• G. Ramírez-Galicia Universidad del Papalopan
  • M. Poisot Universidad del Papaloapan
  • H. Martínez-Pacheco Universidad del Papaloapan
Keywords: oxidative desulfurization, DFT, B3LYP, reaction mechanism, dibenzothiophene


The petrol and diesel combustion in motors produces sulfur and nitrogen oxides, they are the precursors of acid rain. Unfortunately, the Mexican fuel shows high-sulfur content; this concentration should be reduced to 50 ppmw or lower in order to achieve the international regulations. The oxidative desulfurization (OD) is an alternative to obtain it. In this work, we propose a theoretical reaction mechanism for the OD; this pathway is carried out through a combination of the molibdate anion, the hydrogen peroxide and several dibenzothiophenes by Density Functional Theory (DFT) using the B3LYP functional and the DGDZVP double zeta basis. The results show that the energy of the determinant step of the reaction is lower than the experimental amount obtained without catalyst. Finally, the environment provided by water molecules is important for recreasing the reaction mechanism energy


Anisimov, A.V., Fedorova, E.V., Lesnugin, A.Z., Senyavin, V.M., Aslanov, L.A., Rybakov, V.B. and Tarakanova, A.V. (2003). Vanadium peroxocomplexes as oxidation catalysis of sulfur organic compounds by hydrogen peroxide in bi-phase systems. Catalysis Today 78, 319-325.

Babich, I.V. and Moulija, J.A. (2003). Science and technology of novel processes for deep desulfurization of oil refinery: a review. Fuel 82, 607-631.

Becke, A.D. (1988). Density-functional Exchangeenergyapproximation with corect asymptotic behavior. Physical Review A 38, 3098-3100.

Becerra-Hernández. J.S., Gómez-Bernal, H., Navarro-Amador, J.F. and Cede˜no-Caero, L. (2006). Effect of the extraction process on the oxidative desulfuration of benzothiopenic compounds with supported V2O5 catalyst. Revista Mexicana de Ingeniería Química 5,301-310.

Campos-Martínez, J.M., Capel-Sánchez, M.C. and Fierro, J.L.G. (2004). Highly effcient deep desulfurization of fuels by chemical oxidation. Green Chemistry 6, 557-562.

Carpenter, J.E. and Weinhold F. (1988) Analysis of the geometry of the hydroxymethyl radical by the “different hybrids for different spins” natural bond orbital procedure. Journal of Molecular Structure (Theochem) 169, 41-62.

Cede˜no-Caero, L., Martínez-Abarca, E., Gómez-Díaz, M. and Pedraza-Archila, F. (2005) Oxidesulfurization of organosulfur compounds content in diesel. Part I. Copper supported catalyst. Revista Mexicana de Ingeniería Química 4, 241-252.

Djangkung, S., Murti, S., Yang, H., Choi, K., Kora, Y. and Mochida, I. (2003). Influence of nitrogen species on the hydrodesulfurization reactivity of a gas oil over sulfide catalysis of variable activity. Applied Catalysis A 252, 331-346.

Frisch, M.J, Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr., J.A., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S.,Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cui, Q., Baboul, A.G., Cliord, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C. and Pople J. A. (2004). Gaussian 03 revision C02. Gaussian, Inc., Wallingford CT

Foster, J.P. and Weinhold, F. (1980) Natural hybrid orbitals. Journal of the American Chemical Society 102, 7211-7218.

García-Gutierrez, J.L., Fuentes, G.A., Hernández-Terán, M.E., Murrieta, F., Navarrete, J. and Jiménez-Cruz, F. (2006). Ultra-deep oxidative desulfurization of diesel fuel with H2O2 catalyzed under mild conditions by polymolibdates supported on Al2O3. Applied Catalysis A-General 305, 15-20.

Galano, A., Rodríguez-Gattorno, G. and Torres-García, E. (2008). A combined theoreticalexperimental study on the acidity of WOx-ZrO2 systems. Physical Chemistry Chemical Physics 10, 4181-4188.

García-Gutiérrez, J.L., Fuentes, G.A., Hernández- Terán, M.E., García, P., Murrieta-Guevara, F. and Jiménez-Cruz, F. (2008). Ultra-deep oxidative desulfurization of diesel fuel by the Mo/Al2O3-H2O2 system: The effect of system parameters on catalytic activity. Applied Catalysis A-General 334, 366-373.

Gómez-Bernal, H. and Cedeño-Caero, L. (2006). Temperature effect on oxidation-extraction process of dibenzothiophenic compounds from diesel fuel. Revista Mexicana de Inginería Química 5, 269-277.

Hammond, G.S. (1955). A correlation of reaction rates. Journal of the American Chemical Society 77, 334-338.

Huela, V., Fajula, F. and Bousquet, J. (2001). Mild oxidation with H2O2 over Ti-containing molecular sieves. A very effcient method for removing aromatic sulfur compounds from fuels. Journal of Catalysis 198, 179-186.

