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This report presents overview of the authors' results of thermodynamical investigation of some important metallurgical processes and phenomena. Among them: carbo thermal reduction of silica, and boron oxide, silicon carbide obtaining from different precursors, investigations on copper and manganese ores processing, investigations on pollution from different sources. Special attention is paid-to thermodynamical approach to investigation and estimation of multi component multi element compositions stability, developed by the authors. Also are discussed some auxiliary but' important for the thermodynamical investigations issues.

Jan 1, 1997

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

By M. W. Wadsley

"Physical and chemical property models are widely used in process engineering. There exist, in the published literature, completely empirical models of ''thermodynamic properties"", that is, property models that are not consistent with the laws of thermodynamics. There also exist property models that purport to be thermodynamically consistent but are flawed in their implementation. There are also published property models that are consistent with the laws of thermodynamics but that do not reproduce property values with an acceptable accuracy. A practicing engineer might be asked to assess very different property models for which there are a variety of claims. This paper discusses features of thermodynamic and empirical property models that may assist in their practical evaluation and implementation."

Jan 1, 2005

By Jing Zhan, Gui Li, Wei-feng Li, Li-Hua Jiang, Chuan-fu Zhang, Jian-yang Hwang

Thermodynamics analysis for processing the charge with lead concentrate and lead sulfate-containing materials in bottom blowing smelting furnace was conducted. The results show that the technology of large-scale processing PbSO4- containing materials with PbS concentrate in bottom blowing furnace under the condition of using high-iron slag type, batch heat supplement, high temperature and rich oxygen is thermodynamically feasible. The exploration test and industrial experiment confirm the results. When S content in mixed ore is 16~17% with coke foam content of about 5%, the lead paste amount can be increased up to 40%.

Jan 1, 2015

By Huang Chao

The thermodynamics analysis on reducing-matting smelting of sulfide ore of lead, antimony and bismuth which use ferric oxide as sulfur fixed agent is first analyzed. Due to the analysis of reaction mechanism, ferric oxide is first reduced to ferrous oxide, then ferrous oxide produce reducing-matting reaction with sulfide ore and reducing agent as reaction equation: MeS+FeO+CO=Me+FeS+CO2. The reaction thermodynamic calculation shows that the reducing-matting reactions of lead sulfide, antimony sulfide, Jamesonite, and bismuth sulfide are feasible, but is infeasible for zinc sulfide. These conclusion provide a feasible method for solve the pollution which produced in the smelting of sulfide ore of lead, antimony and bismuth.

Jan 1, 2006

By Zhihe Dou, Guozhi Lyu, Liping Liu, Yi Luo, Ting-an ZHANG, Xijuan Pan, Zhuolin Liu

Due to the high energy consumption, long technical process, low usage rate of vanadium during the traditional smelting vanadium steel process, a new method for decarburization by CO2 to directly smelt vanadium-containing steel in blast furnace was proposed. In this paper, the thermodynamics of CO2 decarburization in molten iron process was calculated out by FactSage. The thermodynamic calculations indicated that in standard state, the transformation temperature of C and V was 1357 °C; the oxidation order of element was Si, C, V, Mn and S when using CO2 as oxidant. The experiment of blowing CO2 temperature showed that decarburization reaction temperature was 1550 °C, carbon content could be decreased to 0.676%, the decarburization rate was 88%. There was no effect on vanadium content in molten iron during the decarburization process, vanadium content was 0.323%, which meets the request of vanadium mould steel.

