文献类型：期刊文献

中文题名：合成丙酮酸及其酯类的反应体系热力学计算与分析

英文题名：THERMODYNAMIC ANALYSIS FOR THE SYSTEM OF METHYL GLYOXAL TO PYRUVIC ACID AND PYRUVATE

作者：金宏轩[1];柏子龙[1]

机构：[1]华东理工大学石油加工研究所,上海200237

年份：2008

卷号：25

期号：2

起止页码：75

中文期刊名：精细石油化工

外文期刊名：Speciality Petrochemicals

收录：CSTPCD;;Scopus;北大核心:【北大核心2004】；CSCD:【CSCD_E2011_2012】；

语种：中文

中文关键词：丙酮酸甲酯;氧化;酯化;基团贡献法

外文关键词：methyl pyruvate; oxidation; esterification; group contribution method

摘要：采用Yoneda基团贡献法估算了丙酮醛、丙酮酸和丙酮酸甲酯的标准生成焓△fHm^θ、标准Sm^θ以及拟合等压热容曲线。结合丙酮醛氧化酯化合成丙酮酸及丙酮酸甲酯反应的热力学数据，对丙酮醛氧化制备丙酮酸及丙酮酸酯化制备丙酮酸甲酯的摩尔焓变△tHm^θ，吉布斯自由能变△rG^θ和反应平衡常数K进行了计算与分析。结果表明，丙酮醛氧化制备丙酮酸的反应为强放热反应，标准状态下△rHm^θ为-319．3kJ／mol，丙酮酸酯化制备丙酮酸甲酯的反应为弱的放热反应，标准状态下△tHm^θ为-61．73kJ／mol；两个反应的吉布斯自由能变在考虑的温度范围内均为负值，且丙酮醛氧化温度为450K时，反应的焓变有最小值-345kJ／mol；丙酮酸及丙酮酸甲酯的转化率较高。
The Yoneda （ABWY） group contribution method was app thalpy and the standard entropy of methyl glyoxal （MG）, pyruvic （MP）. The functional correlations between the heat capacity of these lied acid to estimate the standard en （PA） and methyl pyruvate organic compounds and temperature were established. Together with the thermodynamic data from chemical handbooks, the enthalpy, Gibbs free energy and the equilibrium constant of MG oxidation to PA（Reaction 1）and PA esterification to MP（Reaction 2） were calculated and analyzed. The results showed that Reaction 1 was a strongly exothermal reaction with the enthalpy of -319.3 kJ/mol in the standard state; Reaction 2 was a weekly exothermal reaction with the enthalpy of -61.73 kJ/mol in the standard state. △rG^θfor both the reactions were negative. At 450 K, Reaction 1 △rG^θ had a minimum value, -345 kJ/mol. The data provide basic information for the design of the PA and MP synthesis process.