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.     

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.     

Ion structure determinations and ion—molecule reactions by double quadrupole mass spectrometry

The QQ mass spectrometer is shown to be applicable to ion structure determination via collision-induced dissociations of mass-selected ions. The instrument can be scanned so as to record the products of dissociation as well as those of ion—molecule association reactions. The dissociations correspond to those observed at high kinetic energy in mass-analyzed ion kinetic energy spectrometers and the association reactions show parallels with reactions seen in ion cyclotron resonance spectroscopy and in high-pressure mass spectrometry     

Molecular orbital momentum distributions and binding energies for nitric oxide

Binding energy spectra of the valence electrons of the open shell molecule NO have been obtained up to 55 eV at azimuthal angles of 0° and 7° using binary (e, 2e) spectroscopy at an impact energy of 1200 eV. The momentum distribution has been obtained for the least tightly bound (unpaired) electron, removal of which leads to formation of the X ¹Σ⁺ ground state of NO⁺. Momentum distributions have also been measured at 21.0 and 40.5 eV. The measured momentum distributions are compared with several literature wavefunctions of varying complexity. They are found to be in excellent agreement with those calculated using the natural spin orbital wavefunctions of Kouba and Ohrn.     

Properties of reflected sunlight derived from a Green's function method

The inference of optical depth and particle size of clouds and aerosols using remotely sensed reflected radiance at solar wavelengths has received much attention recently. The information these measurements provide is path integrated. However, very little is known about the vertical distribution of this weighting. To characterize it, we first solve the radiative transfer equation (RTE) by a Green's function approach, and then investigate the sensitivity of the weighting to vertical inhomogeneities in the extinction by introducing a function that is closely related to the Green's function, herein called the contribution function. This function calculates the contributions to the radiance at the upper boundary of the medium by underlying layers. Three hypothetical clouds of identical optical depth but exhibiting different extinction profiles were used in this study. The contribution function was found very sensitive to the extinction profile. The global reflection and transmission matrices used to construct the Green's function, derived using an eigenmatrix method, resulted in an efficient, stable, and accurate method for calculating the emerging radiances that can be extended to multi-layered media.     

The role of water vapour on the oxidation of two Ln-Si-Al-O-N glasses (Ln=Y, La)

The oxidation behaviour of LnSiAlON (Ln=Y, La) glasses was studied at different temperatures (990-1150 °C) and under different water vapour pressures (360-2690 Pa). These results were also compared with those obtained under O₂, N₂/H₂O or O₂/H₂O mixtures. When glasses are treated under a N₂/H₂O mixture, optical and SEM observations show porous scales. Transformations of the reaction rate data and a kinetic model show that there is only one limiting process occurring during oxidation. This rate limiting step is the progress of the chemical reaction at the internal interface. Determination of the pressure law dependence and thermodynamics calculations of water vapour molecules dissociation at the investigated temperatures allow us to suggest that the mechanism of oxidation corresponds to decomposition of water molecules on the oxynitride glass surface.