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By Fiseha Tesfaye, Pekka Taskinen

"Thermodynamics of the equilibrium phase assemblage Ago_9Cul.lS-Cu2-xS-CuS have been studied by an EMF -method. The ternary phase was synthesized from the pure Cu2S and Ag2S in vacuum furnace at high-temperature and mixed with appropriate compositions of Cu2S and CuS to form the cathode electrode. The EMF-measurements were made on the solid-state galvanic cell Pt(-) I Ag I RbAg,ils I Ago9Cu1.1S-Cu2-xS-CuS I Pt(+), in a temperature range from 316 K to 498K.Based on the measured EMF vs. T relations, thermodynamic functions (?fG° , ?fS and ?fH°) of stromeyerite (Ag0.9Cu1.1S) in equilibrium with Cu2-xS and CuS have been determined. The obtained experimental values have been compared with the available literature values. New experimentally determined thermodynamic properties of the solid solution (Ag,Cu)2Sss were determined.IntroductionDue to intense mining of high grade sulfide ore minerals in the past, recently, the available sulfide ores are poor in metals and becoming increasingly complex; such that, the production of high grade metals by the conventional pyrometallurgical processes is compromised. Consequently, smelters are in need to modify their operating flow sheets and strategies for processing more complex feed materials economically, while meeting the strict environmental regulations. To make the appropriate modifications, accurate thermochemical data of phases and phase assemblages which exist in these complex ore minerals are essential.Silver-bearing sulfosalts are encountered in ore minerals for the production of base metals and are common sources of silver. Among the silver-based sulfosalts, stromeyerite (Ag0_9Cu1.1S) is relatively common ore mineral in most hydrothermal vein and replacement deposits [1]. Recently, the ternary chalcogenide compound Ago0.93Cu1,07S has been studied, intensively, due to its high ionic conductivity and gradual disorder in the sequential phase transitions [2]. Therefore, accurate knowledge of the thermodynamic properties of stromeyerite has considerable fundamental and practical interest in many aspects of extractive, chemical and physical metallurgy."

Jan 1, 2014

By L. B. Pankratz

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

Jan 1, 1984

A study of the thermodynamic properties of magnesium chloride ammines was carried out with the ultimate objective that the thermal decomposition of the hexammine MgCl2.6NH3 may prove successful on a commercial scale for the manufacture of anhydrous magnesium chloride, which is required for the efficient electrolytic production of magnesium. The experimental data are presented in the form of an equilibrium diagram that aids the understanding of the conditions associated with the thermal decomposition of ammines

Jun 13, 1905

By T. Wang, R. G. Reddy

"A new eutectic of LiNO3-NaNO3-KNO3 ternary system was calculated by using thermodynamic modeling and the eutectic temperature was predicted to be 389.15K. The melting point was determined using Differential Scanning Calorimetry (DSC). On repeated measurements, it was found that the melting point of the eutectic composition showed excellent reproducibility with the predicted value. The heat capacity was also measured using DSC and the data as function of temperature were fit to polynomial functions. Subsequently, the thermodynamic properties such as enthalpy, entropy and Gibbs energies of this novel ternary eutectic salt mixture were deduced as function of temperature.IntroductionIn these days, the provision of the large amount of energy required in the peak period relies more and more on the parabolic trough solar power plant and it works by utilizing the thermal transfer fluid. Consequently, the development of inoovative thermal transfer fluid with higher energy storage density is paramount to lower the expense for generating energy [1-4]."

Jan 1, 2013

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By Sabine Knott

The thermodynamic properties of four liquid ternary zinc alloys, Au-Sn-Zn, Ag-Sn-Zn, AI-Sn- Zn and Cu-In-Zn were measured with an electromotive force (emf) method at three or four cross-sections with an constant X:Sn or Cu-In ratio. At the Au-Sn-Zn and AI-Sn-Zn system calorimetric measurements were also carried out in order to compare the integral enthalpy of mixing from the direct measurements with the data of the emf measurements, which were derived by Gibbs-Duhem integration.

