Search Documents

By Yamada K, Abe H

Magnetic scanning type mass spectrometers have been given improved sensitivity with a large dynamic range and considerable resolution by the addition of a computer-controlled electric equipment. A mass spectrometer equipped with this newly developed electric system was applied to studies of the activities of liquid iron-silicon alloys and of liquid iron-phosphorus alloys at 1600¦C. The range of silicon concentration was 5.8at%-51.1 Si= at%, and values of ySi -3.1+0.15 and es 11.5 +1.5 were obtained. The concentration range of phosphorus was 1.3at%-5.7at% and a value of eP=7.3+0.1 was obtained.

Jan 1, 1980

By Seshadri Seetharuman

The present paper summarises a series of measurements of the interaction parameter of oxygen in liquid copper with respect to a third element, e(M)o, where M is Mn, Zn, As, Se or Te which are common impurities in the liquid metal. The technique employed was the solid electrolyte galvanic cell method. The cell used may be represented as Pt, W or cermet / Cu-O-M // ZrO2 - CaO // AO, A /PT where AO/A represents a suitable oxide/metal reference. The measurements indicate that Mn and Zn interact very strongly with oxygen in liquid copper while, in the case of arsenic the interaction parameter is nearly zero. The behaviour of the elements Se and Te is unique with respect to oxygen interactions in copper bath. At oxygen levels, xo= 10-4 ? 10-5, the apparent interaction parameters are negative, comparable to that for sulphur. On the other hand, at lower oxygen levels, the results indicate that the interaction parameter values are positive. The results are discussed in the light of some of the theoretical models for solute interactions in liquid metals.

Jan 1, 1993

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By Agrawal R. D, Kapoor M. L

Activity of FeO in the ternary system MgO-FeO-CaO in contact with metallic iron has been measured at 1000 K employing the cell.PtIFe, (Mg, Fe, Ca)OIZr02 - CaOIFe, FeOlPt. Measured data are used to study the phase stability relations in the system MgO-FeO-CaO and an isothermal section at 1000 K through this system is drawn.

Jan 1, 1987

By Muhammad A. Imam, Ramana G. Reddy

This study provides a reasonable evaluation of the Mg-B binary system. Magnesium and Boron (Mg-B) alloys were investigated to determine their thermodynamic properties employing solid state electrochemical cells based on CaF2 electrolyte represented as –Pt; Ar= MgþCaMgF4 f gCaF2 k kf½Mg B alloy þ CaMgF4 g=Ar; Pt+ Investigations were performed over the temperature range of 773–873 K to measure the electromotive force (EMF), which was used to derive the partial Gibbs Free energies of the alloys in the composition range of XB = 0.07 to 0.95. The activities of Mg were also calculated from partial Gibbs Free energies. The activities of Mg in MgB2, MgB4, and MgB7 were expressed as a function of temperature respectively, ln aMg = 4.27–9.32 × 103/T, ln aMg = −7.54 + 6.67×103/T, and ln aMg = 4.93–19.57 × 103/T, where T is the temperature in K. From this expression, the activity of Mg for these intermediate phases can be extrapolated at a higher temperature to get the accurate phase boundaries for the Mg-B system.

Mar 1, 2017

By Takashi Nagai, Hideaki Sasaki, Masafumi Maeda

"The production of solar cells is increasing dramatically and the shortage of polycrystalline silicon for these cells has become a serious problem, making development of a low-cost production process for solar grade silicon essential. An electron beam melting technique is known to be effective for the removal of phosphorus from molten silicon. Although the phosphorus is removed by preferential evaporation in this process, the rate of removal is not sufficient, and its improvement requires thermodynamic information on phosphorus in the molten silicon. In this research, the vapor pressure of phosphorus in equilibrium with a siliconphosphorus alloy was measured by double Knudsen cell mass spectrometry with a system blowing gas into the Knudsen cell. The activity of phosphorus in silicon, the Gibbs energy change of the dissolution of phosphorus in silicon, and other factors were estimated from the results. Using these data, we provided guidelines on how this process can be improved.IntroductionSolar energy is in great demand since it is inexhaustible and cleaner than that from conventional energy resources. Silicon is the material most widely used to convert solar energy into electricity. Figure 1 shows the recent production of solar cells. High purity silicon for solar cells, namely solar grade silicon (SOG-Si), has been commercially supplied mainly from off-grade high purity silicon in the semiconductor industry. However, production of solar cells has increased rapidly in recent years, and the shortage of SOG-Si has become a serious problem, so that a new processes which can produce SOG-Si economically are required.Directional solidification was applied to remove transition metal elements such as Fe or Ti by segregating them from the remaining melt. However, such solidification is useless for phosphorus because the segregation coefficient of phosphorus is nearly unity. Numerous approaches have been made in an attempt to produce a resource of low cost SOG-Si from metallurgical-grade silicon (MG-Si). [1,2]"

Jan 1, 2012

By V. L. Stolyarova

As part of an effort to develop the fluoride electrolysis route for the production of rare earth metals and alloys, a study of the thermodynamic properties of DyF3 has been carried out by Knudsen cell mass spectrometry. A quadrupole mass spectrometer QMS 420 was used in conjunction with the Knudsen cell arrangement. The experiments were carried out in the temperature range 1280-1440 K. Vaporization was carried out from platinum, molybdenum and tantalum cells. The Dy*, DyF+, DyF2+ fragment ions and the DyF3 parent ion were identified in the mass spectrum of the DyF3 vapour. The DyF, vapour pressure was obtained by the complete isothermal vaporizadon method as well as the ion current comparison method, and the enthalpy of sublimation of DyF3 was evaluated. From the DyF3 vapour pressure data obtained at different temperatures, the enthalpies of formation of DyF3 in the gaseous as well as condensed phases have been evaluated. The experimental data are compared with the thermodynamic information available in literature.

