Kinetics and mechanisms of the gas-phase reactions of ozone with organic compounds under atmospheric conditions

Atkinson, Roger; Carter, William

doi:10.1021/cr00063a002

Cited by 620 publications

(491 citation statements)

References 46 publications

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“…[2][3][4] Rate constants including the tropospheric temperature range (220-300 K) have been reported previously, and the work reported here validates those rate expressions. [5][6][7][8] High-temperature incineration is considered to be the best available technology for the safe disposal of these toxic compounds.…”

Section: Introductionsupporting

confidence: 85%

“…In the present study, a XeF excimer laser (Lamba Physik Compex model 102) was used to produce OH radicals by 351 nm photodissociation of nitrous acid (HONO) to form nitric oxide and the hydroxyl radical. A competing dissociation channel, production of NO 2 and H atoms has been observed to be negligible under similar experimental conditions. 15 Initial [OH] 0 ranged from ∼3 × 10 10 to 9.0 × 10 10 molecules cm -3 , and was determined based on the measured excimer fluence, the published value of the absorption cross section for HONO, 21.2 × 10 -20 cm 2 /molecule at 351 nm, 16 a quantum yield of 1.0, 17 and measurements of [NO 2 -] (taken to represent [HONO]) determined using ion chromatography.…”

Section: Experimental Approach and Data Reductionmentioning

confidence: 65%

See 1 more Smart Citation

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Tichenor¹,

Graham²,

Yamada³

et al. 2000

J. Phys. Chem. A

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Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C 2 Cl 4 (k 1 ) over an extended temperature range at 740 ( 10 Torr in a He bath gas. These absolute rate measurements were conducted using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. The lower temperature values for k 1 are within (2σ of previous data using different techniques. The overall slope of our Arrhenius plot varies slightly from previously reported values. Agreement within our own data holds up to ∼720 K, but reliable measurement beyond this temperature was hampered by apparent thermal decomposition of our OH source (HONO). An Arrhenius fit to the data yielded the expression k 1 (T) ) (1.68 ( 0.25) × 10 -12 exp(-764.2 ( 79.1/T), whereas a three-parameter Arrhenius fit yielded the expression k 1 (T) ) (1.93 ( 0.20) × 10 -22 (T) 3.2 exp(660.8 ( 54.6/T), where k is in units of cm 3 molecule -1 s -1 . This work shows some deviation from previous low-temperature data. We propose that surface absorption influenced previously measured rate constants. Significant absorption was evident at low temperatures, and an experimental technique was developed to negate this effect. The predicted mechanisms were conceptualized using ab initio calculations to define the activated complex and transient intermediates, and thus predict the most likely path and products. Quantum RRK analysis yielded no overall pressure dependence. Model predictions indicate that trichloroethenol formation via Cl elimination dominates up to temperatures of 2000 K. At flame temperatures, the analysis also predicts increased formation of trichloroacetyl chloride with hydrogen elimination and back reaction to the original reactants.

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Section: Introductionsupporting

confidence: 85%

Section: Experimental Approach and Data Reductionmentioning

confidence: 65%

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Tichenor¹,

Graham²,

Yamada³

et al. 2000

J. Phys. Chem. A

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“…The annual average background ozone concentrations over the midlatitude of the Northern Hemisphere range between 20 ppb and 45 ppb (Vingarzan, 2004) and it is present during day and night. Ozone can react with many organic compounds, such as unsaturated hydrocarbons, aromatics and sulfurcontaining organics in the atmosphere (Atkinson and Carter, 1984;Ljubic and Sabljic, 2002).…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous ozonation of suspended malathion and chlorpyrifos particles

et al. 2010

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a b s t r a c tThe heterogeneous ozonation of suspended malathion and chlorpyrifos particles are studied in real-time with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The pesticide particles with the diameter of hundreds of nanometers are generated by the homogeneous nucleation method using azelaic acid as nucleus. The reactions are carried out in an aerosol reaction chamber under ambient pressure (1 atm) and room temperature (298 K), respectively. The time-of-flight mass spectra of the solid-state ozonation products of malathion and chlorpyrifos are obtained. The assignments of the mass spectra reveal that the major ozonation products of malathion particles are s-(1,2-diethoxycarbonyl)ethyl-O,O-dimethylphosphorothioate (malaoxon), 2-mercapto-succinic acid diethylester, 1,2-dicarbethoxyethyl-dimethoxyphosphinyldisulfide and bis(1,2-bis-ethoxycarbonylethyl)disulfide. The experimental results reveal that water vapor can enhance the formation of malaoxon, 2-mercapto-succinic acid diethylester and bis(1,2-bis-ethoxycarbonyl-ethyl)disulfide. In the case of chlorpyrifos, the sole ozonation product observed is 3,5,6-trichloro-2-pyridyl-diethylphosphate (chlorpyrifos oxon). The pathways of heterogeneous ozonation of malathion and chlorpyrifos particles are proposed. The atmospheric lifetimes of malathion and chlorpyrifos particles towards ozone reaction are estimated based on the time-dependent mass spectrometric signals obtained.

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“…Articles on the atmospheric oxidation of various types of reduced sulfur compounds are given by Atkinson and Carter [5], Yin et al [6], Atkinson [7,8], Tyndall and Ravishankara [9], Barnes el al. [10], and Wine et al [11].…”

mentioning

confidence: 99%

“…The results reveal that in the atmosphere alkyl sulfides are mainly scavenged by the reaction with OH radicals and NO 3 radicals. In the present work, to test our improved smog chamber system and expand our understanding of the atmospheric fate of alkyl sulfide, we conducted relative rate measurements of ethyl methyl sulfide (EMS, C 2 H 5 SCH 3 ) with OH radicals over the temperature range of 297-346 K at 1.01×10 5 Pa pressure of air.…”

mentioning

confidence: 99%

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

Wang

2011

Chin. Sci. Bull.

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Using an improved smog chamber system, the temperature dependence of OH radical reaction with EMS was investigated over the temperature range of 297-346 K at 1.01×10 5 Pa pressure of air. The Arrhenius expression of the reaction was obtained for the first time. The mechanism of the reaction was also investigated. smog chamber, temperature dependence, OH radicals, mechanism, sulfide Citation:Wang K, Ge M F, Wang W G. Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS.

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Kinetics and mechanisms of the gas-phase reactions of ozone with organic compounds under atmospheric conditions

Cited by 620 publications

References 46 publications

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Kinetic and Modeling Studies of the Reaction of Hydroxyl Radicals with Tetrachloroethylene.

Heterogeneous ozonation of suspended malathion and chlorpyrifos particles

Temperature dependent kinetics of the gas-phase reaction of OH radicals with EMS

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