Study of the complexation chemistry and speciation of thallium for on-line preconcentration with immobilised quinolin-8-ol

The effects of various buffering reagents and pH conditions were investigated by flame atomic absorption spectrometry to optimise complexation of T1³⁺ with quinolin-8-ol (8-Q), immobilised on controlled-pore glass beads in a 5-cm column. As Tl³⁺ is a softer acid than the other trivalent cations of the Group III elements, the effects of the buffers are different from those observed previously for Al³⁺, Ga³⁺ and In³⁺. A mixed buffer of 0.1 mol l^–1 acetate and 0.1 mol l^–1 ammonium chloride at pH 10 proved most successful, although 0.1 mol l^–1 maleate was also satisfactory over a pH range of 4–10. As thallium normally exists as Tl⁺ in solution, an oxidation method was developed to convert the ions to Tl³⁺, which is more efficiently complexed by 8-Q. Addition of 1–10 l of bromine per 100 ml of sample was sufficient to oxidise Tl⁺ without heating. Excess bromine was removed by addition of phenol. With a flow-rate of 6 ml min^–1, the detection limit of Tl³⁺ is 3 ng ml^–1, for a 3-miri preconcentration time. The enrichment factor under these conditions is 55 and the characteristic concentration is 2 ng ml^–1. The major ions in sea water did not interfere with Tl³⁺ preconcentration and the tolerable limits of Fe³⁺, Cu²⁺ and Al³⁺ are high enough to permit analysis of river and sea waters. The method was applied successfully to the determination of thallium in potassium-enriched table salt. It was also shown that the concentrations of Tl⁺ and Tl³⁺ in a solution can be derived using the described procedure, allowing speciation of inorganic thallium.     

Electrosurface and Ion-Selective Properties of Track-Etched Nanofilters: The Effect of Polyvalent Metal Adsorption

The effect of polyvalent metal adsorption on the performance and ion selectivity of poly(ethylene terephthalate) track-etched membranes with pores of 10 nm in diameter was studied. Membrane samples were prepared from the track-etched membranes with pores of 20 nm in diameter by thermal shrinkage. It was shown that an effective pore diameter decreases and selectivity of track-etched membranes increases upon filtration of Al(NO₃)₃ and Cr(NO₃)₃ solutions. The results obtained are explained by ion adsorption leading to the formation of complexes between polyvalent metals and carboxyl groups on the pore surface that is confirmed by IR spectroscopy data. The study of electrosurface properties of modified membranes and the dependence of ion selectivity of track-etched membranes on the concentration of Al³⁺ ions in 10^–2 M KCl solution indicates the decrease of membrane negative surface charge resulted from Al³⁺ adsorption and membrane charge reversal at Al³⁺ concentration in a solution higher than 10^–6 M. The dependences of the ion selectivity on pH and Al³⁺ concentration C _Al in a solution are similar. At pH < 3 and C _Al > 10^–6 M, the _1–2 > _1–1 > _2–1 ion selectivity series characteristic of the initial negatively charged membranes for the 1–1, 1–2, and 2–1 electrolyte solutions is reversed into the _2–1 > _1–1 > _1–2 series characteristic of positively charged membranes.     

Analytical separation of antimony(III) from bismuth(III), lead(II), gallium(III), thallium(III), tellurium(IV) and tin(IV) with cyanex 302

A method is proposed for the separation of antimony(III) (100–400 g) from bismuth(III), lead(II), gallium(III), thallium(III), tellurium(IV) and tin(IV) from an aqueous solution of pH 0.5–1.5 using 8×10^–3–1×10^–2 mol dm^–3 cyanex 302 dissolved in toluene as an extractant. The antimony is stripped from the cyanex phase with water and determined spectrophotometrically with iodide. Various experimental parameters are optimized and the probable 13 stoichiometry of the extracted species is evaluated. The method is applicable to the analysis of alloys and pharmaceutical samples. The separation and determination take only 20 min.     

Selective ion-exchangers containing phosphorus in their functional groups

A series of selective ion-exchangers was synthetized, containing phosphinic or phosphonic acid functional groups. The selective sorption of Sc³⁺, Fe³⁺, Ga³⁺, In³⁺, Al³⁺, La³⁺, Pb²⁺, Co²⁺ and Ca²⁺ ions in 0.1–4.0M HNO₃ medium was investigated using a batch experiment technique. The selectivity of these exchangers generally decreased in the order: Sc>Fe>In>Ga>Al>La>Pb>Cu>Co>Ca. The observed large differences in selectivity resulted in effective separation procedures of scandium from lanthanides, and gallium (or indium) from bivalent elements. The selective separation of these ions from their different mixtures is also possible.     