Jan 1, 1995

By Pedro Jorge Walburga Keglevich de Buzin

The steel production in mini mills generates several process residues, among them the electric arc furnace dust (EAFD). This residue has as main elements Fe, O, and Zn, being classified as hazardous by the presence of Pb and Cd. In recent years, a rise in the chlorine content of this residue was observed, motivated by the increased use of scrap with impurities bearing this element. In this work, a qualitative assessment of the presence of chlorine in the electric steelmaking process is made. Complementing it, theoretical considerations based on the computational thermodynamics tool FactSage show the effects of the chlorine on the mineral species in EAFD and on gaseous species in the gas phase (HCl and Cl2). For this study, PVC polymer was used as the chlorine carrier substance which contaminates the EAF charge; presence of other minor elements in the system such as K, Na and Pb were also considered.

Aug 7, 2018

By Kevin Trumble, David Johnson, Kyungjean Min

The electrolytic manganese dioxide (EMD) production through electrodeposition from manganese nodules by reduction leaching in H2SO4 medium using sucrose as reductant followed by purification through 2-stage precipitation methods is described. The purified leach liquor was the starting solution for electrodeposition. Influence of in situ addition of a cationic surfactant Cetyltri-methylammonium bromide (CTAB) (0–500 mg dm −3) on the surface morphology and electrochemical properties of the EMD was examined. The XRD patterns of the deposited material were indexed to the c-MnO2 phase. FESEM results demonstrated that in the presence of CTAB uniform nanofibrous type grains were formed. Higher concentration of CTAB in the electrolytic bath however, drastically decreased the current efficiency (CE) and increased the energy consumption (EC) during electrodeposition. Under the optimum CTAB concentration of 100 mg dm −3 the obtained CE and EC values were 87.64% and 1.70 kWh/Kg respectively.

Mar 1, 2018

By Kapoor M. L

Emf measurements on SE galvanic cell: SS; Ni-NiO I solid electrolyte/ZrO2 + CaO I [Pb + Bi]liq alloy; (PbO); SS were made in the temperature range 913-1034 K to determine the thermodynamic properties of oxygen dissolution in liquid lead. Bismuth alloys with bismuth in the dilute concentration range of 0 to 3.08 mass per cent and oxygen in the alloy varied by equilibrating the metallic system with a suitable (PbO) slag. Wagner's interaction parameter approach was used to calculate the ternary interaction parameter, eBiO at temperatures of 913, 953 and 993 and 1034 K and to observe the temperature dependence eBiO = 19 200/T - 17.454. Quasichemical fonnulation was employed to yield lnf BiO and reveal the effect of bismuth on oxygen in lead. The results obtained are discussed on the basis of theoretical models and the value of Wagner's energy parameter 'h' estimated to predict the results in a Pb-Bi-O system.

Jan 1, 1995

By Katsunori Yamaguchi

Secondary materials, that contain relatively high concentrations of platinum group metals, (PGMs) are treated in copper smelting process. The PGMs lost in the slag is increasing with increasing quantities of scrap treated amount. To determine the portion of the PGMs chemically dissolved and that associated with the mechanically trapped matte in the slag will be a key factor to improve the recovery of those metals. An experimental study was carried out to determine the distribution of palladium between the FeOx–SiO2 slag and the liquid Cu2S–FeS matte at 1573 K and a fixed partial pressure of SO2 of 0.1 atm. It was found that the distribution ratios are around 10−3 for platinum and palladium. The distribution ratios show a tendency to increase when the grade of matte is increased above 60 mass% Cu. In addition, the solubility of platinum in FeOx–SiO2 slag equilibrated with a pure palladium and the Pd-Cu alloy was determined at 1573 K and the range of oxygen partial pressure from 10−9 to 10−7 atm. The solubility of palladium in the slag tends to increase with increasing oxygen partial pressure and activity of CuO0.5 in the slag.

