Activities and their relation to cation distribution in NiAl2O4 MgAl2O4 spinel solid solutions

The activity of NiAl2O4 in NiAl2O4MgAl2O4 solid solutions has been measured by using a solid oxide galvanic cell of the type, Pt, Ni + NiAl2O4 + Al2O3(α)/CaOZrO2/Ni + NixMg1−xAl2O4 + Al2O3(α). Pt, in the temperature range 750–1150°C. The activities in the spinel solid solutions show negative deviations from Raoult's law. The cation distribution in the solid solutions has been calculated using site preference energies independent of composition for Ni2+, Mg2+, and Al3+ ions obtained from crystal field theory and measured cation disorder in pure NiAl2O4 and MgAl2O4, and assumi g ideal mixing of cations on the tetrahedral and octahedral positions. The calculated values correctly predict the decrease in the fraction, α, of Ni2+ ions on tetrahedral sites for 1>x>0.25, observed by Porta et al. [J. Solid State Chem.11, 135 (1974)] but do not support their tentative evidence for an increase in α for x < 0.25. The measured excess free energy of mixing can be completely accounted for by using either the calculated or the measured cation distributions. This suggests that the Madelung energy is approximately a linear function of composition in the solid solutions. The composition of NiOMgO solid solutions in equilibrium with NiAl2O4MgAl2O4 solid solutions has been calculated from the results and information available in literature.

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.

Thermodynamic properties of Cr Mo solid alloys

The activity of Cr in solid Cr-Mo alloys has been measured at 1873 K using a metal-oxide-gas equilibrium technique. Thin foils of Mo were equilibrated with solid Cr203 under flowing gas mixtures of argon, hydrogen and watervapourof known composition. The equilibrium concentration of Cr in Mo was determined by chemical analysis. These measurements indicate positive deviations from Raoult's law. The activity data obtained in the study at 1873 K are combined with free energy of mixing at 1471 K, calorimetric enthalpy of mixing at 1673 K, and experimental evidence of phase separation at lower temperatures, reported in the literature, to obtain an optimised set of thermodynamic parameters for the Cr-Mosystem in the solid state.

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.

Application of composition gradient solid electrolytes in sensors and thermodynamic measurements

New compos~tiong radient solid electrolytes are developed which have application in high temperature solid state galvanic sensors and provide a new tool for thermodynamic measurements. The electrolyte consists oi a solid solution between two ionic conductors with a common mobile ion and spatial variation in composition of otber coxup nents. Incorporation of the composite electrolyte in sensors permits the use oi dissimilar gas electrodes. It is demonsuated, both experimentall y and theoretically, that the composition gradient of the relativeiy immobile species does not give rise to a diffusion potential.The emi of a cell is determined by the activity of the mobile species at the two eiectrodes. The thermodynamic properties of solid solutions can be measured using the gradient solid electrolyte. The experimental stuay is based on model systems A?(COj)x(S04)l-x (A=Na,K),where S \.aria across the electrolyte. The functionally gradient solid electrolytes used for activity measurements consist of pure carbonate at one ena and the solid solution under stuav at the other. The identical vaiues of activity, obtained h m t hree different modes of operation of the ceil. indicate unit transport number for the ddi metal ion in the graciient electrolyte. Tlle activities in the solid solutions exhibit moderate positive deviations from Raoult 's law.

Thermodynamics and phase equilibria involving the spinel solid solution FexMg1-xCr2O4

Activities of FeCr2O4 in the spinel solid solutions Fe X Mg1−X Cr2O4 (0solid-state galvanic cell of the type Pt, Fe + Fe X Mg1−X Cr2O4 + Cr2O3//(Y2O3) ThO2/(CaO) ZrO2//Fe + FeCr2O4 + Cr2O3, Pt Activities of both the components exhibit small negative deviation from the ideal behavior, characterized by the regular solution parameter Ω s =−2260 (±200) J/mol. The lattice parameter of the spinel solid solutions quenched from 1200 K was found to obey Vegard’s law. The phase relations in the FeO-MgO-Cr2O3 system have been deduced from the results obtained in this study together with other relevant thermodynamic data from the literature. The tie-lines between the solid solutions with rock salt and spinel structures represent the influence of intercrystalline ion exchange. The tie-lines are skewed toward the FeCr2O4 corner, primarily because of the higher stability of FeCr2O4 compared to MgCr2O4, with respect to their component binary oxides. The oxygen partial pressure corresponding to the two three-phase regions, Fe + Fe X Mg1−X Cr2O4 + Cr2O3 and Fe + Fe Y Mg1−Y O + Fe X Mg1−X Cr2O4, have been evaluated as a function of composition at 1200 K.

