Practical Methodology in Kinetic Modeling for Complex Reactions: Weighted Error Manipulation to Allow Effective Model Evaluation in a Borderline SN Reaction.

Abstract

This paper details a novel and mechanism-oriented approach to kinetic modeling of complex chemical reactions, which focuses on the importance of a detailed understanding of the reaction mechanism and appropriate experimental data collection in the development and evaluation of accurate reaction models. Instead of using traditional statistical indices centered on the experimental data, this approach introduces a fitting index based on a weighted continuous error range centered on simulated data to accomplish effective model evaluation. Also, as a practical example, the method was applied to distinguish a borderline S_N reaction mechanism involving five elementary steps, and the results showed improved model fit compared to models involving solely S_N1 or S_N2 mechanisms. This approach provides a new aspect for model evaluation and validation in kinetic modeling based on both mechanistic understanding and experimental data.