Über Münzmetall‐Quecksilber‐Chalkogenidhalogenide. V1) Solvothermalsynthese und Kristallstruktur der Hochtemperatur‐Modifikation von AgHgSI

On Coinage Metal Mercury Chalcogenide Halides. V. Solvothermal Synthesis and Crystal Structure of the High Temperature Modification of AgHgSI The solvothermal reaction of AgI and α‐HgS in diluted HI as solvent yields yellow crystals of α‐AgHgSI. The compound crystallizes in space group type P2₁2₁2₁ with a = 707.47(1), b = 773.18(2), c = 847.53(2) pm and Z = 4. The structure consists of a distorted hexagonal close packed array of sulphur and iodine, in which one fourth of the tetrahedral voids is occupied by silver and a half of the octahedral voids is occupied by mercury. The distortion of the hexagonal structure is caused by the steric demand of the lone pairs of sulphur and iodine. This could be shown by the calculation of the electron localisation function (ELF). The here described modification of AgHgSI can be obtained at 273 °C from the earlier published β‐AgHgSI and is therefore called α‐AgHgSI.     

Gas chromatographic determination of trace amounts of vinyl chloride and dichloroethenes in landfill-gas

A method for the determination of vinyl chloride (VC) and dichloroethenes (DCE) in gas samples is presented. The analytes are preconcentrated from a gas-volume of up to 20 l on an adsorption tube filled with 1.0 g of a carbon molecular sieve at a flow rate of 80 l/h and are subsequently desorbed with carbon disulfide. Vinyl bromide is added as internal standard to the extract. The analytes are determined as their 1,2-dibromo-derivatives by capillary gas chromatography with electron capture detection. The detection limits have been found to be 82 ng/m³ = 32 ppt (VC), 190 ng/m³ = 48 ppt (1,1-DCE) and 96 ng/m³ = 24 ppt (cis-/trans-1,2-DCE). The method has been used for the quantification of the anaerobic microbial degradation of tetra- (PCE) and trichloroethene (TCE) to dichloroethenes and vinyl chloride in landfill sites. The substances have been analyzed in landfill-gas as well as in gaseous emissions from the landfill surface. The mean emission rates of tetrachloroethene, trichloroethene and vinyl chloride from the landfill surface into the ambient air are about 0.5 g/(m² × h).     

Darstellung,Isolierung und Charakterisierung gemischter Thiocyanato(ethylendiamin)rhodium(III)-Komplexe

Preparation, Isolation, and Characterization of Mixed Thiocyanato(ethylenediamine)rhodium(III) Complexes The complexes Na[Rh(SCN)₄(en)] and trans-[Rh(SCN)₂(en)₂]SCN are prepared for the first time. They are isolated from the mixture by column chromatography on aluminia and characterized by the spectra and the CHN analysis.     

Hochselektive Anreicherung von Spurenelementen in Quecksilber

Zusammenfassung In Fortsetzung unserer Arbeiten über die Spurenbestimmung in Quecksilber haben wir das zunächst für die Abtrennung des Quecksilbers verwendete Ammoniumjodid durch Jodwasserstoffsäure bzw. Bromwasserstoffsäure ersetzt. Neben einer Verbesserung der Anreicherung erhält man nun die Möglichkeit einer gleichzeitigen spektrochemischen oder polarographischen Bestimmung mehrerer Element in einem Analysengang. Die zunächst mitgeteilten Schwierigkeiten bei der exakten Blindwertbestimmung sind nach Abänderung der Anreicherungsvorschrift behoben. Die Verteilungskoeffizienten der Spurenelemente unterscheiden sich gegenüber der früheren Vorschrift nur unbedeutend.Das zur Analyse angewandte Verfahren der anodischen Amalgamvoltammetrie erwies sich für die gleichzeitige empfindliche Bestimmung von Zn, Cd, Pb und Cu im Anreicherungsrückstand als sehr geeignet.

---

Summary In continuation of our studies on trace determination in mercury we have substituted the ammonium iodide first used for the separation of mercury by hydroiodic or hydrobromic acid. In addition to an improved enrichment this method now permits simultaneous spectrochemical or polarographic determination of several elements in one analytical process. After changing the directions for enrichment, the previously reported difficulties in the determination of the exact blank value have been eliminated. The distribution coefficients of the trace elements differ only insignificantly from those of the previous directions.The method of anodic stripping voltammetry used for analysis proved to be highly suitable for simultaneous sensitive detection of Zn, Cd, Pb and Cu in the enrichment residue.

---

---

I. Mitteilung: Jackwerth, E.: diese Z. 202, 81 (1964).     

o-(2-Hydroxy-5-dodecylphenylazo)-benzoesäure und -arsonsäure als Chelatbildner flüssiger Ionenaustauscher

The syntheses of two new chelating agents o-(2-hydroxy-5-dodecylphenylazo)-benzoic acid and the corresponding arsonic acid, are described. Solutions of these in benzine or in chloroform have been used as liquid ion-exchangers for the separation of Be and Al, and of Zr and Hf. Both have proved useful for the separation of traces of Fe(III) from solutions of salts.     

