Kinetics of ionic migration. Part 3.—Pressure and temperature coefficients of conductance in nitrobenzene

Abstract

A systematic study has been made of the temperature, pressure and concentration dependence of the conductance of a series of alkylammonium salts in anhydrous nitrobenzene. Temperatures from 20 to 70°C and pressures from 1 to 2000 atm were used. The results are analyzed in terms of the transition state theory, particular attention being paid to the isochoric energy of activation and the volume of activation. Both quantities are dependent on the free volume of the system and are consistent with a kinetic model of ionic migration based on fluctuations of the ion-solvent complex.