Linear free-energy relationships in the hydrolysis of metal ions. The effect of the ionic medium

Abstract

The effect of a lithium, sodium, and potassium chloride medium on the hydrolysis of thorium(IV) has been studied by a potentiometric and calorimetric method. The data obtained show that the extent of hydrolysis of thorium, the stability constants of its hydrolytic complexes, and the associated thermodynamic parameters are affected by the ionic medium. Correlations between the free energies of the hydrolytic processes and the properties of the medium are considered by the linear free-energy approach. The uranyl and nickel hydrolysis data imply generality of the proposed relationship.