Transitory sensitivity in automatic chemical kinetic mechanism analysis
Name
Int J of Chemical Kinetics - 2024 - Johnson - Transitory sensitivity in automatic chemical kinetic mechanism analysis.pdf
Description
Published version
Size
4.07 MB
Format
Adobe PDF
Checksum (MD5)
6c73b28b8bf91693c77fc797c0c93cc2
Author(s)
Johnson, Matthew S
McGill, Charles J
Green, William H
Date Issued
October 21, 2024
Journal
International Journal of Chemical Kinetics
Publisher
Wiley
Citation
Johnson, Matthew S, McGill, Charles J and Green, William H. 2024. "Transitory sensitivity in automatic chemical kinetic mechanism analysis." International Journal of Chemical Kinetics, 57 (2).
Version
Final published version
Abstract
Detailed chemical kinetic mechanisms are necessary for resolving many important chemical processes. As the chemistry of smaller molecules has become better grounded and quantum chemistry calculations have become cheaper, kineticists have become interested in constructing progressively larger kinetic mechanisms to model increasingly complex chemical processes. These large kinetic mechanisms prove incredibly difficult to refine and time‐consuming to interpret. Traditional sensitivity analysis on a large mechanism can range from inconvenient to practically impossible without special techniques to reduce the computational cost. We first present a new time‐local sensitivity analysis we term transitory sensitivity analysis. Transitory sensitivity analysis is demonstrated in an example to accurately identify traditionally sensitive reactions at an 18,000x speed up over traditional sensitivities. By fusing transitory sensitivity analysis with more traditional time‐local branching, pathway, and cluster analyses, we develop an algorithm for efficient automatic mechanism analysis. This automatic mechanism analysis at a time point is able to identify the reactions a target is most sensitive to using transitory sensitivity analysis and then propose hypotheses why the reaction might be sensitive using branching, pathway, and cluster analyses. We implement these algorithms within the reaction mechanism simulator (RMS) package, which enables us to report the automatic mechanism analysis results in highly readable text formats and in molecular flux diagrams.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivatives
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1002/kin.21766
