Hostname: page-component-cd9895bd7-jn8rn Total loading time: 0 Render date: 2024-12-26T18:29:51.621Z Has data issue: false hasContentIssue false
  • English
  • Français

Intercalation of Tetraalkylammonium Cations into Smectites and Its Application to Internal Surface Area Measurements

Published online by Cambridge University Press:  28 February 2024

Louis Mercier  and
Christian Detellier
Louis Mercier
Affiliation:
Ottawa-Carleton Chemistry Institute, University of Ottawa Campus, Ottawa, Ontario, Canada K1N 6N5
Christian Detellier
Affiliation:
Ottawa-Carleton Chemistry Institute, University of Ottawa Campus, Ottawa, Ontario, Canada K1N 6N5
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.

Monolayer to bilayer (MTB) and bilayer to pseudotrimolecular (BTP) transitions were observed for smectites exchanged with symmetrical tetraalkylammonium cations of increasing sizes: +NR4, where R = (CH2)nCH3, with 0 ≤ n ≤ 7. In the case of SWy-1, SHCa-1 and SWa-1, the variation in layer spacing observed from intercalation of tetramethylammonium up to tetraoctylammonium cations showed a behavior characteristic of smectites with homogeneously distributed interlayer cations. In the case of STx-1, the change in interlayer spacing with the increase of the alkyl chain length was characteristic of a very high charge heterogeneity. Higher charge smectites (SAz-1 and SCa-3, CEC > 1.20 mmol/g) were found to have decreasing cation exchange with increasing cation size, resulting in a "leveling off’ of the interlayer spacing toward larger cations. The MTB and BTP transitions were used to determine the internal surface area of various smectites. The proposed method was found to be a quicker and simpler alternative to the polar liquid sorption method for this measurement, but was ineffective for high-charge smectites (CEC > 1.20 mmol/g).

Keywords

HectoriteIntercalationInternal surface areaMontmorilloniteQuaternary ammonium cationsSmectiteTetraalkylammonium cations
Type
Research Article
Information
Clays and Clay Minerals , Volume 42 , Issue 1 , February 1994 , pp. 71 - 76
Copyright
Copyright © 1994, Clay Minerals Society

