The dissociation of diacetyl: a shock tube and theoretical study.

Abstract

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(infinity)(T) = 5.029 x 10(19) (T/298 K)(-3.40) exp(-37665/T) s(-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(3) + CH(3) = C(2)H(6) and CH(3) + C(4)H(6)O(2) = CH(3)CO + CH(2)CO + CH(4) (k(T) = 2.818T(4.00) exp(-5737/T) cm(3) mol(-1) s(-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.

• Authors: Xueliang Yang, Ahren W Jasper, John H Kiefer, Robert S Tranter
• Journal: The journal of physical chemistry. A (J Phys Chem A) Vol. 113 Issue 29 Pg. 8318-26 (Jul 23 2009) ISSN: 1520-5215 [Electronic] United States
• PMID: 19569704 (Publication Type: Journal Article)