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By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By T. Markus, K. Hilpert

Discharge vessels of advanced light sources are made of translucent polycrystalline Al2O3(PCA).These tubes contain salt mixtures, which essentially consist of metal halides. The salt mixture is present as a melt at the coldest spot of the vessel under operating conditions and vaporizes partly. The temperatures of the coldest spot range between 1200 K and 1300 K, depending on the lamp performance. The maximum wall temperatures range up to 1500 K and for special purposes up to1700 K. Important constituents of the melt are alkali halides AX (A = Na, Cs, X= Br, I) and rare earth metal halides LnX3(Ln = Dy, Ho, Tm). Severe corrosion attack on the wall material is observed in the PCA discharge vessels. The aim of this work is to elucidate the corrosion mechanism. Annealing experiments under well defined temperatures were carried out in order to understand the complex chemical corrosion processes. Two different annealing vessels were used, one for experiments under isothermal conditions with a temperature of 1473 K and one for experiments with a linear temperature gradient from 1450 K to 1600 K. The vessels were filled with salt mixtures of different compositions and annealed for 1000 h. The corrosion attack was characterised by XRD, analytical electron microscopy, high temperature mass spectrometry, and chemical analysis of the salt melts. The results of our investigations show that the corrosion attack is caused by vapour species and by the salt melt. The most severe corrosion is observed in vessels filled with mixtures of alkali halides and rare earth metal halides. No corrosion of the alumina is practically observed if pure alkali halides or pure rare earth metal halides are present in the annealing vessel. Keywords: thermodynamic, corrosion, lamps, metal halide salt

Jan 1, 2004

By Vladimir Mindin

This paper presents results of thermodynamic investigations and experimental' studies of some essential for pyrometallurgy of sulfide concentrates topics. Among them: 1. Thermodynamic simulation and experimental investigations of roasting process, 2. Thermodynamic investigations of sulfur dioxide off-gases treatment technologies. 3. Investigations on "Mind in -Kiknadze" effect of suppression of sulfur dioxide formation during sulfide concentrates roasting in the vapor containing atmosphere. 4. Thermodynamic simulation and experimental investigations of sulfide concentrates and manganese containing materials co-roasting processes. Some essential aspects of thermodynamic simulation techniques are also discussed.

Jan 1, 1998

By Florian Kongoli

The behavior of cobalt as a by-product in the NilCu smelting and converting processes effects directly the quality of the final products as well as the revenues gained from the overall process. An effective way to evaluate and predict this important behavior is thermodynamic modeling which reduces the time and the cost of experimental investigation. In this work a thermodynamic model of cobalt-containing matte phase in NilCu smelting and converting processes is presented. The model predicts a priori the thermodynamic properties and phase relations of the ternary and multicomponent matte based solely upon the optimized parameters of the binary systems. This model can be used with other models such as those of slag, metal, gas etc. to predict various aspects of cobalt behavior such as matte- slag, metal-slag distribution, etc.

Jan 1, 1999

By P. Taskinen, D. Lindberg, H. Viitala

The formation of copper chlorides in flue dust or deposits in heat recovery boiler of copper smelters or waste-fired boilers may lead to formation of corrosive partially molten deposits on walls and heat exchangers of the boilers. These deposits can contain various other metals, such as alkalis, Fe, Zn, Pb together with oxides and sulfates. In the present study, a thermodynamic model for copper-containing binary and ternary metal chloride systems within multicomponent CuCl-CuCl2-FeCl2-FeCl3- PbCl2-ZnCl2 system has been assessed and optimized based on own experimental phase equilibrium data, as well as literature data. The thermodynamic properties of the liquid phase was modelled using the quasichemical quadruplet model and a thermodynamic database was optimized to predict all available experimental data within the experimental error limits. The thermodynamic database allows for more accurate predictions of potential corrosion-related issues in various heat recovery boilers and waste-fired boilers due to formation of copper chlorides. INTRODUCTION In the copper flash smelting, flue dust can cause severe problems in the gas train, used for separating dust from the SO2-rich off gas, by forming corroding accretions on the walls of the heat recovery boiler. Formation of dust build-ups in the boiler need to be cleaned regularly and potential corrosion damage checked, requiring costly and unscheduled shutdowns of the flash smelting process. Compounds of copper and zinc among other elements having high vapour pressures may volatilize during the smelting of the copper concentrate, forming dust when the process gas cools down. Also, particles of solid or liquid iron oxides originating from the ore get transported with process gas to the heat recovery boiler as a result of entrainment in the flue gas (Miettinen, 2008) The dust deposit build-ups on the boiler walls are formed partly by direct impact of particles and partly by vapour condensation on the boiler walls. The initial deposition takes place by the condensation of vapours that contain zinc, lead, arsenic and other metals having high vapour pressures. Also, low melting point eutectic components of alkali salts such as chlorides and sulphates can act as sticky cohesive particles attaching to the boiler walls. The fine particles landing on the surface of the porous dust deposit layer react in the SO2-rich atmosphere of the boiler to sulphates. The process gas within the boiler contains SO2, O2, SO3, H2O and N2 that diffuse into the porous accretions to form a stagnant gas layer within the dust deposit structure. The composition of this gas layer may differ greatly from the composition of the process gas that is flowing on the surface of the accretion layer. Locally HCl and H2SO4 are formed and even a reducing atmosphere may exist within the dust deposit layer, allowing new reactions to take place. The local micro-atmosphere may enable metal sulphates to be reduced to secondary sulphides and even metallic components. Within the accretion layer, components may be formed that would not be stable in the gas atmosphere inside the boiler (Miettinen, 2008). This may be the mechanism by which for instance chlorides of Cu, Fe and Zn are formed within the deposit layer.

