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Composition, stabilization, and light absorption of Fe(II)Fe(III) hydroxy-carbonate (‘green rust’)

Published online by Cambridge University Press:  09 July 2018

H. C. B. Hansen
H. C. B. Hansen*
Affiliation:
Royal Veterinary & Agricultural Highschool, Chemistry Department, Thorvaldsensvej 40, 1871 Frederiksberg C, Denmark
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Abstract

The chemical composition of the pyroaurite-type compound Fe(II)Fe(III) hydroxy-carbonate (‘green rust’) synthesised from freshly precipitated ferrihydrite and Fe(II) chloride solution at pH 7.0 (‘induced hydrolysis’) was determined. The compound was nearly stoichiometric, with the formula the Fe(II):Fe(III) ratio being independent of the Fe(II):Fe(III) ratio in the initial reaction mixture. It shows all the XRD peaks reported for this compound. Visible-near IR shows a broad peak at 650 nm which is ascribable to intervalence charge transfer and therefore the absorbance maximum decreases with increasing degree of oxidation. Wetting the material with compounds containing hydroxyl groups (such as glycerol or glucose) retards the oxidation of the otherwise very oxidation-sensitive compound. Similar polar organic compounds may stabilize the Fe(II)Fe(III) hydroxy-carbonate in wet soils. The importance of the green rust phase as an intermediate in the formation and transformation reactions of oxides and oxyhydroxides of iron in natural environments should not be ignored.

Information

Type
Research Article
Information
Clay Minerals , Volume 24 , Issue 4 , December 1989, pp. 663 - 669
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1989

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References

Allmann, R. (1968) The crystal structure of pyroaurite. Acta Cryst. B24, 972–977.Google Scholar
Allmann, R. (1970) Doppelschichtstrukturen mit brucitahnlichen Schichtionen [Me(II)1_xMe(III)x,(OH)2]2]x+. Chimia, 24, 99–108.Google Scholar
Bernal, J.D., Dasgupta, D.R. & Mackay, A.L. (1959) The oxides and hydroxides of iron and their structural inter-relationships. Clay Miner. Bull., 4, 15–30.CrossRefGoogle Scholar
Brindley, G.W. & Bish, D.L. (1976) Green rust: a pyroaurite type structure. Nature, 263, 353.CrossRefGoogle Scholar
Burns, R.G. (1980) Mixed-valence minerals of iron and titanium: Correlations of structural, Mossbauer and electronic spectral data. Pp. 295–336, in Mixed-Valence Compounds(Brown, D. B., editor). Proc. NATO Adv. Study Inst. Oxford.CrossRefGoogle Scholar
Butler, G. & Benyon, J.G. (1967) The corrosion of mild steel in boiling salt solutions. Corros. Sci., 7, 385–404. CrossRefGoogle Scholar
Dasgupta, D.R. & Mackay, A.L. (1959) β-ferric oxyhydroxide and green rust. J. Phy. Soc. Japan, 14, 932–935.Google Scholar
Feitknecht, W. (1953) Die festen Hydroxysalze zweiwertiger Metalle. Fortschr. Chem. Forsch., 2, 670–757.Google Scholar
Feitknecht, W. & Keller, G. (1950) Uber die Dunkelgrunen Hydroxyverbindungen des Eisens. Z. Anorg. Chem., 262, 61–68.Google Scholar
Gancedo, J.R., Martinez, M.L. & Oton, J.M. (1983) Formation of green rust in NH4N03 solutions. Anal. Quint., 79, 470–472.Google Scholar
Hashi, K., Kikkawa, S. & Koizumi, M. (1983) Preparation and properties of pyroaurite-like hydroxy minerals. Clay Clay Miner., 31, 152–154.CrossRefGoogle Scholar
Kanzaki, T. & Katsura, T. (1986) Mossbauer Spectra at 77 K of products formed during transformation of Fe(OH)2 to Fe304 in aqueous oxidation. J. Chem. Soc. Dalton Trans., 1243–1246.CrossRefGoogle Scholar
Leussing, D.L. & Kolthoff, I.M. (1953) The solubility product of ferrous hydroxide and the ionization of the aquo-ferrous ion. J. Am. Chem. Soc., 75, 2476–2479.CrossRefGoogle Scholar
McGill, J.R., McEnaney, B. & Smith, D.C. (1976) Crystal structure of green rust foimed by corrosion of cast iron. Nature, 259, 200–201.CrossRefGoogle Scholar
Misawa, T., Hashimoto, K. & Shimodaira, S. (1973) Formation of Fe(II)1 - Fe(III)1, intermediate green complex on oxidation of ferrous ion in neutral and slightly alkaline sulphate solutions. J. Inorg. Nucl. Chem., 35, 4167–4174.CrossRefGoogle Scholar
Misawa, T., Hashimoto, K. & Shimodaira, S. (1974) The mechanism of formation of iron oxide and oxyhydroxides in aqueous solutions at room temperature. Corros. Sci. 14, 131–149.CrossRefGoogle Scholar
Mortatti, J., Krug, F.J., Pessenda, L.C.R., Zagotto, E.A.G. & Storoaard Jorgensen, S. (1982) Determination of iron in natural waters and plant material with 1,10-phenanthroline by flow injection analysis. Analyst, 107, 659–663.CrossRefGoogle Scholar
Murad, E. & Taylor, R.M. (1984) The Mossbauer spectra of hydroxycarbonate green rusts. Clay Miner. 19, 77–83.CrossRefGoogle Scholar
Shriver, D.F. (1969) The Manipulation of Air-Sensitive Compounds, p. 196. McGraw-Hill, New York.Google Scholar
Stampfl, P.P. (1969) Ein basisches eisen-II-III-Karbonat in Rost. Corros. Sci., 9, 185–187.CrossRefGoogle Scholar
Tamaura, Y., Yoshida, T. & Katsura, T. (1984) The synthesis of green rust II and its spontaneous transformation into Fe3O4. Bull. Chem. Soc. Japan, 57, 2411–2416.Google Scholar
Taylor, R.M. (1982) Stabilization of colour and structure in the pyroaurite compounds Fe(II)Fe(IU)Al(in) hydroxycarbonates. Clay Miner., 17, 369–372.CrossRefGoogle Scholar
Taylor, R.M. (1985) A rapid method for the formation of Fe(II)Fe(III) hydroxycarbonate. Clay Miner. 20 147–151.CrossRefGoogle Scholar
Taylor, R.M. & McKenzie, R.M. (1980) The influence of aluminum on iron oxides. VI. The formation of Fe(II)-Al(III) hydroxy-chlorides, -sulfates, and -carbonates as new members of the pyroaurite group and their significance in soils. Clay Clay Miner., 28, 179–187.Google Scholar
Vins, J., Subrt, J., Zapletal, V. & Hanousek, F. (1987) Preparation and properties of green rust type substances. Collect. Czech. Chem. Comm., 52, 93–102.Google Scholar