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By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By Edna A. Dancy, Gerhard J. Derge

Jan 1, 1963

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2'3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By D. H. Gurinsky, D. G. Schweitzer

The empirical equilibrium constantsd the heat of reaction for the reduction have been determined from 300° to 500°C. The mechanisms of the oxidation of uranium and magnesium from dilute bismuth solutions have been investigated. The kinetics of some of the reactions were affected by air adsorbed on the uranium oxides. THE Liquid Metal Fuel Reactor studied at Brook-haven National Laboratory uses a solution of uranium in bismuth as the fuel. Corrosion and stability problems require that the fuel solution contain corrosion inhibitors and deoxidants. Of the additives tested, magnesium has been found to be the best deoxidant and zirconium the best corrosion inhibitor in bismuth. Some experiments1 indicate that magnesium may play a secondary role in increasing the effectiveness of zirconium in inhibiting corrosion. The work reported here was intended to determine the relative concentrations of Mg and U required to prevent oxidation of the uranium fuel in the event of an air leak. In addition, an attempt was made to identify some of the mechanisms of the oxidation and reduction reactions occurring in the liquid bismuth solutions. EXPERIMENTAL Apparatus and Procedure—The equipment shown in Fig. 1 was designed so that the reaction kinetics could be studied as functions of temperature, melt composition, pressure, and flow rate. At the start of a run, the 10-liter bell jar (F) is removed by opening the bottom Dresser fitting (L), and the bismuth and additives are placed in a pyrex crystallizing dish (I). The bell jar is replaced, the system is evacuated to 10-5 to 10-6 mm Hg and then the heater (J) is turned on. When the selected temperature is reached, the oxidizing gas is admitted to the system to the desired pressure as read on the manometer (D). Gas is introduced through the slide tube (Q) which has a pyrex frit (R) sealed to its bottom. Stirring is accomplished by immersing the end of the tube in the melt. To maintain a constant pressure under flow the input and evacuation rates must be equalized. To obtain this condition stopcock (C) is closed and flowmeters (B) are matched. The reaction is "stopped" by closing the inlet flowmeter and quickly evacuating the system. To obtain a liquid metal sample, the system is evacuated with the sampler positioned near the surface of the liquid. The sampler, Fig. 2, is then immersed until its thermocouple reading matches thermocouple (G) Fig. 1. The system is then pressurized with helium which forces the solution through the frit. Twenty to 30 min elapsed between the time the system was evacuated and sampled. During evacuation and pressurization of the system, the temperature variations did not exceed ± 5°C. While bubbling occurred the temperature remained constant to within 1/2 oC. The volume of the equipment was determined by adding a known volume of air at atmospheric pressure to the evacuated system and noting the resulting pressure.

Jan 1, 1962

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By J. H. Bain, D. C. Haigh, L. C. Parsons

Jan 1, 1964

By G. T. Engel, W. G. Gruzensky

Jan 1, 1960

By I. Cadoff, E. Miller, K. Komarek

Jan 1, 1960

By W. J. Kroll

Jan 1, 1960

By Frank E. Woolley, Robert D. Pehlke

Jan 1, 1965

By Thomas C. Wilder

Jan 1, 1965

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By Siegmund Babendererde, Jan O. Babendererde

Extruded Concrete Lining combines technological and financial advantages. The tunnel lining is reliably embedded in the surrounding ground as the fluid concrete is extruded at constant pressure directly behind the TBM supporting the exposed surface. Ground deformation from the TBM passage can be compensated and the ground will be pre-stressed by the extrusion process. Developments in concrete technology permit high speed tunneling by use of a slip formwork attached to the TBM. Realised projects in Milano (Italy), Lyon (France), Frankfurt (Germany) and Akima (Japan) will be demonstrated.

Jan 1, 2001

By F. G. Cottrell

AS previously announced, Van. H. Manning has resigned as director of the Bureau of Mines, effective June 1, to become director of research with the newly organized American Petroleum Institute. Doctor Manning has been connected with the Department of the Interior for 34 years, having been civil engineer with the Geological Survey, from 1885 to 1910, previous to his connection with the Bureau of Mines which was organized in the latter year. Doctor Manning was appointed to an administrative position in the new Bureau under Joseph A. Holmes, its first director, and on Jan. 1, 1911, was made assistant director. On Jan. 1, 1914, when Doctor Holmes had to relinquish active

Jan 1, 1920

By V. I. Kefeli

Public-private partnership efforts are working to create green landscapes from abandoned industrial sites. Fabricated soils, potentially an essential element of such landscapes, are designed to substitute for topsoil on the areas free from ground cover and plant community. The aluminosilicate matrix and humus form the soil micelle - the primary unit of any soil complex. Humus formation is a process based on carbon-nitrogen interaction. Sources of carbon can be materials rich in easily composted products like cellulose and polyphenols (plant leaves) or aged lignin polymers (saw dust from different woody plants). The pathways of carbon-nitrogen complexes are discussed. Properties of the fabricated soil components were examined by bio-tests and plant models.

