The application of discontinuous,countercurrent, liquid-liquid extraction to the study of the distribution of metal ions between hydrochloric acid and methyl isobutyl ketone

Summary The extraction of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi from hydrochloric acid into methyl isobutyl ketone has been studied as a function of hydrochloric acid concentration. The results are presented in graphical form. The data were obtained by studying the distribution patterns of the elements after equilibration on a Craig countercurrent liquid-liquid extraction apparatus.

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Zusammenfassung Die Extraktion der Elemente Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb und Bi mit Methylisobutylketon aus salzsaurer Lösung als Funktion der Säurekonzentration wurde studiert. Die Ergebnisse wurden aus den Spitzen der Verteilungskurven nach Einstellung des Gleichgewichts in einem diskontinuierlichen Gegenstrom-flüssig-flüssig-Extraktionsapparat berechnet.

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Résumé On a étudié l'extraction des éléments Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb et Bi en solution chlorhydrique par la méthylisobutylcétone. On présente les résultats sous forme graphique. Les données ont été obtenues en étudiant les diagrammes de distribution des éléments après équilibrage sur un appareil Craig à extraction à contre-courant liquide-liquide.

     

Extractive concentration of platinum-group elements and their determination by atomic-absorption spectrophotometry

The extraction of Pt, Pd, Ir, Rh, Ru, Ag, Au, Co, Cu, Ni and Fe with n-octylaniline has been investigated. Noble metals are extracted 10(3)-10(4) times better than Cu, Ni, Co and Fe. A method of determination of Pt, Pd, Ir, Rh and Ru is proposed. They are first separated from Cu, Ni, Co and Fe by means of extraction (and then determined, in either the aqueous or organic phase, by atomic-absorption spectrophotometry. The atomic absorption of platinum metals (with the exception of Pd) is affected by other elements of the platinum group and by non-noble metals. La(NO(3))(3) and Nd(NO(3))(3) lower the limit of detection for Pt, Rh, Ir and Ru and inhibit the effect of Co, Cu, Ni, Fe, Bi, Zn, Na, etc. on their determination. Lanthanum and neodymium chlorides and sulphates produce a similar effect but only on the determination of Pt and Rh. The coefficient of variation of the determination, in both phases, is within 2-6.8%.     

Chloroform extraction of metal ethyl xanthates from hydrochloric acid media

The chloroform extraction of 32 elements (Fe, Co, Ni, Zn, Cd, Ge, Sn, Pb, V, As, Sb, Bi, Cu, Ag, Au, Mn, Re, Ga, In, Tl, Ce, Se, Te, Cr, Mo, U, Pt, Pd, Rh, Ir, Ru and Os) from O.1-10M hydrochloric acid media in the presence of potassium ethyl xanthate has been studied. The oxidation states in which some elements react, and potential analytical separations, are discussed. Pd(II), As(III) and Se(IV) are completely extracted as ethyl xanthate complexes, Te(IV) is almost completely extracted, and Au(III) is largely extracted over the range of acid concentration investigated. Mn(II), Zn, Rh(III), Ir(IV), Ru(III), Os(IV), Cr(III), Cr(VI), Ce(III) and Ce(IV) are not extracted. Ge is partly extracted from 6-10M media as the chloro-complex. Depending on the acid concentration, the remaining elements are all partially extracted as xanthate complexes.     

Qualitative analysis of palladium plating by the ring oven technique

Summary A scheme using Weisz Ring Oven techniques for the qualitative analysis of gold plating was extended and modified to cover palladium plating.The plating was sampled by anodic dissolution in brominated hydrochloric acid, and after treatment with hydrogen sulphide the soluble metals were eluted into a ring, leaving behind Cu, Ag, Pd and Au. After bromination the first three were washed into ring II with ammonia saturated with potassium bromide, leaving Au to be washed into ring III.The soluble metals from the first ring were further sub-divided by washing with ammonia/ammonium carbonate into ring I A, in which Ni, Co, Zn, Pt, Ir, Ru and Rh were detected, leaving Fe, Cr, Al, Ti, Mn and In in ring I.

