中文摘要：

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（1．1×10^4）～（3．2×10^4）。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。

英文摘要：

The esterification of abietic acid with methanol was selected as a probe reaction. The thermodynamics of reaction was analyzed by group-contribution method. The reaction enthalpy, entropy, Gibbs free energy and equilibrium constant were calculated in the temperature range of 473--653 K and the pressure range of 0.1--20 MPa. The effects of temperature and pressure on the reaction were also discussed. The calculation indicates that the reaction enthalpy is -- 46.31 -- 10.10 kJ . mol-1 and free energy is --53.26--25.49 kJ . mol- 1, showing an exothermic and spontaneous reaction. The equilibrium constant is 136.32 748.89 at standard pressure and （1.1 × 10^4）-（3. 2 × 10^4） in the range of 5-20 MPa. The experimental results show the conversion of abietic acid of 85.94%--94.89% and 73.80%-- 81.20% without catalyst in super/subcritical methanol, which is in agreement with thermodynamic calculation by the group-contribution method.