ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of isopropylthio radical with oxygen, nitrogen dioxide, and nitric oxide at 296 KGraham Black, Leonard E. Jusinski, and Roger PatrickCite this: J. Phys. Chem. 1988, 92, 5, 1134–1138Publication Date (Print):March 1, 1988Publication History Published online1 May 2002Published inissue 1 March 1988https://pubs.acs.org/doi/10.1021/j100316a026https://doi.org/10.1021/j100316a026research-articleACS PublicationsRequest reuse permissionsArticle Views26Altmetric-Citations3LEARN 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 InRedditEmail Other access options Get e-Alerts

AbstractPulsed laser photolysis of N2O5 near 290 nm coupled with fluorescence detection (calibrated by NO2 photolysis) showed that the O(3P) quantum yield is ≤0.1. A pulsed laser optoacoustic technique in a flow tube (ca. 6 torr of N2) was tested by photolysis of NO2 and then applied to N2O5. Nitric oxide was added to react with NO3 free radical and the resulting increase in the optoacoustic signal confirmed the presence of NO3 free radicals. Based on the relative optoacoustic signals observed for NO2 and N2O5, the quantum yield for NO3 production is 0.8 ± 0.2.

In order to characterize reactions as functions of temperature, pressure (molecular density) and the nature of the species that constitute that molecular density, master equation solutions are required. In this tutorial review, the application of the Multiwell suite of codes to some reactions of interest in atmospheric and combustion chemistry is discussed, with attention given to the details of the molecular and energy transfer values. Uncertainties in data and in structural and energetic molecular parameters combine to assure the need for optimization and collaborative processing of the entire data base when modeling practical systems.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTComputational study of the hydroperoxo + hydroperoxo and hydroperoxo-d + hydroperoxo-d reactionsRoger Patrick, John R. Barker, and David M. GoldenCite this: J. Phys. Chem. 1984, 88, 1, 128–136Publication Date (Print):January 1, 1984Publication History Published online1 May 2002Published inissue 1 January 1984https://pubs.acs.org/doi/10.1021/j150645a031https://doi.org/10.1021/j150645a031research-articleACS PublicationsRequest reuse permissionsArticle Views87Altmetric-Citations30LEARN 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 InRedditEmail Other access options Get e-Alerts

HS radicals were generated by photodissociation of H2S at 193 nm and their disappearance monitored by LIF. The three-body recombination of HS with NO has been studied over the temperature range 250–445 K using He, Ar, and N2 as diluent gases. The temperature dependences of the low-pressure, three-body rate coefficients are given by 10−(22.56±0.60)T−(3.28±0.27), 10−(23.27±0.50)T−(2.98±0.20), and 10−(24.43±0.94)T−(2.48±0.36) cm6 molecule−2 s−1 for He, Ar, and N2, respectively. A tentative value of (2.7±0.5)×10−11 cm3 molecule−1 s−1 for the high pressure limiting rate coefficient over the range 250–300 K is suggested on the basis of extrapolation. These kinetic data are evaluated in terms of unimolecular rate theory.

AbstractCalculations of low‐pressure limit, third‐order rate constants are presented for the association reactions A + O2 + N2 and A + OH + N2 (A = Li, Na, K) over the temperature range 200–2000 K and a comparison is made with the available experimental data.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetics of the reactions of amidogen radicals with ozone and molecular oxygenRoger Patrick and David M. GoldenCite this: J. Phys. Chem. 1984, 88, 3, 491–495Publication Date (Print):February 1, 1984Publication History Published online1 May 2002Published inissue 1 February 1984https://doi.org/10.1021/j150647a034RIGHTS & PERMISSIONSArticle Views154Altmetric-Citations42LEARN 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 (623 KB) Get e-Alerts

AbstractThe bond dissociation energies of tetramethyl germane, triethyl stibine, tetraethyl lead, and triethylphosphine were determined using the technique of very‐low‐pressure pyrolysis. Arguments are presented for log A ≥ 17.0. The respective dissociation energies ΔH298 are 83, 57, 54, and 68 (±2) kcal/mol. A consistent set of methyl bond energies to main group metals is determined from these and previous results, and is examined for trends. Bond energies for various radicals to tin are also derived.

Input data and results are presented for the calculation of a number of third‐order rate constants of atmospheric interest using Troe′s approximate method. A comparison with experimental data indicates that this approach provides a reliable method for predicting unknown rate constants and estimating temperature dependences. These calculations form the basis of the recommendations of the NASA review panel for third‐order rate constants to be used in atmospheric modeling.

The temperature dependence of the rate constant for the reaction HO2 + HO2 → H2O2 + O2 (2k1) has been determined using flash photolysis techniques, over the temperature range 298–510 K, in a nitrogen diluent at a total pressure of 700 Torr. The overall second order state constant is given by k1 = (4.14 ± 1.15) × 10−13 exp[(630 ± 115)/T] cm3 molecule−1 s−1, where the quoted errors refer to one standard deviation. This result is compared with previous findings and the negative activation energy is shown to be consistent with the observation that the rate constant is pressure dependent at 700 Torr.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetics studies of the hydrogen dioxide + hydrogen dioxide and deuterium dioxide + deuterium dioxide reactions at 298 KStanley P. Sander, Mari Peterson, Robert T. Watson, and Roger PatrickCite this: J. Phys. Chem. 1982, 86, 8, 1236–1240Publication Date (Print):April 1, 1982Publication History Published online1 May 2002Published inissue 1 April 1982https://pubs.acs.org/doi/10.1021/j100397a002https://doi.org/10.1021/j100397a002research-articleACS PublicationsRequest reuse permissionsArticle Views136Altmetric-Citations80LEARN 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 InRedditEmail Other access options Get e-Alerts

The rate of reaction of CH 3 H has been measured at 300 K over the pressure range 50–1000 Torr with Ar and SF 6 as diluent gases. Flash photolysis of azomethane/ethylene mixtures was employed, coupled with gas chromatographic analysis and numerical simulation of the product yields. The rate data were compared with a RRKM analysis, using a minimum density of state criterion for locating the activated complex. The limiting high pressure rate constant so obtained is 1.5 ± 0.7) × 10 −10 cm 3 molecule −1s −1. The RRKM model was found to give high temperature, high pressure rate constant for the dissociation of CH 4 which are significantly higher than those found experimentally.

The lifetime of naphthalene 1B3u was measured in the gas phase under Boltzmann conditions (argon pressures > 400 Torr) over the temperature range 368–460 K. The results were found to agree well with calculations based on an assumed energy-dependent decay constant derived from the analysis by Schlag et al. of the decay of single vibronic levels. The Boltzmann distribution over the vibronic levels of the excited state was calculated using densities of vibrational states obtained from a direct count procedure. The results support Schlag's contention that the energy dependence of the single vibronic level lifetimes in naphthalene is predominantly determined by the Franck-Condon factors; they also indicate that no additional mechanism is needed to explain the observed temperature effects.