Hostname: page-component-cd9895bd7-dzt6s Total loading time: 0 Render date: 2024-12-23T14:33:06.913Z Has data issue: false hasContentIssue false

Effect of pH on the cation exchange capacity of some halloysite nanotubes

Published online by Cambridge University Press:  02 January 2018

Nia Gray*
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
David G. Lumsdon
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
Stephen Hillier
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK Department of Soil and Environment, Swedish University of Agricultural Sciences (SLU), Uppsala SE-75007, Sweden
*

Abstract

The cation exchange capacity (CEC) of seven well characterized halloysite nanotubes (HNTs) in the dehydrated 7 Å form has been measured using a method based on cobalt hexammine exchange. In addition to unbuffered measurements, which varied between 2.9 and 9.3 cmol(+)kg−1, CECs were also determined over a wide pH range and proton titration measurements were conducted on two samples. The data were fitted using a constant capacitance model based on the presence of two sites: permanently charged sites and pH-dependent variable charged sites. Normalization of CEC to the average specific surface area (BET) of the halloysite samples reduces considerably the variation of CEC values for the different samples particularly over the intermediate pH range (5–9) with the average value at pH 7 equal to 8.5 cmol(+)kg−1 and a standard deviation of 1.17. Overall the CEC behaviour of the seven samples appears reasonably consistent throughout the set. Calculations based on proton titrations suggest a ratio of variable charge to basal sites for the dehydrated halloysite nanotubes of ∼3:1.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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

