化学组成对蒸发焓和平衡蒸汽压的影响
Effect of Chemical Composition on Enthalpy of Evaporation and Equilibrium Vapor Pressure
摘要：
从Clausius-Clapeyron方程出发，推导出二元溶液的蒸发焓、组分浓度和平衡蒸气压之间的关系。组分从溶液和纯液体中蒸发的速率之差D（DH）取决于溶液的化学性质和浓度X。浓度对D（DH）的影响在理想和非理想溶液中表现不同，但总体上D（DH）随第二组分浓度的增加而增加。介绍了一种模型，它认为D（DH）的能量变化的三个连续的阶段的总和：从散装液体进入表面层的分子通道，在界面的外侧上的分子的出口，和以下的解吸到气相。在该模型框架内，蒸发焓的主要贡献来自于近地层的过程。从溶液中的吸附作用改变了表面层相对于本体溶液的化学组成，这在很大程度上决定了理想溶液和非理想溶液的曲线D（DH）=f（X）的形式的差异。
英文摘要：
Proceeding from the Clausius-Clapeyron equation, the relation is derived that establishes a correlation between the partial enthalpy of evaporation from binary solutions, concentrations of components, and equilibrium vapor pressures. The difference between enthalpies of evaporation of components from solutions and those from the pure liquids, D(DH), depends on the chemical nature and concentrations, X, of solutions. The effect of concentrations on D(DH) makes different appearances in ideal and non-ideal solutions, although, as a whole, D(DH) increases with the growth of concentration of the second component. A model is introduced, which considers D(DH) as the sum of energetic changes of three sequential stages: passage of molecules from the bulk liquid into the surface layer, exit of the molecules on the outer side of the interface, and the following desorption into the gas phase. In the framework of the model, the main contribution to enthalpy of evaporation comes from the processes in the surface layer. It is suggested that adsorption from solutions, which changes the chemical composition of the surface layer with respect to that of the bulk solution, determines, to great extent, the difference in the forms of the curves D(DH)=f(X) for ideal and non-ideal solutions.
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