Proton Transfer Kinetics in Medium-strong Inorganic Acids

Abstract

A method of obtaining relative and absolute rate constants for proton transfer equilibria is described. It is suitable for equilibria of the type[Formula: see text]in dilute (< 0.1 M) solutions of medium strong inorganic acids. To obtain absolute values of kd, kr it is necessary to know the value of ΔV0 for the equilibrium. Ultrasonic absorption data for aqueous solutions of H3PO4, H3AsO4, and H2SO4 at 20, 10, and 0 °C are presented together with data at 20 °C for H3PO3, H2SeO3, HIO4, NaHSO4, KHSO4, and NH4HSO4. From analysis of the concentration dependence of the excess absorption, values of Ka are calculated for these acids, and values of kd, kr for those where ΔV0 is available. The Ka obtained are in reasonable agreement with literature values except for HIO4 and H2SeO4. The absolute values of kr for H3PO4, H3AsO4, and HSO4− indicate that the diffusion controlled recombination process postulated is complete when the ions are about 15 Å from each other.