Statistical Analysis on Rate Parameters of the H2-O2 Reaction System

Quantitative rate determination of elementary reactions is a major task in the study of chemical kinetics. To ensure the fidelity of their determination, progressively tightened constraints need to be placed on their measurement, especially with the development of various notable experimental techniques. However, the evaluation of reaction rates and their uncertainties is frequently conducted with substantial subjectivity due to data source, thermodynamic conditions, sampling range, and sparsity. To reduce the extent of biased rate evaluation, we propose herein an approach of uncertainty-weighted statistical analysis, utilizing weighted average, and weighted least-square regression in statistical inference. Based on the backbone H-2/O-2 chemistry, rate data for each elementary reaction are collected from the time-history profile in shock tube experiments and high-level theoretical calculations, with their assigned weight inversely depending on uncertainty, which would overall avoid subjective assessments and provide more accurate rate evaluation. Aided by sensitivity analysis, the rates of a few key reactions are further constrained in the less investigated low-to intermediate-temperature conditions using high-fidelity flow reactor data. Good performance of the constructed mechanism is confirmed with validation against the target of the high-fidelity flow reactor data. This study demonstrates a systematic approach for reaction rate evaluation and uncertainty quantification.

Automated summary

In the study of chemical kinetics, determining the quantitative rates of elementary reactions is crucial. By using an uncertainty-weighted statistical analysis approach, which includes weighted average and weighted least-square regression, it is possible to reduce subjective evaluations and provide more accurate rate determination.