Prediction of activities of oxygen in dilute quaternary solutions using binary data

Equations are developed for predicting the activity coefficients of oxygen dissolved in ternary liquid alloys. These are extensions of earlier treatments, and are based on a model in which each oxygen atom is assumed to make four bonds with neighboring metal atoms. It is also postulated that the strong oxygen-metal bonds distort the electronic configuration around the metal atoms bonded to oxygen, and that the quantitative reduction of the strength of bonds made by these atoms with all of the adjacent metal atoms is equivalent to a factor of approximately two. The predictions of the quasichemical equation which is derived agree satisfactorily with the partial molar free energies of oxygen in Ag-Cu-Sn solutions at 1200°C reported in literature. An extension of this treatment to multicomponent solutions is also indicated.

Solubility and activity of oxygen in liquid germanium and germanium copper alloys

The solubility of oxygen in liquid germanium in the temperature range 1233 to 1397 K, and in liquid germanium-copper alloys at 1373 K, in equilibrium with GeO2 has been measured by the phase equilibration technique. The solubility of oxygen in pure germanium is given by the relation R470 log(at. pct 0)=-6470/T+4.24 (±0.07). The standard free energy of solution of oxygen in liquid germanium is calculated from the saturation solubility, and recently measured values for the free energy of formation of GeO2, assuming that oxygen obeys Sievert’s law up to the saturation limit. For the reaction, 1/2 O2(g)→ OGe ΔG° =-39,000 + 3.21T (±500) cal = -163,200 + 13.43T (±2100) J. 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 effect of copper on the activity of oxygen dissolved in liquid germanium is found to be in good agreement with that predicted by a quasichemical model in which each oxygen was assumed to be bonded to four metal atoms and the nearest neighbor metal atoms to an oxygen atom are assumed to lose approximately half of their metallic bonds.

Vapor pressure and thermodynamic properties of MgIn2O4

The vapor pressure of pure indium, and the sum of the pressures of (In) and (In2O) species over the condensed phase mixture {In} + 〈MgIn2O4〉 + 〈MgO〉, have been measured by the Knudsen effusion technique in the temperature range 1095–1350 K. The materials under study were contained in a zirconia crucible, which had a Knudsen orifice along the vertical wall. The major vapor species over the condensed phase mixture were identified as (In) and (In2O) using a mass-spectrometer. The vapor pressure of (In2O) corresponding to the reaction,View the MathML source was deduced from the experimental results;View the MathML source The standard free energy of formation of the inverse spinel 〈MgIn2O4〉 from its component oxides, is given by,View the MathML source View the MathML source The entropy of transformation of 〈In2O3〉 from the C rare-earth structure to the corundum structure is evaluated from the measured entropy of formation of (MgIn2O4) and a semi-empirical correlation for the entropy of formation of spinel phases from component oxides with rock-salt and corundum structures.

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.

Revision of thermodynamic data on MnO Al2O3 melts

The high temperature region of the MnO-A1203 phase diagram has been redetermined to resolve some discrepancies reported in the literature regarding the melting behaviour of MnA1,04. This spinel was found to melt congruently at 2108 (+ 15) K. Theactivity of MnOin MnO-Al,03 meltsand in the two phase regions, melt + MnAI,04 and MnAI2O4 + A1203, has been determined by measuring the manganese concentration in platinum foils in equilibrium under controlled oxygen potentials. The activity of MnO obtained in this study for M ~ O - A I ,m~el~ts is in fair agreement with the results of Sharma and Richardson.However. the alumina-rich melt is found to be in equilibrium with MnAl,04 rather than AI2O3. as suggested by ~ha rmaan d Richardson. The value for the acthity of MnO in the M~AI ,O,+ A1,03 two phaseregion permits a rigorous application of the Gibbs-Duhem equation for calculating the activity of A1203 and the integral Gibbs' energy of mixing of MnO-A1203 melts, which are significantly different from those reported in the literature.

Thermodynamic properties of Fe3O4 FeV2O4 and Fe3O4 FeCr2O4 spinel solid solutions

Solid solutions of Fe304-FeV204 and Fe304-FeCr204 were prepared and equilibrated with Pt under controlled streams of CO/CO, gas mixtures at 1673 K. The concentration of Fe in Pt was used to determine the activity of Fe304 in the solid solutions. The activity of the second component was calculated by Gibbshhem integration. From these data, the Gibbs energy of mixing was derived for both systems. The experimental results and theoretical values which are determined from calculated cation distribution compare favorably in the case of vanadite solid solutions but not in the case of chromite solid solutions. The difference is attributed to a heat term arising from lattice distortion due to cation size difference. The positive heat of mixing will give rise to a miscibility gap in the system Fe304-FeCr204 at lower temperatures.

Thermodynamic study of Fe2O3 Fe2(SO4)3 equilibrium using an oxyanionic electrolyte (Na2SO4 I)

The emf of the cell, Pt, Ar + O2 + SO2 + SO3/Na2SO4-I/Fe2O2 + Fe2(SO4)3, Pt, has been measured in the temperature range 800 to 1000 K, using a gas mixture of known input composition as the reference electrode. The equilibrium composition of the reference gas at the measuring temperatures was computed using the thermodynamic data on the gaseous species reported in the literature. A mixture of ferric oxide and sulfate was kept in a closed system to ensure establishment of equilibrium partial pressure at the electrode. The cell was designed to avoid physical contact between Fe2(SO4)3 and Na2SO4 electrolyte. Uncertainties arising from the formation of sulfate solid solution were thus eliminated. The Gibbs’ energy of formation of ferric sulfate calculated from the emf is discussed in comparison with data reported in the literature. There is no evidence for the formation of oxysulfates in the Fe-S-0 system. Based on the results obtained in the present study for Fe2(SO4)3 and literature data for other phases, chemical potential diagrams have been constructed for the Fe-S-O system at 900 and 1100 K.

