Effect of Receiving Phase Anion on Macrocycle-Mediated Cation Transport Rates and Selectivities in Water—Toluene—Water Emulsion Membranes

Abstract

Relative transport rates of metal nitrates (Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, T1⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, and Pb²⁺) were measured alone and in combination with either Pb²⁺, Ag⁺, or T1⁺ in a water-toluene-water emulsion membrane system. The toluene phase contained the surfactant Span 80 and the crown ether dicyclohexano-18-crown-6 (DC18C6). The aqueous receiving phase contained the lithium salt of one of the following anions: pyrophosphate, thiosulfate, hydroxide, chloride, formate, nitrate. In the case of the metal combinations, chloride and formate ions were not studied. Unless significant complexation occurred both between the transported cation and the anion in the receiving phase and between the cation and DC18C6 in the membrane phase, there was little or no transport of the cation from the source phase to the receiving phase. Selective removal of Pb²⁺ and of Ag⁺ from binary mixtures of these cations with each of the cations listed was demonstrated using the emulsion membrane.     

ION EXCHANGE PROPERTIES OF THE SODIUM PHLOGOPITE AND BIOTITE

ABSTRACT

The ion exchange behavior of three sodium micas (phlogopite, Ward's Sci.; phlogopite, Suzorite Inc., biotite, Ward's Sci.) towards Li⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺. Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺ Hg²⁺, Co²⁺, Cu²⁺ Cd²⁺ and Zn²⁺ ions has been studied. The ion exchange isotherms of alkali, alkaline earth and some other divalent cations were determined and concentration equilibrium constants as a function of metal loading and temperature were analyzed. Sodium micas exhibit high affinity for heavy alkali metals with the selectivity order Rb⁺ > Cs⁺ > K⁺. By studying the cesium uptake in the presence of NaNO₃, CaCl₂, NaOH, NaOH+KOH, HNO₃ electrolytes (in the range of 0.01–6 M) it was found that sodium micas could remove cesium efficiently in neutral and alkaline media, which make them promising for certain types of nuclear waste treatment.     

Cation Transport at 25°C from Binary Cd2+–Mn+ Mixtures in a H2O-CHCl3–H2O Liquid Membrane System Containing a Series of Macrocyclic Carriers[1]

Macrocycle-mediated fluxes of Cd(NO₃)₂ and of several binary mixtures of Cd(NO₃)₂ with the nitrate salt of either Na⁺, K⁺, Rb⁺ Cs⁺, Ag⁺, Ca²⁺, Sr²⁺, Pb²⁺, Zn²⁺, or Cu²⁺ have been determined in a H₂O-CHCl₃–H₂O liquid membrane system. Of the macrocycles studied, 2.2 and 2.2DD most successfully transported Cd²⁺ In the Cd²⁺–Mⁿ⁺ mixtures, Cd²⁺ was transported selectively with 2.2 when Mⁿ⁺ was either an alkali or an alkaline earth cation. However, when Mⁿ⁺ was either Ag⁺, Pb²⁺, or Cu²⁺ the Cd²⁺ flux was reduced sharply. Generally, cation flux was greater for 2.2DD than for 2.2 with selectivity for Cd²⁺ being altered also in several cases. Relative fluxes from binary cation mixtures depend on metal cation radius, macrocycle cavity diameter, ligand ring substituent and log K for metal ion-macrocycle interaction.     

Macrocycle-Mediated Transport in a Bulk 1.5 M HNO3-CHCI3-0.01 M HNO3 Membrane System of Pd2+ and Mn+ from Pd2+Mn+ Mixtures

Abstract

Pd²⁺ has been transported using sulfur substituted macrocycles as carriers and several Mⁿ⁺ (Mⁿ⁺ = Lⁱ⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ag⁺, TL⁺, Cd²⁺, and Pb²⁺) have been transported using 18-crown-6 (18C6) and sulfur substituted macrocycles as carriers in a 1.5M HN0₃/CHCL₃3/0.01M HNO₃ bulk liquid membrane system. Competitive Pd²⁺-Mⁿ⁺ transport studies have also been carried out for the same systems. The cyclic polyether 18C6 transports Mⁿ⁺ selectively over Pd²⁺ for all Mⁿ⁺ except Li⁺, Mg²⁺, and Cd²⁺. In the cases of these three cations, no transport was found for either Pd²⁺ or Mⁿ⁺. Generally, the sulfur substituted macrocycles transport Pd²⁺ selectively over Mⁿ⁺.     

