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By P. T. Velu

Solubility of metal oxides in the molten salt electrblytes is an important parameter in the electrochemical processing of metals and alloys. The efficiency of an electrochemical process primarily depends on the quantity of metal oxide present in the electrolyte in the dissolved form and its thermodynamic properties. The activity of CeO2 was calculated using the free energy of fusion of CeO2,{ AG°m, CeO2. The AGOm,CeO2 }was deduced from the values of enthalpy, heat of fusion and melting point of Ce02. The activity coefficients of CeO2 as a function of temperature and melt composition were calculated. The thermodynamic data such as integral molar enthalpy, entropy and Gibbs energy of formation were calculated as a function of composition and temperature.

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 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 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 Xin Zhang, Mengqi Li, Hongxu Li, Xinrong Zhang, Hao Bai, Ning Li

"Organic Rankin Cycle (ORC) is an effective technology to transform low-grade energy resource into electricity. In this paper, based on thermodynamic principle, considering the waste heat resource lower than 120°C, thermodynamic properties of ORC with working fluids ofR245fa, mixed R21/R245fa and mixed Rl52a/R245fa were assessed. The results show that high evaporation temperature contributes to improved system performance. The Rankine Cycle that uses R21/R245fa can increase net cycle output, thermal efficiency and exergy efficiency by 3.02%, 2.35%, and 4.44%,respectively, as compared to that with pure R245fa. When using Rl52a/R245fa as working fluid, the net cycle output can increase by 3.83% at most, while the thermal efficiency decreases by 8.7%. These results indicate that R21/R245fa has a good advantage in improving the cycle thermodynamic performance.IntroductionOrganic Rankine cycle is usually used for low temperature power generation, and is applied to the conversion of geothermal energy, low-temperature solar energy, ocean thermal energy and industrial low-temperature waste heat etc. Traditional Rankine cycle is quite mature already, however, organic working fluids would affect significantly the general efficiency of the entire thermodynamic system. Thus, selection of proper working fluids and development of new highperformance cycle is becoming important."

Jan 1, 2013

Equilibrium in the reaction H2(g) + [%0] (in liquid copper) = H2O (g) was investigated at temperatures between 1200 -and 1350°C with p(H2Oj/p(H2) ratios between 1 to 15. A semi-microbalance was used for direct measurement of dissolved oxygen in molten copper. Oxygen was found to obey Henry's law under the experimental conditions used. The standard free-energy change for the above reaction is given by Equation 1where 1 weight per cent solution is the standard state for dissolved oxygen.For the dissolution of oxygen in copper according to 1/2 O2(g) = [%0] (liq. Cu), the standard free energychange is given byEquation 2.

Jan 1, 1973

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 Joseph Hamuyuni, Dmitry Sukhomlinov, Pekka Taskinen, Mari Lundström

The standard thermodynamic properties of the compound Ca2CuO3 were determined electrochemically by the Electromotive Force (EMF) method. The ternary phase Ca2CuO3 was synthesized from the pure oxides CaO and CuO at CaO saturation using a ceramic route. The EMF measurements were performed over a temperature range 973 T/K 1124. The standard Gibbs energy of formation of the ternary compound Ca2CuO3 was determined using the EMF technique as: DfðoxÞGCa2CuO3 ¼ 21:88422:92 103 T: ð1Þ

Mar 1, 2017