Search Documents

By Sergei A. Degterov

A thermodynamic database for the slag, matte and liquid copper phases in the Cu-Ca-Fe-Pb-Zn-Si-O-S system has been developed for the ranges of compositions of importance to the production of copper. When used with the Gibbs energy minimization software and other databases of the F*A*C*T thermodynamic computing system, this database will permit the calculation of matte-slag-copper-gas phase equilibria that take place during copper smelting and converting. The calculations reproduce within experimental error limits all available experimental data on phase diagrams, activities of components, enthalpies of mixing, matte - alloy miscibility gap and tie-lines. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO2 saturation, in equilibrium with Fe, Cu or Cu-Au alloys, at fixed oxygen or SO2 partial pressures and at different contents of Pb, Zn and CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits. The distribution of Pb and Zn among matte, slag, copper and gas has been calculated. The calculations are in good agreement with experimental data and predict the distributions under conditions which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.

Jan 1, 1999

By T. S. Krishnan

Among the established permanent magnets, SmCo5 magnet occupies the foremost position as it offers a unique combination of high energy product, coercivity and curie temperature. The SmCo5 magnets are thus extensively used for high field applications. These are also best suited for use in environments where high demagnetising field and high temperature are operative. Also, for applications where high performance and miniaturisation are the over-riding considerations, the choice again falls on SmCo 5 magnets. The main deterrent to the widespread use of SmCo5 magnet is its high cost. Both samarium and cobalt metals are high priced, and the magnets prepared from their directly melted alloy are thus naturally very expensive. An alternate process involving calcium reduction of their oxide intermediates has, therefore, been studied and the alloy prepared by this process has been evaluated and found satisfactory for magnet production. The process essentially involves compaction of the charge mix containing samarium oxide, cobalt oxide (or metal) and calcium metal and' reduction of the charge compact at 1000-1300°C in hydrogen atmosphere, followed by water and acid leaching, drying and classification. The calcium reduction process offers three distinct advantages over the conventional melting processes: (i) The oxide intermediates are relatively cheaper and do not pose any handling problems. (ii) The operation temperatures are comparatively lower and hence precise composition control is possible as samarium losses due to volatilisation

Jan 1, 1989

By P. Chris Pistorius

Calcium treatment of alumina inclusions, to convert the alumina to molten or partially molten calcium aluminates, is a well-established treatment for steel, to improve the castability of aluminium-killed steel. However, the role of magnesium in calcium-treated steel is not fully clear, nor is the origin of the several percent of magnesium oxide that is often present in calcium-treated inclusions. To study this, steel was sampled after calcium treatment at an industrial steel plant, and the inclusions identified by energy-dispersive X-ray microanalysis (EDX) on polished sections of the samples (analysing the samples in a scanning electron microscope). The predicted fraction liquid in the inclusion was estimated from the ternary alumina-magnesia-lime phase diagram. Inclusions with higher CaO contents generally had lower MgO contents, indicating that the calcium wire is not the origin of the magnesium in the inclusions; this was also confirmed by wet chemical analysis of the calcium wire. Instead, it appears that magnesium-alumina spinel inclusions form during extended ladle contact after aluminium killing and before calcium treatment. While such spinels have been stated to cause poor castability (clogging the submerged-entry nozzle), it is clear that calcium treatment successfully modifies the spinel inclusions to mixed alumina-lime-magnesia inclusions, where the magnesia content contributes substantially to liquefaction of the inclusions: for typical MgO contents of around 10%, the range of Ca:O ratios which yield liquid (or partially liquid) inclusions is extended substantially to lower Ca:O ratios.

