Gas-phase Reactions Of Hydroxyl Radicals Research Articles

Gas-phase reactions of hydroxyl radicals with the fuel additives methyl tert-butyl ether and tert-butyl alcohol over the temperature range 240-440 K

Gas-phase reactions of hydroxyl radicals with the fuel additives methyl tert-butyl ether and tert-butyl alcohol over the temperature range 240-440 K

Kinetic isotope effects in the gas-phase reaction of hydroxyl radicals with ethylene in the temperature range 343-1173 K and 1-atm pressure

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetic isotope effects in the gas-phase reaction of hydroxyl radicals with ethylene in the temperature range 343-1173 K and 1-atm pressureAndong Liu, William A. Mulac, and Charles D. JonahCite this: J. Phys. Chem. 1988, 92, 13, 3828–3833Publication Date (Print):June 1, 1988Publication History Published online1 May 2002Published inissue 1 June 1988https://doi.org/10.1021/j100324a029RIGHTS & PERMISSIONSArticle Views118Altmetric-Citations36LEARN 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 (1 MB) Get e-Alerts

Comment on "Flash photolysis resonance fluorescence investigation of the gas-phase reactions of hydroxyl radicals with a series of aliphatic ketones over the temperature range 240-440 K"

ADVERTISEMENT RETURN TO ISSUEPREVArticleComment on "Flash photolysis resonance fluorescence investigation of the gas-phase reactions of hydroxyl radicals with a series of aliphatic ketones over the temperature range 240-440 K"Roger Atkinson and Sara M. AschmannCite this: J. Phys. Chem. 1988, 92, 13, 4008Publication Date (Print):June 1, 1988Publication History Published online1 May 2002Published inissue 1 June 1988https://doi.org/10.1021/j100324a064RIGHTS & PERMISSIONSArticle Views77Altmetric-Citations21LEARN 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 (149 KB) Get e-Alerts

Rate constants for the gas-phase reactions of hydroxyl radicals with 1,3-butadiene and allene at 1 atm in argon and over the temperature range 305-1173 K

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRate constants for the gas-phase reactions of hydroxyl radicals with 1,3-butadiene and allene at 1 atm in argon and over the temperature range 305-1173 KAndong Liu, William A. Mulac, and Charles D. JonahCite this: J. Phys. Chem. 1988, 92, 1, 131–134Publication Date (Print):January 1, 1988Publication History Published online1 May 2002Published inissue 1 January 1988https://doi.org/10.1021/j100312a028RIGHTS & PERMISSIONSArticle Views201Altmetric-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 (2 MB) Get e-Alerts

Flash photolysis resonance fluorescence investigation of the gas-phase reactions of hydroxyl radicals with a series of aliphatic ketones over the temperature range 240-440 K

Absolute rate constants have been determined for the gas-phase reactions of OH radicals with a series of aliphatic ketones by the flash photolysis resonance fluorescence measurement technique. Experiments were performed over the temperature range 240-440 K at total pressures (using Ar diluent gas) between 25 and 50 Torr. The rate constant data for acetone (k/sub 1/), 2-butanone (k/sub 2/), and 3-pentanone (k/sub 3/) were used to derive the Arrhenius expressions k/sub 1/ = (1.7 +/- 0.4) x 10/sup -12/ exp(-(600 +/- 75)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/, k/sub 2/ = (2.3 +/- 1.1) x 10/sup -12/ exp(-170 +/- 120)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/, and k/sub 3/ = (2.8 +/- 0.3) x 10/sup -12/ exp(10 +/- 35)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/. At 296 K, the measured rate constants (in units of 10/sup -13/ cm/sup 3/ molecule/sup -1/ s/sup -1/) were k/sub 1/ = 2.16 +/- 0.16, k/sub 2/ = 11.5 +/- 1.0, and k/sub 3/ = 27.4 +/- 1.3. Room temperature rate constants for the reaction of OH radicals with a number of other 2-ketones were also determined. These were (in the above units) 3,3-dimethyl-2-butanone (12.1 +/- 0.5), 2-pentanone (40.0 +/- 2.9), 2-hexanone (66.4 +/- 5.6),more » 2-heptanone (86.7 +/- 8.4reverse arrow, 2-octanone (110 +/- 9), 2-nonanone (122 +/- 13), and 2-decanone (132 +/- 12). The error limits represent 2 standard deviations (from the least-squares analysis); the authors estimate that an additional 5% uncertainty should be added to account for possible systematic error in the measurements. These results are discussed in terms of reactivity trends for C-H bonds located in the ..cap alpha.., ..beta.., and ..gamma.. positions with respect to the carbonyl group.« less