Jan 1, 2019

By Pengfu Tan

Lead blast-furnace bullion cools to near its freezing point in an operation known as copper drossing or hot drossing usually contains 0.02-0.06% copper. The removal of this copper is usually carried out in a batch operation known as sulfur drossing. Sulfur is stirred into the bullion at temperatures near its freezing point, and the dross of copper and lead sulfides that floats to the surface is skimmed off manually. A thermodynamic model has been developed to simulate the copper drossing. The phase diagram of Pb-Cu-S system has been calculated, and the effects of the process parameters, such as temperature, copper content, and sulfur content, on the drossing process have been simulated and discussed.

Jan 1, 2006

By Pengfu Tan

A thermodynamic model has been developed to model the desilverising process of lead by the addition of zinc during lead refining, whereby silver-zinc solid solutions are formed, and floats out of the dissolved zinc/silver in the lead bath. The solubility of silver-zinc solid solutions in lead decreases with falling temperature. A number of variations and modifications of the desilverising process are modeled, and applied to a wide range of silver contents in lead bullions in the industry.

Jan 1, 2005

By Pengfu Tan

A thermodynamic model of KIVCET lead smelting process has been developed. The model has the capability to predict the distribution behaviors of Pb, Zn, Fe, S, O, As, and heat balance in KIVCET direct lead smelting furnace. The compositions of lead bullion, matte, slag and gaseous phases, and heat balance are calculated. The effect of the ratio between oxygen and feed on the chemistry of the smelt and heat balance of the coke checker has been simulated and discussed. The thermodynamic model also helps to understand the tapping issue of the lead bullion. In this paper, some applications of this model in the industry have been presented.

Jan 1, 2006

By S. R. Reddy, R. G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996

By R. G. Reddy

The Margules .equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of 'a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules. equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.

Jan 1, 1996

By Songsong Wang

Recently, replacing Pierce-Smith converting process with the oxygen bottom-blowing continuous converting technology has become a new research focus. Based on the principle of Gibbs free energy minimization, the thermodynamic model of oxygen bottom-blowing continuous converting multiphase equilibrium system has been established. The elements distribution behavior is calculated at the same burden composition and operation parameters as the industrial production. The results show that the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in crude copper are 0.06, 0.0030, 0.070, 0.38, 0.39, 0.020, 0.017, 0.034, 0.010, respectively, and the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in slag are 0.53, 0.81, 0.020, 0.23, 2.5, 0.0048, 0.0010, 0.0030, 1.49, respectively. The calculated results agree well with the actual industrial production data, indicating that the model can be well applied in the oxygen bottom-blowing continuous converting practice.

By Dmitri Nassyrov, In-ho Jung

"All relevant thermodynamic and phase diagram data in the CaO-Fe10-CaF2 system were critically reviewed. One set of model parameters describing the Gibbs energy of all phases has been obtained as a result of critical evaluation of the available data and optimization of the model parameters. The Modified Quasichemical Model was used to describe the interactions in the liquid phase. All calculations were performed using the FactSage thermochemical software.IntroductionSlags contaimng CaF2 are of significant interest to the steelmaking community. Notable examples of slags containing significant amounts of CaF2 include Electro-slag Remelting (ESR) slags [1] and mould flux for continuous casting [2]. The role of these slags is, among other things, to refine steel by absorbing inclusions and dissolved impurities. During slag-steel interaction, some iron from the steel will inevitably get oxidized and form iron oxides which will dissolve into the slag. With this in mind, it is important to understand the interaction between CaF2 and Fe,0 for accurate prediction of slag composition and process optimization. A thermodynamic optimization of the CaO-FetO-CaF2 was thus undertaken."

