Advanced Isoconversional Kinetic Analysis for the Elucidation of Complex Reaction Mechanisms: A New Method for the Identification of Rate-Limiting Steps

高级等转化动力学分析用于阐明复杂反应机理:一种识别限速步骤的新方法

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作者:Nicolas Sbirrazzuoli

Abstract

Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman's method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given α value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation.

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