Hydride generation atomic absorption spectrometry with insitu graphite tube trapping for the determination of Se (IV) and Se (VI) in baltic sea water samples

This paper reports the results of an optimisation study for a procedure to determine the total selenium and its inorganic species, Se(IV) and Se(VI) using atomic absorption spectrometry combined with hydride generation and in-situ trapping of the analyte on the inner walls of the graphite tube. With the use of the proposed modification, a detection limit (3σ) of 0.018 ng/ml is achieved. This paper presents exemplary results, according to the proposed procedure, for selenium determination in samples of marine water. The concentrations of selenium in the samples ranged from <0.02 ng/ml to 0.16ng/ml of Se(IV) and from <0.02 ng/ml to 0.10 ng/ml of Se(VI).     

Spectrophotometric determination of dopamine in microliter scale using microfluidic system based on polymeric technology

In this paper we report two simple and sensitive spectrophotometric procedures for the determination of dopamine in microfluidic system based on poly(dimethylsiloxane) (PDMS) technology and comparison of their interference-susceptibility. The analytical reactions and measurements were carried out at ambient temperature in a microreactor of total volume 6 μl coupled with a spectrophotometric flow-through cuvette.     

Determination of uranium after its selective extraction as phenylacetate

The method described is based on the extraction of uranium with a chloroform solution of phenylacetic acid from slightly acidic solution containing nitrilotriacetic acid, which masks all interfering metals. After stripping into very dilute hydrochloric acid, uranium is reduced with ascorbic acid and determined complexometrically. The method permits reliable determination of uranium in the presence of all quadri-, ter- and bivalent metals investigated, molybdenum(VI), tungsten(VI), and vanadium(V).     

Thermal copolymerization of acrylonitrile with methacrylate units arranged in matrix

Copolymerization of acrylonitrile with methacrylates on a matrix has been examined (using methacrylate of p-cresol-formaldehyde resin). It has been found that the copolymerization proceeds at 70° without an initiator. The reactivity ratios depend on the length of the matrix used. The method of calculating Q and e according to the Alfrey-Price scheme has been discussed for the system under investigation.     

Prediction of adsorption of organic component and water vapour mixture onto activated carbon

A simple isotherm equation is derived for the adsorption of an organic component onto activated carbon in presence of water vapour. The theoretical results are compared with experimental data for toluene-water vapour-activated carbon, which were published byRipperger andGermerdonk [10].

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Vorhersage der Adsorption einer organischen Komponente und Wasserdampf an Aktivkohle

Zusammenfassung Es wird eine einfache Adsorptionsisotherme abgeleitet, welche die gleichzeitige Adsorption eines organischen Stoffes und Wasser an Aktivkohle beschreibt. Die theoretischen Ergebnisse werden mit experimentellen Resultaten vonRipperger undGermerdonk [10] für Toluol-Wasser-Aktivkohle verglichen.

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Symbols a _i adsorbate concentration in adsorbent, kg/kg of carbon - a _0i monolayer capacity, kg/kg of carbon - b _i kinetic parameter of theLangmuir equation - E _j adsorption energy in thej-th layer - i i-th component (1 — water vapour, 2 — organic compound) - j j-th layer - m number of layers - n number of adsorbed components - p partial pressure, Pa - p* saturation partial pressure, Pa - p _C water vapour partial pressure at begining of capillary condensation, Pa - surface coverage     

Reactions of 5-hydroxy-6-oxo steroids-iii : Acid-catalysed reactions of 3β-acetoxy-5-hydroxy-5α-cholestan-6-one

Aromatization of the title compound with selected acidic catalysts has been investigated. It has been established that depending upon the reaction conditions trienone 2,1 -methyltrienone3, dienone 4, diacetoxyketone5 or dione 6 are formed as the major products. Dienone 4 and dione 6 are the main compounds of the reactions of tosyloxyketone 10 with KHSO₄ and HBr_aq, respectively. The reaction of acetoxyketone 8 with HBr_aq furnishes epimeric 3-bromoketones 12 and 13 in the ratio about 1:1.     

SPECTRAL CHARACTERISTICS AND MECHANISM OF CHEMILUMINESCENCE FROM TRYPTOPHAN SOLUTIONS INDUCED BY UV-IRRADIATION

The spectral distribution of the chemiluminescence, fluorescence and phosphorescence of tryptophan aqueous solutions irradiated with high and low pressure mercury lamps has been measured. The blue emission bands in the region of 380–520 nm observed both in the chemi- and photoluminescence, as well as an absorbance increase at 230 and 330 nm, indicate oxidative degradation of tryptophan leading to the formation of derivatives of N-formylkynurenine, xanthurenic and anthranilic acids. Red emission bands at 630 and 705 nm in the spectrum of the chemiluminescence, an enhancement of light intensity by D₂O and its decrease by NaN₃ and DABCO suggest a partial contribution of O₂(¹Δ_g) to the photooxidation and chemiluminescence of tryptophan. The enthalpy of the exergonic reactions, leading to the formation of luminescing products, was calculated to average -270 kJ-mol.     