Vapour-phase chemistry of arenes. Part 13. Reactivity and selectivity in the gas-phase reactions of hydroxyl radicals with monosubstituted benzenes at 563 K

The reactions of hydroxyl radicals with benzene derivatives C6H5Z (Z = H, Me, F, Cl, Br, I, CF3, or CN) have been studied in a flow reactor at 563 K in nitrogen, using the thermolysis of ButOOH as a source of ˙OH. Under these conditions there are two product-forming pathways. The major one involves hydrogen abstraction to give aryl radicals ZC6H4˙(II) as the first step; depending on Z, its displacement to form phenol may also occur. Relative rates for hydrogen abstraction were determined in competition experiments using side-chain hydrogen abstraction from added toluene as a reference. This resulted in the order (for Z =): 1.8(Me), 1.0(H), 0.47(F), 0.29(Cl), 0.34(CF3), 0.20(CN), consonant with the electrophilic nature of ˙OH. The site selectivity of hydrogen abstractions was determined by scavenging part of the aryl radicals (II) with iodine. A Hammett plot, using σ constants for meta and para positions, led to ρ–1.0. The features of hydrogen abstraction by ˙OH are discussed and compared with those for the analogous reaction of Cl. The formation of phenol was found to decrease in importance in the order F, Cl, Br, and I. This result is rationalized on a thermochemical kinetic basis.

Rate constants for the gas-phase reaction of hydroxyl radicals with biphenyl and the monochlorobiphenyls at 295 .+-. 1 K

Rate constants for the gas-phase reactions of OH radicals with biphenyl and the monochlorobiphenyls have been determined by using a relative rate technique in 1 atm of air at 295 +/- 1 K. The rate constants obtained, relative to a rate constant for the reaction of OH radicals with cyclohexane of (7.57 +/- 0.05) x 10/sup -/ cm/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/, were the following (in units of x10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/): biphenyl, 8.5 +/- 0.8; 2-chlorobiphenyl, 2.9 +/- 0.4; 3-chlorobiphenyl, 5.4 +/- 0.8; 4-chlorobiphenyl, 3.9 +/- 0.7. These rate constants lead to estimated atmospheric lifetimes due to reaction with the OH radical of approx.2.7, approx.8, approx.4, and approx.6 days for biphenyl and 2-, 3-, and 4-chlorobiphenyl, respectively, for a 24-h average OH radical concentration of 5 x 10/sup 5/ cm/sup -3/.

ChemInform Abstract: RATE CONSTANTS FOR THE GAS‐PHASE REACTIONS OF HYDROXYL RADICALS WITH A SERIES OF BI‐ AND TRICYCLOALKANES AT 299 .+‐. 2 K: EFFECTS OF RING STRAIN

Chemischer InformationsdienstVolume 14, Issue 23 Preparative Organic Chemistry ChemInform Abstract: RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF HYDROXYL RADICALS WITH A SERIES OF BI- AND TRICYCLOALKANES AT 299 .+-. 2 K: EFFECTS OF RING STRAIN R. ATKINSON, R. ATKINSONSearch for more papers by this authorS. M. ASCHMANN, S. M. ASCHMANNSearch for more papers by this authorW. P. L. CARTER, W. P. L. CARTERSearch for more papers by this author R. ATKINSON, R. ATKINSONSearch for more papers by this authorS. M. ASCHMANN, S. M. ASCHMANNSearch for more papers by this authorW. P. L. CARTER, W. P. L. CARTERSearch for more papers by this author First published: June 7, 1983 https://doi.org/10.1002/chin.198323113Read 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 onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume14, Issue23June 7, 1983 RelatedInformation

