Kinetics and mechanism of oxidation of β-Alanine by <Emphasis Type="Italic">N</Emphasis>-bromophthalimide in the presence of Ru(III) chloride as homogenous catalyst in acidic medium

The kinetics of Ru(III) chloride-catalyzed oxidation of β-Alanine (NH₃ ⁺CH₂CH₂COOH, β-Ala) by N–bromophthalimide (NBP) in aqueous perchloric acid medium was studied at 35 °C. The rate law followed a first-order and zero-order dependence with respect to [NBP] and [β-Ala], respectively. The reaction followed first-order kinetics with respect to [Ru(III)] chloride at a range of low concentrations while the order changed from first- to zero-order at high concentration of [Ru(III)] chloride; demonstrating the catalytic effect for the oxidation of β-Ala by NBP. The rate decreased with increase in acidity. Chloride ions positively influenced the rate of the reaction. Neither phthalimide (NHP) nor Hg(II) influenced the reaction rate. Ionic strength (I) and dielectric constant (D) of the medium had no significant effect on the rate. Activation parameters of the reactions were determined by studying the reaction at different temperatures (30–50 °C). The colorimetric, FTIR, and GC-MS techniques were used to identify methyl cyanide (CH₃CN) and CO₂ as products of the reaction. In the reaction, approximately 2.3 moles of NBP oxidized one mole of β-Ala. A reaction scheme of the oxidation of β-Ala by NBP in the presence of Ru(III) chloride was found to be in consistent with the rate law and the reaction stoichiometry.     

Thermal studies of some biologically active oxovanadium(IV) complexes containing 8-hydroxyquinolinate and hydroxamate ligands

The thermal decomposition behaviours of oxovanadium(IV)hydroxamate complexes of composition [VO(Q)_2?n(HL^1,2)_n]: [VO(C₉H₆ON)(C₆H₄(OH)(CO)NHO)] (I), [VO(C₆H₄(OH)(CO)NHO)₂] (II), [VO(C₉H₆ON)(C₆H₄(OH)(5-Cl)(CO)NHO)] (III), and [VO(C₆H₄(OH)(5-Cl)(CO)NHO)₂] (IV) (where Q?=?C₉H₆NO^? 8-hydroxyquinolinate ion; HL¹?=?[C₆H₄(OH)CONHO]^? salicylhydroxamate ion; HL²?=?[C₆H₃(OH)(5-Cl)CONHO]^? 5-chlorosalicylhydroxamate ion; n?=?1 and 2), which are synthesised by the reactions of [VO(Q)₂] with predetermined molar ratios of potassium salicylhydroxamate and potassium 5-chlorosalicylhydroxamate in THF?+?MeOH solvent medium, have been studied by TG and DTA techniques. Thermograms indicate that complexes (I) and (III) undergo single-step decomposition, while complexes (II) and (IV) decompose in two steps to yield VO(HL^1,2) as the likely intermediate and VO₂ as the ultimate product of decomposition. The formation of VO₂ has been authenticated by IR and XRD studies. From the initial decomposition temperatures, the order of thermal stabilities for the complexes has been inferred as III?>?I > II?>?IV.     

Thermoanalytical studies of oxovanadium(IV)hydroxamate complexes

The thermal decomposition behavior of oxovanadium(IV)hydroxamate complexes of composition [VO(acac)(C₆H₅C(O)NHO)] (I), [VO(C₆H₅C(O)NHO)₂] (II), [VO(acac)(4-ClC₆H₄C(O)NHO)] (III), [VO(4-ClC₆H₄C(O)NHO)₂] (IV) (where acac = (CH₃COCHCOCH₃ ^–) synthesized from the reactions of VO(acac)₂ with equi- and bimolar amounts of potassium benzohydroxamate and potassium 4-chlorobenzohydroxamate in THF + MeOH solvent medium has been studied by TG and DTA techniques. TG curves indicated that complexes I, II, and IV undergo decomposition in single step to yield VO₂ as the final residue, while complex III decomposes in two steps to yield VO(acac) as the likely intermediate and VO₂ as the ultimate product of decomposition. The formation of VO₂ has been authenticated by IR and XRD studies. From the initial decomposition temperatures, the order of thermal stability for the complexes has been inferred as IV > I > III > II.     

Fano Resonant Cuboidal Dielectric Nanoantennas

Optics and Spectroscopy - In this paper, we report Fano resonance in the dielectric disk and rod cuboidal nanoparticles. In these nanoparticles, forward to backward scattering ratio is enhanced as...     