Synthesis and Application of a Novel Poly(Acryl-p-Toluenesulfonamideamidine-p-Toluenesulfonylamide) Chelating Fiber for Preconcentration and Separation of Trace Noble Metal Ions from Solution Samples

A novel poly(acryl-p-toluenesulfonamideamidine-p-toluenesulfonylamide) chelating fiber containing S, N and O elements was synthesized from polyacrylonitrile fiber and p-toluenesulfonamide and used for the preconcentration and separation for traces of Ru(III), Rh(III), Au(III) and Pd(IV) ions from waste water and ore sample solution. The synthesis of this fiber was simple and rapid. The results indicate that 100ngmL^–1 of these ions can be quantitatively enriched by the chelating fiber at a flow rate of 6mLmin^–1 and a pH of 4 and desorbed quantitatively with 20mL of 6molL^–1 HCl and 5% CS(NH₂)₂ solution at 50°C (with recovery>95%). A 50 to 1000-fold excess of Ca²⁺, Mg²⁺, Mn²⁺, Co²⁺, Fe³⁺, Cu²⁺, Zn²⁺, and Al³⁺ ions caused little interference in the concentration and determination of the analyzed ions. When the fiber had been reused twenty times, the recoveries of the ions enriched by the fiber were still over 96%. The saturated adsorption capacities of the fiber were in the range of 22–96mgg^–1. The relative standard deviation (RSD) of the method was between 0.70% and 0.84%. Recoveries of a standard added to actual samples were in range of 95–101%. The results obtained for these ions in real solution samples were basically in agreement with the given values, the average errors being below 5.0%. FT-IR spectra show that the existence of –SO₂–Ar, HN=C–NH–, O=C–NH– and –NH–SO₂ functional groups are verified in the chelating fiber. The experiments show that the method is rapid, precise, simple and convenient.     

Ion-Chromatography Performance of Poly(Aspartic) Acid Bonded Silica with Various Pore Sizes at Different Ionic Strengths and Column Temperatures

A significant effect of pore size on selectivity was observed for anion exchange on polyaspartic acid-coated silica (PolyCAT A). The retention order of halogenide anions, Cl^– <Br^– <I^–, was completely reversed between 30nm and 6nm pore materials. The zwitterionic nature of PolyCAT A made possible the simultaneous separation of anions and cations. With the column temperature, retention of cations is increased whereas retention of anions is decreased. The ionic composition of the eluent had a dramatic effect on separation efficiency with PolyCAT A of 30nm pores. The separation efficiency of ions was optimal in sulfuric acid-based eluents of reasonably high ionic strength.     

Theoretical Evidence of Aromaticity in X3 − (X = B, Al, Ga) Species

We investigated the electronic structure and chemical bonding of the B₃ ^–, Al₃ ^–, and Ga₃ ^– anions, and the gas phase NaB₃, NaAl₃, and NaGa₃ molecules. We found that the ground state of the neutral gas phase salts contains an equilateral triangular anion interacting with a Na⁺ cation. The B₃ ^–, Al₃ ^–, and Ga₃ ^– anions possess two delocalized electrons and are found to be aromatic. The triangular anions have been shown to be related to recently synthesized organometallic compound containing an aromatic -Ga₃ ^2– unit, but they are differ from them by four valence electrons. The reason for earlier appearance of the -orbital in the B₃ ^–, Al₃ ^–, and Ga₃ ^– anions is discussed.     

Cation exchange selectivity of some fission products on strongly acidic cation exchanger of sulfonic acid type-nitric acid system

Distribution coefficients of fission products in nitric acid for strongly acidic cation exchanger of sulfonic acid type with different cross-linking and structure were measured by a column method. Uptake of cationic fission products increases with resin cross-linking and decreases of nitric acid concentration. The distribution coefficient of the ion, [Kd_Mn+]^*, in a given system is expressed as log [Kd_Mn+]^*=B·log[Kd_Mn+]+A where [Kd_Mn+] is the distribution coefficient of the ion at 1M nitric acid for 10% crosslinked gel type cation exchanger, while A and B constants. Deviation from the above relation were observed for Y³⁺ and complex ions of ruthenium upward for macroporous type cation exchanger and downward for highly porous type cation exchanger. Upward deviation of Y³⁺ for 10% cross-linked gel type cation exchanger increased with concentration of nitric acid. Consequently, elution sequence varied from Y³⁺–Eu³⁺–Pm³⁺–Ce³⁺⁺ at 1M nitric acid to Eu³⁺–Pm³⁺–Y³⁺–Ce³⁺ for the same cation exchanger at 2M nitric acid. The same elution sequence, Eu³⁺–Pm³⁺–Y³⁺–Ce³⁺, was observed for 8% cross-linked gel type cation exchanger and 10% cross-linking macroporous type cation exchanger at 1M nitric acid.     

