Sorptionseffekte an Eisen(III)-hydroxid-F?llungen

Zusammenfassung Um Material zur Deutung des Mechanismus der Sorption von Sr²⁺-Ionen an Eisen(III)-hydroxid zu gewinnen, werden Meßreihen mitgeteilt, in denen die pH-Abhängigkeit der Sorption sowie deren Beeinflussung bei Fällung mit verschiedenen Basen (NaOH, Ammoniak, Trimethylamin, Benzylamin) untersucht wird. Aus den charakteristischen Unterschieden der Sorptionskurven muß gefolgert werden, daß die Art der Base für die Sorption eine wichtige Rolle spielt.

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Summary The sorption of Sr²⁺ ions on iron(III) hydroxide was studied as a function of the pH, of the precipitating reagent (NaOH, ammonium hydroxide, benzylamine, trimethylamine), of the temperature and of the total concentration.The curves of the relative sorption vs. pH are found to show characteristic differences which have to be explained in a detailed theory of the mechanism.

     

Anwendung der Streustrahl-Methode zur Bestimmung der Elemente in Mineral?lprodukten mit Hilfe der R?ntgenfluorescenz-Spektral-Analyse am Beispiel der Bleibestimmung in Ottokraftstoffen

Zusammenfassung In einem relativ einfach durchzuführenden Verbundverfahren wird Selen im Sauerstoff-strom innerhalb 15 min bei 1100–1150°C quantitativ aus den Metall- bzw. Metalloxidschmelzen verdampft und in einer mit flüssigem Stickstoff gekühlten Vorlage aufgefangen. Das aus der Vorlage mit einer definierten Menge verdünnter HNO₃ in Gegenwart von Ni-Nitrat gelöste Selen läßt sich direkt durch AAS mit dem Graphitofen (FAAS) äußerst nachweisstark und zuverlässig bestimmen. Die Nachweisgrenze (elektrodenlose Entladungslampe) liegt bei 3×10^–11 g Se. Der Verfahrensverbund erlaubt mit Probenmengen 10 g in Ag und Au Se-Gehalte 0,05 ppb,inCu 0,1 ppb,in Bi 0,2 ppb und in Pb 10 ppb zu erfassen. Für draht-, stab- und spanförmige Proben erhält man für Se-Gehalte von 2–0,002 ppm Variationskoeffizienten zwischen 3 und 6%. Die Vollständigkeit der Se-Verdampfung aus den Matrices Cu, Ag, Au und Bi wurde ebenso wie die Richtigkeit des Gesamtverfahrens durch systematische Untersuchungen belegt.

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Determination of se by furnace atomic absorption spectrometry (FAAS) in the ppb-range in Cu, Cu alloys, Ag, Au, Pb and Bi after volatilization in an oxygen stream

Summary Selenium is evaporated in a multi-stage procedure within 15 min from metals or metal oxides fused at temperatures of 1100–1150°C under a stream of oxygen and is trapped in a receiver cooled with liquid nitrogen. The condensed SeO₂ is dissolved with a definite volume of diluted HNO₃ in the presence of Ni-nitrate and determined with high sensitivity and reliability by FAAS (electrodeless discharge lamp). The detection limit of the FAAS was found to be 3 · 10^–11 g of Se. The multi-stage procedure allows to detect Se levels 0.05 ppb in Ag and Au, 0.1 ppb in Cu, 0.2 ppb in Bi, and 10 ppb in Pb, respectively, with sample weights 10 g. For wire, rod, and chip samples the coefficients of variation are found to be between 3 and 6% for Se contents of 2 to 0.002 ppm. The quantitative evaporation of Se from Cu, Ag, Au, and Bi as well as the accuracy of the whole procedure have been checked systematically.

Die Arbeit wurde durch Mittel der DFG in dankenswerter Weise unterstützt.     

NMR.-Investigation of the Formaldehyde Addition and Oligomerisation Equilibria in the System Formaldehyde/Water/Acetic Acid/Hydrochloric Acid

An NMR. investigation of the state of formaldehyde in acidic solutions has been carried out. Solutions of DCl/D₂O/CD₃COOD containing two sources of formaldehyde, i.e. paraformaldehyde (I) and trioxane (II), were used for this purpose. In systems I and II the effect of various D₂O/CD₃COOD ratios, at a constant DCl concentration, was studied, while for II the effect of changing DCl concentration was also investigated. The results show that in aqueous solution, formaldehyde exists primarily as the monomeric and linear oligomeric forms of methylene glycol. Reducing the amount of D₂O (at constant DCl concentration), while increasing the CD₃COOD content, results in an increase in the polymeric species and in trioxane. In addition, substitution of water by acetic acid results in systems that are catalytically more active than aqueous solutions of the same hydrochloric acid concentration. Along with the usual polymer-monomer equilibria which exist in such solutions, side reactions of methylene glycol with the hydrochloric acid present also occur to a small extent, e.g. acetylation, substitution of OH by Cl and the Cannizzaro reaction. It is suggested that these findings will result in a better understanding of the formaldehyde crosslinking reactions in cotton cellulose.     

