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     

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     

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.

     

Excess noise peaks in porous silicon-based diode structures

Results of an experimental observation of the voltage oscillations associated with a discrete tunneling of holes in porous silicon at room temperature are presented. The noise characteristics of diode structures with a porous silicon interlayer formed on heavily boron-doped silicon single crystals are studied. Peaks of excessive noise are observed at frequencies of ～1 MHz, at which single-electron oscillations should be expected. The peak noise power is found to increase with current according to the ～2.5 power law and, at a current density of 0.15 A/cm², to exceed the noise power of the receiver by three to four orders of magnitude. The complex shape of the noise spectrum and its extension to the higher frequency region with increasing current are explained by the three-dimensionality of the system of nanometer-sized silicon grains embedded in insulating silicon dioxide of porous silicon.