草酸二烷基酯气相脱羰基制碳酸二烷基酯的热力学分析  

THERMODYNAMICS ANALYSIS OF THE PREPARATION OF DIALKYL CARBONATES FROM DIALKYL OXALATES BY GASEOUS DECARBONYLATION

作　　者：郝翠英[1] 王胜平[1] 马新宾[1] 

机构地区：[1]天津大学化工学院绿色合成与转化教育部重点实验室,天津300072

出　　处：《精细石油化工》2006年第4期36-39,共4页Speciality Petrochemicals

基　　金：教育部新世纪人才支持计划。

摘　　要：利用Benson基团贡献法计算了由草酸二乙酯(甲酯)脱羰基制碳酸二乙酯(甲酯)反应中部分物质的热力学数据熵Smθ、热容Cp,并计算了反应的焓变△rHmθ、熵变△rSmθ、Gibbs自由能变△rGmθ、反应平衡常数Kp及草酸二乙酯(甲酯)的平衡转化率。结果表明,由草酸二乙酯(甲酯)气相脱羰基制碳酸二烷基酯反应在热力学上是可行的,在合适的催化剂下草酸酯可完全转化。The standard entropy Sm^θ and heat capacity Cp of some compounds related to the reaction of decarbonylation of diethyl oxalate （dimethyl oxalate） to diethyl carbonate （dimethyl carbonate） were calculated by the method of group contribution. The change of enthalpy ΔrHm^θ, entropy ΔrSm^θ and Gibbs free energy ARGO, equilibrium constant Kp and equilibrium conversion of the reactions were also evaluated according to the chemical thermodynamics principles. The results showed that the direct decarbonylation of diethyl oxalate（dimethyl oxalate） to diethyl carbonate（dimethyl carbonate） is feasible thermodynamically. Complete conversion of the reactants could be achieved provided appropriate catalysts were used.

关 键 词：草酸酯 碳酸酯 脱羰基 基团贡献 热力学分析 

分 类 号：O642.1[理学—物理化学]