Thermodynamics of Al(1-x)Ga(x)N solid solution: Inclination for phase separation and ordering

Although Al(1-x)Ga(x)N semiconductors are used in lighting, displays and high-power amplifiers, there is no experimental thermodynamic information on nitride solid solutions. Thermodynamic data are useful for assessing the intrinsic stability of the solid solution with respect to phase separation and extrinsic stability in relation to other phases such as metallic contacts. The activity of GaN in Al(1-x)Ga(x)N solid solution is determined at 1100 K using a solid-state electrochemical cell: Ga + Al(1-x)Ga(x)N/Fe, Ca(3)N(2)//CaF(2)//Ca(3)N(2), N(2) (0.1 MPa), Fe. The solid-state cell is based on single crystal CaF(2) as the electrolyte and Ca(3)N(2) as the auxiliary electrode to convert the nitrogen chemical potential established by the equilibrium between Ga and Al(1-x)Ga(x)N solid solution into an equivalent fluorine potential. Excess Gibbs free energy of mixing of the solid solution is computed from the results. Results suggest an unusual mixing behavior: a mild tendency for ordering at three discrete compositions (x = 0.25, 0.5 and 0.75) superimposed on predominantly positive deviation from ideality. The lattice parameters exhibit slight deviation from Vegard's law, with the a-parameter showing positive and the c-parameter negative deviation. Although the solid solution is stable in the full range of compositions at growth temperatures, thermodynamic instability is indicated at temperatures below 410 K in the composition range 0.26 <= x <= 0.5. At 355 K, two biphasic regions appear, with terminal solid solutions stable only for 0 <= x <= 0.26 and 0.66 <= x <= 1. The range of terminal solid solubility reduces with decreasing temperature. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

State of bismuth in BaBiO3 and BaBi1-xPbxO3: Bi 4f photoemission and Bi L3 absorption spectroscopic studies

The 2p 6d feature in the Bi L3 spectra has different energies in the semiconducting (0.0≤x<0.7) and the superconducting (x=0.75) compositions of BaBi1−xPbxO3. The Bi 4f core level spectrum shows distinct features ascribable to Bi III and Bi V in BaBiO3 and in the semiconducting compositions; the width of the 4f peaks is also considerably larger in these compositions compared to that in BaBi0.25Pb0.75O3, which shows a single sharp Bi 4f feature.

Morphology Dependence of Ag-Ni Solid Solubility

Electrodeposition produced features with a dendritic morphology and features with a branched wire like morphology made up of about 20 nm sized particles. Both the features contained Ag and Ni atoms in a solid solution arrangement. However, the feature made up of nanoparticles contained a greater concentration of Ni as compared to the Ni content in the dendritic feature. The greater Ni content in the Ag-Ni solid solution for the features with nanoparticles when compared to the dendritic morphology features strongly indicated the effect of curvature in increasing the extent of miscibility between bulk immiscible atoms. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.003202esl] All rights reserved.

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Pure stoichiometric MgRh(2)O(4) could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh(2)O(3) in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh(2)O(3). The spinel phase can be considered as a solid solution of Mg(2)RhO(4) in MgRh(2)O(4). The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg(1+x)Rh(2-x)O(4) was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh(2)O(4) and Mg(2)RhO(4) were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured composition of the spinel solid solution in different phase fields and imposed oxygen partial pressures. The results can be summarized by the equations: MgO + beta -Rh(2)O(3) -> MgRh(2)O(4); Delta G degrees (+ 1010)/J mol(-1) = -32239 + 7.534T; 2MgO + RhO(2) -> Mg(2)RhO(4); Delta G degrees(+/- 1270)/J mol(-1) = 36427 -4.163T; Delta G(M)/J mol(-1) = 2RT(xInx + (1-x)In(1-x)) + 4650x(1-x), where Delta G degrees is the standard Gibbs free energy change for the reaction and G(M) is the free energy of mixing of the spinel solid solution Mg(1+x)Rh(2-x)O(4). (C) 2011 Elsevier B. V. All rights reserved.

