Solubility and activity of oxygen in liquid nickel in equilibrium with -Al2O3 and NiO.(1+x)Al2O3

The limiting solubility of oxygen in liquid nickel in equilibrium withα-alumina and nickel aluminate has been measured by inert gas fusion analysis of suction samples in the temperature range 1730 to 1975 K. The corresponding oxygen potential has been monitored by a solid electrolyte cell consisting of calcia stabilized zirconia as the electrolyte and Mo + MoO2 as the reference electrode. The results can be summarized by the following equations: log(at. pct O) = \frac - 10,005T + 4.944 ( ±0.015)log(atpctO)=T−10005+4944(0015) % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn DmO2 /4.606RT = log P O2 1/2 = \frac - 13,550T + 4.411 ( ±0.009)O24606RT=logPO212=T−13550+4411(0009) From simultaneous measurements of the potential and concentration of oxygen in melts, not in thermodynamic equilibrium with alumina and aluminate phases, information on the composition dependence of the activity coefficient and the standard free energy of solution of oxygen is obtained. For the reaction, $\frac{1}{2} O_2 \to \underset{\raise0.3em\hbox{$Missing close brace ΔG o = -72,930 - 7.11T (±840) J gr.at.–1 = + 0.216 at. pct OlogfO=T−500+0216atpctO where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct) in the limit as concentration approaches zero. The oxygen solubility in liquid nickel in equilibrium with solid NiO, evaluated from thermodynamic data, is compared with information reported in the literature. Implications of the results to the deoxidation equilibria of aluminum in nickel are discussed.

Alloy/Oxide Equilibria in Iron--Vanadium--Oxygen and Iron--Niobium--Oxygen Systems

An experimental characterization of three-phase equilibria in Fe--V--O and Fe--Nb--O systems at 1823, 1873 and 1923K has been carried out using a solid state cell and by analysis of quenched samples. The oxygen potentials corresponding to these three-phase equilibria were monitored by a solid state cell incorporating Y sub 2 O sub 3 doped ThO sub 2 with Cr + Cr sub 2 O sub 3 as reference electrode. Similar measurements were carried out for Fe--Nb--O alloys in equilibrium with a mixture of FeNb sub 2 O sub 6 and NbO sub 2 . These measurements permit evaluation of interaction parameters (e exp V sub O = --6590/T + 2.892 and e exp Nb sub O = --4066/T + 1.502) and activity coefficients of vanadiun and niobium in dilute solution (ln gamma exp O sub V = --35 320/T + 12.68 and ln gamma sub Nb exp O = --12 386/T + 4.34) in liquid iron. The results obtained in this study resolve a number of discrepancies in thermodynamic data reported in the literature, especially regarding the activity coefficients of V and Nb and the stability ranges for V sub 2 O sub 3 and VO sub 1+x . 18 ref.--AA

Low oxygen potential boundary for the stability of YBA2Cu3O7−δ

On lowering the oxygen potential, the tetragonal phase of YBa2Cu3O7−δ was found to decompose into a mixture of Y2BaCuO5, BaCuO2 and BaCu2O2 in the temperature range 773–1173 K. The 123 compound was contained in a closed crucible of yttria-stabilized zirconia in the temperature range 773–1073 K. Oxygen was removed in small increments by coulometric titration through the solid electrolyte crucible at constant temperature. The oxygen potential was calculated from the open circuit e.m.f. of the solid state cell after successive titrations. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The decomposition of the 123 compound manifested as a plateau in oxygen potential. The decomposition products were identified by X-ray diffraction. At temperatures above 1073 K there was some evidence of reaction between the 123 compound, solid electrolyte crucible and platinum. For measurements above 1073 K, the 123 compound was contained in a magnesia crucible placed in a closed outer silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid state cell based on yttria-stabilized zirconia which served both as a pump and sensor. The lower oxygen potential limit for the stability of the 123 compound is given by View the MathML source The oxygen non-stoichiometric parameter δ for the 123 compound has a value of 0.98 (View the MathML source) at dissociation.

