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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 A. Mikula, S. Karlhuber

"Unique physical and mechanical properties made the Pb-Sn solders attractive for low temperature joining of electronic parts. But since lead in solder materials has become a great enviromental problem and health concern, lead will be slowly replaced by other materials in soft solders. Some of these materials which are currently under investigation are ternary tin alloys. Many different physical properties like wetting behavior, electrical and thermal conductivity and surface tension are measured on these alloys, but on the thennodynamic properties and the phase diagram of the alloys under discussion there is only little information available. We investigated the (Ag, Au, Cu)-Sn-Zn systems and determined the thermodynamic properties over the whole composition range by emf-measurements. From these measurements we also got some information on the liquidus. In the Sn-rich corner the phase diagrams are still under investigation.IntroductionSoldering is technically defined as the joining of two base materials, mostly metals or metal coated nonmetallic substrates, with a third metal. The melting temperature of the third metal or metal alloy should be well below those of the substrates. Solder alloys can be categorized in soft and hard solders. Soft solder alloys usually contain lead, tin, bismuth, indium or cadmium and hard solders gold, zinc, aluminium or silicon. The difference between soft and hard solders is the melting temperature of the soldering material. This temperature is around 350°C.An interesting brief history of solders is given by Vianco and Frear [1]. They report, that in 4000 B.C. solders were already used in Mesopotamia. From archaeoligical evidence those solders were gold-based hard solders.Tin-lead soft solders and their use are not easily found, because in course of time tin has been reduced to stannic acid, making the identification quite difficult. Well preserved soft solder artifacts were discovered in King Tut's tomb dating from 1350 B.C. In ancient time Pb-Sn solders were used primarily for the manufacture and repair of cooking utensils and metal tools. The Romans used lead-tin solders extensively in the construction of the aqueducts."

Jan 1, 1996

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 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 P. M. May, J. S. Solis, G. T. Hefter

Chemical speciation plays a critical role in many areas of gold processing. These include the formation of HCN in plant liquors, interference by copper in the extraction efficiency of gold, the recovery of adsorbed gold, and the behaviour of plant effluents in the environment. Thermodynamic modelling provides a cost-efficient method of rationalizing and even predicting of chemical behaviour. Unfortunately, because thermodynamic data for cyanide complexes are of poor quality and few are known under hydrometallurgical conditions. Such models are currently of limited use. This paper describes recent work on the thermodynamics of cyanide complexes of a range of metal ions. Data will be presented on the stabilities and enthal­pies (heats) and entropies of formation of a variety of metal ion species determined by potentiometry and calorimetry. Particular emphasis will be placed on the Cu(I)/CN- system.

Jan 1, 1995

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 H. B. Bell, L. C. Smith

Measurements have been made of the activity of 'FeO' in 'Fe0'-Mn0-Ti02 melts at 1475 degrees C. The results obtained are discussed in terms of ideal mixing of titanates and in terms of a regular solution model. On the basis of the regular solution model activities of Ti02 and MnO in the Fe0-Mn0-Ti02 and Mn0-Ti02 systems have been derived. The data have been shown to be consistent with the liquidus lines in the phase systems. Examples are given of the application of the data to slag-metal equilibria, being used to derive slag-metal data between liquid iron and Fe0-Mn0-Ti02 slags

Dec 1, 1971

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 Yun Soon Han, Joo Hyun Park

Indium (In) solubility in the FeO-SiO2-Al2O3-5%CaO slag was measured under p(O2)=10¯¹¹ atm at 1573 K to clarify the dissolution mechanism of In in FeO-bearing metallurgical slag. The In solubility increased with increasing oxygen partial pressure, whereas it decreased by increasing the activity of basic oxide, viz. FeO. Thus, a dissolution mechanism of In in the FeO-SiO2- Al2O3-5%CaO slag was described by the following equation. In(s)+1/4O2(g)=(In+)+1/2(o2-) The enthalpy change of the In dissolution reaction was negative, indicating that the dissolution reaction was an exothermic reaction. This is consistent with the above reaction mechanism.

Jan 1, 2014

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

Cospidie (3CaO*2SiO2*CaFe2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel, The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiO2-CaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been deterimed by an electromotive force methods using CaF2 as solid electrolyte and a transpiration method as follows: ^fG° (cuspidine) /kjmol-1 = 5198 + 0.825T (+12) (1313<T/K<1329): EMF method ^fG° (cuspidine) /kjmol-1 = 5178 + 0.813T (+8) (1221<T/K<1469): Transpiration method The chemical potential diagram and constituent activities for the CaO-SiO2-CaF2 System have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

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 J. H. E. Jeffes, K. T. Jacob

Solid oxide galvanic cells, of the type: Pt,Ni-NiO | Solid electrolyte | O(metal),Cermet,Pt, were used to measure the activity coefficient of oxygen in liquid Cu at 1 100 and 1 300°C and in Pb at 1 100°C. Similar cells were used to study the activity coefficient of oxygen in the whole range of Cu + Pb alloys at 1 100°C and in Pb-rich alloys at 900 and 750°C. The results obtained are discussed in terms of proposed solution models. An equation based on the formation of 'species' of the form M(2)O in solutions of oxygen in binary alloys is shown to fit the experimental data

Dec 1, 1971

By Takaaki Ishikawa

The distribution equilibria of lead, zinc and copper between CaO-Si02-Ah03 melts and liquid copper were measured at 1623K under a controlled H2-C02 atmosphere. The distribution ratios were plotted against the oxygen partial pressure, and reasonable oxide forms dissolved in the melts were estimated from the slopes of the plots. The activity coefficients of zinc oxide (ZnO), lead oxide (PbO) and cuprous oxide (CuOQs) increased with increasing slag basicity, defined by Xcao /XSiO, The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003

By Takaaki Ishikawa

The distribution equilibria of lead, zinc and copper between CaO-Si02-Ah03 melts and liquid copper were measured at 1623K under a controlled H2-C02 atmosphere. The distribution ratios were plotted against the oxygen partial pressure, and reasonable oxide forms dissolved in the melts were estimated from the slopes of the plots. The activity coefficients of zinc oxide (ZnO), lead oxide (PbO) and cuprous oxide (CuO0.5) increased with increasing slag basicity, defined by XCao/Xsio2 The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003