2565-30-2Relevant articles and documents
Reactions of chloroethenes with atomic chlorine in air at atmospheric pressure
Morozov,Nielsen,Morozova,Vasiliev,Loukhovitskaya
, p. 754 - 760 (2010)
Relative rate method at the temperature of 298 K and pressure of 1013 hPa and GC-MS detection were used for the study of kinetics of the reactions of Cl atoms with H2C=CCl2, cis-ClHC=CHCl, trans-ClHC=CHCl, ClHC=CCl2, and Cl2C=CCl2. The reaction products were identified by FTIR spectroscopy. A mechanism for the atmospheric degradation of chloro-ethenes has been suggested.
Kinetic and product study of the Cl-initiated oxidation of 1,2,3-trichloropropane (CH2ClCHClCH2Cl)
Barnes,Wallington,Inoue,Voicu,Kawasaki,Becker
, p. 5123 - 5130 (2001)
The kinetics and products of the Cl atom initiated oxidation of 1,2,3-trichloropropane were studied using FTIR-smog chamber systems at (295 ± 2) K in 700-760 torr of air. The major oxidation product in terms of carbon balance was 1,3-dichloroacetone with smaller amounts of HC(O)Cl and CH2ClC(O)Cl. Chemical activation effects played a significant role in the atmospheric fate of CH2ClCHClO(·) and CH2ClCO(·)ClCH2Cl radicals. The UV-visible spectrum of CH2ClC(O)CH2Cl was measured at 270-385 nm and has a maximum at 305 nm where σ = (1.6 ± 0.2) × 10-19 sq cm/molecule (base e). Assuming a photolysis quantum yield of 1-0.04, the lifetime of CH2ClC(O)CH2Cl with respect to photolysis on a summer day of 40° latitude was 0.5-12 hr. Photolysis was likely to be the dominant atmospheric loss mechanism of CH2ClC(O)CH2Cl. The results were discussed in the context of the atmospheric chemistry of 1,2,3-trichloropropane.
Matrix isolation study of the photochemically induced reaction of ozone with dibromochloromethane and bromodichloromethane in solid argon at 14 K. FT-IR spectra of the complexes C(O)HCl ... BrX, C(O)HBr ... XCl, C(O)BrCl ... HX, (OC)(HCl)(Br2), (OC)(HBr)(Cl2), and (OC)(BrCl)(HX) (where X = Br or Cl)
Clark, Robin J. H.,Dann, Jonathan R.,Foley, Loraine J.
, p. 73 - 78 (1999)
Quartz-filtered (λ > 240 nm) photolysis of either ozone/dibromochloromethane or ozone/bromodichloromethane in an argon matrix at 14 K has been shown by FT-IR spectroscopy to lead to the formation of the carbonyl ... Lewis acid complexes C(O)HCl ... BrX, C(O)HBr ... XCl, C(O)BrCl ... HX, and C(O)Cl2 ... HBr, where X = Br or Cl, depending on the trihalogenomethane used. Several of these complexes are new and are formed by either hydrogen halide or dihalogen abstraction reactions. Upon further irradiation the carbonyl complexes dissociate to form the new carbon monoxide complexes (OC)(HCl)(Br2), (OC)(HBr)(Cl2), and (OC)(BrCl)(HX). Thus the photo-induced reactions of ozone with trihalogenomethanes lead to the formation of new carbonyl and carbon monoxide complexes whose vibrational properties are well characterised by FT-IR spectroscopy. Suggested pathways for the photolyses are presented.
IR spectroscopic study of the dichloromethyl peroxyl radical and its deuterated analogs in the argon matrix
Baskir, E. G.,Nefedov, O. M.
, p. 2236 - 2240 (2022/01/22)
The dichloromethyl peroxyl radical (CHCl2OO?) and its deuterated analog formed in the reaction of the corresponding dichloromethyl radicals with O2 were studied by matrix IR spectroscopy. Dichloromethyl radicals are genera
Reactions of Three Lactones with Cl, OD, and O3: Atmospheric Impact and Trends in Furan Reactivity
Ausmeel,Andersen,Nielsen,?sterstr?m,Johnson,Nilsson
, p. 4123 - 4131 (2017/06/23)
Lactones, cyclic esters of hydroxycarboxylic acids, are interesting biofuel candidates as they can be made from cellulosic biomass and have favorable physical and chemical properties for distribution and use. The reactions of γ-valerolactone (GVL), γ-crotonolactone (2(5H)-F), and α-methyl-γ-crotonolactone (3M-2(5H)-F) with Cl, OD, and O3 were investigated in a static chamber at 700 Torr and 298 ± 2 K. The relative rate method was used to determine kGVL+Cl = (4.56 ± 0.51) × 10-11, kGVL+OD = (2.94 ± 0.41) × 10-11, k2(5H)-F+Cl = (2.94 ± 0.41) × 10-11, k2(5H)-F+OD = (4.06 ± 0.073) × 10-12, k3M-2(5H)-F+Cl = (16.1 ± 1.8) × 10-11, and k3M-2(5H)-F+OD = (12.6 ± 0.52) × 10-12, all rate coefficients in units of cm3 molecule-1 s-1. An absolute rate method was used to determine k2(5H)-F+O3 = (6.73 ± 0.18) × 10-20 and k3M-2(5H)-F+O3 = (5.42 ± 1.23) × 10-19 in units of cm3 molecule-1 s-1. Products were identified for reactions of the lactones with Cl. In the presence of O2 the products are formic acid (HCOOH), formyl chloride (CHClO), and phosgene (CCl2O), and also maleic anhydride (C2H2(CO)2O) for 2(5H)-F. In addition both reactions produced a number of unidentified products that likely belong to molecules with the ring-structure intact. A review of literature data for reactions of other furans show that the reactivity of the lactones are generally lower compared to that of corresponding compounds without the carbonyl group.
