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Electron Transfer Processes Between Hydroquinone and Hausmannite (Mn3O4)

Published online by Cambridge University Press:  02 April 2024

K.-H. Kung  and
M. B. McBride
K.-H. Kung
Affiliation:
Department of Agronomy, Cornell University, Ithaca, New York 14853
M. B. McBride
Affiliation:
Department of Agronomy, Cornell University, Ithaca, New York 14853
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Abstract

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A kinetic study of the oxidation of hydroquinone by aqueous suspensions of hausmannite at pH 6 was conducted using an on-line analysis system. Electron transfer between hydroquinone and the oxide was monitored by ultraviolet and electron spin resonance spectroscopy to measure the loss of hydroquinone and the appearance of oxidation products. Although hydroquinone oxidized on the surface of the oxide and the oxide surface was altered after the reduction, hydroquinone and its oxidation products did not adsorb strongly on the surface. At a high concentration of hydroquinone, p-benzosemiquinone free radicals persisted in aqueous solution and were oxidized by dissolved O2. Calculations based on the thermodynamic stabilities of the oxide and the organic species involved show that the formation of p-benzosemiquinone radical by Mn reduction is feasible. The presence of the radicals indicates that the oxidation of hydroquinone by the oxide proceeded by a one-electron transfer process. At high organic/ oxide ratios, an increase in the amount of hausmannite dissolved with increasing hydroquinone concentration suggests that the reduction of the oxide by the organic was not limited to the surface layer of the oxide. At a high concentration of hydroquinone, polymers were detected in solution, suggesting that radical-mediated reactions played a role in the polymerization process. A reaction scheme is proposed to explain the effect of the Mn oxide to hydroquinone ratio on the consumption of O2 and the appearance of quinone, p-benzosemiquinone, and polymers in solution.

Keywords

Electron spin resonanceElectron transferHausmanniteHydroquinoneManganeseOxidation
Type
Research Article
Information
Clays and Clay Minerals , Volume 36 , Issue 4 , August 1988 , pp. 297 - 302
Copyright
Copyright © 1988, The Clay Minerals Society

References

Bolt, G. H. and Bruggenwert, M. G. M., 1976 Soil Chemistry Amsterdam Elsevier.Google Scholar
Bricker, O., 1965 Some stability relation in the system MnO2-H2O at 25°C and at atmosphere total pressure Amer. Mineral. 50 1296 – 1354.Google Scholar
Fukuzumi, S., Ono, Y. and Keii, T., 1975 Electron spin resonance studies on the formation of p-benzosemiquinone anion over manganese dioxide Int. J. Chem. Kinetics 7 535 – 546.CrossRefGoogle Scholar
Laird, T., Barton, D. and Ollis, W. D., 1979 Quinones Comprehensive Organic Chemistry, Vol. 1 Oxford Pergamon Press 1213.Google Scholar
Larson, R. A. and Hufnal, J. M. Jr., 1980 Oxidative polymerization of dissolved phenols by soluble and insoluble inorganic species Limnol. Oceanogr. 25 505 – 512.CrossRefGoogle Scholar
Kumada, K. and Kato, H., 1970 Browning of pyrogallol as affected by clay minerals. I. Classification of clay minerals based their catalytic effects on the browning reaction of pyrogallol Soil Sci. Plant Nutr. 16 195 – 200.CrossRefGoogle Scholar
Kyuma, K. and Kawaguchi, K., 1964 Oxidative changes of polyphenols as influenced by allophane Soil Sci. Soc. Amer. Proc. 28 371 – 374.CrossRefGoogle Scholar
McBride, M. B., 1987 Adsorption and oxidation of phenolic compounds by Fe and Mn oxides Soil Sci. Soc. Amer. J. 51 1466 – 1472.CrossRefGoogle Scholar
Murray, J. W., Dillard, J. G., Giovanoli, R., Moers, H. and Stumm, W., 1985 Oxidation of Mn(II): Initial mineralogy, oxidation state and ageing Geochim. Cosmochim. Acta 49 463 – 470.CrossRefGoogle Scholar
Ono, Y., Matsumura, T. and Fukuzumi, S., 1977 Electron spin resonance studies on the mechanism of the formation of p-benzosemiquinone anion over manganese dioxide J. Chem. Soc, Perkin Trans. Part 2 21 1421 – 1424.CrossRefGoogle Scholar
Peover, M. E., 1962 A Polarographic investigation into the redox behavior of quinone: The role of electron affinity and solvent J. Chem. Soc. (London) 4540 – 4549.CrossRefGoogle Scholar
Rex, R. W., 1960 Electron paramagnetic resonance studies of stable free radicals in lignins and humic acids Nature 188 1185 – 1186.CrossRefGoogle Scholar
Schnitzer, M., 1982 Quo vadis soil organic matter research? Whither Soil Research, Panel Disc. Paper 5, 12th Int. Cong. Soil Sci., New Delhi, India, 1982 67 – 78.Google Scholar
Senesi, N. and Schnitzer, M., 1977 Effects of pH, reaction time, chemical reduction and irradiation on ESR spectra of fulvic acid Soil Sci. 123 224 – 234.CrossRefGoogle Scholar
Shindo, H. and Huang, P. M., 1982 Role of Mn(IV) oxide in abiotic formation of humic substances in the environment Nature 305 57 – 58.Google Scholar
Shindo, H. and Huang, P. M., 1984 Catalytic effects of manganese(IV), iron(III), aluminum, and silicon oxides on the formation of phenolic polymers Soil Sci. Soc. Amer. J. 48 927 – 934.CrossRefGoogle Scholar
Shindo, H. and Huang, P. M., 1985 The catalytic power of inorganic components in the abiotic synthesis of hydro-quinone-derived humic polymers Appl. Clay Sci. 1 71 – 81.CrossRefGoogle Scholar
Steelink, C., 1964 Free radical studies of lignin, lignin degradation products and soil humic acid Geochim. Cosmochim. Acta 28 1615 – 1622.CrossRefGoogle Scholar
Stone, A. T. and Morgan, J. J., 1984 Reduction and dissolution of manganese(III) and manganese(IV) oxides by organics. 1. 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
Tollin, G., Reid, T. and Steelink, C., 1963 Structure of humic acid. VI. Electron-paramagnetic-resonance studies Biochim. Biophys. Acta 66 444 – 447.Google Scholar
Wang, T. S. S. Li, S. W. and Ferng, Y. L., 1978 Catalytic polymerization of phenolic compounds by clay minerals Soil Sci. 126 15 – 21.CrossRefGoogle Scholar
Wang, T. S. C. Wang, M. C., Ferng, Y. L. and Huang, P. M., 1983 Catalytic synthesis of humic substances by natural clay, silts, and soils Soil Sci. 135 350 – 360.CrossRefGoogle Scholar
Wertz, J. E. and Vivo, J. L., 1955 Electron spin resonance of semiquinone J. Chem. Physics 23 2441 – 2442.CrossRefGoogle Scholar