Jan 1, 2006

By Asok Kumar Das

"In steel making ferroalloys occupies a commanding role for production of varied quality of steel. Ferroalloys enable alloying elements such as chromium, silicon, manganese, vanadium etc to be safely and economically introduced into metallurgical processes thus giving certain desirable properties of the alloyed metal. Their importance grew with the progress of the steel metallurgy which implied more diversified alloying elements, in better controlled quantities, in purer steel. The ferroalloy industry became a key supplier to the steel industry. Production of ferroalloys generally involves the use of Electric Arc furnace(EAF) into which raw materials(e.g. various metal ores, quartz, coke, lime etc ) with relatively fluctuating physical compositions are loaded. Due to this, one of the major environmental impacts of producing ferroalloys is the emission of dust and fume from the smelting process. INTRODUCTIONFerro Alloys are essential ingredients used for refining, de-oxidation, desulphurization and alloying addition in the production of different types of steel and hence Ferro Alloy industry forms a back bone of iron and steel in the world. Indian ferro alloy industry is more than 45 years old. It produces most of the bulk ferro alloys and a large number of special ferro alloys. The present installed capacity of the Indian ferro alloy industry is sufficient to meet the requirement of existing level of indigenous steel production of about 46 million tonnes. Revised National Steel Policy – 2008 envisages production of more than 100 million tonnes of steel by the year 2011-12, at proportionate annual growth rate per annum. The focus of the policy is to achieve global competitiveness not only in terms of cost, quality and product-mix but also in terms of global benchmarks of efficiency and productivity. In order to achieve the objectives of National Steel Policy and also to meet the requirement of ferro alloys, the Indian Ferro Alloy Industry has to gear up in terms of enhancement in production capacity, sourcing of raw materials, up gradation of technology, improvement in productivity, automation / mechanization, customer satisfaction etc."

Jan 1, 2008

By J. M. Tourre

1995 have seen a continuation of a positive trend in the Rare Earth industry The availability of a greater diversity of Raw Material has brought additional flexibility to the Producers permitting better economics China remains the major raw material source; Chinese concentrate producers have increased capacity in 1995 (Baotou, Sichuan, etc) China's role in the Rare Earth industry will continue to evolve; the acquisition of a majority equity position by San Huan/CNNC will have a significant impact on both the Rare Earth and Magnet markets Chinese producers are increasing the quality of their products and realize their true values Chinese market, itself, is also changing as the internal needs for separated rare earth's grow Already already producer of Lamps, Loudspeakers, Magnets, and TV tubes, China is in an unique position where the potential of its internal market might be more promising than the prospects outside China 1995 has also seen the application market become more diverse and complex. There are new applications growing at a very strong pace (such as battery alloy), applications that are now penetrating their target markets with significantly increased growth rates (such as bonded NdFeB), and some applications that became more complex requiring much more sophisticated products (such as catalysis). Rare Earth producers have to spend significant ressources in order to monitor the market trends in order to predict the demand and then adjust their raw material mix. Even though there is a greater diversity of raw material available, there is still some Rare Earth elements that are in excess, while other are just in balance. As a consequence rare earth producers invest heavily in R&D in order to develop new applications for these excess elements.

Jan 1, 1997

By Georgina De Micco

The National Commission of Atomic Energy is investigating a suitable physicochemical process for the conditioning of spent nuclear fuel and treatment of the scrap of research reactors of the Al-UxSiy type. A possible way of processing is through dry chlorination of the cladding with the purpose of selective separation of the aluminium from the remaining elements such as Fe, Ni, Zn, Cu, etc. transforming them into volatile chlorides. Some important advantages of this method are the thermal stability of the chlorides that allow the easy separation of the halides by physical methods and the low volume of radioactive waste generated. The interactions in the following systems were studied in the range of temperature between 150º-500°C: Al-Fe, Al-Ni, Al-Cu, Al-Zn, Cu-Zn and the pure metals. We found that the reactivity was different depending on if the elements were alloyed or separated. The separation factors of the systems under study were determined. Nickel is perfectly separated from aluminium for all temperatures, whereas good conditions for copper separation were achieved below 400ºC. In the case of iron, complete isolation was never attained. However, by decreasing temperature to 150ºC it is possible to obtain aluminium chloride with less iron content. The separation of zinc from the product was also difficult. It was detected that zinc chloride volatilization decreases when other chlorides were present, for example cooper chlorides. In the Cu-Zn alloy, zinc chlorides remained in the condensed product due to interactions with copper. The samples were characterized by scanning- electron microscopy (SEM), X ray diffraction (XRD) and atomic absorption.

