Comparative distribution coefficients and cation-exchange behaviour of the alkaline earth elements with various complexing agents

Equilibrium distribution coefficients are presented for the alkaline earth metals Be(II), Mg(II), Ca(II), Sr(II) and Ba(II) with the complexing agents acetate, formate, lactate, citrate, tartrate, alpha-hydroxyisobutyrate, malonate, malate, acetylacetonate, EDTA, EGTA and DCTA, and the AG50W-X8 cation-exchange resin. Coefficients in HCl, HNO(3), HClO(4) and NH(4)Cl are included for the sake of completeness. The merits of the various complexing agents for the separation of adjacent element pairs are discussed and experimental elution curves are presented for selected separations. Separation factors for adjacent elements are calculated at eluting agent concentrations corresponding to a distribution coefficient of 10 for the less strongly absorbed element and are presented together with the eluting agent concentrations to form a basis for comparison.     

Distribution coefficients and cation-exchange behaviour of 45 elements with a macroporous resin in hydrochloric acid/methanol mixtures

Cation-exchange distribution coefficients are presented for 45 elements with the macroreticular (macroporous) cation-exchange resin AG MP-50 in mixed hydrochloric acid/methanol media, with acid concentrations ranging from 0.5 to 6.0 M, and methanol concentrations from 0 to 90%. The ion-exchange behaviour of the elements is discussed, some possible separations are indicated, and 3 multi-element elution curves are presented, demonstrating the separations of the combinations In-Zn-Ga-Al-Yb; Cd-Li-Cu(II)-Mg-Ca; and Pt(IV)-Te(IV)-V(IV)-Fe(III)-Mn(II).     

Cation-exchange behaviour of several elements in hydrochloric acid-organic solvent media

In the present paper the cation-exchange characteristics of 20 elements towards the strongly acidic cation-exchange resin Dowex 50 X 8 in media containing varying concentrations of organic solvents and aqueous hydrochloric acid were investigated. Based on the determination of the distribution coefficients of these elements in the organic solvents methanol, ethanol, n-propanol, isopropanol, methyl glycol, acetone, tetrahydrofuran, and acetic acid, the conditions most suitable for their quantitative separation are indicated and discussed.     

Selective separation of uranium from other elements by cation-exchange chromatography in hydrobromic acid and hydrochloric acid-acetone mixtures

U(VI) can be separated from Ga, Fe(III), Bi, Pb, Cd, Zn, Cu(II) and Au(III) by quantitative elution with 0.50M HBr in 86% acetone or with 0.35M HBr in 90% acetone from a column of AG50W-X4 cation-exchange resin of 200-400 mesh particle size. U(VI) and many other ions are retained. U(VI) then can be eluted selectively with 0.50M HCl in 83% acetone or with 0.35M HCl in 85% acetone. Co(II), Mn(II), Mg, Ca, Ti(IV), Al, Zr, Th and La are quantitatively retained by the column. These elements then can be eluted with 5M HNO(3). At the higher acid concentration (0.50M) the separation between U(VI) and Li is not satisfactory but is excellent at the lower acid concentration; the U(VI) peak is sharper at the higher acid concentration. Separations are sharp and quantitative, as is demonstrated by results for some synthetic mixtures. Distribution coefficients and elution curves are presented.     

Anion-exchange separation techniques with methanol-water solutions of hydrochloric and nitric acids

Mixed methanol-water systems were shown to be of use in the analysis of samples containing 500-mg amounts of metallic impurities for rare earths and actinides. Detailed study of the hydrochloric acid-methanol system led to improved separation of einsteinium and californium from americium and curium as well as to lanthanideactinide separations. Comparisons of elution orders are also drawn between these systems and the corresponding lithium salt systems, with emphasis on ion-hydration theories.     

Distribution coefficients and ion-exchange selectivities for 46 elements with a macroporous cation-exchange resin in hydrochloric acid-acetone medium

Distribution coefficients with the macroporous cation-exchange resin AG MP-50 in HCl-acetone mixtures ranging from 0.2 to 4.0M HCl and from 0 to 95% acetone have been determined for 46 elements. The ion-exchange behaviour of the elements is discussed, some possible separations are indicated, and elution curves demonstrating separations of the combinations Au(III)BiZnPbSr; Rh(III)InGaCuNi and CdFe(III)LiAlYb are presented.     

Separation of nickel from other elements by cation-exchange chromatography in dimethylglyoxime/hydrochloric acid/acetone media

Nickel can be separated from Zn, Co, Cu(II), Mn(II), Fe(III), U(VI) and other elements which readily form chloro complex ions, by eluting them with 0.5 M HCl/93% acetone from AG50W-X4 resin. Nickel is then eluted selectivity with 0.5 M HCl/95% acetone containing 0.1 M dimethylglyoxime, while the alkali and alkaline-earth elements, Al, Ti(IV), Sc, Y, La, lanthanides, Zr, Hf and Th are still retained. Separations are sharp and quantitative.     

