FTIR studies of reactions between the nitrate radical and chlorinated butenes

Waengberg, I.; Ljungstroem, E.; Hjorth, J.; Ottobrini, G.

doi:10.1021/j100384a012

Cited by 16 publications

(5 citation statements)

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“…Taking into account the mechanism proposed in this work, we can conclude that, at lower temperatures, the main products found would be epoxichloroethane and NO 2 radical as well as the Markownikoff radical adduct. At higher temperatures an equilibrium distribution between the epoxichloroethane, the Markownikoff and contra-Markownikoff radical adducts, and formyl chloride, formaldehyde, and NO radical will be produced, in agreement with Noremsaune et al and Wängberg et al The reaction has a kinetic control, being the formation of other products avoided due to higher energy barriers.…”

Section: Discussionsupporting

confidence: 79%

“…The one leading to formyl chloride, formaldehyde, and NO radical involves a barrier height of 12.87 kJ/mol at B3LYP level, these products being thermodynamically more stable than the epoxide and the NO 2 radical. These are the products experimentally found by Noremsaune et al and Wängberg et al Then, in these conditions, an equilibrium distribution will be produced between the products of both reaction pathways.…”

Section: Resultsmentioning

confidence: 67%

“…The conformation of P1 shows an asymmetrical three-membered ring, with the C − O and the C − C distances nearly equal and the other C − O distance shorter, corresponding to the substituted C atom. NO 2 radical is one the products experimentally found …”

Section: Resultsmentioning

confidence: 91%

“…Edney et al in their study of the photooxidation of allyl chloride in the presence of NO x propose that the formed alkoxy radical decomposes to give a Cl atom and acrolein. However, the work of Wänberg et al with chlorinated butenes suggests that, at least for this reaction, this is not an important pathway. The principal products they have found are acid chlorides, aldehydes, and NO 2 when the Cl atom is placed on the double bond.…”

Section: Introductionmentioning

confidence: 98%

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Ab Initio Study on the Mechanism of Tropospheric Reactions of the Nitrate Radical with Haloalkenes: Chloroethene

2000

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A mechanism for the reaction of the NO 3 radical with vinyl chloride is proposed on the basis of B3LYP and CASSCF quantum chemistry calculations. Two initial transition states lead to the Markownikoff and contra-Markownikoff addition of NO 3 to chloroethene. From the two initial adducts different interconnected pathways start. We have found epoxichloroethane, chloroethanal, nitrous acid, acetyl chloride, nitric acid, formaldehyde, formyl chloride, and NO radical as main products. The energy of the reactants, products, and all intermediates along with the barrier heights for each reaction path has been calculated. The geometry optimization and characterization of all of the stationary points found on the potential energy hypersurface was made at the B3LYP level with a 6-31G* basis set, and some of the stationary points have been reoptimized with the 6-311+G* basis set. Later, single-point CASSCF calculations were carried out with the same basis set, building the active space with seven active electrons in eight active orbitals. It can be concluded that an equilibrium distribution of formyl chloride, formaldehyde, and the NO radical will be obtained along with small proportions of epoxychloroetane and the Markownikoff radical adduct. An estimation of the reaction rate constant has also been calculated.

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Section: Discussionsupporting

confidence: 79%

Section: Resultsmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 98%

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Ab Initio Study on the Mechanism of Tropospheric Reactions of the Nitrate Radical with Haloalkenes: Chloroethene

2000

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“…They do not find epoxides, but in a later study 9 in anaerobic conditions and at low pressures, they suggest its possible formation. Wa ¨ngber et al, 10 with chlorinated butenes, suggest as main products acid chlorides, aldehyde, and NO 2 when the chlorine atom is placed on the double bond.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Study on the Mechanism of the Reactions of the Nitrate Radical with Haloalkenes: 1,2-Dichloroethene, 1,1-Dichloroethene, Trichloroethene, and Tetrachloroethene

2000

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A general mechanism for the reactions of the NO 3 radical with 1,2-dichloroethene, 1,1-dichloroethene, trichloroethene, and tetrachloroethene is proposed from ab initio DFT calculations. The calculated mechanism shows three main parallel reaction pathways. For the systems where the two carbon atoms are differently substituted, the study includes both the attacks with Markownikoff and contra-Markownikoff orientation. The first reaction pathway leads to the formation of an epoxide along with the NO 2 radical, the second one to the formation of carbonyl compounds, and the third one leads, through the cleavage of the C-C bond, to the formation of carbonyl compounds with a lower number of carbon atoms. The stationary points on the potential energy surface (PES) were found by means of density functional theory (DFT) calculations with the B3LYP functional and the 6-31G* basis set. For each stationary point, the geometry was optimized and the obtained conformation was characterized as an equilibrium structure (reactant, product, or intermediate) or transition state structure.

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A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

Martı́nez¹,

Cabañas²,

Aranda³

et al. 1997

Int. J. Chem. Kinet.

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Absolute rate coefficient for the gas-phase reaction of NO 3 with 3-fluoropropene has been measured using the discharge-flow technique coupled to a LIF detection system for a range of temperatures from 296 K to 430 K. The measured room temperature rate constant is (0.39 Ϯ 0.02) ϫ 10 Ϫ14 molecule Ϫ1 cm 3 s Ϫ1. The Arrhenius expression k ϭ (7.17 Ϯ 3.34) ϫ 10 Ϫ12 exp[Ϫ(2248 Ϯ 169)/T] is proposed for the reaction. The reactivity of alkenes containing halogen atoms is discussed and compared to that of simple alkenes, on the basis of the correlations between the reactivity against NO 3 and the ionization potential of the alkenes.Tropospheric half life of 3-fluoropropene has been estimated at night and during daytime for typical NO 3 and OH trophospheric concentrations.

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FTIR studies of reactions between the nitrate radical and chlorinated butenes

Cited by 16 publications

References 0 publications

Ab Initio Study on the Mechanism of Tropospheric Reactions of the Nitrate Radical with Haloalkenes: Chloroethene

Ab Initio Study on the Mechanism of Tropospheric Reactions of the Nitrate Radical with Haloalkenes: Chloroethene

Ab Initio Study on the Mechanism of the Reactions of the Nitrate Radical with Haloalkenes: 1,2-Dichloroethene, 1,1-Dichloroethene, Trichloroethene, and Tetrachloroethene

A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

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