N‐alkylation of chitosan by β‐halopropionic acids in the presence of various acceptors

N‐carboxyethylation of chitosan by β‐halopropionic acids in the presence of various proton and halogen ion acceptors was investigated. It has been observed that carboxyethylation of chitosan in aqueous medium is accompanied by the by‐processes of hydrolysis and dehydrohalogenation of the β‐halopropionic acids yielding β‐hydroxypropionic acid, bis(2‐carboxyethyl) ether, and acrylic acid. Degree of carboxyethyl substitution (DS) of chitosan and the relative rates of the by‐processes varied significantly depending on the conditions used and nature of the proton or halogen ion acceptor. At carboxyethylation of chitosan with the alkaline β‐bromopropionates, the DS increased in the order Cs⁺ < Rb⁺ < K⁺ ～ Na⁺ < Li⁺. For alkaline earth salts BrCH₂CH₂COOM_0.5 (M = Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), the highest DS was obtained with strontium and barium salts, which could be subsequently removed from the reaction mixture by precipitation as sulfates. Among the organic bases applied (tetrabutylammonium hydroxide, triethylamine, trimethylamine, pyridine, 4‐N,N‐dimethylaminopyridine, 2,6‐lutidine, and 1,5‐diazabicyclo[4.3.0] non‐5‐ene), the highest DS was obtained using a moderately strong base triethylamine. For the halogen acceptors (Pb²⁺, Ag⁺, Tl⁺), the stoichiometrically highest DS was achieved in a system comprising iodopropionic acid plus Tl⁺ and a comparable conversion rate was obtained using also a combination of chloropropionic acid and Ag⁺. A novel alternative preparative approach—gel‐state synthesis—was suggested that provides for the highest DS at the optimum reaction conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

SYNTHETIC INORGANIC ION-EXCHANGE MATERIALS. XLVIII. ION-EXCHANGE REACTION OF ALKALI METAL IONS/H+ ON MONOCLINIC ANTIMONIC ACID

The pH titration curves of monoclinic antimonic acid (M-SbA) showed apparently monobasic acid for the systems of alkali metal ions/H⁺. The uptake order of the metal ions were K⁺ < Rb⁺ < Cs⁺ < Na⁺ < Li⁺ throughout the pH range studied. The low uptakes of K⁺, Rb⁺, Na⁺ and Cs⁺ at high pH might be due to steric or ion sieve effects for large unhydrated cations on M-SbA. Thermodynamic data were derived for Li⁺/H⁺ exchange on M-SbA from pH titration curve.     

Ion-Exchange Properties of lon-Sieve-Type Manganese Oxides Prepared by Using Different Kinds of Introducing Ions

Abstract

Three ion-sieve-type manganese oxides, HMnO(Li), HMnO(Na), and HMnO(K), were prepared by acid treatments of Li⁺-, Na⁺-, and K⁺-introduced manganese oxides, respectively. Three oxides were obtained from γ-MnO² and the corresponding alkali metal hydroxides by heating at 600°C. The ion-exchange properties of the adsorbents were investigated by pH titration, K_d measurements, and the adsorption of metal ions from seawater. The selectivity sequences of alkali metal ions were Na⁺ < Cs⁺ < Rb⁺ < K⁺ < Li⁺ for HMnO(Li) and Li⁺ Na⁺ < Cs⁺ < K⁺ < Rb⁺ for HMnO(Na) and HMnO(K). The high selectivity of Li⁺ on HMnO(Li) can be ascribed to an ion-sieve effect of spinel-type manganese oxide which was produced from LiMn₂O₄ Since HMnO(Na) and HMnO(K) had [2 × 2] tunnels of edge-shared [MnO₆] octahedra, the high selectivities of K⁺ and Rb⁺ on these samples were used to explain that the sizes of the [2 × 2] tunnels were suitable for filling ions of about 1.4 Å in radius in a stable configuration. The order of metal-ion uptake from seawater was Sr²⁺ < K⁺ < Mg²⁺ < Ca²⁺ < Na⁺ < Li⁺ for HMnO(Li), Li⁺ < Sr²⁺ < Mg²⁺ < Ca²⁺ < Na⁺ < K⁺ for HMnO(Na), and Li⁺ < Sr²⁺ < Ca²⁺ < Mg²⁺ < K⁺ < Na⁺ for HMnO(K).     