The Structure of Oxide Ga–Sb–Ni–P–W–O/SiO2 Catalyst and Its Catalytic Properties in Propane Ammoxidation

The structure of the multicomponent catalyst Ga₁Ni₁P₂W_0.5Sb₆O _x /SiO₂ and its catalytic properties in propane ammoxidation are studied. The catalyst is nanostructured and consists of noncoherently spliced blocks of a multiply promoted phase with a structure of gallium antimonate, which covers SiO₂ particles with a thin layer. In the multiply promoted compound with a structure of gallium antimonate, Ni²⁺ ions partially substitute for Ga³⁺ and W⁶⁺ ions partially substitute for Sb⁵⁺. This leads to an increase in the crystalline lattice parameters a and c. Phosphate ions are stabilized in the region of block interfaces. The catalyst is characterized by high efficiency in propane ammoxidation.     

Determination of the complex formation constants for some water-soluble polymers with trivalent metal ions by differential pulse polarography

The formation of metal complexes between water-soluble polymers, poly(vinyl alcohol) [PVA], poly(N-vinylpyrrolidone) [PVP], poly(acrylamide) [PAAm] and poly(ethylene oxide) [PEO] with trivalent metal ions, Fe³⁺, Cr³⁺, and V³⁺ were studied by using differential pulse polarography (DPP). The general experimental observation is the shift of totally reversible reduction peaks (M³⁺+Hg+e^–M²⁺+Hg) towards more negative potentials when the complexing water-soluble polymers are added to the solution of trivalent metal ions. The negative shift in potential permitted the determination of complex formation constants (K_f) between trivalent metal ions and water soluble polymers. The complex formation constants for Fe³⁺, Cr³⁺, and V³⁺ ions with these polymers increased in the order of V³⁺>Cr³⁺>Fe³⁺.     

Selective uptake of toxic elements by an amorphous titanium dioxide ion exchanger

The ion-exchange selectivities for oxoanions of some toxic elements and halogens were studies on an amorphous hydrous titanium dioxide (Am-HTDO) as a function of OH^– and anion concentrations in chloride and nitrate media. The adsorption isotherm was of the Langmuir type. The selectivity sequence increased in the order of ClO ₃ ^– <BrO ₃ ^– <IO ₃ ^– SeO ₃ ^2– <TeO ₃ ^2– <As(OH) ₄ ^– . IO ₃ ^– was efficiently separated from ClO ₃ ^– and BrO ₃ ^– . As(OH) ₄ ^– and SeO ₃ ^2– were selectively separated from seawater. Such high selectivity of Am-HTDO may provide a new concentration technique of these toxic elements in environmental materials.Synthetic inorganic ion-exchange materials LIX.     

Alkali metal ion-selective electrodes based on relevant alkali metal ion doped manganese oxides

Potentiometric properties of manganese oxides doped with alkali metal ions (Na⁺, K⁺, Rb⁺ and Cs⁺), which were prepared by heating mixed solutions (starting solution) of each alkali metal and Mn²⁺ ions, were examined. Electrodes based on mixed phases of Nao₄₄MnO₂/Mn₂O₃ and hollandite KMn₈O₁₆/M₂O₃ found by X-ray powder diffraction (XRD) exhibited Na⁺- and K⁺-selective responses with a near-Nernstian slope, respectively, when the molar ratio of alkali metal ion to Mn²⁺ ion in the starting solution was 0.1. When no alkali metal ions were added in the manganese oxide films, no significant potentiometric response was observed to any alkali metal ions. The selectivity coefficients of these electrodes were = 6.7 × 10^–2, = 7.1 × 10^–3, < 9 × 10^–4 and < 9x 10^–4 for the Na_0.44MnO₂/Mn₂O₃, and <4 × 10^–4 <4x 10^–4, =60 × 10^–2 ×10^–4, < 4 × 10^–4, for the KMn₈O₁₆/Mn₂O₃, respectively. Electrodes based on manganese oxides made from mixed solutions of Rb⁺/Mn²⁺ and Cs⁺/Mn²⁺ also responded to the respective primary ions, that is, Rb⁺ and Cs⁺ ions, although XRD patterns for the manganese oxides thus made did not show any peaks except for Mn₂O₃ (bixbyite); it was concluded in these cases that some amorphous type manganese oxides were formed in the Rb⁺/Mn²⁺ and Cs⁺/Mn²⁺ systems and they responded to the respective ions. Conditioning of these electrodes in an aerated indifferent electrolyte solution, 0.1M tetramethylammonium nitrate (TMA-NO₃), for relatively long time, typically more than 2 hours, was found to be a prerequisite for near-Nernstian response to the respective alkali metal ions. During this electrode conditioning, vacant sites (template) suitable in size for selective uptake of primary ions seemed to be formed by releasing the doped alkali metal ions from the solid phase into the adjacent electrolyte solution accompanying oxidation of the manganese oxide film.     

