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Properties and Acid Dissolution of Metal-Substituted Hematites

Published online by Cambridge University Press:  28 February 2024

M. A. Wells ,
R. J. Gilkes  and
R. W. Fitzpatrick
M. A. Wells*
Affiliation:
CSIRO Exploration and Mining, Wembley, Perth, Western Australia 6913, Australia
R. J. Gilkes
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Perth, Western Australia 6907, Australia
R. W. Fitzpatrick
Affiliation:
CSIRO, Land and Water, Glen Osmond, Adelaide, South Australia, 5064, Australia
*
E-mail of corresponding author: m.wells@per.dem.csiro.au
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Abstract

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The dissolution in 1 M HC1 of Al-, Mn-, and Ni-substituted hematites and the influence of metal substitution on dissolution rate and kinetics of dissolution were investigated. The inhomogeneous dissolution of most of the hematites investigated was well described by the Avrami-Erofe'ev rate equation, kt = √[-ln(l − α)], where k is the dissolution rate in time, t, and α is the Fe dissolved. Dissolution of Al-substituted hematite occurred mostly by edge attack and hole formation normal to (001), with the rate of dissolution, k, directly related to surface area (SA). Dissolution of rhombohedral Mn- and Ni-bearing hematites occurred at domain boundaries, crystal edges, and corners with k unrelated to SA. The morphology of Mn- and Ni-substituted hematites changed during dissolution with clover-leaf-like forms developing as dissolution proceeded, whereas the original plate-like morphology of Al-bearing hematite was generally retained. Acid attack of platy and rhomboidal hematite is influenced by the direct (e.g., metaloxygen bond energy, hematite crystallinity) and indirect (e.g., crystal size and shape) affects associated with incorporation of foreign ions within hematite.

Keywords

Acid DissolutionActivation EnergyFrequency FactorHematiteIron OxideMetal Substitution
Type
Research Article
Information
Clays and Clay Minerals , Volume 49 , Issue 1 , February 2001 , pp. 60 - 72
Copyright
Copyright © 2001, The Clay Minerals Society

