Abstract: Two equations of (r/x)x=0-a modified Kikic-Renon equation and a Valentin-Guiochon equation-have been studied. Values of r1∞ and (dlnr1/dx1)x1=1 by these two equations for 29 binary systems, have been calculated from GLC data, the parameters in some models of excess Gibbs free energy evaluated, and the vapor-liquid equilibrium date predicted. The results are satisfactory. Vlentin-Guiochon equation was simplified leading to a simpler (r/ x)x=0 expression. Then values of r1∞ and (dlnr1/dx1)x=0 by the simplified Valentin-Guiochon equation for 56 binary systems containing alcohols or water were taken from Gmehlings VLE data collection, and the same predicting procedures repeated. These procedures have also been applied to 43 binary systems containing various polar and nonpolar, volatile and nonvolatile component, in which the values of r1∞ and) dlnr1/dx1)x1=0 were calculated by the simplified Valentin-Guiochen equation from GLC data. The predicted VLE data are all consistent with those in the literature. Limits of application of the three equations and methods to transform the two-parameter model of excess Gibbs free energy into one-parameter model, were then discussed.

摘要： 研究了色谱测定(σγ/σx)_(x=0)的两种公式——修正的Kikic-Renon公式及Valentin-Guiochon公式,实测了29个二元系的γ_1~∞,分别按两种公式测定(σγ/σx)_(x=0),求取两参数过量自由焓模型参数,进而预测全浓度范围汽液平衡,得到了较为满意的结果.对Valentin-Guiochon公式合理简化,提出了一个较为简便的(σγ/σx)_(x=0) 公式.利用Gmehling等汇编的56个含醇及含水二元系γ_1~∞数据,直接计算该公式的(σγ/σx)_(x=0)之值,进而推算过量自由焓模型参数,并预测汽液平衡.又用气液色谱测定了各种含有极性与非极性组分、挥发与难挥发组分的不同类型43个二元系的γ_1~∞值,按上述方法预测全浓度范围汽液平衡,与文献中已发表的汽液平衡数据比较,结果都符合良好.最后,讨论了三种斜率公式各自的适用范围和两参数过量自由焓模型转化为单参数模型的一般方法.