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 RF 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 RF 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 RF 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.     

Effect of alkali metals,alkaline earth metals and lanthanides on the adsorption of uranium on activated charcoal from aqueous solutions

Effects of alkali metals, alkaline earth metals and some lanthanides on the adsorption of uranium on activated charcoal from aqueous solutions have been studied. These effects are correlated with the ionic radii of metal ions present in the solutions. Adsorption capacity, X_m and binding energy contant, K for uranium adsorption were calculated from the Langmuir equätion. The mean energy of adsorption, E_s was calculated from adsorption energy constant, K, values determined from the Dubinin-Radushkevich isotherm equation. Wavelength dispersive X-ray fluorescence spectrometry was used for measuring the uranium concentration.     

Adsorption ability of Ga5N10 nanomaterial for removing metal ions contamination from drinking water by DFT

The electronic, magnetic, and thermodynamic properties of alkali/alkaline earth metal ion-adsorbed gallium nitride nanocage (Ga₅N₁₀_NC) have been investigated using density functional theory. The results denote that alkali/alkaline earth-metal ion-adsorbed Ga₅N₁₀_NC systems are stable compounds, with the most stable adsorption site being the center of the cage ring. The partial density of states (PDOS) can estimate a certain charge assembly between Li⁺, Na⁺, K⁺/ Be²⁺, Mg²⁺, Ca²⁺ and Ga₅N₁₀_NC which indicate the complex dominant of metallic features as: Ca²⁺ > Mg²⁺ > Be²⁺ >> K⁺ > Na⁺ > Li⁺. For confirmation of magnetic-alignment of Ga₅N₁₀_NC, monovalent (M⁺) and divalent (M²⁺) metal ions were added to the sample to measure the effects of metals on the magnetic-alignment properties of Ga₅N₁₀_NC. Furthermore, the reported results of NMR spectroscopy have exhibited that both M⁺ and M²⁺ can be optimized to achieve optimal alignment of nanocage in the presence of an applied magnetic field; however, chemical shift anisotropy spans for Ca²⁺– and Mg²⁺–containing samples is due to Ca²⁺ and Mg²⁺ ions binding to Ga₅N₁₀_NC. Regarding IR spectroscopy, Li⁺@ Ga₅N₁₀_NC and Be²⁺@ Ga₅N₁₀_NC with more electronegativity appear the most fluctuations through adsorption process. Moreover, based on NQR analysis, Ca²⁺ has shown a different graph of electric potential during trapping in Ga₅N₁₀_NC compared to other metal cations. Based on the results of $$ amounts in this research, the selectivity of metal ion adsorption by gallium nitride nanocage (ion sensor) has been approved as: K⁺>Na⁺> Li⁺ in alkali metals and Ca²⁺>Mg²⁺> Be²⁺ in alkaline earth metals.     

Alkalimetall-Cluster im Zeolith Y Darstellung,Eigenschaften, Reaktionen

Alkali Metal Clusters in Zeolite Y. Preparation, Properties, Reactions Alkali metal clusters (Type AB₃³⁺) were synthesized by reaction of alkali metal A (Li, Na, K, Rb, Cs) with the cations B (alkali, alkaline earth, and rare earth metals) of zeolite Y. The compounds were characterized by UV/VIS spectroscopy, oxidation by carbon oxides and organic halides, and adsorption of gases and polar molecules. The clusters are less reactive than the free alkali metals, the redox potential depends on the alkali metal as well as the cation of zeolite. Chemical interactions with typical ligands and with N₂, Ar, Kr, CO, CO₂, Benzene, and n-Hexane were observed. Reaction with ammonia leads to solvated electrons in zeolite's super-cage, stable up to 240 K.     

