NSF/CONACyT Cooperative Research: Global Thermodynamics Phase Diagrams of Binary Mixtures

热力学模型对混合物相平衡的准确计算或预测在化工、能源和石油工业中具有重要的应用价值。这些信息对开发新的热力学模型也很有意义，并通过将热力学模型与实验数据相结合，将必须测量的数据量降至最低。目前的热力学模型(状态方程，EOS)对于许多工业应用来说是令人满意的，但在大的温度和压力范围内描述高度非理想混合物仍然是一个困难的问题。本研究将：a)发展用于关联和/或预测具有相同和不相似类型的分子的二元混合物的全局相图(数学拓扑分析)的方法：i.双参数立方van der Waals状态方程和相关混合规则。ii.将利用扩展的Wong Sandler类型混合规则来实现的三参数立方Dw Waals状态方程。iii.理论EOS(类似于转子链，或任何其他基于理论的状态方程)具有新的混合规则。这部分工作将集中在分析状态方程的数学拓扑及其混合规则，这将表明哪种二元相图是可以预测的，以及是否存在一些尚未遇到的相图。b)实验测定选定的二元混合物的PVT(压力、体积、温度)性质和平衡相行为；这些模型特别是水与醇的混合物(1-丙醇、1-丁醇、2-丁醇、……、1-癸醇)的图示将被预测。c)为发展新的状态方程及其混合规则以改进工业混合物的全局相行为的预测提供信息。

ABSTRACTCTS-9903536Stanley I. Sandler/U. of Del.The accurate calculation or prediction of phase equilibria of mixtures by a thermodynamic model is important for applications in the chemical, energy and petroleum industry. Such information is also of interest in developing new thermodynamics models, and by combining a thermodynamic model with experimental data, minimizing the amount of data that must be measured. Current thermodynamic models (equations of state, EOS) are satisfactory for many industrial applications, but the description of highly non-ideal mixtures over large range of temperatures and pressure is still a difficult problem.This research will:A) Develop methods for the correlation and/or prediction of global phase diagrams (the analysis of the mathematical topology) of binary mixtures with equal and dissimilar types of molecules using:I. Two parameter cubic van der Waals EOS and related mixing rules.II. A three parameter cubic der Waals EOS which will be implemented with extended Wong Sandler type mixing rules to be developed for such equations.III. A theoretical EOS (like COR chain of rotators, or any other theoretically-based EOS) with new mixing rules. This part of the work will be focused on the analysis of the mathematical topology of EOS and their mixing rules, it will show which kind of binary phase diagrams can be predicted and whether there exist some that not have yet been encountered.B) Experimental determination of PVT (pressure, volume, temperature) properties and equilibrium phase behavior of selected binary mixtures; the diagrams of will be predicted by the models, specifically mixture of water with alcohols (1-propanol, 1-butanol, 2-butanol,..., 1-decanol).C) To provide information for the development of a new equation of state and their mixing rule to improve the prediction of global phase behavior of mixtures of industrial