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Dissolution of Hectorite in Inorganic Acids

Published online by Cambridge University Press:  28 February 2024

P. Komadel ,
J. Madejová ,
M. Janek ,
W. P. Gates ,
R. J. Kirkpatrick  and
J. W. Stucki
P. Komadel
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36 Bratislava, Slovakia
J. Madejová
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36 Bratislava, Slovakia
M. Janek
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36 Bratislava, Slovakia
W. P. Gates*
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, Illinois 61801, USA
R. J. Kirkpatrick
Affiliation:
Department of Geology, University of Illinois, Urbana, Illinois 61801, USA
J. W. Stucki
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, Illinois 61801, USA
*
4Present address: Savannah River Ecology Laboratory, P.O. Drawer E, Aiken, SC 29801, USA
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Abstract

The effect of acid type and concentration on the reaction rate and products of dissolution of hectorite in inorganic acids was investigated. The dissolution of hectorite in hydrochloric (HCl), nitric (HNO3) and sulphuric (H2SO4) acids was characterized using quantitative chemical analysis, infrared (IR) and multinuclear MAS NMR spectroscopies. The rate of dissolution increased with acid concentration and decreased in the order HCl ≥ HNO3 = H2SO4 at the same molar concentration. No differences were found in the reaction products of hectorite treated with the three acids. The rate of Li dissolution was slightly greater than that of Mg at lesser acid concentrations (0.25 M), indicating that protons preferentially attack Li octahedra. The gradual changes in the Si-O IR bands reflects the extent of hectorite dissolution. The analysis of 29Si MAS NMR spectra relative peak intensities with dissolution time and acid concentration provided direct dissolution rates for tetrahedral (Q3) Si. After acid dissolution, most Si was bound in a three dimensional framework site (Q4), but a substantial part also occurred in the Si(OSi)3OH (Q31OH) and Si(OSi)2(OH)2 (Q220H) environments. These three sites probably occur in a hydrous amorphous silica phase. Both AlJV and AlVt rapidly disappeared from 27Al MAS NMR spectra of the dissolution products with acid treatment. The changes in IR and MAS NMR spectra of hectorite due to acid dissolution are similar to those of montmorillonite.

Keywords

Acid DissolutionHectoriteIRNMR
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 2 , April 1996 , pp. 228 - 236
Copyright
Copyright © 1996, The Clay Minerals Society

