Quantitative electron-probe microanalysis of light elements: Determination ofa-Si∶C∶N∶O∶H insulating films

Amorphous SiCNOH films (1–3 m) are studied by EPMA after deposition of gold (1–5 nm) as a conductive coating. Its influence on thek-ratios (X-ray intensity relative to an uncoated standard) of silicon, carbon, nitrogen and oxygen is described as a linear function of the simultaneously determinedk-ratio of gold. Thek-ratios representing the uncoated specimen are obtained by extrapolation and, in combination with the PAP matrix correction model, quantitative EPMA can be performed with an analytical error of 2–5%, as it is demonstrated by samples of SiC, Si₃N₄ and SiO₂. No systematic shift of the concentrations is observed for layers ofa-SiCNOH determined at various electron energies of 5–12.5 keV. Hydrogen is calculated by difference and the concentrations prove to be a useful estimate in agreement with the results of chemical analysis. Si-K/Si-K spectra recorded on organo-silicon films and binary silicon compounds point out significant differences concerning the formation of Si-C, Si-N and Si-O chemical bonds.     

The supramolecular structures and reactivities of some complexes of chiral crown ethers with borane ammonia

Whereas 1 1 crystalline complexes have been isolated between borane ammonia and methyl 4,6-O-benzylidene-2,3-dideoxy--d-galactopyranosido [2,3-b]-1,4,7,10,13,16-hexaoxacyclo-octadecane (1), methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-b] (methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-k]-1,4,7,10,13,16-hexaoxacyclo-octadecane (3), and (1R,2R,7R,24R)-3,5,8,11,14,17,20,23,26,28-decaoxatricyclo-[21.4.0.0^2,7]octacosane (4), the hosts, methyl, 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido[2,3-b] 1,4,7,10,13,16-hexaoxacyclo-octadecane (2) and 1,4 1,4 3,6 3,6-tetra-anhydro-2,2 5,5-bis-O-oxydiethylenedi-d-mannitol (5) have yielded 2 1 (guest:host) crystalline complexes with borane ammonia as guest. X-ray analyses of the supramolecular structures of BH₃NH₃ ·1, (BH₃NH₃)₂ ·2, BH₃NH₃ ·3, BH₃NH₃ ·4, and (BH₃NH₃)₂ ·5 have been carried out and BH₃NH₃ ·1, BH₃NH₃ ·2, and (BH₃NH₃)₂ ·5 have been shown to reduce acetophenone with enantiomeric excesses of 5, 13, and 10% respectively. Supplementary Data relating to this article (atomic coordinates of the hydrogen atoms and thermal parameters) are deposited with the British Library as Supplementary Publication No. SUP 82017 (74 pages).Dedicated to Professor H. M. Powell.     

Beitr?ge zur Thermostabilit?t und zur Bestimmung des Feuchtigkeitsgehaltes von Vitamin B12-Pr?paraten

Zusammenfassung Die Flüssig-flüssig-Extraktion des Goldes als Polyäthylenglykoloxonium-saccharino-aurat(III) erlaubt seine Trennung von Palladium, Platin, Arsen, Antimon, Mangan, Nickel, Eisen, Kobalt und anderen Metallen bis zu den Verhältnissen AuPdPtAsMnSbNiFeCo =110060070010001500100002000050000. Trennungen Au/Pb sind beim Verhältnis 150000 mit der photometrischen Meßgenauigkeit durchführbar. Das Gold wird in der nichtwäßrigen Phase bei 315 nm photometrisch bestimmt.Teil II: Ziegler, M., u. H.-D. Matschke: diese Z. 184, 166 (1961).     

Micro reversed phase liquid chromatography of Cd-, Ni-, Zn-, Cu-, Co-, Hg-diethyldithiocarbamates at picogram level

Summary The use of micro reversed phase columns (Polygosil C18) for the separation of metal DDTC chelates was investigated and applied to drinking water analysis.Three different eluents have been tested [702010 (MeOH H₂OCHCl₃); 8020 (MeOHH₂O); 7030 (MeOHH₂O)] at flow rates of 7 to 28gml/min. Eluent composition showed strong influence onk of Co(DDTC)₂.The linear working curves fitted at least 3 decades with detection limit of 40–500 pg. Monitoring at _max instead of 254 nm decreases the detection limits. The consume of eluent is 10 to 20 times less than with analytical columnes.Results of micro LC have been compared with predictible data of theoretical considerations.

