%0 Journal Article %1 Gilles:2002p2253 %A Gilles, MK %A Burkholder, JB %A Gierczak, T %A Marshall, P %A Ravishankara, A. R %D 2002 %J Journal of Physical Chemistry A %K 1-Bromopropane, Abstraction, Alkanes, Atoms Br-2, Chlorine Constants, Gas-Phase Hydrogen-Atom Kinetics, Organic-Compounds, Radicals, Rate Reactions, %N 21 %P 5358--5366 %R 10.1021/jp014736+ %T Rate coefficient and product branching measurements for the reaction OH plus bromopropane from 230 to 360 K %U http://pubs.acs.org/doi/abs/10.1021/jp014736%252B %V 106 %X Rate coefficients over the range of 230-360 K were measured for the reaction of OH with the following bromopropane isotopomers: CH3CH2CH2Br (k(1)), CD3CH2CH2Br (k(2)), CD3CH2CD2Br (k(3)), CH3CD2CD2Br (k(4)), and CD3CD2CD2Br (k(5)). The hydroxyl radical was produced by pulsed laser photolysis and detected via laser induced fluorescence. Reaction I can occur by H atom abstraction from three different carbon sites: OH + CH3CH2CH2Br --> CH3CH2CHBr + H2O (1a: alpha): --> CH3CHCH2Br + H2O (1b; beta); or --> CH2CH2-CH2Br + H2O (1c; gamma). Branching ratios obtained from an analysis of the kinetic data at 298 K are k(1c)/k(1) = 0.12 +/- 0.08, k(1b)/k(1) = 0.56 +/- 0.04, and k(1a)/k(1) = 0.32 +/- 0.08; uncertainties given are 2 standard deviations and do not include systematic uncertainties. Stable products formed following reaction 1 in a NOx/O-2 environment were measured using long path infrared absorption. Bromoacetone and propanal were observed in the ratio (CH3C(O)CH2Br)/(CH3CH2CHO) of 1.65 +/- 0.50 with an absolute bromoacetone yield of 0.5 +/- 0.2 at room temperature. The product yields are consistent with the rate coefficient data, Ab initio calculations show that C-H bond energies at both the alpha and beta sites decrease (relative to propane) by the addition of Br at the alpha site. The calculated transition state energies decrease in the order gamma > alpha > beta, in qualitative agreement with the experimental observations.

@article{Gilles:2002p2253, abstract = {Rate coefficients over the range of 230-360 K were measured for the reaction of OH with the following bromopropane isotopomers: CH3CH2CH2Br (k(1)), CD3CH2CH2Br (k(2)), CD3CH2CD2Br (k(3)), CH3CD2CD2Br (k(4)), and CD3CD2CD2Br (k(5)). The hydroxyl radical was produced by pulsed laser photolysis and detected via laser induced fluorescence. Reaction I can occur by H atom abstraction from three different carbon sites: OH + CH3CH2CH2Br --> CH3CH2CHBr + H2O (1a: alpha): --> CH3CHCH2Br + H2O (1b; beta); or --> CH2CH2-CH2Br + H2O (1c; gamma). Branching ratios obtained from an analysis of the kinetic data at 298 K are k(1c)/k(1) = 0.12 +/- 0.08, k(1b)/k(1) = 0.56 +/- 0.04, and k(1a)/k(1) = 0.32 +/- 0.08; uncertainties given are 2 standard deviations and do not include systematic uncertainties. Stable products formed following reaction 1 in a NOx/O-2 environment were measured using long path infrared absorption. Bromoacetone and propanal were observed in the ratio [(CH3C(O)CH2Br)/(CH3CH2CHO)] of 1.65 +/- 0.50 with an absolute bromoacetone yield of 0.5 +/- 0.2 at room temperature. The product yields are consistent with the rate coefficient data, Ab initio calculations show that C-H bond energies at both the alpha and beta sites decrease (relative to propane) by the addition of Br at the alpha site. The calculated transition state energies decrease in the order gamma > alpha > beta, in qualitative agreement with the experimental observations.}, added-at = {2010-06-22T19:38:37.000+0200}, affiliation = {NOAA, Aeron Lab, Boulder, CO 80305 USA}, author = {Gilles, MK and Burkholder, JB and Gierczak, T and Marshall, P and Ravishankara, A. R}, biburl = {https://www.bibsonomy.org/bibtex/29caa5ff3a27278bc1b5f2ff35632f154/gsmith}, date-added = {2010-03-23 14:40:45 -0400}, date-modified = {2010-04-29 13:23:09 -0400}, doi = {10.1021/jp014736+}, interhash = {644372db493fe08ecf6572b12d0fd7ff}, intrahash = {9caa5ff3a27278bc1b5f2ff35632f154}, journal = {Journal of Physical Chemistry A}, keywords = {1-Bromopropane, Abstraction, Alkanes, Atoms Br-2, Chlorine Constants, Gas-Phase Hydrogen-Atom Kinetics, Organic-Compounds, Radicals, Rate Reactions,}, language = {English}, local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Journal%20of%20Physical%20Chemistry%20A/2002/Journal%20of%20Physical%20Chemistry%20A,%20106,%205358-5366%202002.pdf}, month = Jan, number = 21, pages = {5358--5366}, pmid = {000175831400018}, rating = {0}, timestamp = {2010-06-22T19:39:33.000+0200}, title = {Rate coefficient and product branching measurements for the reaction OH plus bromopropane from 230 to 360 K}, uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p2253}, url = {http://pubs.acs.org/doi/abs/10.1021/jp014736%252B}, volume = 106, year = 2002 }