Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory

Abstract

Abstract: The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C₆H₆,HC≡C-C≡N,C₆H₅C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.

Key words: quinoline, isoquinoline, coal, pyrolysis mechanism, density functional theory

摘要： The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C₆H₆,HC≡C-C≡N,C₆H₅C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.

关键词: quinoline, isoquinoline, coal, pyrolysis mechanism, density functional theory

LING Lixia, ZHANG Riguang, WANG Baojun, XIE Kechang. Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory[J]. , 2009, 17(5): 805-813.

凌丽霞, 章日光, 王宝俊, 谢克昌. Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory[J]. , 2009, 17(5): 805-813.

References

1 Tan, L.L., Li, C.Z., “Formation of NO_x and SO_x precursors during the pyrolysis of coal and biomass. Part . Effects of reactor configuration on the determined yields of HCN and NH 3 during pyrolysis”, Fuel, 79, 1883-1889 (2000).
2 Kelemen, S.R., Gorbaty, M.L., Kwiatek, P.J., Fletcher, T.H., Watt, M., Solum, M.S., Pugmire, R.J, “Nitrogen transformations in coal during pyrolysis”, Energ. Fuel, 12, 159-173 (1998).
3 Solomon, P.R., Colket, M.B., “Evolution of fuel nitrogen in coal devolatilization”, Fuel, 57, 749-755 (1978).
4 Mackie, J.C., Colket, M.B., Nelson, P.F., Esler, M., “Shock tube pyrolysis of pyrrole and kinetic modeling”, Int. J. Chem. Kinet., 23, 733-760 (1991).
5 Lifshitz, A., Tamburu, C., Suslensky, A., “Isomerization and decomposition of pyrrole at elevated temperatures. Studies with a single-pulse shock tube”, J. Phys. Chem., 93, 5802-5808 (1989).
6 Dubnikova, F., lifshitz, A., “Isomerization of pyrrole. Quantum chemical calculations and kinetic modeling”, J. Phys. Chem. A, 102, 10880-10888 (1998).
7 Zhai, L., Zhou, X.F., Liu, R.F., “A theoretical study of pyrolysis mechanisms of pyrrole”, J. Phys. Chem. A, 103, 3917-3922 (1999).
8 Martoprawiro, M., Bacskay, G.B., Mackie, J.C., “Ab initio quantum chemical and kinetic modeling study of the pyrolysis kinetics of pyrrole”, J. Phys. Chem. A, 103, 3923-3934 (1999).
9 Bacskay, G.B., Martoprawiro, M., Mackie, J.C., “The thermal decomposition of pyrrole:An ab initio quantum chemical study of the potential energy surface associated with the hydrogen cyanide plus propyne channel”, Chem. Phys. Lett., 300, 321-330 (1999).
10 Mackie, J.C., Colket, M.B, Nelson, P.F., “Shock tube pyrolysis of pyridine”, J. Phys. Chem., 94, 4099-4106 (1990).
11 Memon, H.U.R., Bartle, K.D., Taylor, J.M., Williams, A., “The shock tube pyrolysis of pyridine”, Int. J. Energ. Res., 24, 1141-1159 (2000).
12 Liu, R.F., Huang, T.T.S., Tittle, J., Xia, D.H., “A theoretical investigation of the decomposition mechanism of pyridyl radicals”, J. Phys. Chem. A, 104, 8368-8374 (2000).
13 Ninomiya, Y., Dong, Z.B., Suzuki, Y., Koketsu, J., “Theoretical study on the thermal decomposition of pyridine”, Fuel, 79, 449-457 (2000).
14 Laskin, A., Lifshitz, A., “Isomerization and decomposition of indole. Experimental results and kinetic modeling”, J. Phys. Chem. A, 101, 7787-7801 (1997).
15 Zhou, X.F., Liu, R.F., “A density functional theory study of the pyrolysis mechanisms of indole”, J. Mol. Struct. Theochem., 461/462, 569-579 (1999).
16 Patterson, J.M., Issidorides, C.H., Papadopoulos, E.P., Smith, Jr. W.T., “The thermal interconversion of quinoline and isoquinoline”, Tetrahedron. Lett., 15, 1247-1250 (1970).
17 Bruinsma, O.S.L., Tromp, P.J.J., De Sauvage Nolting, H.J.J., Moulijn, J.A., “Gas phase pyrolysis of coal-related aromatic compounds in a coiled tube flow reactor 2. Heterocyclic compounds, their benzo and dienzo derivatives”, Fuel, 67, 334-340 (1988).
18 Axworthy, A.E., Dayan, V.H., Martin, G.B., “Reactions of fuel-nitrogen compounds under conditions of inert pyrolysis”, Fuel, 57, 29-35 (1978).
19 Laskin, A., Lifshitz, A., “Thermal decomposition of quinoline and isoquinoline. The role of 1-indene imine radical”, J. Phys. Chem. A, 102, 928-946 (1998).
20 Winkler, J.K., Karow, W., Rademacher, P., “Gas phase pyrolysis of heterocyclic compounds (3) Flow pyrolysis and annulation reaction of some nitrogen heterocycles. A product oriented study”, ARKIVOC, 1 (4), 576-602 (2000).
21 Delley, B., “From molecules to solids with the Dmol 3 approach”, J. Chem. Phys., 113 (18), 7756-7764 (2000).
22 Perdew, J.P., Chevary, J.A., Vosko, S.H., Fiolhais, C., “Atoms, molecules, solids and surfaces:Application of the generalized gradient approximation for exchange and correlation”, Phys. Rev. B, 46 (11), 6671-6687 (1992).
23 Lide, D.R., Handbook of Chemistry and Physics, 82nd edition, CRC Press, New York, 9-40 (2001-2002).
24 Zhao, L.J., Ling, L.X., Zhang, R.G., Liu, X.F., Wang, B.J., “Theoretical study on pyrolysis mechanism of O-containing model compound anisole in coal”, J. Chem. Ind. Eng. (China), 59 (8), 2095-2102 (2008). (in Chinese)
25 Zhang, R.G., Huang, W., Wang, B.J., “Theoretical calculation for interaction of CO₂ with H and CH₃ in synthesis of acetic acid from CH₄ and CO₂ ”, Chin. J. Catal. (China), 28 (7), 641-645 (2007). (in Chinese)

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