Thermodynamic analysis and kinetics of cyclization of TOME

doi:10.11949/0438-1157.20191485

Abstract

Abstract:

Thermodynamic analysis of the cyclization reaction of tetramethyl-keto-methyl cenoate (TOME) was performed using the group contribution method. The results indicate that under standard pressure, the reaction is endothermic and it is spontaneous when the temperature is greater than 403 K. The Gibbs free energy decrease with the increase of temperature, indicating that the reaction occurs more easily at higher temperatures. The cyclization kinetics of TOME at atmospheric pressure and temperature range of 463—493 K was studied by batch experiments. The kinetic fitting results show that the reaction is a first-order reaction, and the increase of temperature can significantly accelerate the reaction rate. The activation energy of the reaction is estimated to be 143.72 kJ?mol ^-1 in the studied temperature range.

Key words: TOME, cyclization reaction, group-contribution, thermodynamic analysis, kinetics

摘要：

采用基团贡献法对四甲基-酮-癸烯酸甲酯（TOME）环化反应进行了热力学分析。结果表明，标准压力下该反应为吸热反应，温度高于403 K范围内反应为自发过程；反应的Gibbs自由能变随温度的升高而减小，升温有利于反应正向进行。通过间歇实验研究了非催化条件、常压、463~493 K温度范围内TOME环化反应动力学。动力学拟合结果表明，该反应为一级反应，升温能明显加快反应速率，在所研究温度范围内反应活化能为143.72 kJ?mol ^-1。

关键词: 癸烯酸甲酯, 环化反应, 基团贡献法, 热力学分析, 反应动力学

CLC Number:

TQ 013.1

Hongxiao LIU, Weizhen SUN, Ling ZHAO. Thermodynamic analysis and kinetics of cyclization of TOME[J]. CIESC Journal, 2020, 71(2): 500-506.

刘宏晓, 孙伟振, 赵玲. TOME环化反应热力学分析及反应动力学研究[J]. 化工学报, 2020, 71(2): 500-506.

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