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Determination of the rate constant ratio for the reactions of the ethylperoxy radical with NO and NO2

โœ Scribed by G. Elfers; F. Zabel; K.H. Becker

Publisher
Elsevier Science
Year
1990
Tongue
English
Weight
464 KB
Volume
168
Category
Article
ISSN
0009-2614

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โœฆ Synopsis

The thermal decomposition of ethyl peroxynitrate was studied in a 420 !2 Dural glass reaction chamber in the presence of different initial [NO*]/ [NO] ratios. From an analysis of the data, the following rate constant ratios k2/kl for the reactions of C2H502 radicals with NO (k,) and NOI (kz) were derived at different temperatures and total pressures: 0.81 kO.09 (255.6 R, 994 mbar), 0.50+0.04 (253.8 K, 100 mbar), 0.21 kO.05 (253.9 K, 10.2 mbar), and 0.43kO.05 (264.7 K, 101 mbar). Using literature values for k,, we derived kz from these ratios as a function of pressure. With the kz values from this work and literature values for the thermal decomposition rate constant of CzH,0zN02, the following expression was obtained by a third law analysis for the temperature dependence of the e@Jibrium constant of the reactions C2HJ02+N02~C2H,02N02:

&=3.8x 10-z8

x exp( 107 10 K/T) cm3, Atmospheric implications of these results are discussed.

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