TY - JOUR
T1 - Solvation and complexation of copper (II) and chloride ions in 2,2,2-trifluoroethanol-dimethyl sulphoxide mixtures
AU - Suzuki, Honoh
AU - Ishiguro, Shin Ichi
AU - Ohtaki, Hitoshi
PY - 1989
Y1 - 1989
N2 - The formation of copper(II) chloro-complexes has been studied by calorimetry and spectrophotometry in various 2,2,2-trifluoroethanol (TFE)-dimethyl sulphoxide (DMSO) mixtures at 25 °C. It was shown that as the mole fraction of TFE, x, in the mixtures increased, the formation constant of [CuCl]+ gradually decreased to x = 0.8. The result is contrary to that obtained for acetonitrile (AN)-DMSO mixtures. This is ascribed to the decreased entropy of formation of [CuCl]+ in TFE-DMSO mixtures in contrast to the increased entropy in AN-DMSO mixtures with decreasing DMSO content. The corresponding enthalpy of formation of [CuCl]+ remains practically unchanged over the wide range of solvent composition in TFE-DMSO mixtures, as well as in AN-DMSO mixtures. The different variation trend in the entropy of formation of [CuCl]+ in TFE-DMSO and AN-DMSO mixtures may be explained in terms of the different intermolecular interactions between solvent molecules in the bulk.
AB - The formation of copper(II) chloro-complexes has been studied by calorimetry and spectrophotometry in various 2,2,2-trifluoroethanol (TFE)-dimethyl sulphoxide (DMSO) mixtures at 25 °C. It was shown that as the mole fraction of TFE, x, in the mixtures increased, the formation constant of [CuCl]+ gradually decreased to x = 0.8. The result is contrary to that obtained for acetonitrile (AN)-DMSO mixtures. This is ascribed to the decreased entropy of formation of [CuCl]+ in TFE-DMSO mixtures in contrast to the increased entropy in AN-DMSO mixtures with decreasing DMSO content. The corresponding enthalpy of formation of [CuCl]+ remains practically unchanged over the wide range of solvent composition in TFE-DMSO mixtures, as well as in AN-DMSO mixtures. The different variation trend in the entropy of formation of [CuCl]+ in TFE-DMSO and AN-DMSO mixtures may be explained in terms of the different intermolecular interactions between solvent molecules in the bulk.
UR - http://www.scopus.com/inward/record.url?scp=8544244448&partnerID=8YFLogxK
U2 - 10.1039/F19898502587
DO - 10.1039/F19898502587
M3 - 学術論文
AN - SCOPUS:8544244448
SN - 0300-9599
VL - 85
SP - 2587
EP - 2596
JO - Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
JF - Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
IS - 8
ER -