Institute of Biochemical Physics RAS , Kosygin St. 4, 119334 Moscow, Russia.
J Phys Chem B. 2014 Mar 20;118(11):3115-21. doi: 10.1021/jp410634v. Epub 2014 Mar 7.
Thermodiffusion in binary molecular liquids is examined using the nonequilibrium thermodynamic model, where the thermodynamic parameters are calculated using equations based on statistical mechanics. In this approach, thermodiffusion is quantified through the variation in binary chemical potential and its temperature and concentration dependence. The model is applied to solutions of organic solvents, in order to compare our theoretical results to experimental results from the literature. A measurable contribution of the orientation-dependent Keezom interaction is shown, where the possible orientations are averaged using the Boltzmann weighting factor. Calculations of enthalpies of evaporation from the model yield good agreement with experimental values from the literature. However, calculations of the associated energetic parameters were several times larger than those reported in the literature from numeric simulations of material transport.
使用非平衡热力学模型研究了二元分子液体中的热扩散，其中热力学参数是使用基于统计力学的方程计算的。在这种方法中，通过二元化学势的变化及其对温度和浓度的依赖性来量化热扩散。该模型应用于有机溶剂溶液，以便将我们的理论结果与文献中的实验结果进行比较。结果表明，取向相关的 Keezom 相互作用有可测量的贡献，其中可能的取向使用玻尔兹曼权重因子进行平均。从模型计算的蒸发焓与文献中的实验值吻合较好。然而，与文献中报道的物质输运数值模拟的能量参数相比，相关的能量参数的计算值要大几个数量级。
