Theoretical study on the insertion reaction of CH(X2) into the oh bond in n-C4H9OH

Nguyen Trong Nghia; Duc-Trung Nguyen; Pham Van Tien; Nguyen Thi Minh Hue

doi:10.15625/2525-2518/16725

Author affiliations

Authors

Nguyen Trong Nghia School of Chemical Engineering, Hanoi of Science and Technology, 1 Dai Co Viet road, Hai Ba Trung, Ha Noi, Viet Nam
Duc-Trung Nguyen School of Chemical Engineering, Hanoi of Science and Technology, 1 Dai Co Viet road, Hai Ba Trung, Ha Noi, Viet Nam
Pham Van Tien School of Chemical Engineering, Hanoi of Science and Technology, 1 Dai Co Viet road, Hai Ba Trung, Ha Noi, Viet Nam
Nguyen Thi Minh Hue Faculty of Chemistry and Center for Computational Science, Hanoi National University of Education, 136 Xuan Thuy Street, Cau Giay, Ha Noi, Viet Nam

DOI:

https://doi.org/10.15625/2525-2518/16725

Keywords:

Reaction mechanism, methylidyne radical (CH), n-buthanol (n-C4H9OH), PES

Abstract

CH radicals play an important role in the combustion of hydrocarbon. The insertion mechanism of a CH radical into the O-H bond of n-C₄H₉OH is investigated theoretically by a detailed potential energy surface calculation at the BHandHLYP/6-311++G(3df,2p) and CCSD(T)/6-311++G(d,p) (single-point) levels. Our results show that the CH radical attacks into the oxygen atom in n-C₄H₉OH to form a prereaction complex (COMP) to be followed by an insertion of the CH radical into the O-H bond of the n-C₄H₉OH molecule to form the low-lying intermediate IS1 (CH₂OCH₂CH₂CH₂CH₃). This intermediate can isomerize to form IS2 (CH₃OCH₂CHCH₂CH₃), IS3 (CH₃CH₂CH₂CH₂CH₂O), and IS4 (CH₃CH₂CH₂CH₂CHOH). These intermediates can decompose to yield 9 products (PR1-PR9) in which major ones are PR1 (CH₂CH₂CH₂CH₃+ CH₂O), PR2 (CH₂CHCH₂CH₃ + CH₃O) and PR3 (CH₂CHCH₂OCH₃ + CH₃).

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References

Walsh K. T., Long M. B., Tanoff M. A., and Smooke M. D. - Experimental and Computational Study Of CH, CH*, And OH* in an Axisymmmetric Laminar Diffusion Flame, Twenty-Seventh Symposium (International) on Combustion/The Combustion Institute, 1998, pp. 615-623. DOI: https://doi.org/10.1016/S0082-0784(98)80453-0

Goulay F., Trevitt A. J., Savee J. D., Bouwman J., Osborn D. L., Taatjes C. A., Wilson K. R., and Leone S. R. - Product Detection of the CH Radical Reaction with Acetaldehyd, J. Phys. Chem. A 116 (2012) 6091-6106. DOI: https://doi.org/10.1021/jp2113126

Daugey N., Caubet P., Retail B., Costes M., Bergeat A., and Dorthe G. - Kinetic measurements on methylidyne radical reactions with several hydrocarbons at low temperatures, Phys. Chem. Chem. Phys. 7 (2005) 2921-2927. DOI: https://doi.org/10.1039/b506096f

Goulay F., Trevitt A. J., Meloni G., Selby T. M., Osborn D. L., Taatjes C. A., Vereecken L., and Leone S. R. - Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons, J. Am. Chem. Soc. 131 (2009) 993-1005. DOI: https://doi.org/10.1021/ja804200v

Hickson K. M., Caubet P., Loison J. C. - Unusual Low-Temperature Reactivity of Water: The CH + H2O Reaction as a Source of Interstellar Formaldehyde, J. Phys. Chem. Lett. 4 (2013) 2843-2846. DOI: https://doi.org/10.1021/jz401425f

Blitz M. A., Talbi D., Seakins P. W., Smith I. W. M. - Rate Constants and Branching Ratios for the Reaction of CH Radicals with NH3: A Combined Experimental and Theoretical Study, J. Phys. Chem. A 116 (2012) 5877-5885. DOI: https://doi.org/10.1021/jp209383t

Johnson D. G., Blitz M. A. and Seakins P. W. - The reaction of methylidene (CH) with methanol isotopomers, Phys. Chem. Chem. Phys. 2 (2000) 2549-2553. DOI: https://doi.org/10.1039/b001380n

Zhang X. B., Liu J. J., Li Z. S., Liu J. Y., and Sun C. C. - Theoretical Study on the Mechanism of the CH + CH3OH, J. Phys. Chem. A 106 (2002), 3814-3818. DOI: https://doi.org/10.1021/jp014602w

Marshall E. - Gasoline: the unclean fuel, Science 246 (1989) 199-201. DOI: https://doi.org/10.1126/science.246.4927.199

Katsikadakos D., Zhou C. W., Simmie J. M., Curran H. J., Hunt P. A., Hardalupas Y., Taylor A. M. K. P. - Rate constants of hydrogen abstraction by methyl radical from n-butanol and a comparison of CanTherm, MultiWell and Variflex, Proc. Combust. Inst. 34 (2013) 483-491. DOI: https://doi.org/10.1016/j.proci.2012.06.015

Becke A. D. - Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys. 98 (1993) 5648. DOI: https://doi.org/10.1063/1.464913

Becke A. D. - A new mixing of Hartree-Fock and local density-functional theories, J. Chem. Phys. 98 (1993) 1372-77. DOI: https://doi.org/10.1063/1.464304

Raghavachari K., Binkley J. S., Seeger R., and Pople J. A. - Self-Consistent Molecular Orbital Methods. 20. Basis set for correlated wave-functions, J. Chem. Phys. 72 (1980) 650-54. DOI: https://doi.org/10.1063/1.438955

Purvis III G. D., Bartlett R. J. - A full coupled-cluster singles and doubles model: The inclusion of disconnected triples, J. Chem. Phys. 76 (1982) 1910-1918. DOI: https://doi.org/10.1063/1.443164

Frisch M. J., Trucks G. W., Schlegel H. B., et al. - Gaussian 09, Gaussian, Inc., Wallingford CT, 2009.

Huber K. P., Herzberg G. - Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules, Van Nostrand Reinhold Co., 1979. DOI: https://doi.org/10.1007/978-1-4757-0961-2

Rosi M., Skouteris D., Balucani N., Nappi C., Lago N. F., Pacifici L., Falcinelli S., and Stranges D. - An Experimental and Theoretical Investigation of 1-Butanol Pyrolysis, Front. Chem. 7 (2019) 32601-32614. DOI: https://doi.org/10.3389/fchem.2019.00326