Clays and Clay Minerals

, Volume 37, Issue 5, pp 479–486 | Cite as

Oxidation of 1,2- and 1,4-Dihydroxybenzene by Birnessite in Acidic Aqueous Suspension

  • M. B. McBride


The rate and extent of oxidation of dihydroxybenzenes (DHB) to quinones in acetate-buffered suspensions of synthetic birnessite were studied using Mn dissolution to monitor reaction progress. Concentration of free Mn2+ in the aqueous phase was continuously monitored by electron spin resonance, and ultraviolet-visible (UV-VIS) spectroscopy was utilized to quantify dihydroxybenzene and quinone concentrations. Although dissolution of the oxide and release of Mn2+ to solution generally accompanied phenol oxidation, a threshold oxidation level had to be exceeded before Mn2+ appeared in solution. Once this threshold was surpassed, the mole quantity of Mn2+ dissolved equaled the mole quantity of organic oxidized for 1,4-DHB, but exceeded the quantity of organic oxidized for 1,2-DHB. Thus, the latter phenol was more efficient in dissolving the oxide. Soluble phosphate suppressed Mn2+ release without influencing the degree of organic oxidation, suggesting that phosphate chemically interacted with reduced Mn to hinder its dissolution. UV spectra provided tentative evidence for the transitory existence of Mn3+-1,4-DHB complexes in the solution phase.

Infrared spectra of the birnessite after reaction with 1,4-DHB indicated some new features, which may have been a result of the reduction of surface Mn atoms to the 3+ oxidation state. These features were not present after reaction with 1,2-DHB, confirming that the latter phenol efficiently dissolved the oxide to release Mn2+. Although the initial Mn dissolution was very rapid and was attributed to a surface reaction, further slow Mn release accompanied by more complete oxidation of the phenols suggests a process limited by the rate of dissolution of the solid.

Key Words

Birnessite Dihydroxybenzene Electron spin resonance Manganese Oxidation Phenol Ultraviolet-visible spectroscopy 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Alcock, N. W., Tracy, V. M., and Waddington, T. C. (1976) Acetates and acetato-complexes. Part 2. Spectroscopic studies: J. Chem. Soc. Dalton Trans., 2243–2246.Google Scholar
  2. Cotton, F. A. and Wilkinson, G. (1980) Advanced Inorganic Chemistry, 4th ed. Wiley, New York, 741–744.Google Scholar
  3. Golden, D. C., Chen, C. C., and Dixon, J. B. (1987) Transformation of birnessite to buserite, todorokite, and manganite under mild hydrothermal treatment. Clays & Clay Minerals 35, 271–280.CrossRefGoogle Scholar
  4. Hayashi, S., Takenaka, T., and Gotoh, R. (1969) Infrared spectra of acetic acid adsorbed on alumina in carbon tetrachloride: Bull. Inst. Chem. Res. 47, 378.Google Scholar
  5. Jauregui, M. A. and Reisenauer, H. M. (1982) Dissolution of oxides of manganese and iron by root exudate components: Soil Sci. Soc. Amer. J. 46, 314–317.CrossRefGoogle Scholar
  6. Kung, K.-H. and McBride, M. B. (1988) Electron transfer processes between hydroquinone and hausmannite (Mn3O4): Clays & Clay Minerals 36, 297–302.CrossRefGoogle Scholar
  7. Lehmann, R. G., Cheng, H. H., and Harsh, J. B. (1987) Oxidation of phenolic acids by soil iron and manganese oxides: Soil Sci. Soc. Amer. J. 51, 352–356.CrossRefGoogle Scholar
  8. McBride, M. B. (1982) Electron spin resonance investigation of Mn2+ complexation in natural and synthetic organics: Soil Sci. Soc. Amer. J. 46, 1137–1143.CrossRefGoogle Scholar
  9. McBride, M. B. (1987) Adsorption and oxidation of phenolic compounds by iron and manganese oxides: Soil Sei. Soc. Amer. J. 51, 1466–1472.CrossRefGoogle Scholar
  10. McBride, M. B. (1989) Oxidation of dihydroxybenzenes in aerated aqueous suspensions of birnessite: Clays & Clay Minerals 37, 341–347.CrossRefGoogle Scholar
  11. McKenzie, R. M. (1970) The reaction of cobalt with manganese dioxide minerals: Aust. J. Soil Res. 8, 97–106.CrossRefGoogle Scholar
  12. Potter, R. M. and Rossman, G. R. (1979) The tetravalent manganese oxides: Identification, hydration, and structural relationships by infrared spectroscopy: Amer. Mineral. 64, 1199–1218.Google Scholar
  13. Stone, A. T. (1987) Reductive dissolution of manganese (III/IV) oxides by substituted phenols: Environ. Sci. Technol. 21, 979–988.CrossRefGoogle Scholar
  14. Stone, A. T. and Morgan, J. J. (1984a) Reduction and dissolution of manganese (III) and manganese (IV) oxides by organics. I. Reaction with hydroquinone: Environ. Sci. Technol. 18, 450–456.CrossRefGoogle Scholar
  15. Stone, A. T. and Morgan, J. J. (1984b) Reduction and dissolution of manganese (III) and manganese (IV) oxides by organics. 2. Survey of the reactivity of organics: Environ. Sci. Technol. 18, 617–624.CrossRefGoogle Scholar
  16. Traina, S. J. and Doner, H. E. (1985a) Copper-manganese (II) exchange on a chemically reduced birnessite: Soil Sci. Amer. J. 49, 307–313.CrossRefGoogle Scholar
  17. Traina, S. J. and Doner, H. E. (1985b) Heavy metal induced releases of manganese (II) from a hydrous manganese dioxide: Soil Sci. Soc. Amer. J. 49, 317–321.CrossRefGoogle Scholar
  18. van der Marel, H. W. and Beutelspacher, H. (1976) Atlas of Infrared Spectroscopy of Clay Minerals and their Admixtures: Elsevier, New York, 396 pp.Google Scholar

Copyright information

© The Clay Minerals Society 1989

Authors and Affiliations

  • M. B. McBride
    • 1
  1. 1.Department of AgronomyCornell UniversityIthacaUSA

Personalised recommendations