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Initial State and Transition State Solvation for the Solvolysis of trans-$[Co(N-eten)_2Cl_2]$+ in Binary Aqueous Mixtures: Excess Free Energy, Free Energy Cycle and Reacton Mechanism
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  • Initial State and Transition State Solvation for the Solvolysis of trans-$[Co(N-eten)_2Cl_2]$+ in Binary Aqueous Mixtures: Excess Free Energy, Free Energy Cycle and Reacton Mechanism
  • Initial State and Transition State Solvation for the Solvolysis of trans-$[Co(N-eten)_2Cl_2]$+ in Binary Aqueous Mixtures: Excess Free Energy, Free Energy Cycle and Reacton Mechanism
저자명
Park. Yu-Chul,Cho. Young-Je
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1990년|11권 4호|pp.309-313 (5 pages)
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대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${Delta}H^{ eq}$ and ${Delta}S^{ eq}$ obtained from temperature effect on the rate constants were $80{sim}84 kJmol^{-1}$ and $- 28{sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.