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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.

By J. Petersen, H. Naderi, M. H. Nikzad, M. Karimi

In this research, the thermodynamic study of sodium persulfate (Na2S2O8) solution in the presence and absence of H2SO4 and Fe3(SO4)3 was done. Eh-pH and equilibrium distribution diagrams were constructed using Outotec HSC Chemistry Software and the main stable ionic species were determined. Also, the mean activity coefficient and Pitzer model coefficients were evaluated. Effects of system composition, sodium persulfate concentration and temperature were investigated. According to the results, HS2O7 -, HS2O8 -, S5O3 2-, S4O3 2-, S3O3 2-, HS- and NaSO4 - are the main stable species in these three systems. Increasing of sodium persulfate concentration resulted in disappearing of SO4 2- and the appearance of NaSO4 -. The main effect of increasing the temperature from 25 to 75oC, is changing the stability regions of HS2O7 -, NaSO4 -, SO4 2- and S2-. From equilibrium studies, it was concluded that at 25 and 50oC, increasing the persulfate concentration results in a 55-60% decrease for HS2O7 - and an 20- 30% increase for HS2O8 -. At 75oC, HS2O8 - becomes the main species and its percentage decreases with increasing the persulfate concentration. Keywords: Thermodynamic, sodium persulfate, activity coefficient

Jan 1, 2020

By Wei-Tong Du, Yu Wang, Gang Wen

Carbon dioxide (CO2), a major component of the greenhouse gases, could be comprehensive utilized as a valuable resource to oxidize vanadium during the converter vanadium extraction process. The thermodynamic software, FactSage, was utilized to study the oxidation ability and theoretical cooling ability of using weak oxidant CO2 as coolant in vanadium-containing hot metal. Besides, experimental research on vanadium extraction in CO2 and O2 mixed blowing extracting process had been undertaken. The results indicated that the elements C, Si, V, Mn etc. could be oxidized by weak oxidant CO2, and the content of V2O3 in slag was approached to pure O2 blowing. Furthermore, CO2 had a remarkable cooling ability and the molten bath temperature kept on decreasing as CO2 blowing rate increases. This research has proved that CO2 and O2 mixed blowing in vanadium extraction process are effective.

Jan 1, 2015

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

Thermodynamical data of importance in connection with copper smelting have been reviewed and a collection of the most reliable information is presented in Tables XXV-XXVIII and Figs. 67 and 6 8 (folding plate). The data given in these figures and tables consists of (i) graphs and equations showing the variations in the temperature range 0-2000°C. of the standard free energies of formation of most of the oxides and sulphides met with in copper smelting (Table XXV and Fig. 67); (ii) equations showing the temperature variation of the free energy of formation of iron silicates (Table XXVI); (iii) graphs showing the variation with temperature in the range 1000°-1600°C. of the standard free energies of the principal reactions occurring in the smelter (Fig. 6 8 ); (iv) the standard heats of formation at 1200°C. of the main iron and copper compounds and gases reacting in the smelter (Table XXVII); (v) the standard heats of reaction at 1200°C. of a few of the reactions for which the free energy relationships were given in Fig. 6 8 (Table XXVIII). The data presented are discussed in more detail.

Jan 1, 1953

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

By M. W. Wadsley

"Physical and chemical property models are widely used in process engineering. There exist, in the published literature, completely empirical models of ''thermodynamic properties"", that is, property models that are not consistent with the laws of thermodynamics. There also exist property models that purport to be thermodynamically consistent but are flawed in their implementation. There are also published property models that are consistent with the laws of thermodynamics but that do not reproduce property values with an acceptable accuracy. A practicing engineer might be asked to assess very different property models for which there are a variety of claims. This paper discusses features of thermodynamic and empirical property models that may assist in their practical evaluation and implementation."

Jan 1, 2005

By Zhihe Dou, Guozhi Lyu, Liping Liu, Yi Luo, Ting-an ZHANG, Xijuan Pan, Zhuolin Liu

Due to the high energy consumption, long technical process, low usage rate of vanadium during the traditional smelting vanadium steel process, a new method for decarburization by CO2 to directly smelt vanadium-containing steel in blast furnace was proposed. In this paper, the thermodynamics of CO2 decarburization in molten iron process was calculated out by FactSage. The thermodynamic calculations indicated that in standard state, the transformation temperature of C and V was 1357 °C; the oxidation order of element was Si, C, V, Mn and S when using CO2 as oxidant. The experiment of blowing CO2 temperature showed that decarburization reaction temperature was 1550 °C, carbon content could be decreased to 0.676%, the decarburization rate was 88%. There was no effect on vanadium content in molten iron during the decarburization process, vanadium content was 0.323%, which meets the request of vanadium mould steel.

Mar 1, 2018

By F. T. Da Silva

Concentrates of titaniferous minerals containing around 30 wt% Ta2O5 are processed hydrometallurgically by hydrofluoric acid leaching and solvent extraction, followed by the precipitation of hydrated potassium heptafluorotantalate. A fundamental study of the thermodynamics of this precipitation and recrystallisation was undertaken to increase understanding of the conditions most conducive to the production of pure, well-crystallised K2TaF7. Activity-pH diagrams for the Ta-K-F-H2O system explained the dissolution of Ta2O5 in fluoride solutions quite well and also the precipitation-recrystallisation of K2TaF7.H2O. X-ray diffraction and scanning electron microscopy confirmed the thermodynamic observations. It was concluded that the best precipitating agent for K2TaF7 from fluoride solutions is KF but a recrystallisation step in a HF environment produces purer, well-crystallised K2TaF7.H2O, eliminating oxy-salts and other impurities

Jun 21, 1905

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By I. Barin

The thermodynamics of cyclone smelting of sulphidic copper ores is described using as example the production of copper matte with 75 wt % Cu. Equilibrium calcualtions and material and energy balances show that an increase in process temperature from 1600 K to 1900 K results in the extensive transfer of minor elements such as As, Sb, Bi, Pb, Zn,.... to the gas phase. A pilot plant for carrying out the cyclone smelting process is described. Calculations of material and heat transfer for the reaction of ZnS show that the smelting reactions of sulphides in the cyclone take place very rapidly at high temperatures. The dissociation of the sulphides with subsequent oxidation reactions in the gas phase plays an important part in. the process and is mainly controlled by heat transfer.

Jan 1, 1983