Atmospheric chemistry of n‐CH3(CH2)xCN (x = 0–3): Kinetics and mechanisms. Issue 11 (1st September 2018)

• Record Type: Journal Article
• Authors: Andersen, Simone Thirstrup; Kyte, Mildrid; Andersen, Lene Løffler; Nielsen, Ole John; Sulbaek Andersen, Mads P.
• Is Part Of: International journal of chemical kinetics. Volume 50:Issue 11(2018)
• Page Start: 813
• Page End: 826
• Publication Date: 2018-09-01
• Subjects: atmospheric chemistry -- kinetics -- nitriles; Chemical kinetics -- Periodicals; 541.394
• DOI: 10.1002/kin.21215
• Languages: English
• ISSNs: 0538-8066

Abstract

Abstract: Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure the kinetics of the reaction of n‐ CH3 (CH2 ) x CN ( x = 0–3) with Cl atoms and OH radicals: k (CH3 CN + Cl) = (1.04 ± 0.25) × 10 −14, k (CH3 CH2 CN + Cl) = (9.20 ± 3.95) × 10 −13, k (CH3 (CH2 )2 CN + Cl) = (2.03 ± 0.23) × 10 −11, k (CH3 (CH2 )3 CN + Cl) = (6.70 ± 0.67) × 10 −11, k (CH3 CN + OH) = (4.07 ± 1.21) × 10 −14, k (CH3 CH2 CN + OH) = (1.24 ± 0.27) × 10 −13, k (CH3 (CH2 )2 CN + OH) = (4.63 ± 0.99) × 10 −13, and k (CH3 (CH2 )3 CN + OH) = (1.58 ± 0.38) × 10 −12 cm 3 molecule −1 s −1 at a total pressure of 700 Torr of air or N2 diluents at 296 ± 2 K. The atmospheric oxidation of alkyl nitriles proceeds through hydrogen abstraction leading to several carbonyl containing primary oxidation products. HC(O)CN, NCC(O)OONO2, ClC(O)OONO2, and HCN were identified as the main oxidation products from CH3 CN, whereas CH3 CH2 CN gives the products HC(O)CN, CH3 C(O)CN, NCC(O)OONO2, and HCN. The oxidation of n‐ CH3 (CH2 ) x CN ( x = 2–3) leads to a range of oxygenated primary products. Based on the measured OH radical rate constants, the atmospheric lifetimes of n‐ CH3 (CH2 ) x CN ( x = 0–3) were estimated to be 284, 93, 25, and 7 days for x = 0, 1, 2, and 3, respectively.