Polarographic microdetermination of sulphur in organic compounds after oxygen flask combustion

Summary Three polarographic micro-methods are described for the determination of sulphur in organic compounds after oxygen-flask combustion. The products are converted into sulphuric acid by oxidation with hydrogen peroxide, the excess of which is expelled through boiling. The methods are based upon allowing the sulphuric acid to react with an excess of barium iodate or bromate, then recording polarographically the cathodic reduction wave of the iodate or bromate ion. The bromate methods are superior to the iodate method being simpler and more rapid, and the results are correct to within ca. ±0.5%.

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Zusammenfassung Drei polarographische Mikromethoden zur Bestimmung von Schwefel in organischen Verbindungen nach deren Verbrennung im Sauerstoffkolben wurden beschrieben. Die Verbrennungsprodukte werden durch Oxydation mit Wasserstoffperoxid in Schwefelsäure umgesetzt. Der Überschuß des Oxydationsmittels wird durch Kochen zerstört. Die Schwefelsäure läßt man mit überschüssigem Bariumjodat oder -bromat reagieren und mißt dann polarographisch die kathodische Reduktionswelle des Jodats oder Bromats. Die Bromatmethode ist der Jodatmethode überlegen, da sie einfacher und rascher zu Resultaten führt, die innerhalb ±0,5% korrekt sind.

     

Application of the rotated dropping mercury electrode to the analysis of mixtures of electroactive substances

The use of poylacrylamide is recommended instead of gelatin as an ideal maximum suppressor to be employed with both the rotated dropping mercury electrode (RODE) and conventional dropping electrode (DME). It is retained at the mercury surface over the entire potential range and does not combine with heavy metals. Reproducibility of the measurement of the residual current and that of the limiting current at the RDME were studied, and it was found that accurate determinations of a single constituent (±2%) are possible at concentrations as low as 1 to 2.10^-5M. The variation of the limiting current with potential is much greater at the RDME than at the DME. This effect must be considered in the analysis of a mixture of electroactive species at the RDME. Method have been discussed for making the proper correction for a preceding wave when a limiting current of a mixture of constituents is measured. Because of its high sensitivity and good reproducibility of results, the RDME is recommended for the analysis of solutions containing one or more electroactive species at concentrations less than 10^-4M.     

A simplified sampling technique for use with the Weisz ring oven: application to qualitative analysis of some gold and silver alloys

Up to 100 microg of sample can be collected from gold or silver alloys by rubbing the specimen with the ground hemispherical tip of a 4-mm Pyrex glass rod. Gold alloys are then dissolved in potassium cyanide solution containing hydrogen peroxide; silver alloys are exposed to vapours of nitric acid. Procedures for transfer, ring oven separation and identification of alloy constituents in the sample solutions are described.     

The Photochemistry of Diazomethane the Reactions of Methylene with Toluene and P-Xylene in Liquid Phase (I)

The photochemistry of diazomethane in toluene and p-xylene solutions was investigated. The reactions of methylene with toluene gave eight products. In the diazomethane p-xylene solution, p-ethyltoluene, 1,2,4-trimethylbenzene, 1,4-dimethylcyclohepatriene-1,3,5 and three unidentified compounds were found as products of the reaction of methylene with p-xylene. The relative rates of addition and insertion reaction of methylene with toluene and p-xylene have been calculated.     

Dynamics of charge transfer states on metal surfaces: the competition between reactivity and quenching

The dynamics of excited states of adsorbates on surfaces caused by charge transfer is studied. Both negative and positive charge transfer processes are possible. In particular we are interested in positive charge transfer from a metal surface to molecular or atomic oxygen adsorbed on the surface. Once the negatively charged oxygen on the surface loses an electron it becomes chemically activated. The ability of this species to react depends on the quenching time or back transfer. The analysis of these processes is based on a set of diabatic potential energy surfaces each representing a different charged oxygen species. The dynamics is followed by solving the multichannel time-dependent Schr?dinger equation or Liouville von Neumann equation. Due to the nonadiabatic character of these reactions large isotope effects are predicted.     

