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Complex formation equilibria between Ag(I) and thioureas in n-propanol
Authors:Domenico De Marco  Graziella Zona
Affiliation:Department of Inorganic Chemistry, Analytical Chemistry and Physical Chemistry, University of Messina, Salita Sperone 31, PB 30, 98166 S. Agata, Messina, Italy
Abstract:Complex formation equilibria between Ag(I) and thiourea or N-alkyl-substituted thioureas have been investigated in n-propanol by potentiometry at 10 °C intervals from 5 to 50 °C. Stepwise formation of tris-coordinated AgLn (n = 1-3) complexes has been found for the majority of the ligands. ΔH and ΔS values for the complex formation reactions have been evaluated from the dependence of ln βn on temperature. The alkyl-substituents affect the ligand affinities in different ways in relation with the coordination level n.The reactions are exothermic with few exceptions. Enthalpy favoured complex formation with negative dependence of ΔG on temperature (ΔS > 0) have been found.The enthalpy and entropy changes for the stepwise complex formation equilibria are correlated by two linear compensative relationships with the same isoequilibrium temperature 50-51 °C.
Keywords:Tu, thiourea   MeTu, N-methylthiourea   Me2Tu, N,N&prime  -dimethylthiourea   Me4Tu, N,N,N&prime  ,N&prime  -tetramethylthiourea   EtTu, N-ethylthiourea   Et2Tu, N,N&prime  -diethylthiourea   EnTu, ethylenethiourea   IsPr2Tu, N,N&prime  -diisopropylthiourea   ALTu, N-allylthiourea   Bu2Tu, N,N&prime  -dibutylthiourea   TBu2Tu, N,N&prime  -diterbutylthiourea
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