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.

Measurement and modeling of Alloy-Spinel-Corundum equilibrium in the Ni-Mn-Al-0 system at 1873 K

The oxygen content of liquid Ni-Mn alloy equilibrated with spinel solid solution, (Ni,Mn)O. (1 +x)A12O3, and α-Al2O3 has been measured by suction sampling and inert gas fusion analysis. The corresponding oxygen potential of the three-phase system has been determined with a solid state cell incorporating (Y2O3)ThO2 as the solid electrolyte and Cr + Cr2O3 as the reference electrode. The equilibrium composition of the spinel phase formed at the interface of the alloy and alumina crucible was obtained using EPMA. The experimental data are compared with a thermodynamic model based on the free energies of formation of end-member spinels, free energy of solution of oxygen in liquid nickel, interaction parameters, and the activities in liquid Ni-Mn alloy and spinel solid solution. Mixing properties of the spinel solid solution are derived from a cation distribution model. The computational results agree with the experimental data on oxygen concentration, potential, and composition of the spinel phase.

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.

A new matched thermochemical diagram for vacuum refining of nickel and cupronickel alloys

Sulfur and oxygen dissolved in nickel and cupronickel melts can be remwed as gaseous oxides of sulfur by a vacuum treatment. Presented in this paper is a new matched thermcxhemical disgran~ that permit.. direct evaluation of the equilibrium partial pressure of SO, as a function of temperature wer an alloy of specified compition. The matched thermochemical diagram consists of a central plot which shows the integral Gibbs' energy of mixing for the binary system SO, at different temperatures. The central plot is flanked on either side by terminal plots of the chemical potentials of oxygen and sulfur, as functions of temperature, for different alloy compositions. By projecting the chemical wtentials of oxygen and sulfur from the terminal lots on to the central diagram, ihe equilibrium partial pressure of S0,can be directly ;cad on the nomograms on the central plot at different temperatures. The matched therrnochemical diagrams are useful in assuring the efficiency of vacuum refining.

A thermodynamic study of liquid Cu-Cr alloys and metastable liquid immiscibility

he thermodynamic acitivity of chromium in liquid Cu-Cr alloys is measured in the temperature range from 1473 to 1873 K using the solid state cell: Pt, W, Cr + Cr2O3 |(Y2O3) ThO2|Cu - Cr + Cr2O3, Pt The activity of copper and the Gibbs energy of mixing of the liquid alloy are derived. Activities exhibit large positive deviations from Raoult's law. The mixing properties can be represented by a pseudo-subregular solution model in which the excess entropy has the same type of functional dependence on composition as the enthalpy of mixing: ΔGE = XCr(1 - XCr)[60880 - 18750 XCr)-- T(16.25 - 7.55 XCr)]J mol-1 Pure liquid Cu and Cr are taken as the reference states. The results predict a liquid-liquid metastable miscibility gap, with TC = 1787 (±3) K and XCr = 0.436 (±0.02), lying below the liquidus. The results obtained in this study are in general agreement with experimental information reported in the literature, but provide further refinement of the thermodynamic parameters.

Analysis of Lined Ducts With Mean Flow, With Application to Dissipative Mufflers

Mufflers with at least one acoustically absorptive duct are generally called dissipative mufflers. Generally, for want of systems approach, these mufflers are characterized by transmission loss of the lined duct with overriding corrections for the terminations, mean flow, etc. In this article, it is proposed that dissipative duct should be integrated with other muffler elements, source impedance and radiation impedance, by means of transfer matrix approach. Towards this end, the transfer matrix for rectangular duct with mean flow has been derived here, for the least attenuated mode. Mean flow introduces a coupling between transverse wave numbers and axial wave number, the evaluation of which therefore calls for simultaneous solution of two or three transcendental equations. This is done by means of a Newton-Raphson iteration scheme, which is illustrated here for square ducts lined with porous ceramic tiles.

Reactive interdiffusion: deviation from local equilibrium in the Fe-NiTiO3 couple

Deviation from local equilibrium between Fe–Ni alloy and (Fe,Ni)TiO3 solid solution in the reaction–diffusion zone of the Fe–NiTiO3 couple at 1273 K is evaluated by comparing the measured compositions in the zone with experimentally determined equilibrium tie-lines. The deviation is quantified by computing the Gibbs energy change for the reaction, Fe + NiTiO3 → FeTiO3 + Ni, from measured compositions in the zone and activity data available in the literature. Except near the extremities of the zone, the computed Gibbs energy change is constant, 8.2 kJ mol−1 higher than the standard Gibbs energy change for the reaction.

Kinetics of carbon monoxide oxidation with Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts

Base metal substituted Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts were synthesized by the solution combustion method and characterized by XRD, XPS, TEM and BET surface area analysis. The catalytic activities of these materials were investigated by performing CO oxidation. The rates and the apparent activation energies of the reaction for CO oxidation were determined for each catalyst. All the substituted catalysts showed high rates and lower activation energies for the oxidation of CO as compared to unsubstituted SnO(2). The rate was found to be much higher over copper substituted SnO(2) as compared to other studied catalysts. 100% CO conversion was obtained below 225 degrees C over this catalyst. A bifunctional reaction mechanism was developed that accounts for CO adsorption on base metal and support ions and O(2) dissociation on the oxide ion vacancy. The kinetic parameters were determined by fitting the model to the experimental data. The high rates of the CO oxidation reactions at low temperatures were rationalized by the high dissociative chemisorption of adsorbed O(2) over these catalysts.