Gas-phase Reactions Of Hydroxyl Radicals Research Articles

Kinetics of the reactions of the OH radical with 2-methyl-1-propanol, 3-methyl-1-butanol and 3-methyl-2-butanol between 241 and 373 K

Absolute rate constants have been measured for the gas-phase reactions of hydroxyl radicals with 2-methyl-1-propanol (k1), 3-methyl-1-butanol (k2) and 3-methyl-2-butanol (k3). Experiments were carried out using two different techniques, the relative rate method and the pulsed laser photolysis-laser induced fluorescence technique. The kinetic data were used to derive the following Arrhenius expressions in the temperature range 241–373 K(in units of cm3 molecule−1 s−1):k1 = (3.1±0.9) × 10−12exp[(352±82)/T]k2 = (2.8±0.9) × 10−12exp[(503±98)/T]k3 = (2.6±0.6) × 10−12exp[(456±65)/T]At 298 K, the reaction rate constants obtained by the two methods were in very good agreement. The results are presented, discussed and used to estimate the atmospheric lifetimes for the studied alcohols.

Kinetics of the gas‐phase reactions of hydroxyl radicals with C1–C6 aliphatic alcohols in the presence of ammonium sulfate aerosols

AbstractThe effects of ammonium sulfate aerosols on the kinetics of the hydroxyl radical reactions with C1–C6 aliphatic alcohols have been investigated using the relative rate technique. P‐xylene was used as a reference compound for the C2–C6 aliphatic alcohols study, and ethanol was used as a reference compound for the methanol study. Two different aerosol concentrations that are typical of polluted urban conditions were tested. The total surface areas of aerosols were 1400 μm2 cm−3 (condition I) and 3400 μm2 cm−3 (condition II). Results indicate that ammonium sulfate aerosols promote the ethanol/OH radical and 1‐propanol/OH radical reactions as compared to the p‐xylene/OH radical reaction. The relative rate of the ethanol/·OH reaction versus the p‐xylene/·OH reaction increased from 0.19 ± 0.01 in the absence of aerosols to 0.24 ± 0.01 and 0.26 ± 0.02 under aerosol conditions I and II, respectively. The relative rate of the 1‐propanol/·OH reaction versus the p‐xylene/·OH reaction increased from 0.45 ± 0.03 in the absence aerosols to 0.56 ± 0.02 and 0.55 ± 0.03 under aerosol conditions I and II, respectively. However, significant changes in the relative rates of the 1‐butanol/·OH, 1‐pentanol/·OH, and 1‐hexanol/·OH reactions versus the p‐xylene/·OH reaction were not observed for either aerosol concentration. The relative rates of the methanol/·OH reaction versus the ethanol/·OH reaction were identical in the absence and presence of aerosols. These results indicate that ammonium sulfate aerosols promote the methanol/·OH reaction as much as the ethanol/·OH reaction (as compared to the p‐xylene/·OH reaction). © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 422–430, 2001

Temperature dependence for the rate constants of the reaction of OH radicals with selected alcohols

Absolute rate constants have been measured for the gas-phase reaction of hydroxyl radicals with three alcohols: 1-propanol ( k 1), 2-propanol ( k 2), and 1-butanol ( k 3). Experiments were carried out using the pulsed laser photolysis–laser induced fluorescence (PLP–LIF) technique over the temperature range 253–372 K. The obtained kinetic data were used to derive the following Arrhenius expressions (in units of cm 3 molecule −1 s −1): k 1=(4.68±0.64)×10 −12 exp[(68±41)/T], k 2=(2.80±0.39)×10 −12 exp[(184±40)/T], k 3=(5.30±1.62)×10 −12 exp[(146±92)/T]. At 298 K, the reactions' rate constants obtained were as follows (in units of cm 3 molecule −1 s −1): k 1=(5.83±0.18)×10 −12, k 2=(5.17±0.23)×10 −12, and k 3=(8.47±0.34)×10 −12. The results are compared with the previous determinations and the possible reaction mechanisms are presented.