References

Azuma, K. and Kametani, H., (1964) Kinetics of dissolution of ferric oxide Transactions of the Metallurgical Society of AIME 230 853–862.Google Scholar
Barrön, V. Herruzo, M. and Torrent, J., (1988) Phosphate adsorption by aluminous hematites of different shapes Journal of the Soil Science Society of America 52 647–651 10.2136/sssaj1988.03615995005200030009x.Google Scholar
Baumgartner, E. Blesa, M.A. Marinovich, H. and Maroto, A.J.G., (1983) Heterogeneous electron transfer as a pathway in the dissolution of magnetite in oxalic acid solutions Inorganic Chemistry 22 2226–2228 10.1021/ic00158a002.Google Scholar
Berner, R.A., (1978) Rate control of mineral dissolution under earth surface conditions American Journal of Science 278 1235–1252 10.2475/ajs.278.9.1235.Google Scholar
Bums, R.G., (1970) Mineralogical Applications of Crystal Field Theory. Cambridge University Press .Google Scholar
Colombo, C. Barron, V. and Torrent, J., (1994) Phosphate adsorption and desorption in relation to morphology and crystal properties of synthetic hematites Geochimica et Cosmochimica Acta 58 1261–1269 10.1016/0016-7037(94)90380-8.CrossRefGoogle Scholar
Cornell, R.M. and Giovanoli, R., (1989) Effect of cobalt on the formation of crystalline iron oxides from ferrihydrite into goethite and hematite in alkaline media Clays and Clay Minerals 37 65–70 10.1346/CCMN.1989.0370108.Google Scholar
Cornell, R.M. and Giovanoli, R., (1993) Acid dissolution of hematites of different morphologies Clay Minerals 28 223–232 10.1180/claymin.1993.028.2.04.CrossRefGoogle Scholar
Cornell, R.M. and Schindler, P.W., (1987) Photochemical dissolution of goethite in acid/oxalate solution Clays and Clay Minerals 35 347–352 10.1346/CCMN.1987.0350504.CrossRefGoogle Scholar
Cornell, R.M. Posner, A.M. and Quirk, J.P., (1974) Crystal morphology and the dissolution of goethite Journal of Inorganic and Nuclear Chemistry 36 1937–1946 10.1016/0022-1902(74)80705-0.CrossRefGoogle Scholar
Cornell, R.M. Posner, A.M. and Quirk, J.P., (1975) The complete dissolution of goethite Journal of Applied Chemical Biotechnology 25 701–706 10.1002/jctb.5020250909.CrossRefGoogle Scholar
Cornell, R.M. Posner, A.M. and Quirk, J.P., (1976) Kinetics and mechanisms of the acid dissolution of goethite (α-FeOOH) Journal of Inorganic and Nuclear Chemistry 38 563–567 10.1016/0022-1902(76)80305-3.Google Scholar
Cornell, R.M. Giovanoli, R. and Schindler, P.W., (1987) Effect of silicate species on the transformation of ferrihydrite into goethite and hematite in alkaline media Clays and Clay Minerals 35 21–28 10.1346/CCMN.1987.0350103.Google Scholar
Cornell, R.M. Giovanoli, R. and Schneider, W., (1992) The effect of nickel on the conversion of amorphous iron (III) hydroxide into more crystalline iron oxides in alkaline media Journal of Chemistry and Technical Biotechnology 53 73–79 10.1002/jctb.280530111.Google Scholar
Davies, S.R.H. and Morgan, J.J., (1989) Manganese (II) oxidation kinetics on metal oxide surfaces Journal of Colloid and Interface Science 129 63–77 10.1016/0021-9797(89)90416-5.CrossRefGoogle Scholar
DeGrave, E. Bowen, L.H. Amarasiriwarden, D.D. and Vandenberghe, R.E., (1988) 57Fe Mössbauer effect study of highly substituted aluminum hematites: Determination of the magnetic hyperfine field distributions Journal of Magnetism and Magnetic Materials 72 129–140 10.1016/0304-8853(88)90181-3.Google Scholar
Eggleston, C.M. and Hochella, M.F. Jr., (1992) The structure of the hematite (001) surface by scanning tunneling microscopy: Image interpretation, surface relaxation, and step structure American Mineralogist 77 911–922.Google Scholar
Fischer, W.R. and Schwertmann, U., (1975) The formation of hematite form amorphous iron (III) hydroxide Clays and Clay Minerals 23 33–37 10.1346/CCMN.1975.0230105.CrossRefGoogle Scholar
