Ion specificity and viscosity of rutile dispersions

The isoelectric point (IEP) of rutile is shifted to higher pH values in the presence of greater than 10⁻⁴ mol dm⁻³ Ba²⁺, Ca²⁺ and Mg²⁺, and when a critical concentration (5 × 10⁻⁴ mol dm⁻³ for Ba²⁺ and 1 × 10⁻³ mol dm⁻³ for Ca²⁺) is exceeded there is no IEP at all and the ζ potential is always positive. A common intersection point for the ζ-potential curves of the different concentrations of salt is found, but for the various salts the point is shifted from ζ = 0 mV for Mg²⁺ up to ζ = 20 mV for Ba²⁺. Between the IEP and the charge-reversal point a rheologically unstable region is discovered. The shear stress of rutile dispersions (2.5 g rutile + 4 g electrolyte solution) at shear rates of 116 s⁻¹ shows the same pH dependence irrespective of the concentration of alkaline-earth metal cations up to 10⁻² mol dm⁻³. The shear stress is less than 1 Pa below pH 3.8 and in the pH range 5–12 it assumes a value between 50 and 80 Pa at 116 s⁻¹ with some scatter; however, no systematic trend with concentration of alkaline-earth metal cations and a rather insignificant decrease with pH at pristine conditions are observed. The acidic branch of the yield stress (pH) and low shear rate viscosity (pH) curves is insensitive to the presence of alkaline-earth metal cations, and the same behaviour is found for the ζ potential. The alkaline-earth metal cations induce an increase in viscosity in the basic region and a shift in the pH of maximum viscosity to high pH values. It was also discovered that the effect different alkaline-earth metal cations have on the rheological properties at the same concentration is different from the effect induced by indifferent electrolytes. When the ζ potential increases the viscosity at high pH is increased in a series which follows the increase in size of the cation. Received: 9 September 1998 Accepted in revised form: 12 January 1999     

Voltammetric study of metal ions binding by biindolizine heterocyclophanes and their acyclic analogues

The binding of ions Li⁺, Na⁺, K⁺, (group I), Mg²⁺, Al³⁺, Ga³⁺ (group II), Ca²⁺, Pb²⁺ (group III) ions, Ba²⁺ and paraquat by heterocyclophanes containing biindolizine and quinoxaline fragments connected by 3,6,9-trioxaundecane and 5,8,11,14,17-pentaoxageneicosane spacers, and also their acyclic analogues, in the acetonitrile-0.1 M Bu₄NBF₄ is studied by cyclic voltammetry. A conclusion is drawn that the ions of the group I are not bound by these compounds; the paraquat is not bound by heterocyclophane with the 5,8,11,14,17-pentaoxageneicosan spacers. For ions of the group II, reversible redox-switchable binding by the macrocycles with the 3,6,9-trioxaundecane and 5,8,11,14,17-pentaoxageneicosan spacers is observed: the initial compounds show the binding; their radical cations and dications do not. The binding of the ions of the group III and Ba²⁺ is determined by the macrocycles’ size. In particular, these ions are bound not only by the heterocyclophane with 3,6,9-trioxaundecane spacers but also by its radical cation or dication. The binding results in the corresponding dication stabilization. The heterocyclophane with the 5,8,11,14,17-pentaoxageneicosan spacers demonstrates the redox-switchable binding of Ca²⁺ and Pb²⁺ ions; no effect of Ba²⁺ ions on the cyclic voltammograms of this heterocyclophane was observed. In the ternary system “heterocyclophane with 3,6,9-trioxaundecane spacers + ions of the group II (Al³⁺, Ga³⁺) + ions of the group III (Ca²⁺, Pb²⁺)” either primary binding of the group III ion Pb2+ or concurrent binding of the ions of the group II and the group III, with the system’s reversible redox-switching from one metal complex to another, was observed.     