Jan 1, 2006

By Dhanesh Chandra

Metal carbonyls are of great importance in chemical vapor deposition (CVD), composite materials fabrication, and other near-net shape technologies. Carbonyl CVD application applies to deposition of high-purity metallic/alloy coatings. Vapor pressures of solid Os3(CO)12,Rh6(CO)16, Ru3(CO)12, Ir4(CO)12, Re2(CO)10, Co2(CO)8, Cr(CO)12,, and W(CO)6carbonyls have been measured using gravimetric-torsion effusion system. The vapor pressure data is used for many low and high temperature CVD applications. Interesting decomposition/disproportionation vaporization behavior has been notedfor Rh6(CO)16, Ru3(CO)12 and Co2(CO)8. The vaporization studies of Rh6(CO)16 showed virtually complete decomposition to Rh metal and the measured molecular weight of the effusing gas from the solid Rh6(CO)16 was 27.75 g/mol, close to that of carbon monoxide as compared to 1065.56 g/mol for the value of solid Rh6(CO)16. Electron microscopic characterization, X-ray line broadening results for Rh carbonyl has been performed on the vaporization product. However, Ru3(CO)12, Co2(CO)8 showed very complex behavior. The molecular weights of the vaporizing species have been estimated and the numbers of vaporizing species are proposed. For example, there was partial decomposition of Ru3(CO)12to(approx. 52%) metallic Ru and CO gas during vaporization, as suggested by the difference in the molecular weight of the vaporizing species of 107.58 g/mol compared to the actual value of 639.33 g/mol. The dimer Co2(CO)8 partially disproportionates to tetramer Co4(CO)12, monomer Co(CO)4, and CO gas. Whereas, the Os3(CO)12, Cr(CO)12,, and W(CO)6have shown virtually no disproportionation. The total vapor pressures of all the above-motioned carbonyls, partial pressures of various species, average molecular weights of the effusing gases, equilibrium constants for the vaporization reactions, their enthalpies, entropies, and Gibbs energies will be presented.

Jan 1, 2006

By O. Tiitu

Drying is a unit process that has numerous applications in metallurgical process industry. Kumera Technology Center is a worldwide equipment and process supplier, who has expertise on both direct and indirect drying. In a conventional direct heated dryer, the required energy is obtained from combustion of fossil fuels emitting a considerable amount of off-gases. However, thermal energy can be already available in some metallurgical plants such as modem copper smelters where steam is produced by waste heat boilers of flash smelting furnaces. The total volume of off-gases, and especially the amount of harmful gases, released into atmosphere can be remarkably reduced when using steam as an indirect energy source for drying. Kumera Technology Center has developed a new type of steam dryer for drying of, for example, abrasive copper concentrate with silica sand. In the development of the new dryer, Kumera's approach has been to combine the best properties of both the existing steam dryers and the rotating drum dryers. In the design, special attention has been paid to overcoming the reported problems of excessive wear and clogging of steam tubes and to reducing the required maintenance operations. The Kumera Steam Dryer, having a patented flexible steam tube arrangement inside the rotating shell, has a high effective heating area - drum volume ratio without leading to problems with build-up and clogging. It can also be easily scaled up so that a single dryer can dry all of the feed for a large flash furnace. In this paper, we will present the operational and maintenance experiences from two years operation of the first full-scale Kumera Steam Dryer at Norddeutsche Affinerie Aktiengesellschaft in Hamburg, Germany. We will also provide an overview of the future developments with respect to construction and scale up as a response to market demands.