Ein Kationentrennungsgang auf papierchromatographischer Grundlage

Ohne ZusammenfassungDie vorliegende Arbeit wurde im Anorganisch-Chemischen Institut der Technischen Universität Berlin durchgeführt. Dem Direktor des Institutes, Herrn Prof. Dr. G. Jander, danken wir für Diskussion des Themas und freundliche Unterstützung.     

Chelatbildende Austauscherharze,VII

Preparation and use of a resin with 1.8-dihydroxynaphthalene-O,O-diacetic acid as chelating group are described. Besides the separation of many of the common interfering ions it also permits the separation of Hf. The following ions could be separated quantitatively: Mg(II), Pb(II), Cu(II), Fe(III), La(III), Ce(IV), Th(IV), Ti(IV), and U(VI). During these and further qualitative and quantitative experiments no interfering ions could be found. A method for the separation of⁹⁵Zr from its daughter nuclide⁹⁵Nb is also described. The main problem proved to be the separation of Zr(IV) and Hf(IV), owing to their close resemblance. To accomplish quantitative determination of Zr and Hf without any separation,⁹⁵Zr and^175+181Hf radioisotopes were used. The chelating resin permits the separation of 95% of Hf(IV) from an equimolar solution. The main part of Hf(IV) is eluated by 2M hydrochloric acid, and subsequently Zr(IV) by 0.75M oxalic acid. The rest of Hf is enriched in the first fractions of the oxalic acid eluate, so that when eliminating these, even after a single step experiment hafnium free from zirconium and a rather pure fraction of zirconium are obtained. Even under extreme conditions of concentration (Zr∶Hf=91∶1) 75% of Hf can be separated free from Zr in a single step experiment.

---

---

Vorgetragen auf der IUPAC-Tagung in Prag, 1967.     

Untersuchung der Wackenroderschen Reaktion

Zusammenfassung Die hochspannungsionophoretische Trennung der Polythionate und des Thiosulfats bei 3000 V in 1–2 Std mit Puffern verschiedener p_H-Werte wird beschrieben. Die Vorteile der Methode gegenüber der papierchromatographischen Trennung werden aufgezeigt.

---

Summary The separation of polythionates and thiosulphate is achieved by high-voltage ionophoresis (3,000 V) in 1–2 hours using buffer solutions of different p_H values. The advantages of this method in relation to the paper Chromatographic separation are shown.

---

---

VI. Mitt.: Blasius, E., u. R. Krämer: Z. anorg. allg. Chem. 319, 1 (1962).

---

Für die Bereitstellung von Mitteln und Apparaten danken wir der ERP-Verwaltung, dem Bundesatomministerium und der Deutschen Forschungsgemeinschaft.     

Crystal Orientation Mapping Applied to the Y-TZP/WC Composite

 Crystal orientation measurements made by electron backscattered diffraction (EBSD) in the scanning electron microscope (SEM) and microscopic observations provided the basis for a quantitative investigation of microstructure in an yttria stabilised, tetragonal zirconia-based (Y-TZP) composite. Automatic crystal orientation mapping (ACOM) in a SEM can be preferable to transmission electron microscopy (TEM) for microstructural characterisation, since no sample thinning is required, extensive crystal data is already available, and the analysis area is greatly increased. A composite with a 20 vol.% tungsten carbide (WC) content was chosen since it revealed crystal relationships between the matrix and carbide phase already established by TEM analysis. However, this composite was difficult to investigate in the EBSD/ SEM since it is non-conductive, the Y-TZP grain size is of the order of the system resolution, and the sample surface, though carefully prepared, reveals a distinctive microtopography. In this paper, some useful solutions to these problems are discussed and the resulting data, which confirm crystal correlations previously established by TEM analysis, are presented.     

[C10N2H10][ZnCl(HPO4)]2: A New Templated Zincophosphate Containing Tetrahedral Nets with 63 Topology

The crystal structure of [C₁₀N₂H₁₀][ZnCl(HPO₄)]₂ contains corrugated tetrahedral layers with 6³ topology. Charge balance is achieved by insertion of diprotonated 4,4′‐bipyridine between the layers. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.8832(2) Å, b = 22.673(2) Å, c = 8.1643(4) Å, β = 104.02(1)°; V = 877.0(1) ų; Z = 4; R1 = 0.041 and wR2 = 0.088 for 1836 reflections [I > 2σ(I)]. Tetrahedral layers are also observed in other organo‐ammonium templated compounds. However, their topologies are characterized by 4.8² nets. With the title compound a layered tetrahedral net with 6³‐topology is reported for the first time.