Equilibria and heats of exchange of alkaline-earth metal ions on the Na form of mordenite

Sorption-analytic studies of ion exchange equilibria combined with direct calorimetric measurements of the heats of ion exchange sorption of the Ca²⁺, Sr²⁺, and Ba²⁺ cations were performed over the whole range of solid phase fillings with sorbed cations on the Na forms of two mordenites prepared from natural specimens rich in Na⁺ and Ca²⁺ cations. Ion exchange constants were determined and the Gibbs energies and entropies of ion exchange were calculated. The thermodynamic characteristics obtained were analyzed taking into account the preferable localization of alkaline-earth metal ions on certain exchange centers in the structure of mordenite. The presence of natural mordenite memory effects with respect to extra-framework Ca²⁺ cations in the presence of which these zeolites were crystallized in nature was established.     

Role of metal co-cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

First principle calculations based on density functional theory are conducted to investigate the influence of metal cations including Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, La (OH)²⁺ and Ce (OH)²⁺ in the small cage of zeolite on the electronic environment of adjacent active center, Cu⁺ in CuY zeolite as well as the process of CO insertion into CH₃O to form CH₃OCO for oxidative carbonylation of methanol. The study explains the theoretical reasons for the effects of metal cations on the catalytic activity of zeolites. It was found that, the presence of co-cations in the small cage can affect the electronic properties and also the catalytic activity in two ways. Firstly, the presence of co-cations, viz., Ca²⁺, Sr²⁺, Mg²⁺, Ba²⁺ and La species in small cage hinders the migration of active Cu⁺ cations from the super cage to small cage. Secondly, the co-cations greatly affect the charge transfer from zeolite framework to Cu⁺ present in the adjacent super cage, leading to the increase of the net charge and binding energy of Cu⁺. The findings can improve the CO adsorption and insertion efficiencies, and the stability of transition states, which results in the enhanced catalytic activity of corresponding zeolites.     

Study of complexation reactions between alkali and alkaline-earth metal cations with dibenzo-18-crown-6(DB18C6) in mixed nonaqueous solvents using the conductometry method

The complexation reactions between alkali and alkaline-earth metal cations with DB18C6 were studied in acetonitrile-methanol (AN-MeOH) and tetrahydrofuran-threechloromethane (THF-CHCl₃) binary mixtures at different temperatures using the conductometric method. The obtained results show that in most cases, the DB18C6 forms 1:1 complexes with these metal cations and the stability of the complexes is affected by the nature and composition of the mixed solvents. The stability order of complexes in AN-MeOH binary systems was found to be Na⁺ > Li⁺, and in the case of THF-CHCl₃ binary mixtures was Na⁺ > Ba²⁺ > Li⁺. An anomalous and interesting behavior was observed for the case of complexation of a K+ ion with DB18C6 in the AN-MeOH binary mixture and also for complexation of Mg²⁺ and Ca²⁺ cations with this ligand in pure THF and also in THF-CHCl₃ binary systems. The values of the thermodynamic parameters (ΔH _c ^o and ΔS _c ^o ) for complexation reactions obtained from the temperature dependence of the stability constants and the results show that the complexes are both enthalpy-and entropy-stabilized. The text was submitted by the authors in English.     

Leaching of uranium,radium and thorium from vertisol soil by ground water

Shallow land burial is routinely used for the disposal of low-level radioactive waste. Natural processes causing leaching of radionuclides can lead to contamination of surrounding ground water and soil by the radionuclides. The comparative leachability of radionuclides U_(nat), ²²⁶Ra, ²²⁸Ra and Th_(nat) from the soil of a radioactive waste disposal site, by ground water was evaluated. The probability of leaching was obtained in the following order Ra (≈77%) > U (≈40%) > Th (≈20%). Observed ratios (OR) were calculated to correlate leachability of radionuclides to that of major cations Ca²⁺ and Mg²⁺. The leaching of the radionuclides was seen to be dependent on Ca²⁺ and SO₄²⁻ leached from the soil. This study provides sitespecific leachability of radionuclides, that can be used as indicator of the tendency for migration or retention in soil. It can play an important role during an unforeseen accident like breach of containment at the waste disposal site leading to contamination of soil and ground water and causing hazard to public via drinking water route.     

