The Reaction of OH Radicals with 1,1‐di‐, tri‐ and tetrachloroethylene

Kirchner, K.; Helf, D.; Ott, Philipp; Vogt, Stefan

doi:10.1002/bbpc.19900940116

Cited by 53 publications

(69 citation statements)

References 17 publications

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“…Examination of Figs. 1 and 2 shows agreement at room temperature, within combined experimental uncertainties, between our work and that reported previously (Howard, 1976;Chang and Kaufman, 1977;Davis et al, 1977;Kirchner et al, 1990).…”

Section: Resultssupporting

confidence: 91%

“…Although our room temperature data for both k 1 and k 2 are in agreement with previous studies, the measured temperature dependence di ers considerably with previous studies. For C 2 HCl 3 , the Arrhenius activation energy derived from our lower temperature data ()315 cal/mol) is considerably lower than the values of )885 and )478 cal/mol reported by Chang and Kaufman (1977) and Kirchner et al (1990), respectively, over more limited temperature ranges.…”

Section: Resultscontrasting

confidence: 85%

“…Initial testing of C 2 HCl 3 and C 2 Cl 4 was performed using 193 nm photolysis of N 2 O/H 2 O as the OH source, as had been done previously. The resulting room-temperature rate measurements exceeded previously reported values by a factor of two (C 2 HCl 3 ) and 10 (C 2 Cl 4 ) (Howard, 1976;Chang and Kaufman, 1977;Davis et al, 1977;Kirchner et al, 1990). Due to the large absorption crosssections of C 2 HCl 3 and C 2 Cl 4 b 5 Â 10 À18 cm 2 a molecule (Zabel, 1974), additional measurements were conducted at low excimer laser¯uences (<1 mJ cm À2 ), with no observed reduction in rate coe cients.…”

Section: Experimental Approach and Data Reductioncontrasting

confidence: 53%

“…Rate constants at low temperatures (220±430 K) have been reported previously (Howard, 1976;Chang and Kaufman, 1977;Davis et al, 1977;Kirchner et al, 1990). The reaction mechanism is presumed to be addition to the p electrons associated with the C C double bond.…”

Section: Introductionsupporting

confidence: 54%

“…The reaction mechanism is presumed to be addition to the p electrons associated with the C C double bond. Kirchner et al (1990), measured reaction products from OH reactions with C 2 HCl 3 and C 2 Cl 4 at low temperatures (300±450 K) using electron impact mass spectrometry. The observed product distributions were complex with the dominant mass spectra signals interpreted in terms of a reaction mechanism involving OH addition and subsequent Cl elimination.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

et al. 2001

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Rate coe cients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C 2 HCl 3 (k 1 ) and C 2 Cl 4 (k 2 ) over an extended temperature range at 740 10 Torr in a He bath gas. These absolute rate measurements were accomplished using a laser photolysis/laser-induced¯uorescence (LP/LIF) technique under slow¯ow conditions. The simple Arrhenius equation adequately describes the low temperature data for k 1 (<650 K) and the entire data set for k 2 and is given by (in units of cm 3 molecule À1 s À1 ):Error limits are 2r values. The room temperature values for k 1 and k 2 are within 2r of previous data using di erent techniques. The Arrhenius activation energies for k 1 and k 2 are a factor of 2±3 lower than previously reported values. The experimental measurements for both k 1 and k 2 in conjunction with transition state and variation transition state theory calculations infer an OH addition mechanism. The lack of a measurable kinetic isotope e ect for k 1 is consistent with this mechanism. Insight into the subsequent reactions of the chemically activated intermediate are presented in the form of potential energy diagrams derived from ab initio calculations. Ó

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Section: Resultssupporting

confidence: 91%

Section: Resultscontrasting

confidence: 85%

Section: Experimental Approach and Data Reductioncontrasting

confidence: 53%

Section: Introductionsupporting

confidence: 54%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

et al. 2001

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Abatement of volatile organic compounds by corona discharge. A study of the reactivity of trichloroethylene under atmospheric pressure ionization conditions

Donò

Paradisi

Scorrano

1997

Rapid Commun. Mass Spectrom.

