Department of Chemical and Biomolecular Engineering, Rice University, 6100 S. Main St. Houston, Texas 77005, USA.
J Chem Phys. 2013 May 7;138(17):174109. doi: 10.1063/1.4803023.
In this work, we present three new branched chain equations of state (EOS) based on Wertheim's perturbation theory. The first represents a slightly approximate general branched chain solution of Wertheim's second order perturbation theory (TPT2) for athermal hard chains, and the second represents the extension of first order perturbation theory with a dimer reference fluid (TPT1-D) to branched athermal hard chain molecules. Each athermal branched chain EOS was shown to give improved results over their linear counterparts when compared to simulation data for branched chain molecules with the branched TPT1-D EOS being the most accurate. Further, it is shown that the branched TPT1-D EOS can be extended to a Lennard-Jones dimer reference system to obtain an equation of state for branched Lennard-Jones chains. The theory is shown to accurately predict the change in phase diagram and vapor pressure which results from branching as compared to experimental data for n-octane and corresponding branched isomers.
在这项工作中，我们提出了三个基于 Wertheim 微扰理论的新的支化链状态方程（EOS）。第一个代表了 Wertheim 二级微扰理论（TPT2）的稍微近似的通用无热硬链支化链解，第二个代表了用二聚体参考流体（TPT1-D）扩展的一阶微扰理论到支化无热硬链分子。与支化 TPT1-D EOS 相比，每个无热支化链 EOS 在与支化分子的模拟数据比较时都显示出对线性对应物的改进结果，而支化 TPT1-D EOS 是最准确的。此外，还表明可以将支化 TPT1-D EOS 扩展到 Lennard-Jones 二聚体参考系统，以获得支化 Lennard-Jones 链的状态方程。与正辛烷和相应的支化异构体的实验数据相比，该理论准确地预测了由于支化而导致的相图和蒸气压的变化。
