磷酸三丁酯与醇二元混合体系的热力学性质.pdfVIP

物理化学学报(Wuli Huaxue Xuebao) 124 Acta Phys. Chim. Sin., 2007, 23(1) ：124-128 January [Note] 磷酸三丁酯与醇二元混合体系的热力学性质 刘红丽1 士军1,* 肖忠良1,2 陈启元1 (1 南大学化学化工学院, 长沙 410083; 2 长沙理工大学化学与环境工程系, 长沙 410076) 摘要: 用量热法测定了298.15 K 时, 磷酸三丁酯(TBP)+ 甲醇/乙醇/正丁醇/正丙醇四个二元混合体系的超额混 合焓及293.15 K 和303.15 K 时部分组成下的超额混合焓, 其值均在-0.3 - 0.3 kJ ·mol-1 之间, 且基本不受温度的 影响. 用无热溶液模型计算了各体系的超额熵、超额Gibbs 自由能及各组分的活度系数. 热力学分析表明, TBP+ 甲醇/乙醇/正丙醇二元体系能较好地符合无热溶液模型, 而TBP+正丁醇体系则不符合无热溶液模型. 关键词: 磷酸三丁酯; 醇; 热力学性质; 无热溶液模型 中图分类号: O642; O641 Thermodynamic Properties of Binary Mixture of Tributylphosphate and n Alkanols LIU Hong Li1 LIU Shi Jun1,* XIAO Zhong Liang1,2 CHEN Qi Yuan1 1 2 ( College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China; Depa rtment of Chemistry and Environmental Engineering, Changsha University of Science Technology, Changsha 4100 76, P. R. China) Abstract: The excess molar enthalpies for binary systems of tributylphosphate(TBP) +methanol/ethanol/1 propanol/ 1 butanol were measured by calorimetry at 298.15 K as well as a little mixtures at 293.15 K and 303.15 K. The experimental results were in the range of -0.3 - 0.3 kJ ·mol-1 and were invariant with the change of temperature. The excess molar entropies, excess molar Gibbs free energies, and activity coefficients for the binary mixtu