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Laser magnetic resonance spectroscopy of ClO and kinetic studies of the reactions of ClO with NO and NO 2
Author(s) -
Lee YuanPern,
Stimpfle Richard M.,
Perry Robert A.,
Mucha John A.,
Evenson Kenneth M.,
Jennings Donald A.,
Howard Carleton J.
Publication year - 1982
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/kin.550140612
Subject(s) - chemistry , analytical chemistry (journal) , spectroscopy , kinetic energy , reaction rate constant , resonance (particle physics) , atmospheric temperature range , laser , infrared , nuclear magnetic resonance , kinetics , atomic physics , optics , thermodynamics , physics , chromatography , quantum mechanics
Far‐infrared rotational transitions in ClO(X 2 ∏ 3/2 , υ = 0) have been observed using laser magnetic resonance (LMR) with an optically pumped spectrometer. Five observed transitions at wavelengths between 444 and 713 µm have been compared with values predicted with spectroscopic constants from the literature. LMR detection of ClO has been used to study its reactions with NO and NO 2 in a discharge flow system under pseudo‐first‐order conditions for ClO. The measured rate constants are k (ClO + NO) = (7.1 ± 1.4) × 10 −12 exp[(270 ± 50)/ T ] cm 3 /molec·s for the temperature range of 202 < T < 393 K; k (ClO + NO 2 + M) = (2.8 ± 0.6) × 10 −33 exp[(1090 ± 80)/ T ] cm 6 /molec 2 ·s (M = He, 250 < T < 387 K), (3.5 ± 0.6) × 10 −33 exp[(1180 ± 80)/ T ] (M = O 2 , 250 < T < 416 K), and (2.09 ± 0.3) × 10 −31 (M = N 2 , T = 297 K). All measurements were made at low pressures, between 0.6 and 6.6 torr. These results are compared with those from other studies.