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Kinetic study of reactions of C2H5O2 with NO at 298 K and 0.55 – 2 torr

✍ Scribed by V. Daële; A. Ray; I. Vassalli; G. Poulet; G. Le Bras

Publisher
John Wiley and Sons
Year
1995
Tongue
English
Weight
791 KB
Volume
27
Category
Article
ISSN
0538-8066

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✦ Synopsis

The kinetics of CzH50 and CzH502 radicals with NO have been studied at 298 K using the discharge flow technique coupled to laser induced fluorescence (LIF) and mass spectrometry analysis. The temporal profiles of CzH5O were monitored by LIF. The rate constant for CzH5O + NO -Products (21, measured in the presence of helium, has been found to be pressure dependent: hz = (1.25 2 0.04) X

(1.66 2 0.06) x 10-11, (1.81 t 0.06) X 10-l' a t P (He) = 0.55, 1 and 2 torr, respectively (units are cm3 molecule-l s-I). The Lindemann-Hinshelwood analysis of these rate constant data and previous high pressure measurements indicates competition between association and disproportionation channels: CzH50 + NO + M -C2H50NO + M (2a), CzH50 + NO -CH3CHO + HNO (2b). The following calculated average values were obtained for the low and high pressure limits of kza and for k2b : kga = (2.6 ? 1.0) X cm6 molecule-' s-I, kra = (3.1 ? 0.8) X cm3 molecule-' s-' and kzb ca. 8 X lo-'' cm3 molecule-' s-l. The present value of hga, obtained with He as the third body, is significantly lower than the value (2.0 % 1.0) x 10-27 cm6 molecule-2 s-l recommended in air. The rate constant for the reaction CzH502 + NO + C2H50 + NO2 (3) has been measured at 1 torr of He from the simulation of experimental CzH5O profiles. The value obtained for h3 = (8.2 2 1.6) X cm3 molecule-' s-' is in good agreement with previous studies using complementary methods.

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