A Thermodynamic Study Between 18-Crown-6 with Mg2+, Ca2+, Sr2+and Ba2+ Cations in Water–Methanol and Water–Ethanol Binary Mixtures Using The Conductometric Method

The complexation reactions between Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ cations with the macrocyclic ligand, 18-Crown-6 (l8C6) in water–methanol (MeOH) binary systems as well as the complexation reactions between Ca²⁺ and Sr²⁺ cations with 18C6 in water–ethanol (EtOH) binary mixtures have been studied at different temperatures using conductometric method. The conductance data show that the stoichiometry of all the complexes is 1:1. It was found that the stability of 18C6 complexes with Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ cations is sensitive to solvent composition and in all cases, a non-linear behaviour was observed for the variation of log K _f of the complexes versus the composition of the mixed solvents. In some cases, the stability order is changed with changing the composition of the mixed solvents. The selectivity order of 18C6 for the metal cations in pure methanol is: Ba²⁺ > Sr²⁺ > Ca²⁺ > Mg²⁺. The values of thermodynamic parameters (Δ H _c ° and Δ S _c °) for formation of 18C6–Mg²⁺, 18C6–Ca²⁺, 18C6–Sr²⁺ and 18C6–Ba²⁺complexes were obtained from temperature dependence of the stability constants. The obtained results show that the values of (Δ H _c ° and Δ S _c °) for formation of these complexes are quite sensitive to the nature and composition of the mixed solvent, but they do not vary monotonically with the solvent composition.This revised version was published online in July 2005 with a corrected issue number.     

Cation distribution and interatomic interactions in oxides with heterovalent isomorphism: XII. Gd2Sr1? x Ca x Al2O7 solid solutions

The area of existence of Gd₂Sr_1−x Ca _x Al₂O₇ solid solutions at x ≤ 0.5 was determined by the X-ray phase analysis. It was found by full-profile X-ray structural analysis that, in contrast to La₂Sr_1−x Ca _x Al₂O₇ solid solutions, the Ca²⁺ cations occupy not only AO₉ nine-vertex fragments, but also AO₁₂ oxygen cubooctahedra. Full ordering of Sr²⁺ cations in the perovskite layer is observed at the calcium content x 0.5. Original Russian Text ? I.A. Zvereva, A.G. Cherepova, Yu.E. Smirnov, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 4, pp. 557–563. For communication XI, see [1].     

Complexation of 4′-nitrobenzo-15-crown-5 with Mg<Superscript>2+</Superscript>, Ca<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript> and Ba<Superscript>2+</Superscript> metal cations in acetonitrile-methanol binary solutions

The complex formation reactions between Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ metal cations with macrocyclic ligand, 4′-nitrobenzo-15C5, were studied in acetonitrile (AN)-methanol (MeOH) binary mixtures at different temperatures using conductometric method. The results show that 4′-nitrobenzo-15C5 forms 1:1 [ML] complexes with Mg²⁺, Ca²⁺ and Sr²⁺ metal cations in solutions. But in the case of Ba²⁺ cation a 1:2 [ML₂] complex is formed in these solvent systems. The stability of the complexes is sensitive to the solvent composition and a non-linear behavior was observed for variation of logK _f of the complexes versus the composition of the binary mixed solvents. The stability constants of complexes decrease suddenly with increasing the concentration of methanol in this binary system. The values of thermodynamic parameters (ΔH _c^° and ΔS _c^°) for formation of (4′-nitrobenzo-15C5.Mg)²⁺, (4′-nitrobenzo-15C5.Ca)²⁺ and (4′-nitrobenzo-15C5.Sr)²⁺ complexes were obtained from temperature dependence of the stability constants and the results show that these parameters are affected by the nature and composition of the mixed solvents. A non-linear behavior is observed between the ΔS _c^° and the composition of the mixed solvents.     

