Spectral and voltammetric studies on titanium substituted Keggin-type heteropolyanions

Bonding and redox properties of mono- and dititanium substituted 12-heteropolytungsto-phosphates and their complexes with bivalent Mn, Co, Ni and Cu are studied by UV-Vis, ESR and cyclicvoltammetric techniques. The heteropoly blue analogue [Ti^IIITi^IVW₁₀PO₄₀]⁸⁻ is unstable and its presence in solution is proved by optical and ESR spectroscopy. ESR results reveal that the odd electron is trapped on the titanium atom at 77 K. The optical electronegativity of Ti(III) in this heteropoly blue is estimated to be 2.4 from the intervalence charge transfer (IVCT) bands. X-ray powder diffraction results show that the complexes K₅M^II[Ti₂W₁₀PO₄₀].xH₂O(M^II = Cu or Mn) are isomorphous with K₇[Ti₂W₁₀PO₄₀].6H₂O. Electronic spectroscopy indicates very high symmetry around the bivalent metal ion M in the K₅M^II[Ti₂W₁₀PO₄₀].xH₂O complexes. This high symmetry is confirmed in K₅Cu[Ti₂W₁₀PO₄₀] by the observation of dynamic Jahn-Teller (JT) distortion at 300 K and static JT distortion at 77 K.     

Bromination of 4-substituted thiazolylhydrazones

4-Phenyl- and 4-methylthiazolylhydrazones were brominated in chloroform and acetic acid. The use of 1.5 equivalents of bromine led to the exclusive formation of the 5-halo derivatives. Effects of substituents on the thiazole ring and of the hydrazone fragment aromatic ring on the course of the reaction were discovered.Urals State Technical University-UPI, 620002 Yekaterinburg. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 991–995, July, 1995. Original article submitted March 1, 1995.     

Pulsed gas lenses

The concept of a pulsed gas lens is proposed. Potential applications are envisaged and preliminary experiments with pulsed ray refraction are reported.     

FFT solution of the Robbins problem

An FFT method is described for the solution of Poisson's equationover a rectangular region with Robbins boundary conditions oneither one or two sides of the region, together with suitableconditions on the rest of the boundary. In contrast to earlierapplications of the FFT technique, the equations for the Fourierharmonic amplitudes do not decouple into simpler independentsystems and an effective iterative scheme is developed for thesolution of these equations. A theoretical convergence analysisis shown generally to support the results obtained from practicalcomputation. For the test problems considered the method isfound to take between 3 and 4 times the execution time for problemssoluble directly by the FFT technique.     

The dynamics of desorption induced by atomic hydrogen: HD/Cu(111)

Recent observations of a direct reaction between adsorbates and hydrogen atoms incident from the gas phase are interpreted in terms of an Eley-Rideal reaction. A detailed comparison of the experimental data for the HD/Cu(111) system with quantum mechanical model calculations corroborates such an interpretation. The peculiar isotope effect observed can be understood from the different dynamical implications of appropriately rescaled potential energy surfaces. The width of the measured time-of-flight spectrum is explained from the overlapping contributions of the populated vibrational levels. The angular distributions are rationalized by contributions both from ‘indirect’ events, where the incident atoms make several bounces in the surface well prior to reaction, and ‘direct’ reactive events.     

Optimal Domains for <Emphasis Type="Italic">L</Emphasis><Superscript>0</Superscript>-valued Operators Via Stochastic Measures

We study extension of operators T: E→ L⁰([0, 1]), where E is an F–function space and L⁰([0, 1]) the space of measurable functions with the topology of convergence in measure, to domains larger than E, and we study the properties of such domains. The main tool is the integration of scalar functions with respect to stochastic measures and the corresponding spaces of integrable functions. Partially supported by D.G.I. #MTM2006-13000-C03-01 (Spain).     

Electrooxidation of carbo/thiocarbohydrazide and their hydrazone derivatives at a glassy carbon electrode

Electrochemical oxidation of thio/carbohydrazide and their hydrazone derivatives Benzaldehyde thiocarbohydrazone [BTCH] diacetylene thiocarbohydrazone [DATCH] have been studied in Brit-ton Robinson buffer in aqueous and nonaqueous media at a glassy carbon electrode. The effects of pH, sweep rate, concentration, temperature and surfactants have been studied. The complex bis (carbo/thiocabohydrazide) Zn(II) chloride was also subjected to voltammetric analysis in order to understand the reactivity both in free and metal bound states. The reaction conditions were optimized for the determination of above compounds in micrograms quantities by differential pulse voltammetry, analytical utility of this investigation is also highlighted.     

Rare‐earth site splitting in Sm3MoO7

Trisamarium molybdenum heptaoxide, Sm₃MoO₇, is isomorphous with Ln₃MoO₇ (Ln = La and Pr). The crystal structure consists of chains of corner‐linked MoO₆ octahedra running parallel to the b axis and separated from each other by seven‐ or eight‐coordinate Sm–O polyhedra. In contrast to La₃MoO₇ and Pr₃MoO₇, a splitting of one Sm site into two positions is observed.     

X-ray fluorescence determination of bromine in halogenated organic compounds using quasisolid emitters

A series of quasi-solid emitters is proposed for the X-ray fluorescence determination of bromine in different bromine-containing compounds. It is shown that sucrose-based glasses are the best emitters for analyzing alkali solutions of halogenated organic compounds, saccharose-based glasses and polymer films are best for analyzing powder samples, and organic gels offer most promise for analyzing liquid (at normal conditions) samples. It is noted that the proposed method can expand the possibilities of commercially produced element analyzers, which are currently intended for determining only C, H, O, N, and S in organic compounds and cannot be used for determining halogens.