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By Kelly E. G

NZ Steel's flushing slag typically contains 1.2 per cent V203. Extraction of vanadium from powdered slag using a salt (NaCI or Na2CO3) roast/leach process was investigated. With NaCl, optimum extraction conditions were a charge containing 10 per cent NaCI, roasting in air at 875°C for 4 hours, followed by leaching in dilute H2SO4. Extractions were typically 30-50 per cent. NaCI roasting did not chemically attack the slag; the phase transformations that occurred were due to high temperature oxidation. Slag particle size had a significant effect on extraction.Optimum conditions for extracting vanadium by Na2C03 roasting were 20 per cent Na2CO3 in the charge and roasting in air for 3-4 hours at 850-875°C followed by water leaching.Na2CO3 roasting involved chemical attack that resulted in the formation of perovskite (CaTiO3) and carnegieite (NaAISiO4).The extent of vanadium extraction depended on the amount of Na2CO3 added and the original slag SiO2 content.Compared to the separate roasting treatments, simultaneous treatment with NaCI and Na2CO3 gave lower vanadium extraction, while requiring considerably higher roasting times and temperatures.

Jan 1, 1982

By Georgios Kolliopoulos

Water is a critical commodity of our generation and a key compound for the chemical and mining industries. Sustainable industrial development is directly associated with the ability to recover clean water from contaminated sources. Forward Osmosis (FO) is a low-energy footprint membrane process allowing the recovery of clean water from high salinity effluent streams. In FO, water is recovered spontaneously into a concentrated draw solution (CDS). Energy is required to separate the recovered water from the resulting dilute draw solution (DDS). In the current work, the fundamentals of the FO process and the most important aspects affecting its performance are discussed. An energy comparison of FO and conventional water recovery technologies is presented. Finally, the opportunities FO presents in the field of hydrometallurgy are analyzed.

By T. Ogasawara, J. P. Barbosa, A. J. Monhemius, F. T. Da Silvia

A thermodynamic analysis of the sulphation of rare-earth phosphates and the water-leaching of rare-earth sulphates was used to guide experimental work on the sulphation and leaching of concentrates from Pitinga. It was concluded that the sulphuric acid digestion of xenotime is technically feasible and could be used industrially to produce yttrium and other rare-earth oxides. Yttrium extractions of more than 90% were obtained by digestion at 503 K for 4 h at an acid:concentrate ratio of 2:1 with particle size -0.053 mm. The apparent activation energy at temperatures less than 473 K, as determined from the Arrhenius plot, was 11.0 kJ/mol, indicating that the reaction is controlled by the diffusion of the reactants or products through the sulphate layer

Jun 19, 1905

By Hassan Saalman, Mahmoud Mahmoud, Omneya El Hussaini

The Ferruginous sandstone ore was obtained from Ramlet Hemeyir area, Southwestern Sinai, Egypt, was found to contain 10% rare earth elements (REE). A representative sample has been subjected to sulfuric acid agitation leaching. About 93% of the REE content was released by mixing the ground sample to -100 mesh with concentrated H2SO4 at solid/liquid (S/L) ratio of 1/2 for 5h at a temperature ranged from 250 to 300o C. The REE was precipitated from the prepared sulfate leach liquor of pH 1.0 by adding 35% oxalic acid at 25o C. The precipitation yielded 98% REE. For selective separation of yttrium, the rare earth cake was leached with 31.5% nitric acid. Next, the aqueous solution was contacted with di-(2-ethylhexyl) phosphoric acid (D2EHPA) where 98% yttrium extraction was achieved. Stripping was done with hot H2O (80o C). Finally, a precipitation with oxalic acid was done followed by ignition at 950o C. A yield of 95% yttrium oxide was produced.

Jan 1, 2014

By Hsing Kuang Lin

Extraction of zinc from chloride solution with dibutyl butylphosphonate (DBBP) in Escaid 110 has been investigated. The distribution coefficient of zinc was found to be independent of equilibrium pH. This independence indicates that the mechanism of the extraction may be solvation. Slope analysis for the system of dilute zinc chloride solution reveals that two moles of DBBP react with one mole of zinc. A series of tests were conducted to bring DBBP to its full loading capacity and the analysis of the results confirms this stoichiometric factor of 2. Extraction isotherms were established by varying either the AIO ratio or the concentration of zinc in the aqueous feed. Both curves were found to be identical.

