Thermodynamic modeling for the removal of Cs+, Sr2+, Ca2+and Mg2+ions from aqueous waste solutions using zeolite A</p> </p>

Summary The batch removal ofCs⁺, Sr²⁺, Ca²⁺and Mg²⁺ions from aqueous solutions using synthetic zeolite A was investigated. The influence of the initial ion concentration, pH and temperature was studied. The obtained isotherm data have been correlated with Langumir, Freundlich, and Dubinin-Radushkevich(D-R) isotherm models. The effect of the temperature on the equilibrium distribution values has been utilized to evaluate the standard thermodynamic parameters such as free energy (DG), enthalpy (DH) and entropy (DS). Based on the D-R isotherm expression, the maximum ion-exchange capacity and the mean free energy of each studied ion has been determined. The selectivity sequence, deduced from the equilibrium isotherm data is: Sr²⁺>Ca²⁺>Mg²⁺>Cs⁺>Na⁺.</p> </p>     

Complexation Properties of a Carbon-Bridged Cryptand with Metal Ions in Aqueous Solution at 25°C

Abstract

Thermodynamic quantities (log K, ΔH, and ΔS) for the interactions of a carbon-bridged cryptand with Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, and Pb²⁺ were determined at 25° C by calorimetric titration in aqueous solution. The cryptand forms complexes with Na⁺, Sr²⁺, Ba²⁺, and Pb²⁺ with log K ≤ 2. Complexation was not detected for Li⁺, K⁺, and Ca²⁺. Weak interactions with Li⁺ and K⁺ and a log K value of 2.4 for Na⁺ suggest that the cavity size of the cryptand is close to that of Na⁺ but too small for K⁺ and too large for Li⁺. The carbon-bridged cryptand selectively binds Sr²⁺ (log K = 3.2) over Ca²⁺ and Ba²⁺ by more than one order of magnitude.     

Selectivity of Low- and High-Silica Clinoptilolites with Respect to Alkali and Alkaline–Earth Metal Cations

The ion-exchange equilibria involving K⁺ and Ca²⁺ cations were studied using the Na-forms of nine different clinoptilolite samples. The high-silica (in the native state, sodium–potassium form) clinoptilolites were shown to have the increased selectivity with respect to K⁺ ions, whereas the low-silica (in the native state, calcium form) clinoptilolites to Ca²⁺ ions. The phenomenon found is interpreted as a structural memory of clinoptilolites with respect to alkali and alkaline-earth metal ions which had been present during zeolite crystallization under natural conditions.     

Ion-exchange kinetics in natural heulandite and clinoptilolite

The kinetics of sorption of Ca²⁺ ions from aqueous solution by K⁺-substituted forms of heulandite and clinoptilolite have been studied at 298 K. The K⁺-Ca²⁺ ion exchange in heulandite and clinoptilolite is described by an internal diffusion mechanism. Self-diffusion coefficients were determined for Ca²⁺ ions in these zeolites.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2215–2217, October, 1991.     

A Novel Highly Sensitive Zeolite-Based Conductometric Microsensor for Ammonium Determination

Natural zeolite clinoptilolite was successfully applied in the sensing technology for electrochemical detection of ammonium. A novel ammonium-selective sensor was developed based on clinoptilolite, possessing intrinsic ammonium-sieving and ion exchange capacity. The sensor design allowed measurements in both differential mode and requiring no classical reference electrode. The sensor selectivity towards Na⁺, K⁺, Ca²⁺, Mg²⁺, and Al³⁺ was studied. The limit of detection and the dynamic range of the ammonium-selective conductometric microsensor, determined in the phosphate buffer solution, were 1.0 × 10^?8 M and 0–8 mM, respectively. The ammonium sensor presented high operational and storage stability.     

Kinetics of metal ion sorption on clinoptilolite

From an investigation into the sorption kinetics of Na⁺, K⁺, and Sr²⁺ ions from standard solutions on finely dispersed clinoptilolite incorporated in a highly permeable inert polyacrylamide gel we have determined the characteristic kinetic size of clinoptilolite and the diffusion coefficients for Na⁺, K⁺, and Sr²⁺ in the clinoptilolite microcrystallites and transport pores. Diagrams have been constructed to enable a valid selection of kinetic models for sorption of the ions from any solutions on clinoptilolite.Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, 690022 Vladivostok. V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, 117975 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 273–277, February, 1992.     

