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By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By C. Ernest Birchenall, Robert F. Mehl

APPLICATION of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion coefficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner1 derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smiths on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 ACTIVITIES IN BRASS9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by azn = Pza/Pzn° [I]

Jan 1, 1947

In this study, the effects of slag compositions, slag amount, temperature, and carbon content of steel on the manganese and phosphorus distribution ratios during converter steelmaking were analysed using the classical regular solution theory, and industrial tests were performed using two 80 t top-and-bottom combined blown converters (duplex melting process). The results indicate that the slag amount, temperature, and carbon content in steel are the main factors affecting the manganese yield when converter slag compositions remain constant. The FeO content of the slag has a strong impact on the manganese distribution ratio, while the slag basicity and MgO content have no obvious effect. The calculations and experimental results show that the phosphorus distribution ratio increases sharply with increasing slag basicity R, but then decreases with the increase of MgO and MnO contents in the slag. The final slag in converter steelmaking should have the following characteristics: 3.5 < R < 4.5, 15% < (FeO) < 20%, and 6% < (MgO) < 8%. The slag amount should be controlled appropriately at the same time. The results of this investigation would be useful in deciding on the application of manganese ore in alloying and identifying the slagging regime in converter steelmaking.

Jan 1, 2014

By K. Yamaguchi, Y. Takeda

"Partial pressure - temperature - composition correlation diagrams of the Ga-As, In-As, Ga-P and In-P systems were contracted based on the obtained experimental data of the phase diagram and thermodynamic properties for the III-V systems. The total vapor pressures of arsenic or phosphorus at melting point of GaAs, InAs, GaP and InP were determined as 101, 10.1, 1510 and 253 kPa, respectively, at the corresponding melting points of 1509, 1211, 1739 and. 1336K , These diagrams are applied to the analysis of the horizontal Bridgman method and the liquid phase epitaxial growth technique. On the other hand, the analysis of the equilibrium state of the. chloride-CVD process was carried out using the data of the Gibbs energy of the compounds obtained by· authors.IntroductionThe group III-V compound semiconductors ate important materials used in optoelectronic liquid high speed electronic device. The crystal growth of the III-V compounds can involve processes that require contact between the solid, liquid and vapour phases at near equilibrium condition. Examples of processes that involve contact between the solid, liquid and vapour phases include bulk crystal growth such as the horizontal Bridgman and the liquid encapsulated Czochralski method and liquid epitaxy, and between the solid and vapor include chemical vapour deposition and molecular beam epitaxy. Therefore, the knowledge of the phase diagram and thermodynamic properties for the III-V binary alloys is essential for the analyses of crystal growth techniques of III-V compounds.For these reasons, a series of different · types calorimetric measurements had been carried out: (1) The heat contents of alloys for the Ga-As, In-As, Ga-P and In-P systems by a drop calorimeter [1;2,3]; (2) the heats of formation of the GaAs, InAs, GaP and InP compounds by a twin solution calorimeter [4]; and (3) the standard entropy of these compounds by an adiabatic calorimeter [5]. Based on the third law method, the Gibbs energies of these compounds were derived from the heat capacity, standard heat of formation and standard entropy data obtained by authors. Integral molar thermodynamic quantities of the liquid III-V .alloys were also determined from combining the heat contents of alloys with standard heat of formation and standard entropy data of the compounds· by applying the thermodynamic analysis method developed by Oelsen [6]. In the present study, the thermodynamic calculations for the crystal growth processes of the III-V compound were carried out using newly experimental data of the phase diagram and thermodynamic .properties measured by authors"

Jan 1, 2000

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By D. M. Muir

Thiosulfate offers a non-toxic alternative to cyanide for processing gold ores. The mechanism of leaching gold using ammoniacal thiosulfate solution is driven by the Cu(II)-Cu(I) redox couple and is complicated by competing ligands such as NH3 and S2O32-. It is shown that an understanding of the copper speciation and sulfur speciation is required to optimise this system. This paper presents Eh-pH and speciation diagrams for varying concentrations of Cu(II), S2O32- and NH3 and discusses the conditions under which various copper and sulfur species are stable.

