A thermodynamic study of complexation of 18-crown-6 with Zn2+, Tl+, Hg2+ and $$ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $$ cations in acetonitrile-dimethylformamide binary media and study the effect of anion on the stability constant of (18C6-Na+) complex in methanol solutions

Abstract

The equilibrium constants and thermodynamic parameters for complex formation of 18-crown-6(18C6) with Zn2+, Tl+, Hg2+ and \( {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} \) cations have been determined by conductivity measurements in acetonitrile(AN)-dimethylformamide(DMF) binary solutions. 18-crown-6 forms 1:1 complexes [M:L] with Zn2+, Hg2+ and \( {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} \) cations, but in the case of Tl+ cation, a 1:2 [M:L2] complex is formed in most binary solutions. The thermodynamic parameters (\( \Delta {\text{H}}^{ \circ }_{{\text{c}}} \) and \( \Delta {\text{S}}^{ \circ }_{{\text{c}}} \)) which were obtained from temperature dependence of the equilibrium constants show that in most cases, the complexes are enthalpy destabilized but entropy stabilized and a non-monotonic behaviour is observed for variations of standard enthalpy and entropy changes versus the composition of AN/DMF binary mixed solvents. The obtained results show that the order of selectivity of 18C6 ligand for these cations changes with the composition of the mixed solvent. A non-linear relationship was observed between the stability constants (logKf) of these complexes with the composition of AN/DMF binary solutions. The influence of the \( {\text{ClO}}^{ - }_{{\text{4}}} \), \( {\text{NO}}^{ - }_{{\text{3}}} \) and \( {\text{Cl}}^{ - } \) anions on the stability constant of (18C6-Na+) complex in methanol (MeOH) solutions was also studied by potentiometry method. The results show that the stability of (18C6-Na+) complex in the presence of the anions increases in order: \( {\text{ClO}}^{ - }_{{\text{4}}} \) > \( {\text{NO}}^{ - }_{{\text{3}}} \) > \( {\text{Cl}}^{ - } \).