Complexation study of dibenzo-18-crown-6 with UO2 2+ cation in binary mixed non-aqueous solutions

Abstract

The complexation reaction of macrocyclic ligand, dibenzo-18-crown-6 (DB18C6) with UO22+ cation was studied in ethylacetate-1,2-dichloroethane (EtOAc/DCE), acetonitrile-1,2-dichloroethane (AN/DCE), methanol-1,2-dichloroethane (MeOH/DCE) and ethanol-1,2-dichloroethane (EtOH/DCE) binary solutions at different temperatures using the conductometric method. The conductance data show that the stoichiometry of the complex formed between DB18C6 and UO22+ cation is affected by the nature of the solvent systems. A non-linear behaviour was observed for changes of log Kf of (DB18C6.UO2)+2 complex versus the composition of the binary mixed solvents. The values of thermodynamic quantities (∆S°c, ∆H°c) for formation of (DB18C6.UO2)+2 complex were obtained from temperature dependence of the stability constant using the van’t Hoff plots. The results show that in most cases, the complex is enthalpy stabilized and in all cases entropy stabilized and both parameters are affected by the nature and composition of the mixed solvents. In addition, the complex formation between dicyclohexyl-18-crown-6 (DCH18C6) and UO22+ cation was studied in pure AN and the results were compared with those of the (DB18C6.UO2)+2 complex.