Study the Mechanism of Formation of Different Products of the Reaction Between Propargyl and Methyl Radicals
Main Article Content
Abstract
The mechanism of the reaction between propargyl radical (C3H3) and methyl radical (CH3) has been studied by the quantum-chemistry method using the M06-2X functional in conjunction with the aug-cc-pVTZ basis set. The potential energy surface (PES) for the C3H3 + CH3 system has been established. The calculated results indicate that the C3H3 + CH3 reaction has two main entrance channels leading to two stabilized intermediates, buta-1,2-diene and but-1-yne, which become the major intermediate products of the reaction system. From these two intermediate states, 19 different bimolecular products can be formed. For which, the C2H2 + C2H4 pair is the most thermodynamically favorable product.
Keywords
Reaction mechanism, propargyl radical, methyl radical, M06-2X, PES.
Article Details
References
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[14] T. V. Pham, Theoretical investigation on mechanism, thermochemistry, and kinetics of the gas-phase reaction of 2-propargyl radical with formaldehyde. Chem. Res. Chin. Uni. 35, (2019) 884–891. https://doi.org/10.1007/s40242-019-9054-0
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[3] G. Rotzoll, Molecular beam sampling mass‐spectrometric study of high‐temperature benzene oxidation. Int. J. Chem. Kinet. 17, (1985) 637-653. https://doi.org/10.1002/kin.550170609
[4] R. D. Smith, A. L. Johnson, Mass spectrometric study of the high temperature chemistry of benzene. Combust. Flame 51, (1983) 1-22. https://doi.org/10.1016/0010-2180(83)90079-2
[5] R. D. Smith, Formation of radicals and complex organic compounds by high-temperature pyrolysis: the pyrolysis of toluene. Combust. Flame 35, (1979) 179-190. https://doi.org/10.1016/0010-2180(79)90021-X
[6] R. D. Kern, C. H. Wu, J. N. Yong, K. M. Pamidimukkala, H. J. Singh, Correlation of benzene production with soot yield measurements as determined from fuel pyrolyses. Energy and Fuels. 2, (1988) 454-457. https://doi.org/10.1021/ef00010a011
[7] R. D. Kern, H. J. Singh, C. H. Wu, Thermal decomposition of 1,2 butadiene. Int. J. Chem. Kinet. 20, (1988) 731-747. https://doi.org/10.1002/kin.550200907
[8] C. E. Canosa-Mas, M. Ellis, M. Frey, R. J. Walsh, Studies of methylene chemistry by pulsed laser-induced decomposition of ketene. Part 2. Ketene in the presence of ethylene and acetylene. J. Chem. Soc., Faraday Trans. 81, (1985) 283-300. https://doi.org/10.1039/F29858100283
[9] W. Hack, M. Koch, H. G. Wagner, A. Wilms, Direct Determination of CH2(ã1A1) Removal Rates by C2H2 and C6H6. Ber. Bunsen-Ges. Phys. Chem. 92, (1988) 674-678. https://doi.org/10.1002/bbpc.198800170
[10] K. H. Homann, Ch. Wellmann, Kinetics and Mechanism of Hydrocarbon Formation in the System C2H2/O/H at Temperatures up to 1300 K. Ber. Bunsen-Ges Phys. Chem. 87, (1983) 609-616. https://doi.org/10.1002/bbpc.19830870716
[11] C. L. Morter, C. Domingo, S. K. Farhat, E. Cartwright, G. P. Glass, R. F. Curl, Rotationally resolved spectrum of the ν1 CH stretch of the propargyl radical (H2CCCH). Chem. Phys. Lett. 195, (1992) 316-321. https://doi.org/10.1016/0009-2614(92)85609-E
[12] W. Tsang, Thermal stability of intermediate sized acetylenic compounds and the heats of formation of propargyl radicals. Int. J. Chem. Kinet. 10, (1978) 687-711. https://doi.org/10.1002/kin.550100705
[13] I. R.Slagle, D. Gutman, Kinetics of the reaction of C3H3 with molecular oxygen from 293–900 K. Symposium (International) on Combustion, 21, (1988) 875-883. https://doi.org/10.1016/S0082-0784(88)80319-9
[14] T. V. Pham, Theoretical investigation on mechanism, thermochemistry, and kinetics of the gas-phase reaction of 2-propargyl radical with formaldehyde. Chem. Res. Chin. Uni. 35, (2019) 884–891. https://doi.org/10.1007/s40242-019-9054-0
[15] T. V. Pham, Hoang T. T. Trang, Combination reactions of propargyl radical with hydroxyl radical and the isomerization and dissociation of trans-propenal. J. Phys. Chem. A 124, (2020) 6144-6157. https://doi.org/10.1021/acs.jpca.0c05106
[16] J. D. DeSain, P. Y. Hung, R. I. Thompson, G. P. Glass, G. Scuseria, R. F. Curl, Kinetics of the reaction of propargyl radical with nitric oxide. J. Phys. Chem. A. 104, (2000) 3356 - 3363. https://doi.org/10.1021/jp994227w