Solvation numbers and hydration constant for thorium(IV) in ethanol-water medium

The solvation number and hydration constant of Th4+ in ethanol-water medium were determined at 25°C using UV-spectral and electrochemical measurements. A solvate formation equilibrium is demonstrated and characterized. Three molecules of ethanol (S) can bond to the metal cation with strengths comparable to that for H2O to form ThS3(H2O) 3 4+ Formation of thorium monochelate with lawsone (2-hydroxy-1,4-naphthoquinone) eliminates bonding with alcohol molecules. The dissociation constant of the chelating agentsKa and the formation contant of the monochelated metal ionsK f * that are essentially independent of the solution composition are evaluated. Hydration titrations involving thorium-lawsone monochelate are performed and the data obtained from the changes of pH with solvent composition are analyzed. The solution independent constant,sK f * for thorium-lawsone complex formation in mixed aqueous ethanol is given by $$log_s K_f * = vpK_a + log_s K_h - log[LH] - vpH + 3logv$$ where vpKa is the dissociation constant of the chelating agent LH in the solvent system of ν volume fraction of water andsKh is the solution-independent hydration constant of thorium (IV) in the solvent system. Log-values for the constantssKh,sK f * andsK a * are found to be 7.8±0.02, 11.38±0.04 and −0.753, respectively.