Neimark AV, Vishnyakov A
TRI/Princeton, 601 Prospect Avenue, Princeton, New Jersey 08542, USA.
Phys Rev E Stat Phys Plasmas Fluids Relat Interdiscip Topics. 2000 Oct;62(4 Pt A):4611-22. doi: 10.1103/physreve.62.4611.
A method for Monte Carlo studies of phase equilibrium in confined systems is presented using an example of vapor-liquid equilibrium (capillary condensation and evaporation) in cylindrical pores. The method, named the gauge cell method, allows one to construct the full phase diagram of a confined fluid in the form of a van der Waals loop, which includes stable, metastable, and unstable equilibrium states. The phase coexistence is then determined by thermodynamic integration along the metastable and unstable regions of the phase diagram employing Maxwell's rule of equal areas. The simulation results agree with experimental data on the capillary condensation of nitrogen at its boiling temperature on mesoporous molecular sieves. The method can be applied to other phase transitions in confined systems such as fluid-fluid separation, layering, and freezing.
本文以圆柱孔内的气液平衡（毛细管冷凝和蒸发）为例，介绍了一种用于受限系统相平衡蒙特卡罗研究的方法。该方法称为规范单元法，可构建受限流体的完整相图，呈范德瓦尔斯回路形式，其中包括稳定、亚稳和不稳定平衡态。然后，利用麦克斯韦等面积法则，通过沿相图的亚稳和不稳定区域进行热力学积分来确定相共存。模拟结果与氮气在其沸点下在介孔分子筛上的毛细管冷凝实验数据相符。该方法可应用于受限系统中的其他相变，如流体-流体分离、分层和冻结。