Mar 1, 2018

By F. T. Da Silva

Concentrates of titaniferous minerals containing around 30 wt% Ta2O5 are processed hydrometallurgically by hydrofluoric acid leaching and solvent extraction, followed by the precipitation of hydrated potassium heptafluorotantalate. A fundamental study of the thermodynamics of this precipitation and recrystallisation was undertaken to increase understanding of the conditions most conducive to the production of pure, well-crystallised K2TaF7. Activity-pH diagrams for the Ta-K-F-H2O system explained the dissolution of Ta2O5 in fluoride solutions quite well and also the precipitation-recrystallisation of K2TaF7.H2O. X-ray diffraction and scanning electron microscopy confirmed the thermodynamic observations. It was concluded that the best precipitating agent for K2TaF7 from fluoride solutions is KF but a recrystallisation step in a HF environment produces purer, well-crystallised K2TaF7.H2O, eliminating oxy-salts and other impurities

Jun 21, 1905

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds ;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2 : I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resins may serve as a habitat of microorganisms. In the decomposition of a medium. some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17, 32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established .R3 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2:I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resinsmay serve as a habitat of microorganisms. In the decomposition of a medium, some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17,32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2:I for the combined effect of both factors, as compared to the exclusive effect of either one. if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resins may serve as a habitat of microorganisms. In the decomposition of a medium, some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate. l7,32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By I. Barin

The thermodynamics of cyclone smelting of sulphidic copper ores is described using as example the production of copper matte with 75 wt % Cu. Equilibrium calcualtions and material and energy balances show that an increase in process temperature from 1600 K to 1900 K results in the extensive transfer of minor elements such as As, Sb, Bi, Pb, Zn,.... to the gas phase. A pilot plant for carrying out the cyclone smelting process is described. Calculations of material and heat transfer for the reaction of ZnS show that the smelting reactions of sulphides in the cyclone take place very rapidly at high temperatures. The dissociation of the sulphides with subsequent oxidation reactions in the gas phase plays an important part in. the process and is mainly controlled by heat transfer.

Jan 1, 1983

By A. Mikula, S. Karlhuber

"Unique physical and mechanical properties made the Pb-Sn solders attractive for low temperature joining of electronic parts. But since lead in solder materials has become a great enviromental problem and health concern, lead will be slowly replaced by other materials in soft solders. Some of these materials which are currently under investigation are ternary tin alloys. Many different physical properties like wetting behavior, electrical and thermal conductivity and surface tension are measured on these alloys, but on the thennodynamic properties and the phase diagram of the alloys under discussion there is only little information available. We investigated the (Ag, Au, Cu)-Sn-Zn systems and determined the thermodynamic properties over the whole composition range by emf-measurements. From these measurements we also got some information on the liquidus. In the Sn-rich corner the phase diagrams are still under investigation.IntroductionSoldering is technically defined as the joining of two base materials, mostly metals or metal coated nonmetallic substrates, with a third metal. The melting temperature of the third metal or metal alloy should be well below those of the substrates. Solder alloys can be categorized in soft and hard solders. Soft solder alloys usually contain lead, tin, bismuth, indium or cadmium and hard solders gold, zinc, aluminium or silicon. The difference between soft and hard solders is the melting temperature of the soldering material. This temperature is around 350°C.An interesting brief history of solders is given by Vianco and Frear [1]. They report, that in 4000 B.C. solders were already used in Mesopotamia. From archaeoligical evidence those solders were gold-based hard solders.Tin-lead soft solders and their use are not easily found, because in course of time tin has been reduced to stannic acid, making the identification quite difficult. Well preserved soft solder artifacts were discovered in King Tut's tomb dating from 1350 B.C. In ancient time Pb-Sn solders were used primarily for the manufacture and repair of cooking utensils and metal tools. The Romans used lead-tin solders extensively in the construction of the aqueducts."

Jan 1, 1996

By F. Bonnet, J. Lehmann, H. Gaye

A review of thermodynamic information and models of slags, including associated software when available, is presented. The pertinence and accuracy of these models is discussed by comparison of their predictions for various slag thermodynamic properties with the available experimental data. Practical industrial applications will be illustrated by a literature review of the dephosphorization process of ferromanganese alloys and by the description of Ti behavior during silico-manganese alloys production. This latter example will show how the thermodynamic models have been used to propose a flotation treatment at low temperature to enhance TiC removal.

