Hostname: page-component-78c5997874-dh8gc Total loading time: 0 Render date: 2024-11-02T19:20:35.788Z Has data issue: false hasContentIssue false
  • English
  • Français

Infrared Studies of the Hydroxyl Groups in Intercalated Kaolinite Complexes

Published online by Cambridge University Press:  01 January 2024

Robert L. Ledoux  and
Joe L. White
Robert L. Ledoux
Affiliation:
Université Laval, Québec, P.Qué., Canada
Joe L. White
Affiliation:
Purdue University, Lafayette, Indiana, USA
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Expansion of kaolinite with potassium acetate reduces the intensity of the 3695 cm−1 absorption band and causes the appearance of an additional one at 3600 cm−1. Subsequent deuteration with D2O vapor shifts the 3695 cm−1 and 3600 cm−1 absorption bands to 2725 cm−1 and 2650 cm−1 respectively. The hydroxyls absorbing at 3620 cm−1 do not interact with the acetate anion and do not readily exchange with D2O vapor.

Deuteration of expanded hydrazine-kaolinite complex at room temperature shifts the infrared stretching frequencies 3695, 3670, 3650 and 3620 cm−1 to 2725, 2710, 2698 and 2675 cm−1 respectively. The OH-OD exchanges for the hydroxyls absorbing at 3695, 3670 and 3650 cm−1 are 67, 60 and 62 per cent respectively, and for the 3620 cm−1 only 22 per cent. The 3695, 3670 and 3650 cm−1 absorption bands are correlated predominantly to inner-surface hydroxyls and the 3620 cm−1 to inner hydroxyls located below the holes in the silica tetrahedral layer.

The ν(OH) absorption bands at 3695, 3670 and 3650 cm−1, and the ν(OD) at 2725, 2698, and 2675 cm−1 are pleochroic, whereas the 3620 cm−1 absorption band is non-pleochroic. The direction of the dipole moment change of OH groups absorbing at 3695 cm−1 and 3670 cm−1, and of OD groups absorbing at 2725 cm−1 and 2698 cm−1, is nearly at right angles to the basal plane (001); for the 3650 cm−1 and 2675 cm−1 bands, the angle is large, but less than 90°. The inner hydroxyls absorbing at 3620 cm−1 have their dipole moment change inclined at about 15° to the “ab” cleavage plane.

A comparison of the ν(OH) and ν(OD) absorption intensities for the film rotated 45° and normal to the infrared incident radiation shows that the pleochroism is more intense in the ν(OD) region than in the ν(OH) region. This indicates that partial deuteration perturbs the direction of dipole moment change of the “hydrogen bond” with respect to the initial orientation prior to deuteration; the net result is the formation of larger angles between the direction of the OD dipole moment changes and the basal plane (001) than existed for OH prior to deuteration.

Type
General Session
Information
Clays and Clay Minerals (National Conference on Clays and Clay Minerals) , Volume 13 , February 1964 , pp. 289 - 315
Copyright
Copyright © The Clay Minerals Society 1964

Footnotes

Journal paper No. 2423 of the Purdue University Agricultural Experiment Station, Lafayette, Indiana.

