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基于无模型法和 IKP 法的评估固态反应动力学参数的综合方法。

Comprehensive method based on model free method and IKP method for evaluating kinetic parameters of solid state reactions.

机构信息

Department of Mechanical Engineering, University of Kentucky, Lexington, Kentucky 40506, USA.

出版信息

J Comput Chem. 2012 Dec 5;33(31):2516-25. doi: 10.1002/jcc.23091. Epub 2012 Aug 28.

Abstract

This article presents, firstly, a short review of methods for evaluating kinetic parameters of solid state reactions and a critical analysis of the isoconversional principle of model free methods. It shows theoretically that the activation energy for complex reactions is not only a function of the reaction degree but also of heating programs, and points out that any method that attempts to extract the dependences of activation energy on conversion degree without considering the dependences of heating programs is problematic. Then an analysis is given of the invariant kinetic parameters (IKP) method and recommends an incremental version of it. Based on the incremental IKP method and model free method, a comprehensive method is proposed that predicts the degree of the dependences of activation energy on heating programs, selects reliable values of activation energy and extracts the values of variable pre-exponential factor. This comprehensive method is tested using both simulation data and experimental data, the results of which show it can not only give reliable values of kinetic parameters but also be helpful in explaining inconsistencies of kinetic results in solid state reactions.

摘要

本文首先对评估固态反应动力学参数的方法进行了简要回顾,并对非等转化率动力学方法的等转化率原理进行了批判性分析。理论表明,复杂反应的活化能不仅是反应程度的函数,还是加热程序的函数,并指出任何试图在不考虑加热程序依赖性的情况下提取活化能对转化率依赖性的方法都是有问题的。然后对不变动力学参数(IKP)方法进行了分析,并对其进行了增量改进。基于增量 IKP 方法和非等转化率动力学方法,提出了一种综合方法,用于预测活化能对加热程序依赖性的程度,选择可靠的活化能值,并提取变量前指数因子的值。该综合方法通过模拟数据和实验数据进行了测试,结果表明,它不仅可以提供可靠的动力学参数值,而且有助于解释固态反应中动力学结果的不一致性。

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