Variation of the partial thermodynamic properties of oxygen with composition in YBa2Cu3O7−δ

The variation of equilibrium oxygen potential with oxygen concentration inYBa 2Cu3O7-δhas been measured in the temperature range of 773 to 1223 K. For temperatures up to 1073 K, the oxygen content of theYBa 2Cu3O7-δsample, held in a stabilized-zirconia crucible, was altered by coulometric titration. The compound was in contact with the electrolyte, permitting direct exchange of oxygen ions. For measurements above 1073 K, the oxide was contained in a magnesia crucible placed inside a closed silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid-state cell based on yttria-stabilized zirconia, which served both as a pump and sensor. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The oxygen pressure over the sample was varied from 10-1 to 105 Pa. The oxygen concentrations of the sample equilibrated with pure oxygen at 1.01 × 105 Pa at different temperatures were determined after quenching in liquid nitrogen by hydrogen reduction at 1223 K. The plot of chemical potential of oxygen as a function of oxygen non-stoichiometry shows an inflexion at δ ∼ 0.375 at 873 K. Data at 773 K indicate tendency for phase separation at lower temperatures. The partial enthalpy and entropy of oxygen derived from the temperature dependence of electromotive force (emf ) exhibit variation with composition. The partial enthalpy for °= 0.3, 0.4, and 0.5 also appears to be temperature dependent. The results are discussed in comparison with the data reported in the literature. An expression for the integral free energy of formation of YBa2Cu3O6.5 is evaluated based on measurements reported in the literature. By integration of the partial Gibbs’ energy of oxygen obtained in this study, the variation of integral property with oxygen concentration is obtained at 873 K.

Thermodynamic properties of oxygen in RE-O (RE = Gd, Tb, Dy, Er) solid solutions

The oxygen potentials of four rare-earth metal – oxygen (RE–O: RE=Gd, Dy, Tb, Er) solid solutions have been measured by equilibration with yttrium – oxygen (Y–O) and titanium – oxygen (Ti–O) solid solutions. Rare-earth metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt at temperatures between 1093 and 1233 K. Homogeneous oxygen potential was established in the metallic samples through the fused salt, which contains some dissolved CaO. The metallic samples were analyzed for oxygen after quenching. The oxygen potentials of RE–O solid solutions were determined using either Y–O or Ti–O solid solution as the reference. This method enabled reliable measurement of extremely low oxygen potentials at high temperature (circa pO2=10−48 atm at 1173 K). It was found that the oxygen affinity of the metals decreases in the order: Y>Er>Dy>Tb>Gd>Ti. Values for the standard Gibbs energy of solution of oxygen in RE metals obtained in this study, permit assessment of the extent of deoxidation that can be achieved with various purification techniques. It may be possible to achieve an oxygen level of 10 mass ppm using an electrochemical deoxidation method.

The Thermodynamics of Oxygen in Reactive Metals

For some new applications of metals in functional devices, metals of high purity are required. In recent years, many high-purity metals have been produced commercially for use in electronics, but the demand for ultra-high-purity metals is increasing rapidly because of more stringent specifications for materials used in high-performance information devices.

La-Doped Ba2In2O5 Electrolyte: Pechini Synthesis, Microstructure, Electrical Conductivity, and Application for CO Gas Sensing

Dense (Ba1―xLax)2In2O5+x (BLIO) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were fabricated using powders obtained by the Pechini method. The formation of BLIO powders was investigated by using X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The calcination temperature and time were optimized. The sintered (Ba1―xLax)2In2O5+x electrolytes showed a relative density greater than ∼97%, and the major phase of three electrolyte compositions was indexed as a cubic perovskite. The electrical conductivity of BLIO ceramics at elevated temperatures in air was measured by ac-impedance spectroscopy. The activation energies for conduction in BLIO were 102 kJ mol―1 between 473 and 666 K and 118 kJ mol―1 between 769 and 873 K, which are comparable to that for 8 mol % yttria-stabilized cubic zirconia. Mixed-potential gas sensors utilizing BLIO-based electrolytes exhibited good sensitivity to different CO concentrations from ∼100 to ∼500 ppm and excellent selectivity to methane at around 873 K.