Jan 1, 2001

By Wenjun Duan, Qingbo Yu, Qin Qin, Junxiang Liu

In the study, the coke-oven gas (COG)-steam reforming process using hot blast furnace slag (BFS) as the heat carrier is explored for producing hydrogen and recovering high-grade waste heat of hot BFS. The method of the Gibbs energy minimization approach through Lagrange multiplier is adopted in the thermodynamic analysis of reforming process. The simulation is carried out to study the operation pressure, temperature and steam to carbon ratio (S/C) based on the chemical equilibrium calculations. The optimal operation conditions are determined to improve the yield and fraction of hydrogen in the COG-steam reforming process. The results suggest that the preferential operation conditions for COG-steam reforming process to produce hydrogen are achieved at 600ºC, 1.5MPa and S/C (5.0). Due to the CaO and other melts in BFS, CH4, CO and CO2 in COG are converted and removed efficiently, especially CO2. The hydrogen fraction reaches to 86.7% and its production is about 1.22mol with 1mol of the COG.

Jan 1, 2016

By Maryam Ghodrat, Bijan Samali

Disposal of waste syringes in a safe and eco-friendly way has been an issue of considerable scale for decades. The generated amount of waste syringes has escalated with the rapid growth in population and wide acceptance towards single-use medical devices. Some hospitals have their own on-site incinerators ,but recent tightening of air quality regulations and landfill levies led to the closure of manyon-site incinerators. The solution to this problem implicates the development of an environmentally-sound method that would employ these waste materials. This work investigates a thermodynamic modelling approach for incineration treatment of waste plastic syringes in Electric Arc Furnace (EAF) steelmaking. Mass balance was obtained from HSC Chemistry thermochemical package. The results indicate that the rate of iron oxide reduction in the slag is higher when coke is partially replaced by waste plastic syringes. Furthermore, the amount of dust and stack gas emission was reduced by around 0.4% and 1.25% respectively by replacing 20%-weight of pure coke with waste plastic syringes. The study demonstrates part of the coke can be successfully replaced by waste plastic syringes in electric arc furnace to provide additional energy from combustion without affecting the main process.

Mar 1, 2018

By Xiaolong Lin, Yuanbo Zhang, Guanghui Li, Zhizhong Li, Zhiwei Peng, Tao Jiang, Yan Zhang, Yutian Ma

Pyrometallurgical processes for recovering platinum group metals (PGMs) from spent catalyst have been the focus of current research for many years. They suffer from high energy consumption, large trapping agent consumption and huge slag production. Because of versatility of PGMs-containing spent catalysts, comprehensive recovery of valuable metals from these catalysts from an experimental point of view remains a challenge. In this study, thermodynamic analysis of pyrometallurgical smelting process in the presence of various additives for ef ficient recovery of PGMs was performed. It showed that addition of sodium salts would promote the migration and separation of the precious metals from carrier of the spent catalyst. By replacing calcium oxide with sodium carbonate and sodium borate, the smelting temperature could be reduced by more than 200 °C, which agreed well with the experimental findings.

Mar 1, 2018

By E. V. Bratygin, E. G. Dmitrieva

The aim of the research was to study the thermodynamic characteristics of high-temperature processing of ilmenite concentrate deposits "Central" in a neutral and oxidizing atmosphere, as well as its interaction with alkaline additives. The research was conducted using a scanning colonoscopy on thermogravimetrical analyzer NETZSCH STA 449 F3. A sample of the test material weighing 10 mg was placed in a crucible and heated at a rate of 10 °C/min to 1200 °C in argon or air. Studies have been conducted pure ilmenite concentrate and its mixtures with 5 % and 12.5% of sodium carbonate. The results of the analysis of the thermogravimetric curves it was found that the recovery of the concentrate carbon will come from ulvospinel, not pseudobrookite, and the reaction recovery is possible at temperatures above 900°C. While removing produced in the decay ilmenorutile of iron oxides in an inactive form, for example, iron (III) oxide, it is possible to reduce the quantity of the solution of ilmenite formed during the restoration of the melt anosovite. The analysis of data obtained during heating of ilmenite concentrate with sodium carbonate in concentrations of 5 and 12.5% transition pseudobrookite in ulvospinel is missing, it just breaks down into hematite and titanium oxide, which, in turn, react with N?2??3. It should be noted that increasing the concentration of sodium carbonate in the sample contributes to more complete interaction of iron oxides and N?2??3 with formation of ferrites of sodium. This can ensure full recovery of iron oxides in the concentrate, which is part of secondary ilmenite can not be dissolved in the melt formed by the lower oxides of titanium. In addition, the increase in the content of soda in the mixture significantly reduces the temperature of the initial melting point of the slag and facilitates the coagulation of metallic iron.The obtained results were used for laboratory studies of the solid-phase sintering of briquettes from ilmenite concentrate with additives of sodium carbonate and a reducing – coal, as well as for the development of technological mode of solid-phase sintering of the concentrate with the aim of obtaining product recovery with a titanium dioxide content of more than 75 %.

