稀二元混合物中的亨利定律、表面张力和表面吸附
Henry's law, surface tension, and surface adsorption in dilute binary mixtures
摘要：
本文在考虑梯度自由能的亥姆霍兹自由能的基础上，研究了稀二元流体混合物在两相状态下的平衡性质。讨论了溶质在气液间的分配（亨利定律）和表面张力的变化$Δγ$。给出了以$Γ$为表面吸附的吉布斯定律$Δγ=-TΓ$的推导。计算量包括临界温度和压力相对于溶质摩尔分数$X$的导数$d T_c/dX$和$d p_c/dX$以及共存表面上固定压力$p$下表面张力的温度导数$(\p γ/\p T)_{{\rm cx},p}$。这里，$(\p γ/\p T)_{{\rm cx},p}$可以是正的和负的，这取决于溶质分子大小和溶质-溶剂相互作用，并且在共沸线上发散。在范德瓦尔斯模型中，所有这些量都给出了显式表达式。
英文摘要：
Equilibrium properties of dilute binary fluid mixtures are studied in two-phase states on the basis of a Helmholtz free energy including the gradient free energy. The solute partitioning between gas and liquid (Henry's law) and the surface tension change $Δγ$ are discussed. A derivation of the Gibbs law $Δγ=-TΓ$ is given with $Γ$ being the surface adsorption. Calculated quantities include the derivatives $d T_c/dX$ and $d p_c/dX$ of the critical temperature and pressure with respect to the solute molar fraction $X$ and the temperature-derivative $(\p γ/\p T)_{{\rm cx},p}$ of the surface tension at fixed pressure $p$ on the coexistence surface. Here $(\p γ/\p T)_{{\rm cx},p}$ can be both positive and negative, depending on the solute molecular size and the solute-solvent interaction,and diverges on the azeptropic line. Explicit expressions are given for all these quantities in the van der Waals model.
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