The Azo(Azoxy) Functionality as a π2 Component in Photo [2+2] cycloadditions ‘syn’- and ‘anti’-3,4-diazatricyclo[4.2.2.22,5]dodeca-3,7-diene,syntheses, photolyses,X-ray-structure analysis,and PE spectra

The propensity of the N?N bond to undergo photo [2 + 2] cycloadditions has been further explored. In the specifically designed 1,5-azo/enes 1–3 , no [2 + 2] cycloaddition has been observed upon either direct or sensitized excitation with light of various wave lengths at temperatures down to 77 K, in line with expectations based on X-ray ( 1 : d = 2.71 Å, ω = 129°) and PE measurements ( 1 : I₁ = 8.0₀, I₂ = 9.0₅ eV; 2 ; I₁ = 8.0₀, I₂ = 9.2₅eV). The steric/stereoelectronic demands for the participation of the N?N bond in pericyclic reactions are clearly more stringent than those for the C?C bond.     

Na5AlF2(PO4)2: Darstellung,Kristallstruktur und Ionenleitfähigkeit

Na₅AlF₂(PO₄)₂: Synthesis, Crystal Structure and Ionic Conductivity Two different procedures (precipitation from aqueous solution and solid state reaction) for the synthesis of hitherto unknown Na₅AlF₂(PO₄)₂ were optimized. The crystal structure was determined using diffractometer data (P3 , a = b = 10.483(1), c = 6.607(1) Å, MoKα, 1080 independent reflections, R_w = 0.025). PO₄-tetrahedra and AlO₄F₂-“octahedra” are connected via common vertices forming a twodimensionally extended heteropolyanion. Sodium is located in interconnected spacings of the [AlF₂(PO₄)₂]-part of the structure. Ionic conductivity as expected because of these structural features was affirmed experimentally.     

Die Analytik wasserl?slicher Cellulose?ther

Zusammenfassung Es werden allgemeine und qualitative Merkmale von Natrium-Carboxymethylcellulose, Methylcellulose und Hydroxyäthylcellulose sowie gravimetrische und titrimetrische Bestimmungsmöglichkeiten der wasserlöslichen Celluloseäther insbesondere im Zusammenhang mit dem Substitutionsgrad beschrieben.Verfahren zur Ermittlung der Viscosität von Lösungen, des Polymerisationsgrades und des Gelteilchengehaltes werden besprochen. Abschließend werden charakteristische Beispiele für das analytische Vorgehen bei Substanzgemischen gegeben, die nur einen geringen Anteil Celluloseäther enthalten.

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Analysis of water-soluble cellulose ethers

General and qualitative characteristics of sodium carboxymethylcellulose, methylcellulose and hydroxyethylcellulose are presented and gravimetric and titrimetric methods for the determination of water-soluble cellulose ethers are described, especially with regard to the degree of substitution. Procedures for the measurement of the viscosity of solutions, of the degree of polymerisation and of the content of gel particles are discussed. Characteristic examples are presented for the treatment of mixtures containing only a small percentage of cellulose ethers.

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Erweiterte und umgearbeitete Fassung eines Vortrages, gehalten am 28. 6. 1971 in Baden-Baden.

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Frau Dr. G. Bartelmus, Analyt. Laboratorium der Fa. Kalle AG, sprechen wir an dieser Stelle unseren herzlichen Dank für wertvolle Beratung aus.     

A structure refinement of the high pressure modification BaI2-II

A high pressure phase BaI₂-II, which can be quenched and retained as a metastable form at ambient conditions, is reported. The structure has been determined by X-ray investigations using single crystals. BaI₂-II crystallizes in an anti-Fe₂P-type arrangement, space group $\text{P}\text{6}\text{2m, a = 9.142(6)}$Å, c = 5.173(3)Å, which is slightly denser than the PbCl₂-type structure found at normal pressure. Structural features of the two phases are discussed in comparison.     