Anion exchange behaviour of the transplutonium elements in hydrochloric acid-alcohol media at elevated temperature

The use of instrumental neutron activation analysis (INAA) in determining selected elements in biological materials has been reported by numerous authors. Some of these have detailed the use of INAA to determine an elemental analysis in tobaccos of various geographical origins. This paper describes the first use of INAA to measure the distribution of selected inorganic elements within the tobacco leaf at a single plant stalk position for one tobacco curing routine. Three replicate plots of a common bright tobacco cultivar were grown under normal cultural conditions characteristic for the bright variety. The tobacco leaves were sampled at selected positions in the leaf. The brigh tobacco was cured in a conventional flue-curing barn using standard practices. Immediately after collection, each individual sample was freeze-dried, crushed and sampled. The leaf midrib samples were prepared using a similar procedure. A subsample of about 100 mg was taken from each sample, sealed in a polyethylene bag, irradiated in a thermal neutron flux of 2×10¹⁷ n·m^–2·s^–1 in a pneumatic rabbit system, and subsequently counted to obtain the reported data. A standard reference material was used as a comparator to yield relative elemental concentrations for Ca, Mg, Mn, Na, K, Cl and Br. The data show that chlorine, potassium, sodium and calcium have definite concentration trends within the tobacco leaf. The data also show that some elements, e.g. Mn, were more uniformly distributed throughout the leaf.     

Separation of lithium from sodium,beryllium and other elements by cation-exchange chromatography in nitric acid-methanol

Lithium can be separated from sodium, beryllium and many other elements by eluting lithium with 1 M nitric acid in 80% methanol from a column of AG50W-X8 sulphonated polystyrene cation-exchange resin. The separation factor is not quite as large as that in 1 M hydrochloric acid in 80% methanol, but many elements, such as Zn, Cd, In, Pb(II), Bi(III) and Fe(III), which form chloride complexes in 1 M HCl-80% methanol are retained quantitatively together with Na, Be, Mg, Ca, Mn(II), Al, Ti(IV), U(VI), and many other elements, when 1 M HNO3-80% methanol is used for elution of lithium. A method for the accurate determination of traces of lithium in rock samples is described, and some results obtained are presented together with relevant distribution coefficients, elution curves and results for the analysis of synthetic mixtures.     

Mathematical simulation of the electrochemical intercalation of graphite in concentrated sulfuric and dilute nitric acids

A mathematical model of the process of electrochemical intercalation of a granular graphite bed in nitric and sulfuric acids that takes into account the varying physicochemical properties of the graphite matrix is proposed. The numerical solution of the problem by the finite element method shows that, in agreement with the literature data, the current distribution is nonuniform even for a granular bed of a small height (∼2 × 10⁻² m), which results in the synthesis of a nonuniform product. The methods of assessing the nonuniformity of intercalation and its elimination by passing to a multistage process are proposed. The results of numerical methods can be used in predicting the technological characteristics of the final product.     

Quantitative separation of gold from cadmium, indium, zinc and other elements by cation-exchange chromatography in hydrochloric acid-acetone medium

Gold(III) can be separated from Cd, In. Zn, Ni, Cu(II), Mn(II), Co(II), Mg, Ca, Al, Fe(III), Ga and U(VI) by adsorbing these elements on a column of AG50W-X8 sulphonated polystyrene cation-exchange resin from 0.1M HCl containing 60% v v acetone, while Au(III) passes through and can be eluted with the same reagent. Separations are sharp and quantitative. The amounts of gold retained by the resin are between 1 and 2 orders of magnitude lower than encountered during adsorption from aqueous 0.1M HCl. Recoveries for mg amounts of gold are 99.9% or better and for ng amounts are still better than 99%, as shown by radioactive tracer methods. Hg(II), Bi, Sn(IV), the platinum metals and some elements which tend to form oxy-anions in dilute acid accompany gold. All other elements, though not investigated in detail, should be retained, according to their known distribution coefficients. Relevant elution curves, results of quantitative separations of binary mixtures and of recovery tests are presented.     

Chemical and electrochemical behaviour of nitric and nitrous acids in sulpholane

With a glass electrode filled with mercury as indicator electrode for hydrogen ions, the acidity constant of nitric acid and the stability constants of the complexes HA(-)(2) (A Cl(-), NO(-)(3)) in sulpholane at 303 K have been determined potentiometrically. The acidity constant of nitrous acid has also been determined in supholane medium because of the low stability of this acid in aprotic media. On the basis of the results, some aspects of the electrochemical and thermodynamic properties of oxygen-nitrogen compounds are discussed in order to explain the catalytic effect of NO(+) in aromatic nitration by N(2)O(4) and/or N(2)O(3) in aprotic solvents.     

Cation-exchange behaviour of several elements in nitric acid-organic solvent media

The cation-exchange behaviour of 19 elements towards the strongly acidic cation-exchange resin Dowex 50-X8 in media containing varying concentrations of organic solvents and aqueous nitric acid is reported. Based on the determination of the distribution coefficients of these elements in the organic solvents methanol, ethanol, n-propanol, isopropanol, methyl glycol, acetone, tetrahydrofuran and acetic acid, the conditions most suitable for their quantitative separation are indicated and discussed.     

