Experimental and Theoretical Studies of Model Chemical Reactions Under Variable Pressure and Temperature

在化学部实验物理化学计划的这个项目中，Ben-Amotz将使用依赖于压力和温度的光学光谱研究以及理论建模来研究溶质-溶剂相互作用对化学反应的影响。将研究解离、异构化和离子对模型反应，并将使用高压拉曼光谱、傅里叶变换红外光谱和超临界流体压力室中的UV/可见光光谱测量模型反应在有机溶剂以及超临界Ar、Xe和水中的平衡常数的变化。这些结果将被用来检验液体微扰理论的理论模型，该理论模型使用第一原理方法和半经验扰动硬流体(PHF)模型。预测结果和实验结果将在较宽的压力和温度范围内进行比较，包括在液体和超临界流体溶剂中。使用预测模型来计算系统的性能，特别是那些在极端温度或压力条件下的系统，其价值已被工程师们广泛认识到。这些研究将有助于我们预测在日益极端和复杂的凝聚相条件下的化学反应平衡。这项工作的结果可能对工业化学合成、废物回收和分离技术具有重要意义。

In this project in the Experimental Physical Chemistry Program of the Chemistry Division, Ben-Amotz will study the influence of solute-solvent interactions on chemical reactions using pressure- and temperature-dependent optical spectroscopic studies as well as theoretical modeling. Dissociation, isomerization, and ion-pairing model reactions will be studied, and changes in the equilibrium constants for model reactions will be measured in organic solvents as well as in supercritical argon, xenon, and water using high-pressure Raman, FTIR, and UV/visible spectroscopies in diamond anvil supercritical fluid pressure cells. The results will be used to test theoretical models derived from liquid perturbation theory using both a first-principles approach as well as a semi-empirical perturbed hard fluid (PHF) model. Predicted and experimental results will be compared over a wide pressure and temperature range in both liquid and supercritical fluid solvents. The value of using predictive models to calculate properties of systems, especially those under extreme conditions of temperature or pressure, has become widely recognized by engineers. These studies will contribute to our ability to predict chemical reaction equilibria under increasingly extreme and complex condensed phase conditions. The results of this work are likely to be important to industrial chemical synthesis, waste recovery, and separation technologies.