Jan 1, 1990

By Xudong Liu, Ganghua Fu, Yufeng Guo, Wei Chen, Yujia Tan, Tao Jiang

Willemite is usually found in high-silicon oxide zinc ore and zinc metallurgical secondary resources but without effective extraction method yet. In this study, zinc was extracted from willemite by sodium salt roasting and ammonia-leaching process based on the idea of zinc phase reconstruction. The effects of Na2CO3 dosage, roasting temperature and roasting time on phase transformation and zinc leaching rate were studied, respectively. The results show that Zn2SiO4 was transformed into ZnO or Na2ZnSiO4 during roasting process. After roasting at 800 °C for 2.5 h at ratio of n(Na2CO3)/n(Zn2SiO4) = 2.5:1, willemite was thoroughly transformed into ZnO. The zinc leaching rate of the roasted sample was 97.62% in NH4Cl–NH3–H2O leaching system, which increased by 91.57% compared with zinc leaching rate of 6.05% when willemite was directly leached in NH4Cl–NH3–H2O system.

Mar 1, 2017

By S. Z. El-Tawil, K. A. El-Barawy, M. B. Morsi, M. M. Nasr, Z. I. Zaki

"Tue sulphatization of zinc concentrate produced from heated zinc concentrate of Um Ghieg area, eastern desert by ammonium sulphate as sulphatizing agent is carried out at different conditions to achieve the appreciable formation of soluble sulphates. The maximum zinc recovery as soluble sulphate equfils to 95% upon using 1.5 stoichiometry ammonium sulphate at 600 °C for one hour. Tue obtained leached zinc sulphate solution is subjected· to purification process to prepare high pure zinc metal and zmc compounds such as pure zinc sulphate, zinc caibonate and zinc oxide. The products obtained are analyzed chemically and identified by X-ray analysisTue mechanism and kinetics of the sulphatization process of zinc concentrate are considered where the activation energy is calculated and equals to 33.3 K.J.mol""1 A process flowsheet for the overall sulphatization process of zinc concentrate by ammonium sulphate is proposed.IntroductionConsiderable reserves of zinc ores are present in Um Ghieg area eastern desert, Egypt. The possibility of extraction zinc from these ores and preparing its valuable compounds by choosing a more feasible technology become of vital importance. An attention is focused on the sulphatizing roasting processes (1-9) to achieve the appreciable formation of soluble sulphates. Previous publications are reported in our division by El. Tawil and others (10-16) using ammonium sulphate as sulphatizing agent for the successful treatment of nonferrous bearing materials.Therefore, the present work aims to study the different factors affecting the sulphatizing roasting process of local zinc coocentrate by anunonium sulphate to extract completely zinc and preparing its main compounds. Tue mechanism and kinetics of the different chemical reactloos that 1ake place in the process are considered."

Jan 1, 2000

By K. Saberyan

In this study the extraction of zirconium and hafnium has been investigated by solvent extraction using Cyanex 302 in various media such as nitric, sulfuric and hydrochloric acid has been investigated. Effect of various parameters such as type and acid concentration, extractant concentration, type of diluent, equilibrium time, various foreign ions and finally type and concentration of strip-ping agent have been studied. The results showed that nitric acid was optimum media for extraction of zirconium and hafnium. The extraction of zirconium and hafnium occurred quantitatively in the concentration of higher than 4 M nitric acid but in hydrochloric acid media, quantitative extraction obtains over 8 M HCl. In sulfuric acid media, extraction of zirconium and hafnium is negligible. Stripping studies showed that the optimum reagent for stripping was 0.5M sulfuric acid.

Jan 1, 2014

By Zuomei Jin

The Mineralogical form of Silver in a Ag-rich complex ore was determined. In the complex sulfide ore, acidic thiourea leaching resulted in 35% extraction of silver directly. In the same complex sulfide ore, under the effect of ultrasonic treatment, 65% of silver can be ex¬tracted. After the above ore had been roasted and acidically leached of Zn and Cu, the silver extracted from this Pb-Ag residue was 96.8%. The effets of temperature, thiourea and ferric ion concentrations and partical size were examined. The leaching rate of silver from the Pb-Ag residue was diffusion controlled. The activation energy was calculated to be 10. 49%KJ/mole. The kinetic model for the thiourea leaching of silver from Pb-Ag residue was obtained and is given by, The kinetics of silver cementation by aluminium in thiourea solutions was also investigated. The activation energy was calculated to be 65. 13KJ/mole, which is reasonable fora rate-limiting surface reaction.

