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Molecular‐modulation spectrometry: CH 3 ONO photolysis and detection of nitroxyl
Author(s) -
McGraw G. E.,
Johnston H. S.
Publication year - 1969
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.550010109
Subject(s) - chemistry , reaction rate constant , photodissociation , nitroxyl , mass spectrometry , analytical chemistry (journal) , absorption (acoustics) , steady state (chemistry) , infrared , photochemistry , kinetics , chromatography , optics , physics , quantum mechanics
The method of molecular‐modulation spectrometry for studying photochemical reactions has been applied to methyl nitrite photolysis. The infrared absorption of the nitroxyl radical HNO has been observed in the gas phase at 3300 cm −1 . Under the present experimental conditions the steady‐state concentration of HNO under steady illumination was 1.1 × 10 12 particles/cc, and the observed modulation amplitude was 4.5 × 10 10 particles/cc. At 25°C and 1 atm of nitrogen, the cross section for infrared absorption by HNO at 3300 cm −1 is 1.7 × 10 −19 cm 2 . The rate constant ratio b/cwas found to be 8.0. From the literature value of the rate constant d, the observed rate constant for the reactionis e = (5 ± 1) × 10 −11 cc/particle sec.