---

Mikro-Umkehrphasen-Flüssigkeitschromatographie der Cd-, Ni-, Zn-, Cu-, Co-, Hg-Diethyldithiocarbamatchelate im Picogrammbereich

Zusammenfassung Die Anwendung von Mikro-RP-Säulen (Polygosil C18) für die Trennung von Metall-DDTC-Chelaten wurde untersucht und auf die Analyse von Trinkwasser angewendet. Drei verschiedene Eluentien [702010 (MeOH H₂OCHCl₃); 8020 (MeOHH₃O); 7030 (MeOHH₂O)] bei Fließraten von 7 bis 28gml/min wurden untersucht,k von Co(DDTC)₂ wird von der Eluenszusammensetzung erheblich beeinflußt. Der lineare Meßbereich betrug mindestens 3 Dekaden mit einer Nachweisgrenze von 40–500 pg, die durch Detektion bei _max statt bei 254 nm noch weiter gesenkt werden kann.Der Verbrauch an Eluens ist 10–20mal geringer als bei analytischen Säulen.Die Ergebnisse der Mikro-LC wurden anhand theoretischer Überlegungen mit den vorhersagbaren Daten verglichen.

---

---

Presented in parts at 9th International Symposium on Microchemical Techniques, Amsterdam 1983.     

Electrochemical reduction of actinide ions in aqueous solution

Electrochemical reduction of heavy elements from aqueous solution to amalgams was studied by radiopolarography and radiocoulometry. Mechanism of actinide reduction on a mercury pool is discussed through simulation techniques. Special emphasis is placed on redox reactions and potentials, kinetics of the process and effect of acetate and citrate ions as complexing agents. Three groups of actinides have been found. The first group represents actinium and from uranium to berkelium. Reduction occurs in the experimental conditions via an irreversible 3–0 process. The second group consists of the elements from fermium to nobelium, which are reduced in non-complexing solutions, or with acetate ions, similarly as barium and radium, via a reversible 2–0 reaction. Finally, californium and einsteinium behave as intermediate elements. It is noticeable that such groups are also observed in the actinide series by studying the structure of the trivalent aqua ions. On the basis of the above mentioned investigations of actinides and lanthanides several examples of electrochemical application are presented. Californium has been separated from preceding transuranium and lanthanide elements (except europium) by electrochemical reduction to amalgams in acetic solution. Separation factors from 25–90 are achieved with appropriate cathodic potentials. Similarly, this element could be separated from several heavier actinides with citric media. The electrochemical preparation of mixed uranium-nickel and uranium-tin amalgams from aqueous acetate solutions is investigated. The dependence of redox potentials of mixed amalgams on different atomic ratio UNi and USn in amalgams is measured. The large shift of redox potentials of mixed amalgams to the positive direction is detected when the atomic ratio UNi or USn in amalgams reaches 15. The thermal distillation of mercury from mixed amalgams with different UNi and USn atomic ratios was carried out and the products were identified by chemical analysis and X-ray diffraction. The intermetallics UNi₅ and USn₃ were prepared from mixed amalgams with the atomic ratios UNi=15 and USn=13. The uranium and neptunium amalgams are prepared by electrolysis of aqueous acetate solutions and are processes into metals or nitrides U₂N₃, NpN by thermal distillation of mercury in vacuum or in nitrogen atmosphere.     

Photometric determination of trivalent gallium,indium and thallium with Xylenol orange

Summary Xylenol orange reacts very sensitively with gallium(III), indium (III) and thallium(III) to form reddish violet colored chelates having _max 560 nm in case of Ga and In and _max 590 nm in case of Ti at P_H 4.0. The molar ratio for all the chelates is 1 1 (metal reagent). Optimum conditions including the range for adherence to Beer's law, effect of P_H on the color intensity, effect of excess reagent, and sensitivity are reported for the photometric determination of these metal ions using Xylenol orange.

---

Zusammenfassung Xylenolorange reagiert sehr empfindlich mit Gallium(III), Indium(III) und Thallium(III) unter Bildung rötlich-violetter Chelate mit einem Absorptionsmaximum bei 560 nm im Falle von Ga und In bzw. 590 nm für Tl bei p_H 4,0. Das Molverhältnis ist in jedem Fall 11. Die besten Arbeitsbedingungen, der Gültigkeitsbereich des Beerschen Gesetzes, der Einfluß des P_H auf die Farbintensität und des Reagensüberschusses sowie die Empfindlichkeit werden für die photometrische Bestimmung der genannten Ionen angegeben.

     

Die F?llung des Bleis mit Anionenaustauschersulfaten

Zusammenfassung 5–150 mg Blei werden durch Dowex-I-Sulfat im Säulenverfahren bei Gegenwart von 50% Methanol quantitativ als Sulfat abgeschieden. Dieses wird mit3% iger Natronlauge aus der Säule gelöst und kann photometrisch als Sulfid oder mit Komplexon volumetrisch bestimmt werden. Es sind Trennungen bis zu den Verhältnissen PbFeCoNiCuMgBa Sr = 1235701050042 ausführbar.     

Phthalocyaninartige Bor-Komplexe

Zusammenfassung Aus Halogenboranen und Organohalogenboranen (RBX ₂R=C₆H₅, Cl, Br;X=F, Cl, Br) sowie aus Organoboranen oder Thioboranen entstehen mit Phthalodinitril Triisoindolo-[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8,9a,9b]-hexaazaboraphenalene von denen die B–Cl- und B–F-Verbindungen näher charakterisiert werden.Dekaboran(14), Diboran(6) oder Boranaddukte von Stickstoffbasen liefern hingegen mit Phthalodinitril metallfreies Phthalocyanin.