Intra-molecular hydrogen bonding with organic fluorine in the solution state: Deriving evidence by a two dimensional NMR experiment

The direct evidence for the existence of intra-molecular C-F center dot center dot center dot H-N hydrogen bond in organofluorine molecules, in the liquid state, is derived using NMR spectroscopy by the detection of long range interactions among fluorine, nitrogen and hydrogen atoms. The present study reports the determination of the relative signs and magnitudes of through space and through bond couplings to draw unambiguous evidence on the existence of weak molecular interactions involving organic fluorine. It is a simple, easy to implement, N-15 natural abundant two dimensional heteronuclear N-15-H-1 double quantum-single quantum correlation experiment. The existence of intra-molecular hydrogen bond is conclusively established in the investigated molecules. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis, characterization, thermo- and photoluminescence properties of Bi3+ co-doped Gd2O3:Eu3+ nanophosphors

Gd2O3:Eu3+ (4 mol%) co-doped with Bi3+ (Bi = 0, 1, 3, 5, 7, 9 and 11 mol%) ions were synthesized by a low-temperature solution combustion method. The powders were calcined at 800A degrees C and were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared and UV-Vis spectroscopy. The PXRD profiles confirm that the calcined products were in monoclinic with little cubic phases. The particle sizes were estimated using Scherrer's method and Williamson-Hall plots and are found to be in the ranges 40-60 nm and 30-80 nm, respectively. The results are in good agreement with TEM results. The photoluminescence spectra of the synthesized phosphors excited with 230 nm show emission peaks at similar to 590, 612 and 625 nm, which are due to the transitions D-5(0)-> F-7(0), D-5(0)-> F-7(2) and D-5(0)-> F-7(3) of Eu3+, respectively. It is observed that a significant quenching of Eu3+ emission was observed under 230 nm excitation when Bi3+ was co-doped. On the other hand, upon 350 nm excitation, the luminescent intensity of Eu3+ ions was enhanced by incorporation of Bi3+ (5 mol%) ions. The introduction of Bi3+ ions broadened the excitation band of Eu3+ of which a new strong band occurred ranging from 320 to 380 nm. This has been attributed to the 6s(2)-> 6s6p transition of Bi3+ ions, implying a very efficient energy transfer from Bi3+ ions to Eu3+ ions. The gamma radiation response of Gd2O3:Eu3+ exhibited a dosimetrically useful glow peak at 380A degrees C. Using thermoluminescence glow peaks, the trap parameters have been evaluated and discussed. The observed emission characteristics and energy transfer indicate that Gd2O3:Eu3+, Bi3+ phosphors have promising applications in solid-state lighting.

Catalysis of tRNA Aminoacylation: Single Turnover to Steady-State Kinetics of tRNA Synthetases

Aminoacyl-tRNA synthetases (aaRS) catalyze the bimolecular association reaction between amino acid and tRNA by specifically and unerringly choosing the cognate amino acid and tRNA. There are two classes of such synthetases that perform tRNA-aminoacylation reaction. Interestingly, these two classes of aminoacyl-tRNA synthetases differ not only in their structures but they also exhibit remarkably distinct kinetics under pre-steady-state condition. The class I synthetases show initial burst of product formation followed by a slower steady-state rate. This has been argued to represent the influence of slow product release. In contrast, there is no burst in the case of class H enzymes. The tight binding of product with enzyme for class I enzymes is correlated with the enhancement of rate in presence of elongation factor. EF-TU. In spite of extensive experimental studies, there is no detailed theoretical analysis that can provide a quantitative understanding of this important problem. In this article, we present a theoretical investigation of enzyme kinetics for both classes of aminoacyl-tRNA synthetases. We present an augmented kinetic scheme and then employ the methods of time-dependent probability statistics to obtain expressions for the first passage time distribution that gives both the time-dependent and the steady-state rates. The present study quantitatively explains all the above experimental observations. We propose an alternative path way in the case of class II enzymes showing the tRNA-dependent amino acid activation and the discrepancy between the single-turnover and steady-state rate.

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.