NIST Chemical Kinetics Database

Author(s):   DeSain, J.D.; Klippenstein, S.J.; Miller, J.A.; Taatjes, C.A.
Title:   Measurements, Theory, and Modeling of OH Formation in Ethyl + O₂ and Propyl + O₂ Reactions
Journal:   J. Phys. Chem. A
Volume:   107
Page(s):   4415 - 4427
Year:   2003
Reference type:   Journal article
Squib:   2003DES/KLI4415-4427

Reaction:   (CH₃)2CHO₂ → CH₃CH=CH₂ + HO₂
Reaction order:   1
Temperature:   296 - 700 K
Pressure:  3.65E12 bar
Rate expression:   9.38x10¹⁶ [s^-1] (T/298 K)^-7.86 e^{-153236 [J/mole]/RT}
Bath gas:   He
Category: Theory
Data type:   Ab initio
Comments:   Rate constants are based in part on master equation simulations employing transition states from quantum calculations. This work is a combined experimental, theory, and modeling study. Compared OH profiles with those from modeling. Model describes HO2 profiles well, but is not as good for OH profiles.

Static cell (low flow), 296-700 K, He buffer typically 3.65E17 cm-3 (10-20 torr), O2 typically 6.3E15 cm-3. Radicals produced by RH + Cl -> R + HCl, where Cl produced by 193 nm excimer laser photolysis of CCl3F. OH detected using LIF at 281.996 nm.

Employed earlier quantum calculations (see references below) combined with master equation modeling to provide rate expressions for many reactions in this system. Only a few rate expressions are abstracted here.

Miller and Klippenstein, IJCK 33, 654 (2001)
DeSain et al, Farad. Disc. 119, 101 (2001)

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Rate constant values calculated from the Arrhenius expression:

T (K)	k(T) [s^-1]
296	9.01E-11
300	1.86E-10
325	1.12E-8
350	3.58E-7
375	6.97E-6
400	9.06E-5
425	8.46E-4
450	6.01E-3
475	3.39E-2
500	1.58E-1
525	6.21E-1
550	2.13E0
575	6.43E0
600	1.75E1
625	4.34E1
650	9.91E1
675	2.11E2
700	4.19E2