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

Published online by Cambridge University Press:  02 April 2024

M. B. McBride
M. B. McBride*
Affiliation:
Department of Agronomy, Cornell University, Ithaca, New York 14853
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Abstract

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.

Keywords

BirnessiteDihydroxybenzeneElectron spin resonanceManganeseOxidationPhenolUltraviolet-visible spectroscopy
Type
Research Article
Information
Clays and Clay Minerals , Volume 37 , Issue 5 , October 1989 , pp. 479 - 486
Copyright
Copyright © 1989, The Clay Minerals Society

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References

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.CrossRefGoogle Scholar
Cotton, F. A. and Wilkinson, G., 1980 Advanced Inorganic Chemistry 4th ed. New York Wiley 741 – 744.Google Scholar
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
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
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
Kung, K.-H. and McBride, M. B., 1988 Electron transfer processes between hydroquinone and hausmannite (Mn3O4) Clays & Clay Minerals 36 297 – 302.CrossRefGoogle Scholar
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
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
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
McBride, M. B., 1989 Oxidation of dihydroxybenzenes in aerated aqueous suspensions of birnessite Clays & Clay Minerals 37 341 – 347.CrossRefGoogle Scholar
McKenzie, R. M., 1970 The reaction of cobalt with manganese dioxide minerals Aust. J. Soil Res 8 97 – 106.CrossRefGoogle Scholar
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
Stone, A. T., 1987 Reductive dissolution of manganese (III/IV) oxides by substituted phenols Environ. Sci. Technol 21 979 – 988.CrossRefGoogle ScholarPubMed
Stone, A. T. and Morgan, J. J., 1984 Reduction and dissolution of manganese (III) and manganese (IV) oxides by organics. I. Reaction with hydroquinone Environ. Sci. Technol 18 450 – 456.CrossRefGoogle ScholarPubMed
Stone, A. T. and Morgan, J. J., 1984 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 ScholarPubMed
Traina, S. J. and Doner, H. E., 1985 Copper-manganese (II) exchange on a chemically reduced birnessite Soil Sci. Amer. J 49 307 – 313.CrossRefGoogle Scholar
Traina, S. J. and Doner, H. E., 1985 Heavy metal induced releases of manganese (II) from a hydrous manganese dioxide Soil Sci. Soc. Amer. J 49 317 – 321.CrossRefGoogle Scholar
van der Marel, H. W. and Beutelspacher, H., 1976 Atlas of Infrared Spectroscopy of Clay Minerals and their Admixtures New York Elsevier.Google Scholar