Extraction of Alkali Metal Cations by Lipophilic Dibenzo-14-crown-4-carboxylic Acids

Abstract

The extraction of alkali metal cations by the lipophilic crown ether, bis-t-octylbenzo-14-crown-4 (BOB14C4), three derivatives of BOB14C4 having pendant carboxylic acid sidearms, and a lipophilic carboxylic acid, 2-methyl-2-heptylnonanoic acid (HMHN) was studied by two-phase potentiometric titration and ion-chromatography. The lipophilic, ionizable crown ethers, BOB14C4-acetic acid (BOB14C4AA), BOB14C4-propanoic acid (BOB14C4PA), and BOB14C4-oxyacetic acid (BOB14C4OAA) extract cations efficiently from aqueous mixed alkali metal chloride solutions into 1-octanol by an ion-exchange mechanism in the range p[H] > 7, as does HMHN. The mode of attachment of the ionizable sidearm, via an ether linkage (BOB14C4OAA) versus a carbon linkage (BOB14C4AA and BOB14C4PA), has a significant effect on the cation selectivity and extraction efficiency of these extractants. BOB14C4 exhibits no p[H] dependent extraction behavior and has no significant effect on the extraction of alkali metal cations by HMHN in a mixture of these two compounds. Although BOB14C4AA and BOB14C4PA extract cations at lower p[H] than HMHN, all three compounds exhibit similar selectivity for Li⁺ over Na⁺, K⁺, Rb⁺ and Cs⁺. A significant reversal in selectivity is observed with BOB14C4OAA, which extracts Na⁺ and K⁺ selectively over Li⁺, Rb⁺, and Cs⁺ and at significanty lower p[H] than BOB14C4AA, BOB14C4PA, or HMHN. The unique behavior of BOB14C4OAA may be attributed to the presence of the ether linkage between the crown ether and the pendant carboxylic acid.     

Proton-Ionizable Crown Compounds: Transport of Alkali and Alkaline Earth Cations Using Proton-Ionizable Triazolo Macrocycles

Abstract

The macrocycle-mediated flaxes of the alkali and alkaline earth metal cations have been determined in a H₂O-CH₂Cl₂-H₂O bulk liquid membrane system. Water-insoluble proton-ionizable macrocycles of the triazolo type were used. The proton-ionizable feature allows the coupling of cation transport to reverse H⁺ transport. This feature offers promise for the effective separation and/or concentration of alkali metal ions with the metal transport being driven by a pH gradient. A counter anion in the source phase is not co-transported. Transport of the alkali cations only occurred when the source phase pH was greater than the aqueous pK_a value for the carriers. Transport increased regularly with increasing source phase pH. Transport of alkaline earth cations from neutral pH source phases was minimal. The alkali cation selectivity order was K⁺ > Rb⁺ > Cs⁺ > Na⁺ > Li⁺ for the l8-crown-6 sized macrocycles, while little selectivity was observed with the 15-crown-5 sized macro-cycle.     

Extraction of Alkali Metal Tetraphenylborates by Polyurethane Foam

Abstract

The extraction of alkali metal tetraphenylborates by polyurethane foam was investigated. The extractability sequences are K⁺ ≈ Rb⁺ > Cs⁺ and K⁺ ≈ Rb⁺ ≈ Cs⁺ for polyether and polyester foams, respectively. The high extraction of K⁺ by polyether foam can be explained by the cation chelation mechanism.     

A Striking Effect of Ionic‐Liquid Anions in the Extraction of Sr2+ and Cs+ by Dicyclohexano‐18‐Crown‐6

Abstract

The nature of the ionic‐liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr²⁺ and Cs⁺ by dicyclohexano‐18‐crown‐6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation‐exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr²⁺ over Na⁺, K⁺, and Cs⁺ can be significantly improved through the use of hydrophobic anions for the ILs containing 1‐ethyl‐3‐methylimidazolium or 1‐butyl‐3‐methylimidazolium cations.     

