Hostname: page-component-78c5997874-v9fdk Total loading time: 0 Render date: 2024-11-02T20:00:37.140Z Has data issue: false hasContentIssue false

Kaolinite hydroxyls in dimethylsulphoxide-intercalated kaolinites at 77 K – a Raman spectroscopic study

Published online by Cambridge University Press:  09 July 2018

R. L. Frost*
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001, Australia
J. Kristof
Affiliation:
Department of Analytical Chemistry, University of Veszprem, H 8201 Veszprem, PO Box 158
E. Horvath
Affiliation:
Research Group for Analytical Chemistry, Hungarian Academy of Sciences, H8201 Veszprem, PO Box 158, Hungary
J. T. Kloprogge
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Queensland 4001, Australia
*

Abstract

Kaolinite hydroxyls in dimethylsulphoxide-intercalated (DMSO-intercalated) kaolinites have been determined using Raman spectroscopy at 298 and 77 K. The inner surface hydroxyl frequencies at 3650, 3670, 3684 and 3693 cm-1 move to higher wavenumbers upon cooling to 77 K and are observed at 3659, 3676, 3692 and 3702 cm-1. The inner hydroxyl frequency is at 3620 cm-1 at 298 K and is at 3615 cm-1 at 77 K. Upon intercalation with DMSO, additional bands are found at 3660, 3536 and 3501 cm-1 for the low-defect kaolinite and at 3664, 3543 and 3509 cm-1 for the high-defect kaolinite at 298 K. The 3660 cm-1 band at 298 K is resolved into two bands at 3658 and 3663 cm-1 at 77 K for the low-defect kaolinite and these bands are assigned to the inner surface hydroxyl groups, hydrogen-bonded to the DMSO molecule. It is proposed that the DMSO molecule exists with two different orientations in the intercalate and these two molecular forms are differentiated by the OH-stretching bands of the inner surface hydroxyl groups. This band for the high-defect kaolinite is found at 3664 cm-1 at 298 K and resolves into two bands at 3664 and 3673 cm-1 at 77 K.