Jan 1, 2003

By Sabine Knoll

The thermodynamic properties of four liquid ternary zinc alloys, Au-Sn-Zn, Ag-Sn-Zn, AI-Sn Zn and Cu-In-Zn were measured with an electromotive force (emf) method at three or four cross-sections with an constant X:Sn or Cu-In ratio. At the Au-Sn-Zn and AI-Sn-Zn system calorimetric measurements were also carried out in order to compare the integral enthalpy of mixing from the direct measurements with the data of the emf measurements, which were derived by Gibbs-Duhem integration.

Jan 1, 2003

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 Jafar Safarian, Merete Tangstad, Leiv Kolbeinsen

"Silicon and its binary alloys have several applications in metallurgical, chemical, photovoltaic and semiconductor industries. Silicon goes to its liquid state within its production, refining and when it is alloyed with other elements. Therefore, the characterization of silicon melts thermodynamics is important and useful. The liquidus and activities in several silicon binary systems have been recently calculated by the application of two liquidus constants, which were established using the experimentally determined liquidus data. In the present study, the thermodynamic properties of six silicon binary melts, which are simple eutectics, are calculated by analytical approaches. In this case, the changes in the partial and integral Gibbs free energies and enthalpies of mixing are calculated and compared with the experimental data in literature. The enthalpies are calculated by two methods and the calculation results are compared to the data from the literature. It is shown that thermodynamic properties of silicon binary melts can be accurately predicted without the use of complicated thermodynamic software.IntroductionSilicon and its alloys have several industrial applications. Silicon is used for making aluminium-silicon alloys to produce cast parts, mainly for automotive industry. Silicon in the form of ferro-silicon is used to deoxidize and alloy steel and cast iron. The photovoltaic (PV) industry has had a rapid growth in the recent years and silicon is the dominant material used for the fabrication of solar cells. Silicon is primarily produced through carbothermic reduction of quartz in electric arc furnaces and the produced metallurgical grade silicon (MG-Si) contains around 1 wt% impurities. It is further refined to produce solar grade silicon (SoG-Si) with above 99.9999 wt% Si to fulfil the chemical requirement for PV application. Since molten silicon is processed all along the metallurgical route, obtaining fundamental thermodynamics knowledge about silicon melts is valuable for the related industries."

Jan 1, 2012

By Young-Dae Kim, Dong-Sic Kim, Jong-Jin Pak, Kyung-Hyo Do

"Sulfur is one of the most harmful elements in stainless steel (SIS) products and the specification of sulfur content is getting more severe for high grade SIS. In order to accurately control the desulfurization reaction in high chromium containing SIS melts, it is important to know the thermodynamic interaction between chromium and sulfur in Fe-Cr melts over a wide range of chromium content. In this study, the equilibrium sulfur distribution, Ls, between a Ca0-Alz03 slag and Fe-Cr-C,.,-S melts were measured under CO atmosphere in the temperature range of 1823-1923 K. The specific effect of chromium on the activity coefficient of sulfur in the melts was determined with the consideration of carbon effect on sulfur. A separate experiment was carried to determine. Ls between a slag and FeCr- S melts (Cr: 0-30 mass%) at 1873K to check the validity of the thermodynamic parameter determined in the present study.IntroductionFerritic stainless steels containing chromium (Cr) up to 30 mass% have been developed for a good corrosion resistance and a high formability to replace austenitic SIS. Especially, Sulfur (S) causes a reduction of high-temperature strength and the hydrogen induced cracking (HlC) in stainless steel for line pipes. [l]Many studies on the desulfurization of hot metal and liquid steel have been carried out for several decades and they used HzS-H2 gas equilibrium technique for measuring the effects of many alloying elements on the activity coefficient of S in liquid iron. However, the study on desulfurization of Fe-Cr melts was very scarce.[2] In order to accurately control the desulfurization reaction of high Cr stainless steel, it is essential to know the thermodynamic relation between Cr and S in Fe-Cr melt over a wide range of Cr content and temperature.In the present study, the thermodynamic interaction between Cr and S in liquid iron was determined by measuring the equilibrium distribution ratios of S between Fe-Cr-C,.1-S melts containing a wide range of Cr up to 30 mass% and a 55 mass%Ca0-45 mass%Alz03 slag of which the sulfide capacity was pre-determined using Fe-C,a1-S melts in the temperature range of 1823-1923 K. The validity of thermodynamic parameter determined in the present study was checked by measuring the S distribution between a Ca0-Alz03-Mg0 slag of known sulfide capacity and liquid Fe-Cr-S alloy at 1873 K. Using Wagner's formalism, the results of experiment were thermodynamically considered to determine the effect of a specific concentration of Cr on the activity coefficient of S in liquid iron."

