TLC separations of some metal ions with aqueous and aqueous-organic solvent systems containing formic acid

Summary The chromatographic behaviour of some metal ions on silica gel thin layers has been studied in aqueous formic acid and mixed aqueous-organic solvent systems containing formic acid. Many analytically important separations of cations have been achieved in varying concentrations of formic acid solution in DMSO, acetone, and methyl ethyl ketone. Semiquantitative determination of nine cations has also been attempted.The most suitable concentration range of acid for reliable and reproducible separations was found to be 0.1M to 1.0M.     

Thin layer chromatography of 57 metal ions on an inorganic ion-exchanger in mixed solvent systems

Summary Thin layers of stannic arsenate have been used to study the chromatographic behaviour of 57 metal ions in different mixed solvents. Au³⁺, Hg²⁺, UO ₂ ²⁺ , Be²⁺ and Al³⁺ and others can be easily separated from numerous metal ions. Fast quaternary, ternary and binary separations have been also achieved. Important separations are discussed. The effect of pH, duration of heating of ionexchanger plates and layer thickness on the R_f values has been studied and discussed. It is shown that Lederer's equation is also obeyed by thin layers of stannic arsenate, if instead of concentration of Na⁺ ion its activity is taken into consideration.     

Liquid-liquid extraction of some lanthanide metal ions by polyoxyalkylene systems

Polyoxyalkylene systems, namely, polypropylene glycol (PPG-1025), polyethylene glycol (PEG-600) and polybutadieneoxide (PBDO-700) dissolved in either nitrobenzene or 1,2-dichloroethane have been tested as prospective extractants for some lanthanide metal ions (Eu(3+), Pr(3+) and Er(3+)) from their aqueous solutions in the presence of picrate anions. The metal ions were quantified before and after extraction using the inductively coupled plasma emission spectrophotometry technique. The percent extraction and the distribution coefficients have indicated that pH of the aqueous phase, picrate concentration and the organic solvent are the major parameters that affect the extraction efficiency of the metal ions. The optimum pH range was found to be 3.5-5.5 and the picrate concentration should be as high as possible; however, a picrate concentration of about 0.05 M proved to be adequate for a near quantitative extraction. In all cases, nitrobenzene enhanced a higher percent extraction compared to 1,2-dichloroethane. The efficiency of the polyoxyalkylene systems to extract certain lanthanide metal ions was in the order PBDO-700>PPG-1025>PEG-600 when nitrobenzene was the organic solvent and in the order PPG-1025>PBDO-700 approximately PEG-600 when 1,2-dichloroethane used as the solvent in the organic phase. The extractability of PPG-1025 towards the lanthanide metal ions was in the order Pr(3+)>Eu(3+)>Er(3+) irrespective of the organic solvent used. The stoichiometry of the extracted polyoxyalkylene ion-pairs with the lanthanide metal ions has been estimated. Each mole of metal ions is associated with three moles of picrate anions and 13 to 14 moles of propyleneoxide units in the case of PPG-1025, and about 9 to 10 moles of ethyleneoxide units in the case of PEG-600 and 10 moles of butadieneoxide units in the case of PBDO-700.     

Re-interpretation of the solvent dielectric constant in coordination chemical terms

It is found for common aprotic solvents that the logarithm of the dielectric constants can be represented by a linear combination of the acceptor numbers (AN) and the donor numbers (DN) (or equivalent parameters), $$log \in = c_1 ({\rm A}{\rm N}){\text{ }} + {\text{ }}c_2 (DN){\text{ }} + {\text{ }}c_3 $$ With this equation, concepts of specific and non-specific solvation are brought under the umbrella of one treatment. The equation does not hold for the highly structured solvents. For these, the dielectric constants predicted on the basis of the acceptor and donor numbers are orders of magnitude larger than the experimental values, revealing how poorly the associates are dissociated by the macroscopically attainable electric fields.     

Cation-exchange chromatography of some metal ions using aqueous NH4SCN-organic solvent mixtures

Summary Systematic cation-exchange studies of 19 metal ions have been made in various concentrations of NH₄SCN in 4060 organic solvent-water mixtures. The exchange behaviour of the ions depends on the solvent employed. Most of the metal ions show decreasing distribution coefficients with increasing concentration of ammonium thiocyanate in the solvent. Based on the variation of distribution coefficients as a function of NH₄SCN concentration, separations could be predicted and subsequently column chromatographic separations involving Zn, Hg(II), Mg, Mn(II), Co(II), Ni(II), Cd(II), Ce(III), Fe(III), La and Th(IV) were achieved.     

Behavior of polyelectrolyte solutions in a wide range of solvent dielectric constant

We exploit the strong temperature dependence of dielectric constant of N-methylformamide to control the strength of electrostatic interactions in polyelectrolyte solutions of sodium polystyrene sulfonate, and investigate the dynamic properties of salt-free solutions over a broad temperature range, from 54 to −58 °C. The traditional fast and slow diffusion processes are observed. The ratio of diffusion coefficients, D_s/D_f, increases and the ratio of their amplitudes, A_s/A_f, decreases, both by a factor of about two in this temperature range confirming the expected temperature variation with the Bjerrum length.     