Jan 1, 2013

By I-H. Jung, J. Kim, B. Konar

"The usage of FeNdB permanent magnet, containing Rare earth elements (REEs), is steeply increasing with its demand for wind-turbine and electrical vehicle. The improvement and recycling of the permanent magnet require good understanding of chemistry of all constituent elements. In order to understand the chemical interactions between REEs and Fe, all Fe-RE binary systems have been critically assessed and optimized based on reliable literature data. The Modified Quasichemical Model and Compound energy formalism is employed to model the liquid phase and the solid solutions present in the binary systems respectively. The enthalpy of the liquid and the intermetallic phases showed a systematic trend along the lanthanide series. This helped to mitigate the discrepancies in literature data and also to predict the binary interactions between some less well investigated Fe-RE binary systems. INTRODUCTIONRare Earth elements (REEs) are a group of seventeen elements (including Scandium, Yttrium and the lanthanide series) that exhibit same characteristic chemical and physical properties. These properties make them valuable to the electronic, appliance, green technology, weapon and medical device manufacturing industries. Compounds of REE with other metals (like Co, Fe, Ni etc.) have unique properties of luminescence, thermal and electrical conductivity, magnetism and ability to act as catalysts and polishing compounds (Gschneidner ,2011).They are not only indispensable for some electronic gadgets of today, like computers, music systems, mobile devices, televisions and MRI machines, but also holds a key to more greener technology of the future. They contribute to the development of more efficient and environment friendly version of everyday products such as cars and light bulbs. REE compounds revolutionized the magnet industry by making them smaller and more powerful with increased longevity, and high temperature workability, which are used in motors and generators that power electronics, telecommunications, electric automobiles and turbines(Humphries, 2011)."

Jan 1, 2012

By M. Mezbahul-Islam

Thermodynamic modeling of the Mg-Cu-Ni system is carried out as a part of multi component thermodynamic database for Mg alloys. This system is being modeled for the first time using the modified quasichemical model, which considers the presence of short range ordering in the liquid. The thermodynamic descriptions of the binaries Mg-Cu, Cu-Ni and Mg-Ni have been extrapolated to the ternary Mg-Cu-Ni system using Toop geometric model. The constructed database has been used to calculate and predict thermodynamic properties, isothermal sections and liquidus projections of the Mg¬Cu-Ni system, which showed very good consistency with the experimental data.

Jan 1, 2011

By I-H. Jung, J. Kim

"Mg alloys are extensively used as light structural materials in modern industry. Mn and RE (rareearth) metals are effectively used as alloying elements to enhance the properties of Mg alloys. Therefore, the thermodynamic database of those alloys is important in the Mg alloy design and processing. Critical evaluation and optimization of all available literature data for the Mn-RE systems were conducted to obtain reliable thermodynamic functions. The Mn-RE systems shows systematic changes in the phase diagrams and thermodynamic properties with increasing atomic number in the lanthanide series. This systematic approach for all RE elements allows to resolve inconsistencies in the available experimental data. INTRODUCTIONRare Earth (RE) metals are widely used in many industrial fields including permanent magnet, electronic materials and structural materials. As a small addition of RE can enhance magnetic, electronic, optical and mechanical properties of numerous materials, the usage of the RE is still expanding regardless of the strategic control of their supply.Magnesium alloys are getting great scientific and industrial attention as the lightest structural materials. One of the drawbacks of Mg alloys is their poor formability at room temperature due to the limited slip system with hcp crystal structure. Recently, several studies (Farzadfar et al., 2011; Sandloebes et al., 2010; Stanford, 2010; Stanford et al., 2008; Yan et al., 2010) show that the additions of small amounts of RE can considerably enhance the ductility of Mg alloys. Therefore, a lot of research on Mg-RE alloys is undergoing to clarify the role of RE on the enhanced deformation mechanism and to find out the most optimum Mg alloy compositions. In order to respond to the need of Mg-RE alloy development, a large thermodynamic database for Mg alloys containing RE has been developed with critical systematic analysis and optimization of the entire RE series data. This includes the thermodynamic database of the Mg-RE (Kang et al., 2009), Mg-RE-RE (Kang et al., 2009), Mg-Al-RE (Jin et al., 2011; Jin et al., 2010), Mg-Zn-RE and Mg-Mn-RE systems."

