Complexes of lanthanide perchlorates with 2-N-(pyridyl)benzamide

New complexes of lanthanide perchlorates with 2-N-(pyridyl) benzamide (PyBA) of the type Ln(PyBA)3(ClO4)3 where Ln = Y and La---Yb have been synthesised and characterised by analyses, conductance, IR, 13C NMR (for diamagnetic complexes only) and electronic spectra. The molar conductance and IR data point to the ionic nature of the perchlorate groups in the complexes. IR data along with the 13C NMR data unequivocally proves that the coordination of the ligand to the metal ions taken place in a bidentate fashion through the oxygen of the benzamide group and the nitrogen of the heterocyclic ring. From a comparison of the visible electronic spectral shapes of the Nd3+, Ho3+ and Er3+ complexes with those reported in the literature, a 6-coordinate geometry around the metal ion has been assigned in all the complexes.

Theoretical Maximum Limits on Power-Handling Capacity of HVDC Cables

In the case of an ac cable, power transmission is limited by the length of the cable due to the capacitive reactive current component. It is well known that high-voltage direct current (HVDC) cables do not have such limitations. However, insulation-related thermal problems pose a limitation on the power capability of HVDC cables. The author presents a viable theoretical development, a logical extension to Whitehead's theory on thermal limitations of the insulation. The computation of the maximum power-carrying capability of HVDC cables subject to limits on the maximum operable temperature of the insulation is presented. The limitation on the power-carrying capability is closely associated with the electrothermal insulation failure. The effect of environmental interaction by way of external thermal resistance, an important aspect, is also considered in the formulations. The Lagrange multiplier method has been used to handle the ensuing optimization problem. The theory is based on an accepted theory of thermal breakdown in insulation and is an important and a coherent extension of great significance.

Low-temperature Er3+ emission in Ge-S-Ga glasses excited by host absorption

The photoluminescence (PL) of a series of (GeS2)(80)(Ga2S3)(20) glasses doped with different amounts of Er (0.17, 0.35, 0.52, 1.05 and 1.39 at.%) at 77 and 4.2 K has been studied. The influence of the temperature on the emission cross-section of the PL bands at -> 1540, 980 and 820 nm under host excitation has been defined. A quenching effect of the host photoluminescence has been established from the compositional dependence of the PL intensity. It has been found that the present Er3+-doped Ge-S-Ga glasses posses PL lifetime values about 3.25 ms. (C) 2007 Elsevier B.V. All rights reserved.

Gibbs Energy of Formation of MnO: Measurement and Assessment

Based on the measurements of Alcock and Zador, Grundy et al. estimated an uncertainty of the order of +/- 5 kJ mol(-1) for the standard Gibbs energy of formation of MnO in a recent assessment. Since the evaluation of thermodynamic data for the higher oxides Mn3O4, Mn2O3, and MnO2 depends on values for MnO, a redetermination of its Gibbs energy of formation was undertaken in the temperature range from 875 to 1300 K using a solid-state electrochemical cell incorporating yttria-doped thoria (YDT) as the solid electrolyte and Fe + Fe1-delta O as the reference electrode. The cell can be presented as Pt, Mn + MnO/YDT/Fe + Fe1+delta O, Pt Since the metals Fe and Mn undergo phase transitions in the temperature range of measurement, the reversible emf of the cell is represented by the three linear segments. Combining the emf with the oxygen potential for the reference electrode, the standard Gibbs energy of formation of MnO from alpha-Mn and gaseous diatomic oxygen in the temperature range from 875 to 980 K is obtained as: Delta G(f)(o)/Jmol(-1)(+/- 250) = -385624 + 73.071T From 980 to 1300 K the Gibbs energy of formation of MnO from beta-Mn and oxygen gas is given by: Delta G(f)(o)/Jmol(-1)(+/- 250) = -387850 + 75.36T The new data are in excellent agreement with the earlier measurements of Alcock and Zador. Grundy et al. incorrectly analyzed the data of Alcock and Zador showing relatively large difference (+/- 5 kJ mol(-1)) in Gibbs energies of MnO from their two cells with Fe + Fe1-delta O and Ni + NiO as reference electrodes. Thermodynamic data for MnO is reassessed in the light of the new measurements. A table of refined thermodynamic data for MnO from 298.15 to 2000 K is presented.

Synthesis of multiwall carbon nanotubes by chemical vapor deposition of ferrocene alone

Multiwall carbon nanotubes (MWNTs) filled with Fe nanoparticles (NPs) have been synthesized by thermal chemical vapor deposition of ferrocene alone as the precursor. The MWNTs were grown at different temperatures: 980 and 800 degrees C. Characterization of as-prepared MWNTs was done by scanning and transmission electron microscopy, and X-ray diffraction. The transmission electron microscopy study revealed that Fe NPs encapsulated in MWNTs grown at 980 and 800 degrees C are spherical and rod shaped, respectively. Room-temperature vibrating sample magnetometer studies were done on the two samples up to a field of 1T. The magnetization versus magnetic field loop reveals that the saturation magnetization for the two samples varies considerably, almost by a factor of 4.6. This indicates that Fe is present in different amounts in the MWNTs grown at the two different temperatures. (C) 2009 Elsevier Ltd. All rights reserved.

