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Binary cation exchange in clinoptilolite involving K+, Na+ , Ba2+ and Ca2+ at 30 and 95°C: a calorimetric study

Published online by Cambridge University Press:  09 July 2018

N. Petrova ,
L. Filizova  and
G. Kirov
N. Petrova*
Affiliation:
Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Str. Bl. 107 Sofia, 1113 Bulgaria
L. Filizova
Affiliation:
Dept. of Mineralogy, Petrology and Economic Geology, Sofia University, 15 Tzar Osvoboditel blvd, 1504 Sofia, Bulgaria
G. Kirov
Affiliation:
Dept. of Mineralogy, Petrology and Economic Geology, Sofia University, 15 Tzar Osvoboditel blvd, 1504 Sofia, Bulgaria
*
*E-mail: [email protected]
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Abstract

A binary ion exchange of cationic pairs involving K, Na, Ba and Ca in clinoptilolite was investigated calorimetrically. The selected cations included two pairs equal in charge and two pairs similar in size. The heats of ion exchange and the degrees of exchange were determined at 30 and 95°C. The data obtained are discussed with respect to cationic interactions in the clinoptilolite structure and hydration characteristics (heats of hydration and hydration numbers) of competing cations in the solution. No correlation was found between the heat effects and the degree of exchange. The heat of exchange depends mainly on the difference between the hydration heats of the cations in the solution, whereas the degree of exchange depends on their positioning over the extraframework sites in the clinoptilolite structure. The heats of ion exchange are lower at 95°C than those measured at 30°C, which is due to a decrease of the hydration number with increasing temperature. In all cases the degree of exchange increases with increasing temperature.

Keywords

clinoptilolitebinary cation exchangecalorimetrydegree of exchange
Type
Research Article
Information
Clay Minerals , Volume 46 , Issue 2 , June 2011 , pp. 251 - 259
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