Jan 1, 1995

By Ho-Sung Yoon, Jyothi Rajesh Kumar, Jin-Young Lee

"Global population is a key factor in future energy requirements, especially considering the important elements of global energy resources, electricity production, the accessibility/non-accessibility of electricity, greenhouse gas emissions and the states of nuclear reactors. Everyday human requirements depend on industrial products, and industries need a considerable amount of electricity to run. Nuclear fuel is inexpensive and bolsters industrial growth. As uranium reserves are being consumed rapidly, an alternative source of energy in the nuclear industry is thorium. Here, primary energy supplies by various sources from 1993 to 2011 as well as estimates of future needs to 2020 are discussed. This study finds that primary energy sources are mainly fossil fuels, renewables sources, and nuclear and hydro energy. In addition, growth depends on increases mainly in renewable sources.Recovery of thorium from its ores by using hydrometallurgical routes were described and discussed. The final part of this paper was presented a case study of the thorium extraction from Korean monazite ore leach liquors by using Prieme JM-T diluted in A150 diluent as an extractant system. And possible separation of the thorium from rare earths (REs) and base metals were calculated by measuring of separation factors and finally, the recovery of thorium from loaded organic of Prieme JM-T was established.THORIUM IS FUTURE NUCLEAR FUEL?Global energy consumption is increasing everyday with the high population growth, high industrialization of numerous countries and the higher level of good and services consumption that follows it. If we look at specific sectors of the economy, oil consumption grew by 0.8 million barrels per day, globally, whereas the increase was 0.4 % for natural gas and coal 1.8 % for nuclear power and just under 2.0 % for hydroelectric power (Asheley 2009). Use of renewable sources of energy for power generation and transportation increased by 3% in 2014 (BP 2015)). Thus alternative source of energy must be identified and developed to meet this increasing demand. Thorium is a potential one for the nuclear industry."

Jan 1, 2016

By B Harvey

Achieving community and stakeholder endorsement during life-of-mine planning and implementation requires a business-connected approach, as opposed to charitable giving, disconnected offsets and environmental adventurism.CITATION:Harvey, B, 2014. Extractive companies, development and environmental agendas, in Proceedings Life-of-Mine 2014 , pp 19–22 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jul 16, 2014

As the title indicates the central themes discussed in this contribution are sustainable development, information systems, and extractive industry. More specifically, the objective is to present a prototype for the systematic generation of extractive industry (henceforth: EI) û specific sustainability information. The paper begins with the authorÆs viewpoints on the core notions of sustainability, and development, as well as their relationship to information. These set the stage for the introduction of the information system (IS), as well as the follow-up sustainability information system (SIS) extractive industry sustainability information system (EISIS) concepts and related discussions. The paper continues with a second part, in which, efforts to research and develop an EISIS prototype are described. First, the team is presented. Second, the systemÆs aim and target groups are briefly discussed. After, an articulated overarching EISIS conceptual model emphasising capital accumulation, and service flow concepts û is presented. This is followed by a detailed description of the assembled prototype with a focus on data and information generation. The formulation of data generation, storage and transmission processes, as well as its use in sustainability interpretation rules and their embedment in the conceptual model is made with respect to monetised stock and flow parameters, measured in the appropriate dimensions. In the third part, the author presents and discusses the results of a first round of prototype experimental development in three major EI firms. First, the system observation, and data analysis protocols are described. Second, a review of protocol implementation, and respective results, is made. Finally, the overall performance of the proposed prototype, and development process issues are discussed, before suggesting areas for improvement and future research. The paper ends with a conclusion in which the author provides a retrospective balance of the æknowledge creation projectÆ, as well as a prospective outlook for research in this field; before acknowledgements are made and references provided.

