The dissociation of diacetyl : a shock-tube and theoretical study.
- Chemical Sciences and Engineering Division
The dissociation of diacetyl dilute in krypton has been studied in a shock tube using laser schlieren densitometry at 1200-1800 K and reaction pressures of 55 {+-} 2, 120 {+-} 3, and 225 {+-} 5 Torr. The experimentally determined rate coefficients show falloff and an ab initio/Master Equation/VRC-TST analysis was used to determine pressure-dependent rate coefficient expressions that are in good agreement with the experimental data. From the theoretical calculations k{sub {infinity}} (T) = 5.029 x 10{sup 19} (T/298 K){sup -3.40} exp(-37665/T) s{sup -1} for 300 < T < 2000 K. The laser schlieren profiles were simulated using a model for methyl recombination with appropriate additions for diacetyl. From the simulations rate coefficients were determined for CH{sub 3} + CH{sub 3} = C{sub 2}H{sub 6} and CH{sub 3} + C{sub 4}H{sub 6}O{sub 2} = CH{sub 3}CO + CH{sub 2}CO + CH{sub 4} (k(T) = 2.818T{sup 4.00} exp(-5737/T) cm{sup 3} mol{sup -1} s{sup -1}). Excellent agreement is found between the simulations and experimental profiles, and Troe type parameters have been calculated for the dissociation of diacetyl and the recombination of methyl radicals.
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- SC
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1012804
- Report Number(s):
- ANL/CSE/JA-64158
- Journal Information:
- J. Phys. Chem. A, Journal Name: J. Phys. Chem. A Journal Issue: 29 ; Jul. 1, 2009 Vol. 113; ISSN 1089-5639
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Recombination of methyl radicals. 1. New data between 1175 and 1750 K in the falloff region
Modeling–Experiment–Theory Analysis of Reactions Initiated from Cl + Methyl Formate