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By S Jahanshahi, D R. Swinbourne

The classical metal-slag-gas equilibrium technique was used to study the thermodynamic activity of cobalt, iron and their oxides in iron silicate based slags containing under controlled oxygen potential (3.70 x 10-8 to 2.95 x 10-7 atm) at 1573 K. The measured activity of cobalt oxide in FeOx-25 wt per cent SiO2 slags showed positive deviation from ideal behaviour for melts with up to ten wt per cent CoO. At higher silica contents, the behaviour became closer to ideal and in accord with previous studies on silica saturated slags. The activity coefficient of FeO in these slags had virtually no dependence on the CoO content. Partial substitution of silica by lime resulted in an increase of the activities and activity coefficients of CoO, FeO, Fe2O3 and Fe3O4. The results indicate that saturation of the slag with a magnetite phase occurs at CaO contents of five wt per cent and higher. Phase equilibria studies SiO2-FeO-Fe2O3-CaO slags containing cobalt were also carried out using the drop-quench technique. Results from these experiments confirmed the formation of a magnetite solid solution containing about three wt per cent CoO at lime contents of five wt per cent and higher at 1573 K and 2.9 x 10-7 atm of oxygen.

Jan 1, 2000

By J Rapkoch, M Cerna

As long as the tendency of Chilean copper ores continues to feature high levels of impurities, the smelters will tend to produce high-impurity mattes. The most notable impurities include As, Sb, Pb and Zn. Producing high-quality copper with such materials is a major challenge to metallurgical engineers and operators. More investigations into process optimisations and/or alternatives are needed, using both theoretical knowledge and operational skill. Converting of matte in Chile depends on the matte grade using established technologies. Mattes up to 66 per cent Cu, such as those from Outokumpu Flash furnaces, are converted in two stages, while typical Teniente Converter mattes, ranging from 70 - 74 per cent Cu are converted in one blow, directly to copper. In this paper thermodynamic data are used to evaluate possible variations in the use of traditional technologies applied to smelt copper concentrates with high impurity levels. The results of this analysis help to predict the impurity distributions between matte-slag-gas during the slag blow, and between copper-slag-gas during the copper blow. For converting high-impurity white metal, the effectiveness of volatilisation in the slag blow is analysed. In the copper blow, the type and the amount of flux (SiO2, CaO and others) are altered with the aim of optimising impurity distribution to the slag and gas.

Jan 1, 2005

By P. M. May, J. S. Solis, G. T. Hefter

Chemical speciation plays a critical role in many areas of gold processing. These include the formation of HCN in plant liquors, interference by copper in the extraction efficiency of gold, the recovery of adsorbed gold, and the behaviour of plant effluents in the environment. Thermodynamic modelling provides a cost-efficient method of rationalizing and even predicting of chemical behaviour. Unfortunately, because thermodynamic data for cyanide complexes are of poor quality and few are known under hydrometallurgical conditions. Such models are currently of limited use. This paper describes recent work on the thermodynamics of cyanide complexes of a range of metal ions. Data will be presented on the stabilities and enthal­pies (heats) and entropies of formation of a variety of metal ion species determined by potentiometry and calorimetry. Particular emphasis will be placed on the Cu(I)/CN- system.

Jan 1, 1995

By Yoshinao Kobayashi

he removal of oxygen from titanium and zirconium is important for use in application because it significantly affects the mechanical and physical properties such as ductility and toughness. However, thermodynamic properties of oxygen in molten titanium and zirconium have not been clarified and the effective deoxidation process of molten titanium and zirconium has not been established. In this study, the standard Gibbs energy of reaction of oxygen and yttrium in molten titanium and zirconium have been measured by a chemical equilibrium technique. Molten titanium, zirconium, and their alloys with aluminum were equilibrated with a Y2O3, A12O3, or Zr02 pellet in a cold crucible. The results are summarized as follows:

Jan 1, 2000

By H. B. Bell, L. C. Smith

Measurements have been made of the activity of 'FeO' in 'Fe0'-Mn0-Ti02 melts at 1475 degrees C. The results obtained are discussed in terms of ideal mixing of titanates and in terms of a regular solution model. On the basis of the regular solution model activities of Ti02 and MnO in the Fe0-Mn0-Ti02 and Mn0-Ti02 systems have been derived. The data have been shown to be consistent with the liquidus lines in the phase systems. Examples are given of the application of the data to slag-metal equilibria, being used to derive slag-metal data between liquid iron and Fe0-Mn0-Ti02 slags

Dec 1, 1971

By Hikosaka A, Chiba A

In a fundamental study of the physical chemistry of steelmaking slag, equilibra bet- ween hydrogen-water vapour gas mixtures and liquid slags contained in solid iron crucibles have been measured for four binary slags, FetO-CaO, FetO-Si02, FetO-TiO2 and FetO-Al203 at 14000C. From the data, the activity of iron oxide and the ratio of ferrous and ferric ions (A = Fe3+/Fe2+) were calculated for the slag composition. The best ionic model is found to be that based on regular solution of cations. The oxygen distribution between slag and metal is quantitatively expressed by this model over a wide range of slag composition.

