Theoretical and Experimental Chemistry

, Volume 22, Issue 6, pp 650–656 | Cite as

Photocatalysis by titanium complexes of the reaction of ClO4, ions with alcohol molecules

  • S. Ya. Kuchmii
  • A. V. Korzhak
  • A. I. Kryukov
Article
  • 44 Downloads

Abstract

In the photolysis of perchloric acid solutions of titanium(IV) with additions of ethanol, the formation of titanium(III) compounds was detected. Irradiated solutions ([HClO4]=0.8 M) at 77‡K are characterized by an anisotropic ESR signal with parameters g1=1.994, g1=1.904, which correspond to pseudo-octahedral aqua-complexes of titanium(III). With the passage of time, the signal intensity of the titanium(III) compounds decreases, which is explained by their oxidation by ClO4 ions. During prolonged photolysis of titanium(IV) compounds in 7 M HClO4 with an addition of ethanol, a multicomponent signal of the paramagnetic chlorine oxide ClO2 with parameters gxx=2,004, axx(37Cl)=6.0. mTl axx(35Cl)=7,30 mTl, is recorded instead of the signal of titanium(III) compounds. Evidently ClO2 is formed as a result of a rapid dark reaction between compounds of trivalent titanium (products of the photochemical step) and chlorate ions, which are accumulated in the solution as a result of successive photochemical and dark redox conversions of the titanium compounds, perchlorate ions, arid free radicals from the alcohol molecules. The formation of free radicals in the system was established by the ESR method after irradiation of frozen solutions.

Keywords

Titanium Photolysis Photocatalysis HClO4 Alcohol Molecule 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Literature cited

  1. 1.
    A. W. Adamson and P. D. Fleischauer, eds., Concepts of Inorganic Photochemistry, Wiley Intersci., New York (1975).Google Scholar
  2. 2.
    V. M. Latimer, Oxidation States of the Elements and Their Potentials in Aqueous Solutions [Russian translation], Izd. Inostr. Lit., Moscow (1954).Google Scholar
  3. 3.
    V. S. Korol'kov and A. K. Potapovich, “Analysis of the form of the ESR signal from samples containing randomly distributed paramagnetic centers,” Opt. Spektrosk., 16, No. 3, 461–466 (1964).Google Scholar
  4. 4.
    A. V. Korzhak, S. Ya. Kuchmii, and A. I. Kryukov, “Photocatalytic production of molecular hydrogen under the action of light on hydrochloric acid solutions of titanium tetrachloride with additions of ethanol,” Teor. Eksp. Khim., 20, No. 5, 570–578 (1984).Google Scholar
  5. 5.
    S. Ya. Kuchmii, A. V. Korzhak, and A. I. Kryukov, “Spectroscopic study of the state of titanium(III) ions in aqueous alcohol solutions,” ibid., 19, No. 5, 590–594 (1983).Google Scholar
  6. 6.
    P. J. Premovic and P. R. West, “Electron spin resonance studies on Ti(H2O6)3+ in frozen aqueous solutions of titanium(III) chloride, bromide, iodide, and sulfate,” Can. J. Chem., 53, No. 11, 1630–1634 (1975).Google Scholar
  7. 7.
    P. W. Atkins, J. A. Brivati, N. Keen, et al., “Oxides and oxy-ions of the nonmetals. 3. Oxy-radicals of chlorine,” J. Chem. Soc., No. 12, 4785–4793 (1962).Google Scholar
  8. 8.
    E. T. Denisov, Rate Constants of Homolytic Liquid-Phase Reactions [in Russian], Nauka, Moscow (1971).Google Scholar
  9. 9.
    R. E. Huie and N. C. Peterson, “The photolysis of concentrated perchloric acid solutions”, J. Photochem., 21, No. 1, 31–34 (1983).Google Scholar
  10. 10.
    B. N. Shelimov, N. V. Fok, and V. V. Voevodskii, “Photolysis of solutions of ethanol at 77‡K,” Kinet. Katal., 5, No. 6, 1008–1013 (1964).Google Scholar
  11. 11.
    V. S. Chervonenko, V. A. Roginskii, and S. Ya. Pshezhetskii, “Photochemistry of free radicals. Radicals of alcohols and ethers,” Khim. Vys. Energ., 4, No. 5, 450–451 (1970).Google Scholar
  12. 12.
    S. Ya. Kuchmii and A. I. Kryukov, “Photochemical conversions of coordination compounds of titanium(IV) in alcohol matrices,” Teor. Eksp. Khim., 20, No. 4, 421–427 (1984).Google Scholar
  13. 13.
    Ya. G. Goroshchenko, The Chemistry of Titanium [in Russian], Nauk. Dumka, Kiev (1972).Google Scholar
  14. 14.
    B. N. Nabivanets and V. V. Lukachina, “Hydroxo-complexes of titanium,” Ukr. Khim. Zh., 30, No. 11, 1123–1128 (1964).Google Scholar
  15. 15.
    Yu. Ya. Bobyrenko, “Estimation of standard enthalpies of formation and isobaric potential; of sulfates and hydroxides of tetravalent titanium,” Zh. Neorg. Khim., 12, No. 7, 1771–1773 (1967).Google Scholar
  16. 16.
    V. Caglioti, L. Ciavatta, and A. Liberti, “Complexity of titanium(IV) fluoride solutions”, J. Inorg. Nucl. Chem., 15, No. 1/2, 115–124 (1960).Google Scholar
  17. 17.
    J. Beukenkamp and R. D. Herrington, “Ion exchange investigation of the nature of titanium(IV) in sulfuric acid and perchloric acid,” J. Am. Chem. Soc., 82, No. 12, 3025–3030 (1960).Google Scholar

Copyright information

© Plenum Publishing Corporation 1987

Authors and Affiliations

  • S. Ya. Kuchmii
    • 1
  • A. V. Korzhak
    • 1
  • A. I. Kryukov
    • 1
  1. 1.L. V. Pisarzhevskii Institute of Physical ChemistryAcademy of Sciences of the Ukrainian SSRKiev

Personalised recommendations