CO气相偶联合成草酸二乙酯反应热力学分析

Thermodynamic analysis of process for CO coupling to diethyl oxalate

采用Joback基团贡献法推导了亚硝酸乙酯的摩尔定压热容与温度的关系式,并估算了亚硝酸乙酯和碳酸二乙酯的标准摩尔生成吉布斯自由能。综合物性手册中各化合物的热力学函数,计算了CO偶联合成草酸二乙酯反应中主反应和副反应的反应热、反应吉布斯自由能和平衡常数,并对此进行了分析,发现较低的反应温度有利于草酸二乙酯的生成,且主反应自发进行的程度远高于副反应。

The relationship between molar constant heat capacity and temperature of ethyl nitrite was induced by Joback group contribution method,and the standard molar formation Gibbs free energy of ethyl nitrite and diethyl carbonate was also estimated by this method respectively.Reaction enthalpy change,reaction Gibbs free energy change and equilibrium constant of relevant reactions occurred in the process for CO coupling to diethyl oxalate were calculated and analyzed together with basic chemical thermodynamic data obtained from chemistry and engineer handbooks.The result shows that the lower temperature is advantageous to the formation of diethyl oxalate,and the reaction degree of the main reaction is much higher than that of the side reaction.