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By J. W. Matousek, C. S. Samis

me thermodynamic properties of the components in the Cu-Ni-S ternary system have been studied by measuring the H2S/H2 ratios in a gas phase equilibrated with the molten matte at 1200°C. The measured sulficr potentials have been extended by extrapolation and combtned with previously published data to permit the thermodynamic analysis of the ternary system by integration techniques. A simplifying assumption of ideality in the Ni3Sz-CuS pseudobinary has been made. SINCE copper and nickel metals were first extracted from their sulfide ores the interaction between the two metals and sulfur has been of industrial and theoretical interest. The processes developed to extract copper and nickel have been reported periodically in the literature. The theoretical studies on the Cu-Ni-S ternary have been restricted to problems directly associated with production. It is only within recent years that the binary systems related to this ternary have been analyzed thermodynamically and mathematical devices developed to permit a corresponding treatment of the ternary system. In 1910 an investigation of the role of nickel in Cu-Ni-Fe-S mattes was reported,' It was concluded from this work that nickel is not an element replacing iron in mattes, but rather that Cu-Ni alloys behave as a single metal during the matte converting operation. The laws which govern the converting of Cu-Ni alloys were found to be the same laws as those that govern the conventional converting of copper alone. Although considerable information has been reported on the theoretical aspects of copper smelting, little data is available on the smelting of Cu-Ni ores except for phase diagrams and process descriptions. The available information on the Cu-Fe-S ternary and related systems prior to 1953 has been summarized by Ruddle.2 Since Ruddle's publication, Rosenqvist and coworkers have completed phase equilibria investigations of the Fe-S, Co-S, and Ni-S binaries,3 the Fe-S-O ternary,4 and the Cu-Fe-S-O quaternary.4 An extensive investigation of the Cu-Fe-S ternary system at smelting temperatures has been made by Krivsky and Schuhmann.5 At these temperatures, the Cu-Fe-S system is very similar to the Cu-Ni-S ternary with respect to the location of the single-phase and two-phase liquid matte regions. In the former, however, the area of immiscibility is more extensive and the region of liquid matte-liquid metal-solid metal equilibria is much more extensive. Krivsky and Schumann observed that the Cu2S-FeS pseudobinary system is, for practical purposes, an ideal mixture. This investigation has served as a valuable guide in analyzing the Cu-Ni-S ternary. EXPERIMENTAL The experimental procedure employed in this investigation was the conventional technique of equilibration of the sulfide matte with gaseous mixtures of hydrogen and hydrogen sulfide at 1200°C. The thermodynamic properties of sulfur (S2) in the gas phase are determined by means of Eq. [I] and the activity of sulfur in the matte by Eq. [2].

