The quantitative electrochemical generation of bromine in acetic acid

The quantitative electrochemical generation of bromine at a platinum electrode in acetic acid is described. Coulometric methods for the determination of hydroquinone and 2-methylhydroquinone are reported. The best results are obtained with 0.7–1.1 M potassium acetate solutions as supporting electrolyte, and biamperometric end-point detection. The effects of water and acetic anhydride on the accuracy of titrations are discussed. Determination of the formal redox potential of the Br₂/Br^- system in a 0.9 M potassium acetate solution in acetic acid showed that bromide is oxidized directly to bromine at a platinum electrode with 100% current efficiency.     

The influence of chitosan on in vitro properties of Eudragit RS microspheres

Eudragit RS microspheres containing chitosan hydrochloride were prepared by the solvent evaporation method using acetone/liquid paraffin solvent system and their properties were compared with Eudragit RS microspheres without chitosan, prepared in our previous study. Different stirring rates were applied (400-1200 rpm) and drug content, Higuchi dissolution rate constant, surface and structure characteristics of the microspheres were determined for each size fraction. An increase in average particle size with a reduction of stirring rate appeared in limited interval in both series. The average particle size of microspheres without chitosan, prepared at the same stirring rate, was smaller. Pipemidic acid content increased with increasing fraction particle size, but not with increasing stirring rate as it was observed for microspheres without chitosan. We presume that high pipemidic acid content in larger microspheres is a consequence of cumulation of undissolved pipemidic acid particles in larger droplets during microspheres preparation procedure. Pipemidic acid release was faster from microspheres with chitosan and no correlation between Higuchi dissolution rate constant and stirring rate or fraction particle size was found, though it existed in the system without chitosan. Structure and surface characteristics of microspheres observed by scanning electron microscope (SEM) were not changed significantly by incorporation of chitosan. But in contrast with microspheres without chitosan, the surface of chitosan microspheres was more porous after three hours of dissolution. It is supposed that the influence of particle size fraction and stirring rate on release characteristics is expressed to a great extent through porosity and indirectly through total effective surface area, but the incorporation of highly soluble component i.e. chitosan salt hides these effects on drug release. In conclusion, changes in biopharmaceutical properties due to varying stirring rate and fraction particle size exhibited the same direction as those reported for the microspheres without chitosan, although they are less expressed because of increased experimental variability, likely caused by chitosan.     

Coulometric redox titrations of hydrazine,phenylhydrazine and isoniazid with electrogenerated lead(IV) acetate and manganese(III) acetate in acetic acid

Summary The conditions fox coulometric determination of small quantities of hydrazine, phenylhydrazine and isoniazid in glacial acetic acid with electrogenerated manganese(III) acetate and lead(IV) acetate were investigated. With the direct coulometric method at room temperature, good results were obtained in the determination of hydrazine and isoniazid with lead(IV) acetate and in the determination of phenylhydrazine with manganese(III) acetate. Hydrazine and isoniazid can also be determined by the coulometric back-titration method if the oxidation with manganese(III) acetate is performed at elevated temperature.

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Zusammenfassung Die Bedingungen für die coulometrische Bestimmung kleiner Mengen Hydrazin, Phenylhydrazin und Isoniazid mit elektrolytisch erzeugtem Mangan(III)-Acetat und Blei(IV)-Acetat in Eisessig wurden untersucht. Bei Zimmertemperatur wurden gute Resultate durch direkte coulometrische Titration des Hydrazins und Isoniazids mit Blei(IV)-Acetat und bei Titration des Phenylhydrazins mit Mangan(III)-Acetat erhalten. Durch coulometrische Rücktitration können bei höheren Temperaturen Hydrazin und Isoniazid mit Mangan(III)-Acetat erfolgreich bestimmt werden.

     

Die Zersetzung des Hexacyanoferrates(II) in der Analyse. III

Zusammenfassung Silberionen wirken katalytisch auf die Zersetzung des Hexacyanoferrates(II); in Gegenwart von 2,2-Dipyridyl entsteht als Reaktionsprodukt ein intensiv gefärbter Eisen(II)-Dipyridylkomplex. Bei erhöhter Temperatur und in schwach saurem Medium ist die Wirkung des Silbers sehr stark.Dieser katalytische Effekt wurde für die photometrische Silber-bestimmung verwendet. Der Einfluß der Versuchsbedingungen wurde photometrisch verfolgt und daraus die optimalen Bedingungen abgeleitet. Die Methode ist sehr empfindlich und ermöglicht die Bestimmung von Submikrogrammengen Silber. Die Extinktion wurde mit grünem Filter (oder spektralphotometrisch bei 522 nm) gemessen. Die Eichkurve ist schwach gekrümmt und umfaßt das Konzentrationsbereich von 2 · 10^–7 bis 2· 10^–6 M AgNO₃/l. Bei Einhaltung der genauen Arbeitsbedingungen sind die Resultate innerhalb der Fehlergrenzen photometrischer Bestimmungen reproduzierbar.

