Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Temperature-Dependent Kinetics of the Reaction of a Criegee Intermediate with Propionaldehyde: A Computational Investigation

  • Revathy Kaipara
    Revathy Kaipara
    Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India
  •  and 
  • B. Rajakumar*
    B. Rajakumar
    Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India
    *E-mail: [email protected]. Website: https://www.iitm.ac.in/info/fac/rajakumar and http://www.profrajakumar.com.
    More by B. Rajakumar
Cite this: J. Phys. Chem. A 2018, 122, 43, 8433–8445
Publication Date (Web):October 3, 2018
https://doi.org/10.1021/acs.jpca.8b06603
Copyright © 2018 American Chemical Society

    Article Views

    695

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    The temperature-dependent kinetics for the reaction of a Criegee intermediate (CH2OO) with propionaldehyde (CH3CH2CHO) was investigated using canonical variational transition state theory (CVT) in conjunction with the small curvature tunneling (SCT) method and the interpolated single point energy (ISPE) method at the CCSD(T)/AUG-cc-pVTZ//B3LYP/6-311G(d,p) level of theory. A rich chemistry was depicted by the title reaction, though the contributions of all of the reaction pathways were limited to atmospheric pressure conditions. The reaction of CH2OO with CH3CH2CHO was identified to proceed via the formation of secondary ozonide (SOZ), which then underwent a sequence of unimolecular isomerization and decomposition reactions to form a variety of products. The obtained rate coefficient for the formation of SOZ at 298 K was determined to be k = 2.44 × 10–12 cm3 molecule–1 s–1. At low temperature, collisionally stabilized SOZ was found to be the more stable product. Contrarily, at high temperature, SOZ degraded to HCHO, and CH3CH2COOH was found to be the major product. The complete degradation mechanism and thermochemistry for the reaction of CH2OO with CH3CH2CHO along with their rate coefficients over the temperature range of 200–1000 K are reported.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.8b06603.

    • Optimized geometries and vibrational frequencies of the reactants, pre- and postreactive complexes, transition states, and products, intrinsic reaction coordinate plots, variational effects plot of all transition states and rotamer scan of CH3CH2CHO, T1 diagnostic values and rate coefficients for the title reaction, variations in the bond length of all pathways (except pathway-1) with respect to the reaction coordinate, Arrhenius plots for all reaction channels (except reactions R1, R3, and R4), and branching ratios for the formation of SOZ and the products formed from reaction channels R3, R5, R7, R8, and R10) (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 15 publications.

    1. Haotian Jiang, Yue Liu, Chunlei Xiao, Xueming Yang, Wenrui Dong. Reaction Kinetics of CH2OO and syn-CH3CHOO Criegee Intermediates with Acetaldehyde. The Journal of Physical Chemistry A 2024, Article ASAP.
    2. Yong-Chao Zhao, Bo Long, Joseph S. Francisco. Quantitative Kinetics of the Reaction between CH2OO and H2O2 in the Atmosphere. The Journal of Physical Chemistry A 2022, 126 (38) , 6742-6750. https://doi.org/10.1021/acs.jpca.2c04408
    3. Manas Ranjan Dash, Balaganesh Muthiah, Subhashree Subhadarsini Mishra. Formation of alkoxymethyl hydroperoxides and alkyl formates from simplest Criegee intermediate (CH2OO) + ROH (R=CH3, CH3CH2, and (CH3)2CH) reaction systems. Theoretical Chemistry Accounts 2024, 143 (4) https://doi.org/10.1007/s00214-024-03104-1
    4. Amit Debnath, Balla Rajakumar. Experimental and theoretical study of Criegee intermediate (CH 2 OO) reactions with n -butyraldehyde and isobutyraldehyde: kinetics, implications and atmospheric fate. Physical Chemistry Chemical Physics 2024, 26 (8) , 6872-6884. https://doi.org/10.1039/D3CP05482A
    5. Siyue Liu, Yang Chen, Haotian Jiang, Jiayu Shi, Hongbin Ding, Xueming Yang, Wenrui Dong. Reaction between Criegee Intermediate CH 2 OO and Isobutyraldehyde: Kinetics and Atmospheric Implications. ChemistrySelect 2023, 8 (47) https://doi.org/10.1002/slct.202303129
    6. Siyue Liu, Yang Chen, Haotian Jiang, Jiayu Shi, Hongbin Ding, Xueming Yang, Wenrui Dong. Kinetics for the reaction of Criegee intermediate CH2OO with n-butyraldehyde and its atmospheric implications. Atmospheric Environment 2023, 311 , 120012. https://doi.org/10.1016/j.atmosenv.2023.120012
    7. Yu Xia, Bo Long, Ai Liu, Donald G. Truhlar. Reactions with criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere. Fundamental Research 2023, 564 https://doi.org/10.1016/j.fmre.2023.02.012
    8. Amit Debnath, Balla Rajakumar. Investigation of kinetics and mechanistic insights of the reaction of criegee intermediate (CH2OO) with methyl-ethyl ketone (MEK) under tropospherically relevant conditions. Chemosphere 2023, 312 , 137217. https://doi.org/10.1016/j.chemosphere.2022.137217
    9. Da-Peng Ding, Bo Long. Reaction between propionaldehyde and hydroxyperoxy radical in the atmosphere: A reaction route for the sink of propionaldehyde and the formation of formic acid. Atmospheric Environment 2022, 284 , 119202. https://doi.org/10.1016/j.atmosenv.2022.119202
    10. Weikang Xiao, Simei Sun, Suding Yan, Wenzhong Wu, Jingyu Sun. Theoretical study on the formation of Criegee intermediates from ozonolysis of pentenal: An example of trans-2-pentenal. Chemosphere 2022, 303 , 135142. https://doi.org/10.1016/j.chemosphere.2022.135142
    11. Keng Yoon Yeong, Liam Stephens, Irene Ling. Five-Membered Rings With Three Oxygen or Sulfur Atoms in 1,2,4-Positions. 2022, 146-181. https://doi.org/10.1016/B978-0-12-818655-8.00050-0
    12. Yiqiang Liu, Xiaohu Zhou, Yang Chen, Maodu Chen, Chunlei Xiao, Wenrui Dong, Xueming Yang. Temperature- and pressure-dependent rate coefficient measurement for the reaction of CH 2 OO with CH 3 CH 2 CHO. Physical Chemistry Chemical Physics 2020, 22 (44) , 25869-25875. https://doi.org/10.1039/D0CP04316H
    13. Parth Gupta, B. Rajakumar. Reaction kinetics of CH2OO with 1,3-butadiene: Mechanistic investigation with RRKM calculations. Chemical Physics Letters 2020, 742 , 137157. https://doi.org/10.1016/j.cplett.2020.137157
    14. Jie Cai, Yousong Lu, Weina Wang, Long Chen, Fengyi Liu, Wenliang Wang. Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO. Computational and Theoretical Chemistry 2019, 1170 , 112644. https://doi.org/10.1016/j.comptc.2019.112644
    15. Cuihong Sun, Baoen Xu, Liqiang Lv, Shaowen Zhang. Theoretical investigation on the reaction mechanism and kinetics of a Criegee intermediate with ethylene and acetylene. Physical Chemistry Chemical Physics 2019, 21 (30) , 16583-16590. https://doi.org/10.1039/C9CP02644D