Rate constants for H{sub 2}CO + O{sub 2} {yields} HCO + HO{sub 2} at high temperature
The reaction between H{sub 2}CO and O{sub 2} has been studied in a reflected shock tube apparatus between 1633--2027 K using trioxane, (H{sub 2}CO){sub 3}, as the source of H{sub 2}CO. O-atom atomic resonance absorption spectrometry (ARAS) was used to observe absolute [O]{sub t} under conditions of low [H{sub 2}CO]{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}CO and O{sub 2}. Ab initio theoretical results indicated that the process, H{sub 2}CO + O{sub 2} {yields} HCO + HO{sub 2}, is the only possible reaction. After rapid HCO and HO{sub 2} dissociations, O-atoms are then instantaneously produced from H + O{sub 2} {yields} O + OH. Using the ab initio result, variational transition state theoretical calculations (CTST) give k{sub 1} = 4.4929 x 10{sup {minus}20} T{sup 2.9116} exp{minus}18692/T cm{sup 3} molecule{sup {minus}1} S{sup {minus}1}. This theoretical result is consistent with the present experimental determinations and those at lower temperatures.
- Research Organization:
- Argonne National Laboratory, Argonne, IL (US)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 751868
- Report Number(s):
- ANL/CHM/CP-100829
- Country of Publication:
- United States
- Language:
- English
Similar Records
The branching ratio in the thermal decomposition of H{sub 2}CO
Binding energies of HCO and HCO{sup {minus}} and electron affinities of HCO