Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship: An update

Kwok, Eric S. C.; Atkinson, Roger

doi:10.1016/1352-2310(95)00069-b

Cited by 1,059 publications

(1,567 citation statements)

References 38 publications

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“…12). As noted previously (Atkinson, 1989), the temperature dependence of this rate constant (B=809 K) is higher than the estimated value of B=445 K for the temperature range 245-328 K (Kwok and Atkinson, 1995), and needs to be confirmed. As shown in Table 32, few kinetic studies are available for this reaction, and the available rate constants show significant scatter.…”

Section: Oh+22-dimethylbutanementioning

confidence: 58%

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

2003

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Abstract. The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented over the entire temperature range for which measurements have been made (∼180-2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented. The recommended 298 K rate constants, temperature-dependent parameters, and temperature ranges over which these recommendations are applicable are listed in Table 1.

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Section: Oh+22-dimethylbutanementioning

confidence: 58%

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

2003

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“…On the other hand, laboratory kinetics studies, increasingly aided by the tools of quantum chemistry and modern rate theories, allow the most thorough study of elementary reactions (Miller et al, 2005). Such investigations provide direct and detailed information (e.g., pressure and temperature dependence of rate coefficients, product yields, and branching ratios) for the consituent reactions that are the basis of VOC oxidation schemes, and serve as a guide for the development and validation of structure activity relationships (Kwok and Atkinson, 1995). However, these studies are ideally limited to a single reaction sequence under conditions and time scales that minimize the effect of secondary chemistry, which is generally not the case in the atmosphere.…”

Section: R Glowacki Et Al: Hirac Design and Initial Resultsmentioning

confidence: 99%

Design of and initial results from a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC)

et al. 2007

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Abstract. The design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO 2 radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; NO/NO 2 , CO, O 3 , and H 2 O vapour analysers. Ray tracing simulations and NO 2 actinometry have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O 3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response at a range of atmospheric conditions.Correspondence to: P. W. Seakins

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“…The photolysis laser fluence was varied over the range (7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19) mJ pulse -1 cm -2 . The OH probe laser fluence ranged from 0.2 to 0.4 mJ pulse -1 cm -2 .…”

Section: Methodsmentioning

confidence: 99%

“…In the absence of experimental data, modeling studies 7,8 have assumed hydrogen abstraction from various sites using the empirical structurereactivity relationships of Atkinson. 9,10 In this paper, we report the rate coefficients, k 1 (T)-k 5 (T), for the reaction of various isotopomers of bromopropane with OH:…”

Section: Introductionmentioning

confidence: 99%

Rate Coefficient and Product Branching Measurements for the Reaction OH + Bromopropane from 230 to 360 K

et al. 2002

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Rate coefficients over the range of 230-360 K were measured for the reaction of OH with the following bromopropane isotopomers: CH 3 CH 2 CH 2 Br (k 1 ), CD 3 CH 2 CH 2 Br (k 2 ), CD 3 CH 2 CD 2 Br (k 3 ), CH 3 CD 2 CD 2 Br (k 4 ), and CD 3 CD 2 CD 2 Br (k 5 ). The hydroxyl radical was produced by pulsed laser photolysis and detected via laser induced fluorescence. Reaction 1 can occur by H atom abstraction from three different carbon sites: OH + CH 3 CH 2 CH 2 Br f CH 3 CH 2 CHBr + H 2 O (1a; R); f CH 3 CHCH 2 Br + H 2 O (1b; ); or f CH 2 CH 2 -CH 2 Br + H 2 O (1c; γ). Branching ratios obtained from an analysis of the kinetic data at 298 K are k 1c /k 1 ) 0.12 ( 0.08, k 1b /k 1 ) 0.56 ( 0.04, and k 1a /k 1 ) 0.32 ( 0.08; uncertainties given are 2 standard deviations and do not include systematic uncertainties. Stable products formed following reaction 1 in a NO x /O 2 environment were measured using long path infrared absorption. Bromoacetone and propanal were observed in the ratio [(CH 3 C(O)CH 2 Br)/(CH 3 CH 2 CHO)] of 1.65 ( 0.50 with an absolute bromoacetone yield of 0.5 ( 0.2 at room temperature. The product yields are consistent with the rate coefficient data. Ab initio calculations show that C-H bond energies at both the R and sites decrease (relative to propane) by the addition of Br at the R site. The calculated transition state energies decrease in the order γ > R > , in qualitative agreement with the experimental observations.

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Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship: An update

Cited by 1,059 publications

References 38 publications

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

Design of and initial results from a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC)

Rate Coefficient and Product Branching Measurements for the Reaction OH + Bromopropane from 230 to 360 K

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