Engineering Approximations for Kinetic Parameter Estimation

摘要提案标题：工程近似动力学参数估计提案编号：CTS-0086700主要研究员：理查德·马赛尔机构：伊利诺伊大学本提案的目的是开发改进的工程近似化学动力学。 动力学参数的估计能力对于化工过程工业的过程设计和优化是重要的。 更准确的反应速率常数的相关性将开发使用从头算量子力学方法和实验数据相结合。 在以前的努力，改进的相关性估计原子转移反应的活化能，需要一个可调参数，开发。 在目前的项目中，以前的努力，计算率的一般氢提取反应将得到扩展。 涉及各种自由基，包括羟基，烷基和氯的反应将被检查。 还将研究含有伯，仲和叔碳-氢键的反应物，以拟合和测试模型的适用性。 将进行从头计算以确定反应过程中反应物之间的活化势垒和分子间力。 这些计算将允许估计每个术语在预测的总比率中的相对重要性。 这项工作可能会导致更好的模型用于预测动力学数据，用于化学反应过程模拟器。

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.