique
s, respectively, in viscous water/glycerol mixtures. The rate constant
detected for the recombination process was virtually independent of t
he glycerol concentration within 65-80% v/v, while direct mixing revea
led viscosity-sensitive dispersive kinetics. Thermodynamic parameters
for the ion pair formation pseudo-equilibrium under the high viscosity
conditions were also determined, which, together with the kinetic dat
a, point to at least a two-step mechanism for the ion pair formation.
(C) 1998 Elsevier Science B.V.