Jan 1, 2018

By Xiang-dong XING, Zhen-yang wang, Jian-Liang Zhang

Distribution behavior of titanium between CaO-SiO2-MgO-Al2O3-TiO2 and hot metal was studied between 1350 °C to 1600 °C. Experimental results indicate that the reaction temperature influenced the activity coefficients of titanium and resulted in the variation of equilibrium constant. Finally, the Gibbs free energy formula of titanium carbothermic reduction was fit out using the thermodynamic model of Wagner and congregated electron phase models.

Jan 1, 2015

By Zhan Jing

Keywords: thermodynamic, Ni-Co alloy powders, composition, fibrous The mathematics model of Ni(II)-Co(II)-C2O42?-NH3?H2O-H2O of thermodynamic equilibrium system has been developed theoretically according to the law of conservation of mass and the law of simultaneous equilibrium, and the logarithm concentration-pH (log[Me2+]T-pH) diagrams of this system have been made. The effect of ligand and pH value was studied. Two issues in coprecipitation route to synthesize fibrous nickel-cobalt alloy precursor powder, com-position and morphology which are a first priority, are addressed based on thermodynamic analysis and experiments. The results show that suitable pH value range of coprecipitation of nickel ions and cobalt ions in theory can be obtained to maintain fibrous, excellent compositonal homogeneity and stoichiometry in coprecipitation products. Experimental demonstration is also carried out.

Jan 1, 2005

By Shu Yamaguchi

The behavior of halide impurities in pyrometallurgical processes such as Wealtz kiln and MF process has been discussed based on the thermochemical data and the reported data of PbO activity in PbCl2-PbO melts. The role of PbCl(g) has been estimated to be significant in the chloridization evaporation reaction. From reported data on the PbO activity in PbC12-PbO melts, activity of PbCl2 has been calculated by the numerical integration of Gibbs-Duhem equation, and the stability domains and the composition of the liquid phase as well as the vapor pressure of PbCl2 have been estimated as functions of log P2HCI/PH2O and temperature. From the discussion of the path during cooling process on the log P2 HCI . PH2O vs. temperature diagram, the authors proposed a possible dechioridization process that utilize water vapor as a dechloridizer for the direct precipitation of PbO from gas phase.

Jan 1, 2003

By O. Alonso-Gonzalez, F. Nava-Alonso, A. Uribe-Salas, C. Jimenez-Velasco

"Most of the gold produced worldwide is still obtained by cyanidation, in spite of the difficulties encountered in the processing of some gold ores such as the dissolution of copper-bearing minerals in cyanide solutions. The leached copper forms complexes with cyanide and causes several operating problems, which have led to the development of copper removal/recovery processes, among them the industrially accepted SART process (sulfidization, acidification, recycling and thickening). Although the SART process is in use in gold production plants around the world, new challenges are appearing with the continuous varying of the mineralogy of ores (such as higher copper grades, changing the solution composition and complexity). The optimal SART operating conditions for a specific solution are not the same when the composition of the solution changes; consequently, the efficiency of this process can decrease.The present study is a thermodynamic approach, corroborated by laboratory experiments, to explain how the main variables of the process affect the efficiency of copper precipitation as cuprous sulfide (Cu2S). The variables considered were pH value, copper concentration, cyanide/copper molar ratio and sulfur/copper molar ratio, all of which werevaried within the limits encountered in typical cyanidation solutions presenting the problem of copper.It was found that the variable that most affects the efficiency of the process was the pH value, since poor or no control of it can cause cuprous sulfide redissolution. The S/Cu molar ratio is also important: raising this ratio increases copper removal, but high ratios will also cause sulfide and cyanide losses. The effect of changing the CN/Cu molar ratio was negligible between 4 and 8. For a solution containing 300 mg/L copper and 490 mg/L cyanide, copper removal as high as 98.8% can be obtained with the addition of 0.6 moles of sulfide per mole of copper at pH = 6.IntroductionThe main process for gold production is cyanidation, because it is the most economical and efficient process so far. Precious-metal leaching occurs when the ore is placed in contact with a dilute alkaline cyanide solution. The dissociation of cyanide salts provides free cyanide ions, which allow the formation of the aurocyanide complex Au(CN)2 -. This complex can be retrieved from the solution by adsorption on activated carbon or by zinc precipitation. Although the use of cyanide represents an issue to health and the environment, there are technologies for its management and treatment that can be easily applied. Furthermore, it is a low-cost process compared with other methods that are available or under development."