---

Triisoindolo[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8,9a,9b]-hexa-azaboraphenalene

Triisoindolo[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8, 9a,9b]-hexaazaboraphenalenes are obtained from the reactions of haloboranes and organohaloboranes (RBX ₂R=C₆H₅, Cl, Br;X=F, Cl, Br) as well as from organoboranes or thioboranes with phthalodinitrile. The B–Cl and B–F compound have been characterized by analyses, i.r.-, u.v.- and mass-spectrometry.Diborane(6), dekaborane(14) and amine-boranes, however, upon reaction with phthalodinitrile lead to high yields of metal free phthalocyanine.

---

---

Herrn Prof. Dr.M. Pailer zum 60. Geburtstag gewidmet.     

Kinetics of isotope exchange of dioxygen with a powdered high-temperature superconducting material Ba2YCu3O7?x

It has been found that the rate of isotope exchange in Ba₂YCu₃O_7–x–O₂ system is high. Its kinetics is exponential, first order with respect to dioxygen and the exchange is of the mixed first/third type.

---

Ba₂YCu₃O_7–x–O₂ . -, -, - .

     

Parent and mixed ligand complexes in the copper(II)-ethylene glycol-sulphate system

Eleven copper(II)-ethylene glycol-sulphate complexes of different compositions were prepared, one of them-CuGl₂(H₂O)₂SO₄-in single-crystal form. A thermoanalytical study of these complexes revealed three types of thermal decomposition pattern. The X-ray structure of the single-crystal demonstrated the presence of ethylene glycol bridges resulting in endless chains in the crystal.

---

Zusammenfassung Elf Kupfer(II)-äthylenglykol-sulfat-Komplexe unterschiedlicher Zusammensetzung wurden dargestellt, einer davon — CuGl₂(H₂O)₂SO₄ — in Form von Einkristallen. Die thermoanalytische Untersuchung dieser Komplexe ergab drei Typen der thermischen Zersetzung. Die röntgendiffraktometrische Bestimmung der Struktur des in Form von Einkristallen erhaltenen Komplexes zeigte, daß den Kristall endlose Ketten von Äthylenglykolbrücken durchziehen.

---

() — , — CuGl₂(H₂O)₂SO₄ — . . , , .

     

Untersuchungen zur mikroanalytischen Bestimmung der langkettigen Fetts?uren im Blut

Zusammenfassung Für die im Plasma an Albumin gebundenen sog. freien Fettsäuren (FFS) wird ein neues gas-chromatographisches Analysenverfahren vorgestellt. Das Probenvolumen beträgt 50 l Serum oder Plasma. Die Extraktion erfolgt in 1,1 ml CHCl₃/CH₃OH (21, v/v) mit n-Heptadecansäure als innerem Standard (0,05 Val C₁₇₀/ml). Nach Eindampfen am Rotationsverdampfer werden die FFS im verschlossenen Reaktionskölbchen mit 20 l CH₃J/Essigsäureäthylester (11, v/v) über festem K₂CO₃ bei 90°C 1 h verestert. Die Varianz des Verfahrens errechnet sich bei 15 Parallelbestimmungen zu 4,85%.Vortrag anläßlich der Tagung Spurenanalyse, 2. bis 5. April 1973 in Erlangen.     

Some transformations of 3,4:3'2 tetrahydrofurano-1,2,3,4-tetrahydroquinolines

Conclusions Under the action of KMnO₄ in acetone on derivatives of 3,43,2-tetrahydrofurano-1,2,3,4-tetrahydroquinoline, the nitrogen ring is dehydrogenated with a simultaneous opening of the furan ring, resulting in the formation of quinolylethyl alcohols. Hydrogenated furanoquinolines, containing the vinyl group in the 2-position, are oxidized to-quinolones in this case.     

Schiff base complexes of dioxouranium(VI), III. Commun.: Dioxouranium(VI) complexes of bibasic tetradentateSchiff bases

Bibasic tetradentateSchiff bases having the donor system OH–NX–NX–OH have been shown to form UO₂(NO₃)₂(SBH₂) type of derivatives [SBH₂ is the molecule of the bibasic tetradentateSchiff bases such as HOC₆H₄C(R) N(CH₂) _n NC(R)C₆H₄OH (where R=H or CH₃ andn=2 or 3) and HOC(R)CHC(CH₃)N(CH₂) _n NC(CH₃)CH C(R)OH (where R=CH₃ or C₆H₅ andn=2 or 3)]. The 11 stoichiometry of these complexes is shown by elemental analysis and conductometric titrations. The molar conductence values in nitrobenzene indicate the non-electrolytic behaviour and the magnetic susceptibility measurements by the Gouy method show these complexes to be diamagnetic.With 1 Figure