Jan 1, 2002

By Nicola Baldo, Marco Pasetto

"The paper presents the results of a laboratory study, conducted at the Experimental Road Laboratory of the University of Padova, in order to verify the possibility to use different types of electric arc furnace (EAF) steel slags – in substitution of the natural aggregates – in the composition of both dense graded and porous asphalt mixes for flexible road pavements. The research has been articulated in a preliminary study of the chemical, physical, and mechanical properties of the EAF steel slags, and in the following mix design and performance characterization of the bituminous concretes, through stiffness modulus tests at various temperatures and permanent deformation (creep) tests. All the mixtures with EAF slags have satisfied the requisites for acceptance standardized for the road sector, thus resulting as suitable for use in the construction of infrastructures, moreover presenting higher mechanical characteristics than those of the corresponding asphalts with full natural aggregate. IntroductionSteel is produced industrially employing two main technologies: the integral cycle, which starts from mineral iron, and the electric cycle, which uses scrap metal. A consistent amount of the steel produced in Italy (approx. 55%) comes from Electric Arc Furnaces (EAF), which every year, alongside the steel, produce approximately 2 million tons of slag. The recycling of this waste product to produce new high-quality raw materials would reduce both the exploitation of limited natural resources and the amounts of refuse. In the European Union, 60% of slag from EAF is still today disposed of in dumps. The extremely diverse origins of scrap metal (waste from mechanical manufacturing, industrial and civil demolition, car bodywork, etc.) means that the by-products generated by the smelting, slags and ashes, contain different elements, in varying composition, also depending on the type of steel to be produced and the consequent adding of binding and melting elements during the production process. For this reason, iron and steel industry electric furnace slag - unlike the blast furnace dross utilised in cement works, which has a more uniform composition as it comes from a more standardised cycle – has been viewed in the past with some diffidence and so, at least in Italy, the possibilities of its re-use have never been fully developed."

Jan 1, 2008

By L. E. Murr

Preliminary studies of bacterial attachment to MoSp (molybdenite) have indicated a low correlation between dislocation density in the (0001) basal plane and the density of attached microbes. In the present investigation, poly- crystalline thin sections of CuFeSp (chalcopyrite) have been ion-etched or carefully comminuted to electron transparency and observed in the transmission electron microscope. The thinned test sections were then immersed in a culture solution in which bacterial attachment occurred. The attached bacteria were biologically stained in a uranyl acetate solution and the entire thin CuFeSp sections or tiny particles containing thin, electron transparent edges with bacteria attached were observed in the transmission electron microscope, allowing the coincidence of bacteria and their density to be directly observed in relation to lattice dislocations and crystallographic orientations of the exposed surfaces. This technique has the advantage of exposing crystallographic orientations where dislocation lines intersect the free mineral surface, and the emergence sites of dislocations could in principle be directly investigated as a possible preferential attachment site for bacteria. Bacteria morphologies were also extensively observed in the scanning electron microscope. The implications of the results are that although a strong correlation between dislocation density and distribution and bacterial attachment, density, and distribution has not been established, systematic multiplication of dislocation densities in crystalline mineral particles to be leached could enhance leaching rates by increasing the reaction rates as well as the density of attached bacteria at crystalline, metal-rich phases. Techniques for dislocation production in mineral and ore bodies and the particular implications in chalcopyrite leaching are discussed in relation to in-situ leaching where comminution is attained by explosives and the generation of strong shock waves in an ore body. The present study demonstrates the use of microanalytical and microscopic techniques in the investigation of fundamental microstructural phenomena in hydrometallurgical processes.

Jan 1, 1976

By M. H. Ghandehari

Sintered (Pr,Sm)Co5 displays a multi-phase microstructure in which closely related intermetallic compounds are formed during the process of fabricating useful magnets from over-stoichiornetric compositions. These compounds have much lower magnetic crystalline anisotropies compared to those of SmCo5 and PrCo5. Despite a careful control of the microstructure in producing "single phase" PrCo5 base magnets, sufficient concentrations of the lower anisotropy phases are formed which act as nucleation centers for domain reversal, resulting in a drop in coercivity. This article describes the use of sintering additives, primarily oxides, to prevent the formation of the magnetically soft phases in the final microstructure.