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References

Adams, J.M.. 1987. Synthetic organic chemistry using pillared, cation-exchanged and acid-treated montmorillonite catalysts—A review. Appl Clay Sci 2: 309–342.CrossRefGoogle Scholar
Breen, C.. 1991. Thermogravimetric study of the desorption of cyclohexylamine and pyridine from an acid-treated Wyoming bentonite. Clay Miner 26: 473–486.CrossRefGoogle Scholar
Barrault, J., Gatineau, L., Hassoun, N. and Bergaya, F.. 1992. Selective syngas conversion over mixed Al-Fe pillared laponite clay. Energy Fuels 6: 760–763.CrossRefGoogle Scholar
Bergaya, F., Hassoun, N., Barrault, J. and Gatineau, L.. 1993. Pillaring of synthetic hectorite by mixed [Al13–xFex] pillars. Clay Miner 28: 109–122.CrossRefGoogle Scholar
Carrado, K.A.. 1992. Preparation of hectorite clays utilizing organic and organometallic complexes during hydrothermal crystallization. Ind Eng Chem Res 31: 1654–1659.CrossRefGoogle Scholar
Cetisli, H. and Gedikbey, T.. 1990. Dissolution kinetics of sepiolite from Eskisehir (Turkey) in hydrochloric and nitric acids. Clay Miner 25: 207–215.CrossRefGoogle Scholar
Čičel, B. and Komadel, P.. 1994. Structural formulae of layer silicates. In: Amonette, J.E., Zelazny, L.W., editors. Quantitative methods in soil mineralogy. SSSA Miscellaneous Publication. Madison, WI: Soil Science Society of America. 114–136.Google Scholar
Čičel, B., Komadel, P. and Hronský, J.. 1990. Dissolution of the fine fraction of Jelšový Potok bentonite in hydrochloric and sulphuric acids. Ceramics-Silikáty 34: 41–48.Google Scholar
Čičel, B. and Novák, I.. 1977. Dissolution of smectites in hydrochloric acid. I. Half-time of dissolution as a measure of reaction rate. In: Konta, J., editor. Proc. 7th Conf. Clay Mineral. Petrol. Karlovy Vary, 1976. Prague: Charles University. 163–175.Google Scholar
Corma, A., Mifsud, A. and Sanz, E.. 1987. Influence of the chemical composition and textural characteristics of palygorskite on the acid leaching of octahedral cations. Clay Miner 22: 225–232.CrossRefGoogle Scholar
Corma, A., Mifsud, A. and Sanz, E.. 1990. Kinetics of the acid leaching of palygorskite: Influence of the octahedral sheet composition. Clay Miner 25: 197–205.CrossRefGoogle Scholar
Davison, N., McWhinnie, W.R. and Hooper, A.. 1991. X-ray photoelectron spectroscopic study of cobalt(II) and nickel(II) sorbed on hectorite and montmorillonite. Clays & Clay Miner 39: 22–27.CrossRefGoogle Scholar
Engelhardt, G. and Michel, D.. 1987. High-resolution solid-state NMR of silicates and zeolites. Chichester: J. Wiley and Sons. 147–149.Google Scholar
Fahn, R. and Fenderl, K.. 1983. Reaction products of organic dye molecules with acid-treated montmorillonite. Clay Miner 18: 447–458.CrossRefGoogle Scholar
Farmer, V.C.. 1974. Layer silicates. In: Farmer, V.C., editor. Infrared spectra of minerals. London: The Mineralogical Society. 331–363.CrossRefGoogle Scholar
Gastuche, M.C. and Fripiat, J.J.. 1962. Acid dissolution techniques applied to the determination of the structure of clay and controlled by physical methods. Sci Ceram 1: 121–138.Google Scholar
Hsu, P.H.. 1992. Reaction of OH-A1 polymers with smectites and vermiculites. Clays & Clay Miner 40: 300–305.CrossRefGoogle Scholar
Jaynes, W.F., Traina, S.J., Bigham, J.M. and Johnston, C.T.. 1992. Preparation and characterization of reduced-charge hectorite. Clays & Clay Miner 40: 397–404.CrossRefGoogle Scholar
Kinsey, R.A., Kirkpatrick, R.J., Hower, J., Smith, K.A. and Oldfield, E.. 1985. High resolution aluminum-27 and silicon-29 nuclear magnetic resonance spectroscopic study of layer silicates, including clay minerals. Am Miner 70: 537–548.Google Scholar
Komadel, P., Schmidt, D., Madejová, J. and Číčel, B.. 1990. Alteration of smectites by treatments with hydrochloric acid and sodium carbonate solutions. Appl Clay Sci 5: 113–122.CrossRefGoogle Scholar
