• Login
    View Item 
    •   Home
    • Research
    • Articles
    • View Item
    •   Home
    • Research
    • Articles
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Browse

    All of KAUSTCommunitiesIssue DateSubmit DateThis CollectionIssue DateSubmit Date

    My Account

    Login

    Quick Links

    Open Access PolicyORCID LibguideTheses and Dissertations LibguideSubmit an Item

    Statistics

    Display statistics

    A Systematic Theoretical Kinetics Analysis for the Waddington Mechanism in the Low-Temperature Oxidation of Butene and Butanol Isomers

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Thumbnail
    Name:
    acs.jpca.0c03515.pdf
    Size:
    1.867Mb
    Format:
    PDF
    Description:
    Published version
    Download
    Type
    Article
    Authors
    Li, Yang cc
    Zhao, Qian
    Zhang, Yingjia cc
    Huang, Zuohua
    Sarathy, Mani cc
    KAUST Department
    Chemical Engineering Program
    Clean Combustion Research Center
    Combustion and Pyrolysis Chemistry (CPC) Group
    Physical Science and Engineering (PSE) Division
    Date
    2020-06-23
    Online Publication Date
    2020-06-23
    Print Publication Date
    2020-07-09
    Submitted Date
    2020-04-20
    Permanent link to this record
    http://hdl.handle.net/10754/663905
    
    Metadata
    Show full item record
    Abstract
    The Waddington mechanism, or the Waddington-type reaction pathway, is crucial for low-temperature oxidation of both alkenes and alcohols. In this study, the Waddington mechanism in the oxidation chemistry of butene and butanol isomers was systematically investigated. Fundamental quantum chemical calculations were conducted for the rate constants and thermodynamic properties of the reactions and species in this mechanism. Calculations were performed using two different ab initio solvers: Gaussian 09 and Orca 4.0.0, and two different kinetic solvers: PAPR and MultiWell, comprehensively. Temperature- and pressure-dependent rate constants were performed based on the transition state theory, associated with the Rice Ramsperger Kassel Marcus and master equation theories. Temperature-dependent thermochemistry (enthalpies of formation, entropy, and heat capacity) of all major species was also conducted, based on the statistical thermodynamics. Of the two types of reaction, dissociation reactions were significantly faster than isomerization reactions, while the rate constants of both reactions converged toward higher temperatures. In comparison, between two ab initio solvers, the barrier height difference among all isomerization and dissociation reactions was about 2 and 0.5 kcal/mol, respectively, resulting in less than 50%, and a factor of 2−10 differences for the predicted rate coefficients of the two reaction types, respectively. Comparing the two kinetic solvers, the rate constants of the isomerization reactions showed less than a 32% difference, while the rate of one dissociation reaction (P1 ↔ WDT12) exhibited 1−2 orders of magnitude discrepancy. Compared with results from the literature, both reaction rate coefficients (R4 and R5 reaction systems) and species’ thermochemistry (all closed shell molecules and open shell radicals R4 and R5) showed good agreement with the corresponding values obtained from the literature. All calculated results can be directly used for the chemical kinetic model development of butene and butanol isomer oxidation.
    Citation
    Li, Y., Zhao, Q., Zhang, Y., Huang, Z., & Sarathy, S. M. (2020). A Systematic Theoretical Kinetics Analysis for the Waddington Mechanism in the Low-Temperature Oxidation of Butene and Butanol Isomers. The Journal of Physical Chemistry A. doi:10.1021/acs.jpca.0c03515
    Sponsors
    The authors gratefully acknowledge the KAUST Supercomputing Laboratory (KSL) for providing computing resources and technical support. Research at Xi’an Jiaotong University was supported by the National Natural Science Foundation of China (No. 91741115 and 51888103).
    Publisher
    American Chemical Society (ACS)
    Journal
    The Journal of Physical Chemistry A
    DOI
    10.1021/acs.jpca.0c03515
    Additional Links
    https://pubs.acs.org/doi/10.1021/acs.jpca.0c03515
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.jpca.0c03515
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Engineering Program; Clean Combustion Research Center

    entitlement

     
    DSpace software copyright © 2002-2023  DuraSpace
    Quick Guide | Contact Us | KAUST University Library
    Open Repository is a service hosted by 
    Atmire NV
     

    Export search results

    The export option will allow you to export the current search results of the entered query to a file. Different formats are available for download. To export the items, click on the button corresponding with the preferred download format.

    By default, clicking on the export buttons will result in a download of the allowed maximum amount of items. For anonymous users the allowed maximum amount is 50 search results.

    To select a subset of the search results, click "Selective Export" button and make a selection of the items you want to export. The amount of items that can be exported at once is similarly restricted as the full export.

    After making a selection, click one of the export format buttons. The amount of items that will be exported is indicated in the bubble next to export format.