Hostname: page-component-78c5997874-xbtfd Total loading time: 0 Render date: 2024-11-10T14:38:27.678Z Has data issue: false hasContentIssue false
  • English
  • Français

Effects of chemical composition and temperature of heating on the infrared spectra of Li-saturated dioctahedral smectites. (I) Mid-infrared region

Published online by Cambridge University Press:  09 July 2018

J. Madejová ,
J. Bujdák ,
S. Petit  and
P. Komadel
J. Madejová*
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-842 36 Bratislava, Slovakia
J. Bujdák
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-842 36 Bratislava, Slovakia
S. Petit
Affiliation:
Université de Poitiers, CNRS UMR 6532 ‘HydrASA’, 40, avenue du Recteur Pineau, F-86022 Poitiers Cedex, France
P. Komadel
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-842 36 Bratislava, Slovakia
*
*E-mail: uachjmad@savba.sk
Get access Rights & Permissions [Opens in a new window]

Abstract

Infrared spectroscopy in the mid-IR region was used to follow the structural changes occurring in five Li-saturated dioctahedral smectites upon heating. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Fixation of Li+ ions in the structure even upon heating at 120°C caused the appearance of an AlMgLiOH-stretching band near 3670 cm–1 in the spectra of all three montmorillonites. This band confirmed the presence of Li(I) in the previously vacant octahedral positions in montmorillonites. No similar band was observed in the spectra of ferruginous heated smectites with prevailing tetrahedral charge. A gradual upward frequency shift and decrease in intensity of the AlAlOH-bending band showed that Li(I) present in the hexagonal cavities causes pronouncedperturbation of this OH-bending mode. The Li(I) present in the octahedral sheets causes small perturbations of the OH-bending mode near 850 cm–1 and activation of a new OH-bending mode near 803 cm–1. Reversible changes in the positions of the stretching Si–O and bending OH bands in the spectra of Fe-beidellite and a ferruginous smectite proved that Li was present in these minerals primarily in the hexagonal holes of the tetrahedral sheets.

Keywords

smectiteLi fixationIR spectramid-IR region
Type
Research Article
Information
Clay Minerals , Volume 35 , Issue 5 , December 2000 , pp. 739 - 751
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2000