Jan 1, 1980

By Iwu GO, Almond DP, Joasoo _

The gravimetric integral Knudsen effusion method was used to measure cadmium activity values in binary liquid In-Cd alloys in the range 523 to 573 K. The activity measurements together with other studies from the literature indicate that special bonding conditions exist in the melts near a composition corresponding to InCd3. Sound velocities in In-Cd melts were also measured using a precision pulse-echo over- lap method in the range 404 to 953 K. The frac- tional deviation of experimental and ideal isentropic compressibilities at 623K shows a functional dependence on composition with a pronounced maximum near the composition 75 at.%.

Jan 1, 1980

By Yun Soon Han, Joo Hyun Park

Indium (In) solubility in the FeO-SiO2-Al2O3-5%CaO slag was measured under p(O2)=10¯¹¹ atm at 1573 K to clarify the dissolution mechanism of In in FeO-bearing metallurgical slag. The In solubility increased with increasing oxygen partial pressure, whereas it decreased by increasing the activity of basic oxide, viz. FeO. Thus, a dissolution mechanism of In in the FeO-SiO2- Al2O3-5%CaO slag was described by the following equation. In(s)+1/4O2(g)=(In+)+1/2(o2-) The enthalpy change of the In dissolution reaction was negative, indicating that the dissolution reaction was an exothermic reaction. This is consistent with the above reaction mechanism.

Jan 1, 2014

By Ivan Imris

The iron production has generated many tonnes of very fine residues with high concentration of iron. In addition, during the recycling of galvanised steel scrap in the steel making processes the zinc and lead are largely concentrated in the dust. These kinds of dusts are usually dumped beside the metallurgical plants and cause environmental problems. Therefore the metal recovery from the metallurgical residues has become a major interest not only from the viewpoint of metals recycling but mainly from the viewpoint of environmental land protection. The thermodynamic analyses and laboratory experiments suggested that the metals could be recovered from metallurgical wastes by reduction roasting and by plasma smelting processes. The iron rich pellets with very high metallization may be obtained from metallurgical wastes by the reduction roasting and the inert slag and pig iron could be produced by plasma smelting processes. In both cases the iron rich products are suitable for the steel production. During the reduction roasting or plasma smelting the high volatile zinc and lead metals were removed and enriched as a secondary dust, Zn-Pb concentrate, which is suitable for processing in zinc and lead smelters. Suggested processes are commercially feasible and environmentally friendly without any solid or liquid waste.

Jan 1, 2003

By Toguri JM

A solid electrolyte technique has been used to measure the activity of cobalt in liquid cobalt-gold alloys containing between 0.085 and 0.50 mole fraction of cobalt, and for temperatures from just above the liquidus to around 1550 K. The system exhibits positive deviation from ideality, both in the activities of cobalt and gold, and in the enthalpy and excess entropy of mixing. The results agree with previous measurements using a Knudsen cell - mass spectrometer technique, but differ from those reported for a gas equilibration method. The data have been used to calculate the activity coefficient of cobalt oxide in silica saturated iron silicate slags and to express the solubility of cobalt in such slags as a function of cobalt activity and oxygen pressure.

Jan 1, 1984

Thermodynamic properties of the solutions of hydrogen in metals and carbon in austenite were investigated and it is possible to predict the interstitial solubility in these systems over relatively wide ranges of temperature and solute activity. Monte Carlo methods were used to compute the arrangements of interstitial atoms on the tetrahedral sites in body centred cubic metals and the octahedral sites in face centred cubic metals. It was shown that the non-configurational entropies of solution of hydrogen in metals can be interpreted as being principally vibrational and on this basis the potential value of the isotopic solubility ratio theory in indicating the compositional variation of these non-configurational entropies was discussed. The need for future work along these lines is pointed out.

Jan 1, 1970

Cospidie (3CaO*2SiO2*CaFe2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel, The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiO2-CaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been deterimed by an electromotive force methods using CaF2 as solid electrolyte and a transpiration method as follows: ^fG° (cuspidine) /kjmol-1 = 5198 + 0.825T (+12) (1313<T/K<1329): EMF method ^fG° (cuspidine) /kjmol-1 = 5178 + 0.813T (+8) (1221<T/K<1469): Transpiration method The chemical potential diagram and constituent activities for the CaO-SiO2-CaF2 System have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

