Atmospheric Chemistry of n-CH═CH(CH) CN ( x = 0-4): Kinetics and Mechanisms.

Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure the kinetics of the reaction of n-CH═CH(CH) CN ( x = 0-4) with Cl atoms, OH radicals, and O: k(CH═CHCN + Cl) = (1.03 ± 0.13) × 10, k(CH═CHCHCN + Cl) = (2.02 ± 0.35) × 10, k(CH═CH(CH)CN + Cl) = (2.75 ± 0.45) × 10, k(CH═CHCN + OH) = (4.21 ± 0.95) × 10, k(CH═CHCHCN + OH) = (1.55 ± 0.34) × 10, k(CH═CH(CH)CN + OH) = (2.98 ± 0.64) × 10, k(CH═CH(CH)CN + OH) = (3.34 ± 0.64) × 10, k(CH═CH(CH)CN + OH) = (3.61 ± 0.85) × 10, k(CH═CHCN + O) = (2.55 ± 0.28) × 10, k(CH═CHCHCN + O) = (1.17 ± 0.24) × 10, k(CH═CH(CH)CN + O) = (3.35 ± 0.69) × 10, k(CH═CH(CH)CN + O) = (4.07 ± 0.82) × 10, and k(CH═CH(CH)CN + O) = (7.13 ± 1.49) × 10 cm molecule s at a total pressure of 700 Torr of air or N diluents at 296 ± 2 K. CHClC(O)CN, HC(O)CN, HC(O)Cl, HCN, NCC(O)OONO, and ClC(O)OONO were identified as products from the Cl initiated oxidation of CH═CHCN. The product spectra were compared to experimental and theoretically calculated IR spectra. No products could be determined from the oxidation of n-CH═CH(CH) CN ( x = 1-4). With the determined OH rate constants, the atmospheric lifetimes for n-CH═CH(CH) CN ( x = 0-4) were estimated to be 66, 18, 9.3, 8.3, and 7.7 h, respectively. It was found that these unsaturated nitriles have no significant atmospheric environmental impact.