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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

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 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 Michael Wieland

The resolving capacity of the thermodynamic work-principal model has been seriously refined over its twelve year history, so a review of the innovations, wrong turns and their rectification is warranted to help future researchers. The work-principal model rests upon the four laws of thermodynamics that drive the universe and relatively few other assumptions: like the removing and imposing of constraints on the quasi-potential to yield trapped minimum key-states that represent the wanted process. The formative research was concerned with the role of ingredient changes, the removal of booster influence and the quench temperature with which to reckon toxic fumes. The transfer of reaction-zone energy as work upon the surrounding rock/water/fixture was not fully rationalized until the notion of reversed-inertial pressure was formulated and determined (for water) with underwater trinitrotoluene (TNT) shots. The rock-water-jelly model incorporated that term into its dynamic pressure formula as a way to represent rock blasts or underwater shots, while the zone of reaction gases remained trapped. The real irreversible thermodynamic process, which yielded the total expansion work, was later complemented with a wholly reversible imaginary process, to form a closed thermodynamic loop, with a remarkable consequence – the determination of the theoretical heave and hence, the undissipated-shock by difference from the total work. With the wholly developed model, it was recently possible to quantify the time retardation of reaction chemistry for non-molecular (mining) explosives, as compared to the rather negligible time-retardation found for the molecular (military) explosives in underwater tests.

Jan 1, 2009

By H. F. Feldmann

This work was done to provide thermodynamic, electrical, physical, and compositional data on the seeded combustion plasmas of seven coals for the design of MHD generators. The systems were assumed to be at equilibrium, and the design data were generated by solving for the composition of both gas and liquid phases with a digital computer. The coals reported in this study include a western subbituminous, a Pennsylvania anthracite, and five representative bituminous coals. The data include dewpoint temperatures of both slag and seed. A Mollier diagram for each coal is given to allow graphical generator calculations.

Jan 1, 1970

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 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 S Jahanshahi, D R. Swinbourne

The classical metal-slag-gas equilibrium technique was used to study the thermodynamic activity of cobalt, iron and their oxides in iron silicate based slags containing under controlled oxygen potential (3.70 x 10-8 to 2.95 x 10-7 atm) at 1573 K. The measured activity of cobalt oxide in FeOx-25 wt per cent SiO2 slags showed positive deviation from ideal behaviour for melts with up to ten wt per cent CoO. At higher silica contents, the behaviour became closer to ideal and in accord with previous studies on silica saturated slags. The activity coefficient of FeO in these slags had virtually no dependence on the CoO content. Partial substitution of silica by lime resulted in an increase of the activities and activity coefficients of CoO, FeO, Fe2O3 and Fe3O4. The results indicate that saturation of the slag with a magnetite phase occurs at CaO contents of five wt per cent and higher. Phase equilibria studies SiO2-FeO-Fe2O3-CaO slags containing cobalt were also carried out using the drop-quench technique. Results from these experiments confirmed the formation of a magnetite solid solution containing about three wt per cent CoO at lime contents of five wt per cent and higher at 1573 K and 2.9 x 10-7 atm of oxygen.

Jan 1, 2000

By Toguri JM

A solid electrolyte technique has been used to measure the activity of cobalt in liquid cobalt-gold alloys containing between 0.085 and 0.50 mole fraction of cobalt, and for temperatures from just above the liquidus to around 1550 K. The system exhibits positive deviation from ideality, both in the activities of cobalt and gold, and in the enthalpy and excess entropy of mixing. The results agree with previous measurements using a Knudsen cell - mass spectrometer technique, but differ from those reported for a gas equilibration method. The data have been used to calculate the activity coefficient of cobalt oxide in silica saturated iron silicate slags and to express the solubility of cobalt in such slags as a function of cobalt activity and oxygen pressure.

Jan 1, 1984

Thermodynamic properties of the solutions of hydrogen in metals and carbon in austenite were investigated and it is possible to predict the interstitial solubility in these systems over relatively wide ranges of temperature and solute activity. Monte Carlo methods were used to compute the arrangements of interstitial atoms on the tetrahedral sites in body centred cubic metals and the octahedral sites in face centred cubic metals. It was shown that the non-configurational entropies of solution of hydrogen in metals can be interpreted as being principally vibrational and on this basis the potential value of the isotopic solubility ratio theory in indicating the compositional variation of these non-configurational entropies was discussed. The need for future work along these lines is pointed out.

Jan 1, 1970

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 Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By S. E. Olsen, K. Tang

Slag-metal and slag-metal-gas heterogeneous equilibria involving MnO-containing slags have been simulated using recently developed Mn-based alloy and IRSID oxide thermochemical databases. A large number of experimental equilibrium data have been used to verify the calculation results. The experimental slag-metal and slag-metal-gas equilibria in MnO-SiO2binary, MnO-SiO2-CaO and MnO-SiO2-Al2O3ternary, MnO-SiO2-CaO-Al2O3quaternary andMnO-SiO2-CaO-Al2O3-MgO higher-order system can be reproduced within experimental uncertainties. The influence of temperature, CO partial pressure and slag chemistry on the Mn-and Si-distribution equilibria have been quantitatively evaluated. This leads to a sound basis for optimizing the manganese ferroalloy production processes. Key words: MnO-containing slag, manganese ferroalloy, equilibrium simulation, thermochemical database

Jan 1, 2004

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By M. J. Makhula, R. M. S. Falcon, S. O. Bada, L. M. Falcon

"SynopsisThe combustion and co-combustion behaviour of macadamia nut shell, high-ash coal, and anthracite, along with their blends was studied using thermogravimetry. The reactivities of all samples were analysed in air, oxygen, and CO2 atmospheres and at different heating rates from 10 to 40°C/min. Macadamia shell was found to have a lower ash content, 0.36%, than coal with 27.49% ash. The calorific values were similar, 19.64 MJ/kg and 19.44 MJ/kg respectively. The differential thermogravimetric results indicate that as the heating rates increase the ignition, peak, and burnout temperatures increase significantly, leading to high combustion rates. The interaction between the fuels was evaluated using the weighted average model, and the results indicated that there is more synergetic interaction between 20% macadamia plus 80% coal under oxygen than in air and CO2 atmospheres. The results of the investigation provide the combustion and co-combustion characteristics of various samples and their blends and indicate their combustion compatibilities. IntroductionThe global macadamia nut industry is developing at a very rapid rate. South Africa is currently the world’s third largest producer, with a production of about 35 000 t as of 2012 (Department of Agriculture, Forestry and Fisheries, 2013), compared to 840 t produced in 1996. The greatest numbers of the macadamia nut farms in South Africa can be found in Mpumalanga, Limpopo, and KwaZulu-Natal provinces, with Mpumalanga as the largest producing area. There are many factors influencing the increased demand for macadamia nuts, the most important factor perhaps being their nutritional value (California Dried Fruit and Nuts, 2011; MPC, 2014) and their suitability as a feedstock for manufacturing cosmetics, bakery products, nut paste, chocolates, sauces, and ice-cream. As a fuel, macadamia shell has a high heating value ‘as-fired’ of about 20.71 MJ/kg (Vhathvarothai et al., 2013), which could in turn be used in drying the nust, and the shell could also be milled and applied as a fertilizer."

Jan 1, 2015