The reactions of alkoxy radicals with O2. II. n-C3H7O radicals

✍ Scribed by Steven Zabarnick; Julian Heicklen

• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 910 KB
• Volume: 17
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550170503

✦ Synopsis

n-C3H70N0 was photolyzed with 366 nm radiation at -26, -3,23,55, 88, and 120°C in a static system in the presence of NO, Oz, and N 2 . The quantum yields of C2H5CH0, C z H 5 0 N 0 , and CH3CH0 were measured as a function of reaction conditions. The primary photochemical act is

and it proceeds with a quantum yield The n-C3H70 radicals can react with NO by two routes

Values of k 4 / k 2 = k4b/k2 were determined to be (2.0 t 0.2) x loL4, (3.1 ! I 0.6) x and (1.4 2 0.1) x 1015 molec/cm3 at 55, 88, and 120"C, respectively, a t 150-torr total pressure of N z . Values of k , / k 2 were determined from -26 to 88°C. They fit the Arrhenius expression: log(k,/k,) = -2.17 f 0.20 -(879 f 117)/2.303 T .

For Itz = 4.4 x lo-" cm3/s, It, becomes (2.9 k 1.7) x exp{-(879 5 117)/T} cm3/s. The reaction scheme also provides k 4 b / k 6 = 1.58 X 10" molec/cm3 a t 120°C and k,,/k, = 0.56 ? 0.24 independent of temperature, where (8a) (8b)

-HONO + n-C3H70 HO + n-C3H70N0 -H 2 0 + CzH5CH0 + NO