Jan 1, 1963

By Thomas C. Wilder

Jan 1, 1965

By T. H. Weldon, L. V. Whiton, R. R. McNaughton, J. H. Hargrave

Oxygen enriched air is being used quite extensively in the metallurgical plants of The Consolidated Mining and Smelting Co. of Canada, Limited, at Trail, B.C. The oxygen used for this purpose is a by-product from the Company's chemical plants located in the area. Most of the ore treated in the Trail metallurgical plants comes from Com-inco's Sullivan Mine at Kimberley, B.C. At Kimberley the ore is milled to produce lead and zinc concentrates which are shipped to Trail for further treatment to metal. One section of this paper deals with the use of oxygen enriched air in the suspension roasting of the zinc concentrates. In this process the concentrate is calcined for leaching preparatory to electrolytic recovery of the zinc. A second section of the paper describes the use of oxygen enriched air in operations at the lead smelter. There oxygen enriched air is used in the blast to the lead blast furnaces and in the slag fuming furnace which recovers the lead and zinc contained in lead blast furnace slag. The final section of the paper outlines the precautions necessary for the safe use of oxygen enriched air in any plant operation. The Use of Oxygen Enriched Air in the Suspension Zinc Roasters The suspension roasting of zinc concentrate developed at Trail, B.C., has been described in AIME Vol. 121, "The Electrolytic Zinc Plant of The Consolidated Mining and Smelting Company of Canada, Limited" by B. A. Stimmel, W. 11. Hannay and K. D. McBean. Since the publication of that paper, the use of oxygen enriched air in suspension roasting has been introduced as regular practice with marked advantage. The relative importance of a specific advantage may vary with changing conditions, but, in general, it may be stated that improved operation has been achieved at increased capacities. Suspension roasting is carried out at Trail in converted standard 25 ft diam Wedge roasters. The 2nd, 3rd, 4th and 5th roasting hearths have been removed and the drying hearth covered over. Drying of the concentrate is done on the drying hearth and the 1st roasting hearth. The dried concentrate, after any lump's have been broken up in a ball mill, is fed to a single burner located in the upper part of the combustion chamber. Oxygen is introduced at the burner fan along with the gases from drying, returned combustion gases from the waste heat boiler outlet and the required amount of new air. Up to 60 pct of the concentrate settles out on the 6th roasting hearth, the rest passilig out of the roaster. The product collected in the waste heat boiler is finished calcine, but the dust collected in the cyclones after the boilers is returned to the base of the combustion chamber where the sulphate is decomposed. Gases from the c'yclones go to a Cottrell precipitator. The discharges from the 7th roasting hearth and the waste heat boiler are combined with the Cottrell dust to give the finished calcine. Following small scale tests started in 1933, oxygen enriched air has been used continuously in the suspension roasting of zinc concentrate in Trail, beginning in 1937. A significant factor in promoting its use in this operation was the availability of by-product oxygen from the Company's near-by Chemical and Fertilizer Division. To-day it is standard practice at Trail to use oxygen enriched air for zinc concentrate roasting. The most important requirement in roasting a zinc concentrate for an electrolytic plant is that the zinc in the calcine should have maximum solubility. It is also desirable at Trail that the gas produced for the manufacture of suhhuric acid should have a ~naximum concentration of SO2 and that a substantial recovery of waste heat from the gas be achieved. High solubility of zinc requires that the sulphide sulphur and zinc ferrite in the calcine be kept low. These are both functions of temperature and time, with formation of zinc ferrite also dependent on contact between the iron and zinc particles. One of the inherent advantages of suspension roasting is that minimum time and contact are achieved. The limit on temperature is imposed by the fusion point of the concentrate and not by the need to control zinc ferrite formation. Operating temperatures are normally maintained within the limits of 1725" and 1850°F. A relatively low zinc sulphate in the calcine is required at Trail, and this results from discharging the calcine from the high sulphur dioxide atmosphere at a temperature above 1600°F.

Jan 1, 1950

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By H. H. Kellogg, T. R. Ingraham

Three anhydrous zinc sulfates have been identified. They are: ZnSO,(a), stable below 1007°K; ZnS04(/3), stable above 1007OK; and ZnO.ZZnSO,. The decomposition pressure of each sulfate has been measured and the following relations calculated from the results: The measured data have been combined with the known themzodynamic properties of ZnS, ZnO, Zn, SO,, and SO, to yield univariant and bivariant phase diagrams for the system Zn-S-0. The application of these diagrams to problems of roasting zinc concentrates is discussed. PRESENT knowledge of the equilibrium chemistry of the system Zn-S:O, so essential to scientific control of zinc-blende roasting, is deficient in several respects. A basic sulfate of zinc has been reported by many investigators, but its composition is in doubt and its thermodynamic properties have not been measured. Our scanty knowledge of the properties of the normal sulfate at roasting temperatures is based on old and inexact studies. A crystal transformation in the normal sulfate, involving a sizable heat effect, has been noted by several investigators but has never been quantified. The studies reported herein were designed to fill these gaps in knowledge and to make possible a reasonably complete thermodynamic description of the system Zn-S-0 at roasting temperatures. The results make possible a far more exact understanding of zinc roasting chemistry than was hitherto possible. EXPERIMENTAL The principal experimental technique employed was the measurement of the total gas pressure developed from decomposition of either ZnSO, or ZnO2ZnS0, in a closed system. The apparatus employed was essentially the same as that described by Warner and lngrahaml and Flengas and tngraham.' The unusual feature is a flexible Pyrex bellows used to separate the reaction gas mixture (S03, SOz, and 02) from the mercury in the manometer and thus prevent corrosion of the mercury by SO3. The bellows operates without evidence of hysteresis and, barring accidents, may be used for several months. The response of the bellows varies from manometer to manometer, but is generally of the order of 0.6-cm displacement for a l-cm change in pressure. The response for all manometers has been linear over the range 0 to 1 atm. To prevent condensation and polymerization of sulfur trioxide, the bellows-manometer was maintained at 100.0" * 0.5" by a circulating bath of silicone oil. The connecting tubing between the manometer and the furnace was maintained at 100.0" * 0.2"* also, with a stirred air bath. The open end of the manometer was connected with a chamber which was maintained at a known pressure. The pressure could be varied so that readings of the height of the mercury column, measured with a cathetometer, could be made with both rising and falling mercury column. By using the average of the readings, any error due to sticking of the mercury column was minimized. The sample was placed in a 2-in.-long platinum boat formed into the shape of a half-cylinder. The sample was prepared as a fine powder and pressed against the inner wall of the platinum boat. A silica thermocouple well, covered with a platinum sleeve, was placed lengthwise along the center of the boat. The temperature of the sample was read on a calibrated Pt-10 pct Rh theirnocouple. The temperature profile of the furnace was constant within ± 0.2 C over the length of furnace occupied by the sample. The horizontal furnace used to contain the sample and the quartz reaction tube was electrically heated, with the control thermocouple placed 1/4 in. from the windings. A Brown Pyro-O-Vane temperature controller with a 3-sec response time was used to maintain the furnace temperature. Before beginning a run, the apparatus, including the bellows manometer, was thoroughly washed in sib with acid and distilled water to remove any