Calculating the standard values of the heat capacity of alkaline metal ions and iodide ions in a mixed N-methylpyrrolidone-water solvent at 298.15 K

A system of ionic components of [`(C)]<sub>p,i</sub><sup>0</sup>\bar C_{p,i}^0 is proposed for the standard partial molar heat capacities [`(C)]_p2⁰\bar C_{p2}^0 of electrolytes in a mixed N-methylpyrrolidone (MP)-water solvent. The [`(C)]<sub>p,i</sub><sup>0</sup>\bar C_{p,i}^0 values are calculated for Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>, Rb<sup>+</sup>, Cs<sup>+</sup>, and I<sup>−</sup> ions in a mixed MP-water solvent at 298.15 K. The individual components of [`(C)]_p,i⁰\bar C_{p,i}^0 values and their dependence on the solvent composition and ion size are considered.     

Accumulation of some metal ions on Bacillus licheniformis

Pure species of Bacillus licheniformis was used to remove ions from aqueous and simulated waste solutions. Metal ion accumulation on B. licheniformis was fast. Maximum uptake occurred at pH 4±0.5 and at 25±3 °C. One gram of dry B. licheniformis was found to accumulate 115 mg cerium, 34 mg copper and 11 mg cobalt from aqueous solutions. The presence of certain foreign ions such as calcium, sodium and potassium decreased the uptake of ions by B. licheniformis, while citrate and EDTA prevent the uptake. Electron microscopic investigations showed that cerium (III), copper (II) and cobalt (II) accumulated extracellulary around the surface wall of B. licheniformis cells. A bio-adsorption mechanism between the metal ions and B. licheniformis cell wall was proposed.     

On-line dialysis of some metal ions and metal complexes

The effect of ionic strength, pH and complexing ligands on the dialysis of metal ions, particularly zinc(II), through cellulose acetate membranes, was studied under flow conditions. The dialysis factor, which depends on both the mass transfer and the membrane permeability, was found to be independence of ionic strength in the interaval 0.05–0.3 M and to increase only slightly with pH 4.6 and 7.0. Some common buffer constituents had no effect, but chloride and calcium ions affected the transfer rates. The rate of transfer of the ligands histidine, NTA and EDTA was of the same order of magnitude as that of the metal ions. The transfer rate of the Ni(II)-EDTA complex was the same as that of a mixture of Ni(II) and EDTA. Generally, addition of the chelating agents decreased the metal-ion transfer rates. Partition coefficients between the membrane polymer and the buffers were evaluated and compared with the dialysis factors and there were significant differences with regard to the range of variation, effect of concentration and pH-dependence. The time scale of uptake or release of metal ions by the polymer is much longer than that of a steady-state transfer in dialysis. Partition and dialysis may not be directly related to each other.     

The effect of dielectric constant on the electrical conductivity in double liquid systems

The effect of dielectric constant on the electrical conductivity of double systems containing chemically noninteracting components is considered. An equation has been obtained by means of which it is possible to evaluate the isotherm for electrical conductivity of such systems, the equation being confirmed by all available experimental material.     

Effect of metal ions on monolayer collapses

A Langmuir monolayer of stearic acid on pure water and in the presence of certain divalent metal ions such as Cd and Pb at pH approximately 6.5 of the subphase water collapses at constant area, while for other divalent ions such as Mg, Co, Zn, and Mn at the same subphase pH the monolayer collapses nearly at constant pressure. Films of stearic acid with Cd, Pb, Mn, and Co in the subphase (at pH approximately 6.5) have been transferred onto hydrophilic Si(001) using a horizontal deposition technique, just after and long after collapse. Electron density profiles obtained from X-ray reflectivity analysis show that a three-molecular-layer structure starts to form just after constant area collapse, where in the lowest molecular layer, in contact with the substrate, molecules are in asymmetric configuration, i.e., both hydrocarbon tails are on the same side of the metal-bearing headgroup that touches the substrate, while the molecules above the first layer are in symmetric conformation of the tails with respect to the headgroups. Further along collapse, when the surface pressure starts to rise again with a decrease in area, more layers with molecules in the symmetric configuration are added, but the coverage is poor. On the other hand, only bimolecular layers form after constant pressure collapse, with the lower and upper layers having molecules in asymmetric and symmetric configurations, respectively, and the upper molecular layer density increases with compression of the monolayer after collapse. A "Ries mechanism" for constant area collapse and a "folding and sliding mechanism" for constant pressure collapse have been proposed.     

Adsorption behaviours of inorganic ions on zirconium phosphate from mineral acid-alcohol media

The adsorption behaviours of trivalent and pentavalent antimony on zirconium phosphate from hydrochloric acid solution and hydrochloric acid alcoholic solutions were investigated. The substitution of increasing amounts of water by alcohols was found to decrease the uptake of Sb (III) and increase that of Sb (V). Results were discussed and column separations of the two oxidation states were carried out.     

Protonation constant of salicylidene (N-benzoyl)glycyl hydrazone and its coordination behaviour towards some bivalent metal ions

Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric, molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the ligand at room temperature and stabilization of a single conformer upon complex formation have been established from¹H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed for an orthorhombic crystal system.     

Chromatographic separation of some metal ions on NTA-impregnated thin-layer plates

Summary NTA (nitrilo triacetic acid) has been used as an impregnating agent for an efficient TLC separation of twelve metal ions, using a mixture of 5% aq ammonia, ethanol acetone and acetic acid as the solvent system and dithizone (0.5% in chloroform) for visualization.