Self-Assembly of Metallamacrocycles Using a Dinuclear Organometallic Acceptor: Synthesis, Characterization, and Sensing Study

A dinuclear organometallic acceptor 4,4'-bis[trans-Pt(PEt(3))(2)(O(3)SCF(3))(ethynyl)]biphenyl (1) containing Pt-ethynyl functionality is synthesized. Multinuclear NMR ((1)H, (31)P, and (13)C), infrared (IR), and electrospray ionization mass spectrometry (ESI-MS) including single-crystal X-ray diffraction analysis established the formation of 1. Equimolar treatment of acceptor 1 separately with three different ``clip'' type ditopic donors (L(a)-L(c)) yielded [2 + 2] self-assembled three metallamacrocycles 2a-2c, respectively. These macrocycles were characterized by various spectroscopic techniques, and their sizes/shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) simulations. Attachment of unsaturated ethynyl functionality to biphenyl building unit helped to make the macrocycles (2a-2c) pi-electron rich and thereby fluorescent in nature. Furthermore, 2c in solution has been examined to be suitable for sensing electron-deficient nitroaromatic like picric acid, which is often considered as a secondary chemical explosive. The fluorescence study of 2c showed a marked quenching of initial emission intensity upon titrating with picric acid (PA), and it exhibited the largest fluorescence quenching response with high selectivity among various other electron deficient aromatic compounds tested.

Coordination-driven self-assembly of 2D-metallamacrocycles using a shape-selective Pt(2)(II)-organometallic 90 degrees acceptor: design, synthesis and sensing study

Synthesis of a series of two-dimensional metallamacrocycles via coordination-driven self-assembly of a shape-selective Pt(2)(II)-molecular building unit incorporating carbazole-ethynyl functionality is described. An equimolar (1 : 1) combination of a Pt(2)(II)-organometallic 90 degrees acceptor, 1, with rigid linear ditopic donors (L(a) and L(b)) afforded [4 + 4] self-assembled octanuclear molecular squares, 2 and 3, in quantitative yields, respectively [L(a) = 4,4'-bipyridine; L(b) = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar treatment of 1 with an amide-based unsymmetrical flexible ditopic donor, L(c), resulted in the formation of a [2 + 2] self-sorted molecular rhomboid (4a) as a single product [L(c) = N-(4-pyridyl)isonicotinamide]. Despite the possibility of several linkage isomeric macrocycles (rhomboid, triangle and square) due to the different connectivity of L(c), the formation of a single and symmetrical molecular rhomboid (4a) as the only product is an interesting observation. All the self-assembled macrocycles (2, 3 and 4a) were fully characterized by multinuclear NMR ((1)H and (31)P) and ESI-MS analysis. Further structural insights about the size and shape of the macrocycles were obtained through energy minimization using density functional theory (DFT) calculations. Decoration of the starting carbazole building unit with Pt-ethynyl functionality enriches the assemblies to be more p-electron rich and luminescent in nature. Macrocycles 2 and 3 could sense the presence of electron deficient nitroaromatics in solution by quenching of the initial intensity upon gradual addition of picric acid (PA). They exhibited the largest quenching response with high selectivity for nitroaromatics compared to several other electron deficient aromatics tested.

