Complex activators in analytical catalytic reactions

Summary The influence of pairs of carboxylic acids on the oxidation ofp-phenetidine hydrochloride by chlorate and traces of vanadium(V) as catalyst is studied. The activator systems used are sulphosalicylic acid + tartaric acid, sulphosalicylic acid + citric acid, tartaric acid + citric acid. It is shown that in some cases the joint activating effect is much higher than that of either activator alone. The kinetic data obtained with complex activator systems confirm the concept of different types of activating action in the two stages of the catalytic reaction. Some combinations of activators could be used in catalytic analysis.

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Zusammenfassung Der Einfluß von Carbonsäurepaaren auf die Oxydation von p-Phenetidin-hydrochlorid durch Chlorat und Spuren von Vanadin(V) als Katalysator wurde untersucht. Als Aktivierungssysteme wurden Sulfosalicylsäure und Weinsäure, Sulfosalicylsäure und Zitronensäure, Weinsäure und Zitronensäure verwendet. In manchen Fällen ist der gemeinsame Aktivierungseffekt größer als der eines der jeweiligen Aktivatoren allein. Die kinetischen Daten der komplexen Systeme bestätigen die Annahme einer verschiedenartigen Aktivierung der zwei Stufen der katalytischen Reaktion. Manche Aktivatorkombinationen könnten für die katalytische Analyse von Wert sein.

     

Spectrophotometric determination of ruthenium(III) using diphenylcarbazone

Summary The purple violet ruthenium(III)-diphenylcarbazone complex which is formed at p _h 5–7, and has an absorption maximum at 530 nm with molar absorption coefficient 16.2·10⁴l.cm^–1.mole^–1 is suggested for the estimation of 20–125g ruthenium(III) spectrophotometrically in 30–60% ethanol. The complex is stable over p _h range 3.2–8.4. The limits of interference due to foreign ions have been studied.

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Zusammenfassung Der bei p _h 5 bis7 entstehende Ruthenium(III)-Diphenylcarbazon-Komplex hat ein Absorptionsmaximum bei 530 nm und einen Absorptionskoeffizienten von 16,2·10⁴ l.cm^–1.Mol^–1. Die spektrophotometrische Bestimmung von 20 bis 125g Ruthenium(III) in 30 bis 60%igem Äthanol mit Hilfe dieses zwischen p _h 3,2 und 8,4 beständigen Komplexes wurde vorgeschlagen. Die Störung durch Fremdionen wurde geprüft.

     

Zur Existenz von zwei Kristallmodifikationen der Mellitsäure

Zusammenfassung Es wurde röntgenorgraphisch und mit Hilfe derDTA, festgestellt, daß die Mellitsäure nur in einer Modifikation, der orthorhombischen¹, vorliegt. Die Darstellung der Mellitsäure^2,3 wurde in Einzelheiten modifiziert. Die Reinheit der Präparate wurde spektroskopisch, im IR- bzw. UV-Gebiet, und mit Hilfe der Papierchromatographie geprüft.

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by means of X-ray analysis and DTA it was found that mellitic acid exists only in the orthorhombic modification. The preparation of mellitic acid was modified in part. The purity ot the samples obtained was checked by IR-and UV-spectroscopy and by paper chromatography.

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Zur Kenntnis von Salzen einiger aromatischer Polycarbonsäuren, 3. Mitt.; 2. Mitt.:B. Hájek, E. Kálalová undF. Petr, Z. Chem.5, 230 (1965).

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Gewidmet dem Andenken an Professor Dr.Hans Meyer meinen Lehrer an der ehemaligen Deutschen Universität in Prag. Prof.Meyer geboren am 31. März 1871 in Wien, gestorben am 28. November 1942 in Theresienstadt, beschäftigte sich eingehend (mitH. Raudnitz u. a.) mit der Darstellung und Untersuchung der Mellitsäure und ihrer Derivate.     

Production of oxygen enriched air by rapid pressure swing adsorption

A novel rapid pressure swing adsorption (RPSA) process is described for production of 25–50% oxygen enriched air. The embodiment consists of one or more pairs of adsorbent layers contained in a single adsorption vessel. The layers undergo simultaneous pressurization-adsorption and simultaneous depressurization-purge steps. A total cycle time of 6–20 seconds is used. The process yields a very large specific oxygen production rate and a reasonable oxygen recovery for production of 20–50 mole% oxygen enriched gas.It is demonstrated by a simple mathematical model of isothermal single adsorbate pressure swing ad(de)sorption concept on a single adsorbent particle that the specific production rate of a PSA process cannot be indefinitely increased by reducing the cycle time of operation when adsorbate mass transfer resistances are finite.     

