Atmospheric chemistry of i-butanol.
Smog chamber/FTIR techniques were used to determine rate constants of k(Cl + i-butanol) = (2.06 ± 0.40) × 10(-10), k(Cl + i-butyraldehyde) = (1.37 ± 0.08) × 10(-10), and k(OH + i-butanol) = (1.14 ± 0.17) × 10(-11) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 ± 2K. The UV irradiation of i-butanol/Cl(2)/N(2) mixtures gave i-butyraldehyde in a molar yield of 53 ± 3%. The chlorine atom initiated oxidation of i-butanol in the absence of NO gave i-butyraldehyde in a molar yield of 48 ± 3%. The chlorine atom initiated oxidation of i-butanol in the presence of NO gave (molar yields): i-butyraldehyde (46 ± 3%), acetone (35 ± 3%), and formaldehyde (49 ± 3%). The OH radical initiated oxidation of i-butanol in the presence of NO gave acetone in a yield of 61 ± 4%. The reaction of chlorine atoms with i-butanol proceeds 51 ± 5% via attack on the α-position to give an α-hydroxy alkyl radical that reacts with O(2) to give i-butyraldehyde. The atmospheric fate of (CH(3))(2)C(O)CH(2)OH alkoxy radicals is decomposition to acetone and CH(2)OH radicals. The atmospheric fate of OCH(2)(CH(3))CHCH(2)OH alkoxy radicals is decomposition to formaldehyde and CH(3)CHCH(2)OH radicals. The results are consistent with, and serve to validate, the mechanism that has been assumed in the estimation of the photochemical ozone creation potential of i-butanol.
Copenhagen Center for Atmospheric Research, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark.
V F
VF
Andersen
T J
TJ
Wallington
O J
OJ
Nielsen
D000096:Acetone / Q000737:chemistry; D001272:Atmosphere; D000440:Butanols / Q000737:chemistry*; D002621:Chemistry / Q000379:methods; D002713:Chlorine / Q000737:chemistry; D005557:Formaldehyde / Q000737:chemistry; D005609:Free Radicals; D007700:Kinetics; D008956:Models, Chemical; D010100:Oxygen / Q000737:chemistry; D010777:Photochemistry / Q000379:methods; D017550:Spectroscopy, Fourier Transform Infrared; D013696:Temperature; D014466:Ultraviolet Rays
D000440:Butanols; D005609:Free Radicals; D000096:Acetone; D005557:Formaldehyde; D002713:Chlorine; D010100:Oxygen