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Summary Silver ions have a catalytic action on the decomposition of hexacyano-ferrate(II); in the presence of 2,2-dipyridyl, the reaction product is an intensively colored iron(II)-dipyridyl complex. The action of the silver is very marked at elevated temperatures and in a weakly acid medium.This catalytic effect was employed, for the photometric determination of silver. The influence of the experimental conditions was followed photometrically and the optimal conditions were derived from these findings. The method is very sensitive and permits the determination of submicrogram amounts of silver. The extinction was measured with a green filter (or spectrophotometrically at 522 nm). The calibration curve is slightly bent and includes the concentration range from 2 · 10^–7 to 2 · 10^–6 M AgNO₃ per liter. If the working conditions are strictly maintained, the results are reproducible within the limits of error of photometric determinations.

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Résumé Les ions argent ont une action catalytique sur la décomposition du ferrocyanure; en présence du dipyridyle-2,2, il se forme, comme produit de réaction, un complexe dipyridyle-fer-II, intensément coloré. A température plus élevée et en milieu faiblement acide, l'action de l'argent est très forte.On a appliqué cet effet catalytique au dosage photométrique de l'argent. On a suivi, par photométrie, l'influence des conditions expérimentales et l'on a déduit de ces données les conditions optimales. La méthode est très sensible et permet le,dosage de quantités d'argent submicro. On a mesuré l'extinction avec un filtre vert (ou spectrophotométriquement à 522 nm). La courbe d'étalonnage présente une faible courbure et englobe le domaine de concentration de 2 · 10^–7 à 2 · 10^–6 M AgNO₃/l. Si l'on observe les conditions précises du mode opératoire, les résultats sont reproductibles dans les limites d'erreurs des dosages photométriques.

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II. Croat. Chem. Acta; im Druck.     

Diffuse reflectance spectroscopy—Important developments

Effect of front surface reflectance is incorporated into standard Kubelka-Munk theory of diffuse reflection. A method of obtaining the absorption coefficient independent of scattering coefficient is presented.     

Adsorption configuration and local ordering of silicotungstate anions on Ag(100) electrode surfaces

X-ray reflectivity, cyclic voltammetry, and scanning tunneling microscopy (STM) are used to examine the structure of alpha-SiW12O4(4-) or silicotungstic acid (STA) adsorbed on Ag(100) in acid solution. The voltammetry shows that STA passivates the Ag surface relative to electron transfer to a solution redox species. STM images reveal the formation of a series of lattice structures, one of which can be associated with a commensurate ( radical13x radical13)R33.69 degrees structural model. X-ray reflectivity measurements show uniquely that STA orients with its four-fold axis perpendicular to the Ag(100) surface and that the center of the STA molecule is 4.90 A above the top layer of the Ag substrate. Analysis of bond lengths leads to a footprint of STA on Ag(100), in which the four terminal O atoms are located near the hollow sites and have a Ag-O bond length of 2.06 A. This bond length is consistent with a strong covalent interaction between STA and the Ag surface.     

Semiquantitative determination of micro amounts of phenols using the ring colorimetry method

Summary The semiquantitative determination of micro amounts of pyrocatechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, andp-nitrophenol using the Weisz ring colorimetry method has been described. The results obtained deviated, on an average, from those calculated by about 4% and the amount of phenol required for one determination was about 4 g.

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Zusammenfassung Die halbquantitative Bestimmung von Mikromengen Brenzcatechin, Resorcin, Hydrochinon, Pyrogallol, Phloroglucin und p-Nitrophenol mit Hilfe der vonWeisz angegebenen Ringkolorimetrie wurde beschrieben. Die Resultate weichen von den berechneten Werten durchschnittlich um etwa 4% ab, wobei für eine Bestimmung etwa 4 g benötigt werden.

