Transition metal chemistry of oxime containing ligands,VII

Complexes of pyridine-2-aldoxime (Hpox) with iron(II) and chromium(III) of type, [Fe(Hpox)₂ X ₂] (X=Cl, Br, I or NCS); [Cr(Hpox)₃]Cl₃·3 H₂O; [Cr(Hpox)₂ X ₂]ClO₄ (X=F, Cl or Br) and [Cr(Hpox)₂(H₂O)₂]Br₃·H₂O were prepared and characterized by analytical X-ray powder diffraction, magnetism, vibrational (conventional and far-infrared) and electronic spectroscopy techniques. X-ray and electronic spectral data indicate that all the complexes except [Cr(Hpox)₃]Cl₃·3 H₂O havetrans-pseudo-octahedral microsymmetry around the metal ion. Infrared spectral data indicate that the ligand, Hpox, behaves like a neutral ligand and coordinates to the metal ion through pyridine nitrogen atom and oxime nitrogen atom in all these complexes. The magnetic susceptibilities of chromium(III) complexes, measured over a temperature range 300–78 K, are independent of temperature whereas the magnetic moments of iron(II) complexes over a temperature range 300–20 K are dependent of temperature. The observed temperature dependence of magnetic moments of iron(II) complexes was used to evaluate the magnitude of orbital reduction factor,k, the low-symmetry distortion parameter, , and the extent of reduction in spin-orbital coupling, . In all these iron(II) complexes the magnetic results indicate the presence of an orbitally non-degenerate,⁵B_2g, ground state. Magnetically unperturbed and perturbedMössbauer spectra of iron(II) complexes at various temperatures have also been reported. Magnetically perturbedMössbauer spectra of iron(II) complexes at 4.2 K in an axial field of 60kGauss indicate that the principal component of electric field gradient tensor is positive and consistent with⁵B_2g ground electronic state in a tetragonal (D _4h) local site symmetry.

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Übergangsmetallkomplexe mit Oxim-enthaltenden Liganden, VII. Elektronische und strukturelle Eigenschaften vonFe(II)-undCr(III)-Komplexen mit Pyridin-2-aldoxim

Zusammenfassung Es wurden Komplexe von Pyridin-2-aldoxim (Hpox) mit Fe(II) und Cr(III) vom Typ [Fe(Hpox)₂ X ₂] (X=Cl, Br, I, NCS), [Cr(Hpox)₃]Cl₃·3 H₂O, [Cr(Hpox)₂ X ₂]ClO₄ (X=F, Cl, Br) und [Cr(Hpox)₂(H₂O)₂]Br₃·H₂O hergestellt. Charakterisierung und Diskussion von Geometrie und Bindungsverhalten in den Komplexen erfolgte auf Grund von analytischen Daten, Röntgen-Pulveraufnahmen, Elektronenanregungsspektroskopie, Infrarotspektroskopie, magnetischen Messungen undMössbauer-Spektroskopie.

     

PVC-based dicyclohexano-18-crown-6 sensor for La(III) ions

A new ion-selective electrode (ISE) based on dicyclohexano-18-crown-6 (DC18C6) as a neutral carrier is developed for lanthanum(III) ions. The electrode comprises of dicyclohexano-18-crown-6 (6%), PVC (33%), and ortho-nitrophenyl octyl ether (o-NPOE) (61%). The electrode shows a linear dynamic response in the concentration range of 10⁻⁶ to 10⁻¹ M with a Nernstian slope of 19 mV per decade and a detection limit as 5×10⁻⁷ M. It has a response time of <30 s and can be used for at least 5 months without any significant divergence in potentials. The selectivity coefficients for mono-, di-, and trivalent cations indicate good selectivity for La(III) ions over a large number of interfering cations. The sensor has been used as an indicator electrode in the potentiometric titrations of La(III) with EDTA. The membrane is successfully applied in partially non-aqueous medium. It can be used in the pH range 4-9.     