Radiochemical studies of the sorption behavior of strontium and barium

The sorption behavior of strontium and barium on kaolinite, bentonite and chlorite-illite mixed clay was studied by radioanalytical techniques using the batch method.⁹⁰Sr (29.1 y) and¹³³Ba (10.5 y) were used as radiotracers. Characterization of the solid matrices was done by FTIR and XRD spectrometries and specific surface area measurements. Synthetic groundwater was used as the aqueous phase. The variation of the distribution ratioR _d, as a function of metal ion loading was examined. The sorption isotherms were fitted to various isotherm models. The sorption energies were calculated to be in the range of 8–10 kJ/mol suggesting an ion exchange type of sorption mechanism. In detailed experiments, chlorite-illite mixed clay was first presaturated with K⁺, Sr²⁺, Ca²⁺ and Al³⁺ ions, respectively, prior to sorption studies with Ba²⁺ ions. The results of Ca²⁺ pretreated chlorite-illite were very similar to those of natural chlorite-illite, suggesting that the Ba²⁺ ion exchanges primarily with the Ca²⁺ ion on the clay minerals.     

Thermodynamics of the Exchange Processes between K+, Ca2+ and Cr3+ in Zeolite NaA

In this paper it was analyzed the ion exchange isotherm of K⁺, Ca²⁺ and also Cr³⁺ ions with NaA zeolites at three temperatures: 30, 45 and 60°C. The NaA isotherms were favorable for the metal cations studied. Differences in shape are due to the different influence of temperature in the interaction of the in-going cation with the zeolite framework. As a consequence, sites of different energies were used in the exchange process, which provided non linear Kielland plots. Equilibrium constant, standard free energy, enthalpy and enthopy changes were measured and tabulated. Equilibrium constant is directly proportional to the in-going ion charge. Concerning enthalpy, endothermic and exothermic exchanges were observed due to differences in the cation-framework interaction. The selectivity order based on the standard free energy over the entire temperature range was K⁺ < Cr³⁺ < Ca²⁺, a consequence of different ion exchange mechanisms. It was also noted that the entropy change increases with the polarizibility of the cations.     

Cs and Sr removal from solution using potassium nickel hexacyanoferrate impregnated zeolites</p> </p>

Summary Potassium nickel hexacyanoferrate, KNiFC, was incorporated in the porous matrix of zeolites by successive impregnation with Ni(NO₃)₂ and</o:p></p> K₄Fe (CN)₆.¹ CFC and PFC exchangers were first prepared by impregnating the potassium nickel hexacyanoferrate into the clinoptilolite and the synthetic P zeolite, respectively. Ion-exchange isotherms and breakthrough curves were plotted. Results showed that the CFC sorbent is suitable for removal of Cs⁺ where PFC is more suitable for Sr²⁺. Negative effect of Na⁺ as a competing ion in these exchangers was less than in the parent zeolites. Isotherm plots fitted the Langmuir equation.</p> </p>     

Adsorption of nitrogen from natural gas by clinoptilolite

Much of world’s natural gas reserves are impure, one of the principal contaminants being nitrogen which makes it unsuitable for application and, hence, its separation is important. In this research, clinoptilolite, the most abundant natural zeolite with an open aluminosilicate framework structure and high internal surface area, was modified by ion exchange process to highly exchanged forms of cations of Na⁺, K⁺ and H⁺. The adsorption of N₂, CH₄ and C₂H₆ on natural clinoptilolite (Cp) and on its cation-exchanged forms (Na-Cp, K-Cp and H-Cp) was studied at 25 °C. The influence of cation exchange on equilibrium adsorption of N₂ showed that selectivity decreased in the order of Cp > Na-Cp > K-Cp and H-Cp has no affinity to nitrogen.     

Synthesis and binding studies ofN-(2-Hydroxy-l-phenoxyacetyl) glycylglycine

The synthesis ofN-(2-hydroxy-l-phenoxyacetyl)glycylglycine3 from 2-acetoxyphenoxyacetic acid is described. Compound3, a simple model for the carboxy-containing ionophore, Lasalocid, binds cations in methanol in the order: Ca²⁺ Ba²⁺ > Sr²⁺ 2>> Li⁺ > Na⁺, K⁺.     