Rate constants for the reactions of OH with chlorinated propanes

Absolute rate constants have been measured for the gas-phase reactions of hydroxyl radicals with a series of chlorinated propanes: 1-chloropropane (k1), 2-chloropropane (k2), 1,2-dichloropropane (k3) and 1,2,3-trichloropropane (k4). Experiments were carried out using the pulsed laser photolysis–laser induced fluorescence technique over the temperature range 233–372 K. The kinetic data obtained were used to derive the following Arrhenius expressions (in units of cm3 molecule−1 s−1): k1 = (5.7 ± 1.0) × 10−12 exp[ − (526 ± 53)/T], k2 = (2.4 ± 0.6) × 10−12 exp[ − (365 ± 66)/T], k3 = (2.1 ± 0.5) × 10−12 exp[ − (453 ± 76)/T] and k4 = (1.5 ± 0.5) × 10−12 exp[ − (350 ± 100)/T]. The quoted errors for the pre-exponential factor, A, and E/R are given by ΔA = 2AσlnA and ΔE/R = 2σE/R, respectively. At room temperature, the rate constants obtained were as follows (in units of 10−13 cm3 molecule−1 s−1): k1 = (9.8 ± 1.0), k2 = (7.0 ± 0.7), k3 = (4.6 ± 0.6) and k4 = (4.6 ± 0.7). The results are compared with previous determinations and discussed in terms of structure–activity relationships.

Aerosol formation from the gas-phase reaction of hydroxyl radical with the natural hydrocarbon bornyl acetate

The gas-phase reaction of bornyl acetate (1,7,7-trimethyl-bicyclo[2,2,1]-heptan-2-ol-acetate) with hydroxyl radical has been studied in a smog chamber. It was found that the reaction of bornyl acetate with OH radicals leads to organic aerosols. The chemical composition of the aerosol was studied. On the basis of mass spectral data 1,7,7-trimethyl-6-acetyloxy-bicyclo[2.2.1]-heptan-2,3-dione has been tentatively identified in irradiated CH 3ONO–NO–air–bornyl acetate mixtures. The aerosol carbon yield, the fraction of the carbon initially present that is converted to aerosol, has been estimated to be ≅5%.

Mechanistic and Kinetic Study of the Gas-Phase Reaction of Hydroxyl Radical with Dimethyl Sulfoxide

Time-resolved tunable diode laser spectroscopic detection of CH3, CH4, and SO2 has been coupled with 248 nm laser flash photolysis of H2O2 in the presence of CH3S(O)CH3 (DMSO) to study the mechanis...

Ab initio molecular dynamics simulations of the gas-phase reaction of hydroxyl radical with nitrogen dioxide radical

The reaction between the hydroxyl radical and the nitrogen dioxide radical in the gas phase has been studied with ab initio molecular dynamics simulations based on density functional theory. Nitric acid HONO 2 and cis– cis peroxynitrous acid ONOOH are formed spontaneously, whereas for the formation of the corresponding trans– perp conformer of peroxynitrous acid, a barrier is observed. The relative energetics of the different conformers of ONOOH are in good agreement with MP2 results. The same holds for the structural properties, except for the N–O single bond which turns out to be highly sensitive to the exchange-correlation functional and is generally overestimated.

Rate constant for the gas-phase reaction of hydroxyl radical with the natural hydrocarbon bornyl acetate

Rate constant for the gas-phase reaction of hydroxyl radical with the natural hydrocarbon bornyl acetate

Kinetic Studies of OH Reactions with a Series of Methyl Esters.

