• 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 LibguidePlumX LibguideSubmit an Item

    Statistics

    Display statistics

    Reaction rate constants of H-abstraction by OH from large ketones: Measurements and site-specific rate rules

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Type
    Article
    Authors
    Badra, Jihad cc
    Elwardani, Ahmed Elsaid cc
    Farooq, Aamir cc
    KAUST Department
    Chemical Kinetics & Laser Sensors Laboratory
    Clean Combustion Research Center
    Mechanical Engineering Program
    Physical Science and Engineering (PSE) Division
    Date
    2014
    Permanent link to this record
    http://hdl.handle.net/10754/563205
    
    Metadata
    Show full item record
    Abstract
    Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (CO) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (CO), and the prime is used to differentiate different neighboring environments of a methylene group):P1,CO = 7.38 × 10-14 exp(-274 K/T) + 9.17 × 10-12 exp(-2499 K/T) (285-1355 K)S10,CO = 1.20 × 10-11 exp(-2046 K/T) + 2.20 × 10-13 exp(160 K/T) (222-1464 K)S11,CO = 4.50 × 10-11 exp(-3000 K/T) + 8.50 × 10-15 exp(1440 K/T) (248-1302 K)S11′,CO = 3.80 × 10-11 exp(-2500 K/T) + 8.50 × 10-15 exp(1550 K/T) (263-1370 K)S 21,CO = 5.00 × 10-11 exp(-2500 K/T) + 4.00 × 10-13 exp(775 K/T) (297-1376 K) © 2014 the Partner Organisations.
    Sponsors
    We would like to acknowledge the funding support from Saudi Aramco under the FUELCOM program. We are also thankful for the financial support provided by the Clean Combustion Research Center (CCRC) and King Abdullah University of Science and Technology (KAUST).
    Publisher
    Royal Society of Chemistry (RSC)
    Journal
    Physical Chemistry Chemical Physics
    DOI
    10.1039/c4cp01253d
    PubMed ID
    24817270
    ae974a485f413a2113503eed53cd6c53
    10.1039/c4cp01253d
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Mechanical Engineering Program; Clean Combustion Research Center

    entitlement

    Related articles

    • High-temperature measurements of the reactions of OH with a series of ketones: acetone, 2-butanone, 3-pentanone, and 2-pentanone.
    • Authors: Lam KY, Davidson DF, Hanson RK
    • Issue date: 2012 Jun 14
    • Rate constants for OH with selected large alkanes: shock-tube measurements and an improved group scheme.
    • Authors: Sivaramakrishnan R, Michael JV
    • Issue date: 2009 Apr 30
    • Ab initio and kinetic study of the reaction of ketones with OH for T = 500-2000 K. Part I: hydrogen-abstraction from H3CC(O)CH(3-x)(CH3)x, x = 0 ↦ 2.
    • Authors: Zhou CW, Simmie JM, Curran HJ
    • Issue date: 2011 Jun 21
    • High-temperature measurements of the reactions of OH with small methyl esters: methyl formate, methyl acetate, methyl propanoate, and methyl butanoate.
    • Authors: Lam KY, Davidson DF, Hanson RK
    • Issue date: 2012 Dec 20
    • Site-specific rate constant measurements for primary and secondary H- and D-abstraction by OH radicals: propane and n-butane.
    • Authors: Badra J, Nasir EF, Farooq A
    • Issue date: 2014 Jul 3
    DSpace software copyright © 2002-2021  DuraSpace
    Quick Guide | Contact Us | Send Feedback
    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.