Kinetic study of the reactions of Cl atoms with α,β-unsaturated carbonyl compounds at atmospheric pressure and structure activity relations (SARs)

Teruel, Mariano A.; Achad, Mariana; Blanco, Marı́a B.

doi:10.1016/j.cplett.2009.07.103

Cited by 29 publications

(19 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The value provided by Rodríguez et al,(1.31±0.19)×10 -10 cm 3 molecule -1 s -1 , is the only experimental data for k T2P . However, an estimation of k T2P , calculated using the Structure-J o u r n a l P r e -p r o o f Activity Relationships (SARs) method, 3.47×10 -10 cm 3 molecule -1 s -1 , is not in agreement with the experimental value (Teruel et al, 2009). This value is close to the gas kinetic limit for such a bimolecular elementary reaction.…”

Section: Introductionmentioning

confidence: 62%

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

et al. 2021

View full text Add to dashboard Cite

The gas-phase reaction of trans-2-pentenal (T2P) with Cl atoms was studied at atmospheric pressure and room temperature. A rate coefficient of (2.56±0.83)×10 -10 cm 3 molecule -1 s -1 was obtained using the relative rate method and isoprene, cyclohexane and ethanol as reference compounds. The kinetic study was carried out using a 300-L Teflon bag simulation chamber (IMT Lille Douai-France) and a 16-L Pyrex cell (UCLM-Ciudad Real-Spain), both coupled to the Fourier transform infrared (FTIR) technique. Gas-phase products and secondary organic aerosol (SOA) formation were studied at UCLM using a 16-L Pyrex cell and a 264-L quartz simulation chamber coupled to the FTIR and gas-chromatography-mass spectrometry (GC-MS) techniques. HCl, CO, and propanal were identified as products formed from the studied reaction and quantified by FTIR, being the molar yield of the latter (5.2±0.2)%. Formic acid was identified as a secondary product and was quantified by FTIR with a yield of (6.2±0.4)%.In addition, 2-chlorobutanal and 2-pentenoic acid were identified, but not quantified, by GC-MS as products. The SOA formation was investigated using a fast mobility particle sizer spectrometer. The observed SOA yields reached maximum values of around 7% at high particle mass concentrations. This work provides the first study of the formation of gaseous and particulate products for the reaction of Cl with T2P. A reaction mechanism is suggested to explain the formation of the observed gaseous products. The results are discussed in terms of the structure-reactivity relationship, and the atmospheric implications derived from this study are commented as well.

show abstract

Section: Introductionmentioning

confidence: 62%

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

et al. 2021

View full text Add to dashboard Cite

show abstract

“…The rate constant was a small amount higher, but to within the data scatter, the effect of oxygen addition was minor. Another measurement of this rate constant at ambient temperature and pressure has been made recently, 20 [k ) 2.9((1.1) × 10 -10 cm 3 molecule -1 s -1 ] which overlaps with the ambient temperature values in Table 4 at the maximum of the error limits.…”

Section: Discussionmentioning

confidence: 97%

Products and Mechanism of the Reaction of Chlorine Atoms with 3-Pentanone in 700−950 Torr of N₂/O₂ Diluent at 297−515 K