Jan 1, 2004

By M Hino, D R. Swinbourne

The thermodynamic properties of arsenic in metal, speiss, matte, slag and gas phases are first summarised in this paper. Arsenic associates with sulphide minerals and generally has compounds of high volatility, but it has a weak affinity for sulphur and a strong affinity for metals, especially copper and iron. In the initial stage of the oxidation of sulphide concentrates arsenic is volatilised easily prior to the oxidation of FeS, although it tends to be fixed in the condensed phase as FeAsO4 if the concentrate is over-oxidised. Thermodynamic simulation of oxidative copper smelting reveals the distribution of arsenic between matte, slag and gas, and the possibility of condensation of arsenic from the resulting waste gas is discussed. In reductive smelting more arsenic remains in the metal or matte, and is sometimes concentrated as a separate speiss phase. The phase relations and thermodynamic properties of speiss are also summarised briefly. Arsenic refining from smelted copper metal is shown, from an examination of the basic principles of arsenic removal into slags, to be difficult. Owing to its weak affinity for lead however, arsenic refining from lead bullion is seen to be much easier.

Jan 1, 2000

By R. G. Reddy

To better understand the behavior of bacterial-mineral interfacial reactions, a thermodynamic model based on the- studies of bacteria adhesion on mineral surfaces has been evaluated. The bacteria adhesion to the mineral surface would be increased by l ' d1;1creasing the change in Gibbs free energy of adhesion and it would be reduced if the change in Gibbs free energy of adhesion of the system is increased. From the combination -of Young's equation and equation of state, the change in Gibbs free energy of adhesion -for bacterium-mineral system- was calculated. Influence of liquid surface tension, mineral surface tension on the change in Gibbs free energy of adhesion and consequently bacteria behavior on mineral systems- has been discussed.

Jan 1, 1991

By M. W. Davies, P. N. Smith

The activity of MnO has been measured in the system CaF2-MnO at 1773 and 1873 K and in the system CaF2-CaO-MnO at 1773 K by the method of equilibration with platinum. Large positive deviations from ideal solution laws have been found, but these became less as the lime content rose. The loss of a volatile component made activity measurements impossible in the CaF2-AI203-MnO system, but the boundaries of a two-liquid region have been measured at 1773 K.

Dec 1, 1971

By Do-Hyeong Kim, Tae-Jung Kim, Seung-Yeon Won, Jong-Jin Pak, Min-Kyu Paek

Liquid iron alloys containing V, Mo, and Ni can be produced by the carbothermic reduction of spent catalysts used in petrochemical industry. Thermodynamics of carbon in these alloy melts is important for refining these alloys. In the present study, the carbon solubility in Fe-V, Fe-Mo, Fe-Ni, Fe-V-Mo, Fe-V-Ni, Fe-Mo-Ni and Fe-V-Mo-Ni alloy melts of various compositions was measured at 1873 K. The temperature dependency of vanadium effect on carbon solubility in liquid iron was also measured in the temperature range from 1823K to 1923K. The additions of vanadium and molybdenum significantly increased the carbon solubility in liquid iron alloys while nickel decreased the solubility. The experimental results were thermodynamically analyzed using Lupis’ relation at constant activity to determine the first- and the second-order interaction parameters of vanadium, nickel and molybdenum on carbon at carbon saturated condition. Using thermodynamic parameters determined in the present study, the carbon solubility in Fe-V-Mo-Ni alloy melts of various composition were accurately predicted and verified experimentally at 1873 K.

Jan 1, 2014

By A. J. Monhemius, R. G. Reddy, G. W. Warren, E. Peters

Thermodynamic solubility of chromium in pickling solutions (i.e., HF- HN03-H2O solutions) was determined as a function of HF and HNO3 acid concentrations at 298K. Pure Cr, AISI type 316 and 416 stainless steel were used in this study. The results showed that the solubility of Cr increased with increase in the concentrations of HF and HNO3 acids in solutions. The solubility of Cr increased in the order of pure Cr > 416 SS > 316 SS. The theoretically calculated Cr solubility data were in reasonable agreement with the experimental data.

Jan 1, 1993