Giovanoli, R. and Cornell, R.M., (1992) Crystallization of metal-substituted ferridydrites Zeitschrift Pflanzenemährung Bodenkunde 129 63–77.Google Scholar
Handbook of Chemistry and Physics (1988) Table 1. Bond strengths in diatomic molecules. Weast, R., ed., CRC Press Inc., Florida, F–115.Google Scholar
Heil, J. Wesner, J. Lommel, B. Assmus, W. and Grill, W., (1989) Structural investigations of surfaces of blue bronze and hematite by scanning tunneling microscopy Journal of Applied Physics 65 5220–5222 10.1063/1.343159.CrossRefGoogle Scholar
Hendewerk, M. Salmeron, M. and Somorjai, G.A., (1986) Water adsorption on the (001) plane of Fe2O3: An XPS, UPS, Auger, and TPD study Surface Science 172 544–556 10.1016/0039-6028(86)90500-5.Google Scholar
Jeanroy, E. Rajot, JL P P and Herbillon, A., (1991) Differential dissolution of hematite and goethite in dithionite and its implication on soil yellowing Geoderma 50 79–94 10.1016/0016-7061(91)90027-Q.CrossRefGoogle Scholar
Johnnson, P.A. Eggleston, C.M. and Hochella, M.F. Jr., (1991) Imaging molecular-scale structure and microtopography of hematite with the atomic force microscope American Mineralogist 76 1442–1445.Google Scholar
Johnston, J.H. and Lewis, D.G., (1983) A detailed study of the transformation of feirihydrite to hematite in an aqueous medium at 92°C Geochimica et Cosmochimica Acta 41 1823–1831 10.1016/0016-7037(83)90200-4.Google Scholar
Kabai, J., (1973) Determination of specific activation energies of metal oxides and metal oxide hydrates by measurement of the rate dissolution Acta Chimica Academiae Scientar- um Hungaricae 78 57–73.Google Scholar
Klug, H.P. and Alexander, L.E., (1974) X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials New York John Wiley and Sons.Google Scholar
Krestov, G.A. Shormanov, V.A. and Pimenova, N.I., (1973) Kinetic study of the dissolution of a-iron (III) oxide in aqueous solutions of inorganic acids Izvestiya Vysshikh Uchebnykh Zavedenii, Khimiya i Khimicheskaya Tekhnologiya 16 377–381.Google Scholar
Kuhnel, R.A., (1987) The role of cationic and anionic scavengers in latente Chemical Geology 60 31–40 10.1016/0009-2541(87)90107-0.Google Scholar
Lim-Nunez, R. Gilkes, R.J., Denver, L. G. van Olphen, H. and Mumpton, F.A., (1987) Acid dissolution of synthetic metal-containing goethites and hematites Proceedings of the International Clay Conference, 1985 Bloomington, Indiana Clay Minerals Society 197–204.Google Scholar
Macedo, J. and Bryant, R.B., (1989) Preferential microbial reduction of hematite over goethite in a Brazilian oxisol Journal of the Soil Science Society of America 53 1114–1118 10.2136/sssaj1989.03615995005300040022x.Google Scholar
Maurice, R.A. and Hochella, M.F. Jr. Parks, G.A. Sposito, G. and Schwertmann, U., (1995) Evolution of hematite surface microtopography upon dissolution by simple organic acids Clays and Clay Minerals 43 29–38 10.1346/CCMN.1995.0430104.CrossRefGoogle Scholar
McKeague, J.A. and Day, J.H., (1966) Dithionite- and oxalateextractable Fe and A1 as aids in differentiating various classes of soils Canadian Journal of Soil Science 46 13–22 10.4141/cjss66-003.CrossRefGoogle Scholar
Meike, A., (1990) A micromechanical perspective on the role of dislocations in selective dissolution Geochimica et Cosmochimica Acta 54 3347–3352 10.1016/0016-7037(90)90289-W.CrossRefGoogle Scholar
Melville, M.D. and Atkinson, G., (1985) Soil colour: Its measurement and its designation in models of uniform colour space Journal of Soil Science 36 495–512 10.1111/j.1365-2389.1985.tb00353.x.Google Scholar
Novak, G.A. and Colville, A.A., (1989) A practical interactive least squares cell-parameter program using an electronic spreadsheet and a personal computer American Mineralogist 74 488–490.Google Scholar
