Hostname: page-component-78c5997874-g7gxr Total loading time: 0 Render date: 2024-11-05T15:33:17.497Z Has data issue: false hasContentIssue false
  • English
  • Français

Electron Transfer Processes Between Hydroquinone and Iron Oxides

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
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The kinetics of hydroquinone oxidation by aqueous suspensions of pure hematite and goethite-ferrihydrite mixtures at pH 6.0, 7.4, and 9 was studied using an on-line analysis system. The electron transfer between hydroquinone and the Fe oxides was monitored by UV-visible and electron spin resonance spectroscopy. The adsorption of organics on the Fe oxide surface was detected by Fourier-transform infrared spectroscopy. For different Fe oxides, a higher surface area was correlated with a greater oxidizing ability and greater adsorption of organics, suggesting that the oxidation reaction was a surface process. A reversal of the initially rapid redox reaction was found in this system, suggesting a delayed release of Fe2+ into solution as the reduction of the Fe oxide proceeded. Redox potential calculations confirmed the thermodynamic favorability of the reaction reversal. A distribution of the reduced state over neighboring Fe atoms on the oxide surface probably was responsible for the initial suppression of Fe2+ release into the aqueous phase. Based upon these observations and detection of the semiquinone radical as an intermediate of hydroquinone oxidation, an inner-sphere one-electron transfer mechanism for the oxidation of hydroquinone at the oxide surface is proposed.

Keywords

Electron spin resonanceElectron transferFerrihydriteGoethiteHematiteHydroquinoneIron
Type
Research Article
Information
Clays and Clay Minerals , Volume 36 , Issue 4 , August 1988 , pp. 303 - 309
Copyright
Copyright © 1988, The Clay Minerals Society

References

Bolt, G. H. and Bruggenwert, M. G. M., 1976 Soil Chemistry Amsterdam Elsevier.Google Scholar
Fischer, W. R. and Schwertmann, U., 1972 The formation of hematite from amorphous iron(III) hydroxide Clays & Clay Minerals 23 33 – 37.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
Kung, K.-H. and McBride, M. B., 1988 Electron transfer processes between hausmannite (Mn3O4) and hydroqui-none Clays & Clay Minerals 36 297 – 302.CrossRefGoogle Scholar
McBride, M. B., 1987 Absorption and oxidation of phenolic compounds by Fe and Mn oxides Soil Sci. Soc. Amer. J. 51 1466 – 1472.CrossRefGoogle Scholar
McBride, M. B. and Wesselink, B., 1988 Chemisorption of catechol on gibbsite, boehmite and amorphous alumina surfaces Environ. Sci. Technol. (in press).CrossRefGoogle Scholar
Sherman, D. M., 1986 Cluster molecular orbital description of the electronic structures of mixed-valence iron oxides and silicates Solid State Communications 58 719 – 723.CrossRefGoogle Scholar
Scheffer, F., Meyer, B. and Niederbudde, E. A., 1959 Humingbildung unter katalytischer Einwirkung natürlich vorkommender Eisenverbindungen im Modellversuch X. Pflanzenernaehr. Bodenkd. 87 26 – 44.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
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(VI), iron(III), aluminum, and silicon oxides on the formation of phenolic polymers Soil Sci. Soc. Amer. J. 48 927 – 934.CrossRefGoogle Scholar
Stone, A. T., Davis, J. A. and Hayes, K. F., 1986 Absorption of organic reductants and subsequent electron transfer on metal oxide surfaces Geochemical Processes at Mineral Surface Washington, D.C. ACS Symposium Series 323, Amer. Chem. Soc 446 – 461.Google Scholar
Stone, A. T., Morgan, J. J. and Stumm, W., 1987 Reductive dissolution of metal oxides Aquatic Surface Chemistry New York Wiley 221 – 254.Google Scholar
Traister, G. L. and Schilt, A. A., 1976 Water-soluble sulfonated chromogenic reagents of the ferroin type and determination of iron and copper in water, blood serum, and beer with the tetraammonium salt of 2,4-bis(5,6-diphenyl-l,2,4-triazin-3-yl)pyridinetetrasulfonic acid Anal. Chem. 48 1216 – 1220.CrossRefGoogle 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
Wang, T. S. C. Huang, P. M., Chou, C.-H. Chen, J.-H., Huang, P. M. and Schnitzer, M., 1986 The role of soil minerals in the abiotic polymerization of phenolic compounds and formation of humic substances Soil Minerals with Natural Organics and Microbes Madison, Wisconsin Soil Science Society of America 251 – 281.Google Scholar