Abstract
An apparatus for measurements of equilibrium ligand vapor pressure has been applied in order to determine the stoichiometry of benzene and cyclohexene complexes of silver(I) trifluoroacetate (AgCF 3CO 2) and silver(I) trifluoromethanesulfonate (silver(I) triflate, AgCF 3SO 3) in the solid state. It has been found that the equilibrium leads the formation of such complexes as: (AgCF 3CO 2) 2(C 6H 6), (AgCF 3CO 2) 2(C 6H 10), (AgCF 3CO 2) 2(C 6H 10) 3, (AgCF 3SO 3) 2(C 6H 6), (AgCF 3SO 3)(C 6H 6), (AgCF 3SO 3)(C 6H 10) and (AgCF 3SO 3)(C 6H 10) 2. The temperature dependence of the gas-solid equilibrium ligand pressure has also been examined for these complexes, and the enthalpy and entropy changes according to the following complex dissociation reactions were estimated: (AgCF 3CO 2)L m (s) ⇄ AgCF 3CO 2 (s)+mL (g): and (AgCF 3SO 3)L n (s) ⇄ AgCF 3SO 3 (s)+nL (g), where L's are benzene and cyclohexene. On the basis of the thermodynamic data obtained, the effects of the counter anion as well as the ligand on the complex stability are discussed.
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