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化工学报  2013 

枞酸与甲醇酯化反应的基团贡献法热力学分析

DOI: 10.3969/j.issn.0438-1157.2013.06.002, PP. 1900-1906

Keywords: 枞酸,甲醇,枞酸甲酯,基团贡献法,热力学

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Abstract:

以枞酸为模型化合物、枞酸与甲醇的酯化为探针反应,采用基团贡献法对枞酸与甲醇酯化反应进行了热力学分析,计算了473~653K、0.1~20MPa反应体系的反应焓变、反应熵变、反应Gibbs自由能变以及反应平衡常数,探讨了温度与压力对酯化反应的影响。计算结果表明,反应的焓变为-46.31~-10.10kJ·mol-1,枞酸与甲醇的甲酯化反应为放热反应;反应Gibbs自由能变为-53.26~-25.49kJ·mol-1,反应为自发过程;标准压力下反应平衡常数为136.32~748.89,5~20MPa下反应平衡常数为(1.1×104)~(3.2×104)。实验结果表明,在无催化剂条件下,超/亚临界甲醇与枞酸酯化反应的转化率分别为85.94%~94.89%、73.80%~81.20%,实验结果与基团贡献法热力学计算值相一致。

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