Mean amplitudes of vibration in some tetrahedral tetrahalogeno complexes

The Cyvin method, utilizing symmetry coordinates, has been employed here to compute the mean-square amplitude quantities, generalized mean-square amplitudes (mean-square parallel amplitudes, mean-square perpendicular amplitudes and mean cross products) and mean amplitudes of vibration for the bonded as well as non-bonded atom pairs at the temperaturesT=298°K andT=500°K for the tetrahedral tetrahalogeno complexes of zinc, cadmium, gallium, indium, thallium and arsenic. The non-linear behaviour of the mean amplitudes of vibration in terms of the electronegativities of the central atoms has been discussed, followed by a discussion on the replacement of peripheral atoms.     

Structural and functional analogue of the active site of polysulfide reductase from Wolinella succinogenes

Synthesis of [PPh4]2[Mo(SPh)2(S2C2(CN)2)2] (2) from [PPh4]2[MoO(S2C2(CN)2)2] (1) has been achieved to mimic the postulated [Mo(S)6] core of polysulfide reductase with two thiolates and two bis(ene-dithiolate) ligands. Compound 2 reacts with polysulfide to yield H2S, modeling the function of polysulfide reductase. The facile conversion of 2 back to 1 in moist solvent suggests that the interconversion of the [MoIV = O] and [MoIV - X] (X = O-Ser, S-Cys, Se-Cys) moieties might occur in the DMSO reductase class of enzymes under appropriate hydrophobic/hydrophilic conditions.     

Determination of 2-hydroxy-4-methoxybenzaldehyde in roots of Decalepis hamiltonii (Wight & Arn.) and Hemidesmus indicus R.Br

The roots of Decalepis hamiltonii and Hemidesmus indicus are aromatic and possess the crystalline compound 2-hydroxy-4-methoxybenzaldehyde as the major compound (> 90%) in their volatile oils. A gas chromatographic procedure was developed for the assay of 2-hydroxy-4-methoxybenzaldehyde in both fresh and dried roots of different origin. Benzyl butyrate was used as the internal standard. Among the methods tried, steam hydrodistillation was suitable for extraction of the volatile oils. The quantity of this aromatic compound varied from 0.03 to 0.54%.     

Measurement of internal stresses via the polarization in epitaxial ferroelectric films

The relations between electrical and mechanical properties of constrained ferroelectric films are analyzed. It is shown that the internal stresses and the elastic constants can be determined through the measurement of the electrical response. The change in the polarization is proportional to internal stresses due to film-substrate misfit, whereas the linear electrical and electromechanical responses to external field do not depend on the misfit and are determined by the film constraint. The theoretical results are successfully applied to PbZr 0.2Ti 0.8O (3) films on (001) LaAlO (3) substrate which exhibit a considerable increase in the saturation polarization due to epitaxial stresses. Significant recovery in the piezoelectric constant and susceptibility is theoretically predicted and experimentally verified for specific film configurations which reduce the degree of constraint. The concept presented in this Letter can be expanded to constrained ferromagnetic and superconductor films.     

The use of fractional orders in the determination of birefringence of highly dispersive materials by the channelled spectrum method

The channelled spectrum employing polarized light interference is a very convenient method for the study of dispersion of birefringence. However, while using this method, the absolute order of the polarized light interference fringes cannot be determined easily. Approximate methods are therefore used to estimate the order. One of the approximations is that the dispersion of birefringence across neighbouring integer order fringes is negligible. In this paper, we show how this approximation can cause errors. A modification is reported whereby the error in the determination of absolute fringe order can be reduced using fractional orders instead of integer orders. The theoretical background for this method supported with computer simulation is presented. An experimental arrangement implementing these modifications is described. This method uses a Constant Deviation Spectrometer (CDS) and a Soleil Babinet Compensator (SBC).     

Effect of phenyl group on the structure and formation of transitional alumina from Al (OPh)<Subscript>3</Subscript>

The structure of freshly prepared Al(OPh)₃, its decomposition product, the hydrolyzed products and their structural evolution were investigated employing ²⁷Al MAS NMR spectroscopy, PXRD, TGA/DTA/DSC/FTIR techniques. In the ²⁷Al MAS NMR spectrum of the aluminium phenoxide, three signals with the chemical shift at 3.78, 21 and 45 ppm were observed. The chemical shift at 3.78 and 45 ppm revealed the presence of four and sixfold coordinated aluminum. The signal at 21 ppm corresponded to fivefold coordinated aluminium. When the aluminium phenoxide was directly decomposed in air at 600 °C, it resulted in amorphous product as evidenced from the PXRD pattern. The observed signals with chemical shifts at 10.1, 42, 73.6 ppm in the ²⁷Al MAS NMR spectrum indicated the presence of 6, 5 and 4 coordination for the aluminium atoms suggesting disordered transitional γ-alumina to be the product. The hydrolysis studies of Al(OPh)₃ with excess of water at 70 °C yielded bohemite (γ-AlOOH). The alumina obtained after dehydration at 600 °C was X-ray amorphous. The dehydrated product at 600 °C showed the presence of four and six coordinated aluminium atoms in the ²⁷Al MAS NMR spectrum confirming it to be ordered γ-Al₂O₃. Crystalline γ-Al₂O₃ was obtained on further heating at 800 °C.     

Evaluation of heat capacity measurements by temperature-modulated differential scanning calorimetry

Temperature-modulated differential scanning calorimetry (TMDSC) is known to have the ability to measure heat capacity of materials more accurately than the conventional differential scanning calorimeter. However, the accuracy of the measured heat capacity displays significant dependence on various experimental parameters such as period of modulation (p), amplitude of modulation (a), geometry of sample (g), heating rate (r), etc. One of the key features of this system is the ability to measure heat capacity under quasi-isothermal conditions. In the present investigation, heat capacity of a well-established system namely sapphire and thoria was measured by TMDSC under dynamic mode and also under quasi-isothermal mode. The experimental parameters, mentioned above p, a, g, and r are varied to establish the conditions for measuring heat capacity accurately.     

Thermal expansion and heat capacity of dysprosium hafnate

Dysprosium hafnate is a candidate material for as control rods in nuclear reactor because dysprosium (Dy) and hafnium (Hf) have very high absorption cross-sections for neutrons. Dysprosium hafnate (Dy₂O₃·2HfO₂-fluorite phase solid solution) was prepared by solid-state as well as wet chemical routes. The fluorite phase of the compound was characterized by using X-ray diffraction (XRD). Thermal expansion characteristics were studied using high temperature X-ray diffraction (HTXRD) in the temperature range 298–1973 K. Heat capacity measurements of dysprosium hafnate were carried out using differential scanning calorimetry (DSC) in the temperature range 298–800 K. The room temperature lattice parameter and the coefficient of thermal expansion are 0.5194 nm and 7.69 × 10⁻⁶ K⁻¹, respectively. The heat capacity value at 298 K is 232 J mol⁻¹ K⁻¹.