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By L. B. Pankratz

Thermodynamic data on the elements, oxides, sulfides, halides, and selected hydrides, carbides, nitrides, carbonates, sulfates, silicates, and miscellaneous compounds were reviewed, evaluated, and compiled at the Bureau of Mines. Values for CP°, S°, H° -H°298, ?Hf°, and ?Gf° are given in tabular form. A brief thermodynamic background and a number of examples and applications are presented.

Jan 1, 1984

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 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 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 Merritt RR

The equilibrium phase relations in the Fe- Mn-Ti-0-S system were established at 1380 and 1485 K. The elemental distributions between the equilibrium phases were obtained by chemical- ly analysing selected samples from the phase study. The results are considered in relation to the coal reduction process for upgrading ilmenite. The beneficial effect of adding sulfur to a kiln that uses a manganese-rich feed is ex- plained by the formation of a metal-sulfide solid-solution phase that removes part of the manganese from the oxide system. The optimum conditions for operating the reduction kiln are determined, and the practical need to operate the kiln at other than optimum conditions is explained. It is shown how the experimental data can be used to predict the best compromise conditions for reduction and the resultant purity of the product.

Jan 1, 1980

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 Jianxun Song, Hongmin Zhu, Qiuyu Wang, Jungang Hou, Shuqiang Jiao, Xiaobo Zhu

This work presents the results of a study on the Ti3+/Ti2+ couple redox potentials vs. Cl–/Cl2 at the temperature range (673 to 1073 K) in fused LiCl-KCl eutectic by direct potentiometric method. Initial concentrations of TiClx in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TiCl2+1/2Cl2(g)=TiCl3 were calculated using the temperature dependencies of apparent standard potentials of the couples E* Ti3+ /Ti2+.

Jan 1, 2014

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

By L. B. Pankratz

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

Jan 1, 1987

By M. R. Baren

Unpublished results obtained by Baren on thermodynamic properties of sulfur in liquid Fe. Co. Ni. Fe-Co. Fe-Ni. and Co-Ni are reevaluated. correlated. and interpreted on the basis of recent developments in thermodynamics of alloys:. Existing reliable data are reviewed and compared with the? present results. Sulfur obeys Henry's law up to 0.04 mol fraction. and in this range the standard Gibbs energy of solution of sulfur is expressed as a linear function of temperature for each pure metal. The activity coefficient of sulfur in each binary metal solvent 1s correlated with the composition of alloy.

Jan 1, 1983

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

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 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 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

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 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 Steven Wright, Sharif Jahanshahi, Shouyi Sun

"While there is a large industry based on recovering platinum group metals (PGM) from complex sulphide ores containing Cu and Ni, there is little information on the thermodynamics of the matte phase formed on smelting the ore and in particular the behaviour of Pt in the matte.The equilibrium between metallic platinum and industrial mattes was studied in a series of experiments where a small quantity of matte (5g) and platinum foil of 150 µm thickness (0.5 g) were equilibrated in magnesia crucibles at 1400°C under conditions where the oxygen and sulphur partial pressures were fixed.The chemical composition of the phases was determined from EDS analysis using a scanning electron microscope. Line scans were initially used to confirm that the foils had attained a uniform composition across their thickness. The composition of the matte was determined from analysis of an area of matte including the small metallic droplets and dendrites.The results of the equilibrium study are presented in terms of how the oxygen and the sulphur pressure affect the distribution of Pt, between the matte and the alloy foil (Lmatte/alloy). Other variables investigated were matte chemistry, i.e., the Fe content and the temperature. The activities of platinum in the mattes were calculated using a regular solution model describing the activity-composition relationship in the alloy."

Jan 1, 2003

By Shahab Alizadeh, Ahmad Khodadadi Darban, Mehdi Mohseni, Mahmoud Abdollahy

This study probed the selective separation of lanthanum and yttrium in a nitrate medium in the presence of aluminum and calcium impurities using di-(2-ethylhexyl) phosphoric acid (D2EHPA). The factors studied in a central composite design (CCD) included extractant concentration, pH, concentration ratio of total impurities to rare earth elements, and interaction of these three factors. The extraction mechanism and types of extracted metal-containing species were delineated by the slope analysis method. The obtained thermodynamic data showed that lanthanum and yttrium extraction by the D2EHPA extractant was exothermic. The extraction of both rare earth elements was accompanied by an entropy reduction. The negative magnitude of ΔS in yttrium extraction reaction suggests stronger D2EHPA-Y(III) complexation relative to La(III). As entropy decreased and enthalpy increased, the extraction process became unspontaneous. Using the proposed flowsheet, lanthanum and yttrium products with > 90% purity were obtained.

Aug 10, 2021