Thermodynamics of cationic substitutions on titanyl hydrogen phosphate

Heterophasic substitution of Group I and Group II metal cations for hydrogen ions of titanyl hydrogen phosphate in aqueous solutions has been studied by a potentiometric method. The thermodynamic parameters of the process have been determined. The exchange constants depend on the degree of cation hydration and increase in the following orders: Li⁺ < Na⁺ < K⁺ < Rb⁺ < Cs⁺ and Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺. Our results make it possible to determine conditions for the efficient deactivation of high-salt liquid radioactive wastes and for the synthesis of stoichiometric compounds of the KTP family.     

Microcalorimetric Study of the Interaction between Water and Cation-Substituted Clinoptilolites

Heats of ion exchange and adsorption of water vapors on cation-substituted clinoptilolites are studied by microcalorimetry. Based on the results obtained, the composition of hydrates of Na⁺, Cs⁺, Co²⁺, and Ba²⁺ ions on various ion-exchange sites of clinoptilolite is determined. Their structure is identified using the combined analysis of calorimetric and X-ray diffraction data. The usefulness of energy–stoichiometry approach to the discussion of the results of adsorption calorimetry study of the interaction between water and cation-substituted clinoptilolites is demonstrated.     

Removal of toxic hexavalent chromium by polyaniline modified clinoptilolite nanoparticles

In this work clinoptilolite nanoparticles were modified with conducting polyaniline by the polymerization of anilinium cations in and out side of the clinoptilolite channels and a nanocomposite of polyaniline/clinoptilolite was obtained. Cations (Na⁺, K⁺, Mg²⁺, Ca²⁺...) in the natural clinoptilolite structure were exchanged with anilinium cations by the treatment of clinoptilolite nanoparticles in an acidic solution of aniline monomer. The cation exchange process was confirmed by elemental analysis of nitrogen and carbon atoms of anilinium cations in clinoptilolite dry powder after treatment. The polyaniline/clinoptilolite nanocomposite was obtained by the oxidative polymerization of anilinium cations within the clinoptilolite structure. The polyaniline/clinoptilolite nanocomposite was characterized utilizing FT-IR and X-ray diffraction measurements and was used for the removal of Cr(VI) from aqueous solutions in chromate anion form as an important water pollutant. The effect of a number of parameters such as initial concentration of Cr(VI), amount of nanocomposite and contact time on the removal efficiency of Cr(VI) by polyaniline/clinoptilolite nanocomposite were determined and optimized. It was found that after 5 min of exposure of nanocomposite powder with Cr(VI) solutions in the concentration range of 25 to 100 ppm, more than 98% of chromate anions can be removed and the Cr(VI) removal capacity per one gram of nanocomposite is about 0.3 mmol of Cr(VI).     

Isotherm of exchange of nickel and sodium cations on iron-manganese nodules

The isotherm of ion exchange of Ni²⁺ and Na⁺ cations on iron-manganese nodules was studied. The ion exchange was described by an equation similar to the Langmuir isotherm. The limiting sorption and the apparent ion-exchange constant were calculated.     

Cation exchange, interlayer spacing, and thermal analysis of Na/Ca-montmorillonite modified with alkaline and alkaline earth metal ions

Na-montmorillonites were exchanged with Li⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, while Ca-montmorillonites were treated with alkaline and alkaline earth ions except for Ra²⁺ and Ca²⁺. Montmorillonites with interlayer cations Li⁺ or Na⁺ have remarkable swelling capacity and keep excellent stability. It is shown that metal ions represent different exchange ability as follows: Cs⁺?>?Rb⁺?>?K⁺?>?Na⁺?>?Li⁺ and Ba²⁺?>?Sr²⁺?>?Ca²⁺?>?Mg²⁺. The cation exchange capacity with single ion exchange capacity illustrates that Mg²⁺ and Ca²⁺ do not only take part in cation exchange but also produce physical adsorption on the montmorillonite. Although interlayer spacing d ₀₀₁ depends on both radius and hydration radius of interlayer cations, the latter one plays a decisive role in changing d ₀₀₁ value. Three stages of temperature intervals of dehydration are observed from the TG/DSC curves: the release of surface water adsorbed (36?C84?°C), the dehydration of interlayer water and the chemical-adsorption water (47?C189?°C) and dehydration of bound water of interlayer metal cation (108?C268?°C). Data show that the quantity and hydration energy of ions adsorbed on montmorillonite influence the water content in montmorillonite. Mg²⁺-modified Na-montmorillonite which absorbs the most quantity of ions with the highest hydration energy has the maximum water content up to 8.84%.     