Ion flotation behaviour of thirty-one metal ions in mixed hydrochloric/nitric acid solutions

The ion flotation of 31 metal ions in hydrochloric/nitric acid solution with the cationic surfactant cetylpyridinium chloride was investigated. A 25-ml portion of 0.27-2.87 x 10(-4)M metal ion and 1.8-6.0 x 10(-4)M cetylpyridinium chloride solution in 0.17-3.4M acid mixture ([HCl]:[HNO(3)] = 2.4:1) was subjected to flotation in a cell, 22.5 cm high and 4.0 cm in diameter, for 5 min, with nitrogen bubbles. Ir(IV), Pt(IV), Ge(IV), Sn(IV), Bi(III), Au(III), Tl(III), Pd(II) and Sn(II) were floated from solution in 95-100% yield; Ru(III), Rh(III), Ir(III), Hg(II), Ag(I) and Tl(I) were partly floated, while Cr(VI), Ti(IV), Zr(IV), Ga(III), In(III), Fe(III), Sb(III), Al(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), CD(II) and Pb(II) were floated with less than 20% yield. The flotation behaviour of these metal ions in the mixed acid system was compared with that in hydrochloric acid. The flotation is more efficient in the mixed acid system.     

Distribution coefficients and cation-exchange behaviour of some ammines and aquo complexes of metallic elements in ammonium nitrate solution

Comparative cation-exchange distribution coefficients of ammines and aquo complexes of Cu(II), Ni(II), Cd, Zn, Ag, Co(II)/(III), Hg(II), Pd(II), Au(III) and Pt(II) were determined in 0.1, 0.2, 0.5 and 1.0 M ammonium nitrate solution. The values for mercury(II) in ammonium chloride and of the ammine of copper(II) in ammonium citrate and ammonium sulphosalicylate solutions were also measured. The ion-exchange behaviour of the ammines is discussed and some possible separations are demonstrated by the experimental elution curves for the ion pairs Mg-Ni(II), Ca-Zn, Yb-Cd and Fe(III)-Cu(II).     

A complete dissolution procedure for SnPb solders using nitric and hydrochloric acids with simultaneous determination of major and trace elements by ICP/OES

A complete and fast dissolution procedure for tin and lead based solders is described. Trace and major elemental concentrations are determined by inductively coupled argon plasma emission (ICP) spectroscopy. One gram solder samples in the concentration range of 40-63 wt % tin are completely dissolved using nitric and hydrochloric acids. ICP analyses of certified reference materials prepared by this dissolution method are reported and compared to reference values. Based on comparison, the sample preparation method discussed is successful for quantitative analysis of trace and major elements in tin-lead solders.     

Distribution coefficients and ion exchange behaviour of some elements with Purolite S-950 in hydrochloric acid

Equilibrium distribution coefficients, K_d, are presented for some elements in hydrochloric acid using the phosphonated polystyrene ion exchange resin Purolite S-950. A few possible separations using this resin are demonstrated by elution curves and separations of synthetic mixtures of some elements (Ru, Rh, Mo, I, Li, Te, Si, Y).     

Quantitative separation of lanthanides and scandium from barium,strontium and other elements by cation-exchange chromatography in nitric acid

The lanthanides plus yttrium and scandium are separated from Ba, Sr, Ca, Mg, Pb(II), Bi(III), Zn, Mn(II) and U(VI) by eluting these elements with 2.0 M nitric acid from a column of AG50W-X8 cation exchange resin (200-400 mesh). The lanthanides are retained and can then be eluted with 4 M nitric or hydrochloric acid. Separations are quantitative and applicable to microgram and millimolar amounts of the lanthanides and the other elements. Elements such as Cu(II), Co(II), Ni(II), Cd. Hg(II), T1(I). Ag, Be, Ti(IV) and the alkali metals should accompany barium quantitatively according to their known distribution coefficients. Relevant elution curves and results of analysis of synthetic mixtures are presented.     

Thermodynamic studies of complex formation of actinyl ions extracted with TBP from hydrochloric and nitric acids

The changes of the free energy, enthalpy and entropy accompanying the extraction of the U/VI/, Np/VI/ and Pu/VI/ by TBP have been determined by the method of extraction chromatography. The results obtained indicate outer-sphere complexation.     

Esterification of pyridinecarboxylic acids in the presence of cation-exchange resins

Pyridinecarboxylic acids undergo esterification on refluxing with alcohols in the presence of cation-exchange resins. In the case of pyridine-2,6-dicarboxylic acid, in which the basicity of the nitrogen atom is reduced, esterification products are obtained in high yields. In the case of pyridinecarboxylic acids, in which the pyridine nitrogen atom displays considerable basicity, the cations of the acids are tied up by the cation-exchange resin, and the yields of preparatively isolable esters do not exceed 60%.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 233–237, February, 1976.