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Initiation in H{sub 2}/O{sub 2}: Rate constants for H{sub 2} + O{sub 2} {yields} H + HO{sub 2} at high temperature

Conference ·
OSTI ID:750572
The reaction between H{sub 2} and O{sub 2} has been studied in a reflected shock tube apparatus between 1662--2097 K. O-atom atomic resonance absorption spectrometry (ARAS) was used to observe absolute [O]{sub t} under conditions of low [H{sub 2}]{sub 0} so that most secondary reactions were negligible. Hence, the observed [O]{sub t}, was the direct result of the rate controlling reaction between H{sub 2} and O{sub 2}. Three different reactions were considered, but experimental and ab initio theoretical results both indicated that the process, H{sub 2} + O{sub 2} {yields} H + HO{sub 2}, is the only possible reaction. After rapid HO{sub 2} dissociation, O-atoms are then instantaneously produced by H + O{sub 2} {yields} O + OH. Using the ab initio result, conventional transition state theoretical calculations (CTST) with tunneling corrections give the expression: k = 1.228 x 10{sup {minus}18} T{sup 2.4328} exp({minus}26926 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, applicable between 400 and 2,300 K. This theoretical result agrees with the present experimental determinations and those at lower temperature, derived from earlier work on the reverse reaction.
Research Organization:
Argonne National Lab., IL (US)
Sponsoring Organization:
US Department of Energy (US)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
750572
Report Number(s):
ANL/CHM/CP-100372
Country of Publication:
United States
Language:
English