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The kinetics and mechanism of oxidation of isopropanol with the hydrogen peroxide-vanadate ion-pyrazine-2-carboxylic acid system

  • Chemical Kinetics and Catalysis
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Abstract

The vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA) was found to effectively catalyze the oxidation of isopropanol to acetone with hydrogen peroxide. The electronic spectra of solutions and the kinetics of oxidation were studied. The conclusion was drawn that the rate-determining stage of the reaction was the decomposition of the vanadium(V) diperoxo complex with PCA, and the particle that induced the oxidation of isopropanol was the hydroxyl radical. Supposedly, the HO· radical detached a hydrogen atom from isopropanol, and the Me2 C· (OH) radical formed reacted with HOO· to produce acetone and hydrogen peroxide. The electronic spectra of solutions in isopropanol and acetonitrile and the dependences of the initial rates of isopropanol oxidation without a solvent and cyclohexane oxidation in acetonitrile on the initial concentration of hydrogen peroxide were compared. The conclusion was drawn that hydroxyl radicals appeared in the oxidation of alkanes in acetonitrile in the decomposition of the vanadium diperoxo complex rather than the monoperoxo derivative, as was suggested by us earlier.

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References

  1. G. B. Shul’pin, D. Attanasio, and L. Suber, J. Catal. 142, 147 (1993).

    Article  CAS  Google Scholar 

  2. G. B. Shul’pin and G. Süss-Fink, J. Chem. Soc., Perkin Trans. 2, p. 1459 (1995).

    Google Scholar 

  3. G. B. Shul’pin, R. S. Drago, and M. Gonzalez, Izv. Akad. Nauk, Ser. Khim., p. 2514 (1996) [Russ. Chem. Bull. 45, 2386 (1996)].

  4. G. B. Shul’pin, M. C. Guerreiro, and U. Schuchardt, Tetrahedron 52, 13051 (1996).

  5. M. C. Guerreiro, U. Schuchardt, and G. B. Shul’pin, Izv. Akad. Nauk, Ser. Khim., p. 780 (1997) [Russ. Chem. Bull. 46, 749 (1997)].

    Google Scholar 

  6. A. E. Shilov and G. B. Shul’pin, Chem. Rev. 97, 2879 (1997).

    Article  CAS  Google Scholar 

  7. G. V. Nizova, G. Süss-Fink, and G. B. Shul’pin, Tetrahedron 53, 3603 (1997).

    Article  CAS  Google Scholar 

  8. U. Schuchardt, M. C. Guerreiro, and G. B. Shul’pin, Izv. Akad. Nauk, Ser. Khim., p. 253 (1998) [Russ. Chem. Bull. 47, 247 (1998)].

    Google Scholar 

  9. G. Süss-Fink, G. V. Nizova, S. Stanislas, and G. B. Shul’pin, J. Mol. Catal. A: Chem. 130, 163 (1998).

    Article  Google Scholar 

  10. G. B. Shul’pin, Y. Ishii, S. Sakaguchi, and T. Iwahama, Izv. Akad. Nauk, Ser. Khim., p. 896 (1999) [Russ. Chem. Bull. 48, 887 (1999)].

    Google Scholar 

  11. G. Süss-Fink, S. Stanislas, G. B. Shul’pin, et al., J. Chem. Soc., Dalton Trans., p. 3169 (1999).

  12. A. Shilov and G. B. Shul’pin, Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes (Kluwer, Dordrecht, 2000).

    Google Scholar 

  13. Yu. N. Kozlov, G. V. Nizova, and G. B. Shul’pin, Zh. Fiz. Khim. 75, 865 (2001) [Russ. J. Phys. Chem. 75, 770 (2001)].

