The determination of nickel, zinc, cobalt and manganese impurities in cadmium by pulse polarography

A pulse-polarographic method for the simultaneous determination of traces of nickel, zinc, cobalt and manganese in cadmium and its compounds is described. Interference from the reduction of the cadmium matrix was eliminated by a prior electrolytic deposition of cadmium on a mercury cathode at a controlled potential of –0.90 V vs. S.C.E. Iron in excess interfered with the determination of cobalt and was therefore extracted from the electrolysed solutions. The polarographic determination was performed in 0.1 M lithium acetate -0.025 M lithium thiocyanate as supporting electrolyte. A sample weight of 10 g and a final volume of 10 ml allowed the determination of about 0.08 p.p.m. nickel, 0.01 p.p.m. zinc, 0.02 p.p.m. cobalt and 0.003 p.p.m manganese. Less than 0.01 p.p.m. nickel could be determined with a 0.25 M pyridine 0.05 M potassium chloride supporting electrolyte. Several synthetic samples and commercially available cadmium products were analysed.     

The determination of traces of antimony,tin and arsenic in cadmium by pulse polarography

Traces of antimony, tin and arsenic in cadmium products were determined by pulse polarography. Arsenic was distilled, while antimony and tin were precipitated as hydroxides with manganese dioxide as carrier; some lead was coprecipitated with tin, hence these elements were further separated by distillation. In all cases quantitative recoveries were obtained. Antimony(III) was determined in a hydrochloric acid-sodium hypophosphite mixture, tin(IV) in a hydrochloric-hydrobromic acid mixture and arsenic(III) in sulphuric acid as supporting electrolytes; for arsenic(III), methylene blue had to be added. A sample weight of 10 g and an end volume of 10 ml allowed the determination down to about 0.004 p.p.m. antimony, 0.006 p.p.m. tin and 0.003 p.p.m. arsenic in cadmium. Several synthetic samples and commercially available cadmium products were analysed.     

Electrochemical reduction of the lanthanide ions: Part II. Second reduction step of europium(III), ytterbium(III) and samarium(III) in acidic tetramethylammonium perchlorate solution

The second reduction step of Eu(III), Yb(III) and Sm(III) in 0.04 M tetramethylammonium perchlorate in the pH range 1.8–7 was investigated by cyclic voltammetry and d.c. polarography. The proposed reaction scheme at large hydrogen ion/lanthanide ion concentration ratios involves the reduction of the lanthanide(II) ion to the metallic state accompanied by a surface catalytic reaction in which the reactant is regenerated and also hydroxyl ions are formed which induces the precipitation of lanthanide(II) hydrous oxide on the electrode surface. This lanthanide(II) hydroxide is reduced at more negative potentials than the hydrated lanthanide(II) species. At lower hydrogen ion/lanthanide ion concentration ratios a preceding chemical reaction, probably involving hydrolyzed lanthanide(II) species, becomes rate determining.     

Dipolar excitations at the LIII x-ray absorption edges of the heavy rare-earth metals

We report measured dipolar asymmetry ratios at the LIII edges of the heavy rare-earth metals. The results are compared with a first-principles calculation and excellent agreement is found. A simple model of the scattering is developed, enabling us to reinterpret the resonant x-ray scattering in these materials and to identify the peaks in the asymmetry ratios with features in the spin and orbital moment densities.     

Relating multichannel scattering and production amplitudes in a microscopic OZI-based model

Relations between scattering and production amplitudes are studied in a microscopic multichannel model for meson-meson scattering, with coupling to confined quark-antiquark channels. Overlapping resonances and a proper threshold behaviour are treated exactly in the model. Under the spectator assumption, it is found that the two-particle production amplitude shares a common denominator with the elastic scattering amplitude, besides a numerator consisting of a linear combination of all elastic and some inelastic matrix elements. The coefficients in these linear combinations are shown to be generally complex. Finally, the standard operator expressions relating production and scattering amplitudes, viz. , are fulfilled, while in the small-coupling limit the usual isobar model is recovered.     

The Fermi surface of [Formula: see text

The heavy-fermion compound [Formula: see text] has been studied using the fully relativistic spin-polarized mean muffin-tin orbital method within the local density approximation. Two separate calculations, one where the f electron is treated as a valence electron and the other where it is treated as part of the core, have been performed and the Fermi surface is obtained. The angular-dependent de Haas - van Alphen (dHvA) frequencies are calculated in both cases and they are compared with the experimental dHvA frequencies. We also calculated the electron momentum densities and compared them with the electron - positron momentum densities measured from the two-dimensional angular correlation of electron - positron annihilation radiation. The spin polarization of the Fermi surface is analysed and we present a new interpretation of the experimental data of Harrison et al.     

Electrochemical study of the Sb(V)/Sb(III) couple on a glassy carbon rotating-disk electrode

The kinetics of the reduction of Sb(V) at a glassy carbon rotating-disk electrode have been investigated in 9.5 M HCl. The current-potential curve is characterized by a single irreversible wave, the limiting current being linearly related to the Sb(V) concentration and the square root of the rotation rate. Kinetic parameters of the reaction have been evaluated. Anodic oxidation currents of Sb(III) cannot be quantitatively measured owing to the interference of the oxidation of chloride.