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.

---

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.

     

Heats of adsorption of water on vermiculite having large singly-charged cations in the exchange complex

The isotherms and differential heats of adsorption of water vapor on K-, NH₄-, Rb-, and Cs-vermiculites have been studied by means of a Calvet microcalorimeter having a microweighing adsorption attachment. The results are interpreted taking into account that the large cations K₊, NH₄ ⁺, Rb⁺, and especially Cs⁺, may not replace the initial exchange complexes (Na⁺ or Mg²⁺) of the mineral completely, so that besides hydration of the principal exchange cations the reaction of water molecules being adsorbed with the residual Na⁺ or Mg⁺ cations also takes place. The presence of a certain number of the initial cations (Na⁺ or Mg²⁺) in the Cs form of vermiculite is confirmed by the results of studying the ion exchange equilibria on the Na and natural (Mg) forms of the mineral involving the participation of the Cs₊ ions. The nature of the variation in the dependence of the differential heats of adsorption with an increase in the amount of adsorbed substance indicates the segregation (isolation) of the principal (K⁺, NH₄ ⁺, Rb⁺, Cs⁺) and the residual (Na⁺, Mg²⁺) exchange cation in the structure of the mineral.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 1, pp. 91–96, January–February, 1986.     

Preparation of a K+‐imprinted polymer for the selective recognition of K+ in food samples

An analytical method is reported for the preparation of K⁺‐imprinted nanoparticles using cryptand 222 as the complexing agent, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the crosslinker and 2,2′‐azobisisobutyronitrile as the radical initiator. The prepared particles have a diameter of 200–250 nm. The maximum adsorption capacity of potassium ion‐imprinted polymer particles was 120 μmol/g. The optimum pH for quantitative extraction was 9.0. The nature of the eluent, eluent concentration, adsorption and desorption times, weight of the polymer material, aqueous phase, and desorption volumes were also studied. The relative selectivity coefficients of K⁺/Li⁺, K⁺/Na⁺, K⁺/Rb⁺ and K⁺/Cs⁺ were 48.10, 4.80, 29.70, and 43.4, respectively. The relative standard deviation and limit of detection of the method were obtained 1.61% and 4.62 ng/L, respectively. Finally, the method was applied for the determination of potassium ions from different samples using flame photometry.     

Chromium antimonate as an ion-exchanger

Summary Chromium antimonate has been synthesised under varying conditions of precipitation and the cation-exchange properties of the various samples are reported. Systematic study has resulted in a product suitable for column operations. The effect of equilibration time, concentration of the electrolyte, size and charge of the ion and drying temperature on exchange capacity is reported. The chemical stability and regeneration power of the sample are also investigated. The plots of log K_d against pH for Rb⁺, Cs⁺, Tl⁺, Ca²⁺, Zn²⁺, and Tl³⁺ ions suggest a predominently ion-exchange mechanism in the case of Rb⁺ and Cs⁺ ions. K_d values of 27 metal ions have been determined and some chromatographic separations of analytical and radiochemical importance based on them have been achieved on chromium antimonate columns.Presented at the Annual Convention of Chemists (India), Roorkee, December 1975.     

Facilitated Transfer of Alkali Metal Ions by a Tetraester Derivative of Thiacalix[4]arene at the Liquid–Liquid Interface

The facilitated transfer of alkali metal ions (Na⁺, K⁺, Rb⁺, and Cs⁺) by 25,26,27,28‐tetraethoxycarbonylmethoxy‐thiacalix[4]arene across the water/1,2‐dichloroethane interface was investigated by cyclic voltammetry. The dependence of the half‐wave transfer potential on the metal and ligand concentrations was used to formulate the stoichiometric ratio and to evaluate the association constants of the complexes formed between ionophore and metal ions. While the facilitated transfer of Li⁺ ion was not observed across the water/1,2‐dichloroethane interface, the facilitated transfers were observed by formation of 1 : 1 (metal:ionophore) complex for Na⁺, K⁺, and Rb⁺ ions except for Cs⁺ ion. In the case of Cs⁺ a 1 : 2 (metal:ionophore) complex was obtained from its special electrochemical response to the variation of ligand concentrations in the organic phase. The logarithms of the complex association constants, for facilitated transfer of Na⁺, K⁺, Rb⁺, and Cs⁺, were estimated as 6.52, 7.75, 7.91 (log β₁°), and 8.36 (log β₂°), respectively.     