Isotherm of strontium and sodium cation exchange on iron-manganese nodules

The isotherm of ion exchange of Sr²⁺ and Na⁺ ions on iron-manganese nodules was obtained. It was suggested to describe the ion exchange by an equation analogous to the Langmuir isotherm equation. The limiting sorption and apparent ion exchange constant were calculated. The effective radius of sorbed strontium ions was determined.     

Chromium uptake from tricomponent solution in zeolite fixed bed

Removal of Cr³⁺,Ca²⁺,Mg²⁺ and K⁺ in equilibrium isotherms and in tricomponent solutions (Cr/Ca/K, Cr/Ca/Mg and Cr/Mg/K) were investigated in NaX and NaY packed beds at 30^∘C. The equilibrium selectivity was obtained as Cr⁺³ > Mg²⁺ > Ca²⁺≈K⁺ for zeolite NaY and Ca^{2 +}≫Cr^{3 +} > Mg^{2 +}≈K⁺ for zeolite NaX. The breakthrough curves showed sequential ion exchange where chromium ions are able to replace the competing cations. Some mass transfer parameters, such as length of unused bed and overall mass transfer coefficient, were investigated. Chromium retention was also investigated through a mass balance. Based on the breakthrough results, it was concluded that chromium-uptake mechanism was hardly influenced by the competition and interaction between the entering ions. NaY showed a higher affinity towards Cr³⁺ for both equilibrium and dynamic systems and its sites were more efficiently used in the ion exchange process. Chromium was less retained in NaX due to the high selectivity towards calcium ions.     

Iodide adsorption on the surface of chemically pretreated clinoptilolite

The possibility to use the monoionic Ag⁺-form (eventually Hg⁺- and Hg²⁺- forms) of clinoptilolite of domestic origin for radioactive iodide elimination from waters has been studied. The capacity of the monoforms of clinoptilolite towards iodide exceeds many times that of the capacity of clinoptilolite in natural form. Due to the low solubility product of AgI, Hg₂I₂ and HgI₂ iodides generate precipitates on the zeolite surface. Rtg analyses of the silver form of clinoptilolite after sorption of iodide demonstrate the formation of new crystals on the zeolite surface. The influence of interfering anions on the adsorption capacity of silver clinoptilolite towards iodide was investigated, too. Kinetic curves of iodide desorption from the surface of silver and mercury clinoptilolite were compared. Simultaneously, adsorption isotherms for the systems aqueous iodide solution/Ag^–, Hg-clinoptilolite were determined.     

Trennungen von Kationen in Titanhexacyanoferrat(II)-S?ulen

Zusammenfassung Die Trennung der Ionenpaare Rb⁺/Cs⁺, K⁺/Rb⁺, K⁺/Cs⁺, Na⁺/K⁺, Li⁺/Na⁺ mit Salzsäure oder Ammoniumchloridlösung als Elutionsmittel gelingt quantitativ oder nahezu quantitativ mit Hilfe von Titanhexacyanoferrat(II)-säulen. Die Cäsiumionen können nicht eluiert werden. Ebenso gelingt die Trennung der lonenpaare Sr²⁺/Ba²⁺, Ca²⁺/Ba²⁺, Ba²⁺/Cs⁺ und Sr²⁺/Cs⁺ quantitativ oder nahezu quantitativ. Auch eine partielle Trennung der Seltenen Erden ist möglich; Yttrium ist leichter eluierbar als die Lanthanide.

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Summary The quantitative or nearly quantitative separation of the ion pairs Rb⁺/Cs⁺, K⁺/Rb⁺, k⁺/Cs⁺, Na⁺/K⁺ and Li⁺/Na⁺ can be achieved with hydrochloric acid or ammonium chloride solutions as eluents by means of columns of titanium hexacyanoferrate(II). The elution of the Cs⁺ ions is not possible. In the same way the quantitative or nearly quantitative separation of the ion pairs Sr²⁺/Ba²⁺, Ca²⁺/Ba²⁺, Ba²⁺/Cs⁺ and Sr²⁺/Cs⁺ can be achieved. Also a partial separation of the rare-earth elements is possible; yttrium is more easily eluted than the lanthanides.