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The Effects of Pressure, Temperature and Solvent Composition on Solvolysis of trans-[Co(N-eten)$_2Cl_2]^+$ in Water-t-butyl Alcohol Mixture
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  • The Effects of Pressure, Temperature and Solvent Composition on Solvolysis of trans-[Co(N-eten)$_2Cl_2]^+$ in Water-t-butyl Alcohol Mixture
  • The Effects of Pressure, Temperature and Solvent Composition on Solvolysis of trans-[Co(N-eten)$_2Cl_2]^+$ in Water-t-butyl Alcohol Mixture
저자명
박유철,조영제,Park. Yu Chul,Cho. Young Je
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1988년|9권 1호|pp.1-4 (4 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

Rates of solvolysis of trans-[Co$(N-eten)_2Cl_2$]$^+$ have been investigated using spectrophotometric method at various pressures and temperatures in the mixtures of water with the t-butyl alcohol which possesses a high structure inducing capacity in water. The values of ${Delta}V^{ eq}$ obtained from pressure effect on the rate constants were 2.55∼ 5.83 $cm^3mol^{-1}$. These values were discussed in terms of dissociative mechanism. Extrema found in the variation of ${Delta}H^{ eq}$ and ${Delta}S^{ eq}$ with solvent composition correlated with extrema in the variation of the physical properties of the mixtures. The logarithms of rate constants correlated linearly with both Grunwald-Winstein parameter and the reciprocal of dielectric constant ($Ds^{-1}$). The gradient, m of Grunwald-Winstein plot for the trans-[Co$(N-eten)_2Cl_2$]$^+$ was 0.09, which is significantly lower than those for the other cobalt (Ⅲ)-dichloro complexes. It was suggested that the reaction is an Id mechanism with long extension of Co-Cl bond in the transition state, as found for the C-Cl bond in the transition state for the solvolysis of t-butyl chloride.