Some studies on a solid state sulphur probe for coal gasification system

Measurements on the solid electrolyte cell(Ar -b H2 ~ H2S/CaS + CaF2 ~- ( P t ) / / C a F 2 / / ( P t )-~- CaF2 ~ CaS/H2S ~- H2 ~- At) show that the emf of the cell is directly related through the Nernst equation to the difference in sulfur potentials established at the two Ar ~- H2 ~ H2S/electrode interfaces. The electrodes are designed to convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient with the aid of the reaction, CaF2(s) ~ 1~ S2(g)-e CaS(s) ~- F2(g). The response time of the probe varies from approximately 9 hr at 990~ to 2.5 hr at 1225~ The conversion of calcium sulfide and/or calcium fluoride into calcium oxide should not be a problem in anticipated commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.

A solid-state probe for SO2/SO3 based on Na2SO4 I electrolyte

Conductivity measurements as a function of temperature and partial pressures of SOs, SO2, and O2, and transference experiments indicate that the transport number of Na + ions is unity in Na2SO4-I. A concentration cell based on this electrolyte Pt, O2' + SO2' + SOs'/Na2SO4-I/SOa" + SO~" + O~", Pt produces emf's that are in agreement with those calculated from the Nernst equation when equilibrium is assumed between the gas species at the electrodes. The cell can be used for monitoring the SO#SOs pollution in air, and in combination with an oxygen probe can be used for the determination of SO=/SOs concentrations in coal combustion reactors, for the evaluation of the partial pressure of $2 in coal gasification systems, and for emission control in nonferrous smelters using sulfide ores. The probe is similar to that developed recently by Gauthier et aL (4, 5) using K=SO4 as the electrolyte, but can operate at higher pressures of SO3. Because of the greater polarizing power of the Na+ ion compared to the K + ion, Na2S207 is less stable and can be formed only at a considerably higher pressure of S03 than that required for K~20~.

Some recent developments in solid state galvanic sensors

A critical revi<:w of the possibilities of measuring the ~artlal pressure of sulfur using solid state galvanic cells )'n;;cd on AgI, C" , B-alumina, CaO-Zr02' Na2S04-I and doped ;:":;, ,,,Ilil "Iltl ,,11: auxiliary "jectrodes are presentlOu. SOIll..., df tllc!iL' sYHtcmH h,}vu inherent limltntlol1$ when <:xl'o" ...d to environments contilining both oxygen and sulfur. Electrode polarization due to electronic conduction in the solid electrolyte is a significant factor limiting the ;lC'e,"'acy of isotlwrm:l1 cell",. The electrochemical flux of{lit' !'\)ndlwl Ill}: Ion LhnHO',h tht' ('!('ctrojyt(~ C:Ul },(,! llIinlnliz(,{j pfUjJL!f cell. dL:~) i.t',11. Noni!:iot.herm~ll cells \.Jlth temperaLure compensated reference electrodes have a number of advantages over thC'ir isothermal counterparts.

Phase relations in the system Sr–Ir–O and thermodynamic measurements on SrIrO3, Sr2IrO4 and Sr4IrO6 using solid-state cells with buffer electrodes

The standard Gibbs energies of formation of SrIrO3, Sr2IrO4 and Sr4IrO6 have been determined in the temperature range from 975 to 1400 K using solid-state cells with (Y2O3) ZrO2 as the electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system Sr–Ir–O were investigated at 1350 K. The only stable oxide detected along the binary Ir–O was IrO2. Three ternary oxides, SrIrO3, Sr2IrO4 and Sr4IrO6, compositions of which fall on the join SrO–IrO2, were found to be stable. Each of the oxides coexisted with pure metal Ir. Therefore, three working electrodes were prepared consisting of mixtures of Ir+SrO+Sr4IrO6, Ir+Sr4IrO6+Sr2IrO4, and Ir+Sr2IrO4+SrIrO3. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. Used for the measurements was a novel apparatus, in which a buffer electrode was introduced between reference and working electrodes to absorb the electrochemical flux of oxygen through the solid electrolyte. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The standard Gibbs energies of formation of the compounds, obtained from the emf of the cells, can be represented by the following equations: View the MathML sourcem View the MathML source View the MathML source where Δf (ox)Go represents the standard Gibbs energy of formation of the ternary compound from its component binary oxides SrO and IrO2. Based on the thermodynamic information, chemical potential diagrams for the system Sr–Ir–O were developed.

System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.

An advanced design of the solid-state cell for accurate thermodynamic measurements on ternary oxides: system Sm–Pd–O

An advanced design of the solid-state cell incorporating a buffer electrode has been developed for high temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The application of the novel design and its advantages have been demonstrated by measuring the standard Gibbs energies of formation of ternary oxides of the system Sm–Pd–O. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system Sm–Pd–O were investigated at 1273 K. The two ternary oxides, Sm4PdO7 and Sm2Pd2O5, compositions of which fall on the Sm2O3–PdO join, were found to coexist with pure metal Pd. The thermodynamic properties of the ternary oxides were measured using three-phase electrodes in the temperature range 950–1425 K. During electrochemical measurements a third ternary oxide, Sm2PdO4, was found to be stable at low temperature. The standard Gibbs energies of formation (Δf(ox)Go) of the compounds from their component binary oxides Sm2O3 and PdO, can be represented by the equations: Sm4PdO7: Δf(ox)Go (J mol−1)=−34,220+0.84T(K) (±280); Sm2PdO4: Δf(ox)Go (J mol−1)=−33,350+2.49T(K) (±230); Sm2Pd2O5: Δf(ox)Go (J mol−1)=−59,955+1.80T(K) (±320). Based on the thermodynamic information, three-dimensional P–T–C and chemical potential diagrams for the system Sm–Pd–O were developed.

