Gas-phase chlorine-photosensitized oxidation of trichloroethylene

Huybrechts, G.; Meyers, Liliane

doi:10.1039/tf9666202191

Cited by 41 publications

(32 citation statements)

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“…The product formed, C(O)Cl 2 , is a major product of the TCE oxidation, as shown by experimental studies. [9][10][11][12] Our results concur with the previous literature suggesting addition of the OH to the less substituted carbon. [17][18][19] This is reflected in the lower activation energy barrier, 1.7 kcal · mol -1 for reaction 3, whereas OH addition to carbon 2 (reaction 2) has a barrier of 4.2 kcal · mol -1 .…”

Section: Resultssupporting

confidence: 96%

Atmospheric Oxidation of Trichloroethylene: An Ab Initio Study

Christiansen

Francisco

2010

J. Phys. Chem. A

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The atmospheric oxidation of trichloroethylene has previously been studied experimentally. Phosgene is thought to be the dominant product, although the mechanism of production is not well understood. Additionally, studies omitting a chlorine scavenger show the production of dichloroacetyl chloride. This influence of the chlorine atom on the trichloroethylene oxidation is not well understood. Using ab initio methods, this study presents a comprehensive computational study of both the hydroxyl radical and chlorine atom initiated atmospheric oxidation mechanisms of trichloroethylene (C(2)HCl(3)). Potential energy surfaces, including activation energies and enthalpies, are determined. The results from this study, in connection with experimental work, confirm the influence of the Cl-initiated oxidation in determining the product profile of the trichloroethylene oxidation. These products include dichloroacetyl chloride [Cl(2)CHC(O)Cl], formyl chloride [CH(O)Cl], phosgene [C(O)Cl(2)], and regeneration of the chlorine atom.

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Section: Resultssupporting

confidence: 96%

Atmospheric Oxidation of Trichloroethylene: An Ab Initio Study

Christiansen

Francisco

2010

J. Phys. Chem. A

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“…which is similar to that reported for the reaction of C,C15(8) [2], C,HCI,(8) [7] and C,H5(8.8) [l] with 0,. The rate of the inhibited photochlorination being independent of the total pressure (no influence of added N2), the rate of reaction step(p) (see eq.…”

Section: Equation (Xiii) Holds For Reaction (3) Of Schema (Vi) Comsupporting

confidence: 88%

Oxygen‐inhibited photochlorination of 1,2‐dichloroethane

Leblond

Bizongwako

Huybrechts

et al. 1972

Bulletin des Soc Chimique

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The oxygen-inhibited photochlorination of 1,2-dichloroethane has been studied in the gas-phase between 321 and 489,5"K. The following rate constants have been estimated log(kg, mole-' 1 sec-') = 7.8 and log(k-g, sec-') = -24,000/4.576 T+13 where k9 and k-9 refer to (9) ( -9 ) CH2ClCHCI. + 0 2 + CH2ClCHC103.These results are compared to those observed for the reactions of CzH6, CzHCI5, C2HC13 and C2C14. INTRODUCTIONThe rateequation for the oxygen-inhibited photochlorination of C2H6 [l] is very different from that observed for C,HC15 121, C2HC13 [3] and C,Cl, [2]. This can be explained by the fact that the removal of the alkyl chaincarriers Re by 0, is in equilibrium with the reverse reaction for highly chlorinated ethanes and ethylenes (R. = CHCl,CCI,-[4], CC13CC1,*) but not for ethane (R-= CH,CH2-). The cases p r e viously studied involve R* radicals where the C-atom with the free valency is either completely substituted by C1-atoms or not substituted at all. The study of a reaction where R-has an intermediate structure should lead to a better understanding of the inhibiting effect of oxygen on the photochlorinations of ethane and ethylene and their chlorinated derivatives. The present work deals with the reaction of 1,2-C2H,C1, which involves such a radical (R-= CH2ClCHC1-). EXPERIMENTALThe kinetic apparatus and the experimental technique have already been described [1,2]. The reactions were initiated by light at 436 nm and investigated by photometric measurement of the chlorine partial pressure and by gas chromatographic analysis. Commercial tank chlorine (Solvay) was purified as described earlier [I], 1,2-dichloroethane (*> contained less than 0.5% impurity as determined by gas (*) These unstabilized substances were kindly supplied by the Solvay Research Center, Brussels.14 L. Bertrand, J. Bizongwako, G. Huybrechts and J. Olbregts chromatography. Oxygen (Societe Belge de 1'Air Liquide, 99.95% pure) and nitrogen (I'Oxhydrique Internationale S.A.) containing < 30 ppm oxygen were used without further purification. The purities of the 1,1,2-C,H3C13*, 1,1,1,2-C2H2C14*, 1,1,2,2-C2H2Cl, (Schuchardt, reinst, distilled) and C2H3Cl* used in calibrating the gas chromatograph were all greater than 98%. RESULTSThe photochlorination of 1,2-dichloroethane has been studied in the presence of oxygen between 321 and 489.5"K. The pressure of 1,2-C2H4C1,, C1, and 0, and the absorbed light intensity I, were varied over the range given in table 1.

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“…Huybrechts and Meyers [10] and Bertrand et al [11] previously studied the Cl-initiated oxidation of trichloroethylene at , and found that the T Ն 357 K principal oxidation product was CHCl 2 C(O)Cl (Ն 88%), while detecting CCl 2 O in lower yields. They did not observe CHClO, which presumably decomposed at these higher temperatures and/or is much more reactive towards Cl atoms, which were in higher concentrations than in the present work.…”

Section: Relative Rate Study Of the Reactionmentioning

confidence: 98%