Jan 1, 2014

By Liu Wei

In order to make clear the dissolving characteristic of the chrysocolla (CuSiO3?H2O) in the ammonia-ammonium chloride solution, a thermodynamic model of the chrysocolla (CuSiO3?H2O)-ammonia- ammonium chloride-water system is established using the exponential computation method based on both mass balance and charge balance equations. The equation group of the thermodynamic model is solved by the MATLAB Soft on PC. The condition which is favorable for dissolving high concentration of copper in solution is making out. The stable area of chrysocolla (CuSiO3?H2O) and the condition of chrysocolla (CuSiO3?H2O) converting to atacamite (Cu(OH)1.5Cl0.5) is also studied. A group of experiments are designed to validate the veracity of the results of the thermodynamic calculation.

Jan 1, 2010

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 P. Mokwena

Paper written on project work carried out in partial fulfilment of BSc (Hons) in Chemical Engineering Diamond synthesis has attracted a great deal of interest because of its exceptional properties and various applications. In this study, the chemical catalytic vapour deposition (CCVD) method was used to synthesize diamond films using acetylene as carbon source and hydrogen as carrier gas at a temperature of 1000°C, and their thermodynamic stability was studied. Photographic analysis revealed that these products are diamond films, Ramman spectroscopy confirmed that they are graphitic while confocal laser scanning microscopic image analyses proved that these diamonds films have structural defects due to iron impurity from the catalyst precursor. The quantity of diamonds films produced is also proportional to the acetylene to hydrogen ratio but these films are larger in size at lower acetylene to hydrogen ratio. Thermogravimetric analyses showed that transformation of these materials begins at 25°C but could not be used to determine if a temperature range below 25°C exists. The stability of these CCVD-synthesized diamonds also increases below 25°C when stored at different temperatures.

Jan 1, 2007

By P. Fredriksson, S. Seetharaman

In the ladle refining process, the ?FeO?-content of the ladle slag is of great importance in the chemistry as well as the energetics of the process. An optimization of the process requires an accurate knowledge of the thermodynamic activities of ?FeO? in the ladle slags. Due to the discrepancies in the existing data, renewed attempts are being made at the Royal Institute of Technology to generate reliable data for binary, ternary and multi component slags containing ?FeO? at steelmaking temperatures. In order to measure the activities of ?FeO? in the slags, a gas equilibration technique was employed in the present work. The slags, kept in Pt-crucibles, were equilibrated with a CO-CO2-Ar gas mixture and quenched after equilibration. The chemical composition of the slag was analyszed. From a knowledge of the thermodynamics of Fe-Pt system, the ?FeO? activities in the slag could be evaluated. The results of the present studies, together with other literature values, were optimized in the slag software, THERMOSLAG® developed in the Royal Institute of Technology, Sweden. The results of the optimization are presented. Model calculations were performed with the KTH slag software, THERMOSLAG®, by using plant data from OVAKO Steel, Hofors, Sweden. It was found that oxygen estimations in the metal from the ?FeO? analyses of slags, obtained by conventional sampling and analysis methods, where less reliable. Estimation of the oxygen levels utilizing the sulphur partition between the slag and the metal were carried out using the THERMOSLAG® software. Reasonable estimations of the oxygen contents in the metal confirmed that this could be a very useful tool for the plant operator. Keywords: ladle, thermodynamics, slags, ?FeO?, experimentation, modelling, sulphur partition

Jan 1, 2004

By Yamada K, Abe H

Magnetic scanning type mass spectrometers have been given improved sensitivity with a large dynamic range and considerable resolution by the addition of a computer-controlled electric equipment. A mass spectrometer equipped with this newly developed electric system was applied to studies of the activities of liquid iron-silicon alloys and of liquid iron-phosphorus alloys at 1600¦C. The range of silicon concentration was 5.8at%-51.1 Si= at%, and values of ySi -3.1+0.15 and es 11.5 +1.5 were obtained. The concentration range of phosphorus was 1.3at%-5.7at% and a value of eP=7.3+0.1 was obtained.

