物理化学学报 >> 2007, Vol. 23 >> Issue (01): 124-128.doi: 10.3866/PKU.WHXB20070126

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磷酸三丁酯与醇二元混合体系的热力学性质

刘红丽;刘士军;肖忠良;陈启元   

  1. 中南大学化学化工学院, 长沙 410083; 长沙理工大学化学与环境工程系, 长沙 410076
  • 收稿日期:2006-06-15 修回日期:2006-08-24 发布日期:2007-01-08
  • 通讯作者: 刘士军 E-mail:liushijun@hotmail.com

Thermodynamic Properties of Binary Mixture of Tributylphosphate and n-Alkanols

LIU Hong-Li;LIU Shi-Jun;XIAO Zhong-Liang;CHEN Qi-Yuan   

  1. College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China; Department of Chemistry and Environmental Engineering, Changsha University of Science & Technology, Changsha 410076, P. R. China
  • Received:2006-06-15 Revised:2006-08-24 Published:2007-01-08
  • Contact: LIU Shi-Jun E-mail:liushijun@hotmail.com

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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

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 mixtures had been obtained according to the athermal solution model. The thermodynamic analysis showed that the model provided reliable results for binary mixtures of TBP+methanol/ethanol/propan-1-ol, but did not for TBP+butan-1-ol.

Key words: TBP, Alkanols, Thermodynamic properties, Athermal solution