Role of dimethyl sulfoxide as a solvent for vinyl polymerization

Dimethyl sulfoxide has been used as a solvent in the polymerization of methyl methacrylate and styrene. The chain-transfer coefficients of the solvent and the values of δ [i.e., (2k_t)^1/2/k_p] in solvent-monomer mixtures of various compositions were determined. δ was observed to be dependent on the solvent concentration in the case of methyl methacrylate but remained constant in case of styrene. The lowering of the values of δ with increasing solvent concentration in case of methyl methacrylate has been attributed to an interaction between the solvent and poly(methyl methacrylate) radical resulting in lower termination rate.     

NS and NSO-Donor ligands and their metal complexes. Synthesis and characterisation of a new low-spin iron(III) complex with 1,2-di(o-aminophenylthio)ethane and iron(III), cobalt(III) and manganese(III) complexes of 1,2-di(o-salicylaldiminophenylthio)ethane

Summary Iron(III) complexes of a quadridentate N₂S₂ donor ligand, 1,2-di(o-aminophenylthio)ethane (DAPTE) and its Schiff Base with salicylaldehyde, a hexadentate N₂S₂O₂ donor ligand,viz. 1,2-di(o-salicylaldiminophenylthio)ethane (H₂DSALPTE) have been synthesised and characterised.The Schiff base ligand (1 mol) gave a dark green tri-iron(III) [Fe₃(DSALPTE)(HDSALPTE)Cl₃]Cl₂ complex when reacted with anhydrous iron(III) chloride (1 mol). The Mössbauer data of this complex suggest the presence of three iron sites, one of which is octahedral and the other two tetrahedral. On the other hand, Fe(ClO₄)₃ reacted smoothly with H₂DSALPTE in ethanol to give a mononuclear pseudo-octahedral complex in which the ligand functions in a dibasic hexadentate fashion. Mössbauer data suggest the presence of a low-spin-high-spin equilibrium in the solid state. The manganese(III) and cobalt(III) complexes of the Schiff base, H₂DSALPTE, are also studied for the sake of comparison with the corresponding iron(III) complex. The N₂S₂ ligand, however, formed a low-spin pseudo-octahedral iron(III) complex. The complexes have been characterised by elemental analysis, molar conductance values, cryomagnetic data and i.r., electronic and Mössbauer spectral data.     

Thermodynamics of silver—silver halide electrodes and thermodynamic solubility products of silver halides in glycerol + water mixtures at different temperatures

The standard potentials of silver—silver bromide and silver—silver iodide electrodes in glycerol+water mixtures containing 5, 10, 20 and 30 wt% glycerol were determined from electromotive force measurements of the cell Ag(s), AgX(s), KX(c)//KCl(c), AgCl(s), Ag(s), where X is Br or I, at seven different temperatures in the range 5–35°C. The standard potentials in each solvent are represented as a function of temperature. The standard thermodynamic functions for the electrode reactions, the primary medium effects of various solvents upon X⁻, and the standard thermodynamic quantities for the transfer of 1 g-ion of X⁻ from water to the respective glycerol + water media are evaluated and discussed in the light of ion—solvent interactions as well as the structural changes of the solvents. From the values of the Ag/Ag⁺ and Ag/AgX, X⁻ electrodes, the thermodynamic solubility product constants of silver chloride, silver bromide and silver iodide have been determined in glycerol + water solvent mixtures at different temperatures.     

Standard<Emphasis Type="Italic">SU</Emphasis>(5) supergravity grand unification model and predictions

A review is given of the StandardSU(5) supergravity model. This model has passed an important check regarding unification of the electro-weak and the strong couplings using high precision LEP data. It is shown that for a significant domain of the parameter space the model also satisfies constraints on the SUSY spectrum from CDF and LEP, as well as proton stability and cosmological relic density constraints.     

MoSe2 and WSe2 nanotubes and related structures

MoSe2 and WSe2 nanotubes are obtained by the reduction of the corresponding triselenides in hydrogen or by the decomposition of the ammonium selenometallates in a hydrogen atmosphere.     

Spectrophotometric studies on the zirconium complex of 2-(3,6-disulfo-8-hydroxynaphthylazo)-1,8-dihydroxynaphtualene-3, 6-disulfonic acid

Summary A chromotropic azo dye, DSNADNS, prepared from chromotropic acid and 1-amino-8-naphthol-3,6-disulfonic acid has been found to produce quantitative precipitation of zirconium in acid medium. The blue-violet complex formed is insoluble in all organic solvents commonly used for solvent extraction work, but is soluble in a number of liquid organic bases and solutions of ammonium salts in water showing pink to violet colouration. Spectrophotometric studies as to the nature of the complex in pyridine, triethanolamine ammonium acetate, oxalate and carbonate solutions and the analytical possibility of these solutions have been made. The complex appears to decompose in pyridine, ammonium acetate and ammonium oxalate solutions, but it is fairly stable in ammonium carbonate and triethanolamine solutions. The absorbance peaks of the dye in these solutions occur at 500 and 520 nm respectively, while the complex in triethanolamine and ammonium carbonate both shows absorbance maxima at 540 nm. The solution of the complex in these two solvents obeys Beer's law within a concentration range 4 to 25 mg of zirconium per litre. The molar absorbance coefficients of the complex in triethanolamine and ammonium carbonate are respectively 686 and 823, which indicate poor sensitivity. The solution of the complex in the former solvent is more stable than that in the latter and an analytical procedure for the spectrophotometric determination of zirconium, with little interference from foreign ions, may be developed with ease in the triethanolamine solution.

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Zusammenfassung Ein Azofarbstoff der Chromotropsäure, DSNADNS, der aus Chromotropsäure und 1-Amino-8-naphthol-3,6-disulfonsäure dargestellt werden kann, ergibt mit Zirkonium in saurer Lösung eine quantitative Fällung. Der blauviolett gefärbte Komplex ist in allen üblichen organischen Lösungsmitteln unlöslich, löst sich jedoch in einigen flüssigen organischen Basen sowie wäßrigen Lösungen von Ammoniumsalzen mit rosa bis violetter Färbung. Die Lösungen des Komplexes in Pyridin, Triäthanolamin sowie in Ammoniumacetat, -oxalat und -carbonatlösungen und ihre analytische Verwendbarkeit werden spektrophotometrisch untersucht. In Pyridin sowie in Ammoniumacetat und -oxalatlösungen scheint sich der Komplex zu zersetzen, während er in Triäthanolamin und Ammoniumcarbonatlösungen ziemlich beständig ist. Das Absorptionsmaximum des Farbstoffs in diesen beiden Lösungsmitteln liegt bei 500 bzw. 520 nm, der Komplex weist in beiden Fällen ein Maximum bei 540 nm auf. Das Beersche Gesetz wird in beiden Lösungsmitteln von 4–25 mg Zr/l erfüllt. Der molare Absorptionskoeffizient beträgt 686 bzw. 823. Die Lösung des Komplexes in Triäthanolamin ist stabiler als in Ammoniumcarbonatlösung. Eine spektrophotometrische Bestimmung von Zirkonium, die nur wenig von Fremdionen gestört wird, könnte daher gut in Triäthanolaminlösung durchgeführt werden.

     

Electron impact induced fragmentation of some 1,2,4-triazole derivatives

The mass spectra of eight 1,2,4-triazole derivaties have been recorded and found tao reveal extensive hydrogen and skeletal migrations. The structures of the fragments have been confirmed by deuterium labelling and exact mass measurement. The compounds revealed striking differences in their spectra depending on the nature of the substituents.