Studies on the use of chromium ferrocyanide gels in the treatment of radioactive wastes

The sorption and distribution of some radioisotopes on chromium ferrocyanide gels under different physical conditions has been investigated. The exchanger shows high selectivity for Tl⁺, Cs⁺, Cd²⁺ and Pb²⁺. A complete elution of Cs⁺, Tl⁺ and Rb⁺ is possible with suitable eluants whereas Pb²⁺ and Cd²⁺ cannot be desorbed. The uptake of monovalent ions is by an ion exchange process unlike the sorption of bivalent ions.     

Preparation and adsorption selectivity for Hg(II) and Ag(I) of chelating resin immobilizing benzothiazolyl group on crosslinked polystyrene via hydrophilic sulfur‐containing PEG spacer

A new chelating resin incorporating 2‐mercaptobenzothiazole (MBZ) into macroporous chloromethylated polystyrene via hydrophilic spacer of polyethylene glycol containing sulfur was synthesized. The resin was characterized by elementary analysis and infrared spectra. The adsorption capacity of the resin for Ag⁺, Hg²⁺, Cu²⁺, Zn²⁺, and Pb²⁺ as a function of pH was determined. The effects of interference ions, such as Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺, on percent recovery were also investigated. The results showed that the resin could effectively remove Hg²⁺ and Ag⁺ from solutions containing a large excess of Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺. In column operation, it was observed that Hg²⁺ and Ag⁺ in trace quantities were effectively removed from binary metal ions. The percent recovery of the resin for Hg²⁺ and Ag⁺ was >98.6% and >97.5%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5034–5038, 2006     

THERMODYNAMICS OF ALKALI AND ALKALINE EARTH METAL ION - EXCHANGE ON CERIUM(IV) HYDROGEN PHOSPHATE

ABSTRACT

Thermodynamics of alkali and alkaline earth metal ions/hydrogen ions exchange on a fibrous cerium(IV) hydrogen phosphate have been investigated. Selectivities for alkali and alkaline earth metal ions increase in the order; Na⁺<<K⁺<Rb⁺<Cs⁺ and Mg²⁺<Ca²⁺<Sr²⁺<Ba²⁺, respectively. The enthalpy changes for alkali metal and Ba2+ ions/H⁺ exchange are negative, those for the other alkaline earth metal ions/H⁺ exchange are positive, indicating that the enthalpy changes for monovalent ions are more favorable than those for divalent ions. In comparison with ions of the same valency, the enthalpy change decreases with the atomic number of the metal ion corresponding to a decrease in the entropy change of dehydration in response to enthalpy-entropy compensation.     

CO<Subscript>2</Subscript> retention ability on alkali cation exchanged titanium silicate,ETS-10

ETS-10 was ion exchanged by various alkali cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) and the BET surface area and pore volume was exactly consistent with cationic size; that is, in the order of Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺. It was observed that a single point adsorption capacity was inversely proportional to cationic size. The largest CO₂ capacity was observed for Li⁺-ETS-10 and it is attributed to greater cation–quadrupole interactions with CO₂ than larger cation. The results also suggests that as the CO₂ loading is increased, the accessibility of adsorbing CO₂ to framework basic O⁻ sites should have become difficult with the increase in cationic size due to the blocking effect by extra-framework CO₂-M⁺. The slight decrease in the slope of adsorption capacity with temperature, especially beyond 373 K for Li⁺-ETS-10 and K⁺-ETS-10 suggests that the adsorption of CO₂ on small alkali cation exchanged-ETS-10 at high temperature is somewhat associated with basic oxygen anion sites in framework due to the existence of large pore. The CO₂-TPD results show that the amount of desorbed CO₂ at higher temperature was proportionally increased due to the increased basicity of oxygen anions in framework. It also shows that the desorption temperature associated with alkali cations in extra-framework (corresponding to low temperature desorption peak) has been lowered with the increase in cationic size, indicating weak cation–quadrupole interactions with CO₂ for larger cations.     

Separation of Metal Ions on Titanium(IV) Tungstate Papers

Abstract

Papers impregnated with titanic tungstate have been used to chromatograph 52 cations in 45 aqueous and mixed solvents. Experimentally, a large number of complex cation separations have been achieved easily and rapidly—Au³⁺, Tl³⁺, Ag⁺, Mo⁶⁺, K⁺, Rb⁺, CS⁺, Ni²⁺, Sb²⁺, Bi³⁺, Be²⁺, and Tl⁺ can be easily separated from numerous metal ions. Several quaternary, ternary, and binary separations have also been achieved, and some important separations are discussed.     