Jan 1, 2002

By Toshiharu Teranishi

When we apply the Au nanoparticle superlattices to the future nanooptical and nanoelectronic devices, the control of not only the particle size but also the interparticle spacing and symmetry of superlattice are the essential problems to be overcome. First, we developed a novel synthetic procedure to precisely control the particle size of alkanethiol-protected Au nanoparticles in the range from 1.5 to 9.7 nm by the heat-treatment of the small Au nanoparticles in the solid state. Absorption and nonlinear optical properties of alkanethiol-protected Au nanoparticle superlattices were then elucidated. On the other hand, the hexagonal close-packed (hcp) 2D superlattices of small Au nanoparticles with the interparticle spacings from 1.9 to 3.6 nm were successfully prepared by using newly-synthesized ligand for single electron tunneling devices. Finally, various symmetric superlattices, such as chain (2-fold), quasi-honeycomb (3-fold), square (4-fold), etc., of Au nanoparticles could be produced by making use of interligand interactions or some templates.

Oct 1, 2003

By W. D. Maier, H. V. Eales

Paper presented at the IAGOD international symposium on mineralization related to mafic and ultramafic rocks held in Orleans, France, 1-3 September 1993. A lithological and geochemical study revealed significant lateral variation of the interval over 170 km of strike, from about 30 m at the Union Section to 220 m near Brits. The cumulates also become more evolved and leucocratic with distance from the Union Section both towards the NE (Amandelbult) and SE (Impala, Rustenburg and Brits). It is inferred that the persistent heat flux from a putative major feeder zone near the Union Section impaired deposition of felsic cumulates in the vicinity, delaying crystallisation of successive phases in parts of the chamber near the feeder. New influxes were therefore deposited on a footwall of varying thickness and lithology in response to different degrees of crystallisation and accumulation along strike. The development of cyclic units of chromitite, harzburgite, pyroxenite, norite and anorthosite was interrupted at different stages in different parts of the chamber

Apr 1, 1994

By Vaughan J. P

The Pegmont deposit is a stratiform Pb-Zn sulphide body occurring in a thin, iron-rich metasedimentary unit situated near the top of the Kuridala Formation, a part of the Mary Kathleen Group of the Middle Proterozoic"Eastern Geosyncline" succession of the Mount Isa-Cloncurry district. The deposit appears to have developed in a shallow basin or depression on a sea or lake floor.Detailed chemical and mineralogical study of seven diamond drill cores through the ore horizon shows that in addition to galena and sphalerite the orebody contains a large range of iron-rich silicates and aluminosilicates.Further, five drill cores selected to represent a section from basin centre to basin edge exhibit clear and systematic chemical and mineralogical changes in the ore horizon in both a vertical and, most importantly, ill a lateral sense.Reconstruction of the sedimentary environment of the ore horizon as a whole shows this to be a silicate facies of a phosphatic, manganiferous iron formation or, more accurately, of "ironstone" in the sense of James (1966, U.S. Geol. Surv. Prof. Paper 440, chapter W).On the basis of both mineralogy and chemistry this silicate facies may be subdivided into three microfacies according to the dominant iron silicates characteristic of each: a fayalite microfacies, a hornblende-clinopyroxenemicrofacies, and a garnet microfacies. Significant Pb-Zn sulphide concentrations are confined almost entirely to the fayalite microfacies.

Jan 1, 1979

By Alberto Pacheco

El presente trabajo es un análisis del sistema de organización del sistema de seguridad a través del modelo Reason de causalidad o de "queso suizo", donde se identifica qué aspectos y decisiones se convierten en un factor condicionante para un accidente y también cómo la organización puede aprender de un accidente perfeccionando sus defensas en un ciclo de mejora continua. De forma que este modelo explica que un accidente es la consecuencia final de una superposición de fallas que va desde la última línea de defensa, pasando por el acto inseguro, la condición insegura, la falla de la supervisión, la falla de la asesoría (seguridad) hasta la falla de la organización. Para solucionar dicho problema, se realiza una gestión del error que incluye una serie de medidas preventivas como descubrir, evaluar y eliminar los factores que producen el error dentro de la fuerza laboral y así desarrollar la realidad intrínseca de la organización contra los errores humanos.

Sep 13, 2001