Evaluated Rate Constants for i-Butane + H and CH3: Shock Tube Experiments with Bayesian Model Optimization

Published

March 7, 2018

Author(s)

Laura A. Mertens, Iftikhar A. Awan, Jeffrey A. Manion

Abstract

The reactions of i-butane with CH3 and H were investigated with shock tube experiments (870 K to 1130 K and 140 kPa to 360 kPa). Propene and i-butene, measured with GC/FID and MS, were quantified as characteristic of H-abstraction from the primary and tertiary carbons, respectively. A comprehensive Cantera[1] kinetics model based on JetSurF 2.0[2] was optimized to these experimental measurements and literature data – including early experiments at low temperatures, measurements of the total rate constant, and measurement from ethane for the rate constant for primary carbons – using the Method of Uncertainty Minimization using Polynomial Chaos Expansions (MUM-PCE) – pioneered by David Sheen and Hai Wang.[3] For both H and CH3, the optimization increased the rate H-abstraction from the tertiary carbon relative to the primary carbon. We combined our primary and tertiary rate constants with previous results from our group on n-butane[4] to get site-specific rate constants for the reaction of H and CH3 with a generic primary, secondary and tertiary carbon.

Proceedings Title

Combustion Institute Eastern States Spring Meeting

Conference Dates

March 4-7, 2018

Conference Location

State College, PA

Pub Type

Conferences

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Keywords

kinetics, pyrolysis, combustion, modeling, H-abstraction

Citation

Mertens, L. , Awan, I. and Manion, J. (2018), Evaluated Rate Constants for i-Butane + H and CH3: Shock Tube Experiments with Bayesian Model Optimization, Combustion Institute Eastern States Spring Meeting, State College, PA, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=926190 (Accessed October 11, 2025)