Reaction of sulfate and phosphate radicals with α,α,α-trifluorotoluene

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Janina A. Rosso, Patricia E. Allegretti, Daniel O. Mártire and Mónica C. Gonzalez


Abstract

The aqueous phase reactions of α,α,α-trifluorotoluene (TFT) with sulfate and phosphate radicals have been investigated by conventional flash-photolysis. The bimolecular rate constants obtained for the reactions of SO4˙–, H2PO4˙, HPO4˙– and PO4˙2– with TFT are (2 ± 1) × 107, (3.5 ± 0.5) × 107, (2.7 ± 0.5) × 106 and (9 ± 1) × 105M–1 s–1, respectively. The organic radicals produced from these reactions exhibit a common absorption peak at 290–300 nm. Additionally, the transients generated from sulfate radicals show a shoulder at 360–370 nm and those generated from phosphate radicals a less intense maximum at 400 nm. Based on the experimental results, the nature of the organic radicals is discussed. Additional information on the hydroxycyclohexadienyl radicals of TFT is obtained from independent experiments with hydrogen peroxide solutions containing TFT.


References

  1. (a) B. C. Faust, Environ. Sci. Technol., 1994, 28, 217 A and references cited therein; (b) L. Sigg, W. Stumm, J. Zobrist and F. Zürcher, Chimia, 1987, 41, 159 CAS; (c) R. E. Huie, in Advanced Series in Physical Chemistry, ed. J. R. Barker, World Scientific, New Jersey, 1995, vol. 3 Search PubMed.
  2. G. Merga, C. T. Aravindakumar, B. S. M. Rao, H. Mohan and J. P. Mittal, J. Chem. Soc., Faraday Trans., 1994, 90, 597 RSC and references therein.
  3. P. Haygarth, Scope Newsletter in Europe, 1997, 21, 1 Search PubMed.
  4. P. Maruthamuthu and P. Neta, J. Phys. Chem., 1978, 82, 710 CrossRef and references cited therein.
  5. (a) J. R. Huber and E. Hayon, J. Phys. Chem., 1968, 72, 3820 CrossRef CAS; (b) P. Neta, R. E. Huie and A. B. Ross, J. Phys. Chem. Ref. Data, 1988, 17, 1027 CAS.
  6. P. Maruthamuthu and H. Taniguchi, J. Phys. Chem., 1977, 81, 1944 CrossRef CAS.
  7. (a) L. Dogliotti and E. Hayon, J. Phys. Chem., 1972, 71, 2511; (b) E. Hayon, A. Treinin and J. Wilf, J. Am. Chem. Soc., 1972, 94, 47 CrossRef CAS; (c) M.-S. Tsao and W. K. Wilmarth, J. Phys. Chem., 1959, 63, 346 CrossRef CAS; (d) K. Sehested, J. Holcman, E. Bjerbakke and E. J. Hart, J. Phys. Chem., 1982, 86, 2066 CrossRef CAS.
  8. (a) S. S. Cencione, M. C. Gonzalez and D. O. Mártire, J. Chem. Soc., Faraday Trans., 1998, 94, 2933 RSC; (b) J. A. Rosso, F. J. Rodríguez Nieto, M. C. Gonzalez and D. O. Mártire, J. Photochem. Photobiol. A: Chemistry, 1998, 116, 21 CrossRef CAS.
  9. (a) W. J. McElroy and S. J. Waygood, J. Chem. Soc., Faraday Trans., 1990, 86, 2557 RSC; (b) S. C. Choure, M. M. M. Bamatraf, B. S. M. Rao, R. Das, H. Mohan and J. P. Mittal, J. Phys. Chem. A, 1997, 101, 9837 CrossRef CAS.
  10. R. L. Lussier, W. M. Risen and J. O. Edwards, J. Phys. Chem., 1970, 74, 4039 CrossRef.
  11. J. L. Faria and S. Steenken, J. Phys. Chem., 1992, 96, 10869 CrossRef CAS.
  12. G. L. Hug, Nat. Stand. Ref. Data Ser., (U.S. Nat. Bur. Stand)., 1981, 69 Search PubMed.