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Résumé On décrit le dosage semiquantitatif de microquantités de pyrocatéchol, résorcinol, hydroquinone, pyrogallol, phloroglucinol etp-nitrophénol, à l'aide de la méthode colorimétrique annulaire deWeisz. Les résultats obtenus se sont écartés, en moyenne, d'environ 4% d'avec ceux calculés et la quantité de phénol nécessaire pour un dosage s'élevait à 4 g environ.

     

Ferrocene Compounds. XXXI. Structure of 3-Ferrocenylpropanoic Acid

The title compound was prepared by modified procedure and characterized by means of IR, [¹H] and [¹³C] NMR spectroscopy. The structure was also determined by a single-crystal X-ray diffraction (XRD). 3-Ferrocenylpropanoic acid crystallizes as orange prisms in the triclinic space group P with a = 7.645(1) Å, b = 7.953(1) Å, c = 9.961(1) Å, = 81.67(1), = 68.43(1), = 83.76(1), V = 556.3(1) ų, Z = 2, R = 0.0435. In the ferrocene skeleton, Fe-C distances are in the range 2.033(2)–2.052(2) Å and C C distances in the range 1.412(5)–1.431(3) Å. The angle defined by ring centers and Fe atom is 177.7(1). The cyclopentadienyl rings are twisted from the eclipsed conformation by 8.3(2) (average value). In the structure was observed strong intermolecular hydrogen bond of 2.670(3) Å forming cyclic dimers of the R₂ ² (8) type.     

Decationization and dealumination of clinoptilolite tuff and ammonium exchange on acid-modified tuff

The paper presents results of investigation of exchange of the clinoptilolite tuff cations with hydrogen ions from HCl solution of concentration 0.1 mmol cm(-3) and ammonium ions solutions of concentrations 0.0071 to 2.6 mmol cm(-3). Molal concentrations, x (mmol g(-1)) of cations exchanged in acid solution and in ammonium ions solutions were compared with molal concentrations of cations obtained by determination of the cation-exchange capacity of clinoptilolite tuff. The obtained results show that at ammonium ion concentrations lower than 0.1 mmol cm(-3), with regard to exchange capacity for particular ions, best exchanged are Na+ ions, followed by Mg2+ and Ca2+ ions, while exchange of K+ ions is the poorest (Na+ > Mg2+ > Ca2+ > K+). At ammonium concentrations from 0.2 to 1 mmol cm(-3) the order is Na+ > Ca2+ > Mg2+ > K+. At concentrations higher than 1 mmol cm(-3) the order is Na+ > Ca2+ > K+ > Mg2+. The results are a consequence of the uptake of hydrogen ions by zeolite samples in ammonium ions solutions at concentrations lower than 1 mmol cm(-3) and indicate the importance of Mg2+ (besides Na+ ions) for the exchange between clinoptilolite cations and H+ ions, in contrast to K+ ions, whose participation in the reaction with H+ ions is the lowest. During decationization of the clinoptilolite in acid solution, best exchanged are Na+, Mg2+, and Ca2+ ions, while exchange of K+ ions is the poorest. Due to poor exchange of K+ and H+ ions and good exchange of Na+, Mg2+, and Ca2+ ions, it is to be assumed that preservation of stability of the clinoptilolite structure is caused by K+ ions present in the channel C. Clinoptilolite is dissolved in the clinoptilolite A and B channels where Na+, Mg2+, and Ca2+ ions are present. On the acid-modified clinoptilolite samples, exchange of ammonium ions is poorer than on natural zeolite. The longer the contact time of the zeolite and acid solution, the worse ammonium ions exchange. It can be assumed that H+ ions exchanged with zeolite cations are consumed for solution of aluminum in the clinoptilolite structure; therefore the concentration of H+ ions as exchangeable cations decreases. In the ammonium ion solution at a concentration of 0.0065 mmol cm(-3), from the acid-modified zeolite samples, Al3+ ions are exchanged best, followed by Na+, Mg2+, Ca2+, and K+ ions. Further to the results, it is to be assumed that exchangeable Al3+ ions available from clinoptilolite dissolution are best exchanged with H+ ions in acid solution.     

Distribution of fallout radionuclides through soil surface layer

The distribution of¹³⁷Cs through soil layers has been investigated by field sampling. The investigation deals with¹³⁷Cs concentration found after the Chernobyl accident. The relationship between important soil characteristics, total precipitation and cesium distribution are analyzed. Cesium is strongly sorbed in the top soil layer and its migration downward is limited. Measurements performed over a 3-year period revealed that approximately 20–38 per cent of total¹³⁷Cs is located in the upper soil layer.