%0 Journal Article %1 Orlando:2003p3006 %A Orlando, JJ %A Tyndall, GS %A Apel, EC %A Riemer, DD %A Paulson, SE %D 2003 %J International Journal of Chemical Kinetics %K 298 Atoms, Chlorine Constants, Decomposition, Gas-Phase Halocarbon Initiated K Ketone, Measurements, Methyl Oxidation, Pressure-Dependence, Rate Reactions, Room-Temperature, Unimolecular Vinyl %N 8 %P 334--353 %R 10.1002/kin.10135 %T Rate coefficients and mechanisms of the reaction of Cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions %U http://www3.interscience.wiley.com/journal/104535354/abstract %V 35 %X Rate coefficients and/or mechanistic information are provided for the reaction of Cl-atoms with a number of unsaturated species, including isoprene, methacrolein (MAC R), m ethyl vinyl ketone (MVK), 1,3-butadiene, trans-2-butene, and 1-butene. The following Cl-atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 +/- 0.6) x 10(-10) cm(3) molecule(-1) s(-1) (independent of pressure from 6.2 to 760 Torr); k(MVK) (2.2 +/- 0.3) x 10(-10) cm(3) molecule(-1) s(-1), k(MACR) = (2.4 +/- 0.3) x 10(-10) cm(3) molecule(-1) k(trans-2-butene) = (4.0 +/- 0.5) x 10(-10) cm(3) molecule(-1) s(-1), k(1-butene) = (3.0 +/- 0.4) x 10(-10) cm(3) molecule(-1) s(-1). Products observed in the Cl-atom-initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH2O (9.5 +/- 1.0%), HCOCl (5.1 +/- 0.7%), and 1-chloro-3-methyl-3-buten-2-one (CMBO, not quantihed) from isoprene; chloroacetalclehyde (75 +/- 8%), CO2 (58 +/- 5%), CH2O (47 +/- 7%), CH3OH (8%), HCOCl (7 +/- 1%), and peracetic acid (6%) from MVK; CO (52 +/- 4%), chloroacetone (42 +/- 5%), CO2 (23 +/- 2%), CH2O (18 +/- 2%), and HCOCl (5%) from MACR; CH2O (7 +/- 1%), HCOCl (3%), acrotein (53%), and 4-chlorocrotonaldehyde (CCA, not quantihed) from 1,3-butadiene; CH3CHO (22 +/- 3%), CO2 (13 +/- 2%), 3-chloro-2-butanone (13 +/- 4%), CH2O (7.6 1. 1%), and CH3OH (1.8 +/- 0.6%) from trans-2-butene, and chloroacetaldehyde (20 3%), CH2O (7 +/- 1%), CO2 (4 +/- 1%), and HCOCl (4 +/- 1%) from 1-butene. Product yields from both trans-2-butene and 1-butene were found to be O-2-dependent, in the case of trans-2-butene, the observed O-2-dependence is the result of a competition between unimolecular decomposition of the CH3CH(Cl)-CH(O-)-CH3 radical and its reaction with O-2, with k(decomp)/kO(2) = (1.6 +/- 0.4) x 10(19) molecule cm(-3). The activation energy for decomposition is estimated at 11.5 +/- 1.5 kcal mol(-1). The variation of the product yields with 02 in the case of I-butene results from similar competitive reaction pathways for the two beta-chlorobutoxy radicals involved in the oxidation, ClCH2CH(O-)CH2CH3 and -OCH2CHClCH2CH3. (C) 2003 Wiley Periodicals, Inc.

