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Ion Exchange, Thermal Transformations, and Oxidizing Properties of Birnessite

Published online by Cambridge University Press:  02 April 2024

D. C. Golden ,
J. B. Dixon  and
C. C. Chen
D. C. Golden
Affiliation:
Department of Soil & Crop Sciences, Texas A&M University, College Station, Texas 77843
J. B. Dixon
Affiliation:
Department of Soil & Crop Sciences, Texas A&M University, College Station, Texas 77843
C. C. Chen
Affiliation:
Department of Soil & Crop Sciences, Texas A&M University, College Station, Texas 77843
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Abstract

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Synthetic sodium bimessite, having a cation-exchange capacity (CEC) of 240 meq/100 g (cmol/kg) was transformed into Li, K, Mg, Ca, Sr, Ni, and Mn2+ cationic forms by ion exchange in an aqueous medium. Competitive adsorption studies of Ni and Ba vs. Mg showed a strong preference for Ni and Ba by bimessite. The product of Mg2+-exchange was buserite, which showed a basal spacing of 9.6 Å (22°C, relative humidity (RH) = 54%), which on drying at 105°C under vacuum collapsed to 7 Å. Of the cation- saturated bimessites with 7-Å basal spacing, only Li-, Na-, Mg-, and Ca-bimessites showed cation exchange.

Heating bimessite saturated with cations other than K produced a disordered phase between 200° and 400°C, which transformed to well-crystallized phases at 600°C. K-exchanged bimessite did not transform to a disordered phase; rather a topotactic transformation to cryptomelane was observed. Generally the larger cations, K, Ba, and Sr, gave rise to hollandite-type structures. Mn- and Ni-bimessite transformed to bixbyite-type products, and Mg-bimessite (buserite) transformed to a hausmannite-type product. Li-bimessite transformed to cryptomelane and at higher temperature converted to hausmannite. The hollandite-type products retained the morphology of the parent bimessite. The mineralogy of final products were controlled by the saturating cation. Products obtained by heating natural bimessite were similar to those obtained by heating bimessite saturated with transition elements.

Keywords

BimessiteBixbyiteBuseriteCation exchangeCryptomelaneHausmanniteHollanditeOxidationThermal treatment
Type
Research Article
Information
Clays and Clay Minerals , Volume 34 , Issue 5 , October 1986 , pp. 511 - 520
Copyright
Copyright © 1986, The Clay Minerals Society

References

Adams, S. N., Honeysett, J. L., Tiller, K. G. and Norrish, K., 1969 Factors controlling the increase of cobalt in plants following the addition of cobalt fertilizer Aust. J. Soil Res. 7 29–42.CrossRefGoogle Scholar
Arrhenius, G. O. and Tsai, A. G., 1981 Structure, phase transformation, and prebiotic catalysis in marine manganate minerals SIO Reference Series 81 1–19.Google Scholar
Bricker, O., 1965 Some stability relations in the system Mn-O2-H2O at 25° and one atmosphere total pressure Amer. Mineral. 50 1296–1354.Google Scholar
Bums, R. G. and Bums, Y. M., 1977 The mineralogy and crystal chemistry of deep-sea manganese nodules, a polymetallic resource of the twenty-first century Phil. Trans. R. Soc. Lond(A) 286 283–301.Google Scholar
Chukhrov, F. V. and Gorshkov, A. I., 1981 Iron and manganese oxide minerals in soils Trans. Royal Society of Edinburgh 72 195–200.CrossRefGoogle Scholar
Embrey, P. G. and Fuller, J. P., 1980 A Manual of Mineral Names 1892–1978 New York Oxford University Press 39.Google Scholar
Farmer, V. C. and Farmer, V. C., 1974 The layer silicates The Infrared Spectra of Minerals London Mineralogical Society 331–363.CrossRefGoogle Scholar
Giovanoli, R. and Balmer, B., 1981 A new synthesis of hollandite. A possibility for immobilization of nuclear waste Chimia 35 53–55.Google Scholar
Giovanoli, R. and Brutsch, R., 1979 Über Oxihydroxide des Mn(IV) mit Schichtengitter. 5. Mitteilung: Stoichiometrie, Austauschverhalten und die Rolle bei der Bildung von Tiefsee-Mangankonkretionen Chimia 33 56–60.Google Scholar
Giovanoli, R., Buhler, H. and Sokolowska, K., 1973 Synthetic lithiophorite: electron microscopy and X-ray diffraction J. Microscopie 18 271–284.Google Scholar
Giovanoli, R., Stähli, E. and Feitknecht, W., 1970 Über Oxihydroxide des vierwertigen Mangans mit Schichtengitter 1. Natrium-Mangan(II, III) Manganat(IV) Helv. Chim. Acta 53 209–220.CrossRefGoogle Scholar
Johns, W. D. and Sen Guptha, P. K., 1967 Vermiculitealkylammonium complexes Amer. Mineral. 52 1706–1724.Google Scholar
Lagaly, G., 1982 Layer charge heterogeneity in vermiculites Clays & Clay Minerals 30 215–222.CrossRefGoogle Scholar
Lagaly, G. and Weiss, A., 1969 Determination of the layer charge in mica-type layer silicates Proc. Int. Clay Conf, Tokyo 1969 61–80.Google Scholar
Loganathan, P. and Burau, R. G., 1973 Sorption of heavy metal ions by a hydrous manganese oxide Geochem. Cosmochim. Acta 37 1277–1293.CrossRefGoogle Scholar
Mason, B. and Berry, L. G., 1968 Elements of Mineralogy San Francisco Freeman.Google Scholar
McKenzie, R. M., 1967 The sorption of cobalt by manganese minerals in soils Aust. J. Soil Res. 8 97–106.CrossRefGoogle Scholar
McKenzie, R. M., Dixon, J. B. and Weed, S. B., 1986 Manganese oxides and hydroxides Minerals in Soil Environments 2nd ed. Madison, Wisconsin Soil Science Society of America (in press).Google Scholar
Paterson, E., 1981 Intercalation of synthetic buserite by dodecylammonium chloride Amer. Mineral. 66 424–427.Google Scholar
Potter, R. M. and Rossman, G. R., 1979 The tetravalent manganese oxides: identification, and structural relationships by infrared spectroscopy Amer. Mineral. 64 1199–1218.Google Scholar
Ruehlicke, G. and Kohler, E. E., 1981 A simplified procedure for determining layer charge by the N-alkylammonium method Clay Miner. 16 305–307.CrossRefGoogle Scholar
Stähli, E., 1968 Über Manganate(IV) mit Schichten-Struk- tur Switzerland Ph.D. Thesis, University of Bern.Google Scholar
Taylor, R. M., McKenzie, R. M. and Norrish, K., 1964 The mineralogy and chemistry of manganese in some Australian soils Aust. J. Soil Res. 2 235–248.CrossRefGoogle Scholar
Walker, G. F., 1967 Interaction of n-alkylammonium with mica-type layer lattices Clay Miner. 7 129–143.CrossRefGoogle Scholar
Weed, S. B. and Weber, J. B., 1968 The effect of adsorbent charge on the competitive adsorption of divalent organic cations by layer silicate minerals Amer. Mineral. 53 478–490.Google Scholar
Wilding, L. P., Smeck, N. E., Drees, L. R., Dixon, J. B. and Weed, S. B., 1977 Silica in soils: quartz, cristobalite, tridymite, and opal Minerals in Soil Environments Madison, Wisconsin Soil Science Society of America 471–552.Google Scholar