Determination of the stability constant and thermodynamic parameters between Tl+, Ag+ and Pb2+ cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand

Abstract

The complexation reaction between Tl+, Ag+ and Pb2+ cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand in acetonitrile (ACN)–H2O and methanol (MeOH)–H2O binary solutions has been studied at different temperatures using conductometric method. The conductometric data show that the stoichiometry of the complexes is 1: 1 [M: L] and the stability constant of complexes changes with the binary solutions identity. Also, the structure of the resulting 1: 1 complexes was optimized using the LanL2dz basis set at the B3LYP level of theory using GAUSSIAN03 software. The results show that the change of logKf for (DFMP.Pb)2+ and (DFMP.Ag)+ complexes with the mole ratio of acetonitrile and for (DFMP.Ag)+ and (DFMP.Tl)+ complexes with the mole ratio of methanol have a linear behavior, while the change of logKf of (DFMP.Tl)+complex in ACN–H2O binary solutions (with a minimum in XACN = 0.5) and (DFMP.Ag)+ complex in MeOH–H2O binary solutions (with a minimum in XMeOH = 0.75) show a non-linear behavior. The selectivity order of DFMP ligand for these cations in mol % CAN = 25 and 75 obtain Tl+ > Pb2+ > Ag+ but in mol % CAN = 50, the selectivity order observe Pb2+ > Tl+ > Ag+. Also, this selectivity sequence of DFMP in MeOH–H2O (mol % MeOH = 75 and 100) and (mol % MeOH = 50) is obtained Pb2+ > Ag+ and Tl+ > Ag+ > Pb2+ respectively. The values of thermodynamic parameters show that these values are influenced by the nature and the composition of binary solution. In all cases, the resulting complexes are enthalpy stabilized and entropy destabilized. The TΔSC° versus ΔHC° plot of all obtained thermodynamic data shows a fairly good linear correlation which indicates the existence of enthalpy-entropy compensation in the complexation reactions.