Bulletin of the Chemical Society of Japan p. 2641 - 2650 (1987)
Update date:2022-08-17
Topics:
Morabito, Paul
Heicklen, Julian
n-C4H9ONO was phtolyzed with 366 nm radiation at -8, 23, 55, 88, and 120 deg C in the presence of NO, O2 and N2.The quantum yields of n-C3H7CHO, C2H5CHO, and CH3CHO were measured as a function of reaction conditions.The primary photolytic act produces n-C4H9O. radicals which can react with NO by two routes: n-C4H9O. + NO --> n-C4H9ONO (2a) --> n-C3H7CHO + HNO (2b) or isomerize via an internal H-atom abstraction n-C4H9O. --> I.. (4) where I. is the HOCH2CH2CH2CH2. radical, and ln(k4/K2 mol dm-3) = 1.93+/-1.60-(4014+/-509)/T.If k2 is taken as 2.6*1010 dm3 mol-1 s-1, then log (k4, s-1) = 11.25+/-0.69(4014+/-509)/2.303T.In the presence of O2 n-C4H9O. radicals can also react wit O2: n-C4H9O. + O2 --> n-C3H7CHO + HO2 (6) with ln(k6/K2) = (-4.09+/-0.54)-(1178+/-176)/T.If k2 = 2.6* 10-10 dm3 mol-1 s-1, then k6 = 4.5*108 exp <(-1178+/-176)/T> dm3 mol-1 s-1.The radical I. is removed via I. --> CH3CHO + 2CH2O + HO (12a) --> Undetected aldehydes + HO (12b) I. + O2 --> n-C3H7CHO + HO (13a) --> C2H5CHO + HO (13b) where these reactions are composites of a series of steps.The ratio k13a/k13b ca. 1.3+/-0.2 nearly independent of temperature.The ratio k12/k13 was not found very accurately, but it is ca. 3*10-3 mol dm-3.There was no evidence for the oxidation of I. leading to dioxygenated products.
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