Flow reactor studies of methyl radical oxidation reactions in methane-perturbed moist carbon monoxide oxidation at high pressure with model sensitivity analysis

James J. Scire, Richard A. Yetter, Frederick L. Dryer

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

New rate constant determinations for the reactions (1), (2), (3) were made at 1000 K by fitting species profiles from high-pressure flow reactor on moist CO oxidation perturbed with methane. The experiments were selected to minimize the uncertainty in the rate constant determinations. This uncertainty was estimated using model sensitivity coefficients, derived for time-shifted flow reactor experiments. The model sensitivity analysis was also used to characterize the mechanistic dependence on the new rate constant values. Linear sensitivities of the fitted rate constants to the unfitted values are given. Singular value decomposition was used to determine which of these four could affect the fitted rates without changing the fit norm.

Original languageEnglish (US)
Pages (from-to)75-100
Number of pages26
JournalInternational Journal of Chemical Kinetics
Volume33
Issue number2
DOIs
StatePublished - Feb 1 2001

Fingerprint

Methane
sensitivity analysis
Carbon Monoxide
Carbon monoxide
carbon monoxide
Sensitivity analysis
Uncertainty
Rate constants
methane
reactors
Pressure
Oxidation
oxidation
Singular value decomposition
sensitivity
norms
Experiments
methyl radical
decomposition
coefficients

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{0d80e859666347faa37055281dfbde84,
title = "Flow reactor studies of methyl radical oxidation reactions in methane-perturbed moist carbon monoxide oxidation at high pressure with model sensitivity analysis",
abstract = "New rate constant determinations for the reactions (1), (2), (3) were made at 1000 K by fitting species profiles from high-pressure flow reactor on moist CO oxidation perturbed with methane. The experiments were selected to minimize the uncertainty in the rate constant determinations. This uncertainty was estimated using model sensitivity coefficients, derived for time-shifted flow reactor experiments. The model sensitivity analysis was also used to characterize the mechanistic dependence on the new rate constant values. Linear sensitivities of the fitted rate constants to the unfitted values are given. Singular value decomposition was used to determine which of these four could affect the fitted rates without changing the fit norm.",
author = "Scire, {James J.} and Yetter, {Richard A.} and Dryer, {Frederick L.}",
year = "2001",
month = "2",
day = "1",
doi = "10.1002/1097-4601(200102)33:2<75::AID-KIN1000>3.0.CO;2-9",
language = "English (US)",
volume = "33",
pages = "75--100",
journal = "International Journal of Chemical Kinetics",
issn = "0538-8066",
publisher = "John Wiley and Sons Inc.",
number = "2",

}

TY - JOUR

T1 - Flow reactor studies of methyl radical oxidation reactions in methane-perturbed moist carbon monoxide oxidation at high pressure with model sensitivity analysis

AU - Scire, James J.

AU - Yetter, Richard A.

AU - Dryer, Frederick L.

PY - 2001/2/1

Y1 - 2001/2/1

N2 - New rate constant determinations for the reactions (1), (2), (3) were made at 1000 K by fitting species profiles from high-pressure flow reactor on moist CO oxidation perturbed with methane. The experiments were selected to minimize the uncertainty in the rate constant determinations. This uncertainty was estimated using model sensitivity coefficients, derived for time-shifted flow reactor experiments. The model sensitivity analysis was also used to characterize the mechanistic dependence on the new rate constant values. Linear sensitivities of the fitted rate constants to the unfitted values are given. Singular value decomposition was used to determine which of these four could affect the fitted rates without changing the fit norm.

AB - New rate constant determinations for the reactions (1), (2), (3) were made at 1000 K by fitting species profiles from high-pressure flow reactor on moist CO oxidation perturbed with methane. The experiments were selected to minimize the uncertainty in the rate constant determinations. This uncertainty was estimated using model sensitivity coefficients, derived for time-shifted flow reactor experiments. The model sensitivity analysis was also used to characterize the mechanistic dependence on the new rate constant values. Linear sensitivities of the fitted rate constants to the unfitted values are given. Singular value decomposition was used to determine which of these four could affect the fitted rates without changing the fit norm.

UR - http://www.scopus.com/inward/record.url?scp=0035252519&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035252519&partnerID=8YFLogxK

U2 - 10.1002/1097-4601(200102)33:2<75::AID-KIN1000>3.0.CO;2-9

DO - 10.1002/1097-4601(200102)33:2<75::AID-KIN1000>3.0.CO;2-9

M3 - Article

AN - SCOPUS:0035252519

VL - 33

SP - 75

EP - 100

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

SN - 0538-8066

IS - 2

ER -