Nickel peroxide: A more probable intermediate in the Ni(II)‐catalyzed decomposition of peroxomonosulfate

The Ni(II) ion catalyzed thermal decomposition of peroxomonosulfate (PMS) was studied in the pH range 3.42–5.89. The rate is first order in [PMS] and Ni(II) ion concentrations. At pH greater than or equal to 5.23, the reaction becomes zero order in [PMS] and this changeover in the order of the reaction occurs at a higher concentration of nickel ions. The first‐order kinetics in PMS can be explained as a rate‐limiting step and is the transformation of nickel peroxomonosulfate into nickel peroxide. This peroxide intermediate reacts rapidly with another PMS to give oxygen and Ni(II). The formation of nickel peroxide is associated with a small negative or nearly zero entropy of activation. The zero‐order kinetics in [PMS] can be explained by the fact that the hydrolysis of aquated nickel(II) ions into hydroxocompounds is the rate‐limiting step. The turnover number is 2 at pH 3.42 and increases with pH. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 320–237, 2007     

Statistical characteristics of quasi-elastically scattered light in analysis of size of aggregated biological particles

The spectra of the intensity fluctuations of light scattered by large (erythrocytes of whole blood) and small (vesicles of surgical bile) particles in natural conditions were studied. It is shown that photon correlation spectroscopy can be used in analysis of variations in the size of biological particles in normal and pathological conditions and as an express method of noninvasive diagnostics of diseases.     

Inner-sphere oxidation of iron(II) by tris(malonato)cobaltate(III)

The kinetics of oxidation of Fe²⁺ by [Co(C₃H₂O₄)₃]^3? in acidic solutions at 605 nm showed a simple first-order dependence in each reactant concentration. The second-order rate constant dependence on [H⁺] is in accordance with eqn (i) k₂ = k′₂ + k₃[H⁺] (i) where k′₂ and k₃ have values of 73.4 ± 14.0 M ^?1 s^?1 and 353 ± 41 M^?2 s^?1, respectively, at 1.0 M ionic strength (NaClO₄) and 25°C. At 310 nm the formation and decomposition of an intermediate, believed to be [FeC₃H₂O₄]⁺, was observed. The increase in the rate of oxidation with increasing [H⁺] was interpreted in terms of a “one-ended” dissociation mechanism which facilitates chelation of Fe₂₊ by the carbonyl oxygens of malonate in the transition state.     

Characteristics of thermoradiative destruction of BaS2O6·2H2O

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 55, No. 4, pp. 613–618, October, 1991.     

Riemannian Hilbert submanifolds of nonpositive extrinsic curvature

We consider strongly parabolic, Hilbert submanifolds in Riemannian Hilbert manifolds. We prove that their properties are analogous to the known properties in the finite-dimensional case. The main geometric result consists of Theorem 3: a complete, Riemannian, Hilbert submanifold of nonpositive extrinsic curvature and finite codimension in a Hilbert sphere is a great sphere.Translated from Ukrainskii Geometricheskii Sbornik, No. 33, pp. 91–100, 1990.The author expresses his thanks to Professor A. A. Borisenko for posing the problem and guiding the work.     

The large-particle method in arbitrary nets and its application to the solution of problems in the aeroelasticity of a parachute

Modifications are introduced into the large-particle method to make it possible to use the method in arbitrary nonrectangular computing nets in the study of the flow of an ideal compressible gas over mobile thin permeable membranes. A problem in the aeroelasticity of a parachute is stated. An example is given of the solution of a problem in the stationary formulation for an axially symmetric parachute in the wake of a cylindrical leading body for supersonic flow.Translated fromDinamicheskie Sistemy, No. 6, 1987, pp. 16–22     

High-frequency asymptotics of acoustic pressure for bounded wave beam scattering by an elastic sphere

Asymptotic high-freqeuncy estimates are obtained for the amplitudes of specular and non-specular reflections with extraction of the contribution of sound reradiation into the surrounding medium by Rayleigh type surface elastic waves. The conditions are found that govern the magnification of scattering in the opposite direction. The theoretical explanation of the book reflection effect /1/ for bounded sound beam incidence on the plane interface of a fluid-elastic solid is given by many authors in different situations (/12/, say). As for non-specular reflection of a plane sound wave by bounded elastic bodies (plates, cylinders, rods, and shells enclosed in a screen), studied most thoroughly in /3–9/, this effect is a consequence of satisfying the space-time resonance conditions between the incident acoustic wave and the normal surface waves excited in an elastic solid under total internal reflection.     

A new group of fluorescent pH-indicators for an extended pH-range

Summary The pH versus fluorescence intensity profiles of a series of new pH-indicators are reported. They are characterized by two pK_a-values in the 3.7–4.9 and 6.9–7.9 range, respectively. The strong change in fluorescence intensity with pH allows the determination of pH's over a much wider range (typically 2–9) than with one-step indicators. They are therefore considered to be of potential utility for measurement of pH over the neutral and slightly acidity range which occurs, for instance, in bioliquids such as urine.

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Eine neue Gruppe fluorescierender pH-Indicatoren für einen erweiterten pH-Bereich

Zusammenfassung Die Fluorescenzintensitätsprofile als Funktion des pH-Wertes einer Reihe von neuen pH-Indicatoren werden untersucht. Sie sind charakterisiert durch zwei pK_a-Werte im Bereich 3,7–4,9 bzw. 6,9–7,9. Die gefundene starke Änderung der Fluorescenzintensität mit dem pH-Wert erlaubt eine pH-Bestimmung über einen viel weiteren Bereich (typischerweise 2 – 9) als mit einstufigen Indicatoren. Aus diesem Grund werden sie als potentiell nützlich angesehen zur Messung von pH-Werten im neutralen und schwach sauren Bereich, wie er z.B. in biologischen Flüssigkeiten, etwa im Urin, gegeben ist.