Engineering Approximations for Kinetic Parameter Estimation

建议题目：动力学参数估计的工程近似建议编号：CTS-0086700主要研究人员：理查德·梅塞尔研究所：伊利诺斯大学这项建议的目的是开发改进的化学动力学工程近似。估计动力学参数的能力对于化工过程工业的过程设计和优化是很重要的。结合从头算量子力学方法和实验数据，将开发出更精确的反应速率常数关联式。在以前的工作中，一个改进的关联式被用来估计原子转移反应的活化能，只需要一个可调参数。在目前的项目中，将扩大以前计算一般氢提取反应速率的努力。将研究涉及各种自由基的反应，包括羟基、烷基和氯。还将研究含有初级、二级和三级碳氢键的反应物，以拟合和测试该模型的适用性。将进行从头计算来确定反应过程中的活化势垒和反应物之间的分子间力。这些计算将允许估计每一项在预测的总体比率中的相对重要性。这项工作可能会为化学反应过程模拟器中使用的动力学数据预测提供更好的模型。

AbstractProposal Title: Engineering Approximations for Kinetic Parameter EstimationProposal Number: CTS-0086700Principal Investigator: Richard MaselInstitution: University of IllinoisThe objective of this proposal is to develop improved engineering approximations for chemical kinetics. The ability to estimate kinetic parameters is of importance to the chemical process industry for process design and optimization. More accurate correlations for reaction rate constants will be developed using a combination of ab initio quantum mechanics methods and experimental data. In previous efforts an improved correlation for estimating the activation energy of atom transfer reactions, requiring one adjustable parameter, was developed. In the current project previous efforts to calculate rates of the general hydrogen abstraction reaction will be extended. Reactions involving various free radicals including hydroxyl, alkyl, and chlorine will be examined. Reactants containing primary, secondary, and tertiary carbon-hydrogen bonds will also be studied to fit and test the applicability of the model. Ab initio calculations will be performed to determine the activation barriers and the intermolecular forces between reactants during reaction. These calculations will permit an estimate of the relative importance of each term in the predicted overall rate. This work may lead to better models for the prediction of kinetic data for use in chemical reaction process simulators.