Jan 1, 2009

By Theophile S. Yameogo

Les ressources naturelles ont en général été le moteur du développement économique et social des nations. Les pays aujourd?hui développés sont pour la plupart d?anciens eldorado, charbonniers ou pétroliers. D?autres le sont toujours. L?Afrique fait cependant figure d?exception : même en étant comblé de ressources naturelles exceptionnelles, les pays de ce continent croulent sous le poids de la pauvreté et de ses acabits que sont les maladies, la famine, la guerre et l?insurrection sociale. On reconnaît néanmoins qu?il y a des cas particuliers comme le Botswana, la Namibie, l?Afrique du Sud. Face à cette situation, beaucoup de scénarii ont été proposés sans pour autant porté les fruits espérés. Le rapport Brundtland suggère que le développement durable est la clé du succès car elle veille à la prospérité économique, à l?équité dans la société et à la pérennité dans l?environnement. Pour l?Afrique, beaucoup de facteurs doivent être considérés et les solutions se doivent d?être pratiques et éthiques. Le futur ingénieur des mines qui a écrit ce rapport, apporte sa vision de la situation non sans avoir auparavant analysé les faits. Cette démarche, qui se veut avant tout éthique, inclut les aspects sociaux, économiques et politiques. Introduction In the 40s, 50s and the 60s, many economists, among which Harold Hotelling from South Carolina University, thought that developing countries could reach socio-economical success by extracting their natural resources such as oil and minerals. The current economical disaster seems to have contradicted that belief and critics like Davis Graham (Colorado School of Mines) and Michael Ross (University of California at Los Angeles) even suggested that extractive activities stop in Africa. But the experts of the World Bank (Mining Department) and some mining and oil companies are committed to reverse the tendency by implementing a new approach. Considering the principles of sustainable development defined in the Brundtland report (1987), we decided to analyze the possibility of giving the extractive industry a catalytic role in creating a socially, economically and environmentally development in Africa. In other words, can we continue to mine and extract oil in Africa for its blossoming future under the ruling of the sustainable development? In the following, we start by explaining the African socio-economic and political context. After a brief definition of the sustainable development, we explain why, for Africa, some believe in the extractive industry and some don?t. In the end, we draw out conciliatory arguments.

Apr 1, 2005

By S. W. Ross

In 1936 a description of the plant (Fig 1) and process employed by the Electrolytic Zinc Co. of Australasia Ltd. for the recovery of zinc from zinc concentrate by the electrolytic process was prepared. † During the twelve years which have elapsed since the preparation of the earlier paper, several major changes in the metallurgy of the process have been introduced. It is the purpose of the present paper to give a general description of these changes and thus to bring up to date the description of the plant and process. Summary The major changes in Risdon practice since 1936 have been: 1. Replacement of two stage roasting by a preliminary roast followed by the flotation of all the leach residue and the roasting of the flotation concentrate. 2. Screening of all calcine fed to the pachucas. 3. Continuous leaching of calcine and improved classification of pachuca discharge. 4. Close control of hydrogen ion concentration during purification for iron removal. 5. Recovery of cobalt as a good grade oxide. 6. Production of part of the zinc output in the form of "four nines" metal (99.99 pct purity). 7. Closer spacing of electrodes thus increasing the potential output of cathode zinc per cell by 50 pct. Changes which are in prospect and for which construction work is proceeding at the present time involve the starting up of: 1. Two suspension roasters. 2. A contact acid plant to produce 150 tons‡ of acid per day and replacing the existing Mills Packard chamber plant. 3. Extra power station capacity to permit greater current flow to existing cell room units. This will increase the output of cathode zinc from about 245 to 290 tons per day. Plans for the future envisage the building of an ammonium sulphate plant, the first unit of which will produce about 50,000 tons per year, and improved treatment of zinc plant residue for the recovery of zinc, lead and other metals. At the end of this paper tables of metallurgical data are presented relating to the year ending June 30, 1948. Details of Changed Practice Output In 1936 the production of cathode zinc amounted to about 200 tons per day. This has since been increased to about 245 tons per day while plant extensions are practically complete which will permit of an output of about 290 tons per day in the near future. Roasting Division ROASTING POLICY A major change has occurred in the roasting policy. Twelve years ago the method in use was to carry out a two stage roast in the first stage of which sulphide sulphur was reduced to about 6 pct. The pre-roast calcine was re-roasted in modified Leggo furnaces using coal as fuel, sulphide sulphur being reduced to about 0.8 pct. The whole procedure was described on pp. 482491 of the earlier paper. Although this roasting procedure had certain advantages it possessed some distinct disadvantages. For instance, it appeared uneconomical to heat up the entire input of pre-roast calcine to roasting temperature by the expenditure of fuel in order to oxidise a few percent of sulphide sulphur. It was argued that if the pre-roast calcine were leached and a process could be developed for the recovery of a zinc sulphide concentrate from the leach residue, this concentrate, small in weight compared with the pre-roost calcine, would probably roast autogenously, thus virtually eliminating the expenditure of fuel as well as greatly increasing the weight of sulphur oxidised per square foot of furnace hearth area. The obvious method of producing a suitable concentrate from leach residue was by flotation. It will be recalled (see p. 495 of the earlier paper) that when two-stage roasting was practised the leach residue was classified, the granular fraction was ground and floated while the slime fraction was thickened, filtered and dried ready for shipment to a lead smelter. This process worked quite successfully. However, when trials were made of leaching a calcine carrying several percent of sulphide sulphur the granular fraction still floated well, but the slime fraction carrying 8-10 pct sulphide sulphur yielded very poor results when subjected to flotation. This fact held up the application of "pre-roast" leaching for many years. However, successful flotation of the slime fraction of leach residue was finally achieved and in August 1940 the slime flotation plant began operation, while the leach-

