Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on Clinoptilolite
The exchange equilibrium between Mg 2+ and Ca 2+ ions and the corresponding microcalorimetric ion-exchange heats were studied on two clinoptilolite (Cli) samples. Using the experimental values of the ion-exchange constants (free energies) and heats (enthalpies), reliable estimates of the entropy wer...
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SAGE Publishing
2007-02-01
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Series: | Adsorption Science & Technology |
Online Access: | https://doi.org/10.1260/026361707781485690 |
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author | Yuri I. Tarasevich Valeri E. Polyakov Dmytro O. Krysenko Eugene V. Aksenenko |
author_facet | Yuri I. Tarasevich Valeri E. Polyakov Dmytro O. Krysenko Eugene V. Aksenenko |
author_sort | Yuri I. Tarasevich |
collection | DOAJ |
description | The exchange equilibrium between Mg 2+ and Ca 2+ ions and the corresponding microcalorimetric ion-exchange heats were studied on two clinoptilolite (Cli) samples. Using the experimental values of the ion-exchange constants (free energies) and heats (enthalpies), reliable estimates of the entropy were obtained for the direct (Mg 2+ -Ca 2+ -Cli) and inverse ion-exchange reactions. It was shown that the sign (negative or positive) of the ion-exchange free energy in the case under study was determined essentially by the entropy constituent of the ion-exchange process. The selectivity of clinoptilolite towards Ca 2+ cations rather than to Mg 2+ cations was demonstrated. The ab initio calculations undertaken confirmed the experimental results and provided structural information concerning the localisation of ions in the crystalline environment. In particular, it was shown that the 10-membered structural clinoptilolite rings provide favourable positions for hydrated Ca 2+ cations. The energy gain of the system arising from the Ca 2+ -Mg-Cli exchange was -E = 8.0–3.4 kJ/mol depending on the localisation sites for the Ca 2+ cations; these values are in acceptable quantitative agreement with experimental data for the exchange enthalpy variation –ΔH = (7.3-8.4) kJ/(g equiv). Data were obtained for the energetics of interaction of Ca 2+ and Mg 2+ ions with water molecules located in the first and second hydration spheres. |
format | Article |
id | doaj-art-7712c20bcdd64572902178a3a899ae89 |
institution | Kabale University |
issn | 0263-6174 2048-4038 |
language | English |
publishDate | 2007-02-01 |
publisher | SAGE Publishing |
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series | Adsorption Science & Technology |
spelling | doaj-art-7712c20bcdd64572902178a3a899ae892025-01-03T00:11:13ZengSAGE PublishingAdsorption Science & Technology0263-61742048-40382007-02-012510.1260/026361707781485690Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on ClinoptiloliteYuri I. TarasevichValeri E. PolyakovDmytro O. KrysenkoEugene V. AksenenkoThe exchange equilibrium between Mg 2+ and Ca 2+ ions and the corresponding microcalorimetric ion-exchange heats were studied on two clinoptilolite (Cli) samples. Using the experimental values of the ion-exchange constants (free energies) and heats (enthalpies), reliable estimates of the entropy were obtained for the direct (Mg 2+ -Ca 2+ -Cli) and inverse ion-exchange reactions. It was shown that the sign (negative or positive) of the ion-exchange free energy in the case under study was determined essentially by the entropy constituent of the ion-exchange process. The selectivity of clinoptilolite towards Ca 2+ cations rather than to Mg 2+ cations was demonstrated. The ab initio calculations undertaken confirmed the experimental results and provided structural information concerning the localisation of ions in the crystalline environment. In particular, it was shown that the 10-membered structural clinoptilolite rings provide favourable positions for hydrated Ca 2+ cations. The energy gain of the system arising from the Ca 2+ -Mg-Cli exchange was -E = 8.0–3.4 kJ/mol depending on the localisation sites for the Ca 2+ cations; these values are in acceptable quantitative agreement with experimental data for the exchange enthalpy variation –ΔH = (7.3-8.4) kJ/(g equiv). Data were obtained for the energetics of interaction of Ca 2+ and Mg 2+ ions with water molecules located in the first and second hydration spheres.https://doi.org/10.1260/026361707781485690 |
spellingShingle | Yuri I. Tarasevich Valeri E. Polyakov Dmytro O. Krysenko Eugene V. Aksenenko Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on Clinoptilolite Adsorption Science & Technology |
title | Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on Clinoptilolite |
title_full | Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on Clinoptilolite |
title_fullStr | Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on Clinoptilolite |
title_full_unstemmed | Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on Clinoptilolite |
title_short | Sorption-Analytic, Microcalorimetric and Study of Ion-Exchange Equilibria Involving Mg and Ca Cations on Clinoptilolite |
title_sort | sorption analytic microcalorimetric and study of ion exchange equilibria involving mg and ca cations on clinoptilolite |
url | https://doi.org/10.1260/026361707781485690 |
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