References

Barrer, R. M., and MacLeod, D. M., (1955) Activation of montmorillonite by ion exchange and sorption complexes of tetra-alkyl ammonium montmorillonite: Trans. Farad. Soc. 51, 1290–1300.CrossRefGoogle Scholar
Barrer, R. M., and Reay, J. S. S., (1957) Sorption and intercalation by methyl-ammonium montmorillonite: Trans. Farad. Soc. 53, 1253–1261.CrossRefGoogle Scholar
Barrer, R. M., and Hampton, M. G., (1957) Gas chromatography and mixtures isotherms in alkyl ammonium bentonites: Trans. Farad. Soc. 53, 1462–1475.CrossRefGoogle Scholar
Barrer, R. M., and Perry, G. S., (1961) Sorption of mixtures, and selectivity in alkylammonium montmorillonites. Parts I & II: J. Chem. Soc., 842–849 and 850–858.Google Scholar
Barrer, R. M., and Brummer, K., (1963) Relations between partial ion exchange and interlamellar sorption in alkylammonium montmorillonites: Trans. Farad. Soc. 59, 959–968.CrossRefGoogle Scholar
Barrer, R. M., and Millington, A. D., (1967) Sorption and intracrystalline porosity in organo-clays: J. Colloid Interface Sci. 25, 359–372.CrossRefGoogle Scholar
Barrer, R. M., (1986) Expanded clay minerals: A major class of molecular sieves: J. Inclusion Phen. 4, 109–119.CrossRefGoogle Scholar
Barrer, R. M., (1989a) Clay minerals as selective and shape-selective sorbents: Pure & Appl. Chem. 61, 1903–1912.CrossRefGoogle Scholar
Barrer, R. M., (1989b) Shape-selective sorbents based on clay minerals: A review: Clays & Clay Minerals 37, 385–395.CrossRefGoogle Scholar
Byrne, P. J. S., (1954) Some observations on montmorillonite-organic complexes: Clays & Clay Minerals 2, 241–253.CrossRefGoogle Scholar
Carter, D. L., Heilman, M. D., and Gonzalez, C. L., (1965) Ethylene glycol monoethyl ether for determining surface area of silicate minerals: Soil Sci. 100, 356–360.CrossRefGoogle Scholar
Chen, C. C., Turner, F. T., and Dixon, J. B., (1989) Ammonium fixation by high-charge smectite in selected Texas Gulf Coast soils: Soil Sci. Soc. Am. J. 53, 1035–1040.CrossRefGoogle Scholar
Clementz, D. M., and Mortland, M. M., (1974) Properties of reduced charge montmorillonite: Tetra-alkylammonium ion exchange forms: Clays & Clay Minerals 22, 223–229.CrossRefGoogle Scholar
Diamond, S., and Kinter, E. B., (1958) Surface area of clay minerals as derived from measurements of glycerol retention: Clays & Clay Minerals 5, 334–347.CrossRefGoogle Scholar
Dyal, R. S., and Hendricks, S. B., (1950) Total surface of clays in polar liquids as a characteristic index: Soil Sci. 69, 421–432.CrossRefGoogle Scholar
Favre, H., and Lagaly, G., (1991) Organo-bentonites with quaternary alkylammonium ions: Clay Miner. 26, 19–32.CrossRefGoogle Scholar
Ghabru, S. K., Mermut, A. R., and St. Arnaud, R. J., (1989) Layer-charge and cation-exchange characteristics of vermiculite (weathered biotite) isolated from a gray luvisol in northeastern Saskatchewan: Clays & Clay Minerals 37, 164–172.CrossRefGoogle Scholar
Häusler, W., and Stanjek, H., (1988) A refined procedure for the determination of the layer charge with alkylammonium ions: Clay Miner. 23, 333–337.CrossRefGoogle Scholar
Jonas, E. C., and Roberson, H. E., (1966) Structural charge density as indicated by montmorillonite hydration: Clays & Clay Minerals 13, 223–230.CrossRefGoogle Scholar
Lagaly, G., and Weiss, A., (1975) The layer charge of smectitic layer silicates: Proc. Int. Clay Conf. Mexico: Applied Publishing Ltd., Willamette, Ill., 157–172.Google Scholar
Lagaly, G., Fernandez Gonzalez, M., and Weiss, A., (1976) Problems in layer-charge determination of montmorillonites: Clay Miner. 11, 173–187.CrossRefGoogle Scholar
Lagaly, G., (1981) Characterisation of clays by organic compounds: Clay Miner. 16, 1–21.CrossRefGoogle Scholar
Lagaly, G., (1982) Layer charge heterogeneity in vermiculites: Clays & Clay Minerals 30, 215–222.CrossRefGoogle Scholar
Laird, D. A., Scott, A. D., and Fenton, T. E., (1987) Interpretation of alkylammonium characterization of soil clays: Soil Sci. Soc. Am. J. 51, 1659–1663.CrossRefGoogle Scholar
Laird, D. A., Fenton, T. E., and Scott, A. D., (1988) Layer charge of smectites in an Argiaboll-Argiaquoll sequence: Soil Sci. Soc. Am. J. 52, 463–467.CrossRefGoogle Scholar
Laird, D. A., Scott, A. D., and Fenton, T. E., (1989) Evaluation of the alkylammonium method of determining layer charge: Clays & Clay Minerals 37, 41–46.CrossRefGoogle Scholar
Lao, H., Latieule, S., and Detellier, C., (1991) Molecular recognition in microporous organo-minerals. Shape-specific interactions of carbon dioxide in functionalized organo-montmorillonite microcavities: Chem. Mater. 3, 1009–1011.CrossRefGoogle Scholar
Madsen, F. T., (1977) Surface area measurements of clay minerals by glycerol sorption on a thermobalance: Thermochimica Acta 21, 89–93.CrossRefGoogle Scholar
Malla, P. B., and Douglas, L. A., (1987) Layer charge properties of smectites and vermiculites: Tetrahedral vs. octahedral: Soil Sci. Soc. Am. J. 51, 1362–1366.CrossRefGoogle Scholar
McAtee, J. L., (1958a) Heterogeneity in montmorillonite: Clays & Clay Minerals 5, 279–288.CrossRefGoogle Scholar
McAtee, J. L., (1958b) Random interstratification in organophilic bentonites: Clays & Clay Minerals 5, 308–317.CrossRefGoogle Scholar
McAtee, J. L., (1962) Cation exchange of organic compounds on montmorillonite in organic media: Clays & Clay Minerals 9, 444–450.CrossRefGoogle Scholar
McAtee, J. L., (1963) Organic cation exchange on montmorillonite as observed by ultraviolet analysis: Clays & Clay Minerals 10, 53–162.Google Scholar
Mercier, L., (1991) Intercalation of tetraalkylammonium cations into smectites: Honours thesis, University of Ottawa, 55 pp.Google Scholar
Olis, A. C., Malla, P. B., and Douglas, L. A., (1990) The rapid estimation of the layer charges of 2: 1 expanding clays from a single alkylammonium ion expansion: Clay Miner. 25, 39–50.CrossRefGoogle Scholar
Rüehlicke, 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
Rüehlicke, G., and Niederbudde, E. A., (1985) Determination of layer-charge density of expandable 2: 1 clay minerals in soils and loess sediments using the alkylammonium method: Clay Miner. 20, 291–300.CrossRefGoogle Scholar
Stanjek, H., and Friedrich, R., (1986) The determination of layer charge by curve-fitting of Lorentz- and polarization-corrected X-ray diagrams: Clay Miner. 21, 183–190.CrossRefGoogle Scholar
Stanjek, H., Niederbudde, E. A., and Häusler, W., (1992) Improved evaluation of layer charge of n-alkylammonium-treated fine soil clays by Lorentz- and polarization-correction and curve fitting: Clay Miner. 27, 3–19.CrossRefGoogle Scholar
Stul, M. S., and Mortier, W. J., (1974) The heterogeneity of the charge density in montmorillonites: Clays & Clay Minerals 22, 391–396.CrossRefGoogle Scholar
Tettenhorst, R., and Johns, W. D., (1966) Interstratification in montmorillonites: Clays & Clay Minerals 25, 85–93.Google Scholar
Val Olphen, H., (1977) An Introduction to Clay Colloid Chemistry: Wiley Interscience, New York , 318 pp.Google Scholar
Villemure, G., (1987) Photochemical applications of the intercalation of organic cations in clay minerals: Ph.D. thesis, University of Ottawa, 238 pp.Google Scholar
Weiss, A., Becker, H. O., and Lagaly, G., (1969) Determination of charge density sequence in regular interstratified mica-type layer silicates by means of their n-alkylammonium derivatives: Proc. Int. Clay Conf. Tokyo 1, 67–72.Google Scholar