Type
Research Article
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

Brindley, G.W., Kao, C., Harrison, J.L., Lipsiscas, M. & Raythatha, R. (1986) Relation between the structural disorder and other characteristics of kaolinites and dickites. Clays Clay Miner. 34, 233–249.CrossRefGoogle Scholar
Churchman, G.J. (1990) Relevance of different intercalation tests for distinguishing halloysite from kaolinite in soils. Clays Clay Miner. 38, 591–599.Google Scholar
Costanzo, P.M. & Giese, R.F. (1986) Ordered halloysite: dimethyl sulphoxide intercalate. Clays Clay Miner. 34, 105–107.Google Scholar
Costanzo, P.M. & Giese, R.F. (1990) Ordered and disordered organic intercalates of 8.4 Å synthetically hydrated kaolinite. Clays Clay Miner. 38, 160–170.Google Scholar
Costanzo, P.M., Giese, R.F. & Clemency, C.V. (1984) Synthesis of a 10 Å hydrated kaolinite. Clays Clay Miner. 32, 29–35.Google Scholar
Farmer, V.C. (1974) The Infrared Spectra of Minerals (Farmer, V.C., editor). Monograph 4, Mineralogical Society, London.Google Scholar
Farmer, V.C. (1998) Differing effects of particle size and shape in the infrared spectra of kaolinite. Clay Miner. 33, 601–604.Google Scholar
Frost, R.L. (1995) Fourier transform Raman spectroscopy of kaolinite, dickite and halloysite. Clays Clay Miner. 43, 191–195.Google Scholar
Frost, R.L. (1997) The structure of the kaolinite clay minerals–an FT Raman study. Clay Miner. 32, 73–85.Google Scholar
Frost, R.L. & Kristof, J. (1997) Intercalation of halloysite–a Raman spectroscopic study. Clays Clay Miner. 45, 68–72.Google Scholar
Frost, R.L. & Shurvell, H.F. (1997) Raman microprobe spectroscopy of halloysite. Clays Clay Miner. 45, 68–72.Google Scholar
Frost, R.L. & Van der Gaast, S.J. (1997) Kaolinite hydroxyls–a Raman microscopy study. Clay Miner. 32, 293–306.Google Scholar
Frost, R.L., Tran, T.H. & Kristof, J. (1997) Intercalation of an ordered kaolinite–a Raman microscopy study. Clay Miner. 32, 587–596.Google Scholar
Frost, R.L., Kristof, J., Paroz, G.N. & Kloprogge, J.T. (1998) Molecular structure of dimethylsulphoxide intercalated kaolinite. J. Phys. Chem. B, 102, 8519–8532.CrossRefGoogle Scholar
González, G.S. & Sánchez, C. (1968) Differentiation of kaolinite from chlorite by treatment with dimethyl sulphoxide. Clay Miner. 7, 447–450.Google Scholar
Hayashi, S. (1995) NMR study of dynamics of dimethyl sulfoxide molecules in kaolinite/dimethyl sulfoxide intercalation compound. J. Phys. Chem. 99, 7120–7129.Google Scholar
Hayashi, S. (1997) NMR study of dynamics and evolution of guest molecules in kaolinite/dimethyl sulfoxide intercalation compound. Clays Clay Miner. 45, 724–732.Google Scholar
Hayashi, S. & Akiba, E. (1994) Interatomic distances in layered silicates and their intercalation compounds as studied by cross polarization NMR. Chem. Phys. Lett. 26, 495–500.Google Scholar
Heller-Kallai, L., Huard, E. & Prost, R. (1991) Disorder induced by de-intercalation of DMSO from kaolinite. Clay Miner. 26, 245–253.CrossRefGoogle Scholar
Johansson, U., Frost, R.L., Forsling, W. & Kloprogge, J.T. (1998) Raman spectroscopy of the kaolinite hydroxyls at 77 K. Appl. Spectrosc. 52, 1277–1282.Google Scholar
Johnston, C.T, Sposito, G., Bocian, D.F. & Birge, R.R. (1984) Vibrational spectroscopic study of the interlamellar kaolinite-dimethyl sulfoxide complex. J. Phys. Chem. 88, 5959–5964.Google Scholar
Johnston, C.T., Sposito, G. & Birge, R.R. (1985) Raman spectroscopic study of kaolinite in aqueous suspension. Clays Clay Miner. 33, 483–489.Google Scholar
Lahav, N. (1990) Preparation of stable suspensions of delaminated kaolinite by combined dimethylsulfoxide- ammonium fluoride treatment. Clays Clay Miner. 38, 219–222.Google Scholar
Lapides, I., Lahav, N., Michaelian, K.H. & Yariv, S. (1997) X-ray study of the thermal intercalation of alkali halides into kaolinite. J. Therm. Anal. 49, 1423–1432.Google Scholar
Michaelian, K.H. (1986) The Raman spectrum of kaolinite #9 at 21°C. Can. J. Chem. 64, 285–289.Google Scholar
Olejnik, S., Alymore, L.A.G., Posner, A.M. & Quirk, J.P. (1968) Infrared spectra of kaolin-dimethyl sulphoxide complexes. J. Phys. Chem. 72, 241–249.Google Scholar
Olejnik, S., Posner, A.M. & Quirk, J.P. (1970) Intercalation of polar organic compounds into kaolinite. Clay Miner. 8, 421–434.Google Scholar
Prost, R., Damene, A.S., Huard, E., Driard, J. & Leydecker, J.P. (1989) Infrared study of structural OH in kaolinite, dickite, and nacrite and poorly crystalline kaolinite at 5 to 600 K. Clays Clay Miner. 37, 464–468.Google Scholar
Raupach, M. (1988) Infrared band frequency shifts and dipole interactions at surfaces of inorganic and organic clay intercalates. J. Coll. Interf. Sci. 121, 476–485.Google Scholar
Raupach, M., Barron, P.F. & Thompson, J.G. (1987) Nuclear magnetic resonance, infrared, and X-ray powder diffraction study of dimethylsulfoxide and dimethylselenoxide intercalates with kaolinite. Clays Clay Miner. 35, 208–219.Google Scholar
Rintoul, L. & Shurvell, H.F. (1990) A Raman spectroscopic study of complex formation of dimethylsulphoxide in chloroform. J. Raman Spectr. 21, 501–511.Google Scholar
Rouxhet, P.G., Samudacheata, N., Jacobs, H. & Anton, O. (1977) Attribution of the OH stretching bands of kaolinite. Clay Miner. 12, 171–178.Google Scholar
Thompson, J.G. (1985) Interpretation of solid state 13C and 29Si nuclear magnetic resonance spectra of kaolinite intercalates. Clays Clay Miner. 33, 173–180.Google Scholar
Thompson, J.G. & Cuff, C. (1985) Crystal structure of kaolinite:dimethyl sulfoxide intercalate. Clays Clay Miner. 33, 490–500.Google Scholar
van der Marel, H.W. & Beutelspacher, H. (1976) Atlas of Infrared Spectroscopy of Clay Minerals and their Admixtures. Elsevier, Amsterdam.Google Scholar
Wada, K. (1967) A study of hydroxyl groups in kaolin minerals utilising selective deuteration and infrared spectroscopy. Clay Miner. 7, 51–61.Google Scholar
Wiewiora, A., Wieckowski, T. & Sokolowska, A. (1979) The Raman spectra of kaolinite subgroup minerals and of pyrophyllite. Arch. Mineral. 135, 5–14.Google Scholar