%0 Journal Article %1 Sharma:2010p3363 %A Sharma, A %A Pushpa, K. K %A Dhanya, S %A Naik, P. D %A Bajaj, P. N %D 2010 %J International Journal of Chemical Kinetics %K Air Alkenes, Atmospheric Atoms, Chemistry, Cl Constants, Kinetics, Oh Organic-Compounds, Predicting Radicals, Rate Room-Temperature, Series, %N 2 %P 98--105 %R 10.1002/kin.20467 %T Rate Coefficients and Products for Gas-Phase Reactions of Chlorine Atoms with Cyclic Unsaturated Hydrocarbons at 298 K %U http://www3.interscience.wiley.com/journal/123210296/abstract?CRETRY=1&SRETRY=0 %V 42 %X Rate coefficients for the reaction of Cl atoms with cycloalkenes have been determined using the relative rate method, at 298 K and atmospheric pressure of N-2. Reference molecule was n-hexane, and the concentrations of the organics were followed by gas chromatographic analysis, Cl atoms were prepared by photolysis of trichloroacetyl chloride at 254 nm. The relative rates of reactions of Cl atoms with cycloalkenes, with respect to n-hexane, are measured as 1.12 +/- 0.38, 1.31 +/- 0.14, and 1.69 +/- 0.18 for cyclopentene, cyclohexene, and cycloheptene, respectively. Considering the absolute value of the rate coefficient of the reaction of Cl atom with n-hexane as 3.03 +/- 0.06 x 10(-10) cm(3) molecule(-1) s(-1), the rate coefficient values for cyclopentene, cyclohexene, and cycloheptene are calculated to be (3.39 +/- 1.08) x 10(-10), (3.97 +/- 0.43) x 10(-10), and (5.12 +/- 0.55) x 10(-10) cm(3) molecule(-1) s(-1), respectively. The experiments for each molecule were repeated six to eight times, and the slopes and the rate coefficients given above are the average values of these measurements, and the quoted error includes 2 sigma as well as all other uncertainties in the measurement and calculations. The rate coefficient increases linearly with the n umber of carbon atoms, with an increment per additional CH2 group being (8.7 +/- 1.6) x 10(-12) cm(3) molecule(-1) s(-1). Chloroketones and chloroalcohols, along with unsaturated ketones and alcohols, were found to be the major products of Cl-atom-initiated oxidation of cycloalkenes in the presence of air. The atmospheric implications of these results are discussed, along with a comparison with the reported structure activity relationships. (C) 2009 Wiley Periodicals, Inc. Int I Chem Kinet 42: 98-105, 2010

@article{Sharma:2010p3363, abstract = {Rate coefficients for the reaction of Cl atoms with cycloalkenes have been determined using the relative rate method, at 298 K and atmospheric pressure of N-2. Reference molecule was n-hexane, and the concentrations of the organics were followed by gas chromatographic analysis, Cl atoms were prepared by photolysis of trichloroacetyl chloride at 254 nm. The relative rates of reactions of Cl atoms with cycloalkenes, with respect to n-hexane, are measured as 1.12 +/- 0.38, 1.31 +/- 0.14, and 1.69 +/- 0.18 for cyclopentene, cyclohexene, and cycloheptene, respectively. Considering the absolute value of the rate coefficient of the reaction of Cl atom with n-hexane as 3.03 +/- 0.06 x 10(-10) cm(3) molecule(-1) s(-1), the rate coefficient values for cyclopentene, cyclohexene, and cycloheptene are calculated to be (3.39 +/- 1.08) x 10(-10), (3.97 +/- 0.43) x 10(-10), and (5.12 +/- 0.55) x 10(-10) cm(3) molecule(-1) s(-1), respectively. The experiments for each molecule were repeated six to eight times, and the slopes and the rate coefficients given above are the average values of these measurements, and the quoted error includes 2 sigma as well as all other uncertainties in the measurement and calculations. The rate coefficient increases linearly with the n umber of carbon atoms, with an increment per additional CH2 group being (8.7 +/- 1.6) x 10(-12) cm(3) molecule(-1) s(-1). Chloroketones and chloroalcohols, along with unsaturated ketones and alcohols, were found to be the major products of Cl-atom-initiated oxidation of cycloalkenes in the presence of air. The atmospheric implications of these results are discussed, along with a comparison with the reported structure activity relationships. (C) 2009 Wiley Periodicals, Inc. Int I Chem Kinet 42: 98-105, 2010}, added-at = {2010-06-22T19:38:37.000+0200}, affiliation = {Bhabha Atom Res Ctr, Radiat {\&} Photochem Div, Bombay 400085, Maharashtra, India}, author = {Sharma, A and Pushpa, K. K and Dhanya, S and Naik, P. D and Bajaj, P. N}, biburl = {https://www.bibsonomy.org/bibtex/23a6c00d27654b57f603058860d4f5d2e/gsmith}, date-added = {2010-05-04 15:13:17 -0400}, date-modified = {2010-05-04 15:13:29 -0400}, doi = {10.1002/kin.20467}, interhash = {1dc7ec0a3e31383562854650e4e45799}, intrahash = {3a6c00d27654b57f603058860d4f5d2e}, journal = {International Journal of Chemical Kinetics}, keywords = {Air Alkenes, Atmospheric Atoms, Chemistry, Cl Constants, Kinetics, Oh Organic-Compounds, Predicting Radicals, Rate Room-Temperature, Series,}, language = {English}, local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/International%20Journal%20of%20Chemical%20Kinetics/2010/International%20Journal%20of%20Chemical%20Kinetics,%2042,%2098-105%202010.pdf}, month = Jan, number = 2, pages = {98--105}, pmid = {000273635500004}, rating = {0}, timestamp = {2010-06-22T19:38:51.000+0200}, title = {Rate Coefficients and Products for Gas-Phase Reactions of Chlorine Atoms with Cyclic Unsaturated Hydrocarbons at 298 K}, uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p3363}, url = {http://www3.interscience.wiley.com/journal/123210296/abstract?CRETRY=1&SRETRY=0}, volume = 42, year = 2010 }