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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

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 R. G. Reddy

To better understand the behavior of bacterial-mineral interfacial reactions, a thermodynamic model based on the- studies of bacteria adhesion on mineral surfaces has been evaluated. The bacteria adhesion to the mineral surface would be increased by l ' d1;1creasing the change in Gibbs free energy of adhesion and it would be reduced if the change in Gibbs free energy of adhesion of the system is increased. From the combination -of Young's equation and equation of state, the change in Gibbs free energy of adhesion -for bacterium-mineral system- was calculated. Influence of liquid surface tension, mineral surface tension on the change in Gibbs free energy of adhesion and consequently bacteria behavior on mineral systems- has been discussed.

Jan 1, 1991

By M. W. Davies, P. N. Smith

The activity of MnO has been measured in the system CaF2-MnO at 1773 and 1873 K and in the system CaF2-CaO-MnO at 1773 K by the method of equilibration with platinum. Large positive deviations from ideal solution laws have been found, but these became less as the lime content rose. The loss of a volatile component made activity measurements impossible in the CaF2-AI203-MnO system, but the boundaries of a two-liquid region have been measured at 1773 K.

Dec 1, 1971

By Do-Hyeong Kim, Tae-Jung Kim, Seung-Yeon Won, Jong-Jin Pak, Min-Kyu Paek

Liquid iron alloys containing V, Mo, and Ni can be produced by the carbothermic reduction of spent catalysts used in petrochemical industry. Thermodynamics of carbon in these alloy melts is important for refining these alloys. In the present study, the carbon solubility in Fe-V, Fe-Mo, Fe-Ni, Fe-V-Mo, Fe-V-Ni, Fe-Mo-Ni and Fe-V-Mo-Ni alloy melts of various compositions was measured at 1873 K. The temperature dependency of vanadium effect on carbon solubility in liquid iron was also measured in the temperature range from 1823K to 1923K. The additions of vanadium and molybdenum significantly increased the carbon solubility in liquid iron alloys while nickel decreased the solubility. The experimental results were thermodynamically analyzed using Lupis’ relation at constant activity to determine the first- and the second-order interaction parameters of vanadium, nickel and molybdenum on carbon at carbon saturated condition. Using thermodynamic parameters determined in the present study, the carbon solubility in Fe-V-Mo-Ni alloy melts of various composition were accurately predicted and verified experimentally at 1873 K.

Jan 1, 2014

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 Yoshinao Kobayashi

he removal of oxygen from titanium and zirconium is important for use in application because it significantly affects the mechanical and physical properties such as ductility and toughness. However, thermodynamic properties of oxygen in molten titanium and zirconium have not been clarified and the effective deoxidation process of molten titanium and zirconium has not been established. In this study, the standard Gibbs energy of reaction of oxygen and yttrium in molten titanium and zirconium have been measured by a chemical equilibrium technique. Molten titanium, zirconium, and their alloys with aluminum were equilibrated with a Y2O3, A12O3, or Zr02 pellet in a cold crucible. The results are summarized as follows:

Jan 1, 2000

By Iwu GO, Almond DP, Joasoo _

The gravimetric integral Knudsen effusion method was used to measure cadmium activity values in binary liquid In-Cd alloys in the range 523 to 573 K. The activity measurements together with other studies from the literature indicate that special bonding conditions exist in the melts near a composition corresponding to InCd3. Sound velocities in In-Cd melts were also measured using a precision pulse-echo over- lap method in the range 404 to 953 K. The frac- tional deviation of experimental and ideal isentropic compressibilities at 623K shows a functional dependence on composition with a pronounced maximum near the composition 75 at.%.

Jan 1, 1980

By Ivan Imris

The iron production has generated many tonnes of very fine residues with high concentration of iron. In addition, during the recycling of galvanised steel scrap in the steel making processes the zinc and lead are largely concentrated in the dust. These kinds of dusts are usually dumped beside the metallurgical plants and cause environmental problems. Therefore the metal recovery from the metallurgical residues has become a major interest not only from the viewpoint of metals recycling but mainly from the viewpoint of environmental land protection. The thermodynamic analyses and laboratory experiments suggested that the metals could be recovered from metallurgical wastes by reduction roasting and by plasma smelting processes. The iron rich pellets with very high metallization may be obtained from metallurgical wastes by the reduction roasting and the inert slag and pig iron could be produced by plasma smelting processes. In both cases the iron rich products are suitable for the steel production. During the reduction roasting or plasma smelting the high volatile zinc and lead metals were removed and enriched as a secondary dust, Zn-Pb concentrate, which is suitable for processing in zinc and lead smelters. Suggested processes are commercially feasible and environmentally friendly without any solid or liquid waste.

Jan 1, 2003