Absolute rate constants have been measured for the gas-phase reactions of hydroxyl radicals with a series of methyl esters: methyl propionate (k 1), methyl butyrate (k 2), methyl valerate (k 3), and methyl caproate (k 4). Experiments were carried out using the pulsed laser photolysis-laser induced fluorescence technique over the temperature range 253-372 K. The obtained kinetic data were used to derive the following Arrhenius expressions: k 1 = (1.45 ± 0.42) × 10-12 exp[-(148 ± 86)/T]; k 2 = (0.96 ± 0.29) × 10-12 exp[(380 ± 91)/T]; k 3 = (1.37 ± 0.64) × 10-12 exp[(401 ± 142)/T]; k 4 = (2.46 ± 1.04) × 10-12 exp[(326 ± 130)/T] (in units of cm3 molecule-1 s-1). At room temperature, the rate constants obtained (in units of 10-12 cm3 molecule-1 s-1) were as follows: methyl propionate (0.83 ± 0.09); methyl butyrate (3.30 ± 0.25); methyl valerate (4.83 ± 0.55); methyl caproate (7.15 ± 0.70). Our results are compared with the previous determinations and discussed in terms of structure-activity relationships.

Determination of rate constants for reactions of some hydrohaloalkanes with OH radicals and their atmospheric lifetimes

Rate constants have been measured for the gas-phase reactions of hydroxyl radical with partly halogenated alkanes using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units 10−13 cm3 molecule−1 s−1): (8.1−1.2+1.5) exp{−(1516±53)/T} for CHF2Cl (HCFC-22); (10.3−1.5+1.8) exp{−(1588±52)/T} for CH2FCF3 (HFC-134a); (11.3−1.6+2.1) exp{−(918±52)/T} for CHCl2CF2Cl (HCFC-122); (9.2−2.0+2.5) exp{−(1281±85)/T} for CHFClCF2Cl (HCFC-123a).

Product formation from the gas-phase reactions of hydroxyl radicals and ozone with .beta.-phellandrene

4-Isopropyl-2-cyclohexen-1-one was identified as a product of the gas-phase reactions of β-phellandrene with OH radicals (in the presence of NO x ) and with ozone, and formation yields of 0.29±0.07 and 0.29±0.06, respectively, were determined. Sampling several 500-L volumes from the reaction chamber onto polyurethane foam solid adsorbent, followed by solvent extraction and HPLC cleanup, gave sufficient product for identification by 1 H NMR

Rate constants for reactions of OH radicals with some Br-containing haloalkanes

Rate constants have been measured for the gas-phase reactions of hydroxyl radical with two halons and three of their proposed substitutes and also with CHClBr-CF3 using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units are 10−13 cm3 molecule−1 s−1): (9.3−0.9+1.0) exp{−(1326±33)/T} for CHF2Br; (7.2−0.6+0.7) exp{−(1111±32)/T} for CHFBrCF3; (8.5−0.8+0.9) exp{−(1113±35)/T} for CH2BrCF3; (12.8−1.2+1.5) exp{−(995±38)/T} for CHClBrCF3. The rate constants at 298 K have been estimated to be <2×10−17 cm3 molecule−1 s−1 for CF3Br and CF2Br—CF2Br. The atmospheric lifetimes due to hydroxyl attack have been estimated to be 5.5, 3.3, 2.8, and 1.2 years for CHF2Br, CHFBr—CF3, CH2Br—CF3 and CHClBr—CF3, respectively.

Rate coefficients for the gas-phase reactions of hydroxyl radicals with furan, 2-methylfuran, 2-ethylfuran and 2,5-dimethylfuran at 300 ± 2 K

Abstract Rate coefficients have been determined for the gas-phase reaction of hydroxyl (OH) radicals with the cyclic ethers furan, 2-methylfuran, 2-ethylfuran and 2,5-dimethylfuran at 300 ± 2 K in 760 Torr of synthetic air using a relative kinetic technique. The rate constants obtained using propene and trans-2-butene as reference compounds are (in units of 10−11 cm3 molecule−1 s−1): furan, 4.19 ± 0.21; 2-methylfuran, 6.19 ± 0.30; 2-ethylfuran, 10.77 ± 2.11; 2,5-dimethylfuran, 13.21 ± 0.92. With the exception of furan, this study represents the first determination of the rate coefficients for these cyclic ethers. The relevance of the rate coefficients for the atmospheric chemistry of furan and its derivatives is briefly discussed.

