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     

The solution of a convection–diffusion–reaction equation arising from cathodic reduction in a pulsating crack

This paper derives the convection–diffusion-reaction equation governing the reaction between the dissolved oxygen in sea-water and the steel walls of a pulsating crack. By the neglect of the diffusion term it is shown that an exact solution of the convection-reaction equation can be obtained. A numerical method for the solution of the complete convection–diffusion-reaction equation is derived by the use of finite differences. The numerical computation of the initial transient and the final periodic steady-state values is also discussed.     

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.     

Vortices in the superconducting transition of the 2+1 Abelian Higgs model

We study the phase transitions to the Higgs phase of the finite temperature 2+1 dimensional Abelian Higgs model in terms of Ginzburg-Landau vortices. We find that vorticity is a good order parameter which allows us to determine the order of the transitions.     

Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al2O3 catalysts

Four NiMo catalyst supported on Al₂O₃ with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 Å for HDS and HDN.     

Study of the structural and optical properties of GaN/AlN quantum dot superlattices

We study GaN/AlN Quantum Dot (QD) superlattices utilizing the STREL environment which allows the building of atomistic models, relaxation of the structures, the calculation of the electronic states and optical transitions and the visualization of the results. The forces are calculated using an appropriate Keating or Stillinger–Weber interatomic potential model and the electronic states and optical transitions using a tight-binding formulation which is economical and produces realistic electronic properties. The relaxed structure has strains mainly in the GaN region which are compressive and small tensile strains in the AlN region, mainly below the QD. In the calculation of the electronic states and of the optical transitions the strains are included realistically at the atomistic level. The study of the wavefunctions close to the fundamental gap show how these strains influence the form and spatial extent of the wavefunction. Very close to the fundamental gap the valence and some conduction states are confined in the QD and have considerable oscillator strength.     

Phase modulation of the signal beam in three-wave forward mixing in photorefractive bismuth silicon oxide

The interaction of three forward beams in a BSO crystal is investigated under conditions when the two pump beams are anti-symmetrically detuned and the signal beam is phase modulated. For sinusoidal phase modulation the signal gain is shown to be dependent on the instantaneous frequency detuning. Single and double maxima in gain are obtained depending on the voltage amplitude applied to the piezoelectric mirror. For triangular phase modulation a slight asymmetry is found in the gain versus detuning curve.     

High pressure mössbauer studies of magnetic actinide systems

Due to the wider radial extent of 5f electrons when compared to their 4f counterparts, intermetallics of the light actinides show a broad spectrum of magnetic properties ranging from the localized magnetism of the lanthanides to the itinerant magnetism often found in transition metal compounds. One parameter which strongly influences the magnetic character of the compound is the actinide-actinide separation which can experimentally be varied by the application of high pressure. The question of 5f electron delocalization will be reviewed with respect to Moesshauer high pressure data on NpCo₂si₂, NpAl₂, NpOs₂ and new results will be presented of NpAs. The connection of hyperfine parameters with results of X-ray diffraction studies will be discussed.Work supported by the Bundesministerium für Forschung und Technologie, Federal Republic of Germany