Jan 1, 1980

By Muhammad A. Imam, Ramana G. Reddy

This study provides a reasonable evaluation of the Mg-B binary system. Magnesium and Boron (Mg-B) alloys were investigated to determine their thermodynamic properties employing solid state electrochemical cells based on CaF2 electrolyte represented as –Pt; Ar= MgþCaMgF4 f gCaF2 k kf½Mg B alloy þ CaMgF4 g=Ar; Pt+ Investigations were performed over the temperature range of 773–873 K to measure the electromotive force (EMF), which was used to derive the partial Gibbs Free energies of the alloys in the composition range of XB = 0.07 to 0.95. The activities of Mg were also calculated from partial Gibbs Free energies. The activities of Mg in MgB2, MgB4, and MgB7 were expressed as a function of temperature respectively, ln aMg = 4.27–9.32 × 103/T, ln aMg = −7.54 + 6.67×103/T, and ln aMg = 4.93–19.57 × 103/T, where T is the temperature in K. From this expression, the activity of Mg for these intermediate phases can be extrapolated at a higher temperature to get the accurate phase boundaries for the Mg-B system.

Mar 1, 2017

By Pedro Jorge Walburga Keglevich de Buzin

The steel production in mini mills generates several process residues, among them the electric arc furnace dust (EAFD). This residue has as main elements Fe, O, and Zn, being classified as hazardous by the presence of Pb and Cd. In recent years, a rise in the chlorine content of this residue was observed, motivated by the increased use of scrap with impurities bearing this element. In this work, a qualitative assessment of the presence of chlorine in the electric steelmaking process is made. Complementing it, theoretical considerations based on the computational thermodynamics tool FactSage show the effects of the chlorine on the mineral species in EAFD and on gaseous species in the gas phase (HCl and Cl2). For this study, PVC polymer was used as the chlorine carrier substance which contaminates the EAF charge; presence of other minor elements in the system such as K, Na and Pb were also considered.

Aug 7, 2018

By Kevin Trumble, David Johnson, Kyungjean Min

The electrolytic manganese dioxide (EMD) production through electrodeposition from manganese nodules by reduction leaching in H2SO4 medium using sucrose as reductant followed by purification through 2-stage precipitation methods is described. The purified leach liquor was the starting solution for electrodeposition. Influence of in situ addition of a cationic surfactant Cetyltri-methylammonium bromide (CTAB) (0–500 mg dm −3) on the surface morphology and electrochemical properties of the EMD was examined. The XRD patterns of the deposited material were indexed to the c-MnO2 phase. FESEM results demonstrated that in the presence of CTAB uniform nanofibrous type grains were formed. Higher concentration of CTAB in the electrolytic bath however, drastically decreased the current efficiency (CE) and increased the energy consumption (EC) during electrodeposition. Under the optimum CTAB concentration of 100 mg dm −3 the obtained CE and EC values were 87.64% and 1.70 kWh/Kg respectively.

Mar 1, 2018

By Katsunori Yamaguchi

Secondary materials, that contain relatively high concentrations of platinum group metals, (PGMs) are treated in copper smelting process. The PGMs lost in the slag is increasing with increasing quantities of scrap treated amount. To determine the portion of the PGMs chemically dissolved and that associated with the mechanically trapped matte in the slag will be a key factor to improve the recovery of those metals. An experimental study was carried out to determine the distribution of palladium between the FeOx–SiO2 slag and the liquid Cu2S–FeS matte at 1573 K and a fixed partial pressure of SO2 of 0.1 atm. It was found that the distribution ratios are around 10−3 for platinum and palladium. The distribution ratios show a tendency to increase when the grade of matte is increased above 60 mass% Cu. In addition, the solubility of platinum in FeOx–SiO2 slag equilibrated with a pure palladium and the Pd-Cu alloy was determined at 1573 K and the range of oxygen partial pressure from 10−9 to 10−7 atm. The solubility of palladium in the slag tends to increase with increasing oxygen partial pressure and activity of CuO0.5 in the slag.