By J. Petersen, H. Naderi, M. H. Nikzad, M. Karimi

In this research, the thermodynamic study of sodium persulfate (Na2S2O8) solution in the presence and absence of H2SO4 and Fe3(SO4)3 was done. Eh-pH and equilibrium distribution diagrams were constructed using Outotec HSC Chemistry Software and the main stable ionic species were determined. Also, the mean activity coefficient and Pitzer model coefficients were evaluated. Effects of system composition, sodium persulfate concentration and temperature were investigated. According to the results, HS2O7 -, HS2O8 -, S5O3 2-, S4O3 2-, S3O3 2-, HS- and NaSO4 - are the main stable species in these three systems. Increasing of sodium persulfate concentration resulted in disappearing of SO4 2- and the appearance of NaSO4 -. The main effect of increasing the temperature from 25 to 75oC, is changing the stability regions of HS2O7 -, NaSO4 -, SO4 2- and S2-. From equilibrium studies, it was concluded that at 25 and 50oC, increasing the persulfate concentration results in a 55-60% decrease for HS2O7 - and an 20- 30% increase for HS2O8 -. At 75oC, HS2O8 - becomes the main species and its percentage decreases with increasing the persulfate concentration. Keywords: Thermodynamic, sodium persulfate, activity coefficient

Jan 1, 2020

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By Kazuaki Mita

There are various intermetallic compounds in the Zn-Fe system. We synthesized them at about 673K. A specimen was examined chemically and X-ray diffraction was applied to ensure the formation of intermetallic compounds. Material containing two phases was placed in a Knudsen type effusion cell and the mass spectrum studied to evaluate the vapor pressure of zinc. The thermodynamic properties of intermetallics was then evaluated through measured intensity.

Jan 1, 1999

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen ternary system, which is of fundamental importance for discussing the' recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, SbO1.5 and Sb2O3) in the PbO-SbO1.5 and PbO-Sb2O3 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Wei-Tong Du, Yu Wang, Gang Wen

Carbon dioxide (CO2), a major component of the greenhouse gases, could be comprehensive utilized as a valuable resource to oxidize vanadium during the converter vanadium extraction process. The thermodynamic software, FactSage, was utilized to study the oxidation ability and theoretical cooling ability of using weak oxidant CO2 as coolant in vanadium-containing hot metal. Besides, experimental research on vanadium extraction in CO2 and O2 mixed blowing extracting process had been undertaken. The results indicated that the elements C, Si, V, Mn etc. could be oxidized by weak oxidant CO2, and the content of V2O3 in slag was approached to pure O2 blowing. Furthermore, CO2 had a remarkable cooling ability and the molten bath temperature kept on decreasing as CO2 blowing rate increases. This research has proved that CO2 and O2 mixed blowing in vanadium extraction process are effective.

Jan 1, 2015

By Michael Wieland

The resolving capacity of the thermodynamic work-principal model has been seriously refined over its twelve year history, so a review of the innovations, wrong turns and their rectification is warranted to help future researchers. The work-principal model rests upon the four laws of thermodynamics that drive the universe and relatively few other assumptions: like the removing and imposing of constraints on the quasi-potential to yield trapped minimum key-states that represent the wanted process. The formative research was concerned with the role of ingredient changes, the removal of booster influence and the quench temperature with which to reckon toxic fumes. The transfer of reaction-zone energy as work upon the surrounding rock/water/fixture was not fully rationalized until the notion of reversed-inertial pressure was formulated and determined (for water) with underwater trinitrotoluene (TNT) shots. The rock-water-jelly model incorporated that term into its dynamic pressure formula as a way to represent rock blasts or underwater shots, while the zone of reaction gases remained trapped. The real irreversible thermodynamic process, which yielded the total expansion work, was later complemented with a wholly reversible imaginary process, to form a closed thermodynamic loop, with a remarkable consequence – the determination of the theoretical heave and hence, the undissipated-shock by difference from the total work. With the wholly developed model, it was recently possible to quantify the time retardation of reaction chemistry for non-molecular (mining) explosives, as compared to the rather negligible time-retardation found for the molecular (military) explosives in underwater tests.

Jan 1, 2009

By H. F. Feldmann

This work was done to provide thermodynamic, electrical, physical, and compositional data on the seeded combustion plasmas of seven coals for the design of MHD generators. The systems were assumed to be at equilibrium, and the design data were generated by solving for the composition of both gas and liquid phases with a digital computer. The coals reported in this study include a western subbituminous, a Pennsylvania anthracite, and five representative bituminous coals. The data include dewpoint temperatures of both slag and seed. A Mollier diagram for each coal is given to allow graphical generator calculations.

Jan 1, 1970

Thermodynamical data of importance in connection with copper smelting have been reviewed and a collection of the most reliable information is presented in Tables XXV-XXVIII and Figs. 67 and 6 8 (folding plate). The data given in these figures and tables consists of (i) graphs and equations showing the variations in the temperature range 0-2000°C. of the standard free energies of formation of most of the oxides and sulphides met with in copper smelting (Table XXV and Fig. 67); (ii) equations showing the temperature variation of the free energy of formation of iron silicates (Table XXVI); (iii) graphs showing the variation with temperature in the range 1000°-1600°C. of the standard free energies of the principal reactions occurring in the smelter (Fig. 6 8 ); (iv) the standard heats of formation at 1200°C. of the main iron and copper compounds and gases reacting in the smelter (Table XXVII); (v) the standard heats of reaction at 1200°C. of a few of the reactions for which the free energy relationships were given in Fig. 6 8 (Table XXVIII). The data presented are discussed in more detail.

Jan 1, 1953