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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

By A. D. Pelton

The evolution of thermodynamic models of molten salts and slags, starting with Temkin in 1948, has culminated in today?s sublattice models. These modern models have permitted the development of large thermodynamic databases of model parameters, which can be used to calculate and predict accurately the properties of multicomponent solutions. The model parameters are mainly obtained by the critical evaluation and optimization of available thermodynamic and phase equilibrium data for binary and ternary subsystems. The models are then used to estimate the properties of multi component slags and salts from these assessed binary and ternary parameters. When used in conjunction with thermodynamic databases for solids and solid solutions (salts, oxides, sulphides, metals, etc.), other liquid solutions (such as liquid metals),and gases, these databases permit the calculation of complex multiphase equilibria in multicomponent systems, with applications in a wide variety of industries. These calculations can be performed with general commercial software for Gibbs energy minimization, which can also be incorporated into process simulation software packages. Keywords: slags, salts, solution models, thermodynamics, phase diagrams, oxide systems, molten salts

Jan 1, 2004

By Tuncel M. Yegulalp, Anuta Belova

This paper expands on the ZECA (Zero Emission Coal Alliance) technology, which is aimed at making coal a sustainable source of clean energy in the near future. The technology proposed immediate capture of carbon dioxide and other pollutants upon generation, thus alleviating their negative effects in the Earth’s atmosphere. ZECA proposes using chemical energy of coal to produce hydrogen; the latter is then used to produce electricity via fuel cells or Hyrogen-Oxygen turbines. In this study, a chemical engineering package, AspenPlus 12.1, is used to simulate the reactor (reformer) in which hydrogen is produced from methane water and lime as part of the zero emission power plant. Thermodynamic conditions, pressure and temperature, are optimized with respect to molar hydrogen production. Under the proposed conditions, molar conversion efficiency, carbon to hydrogen, of 95% is achieved. Further studies are required to model the complete power plant and to optimize it for efficiency.

Jan 1, 2005

By Youn-Bae Kang, Jong-Jin Pak, Min-Kyu Paek

The critical evaluation and thermodynamic optimization of Mn-Si-C and its sub-binary systems have been carried out over the whole composition range from room temperature to above the liquidus temperature. The solution properties of the liquid systems have not been clearly described because the liquid solution exhibits a high degree of short-range-ordering. In order to predict the thermodynamics of the liquid solution, the liquid phases were optimized by the modified quasichemical model. The model parameters of the solid phases were also optimized by the compound energy formalism to best reproduce the phase diagram and important thermodynamic properties in Mn-Si-C system. Using the model parameters, various thermodynamic calculations were carried out. The present database will be a part of larger thermodynamic database for the ferromanganese alloy database.

Jan 1, 2014

By Q. Liu, P. Katsabanis, J. A. Meech

A thermohydrodynamic computer code has been used to simulate dust explosions. For sulphide dusts, the thermodynamic predictions are used to investigate the effect of dust concentration, mineral content and inert materials as well as the quantity of sulphur dioxide produced. It was found that the amount of oxygen available for the explosion is very important and that the dust concentration which gives maximum explosion pressures is obtained at zero or slightly negative oxygen balance values. The sulphide minerals were found to have the following explosibility sequence: pyrrhotite, pyrite, chalcopyrite, sphalerite, covellite, chalcocite and galena, which is in agreement with mine experience. The results show that theoretical calculations can be used to predict explosion pressures and toxic gases produced by a dust explosion and therefore they can assist in the design of protective measures .

May 11, 1988

By L. B. Pankratz

Thermodynamic data on carbides, nitrides, and other selected substances were reviewed, evaluated, and compiled at the U.S. Bureau of Mines Albany Research Center. Values for Cp°, S°, H° - H°298, -(G° - H298)/T, ?Hf, ?Gf, and log Kf are given in tabular form. Cp°, H° - H°248, ?Hf°, and ?Gf° are also expressed algebraically.

Jan 1, 1994

By A. V. Tarasov

Investigations of thermodynamic properties of Cu-Ni and Cu-Ni-S systems and mattes have been conducted with the aid of a MC-1301 mass-spectrometer designed for studies-of processes of vapor formation of hardly volatile substances. The instrument comprised a combination of an evaporator of Knudsen chamber type with a mass-spectrometer for analysis of the vapor phase, In the process of studies of molten Cu-Ni-S systems and commercial-grade mattes within a temperature interval of 1400-1800 K the partial pressure of sulfur was measured by means of complete isothermal evaporation and the partial pressure of copper and nickel by comparison of ionic currents. The partial pressure values of the components above the molten Cu-Ni-S were used for calculation of activities of the respective components in the melt. The copper and nickel activity data obtained was used for assessing the amount of dissolved losses of these metals in autogenous smelting slags.

Jan 1, 2003

By A. V. Tarasov

Investigations of thermodynamic properties of Cu-Ni and Cu-Ni-S systems and mattes have been conducted with the aid of a MC-130 I mass-spectrometer designed for studies of processes of vapor formation of hardly volatile substances. The instrument comprised a combination of an evaporator of Knudsen chamber type with a mass-spectrometer for analysis of the vapor phase. In the process of studies of molten Cu-Ni-S systems and commercial-grade mattes within a temperature interval of 1400-1800 K the partial pressure of sulfur was measured by means of complete isothermal evaporation and the partial pressure of copper and nickel by comparison of ionic currents. The partial pressure values of the components above the molten Cu-Ni-S were used for calculation of activities of the respective components in the melt. The copper and nickel activity data obtained was used for assessing the amount of dissolved losses of these metals in autogenous smelting slags.

Jan 1, 2003

By L. B. Pankratz

Thermodynamic data on the elements and oxides were reviewed, evaluated, and compiled at the Bureau of Mines Albany Research Center. Values for Cp°, S°, H° - H°298, - (G° - H°298)/T, ?HP, ?Gf°, and log K are given in tabular form. Cp°, H° - H°298, ?Hf°, and ?Gf° are also expressed algebraically. Examples of calculations using these data are given.

Jan 1, 1982