Jan 1, 2015

By Kun Wang, Xinhui Li, Huaqing Xie, Qingbo Yu, Qin Qin

"Three typical model compounds of bio-oil (ethanol, acetone and phenol) were studied in the steam reforming process for hydrogen production. In the thermodynamic analysis, the three componds showed the similar trends. The hydrogen yields increased with the increase of steam/carbon (S/C) ratios, and the temperatures of the maximum hydrogen yields moved afterward to low temperature zone. However, the hydrogen contents were just about 70%. For improving hydrogen yield, a new system for steam reforming of bio-oil with site CO2 capture was put forward. This system required the catalst with the larger granularity having greater mechanical strength and higher abrasion resistance. So, six Ni-base catalysts loaded on Al2O3 particles prepared were used and among them, Mg-Ni/Co catalyst showed the best catalytic performance. For the simulated bio-oil (the mixture of the compounds), the hydrogen yield can attain 63% with Mg-Ni/Co catalyst with the good stability and regeneration ability.IntroductionCurrently the interest in the use of hydrogen as a clean energy carrier is increasing, and the main way for producing hydrogen is steam reforming of fossil fuels, containing steam reforming of nature gas, naphtha and coal. But this way caused substantial amounts of CO2 emitted, and these sources of hydrogen which are non-renewable energy will eventually be used up [1, 2]. As a kind of renewable energy, biomass is recognized as an attractive alternative to fossil fuels, because of its neutral CO2 emissions [3]. There are mainly two thermochemical processes using biomass to produce hydrogen, gasification and flash pyrolysis followed by steam reforming (SR) of the biooil produced in the flash pryolysis process [4]. The latter was known as one of the most promising and economically viable methods for hydrogen production [5]. In the last decades, the biomass flash pyrolysis technology was adequately developed and fairly mature [6]. But the steam reforming of bio-oil is still at the research stage and yet has been leading to more and more concerns by the researchers. In their research, the catalysts were widely studied and yet mainly were powdery[7-10], and the reactors manily were fixed bed reactors[11-13], readly causing the carbon deposition and the catalyst deactivation, against the continuous running. In this paper, a new systerm was put forward and could realize continuous production of hydrogen, yet needed catalysts with the larger granularity having greater mechanical strength and higher abrasion resistance, as well as powdery CO2 sorbents which mainly calcium oxide based ones.In this paper, the thermodynamic analysis of the steam reforming processes of three typical bio-oil model compounds (ethanol, acetone, phenol) was performed, and the effect of S/C ratio and temperature on the hydrogen yield and the compositions of gaseous products were investigated. Then, a new systerm for steam reforming of bio-oil with site CO2 capture was put forward, and the catalysts with a certain granularity were prepared and studied."

