Thermal reactions of inorganic hydroxy-compounds under applied electric fields, III

Abstract

The energy level separation in symmetrical and unsymmetrical double minimum potentials in the presence of electric fields is calculated by first-order perturbation theory, from which the tunnelling probability of protons is obtained for both perturbed and unperturbed potentials. Tunnelling probability is slightly increased by fields of about 105 V/m, but a greater increase in tunnelling probability occurs when a symmetric potential becomes unsymmetric. The tunnelling process is too rapid to account for observed differences in dehydroxylation behaviour of Al(OH)3, Mg(OH)2 and kaolinite under electrolysis. Estimates, from indirect evidence, of the rates of anion defect generation and annihilation support the theory that the rate-determining field-dependent process is the surmounting of anionic lattice vacancies by oxygen-containing species.