Thermodynamics of CuAlO2 and CuAl2O4 and phase equilibria in the system Cu2O CuO-Al2O3

The standard Gibbs free energies of formation of CuAlO2 and CuAl2O4 were determined in the range 700° to 1100°C, using emf measurements on the galvanic cells (1) Pt,CuO +] Cu2O/CaO-ZrO2/O2,Pt; (2) Pt,Cu +] CuAlO2+] Al2O3/CaO-ZrO2/ Cu +] Cu2O,Pt; and (3) Pt,CuAl2O4+] CuAlO2+]Al2O3/CaO-ZrO2/O2,Pt. The results are compared with published information on the stability of these compounds. The entropy of transformation of CuO from tenorite to the rock-salt structure is evaluated from the present results and from earlier studies on the entropy of formation of spinels from oxides of the rock-salt and corundum structures. The temperatures corresponding to 3-phase equilibria in the system Cu2O-CuO-Al2O3 at specified O2 pressures calculated from the present results are discussed in reference to available phase diagrams.

Gibbs free energies of formation of ZnAl2O4 and ZnCr2O4

The standard free energies of formation of zinc aluminate and chromite were determined by measuring the oxygen potential over a solid CuZn alloy, containing 10 at.−% Zn, in equilibrium with ZnO, ZnAl2O4+Al2O3(χ) and ZnCr2O4+Cr2O3, in the temperature range 700–900°C. The oxygen potential was monitored by means of a solid oxide galvanic cell in which a Y2O3 ThO2 pellet was sandwiched between a CaOZrO2 crucible and tube. The temperature dependence of the free energies of formation of the interoxidic compounds can be represented by the equations, The heat of formation of the spinels calculated from the measurements by the “Second Law method” is found to be in good agreement with calorimetrically determined values. Using an empirical correlation for the entropy of formation of cubic spinel phases from oxides with rock-salt and corundum structures and the measured high temperature cation distribution in ZnAl2O4, the entropy of transformation of ZnO from wurtzite to rock-salt structure is evaluated.

Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites

The standard Gibbs free energy of formation of magnesium and cadmiumchromites have been determined by potentiometric measurements on reversiblesolid-state electrochemical cells [dformula (Au-5%Cd, , Au-5%Cd; Pt, + , CaO-ZrO[sub 2], + ,Pt; CdO, , CdCr[sub 2]O[sub 4] + Cr[sub 2]O[sub 3])] in the temperature range 500°–730°C, and [dformula Pt, Cr + Cr[sub 2]O[sub 3]/Y[sub 2]O[sub 3]-ThO[sub 2]/Cr + MgCr[sub 2]O[sub 4] + MgO, Pt] in the temperature range 800°–1200°C. The temperature dependence of the freeenergies of formation of the ternary compounds can be represented by theequations [dformula CdO(r.s.) + Cr[sub 2]O[sub 3](cor) --> CdCr[sub 2]O[sub 4](sp)] [dformula Delta G[sup 0] = - 42,260 + 7.53T ([plus-minus]400) J] and [dformula MgO(r.s.) + Cr[sub 2]O[sub 3](cor) --> MgCr[sub 2]O[sub 4](sp)] [dformula Delta G[sup 0] = - 45,200 + 5.36T ([plus-minus]400) J] The entropies of formation of these spinels are discussed in terms of cationdisorder and extent of reduction of Cr3+ ions to Cr2+ ions. Thermodynamicdata on the chromates of cadmium and magnesium are derived by combiningthe results obtained in this study with information available in the literatureon high temperature, high pressure phase equilibria in the systems CdO-Cr2O3-O2 and MgO-Cr2O3-O2.

Gibbs free energy of formation of magnesium stannate

he thermodynamic properties of the spinel Mg2SnO4 have been determined by emf measurements on the solid oxide galvanic cell,View the MathML source in the temperature range 600 to 1000°C. The Gibbs' free energy of formation of Mg2SnO4 from the component oxides can be expressed as View the MathML source,View the MathML source These values are in good agreement with the information obtained by Jackson et al. [Earth Planet. Sci. Lett.24, 203 (1974)] on the high pressure decomposition of magnesium stannate into component oxides at different temperatures. The thermodynamic data suggest that the spinel phase is entropy stabilized, and would be unstable below 207 (±25)°C at atmospheric pressure. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that the stannates of nickel and copper(II) are unstable.