Stability Constants of Some Univalent Cation Complexes of 2,3-Naphtho-15-crown-5 in Nitrobenzene Saturated with Water

The extraction of micro amounts of cesium by nitrobenzene solutions of sodium, potassium and rubidium dicarbollylcobaltates (M⁺B⁻;M⁺=Na⁺,K⁺,Rb⁺) has been investigated in the presence of 2,3-naphtho-15-crown-5 (N15C5, L). The equilibrium data were explained by assuming that ML⁺ and ML₂⁺ complexes (M⁺=Na⁺,K⁺,Rb⁺, Cs⁺; L=N15C5) were present in the organic phase. The stability constants of the complex species ML⁺ and ML₂⁺ have been determined in nitrobenzene saturated with water. It was found that the stability of the complex cation ML⁺ (where M⁺=Na⁺,K⁺,Rb⁺, Cs⁺; L=N15C5) in water-saturated nitrobenzene solutions increases along the series Cs⁺<Rb⁺<K⁺<Na⁺, whereas that of the species ML₂⁺ in the same medium increases in the order Cs⁺<Rb⁺<Na⁺<K⁺.     

Novel Methods of Synthesis of Dibenzo[3n]crown-n and Their Cation Binding Studied by Fluorescence Spectroscopy. Part V

The dibenzo[3n]crown-n were synthesised starting from bis[2-(o-hydroxyphenoxy)ethyl]ether obtained from bis[2-(o-formylphenoxy)ethyl]ether via Baeyer-Villiger oxidation in H₂O₂/CH₃COOH in a good yield. The cyclic condensation ofbis[2-(o-hydroxyphenoxy)ethyl]etherwith tri- and tetraethylene glycol bisdichlorides andthe bisditosylate of pentaethylene glycol in DMF/Me₂CO₃ afforded the large cyclic ethers of dibenzo[21]crown-7, dibenzo[24]crown-8 and dibenzo[27]crown-9. The structures were analysed with IR, ¹H NMR, ¹³C NMR and low-resolution mass spectroscopy methods. The Na⁺, K⁺, Rb⁺ and Cs⁺ cations' recognition of the molecules were conducted withsteady-state fluorescence spectroscopy. The 1:1 association constants, K_a, in acetonitrile were estimated. Dibenzo[21]crown-7 was the best both for K⁺ and Rb⁺ binding but showed too small an effect on Cs⁺. Dibenzo[24]crown-8 exhibited the binding power in the order of Rb⁺ > K⁺ > Na⁺ > Cs⁺. However, dibenzo[27]crown-9 displayed marked binding with only K⁺ but not with Rb⁺ or with Cs⁺ cations probably due to the heavy atom effect of fluorescence quenching.     

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%.     

Adsorption kinetics and equilibrium modeling of cesium on copper ferrocyanide

The copper ferrocyanide (CuFC) prepared in this study was characterized using X-ray diffraction and scanning election microscopy. The distribution of particle sizes of the CuFC suspension was determined. The adsorption kinetics data were evaluated for an intraparticle diffusion model, a pseudo-first order model and a pseudo-second order model at temperatures of 288, 298 and 308 K, respectively. It was found that the adsorption process of Cs⁺ on CuFC was best described by a pseudo-second order kinetic model, with a correlation coefficient (R ²) equal to 1.000, and the adsorption rate constant increased with increasing temperature. This result indicated that chemisorptions took place during the adsorption process. The adsorption equilibrium data fit well to the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. The mean adsorption energy (E) between 11 and 13 kJ/mol at different temperatures indicated that ion exchange was the main mechanism during the adsorption process. Thermodynamic parameters were also evaluated during the adsorption. The values of the standard Gibbs free energy change (ΔG ^o) and standard enthalpy change (ΔH ^o) suggested that the adsorption was a spontaneous and endothermic process. The distribution coefficient (K _d) was more than 2.94 × 10⁶ mL/g when the pH of solution was between 2.6 and 10.9, and the initial Cs⁺ concentration was 100 μg/L. The existence of K⁺ and Na⁺ did not affect the adsorption of Cs⁺ on CuFC when the concentration of K⁺ and Na⁺ in the solution was below 20 and 1,000 mg/L, respectively.     

Preparation and ion-exchange properties of zirconium tungstoarsenate

A new inorganic ion-exchanger, zirconium tugnstoarsenate, has been synthesized which has been characterized by chemical analysis, thermogravimetry, X-ray and infrared spectroscopy. The ion exchanger has been found to be stable in acids and neutral salt solutions. The K_d values for 30 metal ions have been determined at pH 3–4 which show that the exchanger has high affinity for UO ₂ ²⁺ , ZrO²⁺, Cs⁺ and Tl⁺ ions. The variation of K_d for a number of metal ions as a function of concentration of nitric acid and ammonium nitrate has been investigated to elucidate the probable exchange mechanism and to work out conditions for elution. Some binary separations, viz. Sr²⁺−Cs⁺, Sr²⁺−Rb⁺, Sr²⁺−Y³⁺, Fe³⁺−Al³⁺, Fe³⁺−Zn²⁺ and Zn²⁺−Hg²⁺ in trace amounts have been carried out on the column of the exchanger which demonstrate the utility of the exchanger in radionalytical and analytical chemistry.     

