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

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

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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 ΔHo298 (-78±3 kJ mol-1) and ΔSo298 (-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

ASJC Scopus subject areas

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

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