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KMID : 1059519850290060629
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Journal of the Korean Chemical Society
1985 Volume.29 No. 6 p.629 ~ p.636
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The Effects of Solvent Composition and Pressure on the Rate of Solvolysis of trans-[Co(en)2Cl2]+, trans-[Co(N-eten)2Cl2]+, trans-[Co(N-meen)2Cl2]+ and trans-[Co(tn)2Cl2]+ in Aceton-Water Mixture. Excess Free Energy & Free Energy Cycle and Reaction Mecha
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Park Yu-Chul
Cho Young-Jae
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Abstract
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The rates of solvolysis of trans-[Co(AA)2Cl2]+ in which AA indicates ethylenediamine(en), N-ethylethylenediamine (N-eten), N-methylethylenediamino (N-meen) and trimethylenediamine(tn) respectively have been investigated using conductometric and spectrophotometric methods at various pressure up to 2,000 bar in acetone-water mixture. The activation volumes (ΔV≠) obtained from the pressure effect on rate constants were -0.2∼0.9 cm3mole-1 for en, -0.2∼0.6 cm3mole-1 for N-eten, -0.8∼6.0 cm3mole-1 for N-meen and 0.7∼7.0cm3mole-1 for tn. The rates of solvolysis of these complexes were analyzed by comparing with the results obtained from excess free energy (GE) and free energy cycle. It was found that SN1 character was increased with decreasing the pressure and increasing the content of acetone in the mixture solvent. In addition to that, the effect of charge separation on the mechanism of solvolysis was discussed.
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