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Title: Rate constants for CH{sub 3} + O{sub 2} {yields} CH{sub 3}O + O at high temperature and evidence for H{sub 2}CO + O{sub 2} {yields} HCO + HO{sub 2}

Journal Article · · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
DOI:https://doi.org/10.1021/jp9909457· OSTI ID:677959
; ;  [1]
  1. Argonne National Lab., IL (United States). Chemistry Div.

The reaction of CH{sub 3} with O{sub 2} has been studied in a reflected shock tube apparatus between 1600 and 2100 K. CH{sub 3} was prepared from the fast thermal decomposition of CH{sub 3}I and O atom atomic resonance absorption spectrometry (ARAS) was used to observe absolute [O]{sub t}. [CH{sub 3}I]{sub 0} was sufficiently low so that most secondary reactions were negligible, allowing for unambiguous determination of the rate constant for CH{sub 3} + O{sub 2} {yields} CH{sub 3}O + O. The rate constant expression for this reaction derived to match the experimental data is {kappa} = (3.90 {+-} 0.40) {times} 10{sup {minus}11} exp({minus}16858 {+-} 1127 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. To explain O atom concentration buildup at longer times, a fast reaction between H{sub 2}CO and O{sub 2} was postulated. Rate constants for this process were derived by fitting the long-time O atom profiles. Last, the four-center reaction CH{sub 3} + O{sub 2} {yields} CH{sub 2}O + OH was found to be of negligible importance over the temperature range of the study.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
677959
Journal Information:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Vol. 103, Issue 30; Other Information: PBD: 29 Jul 1999
Country of Publication:
United States
Language:
English