Jan 1, 1950

By G. H. Anderson

H. R. HANLEY*—I have been asked to discuss briefly the development of rotating cathodes for the electrolytic deposition of cadmium. The earliest recorded use of rotating cathodes was by Hoepfner at Frufurt, Germany about sixty years ago. He elec-trolized zinc chloride solution using diaphragms to separate electrodes. In the early experimental work of the Bully Hill Copper Mining and Smelting Co., Shasta County, Calif., rotating aluminum cathodes 4 ft in diam were used in the electrolysis of an acid zinc sulphate solution. Finished cathodes weighing up to 400 lb were produced. Because of mechanical difficulties, this type of cathode was abandoned for zinc, but was later used for cadmium because of the relative smoothness of deposit in comparison with stationary plates with comparable current densities. Cadmium sponge which forms on the cathode at moderate current densities (without special treatment) is entirely eliminated by a slow rotation. The rate of rotation of the cathode has an effect on the mechanical nature of the deposit. A high rate of rotation concentrates the adhering electrolyte on the shaft; a moderate rate appears to concentrate on the cathode a short distance out from the shaft tending to corrode the deposit in the form of a ring. At a very slow rotation (2 to 3 rpm) the adhering electrolyte gravitates nearly vertically, thus avoiding the cutting ring referred to above. The true explanation for the smoother deposits obtained on rotating cathodes may not be given definitely as the numerous factors involved are not thoroughly understood. Smooth deposits are obtained when the orderly growth of the metal crystals in the cathode lattice are disorganized. Thus the crystals form and grow for a very short interval when they are arrested and a new crystal forms. The continued growth of the original crystals provides large crystals and a rough deposit. Also if the acidity of the electrolyte is low, hydrogen gas bubbles adhere to the deposit. As the cathode is rotated the gas surface is brought into the atmosphere where they burst; thus the deposit is made on a surface relatively gas-free. An aluminum hub distance piece was riveted to each aluminum disk 4 ft in diam, slipped on a 4 1/2 in. steel shaft and pressed tight to prevent acid electrolyte seeping through to the shaft. The 9-cathode assembly was supported on insulated bearings. Electrical contact to the shaft was made through what was equivalent to a copper pulley. Sufficiently high conductivity brushes were placed on the face of the pulley to lead the current to the cathode bus bar. The assembly was driven by a link belt contacting a sprocket insulated from the shaft. The lead anodes were semicircular and supported on porcelain insulators placed on the bottom of the cell. Two anodes were provided for each cathode to permit an 8-in. space between them without increasing the ohmic resistance. This ample spacing permitted easy stripping of deposit with the assembly in place. Cathode cadmium was melted under 650 W cylinder oil. After casting, the primary slabs were remelted under molten caustic soda and cast into pencils 1 1/32 in. in diam. Rotating cathodes for deposition of cadmium are used at Risdon, Tasmania, and at Magdeburg, Germany. W. G. WOOLF*—This paper is very-interesting to me because in our work at the Electrolytic Zinc Plant of the Sullivan Mining Co. we had an exactly similar problem—that is, a method of producing cadmium from our purification residue, the recovery of the contained copper as a copper precipitate which could be sent to a copper smelter and the production of merchantable cadmium. It is interesting to me, not knowing of the work of the Risdon people, how closely we approximate them in their main metallurgy, diverging at several interesting steps which I would like to discuss for just a moment. For example, at Risdon they oxidize their purification residue. In our practice we take the current residue as it is produced in the purification department of the zinc plant and process it in the cadmium plant. The only oxidation that it obtains is the oxidation in the presses, the dumping of the presses and the collection and transportation of the residue to the cadmium plant. We find that the leaching of that residue does not necessarily require the oxidation step that the Risdon people evidently find necessary. The discussion of oxidation comes in again in the matter of the treatment of the precipitated cadmium sponge with zinc dust which again at Risdon is oxidized but which we do not attempt to oxidize except as it oxidizes itself in the storage. There is a partial oxidation which cannot be avoided, as Mr. David-sou pointed out, but we make no attempt to attain a complete oxidation and we dissolve the cadmium sponge in the sul-