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Zusammenfassung Ein Untersuchungsgang zur qualitativen Analyse von Goldplattierungen nach dem Ringofenverfahren wurde für Palladiumplattierungen erweitert und modifiziert. Nach anodischer Auflösung der Plattierung in bromhaltiger Salzsäure werden die löslichen Metalle nach Behandlung mit Schwefelwasserstoff in einen Ring gewaschen, wobei Cu, Ag, Pd und Au zurückbleiben. ach Behandlung mit Brom wurden die drei erstgenannten mit kaliumbromid-gesättigtem Ammoniak in den Ring II gewaschen, wobei Au zurückbleibt und schließlich in den Ring III gewaschen wird. Die löslichen Metalle im ersten Ring werden durch Waschen mit Ammoniak-Ammoniumcarbonat weiter getrennt, wonach im Ring I A Ni, Co, Zn, Pt, Ir, Ru und Rh, im Ring I Fe, Cr, Al, Ti, Mn und In nachgewiesen werden.

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Résumé On a modifié un mode opératoire utilisant les techniques de l'anneau de Weisz dans l'analyse qualitative de l'or plaqué, pour l'étendre au palladium plaqué.La couche plaquée a été prélevée par dissolution anodique dans l'acide chlorhydrique bromé et après traitement par l'hydrogène sulfuré les métaux solubles ont été élués sur un anneau, abandonnant Cu, Ag, Pd et Au. Après bromation, les trois premiers ont été lessivés sur l'anneau II par de l'ammoniaque saturée par du bromure de potassium, en laissant Au à laver sur l'anneau III.Les métaux solubles du premier anneau ont été ensuite subdivisés par lessivage avec ammoniaque, carbonate d'ammonium en anneau I A, sur lequel on a décelé Ni, Co, Zn, Pt, Ir, Ru et Rh tandis que Fe, Cr, Al, Ti, Mn et In restent sur l'anneau I.

     

Chloroform extraction of ethyl xanthate complexes from sulphuric acid media

The chloroform extraction of 30 elements (Fe, Co, Ni, Zn, Cd, Ge, Sn, V, As, Sb, Bi, Cu, Ag, Au, Mn, Re, Ga, In, Tl, Se, Te, Cr, Mo, U, Pt, Pd, Rh, Ir, Ru and Ce) from 0.1-8M sulphuric acid in the presence of potassium ethyl xanthate has been studied. Pd(II), Bi, As(III), Sb(III), Se(IV) and Te(IV) are completely extracted and Au(III) is largely extracted over the range of acid concentration investigated. Fe(II), Tl(I), Rh(III) and Cr(VI) are only slightly extracted and Se(VI), Te(VI), Ru(III), Cr(III), Mn(II), Zn, Ce(IV), Ir(IV) and Ge(IV) are not extracted at all. Depending on the acid concentration, the remaining elements are all partly extracted. Results are compared with those obtained in an earlier study of the extraction of xanthate complexes from hydrochloric acid media. The processes involved in the formation of some xanthate complexes and potential analytical separations are discussed.     

Crystallographic and structural characterization of heterometallic platinum compounds. Part II. Heterobinuclear Pt compounds with Pt?M (M = transition or lantanide metal) > 3.0 ?

This review covers almost two hundred and twenty heterobinuclear platinum compounds in which Pt?M separation is over 3.0 ?. The M is a transition metal (Cu, Ag, Au, Ti, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni and Pd). There is an example of a lanthanide, Yb and a actinide, U. The Pt atom has oxidation numbers 0, +2 and +4. The Pt coordination geometries include trigonal planar Pt(0); square planar Pt(II); trigonal bipyramidal, and pseudo octahedral Pt(IV), with the most frequent being square planar. The most common ligands for Pt are P and C donor atoms, as well as a chlorine atom. The Pt ?? Ag distance of 3.002(1) ? is the shortest found in this series. There are examples which contain two crystallographically independent molecules, which differ mostly by degree of distortion and even one unique example, which contains eight such molecules. These are examples of distortion isomerism. Factors affecting bond lengths and angles are discussed and some ambiguities in coordination polyhedral are outlined.     

Theoretical Investigations of the Activation of CO_2 on the Transition Metal-doped Cu(100) and Cu(111) Surfaces

Periodic density functional theory calculations have been performed to investigate the chemisorption behavior of CO_2 molecule on a series of surface alloys that are built by dispersing individual middle-late transition metal(TM) atoms(TM = Fe, Co, Ni, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au) on the Cu(100) and Cu(111) surfaces. The most stable configurations of CO_2 chemisorbed on different TM/Cu surfaces are determined, and the results show that among the late transition metals, Co, Ru, and Os are potentially good dopants to enhance the chemisorption and activation of CO_2 on copper surfaces. To obtain a deep understanding of the adsorption property, the bonding characteristics of the adsorption bonds are carefully examined by the crystal orbital Hamilton population technique, which reveals that the TM atom primarily provides d orbitals with z-component, namely d_z~2, d_(xz), and d_(yz) orbitals to interact with the adsorbate.     

