Research on Chemical Intermediates

, Volume 30, Issue 6, pp 647–661 | Cite as

Ascorbate-induced oxidation of formate by peroxodisulfate: product yields, kinetics and mechanism

  • Maria A. Curtin
  • Irwin A. Taub
  • Kenneth Kustin
  • Narith Sao
  • Jeremy R. Duvall
  • Katharine I. Davies
  • Christopher J. Doona
  • Edward W. Ross


The slow reaction between peroxodisulfate and formate is significantly accelerated by ascorbate at room temperature. The products of this induced oxidation, CO2 and oxalate (C2O2–4), were analyzed by several methods and the kinetics of this reaction were measured. The overall mechanism involves free radical species. Ascorbate reacts with peroxodisulfate to initiate production of the sulfate radical ion (SO•–4), which reacts with formate to produce carbon dioxide radical ion (CO•–2) and sulfate. The carbon dioxide radical reacts with peroxodisulfate to form CO2 or self-combines to form oxalate. Competition occurring between these two processes determines the overall fate of the carbon dioxide radical species. As pH decreases, protonation of the carbon dioxide radical ion tends to favor production of CO2.



Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    USEPA, Fed. Reg. 63, 69389 (1998).Google Scholar
  2. 2.
    J. Katz (Ed.), in: Ozone and Chlorine Dioxide Technology for Disinfection of Drinking Water, p. 15. Noyes Data, Park Ridge, NJ (1980).Google Scholar
  3. 3.
    F. Minisci, A. Citterio and C. Giordano, Acc. Chem. Res. 16, 27 (1983).Google Scholar
  4. 4.
    J. W. Owens, Environ. Toxicol. Chem. 10, 1511 (1991).Google Scholar
  5. 5.
    S. Gilman and P. Bramhall, J. Electrochem. Soc. 125, 1924 (1978).Google Scholar
  6. 6.
    I. A. Taub and K. Kustin, US Patent No. 5,517,981 (1996).Google Scholar
  7. 7.
    D. A. House, Chem. Rev. 62, 185 (1962).Google Scholar
  8. 8.
    I. M. Kolthoff and I. K. Miller, J. Am. Chem. Soc. 73, 3055 (1951).Google Scholar
  9. 9.
    S. M. Walas, in: Perry’s Chemical Engineers’ Handbook, R. H. Perry, D. W. Green and J. O. Maloney (Eds), 7th edn, p. 7-1. McGraw-Hill, New York, NY (1997).Google Scholar
  10. 10.
    K. Kustin and E. W. Ross, J. Chem. Educ. 70, 455 (1993).Google Scholar
  11. 11.
    D. R. Lide (Ed.) CRC Handbook of Chemistry and Physics, 74th edn. CRC Press, Boca Raton, FL (1993).Google Scholar
  12. 12.
    G. P. Laroff, R. W. Fessenden and R. H. Schuler, J. Am. Chem. Soc. 94, 9062 (1972).PubMedGoogle Scholar
  13. 13.
    B. H. J. Bielski, Adv. Chem. 200, 81 (1982).Google Scholar
  14. 14.
    N. H. Williams and J. K. Yandell, Austr. J. Chem. 35, 1133 (1982).Google Scholar
  15. 15.
    H. B. Gray and W. R. Ellis, Jr., in: Bioinorganic Chemistry, I. Bertini, H. B. Gray, S. J. Lippard and J. S. Valentine (Eds), p. 334. University Science Books, Mill Valley, CA (1994).Google Scholar
  16. 16.
    D. M. Stanbury, Adv. Inorg. Chem. 33, 69 (1989).Google Scholar
  17. 17.
    H. Hermann, A. Reese and R. Zellner, J. Mol. Struct. 348, 183 (1995).CrossRefGoogle Scholar
  18. 18.
    S. K. Chandra, E. Gelerinter and E. S. Gould, Res. Chem. Intermed. 22, 43 (1996).Google Scholar
  19. 19.
    R. Flyunt, M. N. Schuchmann and C. von Sonntag, Chem. Eur. J. 7, 796 (2001).CrossRefGoogle Scholar
  20. 20.
    G. V. Buxton, G. A. Salmon and N. D. Wood, in: Proceedings of the 5th European Symposium of Physical Chemistry Behavior of Atmospheric Pollutants, G. Restelli and G. Angeletti (Eds), p. 245. Kluwer, Dordrecht (1990).Google Scholar
  21. 21.
    Q. G. Mulazzani, M. D'Angelantonio, M. Venturi, M. Z. Hoffman and M. A. Rodgers, J. Phys. Chem. 90, 5347 (1986).Google Scholar
  22. 22.
    P. H. Wine, Y. Tang, R. P. Thorn, J. R. Wells and D. D. Davis, J. Geophys. Res. D 94, 1085 (1989).Google Scholar

Copyright information

© 2004 VSP 2004

Authors and Affiliations

  • Maria A. Curtin
  • Irwin A. Taub
  • Kenneth Kustin
  • Narith Sao
  • Jeremy R. Duvall
  • Katharine I. Davies
  • Christopher J. Doona
  • Edward W. Ross

There are no affiliations available

Personalised recommendations