Liron Z, Srebrenik S, Martin A, Cohen S
J Pharm Sci. 1986 May;75(5):463-8. doi: 10.1002/jps.2600750509.
In a binary mixture, partial vapor pressure may show either a positive or negative deviation from the predicted value of an ideal solution. In this report we derive the deviation from Raoult's law from the heat of mixing, delta H mix, and the molal volume, V, of each of the components of a binary solution. This derivation is then tested for seven sets of combinations of two different solvents, taken at random from the literature. Each set consists of several different ratios of solute-solvent. The correlation between the reported experimental values of the partial vapor pressure of a given component, P1, and the theoretically derived values is excellent. The same derivation is further applied to calculate the solute-solvent interaction parameter, beta 12, independently from the geometric mean assumption of regular solution theory. In a number of cases, especially in hydrocarbon-alcohol mixtures, beta 12 proves to be significantly different from the calculated geometric mean square root beta 11 beta 22 or from the Walker interaction parameter term, K.
在二元混合物中，分压可能相对于理想溶液的预测值呈现正偏差或负偏差。在本报告中，我们从混合热（ΔH mix）以及二元溶液各组分的摩尔体积（V）推导出与拉乌尔定律的偏差。然后，针对从文献中随机选取的两组不同溶剂的七种组合对该推导进行检验。每组由溶质 - 溶剂的几种不同比例组成。给定组分的分压（P1）的报告实验值与理论推导值之间的相关性非常好。同样的推导进一步用于独立于正规溶液理论的几何平均假设来计算溶质 - 溶剂相互作用参数β12。在许多情况下，特别是在烃 - 醇混合物中，β12被证明与计算出的几何平均平方根β11β22或沃克相互作用参数项K有显著差异。