Thin-layer chromatographic behavior of rare earths on silica gel with aqueous alkaline earth metal nitrate solutions as mobile phases

The TLC behavior of all the rare earths except Pm has been surveyed on silica gel (pH 7.0) pretreated with 0.1 mol L^–1 tris(hydroxymethyl)aminomethane and 0.1 mol L^–1 HCl with aqueous nitrate solutions of alkaline earth metals as mobile phases. The R_F values of the lanthanides varied in a regular and characteristic way accompanied by the tetrad effect with increasing atomic number, and when the mobile phases were changed the R_F values of each metal decreased in the order Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺, as the crystal ionic radii of the alkaline earth metals increased. This adsorption sequence was not observed with alkali metal nitrate and alkali metal chloride mobile phases. A brief discussion concerning the effect on R_F values of the solvent cations and the adsorption mechanism is included; also presented are typical chromatograms for the separation of multi-component mixtures containing adjacent lanthanides. Received: 9 October 2000 / Revised: 20 February 2001 / Accepted: 26 February 2001     

Cation and anion ordering in the layered oxyfluorides Sr3−xAxAlO4F (A=Ba, Ca)

The synthesis and structural characterization of mixed oxyfluorides of the type Sr_3−xA_xAlO₄F is reported, where A is either calcium or barium. In these compounds the fluoride and oxide ions are ordered onto two distinct crystallographic sites. There is also an ordering of the alkaline earth cations over two crystallographic sites upon substitution of Ba²⁺ or Ca²⁺ for Sr²⁺. The solid solubility limits extend to x∼1 for substitution of both barium and calcium, but the larger Ba²⁺ cations show a strong site preference for the ten-coordinate strontium sites, while the smaller Ca²⁺ cations prefer the eight-coordinate strontium sites.     

Crown-containing butadienyl dyes 8. Structures and complexation of chromogenic dithia-15(18)-crown-5(6) ethers

The structures of new butadienyl dyes of the benzothiazole series containing the dithia-15-crown-5 (2a) or dithia-18-crown-6 (2b) fragments were established by X-ray diffraction. Complexation of dyes 2a,b with Hg²⁺, Pb²⁺, Cd²⁺, Ag⁺, Zn²⁺, and alkaline-earth cations in aqueous-acetonitrile solutions was studied by spectrophotometry. At a high percentage of water in solutions (P _w ≈ 50%), these dyes have a very low ability to bind Pb²⁺ cations (logK < 2) and virtually do not bind Cd²⁺, Zn²⁺, and alkaline-earth cations. At the same time, these dyes form stable 1: 1 complexes with Hg²⁺ and Ag⁺ cations at all P _w. The stability constants of complexes with the Ag⁺ cation increase with increasing P _w because the free energy of hydration of this cation is much lower than the free energy of solvation in acetonitrile. In the P _w range from 0 to 75%, the stability constants of the complexes of dyes 2a,b with the Hg²⁺ cation are larger than those of the corresponding complexes with the Ag⁺ cation by more than four orders of magnitude. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 90–96, January, 2006.     

Electrochemical behavior of single crystals of nonstoichiometric cerium(III) fluorides