Synthesis and characterization of heavier dioxouranium(VI) dihalides

The synthesis and characterization of the dioxouranium(VI) dibromide and iodide hydrates, UO(2)Br(2)x3H(2)O (1), [UO(2)Br(2)(OH(2))(2)](2) (2), and UO(2)I(2)x2H(2)Ox4Et(2)O (3), are reported. Moreover, adducts of UO(2)I(2) and UO(2)Br(2) with large, bulky OP(NMe(2))(3) and OPPh(3) ligands such as UO(2)I(2)(OP(NMe(2))(3))(2) (4), UO(2)Br(2)(OP(NMe(2))(3))(2) (5), and UO(2)I(2)(OPPh(3))(2)(6) are discussed. The structures of the following compounds were determined using single-crystal X-ray diffraction techniques: (1) monoclinic, P2(1)/c, a = 9.7376(8) A, b = 6.5471(5) A, c = 12.817(1) A, beta = 94.104(1) degrees , V = 815.0(1) A(3), Z = 4; (2) monoclinic, P2(1)/c, a = 6.0568(7) A, b = 10.5117(9) A, c = 10.362(1) A, beta = 99.62(1) degrees , V = 650.5(1) A(3), Z = 2; (4) tetragonal, P4(1)2(1)2, a = 10.6519(3) A, b = 10.6519(3) A, c = 24.0758(6) A, V = 2731.7(1) A(3), Z = 4; (5) tetragonal, P4(1)2(1)2, a = 10.4645(1) A, b = 10.4645(1) A, c = 23.7805(3) A, V = 2604.10(5) A(3), Z = 4, and (6) monoclinic, P2(1)/c, a = 9.6543(1) A, b = 18.8968(3) A, c = 10.9042(2) A, beta =115.2134(5) degrees , V = 1783.01(5) A(3), Z = 2. Whereas 1 and 2 are the first UO(2)Br(2) hydrates and the last missing members of the UO(2)X(2) hydrate (X = Cl --> I) series to be structurally characterized, 4 and 6 contain room-temperature stable U(VI)-I bonds with 4 being the first structurally characterized room temperature stable U(VI)-I compound which can be conveniently prepared on a gram scale in quantitative yield. The synthesis and characterization of 5 using an analogous halogen exchange reaction to that used for the preparation of 4 is also reported.     

Isolierung und Eigenschaften der sauren Phosphatase aus Ananas comosus

Zusammenfassung Im Bromelin, einer Protease aus Ananas comosus Var. Cayenne, sind einige Fremdaktivitäten enthalten. Durch Gel-Chromatographie an Sephadex G-75 läßt sich die saure Phosphatase und eine Esterase, die N-Acetyl-l-tyrosinäthylester spaltet, von der Protease abtrennen. Durch Blektrofokussierung konnte die saure Phosphatase in mindestens zwei Isoenzyme vom isoelektrischen Punkt 4, 3 bzw. 6,1 aufgetrennt werden.Die Michaelis-Konstante der sauren Phosphatase gegenüber p-Nitrophenylphosphat beträgt 0,76 · 10^–3 M (nach Lineweaver-Burk) bzw. 0,73 · 10^–3 (nach Eadie). Das pH-Optimum in Citratpuffer liegt bei pH 5,5. Es bestehen Anzeichen dafür, daß neben der höhermolekularen Phosphatase (Mol.-Gew. > 100000) auch eine niedermolekulare saure Phosphatase in den Stengeln der Ananas comosus vorkommt.In den Strünken der Ananas lassen sich erhebliche Mengen einer pflanzlichen Ribonuclease nachweisen. Dieses Enzym läßt sich durch Ionenaustausch-Chromatographie an DEAE-Cellulose von den anderen Begleitenzymen abtrennen.Eine weitere Varietät von Ananas comosus, die in Brasilien vorkommt, enthält ebenfalls große Aktivitäten an saurer Phosphatase sowie Ribonuclease, jedoch wenig Protease und keine Aktivität gegenüber N-Acetyl-l-tyrosinäthylester.

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Isolation and properties of the acid phosphatase from ananas comosus

Bromelin, a protease from pineapple (ananas comosus var. Cayenne), contains several foreign activities. Acid phosphatase and an esterase splitting N-acetyl-l-tyrosineethyl ester can be separated from the protease by gel chromatography on Sephadex G-75. The acid phosphatase can be separated into at least two isoenzymes with isoelectric points of 4.3 and 6.1, resp., by means of electrofocusing.The Michaelis constant of acid phosphatase for p-nitrophenylphosphate is 0.76×10^–3 M (according to Lineweaver-Burk) and 0.73×10^–3M (according to Eadie). The optimum pH value in citrate buffer is about 5.5. Besides the higher-molecular phosphatase (mol.-weight > 100000) also a lower-molecular acid phosphatase seems to occur in the stems of ananas comosus.Considerable amounts of a vegetable ribonuclease can be detected in the stalks of ananas. This enzym can be separated from other accompanying enzymes by ionexchange chromatography on DEAE-cellulose. Another variety of ananas comosus, occurring in Brazil, also contains high activities of acid phosphatase and ribonuclease, but only small amounts of protease and no activity towards N-acetyl-l-tyrosineethyl ester.