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Primary photochemical processes in the photolysis of alkyl nitrites at 366 NM and 23°c in the presence of 15 NO
Author(s) -
Morabito Paul,
Heicklen Julian
Publication year - 1985
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.550170506
Subject(s) - chemistry , photodissociation , alkyl , excited state , mass spectrometry , photochemistry , torr , irradiation , medicinal chemistry , analytical chemistry (journal) , organic chemistry , chromatography , atomic physics , nuclear physics , physics , thermodynamics
The alkyl nitrites, C 2 H 5 ONO, n ‐C 3 H 7 ONO, n ‐C 4 H 9 ONO, and i ‐C 4 H 9 ONO were photolyzed at 23°C in the presence of 15 NO at 366‐nm incident radiation. The quantum yields of the corresponding isotopically‐enriched alkyl nitrites were measured by mass spectrometry. The results indicated that only part of the absorption leads to photodecomposition. The remainder forms an electronically excited state which isotopically exchanges with 15 NO. The indicated reactions of the electronically excited state RONO*, arewhere k 3 / k 2 = 0.50 ± 0.10, 0.62 ± 0.20, 0.42 ± 0.06, and 0.24 ± 0.03 torr, and that k 2a / k 2 = 1.0, 1.0, 0.64 ± 0.04, and 0.56 ± 0.03, respectively, for C 2 H 5 ONO, n ‐C 3 H 7 ONO, n ‐C 4 H 9 ONO, and i ‐C 4 H 9 ONO.