Jan 1, 1963

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

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 D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty 'metallic' orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By R. J. Hopkins, L. B. Haney

On the basis of limited experimental work conducted at the Port Pirie smelter, it would appear that, by increasing the specific surface of sinter, and possibly that of coke as well, a marked increase in the rate and degree of sinter reduction in the furnace shaft can be achieved. Fusion-point tests have shown that this increased reduction means a much higher sinter fusion point and narrower plastic zone, while the more efficient utilization of coke in the furnace is inherent in the intensification of reduction by the provision of a more reactive sinter surface. Investigations aimed at increasing the ability to operate the blast furnace with a higher lead tenor of sinter reducing fuel cost proportionately, and at eliminating the loss in reduction potential in coke entering the furnace, as shown by the presence of appreciable proportions of CO in the top gases, are reported. Several lines for future investigations that could result in improved smelting methods are proposed. A SOMEWHAT informal presentation of ideas on lead blast-furnace smelting will be given in this paper. These ideas have been developed during observations of furnace behavior at Port Pirie and earlier at Mt. Isa, and have been guided by the results of laboratory experiments at Port Pirie. The authors do not intend to propound any particularly new theories, but present their ideas as a basis for discussion which may help toward a better understanding and improved control of blast-furnace operation. Performance variations of considerable magnitude occur from time to time at most lead blast-furnace plants. While Port Pirie is fortunate in having a very regular supply of high grade concentrates, it is no exception in this respect. Such irregularities are of considerable economic importance and they constitute a challenge to present-day metallurgists in their efforts to obtain an ever greater degree of control over furnace operation. In operating as Port Pirie does with a relatively high lead charge, it has been recognized for a long time that shaft conditions are ,of the greatest importance. A practical, or engineering, attack on the problem of accretions consisted of changes in furnace design, e.g., by widening the shaft to 10 ft above the bottom row of tuyeres, and by the provision of curved ends and vertical walls.' That this attack has had a great measure of success is shown by the fact that barring down of these wide furnaces is rarely necessary, shaft conditions have greatly improved, and sensitivity to charge variations has been markedly reduced. These modifications, followed by some metallurgical changes (chiefly the incorporation of pig iron into the furnace charge in 1948), have brought furnace operation to a point where some variables which were previously masked can now be studied. Accordingly, over different periods of time during the last five years, such variables as could be given numerical values have been recorded and subjected to statistical examination. The objectives of this work were: 1—to reveal the true importance of the different variables and 2—to show the proportion of total furnace variation which is unexplained and therefore referable to causes not measured at present? e.g., shaft accretions, sinter structure, coke structure, and others. Statistical Study of Variables In this work factors relating to furnace speed and lead reduction have been examined: 1—slag com-