Structures of the nearest surroundings of the K<Superscript>+</Superscript>, Rb<Superscript>+</Superscript>, and Cs<Superscript>+</Superscript> ions in aqueous solutions of their salts

Published data on structural characteristics of hydration of K⁺, Rb⁺, and Cs⁺ ions in aqueous solutions of their salts under standard conditions, including authors’ X-ray diffraction data, are summarized and correlated. The structural parameters of the nearest surrounding of the K⁺, Rb⁺, and Cs⁺ ions, such as the coordination numbers, interparticle distances, and types of ionic association, are discussed. It is noted that, because of weak tendency of these cations to hydration, the parameters of their coordination spheres strongly depend on the concentration and chemical nature of counterions.     

Preparation of Thallium Hexacyanoferrate Film and Mixed‐Film Modified Electrodes with Cobalt(II) Hexacyanoferrate

Thallium hexacyanoferrate films have been prepared from various aqueous electrolyte solutions using consecutive cyclic voltammetry. The cyclic voltammograms recorded the direct deposition of thallium hexacyanoferrate films from the mixing of Tl³⁺ and [Fe(CN)₆]^3? ions from solutions of seven cations: Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, H⁺, and Tl⁺. An electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry were used to study the in situ growth of the thallium hexacyanoferrate films. The thallium hexacyanoferrate film shows a single redox couple with a formal potential between +0.6 V and +1.2 V, and shows a cation effect (H⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, and Tl⁺). A mixed film and a two‐layered modified electrodes composed of a thallium hexacyanoferrate film with cobalt(II) hexacyanoferrate film were prepared.     

Adsorption of polymers with crown ether substituents on muscovite mica

Ultrahigh specific surface area muscovite with different ions at the surface (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Ca²⁺, Sr²⁺, Ba²⁺, Cu²⁺) was treated with aqueous solutions of low molecular weight crown ethers and polymers with crown ether substituents. The adsorption was assessed by UV analysis of the supernatant solution, and with TGA and IR spectroscopy of the mica solids. In contrast to other layered silicates, the low molecular weight crown ethers show no affinity to any of the muscovite surfaces. The polymers can adsorb, however, depending on the type of surface cation. The results indicate that at least some of the crown ether moieties are complexed to surface cations and that the diameter of the ions at the surface plays an important role in the adsorption process.     

Selective complexation of alkali metal ions and nanotubular cyclopeptides: a DFT study

A density functional theory based on interaction of alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) with cyclic peptides constructed from 3 or 4 alanine molecule (CyAla3 and CyAla4), has been investigated using mixed basis set (C, H, O, Li⁺, Na⁺ and K⁺ using 6-31+G(d), and the heavier cations: Rb⁺ and Cs⁺ using LANL2DZ). The minimum energy structures, binding energies, and various thermodynamic parameters of free ligands and their metal cations complexes have been determined with B3LYP and CAM-B3LYP functionals. The order of interaction energies were found to be Li⁺ > K⁺ > Na⁺ > Rb⁺ > Cs⁺ and Li⁺ > Na⁺ > K⁺ ? Rb⁺ > Cs⁺, calculated at CAM-B3LYP level for the M/CyAla3 and M/CyAla4 complexes, respectively. Their selectivity trend shows that the highest cation selectivity for Li⁺ over other alkali metal ions has been achieved on the basis of thermodynamic analysis. The main types of driving force host–guest interactions are investigated, the electron-donating O offers lone pair electrons to the contacting LP* of alkali metal cations.     

Spectrophotometric studies of alkali and alkali earth metal ions complexes of mono amino derivative of calix[4]arene

The synthesis and complexive abilities of 5,11,17-tris(tert-butyl)-23 amino-25,26,27,28-tetra-propoxycalix[4]arene towards alkali cations Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and alkali earth cations Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ in methanol-chloroform mixture have been evaluated at 25°C, using UV-Vis spectrophotometric techniques. The results showed that the ligand is capable to complex with all the cations by 1: 1 metal to ligand ratios. The selectivity presented considering the calculated formation constants are in the order Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺ and Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ with the ligand.     