The electrochemical properties of single crystals of cerium fluoride alloyed with bivalent cations Sr²⁺, Ca²⁺, Ba²⁺, Sr²⁺ + Ca²⁺, Sr²⁺ + Ba²⁺, Ba²⁺ + Ca²⁺ and also with La³⁺ and La³⁺ + Ba²⁺ cations are studied using the dynamic voltammetry and impedance spectroscopy. The conductivity of symmetrical cells with Ag electrodes is determined using the method of impedance spectroscopy in the frequency range from 450 to 5 kHz at the temperatures from 20 to 100°C: for CeF₃: Sr²⁺ (0.5 mol %) + Ba²⁺ (0.5 mol %), σ = σ₀ exp[(?0.284 ± 0.005/kT]; for CeF₃:Ca²⁺ (0.5 mol %) + Sr²⁺ (0.5 mol %), σ = σ₀ exp[(?0.292 ± 0.017/kT]. The steady-state and dynamic voltammogams of symmetrical electrochemical cells with nonpolarizable reference electrodes and CeF₃ single crystals alloyed with Sr²⁺, Ca²⁺, and Ba²⁺ bivalent cations exhibited ohmic polarization. For cells with CeF₃ containing La³⁺ as an admixture, a hysteresis was observed, which could not be eliminated by chemical and electrochemical treatment of crystals. In the dynamic voltammetric curves of asymmetric cells with nonpolarizable and silver electrode and CeF₃ crystals alloyed with Sr²⁺, Ca²⁺, and Ba²⁺, a range of ideal polarizability (from 0 to ～?2.7 V), and also cerium redox processes and silver fluorination-boundary regeneration were observed. In the dynamic voltammetric curves of asymmetric cells with CeF₃ containing La³⁺ admixture, no range of ideal polarizability was observed; however, the reactions of silver fluorination and reduction of solid-electrolyte cerium were well pronounced at the corresponding potentials.     

Mononuclear Thiolatecobalt Carbonyls

A Partial Statistically Incorporation of Ca²⁺ into the Ba₆Nd₂Al₄O₁₅-Type: Ba₅CaLa₂Fe₄O₁₅ Using high temperature reactions we succeeded in incorporating Ca²⁺ into the Ba₆Nd₂Al₄O₁₅ type. Single crystal X-ray methods reveal a partly ordered alkaline earth distribution. Ba²⁺ and Ca²⁺ occupy face connected MO₆-octahedra as well as a further point position together with La³⁺ ions (space group C−P6₃mc; a = 11.770; c = 7.039 Å; Z = 2).     

On the molecular models of lewis acid sites on the surface of γ-Al2O3 and in zeolites: a density functional study of CO adsorption

Adsorption complexes of CO-Lewis acid sites with 3- and 5-coordinated Al³⁺ are modeled by the density functional method using the cluster approach. Cluster models of the site with 4-coordinated Al³⁺ on the surface of γ-Al₂O₃ and in zeolites are suggested. For these models of adsorption complexes, C-O vibration frequencies are calculated and the energetics of CO adsorption is evaluated. Translated fromZhurnal Struktumoi Khimii, Vol. 38, No. 5, pp. 834–839, September–October, 1997.     

Exchange of alkaline earth cations with the butylamine intercalate of α-zirconium phosphate

The ion uptake behavior of the butylamine intercalate of -zirconium phosphate, Zr(HPO₄) · H₂O, towards alkaline earth cations has been examined. The rates of uptake are in the order Sr²⁺Ca²⁺>Ba²⁺Mg²⁺. Because of the high pH afforded by the amine intercalate, the exchanged phase is always the fully exchanged one, ZrM(PO₄)₂·nH₂O. The values ofn were found to be 4 for Mg²⁺ and Ca²⁺, 3 for Sr²⁺ and 2 for Ba²⁺. Uptake of ions is quantitative to about 6 meq/g loading when no excess amine is present. Sharply reduced loadings occur in the presence of excess of free amine. A solution containing equal amounts of Ca²⁺ and Mg²⁺ yields a new solid solution phase with a 12.6 Å spacing.     

Complex formation of alkaline-earth cations with crown ethers and cryptands in methanol solutions

The complexation of alkaline-earth cations by different crown ethers, azacrown ethers, and cryptands has been studied in methanol solutions by means of calorimetric and potentiometric titrations. The smallest monocyclic ligands examined form 21 complexes (ratio of ligand to cation) with cations which are too large to fit into the ligand cavity. With the smallest cryptand, only Sr²⁺ and Ba²⁺ ions are able to form exclusive complexes. In the case of the reaction of cryptand (211) with Ca²⁺, a separate estimation of stability constants for the formation of exclusive and inclusive complexes was possible for the first time. Higher values for stability constants are found for the reaction of alkaline-earth cations with cryptands compared to the reaction with alkali ions. This increase is only caused by favorable entropic contributions.     