Synthesis and characterization of calix[4]arene-based copolyethers and polyurethanes. Ionophoric properties and extraction abilities towards metal cations of polymeric calix[4]arene urethanes

Copolyethers and polyurethanes containing lower and upper rim calix[4]arene units in the fixed cone conformation were prepared in good yield by polycondensation reactions of distal calix[4]arene diols with bisphenol-A/dibromomethane and 2,4-tolylendiisocyanate (TDI), respectively. In a similar way were prepared calix[4]arene-crown-5 and -crown-6 polyurethanes in the fixed 1,3-alternate conformation by condensation of TDI with lower rim calixcrown-5 and calixcrown-6 diols. However, the poor solubility in common organic solvents of the copolyether derivatives (M_w=11,100-11,600 g/mol) hampered further studies on their ionophoric properties. Aiming to obtain model compounds for the investigation of both extraction abilities and ionophoric properties of the polyurethane materials, several bis-urethanes were also synthesized by reaction of the calix[4]arene diols with p-tolylisocyanate (TI). The extraction ability measurements of monomeric and polymeric calix[4]arene urethanes (M_w=12,300-83,500 g/mol) towards alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) and Ag⁺showed a remarkable efficiency and selectivity of calixcrown-6 polyurethane toward Rb⁺, Cs⁺and Ag⁺.     

Removal of Cs1+, Sr2+ and Co2+ from aqueous solutions by adsorption on natural clinoptilolite

The adsorption properties of local clinoptilolite (Serbia) towards Cs⁺, Co²⁺, and Sr²⁺ were investigated by batch equilibration technique. The influence of equilibration time, initial metal cation concentration, solution pH and presence of EDTA on these properties was studied and discussed. Kinetic data were found to be well fitted with pseudo-second order kinetic model. Cs⁺ is preferably adsorbed by the natural clinoptilolite, followed by Sr²⁺ and Co²⁺. The Langmuir adsorption isotherm was used to determine the adsorption capacities from both single and mixed metal solutions. At pH range of 3–12 the adsorption of Cs⁺ remains almost constant, while at low pH (2–3) the adsorption is lesser. At initial pH range of 2–10 adsorption of Sr²⁺ remains approximately stable, whereas at initial pH > 10 adsorption increases significantly. The adsorption of Co²⁺ is low at low pH but increased remarkably with increasing pH and precipitated at pH > 8. Cs⁺ adsorption on the clinoptilolite was not affected by the presence of EDTA, while the presence of EDTA hinders the adsorption of Co²⁺ and Sr²⁺ on clinoptilolite.     

Synthesis of a highly selective bis-rhodamine chemosensor for naked-eye detection of Cu2+ ions and its application in bio-imaging

A bis-rhodamine based fluorescent chemosensor for naked-eye detection of Cu²⁺ with enhanced sensitivity as compared to mono-rhodamine derivative has been synthesized, and its selectivity for Cu²⁺ in the presence of other competitive metal ions (Li⁺, Na⁺, K⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺), and application in bio-imaging are demonstrated.     

Competitive Adsorption of Ag+, Pb2+, Ni2+, and Cd2+ Ions on Vermiculite

Competitive adsorption of Ag⁺, Pb²⁺, Ni²⁺, and Cd² ions on vermiuculite in a binary, ternary, and quaternary mixture was investigated in batch experiments. The effects of the presence of Ag⁺, Ni²⁺, and Cd²⁺ ions on the adsorption of Pb²⁺ ions were investigated in terms of the equilibrium isotherm. Experimental results indicated that Pb²⁺ ions always favorably adsorbed on vermiculite over Ag⁺, Ni²⁺, and Cd²⁺ ions. The adsorption equilibrium data of Pb²⁺ ions better fitted the Langmuir model than the Freundlich model. The results showed that the pseudo-second-order kinetics model was in good agreement with the experimental results for all metal ions, and the adsorption rate among the metal ions followed Ag⁺ > Pb²⁺ > Ni²⁺ > Cd²⁺. The desorption and regenration study indicated that vermiculite can be used repeatedly and be suitable for the design of a continuous process.