  13. P. Neta, V. Madhavan, H. Zemel and R. W. Fessenden, J. Am. Chem. Soc., 1977, 99, 163 CrossRef CAS.
  14. M. Charton, in Progress in Physical Chemistry, ed. R. W. Taft, Interscience, New York, 1987, vol. 16, p. 287 Search PubMed.
  15. (a) S. Steenken, in Free Radicals in Synthesis and Biology, NATO ASI Series C - 260, ed. F. Minisci, Kluwer Academic Publishers, Dordrecht, 1989, 220 Search PubMed; (b) G. Merga, B. S. M. Rao, H. Mohan and J. P. Mittal, J. Phys. Chem., 1994, 98, 9158 CrossRef CAS.
  16. C. von Sonntag and H. P. Schuchmann, Angew. Chem., Int. Ed. Engl., 1991, 30, 1229 CrossRef.
  17. H. Mohan, M. Mudaliar, C. T. Aravindakumar, B. S. Rao and J. P. Mittal, J. Chem. Soc., Perkin Trans. 2, 1991, 1387 RSC.
  18. N. Karpel Vel Leitner, B. Gombert, R. Ben Abdessalem and M. Doré, Chemosphere, 1996, 32, 893 CrossRef CAS.
  19. L. S. Villata, J. A. Rosso, M. C. Gonzalez and D. O. Mártire, J. Chem. Res. (S), 1997, 172 RSC.
  20. G. V. Buxton, C. L. Greenstock, W. P. Helman and A. B. Ross, J. Phys. Chem. Ref. Data, 1988, 17, 513 CAS.
  21. (a) E. J. Land and M. Ebert, Trans. Faraday Soc., 1967, 63, 1181 RSC; (b) P. B. Draper, M. A. Fox, E. Pelizetti and N. Serpone, J. Phys. Chem., 1989, 93, 1938 CrossRef CAS.
  22. M. K. Eberhardt, J. Phys. Chem., 1974, 78, 1795 CrossRef CAS.
  23. A. J. Swallow, in Progress in Reaction Kinetics, eds. K. R. Jennings and R. B. Cundall, Pergamon Press, Oxford, 1979, vol. 9 Search PubMed.
  24. H. Mohan and J. P. Mittal, J. Phys. Chem., 1995, 99, 6519 CrossRef CAS.
  25. H. Mohan and J. P. Mittal, J. Chem. Soc., Faraday Trans., 1995, 91, 2121 RSC.
  26. P. Neta, R. E. Huie and A. B. Ross, J. Phys. Chem. Ref. Data, 1990, 19, 413 CAS.
  27. R. Filler, in Trifluoromethyl Aromatic Compounds, Advances in Fluorine Chemistry, 1970, Series 6, eds. J. C. Tatlow, R. D. Peacock, H. H. Hyman and M. Stacey, Butterworth, London, 1970 and references therein Search PubMed.
  28. W. B. Whalley, J. Chem. Soc., 1949, 3016 RSC.
  29. J. E. Lefler, An Introduction to Free Radicals, John Wiley and Sons, New York, 1993, p. 121 Search PubMed.
  30. P. Y. Jiang, Y. Katsumura, R. Nagishi, M. Domae, K. Ishikawa and K. Ishigure, J. Chem. Soc., Faraday Trans., 1992, 88, 1653 RSC.
  31. (a) R. H. Schule and G. Buzzard, Int. J. Radiat. Phys. Chem., 1976, 8, 563 Search PubMed; (b) M. Jonsson, J. Lind, T. Reitberger, T. E. Eriksen and G. Merényi, J. Phys. Chem., 1993, 97, 8229 CrossRef CAS; (c) G. E. Adams, B. D. Michael and E. J. Land, Nature, 1966, 294.
  32. (a) P. M. Sommeling, P. Mulder, R. Louw, D. V. Avila, J. Lusztyk and K. U. Ingold, J. Phys. Chem., 1993, 97, 8361 CrossRef CAS; (b) Z. B. Alfasi, S. Maguet and P. Neta, J. Phys. Chem., 1993, 98, 8019.
  33. J. K. Kochi, in Free Radicals, ed. J. K. Kochi, John Wiley, New York, 1993, vol. 1 Search PubMed.
  34. I. I. Creaser and J. O. Edwards, Top. Phosphorus Chem., 1972, 7, 379 Search PubMed.
  35. M. C. Gonzalez and D. O. Mártire, Int. J. Chem. Kinet., 1997, 29, 589 CrossRef CAS.
  36. Riedel de Häen (Germany), personal communication.
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