Structure and surface properties of ZrO<Subscript>2</Subscript>, CeO<Subscript>2</Subscript>, and Zr<Subscript>0.5</Subscript>Ce<Subscript>0.5</Subscript>O<Subscript>2</Subscript> prepared by a microemulsion method according to X-ray diffraction,TPR, and EPR data

It was established by X-ray diffraction, TPR, and EPR that microemulsion (m.e.) synthesis yields the binary oxides ZrO₂(m.e.) and CeO₂(m.e.) and the mixed oxide Zr_0.5Ce_0.5O₂(m.e.) in the form of a tetragonal, cubic, and pseudocubic phase, respectively, having crystallite sizes of 5–6 nm. The bond energy of surface oxygen in the (m.e.) samples is lower than in their analogues prepared by pyrolysis. Hydrogen oxidation on the oxides under study occurs at higher temperatures than CO oxidation. ZrO₂(m.e.) and CeO₂(m.e.) are active in O₂⁻ formation during NO + O₂ adsorption, while CeO₂ is active during CO + O₂ adsorption, too. However, its amount here is one-half to one-third its amount in the pyrolysis-prepared samples, signifying a reduced number of active sites, which are Zr⁴⁺ and Ce⁴⁺ coordinatively unsaturated cations and Me⁴⁺-O²⁻ pairs. O₂⁻ radical anions are stabilized in the coordination sphere of Zr⁴⁺ coordinatively unsaturated cations via ionic bonding, and in the sphere of Ce⁴⁺ cations, via covalent bonding. Ionic bonds are stronger than ionic-covalent bonds and do not depend on the ZrO₂ phase composition. Zr_0.5Ce_0.5O₂ is inactive in these reactions because of the strong interaction of Zr and Ce cations. It is suggested that Ce^{(4 + β)+} coordinatively unsaturated cations exist on its surface, and their acid strength is lower than that of Zr⁴⁺ and Ce⁴⁺ cations in ZrO₂ and CeO₂, according to the order ZrO₂ > CeO₂ ≥ Zr_0.5Ce_0.5O₂. Neither TPR nor adsorption of probe molecules revealed Zr cations on the surface of the mixed oxide.     

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%.     

Conductometric and microcalorimetric analysis of the alkaline-earth/alkali-metal ion exchange onto polyacrylic acid

The specificity of the exchange between divalent (Di²⁺ = Ca²⁺ or Ba²⁺) and monovalent (M⁺ = Li⁺, Na⁺ or K⁺) ions onto a polyacrylic chain is examined using conductometric and microcalorimetric techniques. Assuming the formation of a bidentate complex between the Di²⁺ and the carboxylate groups, the conductometric data give the exchange ratio (Di²⁺/M⁺) and the speciation of the acrylic groups. No significant difference is observed between the three alkali-metal ions for a given Di²⁺ ion. Comparisons between Ca²⁺ and Ba²⁺ show a stronger hydrophobicity of the former as it precipitates at a complexation ratio r = 0.33 versus r = 0.45 for the Ba²⁺ salt. Microcalorimetric data show that all Di²⁺/M⁺ exchange energies are positive and depend significantly on the type of cations. The largest displacement energy (the more positive) is found for the binding of Ca²⁺ with sodium polyacrylate (8.13 kJ · mol⁻¹) and the smallest for Ba²⁺ with lithium polyacrylate (1.88 kJ · mol⁻¹). The interpretation of the data leads to the conclusion that specificity of the Di²⁺ binding originates in the dehydration phenomenon and specificity between the three alkali-metal ions is due to the decrease in the electrostatic bond strength with an increase in the ionic radii. The Di²⁺/M⁺ exchange is entropically driven. Received: 28 January 1999 Accepted in revised form: 7 April 1999