Jan 1, 1989

By Giovanni Principi

The activity of the ?Hydrogen Group? of Padova University, addressed to the study of materials for solid state hydrogen storage, is illustrated. Various Mg-based materials have been considered and are being studied: a) MgH2 and 0.5% mol Nb2O5 mixture ball milled under argon atmosphere; b) Mg-Ni-Fe intermetallic compounds prepared by short time ball milling of ribbons obtained by melt spinning and by long time ball milling of a mixture of MgH2, Ni and Fe powders; c) MgH2 ball milled in argon with Mm-Ni-Al (Mm = La-rich mishmetal) and Zr-Cr-Fe catalyst alloys. All the samples have been structurally characterized by X-ray diffraction (Rietveld refinement) before and after hydrogen absorption/desorption cycling and tested with a Sievert apparatus as regarding their thermodynamic and kinetic properties.

Jan 1, 2006

By Shunichi Ajima

PT. Smelting Co. was established in February, 1996 to construct and operate the Gresik Smelter and Refinery. The construction work of first Copper Smelter and Refinery in Indonesia was completed in the end of August, 1998 and it was put into the integrated test operation in December, 1998. Gresik Smelter and Refinery is designed to produce 200,000 tpy of copper cathode from copper concentrate supplied from Grasberg Mine of PT. Freeport Indonesia Company in Irian Jaya, Indonesia. As by product 592,000 tpy of sulfuric acid, 382,000 tpy of slag, 31,000 tpy of gypsum and 480 tpy of slime will be produced in the full operation. Major processes applied at Gresik Smelter and Refinery are: Smelter: Mitsubishi Continuous Copper Smelting and Converting Process ( Mitsubishi Process ) Anode Casting: Continuous Casting of Copper Anodes with the Hazelett Twin Belt Caster Refinery: ISA Process Acid Plant: Lurgi Mitsubishi Double Contact Process

Jan 1, 1999

By Seung-Whee Rhee

Characteristics of ceramic support made by spent foundry sand-loess mixtures are investigated by bulk density, porosity, durability, and compressive strength. And the basic properties of SFS and loess are estimated. The effect of drying time after cutting process, elevated temperature time, sintering temperature, and sintering time is also estimated to obtain the optimal condition in the process of manufacture ceramic supports. From the basic properties of SFS and loess, the content of SiO2 in furan sand is much higher than that in loess but the content of Al2O3and Fe2O3 in furan sand is much lower than that in loess. In order to make ceramic supports cylinder shape is the most desirable to sustain the properties of ceramic support. If annulus shape has a enough compressive strength, however, annulus shape may be decided. For the optimal condition to manufacture ceramic supports, drying time after cutting process is decided to 24 hrs and elevated temperature time is decided by 9hrs. And sintering temperature and sintering time are decided to 900 and 9hrs, respectively in order to prevent solidification of sand materials.

Jan 1, 2006

By Ronald J. Roman

The shrinking core model for coarse particle leaching has been generally accepted as describing the leaching of a copper oxide or sulfide ore. However, when a mixed oxide/sulfide ore-is leached this model can not be used in its simple form because at least two and possibly three separate leaching processes are occurring simultaneously (dissolution of oxide copper minerals, secondary copper minerals and primarily copper minerals). It has been impossible to isolate their individual leaching curves from the recovery/time curve generated by the column leach test. This paper describes a tests program carried out at the Groupo Mexico, Mexicana de Cobre's La Caridad operation in which the individual recovery/time curves for the leaching of copper oxide mineral, secondary copper mineral and primary copper minerals were developed from standard column leach tests. Once the individual recovery/time curves were developed scale-up of the column leach test results to the commercial heap leaching operation is possible by using the shrinking core model.