Thermodynamics of Non-Cyanide Gold Solvents The present status of the raw material base in the gold industry requires specific ways to recover gold and silver from ores. Most gold is closely associated with sulfides which require flotation followed by pressure or bacterial oxidation. The next stages of processing usually require using expensive operations for the preparation of leaching. A lot of researchers want to find a new alternative solvent for the extraction of precious metals from these products. According to the authors, one of the best ways is to use sulfur-based solvents (thiosulfate, sulfite, and their various mixtures). Thermodynamics of gold and silver thiosulfate dilution are calculated for conditions: the concentration of Au - 200 mg/L, oxygen - 3.2 mg/L, thiosulfate - 79 mg/L, OH- - 170 mg/L. the general result is the possibility of process remains under standard conditions. (erAu = = 0.035 V, ?G298 = - 29.18 kJ/g-atom ??). Silver with thiosulfate forms two strong complexes: [AgS203]- and [Ag(S203)2]3-. ?G0 = -1027 kJ/mol. The complex [AgS203]- is less stable: ?G0 = 486 kJ/mol. It should be noted that despite the high stability of gold complexes, the sodium thiosulfate may decompose to sulfite and elemental sulfur during the process, especially when heating. Gold is slightly soluble in the sodium sulfite solution, however it forms the strong complex [Au(SO3)2]3-. Depending on the concentration of free S2O32-ions, silver with sodium sulfite forms three complexes: [AgSO3]-, [Ag(SO3)2]3- and [Ag(SO3)3]5-. The dissolution speed of gold in sodium sulfite solution may be in the same range as it is during cyanidation. In this case, a practical application of sulfite process can be also used, especially for the products containing free elemental sulfur. In conclusion, sulfite-thiosulfate gold lixiviants can be used for concentrates after pressure oxidation of the cakes.

Sep 13, 2010

By J. H. E. Jeffes, K. T. Jacob

Solid oxide galvanic cells, of the type: Pt,Ni-NiO | Solid electrolyte | O(metal),Cermet,Pt, were used to measure the activity coefficient of oxygen in liquid Cu at 1 100 and 1 300°C and in Pb at 1 100°C. Similar cells were used to study the activity coefficient of oxygen in the whole range of Cu + Pb alloys at 1 100°C and in Pb-rich alloys at 900 and 750°C. The results obtained are discussed in terms of proposed solution models. An equation based on the formation of 'species' of the form M(2)O in solutions of oxygen in binary alloys is shown to fit the experimental data

Dec 1, 1971

By J. W. Matousek

Tonnage oxygen plays a critical role in the primary production of two of the most important industrial metals - copper and iron - and minute quantities of oxygen play equally critical roles in determining the properties of the market products. For refined copper, oxygen in the final metal is balanced between maximizing electrical conductivity, neutralizing the effects of harmful impurities, and ensuring that the metal takes on the desired "set" during casting - the surface texture and physical properties required for subsequent rolling and drawing. For refined iron, oxygen must be removed to minimize reaction with carbon during cooling from the molten state with the generation of CO and CO2 - leading to a loss of carbon and the creation of "blow-holes" in the solid ingots and the potential for defects in rolled and forged products. This paper reviews the thermodynamics of oxygen in molten copper and iron at the levels of primary interest to production metallurgists.

Jan 1, 2014

By Takaaki Ishikawa

The distribution equilibria of lead, zinc and copper between CaO-Si02-Ah03 melts and liquid copper were measured at 1623K under a controlled H2-C02 atmosphere. The distribution ratios were plotted against the oxygen partial pressure, and reasonable oxide forms dissolved in the melts were estimated from the slopes of the plots. The activity coefficients of zinc oxide (ZnO), lead oxide (PbO) and cuprous oxide (CuOQs) increased with increasing slag basicity, defined by Xcao /XSiO, The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003

By Takaaki Ishikawa

The distribution equilibria of lead, zinc and copper between CaO-Si02-Ah03 melts and liquid copper were measured at 1623K under a controlled H2-C02 atmosphere. The distribution ratios were plotted against the oxygen partial pressure, and reasonable oxide forms dissolved in the melts were estimated from the slopes of the plots. The activity coefficients of zinc oxide (ZnO), lead oxide (PbO) and cuprous oxide (CuO0.5) increased with increasing slag basicity, defined by XCao/Xsio2 The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003

By Mansoor Barati, Leili Tafaghodi Khajavi

"This study involves employing solvent refining as a purification process in which silicon recrystallization takes place from an iron-silicon melt. It is believed that iron will act as the impurity “getter” and purified silicon crystals will grow from the alloy melt, while the impurities are segregated to the liquid alloy. Phosphorous is a problematic impurity to remove since its segregation coefficient in pure silicon is relatively large. To assess the feasibility and efficiency of phosphorous removal through solvent refining, it is critical to study its equilibrium distribution between solid Si and the Fe–Si alloy phase.The distribution of phosphorous between solid silicon and iron-silicon melt at 1210-1310 °C was measured to evaluate the impurity removal potential of each alloy. Interaction parameter between phosphorous and iron was calculated by varying the concentration of phosphorous in silicon.IntroductionAmong various semiconductor materials for manufacture of solar cells, silicon accounts for over 90 percent of today's PV materials [1, 2].The major challenge in producing solar silicon that operates efficiently is to meet purity level requirement through a cost efficient route. Silicon solar cells can play a significant role in answering the world's need for energy if cost reductions can be achieved through manufacturing process. Considerable effort has been made to replace the expensive, complex vapor-phase purification by a simpler and less costly process. One of the refining approaches that have attracted wide research interests is producing low-cost solar grade silicon by purification of metallurgical grade silicon. Since metallurgical processes are selective in removing impurities, a combination of various purification processes can be used to reduce the impurity level in silicon. Considering different thermodynamic characteristics of impurities, each refining step is responsible for lowering specific impurities."

Jan 1, 2012

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998