Elementary bimolecular processes that involve the formation of a chemically activated intermediate are common. In a previous paper we described the information required to ensure that a kinetic model will extrapolate the rate constants involved over wide ranges of temperature and pressure. This approach is illustrated here for the system centered around the ethane intermediate. It is necessary and sufficient to specify the temperature and pressure dependence of three rate constants k(T,P) and the temperature dependence of two equilibrium constants K(T), viz.,

AbstractElementary bimolecular processes that involve formation of a chemically activated intermediate species are common. We address the general problem of modeling these processes and describe the necessary and sufficient information that must be specified to assure that a kinetics model will extrapolate the rate constants for those reactions over wide ranges of temperature and pressure. The approach is illustrated for the system centered around the HOCO intermediate. Here, specification of the temperature and pressure dependence of three rate constants, k(T,P) and the temperature dependence of two equilibrium constants, K(T), is necessary and sufficient, viz: equation image Rate constants are cast in the form of an analytical expression, suggested by Troe, and appropriate parameters are tabulated.

Chemischer InformationsdienstVolume 17, Issue 7 Preparative Organic Chemistry ChemInform Abstract: Mechanism of Decomposition of Nitroaromatics. Laser-Powered Homogeneous Pyrolysis of Substituted Nitrobenzenes (Nitro-, m-Dinitro-benzol, o-, p-Nitro- und 2,4-Dinitro-toluol). A. C. GONZALEZ, A. C. GONZALEZSearch for more papers by this authorC. W. LARSON, C. W. LARSONSearch for more papers by this authorD. F. MCMILLEN, D. F. MCMILLENSearch for more papers by this authorD. M. GOLDEN, D. M. GOLDENSearch for more papers by this author A. C. GONZALEZ, A. C. GONZALEZSearch for more papers by this authorC. W. LARSON, C. W. LARSONSearch for more papers by this authorD. F. MCMILLEN, D. F. MCMILLENSearch for more papers by this authorD. M. GOLDEN, D. M. GOLDENSearch for more papers by this author First published: February 18, 1986 https://doi.org/10.1002/chin.198607117AboutPDF 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. Volume17, Issue7February 18, 1986 RelatedInformation

The current status of quantitative understanding of reaction rate constant data for use in combustion modeling is discussed. It is pointed out that simple biomelecular and unimolecular reactions can be tabulated as functions of various physically meaningful parameters over wide ranges of temperature and pressure. Also discussed are the more complicated problems of complex surfaces and their manifestations. Major emphasis is placed on the underlying framework for critical evaluation of rate data. We point out that currently used values for2CH3→k+C2H5+H are incompatible with the reverse reaction and that the temperature dependence of the branching ratioDownload : Download full-size imagecan be understood in terms of an energy-dependent transition state for the NH channel.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMechanism of decomposition of nitroaromatics. Laser-powered homogeneous pyrolysis of substituted nitrobenzenesAlicia C. Gonzalez, C. William Larson, Donald F. McMillen, and David M. GoldenCite this: J. Phys. Chem. 1985, 89, 22, 4809–4814Publication Date (Print):October 1, 1985Publication History Published online1 May 2002Published inissue 1 October 1985https://doi.org/10.1021/j100268a030RIGHTS & PERMISSIONSArticle Views345Altmetric-Citations93LEARN 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

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.