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Paper
Phys. Chem. Chem. Phys., 2007, 9, 4211 - 4217, DOI: 10.1039/b702933k
Kinetics and mechanism of the gas phase reaction of chlorine atoms with i-propanol
T. Yamanaka, M. Kawasaki, M. D. Hurley, T. J. Wallington, W. F. Schneider and J. Bruce
FTIR smog chamber techniques and ab initio calculations have been used to investigate the kinetics and mechanism of the reaction of Cl atoms with i-propanol in 700 Torr of N2 at 296 K. The reaction is observed to proceed with a rate constant of k1 = (8.28 ± 0.97) × 10–11 cm3 molecule–1 s–1 and gives CH3C(OH)CH3 and CH3CH(OH)CH2 radicals in yields of 85 ± 7 and 15 ± 7%, respectively. Calculations indicate that abstraction of the secondary H can proceed through a lower energy pathway than the primary. Rapid decomposition of the chlorination product CH3CCl(OH)CH3 complicates its direct detection, likely due to heterogeneous chemistry. IR spectra for the chlorides CH3CCl(OH)CH3 and CH3CH(OH)CH2Cl were inferred experimentally and assignments confirmed via comparison with ab initio computed spectra.
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