Jan 1, 1999

By Carlos Eduardo Gomes de Souza, Luis G. S. Sobral, Paulo A. Medeiros da Silva, Selma G. F. Leite, Renata de B. Lima

"The use of mixed cultures of acidophilus microorganisms that act in different temperature ranges, aims at speeding up the digestion of chalcopyrite, highly refractory sulphide mineral, the major mineral in the flotation concentrate of Caraíba Mining Co., with an attractive processing cost. The concentrate under consideration contains mainly chalcopyrite (CuFeS2) and bornite (Cu5FeS4) with contents of, approximately, 70 and 30%, respectively. It was observed in this study, the performance of consortium of mesophiles, moderate and extreme thermophile microorganisms, in the oxidation of the aforementioned sulphides minerals, evaluating operational parameters such as pH of the leaching solution, the reaction temperature and redox potential, with consequent extraction of 80% of the concentrate copper content within 60 days of bioleaching. Such high copper extraction was achieved in column bioleaching tests.INTRODUCTIONThe solubilization of metals by the application of microorganisms from the mineral ores and the subsequent recovery of metals from solution are referred to as bioleaching (Rohwerder, T et al, 2003). This is an economical method for the recovery of metals from minerals; especially lowgrade ores, overburden, and waste from current mining operations which requires moderate capital investment with operating cost (Watling, 2006).Furthermore, bioleaching is generally more environmentally friendly than conventional metal recovery processes such as concentration and smelting. Those physicochemical metal extraction processes generate sulphur dioxide, a toxic emission that is increasingly the target of regulatory legislation (Stott et al., 2000; Olson et al., 2003). Bioleaching of chalcopyrite is the key industry target. The main problem hindering commercial application of chalcopyrite bioleaching is the slow dissolution rate (Fu et al, 2008).Dissolution of acid-soluble sulphide minerals such as sphalerite, and to a lesser extent chalcopyrite, occurs by a combination of ferric iron and proton attack via the polysulphide pathway (Rohwerder et al., 2003)."

Jan 1, 2008

By David Ellis

The next generation of Reusable Launch Vehicle (RLV) will utilize regeneratively cooled combustion chamber liners in the engines. The current design calls for using a new Cu-8 at. % Cr-4 at. % Nb (Cu-8 Cr-4 Nb) alloy for the liners. Work is ongoing to characterize the thermophysical and mechanical properties of the alloy from - 253 to 800°C, the temperature range to which the alloy will be subjected during service. The alloy has been commercially produced in quantity for NASA. The powder size has been characterized and the microstructure examined. The powder was extruded into bar using a commercial extrusion press. In addition, samples have been hot isostatically pressed (HIPed) at NASA Glenn Research Center. Both processing methods produced fully consolidated material. Transmission electron microscopy (TEM) revealed highly faulted Cr2Nb and some elemental precipitates. Cryogenic tensile testing showed the extruded specimens had significantly higher strengths than NARloy-Z (Cu-3 wt % Ag-0.5 wt % Zr) even after being subjected to a simulated braze cycle. The Young's moduli (Cu-8 Cr-4 Nb) were lower than NARloy-Z. The lower moduli is highly beneficial for reducing thermally induced stresses in rocket engine combustion chamber liners and similar applications.