The RS-.HSR Hydrogen Bond: acidities of alpha,omega-dithiols and electron affinities of their monoradicals

Gas-phase acidities (deltaGo(acid)) have been measured for 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol, using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Adiabatic electron affinities (EAs) of the thiolate monoradicals of these compounds were assigned from electron photodetachment spectra of their corresponding thiolate monoanions, acquired using a cw-ICR. The dithiols exhibit enhanced acidities (up to 8.7 kcal/mol in deltaGo(acid)) and greater EAs (up to 6.7 kcal/mol) than analogous monothiol species. These differences are attributed to an intramolecular RS-.HSR hydrogen bond in the thiolate anion. Considerations of the RO-.HOR hydrogen bond in monoanions of alpha,omega-diols and in the [CH(3)O-.HOCH(3)] complex anion suggest that the RS-.HSR hydrogen bond provides up to 9 kcal/mol extra stabilization.     

Theoretical study of the effect of frit quality on chromatography using computational fluid dynamics

Summary Frits at both ends of a chromatographic column, especially for a preparative column, have significant influence on the flow distribution within the column and thus the column efficiency. However, frits have received little attention from chromatographers in the past. Here a theoretical study was conducted with the aid of CFD software FLUENT to investigate the effect of frits on the performance of homogeneous and heterogeneous chromatographic columns. A dimensionless number,FQ, was applied to characterize frit quality. This study visualized how frit quality affects the flow distribution and the concentration band, the shape of eluted pulse at the colum exit and column efficiency. Simulation results show that the development length of the flow distribution is related toFQ but has nothing to do with the packing heterogeneity. The curvature of the concentration band in a column depends onFQ and packing quality. This study shows column efficiency can be improved significantly by increasingFQ and/or frit permeability.     

Analytical Application of Silica Gel Modified with Didecylaminoethyl-beta-Tridecylammonium Iodide

Sorption of a high molecular weight quaternary ammonium salt, didecylaminoethyl-β-tridecylammonium iodide (DDATD) on different types of sorbents was investigated. The nature of reagent adsorption on silica gel was examined by spectroscopic and computer methods. The sorption of anionic metal complexes of cobalt, copper, zinc and manganese on silica gel modified with DDATD was studied. The possibility of recovery of cobalt and copper thiocyanate complexes and their further atomic absorption determination is shown. Modified sorbent was applied to cobalt chemiluminescence and determined in natural water and a nickel preparation (detection limit, 2 μg/l.).     

Preparation of acetylmercapto-3-carboxypropanoyl insulins using preparative high-performance liquid chromatography on an anion-exchange column.

A method for the preparation of insulin derivatives which have protected sulfhydryl group(s) at definite site(s) on the molecule is described. Porcine insulin reacts with S-acetylmercaptosuccinic anhydride to afford four species of insulin derivatives that have 2 (or 3)-acetylmercapto-3-carboxypropanoyl group(s) at i) Gly(A1), ii) Gly(A1) and Phe(B1), iii) Gly(A1) and Lys(B29), and iv) Gly(A1), Phe(B1) and Lys(B29) positions. The derivatives are efficiently separated in a preparative scale by anion-exchange high-performance liquid chromatography on a TSKgel DEAE-2SW column. The four derivatives are all readily deacetylated with hydroxylamine to give the corresponding sulfhydryl insulin derivatives.     

The crystal structure and absolute configuration of the antitumor platinum complex trans(OH)-Pt(OH)2(malonato)(1R,2R-cyclohexanediamine).

The absolute configuration of the anti-tumor complex trans(OH)-Pt(OH)2(malonato)(1R,2R-cyclohexanediamine) was determined by X-ray anomalous scattering technique. The final unit cell was monoclinic, space group P2(1) with a = 9.142 A, b = 7.788 A, c = 11.946 A, beta = 96.48 degrees, Z = 2. The crystal structure was determined by direct method and difference Fourier synthesis, and refined to R = 0.025 and Rw = 0.033 based on 2768 independent reflections. The platinum atom has roughly octahedral coordination. The cyclohexane ring has the expected chair configuration, with two amino groups in equatorial positions while the malonato ligand, in contrast, shows a boat conformation for six membered Pt O-C-C-C-O ring.