Application of Chitosan Functionalized with 8-Hydroxyquinoline: Determination of Lead by Flow Injection Flame Atomic Absorption Spectrometry

This work describes the application of chitosan – chemically modified with 8-hydroxyquinoline – in a simple and efficient preconcentration system using flow injection flame atomic absorption spectrometry (FI-FAAS) for the determination of Pb²⁺ ions. The efficiency of the chelating resin and the accuracy of the proposed method were evaluated by the metal ion recovery technique in samples of mineral water, potable water and lake water. The recovery of Pb²⁺ ions from spiked solutions was less than 70% due to matrix effects, which were eliminated by addition of Ba²⁺ metal ions, resulting in recoveries of approximately 100% for all water samples. Ag⁺, Cd²⁺, Cu²⁺, Mn²⁺, Ni²⁺, Zn²⁺, Hg²⁺, Ca²⁺, Mg²⁺, Cr³⁺, Al³⁺ and Fe³⁺ metal ions were studied with respect to their interference with Pb²⁺ metal ion determination, and the chelating resin exhibited high selectivity for Pb²⁺ at pH 7. The analytical properties of merit were obtained using the parameters previously optimized. The method shows high precision with a relative standard deviation (R.S.D.) of 1.1% (n=7) for a solution containing 50µgL^–1 of Pb²⁺ and a detection limit (L.O.D.) of 1.7µgL^–1.     

Adsorption of some hazardous radionuclides on cerium (IV) antimonate

Cerium(IV) antimonate was prepared by dropwise addition of 0.6M antimony pentachloride and 0.6M cerium ammonium nitrate solutions by a molar ratio of Ce/Sb 0.75. Exchange isotherms for H⁺/Co²⁺, H⁺/Cs⁺, H⁺/Zn²⁺, H⁺/Sr²⁺ and H⁺/Eu³⁺ were determined at 25, 40 and 60°C. Besides, it was proved that europium is physically adsorped, while zinc, strontium, cobalt and cesium are chemically adsorbed. Moreover, the heat of adsorption of zinc, strontium, cobalt and cesium on cerium (IV) antimonate was calculated and indicated that cerium(IV) antimonate is of endothermic behavior towards these ions. Also the distribution coefficients of these ions were determined and it was found that the selectivity is in the order: Eu³⁺>Sr²⁺>Cs⁺>Na⁺.     

Synthesis and characterization of tin(IV) antimonate and study of its ion-exchange equilibria

Tin(IV) antimonate with different Sb/Sn molar ratios has been prepared. The characterization of the product materials was carried out using X-ray diffraction pattern, themal analysis and infrared spectra. The saturation capacities of sodium and cesium were found to increase with Sb/Sn molar ratios. TheK _d values on thermal treatment of tin(IV) antimonate, as a cation exchanger, have been measured for some heavy metal ions in the temperature range of 50–400 °C. The maximum adsorption of 10^–4M of the metal ions studied was obtained at 400 °C. The selectivity sequence was Eu³⁺>Co²⁺>Sr²⁺>Cs⁺ for the sample heated up to 400 °C. No adsorption was observed on the sample heated at 700 °C because of the formation of SnO₂ and Sb₆O₁₃.     