Determination of the quaternary compound ciclotropium in human biological material after hydrolysis and derivatization with the fluorophor flunoxaprofen chloride

The quantitative determination of the quaternary spasmolytic compound ciclotropium and its metabolite N-isopropyltropinium is described for human plasma and urine. The analytical procedure consists of ion-pair extraction from biological material, alkaline hydrolysis, subsequent derivatization with the fluorophor flunoxaprofen chloride and separation by high-performance liquid chromatography on a reversed-phase column with fluorimetric monitoring. The detection limits of 0.5 ng/ml in plasma and 10 ng/ml in urine at signal-to-noise ratios higher than 3 permit the determination of pharmacokinetic parameters after therapeutic doses.     

Cyclopentadienyl ruthenium, rhodium, and iridium vertices in metallaboranes: geometry and chemical bonding

Most cyclopentadienylmetallaboranes containing the vertex units CpM (M = Co, Rh, Ir; Cp = eta(5)-cyclopentadienyl ring, mainly eta(5)-Me(5)C(5)) and CpRu donating two and one skeletal electrons, respectively, have structures closely related to binary boranes or borane anions. Smaller clusters of this type, such as metallaborane analogues of arachno-B(4)H(10) (e.g., (CpIr)(2)B(2)H(8)), nido-B(5)H(9) (e.g., (CpRh)(2)B(3)H(7) and (CpRu)(2)B(3)H(9)), arachno-B(5)H(11) (e.g., CpIrB(4)H(10)), B(6)H(6)(2)(-) (e.g., (CpCo)(4)B(2)H(4)), nido-B(6)H(10) (e.g., CpIrB(5)H(9) and (CpRu)(2)B(4)H(10)), and arachno-B(6)H(12) (e.g., (CpIr)(2)B(4)H(10)), have the same skeletal electron counts as those of the corresponding boranes. However, such clusters with eight or more vertices, such as metallaborane analogues of B(8)H(8)(2)(-) (e.g., (CpCo)(4)B(4)H(4)), arachno-B(8)H(14) (e.g., (CpRu)(2)B(6)H(12)), and nido-B(10)H(14) (e.g., (CpRu)(2)B(8)H(12)), have two skeletal electrons less than those of the corresponding metal-free boranes, analogous to the skeletal electron counts of isocloso boranes relative to those of metal-free deltahedral boranes. Some metallaboranes have structures not analogous to metal-free boranes but instead analogous to metal carbonyl clusters such as 3-capped square pyramidal (CpRu)(2)B(4)H(8) and (CpRu)(3)B(3)H(8) analogous to H(2)Os(6)(CO)(16) and capped octahedral (CpRh)(3)B(4)H(4) analogous to Os(7)(CO)(21). In the metallaborane structures closely related to metal-free boranes, the favored degrees of BH and CpM vertices appear to be 5 and 6, respectively.     

Viscosity of confined inhomogeneous nonequilibrium fluids

We use the nonlocal linear hydrodynamic constitutive model, proposed by Evans and Morriss [Statistical Mechanics of Nonequilibrium Liquids (Academic, London, 1990)], for computing an effective spatially dependent shear viscosity of inhomogeneous nonequilibrium fluids. The model is applied to a simple atomic fluid undergoing planar Poiseuille flow in a confined channel of several atomic diameters width. We compare the spatially dependent viscosity with a local generalization of Newton's law of viscosity and the Navier-Stokes viscosity, both of which are known to suffer extreme inaccuracies for highly inhomogeneous systems. The nonlocal constitutive model calculates effective position dependent viscosities that are free from the notorious singularities experienced by applying the commonly used local constitutive model. It is simple, general, and has widespread applicability in nanofluidics where experimental measurement of position dependent transport coefficients is currently inaccessible. In principle the method can be used to predict approximate flow profiles of any arbitrary inhomogeneous system. We demonstrate this by predicting the flow profile for a simple fluid undergoing planar Couette flow in a confined channel of several atomic diameters width.     

J Aggregation of Thiacarbocyanine in Aqueous Gelatin Solutions

The aggregation processes of 3,3′-disulfopropyl-4,4′,5,5′-dibenzo-9-ethylthiacarbocyanine betaine were studied in aqueous gelatin solutions. Gelatin molecules were shown to favor the formation of J aggregates from dye dimers according to the block mechanism. Acidic gelatins much stronger favor J aggregation of the dye than alkaline and, especially, modified gelatins. High contents of microgels and high-molecular-mass fractions in gelatin retard the formation of long-wavelength aggregates.     

Mössbauer investigation of the reaction between HCl and tin dopant ions located on the surface of Cr2O3 microcrystals

The chemical behavior of surface-located tin dopant ions depends strongly on their valence state. At room temperature all Sn(II) ions readily react with gaseous hydrogen chloride while, under similar conditions, the predominant part of Sn(IV) ions is not affected by this gas. The results of this study, along with those previously obtained for both valence states of tin dopant exposed to a H₂S atmosphere, suggest that lower reactivity of Sn(IV) ions is essentially due to their higher coordination number and concomitant steric hindrance effects.