Molecular Modeling of Thermodynamic Properties of Fluids and Fluid Mixtures

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The goal of my research program is the development and application of computational algorithms based on fundamental statistical mechanical and quantum mechanical descriptions of the complex fluid systems arising in chemical engineering. The objectives are the prediction of macroscopic thermodynamic properties and elucidation of their underlying molecular basis. Such capabilities are useful in facilitating the improved design of fluid-based systems and processes.Macroscopic models (e.g., equations of state) are conventionally used for property prediction in computer-based process simulators. Although constructed to satisfy the constraints of thermodynamic and other scientific laws, they retain a significant empirical component and contain multiple parameters, whose determination requires significant amounts of experimental data. Our approach is to use relatively simple (requiring relatively few parameters) molecular models describing the underlying system inter- and intra-molecular forces, coupled with their study using the fundamentally exact machinery of statistical mechanics. The rapidly improving capabilities and decreasing costs of computer hardware and software make this approach applicable to increasingly complex systems, and is much less expensive than the use of experimental investigations alone. The goal is to use this methodology to make predictions of the properties and behaviour of previously unstudied compounds and processes, for which experimental data is either unavailable or sparse. Such predictions generate exact pseudo-experimental data for the model systems that can be analyzed and interpreted in the context of conventional macroscopic thermodynamic models. This yields the ability to perform computationally rapid predictions within process simulators. The main impediment to the more widespread application of molecular simulation methodology is the lack of computationally efficient algorithms for the simulation of certain properties and processes. The development of the required algorithms requires the integration of deep understanding of both macroscopic chemical engineering thermodynamics and the statistical mechanics of complex fluid mixtures, in both of which my group has considerable experience.The proposed project focuses on the development and applications of algorithms for the simulation of chemical reaction and phase equilibria, and on the modeling of thermochemical properties of aqueous electrolyte systems. A goal of the former project is to improve upon the primary existing algorithm in that area, developed by my group in the mid 1990's and which is now in widespread use by researchers worldwide. Applications of this proposal encompass a wide variety of processes and applications, including both traditional engineering fluid systems and aqueous systems arising in biology.