Hostname: page-component-586b7cd67f-r5fsc Total loading time: 0 Render date: 2024-11-26T23:32:39.612Z Has data issue: false hasContentIssue false

Crystal Nucleation and Growth in Hydrolysing Iron(III) Chloride Solutions

Published online by Cambridge University Press:  01 July 2024

R. J. Atkinson*
Affiliation:
Department of Chemistry, University of Papua New Guinea, Box 4820, University P.O., Papua New Guinea
A. M. Posner
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia 6009
J. P. Quirk*
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia 6009
*
*Present address: Department of Soil Science and Plant Nutrition, University of Western Australia, Nedlands, Western Australia 6009.
Present address: Director, Waite Agricultural Research Institute, Glen Osmond, South Australia.
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.

0.5 molal iron(III) chloride solutions were hydrolysed at room temperature by base additions in the range OH/Fe mole ratio 0–2.75. After an ageing period the hydrolysed solutions were used to produce amorphous hydroxide gels from which crystalline products were grown at 65°C, at low pH or high pH. Examination of crystal composition and morphology and comparison with similarly treated nitrate solutions showed that the nucleation of hematite and goethite is inhibited in chloride containing solutions, which allow growth of small rod shaped β-FeOOH to predominate or occur exclusively in gels at pH 1–2. The addition of seed crystals of hematite and goethite allows competitive growth of all three minerals. The transformations β-FeOOH → α-Fe2O3 and β-FeOOH → α-FeOOH at pH 1–2 proceed by dissolution and reprecipitation and are promoted by adding seed crystals.

Type
Research Article
Copyright
Copyright © Clay Minerals Society 1977

References

Atkinson, R. J., Posner, A. M. and Quirk, J. P. (1968) Crystal nucleation in Fe(III) solutions and hydroxide gels: J. Inorg. Nucl. Chem. 30, 23712381. (Note: Legends to plates should read: Electron micrographs of goethite. Magnification × 40,000).CrossRefGoogle Scholar
Atkinson, R. J., Posner, A. M. and Quirk, J. P. (1972) Kinetics of isotopic exchange of phosphate at the α-FeOOH–aqueous electrolyte interface: J. Inorg. Nucl. Chem. 34, 22012211.CrossRefGoogle Scholar
Christensen, A. N. (1968) Hydrothermal preparation of goethite and hematite from amorphous iron(III) hydroxide: Acta Chem. Scand. 22, 14871490.CrossRefGoogle Scholar
Collepardi, M., Massidda, L. and Rossi, G. (1972) Ageing of iron oxide gels: Trans. Instn. Mining Metall. (Sect. C. Mineral Process. Extr. Metall.) 81, C43C46.Google Scholar
Collepardi, M., Massidda, L. and Rossi, G. (1973) Effect of pH and salt additions on ageing of ferric iron oxide gels: Trans. Instn. Mining Metall. (Sect. C. Mineral Process. Extr. Metall.) 82, C88C91.Google Scholar
Cornell, R. M., Posner, A. M. and Quirk, J. P. (1974a) Crystal morphology and the dissolution of goethite: J. Inorg. Nucl. Chem. 36, 19371946.CrossRefGoogle Scholar
Cornell, R. M., Posner, A. M. and Quirk, J. P. (1974b) The dissolution of synthetic goethites: the early stage: Soil Sci. Soc. Proc. 38, 377378.CrossRefGoogle Scholar
Feitknecht, W. and Michaelis, W. (1962) Ueber die Hydrolyse von Eisen(III)-perchlorat-Loesungen: Helv. Chim. Acta. 45, 212224.CrossRefGoogle Scholar
Fischer, W. R. and Schwertmann, U. (1975) The formation of hematite from amorphous iron(III) hydroxide: Clays & Clay Minerals 23, 3337.CrossRefGoogle Scholar
Fordham, A. W. (1970) Sorption and precipitation of iron on kaolinite III. The solubility of iron(III) hydroxides precipitated in the presence of kaolinite: Aust. J. Soil. Res. 8, 107122.CrossRefGoogle Scholar
Gallagher, K. J. (1970) The atomic structure of tubular subcrystals of β-Iron(III) oxide hydroxide: Nature 226, 12251228.CrossRefGoogle ScholarPubMed
Haigh, C. J. (1967) The hydrolysis of iron in acid solutions: Proc. Aust. Inst. Mining and Metallurgy 223, 4956.Google Scholar
Hsu, Pa Ho (1973) Appearance and stability of hydrolysed Fe(ClO4)3 solutions: Clays & Clay Minerals 21, 267277.CrossRefGoogle Scholar
Knight, R. J. and Sylva, R. N. (1974) Precipitation in hydrolysed iron(III) solutions: J. Inorg. Nucl. Chem. 36, 591597.CrossRefGoogle Scholar
Mackay, A. L. (1960) β-Ferric oxyhydroxide: Mineralog. Mag. 32, 545557.Google Scholar
Mackenzie, R. C. and Meldau, R. (1959) The ageing of sesquioxide gels I. Iron oxide gels: Mineralog. Mag. 32, 153165.Google Scholar
Murphy, P. J., Posner, A. M. and Quirk, J. P. (1975) Chemistry of iron in soils. Ferric hydrolysis products: Aust. J. Soil Res. 13, 189201.CrossRefGoogle Scholar
Robins, R. G. (1967) Hydrothermal precipitation in solutions of thorium nitrate, ferric nitrate and aluminium nitrate: J. Inorg. Nucl. Chem. 29, 431435.CrossRefGoogle Scholar
Schwertmann, U. and Fischer, W. R. (1966) Zur Bildung von α-FeOOH und α-Fe2O3 aus amorphem Eisen(III)-hydroxid: Z. Anorg. Allgem. Chem. 346, 137142.CrossRefGoogle Scholar
Soderquist, R. and Jansson, S. (1966) On an X-ray and electron microscope study of precipitates formed by the hydrolyses of iron(III) in 0.5 M NaCl ionic medium: Acta Chem. Scand. 20, 14171418.CrossRefGoogle Scholar
Sylva, R. N. (1972) The hydrolysis of iron(III): Rev. Pure Appl. Chem. 22, 115132.Google Scholar
Wefers, K. (1966a) Zum System Fe2O3-H2O. 1. Teil: Ber. Dtsch. Keram. Ges. 43, 677684.Google Scholar
Wefers, K. (1966b) Zum System Fe2O3–H2O. 2. Teil: Ber. Dtsch. Keram. Ges. 43, 703708.Google Scholar
Wolf, R. H. H., Wrischer, M. and Sipalo–Zuljevic, J. (1967) Electron-microscope investigation of the formation of colloidal beta FeOOH during slow hydrolysis of an aqueous ferric chloride solution at room temperature: Kolloid-Zeit. u. Zeit Polymere 215, 5760.CrossRefGoogle Scholar