Angove, M.J., Johnson, B.B. & Wells, J.D. (1997) Adsorption of cadmium(II) on kaolinite. Colloids and Surfaces A — Physicochemical and Engineering Aspects, 126, 137147.Google Scholar
Aran, D., Maul, A. & Masfaraud, J.F. (2008) A spectro-photometric measurement of soil cation exchange capacity based on cobaltihexamine chloride absorb-ance. Comptes Rendus Geoscience, 340, 865871.10.1016/j.crte.2008.07.015CrossRefGoogle Scholar
Bailey, S.W. (1990) Halloysite - a critical assessment. Sciences Geologiques-Memoires, 86, 8998.Google Scholar
Berthier, P. (1826) Analyse de l'halloysite. Annali di chimica Physical, 32, 332335.Google Scholar
Churchman, G.J. & Lowe, D.J. (2012) Alteration, formation and occurence of minerals in soils. Pp. 20.21-20.72 in: Handbook of Soil Sciences. Properties and Processes, Second Edition (P.M. Huang, Y Li & M.E. Sumner, editors). CRC Press, Boca Raton, Florida, USA.Google Scholar
Ciesielski, H. & Sterckeman, T. (1997a) A comparison between three methods for the determination of cation exchange capacity and exchangeable cations in soils. Agronomie, 17, 916.CrossRefGoogle Scholar
Ciesielski, H. & Sterckeman, T. (1997b) Determination of cation exchange capacity and exchangeable cations in soils by means of cobalt hexamine trichloride. Effects of experimental conditions. Agronomie, 17, 17.10.1051/agro:19970101CrossRefGoogle Scholar
Delavernhe, L., Steudel, A., Darbha, G.K., Schäfer, T., Schuhmann, R., Wöll, C., Geckeis, H. & Emmerich, K. (2015) Influence of mineralogical and morphological properties on the cation exchange behavior of dioctahe-dral smectites. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 481, 591599.10.1016/j.colsurfa.2015.05.031CrossRefGoogle Scholar
Dohrmann, R. & Kaufhold, S. (2009) Three new, quick CEC methods for determining the amounts of exchangeable calcium cations in calcareous clays. Clays and Clay Minerals, 57, 338352.10.1346/CCMN.2009.0570306CrossRefGoogle Scholar
Du, M.L., Guo, B.C. & Jia, D.M. (2010) Newly emerging applications of halloysite nanotubes: a review. Polymer International, 59, 574582.CrossRefGoogle Scholar
Garrett, W. & Walker, G. (1959) The cation-exchange capacity of hydrated halloysite and the formation of halloysite-salt complexes. Clay Minerals Bulletin, 4, 7580.10.1180/claymin.1959.004.22.02CrossRefGoogle Scholar
Gu, X.Y. & Evans, L.J. (2008) Surface complexation modelling of Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) adsorption onto kaolinite. Geochimica et Cosmochimica Acta, 72, 267276.10.1016/j.gca.2007.09.032CrossRefGoogle Scholar
Hadi, J., Tournassat, C. & Lerouge, C. (2016) Pitfalls in using the hexaamminecobalt method for cation exchange capacity measurements on clay minerals and clay-rocks: Redox interferences between the cationic dye and the sample. Applied Clay Science, 119, 393400.10.1016/j.clay.2015.03.017CrossRefGoogle Scholar
Hillier, S., Brydson, R., Delbos, E., Fraser, T., Gray, N., Pendlowski, H., Phillips, I., Robertson, J. & Wilson, I. (2016) Correlations among the mineralogical and physical properties of halloysite nanotubes (HNTs). Clay Minerals, 51, 325350.CrossRefGoogle Scholar
Huertas, E.J., Chou, L. & Wollast, R. (1998) Mechanism of kaolinite dissolution at room temperature and pressure: part 1. Surface speciation. Geochimica etCosmochimica Acta, 62, 417431.10.1016/S0016-7037(97)00366-9CrossRefGoogle Scholar
Ikhsan, J., Johnson, B.B. & Wells, J.D. (1999) A comparative study of the adsorption of transition metals on kaolinite. Journal of Colloid and InterfaceScience, 217, 403410.10.1006/jcis.1999.6377CrossRefGoogle ScholarPubMed
ISO23470 (2007) Determination of effective cation exchange capacity (CEC) and exchangeable cations using a hexammine trichloride solution.Google Scholar
Joussein, E., Petit, S., Churchman, J., Theng, B., Righi, D. & Delvaux, B. (2005) Halloysite clay minerals - A review. Clay Minerals, 40, 383426.CrossRefGoogle Scholar
Kamble, R., Ghag, M., Gaikawad, S. & Panda, B.K. (2012) Halloysite nanotubes and applications: a review. Journal of Advanced Scientific Research, 2, 2529.Google Scholar
Kaufhold, S. & Dohrmann, R. (2013) The variable charge of dioctahedral smectites. Journal of Colloid andInterface Science, 390, 225233.CrossRefGoogle ScholarPubMed
Ma, C. & Eggleton, R.A. (1999) Cation exchange capacity of kaolinite. Clays and Clay Minerals, 47, 174180.Google Scholar
Norrish, K. (1995) An inusual fibrous halloysite. Pp. 275284 in: Clays Control the Environment -Proceedings of the 10th Internatiopnal Clay Conference, Adelaide 1993 (G.J. Churchman, R.W. Fitzpatrick & R.A. Eggleton, editors). CSIRO Publishing, Melbourne, Australia.Google Scholar
Peacock, C.L. & Sherman, D.M. (2005) Surface complex-ation model for multisite adsorption of copper(II) onto kaolinite. Geochimica et Cosmochimica Acta, 69, 37333745.10.1016/j.gca.2004.12.029CrossRefGoogle Scholar
Sposito, G. (1984) The Surface Chemistry of Soils. Pp. 234. Oxford University Press, New York.Google Scholar
Venema, P., Hiemstra, T. & Van Riemsdijk, W.H. (1996) Multisite adsorption of cadmium on goethite. Journal of Colloid and Interface Science, 183, 515527.10.1006/jcis.1996.0575CrossRefGoogle ScholarPubMed
Wendlandt, W.W. (1963) Thermal decomposition of metal complexes .3. stoicheiometry of the thermal dissociation of some hexamminecobalt (III) complexes. Journal of Inorganic and Nuclear Chemistry, 25, 545551.10.1016/0022-1902(63)80239-0CrossRefGoogle Scholar
Westall, J.C. & Herbelin, A.L. (1994) FITEQL: A Program for Determination of Chemical Equilibrium Constants From Experimental Data. Version 3.1. Oregon State University, Corvallis, Or.Google Scholar
Wieland, E. & Stumm, W. (1992) Dissolution kinetics of kaolinite in acidic aqueous solutions at 25°C. Geochimica et Cosmochimica Acta, 56, 33393355.CrossRefGoogle Scholar
Wilson, I. & Keeling, . (2016) Global occurrence and geology of halloysite. Clay Minerals, 51, 309324.10.1180/claymin.2016.051.3.12CrossRefGoogle Scholar