Pulspolarographische Bestimmung von Metallionen unter Ausnutzung der Ligandenkatalyse

Zusammenfassung Es wird eine anioneninduzierte Adsorptionsstufe des Ga³⁺ beschrieben. Ihre Empfindlichkeit ist von der Aliz S-Konzentration abhängig. Sie eignet sich zur puls-polarographischen Bestimmung kleiner Ga³⁺-Gehalte. Die Methode ist bis hinunter zu 50 ppb Ga³⁺ anwendbar. Ihr Vorteil gegenüber der Bestimmung mit Thiocyanat [7] liegt vor allem in dem geringeren Zusatz von Fremdionen, wodurch der Einfluß der Kontamination klein gehalten wird: Die Ga³⁺-Reduktion wird bereits von Aliz S-Mengen < 1·10^–4 M induziert, während man bei der Thiocyanatmethode mit Konzentrationen von 0.5 M Thiocyanat arbeiten muß. Die Funktion des Leitsalzes wird von der Pufferlösung übernommen, die 0,2 M gehalten werden kann.

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Pulse-polarographic determination of metal ions utilising ligand catalysis

Summary An anion-induced adsorption wave of Ga³⁺ is described. Its sensitivity depends on the Aliz S concentration. The wave is suitable for the pulsepolarographic determination of small Ga³⁺ contents down to at least 50 ppb Ga³⁺. The advantage as against the thiocyanate method [4] is the lower concentration of reagents and consequently the diminished influence of contamination: the Ga³⁺ reduction is already induced by Aliz S contents of < 1×10^–4M, whereas the thiocyanate method needs concentrations of about 0.5 M thiocyanate. The buffer solution, which can be kept 0.2 M, serves also as supporting electrolyte.

Wir danken der Deutschen Forschungsgemeinschaft, Bonn-Bad Godesberg, dem Minister für Wissenschaft und Forschung des Landes Nordrhein-Westfalen, Düsseldorf, sowie dem Verband der Chemischen Industrie, Fonds der Chemie, Frankfurt/Main, für finanzielle Unterstützung.     

Structural Arrangement of Fe–Sb–O Catalysts

In iron–antimony catalysts containing excess antimony oxide and consisting of a mixture of FeSbO₄ and -Sb₂O₄ phases, the structure of iron antimonate changes compared to the catalyst with an equimolar composition, which is the pure FeSbO₄ phase. In the presence of excess antimony oxide in the near-surface layer of iron antimonate, extended defects with a structure of crystallographic shift are formed. These accumulate overstoichiometric antimony. Such a structural change is associated with changes in the acid–base properties and the surface oxygen binding strength.     

Possible radiochemical separations of anionic radionuclides by amorphous hydrous titanium dioxide

Ion-exchange selectivities towards oxoanions and halide ions were studied for radio-chemical applications by an amorphous hydrous titanium dioxide (Am-HTDO) as functions of pH and concentration. The selectivity series was found to be Mo(VI)<W(VI)<P(V)<As(V)<Sb(V) for micro-amounts at pH 9 and Br^–Cl^–F^– for macro-amounts. A feasibility was suggested for radiochemical separations of³²P by³⁵Cl(n,)³²P and⁷⁷Br by⁷⁵As(, 2n)⁷⁷Br, and selective removal of anionic radionuclides.Synthetic Inorganic Ion-Exchange Materials. XLIII.     

Extraction of tri- and tetravalent actinides with dihexyl N,N-diethylcarbamoylmethyl phosphonate (DHDECMP) and TBP from nitric acid solutions

Extraction of trivalent (Pu³⁺, Am³⁺, actinides and Eu³⁺, a representative of lanthanides) and tetravalent (Np⁴⁺ and Pu⁴⁺) actinides has been studied with dihexyl N,N-di-ethylcarbamoylmethyl phosphonate (DHDECMP) in combination with TBP in benzene from 2M nitric acid. The stoichiometries of the species extracted were found to be M(NO₃)₃·(3–n) TBP·n DHDECMP (for trivalent ions) and M(NO₃)₄·(2–n) TBP·n DHDECMP (for tetravalent ions) by the slope ratio method. The extraction constants evaluated (from the distribution data) indicate that for tetravalent ions (with solvation number two) the extraction constant increases when TBP (Kh=0.17) molecules are successively replaced by more basic DHDECMP (Kh=0.34) molecules. However, for trivalent ions (with solvation number three) when TBP molecules are totally replaced by DHDECMP molecules stereochemical factors appear and instead of increase, a substantial decrease in extraction constants is observed for Eu³⁺ and Am³⁺, a lesser decrease being observed for Pu³⁺ (larger ion).