Co-Oriented Fluid Functional Equation for Electrostatic interactions (COFFEE)
Co-Oriented Fluid Functional Equation for Electrostatic interactions (COFFEE)
复制标题
静电相互作用的同向流体泛函方程 (COFFEE)
DOI：
10.1016/j.ces.2017.08.025
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发表时间：
2017
影响因子：
4.7
通讯作者：
K. Langenbach
中科院分区：
文献类型：
--
作者：
K. Langenbach
在化学工程中，经常出现具有不对称电荷分布的官能团，如OH、C双键O或NHX。除了极性相互作用外，这些基团通常表现出氢键相互作用。这两种类型的组合特别难以用状态方程描述。这导致这样的效果，即对于极性明显的纯化合物，包括极性相互作用可能导致对含有该组分的混合物的描述更差。这种行为的一个可能原因是状态方程通常基于微扰理论，忽略了由于相互作用引起的流体结构的变化。这种近似是很好的，例如色散相互作用，但已知是坏的，至少是气相的极性流体到中等density.The问题是在这篇文章中解决的目标流体，而不是参考流体周围的扰动理论，通常的情况下。这使得有可能将有序效应纳入状态方程，并在分子模拟或积分方程理论等典型方法所用时间的一小部分内计算额外的结构信息。微扰理论是根据分子模拟计算的斯托克迈耶流体的结构和气液平衡参数化的，并且与它们定量一致。这是验证第二个简单的流体，移位Stockmayer流体，其中的偶极子是沿沿着其轴远离Lennard-Jones中心。对于这种流体也进行分子模拟的结构和汽液平衡。这两种性质的预测新的状态方程，并再次同意定量模拟。新的理论，然后应用到氯化氢和现有的理论模型的改进。也就是说，液体密度的描述是改善了PCP-SAFT的文献模型，其中氯化氢的偶极性质被认为是，和蒸汽压的描述是改善了PC-SAFT的文献模型，其中弱H-键合性质被认为是。对于PCP-SAFT模型，通过使用文献中的偶极位移的量子力学结果，参数的数量可以保持在三个。与文献中的两种模型相比，该模型显示了预测蒸汽密度的改进。除了改进热力学性质的描述和预测外，新理论还可以快速计算流体的相互取向结构。这对于例如评估两个反应物基团彼此的可用性是有用的，从而允许更好地描述反应动力学。这是以前任何状态方程都没有实现过的。
In chemical engineering often functional groups like OH, Cdouble bondO, or NHxwith an asymmetric charge distribution occur. Aside from polar interactions, such groups often show H-bonding interactions. The combination of both types is especially hard to describe with equations of state. This leads to the effect that including polar interactions for clearly polar pure compounds may lead to a worse description of mixtures containing this component. One possible reason for this behavior is that equations of state are usually based on perturbation theory that ignores the change in fluid structure due to interactions. This approximation is good for e.g. dispersive interactions, but is known to be bad for at least the gaseous phase of polar fluids up to moderate densities.The issue is addressed in this article by developing a perturbation theory around the target fluid rather than the reference fluid, as is usually the case. This makes it possible to include ordering effects into the equation of state and to calculate additional structural information in a fraction of the time used by typical methods like molecular simulation or integral equation theory. The perturbation theory is parameterized on the Stockmayer fluid’s structure and vapor-liquid equilibria, calculated from molecular simulation, and agrees quantitatively with them. It is verified on a second simple fluid, the shifted Stockmayer fluid, where the dipole is shifted along its axis away from the Lennard-Jones center. For this fluid also molecular simulations are performed for both structure and vapor-liquid equilibria. Both properties are predicted by the new equation of state and again agree quantitatively with simulation.The new theory is then applied to hydrogen chloride and shows improvements over models for existing theories. Namely, liquid density description is improved over a literature model for PCP-SAFT, where the dipolar nature of hydrogen chloride is considered, and vapor pressure description is improved over a literature model for PC-SAFT, where the weak H-bonding nature is considered. The number of parameters can be kept at three, as for the PCP-SAFT model, by using quantum mechanics results from literature for the dipole shift. The model shows improvements for the predicted vapor density compared to both models from literature. Aside from improving thermodynamic property description and prediction, the new theory allows the fast calculation of a fluid’s mutual orientation structure. This is useful e.g. for assessing availability of two reactant groups to each other, thereby allowing a better description of reaction kinetics. This has not been accomplished by any equation of state before.
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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