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Temperature‐dependent kinetics studies of the reactions of C 2 H 5 O 2 and n ‐C 3 H 7 O 2 radicals with NO
Author(s) -
Eberhard Jürg,
Howard Carleton J.
Publication year - 1996
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1996)28:10<731::aid-kin3>3.0.co;2-o
Subject(s) - chemistry , radical , kinetics , photochemistry , organic chemistry , quantum mechanics , physics
The rate coefficients for the gas‐phase reactions of C 2 H 5 O 2 and n ‐C 3 H 7 O 2 radicals with NO have been measured over the temperature range of (201–403) K using chemical ionization mass spectrometric detection of the peroxy radical. The alkyl peroxy radicals were generated by reacting alkyl radicals with O 2 , where the alkyl radicals were produced through the pyrolysis of a larger alkyl nitrite. In some cases C 2 H 5 radicals were generated through the dissociation of iodoethane in a low‐power radio frequency discharge. The discharge source was also tested for the i ‐C 3 H 7 O 2 + NO reaction, yielding k 298 K = (9.1 ± 1.5) × 10 −12 cm 3 molecule −1 s −1 , in excellent agreement with our previous determination. The temperature dependent rate coefficients were found to be k (T) = (2.6 ± 0.4) × 10 −12 exp{(380 ± 70)/T} cm 3 molecule −1 s −1 and k (T) = (2.9 ± 0.5) × 10 −12 exp{(350 ± 60)/T} cm 3 molecule −1 s −1 for the reactions of C 2 H 5 O 2 and n ‐C 3 H 7 O 2 radicals with NO, respectively. The rate coefficients at 298 K derived from these Arrhenius expressions are k = (9.3 ± 1.6) × 10 −12 cm 3 molecule −1 s −1 for C 2 H 5 O 2 radicals and k = (9.4 ± 1.6) × 10 −12 cm 3 molecule −1 s −1 for n ‐C 3 H 7 O 2 radicals. © 1996 John Wiley & Sons, Inc.