Raman spectra of ferro-electric crystals Part IV. Lithium hydrazinium sulphate (LiN2H5SO4)

The Raman spectrum of lithium hydrazinium sulphate has been recorded both in the single crystal form and in aqueous solutions. The crystal exhibits thirty-eight Raman lines having the frequency shifts 52, 70, 104, 146, 174, 220, 260, 302, 350, 454, 470, 610, 630, 715, 977, 1094, 1115, 1132, 1177, 1191, 1260, 1444, 1493, 1577, 1630, 1670, 2205, 2484, 2553, 2655, 2734, 2848, 2894, 2939, 3028, 3132, 3290 and 3330 cm.−1 The aqueous solution gave rise to six Raman lines at 452, 980, 1050–1200, 1260, 1425 and 1570 cm.−1 apart from a maximum at 180 cm.−1 in the ‘wing’ accompanying the Rayleigh line. The observed Raman lines have been assigned as arising from the vibrations of the SO4 ion, N2H5+ ion, Li-O4 group, hydrogen bond and the lattice. The influence of the hydrogen bond on the N-H stretching vibrations has been pointed out. The various features of the observed spectrum strongly support the hypothesis that the NH3 group in the crystal is rotating around the N-N axis at room temperature.

Infrared absorption studies on some derivatives of xanthic, dithiocarbamic and trithiocarbonic acids

The infrared absorption spectra of some of the derivatives of xanthic Image dithiocarbamic Image and trithiocarbonic Image acids are studied in the sodium chloride optics region and the bands assigned to group frequencies. The position of C---O---C and C=S bands in the derivatives of xanthic acid has been discussed from theoretical and experimental evidences and it is suggested that the two strong bands around 1200 and 1030 cm−1 are due to the Image group. The bands around 980 and 1050 cm−1 in the derivatives of dithiocarbamic and trithiocarbonic acids respectively have been assigned to C=S group frequencies. These bands shift to lower frequency in the corresponding ionic compounds while the bands around 1030 and 1200 cm−1 in the ionic compounds of xanthic acid shift to higher and lower frequencies respectively.

The structure of 11[alpha]-hydroxycon-1,4-dienine-3-one monohydrate

C22H31NO2.H2 O, M r = 359" 5, orthorhombic,P2~212 ~, a= 10.032 (1), b= 11.186 (1), C = 17.980 (1)/~,, U= 2017.48/~3, Z = 4, D x = 1.276 Mg m -a, 2(Cu Kct) = 1.5418/~, # = 0.69 mm -~,F(000) = 784, T = 293 K. Final R = 0.05 for 1972 unique reflections with I > 3o(/). Ring A is planar, and rings B and C adopt a chair conformation. Rings D and E are envelopes, with C(14) and C(20) displaced from their respective ring planes by 0-616 (2) and 0.648 (3)/~. The A/B ring junction is quasi-trans,whilst ring systems B/C and C/D are trans fused about the bonds C(8)-C(9) and C(13)-C(14) respectively.The D/E junction shows cis fusion.

Potentiometric determination of activities in the two-phase fields of the system Na2O---(α)Al2O3

Three compounds have been found to be stable in the pseudobinary system Na2O---(α)Al2O3 between 825 and 1400 K; two nonstoichiometric phases, β-alumina and β″-alumina, and NaAlO2. The homogeneity of β-alumina ranges from 9.5 to 11 mol% Na2O, while that of β″-alumina from 13.3 to 15.9 mol% Na2O at 1173 K. The activity of Na2O in the two-phase fields has been determined by a solid-state potentiometric technique. Since both β- and β″-alumina are fast sodium ion conductors, biphasic solid electrolyte tubes were used in these electrochemical measurements. The open circuit emf of the following cells were measured from 790 to 980 K: [GRAPHICS] The partial molar Gibbs' energy of Na2O relative to gamma-Na2O in the two-phase regions can be represented as: DELTA-GBAR(Na2O)(alpha- + beta-alumina) = -270,900 + 24.03 T, DELTA-GBAR(Na2O)(beta- + beta"-alumina) = -232,700 + 56.19 T, and DELTA-GBAR(Na2O)(beta"-alumina + NaAlO2) = -13,100 - 4.51 T J mol-1. Similar galvanic cells using a Au-Na alloy and a mixture of Co + CoAl(2+2x)O4+3x + (alpha)Al2O3 as electrodes were used at 1400 K. Thermodynamic data obtained in these studies are used to evaluate phase relations and partial pressure of sodium in the Na2O-(alpha) Al2O3 system as a function of oxygen partial pressure, composition and temperature.