@article{Orlando:2003p3006, abstract = {Rate coefficients and/or mechanistic information are provided for the reaction of Cl-atoms with a number of unsaturated species, including isoprene, methacrolein (MAC R), m ethyl vinyl ketone (MVK), 1,3-butadiene, trans-2-butene, and 1-butene. The following Cl-atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 +/- 0.6) x 10(-10) cm(3) molecule(-1) s(-1) (independent of pressure from 6.2 to 760 Torr); k(MVK) (2.2 +/- 0.3) x 10(-10) cm(3) molecule(-1) s(-1), k(MACR) = (2.4 +/- 0.3) x 10(-10) cm(3) molecule(-1) k(trans-2-butene) = (4.0 +/- 0.5) x 10(-10) cm(3) molecule(-1) s(-1), k(1-butene) = (3.0 +/- 0.4) x 10(-10) cm(3) molecule(-1) s(-1). Products observed in the Cl-atom-initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH2O (9.5 +/- 1.0%), HCOCl (5.1 +/- 0.7%), and 1-chloro-3-methyl-3-buten-2-one (CMBO, not quantihed) from isoprene; chloroacetalclehyde (75 +/- 8%), CO2 (58 +/- 5%), CH2O (47 +/- 7%), CH3OH (8%), HCOCl (7 +/- 1%), and peracetic acid (6%) from MVK; CO (52 +/- 4%), chloroacetone (42 +/- 5%), CO2 (23 +/- 2%), CH2O (18 +/- 2%), and HCOCl (5%) from MACR; CH2O (7 +/- 1%), HCOCl (3%), acrotein (53%), and 4-chlorocrotonaldehyde (CCA, not quantihed) from 1,3-butadiene; CH3CHO (22 +/- 3%), CO2 (13 +/- 2%), 3-chloro-2-butanone (13 +/- 4%), CH2O (7.6 1. 1%), and CH3OH (1.8 +/- 0.6%) from trans-2-butene, and chloroacetaldehyde (20 3%), CH2O (7 +/- 1%), CO2 (4 +/- 1%), and HCOCl (4 +/- 1%) from 1-butene. Product yields from both trans-2-butene and 1-butene were found to be O-2-dependent, in the case of trans-2-butene, the observed O-2-dependence is the result of a competition between unimolecular decomposition of the CH3CH(Cl)-CH(O-)-CH3 radical and its reaction with O-2, with k(decomp)/kO(2) = (1.6 +/- 0.4) x 10(19) molecule cm(-3). The activation energy for decomposition is estimated at 11.5 +/- 1.5 kcal mol(-1). The variation of the product yields with 02 in the case of I-butene results from similar competitive reaction pathways for the two beta-chlorobutoxy radicals involved in the oxidation, ClCH2CH(O-)CH2CH3 and -OCH2CHClCH2CH3. (C) 2003 Wiley Periodicals, Inc.}, added-at = {2010-06-22T19:38:37.000+0200}, affiliation = {Natl Ctr Atmospher Res, Div Atmospher Chem, Boulder, CO 80307 USA}, author = {Orlando, JJ and Tyndall, GS and Apel, EC and Riemer, DD and Paulson, SE}, biburl = {https://www.bibsonomy.org/bibtex/2ac3fd2c81b26f63b6740bc87378df0d3/gsmith}, date-added = {2010-04-28 10:15:11 -0400}, date-modified = {2010-04-28 10:15:21 -0400}, doi = {10.1002/kin.10135}, interhash = {e67627843439ec79961f64023f97d7b0}, intrahash = {ac3fd2c81b26f63b6740bc87378df0d3}, journal = {International Journal of Chemical Kinetics}, keywords = {298 Atoms, Chlorine Constants, Decomposition, Gas-Phase Halocarbon Initiated K Ketone, Measurements, Methyl Oxidation, Pressure-Dependence, Rate Reactions, Room-Temperature, Unimolecular Vinyl}, language = {English}, local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/International%20Journal%20of%20Chemical%20Kinetics/2003/International%20Journal%20of%20Chemical%20Kinetics,%2035,%20334-353%202003.pdf}, month = Jan, number = 8, pages = {334--353}, pmid = {000184090600002}, rating = {0}, timestamp = {2010-06-22T19:38:58.000+0200}, title = {Rate coefficients and mechanisms of the reaction of Cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions}, uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p3006}, url = {http://www3.interscience.wiley.com/journal/104535354/abstract}, volume = 35, year = 2003 }