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Non-equilibrium plasma based technologies are currently being developed for the abatement of volatile organic compounds (VOCs). The promising results obtained so far encourage efforts in fundamental research to improve our knowledge of the processes involved. To gain insight into the role played by analyte-derived ionic species we have investigated the ion chemistry of trichloroethylene (TCE), a representative VOC, in air at ambient pressure by means of an atmospheric pressure chemical ionization commercial mass spectrometer. Different experimental conditions were examined with regard to the following parameters: ion source temperature, water and TCE concentrations, and extraction potential. Notably, modulation of the variable extraction potential provided a means to probe structure and reactivity of the ionic species of interest. Products resulting from TCE oxidation were observed in the analysis of both positive and negative ions. Particularly prominent is a C 2 H 2 Cl 2 O + . species, likely of enol structure, due to reaction with water. A reaction scheme is proposed based on nucleophilic addition of water to ionized TCE followed by elimination of HCl. The negative ion chemistry of TCE is dominated by Cl -and its clusters with water and TCE. At low temperature and with water in high concentration very large positive and negative ion hydrate clusters (with up to 50 water molecules) could be observed. © 1997 by John Wiley & Sons, Ltd. Received 8 July 1997; Revised 2 September 1997; Accepted 8 September 1997 Rapid. Commun. Mass Spectrom. 11, 1687-1694 (1997 Control of volatile organic compounds (VOCs) in the atmosphere is a major environmental problem due to their great proliferation and to limitations of the traditional methods of abatement (incineration, catalytic oxidation and carbon adsorption).1 Among the alternative approaches being presently developed, nonequilibrium plasma-based technologies, using either high energy electron beams or electrical discharges including corona discharges, appear particularly promising. [2][3][4] Since most of the electrical energy used for producing a non-equilibrium plasma ends up in energetic electrons rather than gas heating, this approach is particularly suited for the cost-effective treatment of large volumes of gaseous effluents containing low concentrations of VOC produced by many different manufacturing industries in which volatile organic solvents are used. The products observed under most conditions include CO, CO 2 , and, for chlorinated VOCs, HCl and Cl 2 . In some cases additional products have been detected corresponding to some intermediate stages of oxidation, such as phosgene, 1,1-dichloroethene and chloroacetylchloride from 1,1,1-trichloroethane 5 and phosgene and dichloroacetylchloride from trichloroethylene (TCE). 6 In recent publications, kinetic analysis and mechanistic interpretations have also been presented for the decomposition of representative VOCs in non-equilibrium plasma. 3,5,7 It is generally accepted that the major decay routes involve radic...

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Tunable diode laser studies of the reaction of Cl atoms with CH3CHO

et al. 1999

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The reaction Cl ϩ CH 3 CHO : HCl ϩ CH 3 CO (1) was studied using flash photolysis / tunable diode laser absorption spectroscopy to monitor the production of HCl. The rate coefficient, k 1 , was measured to be (7.5 Ϯ 0.8) ϫ 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1 at 298 K. HCl (v ϭ 0) and HCl † (v ϭ 1) were measured directly in this study and the yields of HCl (v ϭ 0, 1, Ͼ1) for the reaction of Cl with CH 3 CHO were determined to be 0.44 Ϯ 0.15, 0.56 Ϯ 0.15, and Ͻ0.04, respectively. The rate coefficient for the quenching of HCl † (v ϭ 1) by CH 3 CHO was k 17e ϭ (4.8 Ϯ 1.2) ϫ 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1.

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The Reaction of OH Radicals with 1,1‐di‐, tri‐ and tetrachloroethylene

Cited by 53 publications

References 17 publications

Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

Abatement of volatile organic compounds by corona discharge. A study of the reactivity of trichloroethylene under atmospheric pressure ionization conditions

Tunable diode laser studies of the reaction of Cl atoms with CH3CHO

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