Research Initiation: Development of a Thermodynamic Perturbation Theory for Electrolyte Solutions

研究启动：电解质溶液热力学微扰理论的发展

• 批准号: 8811789
• 负责人: John Eggebrecht
• 金额: $ 4.7万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-06-15 至 1990-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8811789&HistoricalAwards=false
• 关键词: Research; Initiation; Development; Thermodynamic; Perturbation

An equation of state of aqueous electrolyte solutions at finite concentrations is developed in this work. The approach is based upon a new thermodynamic perturbation theory in which the reference fluid is taken to be a mixture of neutral and charged spheres. Interactions arising from solvent polarity are treated as the perturbation. The properties of the new reference fluid are obtained from numerical solutions of the Ornstein-Zernicke integral equation using finite element methods. The direct correlation function for charged pairs is approximated by the HNC equation and PY closure used for other pairs. The accuracy of these correlation functions are tested by comparison with computer simulations. This basic research is required in the development of a predictive description of electrolyte solution thermodynamics and phase equilibria. The work is partially motivated by a continuing interest in the application of statistical mechanics to the description of fluid interfaces. Aside from the role played in the development of interfacial science, a predictive description of ionic solutions is urgently needed for the synthesis and optimization of industrial processes, for the description of chemically complex aqueous environments, and for an understanding of some biological systems.

本文建立了有限浓度电解质水溶液的状态方程。该方法基于一种新的热力学微扰理论，在该理论中，参考流体被视为中性球体和带电球体的混合物。由溶剂极性引起的相互作用被视为微扰。用有限元方法从Ornstein-ZerNicke积分方程的数值解中得到了新参考流体的性质。电荷对的直接关联函数用HNC方程和其他对的PY闭包来近似。通过与计算机模拟的比较，验证了这些相关函数的准确性。这项基础研究是开发电解液溶液热力学和相平衡的预测性描述所必需的。这项工作的部分动机是对统计力学应用于描述流体界面的持续兴趣。除了在界面科学的发展中所起的作用外，离子溶液的预测性描述对于工业过程的合成和优化、对化学上复杂的水环境的描述以及对某些生物系统的理解都是迫切需要的。