Effect of blockage on free vibration of a circular cylinder at low Re

The effect of the blockage on vortex‐induced vibrations of a circular cylinder of low non‐dimensional mass (m^*=10) in the laminar flow regime is investigated in detail. A stabilized space–time finite element formulation is utilized to solve the incompressible flow equations in primitive variables form in two dimensions. The transverse response of the cylinder is found to be hysteretic at both ends of synchronization/lock‐in region for 5% blockage. However, for the 1% blockage hysteresis occurs only at the higher Re end of synchronization/lock‐in region. Computations are carried out at other blockages to understand its effect on the hysteretic behavior. The hysteresis loop at the lower Re end of the synchronization decreases with decrease in blockage and is completely eliminated for blockage of 2.5% and less. On the other hand, hysteresis persists for all values of blockage at the higher Re end of synchronization/lock‐in. Although the peak transverse oscillation amplitude is found to be same for all blockage (～0.6D), the peak value of the aerodynamic coefficients vary significantly with blockage. The r.m.s. values show lesser variation with blockage. The effect of streamwise extent of computational domain on hysteretic behavior is also studied. The phase between the lift force and transverse displacement shows a jump of almost 180° at, approximately, the middle of the synchronization region. This jump is not hysteretic and is independent of blockage. Copyright © 2008 John Wiley & Sons, Ltd.     

A compton profile study of tantalum

We report the results of Compton profile study on polycrystalline tantalum. Measurements have been made using 59.54 keV gamma-rays. The results are compared with the APW band structure calculations of Papanicolaouet al and other available data. In contrast to the work of Changet al the overall agreement is better with the APW band structure which worsens on incorporating the electron correlation correction. Estimates of the errors due to the contribution from bremsstrahlung, non-validity of impulse-approximation and anomalous dispersion are also briefly discussed.     

Discrete system order reduction using multipoint step response matching

The proposed method of linear time invariant discrete system order reduction is based on multipoint step response matching for both pole and zero evaluation of the low order model. Depending on the number of zeros and poles of the low order model, the number of points are selected on the time axis of the unit step response such that the unknown poles and zeros can be determined by solving a set of nonlinear equations using Newton's method.     

Optimal airfoil shapes for low Reynolds number flows

Flow over NACA 0012 airfoil is studied at α = 4^° and 12^° for Re?500. It is seen that the flow is very sensitive to Re. A continuous adjoint based method is formulated and implemented for the design of airfoils at low Reynolds numbers. The airfoil shape is parametrized with a non‐uniform rational B‐splines (NURBS). Optimization studies are carried out using different objective functions namely: (1) minimize drag, (2) maximize lift, (3) maximize lift to drag ratio, (4) minimize drag and maximize lift and (5) minimize drag at constant lift. The effect of Reynolds number and definition of the objective function on the optimization process is investigated. Very interesting shapes are discovered at low Re. It is found that, for the range of Re studied, none of the objective functions considered show a clear preference with respect to the maximum lift that can be achieved. The five objective functions result in fairly diverse geometries. With the addition of an inverse constraint on the volume of the airfoil the range of optimal shapes, produced by different objective functions, is smaller. The non‐monotonic behavior of the objective functions with respect to the design variables is demonstrated. The effect of the number of design parameters on the optimal shapes is studied. As expected, richer design space leads to geometries with better aerodynamic properties. This study demonstrates the need to consider several objective functions to achieve an optimal design when an algorithm that seeks local optima is used. Copyright © 2008 John Wiley & Sons, Ltd.     

Probability distribution for the number of cycles between successive regime transitions for the Lorenz model

The Lorenz model has been widely used for exploring many real world problems. In this paper we obtain, with the help of an invariant manifold technique, the return map for the maximum value of the variable x of the model and use this return map to derive the simple, empirically obtained, regime transition rules for forecasting regime changes and length in the new regime for the model. The probability distribution for number of cycles between successive regime transitions of the Lorenz model may be of interest in many disciplines. We apply the Perron-Frobenius algorithm over the return map to estimate the probability distribution for the number of cycles between successive regime transitions. These probabilities are also estimated for the forced Lorenz model, which is a conceptual model to explore the effects of sea surface temperature on seasonal rainfall.     

Design of Wide-Band Microstrip Antenna Array at Millimeter Wave Frequencies

This paper describes the Design of Broadside 8-Elements Microstrip Antenna Array at Ka-Band using corporate feed. Array is designed for the Broadband applications for 32 GHz to 36 GHz (4 GHz Bandwidth). The Gain of the Antenna Array is 18 dBi and the 3-dB Beamwidth in E - & H - Plane is 18 degree and 27 degree respectively with minimum sidelobe level of 15 dBc. Antenna test results show a close agreement between the designed and measured values. The Antenna Array has been printed on 10 mil RT-Duriod (_r = 2.22) substrate.