阳离子交换色谱中色谱柱温度对碱金属与碱土金属离子保留的影响

研究了非抑制型阳离子交换色谱中色谱柱温度(25~50℃)对碱金属离子(Li+、Na+、K+、Rb+)和碱土金属离子(Mg2+、Ca2+、Sr2+)以及NH4+保留的影响。在Shim-pack IC-C1磺酸型阳离子交换柱上,以硝酸为流动相分离碱金属离子,以乙二胺或乙二胺-草酸(柠檬酸)为流动相分离碱土金属离子,随着色谱柱温度的升高,碱金属和碱土金属离子的保留时间均增长,其范特霍夫曲线具有良好的线性关系,斜率为负值,表明在此条件下碱金属和碱土金属离子的保留为吸热过程。在Shim-pack IC-SC1羧酸型阳离子交换柱上,以硫酸为流动相同时分离碱金属和碱土金属离子,随着色谱柱温度的升高,Mg2+、Ca2+的保留时间增长,而K+、Rb+的保留时间缩短,Li+、Na+、NH4+的保留时间基本不变。在此条件下,Mg2+、Ca2+、K+和Rb+的范特霍夫曲线具有良好的线性关系,其中Mg2+和Ca2+的曲线斜率为负值,K+和Rb+的曲线斜率为正值,表明Mg2+和Ca2+的保留表现为吸热过程,K+和Rb+的保留表现为放热过程。研究表明在不同固定相和流动相条件下,色谱柱温度对碱金属和碱土金属离子保留行为的影响不同。     

Ion Chromatographic Separation on Silica Grafted with Benzo-18-C-6 Crown Ether

Abstract

Benzo-18-C-6 crown ether has been grafted on silica gel modified with a spacer. By very carefull control of each step of the synthesis an exchanger for alkali and alkaline earth cations with high capacity and low equilibrium time has been prepared. The chromatographic behavior of alkali and alkaline earth metal halides on this benzo-18-C-6 crown ether modified silicas was investigated with water as the mobile phase. With alkali metal chlorides, very good separations are obtained in less than 30 minutes. With alkaline earth metal chlorides, very good separations are also obtained except for Ca²⁺/Mg²⁺. Separations are also observed with mixtures of alkali and alkaline earth cations. Moreover, a very efficient separation of anions is observed, partly as a result of the hydrophobic character of the exchanger.     

Ion exchange with silica-titania gels

Silica-titania gels containing 25, 50 and 75 mol% TiO₂ were prepared and the sorption of alkali and alkaline earth metal ions by these materials has been studied. Distribution coefficient values for Cs⁺ and Sr²⁺ ions were found to pass through broad maxima as a function of TiO₂ content except in the case of Sr under alkaline conditions where there was a continuous increase. Capacity values also increased with TiO₂ content and samples containing 50% (for K⁺ and Cs⁺), 75% (for Li⁺ and Na⁺) and 25%/50% (for Ca²⁺, Sr²⁺ and Ba²⁺) TiO₂ exhibited maximum capacities. However, unlike with alkali metals, capacities of a given sorbent for the three alkaline earth ions were almost the same. Large capacities obtained for the latter ions seem to indicate a mineral-forming reaction with 25% and 50% materials. On the other hand, the 25% TiO₂ gel seems to sorb Sr at trace level by an ion exchange mechanism. Coupled with its Cs sorption capability, this material may find potential use in large scale decontamination of low level waste solutions.     

Determination of alkali, alkaline earth and transition metal ions in UO2, ThO2 powders and sintered (Th,U)O2 pellets by ion chromatography