An implementation of the Spalart–Allmaras DES model in an implicit unstructured hybrid finite volume/element solver for incompressible turbulent flow

In this paper, we describe an implicit hybrid finite volume (FV)/element (FE) incompressible Navier–Stokes solver for turbulent flows based on the Spalart–Allmaras detached eddy simulation (SA‐DES). The hybrid FV/FE solver is based on the segregated pressure correction or projection method. The intermediate velocity field is first obtained by solving the original momentum equations with the matrix‐free implicit cell‐centered FV method. The pressure Poisson equation is solved by the node‐based Galerkin FE method for an auxiliary variable. The auxiliary variable is closely related to the real pressure and is used to update the velocity field and the pressure field. We store the velocity components at cell centers and the auxiliary variable at vertices, making the current solver a staggered‐mesh scheme. The SA‐DES turbulence equation is solved after the velocity and the pressure fields have been updated at the end of each time step. The same matrix‐free FV method as the one used for momentum equations is used to solve the turbulence equation. The turbulence equation provides the eddy viscosity, which is added to the molecular viscosity when solving the momentum equation. In our implementation, we focus on the accuracy, efficiency and robustness of the SA‐DES model in a hybrid flow solver. This paper will address important implementation issues for high‐Reynolds number flows where highly stretched elements are typically used. In addition, some aspects of implementing the SA‐DES model will be described to ensure the robustness of the turbulence model. Several numerical examples including a turbulent flow past a flat plate and a high‐Reynolds number flow around a high angle‐of‐attack NACA0015 airfoil will be presented to demonstrate the accuracy and efficiency of our current implementation. Copyright © 2008 John Wiley & Sons, Ltd.     

Evaluation of kinetic parameters for oxidation of thioacids by benzimidazolium dichromate: A mechanistic study

In a non-aqueous medium, oxidation kinetics of thioglycolic, thiolactic and thiomalic acids by benzimidazolium dichromate have been studied. In the temperature range of 20°C–50°C, oxidation kinetics were examined by spectrophotometry. In terms of oxidant, the reaction is dependent on the unitary order. In the case of thioacids, we find the Michaelis-Menten type kinetics. Hydrogen-ions act as catalyst in this process. The reaction rate slows down as the Mn²⁺ ion concentration increases. The reaction does not cause acrylonitrile to polymerize. The formation of a thioester into the pre-equilibrium followed by its progressive degradation was postulated as a mechanism.     

Kinetic study of the ruthenium(III)-catalyzed oxidation of glycine by <Emphasis Type="Italic">N</Emphasis>-bromophthalimide in acidic medium

The kinetics of ruthenium(III) chloride-catalyzed oxidation of glycine by N–bromophthalimide (NBP) was studied in aqueous perchloric acid at 35 °C. The results showed first- and zero-order behavior with respect to NBP and Gly, respectively. Ru(III) showed a catalytic effect on the reaction which followed first-order kinetics with respect to [Ru(III)] at a low concentration range and tended to zero order at high concentration range. The rates decreased with increase in the proton concentration, while chloride positively influenced the rate of the reaction. Two moles of NBP were required to oxidize one mole of Gly, and the products were identified as phthalimide (NHP), HCN, CO₂, and Br⁻. Neither added NHP nor Br⁻ influenced the reaction rate. Ionic strength and dielectric constant of the medium had no significant effect on the rate. Activation parameters were determined by studying the reaction at different temperatures. A reaction scheme of the catalytic oxidation is proposed.     

Solidification and microstructural aspects of laser-deposited Ni-Mo-Cr-Si alloy on stainless steel

Laser cladding of stainless steel substrate was carried out using Ni-32Mo-15Cr-3Si (wt%) alloy powder. Laser cladding parameters were optimized to obtain defectfree and metallurgically bonded clad. Variation in solidification rate, cooling rate and compositional variation resulted in heterogeneous microstructure. Microstructure was found to be distinctly different in regions of clad cross-section. Majority of the region was found to consist of eutectic of Mo-rich hcp intermetallic Laves phase and NiFe fcc gamma solid solution phases. Extensive microstructural examinations of different clad regions have been carried out using microscopy and microanalysis techniques.     

Effect of dust particles on a layer of micropolar ferromagnetic fluid heated from below saturating a porous medium

The problem of the effect of dust particles on the thermal convection in micropolar ferromagnetic fluid saturating a porous medium subject to a transverse uniform magnetic field has been investigated theoretically. Linear stability analysis and normal mode analysis methods are used to find an exact solution for a flat micropolar ferromagnetic fluid layer contained between two free boundaries. In case of stationary convection, the effect of various parameters like medium permeability, dust particles, non-buoyancy magnetization, coupling parameter, spin-diffusion parameter and micropolar heat conduction parameter are analyzed. For sufficiently large values of magnetic parameter M₁, the critical magnetic thermal Rayleigh number for the onset of instability is determined numerically and results are depicted graphically. It is also observed that the critical magnetic thermal Rayleigh number is reduced solely because the heat capacity of clean fluid is supplemented by that of the dust particles. The principle of exchange of stabilities is found to hold true for the micropolar ferromagnetic fluid saturating a porous medium heated from below in the absence of micropolar viscous effect, microinertia and dust particles.