Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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The Effect of Pressure and Catalyst on the Rate of Solvolysis of Chloro-cobalt (Ⅲ) cation in Binary-Aqueous Mixtures (Water-methyl Alcohol, Water-Acetone, Water-Isopropyl Alcohol and Water-Ethylene Glycol)

물-메틸알코올, 물-아세톤, 물-이소프로필알코올, 물-에틸렌글리코올에서 클로로-코발트 (Ⅲ) 착이온의 가용매분해반응에 미치는 압력 및 촉매의 영향

  • Yu-Chul Park (Department of Chemistry, Kyungpook National University) ;
  • Zun-Ung Bae (Department of Chemistry, Kyungpook National University) ;
  • Sang-Woong Kim (Department of Chemistry, Kyungpook National University)
  • 박유철 (경북대학교 자연과학대학 화학과) ;
  • 배준웅 (경북대학교 자연과학대학 화학과) ;
  • 김상웅 (경북대학교 자연과학대학 화학과)
  • Published : 1987.02.20
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Abstract

The rates of solvolysis of $cis-[Co(en)_2Cl_2]^+$ complex have been investigated using spectrophotometric method at various pressures up to 1500 bar in several binary-aqueous mixtures(water-methyl alcohol, water-acetone, water-isopropyl alcohol and water-ethylene glycol). The activation volumes obtained from the pressure effect on rate constants were 1.13∼4.44 cm3mole-1 for methyl alcohol, 1.13∼3.59$cm^3mole^{-1}$ for acetone, 0.82∼3.44$cm^3mole^{-1}$ for isopropyl alcohol and 1.13∼2.68cm3mole-1 for ethylene glycol. In case of water-methyl alcohol, in addition to, the rates of solvolysis of this complex were determined in the presence of Fe(Ⅱ) ion and the activation volumes were -0.56∼1.59cm3mole$^{-1}$. The rates of solvolysis of this complex were analyzed by comparing with the results obtained from activation volumes and free energy cycle.

몇가지 이성분 혼합용매(물-메틸알코올, 물-아세톤, 물-이소프로필알코올, 물-에틸렌글리코올)에서 $cis-[Co(en)_2Cl_2]^+$착이온의 가용매분해반응속도를 분광광도법을 이용하여 압력(1~1500bar)에 따라 측정하였다. 속도상수에 대한 압력의 영향으로부터 구한 활성화체적은 메틸알코올, 아세톤, 이소프로필알코올, 에틸렌글리코올에서 각각 1.13∼4.44, 1.13~3.59, 0.82~3.44, 1.13~2.68cm3mole-1이었다. 또한 메틸알코올에서는 촉매제로 Fe(Ⅱ)이온을 사용하여 가용매분해반응속도를 측정하였고, 활성화체적은 -0.56∼1.59cm3mole$^{-1}$이었다. 가용매분해반응성은 자유에너지변화사이클과 활성화체적을 이용하여 고찰하였다.

Keywords

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