A multi-stage model for drop breakage in stirred vessels

Existing models for dmax predict that, in the limit of μd → ∞, dmax increases with 3/4 power of μd. Further, at low values of interfacial tension, dmax becomes independent of σ even at moderate values of μd. However, experiments contradict both the predictions show that dmax dependence on μd is much weaker, and that, even at very low values of σ,dmax does not become independent of it. A model is proposed to explain these results. The model assumes that a drop circulates in a stirred vessel along with the bulk fluid and repeatedly passes through a deformation zone followed by a relaxation zone. In the deformation zone, the turbulent inertial stress tends to deform the drop, while the viscous stress generated in the drop and the interfacial stress resist deformation. The relaxation zone is characterized by absence of turbulent stress and hence the drop tends to relax back to undeformed state. It is shown that a circulating drop, starting with some initial deformation, either reaches a steady state or breaks in one or several cycles. dmax is defined as the maximum size of a drop which, starting with an undeformed initial state for the first cycle, passes through deformation zone infinite number of times without breaking. The model predictions reduce to that of Lagisetty. (1986) for moderate values of μd and σ. The model successfully predicts the reduced dependence of dmax on μd at high values of μd as well as the dependence of dmax on σ at low values of σ. The data available in literature on dmax could be predicted to a greater accuracy by the model in comparison with existing models and correlations.

A multi-stage model for drop breakage in stirred vessels

Existing models for dmax predict that, in the limit of μd → ∞, dmax increases with 3/4 power of μd. Further, at low values of interfacial tension, dmax becomes independent of σ even at moderate values of μd. However, experiments contradict both the predictions show that dmax dependence on μd is much weaker, and that, even at very low values of σ,dmax does not become independent of it. A model is proposed to explain these results. The model assumes that a drop circulates in a stirred vessel along with the bulk fluid and repeatedly passes through a deformation zone followed by a relaxation zone. In the deformation zone, the turbulent inertial stress tends to deform the drop, while the viscous stress generated in the drop and the interfacial stress resist deformation. The relaxation zone is characterized by absence of turbulent stress and hence the drop tends to relax back to undeformed state. It is shown that a circulating drop, starting with some initial deformation, either reaches a steady state or breaks in one or several cycles. dmax is defined as the maximum size of a drop which, starting with an undeformed initial state for the first cycle, passes through deformation zone infinite number of times without breaking. The model predictions reduce to that of Lagisetty. (1986) for moderate values of μd and σ. The model successfully predicts the reduced dependence of dmax on μd at high values of μd as well as the dependence of dmax on σ at low values of σ. The data available in literature on dmax could be predicted to a greater accuracy by the model in comparison with existing models and correlations.

An experimental study of reverse transition in two-dimensional channel flow

An experimental investigation on reverse transition from turbulent to laminar flow in a two-dimensional channel was carried out. The reverse transition occurred when Reynolds number of an initially turbulent flow was reduced below a certain value by widening the duct in the lateral direction. The experiments were conducted at Reynolds numbers of 625, 865, 980 and 1250 based on half the height of the channel and the average of the mean velocity. At all these Reynolds numbers the initially turbulent mean velocity profiles tend to become parabolic. The longitudinal and vertical velocity fluctuations ($\overline{u^{\prime 2}}$ and $\overline{v^{\prime 2}}$) averaged over the height of the channel decrease exponentially with distance downstream, but $\overline{u^{\prime}v^{\prime}} $ tends to become zero at a reasonably well-defined point. During reverse transition $\overline{u^{\prime}}\overline{v^{\prime}}/\sqrt{\overline{u^{\prime 2}}}\sqrt{\overline{v^{\prime 2}}}$ also decreases as the flow moves downstream and Lissajous figures taken with u’ and v’ signals confirm this trend. There is approximate similarly between $\overline{u^{\prime 2}} $ profiles if the value of $\overline{u^{\prime 2}_{\max}} $ and the distance from the wall at which it occurs are taken as the reference scales. The spectrum of $\overline{u^{\prime 2}} $ is almost similar at all stations and the non-dimensional spectrum is exponential in wave-number. All the turbulent quantities, when plotted in appropriate co-ordinates, indicate that there is a definite critical Reynolds number of 1400±50 for reverse transition.

Measurement of the Gibbs energy of formation of URh3 using an oxide solid electrolyte

The Gibbs' energy offormation of the intermetallic compound URh3has been measured in the temperature range 980 to 1320 K using an oxide solid state cell incorporating yttria-doped thoria as the solid electrolyte and a mixture of manganese and manganese oxide as the reference electrode. The cell can be represented as Pt, Mn + MnO I (Y203)Th02 I Rh + URh3 + U02 + x' Rh, Pt The reversible emf of the cell was a linear function of temperature E = 15.60 +0.0237 T (±0.8) mY. Using auxiliary thermodynamic data for MnO and U02+ x the Gibbs' energy of formation of URh3 from component metals has been computed. The results can be expressed by the equation L'.G?< URh3 > = -316240 + 13.22 T (± 3000) J mol-1. The "third-law" enthalpy of formation of URh3at 298 K is -293.2 (± 4) kJ mol-1, significantly more negative than the value of -181.5 kJ mol-1 calculated using Miedema's model.