Jan 1, 1950

By W. R. Opie, O. W. Mole

By confining the electrolytic reduction of TiCl4 to the interior of a porous basket-cathode the electrolyte between the anode and the cathode can be kept free of reduced chlorides of titanium eliminating undesirable reactions of reduced titanium chlorides with brickwork or oxygen in the cell atmosphere. Semiwalls are not needed. Operating conditions are given and discussed. Titanium yields based on TiCl4 introduced are 93 pct. Cell voltage and amperage characteristics are adaptable to multiple cathode-series cell urmngements. EXPERIMENTS conducted in the National Lead Co., Titanium Division, Research Laboratories showed that titanium metal could be deposited in an electrolytic cell in which titanium tetrachloride was introduced through a tubular cathode.' The reduced chlorides as formed were confined to the vicinity of the cathode. They were reduced to form a cocoon-shaped growth of sponge titanium metal at the end of the cathodic tube below the surface of a sodium chloride-strontium chloride electrolyte. No diaphragm was needed.' Although high-purity, coarse crystalline metal was produced in the cocoon growth, the yields of metal removed from the cell, based on the amount of titanium introduced as TiCl4, were usually only 40 to 60 pct. The growth of the cocoon deposits was away from the cathodic tube for introduction of TiC14 toward the anode following the flu lines. The reduced chlorides of titanium diffused through the deposit and were reduced to titanium electrolytically within the deposit or on the outer surfaces. Deposition within the pores of the cocoon was detrimental to further deposition because it plugged the passages used by the reduced chlorides to diffuse away from the point of titanium introduction. As plugging due to deposition in the pores proceeded, the reduced chlorides in the center of the cocoon would force their way out by forming a channel and would escape from the vicinity of the cathode without being reduced to metal. Some work had been done previously1, 2 which indicated that if the end of the cathodic tube for introducing TiC14 was surrounded by a screen connected to the tube so that it too was cathodic, growth could be made to occur within the screen. Direction of growth was observed to be from the screen toward the point of TiCl4 introduction. Through a series of design modifications a cathode evolved which consisted of an introduction tube surrounded by a perforated metal basket as shown in Fig. 1. Modifications of this design are described in Refs. 3, 4, and 5. This basic cathode designa" was incorporated in electrolytic cells containing graphite anodes and constructed of high-silica brick refractory for containing the electrolyte (see Fig. 2). The inner crucible was surrounded by insulating brick and the entire unit contained in a welded steel shell. Suitable cooling chambers with inert gas atmospheres were devised so that the cathode could be removed from the cell without exposing the deposit to air while hot. Various alkali and alkaline earth chlorides were used as electrolytes.

Jan 1, 1961

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

By John Chipman, Wayne L. Worrell

Using recent thermodynamic data for the carbides and oxides of tantalum, columbium, and vanadium, the stable solid phases aboue 1300°K and at 1 atm CO(g) pressure in each M-C-O system have been determined. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures necessary to obtain these metals by carbothermic reduction under reduced pressures. TANTALUM, columbium, and vanadium react with carbon to form the M,C and MC carbide phases. The M,C carbides have narrow homogeneity ranges, but the MC phases possess considerable ranges of homogeneity.' The free energies of formation of the MC carbides were recently measured, and those of MC and M2Ccarbides have been estimated., (The notations MC and MC denote, respectively, the carbide compositions at the carbon-rich and at the metal-rich boundaries of the homogeneous MC phase.) In this paper, these carbide data are combined with thermodynamic data for the oxides to predict the stable phases in the Ta-C-O, Cb-C-O, and V-C-O systems at specified temperatures and oxygen pressures. M-C-O PHASE DIAGRAMS The solid phases in equilibrium above 1300°K for each M-C-0 system are shown in Figs. 1, 2, and 3. Above 1300°K, the vapor would consist entirely of carbon monoxide; and these phase diagrams were obtained by specifying the vapor pressure of CO(g) to be 1 atm. The temperature at which any two solid phases become unstable is specified along the two-phase equilibrium lines in each diagram. To simplify the diagrams, all solid phases in the Ta-C-O and Cb-C-O systems are represented as stoichiometric compounds. However, the homogeneity ranges of VO and VC are indicated, because they form a complete series of solid solutions.3 It also should be noted that the homogeneity range of

Jan 1, 1964

By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950