Tropospheric chemical degradation of vinyl and allyl acetate initiated by Cl atoms under high and low NOx conditions
Blanco, María B.,Bejan, Iustinian,Barnes, Ian,Wiesen, Peter,Teruel, Mariano A.
, p. 48154 - 48163 (2015/06/16)
The products of the reactions of Cl atoms with vinyl acetate (VA) and allyl acetate (AA) have been investigated in a 1080 L chamber using in situ FTIR. The experiments were performed at 296 K and atmospheric pressure of synthetic air in the presence and in the absence of NOx. For the reaction of Cl with VA in the presence of NOx formic acetic anhydride, acetic acid and formyl chloride are the major reaction products. In the absence of NOx, the yields of these products are significantly reduced and formation of the carbon-chain-retaining compound CH3C(O)OC(O)CH2Cl is observed. For the reaction of Cl with AA in the presence of NOx acetoxyacetaldehyde and formaldehyde were observed as the main products. In contrast, without NOx, the observations support that the major reaction pathway is the formation of the carbon-chain-retaining compound CH3C(O)OCH2C(O)CH2Cl. The reaction mechanisms leading to the products are discussed. The formation of the high yields of formyl chloride and formaldehyde in the reactions of Cl with VA and AA, respectively, are at odds with currently accepted mechanistic pathways.
Atmospheric chemistry of t-CF3CHCHCl: Products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals
Andersen, M. P. Sulbaek,Nielsen,Hurley,Wallington
experimental part, p. 1735 - 1748 (2012/04/23)
FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1- chloro-propene, t-CF3CHCHCl, in 700 Torr of air or N 2/O2 diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF3CHCHCl occur via addition to the CC double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF3CHCHCl were CF3CHClCHO and CF3C(O)CHCl2, minor products were CF3CHO, HCOCl and CF3COCl. The yields of CF3C(O)CHCl2, CF3CHClCOCl and CF3COCl increased at the expense of CF3CHO, HCOCl and CF3CHClCHO as the O2 partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF3CH(O)CHCl2 and CF 3CClHCHClO radicals. In addition to reaction with O2 to yield CF3COCl and HO2 the major competing fate of CF 3CHClO is Cl elimination to give CF3CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF 3C(O)CHCl2) = (2.3 ± 0.3) × 10-14 and k(Cl + CF3CHClCHO) = (7.5 ± 2.0) × 10-12 cm3 molecule-1 s-1 were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF3CHCHCl. Chlorine atom elimination giving the enol CF3CHCHOH appears to be the sole atmospheric fate of the CF 3CHCHClOH radicals. The yield of CF3COOH in the atmospheric oxidation of t-CF3CHCHCl will be negligible (3CHCHCl. the Owner Societies 2012.
Atmospheric chemistry of CF3CF{double bond, long}CH2: Products and mechanisms of Cl atom and OH radical initiated oxidation
Hurley,Wallington,Javadi,Nielsen
experimental part, p. 263 - 267 (2008/10/09)
The products of Cl atom and OH radical initiated oxidation of CF3CF{double bond, long}CH2 were studied in 700 Torr of N2/O2 diluent at 296 ± 1 K. The reactions of Cl atoms and OH radicals with CF3CF{double bond, long}CH2 proceed via electrophilic addition to the double bond. The reaction with chlorine atoms proceeds 56 ± 5% via addition to the central carbon. The chlorine atom initiated oxidation of CF3CF{double bond, long}CH2 gives CF3C(O)F in a molar yield which is indistinguishable from 100% and independent of [O2], and HC(O)Cl in a molar yield which increased from 30% to 59% as [O2] was increased from 3 to 700 Torr. The OH radical initiated oxidation of CF3CF{double bond, long}CH2 gives CF3C(O)F as major product in a yield of 91 ± 6%. The results are discussed with respect to the atmospheric chemistry and environmental impact of CF3CF{double bond, long}CH2.
Rate coefficients and mechanisms of the reaction of Cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions
Orlando, John J.,Tyndall, Geoffrey S.,Apel, Eric C.,Riemer, Daniel D.,Paulson, Suzanne E.
, p. 334 - 353 (2007/10/03)
The rate coefficients and mechanisms of the reaction of Cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions were studied. It was observed the product yielded from both trans-2-butene and 1-butene were found to be oxygen dependent. The results showed that the variation of the product yielded with O2 in the case of 1-butene resulted from competitive reaction pathways for the two β-chlorobutoxy radicals involved in the oxidation.
