Kinetics and mechanism of the gas phase reaction of chlorine atoms with i-propanol.
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 N(2) at 296 K. The reaction is observed to proceed with a rate constant of k(1) = (8.28 +/- 0.97) x 10(-11) cm(3) molecule(-1) s(-1) and gives CH(3)C(OH)CH(3) and CH(3)CH(OH)CH(2) 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 CH(3)CCl(OH)CH(3) complicates its direct detection, likely due to heterogeneous chemistry. IR spectra for the chlorides CH(3)CCl(OH)CH(3) and CH(3)CH(OH)CH(2)Cl were inferred experimentally and assignments confirmed via comparison with ab initio computed spectra.
Department of Molecular Engineering, Kyoto University, Kyoto 615-8510, Japan.
T
T
Yamanaka
M
M
Kawasaki
M D
MD
Hurley
T J
TJ
Wallington
W F
WF
Schneider
J
J
Bruce
D000433:1-Propanol / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods*; D002713:Chlorine / Q000737:chemistry*; D005740:Gases; D006859:Hydrogen / Q000737:chemistry; D017665:Hydroxyl Radical; D007700:Kinetics; D008956:Models, Chemical; D008962:Models, Theoretical; D008968:Molecular Conformation; D012984:Software; D013055:Spectrophotometry, Infrared; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013499:Surface Properties; D013696:Temperature
D005740:Gases; D017665:Hydroxyl Radical; D002713:Chlorine; D006859:Hydrogen; D000433:1-Propanol