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1965年以前,作者曾研究过一系列盐类(如NaI、NaCIO_4、NaSCN和NH_4I)对苯—甲醇体系混溶性的影响。发现这些能溶于甲醇而在苯中微溶的盐类,会使苯—甲醇体系成为部分混溶。还发现,当两种液体的分子比固定时,加入能引起分层的盐量与其相应的分层温度之间,存在有良好的线性关系。这些直线的上端,位于盐饱和溶液的分层温度曲线上,而下端则可外推至无盐时的分层曲线。苯—甲醇体系,以NaI饱和时即由完全混溶变为部分混溶,上临界温度是130.5℃,但若将直线外推至盐量为零时,其上临界温度约为-60℃～ 70℃。最近,为了进行比较,我们根据 Eckfeldt和Lucasse的工作,重新计算了环己烷—甲醇体系中盐的数据。不仅直线关系仍然存在,而且外推至无盐时的曲线,与常压下这种部分混溶体系的实验曲线几乎完全重合。根据 Prisosine有关加入第三种组分所引起严格正规溶液临界溶解温度改变的关系式,可从热力学分析得到线性方程式T=mXs+T_O,该式的应用范围,不限于严格正规溶液,也不限于临界温度,具有普遍意义。
Prior to 1965, the authors studied the effects of a range of salts (such as NaI, NaCIO_4, NaSCN and NH_4I) on the miscibility of benzene-methanol systems. It was found that these salts, soluble in methanol and sparingly soluble in benzene, make the benzene-methanol system partially miscible. It has also been found that there is a good linear relationship between the amount of salt that can cause delamination and its corresponding delamination temperature when the molecular ratios of the two liquids are fixed. The upper end of these lines lies in the stratification temperature profile of the salt-saturated solution, while the lower end can be extrapolated to the stratification profile without salt. Benzene - methanol system, when saturated with NaI from complete miscibility into partial miscibility, the upper critical temperature is 130.5 ℃, but if the straight line extrapolated to the amount of salt is zero, the upper critical temperature of about -60 ℃ ~ 70 ° C. Recently, for comparison, we recalculated the data for the salts in the cyclohexane-methanol system based on the work of Eckfeldt and Lucasse. Not only does the linear relationship still exist, but extrapolation to the curve without salt almost coincides with the experimental curve of this partially miscible system at atmospheric pressure. The linear equation T = mXs + T_O can be derived from the thermodynamic analysis according to Prisosine’s relation to the critical solution temperature change of a strictly formal solution caused by the addition of the third component. The application range of this formula is not limited to a strictly normal solution nor is it limited to The critical temperature has a universal meaning.