An ion chromatographic method has been developed for the determination of traces of Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, Sr²⁺, Fe³⁺, Cu²⁺, Ni^2+, Co²⁺, Zn²⁺, Cd²⁺, Mn²⁺ in UO₂, ThO₂ powders and sintered (Th,U)O₂ pellets. This new method utilizes poly-(butadiene-maleic acid) (PBDMA) coated silica cation exchange column and mixed functionality column of anion and cation exchange to achieve the separation of alkali, alkaline earths and transition metal ions, respectively. It involves matrix separation after sample dissolution by solvent extraction with TBP (tri butyl phosphate)-TOPO (tri octyl phosphine oxide)/CCl₄. Interference of transition metal ions in the determination of alkali, alkaline earth metal ions are removed by using pyridine 2,6-dicarboxylic acid (PDCA) in the tartaric acid mobile phase. Mobile phase composition is optimized for the base line separation of alkali, alkaline earth and transition metal ions. Linear calibration graphs in the range 0.01–20 μg mL⁻¹ were obtained with regression coefficients better than 0.999. The respective relative standard deviations were also determined. Recoveries of the spiked samples are within ±10% of the expected value. The developed method is authenticated by comparison with certified standards of UO₂ and ThO₂ powders.     

Structure and Bonding in Organometallic Anions of Heavy Group 14 and 15 Elements

Alkali metal organometallic complexes (containing C–metal bonds) and the frequently structrually related alkali metal amides and alkoxides have been investigated extensively both in the solid state and in solution in the past two decades. However, until recently, the related complexes containing the heavier metallic and semi-metallic p block elements and the alkali and alkaline earth metals had rarely been studied in their own right. Recent solid-state structural studies have illustrated the immense structural diversity and bonding modes to be found within these species. One of the principal focuses of recent studies has been complexes containing organometallic anions of p block metals (e.g., triorganostannates, containing R₃Sn^?) in which metal–metal bonds occur between the heavy p block metal and the alkali or alkaline earth metal and the investigation of the nature of this bonding. The development of new synthetic routes has also allowed the preparation of a variety of anionic ligands with p block metal centers which promise new opportunities in coordination chemistry. In addition, the synthesis of a family of homologous anionic π complexes has given a fresh direction in the chemistry of p block metal metallocene complexes.     

Die Reaktion von Isonitrilen und Nitrilen mit Alkali- und Erdalkalimetallen

Isocyanides RNC and the isomeric nitriles, RCN, reacting with alkali or alkaline earth metals in liquid ammonia undergo reductive fission to metal cyanides and carbanions R^?. The latter are ammonolized to the corresponding hydrocarbons.     

Use of Different Salt Solutions in Salting-Out TLC of Co(III) Complexes on Silica Gel

Saturated aqueous solutions of 28 different salts have been studied as a potential mobile phases for salting-out thin-layer chromatography, on silica gel, of a series of four mixed bis-aminocarboxylato cobalt(III) complexes. In addition, by linear regression analysis of chromatographic data obtained for fifteen mixed aminocarboxylato Co(III) complexes (four series) with solutions of ammonium chloride, three alkali metal chlorides, and four alkaline earth metal chlorides, four linear dependences previously established on different adsorbents with (NH₄)₂SO₄ solutions were confirmed. The qualities of the separations achieved with the salts were compared and Li⁺, Mg²⁺, and Ca²⁺ chlorides are proposed as the most suitable.     

On solute-mercury interactions in dilute amalgams of main group metals

The paper challenges the concept of intermetallic compound formation in dilute (mole fraction <10⁻³) amalgams of s-block metals. Although the formation of these amalgams is strongly exothermic the generated energy is much lower than the Fermi level difference between pure solutes and mercury. Thermodynamic considerations suggest that the energy of metal ions is higher in amalgams than in pure s-block metals. Repulsive interactions between the cores of these metals and mercury ions are responsible for abnormally low diffusion coefficients of alkali and alkaline earth metals in mercury. The mercurophobic character of alkali metal ions demonstrates itself in the strong adsorption of these metals on the Hg-vacuum interface, and in the high rates of ion exchange between electrolytic solutions and amalgams.     

