Studies on the Complexation Behavior of Thorium(IV). 1. Hydrolysis Equilibria

The stability constants of thorium(IV) hydrolysis species have been measured at15, 25, and 35°C (in 1.0 mol dm−3 NaClO4) using both potentiometry and solventextraction. The results indicate the presence of the monomeric speciesTh(OH)3+, Th(OH)2+2, Th(OH)+3, and Th(OH)4, in addition to the polymericspecies Th4(OH)8+8 and Th6(OH)9+15. The polymeric species were found to beimportant, although the total thorium concentration was limited to 0.01–0.1mmol-dm−3. The solvent extraction measurements required the use of acetylacetone.As such, the stability constants of thorium(IV) with acetylacetone were alsomeasured using both potentiometry and solvent extraction. All logarithms of thestability constants were found to be linear functions of the reciprocal absolutetemperature indicating that ΔHo and ΔSo of reaction are both independent oftemperature (over the temperature range examined in the study).