Jan 1, 2012

By Omid Marzoughi

Chromium has a wide range of applications, including as an alloy addition in various steels and also as a corrosion resistance coating. Carbothermal reduction of chromite ore (FeCr2O4) in a submerged arc furnace is an important industrial process for extracting chromium, but the energy consumption is excessive. It is suggested that one area for future research is the low temperature carbothermic solid state reduction of chromite to produce an intermediate product, which can subsequently be upgraded to ferrochromium. In this regard, a thermodynamic model has been developed to investigate this process and the effects of temperature, carbon additions and ore composition on the recovery of chromium and the grade of the ferrochromium, have been studied. Further development of the model may allow it to be applied to the simulation of other processes for the recovery of chromium from chromite ores.

By M. Bugdayci, Onuralp Yucel, K. C. Tasyurek

This paper is a contribution to the theory and quantitative understanding of the processes for the production of magnesium, calcium and strontium metals by metallothermic process. In the present study, effect of reductant type was investigated. Thermodynamic simulation of system was made by Fact Sage 6.4 program. In order to produce magnesium metal, effects of reductants “FeSi, Al, Si and CaC2” were investigated. To understand Calcium-oxide reduction system, effects of Al and CaF2 addition were investigated for different temperatures. In the last simulations, SrO reduction parameters were simulated. Al used as main reductant and BaO, CaO, CaC2 were added to green mixture as a functional additive. Finally probable phases and minimum reduction temperatures are determined.

Mar 1, 2018

By H. Y. Sohn, Hang Goo Kim

Computer simulations were carried out using calcium ferrite slags containing 25 wt% CaO, and the results compared with those obtained using fayalite slags. There was little difference in overall elimination of Pb and Bi, but elimination of Sb and As was much lower with calcium ferrite slag. When calcium ferrite slag is used only in the converting stage and fayalite slag in the smelting stage, as in the Mitsubishi process, the contents of Sb and As in the blister copper can be kept to reasonable levels. This allows advantage to be taken of the considerably higher iron oxide-holding capacity of calcium ferrite slag than of fayalite slag at the high oxygen potential under converting conditions, thus preventing precipitation of magnetite. Satisfactory agreement was obtained between predicted values and observed data from a Mitsubishi converter

Jun 18, 1905

By M K. Nahian, R G. Reddy

The thermodynamic model for species distribution in aluminium chloride (AlCl3) and 1-butyl-3- methylimidazolium chloride (BMIC) system was developed. The experimental thermodynamic data, considering a range of aluminium chloride species, such as AlCl4-, Al2Cl7-, Al3Cl10-, Al4Cl13-, and Al2Cl6 were used in developing the model. When the XAlCl3 was in the range of 0 to 0.50, only anion species Cl- and AlCl4- were existing in the solution. As the XAlCl3 value increased more than 0.50, the available anions were Al2Cl7-, Al3Cl10-, Al4Cl13-, and Al2Cl6. Specifically, the concentration of Al2Cl7- increased in the composition range from 0.50 to 0.67 XAlCl3, after which it decreased. This change in the concentration of Al2Cl7- was due to its reaction with excess AlCl3, leading to the formation of Al3Cl10-. The average cathode current density was determined by the electrochemical experiments varying XAlCl3 from 0.50 to 0.71 in the AlCl3:BMIC solutions. The average cathode current density increased as the XAlCl3 increased from 0.50 to 0.67. However, it decreased when the XAlCl3 > 0.67. This trend can be attributed to the electroactive species Al2Cl7-. The Al2Cl7- promotes the reduction rate at the cathode, resulting in an increase in the average cathode current density.

Aug 21, 2024

By A. D. Pelton, Y. -B. Kang, S. A. Decterov

Computerized thermodynamic databases for solid and liquid metal, slag and solid oxide phases in the Al2O3-CaO-CoO-CrO-Cr2O3-FeO-Fe2O3-MgO-MnO-NiO-SiO2-S system have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for molten slags, liquid steel and solid oxide solutions such as spinels, pyroxenes, olivine, monoxide (wustite, periclase, lime), corundum, etc. By means of the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits. Furthermore, the models permit extrapolation into regions of temperature and composition where data are not available. The databases are automatically accessed by user-friendly software that calculates complex equilibria involving simultaneously slag, metal, refractories and gases, for systems with many components, over wide ranges of temperature, oxygen potential and pressure. A short review of the available databases is presented. The critical evaluation/optimization procedure is outlined using the Al2O3-CaO-FeO-Fe2O3-SiO2and Al2O3-CaO-MnO-SiO2systemsas examples. Several applications of the databases to deoxidation of iron and to inclusion control in steel are discussed. Keywords: thermodynamics, phase equilibrium, phase diagrams, databases, ferrous metallurgy, steelmaking, inclusion control, slags, oxide systems.

Jan 1, 2004