Jan 1, 1955

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962

By R. E. Steiner, A. F. Weinberg, R. J. Van Thyne

Uranium solubility in molten bismuth was determined in the temperature range 350" to 600°C, varying from 0.09 wt pct to near 2 wl pct, respectively. Zirconium and magnesium, simulated fission products, and sodium were found to increase or decrease uranium solubility in bismuth in the temperature range 370° to 420°C, depending upon the addition or temperature. Data were obtained by both chemical analysis of samples obtained by filtration from saturated melts and by measurement of the variation of electrical resistance with temperature. IN a study for the United States Atomic Energy Commission, a Liquid Metal Fuel Reactor Experiment (LMFRE) was proposed in which a solution of uranium dissolved in molten bismuth served as both the fuel solution and the primary coolant. It was proven necessary to add other elements to this solution for certain desirable properties: 1) zirconium acts to prevent reaction of the fuel solution with the graphite core (which would result in the formation of uranium carbide) and also to inhibit mass transfer of iron and chromium from the walls of the reactor tubing to cold spots resulting in blockage; and 2) magnesium acts as a deoxidant and prevents loss of uranium. In addition to these intentional additives, other elements entering the solution are: 1) fission products which are a by-productof reactor operation, 2) sodium (the secondary coolant) through possible small leaks in the heat exchange system, and 3) iron and chromium from the container walls. Each of these elements may affect the solubility of uranium in the fuel solution. Since the concept of this reactor is based upon a liquid solution, the relatively low solubility of uranium in bismuth will dictate the minimum temperature at which the reactor heat exchanger can be operated. The solubility of uranium in liquid bismuth and the effect of some additives on this solubility have pre- viously been investigated1-' (more recent results6" became avaliable after initiation of this investigation). However, some discrepancies between the various results have been noted, and also the cumulative effect of the several additions or impurities was not known. This investigation was commenced to obtain definitive results. MATERIALS Analyses of the materials used are presented in Table I. Although ostensibly of extreme purity (99.999 wt pct), the bismuth was found to contain a significant amount of impurities, probably oxides. Except for determination of the binary system, Bi-U, prior to use all bismuth was hydrogen-refined and

Jan 1, 1962

By R. W. Mancantelli, J. R. Woodward

IN 1947 a large low grade deposit of uranium was located in the northwest corner of Saskatchewan, in the Beaverlodge property of Eldorado Mining & Refining Ltd. Most of the values occur as thin seams and as coatings on other minerals, and the ore, which is light and friable, is not amenable to the usual gravity methods of concentration. The acid leaching process developed to retreat the company's Port Radium tailings was also impractical, as the percentage of carbonates is high and the percentage of sulphides relatively low. Construction of the mill building and installation of equipment, both scheduled for 1952, awaited selection of a satisfactory ore dressing process on or before Oct. 1, 1951. An extensive research program on dressing of ores from the Ace mine therefore was undertaken by the Mines Branch in Ottawa, a research team at the University of British Columbia, and an ore dressing group at the company's Port Hope refinery. Pilot plant operations were conducted at the Ottawa plant of Sherritt Gordon Mines Ltd. under the general direction of C. S. Parsons, consultant on metallurgy and ore dressing for Eldorado. In mid-September, having compared results of the several research programs, Dr. Parsons recommended a process employing a carbonate or basic leach. He reported that, while the chemistry of the process had been proved, engineering of the flowsheet was incomplete, and he suggested that under normal conditions further pilot plant work at the Ace mine might be profitable. However, since this would involve a delay of 12 to 18 months in bringing the property into operation, he recommended that design of the concentrator proceed immediately. Concentrator capacity was determined by two considerations: 1) the amount of ore then available and 2) the expectation that continued improvements would be made in the ore dressing process as a result of the intensive research being carried out by the Mines Branch of the Department of Mines and Technical Surveys. As these improvements could affect both the chemistry and the en-