Expanding the scope of chemical vapor generation for noble and transition metals.

A modified Bergener parallel path nebulizer was used for the generation of volatile metal species of Pt, Co, Ag, Cu, Rh, Pd, Au, Ni, Ir, Ti and Mn through reaction with tetrahydroborate (III). Several physicochemical factors were identified which impact on their yield which, at present, is estimated to range from 0.02-2% absolute.     

Catalytic hydrogenation of C60 on transition metals

The catalytic hydrogenation of C₆₀ on Ru, Rh and Ir produced C₆₀H₁₈ mainly, while Pd, Pt, Co and Ni catalysts gave C₆₀H₃₆ principally. Very little activity was observed on Au and Fe. The higher hydrogenated fullerene obtained on Pd, Pt, Co and Ni was ascribed to the smaller % d-character of the metallic bond, on which the fullerene and hydrogen may more strongly be adsorbed. This revised version was published online in August 2006 with corrections to the Cover Date.     

CO\begin{document}$ _{2} $\end{document} Reduction on Metal-Doped SnO\begin{document}$ _{2} $\end{document}(110) Surface Catalysts: Manipulating the Product by Changing the Ratio of Sn:O

The electrocatalytic carbon dioxide reduction reaction (CO₂RR) producing HCOOH and CO is one of the most promising approaches for storing renewable electricity as chemical energy in fuels. SnO₂ is a good catalyst for CO₂-to-HCOOH or CO₂-to-CO conversion, with different crystal planes participating the catalytic process. Among them, (110) surface SnO₂ is very stable and easy to synthesisze. By changing the ratio of Sn: O for SnO₂(110), we have two typical SnO₂ thin films: fully oxidized (stoichiometric) and partially reduced. In this work, we are concerned with different metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au)-doped SnO₂(110) with different activity and selectivity for CO₂RR. All these changes are manipulated by adjusting the ratio of Sn: O in (110) surface. The results show that stochiometric and reduced Cu/Ag doped SnO₂(110) have different selectivity for CO₂RR. More specifically, stochiometric Cu/Ag-doped SnO₂(110) tends to generate CO(g). Meanwhile, the reduced surface tends to generate HCOOH(g). Moreover, we also considered the competitive hydrogen evolution reaction (HER). The catalysts SnO₂(110) doped by Ru, Rh, Pd, Os, Ir, and Pt have high activity for HER, and others are good catalysts for CO₂RR.     

First-principles Density Functional Theory Elucidation of the Hydrogen Evolution Reaction on TM-promoted TiC2 (TM=Fe,Co, Ni,Cu, Ru,Rh, Pd,Ag, Os,Ir, Pt,and Au)

Single-atom-catalyst-based systems have been attractive by virtue of their desirable catalytic performance. Herein, the possibility of the 15 transition-metal (TM)-promoted (TM=Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, and Hg) and their hydrogen evolution reaction (HER) performance were investigated on two-dimensional titanium carbides (TiC₂). It is found that the adsorption strength of TMs on TiC₂ is stronger than that of TMs on γ-graphyne and weaker than that of TMs on Ti₃C₂. Among the fifteen investigated catalysts, Ru−TiC₂, Ag−TiC₂, Ir−TiC₂, Au−TiC₂, and Fe−TiC₂ exhibits overpotential of −0.18, −0.15, −0.18, −0.17, and −0.04 V, respectively. In addition, the Volmer-Tafel step was preferred to the Volmer-Heyrovsky step on Fe−TiC₂. This work suggests that Fe−TiC₂ is possibly a superior HER electrocatalyst.     

Qualitative and Quantitative Analysis of Medieval Silver Coins by Energy Dispersive X-Ray Fluorescence Method

Energy-dispersive X-ray fluorescence spectrometry was applied for the analysis of historical silver coins to determine the elemental composition in a fast and non-destructive way. Ag, Cu and trace elements (V, Cr, Mn, Fe, Co, Ni, Hg, Pd, Zr, Mo, Rh, Ru) were determined in coins of King Mathias (Hungary, 1458–1490). A new data evaluation technique was used to avoid the problems arising from the different sizes, surfaces and geometries. The appropriateness of this method was confirmed by analysing certified silver/copper standard alloys.     

