针对三羟甲基丙烷(TMP)与油酸(OA)合成三羟甲基丙烷油酸酯(TMPTO)的反应体系,采用基团贡献法对TMP、OA、TMPTO以及反应过程中所涉及的中间产物进行热力学数据的相关计算和分析.研究了在403~493 K温度范围内反应体系的反应焓变ΔrHθm、反应熵变ΔrSθm、反应吉布斯自由能变ΔrGθm和反应平衡常数Kθ.计算结果表明,该反应为吸热反应;在温度范围内,吉布斯自由能变随反应温度的升高而降低,升高温度有利于反应向正方向进行.通过对计算结果与已知文献数据进行比较,表明文章提出的分析方法是可行的.
In this study,the thermodynamic data of trimethylolpropane(TMP),oleic acid(OA),trimethylolpropane trioleate(TMPTO),and the intermediate products involved in the reaction process were calculated and analyzed using the group con-tribution method.The enthalpy change ΔHθm,entropy change ArSm,Gibbs free energy change ΔrGθm,and equilibrium constant Kθ of the reaction system were investigated within a temperature range of 403-493 K.The calculation results indicate that it is an endothermic reaction.Within the temperature range,the Gibbs free energy change decreases with increasing reaction temperature,indicating that higher temperatures favor the forward reaction.A comparison between the calculated results and known literature data demonstrates the feasibility of the group-contribution analysis method proposed herein.