Reactions of alkoxy radicals with O2. III. i-C4H9O radicals

✍ Scribed by Steven Zabarnick; Julian Heicklen

• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 826 KB
• Volume: 17
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550170504

✦ Synopsis

i-C4HgON0 was photolyzed with 366-nm radiation at -8, 23, 55, 88, and 120°C in a static system in the presence of NO, O,, and N2. The quantum yield of i-C,H7CH0, @{i-C3H7CHO}, was measured as a function of reaction conditions. The primary photochemical act is

and it proceeds with a quantum yield & = 0.24 2 0.02 independent of temperature.

The i-C4Hg0 radicals can react with NO by two routes

O or react with O2 via (6) i-C4Hg0 + O2i-C,H,CHO + H o p Values of k4/kz = k4,,/k, were determined to be (2.8 r?I 0.6) x and (3.5 2 1.3) x l O I 5 molec/cm3 a t 23, 55, and 88"C, respectively, a t 150-torr total pressure of NO. Values of k,/k, were determined from -8 to 120°C. They fit the Arrhenius expression: (1.7 It 0.2) x log(k,/k,) = -2.15 2 0.22 -(836 2 159)/2.303 T For k2 = 4.4 x 10" cm3/s, K, becomes (3.2 r?I 2.0) x Wi3 exp{-(836 t 159)/T} cm3/s.

The reaction scheme also provides klb/k6 = 3.59 x 10" and 5.17 x 10" molec/cm3 at 55 and 88"C, respectively, and kEb/kE = 0.66 2 0.12 independent of temperature, where

HO + i-C4H90N0 -HzO + C(CH3),CH20* + NO (8b)

-HONO + i-C4H90