    CAS  Google Scholar 

  14. G. B. Shul’pin, Y. N. Kozlov, G. V. Nizova, et al., J. Chem. Soc., Perkin Trans. 2, p. 1351 (2001).

    Google Scholar 

  15. G. B. Shul’pin, J. Mol. Catal. A: Chem. 189, 39 (2002).

    Article  CAS  Google Scholar 

  16. M. H. C. de la Cruz, Y. N. Kozlov, E. R. Lachter, and G. B. Shul’pin, New J. Chem. 27, 634 (2003).

    Article  Google Scholar 

  17. G. B. Shul’pin, C. R. Acad. Sci., Ser. II: Chim. 6, 163 (2003).

    CAS  Google Scholar 

  18. Y. N. Kozlov, G. V. Nizova, and G. B. Shul’pin, J. Mol. Catal. A: Chem. 227, 247 (2005).

    Article  CAS  Google Scholar 

  19. R. Z. Khaliullin, A. T. Bell, and M. Head-Gordon, J. Phys. Chem. B 109, 17984 (2005).

    Google Scholar 

  20. A. Butler, M. J. Clague, and G. E. Meister, Chem. Rev. 94, 625 (1994).

    Article  CAS  Google Scholar 

  21. E. P. Talsi and K. V. Shalyaev, J. Mol. Catal. 92, 245 (1994).

    Article  CAS  Google Scholar 

  22. V. Conte, F. Di Furia, and G. Licini, Appl. Catal., A 157, 335 (1997).

    Article  CAS  Google Scholar 

  23. M. Bonchio, O. Bortolini, M. Carraro, et al., J. Inorg. Biochem. 80, 191 (2000).

    Article  CAS  Google Scholar 

  24. M. Bonchio, O. Bortolini, V. Conte, and S. Primon, J. Chem. Soc., Perkin Trans. 2, p. 763 (2001).

    Google Scholar 

  25. C. Li, P. Zheng, J. Li, et al., Angew. Chem., Int. Ed. Engl. 42, 5063 (2003).

    Article  CAS  Google Scholar 

  26. M. Sam, J. H. Hwang, G. Chanfreau, and M. M. Abu-Omar, Inorg. Chem. 43, 8447 (2004).

    Article  CAS  Google Scholar 

  27. Yu. N. Kozlov, L. Gonzalez-Cuervo, G. Süss-Fink, and G. B. Shul’pin, Zh. Fiz. Khim. 77, 652 (2003) [Russ. J. Phys. Chem. 77, 575 (2003)].

    CAS  Google Scholar 

  28. G. B. Shul’pin, G. V. Nizova, Y. N. Kozlov, et al., Adv. Synth. Catal. 346, 317 (2004).

    Article  CAS  Google Scholar 

  29. Farhataziz and A. B. Ross, Selected Specific Rates of Reactions of Transients from Water in Aqueous Solution. III. Hydroxyl Radical and Perhydroxyl Radical and Their Radical Ions (National Bureau of Standards, Washington, D.C., 1977), No. NSRDS-NBS 59.

    Google Scholar 

  30. E. S. Rudakov, L. K. Volkova, and V. P. Tret’yakov, Soobshch. Kinet. Katal. 16, 333 (1981).

    CAS  Google Scholar 

  31. T. V. Khar’kova, I. L. Arest-Yakubovich, and V. V. Lipes, Kinet. Katal. 30, 954 (1989).

    CAS  Google Scholar 

  32. L. M. Dorfman and G. E. Adams, Reactivity of the Hydroxyl Radical in Aqueous Solutions (National Bureau of Standards, Washington, D.C., 1973), NSRDS-NBS 46, p. 24.

    Google Scholar 

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Authors and Affiliations

  1. Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow, 117977, Russia

    V. B. Romakh, Yu. N. Kozlov & G. B. Shul’pin

  2. Institute of Chemistry, University of Neuchâtel, Neuchâtel, Switzerland

    V. B. Romakh & G. Süss-Fink

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  1. V. B. Romakh
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  2. Yu. N. Kozlov
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  3. G. Süss-Fink
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  4. G. B. Shul’pin
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Original Russian Text © V.B. Romakh, Yu.N. Kozlov, G. Suss-Fink, G.B. Shul’pin, 2007, published in Zhurnal Fizicheskoi Khimii, 2007, Vol. 81, No. 8, pp. 1389–1397.

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Romakh, V.B., Kozlov, Y.N., Süss-Fink, G. et al. The kinetics and mechanism of oxidation of isopropanol with the hydrogen peroxide-vanadate ion-pyrazine-2-carboxylic acid system. Russ. J. Phys. Chem. 81, 1221–1229 (2007). https://doi.org/10.1134/S0036024407080080

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  • DOI: https://doi.org/10.1134/S0036024407080080

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