FACILITATED ALKALI ION TRANSFER AT THE WATER 1,2-DICHLOROETHANE INTERPHASE - AB-INITIO CALCULATIONS CONCERNING ALKALINE METAL CATION-1,10-PHENANTHROLINE COMPLEXES/
Cg. Sanchez et al., FACILITATED ALKALI ION TRANSFER AT THE WATER 1,2-DICHLOROETHANE INTERPHASE - AB-INITIO CALCULATIONS CONCERNING ALKALINE METAL CATION-1,10-PHENANTHROLINE COMPLEXES/, Journal of electroanalytical chemistry [1992], 451(1-2), 1998, pp. 111-119
A series of calculations on the energetics of complexation of alkaline
metal cations with 1,10-phenanthroline are presented. It is an experi
mental fact that the ordering of the Gibbs energy of transfer across t
he water/1,2-dichloroethane interphase is governed by the charge/size
ratio of the different cations; the larger cations showing the lower G
ibbs energy of transfer. This ordering of the Gibbs energies of transf
er is reverted in the presence of 1,10-phenanthroline in the organic p
hase. We have devised a thermodynamic cycle for the transfer process a
nd, by means of ab initio calculations, have drawn the conclusion that
in the presence of phenanthroline the Gibbs energy of transfer is gov
erned by the stability of the phenanthroline/M+ complex, which explain
s the observed tendency from a theoretical point of view. (C) 1998 Els
evier Science S.A. All rights reserved.