Synthesis and ion-exchange properties of zirconium antimonate

Samples of zirconium antimonate have been prepared under varying conditions of precipitation. Their properties, composition, and ion-exchange behaviour are reported. The 1g K_d vs. pH curves are given for Rb⁺, Cs⁺, Zn²⁺, Ca²⁺ and Tl³⁺ ions. The distribution coefficients of 26 metal ions have been measured and several separations of analytical and radiochemical importance achieved.     

Extraction of NH4 +, K+, Rb+ and Tl+ into nitrobenzene using cesium dicarbollylcobaltate in the presence of dibenzo-21-crown-7

Summary From extraction experiments and g-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq) + CsL⁺(nb) ? ML⁺(nb) + Cs⁺(aq) taking place in the two-phase water-nitrobenzene system (M⁺ = NH, K⁺, Rb⁺, Tl⁺; L = dibenzo-21-crown-7; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Further, the stability constants of the ML⁺ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Cs⁺<K⁺ = Rb⁺?NH<Tl⁺.     

Studies on the ion-exchange behaviour of chromium ferrocyanide

The sorption of univalent, bivalent and trivalent ions has been studied on chromium ferrocyanide gel. The studies reveal a high sorption capacity for Cs⁺, Tl⁺, Ag⁺, Cu²⁺, Zn²⁺, Cd²⁺, Fe³⁺ and Th⁴⁺. The sorption of monovalent cations show purely ion-exchange mechanism while the uptake of bivalent and trivalent cations is non-equivalent in nature. Single elution of Rb⁺, Cs⁺ and Tl⁺ has been performed from the columns of this exchanger and the recovery is almost complete in all the cases. Cu²⁺ and Ag⁺ get completely adsorbed on the gel column and their elution is not possible probably due to the formation of some new solid phases. Depending on the K_d values of the metal ions, a large number of separations of radiochemical as well as analytical importance can be performed on the columns of this exchanger material.     

Die Selektivität Kristalliner Cer(IV)-Phosphatsulfathydrate gegenüber Li+, Na+, K+, Rb+, Cs+ und NH in absolutem Methanol und absolutem Dimethylsulfoxid

Selectivity of Crystalline Ce^IV Phosphate Sulphate Hydrates for Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, and NH in Absolute Methanol and Absolute Dimethylsulphoxide The sequence of exchange capacities of Cerium(IV) phosphate sulphate hydrate (CePO₄)₂(HPO₄)_0.74(SO₄)_0.26 · 4,74 H₂O for alkalimetal ions and ammoniumions in absolute methanol at 25°C for the case of a small excess of the exchanger (in relation to the equivalent amount) is given by K⁺ > Rb⁺ ≥ NH₄⁺ > Cs⁺ > Na⁺ > Li⁺. Between the exchange capacity A of these cations and their ionic radii r (given by Ladd) exists the simple relation A = const./r. For Na⁺ the radius of the inner hydration shell must be considered. In absolute dimethyl-sulphoxide under the same conditions the sequence is K⁺ ≥ NH₄ > Rb⁺ > Na⁺ > Cs⁺ > Li⁺. For K⁺, NH₄, Rb⁺ and Cs⁺ the exchange capacity is given by A = const./r + const. · r⁴. The sequences of the alkali ions in both solvents are among the group of 13 sequences which are physicaly significant according to EISENMANNS 's theory. The results are compared with the observations made with water as solvent.     

Metal ion complexation in acetonitrile by di-ionized calix[4]arenes bearing two dansyl fluorophores

The influence of metal cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ag⁺, Cd²⁺, Co²⁺, Fe²⁺, Hg²⁺, Mn²⁺, Pb²⁺, Zn²⁺ and Fe³⁺) on the spectroscopic properties of two dansyl (1-dimethylaminonaphthalene-5-sulfonyl) groups linked to the lower rims of a series of three, structurally related, di-ionized calix[4]arenes was investigated by means of absorption and emission spectrophotometry. Di(tetramethylammonium) salts of the di-ionized ligands, (TMA)₂L1, (TMA)₂L2 and (TMA)₂L3, which differ in having zero, two and four tert-butyl groups, respectively, on the upper rim of the calix[4]arene scaffold were utilized for the spectrofluorimetric titration experiments in acetonitrile. On complexation by alkaline earth metal cations, both the absorption and emission spectra undergo marked red shifts and quenching of the dansyl fluorescence. These effects are weaker with alkali metal cations. Transition metal cations interact strongly with the ligands. In particular, Fe³⁺, Hg²⁺ and Pb²⁺ cause greater than 97% quenching of the dansyl fluorescence in the di-ionized ligands.