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Alba, M.D., Alvero, R., Becerro, A.I., Castro, M.A. & Trillo, J.M. (1998) Chemical behaviour of lithium ions in reexpanded Li-montmorillonites. J. Phys. Chem. 102, 2207–2213.Google Scholar
Alvero, R., Alba, M.D., Castro, M.A. & Trillo, J.M. (1994) Reversible migration of lithium in montmorillonite. J. Phys. Chem. 98, 7848–7853.Google Scholar
Calvet, R. & Prost, R. (1971) Cation migration into empty octahedral sites and surface properties of clays. Clays Clay Miner. 19, 175–186.Google Scholar
Chorom, M. & Rengasamy, P. (1996) Effect of heating on swelling and dispersion of different cationic forms of a smectite. Clays Clay Miner. 44, 783–790.CrossRefGoogle Scholar
Drits, V.A., Dainyak, L.G., Muller, F., Besson, G. & Manceau, A. (1997) Isomorphous cation distribution in celadonites, glauconites and Fe-illites determined by infrared, Mössbauer and EXAFS spectroscopies. Clay Miner. 32, 153–179.CrossRefGoogle Scholar
Emmerich, K., Madsen, F.T. & Kahr, G. (1999) Dehydroxylation behaviour of heat-treated and steam-treated homoionic cis-vacant octahedra. Clays Clay Miner. 47, 591–604.CrossRefGoogle Scholar
Farmer, V.C. (1974) Layer silicates. Pp. 331–363 in: Infrared Spectra of Minerals (Farmer, V.C., editor). Monograph 4, Mineralogical Society, London.Google Scholar
Heller-Kallai, L. & Mosser, C. (1995) Migration of Cu ions in Cu montmorillonite heated with and without alkali halides. Clays Clay Miner. 43, 738–743.CrossRefGoogle Scholar
Hofmann, U. & Klemen, R. (1950) Verlust der Austauschfähigkeit von Lithiuminonen an Bentonit durch Erhitzung. Z. Anorg. Allg. Chem. 262, 95–99.CrossRefGoogle Scholar
Jaynes, W.F. & Bigham, J.M. (1987) Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites. Clays Clay Miner. 35, 440–448.Google Scholar
Karakassides, M.A., Petridis, D. & Gournis, D. (1997) Infrared reflectance study of thermally treated Li- and Cs-montmorillonites. Clays Clay Miner. 45, 649–658.Google Scholar
Karakassides, M.A., Gournis, D. & Petridis, D. (1999) An infrared reflectance study of Si-O vibrations in thermally treated alkali-saturated montmorillonites. Clay Miner. 34, 429–438.Google Scholar
Kitajima, K., Taruta, S. & Takusagawa, N. (1991) Effect of layer charge on the IR spectra of synthetic fluorine micas. Clay Miner. 26, 435–440.Google Scholar
Komadel, P., Bujdák, J., Madejová, J., Šucha, V. & Elsass, F. (1996) Effect of non-swelling layers on the dissolution of reduced-charge montmorillonite in hydrochloric acid. Clay Miner. 31, 333–345.Google Scholar
Madejová, J., Bujdák, J., Gates, W.P. & Komadel, P. (1996) Preparation and infrared spectroscopic characterization of reduced-charge montmorillonite with various Li content. Clay Miner. 31, 233–241.CrossRefGoogle Scholar
Madejová, J., Bujdák, J., Janek, M. & Komadel, P. (1998) Comparative FT-IR study of structural modifications during acid treatment of dioctahedral smectites and hectorite. Spectrochim. Acta, Part A, 54, 1397–1406.CrossRefGoogle Scholar
Madejová, J., Arvaiová, B. & Komadel, P. (1999) FTIR spectroscopic characterization of thermally treated Cu2+, Cd2+, and Li+ montmorillonites. Spectrochim. Acta, Part A, 55, 2467–2476.CrossRefGoogle Scholar
McBride, M.B. & Mortland, M.M. (1974) Copper (II) interactions with montmorillonite: Evidence from physical methods. Soil Sci. Soc. Am. Proc. 38, 408–415.CrossRefGoogle Scholar
Moenke, H.H.W. (1974) Silica, the three-dimensional silicates, borosilicates and beryllium silicates. Pp. 365–382 in: Infrared Spectra of Minerals (Farmer, V.C., editor). Monograph 4, Mineralogical Society, London.Google Scholar
Mosser, C., Michot, L.J., Villieras, F. & Romeo, M. (1997) Migration of cations in copper(II)-exchanged montmorillonite and laponite upon heating. Clays Clay Miner. 45, 789–802.CrossRefGoogle Scholar
Muller, F., Besson, G., Manceau, A. & Drits, V.A. (1997) Distribution of isomorphous cations within octahedral sheets in montmorillonite from Camp-Bertaux. Phys. Chem. Miner. 24, 159–166.Google Scholar
Odom, I.E. (1984) Smectite clay minerals: Properties and uses. Phil. Trans. Royal Soc. London, A311, 391–409.Google Scholar
Robert, J.L. & Kodama, H. (1988) Generalization of the correlations between hydroxyl- stretching wave-numbers and composition of micas in the system K2O-MgO-Al2O3-SiO2-H2O: A single model for trioctahedral and dioctahedral micas. Am. J. Sci. 228A, 196–212.Google Scholar
Rothbauer, R. (1971) Study of 2M1-muscovite by neutron diffraction. Neues Jahrb Miner. Mh. 4, 143–159.Google Scholar
Russell, J.D. & Farmer, V.C. (1964) Infrared spectroscopic study of the dehydration of montmorillonite and saponite. Clay Miner. Bull. 5, 443–464.CrossRefGoogle Scholar
Russell, J.D. & Fraser, A.R. (1994) Infrared methods. Pp. 11–67 in: Clay Mineralogy: Spectroscopic and Chemical Determinative Methods (Wilson, M.J., editor). Chapman & Hall, London.Google Scholar
Sanz, J. & Robert, J.L. (1992) Influence of structural factors on 29Si and 27Al NMR chemical shifts of phyllosilicates 2:1. Phys. Chem. Miner. 19, 39–45.Google Scholar
Sposito, G., Prost, R. & Gaultier, J.P. (1983) Infrared spectroscopic study of adsorbed water on reduced-charge Na/Li montmorillonites. Clays Clay Miner. 31, 9–16.CrossRefGoogle Scholar
Srasra, E., Bergaya, F. & Fripiat, J.J. (1994) Infrared spectroscopy study of tetrahedral and octahedral substitutions in an interstratified illite-smectite clay. Clays Clay Miner. 42, 237–241.Google Scholar
Theng, B.K.G., Hayashi, S., Soma, M. & Seyama, H. (1997) Nuclear magnetic resonance and X-ray photoelectron spectroscopic investigation of lithium migration in montmorillonite. Clays Clay Miner. 45, 718–723.CrossRefGoogle Scholar
Wilson, M.J. (editor) (1994) Clay Mineralogy: Spectroscopic and Chemical Determinative Methods. Chapman & Hall, London.Google Scholar
Yan, L. & Stucki, J.W. (1999) Effects of structural Fe oxidation state on the coupling of interlayer water and structural Si-O stretching vibrations in montmorillonite. Langmuir, 15, 4648–4657.Google Scholar