Jan 1, 1956

By A. W. Schlechten, R. F. Doelling

Parkes' process crusts were vacuum distilled using a shortened Pidgeon retort. Zinc was effectively removed below 800°C and recovered as a zinc sheet easily stripped from the furnace liner. Lead dasdistillationazinc required about 950°C and the resulting lead condensate tillationtended to stick to the thin metal liner. Final purity of residue is limited only by nonvolatile metals such as copper. THE successful commercial application of vacuum distillation for the removal of zinc from lead, as described by W. T. Isbell,' raises the question of whether or not a similar method can be used for other metal separations. Preliminary laboratory experiments on the vacuum distillation of Parkes' crusts by one of the authors' gave such encouraging results that it was decided to make a series of tests with large scale equipment to determine the results that might be expected in plant operation. The pilot-plant test results are reported in this paper. The great advantages of vacuum dezincing are its simplicity, the relatively low temperature of operation, and the fact that the zinc is recovered in the metallic state ready for use again in the desilveriza-tion of lead bullion. These same advantages and others would be realized from the vacuum distillation of the zinc-lead-silver crusts made in the Parkes' process. Zinc readily will distill over at temperatures of 800" to 900 °C as contrasted with the 1200°C or more used in the Faber du Faur furnace. Furthermore, the recovery of zinc as metal is practically perfect since there is no loss by oxidation or fuming. If the vacuum distillation is continued and hastened by raising the temperature to around 1000°C, the lead will distill over at an appreciable rate and deposit in a warmer zone of the condenser. This lead will contain a small amount of silver, but it can be returned to the desilverizing kettles and there is not the chance of loss that there is in disposing of the rich litharge from cupelling. The lower temperatures required will mean a saving of fuel and less wear on the equipment. One further point is that the vacuum distillation could be run on a small scale practically continuously, so as to avoid the accumulation of large amounts of silver-rich material and the need of assembling a large crew for special cupellation runs. It should be pointed out here that the final purity of the silver residue will depend on the copper or iron content of the crusts, as these and other metals with low vapor pressure will not be eliminated. The idea of treating the silver-zinc-lead crusts from the desilverization of lead bullion by vacuum distillation is not a new one, but such experiments have not been reported, as far as can be determined. In 1912, T. Turner presented a paper3 before the Institute of Metals on the vacuum distillation of brass, and a member of the audience suggested that he try his method on Parkes' crusts. In 1935, W. J. Kroll, noted for his discovery of debismuthiz-ing lead by calcium additions, published a paper' on vacuum distillation of metals and pointed out possible applications in the lead industry. Principles of Separation The successful separation of two or more metals by distillation depends upon an appreciable difference in the effective vapor pressures of the metals in the alloy to be treated. The vapor pressures of the common metals have been determined with considerable accuracy; for example, at 800°C the vapor pressures of the individual metals which are of particular interest in this paper are about .as follows: Zn, 241 mm; Pb, 0.0553 mm; and Ag, 0.0000276 mm. Unfortunately,, data are not available on the activities of the components in the ternary system Zn-Pb-Ag, but it can be estimated that on the basis of the vapor pressures of the individual metals a good separation can be made by distillation. The preliminary laboratory tests previously mentioned' supported this assumption. The pilot-plant size vacuum distilling furnace is shown in Fig. 1. It consisted of an abbreviated Pidgeon retort, 5 ft long with an ID of 8 in., heated by six silicon carbide elements placed symmetrically

Jan 1, 1952

By F. Habashi

"A short account will be presented on the extraction of rare earths from monazite sand, bastnasite ore, and phosphate rock of igneous origin. This includes mineral beneficiation, leaching methods, fractional crystallization [of historical interest], ion exchange, solvent extraction, precipitation from solution, and reduction to metals. INTRODUCTIONOriginally, the term rare earths was only used for the oxides, R2O3, which are similar to one other in their chemical and physical properties and are therefore difficult to separate. Within the rare earth group, the elements scandium, yttrium, and lanthanum differ in their atomic structure from the elements cerium to lutetium (the lanthanides, Ln). Scandium occupies a special position with respect to this classification and its other properties, and therefore does not belong to either of these groups. The rare earth elements always occur in nature in association with each other. The isolation of groups of rare earth elements or of individual elements requires costly separation and fractionation processes owing to the great similarity of the chemical and physical properties of their compounds, which explains why the history of their discovery has extended over such a long period.The word “rare”, when used to describe this group of elements, originates from the fact it was thought that these elements could only be isolated from very rare minerals. Considering their abundance in the Earth’s crust, the term rare is now inappropriate. These elements are lithophilic and are therefore concentrated in oxidic compounds such as carbonates, silicates, titano-tantalo-niobates, and phosphates.The abundance of the rare earth elements taken together is quite considerable. Cerium, the most common rare earth, is more abundant than cobalt. Yttrium is more abundant than lead, whereas Lu and Tm are as abundant as Sb, Hg, Bi, and Ag. For all practical purposes promethium does not occur in nature. It forms only in nuclear reactors."

Jan 1, 2012

By C. D. Anderson

A variety of processing technologies exist for recovery from both primary and secondary sources of rhenium. Currently, there are no known primary rhenium deposits, thus, the method in which primary rhenium is produced is dependent on the commodity of which it is a byproduct, e.g., copper, molybdenum, uranium, etc. In addition, focus on the recovery of rhenium from secondary sources, such as alloy scraps and catalysts, is continually growing. This paper presents a review of both primary and secondary processing technologies for the recovery of rhenium. Key Words: Rhenium, Ammonium Perrhenate, Extractive Metallurgy

Feb 27, 2013

By C. D. Anderson

A variety of processing technologies exist for recovery from both primary and secondary sources of rhenium. Currently, there are no known primary rhenium deposits; thus, the method in which primary rhenium is produced is dependent on the commodity of which it is a byproduct, e.g., copper, molybdenum, uranium, etc. In addition, focus on the recovery of rhenium from secondary sources, such as alloy scraps and catalysts, is continually growing. This paper presents a review of both primary and secondary processing technologies for the recovery of rhenium.