Komadel, P., Stucki, J.W. and Číčel, B.. 1993. Readily HCl-soluble iron in the fine fractions of some Czech bentonites. Geol Carpathica Ser Clays 44: 11–16.Google Scholar
Komarneni, S., Fyfe, C.A., Kennedy, G.J. and Strobl, H.. 1986. Characterization of synthetic and naturally occurring clays by 27Al and 29Si magic-angle spinning NMR spectroscopy. J Am Ceram Soc 69: C45–C47.CrossRefGoogle Scholar
Luca, V., Chen, X. and Kevan, L.. 1991. Characterization of copper(II)-substituted synthetic fluorohectorite clay and interaction with adsorbates by ESR, ESEM and IR spectroscopies. Chem Mater 3: 1073–1081.CrossRefGoogle Scholar
Luca, V. and MacLachlan, D.J.. 1992. Site occupancy in nontronite studied by acid dissolution and Mössbauer spectroscopy. Clays & Clay Miner 40: 1–7.CrossRefGoogle Scholar
Mäji, M., Lippmaa, E., Samoson, A., Engelhardt, G. and Grimmer, A.R.. 1984. Solid-state high-resolution silicon-29 chemical shifts in silicates. J Phys Chem 88: 1518–1522.Google Scholar
Moenke, H.H.W.. 1974. Silica, the three-dimensional silicates, borosilicates, and berylium silicates. In: Farmer, V.C., editor. Infrared spectra of minerals. London: The Mineralogical Society. 365–382.CrossRefGoogle Scholar
Novák, I. and Číčel, B.. 1978. Dissolution of smectites in hydrochloric acid: II. Dissolution rate as a function of crystal-lochemical composition. Clays & Clay Miner 26: 141–144.CrossRefGoogle Scholar
Osthaus, B.B.. 1956. Kinetic studies on montmorillonites and nontronite by the acid-dissolution technique. Clays & Clay Miner 4: 301–321.CrossRefGoogle Scholar
Rhodes, C.N. and Brown, D.R.. 1992. Structural characterisation and optimisation of acid-treated montmorillonite and high-porosity silica supports for ZnCl2 alkylation catalysts. J Chem Soc Faraday Trans 88: 2269–2274.CrossRefGoogle Scholar
Rhodes, C.N. and Brown, D.R.. 1993. Surface properties and porosities of silica and acid-treated montmorillonite catalyst supports: Influence on activities of supported ZnCl2 alkylation catalysts. J Chem Soc Faraday Trans 89: 1387–1391.CrossRefGoogle Scholar
Rhodes, C.N., Franks, M., Parkes, G.M.B. and Brown, D.R.. 1991. The effect of acid treatment on the activity of clay supports for ZnCl2 alkylation catalysts. J Chem Soc Chem Comm 804–807.CrossRefGoogle Scholar
Sanz, J. and Robert, J.L.. 1992. Influence of structural factors on 29Si and 27A1 NMR chemical shifts of phyllosilicates 2: 1. Phys Chem Minerals 19: 39–45.CrossRefGoogle Scholar
Schmidt, D., Komadel, P., Madejová, J. and Číčel, B.. 1990. Changes in mixed-layer clay from Friedland upon HC1 and Na2CO3 treatments. Silikattechnik 41: 347–349.Google Scholar
Siddiqui, M.K.H.. 1968. Bleaching Earths. Oxford: Pergamon Press. 32p.CrossRefGoogle Scholar
Slade, P.G., Quirk, J.P. and Norrish, K.. 1991. Crystalline swelling of smectite samples in concentrated NaCl solutions in relation to layer charge. Clays & Clay Miner 39: 234–238.10.1346/CCMN.1991.0390302CrossRefGoogle Scholar
Tkáč, I., Komadel, P. and Müller, D.. 1994. Acid treated montmorillonites—a 29Si and 27Al MAS-NMR study. Clay Miner 29: 11–19.CrossRefGoogle Scholar
Villemure, G.. 1990. Effect of negative surface-charge densities of smectite clays on the adsorption isotherms of racemic and enantiomeric tris(2,2'-bypyridyl)ruthenium(II) chloride. Clays & Clay Miner 38: 622–630.CrossRefGoogle Scholar
Weiss, C.A., Altaner, S.P. and Kirkpatrick, R.J.. 1987. High resolution 29Si NMR spectroscopy of 2: 1 layer silicates: correlations among chemical shifts, structural distortions and chemical variations. Am Miner 72: 935–942.Google Scholar
White, W.B.. 1974. The carbonate minerals. In: Farmer, V.C., editor. Infrared spectra of minerals. London: The Mineralogical Society. 227–284.CrossRefGoogle Scholar