2009

View full text Add to dashboard Cite

The products, kinetics, and mechanism of the reaction Cl + 3-pentanone have been measured by UV irradiation of Cl(2)/3-pentanone/N(2) (O(2)) mixtures using primarily GC analysis with selected cross checks by FTIR. In the absence of O(2), the products are 1- and 2-chloro-3-pentanone with yields of 21 and 78%, respectively. As the temperature is increased, the yield of 1-chloro-3-pentanone increases modestly relative to the 2-chloro-3-pentanone yield. On the basis of this increase, the activation energy for hydrogen abstraction at the 1 position is determined to be 500 (+/-500) cal mole(-1) relative to abstraction at the 2 position. In the presence of 500 ppm of O(2) with 900-1000 ppm of Cl(2) at 297 K, the yield of 2-chloro-3-pentanone decreases dramatically from 78 to 2.5%, while the 1-chloro-3-pentanone decreases only modestly from 21 to 17%. The observed oxygenated species are acetaldehyde (59%), 2,3-pentanedione (9%), and propionyl chloride (56%). Increasing the temperature to 420 K (O(2) = 500 ppm) suppresses these oxygenated products, and 2-chloro-3-pentanone again becomes the primary product, indicating that the O(2) addition reaction to the 2-pentanonyl radical has become reversible. At 500 K and 10 000 ppm O(2), a new product channel opens which forms a small yield ( approximately 4%) of ethylvinylketone. Computer modeling of the product yields has been performed to gain an understanding of the overall reaction mechanism in the presence and absence of O(2). The reaction of chlorine atoms with 3-pentanone proceeds with a rate constant of 8.1 (+/-0.8) x 10(-11) cm(3) molecule(-1) s(-1) independent of temperature over the range of 297-490 K (E(a) = 0 +/- 200 cal mole(-1)). Rate constant ratios of k(C(2)H(5)C(O)CHCH(3) + Cl(2))/k(C(2)H(5)C(O)CHCH(3) + O(2)) = 0.0185 +/- 0.0037 and k(C(2)H(5)C(O)CH(2)CH(2) + Cl(2))/k(C(2)H(5)CH(2)C(O)CH(2)CH(2) + O(2)) = 2.7 +/- 0.4 were determined at 297 K in 800-950 Torr of N(2)/O(2) diluent. In 800-950 Torr of N(2)/O(2) diluent, the major fate of the alkoxy radical CH(3)CH(O)C(O)C(2)H(5) is decomposition to give C(2)H(5)C(O) radicals and CH(3)CHO. These results show that the chemical mechanisms of the 3-pentanone reactions are very similar to those observed for butanone. In addition, the rate constants of the reactions of chlorine atoms with 1-chloro-3-pentanone [3 (+/-0.6) x 10(-11) over the range of 297-460 K], 2,3-pentanedione [1.4 (+/-0.3) x 10(-11) at 297 K], and ethylvinylketone [1.9 (+/-0.4) x 10(-10) over the range of 297-400 K, decreasing rapidly above 400 K] were measured at ambient pressure.

show abstract

“…The method is based on the structure of the alkene, the number of unconjugated double bonds and the degree, identity, position and configuration of the substitution around the double bonds. The rate coefficients for the 'basic structures' are calculated from the average of the experimental rate coefficients for the following parent alkenes; basic structure CH 2 @CHR from propene with k basic = 2.89 Â 10 À10 cm 3 molecule À1 s À1 ; CH 2 @CR 2 from 2-methylpropene with k basic = 3.40 Â 10 À10 cm 3 molecule À1 s À1 ; (E/Z)-RHC@CHR from (E/Z)-2-butene with k basic = 3.63 Â 10 À10 cm 3 molecule À1 s À1 ; RHC@CR 2 from 2-methyl-2-butene with k basic = 3.95 Â 10 À10 cm 3 molecule À1 s À1 [17]. The reactivity factor for CH 3 is set as unity.…”

Section: Discussionmentioning

confidence: 99%

“…The reactivity factor for CH 3 is set as unity. The group factors (Cx) are defined by the following equation: [17]. A correlation between the calculated and experimental roomtemperature rate coefficients for unsaturated esters and aldehydes with C@C bonds is provided in Fig.…”

Section: Discussionmentioning

confidence: 99%

FTIR gas-phase kinetic study of the reactions of Cl atoms with (CH3)2CCHC(O)H and CH3CHCHC(O)OCH3

Blanco

Barnes

Teruel

2010

Chemical Physics Letters

Self Cite

View full text Add to dashboard Cite

Kinetic study of the reactions of Cl atoms with α,β-unsaturated carbonyl compounds at atmospheric pressure and structure activity relations (SARs)

Cited by 29 publications

References 18 publications

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

Products and Mechanism of the Reaction of Chlorine Atoms with 3-Pentanone in 700−950 Torr of N₂/O₂ Diluent at 297−515 K

FTIR gas-phase kinetic study of the reactions of Cl atoms with (CH3)2CCHC(O)H and CH3CHCHC(O)OCH3

Contact Info

Product

Resources

About

Kinetic study of the reactions of Cl atoms with α,β-unsaturated carbonyl compounds at atmospheric pressure and structure activity relations (SARs)

Cited by 29 publications

References 18 publications

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation

Products and Mechanism of the Reaction of Chlorine Atoms with 3-Pentanone in 700−950 Torr of N2/O2 Diluent at 297−515 K

FTIR gas-phase kinetic study of the reactions of Cl atoms with (CH3)2CCHC(O)H and CH3CHCHC(O)OCH3

Contact Info

Product

Resources

About

Products and Mechanism of the Reaction of Chlorine Atoms with 3-Pentanone in 700−950 Torr of N₂/O₂ Diluent at 297−515 K