Solid-state cells with buffer electrodes for accurate thermodynamic measurements: system Nd-Ir-O

A new design for the solid-state cell incorporating a buffer electrode for high-temperature thermodynamic measurements is presented. The function of the buffer electrode, placed between the reference and working electrodes, is to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevents polarization of the measuring electrode and ensures accurate data. The application of this novel design and its advantages are demonstrated by measurement of the standard Gibbs energies of formation of Nd6Ir2O13 (low-temperature form) and Nd2Ir2O7 in the temperature range from 975 to 1450 K. Yttria-stabilized zirconia is used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system NdIrO were investigated at 1350 K. The two ternary oxides, Nd6Ir2O13 and Nd2Ir2O7, compositions of which fall on the join Nd2O3IrO2, were found to coexist with pure metal Ir. Therefore, two working electrodes were prepared consisting of mixtures of Ir+Nd2O3+Nd6Ir2O13 and Ir+Nd6Ir2O13+ Nd2Ir2O7. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. The standard Gibbs energies of formation (ΔG°f (ox)) of the compounds from their component binary oxides Nd2O3 and IrO2, obtained from the emf of the cells, can be represented by the equations:View the MathML source View the MathML source Based on the thermodynamic information, chemical potential diagrams for the system NdIrO are developed.

Solid state electrochemical sensor for monitoring Mg in Al refining process

Novel solid-state electrochemical sensors have been designed using the Mg2+ cation conductors incorporating novel solid-state reference electrodes for in-line monitoring of Mg in molten Al during the refining process and also for in-line monitoring of Mg content in molten Al in the alloying process. In this paper we report the preparation of Mg2+ ion conductors, MgAl2O4 and MgZr4(PO4)6, by the solid state ceramic synthesis route, measurement of their electrical properties using ac-impedance spectroscopy and application of the above cation conductors for designing novel electrochemical sensors for monitoring Mg dissolved in molten Al. The activation energy for Mg2+ ion conduction in MgAl2O4 is 2.08 eV and in MgZr4(PO4)6 is 1.7 eV, respectively. The sensors have been found to respond rapidly to change in Mg content in molten aluminium around 1000 K.

Specification Based Regression Testing Using Explicit State Space Enumeration

This paper presents a method of partial automation of specification based regression testing, which we call ESSE (Explicit State Space Enumeration). The first step in ESSE method is the extraction of a finite state model of the system making use of an already tested version of the system under test (SUT). Thereafter, the finite state model thus obtained is used to compute good test sequences that can be used to regression test subsequent versions of the system. We present two new algorithms for test sequence computation - both based on our finite state model generated by the above method. We also provide the details and results of the experimental evaluation of ESSE method. Comparison with a practically used random-testing algorithm has shown substantial improvements.

On Convergence of Differential Evolution Over a Class of Continuous Functions With Unique Global Optimum

Differential evolution (DE) is arguably one of the most powerful stochastic real-parameter optimization algorithms of current interest. Since its inception in the mid 1990s, DE has been finding many successful applications in real-world optimization problems from diverse domains of science and engineering. This paper takes a first significant step toward the convergence analysis of a canonical DE (DE/rand/1/bin) algorithm. It first deduces a time-recursive relationship for the probability density function (PDF) of the trial solutions, taking into consideration the DE-type mutation, crossover, and selection mechanisms. Then, by applying the concepts of Lyapunov stability theorems, it shows that as time approaches infinity, the PDF of the trial solutions concentrates narrowly around the global optimum of the objective function, assuming the shape of a Dirac delta distribution. Asymptotic convergence behavior of the population PDF is established by constructing a Lyapunov functional based on the PDF and showing that it monotonically decreases with time. The analysis is applicable to a class of continuous and real-valued objective functions that possesses a unique global optimum (but may have multiple local optima). Theoretical results have been substantiated with relevant computer simulations.

Convergence problems in a class of model reference adaptive control systems

A class of model reference adaptive control system which make use of an augmented error signal has been introduced by Monopoli. Convergence problems in this attractive class of systems have been investigated in this paper using concepts from hyperstability theory. It is shown that the condition on the linear part of the system has to be stronger than the one given earlier. A boundedness condition on the input to the linear part of the system has been taken into account in the analysis - this condition appears to have been missed in the previous applications of hyperstability theory. Sufficient conditions for the convergence of the adaptive gain to the desired value are also given.

Colossal electroresistance and current induced switching in ferromagnetic insulating state of La0.82Ca0.18MnO3

Colossal electroresistance and current induced resistivity switching have been measured in the ferromagnetic insulating (FMI) state of single crystal manganite La0.82Ca0.18MnO3. The sample has a Curie transition temperature TC = 165 K and the FMI state is realized for temperatures T<100 K. The electroresistance (ER), arising from a strong nonlinear resistivity, attains a large value ( ≈ 100%) in the FMI state. However, this is accompanied by a collapse of the magnetoresistance (MR) to a small value even in magnetic field (H) of 10 T. This demonstrates that the mechanisms that give rise to ER and MR are effectively decoupled.

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.