Jang, Y.H. and Goddard II.,W.A. (2002). Mechanism of selective oxidation and ammoxidation of propene on bismuth molybdates from DFT calculations on model clusters. Journal of Physical Chemistry B 106, 5997-6013.

Lee, C.T, Yang, W.T. and Parr R.G. (1998). Developtment of the Colle-Salvetti correlationenergy formula into a functional of the electron density. Physical Review B 37, 785-789.

Navarro-Amador J.F., Gómez-Bernal, H. and Cedeño-Caero. L. (2006). Oxidesulfurization of organosulfur compounds prevailing in diesel and jet fuel, with supported V2O5 catalyst. Revista Mexicana de Ingeniería Química 5, 293-300.

Palomeque, J., Clacens, J.M. and Figueras, F. (2002). Oxidation of dibenzothiophene by hydrogen peroxide catalyzed by solid bases. Journal of Catalysis 211, 103-108.

Pettersson, L., Andersson, I., Taube, F., Toth, I., Hashimoto, M. and Howarth O.W. (2003). 17O NMR study of aqueous peroxoisopolymolybdate equilibria at lower peroxide/Mo ratios. Dalton Transactions 1, 146-152.

Pudar, S., Oxgaard, J., Chenoweth, K., van Duin, A.C.T. and Goddard III., W.A. (2007). Mechanism of selective oxidation on propene to acrolein on bismuth molybdates from quantum mechanical calculations. Journal of Physical Chemistry C 111, 16405-16415.

Ramírez-Verduzco, L.F., Murrieta-Guerrero, F., García-Gutiérrez, J.L., Saint Martin-Castañon, R., Martínez-Guerrero, M., Montiel-Pacheco, M. and Mata-Díaz, R. (2004). Desulfurization of middle distillates by oxidation and extraction process. Petroleum Science and Technology 22,129-139.

Reed, A.E. and Weinhold, F. (1983) Natural bond orbital analysis of near Hartree-Fock water dimer. Journal of Chemical Physics 78, 4066-4073.

Reed, A.E., Weinstock, R.B. and Weinhold, F. (1985) Natural population analysis. Journal of Chemical Physics 83, 735-746.

Reed, A.E., Curtis, L.A. and Weinhold, F. (1988) Intramolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chemical Reviews 88, 899-926.

Rodríguez-Gattorno, G., Galano, A. and Torres-García, E. (2009). Surface acid-basic properties of WOx-ZrO2 and catalytic effciency in oxidative desulfurization. Applied Catalysis BEnviromental 92, 1-8.

Scott, A.P. and Radom, L. (1996). Harmonic vibrational frequencies: An evaluation of Hartree-Fock, Moller-Plesset, Quadratic configuration integration, density functional theory, and semiempirical scale factors. Journal of Physical Chemistry 100, 16502-16513.

Shiraishi, Y., Naito, T. and Hirai, T. (2003). Vanadosilicate molecular sieve as a catalyst for oxidative desulfuration of light oil. Industrial and Engineering Chemistry Research 42, 6034-6039.

Srinivasan, B.R. (2004). Does an all-sulphur analogue of heptamolybdate exist? Journal of Chemical Sciences 116, 251-259.

Thorton, E. R. (1967). A simple theory for predicting the effects of substituents changes on transitionstate geometry. Journal of the American Chemical Society 89, 2915-2927.

Torres-García, E., Galano, A. and Rodríguez-Gattorno, G. (2001). Oxidative desulfurization (ODS) of organosulfur compounds by peroxo-metallate complexes of WOx-ZrO2: Thermochemical, structural, and reactivity indexes analysis. Journal of Catalysis 282, 201-208.

Vergara-Méndez, B.Z., García-Gómez, A.A., Poisot, M. and Ramírez-Galicia, G. (2011) Theoretical study of peroxo- and diperoxomolybdate formation as catalyst in the oxidative desulfurization of diesel. Topics in Catalysis 54, 527-534.

Yazu, K., Yamamoto, Y., Furuya, T., Miki, K. and Ukegawa, K. (2001). Oxidation of dibenzothiophenes in an organic biphasic system and its application to oxidative desulfurization of light oil. Energy and Fuels 15, 1535-1536.

Zanella, R., Cedeño-Caero, L., Viveros, O. and Mireles, E. (2007). Oxidesulfurization of organosulfur compounds with gold and silver catalysts supported on titania. Revista Mexicana de Ingeniería Química 6, 147-156.

Zhu, W.S., Li, H.M., Jiang, X., Yan, Y.S., Lu, J.D., He, L.N. and Xia, J.X. (2008). Commercially available molybdic compound-catalyzed ultradeep desulfurization of fuels in ionic liquid. Green Chemistry 10, 641-646.
How to Cite
Ramírez-Galicia, G., Poisot, M., & Martínez-Pacheco, H. (2020). THEORETICAL EVALUATION OF THE DEACTIVATION MECHANISM OF SUBSTITUTED DIBENZOTHIOPHENES. Revista Mexicana De Ingeniería Química, 11(3), 475-483. Retrieved from
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