Pryor, M.J. and Evans, U.R., (1950) The reductive dissolution of ferric oxide in acid. Part I. The reductive dissolution of oxide films present on iron Journal of the Chemical Society 1259–1266.Google Scholar
Schwertmann, U., (1984) The influence of aluminium on iron oxides. IX. Dissolution of Al-goethite in 6M HCl Clay Minerals 19 9–19 10.1180/claymin.1984.019.1.02.Google Scholar
Schwertmann, U., (1991) Solubility and dissolution of iron oxides Plant and Soil 130 1–25 10.1007/BF00011851.Google Scholar
Schwertmann, U. and Murad, E., (1983) Effect of pH on the formation of goethite and hematite from ferrihydrite Clays and Clay Minerals 31 277–284 10.1346/CCMN.1983.0310405.Google Scholar
Schwertmann, U. Taylor, R.M., Dixon, J.B. and Weed, S.B., (1989) Iron oxides Minerals in Soil Environments Wisconsin, USA Soil Science Society of America, Madison 379–438.Google Scholar
Schwertmann, U. Fitzpatrick, R.W. Taylor, R.M. and Lewis, D.G., (1979) The influence of aluminum on iron oxides. Part II. Preparation and properties of Al-substituted hematites Clays and Clay Minerals 27 105–112 10.1346/CCMN.1979.0270205.Google Scholar
Schwertmann, U. Cambier, P. and Murad, E., (1985) Properties of goethite of varying crystallinity Clays and Clay Minerals 33 369–378 10.1346/CCMN.1985.0330501.Google Scholar
Segal, M. and Sellers, R., (1980) Reduction of solid iron (III) oxides with aqueous reducing agents Journal of the Chemical Society and Chemical Communications 991–993.Google Scholar
Shannon, R.D., (1976) Revised effective ionic radii and systematic studies of inter-atomic distances in halides and chalcogenides Acta Crystallographica A32 751–767 10.1107/S0567739476001551.Google Scholar
Sidhu, P.S. Gilkes, R.J. and Posner, A.M., (1980) The behaviour of Co, Ni, Zn, Cu, Mn and Cr in magnetite during alteration to maghemite and hematite Journal of the Soil Science Society of America 44 135–138 10.2136/sssaj1980.03615995004400010028x.Google Scholar
Sidhu, P.S. Gilkes, R.J. Cornell, R.M. Posner, A.M. and Quirk, J.P., (1981) Dissolution of iron oxides and oxyhydroxides in hydrochloric and perchloric acids Clays and Clay Minerals 29 269–276 10.1346/CCMN.1981.0290404.Google Scholar
Stanjek, H. and Schwertmann, U., (1992) The influence of aluminium on iron oxides. Part XVI: Hydroxyl and aluminium substitution in synthetic hematites Clays and Clay Minerals 40 347–354 10.1346/CCMN.1992.0400316.Google Scholar
Sulzberger, B. Suter, D. Siffert, C. Banwart, S. and Stumm, W., (1989) Dissolution of Fe(II) (hydr) oxides in natural waters; Laboratory assessment on the kinetics controlled by surface coordination Marine Chemistry 28 127–144 10.1016/0304-4203(89)90191-6.Google Scholar
Sunagawa, I., (1962) Mechanism of natural etching of hematite crystals American Mineralogist 47 1332–1345.Google Scholar
Surana, V.S. and Warren, I.H., (1969) The leaching of goethite Transactions of the Institute of Mining and Metallurgy 80 C152 155.Google Scholar
Torrent, J. Schwertmann, U. and Barrön, V., (1987) The reductive dissolution of synthetic goethite and hematite by dithionite Clay Minerals 22 329–337 10.1180/claymin.1987.022.3.07.Google Scholar
Vandenberghe, R.E. Verbeeck, A.E. DeGrave, E. and Stiers, W., (1986) 57Fe Mössbauer effect study of Mn-substituted goethite and hematite Hyperfine Interactions 29 1157–1160 10.1007/BF02399440.Google Scholar
Warren, I.H. and Roach, G.I.D., (1971) Physical aspects of the leaching of goethite and hematite Transactions of the Institute of Mining and Metallurgy 80 C151 155.Google Scholar
Warren, I.H. Bath, M.D. Posner, A.P. and Armstrong, J.T., (1969) Anisotropic dissolution of hematite Transactions of the Institute of Mining and Metallurgy 78 C21 27.Google Scholar
Wells, M.A. Gilkes, R.J. and Anand, R.R., (1989) The formation of corundum and aluminous hematite by the thermal dehydroxylation of aluminous goethite Clay Minerals 24 513–530 10.1180/claymin.1989.024.3.05.Google Scholar