Oxygen displacement in a 107Ag17+ ion irradiated Bi2Sr2CaCu2O8 single crystal

We have studied the magnetic field (H∥c) dependent rf dissipation (Hrf∥a) in an as-grown Bi2Sr2CaCu2O8 single crystal prior to and after irradiation with 250 MeV 107Ag17+ ions. In a comparison of the responses from the as-grown crystal with an air-annealed crystal, features due to oxygen deficient regions acting as weak links in the former are identified. These features disappear immediately after irradiation of the as-grown crystal. We attribute such behavior to the displacement of oxygen from columnar tracks to deficient regions thus eliminating the weak links. Losses from the same irradiated as-grown crystal stored at 300 K for 60 days show that the features similar but not identical to those observed in the pristine state have reappeared implying that the displaced oxygen is in a metastable configuration in the deficient regions and hence is mobile due to thermal effects even at 300 K.

Influence of substrate temperature on the properties of oxygen‐ion‐assisted deposited CeO2 films

Substrate temperature and ion bombardment during deposition have been observed to modify significantly the optical and structural properties of dielectric thin films. Single‐layer films of CeO2 have been deposited by electron beam evaporation with simultaneous oxygen‐ion bombardment using a Kaufman broad beam ion source and maintaining the substrates at elevated temperature. A systematic study has been made on the influence of (a) substrate temperature in the range ambient to 300 °C, (b) ion energy in the range 300–700 eV, and (c) ion current density 100–220 μA/cm2 on optical properties such as refractive index, extinction coefficient, inhomogeneity, packing density, and structural properties. The refractive index increased with in increase in substrate temperature: ion energy up to 600 eV and ion current density. Homogeneous, absorption free and high index (2.48) films have been obtained at 600 eV, 220 μA/cm2 and at substrate temperature of 300 °C. The packing density of the films was observed to be unity for the same deposition conditions. Substrate temperature with simultaneous ion bombardment modified the structure of the films from highly ordered to fine grain structure.

Monitoring Himalayan cryosphere using remote sensing techniques

In the Himalayas, large area is covered by glaciers, seasonal snow and changes in its extent can influence availability of water in the Himalayan Rivers. In this paper, changes in glacial extent, glacial mass balance and seasonal snow cover have been discussed. Field and satellite based investigations suggest, most of the Himalayan glaciers are retreating though the rate of retreat is varying from glacier to glacier, ranging from few meters to almost 50 meters per year, depending upon the numerous glacial, terrain and meteorological parameters. Retreat was estimated for 1868 glaciers in eleven basins distributed across the Indian Himalaya since 1962 to 2001/02. Estimates show an overall reduction in glacier area from 6332 to 5329 sq km, an overall deglaciation of 16 percent.Snow line at the end of ablation season on the Chhota Shigri glacier suggests a change in altitude from 4900 to 5200 m from late 1970’s to the present. Seasonal snow cover monitoring of the Himalaya has shown large amounts of snow cover depletion in early part of winter, i.e. from October to December. For many basins located in lower altitude and in south of Pir Panjal range, snow ablation was observed through out the winter season. In addition, average stream runoff of the Baspa basin during the month of December shows an increase by 75 per cent. This combination of glacial retreat, negative mass balance, early melting of seasonal snow cover and winter time increase in stream runoff suggest an influence of climate change on the Himalayan cryosphere.

Photo-induced DNA cleavage activity and remarkable photocytotoxicity of lanthanide(III) complexes of a polypyridyl ligand

