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含有氢键的溶液,例如醇、羧酸等,由于氢键的作用,分子间缔合形成缔合体。当处理这些溶液的汽液平衡关系时,凡考虑了缔合作用影响的,一般都可以得到满意的结果。表达缔合作用的汽液平衡关系式,大致可分为两类:一类是最早由Marek等提出,表示只存在单一同种分子缔合时汽液平衡关系的模型;另一类是在此基础上,Tamir等表示溶液中的每个组分自身或和其它组分都能缔合的二元、三元溶液汽液平衡关系的模型。随着汽液平衡关系测示技术的发展,和一些新的相平衡关联式的出现,应用Manek模型关联含有低级羧酸的溶液平衡数据已比较成熟,关联的精度逐步提高,但大多数作者应用Marek模型时只考虑了汽相缔合,而忽略了液相缔合的影响。Jenkins等改进了Marek模型,在考虑了汽相和液相都缔合的情况下,用Willson等方程关联了醋酸-甲苯汽液平衡数据,并与只考虑汽相缔合的关联结果作了比较,结果表明:考虑两相缔合拟合的结果误差
Hydrogen bond-containing solutions, such as alcohols, carboxylic acids and the like, associate with each other to form an association due to hydrogen bonding. When dealing with the vapor-liquid equilibrium of these solutions, satisfactory results can generally be obtained wherever the effects of association are considered. The relationship between vapor-liquid equilibrium expression of association can be divided into two categories: one is the earliest proposed by Marek et al., That there exists only a single model of the same species molecular vapor-liquid equilibrium relationship; the other is here On the basis of Tamir et al., A model for the vapor-liquid equilibrium relationship of each of the components in the solution, either alone or in combination with other components, is shown. With the development of vapor-liquid equilibrium measurement technology and the emergence of some new phase equilibrium equations, the application of Manek model has been relatively mature in the correlation of solution containing lower carboxylic acids, and the accuracy of correlation has been gradually improved. However, most authors applied The Marek model considers only the association of the vapor phase, ignoring the effect of liquid association. Jenkins et al. Improved Marek’s model. Considering the association of vapor phase and liquid phase, the equation of Willson equation was used to correlate the acetic acid-toluene vapor-liquid equilibrium data with the correlation results which only consider the association of vapor phase The results show that the result error of two-phase association fitting is considered