Rate constants for the gas-phase reactions of hydroxyl radicals with tetramethyllead and tetraethyllead

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRate constants for the gas-phase reactions of hydroxyl radicals with tetramethyllead and tetraethylleadOle John Nielsen, Denis J. O'Farrell, Jack J. Treacy, and Howard W. SidebottomCite this: Environ. Sci. Technol. 1991, 25, 6, 1098–1103Publication Date (Print):June 1, 1991Publication History Published online1 May 2002Published inissue 1 June 1991https://doi.org/10.1021/es00018a013RIGHTS & PERMISSIONSArticle Views62Altmetric-Citations8LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (744 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: Flash Photolysis Resonance Fluorescence Investigation of the Gas‐Phase Reactions of Hydroxyl Radicals with Cyclic Ethers

ChemInformVolume 21, Issue 25 Preparative Organic Chemistry ChemInform Abstract: Flash Photolysis Resonance Fluorescence Investigation of the Gas-Phase Reactions of Hydroxyl Radicals with Cyclic Ethers P. DAGAUT, P. DAGAUT Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this authorR. LIU, R. LIU Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this authorT. J. WALLINGTON, T. J. WALLINGTON Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this authorM. J. KURYLO, M. J. KURYLO Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this author P. DAGAUT, P. DAGAUT Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this authorR. LIU, R. LIU Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this authorT. J. WALLINGTON, T. J. WALLINGTON Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this authorM. J. KURYLO, M. J. KURYLO Chem. Sci. Technol. Lab., Natl. Inst. Stand. Technol., Gaithersburg, MD 20899, USASearch for more papers by this author First published: June 19, 1990 https://doi.org/10.1002/chin.199025084Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume21, Issue25June 19, 1990 RelatedInformation

Flash photolysis resonance fluorescence investigation of the gas-phase reactions of hydroxyl radicals with cyclic ethers

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFlash photolysis resonance fluorescence investigation of the gas-phase reactions of hydroxyl radicals with cyclic ethersPhilippe. Dagaut, Renzhang. Liu, Timothy J. Wallington, and Michael J. KuryloCite this: J. Phys. Chem. 1990, 94, 5, 1881–1883Publication Date (Print):March 1, 1990Publication History Published online1 May 2002Published inissue 1 March 1990https://doi.org/10.1021/j100368a030RIGHTS & PERMISSIONSArticle Views154Altmetric-Citations29LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (360 KB) Get e-Alerts

Kinetic measurements of the gas-phase reactions of hydroxyl radicals with hydroxy ethers, hydroxy ketones, and keto ethers

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetic measurements of the gas-phase reactions of hydroxyl radicals with hydroxy ethers, hydroxy ketones, and keto ethersPhilippe Dagaut, Renzhang Liu, Timothy J. Wallington, and Michael J. KuryloCite this: J. Phys. Chem. 1989, 93, 23, 7838–7840Publication Date (Print):November 1, 1989Publication History Published online1 May 2002Published inissue 1 November 1989https://doi.org/10.1021/j100360a022RIGHTS & PERMISSIONSArticle Views190Altmetric-Citations47LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (364 KB) Get e-Alerts

Pulse radiolysis study of the gas-phase reaction of hydroxyl radicals with vinyl chloride at 1 atm and over the temperature range 313-1173 K

Pulse radiolysis study of the gas-phase reaction of hydroxyl radicals with vinyl chloride at 1 atm and over the temperature range 313-1173 K

The gas-phase reactions of hydroxyl radicals with several unsaturated hydrocarbons at atmosphere pressure

The principle and technique of the High Temperature Gas Phase Pulse Radiolysis is described. The experimental results of the gas phase reactions of hydroxyl radicals with acetylene, ethylene, vinylchloride, propylene, 1-butene, allene and 1, 3-butadiene at 1 atm and from 313 to 1200 K are given and discussed briefly.

A kinetic investigation of the gas-phase reactions of hydroxyl radicals with cyclic ketones and diones: mechanistic insights

Reactions des radicaux hydroxyles avec la cyclobutanone, la cyclopentanone, la cyclohexanone, la butanedione-2,3, la pentanedione-2,4, et l'hexanedione-2,5