Jan 1, 2014

By Lloyd R. Nelson

The feasibility of producing low carbon (LC) ferromanganese (FeMn) by lime-&apos;ore&apos; melt refining of high-grade ferromanganese silicon (FeMnSi) was investigated. Thermodynamic simulations demonstrated significant benefits in moving from a single-stage ladle operation to a two-stage counter-current reladling operation (to emulate the commercial Penin Process). The theoretical alloy silicon content was predicted to be refined from 1.57 to 0.005 per cent silicon, at a 6.2 per cent higher manganese yield (yield predicted to increase from 82.3 to 88.5 per cent). Extension of this counter-current refining principle, to a multistage Counter-Current Reaction Launder (CCRL) was investigated using the Slag Metal And Gas Klnetics (SMAK) software to model the mass transfer kinetics of the multicomponent coupled reaction system. Simulation results suggested that commercial production of 50 000 tonnes per annum (tpa) of refined LC FeMn, containing less than 0.5 per cent silicon, at manganese yields of up to 90 per cent, should be feasible in a compact CCRL (7 m long by 0.7 m wide).

Jan 1, 1994

By RIINA SALMIMIES, Paula Vehmaanperä, Antti Häkkinen

The dissolution of iron oxides in mixtures of acids is fairly uncommon but can result in a more efficient dissolution process. The objective in this work was to investigate the dissolution of synthetic hematite powder in mixtures of oxalic and sulfuric acid. Experiments were done at different acid ratios and temperatures. An increase in temperature from 15 to 35 °C increased solubility, whereas an increase from 35 to 50 °C did not change the solubility but had a profound effect on the kinetics. An important finding was that oxalic acid advanced the dissolution process since increasing the amount of oxalic acid in the system resulted in faster kinetics and higher solubilities. The dissolution kinetics were well described with the Kabai model, which was the only studied model able to describe the whole reaction time. However, the solid specific constant a varied for the different acid ratios and this is argued to be a result of changes in the solid phase. The changes in the constant a were not in line with the original study of Kabai, which indicates that a cannot be the solid specific constant but it can be the constant connected to dissolving media describing the changes in the dissolution mechanism.

Sep 23, 2020

By RIINA SALMIMIES, ANTTI HAKKINEN, PAULA VEHMAANPERA

Better understanding of the mechanisms and kinetics of dissolution can benefit several industrial processes. For example, iron can be leached from clays, which can be further used as a raw material in the ceramic industry. Another important application is the regeneration of ceramic filter media, which are used in the dewatering of iron ores. Dissolution of iron oxides in mixtures of acids is fairly uncommon and a less well-understood phenomenon, but it can result in a more efficient process. This work also shows that the determination of dissolution mechanisms and kinetics is not straightforward in different acid systems.

The published liquidus data on the Pb-PbS system have been correlated on the basis of one-coefficient Margules equations. Thermodynamic properties of the components of this system have been obtained, and it has also been found that the calculated miscibility gap of this system exists over a very narrow range of temperature (1041 to 1058&#176;C).

Jan 1, 1972

By M. Nagamori, A. J. Plumpton

"Commercial HCl-leaching of magnesite and serpentine yields highly concentrated aqueous solutions containing 25 mass % to 33 mass % MgCl2. The partial molar enthalpies and heat capacities, the ionic activities of Mg2+ and Cl–, and the Raoultian activity of H2O have been assessed for the concentrated MgCl2-H2O solutions at temperatures of 348 to 373 K. These thermodynamic data are used to calculate the pH of aqueous MgCl2 solutions saturated with a Mg-bearing mineral such as magnesite, serpentine, brucite, forsterite, enstatite or talc. On the basis of these thermodynamic data, technico-economic aspects are discussed as to neutralization with pulverized MgCO3, water evaporation from the MgCl2 solutions, and ore composition including such minor constituents as CaCO3, FeCO3 and Fe3O4. IntroductionA major magnesium electrolytic reduction plant operates in Quebec, where another will begin its production in the year 2000. One uses imported magnesite ore as raw material, while the other will utilize local asbestos tailings (serpentine). Both processes produce a concentrated salt solution of 25 mass % to 33 mass % MgCl2 by leaching the ore with concentrated hydrochloric acid. Thus, the two processes differ mainly in the HCl-leach and related operations. After the HCl-leach of the ore, the serpentine process yields about 25 times more wet cake to filter and wash than the magnesite counterpart. A comparative cost-engineering study with respect to slurry filtration and cake washing has been published elsewhere (Blackburn and Nagamori, 1994). By contrast, the present study considers the thermodynamics and technicoeconomics of the HCl-leach itself for both ores."

Jan 1, 1999