Emission of secondary ions from 3d, 4d, and 5d transition metals under chloro-trifluoro-methane CClF3 as reactant gas

Surface interactions of CClF₃ with polycrystalline samples of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Rh, Pd, Ag, Ta, W, Re, Ir, and Pt were investigated by means of moderate dynamic SIMS. As observed with other reactant gases these transition metals in most cases appear to be discernible into “dissociative” and (partial) “molecular” adsorbents. Small signals of oxidic secondary ions which are detectable for residual gas conditions vanished under the action of CClF₃. However, due to strong polarization by either of the halogens, the emission of Me²⁺ ions is enhanced for Ti, V, and Nb.     

Oximidobenzotetronic acid as a reagent for the separation and gravimetric determination of palladium and cobalt

Oximidobenzotetronic acid is recommended for the separation and gravimetric determination of palladium and cobalt An ethanolic solution of the reagent quantitatively precipitates palladium(II) from solutions which are 0.75 N in acid up to pH 5.1, the complex is weighed as Pd(C₉H₅NO₄)₂. Cobalt(II) can be determined in the filtrate after the precipitation of palladium. With 0.5 N acid solutions, no interference was found from Pt(IV), Ir(IV), Rh(III), Ru(III), Os(IV), Au(III), Ag(I), Cu(II), Fe(III), Ni(II), Hg(II). Pb(II), Bi(III), Cd(II), As(V), Se(VI), Te(IV), Mo(VI), Sb(III), Al(III), Cr(III), Zn(II), Ti(IV), Zr(IV). acetate, oxalate, citrate, tartrate, phosphate and fluoride.     

Luminol-K2S2O8体系中金属离子化学发光行为的研究

报导了在自行设计的流动注射式化学发光分析仪上,对Luminal-K2S2O8体系中32种金属离子的化学发光行为的系统研究.确定了对金属离子的最优测定条件以及大多数金属离子的检出极限和线性范围.     

Trace characterisation of lithium niobate by neutron activation analysis

Summary Coprecipitation behaviour of As, Au, Co, Cr, Cu, Eu, Fe, Ir, La, Lu, Mn, Mo, Nb, Ni, Pd, Pt, Sb, Sc, Ta, W, Zn and Zr during precipitation of hydrous oxide of niobium from lithium niobate was investigated. The matrix was dissolved in HF-HNO₃, evaporated to dryness and niobium was precipitated from HNO₃-H₂O₂ medium. The recovery studies were made using radiotracers. A radiochemical separation scheme based on group precipitation has been developed for the determination of Au, Co, Cr, Cu, Fe, Mn, Ni, Pd, Pt, Zn, Zr and rare earth elements. The method was applied to the analysis of lithium niobate. This analysis has provided fruitful information for improving the quality of the crystal.     

“Multitracer” a new tracer technique — Its principle,features, and application

We established Multitracer, a new versatile radiotracer technique, for simultaneous tracing of a number of elements in various chemical, environmental, and biological systems. Metal foil targets (typically Au, Ag, Ge, Cu and Fe) are irradiated with C, N, or O ions accelerated up to 135 MeV/nucleon by RIKEN Ring Cyclotron. Radiochemical procedures have been developed to remove the target material leaving the nuclides as Multitracer solutions containing various radionuclides of Be, Na, Mg, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Te, I, Ba, Ce, Pm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, W, Re, Os, Ir, Pt, and Hg. Multitracers enable efficient tracing of a number of elements, and comparison of their behavior under strictly identical experimental conditions. Such features will be demonstrated by means of an example of application to a model experiment for the study of removal mechanism of various elements from the ocean.     

Irradiation of elements from Z = 44 to Z = 82 with 10-mev protons and application to activation analysis

The sensitivities for the determination of 19 elements from Z = 44 to Z = 82, by means of 10-MeV proton activation, have been calculated from experimentally measured yields for 51 radioisotopes obtained mainly via (p,n) reactions. For an irradiation of 1 h at a beam current of 1 μA, the sensitivities established experimentally are about 0.02–2 p.p.m. for Ru, Pd, Ag, Cd, Sn, Sb, Te and I, 0.5–100 p.p.m. for In, W, Re, Ir, Pt, Au, Hg, Tl and Pb, and 15–900 p.p m- for Rh and Ba. Experimental results for the non-destructive analysis of these 19 elements in Al, Ag, Au, Co, Dy, Ho, Ir, Nb, Pr, Rh, Si, Ta and Tb, are presented.