Metal cations selectivity

NaCl from water.27 Moore and Pressman s discovery that the antibiotic valinomydn exhibits alkali metal cation selectivity in rat liver mitochondria then provided a starting point for studies in the area of M"+ selectivity by biological and model systems.28... 

Sevenich and Fritz [9] published a comprehensive study of metal cation selectivity with resins of a more modern type. The studies were made on a column packed with a 12% cross-linked polystyrene-divinylbenzene resin 12-15 mm in diameter and with an exchange capacity of 6.1 pequiv/g. The resins were prepared by rapid sulfonation so that the sulfonic acid groups are concentrated on the outer perimeter of the resin beads [10]. 

Kempen. E.C. Brodbelt. J.S. Bartsch, R.A. Jang. Y. Kim. J.S. Investigation of alkali metal cation selectivities of lariat ethers by electrospray ionization mass spectrometry. Anal. Chem. 11999. 71. 5493-5500. 

Permeates alkali metallic cation selectively and does not allow a negative ion through. f 130°C... 

Yosida et al. [41] found that p-t< rr-butylcalix[6]ar-ene can extract Cu from the alkaline-ammonia solution to the organic solvent. Nagasaki and Shinkai [42] described the synthesis of carboxyl, derivatives of calix-[n]arenes ( = 4 and 6) and their selective extraction capacity of transition metal cations from aqueous phase to the organic phase. Gutsche and Nam [43] have synthesized various substituted calix[n]arenes and examined the complexes of the p-bromo benzene sulfonate of p-(2-aminoethyl)calix[4]arene with Ni, Cu , Co-, and Fe. ... 

Based on the above results they have concluded that the ligand groups circularly arranged on the lower rim of the calixarene cavity construct a novel cyclic metal receptor for selective extraction of transition metal cations. Results suggest that the fine tuning in molecular... 

Recently, Deligoz and Yilmaz [51] prepared three polymeric calix[4]arenes, which were synthesized by reacting chloromethylated polystyrene with 25,26,27-tribenzoyloxy-28-hydroxy calix[4]arene (2a, 3a) and po-lyacryloyl chloride with 25,26,27,28-tetraacetoxy ca-lix[4]arene (4a). After alkaline hydrolysis of the polymers, they were utilized for selective extraction of transition metal cations from aqueous phase to organic phase. 

Selective extraction experiments were then performed to see transference of some transition elements (Cu ", Ni ", Co ", and Fe " ) from the aqueous phase to the organic phase by the synthesized polymeric calixarenes. Phase-transfer studies in water-chloroform confirmed that polymer 2b and 3b were Fe ion-selective as was its monomer (1). Extraction of Fe " cation with 2b and 3b was observed to be maximum at pH 5.4. Only trace amounts of other metal cations such as Cu, Ni ", and Co " were transferred from the aqueous to the organic phase (Table 3). Furthermore, the extracted quantities of these cations remained unaffected with increasing pH. The effect of pH on the extraction of 3b was lower and 56% extraction was accomplished even at pH 2.2. The extraction experiments were also performed with calix[4]arene (1) the ratio was 8.4% at pH 2.2. The polymeric calix[4]arenes were selective to extract Fe " from an aqueous solution, which contained Cu +, Ni, Co ", and Fe " cations, and it was observed that the... 

The results of the extraction of metal cations are summarized in Table 3. The 4b showed the selectivity toward Fe " cation and cannot act as an extractant for Fe " at pH 2.2. The extraction of Fe cation with 4b was increased with increasing pH, but the Fe cation ratios at all pH decrease than that of 2b and 3b. The results suggested that the conformation of 4b and the C=0 groups in the polymer affected the extraction of Fe in this process. 

