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Investigation into the Pressure Dependence between 1 and 10 Torr of the Reactions of NO2 with CH3 and CH3O

DOI: 10.1039/ft9938904163

Source and publish data:

Journal of the Chemical Society - Faraday Transactions p. 4163 - 4170 (1993)

Update date:2022-08-11

Topics:

Authors:

Biggs, PeterBiggs, Peter

Canosa-Mas, Carlos E.Canosa-Mas, Carlos E.

Fracheboud, Jean-MarcFracheboud, Jean-Marc

Parr, A. DouglasParr, A. Douglas

Shallcross, Dudley E.Shallcross, Dudley E.

et al.et al.

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Article abstract of DOI:10.1039/ft9938904163

The kinetic and pressure dependence of the reactions of NO2 with CH3 and CH3O have been investigated in the gas phase at 298 K, at pressure from 1 to 10 Torr.A low-pressure discharge-flow laser-induced fluorescence (LIF) technique was used.In a consecutive process, CH3 reacted with NO2 to form CH3O, CH3 + NO2 --> CH3O + NO (1), which further reacted with NO2 to form products, CH3O + NO2 --> products (2).Reaction (1) displayed no discernible pressure dependence over the pressure range 1-7 Torr, and k1 was calculated to be (2.3 +/- 0.3)E-11 cm3 molecule-1 s-1.Reaction (2) displayed a strong pressure dependence and an RRKM analysis yielded the following limiting low- and high-pressure rate constants in He, k0 = 5.9E-29 cm6 molecule-2 s-1 and k<*> = 2.1E-11 cm3 molecule-1 s-1.It is unrealistic to quote errors for this type of analysis.Parametrisation in the standard Troe form with Fc = 0.6 yielded k0 = (5.3 +/-)E-29 cm6 molecule-2 s-1 and k<*> = (1.4 +/- 0.1)E-11 cm3 molecule-1 s-1.Atmospheric implications and possible reaction mechanisms are discussed.

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