Electrophilic acetylation and bromination reactions of benzo[b]naphtho[2,3-e][1,4]dioxin

The reactivity of benzo[b]naphtho[2,3-e][1,4]dioxin in the electrophilic aromatic substitution reactions has been studied. Friedel-Crafts acetylation resulted in the formation of three out of the possible five monoacetylated products, with the acetyl group located in positions 8 (major), 7 and 6 (minor) of the heterocycle. In the bromination reaction a higher selectivity was observed with the 6-bromo derivative found as the only monobrominated product and the 6,11-dibromo derivative found as the only polybrominated product. A ratio of unreacted heterocycle:6-bromo:6,11-dibromo derivatives in the bromination reaction has been found to depend strongly on the reaction conditions and on the heterocycle:bromine ratio.     

Über eine neue automatische Apparatur zur Zentigramm-Bestimmung von Kohlenstoff und Wasserstoff in organischen Substanzen

Zusammenfassung Das vom Verfasser undE. Sucharda schon 1928 angewandte Prinzip, die durch das Verhalten der Substanz beim Erhitzen bewirkten Druckschwankungen im Verbrennungsrohre zum Zwecke der automatischen Regulierung der Vergasungsgeschwindigkeit der Substanz bei der Elementaranalyse auszunutzen, wurde bei der Konstruktion einer neuen, elektrisch betriebenen, automatischen Apparatur angewandt. Hierbei wird das mit der Substanz gefüllte Mikroschiffchen mittels eines elektrischen Hochfrequenzgenerators erhitzt. Der Stromzufluß zu dem Hochfrequenzgenerator wird durch die erwähnten Druckschwankungen einoder ausgeschaltet. Die Verbrennung verläuft dann bei praktisch konstantem Druck im Verbrennungsrohre, also auch bei konstantem Sauerstoffüberschuß. Die neue Apparatur wird an Hand beigefügter Abbildungen beschrieben. Als Absorptionsmittel für Stickstoffoxyde werden 1 bis 2 g Bleidioxyd in einem 12 cm langen Porzellanschiffchen bei 190° angewandt. Die Absorption des Wassers erfolgt durch wasserfreies Kobaltchlorid, die der Kohlensäure ausschließlich durch Ascarit. Die Sauerstoffgeschwindigkeit im Verbrennungsrohre beträgt 8 ml pro Minute. Bei Substanzen, die mehr als 10% N enthalten, wird zwischen den Kohlensäureabsorptionsapparat und den Wasserabsorptionsapparat ein mit Mangandioxyd gefüllter Apparat eingeschaltet.

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Summary The principle used by the author andE. Sucharda as early as 1928, which employs the variations in pressure in the combustion tube resulting from the behavior of the substance when heated, for automatically regulating the rate of gasifying the substance was applied in the construction of a new electrically operated automatic apparatus. The micro boat charged with the sample is heated by means of a high frequency generator. The flow of current to the high frequency generator is switched on and off by the variations in pressure mentioned above. The combustion then proceeds at practically constant pressure in the combustion tube, and even when there is a constant excess of oxygen. The new apparatus is described in the accompanying figures. The nitrogen oxides are absorbed in 1 to 2 grams of lead dioxide contained in a porcelain boat (12 cm long) at 190°. The absorption of the water is by means of anhydrous cobalt chloride, while the carbon dioxide is taken up in ascarite. The speed of the oxygen in the combustion tube is 8 ml per minute. In the case of samples that contain more than 10% nitrogen, an apparatus filled with manganese dioxide is placed between the carbon dioxide absorber and the apparatus for taking up the water.

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Résumé Le principe de l'utilisation des variations de pression qui se produisent dans un tube à combustion en analyse élémentaire, lors du chauffage de la substance, a été utilisé dès 1928 par l'auteur etE. Sucharda pour la régulation automatique de la gazéification de cette substance. Il a été appliqué à la construction d'un nouvel appareil automatique commandé électriquement. La micronacelle qui contient la substance est chauffée électriquement à l'aide d'un générateur de courant de haute fréquence. Les variations de pression pendant la combustion provoquent l'ouverture ou la fermeture du circuit d'alimentation de ce générateur. Il en résulte que la combustion est effectuée à pression pratiquement constante ainsi qu'à excès d'oxygène constant. Ce nouvel appareil est décrit sur les figures de la publication.On utilise 1 à 2 grammes de bioxyde de plomb disposés dans une nacelle de porcelaine de 12 cm de longueur, portée à 190° pour absorber les oxydes de l'azote. L'eau est absorbée par du chlorure de cobalt anhydre et l'anhydride carbonique exclusivement par de l'ascarite. Le débit du courant d'oxygène dans le tube de combustion est de 8 ml par minute. Pour les substances contenant plus de 10% d'azote, on intercale un absorbeur à bioxyde de manganèse entre l'absorbeur à anhydride carbonique et l'absorbeur à eau.

     

Preparation of unsymmetrical disulfides by using sulfines1

Acidolytic cleavage of unsymmetrically substituted dithioacetal monoxides, ArCH(SR)S(O)Me has been used to prepare linear unsymmetrical disulfides RSSMe. Disproportionation was suppressed by the addition of a small amount of benzyl mercaptan. The required starting materials were conveniently obtained from appropriately substituted sulfines ArC(=SO)SR and methyl lithium. The following disulfides were prepared: R =n-C₄H₉ (73.5%), n-C₇H₁₅ (78%), Ph (77.3%), AcO(CH₂)₁₀ (81.5%).The unsymmetrical dithioacetal PhCH(SEt)SC₇H₁₅-n gave upon oxidation with one equivalent of peracid a mixture of two dithioacetal monoxides which on treatment with HClO₄ led to three disulfides. This result is discussed in term of the mechanism of acidolysis.