The reactions of atomic chlorine with acrolein, methacrolein and methyl vinyl ketone

Canosa‐Mas, Carlos E.; Cotter, E. S. N.; Duffy, Justin M.; Thompson, Katherine C.; Wayne, Richard P.

doi:10.1039/b101434j

Cited by 35 publications

(49 citation statements)

References 20 publications

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“…The CO observed by Fantechi et al [29], but not seen in our work, may result from oxidation of the primary CH 2 O product. Canosa-Mas et al [40] report the observation of chloroacetaldehyde and CH 2 O (in agreement with our work, though no yield data were given), and CO (yield ≈0.05). They also conclude that external addition of Cl to the MVK double bond leads to Fig.…”

Section: Mvksupporting

confidence: 95%

“…The only previous studies of the Cl-initiated oxidation of MVK were brief investigations by Fantechi et al [29] and Canosa-Mas et al [40]. Products identified in [29] were chloroacetaldehyde, HCOCl, methylglyoxal, CH 2 O, HCl, CO, and CO 2 ; no yields are reported.…”

Section: Mvkmentioning

confidence: 94%

“…No evidence of any variation in the ratio k 1 /k 2 with either total pressure or diluent gas identity was noted; the nonweighted mean of all data gives k 1 /k 2 = 2.99 ± 0. 27 [30], and All data were obtained at 296 K. [40], made at a total pressure of 1.6 Torr, indicates a pressure dependence to the rate coefficient.…”

Section: Methodsmentioning

confidence: 99%

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Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

Orlando

Tyndall

Apel

et al. 2003

Int J of Chemical Kinetics

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Rate coefficients and/or mechanistic information are provided for the reaction of Clatoms with a number of unsaturated species, including isoprene, methacrolein (MACR), methyl 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) × 10 −10 cm 3 molecule −1 s −1 (independent of pressure from 6.2 to 760 Torr); k(MVK) = (2.2 ± 0.3) × 10 −10 cm 3 molecule −1 s −1 ; k(MACR) = (2.4 ± 0.3) × 10 −10 cm 3 molecule −1 s −1 ; k(trans-2-butene) = (4.0 ± 0.5) × 10 −10 cm 3 molecule −1 s −1 ; k(1-butene) = (3.0 ± 0.4) × 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): CH 2 O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1-chloro-3-methyl-3-buten-2-one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO 2 (58 ± 5%), CH 2 O (47 ± 7%), CH 3 OH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK; CO (52 ± 4%), chloroacetone (42 ± 5%), CO 2 (23 ± 2%), CH 2 O (18 ± 2%), and HCOCl (5%) from MACR; CH 2 O (7 ± 1%), HCOCl (3%), acrolein (≈3%), and 4-chlorocrotonaldehyde (CCA, not quantified) from 1,3-butadiene; CH 3 CHO (22 ± 3%), CO 2 (13 ± 2%), 3-chloro-2-butanone (13 ± 4%), CH 2 O (7.6 ± 1.1%), and CH 3 OH (1.8 ± 0.6%) from trans-2-butene; and chloroacetaldehyde (20 ± 3%), CH 2 O (7 ± 1%), CO 2 (4 ± 1%), RATE COEFFICIENTS AND MECHANISMS OF THE REACTION OF Cl-ATOMS 335and 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 CH 3 CH(Cl) CH(O • ) CH 3 radical and its reaction with O 2 , with k decomp /k O2 = (1.6 ± 0.4) × 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 O 2 in the case of 1-butene results from similar competitive reaction pathways for the two β-chlorobutoxy radicals involved in the oxidation, ClCH 2 CH(O • )CH

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Section: Mvksupporting

confidence: 95%

Section: Mvkmentioning

confidence: 94%

See 1 more Smart Citation

Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

Orlando

Tyndall

Apel

et al. 2003

Int J of Chemical Kinetics

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“…If the reaction occurs only through addition to the vinyl group, substitution of a hydrogen atom by chlorine on the terminal methyl group does not alter the rate constant, consistent with our observation and that of Canosa-Mas et al 34 that abstraction represents less than 3% of the overall reaction.…”

Section: Impact Of Chlorine Substitution On Rate Constantsupporting

confidence: 81%

“…Kinetics studies of the reactions of chlorine atoms with ACR, MACR, CA and MVK have been reported recently, [32][33][34][35] but there are no reports of the rate constants for the CCA or CMVK reactions. Our combined data set permits probing structure-reactivity relationships for this series of unsaturated aldehydes and ketones.…”

Section: à3mentioning

confidence: 99%

Rate constants for the reactions of chlorine atoms with a series of unsaturated aldehydes and ketones at 298 K: structure and reactivity

Wang

Ezell

et al. 2002

Phys. Chem. Chem. Phys.

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Falloff curves for the unimolecular decomposition of two acyl radicals: RCO (+M) → R + CO (+M) by pulsed laser photolysis coupled to time‐resolved infrared diode laser absorption

Dusanter

Elmaimouni

Fittschen

et al. 2005

Int J of Chemical Kinetics

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The rate constants k d for the unimolecular decomposition of two acyl (RĊO) radicals: 2,2-dimethylpropionyl (CH 3 ) 3 CĊO and 2-methylpropionyl (CH 3 ) 2 CHĊO (pivaloyl and isobutyryl, respectively in what follows) have been directly measured via the time-resolved kinetics of CO formation as a function of pressure and temperature. The acyl radicals are generated by H-atom abstraction of the aldehydic hydrogen from the corresponding substituted propanals using pulsed laser photolysis of aldehyde/Cl 2 /N 2 mixtures. The buildup of CO concentration is monitored by time-resolved infrared absorption at ∼ =2177 cm −1 . The extent of the chain reactions triggered by the reactions of Cl 2 with alkyl and acyl radicals (thus generating further Cl atoms after the initial laser pulse) has been limited by adding variable known concentrations of O 2 , a radical scavenger which is sequestering all radicals to form less reactive RO 2 radicals. Besides k d , we have also determined for the first time the rate constants of the reactions of the two acyl radicals with O 2 ; since the latter do not exhibit any clear trend with either temperature or pressure, we thus adopt the average of all experimental values: i.e. for pivaloyl : k O 2 = (3.5 ± 1.0) × 10 −12 cm 3 molecule −1 s −1 , and for isobutyryl : k O 2 = (3.2 ± 1.0) × 10 −12 cm 3 molecule −1 s −1 . Our values of k d , which are in the falloff range, are compared to those obtained from theoretical calculations using the Troe formalism [5]. For pivaloyl at 298 K, we obtain the following limiting rate constants : k 0 = 2.1 × 10 −13 cm 3 molecule −1 s −1 , k ∞ = 4.3 × 10 5 s −1 , F C = 0.515, which are at variance with the theoretical predictions of Tomas et al. (Phys Chem Chem Phys 2000, 2, 1165-1174

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The reactions of atomic chlorine with acrolein, methacrolein and methyl vinyl ketone

Cited by 35 publications

References 20 publications

Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

Rate constants for the reactions of chlorine atoms with a series of unsaturated aldehydes and ketones at 298 K: structure and reactivity

Falloff curves for the unimolecular decomposition of two acyl radicals: RCO (+M) → R + CO (+M) by pulsed laser photolysis coupled to time‐resolved infrared diode laser absorption

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