Lanthanide(III) complexes [Ln(pyphen)(acac)(2)(NO3)] (1, 2), [Ln(pydppz)(acac)(2)(NO3)] (3, 4) and [La(pydppz)(anacac)(2)(NO3)] (5), where Ln is La(III) (in 1, 3, 5) and Gd(III) (in 2, 4), pyphen is 6-(2-pyridyl)-1,10-phenanthroline, pydppz is 6-(2-pyridyl)-dipyrido[3,2-a:2',3'-c] phenazine, anacac is anthracenylacetylacetonate and acac is acetylacetonate, were prepared, characterized and their DNA photocleavage activity and photocytotoxicity studied. The crystal structure of complex 2 displays a GdO6N3 coordination. The pydppz complexes 3-5 show an electronic spectral band at similar to 390 nm in DMF. The La(III) complexes are diamagnetic, while the Gd(III) complexes are paramagnetic with seven unpaired electrons. The molar conductivity data suggest 1 : 1 electrolytic nature of the complexes in aqueous DMF. They are avid binders to calf thymus DNA giving K-b in the range of 5.4 10(4)-1.2 x 10(6) M-1. Complexes 3-5 efficiently cleave supercoiled DNA to its nicked circular form in UV-A light of 365 nm via formation of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) species. Complexes 3-5 also exhibit significant photocytotoxic effect in HeLa cancer cells giving respective IC50 value of 0.16(+/- 0.01), 0.15(+/- 0.01) and 0.26 +/-(0.02) mu M in UV-A light of 365 nm, while they are less toxic in dark with an IC50 value of >3 mu M. The presence of an additional pyridyl group makes the pydppz complexes more photocytotoxic than their dppz analogues. FACS analysis of the HeLa cells treated with complex 4 shows apoptosis as the major pathway of cell death. Nuclear localization of complex 5 having an anthracenyl moiety as a fluorophore is evidenced from the confocal microscopic studies.

Monitoring of seasonal snow cover in Bhutan using remote sensing technique

All major rivers in Bhutan depend on snowmelt for discharge. Therefore, changes in snow cover due to climate change can influence distribution and availability of water. However, information about distribution of seasonal snow cover in Bhutan is not available. The MODIS snow product was used to study snow cover status and trends in Bhutan. Average snow cover area (SCA) of Bhutan estimated for the period 2002 to 2010 was 9030 sq. km, about 25.5% of the total land area. SCA trend of Bhutan for the period 2002-2010 was found to decrease (-3.27 +/- 1.28%). The average SCA for winter was 14,485 sq. km (37.7%), for spring 7411 sq. km (19.3%), for summer 4326 sq. km (11.2%), and for autumn 7788 sq. km (20.2%), mostly distributed in the elevation range 2500-6000 m amsl. Interannual and seasonal SCA trend both showed a decline, although it was not statistically significant for all sub-basins. Pho Chu sub-basin with 19.5% of the total average SCA had the highest average SCA. The rate of increase of SCA for every 100 m elevation was the highest (2.5%) in the Pa Chu sub-basin. The coefficient of variance of 1.27 indicates high variability of SCA in winter.

Regioselective Deiodination of Thyroxine by Iodothyronine Deiodinase Mimics: An Unusual Mechanistic Pathway Involving Cooperative Chalcogen and Halogen Bonding

Iodothyronine deiodinases (IDs) are mammalian selenoenzymes that catalyze the conversion of thyroxine (T4) to 3,5,3'-triiodothyronine (T3) and 3,3',5'-triiodothyronine (rT3) by the outer- and inner-ring deiodination pathways, respectively. These enzymes also catalyze further deiodination of T3 and rT3 to produce a variety of di- and monoiodo derivatives. In this paper, the deiodinase activity of a series of pen-substituted naphthalenes having different amino groups is described. These compounds remove iodine selectively from the inner-ring of T4 and T3 to produce rT3 and 3,3'-diiodothyronine (3,3'-T2), respectively. The naphthyl-based compounds having two selenols in the pen-positions exhibit much higher deiodinase activity than those having two thiols or a thiol selenol pair. Mechanistic investigations reveal that the formation of a halogen bond between the iodine and chalcogen (S or Se) and the pen-interaction between two chalcogen atoms (chalcogen bond) are important for the deiodination reactions. Although the formation of a halogen bond leads to elongation of the C-I bond, the chalcogen bond facilitates the transfer of more electron density to the C-I sigma* orbitals, leading to a complete cleavage of the C-I bond. The higher activity of amino-substituted selenium compounds can be ascribed to the deprotonation of thiol/selenol moiety by the amino group, which not only increases the strength of halogen bond but also facilitates the chalcogen chalcogen interactions.