Spectrophotometric and Calorimetric Studies of Np(V) Complexation with Acetate at Variable Temperatures (T = 283 - 343 K)

Spectrophotometric titrations were performed to identify the Np(V)/acetate complex and determine the equilibrium constants at variable temperatures (T = 283 - 343 K) and at the ionic strength of 1.05 mol {center_dot} kg{sup -1}. The enthalpy of complexation at corresponding temperatures was determined by microcalorimetric titrations. Results show that the complexation of Np(V) with acetate is weak but strengthened as the temperature is increased. The complexation is endothermic and is entropy-driven. The enhancement of the complexation at elevated temperatures is primarily due to the increasingly larger entropy gain when the solvent molecules are released from the highly-ordered solvation spheres of NpO{sub 2}{sup +} and acetate to the bulk solvent where the degree of disorder is higher at higher temperatures

Complexation of Gluconate with Uranium(VI) in Acidic Solutions: Thermodynamic Study with Structural Analysis

Within the pC{sub H} range of 2.5 to 4.2, gluconate forms three uranyl complexes UO{sub 2}(GH{sub 4}){sup +}, UO{sub 2}(GH{sub 3})(aq), and UO{sub 2}(GH{sub 3})(GH{sub 4}){sup -}, through the following reactions: (1) UO{sub 2}{sup 2+} + GH{sub 4}{sup -} = UO{sub 2}(GH{sub 4}){sup +}, (2) UO{sub 2}{sup 2+} + GH{sub 4}{sup -} = UO{sub 2}(GH{sub 3})(aq) + H{sup +}, and (3) UO{sub 2}{sup 2+} + 2GH{sub 4}{sup -} = UO{sub 2}(GH{sub 3})(GH{sub 4}){sup -} + H{sup +}. Complexes were inferred from potentiometric, calorimetric, NMR, and EXAFS studies. Correspondingly, the stability constants and enthalpies were determined to be log {Beta}{sub 1} = 2.2 {+-} 0.3 and {Delta}H{sub 1} = 7.5 {+-} 1.3 kJ mol{sup -1} for reaction (1), log {Beta}{sub 2} = -(0.38 {+-} 0.05) and {Delta}H{sub 2} = 15.4 {+-} 0.3 kJ mol{sup -1} for reaction (2), and log {Beta}{sub 3} = 1.3 {+-} 0.2 and {Delta}H{sub 3} = 14.6 {+-} 0.3 kJ mol{sup -1} for reaction (3), at I = 1.0 M NaClO{sub 4} and t = 25 C. The UO{sub 2}(GH{sub 4}){sup +} complex forms through the bidentate carboxylate binding to U(VI). In the UO{sub 2}(GH{sub 3})(aq) complex, hydroxyl-deprotonated gluconate (GH{sub 3}{sup 2-}) coordinates to U(VI) through the five-membered ring chelation. For the UO{sub 2}(GH{sub 3})(GH{sub 4}){sup -} complex, multiple coordination modes are suggested. These results are discussed in the context of trivalent and pentavalent actinide complexation by gluconate

Spectrophotometric and Calorimetric Studies of Np(V) Complexation with Acetate at Variable Temperatures (T = 283 -343 K)

Abstract Spectrophotometric titrations were performed to identify the Np(V)/acetate complex and determine the equilibrium constants at variable temperatures (T = 283 -343 K) and at the ionic strength of 1.05 mol·kg -1 . The enthalpy of complexation at corresponding temperatures was determined by microcalorimetric titrations. Results show that the complexation of Np(V) with acetate is weak but strengthened as the temperature is increased. The complexation is endothermic and is entropy-driven. The enhancement of the complexation at elevated temperatures is primarily due to the increasingly larger entropy gain when the solvent molecules are released from the highly-ordered solvation spheres of NpO 2 + and acetate to the bulk solvent where the degree of disorder is higher at higher temperatures