三元系热力学图解计算方法——评Darken法与周国治法的内在联系
On Graphic Methods for Calculating Thermodynamic Properties of Ternary Systems——Comments on the Inherent Links Between Darken's and Chou's Methed
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摘要: 本文系统讨论了三元系中由已知一组元活度计算其它组元活度的图解计算方法,并侧重于间接计算方法(\rm\bar G_1-\rm\bar G或\rmR(R=\frac\rmG1-\rmx_1\rm) \to \rm\bar G_2,\rm\bar G_3,借助于热力学基本公式,大大简化了Darden公式和周国治公式的推导过程,指出两种方法的内在联系,给出周国治公式中变量代换R,y的引入思路及意义。经过讨论,从理论上证明了周国治法实际上是Darken法的发展和完善,是三元系热力学计算的好方法。本文还提出两个有用的判别式,可由有关二元系的热力学数据分别对三元系实验结果和图解计算结果加以检验,使计算方法更加完善。Abstract: The graphic methods for calculating \rm\bar G_2 and \rm\bar G_ from the known \rm\bar G_1 (\rm\bar Gi is the partial molar property of ith component) are systematically discussed with emphasis on the indirect methods following the way \rm\bar G_1 \to \rm\bar G or \rmR(R=\frac\rmG1-\rmx_1\rm) \to \rm\bar G_2 and \rm\bar G_3. An new and simple way of de-riving Darken's and Chou's equations based on the efficient uses of fun damental thermodynamic relationships is proposed, which shosvs clearly the close links between two methods, the significances of introducing R and y (y=x3/(x2 +x3)) in Chou's equations, and the main points of the indirect methods.It is theoretically concluded that Chou's method developed from and perfected Darken's method and is a good method for graphic calculations of thermodynamic properties of ternary systems. Moreover, this paper presents two criteria for verifying respectively the reliability of experimental data and calculated results in ternary systems from the known data in the related binary systems.