By D. R. Spink

An historical background is presented to provide a basis for the lack of normally expected developmental effort over the first 20-25 years of viable zirconium production operations. This is followed by a description of developing technology, which is the result of years of research and piloting effort directed to the development of a more economical method to produce high-grade metallic zirconium. It is predicted that many of the process improvements described will have a significant impact on future zirconium production methods and consequently on future prices and markets.

Jan 1, 1977

By R. E. Allen, A. C. Jephson

ELECTROLYTIC zinc plants of the American Smelting and Refining Co. are located adjacent to the present city limits of Corpus Christi, Texas. The original plant commenced operations during 1942, and is designed for the production of special high grade zinc from zinc sulfide concentrates.' Subsequent changes include the erection of an additional acid plant during 1950, and additions for increased generating and production capacity during 1951. New Electrolytic Plant—The new electrolytic plant is a separate unit erected for the treatment of densified fume produced at Asarco plants located in El Paso, Texas and Chihuahua, Mexico. Construction was completed and operation commenced during June, 1953. Decision for the erection of a separate plant for the treatment of densified fume is based on several factors. One of the principal reasons is the assurance of continued production rate of the original plant, which might have been jeopardized by combined treatment of calcine and fume. Of equal importance is the advantage of locating a plant on a site with adequate space for eventual expansion. General Description—The new plant for the treatment of densified fume consists of four main buildings for the following operations: storage and grinding of fume, leaching and purification, electrolyzing and casting, and rectifier units. Auxiliary buildings include a baghouse, reagent storage, and a lunch room. Leaching of ground fume with electrolyte from the cells is a batch type operation in tanks equipped with mechanical agitators and weightometers. Completed leaches are pressure filtered, the resultant residue being recovered for shipment to El Paso by conventional use of thickeners, drum type vacuum filters, and a direct-fired dryer. Filtrates from the filter section are purified in mechanically agitated tanks, filtered after completion through plate and frame presses, and then pumped to an evaporative type cooling tower. Solution discharged from the basin of the cooling tower is collected in storage tanks for use in the cells. The cool purified solutions are pumped as required from storage to the solution circuit for circulation of electrolyte through the cells. Except for the addition of purified feed solution and withdrawal of electrolyte for leaching, the circulating system for the cells is essentially a closed continuous circuit that includes the use of evaporative cooling towers for control of solution temperatures. Aluminum cathodes and Ag-Pb anodes are used for electrolysis, which is maintained at a current density of about 82 amp per sq ft. Cathode zinc produced is melted in a gas-fired reverberatory furnace and then cast into slabs on a straight line casting machine. Unloading and Storage—Fume produced by the Chihuahua plant is shipped in box cars, and fume by the El Paso plant in hopper bottom dump cars. Shipments as received are weighed on a 7 5-ton capacity railroad scale, sampled, and then moved over one of the two unloading hoppers with a car puller. The cars are then unloaded with mechanized equipment, a car scoop being used for unloading of box cars and a car shaker for the hopper bottom cars

Jan 1, 1958

By J. F. Mitchell, R. Bainbridge, E. A. Melvin

IN the fall of 1953, The Consolidated Mining and Smelting Co. of Canada Ltd. put into operation a completely new and modern plant for sintering the rather complex assortment of materials which comprise the feed to the Lead Smelter at Trail, British Columbia. This Lead Smelter is one section of an integrated metallurgical plant producing lead, zinc, silver, gold, cadmium and other metals. Since most of the incoming lead concentrate contains appreci- able zinc values, and most of the zinc concentrate similarly contains appreciable lead values, the cross-routing of residues or tails from the respective lead and zinc plants offers obvious advantages in recovery of metals, and has been practiced for many years. A disparity has existed, however, between the output of zinc plant residue and the capacity of the Lead Smelter to treat it, with the result that over the years a stock-pile of residue had been accumulating, and by the end of World War II had reached the formidable total of half a million tons. To treat this stock-pile, in addition to all current zinc plant residues and, of course, the regular quota of lead concentrates, became a prime objective of the Lead Smelter following World War 11. As zinc plant residue plays an important part in the operations to be discussed in this paper, some consideration of its

Jan 1, 1958