References

Andrew, R. M., Jackson, M. L·., and Wada, K. (1960) Intersalation as a technique for identification of kaolinite from chloritic materials by X-ray diffraction, Soil Sci. Soc. Am., Proc. 24, 422–4.CrossRefGoogle Scholar
Auskern, A, and Grimshaw, R. W. (1955) Differences between the infrared absorption spectra of some clays and related minerals (abstract), Program of the Fourth National Clay Conference, Pennsylvania State University.Google Scholar
Bassett, W. A. (1960) Role of hydroxyl orientation in mica alteration, Bull. Geol. Soc. Am. 71, 449–56.CrossRefGoogle Scholar
Busing, W. R., and Levy, H. A. (1958) A single crystal neutron diffraction study of diaspore, AIO(OH), Acta Cryst. 11, 798–803.CrossRefGoogle Scholar
Catalano, E., Sanborn, R. H., and Frazer, J. W. (1963) On the infrared spectrum of hydrazine matrix-isolation studies of the system NH2NH2: N2 (1), J. Chem. Phys. 38, 2265–72.Google Scholar
Diamond, S., and Kinter, E. V. (1958) Surface area of clay minerals as derived from measurements of glycerol retention, Clays and Clay Minerals, Nat. Acad. Sci.— Nat. Res. Council, Publ. 566, pp. 334–7.Google Scholar
Frederickson, L. D. (1954) Characterization of hydrated aluminas by infrared spectroscopy; application to study of bauxite ores, Anal. Chem. 26, 1883–5.Google Scholar
Fripiat, J. J., and Toussaint, F. (1960) Pre-dehydroxylation state of kaolinite, Nature 186, 627.CrossRefGoogle Scholar
Fripiat, J. J., and Toussaint, F. (1963) Dehydroxylation of kaolinite, II, Conductometric measurements and infrared spectroscopy, J. Phys. Chem. 67, 30–6.CrossRefGoogle Scholar
Giguere, P. A., and Liu, I. D. (1952) Infrared spectrum of hydrazine, J. Chem. Phys., 20, 136–40.CrossRefGoogle Scholar
Hallan, E. E. (1963) Infra-Red Spectroscopy and Molecular Structure (Edited by Davies, M.), p. 418, Elsevier, New York.Google Scholar
Huggins, C. M., and Pimentel, G. C. (1956) Systematics of the infrared spectral properties of hydrogen bonding systems: frequency shift, half width, and intensity,, J. Phys. Chem. 60, 1615–19.CrossRefGoogle Scholar
Krimm, S. (1963) Infra-Red Spectroscopy and Molecular Structure (Edited by M, Davies)., p. 287, Elsevier, New York.Google Scholar
McDonald, R. S. (1958) Surface functionality of amorphous silica by infrared spectroscopy, J. Phys. Chem. 62, 1168–78.CrossRefGoogle Scholar
Nakamoto, K, (1963) Infrared Spectra of Inorganic and Coordination Compounds, John Wiley, New York.Google Scholar
Newnham, R. E. (1960) A refinement of the dickite structure and some remarks on polymorphism in kaolin minerals, Massachusetts Inst. Technology, Lab. Insulation. Res., Tech. Rep. 148, pp. 1–30.Google Scholar
Rosenqvist, Th. (1963) Studies in position and mobility of the H atoms in hydrous micas, Clays and Clay Minerals, 11th Conf. [1962], pp. 117–35, Pergamon Press, New York.Google Scholar
Roy, D. M., and Roy, R. (1957) Hydrogen-deuterium exchange in clays and problems in the assignment of infrared frequencies in the hydroxyl region, Geochim. Cosmochim. Acta 11, 72–85.CrossRefGoogle Scholar
Serratosa, J. M., and Bradley, W. F. (1958) Determination of the orientation of OH bond axes in layer silicates by infrared absorption, J. Phys. Chem. 62, 1164–7.CrossRefGoogle Scholar
Serratosa, J. M., Hidalgo, J. M. A., and Vinas, J. M. (1962) Orientation of OH bonds in kaolinite, Nature, 195, 486–7.CrossRefGoogle Scholar
Serratosa, J. M., Hidalgo, J. M. A., and Vinas, J. M. (1963) Infrared study of the OH groups in kaolin minerals, International Clay Conference, Sweden (Edited by Rosenqvist, Th. and Graff-Petersen, P.), pp. 17–26, Pergamon Press, New York.Google Scholar
Van der Marel, H. W., and Zwiers, J. H. L. (1958) OH stretching bands of the kaolin minerals, Silicates Ind. 24, 359–68.Google Scholar
Vedder, W., and McDonald, R. S. (1963) Vibrations of the OH ions in muscovite, J. Chem. Phys. 38, 1583–90.CrossRefGoogle Scholar
Wada, K. (1961) Lattice expansion of kaolin minerals by treatment with potassium acetate, Am. Mineralogist 46, 78–91.Google Scholar
Wadsworth, M. E., Mackay, T. L., and Cutler, I. V. (1955) Surface and internal structure of clay minerals as indicated by infrared spectra, Am. Ceram. Soc. Bull. 33, 15–20.Google Scholar
Weiss, A., Thielepape, W., Goring, G., Ritter, W., and Schafer, H. (1963a) Kaolinite-einlagerungs-verbindungen, International Clay Conference, Sweden (Edited by Rosenqvist, Th. and Graff-Petersen, P.), pp. 287–301, Pergamon Press, New York.Google Scholar
Weiss, A., Thielepape, W., Ritter, W., Schafer, E., and Goring, W. (1963b) Zur Kenntnis von hydrazin-kaolinit, Z. Anorg. Allgem. Chem. 320, 183–204.CrossRefGoogle Scholar
White, J. L. (1956) Reactions of molten salts with layer-lattice silicates, Clays and Clay Minerals, Nat. Acad. Sci.—Nat. Res. Council, Publ. 456, pp. 133–46.Google Scholar
Wolff, R. G. (1963) Structural aspects of kaolinite using infrared absorption, Am. Mineralogist 48, 390–9.Google Scholar