Jan 1, 1999

By Petr Sulovsky, Pavel Leber, Jaroslava Ledererova, Miroslav Svoboda

"The properties of raw materials used for the production of building materials play an essential role in their choice. Industrial waste materials can in some cases improve the performance of new building materials, when compared with classical raw materials. The addition of waste can however negatively impact some of the building material´s characteristics, influencing its stability, service time, durability, and can introduce undesirable variation of certain characteristics over time. It is necessary that each secondary raw material intended for such use be thoroughly investigated in terms of its chemical, physical, and mechanical properties, with special attention paid to the risk components and risk parameters. It is necessary to make many- sided technological tests in relation to the required characteristics of the resulting materials for each chosen application. Moreover, the limit values for the critical (risk) parameters, which the given secondary raw material must satisfy to be used in a specific technology, need to be defined. Introduction The risk components in the industrial waste materials to be used in the production of building materials fall into two groups: - components that pose a risk of development (instant or delayed) of a process deleterious to the utility properties and durability of the resulting materials. Such processes include volume change (expansion as well as shrinkage), alkali-silica reaction, delayed ettringite formation, thaumassite attack, aggressive carbonation, etc. - elements or components that can, if released from the waste-containing building material, pollute the environment. They involve the so called potentially hazardous elements as well as compounds like fenols, PCB, PAHs etc. From the viewpoint of the presence of both groups of risk components, the wastes can be classified as: • environmentally inert waste materials. They are produced in the largest volumes and do not pose a threat to human health. Their physical and/or chemical characteristics fail to satisfy all requirements for utilization in ordinary production. The aim of technology design is to work them into the building products with suitable utility properties. • easier workable waste materials containing toxic components are produced in large volumes. In spite of the content of toxic components, their physical and chemical properties make them suitable for ordinary production, provided that the harmful substances are immobilized by the chosen technology."

Jan 1, 2008

By Tiffany Brown

In the thiosulfate gold leaching process, thiosulfate is used to complex gold following electrocatalytic oxidation of the native metal by Cu(II)-ammines. Unfortunately, Cu(II) complexes also catalyse the undesirable conversion of thiosulfate to polythionates. We have been seeking alternatives to ammonia, which fulfil the role of ammonia but minimize thiosulfate decomposition. One aspect of these studies has involved the determination of the rate of thiosulfate oxidation by the Cu(II) complexes from UV-Visible spectral changes. Various ligand classes, including pyridyls, polyamines, aminocarboxylates and picolinates, have been tested and the majority found to inhibit thiosulfate decomposition. Interesting variations in reactivity with the nature and denticity of the ligand and L/M ratio have been observed. In the case of open chain polyamine ligands with 2 to 5 nitrogen donors, the rate of thiosulfate oxidation was generally found to decrease with the denticity and the concentration of each ligand. Saturation of the Cu(II) coordination sphere appears to inhibit the oxidation of thiosulfate when excess thiosulfate is present. The Cu(II) complex of the branched polyamine ligand, tris(2-aminoethyl)amine (tren) exhibits this behaviour in excess thiosulfate. Interestingly, when the [Cu(tren)(OH2)]2+ complex is in excess oxidation of thiosulfate was observed. This unexpected finding prompted a spectrophotometric study of this reaction which has revealed that the oxidation of thiosulfate involves several processes, two of which involve the formation and decay of a tetrathionate radical.

Jan 1, 2003

By Ray Y. Lin

This study explores the formation of sodium pyrosulfate in molten sodium sulfate resulting from dissolution of SO3 at temperatures between 1160 and 1250 K. Solubility of SO3 in Na2SO4 melts at temperatures between 1160 and 1250 K under gas mixtures of SO2, O2 and argon was investigated applying a thermogravemetric analysis (TGA) technique. The activity of Na2O in the melt was determined with a high temperature electrochemical cell (ECC). Results showed that the SO3 solubility in molten Na2SO4 increases with decreasing temperatures and increasing SO3 partial pressures. Enthalpy of SO3 dissolution in molten Na2SO4 was calculated to be -119 kJ/mol for infinite dilute solutions. Thermochemistry of Na2SO4-Na2S2O7 melts was analyzed based on information obtained from both TGA and ECC techniques. Detailed examinations of the earlier low temperature measurements in the Na2SO4-Na2S2O7 system along with data from this study reveal that the solution behavior between Na2SO4 and Na2S2O7 can be satisfactorily treated as regular with the interaction parameter, , being 2.7 kJ/mol. The phase diagram and the field of SO3 partial pressure has been generated with the thermodynamic calculation using a regular solution approach.

Jan 1, 2006