The solvation effect on the reactions in solution. I The solvation model for the interpretation of entropy changes in the complex formation of dichlorodimethylstannane with pyridine.

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概要

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• A complex-formation reaction has been studied for the Me<SUB>2</SUB>SnCl<SUB>2</SUB> plus pyridine system in dimethyl phthalate (DMP) and dioctyl phthalate (DOP) by means of titration calorimetry. The resulting entropy changes in the reactions of A+B=AB and AB+B=AB<SUB>2</SUB>, with A=Me<SUB>2</SUB>SnCl<SUB>2</SUB> and B=pyridine, were compared with those calculated for the gas-phase reactions. The values in solution amounted only to 1/3–1/4 of the gas-phase values. Correction for the entropy of solution of each component failed to explain the observed values in the absence of a strong solvation. The solvation model is presented to allow for such a discrepancy, assuming a strong solvation for Me<SUB>2</SUB>SnCl<SUB>2</SUB> as well as for the 1:1 pyridine complex by definite numbers of solvents. To test the applicability of the model, calculations were made based on molecular statistical thermodynamics. The results obtained were reasonable, indicating that a free molecule, Me<SUB>2</SUB>SnCl<SUB>2</SUB>, is solvated by 1.3 molecules of the solvent of DMP, which are released about half by half on the formation of the 1:1 and 1:2 complexes with pyridine.

• 公益社団法人 日本化学会の論文

著者

• Fujiwara Hideaki

  Faculty Of Medicine Osaka University

• SASAKI YOSHIO

  Faculty of Pharmaceutical Sciences Osaka University

• Arakawa Hiroyuki

  Faculty of Pharmaceutical Sciences, Osaka University

• Murata Saburo

  Faculty of Pharmaceutical Sciences, Osaka University

• Ohtaku Ikuzi

  Faculty of Pharmaceutical Sciences, Osaka University

• Ishii Motoko

  Faculty of Pharmaceutical Sciences, Osaka University

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