Kinetics and thermochemistry of the oxidation of unsaturated radicals: C4H5+O2

Irene R. Slagle, A. Bencsura, Shi Ben Xing, David Gutman

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The kinetics and mechanism of the reaction of C4H5 (methylpropargyl radical) with O2 were investigated from 296 to 900 K in a tubular reactor coupled to a photoionization mass spectrometer. At room temperature the reaction proceeds by a simple pressure-dependent addition reaction. Between 369 and 409 K the equilibrium C4H5 + O2 ⇄ C4H5O2 was clearly observable and equilibrium constants were measured as a function of temperature. These measurements yielded the values of ΔHo 298 (-78±3 kJ mol-1) and ΔSo 298 (-122±9 J mol-1 K-1). Above 600 K the rate of reaction of methylpropargyl with O2 is independent of density and increases with temperature with a phenomenological rate constant equal to 6.9×10-14 exp(-10.5 kJ mol-1/RT) cm3 molecule-1 s-1. A mechanism of the C4H5+O2 reaction is proposed which involves initial formation of a C4H5O2 adduct. At temperatures above 600 K, decomposition of the chemically activated adduct competes with redissociation to C4H5+O2. The role of elementary reactions between unsaturated radicals and molecular oxygen in combustion processes is briefly reviewed.

Original languageEnglish
Pages (from-to)653-660
Number of pages8
JournalSymposium (International) on Combustion
Volume24
Issue number1
DOIs
Publication statusPublished - 1992

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Thermochemistry
thermochemistry
Oxidation
oxidation
Kinetics
kinetics
Temperature
Photoionization
Addition reactions
adducts
Molecular oxygen
Equilibrium constants
Mass spectrometers
Rate constants
Decomposition
mass spectrometers
Molecules
temperature
photoionization
reactors

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Fluid Flow and Transfer Processes
  • Physical and Theoretical Chemistry
  • Energy Engineering and Power Technology
  • Fuel Technology
  • Mechanical Engineering

Cite this

Kinetics and thermochemistry of the oxidation of unsaturated radicals : C4H5+O2. / Slagle, Irene R.; Bencsura, A.; Xing, Shi Ben; Gutman, David.

In: Symposium (International) on Combustion, Vol. 24, No. 1, 1992, p. 653-660.

Research output: Contribution to journalArticle

Slagle, Irene R. ; Bencsura, A. ; Xing, Shi Ben ; Gutman, David. / Kinetics and thermochemistry of the oxidation of unsaturated radicals : C4H5+O2. In: Symposium (International) on Combustion. 1992 ; Vol. 24, No. 1. pp. 653-660.
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