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

[摘要]stanley I. Sandler/U。德尔。用热力学模型准确地计算或预测混合物的相平衡对于化学、能源和石油工业的应用是重要的。这些信息也有助于开发新的热力学模型，并通过将热力学模型与实验数据相结合，最大限度地减少必须测量的数据量。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，但是在大温度和压力范围内描述高度非理想混合物仍然是一个难题。本研究将：A)开发具有相同和不同类型分子的二元混合物的整体相图（数学拓扑分析）的关联和/或预测方法：二参数三次范德华方程及相关混合规则。一个三参数三次der Waals EOS将与扩展的Wong Sandler型混合规则实现，将为此类方程开发。具有新混合规则的理论EOS（如COR旋转链或任何其他基于理论的EOS）。这部分工作将侧重于分析EOS的数学拓扑及其混合规则，它将显示哪些类型的二元相图可以预测，以及是否存在一些尚未遇到的。B)实验测定所选二元混合物的PVT（压力、体积、温度）特性和平衡相行为；模型可以预测水与醇(1-丙醇、1-丁醇、2-丁醇、…c)为建立新的状态方程及其混合规则提供信息，以改进对工业混合料整体相行为的预测

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