Gibbs free energies of formation of indium (III) oxide and sulphate

Emf measurements on the galvanic cell Pt, Ta, In + In,O, / Tho,-Y,03 / Cu + C+O, Pt were used to obtain the standard free energy of formation of 1%03fr om 600 to 900°C. Differential thermal analysis was used to detect the decomposition of In2(S0,), under controlled SO2 + O2 + Ar mixtures in thqtemperature range 640-8wC. X-ray diffraction analysis indicated that the decomposition product was 1%03 without an oxywlphate intermediate. The following equations were obtained for the variation of the standard free-energy change(Jlmole) with temperature:

Mass spectrometric and electrochemical studies of thermodynamic properties of liquid and solid phases in the CaO Al2O3 system

The activities of CaO and Al2O3 in lime-alumina melts were studied by Knudsen cell-mass spectrometry at 2060 K. Emf of solid state cells, with CaF2 as the electrolyte, was measured from 923 to 1223 K to obtain the free energies of formation of the interoxide compounds. The results are critically evaluated in the light of data reported in the literature on phase equilibria, activities in melts, and stabilities of compounds. A coherent set of data is presented, including the previously unknown free energy of formation of CaO.6Al2O3 and the temperature dependence of activities in the liquid phase.

Highly efficient dialkylphosphate-mediated syntheses of hydantoins and a bicyclohydantoin under solvent-free conditions

Diversely substituted hydantoins have been synthesized by new strategy from cyanamide based precursor, that is, methyl N-cyano-N-alkyl/arylaminoacetate. Dialkylphosphates were employed as the mild reagent to hydrolyze and cyclize the substrate in one step to give quantitative yields of the desired products. Syntheses of multivalent hydantoins viz bis-hydantoin, bicyclohydantoin have potentially widened the scope and applicability of the present method. Solvent-free conditions and very easy work-up procedure make the reaction convenient and eco-friendly. Single crystal structures of some of the representative compounds are also reported. (C) 2011 Elsevier Ltd. All rights reserved.

Gibbs’ free energies of formation of Cu2Ln2O5 (Ln = Tb, Dy, Er, Yb) compounds

The standard Gibbs' free energies of formation of compounds of type Cu2L%05 (Ln = Tb,Dy,Er,Yb) were measured using the solid state cell in the temperature range of 970 to 1323 K For formation of Cu2L?O5 compounds from their binary component oxides according to the reaction 2 CUO (s) + L%03 (s) -, Cu,,L%05 (s),the Gibbs' free energy changes can be represented by the following equations:AGO = 13 080 - 13.70 'I" (+80) J mol-' (Ln = Tb)AGq = 11 480 - 13.51 T (260) J mol-I (Ln = Dy)AGO = 10 750 - 13.99 T (260) J mol-I (Ln = Er)AGO = 9 920 - 13.90 T (260) J mol-' (Ln = Yb) Since formation of the compounds is endothermic, the compounds become thermodynamically unstable with respect to their component oxides below 955 K for Cu2Tb205, 850 K for Cu2Dy205, 768 K for Cu2Er205 and 714 K for Cu2Yb2OS When the oxygen partial pressure over Cu2L%05 is lowered, they decompose according to the scheme, 2 CU,L%O, (s) -r 2 L%03 (s) +2 cu20 (s) + 02(g)The equilibrium chemical potentials of oxygen corresponding to the dissociation reactions are computed from the emf data and auxiliary information on Cu20 and CuO. The computed decomposition temperatures at an oxygen partial pressure of 5.0 x ld Pa are compared with those obtained directly from combined thermogravimetric (TGA) and differential thermal analyses (DTA).The free energy, enthalpy and entropy of formation of Cu2Ln205 compounds show systematic variation with the ionic radius of the trivalent lanthanide ion. The trends obtained in this study are compared with information available in the literature. The staZbility of Cu2Ln205 compounds increases with the decrease in ionic radii of the ~ n ion~. +

Temperature dependence of the energy gap and free carrier absorption in bulk InAs0.05Sb0.95 single crystals

Temperature dependence of the energy gap and free carrier absorption in a high-quality InAs0.05Sb0.95 single crystal was studied between 90 K and 430 K through the absorption spectra. At this alloy concentration, the room-temperature energy gap was measured to be 0.15 eV. Varshni- and the Bose–Einstein-type fit parameters were obtained from the measured temperature dependence of the energy gap, and the latter gave the zero-temperature gap to be 0.214 eV. It was found that although Weider’s empirical formula for the dependence of the energy gap on temperature and the alloy concentration agrees with the value of the gap at room temperature, it is inaccurate in describing its temperature dependence. From the free carrier absorption measurements, the phonon limited cross section of 7.35×10−16 cm2 at 15 μm was deduced at room temperature.