An active transport mimetic system based on thioctic acid as carrier for alkaline earth metal ions

Liquid membranes incorporating thioctic acid as a carrier to mimic an active transport system for alkaline earth metals has been described. A transport cell, operating on the same principle as the Schulman Bridge was used. It has been demonstrated that such a system is capable of transporting alkaline earth metals against a proton gradient, as driving force. The potential of thioctic acid to complex and transport these metal ions particularly Mg²⁺, Ca²⁺, and Ba²⁺ was verified. Furthermore, this transport phenomenon was extended to some different barium salts (Cl^?, Br^? NO₃ ^?, and SCN^?) to determine the effect of nature of anion on the transport of the Ba²⁺ ions. The order of the transport rate was found to be Ba²⁺ > Ca²⁺ > Mg²⁺ which is inconsistent with the stability of coordination to the carboxyl group. The rate of transport of Ba²⁺ ions were found to decrease with the anion type in the order SCN^? > Br^? > NO₃ ^? > Cl^? which is related to the extent of hydration of the anions.     

A theoretical study of cation--π interactions: Li+, Na+, K+, Be2+, Mg2+ and Ca2+ complexation with mono- and bicyclic ring-fused benzene derivatives

DFT (B3LYP functional) and MP2 methods using 6-311+G(2d,2p) basis set have been employed to examine the effect of ring fusion to benzene on the cation--π interactions involving alkali metal ions (Li⁺, Na⁺, and K⁺) and alkaline earth metal ions (Be²⁺, Mg²⁺ and Ca²⁺). Our present study indicates that modification of benzene (π-electron source) by fusion of monocyclic or bicyclic (or mixture of these two kinds of rings) strengthens the binding affinity of both alkali and alkaline earth metal cations. The strength of interaction decreases in the following order: Be²⁺ > Mg²⁺ > Ca²⁺ > Li⁺ > Na⁺ > K⁺ for any considered aromatic ligand. The interaction energies for the complexes formed by divalent cations are 4–6 times larger than those for the complexes involving monovalent cations. The structural changes in the ring wherein metal ion binds are examined. The distance between ring centroid and the metal ion is calculated for all of the complexes. Strained bicyclo[2.1.1]hexene ring fusion has substantially larger effect on the strength of cation--π interactions than the monocyclic ring fusion for all of the cations due to the π-electron localization at the central benzene ring.     

Role of bimetallic active centres in anionic polymerization of hydrocarbon monomers

Polymerization of hydrocarbon monomers initiated by organometallic compounds of alkali and alkaline earth metals modified by derivatives of other metals of Groups I-III is reviewed. Various mixed initiators, such as RLi-RONa, RLi-RNa, R₂Ba-R₃Al, RNa-R₃Al, are discussed in details. It is shown that the presence of a second metal greatly affects the kinetics of elementary steps of chain propagation and chain transfer and also the structure and molecular weight of polymer formed. Active centres in all the systems are complexes containing two or more metal atoms linked by a bridge bond; the addition of a monomer occurs by an insertion either into the “usual” metal-carbon bond which is external with respect to the polymetal nucleus of the complex or directly into Mt¹-R-Mt² bridge bond.     

Binding and chemical fractionation of heavy metals in typical peat matter

Laboratory batch studies were conducted to evaluate the binding capacity and the mobility of metal species bound to typical humus peat matter. The identification of phase composition of mineral fractions and functional groups in the organic matter was assessed. The results showed generally high, but different retention capacity and binding strength, suggesting distinct diversity in binding mechanisms, phases and chemical nature of binding sites, depending on the metal species and their input concentrations. In general, the binding capacity of peat for the metal ions studied follows the order: Cr³⁺ > Cu²⁺ > Zn²⁺ > Cd²⁺ and results in the decrease of pH in the same order, due to displacement of H₃O⁺ from the peat by metal ions. The highest metal enrichment occurs in fractions F1(EXC), F2(CARB), F4(MRO) and F5(OM) of different binding strength adequate to exchangeable, carbonatic, moderately reducible amorphous Fe-oxide and organic/ sulphidic fractions in soils and sediments. In relation to species distribution in peats, the prevailing part of Cr³⁺ is strongly bound in oxidizable organic substrate, while Cu²⁺ is highly enriched in the moderately reducible F4(MRO) and the most labile F2(EXC) fractions. Cd²⁺ and Zn²⁺ are predominantly bound in the labile F1(EXC) and F2(CARB) fractions. Diversity of the predominant binding phases for the studied metals suggests rather weak competition for binding sites between chromium and copper ions; the strongest competition between the sorbed metal ions is anticipated for F1(EXC) and F2(CARB) fractions.     