ChemInform Abstract: KINETICS OF THE GAS‐PHASE REACTIONS OF HYDROXYL RADICALS WITH ALKYL NITRATES AT 299 .+‐. 2 K

Chemischer InformationsdienstVolume 13, Issue 48 Preparative Organic Chemistry ChemInform Abstract: KINETICS OF THE GAS-PHASE REACTIONS OF HYDROXYL RADICALS WITH ALKYL NITRATES AT 299 .+-. 2 K R. ATKINSON, R. ATKINSONSearch for more papers by this authorS. M. ASCHMANN, S. M. ASCHMANNSearch for more papers by this authorW. P. L. CARTER, W. P. L. CARTERSearch for more papers by this authorA. M. WINER, A. M. WINERSearch for more papers by this author R. ATKINSON, R. ATKINSONSearch for more papers by this authorS. M. ASCHMANN, S. M. ASCHMANNSearch for more papers by this authorW. P. L. CARTER, W. P. L. CARTERSearch for more papers by this authorA. M. WINER, A. M. WINERSearch for more papers by this author First published: November 30, 1982 https://doi.org/10.1002/chin.198248116AboutPDF 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. Volume13, Issue48November 30, 1982 RelatedInformation

Gas-phase reactions of hydroxyl radicals with alkyl nitrite vapours in H2O2+ NO2+ CO mixtures

The yields of CO2 from the chain reaction in H2O2+ NO2+ CO + alkyl nitrite mixtures, in which OH is the chain carrier and alkyl nitrites induce a chain termination step, have been used to deduce rate constants (ks) for OH attack on alkyl nitrites (RONO) in the vapour phase at ambient temperatures. Values of ks/109 dm3 mol–1 s–1 as a function of R were determined as follows: 0.71 ± 0.12 (CH3), 1.15 ± 0.23 (C2H5), 1.56 ± 0.32 (n-C3H7), 3.41 ± 1.48 (n-C4H9), 3.89 ± 0.58 (sec-C4H9), 3.47 ± 0.52 (i-C4H9), 0.91 ± 0.15 (t-C4H9), all based on ks=(1.63 ± 0.16)× 109 dm3 mol–1 s–1 for OH + n-butane. The small increase in ks from R = CH3 to t-C4H9 is considered to support a recent postulate that both H-abstraction and NO-abstraction pathways are operative, at least for R = CH3.

Gas-phase reactions of hydroxyl radicals with aldehydes in flowing H2O2+ NO2+ CO mixtures

The chain reaction in gaseous H2O2+ NO2+ CO mixtures, previously used as a thermal source of OH radicals in static systems, has been adapted for use in a flow system operating at total pressures of 39.9 kPa and 298.2 K. The reaction mechanism is H2O2+ NO2→ OH + HNO3(1), OH + CO → CO2+ H (2), H + NO2→ OH + NO (3), OH + NO2(+M)→ HNO3(+M). (4), Addition of a substrate S reactive towards OH induces the competitive reaction OH + S → products. (S) From the variation in the yield of CO2(monitored by gas chromatography) as a function of [S] the rate constant ratio kS/k2 may be derived. It is shown that such ratios can be successfully measured for systems (in this case a series of aldehydes) which would be difficult to study in the corresponding static system.The aldehyde rate constants, kS, are expressed relative to kS(acetaldehyde), and taking kS(acetaldehyde)= 0.94 × 1010 dm3 mol–1 s–1 values of 10–10kS/dm3 mol–1 s–1 of 1.08 ± 0.14, 1.52 ± 0.19, 1.05 ± 0.12, 0.83 ± 0.10, 1.11 ± 0.12 and 0.51 ± 0.05 are obtained for, respectively, propionaldehyde, n-butyraldehyde, i-butyraldehyde, n-valeraldehyde, i-valeraldehyde and trimethylacetaldehyde.Comparison with other measurements is made and the variations in these values are discussed.