Thermodynamics of U(VI) and Eu(III) complexation by unsaturated carboxylates

The thermodynamic parameters (ΔG, ΔH and ΔS) of complexation of U(VI) and Eu(III) by unsaturated dicarboxylic acids, namely, maleic and fumaric acid, has been determined by potentiometric and microcalorimetric titrations at fixed ionic strength (I = 1.0 M) and temperature (298 K). The results show formation of 1:1 complexes by both the ligands with Eu(III). In the case of U(VI), maleate forms both 1:1 and 1:2 complexes, while only 1:1 complex was formed with fumarate. The fluorescence emission spectra of Eu(III)–dicarboxylate solutions at varying ligand to metal ratio were also used to obtain their stability constants. In addition, the fluorescence lifetimes reveal higher dehydration of Eu(III)–maleate compared to Eu(III)–fumarate which corroborates the ΔS values. The thermodynamic quantities suggest charge polarization effects in the case of U(VI) and Eu(III) complexes of fumarate, which is further corroborated by theoretical calculations. For the same ligand, U(VI) complexes were found to be more stable which was mainly due to higher entropy term.

► ΔH and log K determined for U(VI) and Eu(III) complexes with maleate and fumarate. ► log K and coordination environment of Eu(III) complexes has been studied by TRFS. ► Higher log K of U(VI) complexes than Eu(III) complexes is due to higher entropy. ► Plot of log K vs log KP suggest charge polarization in fumarate complexes. ► Ab initio calculations support charge polarization in fumarate complexes.