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References

Barrer, R.M., Bartholomew, R.F. & Rees, L.V.C. (1963) Ion exchange in porous crystals. Part I. Self- and exchange-diffusion of ions in chabazites. Journal of Physics and Chemistry of Solids, 24, 51–62.Google Scholar
Breck, D. (1974) Zeolite Molecular Sieves, J. Wiley & Sons, New York, 771 pp.Google Scholar
Caputo, D. & Pepe, F. (2007) Experiments and data processing of ion exchange equilibria involving Italian natural zeolites: a review. Microporous and Mesoporous Materials, 105, 222–231.Google Scholar
Collela, C. (1996) Ion exchange equilibria in zeolite minerals. Mineralium Deposita, 31, 554–562.Google Scholar
Filizova, L., Petrova, N. & Kirov, G. (1993) Ion exchange of clinoptilolite in solution with different concentration: a calorimetric study. Geologica Carpathica — Series Clays, 44, 31–34.Google Scholar
Gunter, M.E., Armbruster, T., Kohler, T. & Knowles, C.R. (1994) Crystal structure and optical properties of Naand Pb-exchanged heulandite-group zeolites. American Mineralogist, 79, 675–682.Google Scholar
Kirov, G., Petrova, N. & Filizova, L. (1989) Calorimetric study of ion-exchange on clinoptilolite. Comptes Rendus de l'Academie Bulgare des Sciences, 42, 2, 89–91 (in Russian).Google Scholar
Koyama, K. & Takeuchi, Y. (1977) Clinoptilolite: the distribution of potassium atoms and its role in thermal stability. Zeitschrifi für Kristallographie, 145, 216–239.Google Scholar
Larsen, A., Nordrum, F., Dobelin, N., Armbruster, T., Petersen, O. & Eramberg, M. (2005) Heulandite-Ba, a new zeolite species from Norway. European Journal of Mineralogy, 17, 143–153.Google Scholar
Mishchenko, K.P. & Poltoratski, G.M. (1968) Thermodynamic Properties of Aqueous and Nonaqueous Solutions of Electrolytes. Chemistry, Moscow (in Russian), 352 pp.Google Scholar
Pabalan, R.T. & Bertetti, F.P. (1999) Experimental and modeling study of ion exchange between aqueous solutions and the zeolite mineral clinoptilolite. Journal of Solution Chemistry, 28, 367–393.Google Scholar
Pabalan, R.T. & Bertetti, F.P. (2001) Cation-exchange properties of natural zeolites. Pp. 453–508 in: Natural Zeolites (Bish, D. & Ming, D., editors). Reviews in Mineralogy and Geochemistry, 45, Mineralogical Society of America.Google Scholar
Petrov, O., Karamanewa, T. & Kirov, G. (1984) Cation distribution in the clinoptilolite structure: natural samples. Comptes Rendus de VAcademie Bulgare des Sciences, 37, 6, 785-788.Google Scholar
Petrov, O., Filizova, L. & Kirov, G. (1985) Cation distribution in the clinoptilolite structure: Ba-exchanged sample. Comptes Rendus de VAcademie Bulgare des Sciences, 38, 603–606.Google Scholar
Petrova, N. & Kirov, G. (1995) Zeolitization of glasses: a calorimetric study. Thermochimica Ada, 269/270, 443–452.CrossRefGoogle Scholar
Petrova, N., Filizova, L. & Kirov, G. (1997) Calorimetric study of ion exchange on clinoptilolite and mordenite at different temperatures. Pp. 173–181 in: Natural Zeolites — Sofia ‘95 (Kirov, G., Filizova, L. & Petrov, O., editors), Pensoft Publisher, Sofia and Moscow.Google Scholar
Petrova, N., Mizota, T. & Fujiwara, K. (2001) Hydration heats of zeolites for evaluation as heat exchangers. Journal of Thermal Analysis and Calorimetry, 64, 157–166.Google Scholar
Roque-Malherbe, R., Berazain, A. & Del Rosario, J.A. (1987) Calorimetric measurements of ion-exchange heats of homoionic heulandite and mordenite. Journal of Thermal Analysis, 37, 941–943.Google Scholar
Tarasevich, Yu.L., Poliakov, V.E. & Badekha, L.I. (1988) Structure and localization of hydrated alkali, alkaline-earth and transition metal cations in clinoptilolite determined by ion exchange, calorimetric and spectral measurements. Pp. 421–430 in: Occurence, Properties and Utilization of Natural Zeolites (Kallo, D. & Sherry, H., editors) Akademiai Kiado, Budapest, Hungary.Google Scholar
Tarasevich, Yu.L., Poliakov, V.E., Penchev, V., Kirov, G., Minchev, H., Poliakova, I.G. & Badekha, L.I. (1991) Ion-exchange properties and structural peculiarities of clinoptilolite from different deposits. Chemistry Technology of Water, 13, 132–140 (in Russian).Google Scholar
Tarasevich, Yu.L., Kardashova, M.V. & Poliakov, V.E. (1997) Ion exchange selectivity of the clinoptilolite. Colloid Journal, 59, 813–818 (in Russian).Google Scholar
Tarasevich, Yu.L., Krisenko, D.A., Poliakov, V.E. & Aksenenko, E.V. (2008) Heat of ion exchange of transition metals on the Na-form of clinoptilolite. Journal of Physical Chemistry, 82, 1692–1698 (in Russian).Google Scholar
Yang, P. & Armbruster, T. (1996) Na, K, Rb, and Cs exchange in heulandite single-crystals: X-ray structure refinements at 100 K. Journal of Solid State Chemistry, 123, 140–149.Google Scholar
Yang, P., Stolz, Y., Armbruster, T. & Gunter, M. (1997) Na, K, Rb, and Cs exchange in heulandite single crystals: diffusion kinetics. American Mineralogist, 82, 527–525.Google Scholar
Zavitsas, A. (2001) Properties of water solutions of electrolytes and nonelectrolytes. The Journal of Physical Chemistry B, 105, 7805–7817.CrossRefGoogle Scholar
Zavitsas, A. (2005) Aqueous solution of calcium ions: Hydration numbers and effect of temperature. Journal of Physical Chemistry B, 109, 20636–20640.Google Scholar
Zavitsas, A. (2010) The nature of aqueous solutions: insights into multiple facets of chemistry and biochemistry from freezing-point depressions. Chemistry, 16, 5942–5960.CrossRefGoogle ScholarPubMed