Complexation of di-benzyloxy ether derivatives of calix[4]arene with alkali earth metal cations

The synthesis and complexing abilities of 26,28-bis-benzyloxy-25,27-dihydroxy-5,11,17,23-tetra-tertbutyl-calix[4]arene towards alkali earth metal ions Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ in a methanol-chloroform mixture have been evaluated at 25°C, using UV-Vis spectrophotometric techniques. The results showed that the ligand is capable to complex all alkali earth cations by 1:1 metal to ligand ratios. The selectivity presented considering the calculated stability constants are in the order Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ towards the ligand.     

The colours of simple salts of the violurate anion

Salts of the violurate anion with the alkali and alkaline earth metals, the d¹⁰ ions Zn²⁺ and Cd²⁺, Mn²⁺, Pb²⁺, Ag⁺ and the lanthanides show a variety of spectacular colours in the solid state. The metal ions have no intrinsic absorption in the visible region (apart from the weak spin-forbidden bands of Mn²⁺) and do not normally show charge-transfer absorption. The colours are ascribed to the n→π* transition of the violurate anion. As confirmation of this assignment the visible absorption of the K⁺ salt is shown to be polarized perpendicular to the plane of the violurate anion. Low temperature (∼20 K) absorption spectra of the Na⁺, K⁺ and Rb⁺ salts are reported.     

The ion exchange of strontium on sodium titanate Na4Ti9O20.xH2O

The ion exchange behaviour of the exchanger Na₄Ti₉O₂₀.xH₂O was studied with particular emphasis on Sr²⁺ exchange. Titration of H₄Ti₉O₂₀.xH₂O with 0.1M [Sr/OH/₂+SrCl₂] solution yielded a strontium ion exchange capacity of 5.30 meq g^–1 corresponding well with the theoretical value. When strontium was absorbed on Na₄Ti₉O₂₀.xH₂O from neutral solutions, Sr₂Ti₉O₂₀.xH₂O was formed. This compound decomposed to SrTiO₃ and TiO₂ when heated to 870 °C. From alkaline solutions strontium was absorbed both as Sr/OH/⁺ and Sr²⁺ with the proportion of the former species increasing with pH. At pH 12.8 only exchange of Sr/OH/⁺ was observed and the exchanged form was Na₂/SrOH/₂Ti₉O₂₀.xH₂O. This compound decomposed to Na₂Ti₆O₁₃ and an unidentified strontium titanate when heated to 870 °C. Distribution coefficients were determined for alkali and alkaline earth metal ions as a function of pH. The selectivity sequence for alkaline earth metal ions was Ba>SrCa>Mg, and that for alkali metal ions was Cs>K>Li /pH 2–6/ and Li>Cs>K /pH 7/.     

Proton ionizable crown compounds. 18. Comparison of alkali metal transport in a H2O-CH2Cl2-H2O liquid membrane system by four proton-ionizable macrocycles containing the dialkylhydrogenphosphate moiety

The macrocycle-mediated fluxes of alkali, alkaline earth, and several transition metal cations have been determined and compared in a H₂O-CH₂Cl₂-H₂O liquid membrane system using four water-insoluble macrocycles containing a dialkylhydrogenphosphate moiety. Transport of alkali metal cations by these ligands was greatest from a source phase pH = 12 or above into an acid receiving phase (pH = 1.5). Very low fluxes were observed for the transport of the alkaline earth cations and all transition metal ions studied except Ag⁺ and Pb²⁺ which were transported reasonably well by these new macrocycles.Deceased: September 5, 1987.