Deligoz and Yilmaz [52] reported that the selective liquid-liquid extraction of various alkali and transition metal cations from the aqueous phase to the organic phase as carried out by using p-tert-h iy calix[4]arene (1), p-tert-b x. y calix[6]arene (2), tetra-ethyl-p-tm-butylcalix[4]arene-tetra-acetate (3), tetra-methyl-p-/< /-/-butyl calix[4]arene-tetraketone (4), calix[n]arenes ( = 4 and 6) bearing oxime groups on the lower rim (5 and 6) and a polymeric calix(4]arene (8). It was found that compounds 5 and 6 showed selectivity towards Ag, Hg, Hg, Cu, and Cr and the order of the ex-tractability was Hg > Hg > Ag > Cu > Cr. The polymeric calix[4]arene (8) was selective for Ag, Hg, and Hg , unlike its monomeric analog. 

To avoid homopolymer formation, it is necessary to ensure true molecular contact between the monomer and the polymer. Even if this is initially established, it needs to be maintained during the radiation treatment while the monomer is undergoing conversion. Several methods are used for minimizing the homopolymer formation. These include the addition of metal cations, such as Cu(II) and Fe(II). However, by this metal ion technique, both grafting and homopolymerization are suppressed to a great extent, thus permitting reasonable yield of graft with little homopolymer contamination by the proper selection of the optimum concentration of the inhibitor [83,90,91]. 

Pourbaix has evaluated all possible equilibria between a metal M and HjO (see Table 1.7) and has consolidated the data into a single potential-pH diagram, which provides a pictorial summary of the anions and cations (nature and activity) and solid oxides (hydroxides, hydrated oxides and oxides) that are at equilibrium at any given pH and potential a similar approach has been adopted for certain M-H2O-X systems where A" is a non-metal, e.g. Cr, CN , CO, SOj , POj", etc. at a defined concentration. These diagrams give the activities of the metal cations and anions at any specified E and pH, and in order to define corrosion in terms of an equilibrium activity, Pourbaix has selected the arbitrary value of 10 ° g ion/1, i.e. corrosion of a metal is defined in terms of the pH and potential that give an equilibrium activity of metal cations or anions > 10 g ion/1 conversely, passivity and immunity are defined in terms of an equilibrium activity of < 10 g ion/1. (Note that g ion/1 is used here because this is the unit used by Pourbaix in the S.I, the relative activity is dimensionless.)... 

In mimicking this type of function, noncyclic artificial carboxylic ionophores having two terminal groups of hydroxyl and carboxylic acid moieties were synthesized and the selective transport of alkali metal cations were examined by Yamazaki et al. 9 10). Noncyclic polyethers take on a pseudo-cyclic structure when coordinating cations and so it is possible to achieve the desired selectivity for specific cations by adjusting the length of the polyether chain 2). However, they were not able to observe any relationship between the selectivity and the structure of the host molecules in an active transport system using ionophores 1-3 10). (Table 1)... 

By considering the stability constant and the lipophilicity of host molecules, Fyles et al. synthesized a series of carboxylic ionophores having a crown ether moiety and energetically developed the active transport of alkali metal cations 27-32). Ionophores 19-21 possess appropriate stability constants for K+ and show effective K+-selective transports (Fig. 5). Although all of the corresponding [15]crown-5 derivatives (22-24) selectively transport Na+, their transport rates are rather slow compared with... 

On the other hand, Bartsch et al. have studied cation transports using crown ether carboxylic acids, which are ascertained to be effective and selective extractants for alkali metal and alkaline earth metal cations 33-42>. In a proton-driven passive transport system (HC1) using a chloroform liquid membrane, ionophore 31 selectively transports Li+, whereas 32-36 and 37 are effective for selective transport of Na+ and K+, respectively, corresponding to the compatible sizes of the ring cavity and the cation. By increasing the lipophilicity from 33 to 36, the transport rate is gradually... 

Of fundamental importance in understanding the electrochemistry of ion-selective membranes and also of biomembranes is the research in the field of voltammetry at ITIES mainly pioneered by Koryta and coworkers 99 101 . Koryta also demonstrated convincingly that a treatment like corroding metal electrodes is possible 102). For the latter, the description in the form of an Evans-diagram is most appropriate Fig. 4 shows schematically some mixed potentials, which are likely to arise at cation-selective membranes if interfering ions disturb an ideal Nernstian behavior82. Here, the vertical axis describes the galvani potential differences (absolute po-... 

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