Influence of two photon absorption induced free carriers on coherent polariton and phonon generation in ZnTe crystals

Combination of femtosecond Kerr, two photon absorption, and impulsive stimulated Raman scattering (ISRS) experiments have been carried out to investigate the effect of pulse energy and crystal temperature on the generation of coherent polaritons and phonons in 〈110〉 cut ZnTe single crystals of three different resistivities. We demonstrate that the effect of two photon induced free carriers on the creation of both the polaritons and phonons is largest at 4 K where the free carrier lifetime is enhanced. The temperature dependant ISRS on high and low purity ZnTe crystals allows us to unambiguously assign the phonon mode at 3.5 THz to the longitudinal acoustic mode at X-point in the Brillouin zone, LA(X).

Automatic extraction of free-form surface features (FFSFs)

This paper presents a new algorithm for extracting Free-Form Surface Features (FFSFs) from a surface model. The extraction algorithm is based on a modified taxonomy of FFSFs from that proposed in the literature. A new classification scheme has been proposed for FFSFs to enable their representation and extraction. The paper proposes a separating curve as a signature of FFSFs in a surface model. FFSFs are classified based on the characteristics of the separating curve (number and type) and the influence region (the region enclosed by the separating curve). A method to extract these entities is presented. The algorithm has been implemented and tested for various free-form surface features on different types of free-form surfaces (base surfaces) and is found to correctly identify and represent the features irrespective of the type of underlying surface. The representation and extraction algorithm are both based on topology and geometry. The algorithm is data-driven and does not use any pre-defined templates. The definition presented for a feature is unambiguous and application independent. The proposed classification of FFSFs can be used to develop an ontology to determine semantic equivalences for the feature to be exchanged, mapped and used across PLM applications. (C) 2011 Elsevier Ltd. All rights reserved.

Evidences for ambient oxidation of indium nitride quantum dots

Investigations were carried out on the ambient condition oxidation of self-assembled, fairly uniform indium nitride (InN) quantum dots (QDs) fabricated on p-Si substrates. Incorporation of oxygen in to the outer shell of the QDs was confirmed by the results of transmission electron microscopy (TEM), X-ray photoemission spectroscopy (XPS). As a consequence, a weak emission at high energy (similar to 1.03?eV) along with a free excitonic emission (0.8?eV) was observed in the photoluminescence spectrum. The present results confirm the incorporation of oxygen into the lattice of the outer shell of InN QDs, affecting their emission properties. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

C-H functionalization of tertiary amines by cross dehydrogenative coupling reactions: solvent-free synthesis of alpha-aminonitriles and beta-nitroamines under aerobic condition

A solvent-free synthesis of alpha-aminonitriles and beta-nitroamines by oxidative cross-dehydrogenative coupling under aerobic condition is reported. A catalytic amount of molybdenum(VI) acetylacetonoate was found to catalyze cyanation of tertiary amines to form alpha-aminonitriles, whereas vanadium pentoxide was found to promote aza-Henry reaction to furnish beta-nitroamines. Both of these environmentally benign reactions are performed in the absence of solvents using molecular oxygen as an oxidant.

A novel free floating accelerometer force balance system for shock tunnel applications

In order to overcome the interference of the model mounting system with the external aerodynamics of the body during shock tunnel testing, a new free floating internally mountable balance system that ensures unrestrained model motion during testing has been designed, fabricated and tested. Minimal friction ball bearings are used for ensuring the free floating condition of the model during tunnel testing. The drag force acting on a blunt leading edge flat plate at hypersonic Mach number has been measured using the new balance system. Finite element model (FEM) and CFD are exhaustively used in the design as well as for calibrating the new balance system. The experimentally measured drag force on the blunt leading edge flat plate at stagnation enthalpy of 0.7 and 1.2 MJ/kg and nominal Mach number of 5.75 matches well with FEM results. The concept can also be extended for measuring all the three fundamental aerodynamic forces in short duration test facilities like free piston driven shock tunnels.