Abstract
The electrical conductances of aqueous solutions of MgSO4, Mn(II)SO4 and Cu(II)SO4, of concentrations 2 x 10[-4] to 2 x 10[-3] equiv.1.[-1], have been measured at several frequencies, from 1 Kc. sec.[-1] to 50 Mc. sec[-1], using two radio-frequency transformer ratio-arm bridges and an audio-frequency Wheatstone bridge network. A relative method, which employs KCl as the reference electrolyte, was used for the measurement of the radio-frequency conductances (1 to 50 Mc. sec.[-1]). The measured increases in conductance, brought about by the high-frequency electric field, were often greater than those predicted from the theory for the relaxation of the ion atmosphere. [4,30]. This was particularly true the "weaker" the electrolyte, and the greater the electrolyte concentration. This effect has been attributed to an additional dispersion of conductance due to the relaxation of the equilibrium: ion-pair free ions. The experimentally-measured values of these dispersions were of the order of magnitude required by the Gilkerson [24] theory for the relaxation of the ion-pair equilibrium; using this theory, specific rate constants for ion-pair dissociation have been calculated. Considering the difficult nature of the measurements and the approximations made in the calculations, these rate constant values are in good agreement with those obtained by other workers [40,41] using ultrasonic techniques.