水- dmso共溶剂效应、酸催化甲酸丁酯水解动力学及对活化参数的影响

A. K. Singh
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引用次数: 0

摘要

在20-400℃的温度范围内,研究了在0.1N-HCI和30-70% (v/v)的水- dmso混合物存在下甲酸丁酯的酸催化水解。反应速率随溶剂混合物含水量的降低而降低,在有机溶剂含量为70%左右时达到最小。随着温度的升高,活化配合物的水分子数呈减少趋势,表明反应介质由单分子向双分子转变。利用ΔH*与ΔS*的对比图,从溶剂效应的角度对热力学活化参数进行了计算和讨论,计算了等动温度,发现等动温度大于300。
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Water-DMSO Co–Solvent effect and kinetics of acid catalyzed Hydrolysis of butyl formate and Influence on Activation Parameters
The acid catalyzed hydrolysis of butyl formate in presence of 0.1N-HCI in water and the presence of water-DMSO mixture containing up to 30-70% (v/v) was studied over the temperature ranging from 20-400C. The rate of reaction decreases with decrease of water content of the solvent mixture and reached minima at about 70% of organic solvent. The number of water molecule associated with activated complex was showing decrease in trend with increase of temperature, is an indication of change in mechanism from unimolecular to bimolecular in reaction media. The parameters of thermodynamic activation were also calculated and discussed in terms of solvent effect with help of plots of ΔH* versus ΔS*, the isokinetic temperature was calculated and found to be greater than 300.
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